TW201715308A - Composition, cured film, pattern, pattern manufacturing method, optical sensor, and imaging element - Google Patents

Abstract

This composition contains (A) a binder, (B) a monomer, (C) a polymerization initiator, (D) particles having an average diameter of 50nm or greater, and (E) a solvent; this cured film is formed using said composition; the pattern manufacturing method uses said composition; the pattern is manufactured by said manufacturing method; and the optical sensor and imaging element use said cured film.

Description

Composition, cured film, pattern, pattern manufacturing method, optical sensor, and imaging element

The present invention relates to a composition, a cured film using the composition, a pattern, a method for producing a pattern, an optical sensor, and an image pickup element.

In recent years, a white resist is required in order to adjust the appearance of various sensors and optical members. In order for such white resists to withstand processes such as assembly of sensors, high resistance and adhesion are required. Further, the white resist requires photolithography in order to form a pattern only at a desired portion. Further, since the white resist uses relatively large particles having a particle diameter of 50 nm or more by scattering of light, there is a problem in safety. Therefore, storage stability and redispersibility have become important. For example, Patent Document 1 describes a white photosensitive resin composition that uses a reducing blue dye to obtain a cured product that suppresses discoloration due to a thermal process. However, it is required to add a coloring agent, and there is a problem in the resolution of the pattern.

Further, Patent Document 2 discloses a white photosensitive resin composition using an oxime ester photopolymerization initiator, which is described as being capable of accurately forming a pattern latent image, but has a problem in coloring resistance. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2008-150461 [Patent Document 2] JP-A-2008-134621

The present invention has been made in view of the above-described problems of the prior art, and provides a uniform in-plane uniformity and a flat transmittance in a visible region, resistance, lithography, storage stability, adhesion, redispersibility, A composition of a cured film having excellent coating uniformity, a cured film, a pattern, a method for producing a pattern, an optical sensor, and an image pickup element.

The specific method for solving the above problems is as follows. (1) A composition comprising (A) a binder, (B) a monomer, (C) a polymerization initiator, (D) particles having an average particle diameter of 50 nm or more, and (E) a solvent. (2) The composition according to (1), wherein the particles of (D) are metal particles. (3) The composition according to (2), wherein the particles of (D) are titanium dioxide. (4) The composition according to any one of (1) to (3), wherein (D) has an average particle diameter of 150 nm or more. (5) The composition according to any one of (1) to (4), further comprising (F) a coloring preventive agent. (6) The composition according to (5), wherein the (F) coloring preventing agent is a phenol compound. (7) The composition according to (6), wherein the (F) coloring preventing agent is a phenol compound having a substituent in the ortho position of the phenolic hydroxyl group. (8) The composition according to any one of (1) to (7), further comprising a dispersant, wherein the dispersant is a polymer dispersant having an adsorption site. (9) The composition according to (8), wherein the adsorption site is an acid adsorption site. (10) The composition according to (9), wherein the acid-based adsorption site is at least one of a phosphorus atom-containing group and a carboxylic acid group. (11) The composition according to (1), wherein the (C) polymerization initiator is an anthracene compound. (12) The composition according to any one of (1) to (11) further comprising a color material. (13) A cured film formed using the composition according to any one of (1) to (12). (14) A method for producing a pattern, comprising: a process of applying the composition according to any one of (1) to (12) on a substrate; a process of performing exposure through a mask; and performing the film after the exposure A process of developing to form a pattern. (15) A pattern produced by the production method described in (14). (16) An optical sensor using the cured film formed using the composition according to any one of (1) to (12). (17) An image pickup element using the cured film formed using the composition according to any one of (1) to (12).

According to the present invention, it is possible to provide a cured film which is excellent in uniformity in the in-plane and which has flat transmittance in the visible region, and is excellent in resistance, photolithography, storage stability, adhesion, redispersibility, and coating uniformity. A composition, a cured film, a pattern, a method of manufacturing a pattern, an optical sensor, and an image pickup element.

In the label of the group (atomic group) of the present specification, the unsubstituted and unsubstituted label includes a group having no substituent (atomic group) and a group having a substituent (atomic group). For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). The description of the constituent elements described below may be performed in accordance with a representative embodiment of the present invention, but the present invention is not limited to the embodiment. In addition, the numerical range represented by "-" in this specification is a range which shows the numerical value of the below-mentioned and the upper- In the present specification, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic" means acrylic acid and methacrylic acid, and "(meth)acrylic acid" means acrylonitrile and methacrylic acid. Acryl hydrazine. Further, in the present specification, "single body" has the same meaning as "monomer". The "single amount" in the present invention is distinguished from the oligomer and the polymer by a compound having a weight average molecular weight of 2,000 or less. In the present specification, the term "polymerizable compound" means a compound having a polymerizable group, and may be a single amount or a polymer. The "polymerizable group" is a group which participates in a polymerization reaction.

<Composition (Photosensitive Resin Composition)> The composition of the present invention contains (A) a binder, (B) a monomer, (C) a polymerization initiator, (D) particles having an average particle diameter of 50 nm or more, and (E) ) Solvent. This has the appearance of a white color derived from the scattering of the particles.

The composition of the present invention can also be used for the purpose of adjusting the appearance of various optical sensors. In this case, in order to exhibit the function of the optical sensor, the lowest transmittance in the range of 400 nm to 700 nm is preferably 1% or more, more preferably 5% or more, and still more preferably 10% or more. Further, from the viewpoint of the appearance adjustment, in order to maintain a white hue, the average transmittance in the range of 400 nm to 700 nm is preferably 70% or less, more preferably 60% or less, still more preferably 50% or less.

[(A) Adhesive] The composition of the present invention contains a binder from the viewpoint of improving film properties and the like. It is preferred to use a linear organic polymer as the binder. As such a linear organic polymer, a known organic polymer can be used arbitrarily. In order to achieve water development or weak alkaline water development, a linear organic polymer which is soluble or swellable in water or weakly alkaline water is preferred. The linear organic polymer is used not only as a film forming agent but also as a developer for water, weak alkaline water or an organic solvent. For example, if a water-soluble organic polymer is used, water development can be achieved. Examples of the linear organic polymer include a radical polymer having a carboxylic acid group in a side chain. For example, JP-A-59-44615, JP-A-54-34327, and JP-A-58-12577 Japanese Patent Publication No. Sho 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, and JP-A-59-71048 a resin which is polymerized or copolymerized alone, a resin which polymerizes or copolymerizes the monomer having an acid anhydride alone to hydrolyze or semi-esterify or semi-esterify the acid anhydride unit, and reforms the epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride. Epoxy acrylate and the like. Examples of the monomer of the carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Examples of the monomer having an acid anhydride include maleic anhydride. Further, there is an acidic cellulose derivative which also has a carboxylic acid group in the side chain. It is useful to add a cyclic acid anhydride to a polymer having the other hydroxyl group. It is preferred that the composition of the present invention has a binder dissolved in an alkaline developer.

In the present invention, when a copolymer is used as the binder, a monomer other than the monomers exemplified above can be used as the compound to be copolymerized. Examples of the other monomer include the following compounds (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl Acrylates and methacrylates having aliphatic hydroxyl groups such as methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate. (2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid - 2-chloroethyl ester, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-ene acrylate An alkyl acrylate such as propoxyethyl acrylate or propargyl acrylate.

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, methacrylic acid 2 -ethylhexyl ester, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, Vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate, etc. Methacrylic acid. (4) Acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyl Ethyl acrylamide, N-phenyl acrylamide, N-nitrobenzene acrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide , N,N-diallyl acrylamide, N,N-diallyl methacrylamide, allyl acrylamide, allyl methacrylamide, acrylamide or methacryl Guanamine.

(5) Ethylene vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether and other ethylene Base ethers. (6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate. (7) Styrene such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene or p-ethoxylated styrene. (8) A ketene such as methyl ketene, ethyl ketene, propyl ketene or phenyl ketene. (9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene. (10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, and the like. (11) Maleidin, N-propylene propylene amide, N-ethyl methacrylamide, N-propyl methacrylamide, N-(p-chlorobenzoyl) A An unsaturated quinone imine such as acrylamide. (12) A methacrylic monomer which bonds a hetero atom at the α-position. For example, the compounds described in each of the publications such as JP-A-2002-309057 and JP-A-2002-311569 can be cited.

In the present invention, the monomers are not particularly limited within the scope of the present invention, and the copolymer can be synthesized by combination. For example, an example in which a copolymer containing a single component of the monomers is polymerized is shown below, but the present invention is not limited thereto. The composition ratio of the exemplified compounds described below is mol%.

[Chemical Formula 1]

The above-mentioned binder is preferably a repeating unit obtained by polymerizing a monomer component of a compound represented by the following formula (ED) (hereinafter sometimes referred to as "ether dimer").

[Chemical Formula 2]

(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.)

Thereby, the composition of the present invention can form, for example, a cured film excellent in coloring resistance for heating by heating at 265 ° C for 15 minutes or the like. In the general formula (ED) which is an ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include a methyl group and an ethyl group. a linear or branched alkyl group such as n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl or 2-ethylhexyl; phenyl Isoaryl; cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, 2-methyl-2-adamantyl and the like alicyclic; An alkyl group substituted with an alkoxy group such as a methoxyethyl group or a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as a benzyl group or the like. From the viewpoint of heat resistance, such a substituent such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group which is not easily desorbed by an acid or heat is particularly preferable.

Specific examples of the ether dimer include the ether dimer described in paragraph <0565> of the specification of the Japanese Patent Application Laid-Open No. 2012/235099, which is incorporated herein by reference. Specific examples, and the contents are incorporated in the present specification. As a specific example of the ether dimer, dimethyl-2,2'-[oxybis(methylene)]bis-2-propionic acid, diethyl-2,2'-[oxybis(Asian) Methyl)]bis-2-propionic acid, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-propionic acid, dibenzyl-2,2'-[oxy double (Methylene)]bis-2-propionic acid is especially preferred. These ether dimers may be used alone or in combination of two or more. Further, the structure derived from the compound represented by the general formula (ED) may copolymerize other monomers.

Examples of the other monomer which can be copolymerized with the ether dimer include a single amount for introducing an acid group, a single amount for introducing a radical polymerizable double bond, and an epoxy group for introducing an epoxy group. Monoliths and other copolymerizable monoliths other than those. These single bodies may be used alone or in combination of two or more.

Examples of the monomer for introducing an acid group include a monomer having a carboxyl group such as (meth)acrylic acid and itaconic acid, and a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide or a horse. A monomer having a carboxylic acid anhydride group such as phthalic anhydride or itaconic anhydride. Among these, (meth)acrylic acid is particularly preferred. Further, the monomer to be introduced into the acid group may be a monomer which can give an acid group after the polymerization, and examples thereof include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, and (meth). A monomer having an epoxy group such as a monovalent amount of an epoxy group such as glycidyl acrylate or an isocyanate group such as 2-isocyanatoethyl (meth)acrylate. In the case of using a monomer for introducing a radical polymerizable double bond, it is preferred to carry out a treatment for imparting an acid group after polymerization, in the case where a single amount of an acid group can be used after the polymerization. The treatment for giving the acid radical after the polymerization differs depending on the type of the monomer, and examples thereof include the following treatments. When a monomer having a hydroxyl group is used, for example, a treatment of an addition anhydride such as succinic anhydride, tetrahydrophthalic anhydride or maleic anhydride can be mentioned. In the case of using a monomer having an epoxy group, for example, a compound having an amine group and an acid group such as N-methylamino benzoate or N-methylaminophenol may be added or, for example, added. The hydroxyl group produced after the acid of (meth)acrylic acid is added, for example, to an anhydride such as succinic anhydride, tetrahydrophthalic anhydride or maleic anhydride. When a monomer having an isocyanate group is used, for example, a treatment of a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

In the case where a polymer comprising a monomer component of the compound represented by the general formula (ED) is contained in a single amount for introducing an acid group, the content thereof is not particularly limited, and is 5 to 5 in the total monomer component. 70% by mass is more preferable, and 10 to 60% by mass is more preferable.

Examples of the monomer for introducing a radical polymerizable double bond bond include a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid; and a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride. a monomer having an epoxy group such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, o- (or m- or p-)vinylbenzyl glycidyl ether Body and so on. In the case of using a single body for introducing a radical polymerizable double bond, it is preferred to carry out a treatment for imparting a radical polymerizable double bond after polymerization. The treatment for imparting radical polymerizable double bond bonding after the polymerization differs depending on the type of the monomer which can be used to impart radical polymerizable double bond bonding, and examples thereof include the following treatments. In the case of using a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid, addition of glycidyl (meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate may be mentioned. The treatment of a compound having an epoxy group and a radically polymerizable double bond, such as o- (or m- or p-) vinylbenzyl glycidyl ether. When a monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride is used, an addition of a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a radical polymerizable double bond may be mentioned. Treatment of the compound. In the case of using an epoxy group-containing monomer such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, o- (or m- or m-) vinylbenzyl glycidyl ether In the case of addition, a compound having an acid group and a radical polymerizable double bond-bonded compound such as (meth)acrylic acid may be added.

In the case where a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) contains a single body for introducing a radical polymerizable double bond, the content ratio thereof is not particularly limited, and The amount of the monomer component is preferably 5 to 70% by mass, more preferably 10 to 60% by mass.

Examples of the monomer for introducing an epoxy group include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and o- (or m- or p-)ethylene. Glycidyl glycidyl ether and the like. In the case where a polymer comprising a monomer component of the compound represented by the general formula (ED) is contained, and a monomer for introducing an epoxy group is contained, the content ratio thereof is not particularly limited, and is contained in the total monomer component. It is preferably from 5 to 70% by mass, more preferably from 10 to 60% by mass.

Examples of the other copolymerizable monovalent body include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (methyl). ) n-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid (meth) acrylate such as benzyl ester or 2-hydroxyethyl (meth)acrylate; aromatic vinyl compound such as styrene, vinyl toluene or α-methylstyrene; N-phenylmaleimide N-substituted maleimide such as N-cyclohexylmaleimide; butadiene or substituted butadiene compound such as butadiene or isoprene; ethylene, propylene, vinyl chloride, acrylonitrile, etc. Ethylene or substituted vinyl compounds; vinyl esters such as vinyl acetate, and the like. From the viewpoints of good transparency and resistance to heat resistance, such (meth)acrylic acid methyl ester, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and styrene are preferred.

In the case where a polymer comprising a monomer component of the compound represented by the general formula (ED) is contained in another monomer which is copolymerizable, the content ratio is not particularly limited, and 95% by mass or less is preferable. The mass % or less is more preferable. The weight average molecular weight of the polymer obtained by polymerizing the monomer component of the compound represented by the general formula (ED) is not particularly limited, and is considered from the viewpoint of the viscosity of the composition and the heat resistance of the coating film formed by the composition. More preferably, it is more preferably from 5,000 to 100,000, more preferably from 5,000 to 20,000, and further preferably from 5,000 to 20,000. Further, when the polymer obtained by polymerizing the monomer component of the compound represented by the formula (ED) has an acid group, the acid value is preferably from 30 to 500 mgKOH/g, more preferably from 50 to 400 mgKOH/g.

Polymerization of a polymer comprising a single component of a compound represented by the general formula (ED) polymerizes at least a single amount of an ether dimer, which can be easily obtained. At this time, the cyclization reaction of the ether dimer is carried out simultaneously with the polymerization to form a tetrahydropyran ring structure. The polymerization method for the synthesis of a polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) is not particularly limited, and various conventionally known polymerization methods can be employed, and polymerization by a solution polymerization method is particularly preferable. good. Specifically, for example, the polymerization of the polymer (a) described in JP-A-2004-300204 can be used to synthesize and polymerize a monomer component containing a compound represented by the formula (ED). Things.

Hereinafter, an exemplary compound in which a polymer comprising a monomer component of the compound represented by the general formula (ED) is polymerized is shown, but the present invention is not limited thereto. The composition ratio of the exemplified compounds shown below is mol%.

[Chemical Formula 3]

[Chemical Formula 4]

In the present invention, dimethyl-2,2'-[oxybis(methylene)]bis-2-propionic acid (hereinafter referred to as "DM"), benzyl methacrylic acid (hereinafter referred to as "BzMA") ") polymerization of methyl methacrylate (hereinafter referred to as "MMA"), methacrylic acid (hereinafter referred to as "MAA"), 2-hydroxypropylene glycol dimethacrylic acid (hereinafter referred to as "X") copolymerization Things are especially good. DM: BzMA: MMA: MAA: X has a molar ratio of 5 to 15:40 to 50:5 to 15:5 to 15:20 to 30. It is preferred that 95% by mass or more of the components constituting the copolymer used in the present invention are these components. Further, the polymer preferably has a weight average molecular weight of 9000 to 20,000. The weight average molecular weight (polystyrene equivalent value measured by GPC method) of the polymer used in the present invention is preferably from 1,000 to 2 × 10 ⁵ , more preferably from 2,000 to 1 × 10 ⁵ , and from 5,000 to 5 × 10 ⁴ is further preferred.

The weight average molecular weight (the polystyrene equivalent value measured by the GPC method) of the binder used in the composition of the present invention is preferably 5,000 or more, more preferably 10,000 or more and 300,000 or less. The number average molecular weight is preferably 1,000 or more, more preferably 2,000 or more and 250,000 or less. The degree of dispersion (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 or more and 10 or less. The binder may be any of a random polymer, a block polymer, a graft polymer, and the like.

The binder used in the present invention can be synthesized by a conventionally known method. Examples of the solvent used in the synthesis include tetrahydrofuran, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. 2-methoxyethyl acetate, diglyme, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethyl Formamide, N,N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water, and the like. These solvents may be used singly or in combination of two or more. The radical polymerization initiator used in the synthesis of the binder used in the composition of the present invention may, for example, be a known compound such as an azo initiator or a peroxide initiator.

In the composition of the present invention, the binder may be used singly or in combination of two or more. The content of the binder is preferably 1% by mass or more and 90% by mass or less based on the total solid content of the composition, more preferably 5% by mass or more and 80% by mass or less, and particularly preferably 10% by mass or more and 70% by mass or less.

[(B) Monomer] As the (B) monomer, an addition polymerizable compound having at least one ethylenically unsaturated double bond bond is preferably used, and at least one terminal ethylenically unsaturated bond is used. The compound of the knot is preferably a compound having two or more terminal ethylenically unsaturated bonds. Such a compound is widely known in the corresponding technical field, and can be used without being particularly limited in the present invention.

Further, as the (B) monomer, a compound having at least one addition-polymerizable vinyl group and an ethylenically unsaturated group having a boiling point of 100 ° C or higher at normal pressure is also preferable. As such an example, a monofunctional acrylate or methacrylic acid such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate or phenoxyethyl (meth)acrylate may be mentioned. Ester; polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tri (propylene oxy propylene propylene) Ethyl ether, tris(propylene methoxyethyl) isocyanurate and such mixtures, pentaerythritol tetra(meth) acrylate are preferred.

In addition to the above, the radical polymerizable monomer represented by the following general formulae (MO-1) to (MO-5) can also be suitably used. Further, in the case where T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

[Chemical Formula 5]

In the formula, n is an integer of 0 to 14, and m is an integer of 1 to 8. The plurality of R and T existing in one molecule may be the same or different. In each of the radical polymerizable monomers represented by the above formulas (MO-1) to (MO-5), at least one of the plurality of R represents -OC(=O)CH=CH ₂ or -OC (=O) C(CH ₃ )=CH ₂ represents a group. Specific examples of the radical polymerizable monomer represented by the above formulas (MO-1) to (MO-5) can also be suitably used in the present invention in paragraphs 0248 to 0251 of JP-A-2007-269779. The compound described in the above. Further, in JP-A No. 10-62986, the general formula (1) and (2) are carried out after adding ethylene oxide or propylene oxide to a polyfunctional alcohol as described in the specific example (A) The acrylated compound can also be used as a monomer.

Among them, pentaerythritol tetraacrylate (commercially available as A-TMMT; manufactured by Shin-Nakamura Chemical Co., Ltd.) and dipentaerythritol triacrylate (commercially available as KAYARAD D-330; Nippon Kayaku) are used as a monomer. Co., Ltd., dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD) D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), preferably pentaerythritol tetraacrylate It is better.

The monomer may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. For example, an ethylenically unsaturated compound having an acid group can be suitably mentioned. The ethylenically unsaturated compound having an acid group is obtained by a method of esterifying a part of a hydroxyl group of a polyfunctional alcohol (meth) acrylate and adding an acid anhydride to a residual hydroxyl group to form a carboxyl group. The ethylenic compound may be used as it is in the case of a mixture as described above, and may be used as it is, or may be introduced into the hydroxyl group of the ethylenic compound and a non-aromatic carboxylic acid anhydride as needed. . In this case, specific examples of the non-aromatic carboxylic anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated hexahydroortane. Phthalic anhydride, succinic anhydride, maleic anhydride.

The acid group-containing monomer is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and reacts with a non-aromatic carboxylic anhydride on an unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid radical polyfunctional monomer. Preferably, the aliphatic polyhydroxy compound in the ester is preferably pentaerythritol and/or dipentaerythritol. As a commercial item, M-510, M-520, etc. which are polyacid-acid-modified acrylic oligomer manufactured by Toagosei Co., Ltd. are mentioned, for example.

These monomers may be used singly, but it is also difficult to use a single compound in the production process, and therefore it is also possible to use two or more types. 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. The preferred acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mgKOH/g, more preferably 5 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, it is difficult to manufacture or handle, and the photopolymerization performance is lowered, and the surface smoothness of the pixel is poor. Therefore, in the case where a polyfunctional monomer having two or more different acid groups is used in combination or a polyfunctional monomer having no acid group is used in combination, it is preferred that the acid group of the polyfunctional monomer as a whole is brought into the above range.

Further, as the monomer, a polyfunctional monomeric body having a caprolactone structure is preferred. The polyfunctional monothomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, and for example, trimethylolethane and ditrihydroxymethyl can be mentioned. Polyols such as ethyl ethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, trimethylol melamine, and (meth)acrylic acid and ε-caprolactone The ε-caprolactone modified polyfunctional (meth) acrylate obtained by esterification. Among them, a polyfunctional monomeric body having a caprolactone structure represented by the following formula (1) is preferred.

[Chemical Formula 6]

(In the formula, all of the six R groups are represented by the following formula (2), or one to five of the six R's are groups represented by the following formula (2), and the residue is represented by the following formula (3). Group.)

[Chemical Formula 7]

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

[Chemical Formula 8]

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

A polyfunctional monolith having such a caprolactone structure is commercially available, for example, from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (in the above formulas (1) to (3), m =1, the number of groups represented by the formula (2) = 2, the compound in which R ¹ is a hydrogen atom), DPCA-30 (in the above formulas (1) to (3), m=1, and the formula (2) (the number of groups indicated by 3 = 3, the compound in which R ¹ is a hydrogen atom), DPCA-60 (in the above formulas (1) to (3), m = 1, the number of groups represented by the formula (2) =6, R ¹ is a compound of a hydrogen atom), DPCA-120 (in the above formulas (1) to (3), m = 2, the number of groups represented by the formula (2) = 6, and R ¹ are both a compound of a hydrogen atom). In the present invention, a polyfunctional monolith having a caprolactone structure can be used singly or in combination of two or more.

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

[Chemical Formula 9]

In the general formulae (i) and (ii), E each independently represents -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)-, y each independently represents An integer of 0 to 10, and X each independently represents an acryloyl group, a methacrylinyl group, a hydrogen atom or a carboxyl group. In the general formula (i), the acryloyl group and the methacryl fluorenyl group are three or four in total, and m each independently represents an integer of from 0 to 10, and each m is a total 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 acrylonitrile group and the methacryl 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, and more preferably an integer of 0 to 4. Further, an integer of 2 to 40 in total for each m is preferable, an integer of 2 to 16 is more preferable, and an integer of 4 to 8 is particularly preferable. In the formula (ii), n is an integer of 0 to 6 and preferably an integer of 0 to 4 is more preferable. Further, an integer of 3 to 60 in total for each n is preferable, an integer of 3 to 24 is more preferable, and an integer of 6 to 12 is particularly preferable. Further, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in the formula (i) or the formula (ii) is an end on the oxygen atom side The form of the X bond is preferred. 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 six X are all acrylonitrile groups. In addition, the total content of the monomer of the compound represented by the formula (i) or the formula (ii) is preferably 20% by mass or more, more preferably 50% by mass or more.

The compound represented by the formula (i) or the formula (ii) can be synthesized by a conventionally known process, that is, by a ring-opening addition of ethylene oxide or propylene oxide on pentaerythritol or dipentaerythritol. The reaction is carried out by a process of bonding a ring-opening skeleton; and a process of introducing a (meth)acrylonitrile group by reacting a terminal hydroxyl group such as (meth)acryloyl chloride in the ring-opening skeleton. Each process is a well-known process, and those skilled in the art can easily synthesize a compound represented by the formula (i) or (ii).

Among the compounds represented by the formula (i) or the formula (ii), a pentaerythritol derivative and/or a dipentaerythritol derivative are more preferable. Specific examples thereof include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as "exemplary compounds (a) to (f)"), wherein the compounds (a) and (b) are exemplified. , (e), (f) are preferred.

[Chemical Formula 10]

[Chemical Formula 11]

The commercially available product of the compound represented by the general formula (i) or (ii) is, for example, a tetrafunctional acrylate having four ethylene ethoxylate chains, i.e., SR-494, Nippon Kayaku Co., manufactured by Sartomer Company. A 6-functional acrylate having six pentyloxy chains, that is, DPCA-60, a trifunctional acrylate having three extended-butoxy-chains, that is, TPA-330, etc., manufactured by the company.

Further, as a monomer, an amine ester acrylate described in Japanese Patent Publication No. Sho 48-41708, JP-A-53-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765, and Japan An amine ester compound having an ethylene oxide-based skeleton described in JP-A-58-49860, JP-A-56-17654, JP-A-62-39417, and JP-A-62-39418 is also preferred. Further, as the monomer, an addition polymerization having an amine structure and a thioether structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-10-15238 can be used. The compound is a compound which can obtain a hardening composition which is excellent in the photosensitivity. As a commercial product of a monomer, an amine ester oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp Co., Ltd.), U-4HA, U-6LPA, UA-32P, U-10HA are mentioned. , U-10PA, UA-122P, UA-1100H, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Co., Ltd.), UA-9050, UA-9048 (manufactured by BASF Corporation).

The details of the method of using the monomers, whether they are used singly or in combination, and the amount of addition, can be arbitrarily set depending on the final properties of the photosensitive composition. For example, from the viewpoint of sensitivity, a structure having a large content of unsaturated groups per molecule is preferable, and in the case of many, a plurality of functional groups are preferable. Further, from the viewpoint of enhancing the strength of the cured film, a trifunctional or higher functional group is preferable, and a different functional number/different polymerizable group (for example, an acrylate, a methacrylate, a styrene compound, or a vinyl group) is used in combination. The method of adjusting both sensitivity and strength is also effective for the ether compound. Further, in addition to the trifunctional or higher functional group, a monomer having a different ethylene oxide chain length is preferably used, which is preferable in that the developability of the photosensitive composition can be adjusted and excellent pattern formation can be performed. Further, the selection/use method of the monomer becomes an important factor with respect to compatibility and dispersibility with other components (for example, a photopolymerization initiator, an alkali-soluble resin, etc.) contained in the photosensitive composition, for example, The compatibility is sometimes improved by the use of a low-purity compound or a combination of two or more. Further, from the viewpoint of improving the adhesion to a hard surface such as a support, a specific structure may be selected. Specific examples of the monomer are given below, but are not limited thereto.

[Chemical Formula 12]

Further, the monomer may be a compound having a polymerizable group and a decyl group (hereinafter, also referred to as a decane compound). When the photosensitive composition containing the above decane compound is supplied (for example, coated) onto a support, adhesion of the photosensitive composition to the support is enhanced by interaction of Si atoms of the decane compound with components constituting the support. Sex. The decane compound is preferably a compound represented by the following formula (a) (hereinafter also referred to as "specific decane compound") from the viewpoint of improving the interaction with the support and the compatibility.

[Chemical Formula 13]

In the formula (a), X is a hydrogen atom or an organic group, and an organic group having one or more polymerizable groups and having an amine group is preferred. Y ¹ , Y ² , and Y ³ each independently represent alkyl, alkenyl, alkynyl, aryl, hydroxy, alkoxy, halogen, allyloxy, amine, decyl, heterocyclyl or A hydrogen atom, an alkyl group or an alkoxy group is preferred. 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 vinyl group or the like). Examples of the decane compound include a decane compound having a polymerizable group in paragraphs 0056 to 0066 of JP-A-2009-242604. As the polymerizable compound, a thio(meth)acrylate compound described in paragraphs 0024 to 0031 of the specification of Japanese Patent No. 4,176,767 (paragraphs 0027 to 0033 of US2005/0261406A) can be used, and the contents can be incorporated and incorporated. In the specification of this application.

The monomer or the like may be a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. Therefore, the ethylenic compound can be directly used as long as it has an unreacted carboxyl group as in the case of a mixture as described above, but it is also possible to react a non-aromatic carboxylic anhydride on the hydroxyl group of the above ethylenic compound as needed. And introduce the acid root. In this case, specific examples of the non-aromatic carboxylic anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated hexahydrohydride. Phthalic anhydride, succinic anhydride, maleic anhydride.

In the present invention, as an acid group-containing monomer, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid reacts with a non-aromatic carboxylic acid anhydride on an unreacted hydroxyl group of an aliphatic polyhydroxy compound to have an acid multi-functionality. A monomer is preferred, and among the esters, an aliphatic polyhydroxy compound is preferably pentaerythritol and/or dipentaerythritol. For example, M-305, M-510, M-520, etc. of the ARONIX series which are polybasic acid-modified acrylic oligomer manufactured by Toagosei Co., Ltd. are mentioned as a commercial item. The preferred acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mg-KOH/g, more preferably 5 to 30 mg-KOH/g. In the case where a polyfunctional monomer having two or more different acid groups is used in combination or a polyfunctional monomer having no acid group is used in combination, the acid value of the polyfunctional monomer as a whole must be prepared to enter the above range.

The details of the method of using the monomers, whether they are used singly or in combination, and the amount of addition, can be arbitrarily set depending on the final properties of the composition. For example, choose according to the following points. In the composition of the present invention, the monomers may be used alone or in combination of two or more. From the viewpoint of sensitivity, a structure having a large content of an unsaturated group per molecule is preferable, and in the case of a large amount, a bifunctional or higher is preferable. Further, in order to increase the strength of the cured film, a trifunctional or higher functional group is preferable, and a different functional number/different polymerizable group (for example, an acrylate, a methacrylate, a styrene compound, or a vinyl ether compound) is used in combination. The method of adjusting both sensitivity and intensity is also effective. Further, the compatibility and dispersibility of other components (for example, a polymerization initiator, titanium dioxide particles, and the like) contained in the composition, and the selection/use method of the monomer are important factors, for example, sometimes by low purity. The use of the compound or in combination with two or more other ingredients serves to improve compatibility. Further, in order to improve the adhesion to a hard surface such as a substrate, a specific structure may be selected.

The content of the monomer (B) is preferably in the range of 1% by mass to 50% by mass based on the total solid content of the composition, more preferably in the range of 3% by mass to 40% by mass, and preferably 5% by mass to 30% by mass. The range is further preferred. When it is in this range, it is preferable because coloring is prevented and the hardenability is good.

[(C) Polymerization Initiator] The composition of the present invention contains (C) a polymerization initiator. The polymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the monomer, and can be appropriately selected from known polymerization initiators. As the polymerization initiator, a photopolymerization initiator is preferred. As the photopolymerization initiator, for example, it is preferred to be photosensitive from an ultraviolet region to visible light. Further, it may be an active agent which activates the action of the sensitizer for exciting light and generates a living radical, and may also be an initiator which initiates cationic polymerization depending on the kind of the monomer. Further, the photopolymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 moles in the range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton or a oxadiazole skeleton), a mercaptophosphine compound such as a mercaptophosphine oxide, or a hexaarylbisimidazole or an anthracene. An anthracene compound such as a derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, or a hydroxyacetophenone. Examples of the halogenated hydrocarbon compound having a triazine skeleton include a compound described in R. Lin et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), and a compound described in British Patent No. 1,388,492. The compound described in the publication No. 53-133428, the compound described in the specification of the German Patent No. 3337024, and the compound described in J. Org. Chem.; 29, 1527 (1964) of FC Schaefer et al., JP-A-62-58241 The compound described in JP-A-H05-281728, the compound described in JP-A-H05-34920, and the compound described in the specification of U.S. Patent No. 4,212,976.

Further, from the viewpoint of exposure sensitivity, it is selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a mercaptophosphine compound, and a phosphine oxide compound. , metallocene compound, hydrazine compound, triallyl imidazole dimer, hydrazine compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron mismatch Preferably, the compound and its salt, the halogenated methyl oxadiazole compound, and the 3-aryl substituted coumarin compound are preferred.

a trihalomethyltriazine compound, an α-amino ketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triallyl imidazole dimer, an anthraquinone compound, a benzophenone compound, and an acetophenone compound are Further preferably, at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an anthraquinone compound, a triallyl imidazole dimer, and a benzophenone compound is particularly preferred.

In particular, when the composition of the present invention is used for producing a color filter of a solid-state image sensor, since it is necessary to form a fine pattern into a clear shape, it is not only hardenability but also development without leaving residue in the unexposed portion. good. From such a viewpoint, it is particularly preferable to use a ruthenium compound as a photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state image sensor, a stepper is used for exposure for curing, but the exposure machine may be damaged by halogen. Therefore, it is also necessary to suppress the addition amount of the photopolymerization initiator to be low. Therefore, in consideration of such points, it is particularly preferable to use a ruthenium compound as a photopolymerization initiator for forming a fine pattern such as a solid-state image sensor. Further, by using a ruthenium compound, the transferability can be further optimized. As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP-A-2013-29760 can be referred to, and the contents are incorporated in the present specification.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and a mercaptophosphine-based initiator as described in JP-A No. 4,258,899 can be used. As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade name: all manufactured by BASF Corporation) can be used. As the amino acetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF Corporation) which are commercially available products can be used. The amine acetophenone-based initiator can also be used as a compound described in JP-A-2009-191179, which has an absorption wavelength matched to a long-wavelength light source such as 365 nm or 405 nm. As the mercaptophosphine-based initiator, IRGACURE-819 and DAROCUR-TPO (trade names: all manufactured by BASF Corporation) which are commercially available products can be used.

As the photopolymerization initiator, a ruthenium compound is more preferable. As a specific example of the ruthenium compound, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and a compound described in JP-A-2006-342166 can be used. In the present invention, examples of the ruthenium compound which can be suitably used include 3-benzylideneoxyimidobutan-2-one and 3-ethyloxyiminobutane-2-one. 3-propenyloxyimidobutan-2-one, 2-ethyloxyiminopentan-3-one, 2-ethyloxyimino-1-phenylpropane-1- Ketone, 2-benzylideneoxyimido-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2one and 2-ethoxycarbonyloxyl Iminoamino-1-phenylpropan-1-one and the like. Also, JCS Perkin II (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, and Japanese specials are also mentioned. The compound described in each of the publications of the Japanese Patent Publication No. 2000-342166, and the Japanese Patent Publication No. 2004-342166, and the like. In the commercial product, IRGACURE-OXE01 (manufactured by BASF Corporation) and IRGACURE-OXE02 (manufactured by BASF Corporation) can be suitably used.

In addition, as the ruthenium compound other than the above, a compound described in JP-A-2009-519904, in which a carbazole is bonded to the N-position, and a US Patent No. The compound described in the specification of the No. 7626957, the compound described in the specification of the Japanese Patent Publication No. 2010-15025, and the specification of the U.S. Patent Application Publication No. 2009-292039, the disclosure of which is incorporated herein by reference. The ketone oxime compound, the compound described in the specification of the U.S. Patent No. 7556910, which contains a triazine skeleton and an anthracene skeleton in the same molecule, has a large absorption at 405 nm and has a good sensitivity to a g-ray source. JP-A-2009-221114 The compound or the like described in the publication. For example, paragraphs 0274 to 0275 of JP-A-2013-29760 can be referred to, and the contents are preferably incorporated in the present specification. Specifically, a compound represented by the following formula (OX-1) is preferred as the oxime compound. Further, the N-O bond of ruthenium may be a ruthenium compound of the (E) form or a ruthenium compound of the (Z) form, or may be a mixture of the (E) form and the (Z) form.

[Chemical Formula 14]

In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. In the general formula (OX-1), a monovalent non-metal atomic group is preferred as a substituent having a monovalent value represented by R. The monovalent non-metal atomic group may, for example, be an alkyl group, an aryl group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group or an arylthiocarbonyl group. Further, the groups may have one or more substituents. Further, the aforementioned substituent may be further substituted with another substituent. The substituent may, for example, be a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a decyloxy group, a decyl group, an alkyl group or an aryl group. In the formula (OX-1), as the substituent represented by B, an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group is preferred. These groups may have one or more substituents. The above substituent can be exemplified as the substituent. In the general formula (OX-1), as the divalent organic group represented by A, an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group or an extended alkynyl group is preferred. These groups may have one or more substituents. The above substituent can be exemplified as the substituent.

In the present invention, a ruthenium compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the ruthenium compound having a fluorine atom include the compounds described in JP-A-2010-262028, and the compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471 The compound (C-3) or the like described in the publication. This content is incorporated in this specification. In the present invention, an anthracene compound can be used as a ruthenium compound having a nitro group. Specific examples of the compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP-A-2013-114249, and paragraphs 0008 to 0102 and 0070 to 0079 of JP-A-2014-137466. And ADEKA ARKLS NCI-831 (made by ADEKA CORPORATION).

In the present invention, as the photopolymerization initiator, a compound represented by the following formula (1) or (2) can also be used.

[Chemical Formula 15]

In the formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or a carbon number of 7 to 30. When an aralkyl group, when R ¹ and R ² are a phenyl group, the phenyl groups may be bonded to each other to form a fluorenyl group, and R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 6 to 6; An aryl group of 30, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

Formula ^{(2), R 1, R 2, 1} , R 2, the same meaning as R ³ and R ⁴ R ³ and R ⁴ of the formula R (1) in the, R ⁵ represents -R ^6, -OR ^6, -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, halogen atom or Hydroxy group, R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group. , a represents an integer from 0 to 5.

In the above formulas (1) and (2), R ¹ and R ² each independently represent a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclohexyl group or a phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. It is preferred that X is a direct bond. Specific examples of the compound represented by the formula (1) and the formula (2) include, for example, the compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. And the content is incorporated in this specification.

Specific examples of the ruthenium compound which is preferably used in the present invention are shown below, but the present invention is not limited thereto.

[Chemical Formula 16]

The ruthenium compound is preferably one having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably having an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably having a higher absorbance at 365 nm and 455 nm. From the viewpoint of sensitivity, the molar absorption coefficient of the ruthenium compound at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, particularly preferably from 5,000 to 200,000. The molar absorption coefficient of the compound can be preferably measured by a known method, for example, by an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian Co., Ltd.) and using an ethyl acetate solvent at a concentration of 0.01 g/L.

The content of the photopolymerization initiator is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, even more preferably from 1 to 20% by mass, based on the total solid content of the composition. Within this range, better sensitivity and pattern formation can be obtained. The composition of the present invention may contain only one kind of photopolymerization initiator, or may contain two or more types. When two or more types are contained, the total measurement is preferably in the above range.

[(D) Particles having an average particle diameter of 50 nm or more] The particles in the present invention are preferably those having a high refractive index and scattering light. The particles of the light are not particularly limited, and metal particles are preferred, and titanium dioxide and zirconium dioxide are further preferred, and titanium dioxide particles are particularly preferred. The titanium dioxide particles are preferably represented by the chemical formula TiO ₂ and have a purity of 70% or more, more preferably 80% or more, and more preferably 85% or more. The low-order titanium oxide, the titanium oxynitride, etc. represented by the general formula Ti _n O _2n-1 (n represents a number of 2 to 4) is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass. The following is further preferred. The titanium dioxide particles in the present invention are not particularly limited as long as the average particle diameter is 50 nm or more, and can be appropriately selected from commercially available titanium oxide particles, for example. The average particle diameter (number average particle diameter) of the titanium dioxide particles is preferably 50 nm or more from the viewpoint of scattering light and white, and more preferably 100 nm or more, and particularly preferably 150 nm or more. When the average particle diameter of the titanium dioxide particles is less than 50 nm, the reflectance may be lowered. The upper limit of the average particle diameter of the titanium dioxide particles is not particularly limited, and is preferably 1000 nm or less, more preferably 500 nm or less. The "average particle diameter" herein means the average particle diameter of the secondary particles obtained by the aggregation of primary particles. Further, the particle size distribution of the secondary particles of the particles which can be used (hereinafter also referred to as "particle size distribution" for short) is preferably 70% by mass or more of the secondary particles having an average particle diameter of ±100 nm. 80% by mass or more is preferred. Further, the particle size distribution of the secondary particles can be measured using a dynamic light scattering method (scattering intensity distribution). Further, the average particle diameter of the primary particles can be observed by a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and 100 particle sizes are measured in a portion where the particles are not aggregated, and an average value is calculated. So find out.

In the present invention, the refractive index of the titanium dioxide particles is not particularly limited, and from the viewpoint of obtaining a high refractive index, 1.75 to 2.70 is preferable, and 1.90 to 2.70 is further more preferable. And a specific surface area of titanium dioxide particles is 10m ² / g to 400m ² / g is preferred, 10m ² / g to 200m ² / g is more excellent, 10m ² / g to 150m ² / g is further preferred, 10m ² /g to 40m ² /g is the best. Further, the shape of the titanium dioxide particles is not particularly limited. For example, it may be a rice grain shape, a ball shape, a cube shape, a spindle shape or an irregular shape.

The titanium dioxide particles in the present invention may be surface treated by an organic compound. Examples of the organic compound used in the surface treatment include a polyol, an alkanolamine, a stearic acid, a decane coupling agent, and a titanate coupling agent. Among them, a decane coupling agent is preferred. Further, the titanium dioxide particles in the present invention are preferably Al (aluminum) or Si (yttrium) and treated with an organic substance. The surface treatment may be carried out by using one type of single surface treatment agent, or may be carried out by combining two or more surface treatment agents. Further, it is also preferred that the surface of the titanium dioxide particles is covered with an oxide such as aluminum, lanthanum or zirconium. Thereby, the weather resistance is further improved.

The titanium dioxide particles in the present invention can be preferably used commercially. As a commercial item of the titanium dioxide particle, the product name TIPAQUE R-550, R-580, R-630, R-670, R-680, R-780, R-780 by ISHIHARA SANGYO KAISHA, LTD. -2, R-820, R-830, R-850, R-855, R-930, R-980, CR-50, CR-50-2, CR-57, CR-58, CR-58-2 , CR-60, CR-60-2, CR-63, CR-67, CR-Super70, CR-80, CR-85, CR-90, CR-90-2, CR-93, CR-95, CR -953, CR-97, PF-736, PF-737, PF-742, PF-690, PF-691, PF-711, PF-739, PF-740, PC-3, S-305, CR-EL , PT-301, PT-401M, PT-501A, PT-501R, UT771, SAKAI CHEMICAL INDUSTRY CO., LTD., trade names R-3L, R-5N, R-7E, R-11P, R-21 , R-25, R-32, R-42, R-44, R-45M, R-62N, R-310, R-650, SR-1, D-918, GTR-100, FTR-700, TCR -52, trade names of TAYCA CORPORATION, JR, JRNC, JR-301, JR-403, JR-405, JR-600A, JR-600E, JR-603, JR-605, JR-701, JR-800, JR -805, JR-806, JR-1000, MT-01, MT-05, MT-10EX, MT-100S, MT-100TV, MT-100Z, MT-100AQ, MT-100WP, MT-100SA, MT-100HD , MT-150EX, MT-150W, MT-300HD, MT-50 0B, MT-500SA, MT-500HD, MT-600B, MT-600SA, MT-700B, MT-700HD, Titan Kogyo, Ltd. Trade names KR-310, KR-380, KR-380N, Fuji Titanium Industry Trade names TR-600, TR-700, TR-750, TR-840, TR-900, etc., manufactured by Co., Ltd., TIPAQUE CR-90-2 is preferred. In the present invention, the particles (D) may be used singly or in combination of two or more.

As the particles (D), inorganic fine particles can be used, and as the inorganic fine particles, not only a single inorganic substance but also particles which are combined with other raw materials can be used. For example, from the viewpoint of improving the sedimentation property, particles having pores or other materials inside, particles in which a plurality of inorganic particles are attached to the core particles, core particles including the polymer particles, and a shell layer including the inorganic nanoparticles are used. Core/shell composite particles are preferred. In addition, as the core/shell composite particle including the core particle including the polymer particle and the shell layer including the inorganic nanoparticle, for example, the description of paragraphs 0012 to 0044 of JP-A-2015-47520 can be referred to, and the content is incorporated. In this manual.

The content of the titanium oxide particles in the composition of the present invention is preferably 1% by mass or more based on the total solid content of the composition, more preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit of the content is not particularly limited, and is preferably 70% by mass or less based on the total solid content of the composition, more preferably 60% by mass or less, and most preferably 50% by mass or less. Further, when it is used as a material for an optical sensor or an optical member, 40% by mass or less is preferable, and 30% by mass or less is more preferable, and 20% by mass or less is particularly preferable.

[Dispersant] From the viewpoint of improving the dispersibility of the particles (D) in the composition, the composition of the present invention preferably contains a dispersant, and more preferably contains a polymer dispersant having an adsorption site. In the present invention, the sites having the adsorption energy to the particles (D) are collectively referred to as "adsorption sites" as appropriate. The adsorption site in the present invention may have at least one selected from the group consisting of an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, and a heterocyclic ring. a monovalent substituent of a group in the group of a group, an alkoxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonylamino group, an alkoxyalkyl group, an epoxy group, an isocyano group, and a hydroxyl group Wait.

As the "acid radical", for example, a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphorus atom-containing group (phosphoric acid group, a monophosphate group, a polyphosphate group, etc.) or a boric acid group can be exemplified as a preferred example. A carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphorus atom-containing group (phosphoric acid group, a monophosphate group, a polyphosphate group, etc.) is more preferable, and a carboxylic acid group or a phosphorus atom-containing group is particularly preferable. As the "urea group", for example, -NR ¹⁵ CONR ¹⁶ R ¹⁷ (herein, R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms or An aralkyl group having a carbon number of 7 or more may be exemplified as -NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, More preferably, the aryl group having 6 or more carbon atoms or the aralkyl group having 7 or more carbon atoms is more preferably -NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and an aromatic group having 6 or more carbon atoms). The aralkyl group having a carbon number of 7 or more is particularly preferred. As a "urethane group", for example, -NHCOOR ¹⁸ , -NR ¹⁹ COOR ²⁰ , -OCONHR ²¹ , -OCONR ²² R ²³ (here, R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, etc., and the like may be exemplified as -NHCOOR ¹⁸ and -OCONHR ²¹ (In this case, R ¹⁸ and R ²¹ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms), etc., more preferably -NHCOOR ¹⁸ , - OCONHR ²¹ (In this case, R ¹⁸ and R ²¹ each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms). Examples of the "group having a coordinating oxygen atom" include an acetoacetone group and a crown ether.

Also, "a group having a basic nitrogen atom", such as an amine group (-NH ₂ ), a substituted imido group (-NHR ⁸ , -NR ⁹ R ¹⁰ , where R ⁸ , R ⁹ and R ¹⁰ are each independently The alkyl group having 1 to 20 carbon atoms, the aryl group having 6 or more carbon atoms, and the aralkyl group having 7 or more carbon atoms. The mercapto group represented by the following formula (a1) and the mercapto group represented by the following formula (a2) Etc. can be cited as a preferred example.

[Chemical Formula 17]

In the formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms. In the formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms.

In the above, an amine group (-NH ₂ ), a substituted imido group (-NHR ⁸ , -NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ and R ¹⁰ each independently represent an alkyl group having 1 to 10 carbon atoms The thiol group represented by the formula (a1): wherein R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group. In the formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group. 〕More is better. In particular, it is preferred to use an amine group (-NH ₂ ), a substituted imido group (-NHR ⁸ , -NR ⁹ R ¹⁰ , where R ⁸ , R ⁹ , and R ¹⁰ each independently represent a carbon number of 1 to 5 Alkyl, phenyl, benzyl.), a fluorenyl group represented by the formula (a1). In the formula (a1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group, and a benzyl group. base. In the formula (a2), R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 5 carbon atoms, a phenyl group or a benzyl group. 〕Wait. The alkyl group in the "alkoxycarbonyl group" is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group and an ethyl group. The alkyl group in the "alkylaminocarbonyl group" is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The "carboxylate group" may, for example, be a group including an ammonium salt of a carboxylic acid. As the "sulfonylamino group", a hydrogen atom bonded to a nitrogen atom may be substituted with an alkyl group (methyl group or the like), a mercapto group (ethyl fluorenyl group, a trifluoroethyl fluorenyl group or the like).

As a "heterocyclic structure", for example, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, Triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiamide, isoindoline, isoindolinone, benzimidazole An an amine group such as a ketone, a benzothiazole, a butyl succinimide, a phthalimide, a naphthyl phthalimide, a carbendazim, an anthracene, a quinoline, an oxazole, an acridine, Acridone and hydrazine can be exemplified as preferred examples.

In addition, the "heterocyclic structure" may further have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, and an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. a hydroxyl group having 1 to 20 carbon atoms such as a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-sulfonylamino group or an ethoxylated group having 1 to 6 carbon atoms such as a methoxy group, a methoxy group or an ethoxy group. a carbonate group having a carbon number of 2 to 7 such as a halogen atom such as an oxy group, a chlorine group or a bromine group, a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group; a carbonyl group such as a cyano group or a t-butyl carbonate group; Wait.

The "alkoxyalkylene group" may be any of a monoalkoxyalkyl group, a dialkoxyalkyl group or a trialkoxyalkyl group, and a trialkoxyalkyl group is preferably used, for example, Trimethoxydecyl, triethoxydecyl, and the like. The "epoxy group" may, for example, be a substituted or unsubstituted oxiranyl group (oxidized ethyl group). As the adsorption site, an acid adsorption site is preferred. An acid group etc. are mentioned as an acid adsorption site. Among them, the acid-based adsorption site is preferably at least one of a phosphorus atom-containing group and a carboxylic acid group. In the present invention, the polymer dispersant having an adsorption site is preferably a polymer dispersant represented by the following formula (1).

[Chemical Formula 18]

In the above formula (1), R ¹ represents a (m+n)-valent linking group, and R ² represents a single bond or a divalent linking group. A ¹ represents at least one selected from the group consisting of an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a heterocyclic group, an alkoxycarbonyl group, and an alkane group. a monovalent substituent of a group in the group of an aminocarbonyl group, a carboxylate group, a sulfonylamino group, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ¹ and R ² may be the same or different. m represents a positive number of 8 or less, n represents an integer of 1 to 9, and m+n satisfies 3 to 10. P ¹ represents a polymer chain. m P ¹ may be the same or different. For example, the polymer compound represented by the above formula (1) can be referred to in the following paragraphs 0039 of the Japanese Patent Application Laid-Open No. 2007-277514 (the <0053> in the specification of the corresponding US Patent Application Publication No. 2010/0233595), and These contents are incorporated in this specification.

Since the substituent A ¹ of the polymer dispersant represented by the formula (1) can interact with the particles (D), the dispersant represented by the formula (1) has n (1 to 9) The substituent A ^{1 is} capable of strongly interacting with the particles (D). In addition, the polymer dispersing agent represented by the formula (1) has a function in which the polymer chain P ¹ exhibits a steric repulsion group, and exhibits good steric repulsive force by having m particles, thereby enabling particles ( D) Disperse evenly. In addition, it is estimated that the polymer dispersing agent represented by the formula (1) does not cause aggregation of particles due to cross-linking between particles which can be caused by a conventional grafting random dispersant. .

Hereinafter, each group in the formula (1) will be described in detail. Further, the polymer dispersing agent represented by the formula (1) is similarly disclosed in JP-A-2007-277514 (Japanese Patent Application No. 2006-269707), and the contents thereof are described in the description. A suitable configuration can also be applied to the following description, and the description of the repetition is omitted as appropriate. A ¹ represents a monovalent substituent having at least one functional group having an adsorption energy with respect to the particle (D) and a structure having an adsorption energy with respect to the particle (D) such as a heterocyclic structure. Further, the site having the adsorption energy (the above-mentioned functional group and structure) with respect to the particle (D) corresponds to the above-mentioned "adsorption site".

The adsorption site may include at least one of one A ¹ and may contain two or more types. For at least one group related to A ¹ selected from the group consisting of an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a heterocyclic group, an alkoxycarbonyl group The details of the monovalent substituent of the group in the group of the alkylaminocarbonyl group, the carboxylate group, the sulfonylamino group, the alkoxyalkyl group, the epoxy group, the isocyanate group and the hydroxyl group are as described above. That is, as the adsorption site, at least one selected from the group consisting of an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a heterocyclic group, and an alkoxy group. A monovalent substituent of a group in the group of a carbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonylamino group, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group. In the present invention, the "monovalent substituent having at least one type of adsorption site" is such that the adsorption site is composed of 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, and 0 to 100 A monovalent substituent in which an oxygen atom, one to 400 hydrogen atoms, and 0 to 40 sulfur atoms are bonded to each other. Further, the adsorptive moiety itself can constitute a case where the monovalent substituent group, the adsorptive moiety itself can also represent the lines A ¹ 1 to a monovalent substituent group.

As a linking group bonded to the adsorption site, a single bond or from 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 A linking group of up to 20 sulfur atoms is preferred, and the organic linking group may further have a substituent even if it is unsubstituted.

In the above, as A ¹ is a group having at least one selected from the group consisting of an acid group, a urea group, a urethane group, a sulfonylamino group, an imine group, and a group having a coordinating oxygen atom. The monovalent substituent is preferred. In particular, from the viewpoint of optimizing the interaction with the particles (D), increasing the refractive index, and lowering the viscosity of the composition, A ¹ is preferably a monovalent substituent having at least one functional group having a pKa of 5 to 14. Here, the "pKa" is defined in the Chemical Handbook (II) (Revised 4th Edition, 1993, Japanese Chemical Collection, Maruzen Publishing Co., Ltd.). Examples of the functional group of pKa 5 to 14 include a urea group, a urethane group, a sulfonylamino group, an imine group, or a group having a coordinating oxygen atom. Specific examples thereof include a urea group (about 12 to 14 pKa), a urethane group (about pKa of 11 to 13), and -COCH ₂ CO- (a pKa of about 8 to 10) as a coordinating oxygen atom. Sulfhydrylamino group (pKa 9 to 11 or so).

A ¹ is preferably a monovalent substituent represented by the following formula (4).

[Chemical Formula 19]

In the formula (4), B ¹ represents an adsorption site (that is, an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, and an alkoxycarbonyl group). , alkylaminocarbonyl, carboxylate, sulfonylamino, heterocyclyl, alkoxyalkyl, epoxy, isocyanate or hydroxy), R ²⁴ represents a single bond or (a+1) valence linkage base. a represents an integer of 1 to 10, the presence of a number of general formula B (4) ¹ may be the same, also be different.

The adsorption site represented by B ¹ may be the same as the adsorption site of A ¹ constituting the above (1), and the preferred examples are also the same. Among them, an acid group, a urea group, a urethane group, a sulfonylamino group, an imido group or a group having a coordinating oxygen atom is preferred, and a functional group having a pKa of 5 to 14 is more preferable. More preferably, it is a urea group, a urethane group, a sulfonylamino group, an imido group or a group having a coordinating oxygen atom.

R ²⁴ represents a single bond or a (a+1)-valent linking group, and a represents an integer of 1 to 10. a is preferably 1 to 7, a is preferably 1 to 5, and a is preferably 1 to 3. The (a+1)-valent linking group includes from 1 to 100 carbon atoms, from 0 to 10 nitrogen atoms, from 0 to 50 oxygen atoms, from 1 to 200 hydrogen atoms, and from 0 to 20 sulfurs. The atom-forming group may further have a substituent even if it is unsubstituted.

As R ²⁴ , a single bond or from 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 sulfur atoms ( A+1) a valent linking group is preferred, a single bond or from 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to The (a+1)-valent linking group of 7 sulfur atoms is more preferable, and a single bond or 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, and 1 to A (a+1)-valent linking group of 30 hydrogen atoms and 0 to 5 sulfur atoms is particularly preferred.

In the above, when the (a+1)-valent linking group has a substituent, examples of the substituent include a carbon number of 1 to 20 carbon atoms such as a methyl group or an ethyl group, and a carbon number such as a phenyl group or a naphthyl group. 6 to 16 carbon such as an aryloxy group, a methoxy group, an ethoxy group or the like having 1 to 6 carbon atoms such as an aryl group, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-sulfonylamino group or an ethoxycarbonyl group. Alkoxy group having 1 to 6 alkoxy group such as alkoxy group, chlorine atom or bromine atom, methoxycarbonyl group, ethoxycarbonyl group or cyclohexyloxycarbonyl group having 2 to 7 carbon atoms, cyano group and tert-butyl group A carbonate group such as a carbonate group or the like.

In the formula (1), R ² represents a single bond or a divalent linking group. The n R ^{2 's} may be the same or different. The divalent linking group is composed of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. The group, even if unsubstituted, may further have a substituent.

As R ² , a single bond or 2 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 10 sulfur atoms A preferred linking group is a single bond or consists of 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms. The divalent linking group is more preferably a single bond or from 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to A bivalent linking group of five sulfur atoms is preferred.

In the above, when the divalent linking group has a substituent, examples of the substituent include a carbon number of 1 to 20 such as a methyl group or an ethyl group, and a carbon number of 6 to 16 such as a phenyl group or a naphthyl group. Carbon number 1 to 6 having a carbon number of 1 to 6 such as an aryl group, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-sulfonylamino group or an ethoxycarbonyl group, and a methoxy group, a methoxy group, an ethoxy group or the like Alkoxycarbonyl group such as alkoxy group, chlorine atom or bromine atom, methoxycarbonyl group, ethoxycarbonyl group or cyclohexyloxycarbonyl group having 2 to 7 carbon atoms, cyano group and t-butyl carbonate group Such as carbonate groups and the like.

In the formula (1), R ¹ represents a (m+n)-valent linking group. m+n satisfies 3 to 10. The (m+n) valent linking group represented by R ¹ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0. A group of up to 20 sulfur atoms may further have a substituent even if it is unsubstituted.

Specific examples of the (m+n)-valent linking group represented by R ¹ include specific examples (1) to (17) disclosed in paragraphs 0082 and 008 of JP-A-2007-277514. In the formula (1), m represents a positive number of 8 or less. As m, 0.5 to 5 is preferable, 1 to 4 is more preferable, and 1 to 3 is particularly preferable. Further, in the formula (1), n represents an integer of 1 to 9. As n, 2 to 8 is preferable, 2 to 7 is more preferable, and 3 to 6 is particularly preferable.

In the formula (1), P ¹ represents a polymer chain, and can be selected from known polymers and the like depending on the purpose and the like. m P ¹ may be the same or different. In the polymer, when the polymer chain is formed, it is selected from a polymer or copolymer including an ethylene monomer, an ester polymer, an ether polymer, an amine ester polymer, a guanamine polymer, and an epoxy polymer. An anthrone-based polymer and a modified or copolymer thereof (for example, a copolymer comprising a polyether/polyurethane copolymer, a polymer of a polyether/ethylene monomer, etc. (may be a random copolymer, a block copolymer, Any of the graft copolymers.). At least one of the group is preferably selected from the group consisting of polymers or copolymers including ethylene monomers, ester polymers, ether polymers, amine ester polymers, and groups of such modifiers or copolymers. At least one of the groups is more preferred, and a polymer or copolymer of an ethylene monomer is particularly preferred.

It is preferred that the polymer chain P ¹ contains at least one repeating unit. From the viewpoint of exerting the steric repulsive force and improving the dispersibility, the number k of repetitions of at least one repeating unit in the polymer chain P ¹ is preferably 3 or more, more preferably 5 or more. In addition, from the viewpoint of suppressing an increase in the polymer dispersant represented by the formula (1) and making the particles (D) compact in the cured film, the number k of repeating units of at least one type of repeating unit is 50 or less. Preferably, 40 or less is more preferable, and 30 or less is further preferable.

Further, it is preferred that the polymer chain is dissolved in an organic solvent. When the affinity with the organic solvent is low, the affinity with the dispersion medium is weakened, and the adsorption layer may not be sufficiently ensured in the dispersion stabilization.

Among the polymer dispersants represented by the formula (1), a polymer dispersant represented by the following formula (2) is preferred.

[Chemical Formula 20]

In the formula (2), A ² represents at least one selected from the group consisting of an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, and an alkoxy group. a monovalent substituent of a group in the group of a carbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonylamino group, a heterocyclic group, an alkoxyalkyl group, an epoxy group, an isocyanate group, and a hydroxyl group. n A ² may be the same or different. Further, A ² has the same meaning as A ¹ in the formula (1), and the preferred embodiment is also the same.

In the formula (2), R ⁴ and R ⁵ each independently represent a single bond or a divalent linking group. The n R ^{4 's} may be the same or different. Also, m R ^{5 's} may be the same or different. The divalent linking group represented by R ⁴ and R ⁵ is the same as the divalent linking group represented by R ² in the general formula (1), and the preferred embodiment is also the same.

In the formula (2), R ³ represents a (m+n)-valent linking group. m+n satisfies 3 to 10. As a linking group of (m+n) valence represented by R ³ , it contains 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0. A group of up to 20 sulfur atoms may further have a substituent even if it is unsubstituted. As to R ³ represents the (m + n) valent linking group, and specifically, using a ¹ indicates the (m + n) valent linking group exemplified as the general formula (1) are the same as those of R, The preferred aspect is also the same.

In the formula (2), m represents a positive number of 8 or less. It is preferable that m is 0.5 to 5, more preferably 1 to 4, and particularly preferably 1 to 3. Further, in the formula (2), n represents an integer of 1 to 9. It is preferable that n is 2 to 8, 2 to 7 is more preferable, and 3 to 6 is particularly preferable.

Further, P ² in the general formula (2) represents a polymer chain, and can be selected from known polymers or the like depending on the purpose and the like. m P ² may be the same or different. A preferred aspect of the polymer is the same as P ¹ in the formula (1).

In the polymer dispersant represented by the formula (2), it is preferable to satisfy the following R ³ , R ⁴ , R ⁵ , P ² , m and n. R ³ : Specific examples (1), (2), (10), (11), (16) or (17) described in paragraphs 0082 to 0083 of JP-A-2007-277514 R ⁴ : single bond or lower The structural unit or the structural unit is composed of "1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfurs. a two-valent linking group (which may have a substituent), and examples of the substituent include, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group or an ethyl group, and a carbon number of 6 to 16 such as a phenyl group or a naphthyl group. a carbon number of 1 to 6 carbon atoms such as an aryl group, a hydroxyl group, an amine group, a carboxyl group, a sulfonylamino group, an N-sulfonylamino group or an ethoxycarbonyl group, and a methoxy group such as a methoxy group or an ethoxy group Alkoxycarbonyl group such as alkoxy group, chlorine atom or bromine atom, alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a cyclohexyloxycarbonyl group, a cyano group or a t-butyl carbonate. Base and other carbonate groups, etc.)

[Chemical Formula 21]

R ⁵ : a single bond, a vinyl group, a propenyl group, the following group (a), or the following group (b) Further, in the following group, R ¹² represents a hydrogen atom or a methyl group, and 1 represents 1 or 2.

[Chemical Formula 22]

P ² : a polymer or copolymer of an ethylene monomer, an ester polymer, an ether polymer, an amine ester polymer, and the modified material m: 1 to 3 n: 3 to 6

The acid value of the polymer dispersant represented by the formula (1) or (2) is not particularly limited, and from the viewpoint of dispersibility, the acid value is preferably 400 mgKOH/g or less, more preferably 300 mgKOH/g or less, and 250 mgKOH. Below /g is especially good. In addition, the lower limit of the acid value is not particularly limited, and from the viewpoint of dispersion stability of the titanium oxide particles, 5 mgKOH/g or more is preferable, and 10 mgKOH/g or more is more preferable.

Here, the acid value of the polymer dispersant represented by the general formula (1) or (2) is a solid component acid value. In the present invention, the acid value of the polymer dispersant represented by the formula (1) or (2) can be calculated, for example, based on the average content of the acid groups in the dispersant represented by the formula (1) or (2). The molecular weight of the polymer dispersant represented by the formula (1) or (2) is preferably from 1,000 to 50,000, more preferably from 3,000 to 30,000, even more preferably from 3,000 to 20,000, in terms of a weight average molecular weight. When the weight average molecular weight is within the above range, the effect of introducing a plurality of adsorption sites at the end of the polymer is sufficiently exhibited, and excellent performance can be exhibited for the adsorption property on the surface of the titanium oxide particles. Specific examples of the polymer compound represented by the above formula (1) can be referred to in paragraph 0266 of JP-A-2007-277514 (the <0389> of the specification of the corresponding US Patent Application Publication No. 2010/0233595). The description of the compounds C-1 to C-57 synthesized in the examples is as described in the present specification.

(Synthesis method of the polymer dispersing agent represented by the formula (1) or (2)) The polymer dispersing agent represented by the formula (1) or (2) is not particularly limited, and can be used according to JP-A-2007-277514 The synthesis methods described in paragraphs 0114 to 0140 and 0266 to 0348 of the publication are synthesized.

As the dispersing agent, a resin described below (hereinafter, referred to as "dispersion resin 2" as appropriate) can be used. The dispersion resin 2 has: a repeating unit having a group X having a functional group of pKa 14 or less; and an oligomer chain or polymer chain Y having an atomic number of 40 to 10,000 in a side chain, and containing a base A nitrogen atom.

As described in detail later, the nitrogen atom in the dispersion resin 2 and the functional group having a pKa of at least 14 in the group X interact with the particles (D), and the dispersed resin 2 has an atomic number of 40 to 40. The oligo polymer chain of 10,000 or the polymer chain Y functions as a steric repulsion group by, for example, an oligomer chain or a polymer chain Y, so as to exhibit good dispersibility, thereby enabling the particles (D) to be uniformly dispersed. . Further, when the composition is stored for a long period of time at room temperature or the like, the oligomer chain or the polymer chain Y is also allowed to interact with the solvent, whereby the sedimentation of the particles (D) can be suppressed for a long period of time. Further, the oligomer chain or the polymer chain Y functions as a steric repulsion group, thereby preventing aggregation of the particles (D), so even if the content of the particles (D) is increased, the dispersibility and dispersion stability are not easily impaired as described above. .

Here, the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom, and the dispersion resin 2 preferably has a structure having a nitrogen atom of pKb14 or less, and has a structure containing a nitrogen atom of pKb10 or less. good. In the present invention, the "base strength pKb" means pKb at a water temperature of 25 ° C, and is one of the indexes for quantitatively indicating the strength of the alkali, and has the same meaning as the basicity constant. The relationship between the alkali strength pKb and the acid strength pKa is pKb = 1 - pKa. The group X having a functional group having a pKa of 14 or less has the same meaning as the group X to be described later for the dispersion resin 2-1. The oligomer chain or polymer chain Y having 40 to 10,000 atoms in the side chain of the dispersion resin 2, and the oligomer chain having 40 to 10,000 atoms as described later for the dispersion resin 2-1 Or the meaning of the polymer chain Y is the same. The dispersing resin 2 is a repeating unit having a group X having a functional group of pKa 14 or less represented by the following formula, and a repeating unit having a basic nitrogen atom represented by the following formula. And a repeating unit having an oligomer chain or a polymer chain Y having an atomic number of 40 to 10,000 represented by the following formula (the structure of the repeating unit described below corresponds to the order from the left).

[Chemical Formula 23]

In the above formula, x, y and z each represent a polymerization molar ratio of the repeating unit, and x is 5 to 50, y is 5 to 60, and z is preferably 10 to 90. l represents the number of bonds of the polyester chain, and is an integer of an oligomer chain or a polymer chain having an atomic number of 40 to 10,000, and preferably 70 to 2,000. The dispersion resin 2 is preferably a repeating unit containing a nitrogen atom bonded to a group X having a functional group of pKa 14 or less, and a resin having an oligomer chain or a polymer chain Y having an atomic number of 40 to 10,000 in the side chain. The dispersion resin 2 contains a (i) poly(lower alkyleneimine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, and a metaxylenediamine-table. a repeating unit of at least one nitrogen atom of a chlorohydrin polycondensate-based repeating unit and a polyvinylamine-based repeating unit, which is bonded to a nitrogen atom and has the following resin 2-1 (hereinafter, suitably referred to as "dispersion resin 2" -1") is particularly preferred, that is, it has: a repeating unit having a group X having a functional group of pKa 14 or less; and (ii) an oligomer chain having a molecular weight of 40 to 10,000 in the side chain or Polymer chain Y.

(containing a poly (lower alkylene imine)-based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, and a meta-xylenediamine-epichlorohydrin polycondensation unit) a repeating unit of at least one nitrogen atom of the repeating unit of the system and the repeating unit of the polyvinylamine-based repeating unit) The dispersing resin 2-1 has a repeating unit (i) containing a poly(lower alkylene group) selected from the group consisting of poly(lower alkylene) At least one of an amine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, a metaxylenediamine-epichlorohydrin polycondensate repeating unit, and a polyvinylamine repeating unit Nitrogen atom. Thereby, the adsorption force to the surface of the particle (D) can be improved, and the interaction with the aforementioned particle (D) can be reduced. The poly(lower alkylene imine) may be chain-like or may be in the form of a grid. The polymerization contains a repeating unit selected from the group consisting of a poly(lower alkyleneimine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, and a metaxylenediamine-epichlorohydrin polycondensate repeating unit. The number average molecular weight of the main chain obtained by repeating the unit (i) of at least one nitrogen atom of the unit and the polyvinylamine-based repeating unit, that is, the aforementioned oligomer chain or polymer chain from which the side chain is removed from the dispersion resin 2-1 The number average molecular weight of the Y moiety is preferably from 100 to 10,000, more preferably from 200 to 5,000, and most preferably from 300 to 2,000. The number average molecular weight of the main chain portion can be determined from the ratio of the end group of the main chain portion measured by the nuclear magnetic resonance spectrometry to the integral value of the hydrogen atom of the main chain portion, or by measuring the oligomer or polymer containing the amine group as a raw material. The molecular weight was determined by measurement.

As the repeating unit (i) containing a nitrogen atom, a poly(lower alkyleneimine) repeating unit or a polyallylamine based repeating unit is particularly preferable. Further, in the present invention, the lower order of the poly(lower alkyleneimine) means a carbon number of 1 to 5, and the lower alkyleneimine means an alkyleneimine having 1 to 5 carbon atoms. When the structure is clarified, the dispersion resin 2-1 contains a structure having a repeating unit represented by the formula (I-1) and a repeating unit represented by the formula (I-2) or having a formula (II-1) The structure of the repeating unit represented by the formula (II-2) and the repeating unit represented by the formula (II-2) are preferred.

(Repeating unit represented by the formula (I-1) and repeating unit represented by the formula (I-2)), which is a preferred constituent component of the dispersion resin 2-1, represented by the formula (I-1) The repeating unit and the repeating unit represented by the formula (I-2) will be described in detail.

[Chemical Formula 24]

In the above formulae (I-1) and (I-2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom or an alkyl group. a each independently represents an integer of 1 to 5. * indicates the joint between the repeating units. X represents a group having a functional group of pKa14 or less. Y represents an oligomer chain or a polymer chain having an atomic number of 40 to 10,000.

In addition to the repeating unit represented by the formula (I-1) or the formula (I-2), the dispersing resin 2-1 further preferably has a repeating unit represented by the formula (I-3) as a copolymerization component. . By using the repeating unit in combination, the dispersion property of the particles (D) is further improved.

[Chemical Formula 25]

In the above formula (I-3), *, R ¹ , R ² and a have the same meanings as in the formula (I-1). Y' represents an oligomer chain or a polymer chain having an anion group having an atomic number of 40 to 10,000. The repeating unit represented by the above formula (I-3) can be carried out by adding an oligomer or a polymer having a group which forms a salt by reacting with an amine in a resin having a primary or secondary amine group in the main chain portion. reaction.

In the formula (I-1), the formula (I-2) and the formula (I-3), R ¹ and R ² are particularly preferably a hydrogen atom. From the viewpoint of easily obtaining a raw material, a is preferably 2.

The dispersion resin 2-1 may have a lower-order alkyleneimine as a repeating unit, in addition to the repeating unit represented by the general formula (I-1), the general formula (I-2), and the general formula (I-3). Similarly to the above, the lower alkyleneimine represents an alkyleneimine having 1 to 5 carbon atoms. The dispersion resin 2-1 may contain such a lower-order alkyleneimine repeating unit, or may not contain, in the case of containing, the total amount of the lower-order alkyleneimine repeating unit contained in the dispersion resin 2-1. It is preferred that the repeating unit contains 1 to 70 mol%. Further, a group represented by X, Y or Y' may be further bonded to a nitrogen atom in the lower-order alkyleneimine repeating unit. A resin containing both a repeating unit in which a group represented by X is bonded to a main chain structure and a repeating unit in which Y is bonded is contained in the dispersion resin 2-1.

The repeating unit represented by the formula (I-1) is a repeating unit containing a nitrogen atom to which a group X having a functional group of pKa14 or less is bonded, and the repeating unit containing the nitrogen atom is from storage stability/developability. In view of the above, it is preferred to contain 1 to 80 mol% of the total repeating unit contained in the dispersion resin 2-1. The repeating unit represented by the formula (I-2) is a repeating unit having an oligomer chain or a polymer chain having an atomic number of 40 to 10,000, and the repeating unit is in the dispersion resin 2-1 from the viewpoint of storage stability. It is preferred that the total repeating unit contains 10 to 90 mol%. Regarding the content ratio of the two, the repeating unit (I-1): (I-2) is in the range of 10:1 to 1:100 in terms of molar ratio from the viewpoint of dispersion stability and balance of hydrophilicity. good.

Further, the repeating unit represented by the formula (I-3), which is used in combination as required, is an oligo-chain having a molecular weight of 40 to 10,000 or a partial structure of a polymer chain ionicly bonded to a nitrogen atom of the main chain, From the viewpoint of the effect, the dispersion resin 2-1 is preferably contained in an amount of from 0.5 to 20 mol% in the total repeating unit.

(Repeating unit represented by the formula (II-1) and repeating unit represented by (II-2)) Repetition represented by the formula (II-1) as another preferred constituent component of the dispersion resin 2-1 The unit and the repeating unit represented by the formula (II-2) will be described in detail.

[Chemical Formula 26]

In the general formulae (II-1) and (II-2), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group. *, X and Y have the same meanings as *, X and Y in the general formulae (I-1) and (I-2).

The dispersion resin 2-1 further contains a repeating unit represented by the formula (II-3) in addition to the repeating unit represented by the formula (II-1) and the repeating unit represented by the formula (II-2). The copolymerization component is preferred. By using the repeating unit in combination, the dispersibility of the particles (D) is further improved.

[Chemical Formula 27]

In the formula (II-3), *, R ³ , R ⁴ , R ⁵ and R ⁶ have the same meanings as in the formula (II-1). Y' has the same meaning as Y' in the formula (I-3).

In the general formulae (II-1), (II-2) and (II-3), R ³ , R ⁴ , R ⁵ and R ⁶ are preferably a hydrogen atom from the viewpoint of availability of a raw material.

The formula (II-1) is a repeating unit containing a nitrogen atom bonded to a group having a functional group of pKa14 or less, and the repeating unit containing the nitrogen atom is dispersed from the viewpoint of storage stability/developability. It is preferred that the total repeating unit contained in the resin 2-1 contains 1 to 80 mol%. The general formula (II-2) is a repeating unit having an oligomer chain of 40 to 10,000 or a polymer chain Y, and the repeating unit is a total repeating unit of the dispersed resin 2-1 from the viewpoint of storage stability. It is preferably contained in an amount of 10 to 90 mol%.

With respect to the content ratio of the two, from the viewpoint of the balance of dispersion stability and hydrophilicity, the repeating unit (II-1): (II-2) is in the range of 10:1 to 1:100 in terms of molar ratio. good. The repeating unit represented by the formula (II-3) used in combination as required is preferably contained in an amount of from 0.5 to 20 mol% in the total repeating unit of the dispersion resin 2-1. In the dispersion resin 2-1, from the viewpoint of dispersibility, it is particularly preferable to include both a repeating unit represented by the formula (I-1) and a repeating unit represented by the formula (I-2).

<Group X having a functional group having a pKa of 14 or less X> X has a functional group having a pKa of 14 or less at a water temperature of 25 °C. The "functional group having a pKa of 14 or less" is not particularly limited as long as the physical properties thereof satisfy the above conditions, and the pKa of the known functional group satisfies the above range, and a functional group having a pKa of 12 or less is preferable, pKa is preferable. The functional group of 11 or less is preferred. Specific examples thereof include a carboxylic acid (about 3 to 5 pKa), a sulfonic acid (about pKa -3 to 2), -COCH ₂ CO- (about pKa 8 to 10), and -COCH ₂ CN (pKa 8 to). 11 or so), -CONHCO-, phenolic hydroxyl group, -R _F CH ₂ OH or -(R _F ) ₂ CHOH (R _F represents a perfluoroalkyl group, pKa 9-11 or so), sulfonamide group (pKa 9~) 11 or so) and so on. The functional group of the group X has a pKa of 14 or less, so that interaction with the particles (D) can be achieved. The group X having a functional group having a pKa of 14 or less is preferably directly bonded to a nitrogen atom in a repeating unit containing a nitrogen atom, but the nitrogen atom of the repeating unit containing a nitrogen atom may be covalently bonded to X in addition to X. Ionic bonding forms a salt-like linkage.

The group X having a functional group having a pKa of 14 or less in the present invention is particularly preferably a structure represented by the formula (V-1), the formula (V-2) or the formula (V-3).

[Chemical Formula 28]

In the above formula (V-1) and formula (V-2), U represents a single bond or a divalent linking group. d and e each independently represent 0 or 1. In the above formula (V-3), Q represents a mercapto group or an alkoxycarbonyl group.

Examples of the divalent linking group represented by U include an alkylene group (for example, -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CHMe-, -(CH ₂ ) ₅ -, -CH _{2 ).} CH(nC ₁₀ H ₂₁ )-etc.), an alkyl group containing oxygen (for example, -CH ₂ OCH ₂ -, -CH ₂ CH ₂ OCH ₂ CH ₂ -, etc.), an arylene group (for example, a phenyl group, Tolyl, biphenylene, anthranyl, furan, pyrrolidine, etc.), alkyleneoxy (eg, ethoxy, propenoxy, phenyloxy, etc.), alkenyl (eg, , stretched vinyl) and so on. Further, from the viewpoint of productivity, d is preferably 1 and e is preferably 0.

Q represents a mercapto or alkoxycarbonyl group. It is preferable that Q is a thiol group, and it is preferable from the viewpoint of easy availability and availability of a raw material (precursor X' of X).

The group X in the present invention is preferably bonded to the aforementioned nitrogen atom of a repeating unit containing a nitrogen atom. Thereby, the dispersibility/dispersion stability of the particles (D) is drastically improved.

Further, since the group X is a functional group having a pKa of 14 or less as a partial structure, it also functions as an alkali-soluble group. Thereby, the developability of the alkaline developing solution in the uncured region is improved, and the three effects of dispersibility/dispersion stability/developability can be simultaneously achieved.

The content of the functional group having a pKa of 14 or less in X is not particularly limited, and is preferably 0.01 to 5 mmol per 1 g of the dispersion resin 2. Within this range, the dispersibility and dispersion stability of the particles (D) are improved, and the developability of the uncured portion is excellent. In addition, the acid value of the dispersion resin 2 is preferably from about 5 to 50 mgKOH/g from the viewpoint of acidity, and is preferably from the viewpoint of developability.

(Oligomer chain or polymer chain Y having an atomic number of 40 to 10,000) Examples of Y include polyester, polyamine, polyimine, and poly(methyl) which can be bonded to the main chain portion of the dispersion resin 2. A well-known polymer chain such as acrylate. The bonding site with the dispersion resin 2 of Y is preferably an end of the oligomer chain or the polymer chain Y.

Y and containing a poly(lower alkyleneimine)-based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a meta-xylenediamine-epichlorohydrin polycondensate system The nitrogen atom bonding of the repeating unit of at least one nitrogen atom of the repeating unit and the polyvinylamine-based repeating unit is preferred. Containing a repeating unit selected from the group consisting of a poly(lower alkyleneimine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, and a meta-xylenediamine-epichlorohydrin polycondensate repeating unit The bonding method of the main chain portion and the Y of the repeating unit of at least one nitrogen atom of the polyvinylamine-based repeating unit and the Y 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, and 95:5 to 5:95 is preferable. If it is outside this range, the dispersibility/dispersion stability will deteriorate, and solvent solubility will fall. Y is preferably a guanidine bond with a nitrogen atom of a repeating unit containing a nitrogen atom or an ionic bond as a carboxylate.

The number of atoms of the oligomer chain or the polymer chain Y is preferably from 50 to 5,000, more preferably from 60 to 3,000, from the viewpoint of dispersibility/dispersion stability/developability. When the number of atoms per one oligomer chain or polymer chain Y is less than 40, the graft chain is short, and thus the steric repulsion effect is small and the dispersibility is lowered. On the other hand, if the number of atoms per one oligomer chain or polymer chain Y exceeds 10,000, the oligomer chain or the polymer chain Y becomes too long, so that the adsorption force against the particles (D) is lowered. The dispersion is reduced. Further, the number average molecular weight of Y can be measured by a polystyrene-converted value based on the GPC method. The number average molecular weight of Y is particularly preferably from 1,000 to 50,000, and from 1,000 to 30,000 is preferable from the viewpoint of dispersibility/dispersion stability/developability. It is preferable that two or more of the side chain structure represented by Y is linked to the main chain in one molecule of the resin, and it is preferable to connect five or more.

Y is particularly preferably a structure having a structure represented by the formula (III-1).

[Chemical Formula 29]

In the formula (III-1), Z is a polymer or oligomer having a polyester chain as a partial structure, and represents a residue obtained by removing a carboxyl group from a polyester of a free carboxylic acid represented by the following formula (IV). .

[Chemical Formula 30]

In the general formula (IV), Z has the same meaning as Z in the general formula (III-1). When the dispersion resin 2-1 contains a repeating unit represented by the formula (I-3) or (II-3), Y' is preferably a formula (III-2).

[Chemical Formula 31]

In the formula (III-2), Z has the same meaning as Z of the formula (III-1).

A polyester having a carboxyl group at a single terminal (polyester represented by the general formula (IV)) can be polycondensed by (IV-1) a carboxylic acid and a lactone, (IV-2) a polycondensation of a hydroxyl group-containing carboxylic acid, ( IV-3) obtained by polycondensation of a divalent alcohol and a divalent carboxylic acid (or a cyclic acid anhydride).

The carboxylic acid used in the polycondensation reaction of the (IV-1) carboxylic acid and the lactone is preferably an aliphatic carboxylic acid (a linear or branched carboxylic acid having 1 to 30 carbon atoms). These carboxylic acids can also be used in combination. A lactone can be used as a lactone. These lactones may be used in combination of plural kinds. The molar ratio of the carboxylic acid to the lactone is different depending on the molecular weight of the polyester chain required, and therefore is not absolutely correct, but a carboxylic acid: lactone = 1:1 to 1:1,000 is preferred, 1 : 3 to 1:500 is the best.

(IV-2) The hydroxyl group-containing carboxylic acid in the polycondensation of the hydroxyl group-containing carboxylic acid is the same as the hydroxyl group-containing carboxylic acid in (IV-1), and the preferred range is also the same. As a divalent alcohol in the polycondensation reaction of (IV-3) a divalent alcohol and a divalent carboxylic acid (or a cyclic acid anhydride), a linear or branched aliphatic diol (a diol having 2 to 30 carbon atoms) Good) is better. As the divalent carboxylic acid, a linear or branched divalent aliphatic carboxylic acid (more preferably a divalent aliphatic carboxylic acid having 1 to 30 carbon atoms) is preferred. The divalent carboxylic acid and the divalent alcohol are preferably 1:1 blended in molar ratio. Thereby, a carboxylic acid can be introduced at the terminal.

It is preferred to carry out the addition of a catalyst in the polycondensation in the production of the polyester. As a catalyst, a catalyst which functions as a Lewis acid is preferred.

The number average molecular weight of the polyester can be measured as a polystyrene-converted value based on the GPC method. The polyester has a number average molecular weight of 1,000 to 1,000,000, preferably 2,000 to 100,000, and most preferably 3,000 to 50,000. When the molecular weight is within this range, both dispersibility and developability can be achieved at the same time.

The polyester moiety forming the polymer chain in Y is a polyester obtained by polycondensation of (IV-1) a carboxylic acid and a lactone and polycondensation of a (IV-2) hydroxyl group-containing carboxylic acid, which is easy to manufacture. The point of view is especially good.

Hereinafter, specific examples of the dispersion resin 2 [(A-1) to (A-61)]) are shown by a specific structure of a repeating unit of the resin, and the present invention is not limited thereto. In the following formula, k, l, m and n respectively represent the polymerization molar ratio of the repeating unit, k is from 1 to 80, l is from 10 to 90, m is from 0 to 80, n is from 0 to 70, and k+ l+m+n=100. p and q represent the number of linkages of the polyester chains, and each independently represents 5 to 100,000. R' represents a hydrogen atom or an alkylcarbonyl group.

[Chemical Formula 32]

[Chemical Formula 33]

[Chemical Formula 34]

[Chemical Formula 35]

[Chemical Formula 36]

[Chemical Formula 37]

[Chemical Formula 38]

[Chemical Formula 39]

[Chemical Formula 40]

[Chemical Formula 41]

[Chemical Formula 42]

The method of synthesizing the dispersion resin 2 can be synthesized by the method described in Japanese Laid-Open Patent Publication No. 2011-190180.

In the dispersion resin 2 of the present invention, the weight average molecular weight measured by the GPC method is preferably 3,000 to 100,000, more preferably 5,000 to 55,000. The molecular weight within the above range has an advantage of achieving high developability/high storage stability. Further, the presence of a nitrogen atom in the repeating unit (i) containing a nitrogen atom in the dispersion resin 2 can be confirmed by a method such as acid titration, the presence of a functional group having a pKa of 14 or less, and the functional group and the aforementioned repeating unit. The nitrogen atom bonding can be confirmed by a method such as alkali titration/nuclear magnetic resonance spectroscopy/infrared spectroscopy. Further, the side chain having (ii) an oligomer chain having 40 to 10,000 atoms or a polymer chain Y can be confirmed by a method such as nuclear magnetic resonance spectroscopy/GPC method.

Hereinafter, the molecular weight will be described together with a specific example of the dispersion resin 2. R' represents an alkyl group.

[Chemical Formula 43]

[Chemical Formula 44]

[Chemical Formula 45]

[Chemical Formula 46]

[Chemical Formula 47]

[Chemical Formula 48]

[Chemical Formula 49]

(polymer dispersing agent represented by the formula (1) or (2), dispersing agent other than the dispersing resin 2) The composition of the present invention may contain a polymer dispersing agent represented by the formula (1) or (2), A dispersing agent other than the dispersion resin 2 (hereinafter sometimes referred to as "other dispersing agent"). The other dispersing agent which can be used in the present invention is a polymer dispersing agent (for example, a polymer dispersing agent having a phosphorus atom group or an acid group such as a carboxylic acid as an acid-based adsorption site, and a polyamine amine group and Salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic copolymers, and fumarin condensation And polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine, pigment derivative and the like. In particular, a polymer dispersant having at least one of a phosphorus atom-containing group or a carboxylic acid group as the acid-based adsorption site is preferable from the viewpoint of forming a fine pore-shaped pattern. Examples of the phosphorus atom-containing group include a phosphate group, a polyphosphate group, and a phosphate group. Other dispersants can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer depending on the structure. Other dispersants act on the surface of the titanium dioxide particles and prevent reaggregation. Therefore, the terminal-modified polymer, the graft-type polymer, and the block-type polymer having an anchoring site on the surface of the titanium dioxide particles can be preferably configured. On the other hand, other dispersants have an effect of promoting adsorption of the dispersant by modifying the surface of the titanium dioxide particles.

Specific examples of other dispersants are "DISPERBYK101 (polyamide amine citrate), 107 (carboxylate), 110, 180 (copolymer containing acid), 130 (polyamide), 161, by BYK Chemie. 162, 163, 164, 165, 166, 170 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), EFKA 4047, 4050, 4010, 4165 (polyurethane) , EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyester decylamine), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (酞"Cyanine derivative", 6750 (azo pigment derivative), "AJISPER PB821, PB822" manufactured by Ajinomoto Fine-Techno Co., Inc., "Flowlen TG-710 (manufactured by Kyoeisha Chemical Co., Ltd.)" "), "Polyflow No. 50E, No. 300 (acrylic copolymer)", "Disparon KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 by Kusumoto Chemicals, Ltd. (polyether ester), DA-703-50, DA-705, DA-725", "DOMOL RN, N" by Kao Corporation Sulfosulfonate polycondensate), MS, C, SN-B (aromatic sulfonate fumarate polycondensate), "HOMOGENOL L-18 (polymer polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether), "ACETAMIN 86 (stearylamine acetate)", "SOLSPERSE 5000 (SOLSPERSE 5000) (phthalocyanine derivative), 22000 (azo pigment derivative), manufactured by Lubrizol Japan Limited, 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 26000, 28000, 32000, 36000, 38500 (graft type polymer), 41000", Nikko Chemicals Co. , Ltd., "NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)", etc. In the present invention, it has a phosphorus atom in an acid adsorption site. A polymer dispersant of a base (for example, a phosphoric acid group or the like) can be suitably used with SOLSPERSE 26000 (SOLSPERSE 26000), 36000 or 41000. In the composition of the present invention, the dispersing agent can be used singly or in combination of two or more.

From the viewpoint of dispersibility, the content of the dispersant of the total solid content of the composition of the present invention is preferably in the range of 1 to 40% by mass, more preferably in the range of 1.3 to 30% by mass, and more preferably 1.5 to 20% by mass. The range of % is more preferably, and the range of 2 to 10% by mass is particularly preferable, and the range of 2 to 6% by mass is most preferable. Further, when the composition of the present invention contains a dispersing agent, if the dispersing agent is too large, it may cause peeling. Therefore, the mass of the dispersing agent in the composition is preferably less than the mass of the particles (D), and the dispersing agent and The mass ratio in the composition of the particles (D) is more preferably a dispersant/particle (D) = 0.01 to 0.8, and a dispersant/particle (D) = 0.03 to 0.5 is further preferably a dispersant/particle (D). =0.05 to 0.3 is especially preferred. Moreover, the total content of the binder (A) and the dispersant (sometimes referred to as the polymer content) is very advantageous for the resolution, and the polymer content is in the range of 10 to 80% by mass in the total solid content of the composition. Preferably, the range of 20 to 80% by mass is more preferable, and the range of 30 to 75% by mass is particularly preferable. In this case, a binder having an acid radical as a binder is preferred, and a dispersant having an acidic group and/or a basic group as a dispersant is preferred.

[(E) Solvent] The composition of the present invention contains a solvent. The solvent can be formed using various organic solvents. As the organic solvent which can be used herein, there are acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether. , ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetamidine acetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether Acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, two Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxy propyl Acetate, N,N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate, and the like. These organic solvents can be used singly or in combination. The concentration of the solid content in the composition of the present invention is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less. Further, from the viewpoint of coating uniformity, 30% by mass or less is most preferable.

Further, in the present invention, a solvent having a small metal content is preferably used, and for example, a metal content of 10 ppb or less is preferable. It is also possible to use the ppt grade, which is supplied by TOYO GOSEI LTD (Chemical Industry Daily, November 13, 2015). Further, as a method of removing impurities such as metal from a solvent, for example, distillation (such as molecular distillation or thin film distillation) and filtration using a filter can be mentioned. As the filter pore size of the filter for filtration, the pore size is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable. Further, the solvent may contain isomers (compounds having the same atomic number but different structures). Further, the isomer may be contained alone or in combination of plural kinds.

The composition of the present invention may further contain any of the components detailed below as needed. The composition of the present invention can contain a color material, and examples of the color material include a coloring agent or an organic black coloring agent.

(Colorful Colorant) In the present invention, the coloring agent is preferably a coloring agent selected from the group consisting of a red coloring agent, a green coloring agent, a blue coloring agent, a yellow coloring agent, a purple coloring agent, and an orange coloring agent.

In the present invention, the coloring agent may be a pigment or a dye. Pigments are preferred. The average particle diameter (r) of the pigment is preferably 20 nm ≤ r ≤ 300 nm, more preferably 25 nm ≤ r ≤ 250 nm, and further preferably 30 nm ≤ r ≤ 200 nm. Here, the "average particle diameter" means the average particle diameter of the secondary particles in which the primary particles of the pigment are aggregated, and the particle size distribution of the secondary particles as the pigment which can be used (hereinafter, also simply referred to as "particle size distribution". The secondary particles having an average particle diameter of ±100 nm are preferably 70% by mass or more of the total, and more preferably 80% by mass or more. Further, the particle size distribution of the secondary particles can be measured using a scattered intensity distribution.

As a method of preparing the pigment having the above average particle diameter (secondary particle diameter) and particle size distribution of secondary particles, the following method can be mentioned. First, it is preferred to mix a commercially available pigment with a resin and an organic solvent to prepare a pigment mixture. Further, it is also possible to mix with other pigments (the average particle diameter of the secondary particles is usually more than 300 nm) as needed. Thereafter, the pigment in the pigment mixture liquid is pulverized by mixing with a pulverizer such as a bead mill or a roll mill, and mixed/dispersed, whereby a pigment having predetermined characteristics can be prepared. The pigment thus obtained is usually in the form of a pigment dispersion.

The pigment is preferably an organic pigment, and the following pigments can be mentioned. However, the invention is not limited to these. Colorimetric Index (CI) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35, 35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93, 94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129, 137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175, 176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc. (above yellow pigment), CIPigment Orange 2,5,13,16,17:1, 31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73, etc. (above orange pigment), CIPigment Red 1,2, 3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1, 49:2, 52:1, 52:2 53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144, 146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208, 209,210,216,220,224,226,242,246,254,255,264,270,272,279, etc. (above red pigment), CIPigment Green 7,10,36,37,58,59, etc. (The above are green pigments), CIPigment Violet 1,19,23,27,32,37,42, etc. (above purple pigment), CIPigment Blue 1,2,15,15:1,15:2,15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc. (the above are blue pigments), these organic pigments can be used singly or in combination of plural kinds.

The dye is not particularly limited, and a known dye can be used. As the chemical structure, a pyrazole azo type, an aniline azo type, a triphenylmethane type, an anthraquinone type, an anthrapyridone type, a benzylidene type, an oxaphthalocyanine type, and a pyrazolotriazole azo type can be used. Dyes such as pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo or pyrromethene. Further, a polymer of these dyes can also be used. In addition, the dye described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.

Further, as the dye, an acid dye and/or a derivative thereof may be suitably used. Further, direct dyes, basic dyes, mordant dyes, acid mord dyes, ice dyes, disperse dyes, oil-soluble dyes, food dyes, and/or such derivatives can be effectively used.

Specific examples of the acid dye are listed below, but are not limited thereto. For example, the following dyes and derivatives of such dyes can be mentioned. Acid alizarin violet N, acid blue 1,7,9,15,18,23,25,27,29,40-45,62,70,74,80,83,86,87,90,92,103,112 ,113,120,129,138,147,158,171,182,192,243,324:1, acid chrome violet K, acid Fuchsin;acid green 1,3,5,9,16,25,27,50 , acid orange 6,7,8,10,12,50,51,52,56,63,74,95, acid red 1,4,8,14,17,18,26,27,29,31,34 ,35,37,42,44,50,51,52,57,66,73,80,87,88,91,92,94,97,103,111,114,129,133,134,138,143 ,145,150,151,158,176,183,198,211,215,216,217,249,252,257,260,266,274, acid violet 6B,7,9,17,19, acid yellow 1 ,3,7,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116,184,243, Food Yellow 3

Further, azo-based, xanthene-based, and phthalocyanine-based acid dyes other than the above are also preferable, and CISolvent Blue 44, 38; CISolvent orange 45; acid dyes such as Rhodamine B and Rhodamine 110, and the like are preferably used. Derivatives of such dyes are also preferred.

Wherein, the dye is selected from the group consisting of triarylmethane, anthraquinone, azomethine, benzylidene, oxaphthalocyanine, cyanine, phenothiazine, pyrrolopyrazole azo Base, xanthene, phthalocyanine, benzopyran, indigo, pyrazole azo, aniline azo, pyrazolotriazole azo, pyridone azo, anthrapy At least one of the pyrromethene systems is preferred. Moreover, pigments and dyes can also be used in combination.

(Organic black coloring agent) In the present invention, examples of the organic black coloring agent include a bisbenzofuranone compound, a methylimine compound, an anthraquinone compound, an azo compound, and the like, and a bisbenzofuranone compound. Anthraquinone compounds are preferred. Examples of the bisbenzofuranone compound include those described in JP-A-2010-534726, JP-A-2012-515233, and JP-A-2012-515234, and can be obtained, for example, from BASF Corporation. Irgaphor Black". Examples of the ruthenium compound include C.I. Pigment Black 31, 32 and the like. For example, it is possible to obtain "CHROMOFINE Black A1103" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., as disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei. .

[Blue pigment or even violet pigment] The composition of the present invention can contain a blue pigment or a violet pigment from the viewpoint of improving the coloring resistance of the cured film formed by the composition of the present invention. As a blue pigment or purple pigment, selected from CIPigment Violet 1,19,23,27,32,37,42 and CIPigment Blue 1,2,15,15:1,15:2,15:3,15: One or more of 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 is preferable.

- Formulation of Pigments - (Color Matching) These organic pigments can be used singly or in combination for improving color purity. Specific examples of the above combinations are shown below. As the blue pigment, one type of phthalocyanine type pigment can be used alone or a dioxazine-based purple pigment can be mixed therewith. As a particularly suitable example, a mixture of C.I. pigment/blue 15:6 and C.I. pigment/purple 23 can be mentioned. The mass ratio of the blue pigment to the violet pigment is preferably from 100:0 to 100:100, more preferably less than 100:70.

It is preferred to contain a dispersing agent when dispersing the blue pigment or the violet pigment. The type of the dispersing agent is not particularly limited, and a polymer dispersing agent is preferably used. Examples of the polymer dispersant include DisperBYK-101, DisperBYK-102, DisperBYK-103, DisperBYK-106, DisperBYK-111, DisperBYK-161, DisperBYK-162, DisperBYK-163, DisperBYK-164, DisperBYK-166, DisperBYK -167, DisperBYK-168, DisperBYK-170, DisperBYK-171, DisperBYK-174, DisperBYK-182 (above, BYK Chemie), EFKA4010, EFKA4046, EFKA4080, EFKA5010, EFKA5207, EFKA5244, EFKA6745, EFKA6750, EFKA7414, EFKA7462 , EFKA7500, EFKA7570, EFKA7575, EFKA7580 (above, EFKA Additives C/O EJ Chemicals Co. Ltd.), Disperse Aid6, Disperse Aid8, Disperse Aid15, Disperse Aid9100 (made by SAN NOPCO LIMITED) and other polymer dispersants; Solsperse3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, 32000, 36000, 39000, 41000, 71000 and other Solsperse dispersants, (made by Zeneca); ADEKA Pluronic L31, F38, L42, L44, L61 , L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (made by ASAHIDENKA) and IsonetS-20 (Sa "Disaron KS-860, 873SN, 874 (polymer dispersant), #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyether ester type) manufactured by Kusumoto Chemicals, Ltd." by Nyo Chemical Industries, Ltd.) . Further, a pigment derivative such as a phthalocyanine derivative (trade name: EFKA-745 (manufactured by EFKA)), Solsperse 5000, 12000, and Solsperse 22000 (manufactured by Zeneca) can be used.

Further, the composition may contain a black pigment as a color material. The black pigment is not particularly limited, and a known pigment can be used. For example, carbon black, titanium black, graphite, etc. may be mentioned, carbon black and titanium black are preferable, and titanium black is more preferable. The titanium black is a black particle containing a titanium atom, and a low-order titanium oxide and a titanium oxynitride are preferred. The titanium black particles may be modified as needed to enhance the dispersibility and inhibit the agglutination. The surface of titanium black can be coated with cerium oxide, titanium oxide, cerium oxide, aluminum oxide, magnesium oxide or zirconium oxide. Further, it is also possible to carry out a treatment using a hydrophobic substance as shown in Japanese Laid-Open Patent Publication No. 2007-302836. Specific examples of the black pigment include C.I. Pigment Black 1, 7, titanium black pigment, and the like.

Titanium black is a typical titanium black particle, and it is preferred that each particle has a smaller primary particle diameter and an average primary particle diameter. Specifically, it is preferred that the average primary particle diameter is in the range of 10 nm to 45 nm. Further, the particle diameter in the present invention, that is, the particle diameter, has a diameter of a circle having an area equal to the projected area of the outer surface of the particle. The projected area of the particles is an area obtained by photographing by electron micrograph, and is obtained by correcting the imaging magnification.

The specific surface area of titanium black is not particularly limited, but the hydrophobicity after surface treatment of titanium black using a hydrophobic agent reaches a predetermined property, and the value measured by a BET (Brunauer, Emmett, Teller) method is 5 m ² /g or more. 150m ² / g or less is preferred, 20m ² / g or more and 120m ² / g or less is more preferred. Examples of commercially available products of titanium black include titanium blacks 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, and 13M-T (product name: manufactured by Mitsubishi Materials Corporation) and Tilack D (products). Name: manufactured by Akokasei Co. Ltd.).

Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and cerium oxide particles in a range in which the content ratio of Si atoms and Ti atoms in the dispersion is adjusted to 0.20 to 0.50 is exemplified. The above-mentioned dispersion can be referred to in paragraphs 0020 to 0105 of JP-A-2012-169556, and the contents are incorporated in the present specification.

When the total amount of the particles having an average particle diameter of 50 nm or more and the color material is 100 parts by mass, the upper limit is preferably 50 parts by mass or less, more preferably 20 parts by mass or less, and 10 parts by mass. The following is further preferred, and it is particularly preferably 5 parts by mass or less. When it is in the above range, the dispersion stability of the composition is not affected, and the function of color adjustment can be appropriately exhibited. The lower limit is preferably 0.01 parts by mass or more, more preferably 0.1 part by mass or more. As long as it is within the above range, the amount of addition is not too small, and thus the performance is stable.

[Hydrane coupling agent] A decane coupling agent can be used in the composition of the present invention from the viewpoint of further improving the adhesion to the substrate. The decane coupling agent is preferably an alkoxyalkylene group which is a hydrolyzable group which can be chemically bonded to an inorganic material. Further, it is preferred to have a group which exhibits affinity or interaction with an organic resin to form an affinity, and as such a group, has a (meth)acryl fluorenyl group, a phenyl group, a fluorenyl group, a glycidyl group, or an oxa group. The cyclobutyl group is more preferred, and those having a (meth) acrylonitrile group or a glycidyl group are further preferred. In other words, as the decane coupling agent to be used in the present invention, a compound having an alkoxyalkyl group, a (meth) acryl fluorenyl group or an epoxy group is preferable, and specifically, the following structure is exemplified. (Meth) propylene fluorene-trimethoxy decane compound, glycidyl-trimethoxy decane compound, and the like.

[Chemical Formula 50]

Further, the decane coupling agent in the present invention is preferably a decane compound having at least two functional groups having different reactivity in one molecule, and particularly preferably a functional group having an amine group and an alkoxy group. As such a decane coupling agent, for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane (N-β-aminoethyl-γ-aminopropyl-methyldiene) Methoxy decane) (trade name: KBM-602, manufactured by Shin-Etsu Chemicals Co., Ltd.), N-β-amine ethyl-γ-aminopropyl-trimethoxydecane (Shin-Etsu Chemicals Co., Ltd.) . Product name KBM-603), N-β-amine ethyl-γ-aminopropyl-triethoxydecane (trade name KBE-602, manufactured by Shin-Etsu Chemicals Co., Ltd.), γ-amine C Base-trimethoxydecane (trade name: KBM-903, manufactured by Shin-Etsu Chemicals Co., Ltd.), γ-aminopropyl-triethoxydecane (trade name KBE-, manufactured by Shin-Etsu Chemicals Co., Ltd.) 903) and so on. As the decane coupling agent, a compound having two or more alkoxyalkylalkyl groups can also be suitably used. Examples of the compound having two or more alkoxyalkylalkyl groups include 1,6-bis(trimethoxydecane)hexane, tris-(3-trimethoxymethane) isocyanurate, and KBM-. 3066, KBM-3086, KC-89S, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-9218, KR-213, KR-510, X-40-9227, X-40-9247, X-40-2308, X-40-9238 (manufactured by Shin-Etsu Chemicals Co., Ltd.).

The amount of addition in the case of using a decane coupling agent is preferably 0.01% by mass to 15.0% by mass in the total solid content of the composition, and more preferably 0.05% by mass to 10.0% by mass. In the composition of the present invention, the decane coupling agent can be used singly or in combination of two or more.

[(F) Coloring Preventing Agent] The composition of the present invention preferably contains a coloring preventing agent. The coloring inhibitor of the present invention is preferably a phosphite compound or a thioether compound which is well known as a polymerization inhibitor, a phenol compound or an antioxidant described in the present application, and has a phenol compound having a molecular weight of 500 or more and a subunit having a molecular weight of 500 or more. A phosphate compound or a thioether compound is more preferable. These may be used in combination of two or more. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. It is particularly preferable to have a substituent at a site adjacent to the phenolic hydroxyl group (ortho). As the substituent in this case, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, and a pentyl group are preferable. More preferably, the group is isoamyl, tert-amyl, hexyl, octyl, isooctyl or 2-ethylhexyl. Further, a stabilizer having a phenol group and a phosphite group in the same molecule is also mentioned as a preferable raw material.

Further, a phosphorus-based antioxidant is also suitably used as a coloring preventive agent. The phosphorus-based antioxidant may be selected from the group consisting of tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3, 2] dioxaphosphocycloheptan-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1 a group of 3,2]dioxaphosphocycloheptan-2-yl)oxy]ethyl]amine and ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite At least one compound.

These are readily available as commercial products and are sold by the following manufacturers. ADKSTAB AO-20, ADKSTAB AO-30, ADKSTAB AO-40, ADKSTAB AO-50, ADKSTAB AO-50F, ADKSTAB AO-60, ADKSTAB AO-60G, ADKSTAB AO-80, ADKSTAB AO- from ASAHIDENKA 330 and so on. The content of the coloring inhibitor in the composition is preferably 0.01% by mass or more and 20% by mass or less, and more preferably 0.3% by mass or more and 15% by mass or less, in terms of solid content. Further, the coloring preventing agent may be used in combination of two or more kinds.

[Sensitizer] The composition of the present invention may contain a sensitizer for the purpose of improving the radical generating efficiency of the (C) polymerization initiator and the long wavelength of the photosensitive wavelength. As the sensitizer which can be used in the present invention, it is preferred that the (C) polymerization initiator is rubbed by an electron-moving mechanism or an energy-moving mechanism.

Examples of the sensitizer include those exemplified below, and those having an absorption wavelength in a wavelength region of 300 nm to 450 nm. The sensitizer is specifically described in paragraphs 0231 to 0253 of the Japanese Patent Application Laid-Open No. 2010-106268 (the <0256> to <0273> of the specification of the corresponding US Patent Application Publication No. 2011/0124824), and These contents are incorporated in this specification. The content of the sensitizer in the composition is preferably 0.1% by mass or more and 20% by mass or less based on the solid content, and is preferably 0.5% by mass or more, from the viewpoint of the light absorption efficiency in the deep portion and the decomposition efficiency of the initiator. 15% by mass or less is more preferable. The sensitizer may be used alone or in combination of two or more.

[Common sensitizer] It is also preferred that the composition of the present invention further contains a co-sensitizer. The co-sensitizer of the present invention has an effect of further increasing the sensitivity to the active radiation of the (C) polymerization initiator and the sensitizer, or suppressing the polymerization inhibition of the (B) monomer by oxygen. The description of the co-sensitizer can be specifically described in paragraphs 0254 to 0257 of the Japanese Patent Application Laid-Open No. 2010-106268 (the <0277> to <0279> of the specification of the corresponding US Patent Application Publication No. 2011/0124824). And such content is incorporated in this specification. The content of the co-sensitizer is in a range of 0.1% by mass or more and 30% by mass or less based on the mass of the total solid content of the composition, from the viewpoint of improving the curing rate based on the equilibrium between the polymerization growth rate and the chain movement. Preferably, the range of 1% by mass or more and 25% by mass or less is more preferable, and the range of 1.5% by mass or more and 20% by mass or less is further more preferable. These may be used alone or in combination of two or more.

[Polymerization Inhibitor] In the present invention, a polymerization inhibitor may be added in order to prevent unnecessary polymerization of a compound having a polymerizable ethylenically unsaturated double bond bond when the composition is produced or stored. Examples of the polymerization inhibitor which can be used in the present invention include a phenolic hydroxyl group-containing compound, an N-oxide compound, a piperidine 1-oxy radical compound, and a pyrrolidine 1-oxy radical compound. , N-nitrosophenylhydroxylamine groups, diazo compounds and cationic dyes, sulfide group-containing compounds, nitro group-containing compounds, transition metal compounds such as FeCl ₃ and CuCl ₂ .

As a further preferred aspect, the following is given. The phenolic hydroxyl group-containing compound is selected from the group consisting of hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4 , 4-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,6-di-tert Compounds of the group of butyl-4-methylphenol (BHT), phenolic resins and cresol resins are preferred. The N-oxide compound is selected from the group consisting of 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N Compounds of the group of -oxide, 3-hydroxypyridine N-oxide, pyridinecarboxylic acid N-oxide, nicotinic acid N-oxide and isonicotinic acid N-oxide are preferred. The piperidine 1-oxyl radical compound is selected from the group consisting of piperidine 1-oxyl radicals, 2,2,6,6-tetramethylpiperidine 1-oxyl radicals, 4-oxo-2,2 6,6-tetramethylpiperidine 1-oxyl radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-acetamidamine-2,2 6,6-tetramethylpiperidine 1-oxyl radical, 4-maleimide-2,2,6,6-tetramethylpiperidine 1-oxyl radical and 4-phosphine-2 Compounds in the group of 2,6,6-tetramethylpiperidine 1-oxyl radicals are preferred. The pyrrolidine 1-oxyl radical compound is preferably a 3-carboxypropoxy radical (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl radical). The N-nitrosophenylhydroxylamine group is preferably a compound selected from the group consisting of N-nitrosophenylhydroxylamine first sulfonium salt and N-nitrosophenylamine aluminum salt. The diazo compound is a hexafluorophosphate selected from the group consisting of hydrogen sulfate including 4-diazobenzenedimethylamine, tetrafluoroborate of 4-diazodiphenylamine, and 3-methoxy-4-diazonium diphenylamine. Compounds in the group of salts are preferred.

Suitable polymerization inhibitors which can be used in the present invention are exemplified below, but the present invention is not limited to these. In addition, examples of the phenolic polymerization inhibitor include the following exemplified compounds (P-1) to (P-24).

[Chemical Formula 51]

[Chemical Formula 52]

[Chemical Formula 53]

[Chemical Formula 54]

The amine-based polymerization inhibitors include the following exemplified compounds (N-1) to (N-7).

[Chemical Formula 55]

The sulfur-based polymerization inhibitors include the following exemplified compounds (S-1) to (S-5).

[Chemical Formula 56]

The phosphite-based polymerization inhibitors include the following exemplified compounds (R-1) to (R-5).

[Chemical Formula 57]

Further, each of the compounds shown below can also be used as a suitable polymerization inhibitor.

[Chemical Formula 58]

Among the above exemplified compounds, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4-thio Bis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), a phenolic hydroxyl group-containing compound, piperidine 1- Oxy radical compound or 2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-oxy-2,2,6,6-tetramethylpiperidine 1-oxyl free Base, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamidamine-2,2,6,6-tetramethylpiperidine 1-oxyl free Base, 4-maleimide-2,2,6,6-tetramethylpiperidine 1-oxyl radical and 4-phosphino-2,2,6,6-tetramethylpiperidine 1 - an oxygen radical piperidine 1-oxyl radical compound or N-nitrosophenylhydroxylamine first sulfonium salt and N-nitrosophenylhydroxylamine aluminum salt N-nitrosophenylhydroxylamine compound Preferably, 2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-oxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4- Hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4-acetamide-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 4- Malayia -2,2,6,6-tetramethylpiperidine 1-oxyl radical and 4-phosphono-2,2,6,6-tetramethylpiperidine 1-oxyl free piperidine 1 - an oxy-radical compound or an N-nitrosophenyl hydroxylamine compound of N-nitrosophenylhydroxylamine first sulfonium salt and N-nitrosophenylhydroxylamine aluminum salt, N-nitrosobenzene The N-nitrosophenylhydroxylamine compound of the hydroxylamine first sulfonium salt and the N-nitrosophenylhydroxylamine aluminum salt is further preferred.

The amount of the polymerization inhibitor to be added is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.01 parts by mass or more and 8 parts by mass or less, based on 100 parts by mass of the (C) polymerization initiator. A range of 0.01 part by mass or more and 5 parts by mass or less is preferred. By setting it as the said range, the suppression of the hardening reaction in the non-image part, and the hardening reaction promotion in an image part are fully performed, and image formation property and sensitivity are favorable. In the composition of the present invention, the polymerization inhibitor can be used singly or in combination of two or more.

[Interacting Agent] From the viewpoint of further improving the coating property, various surfactants can be added to the 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.

In particular, since the composition of the present invention contains a fluorine-based surfactant, the liquid properties (particularly, fluidity) when the coating liquid is prepared are further improved, so that the uniformity of the coating thickness and the liquid-saving property can be further improved. In other words, when a film is formed using a coating liquid containing a composition containing a fluorine-based surfactant, the interfacial tension between the coated surface and the coating liquid is lowered, and the wettability of the surface to be coated is improved. And the coating property to the coated surface is improved. Therefore, even when a film having a small amount of liquid is formed by a small amount of liquid, it is effective to appropriately form a film having a uniform thickness with a small film thickness unevenness.

The fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by mass. The lower limit is preferably 5% by mass or more, and more preferably 7% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less. When the fluorine content is within the above range, it is effective in the uniformity of the thickness of the coating film and the liquid-saving property, and the solubility is also good. Specific examples of the fluorine-based surfactant include the interfacial activity described in paragraphs 0060 to 0064 of JP-A-2014-41318 (paragraphs 0060 to 0064 of the corresponding International Publication No. 2014/17669 pamphlet). Agents, and such contents are incorporated in the present specification. Examples of commercially available fluorine-based surfactants include Magafac F-171, Magafac F-172, Magafac F-173, Magafac F-176, Magafac F-177, Magafac F-141, and Magafac F-142. Magafac F-143, Magafac F-144, Magafac R30, Magafac F-437, Magafac F-475, Magafac F-479, Magafac F-482, Magafac F-554, Magafac F-780 (above, manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH -40 (above, manufactured by ASAHI GLASS CO., LTD.) and the like. As the fluorine-based surfactant, the compound described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used. Further, the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

[Chemical Formula 59]

The weight average molecular weight of the above compound is preferably from 3,000 to 50,000, for example, 14,000. Further, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can be used as the fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A-2010-164965, for example, Magafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and the like, and ethoxylates and propoxylates (for example, glycerol propoxylate, Glycerol ethoxylate, etc., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethyl b Diol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704 by BASF Corporation) , 901, 904, 150R1, Pionin D-6512, D-6414, D-6112, D-6115, D-6120, D-6131, D-6108-W, D-6112-W, D-6115-W, D-6115-X, D-6120-X (manufactured by TAKEMOTO OIL & FAT Co., Ltd.), solsperse 20000 (manufactured by Lubrizol Japan Limited), etc. Specific examples of the cationic surfactant include phthalocyanine derivatives ( Product name: EFKA-745, manufactured by MORISHITA & CO., LTD.), organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid ( Polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), etc. As an anionic surfactant, specifically, W004, W005, W017 (manufactured by Yusho Co., Ltd.), etc. Examples of the anthrone-based surfactant include "Toray Silicone DC3PA" and "Toray Silicone SH7PA" manufactured by Dow Corning Toray Co., Ltd. "Toray Silicone DC11PA", "Toray Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Toray Silicone SH30PA", "Toray Silicone SH8400", "TSF-4440" by Momentive Performance Materials Inc., "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452", "KP341", "KF6001", "KF6002", BYK Chemie, manufactured by Shin-Etsu Silicone Co., Ltd. "BYK307", "BYK323", "BYK330", etc. The surfactant may be used singly or in combination of two or more.

The composition may or may not contain a surfactant. When it is contained, the amount of the surfactant added is preferably 0.001% by mass to 2.0% by mass based on the total mass of the composition, and 0.005% by mass to 1.0% by mass. Better.

[Other Additives] Further, a known additive such as a plasticizer and a lipid-sensitizing agent for improving the physical properties of the hardened film may be added to the composition. As a plasticizer, for example, dioctyl phthalate, dodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate In the case of using a binder, the dioctyl adipate, dibutyl sebacate, triethyl decyl glycerin, etc., can be added in an amount of 10% by mass or less based on the total mass of the monomer and the binder.

[Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, a compound represented by the following formula (I) is particularly preferable as the conjugated diene compound.

[Chemical Formula 60]

In the formula (I), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ¹ and R ² may be the same as each other. Different, but not the same as the hydrogen atom. Further, R ¹ and R ² may form a cyclic amino group together with a nitrogen atom to which R ¹ and R ² are bonded. Examples of the cyclic amino group include a piperidinyl group, a morpholinyl group, a pyrrolidinyl group, a hexahydroheptyl group, and a piperazinyl group. R ³ and R ⁴ represent an electron withdrawing group. Here, the electron withdrawing group is a substituent constant σ _p value of Hammett (hereinafter, simply referred to as “σ _p value”) is an electron withdrawing group of 0.20 or more and 1.0 or less. The electron withdrawing group having a σ _p value of 0.30 or more and 0.8 or less is preferable. R ³ and R ⁴ may also be bonded to each other to form a ring. Further, at least one of R ¹ , R ² , R ³ and R ⁴ may be in the form of a polymer introduced through a monomer bonded to a vinyl group via a linking group. It is also possible to copolymerize with other monomers. The description of the substituent of the ultraviolet absorber represented by the formula (I) can be referred to the description in paragraphs 0024 to 0033 of WO2009/123109A (the <0040> to <0059> of the specification of the corresponding US Patent Application Publication No. 2011/0039195). And such content is incorporated in this specification. For a preferred embodiment of the compound represented by the above formula (I), reference is made to the exemplified compounds (1) to (the <0060> of the specification of U.S. Patent Application Publication No. 2011/0039195). The description in 14), and the contents are incorporated in the present specification.

The composition of the present invention may contain an ultraviolet absorber or may not contain an ultraviolet absorber. When it is contained, the content of the ultraviolet absorber is preferably 0.1% by mass to 10% by mass based on the total solid content of the composition, and 0.1% by mass. ～5% by mass is more preferable, and 0.1% by mass to 3% by mass is particularly preferable. Further, in the present invention, the various ultraviolet absorbers may be used singly or in combination of two or more. The composition of the present invention is preferably filtered by a filter for the purpose of removing foreign matter or reducing defects. The filter is not particularly limited as long as it is used by a user such as a filter, and can be used. For example, a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon-6 or nylon-6,6, or a polyolefin resin such as polyethylene or polypropylene (PP) may be used (including high density, Ultra high molecular weight) filter. Among these raw materials, polypropylene (including high density polypropylene) is preferred. The pore diameter of the filter is suitably about 0.2 to 10.0 μm, preferably about 0.3 to 7.0 μm, and more preferably about 0.4 to 5.0 μm. By setting it as this range, it mixes in the pigment|dissolution which melt|dissolved, etc., and can remove the fine- When using filters, you can combine different filters. In this case, the filtration by the first filter may be performed only once, or may be performed twice or more. Further, the first filter having a different pore diameter within the above range can be combined. The aperture here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL., Ltd., Advantec Toyo kaisha, Ltd., Japan Entegris Inc. (formerly Nippon Mykrolis Corporation) or KITZ MICROFILTER CORPORATION. The second filter can be formed of the same material or the like as the first filter described above. For example, the filtration by the first filter can be carried out using only the dispersion, and after mixing the other components, the filtration by the second filter is performed.

The method for producing the composition of the present invention is not particularly limited, and a method for producing a generally used composition can be applied.

<Cured film> The present invention has been made in view of the above-described problems of the prior art, and it is possible to obtain a uniform in-plane uniformity and a flat transmittance in a visible region, and resistance, lithography, storage stability, adhesion, and further A cured film excellent in dispersibility and coating uniformity can be suitably used as an appearance adjusting material such as various optical sensors and optical members. That is, the composition of the present invention is preferably used for forming a cured film. Further, the present invention relates to a cured film formed using the composition of the present invention. [Method for Producing Cured Film] As a method for producing a cured film of the present invention, the composition is applied to a substrate by a spray coating method, a roll coating method, a spin coating method (spin coating method), a bar coating method, or the like. The above process; the first heating process; and the hardening process by the second heating and/or exposure hardening at a higher temperature. It is preferable to dry at a temperature of 70 ° C or more and 110 ° C or less for 2 minutes or more and 4 minutes or less as a condition in the first heating process.

The film thickness of the cured film is not particularly limited, and from the viewpoint of further effectively obtaining the effect of the present invention, it is preferably 0.2 μm or more and 50 μm or less, more preferably 0.5 μm or more and 30 μm or less, in terms of film thickness after drying. 0.7 μm or more and 20 μm or less are particularly preferable.

<Pattern and Method of Manufacturing the Same> Hereinafter, the pattern of the present invention will be described in detail by the method for producing a pattern of the present invention. The method for producing a pattern of the present invention includes a process of forming a film by using the composition of the present invention on a substrate, and a process of exposing the film through a mask (hereinafter, simply referred to as "exposure process" as appropriate) and The film after exposure is subjected to development to form a pattern (hereinafter, appropriately referred to simply as "developing process"). The method for producing a pattern of the present invention preferably has a hardening process in which the formed pattern is further hardened by heating and/or exposure after performing the film forming process, the exposure process, and the developing process. Specifically, the composition of the present invention is applied onto a substrate directly or via another layer to form a film (film formation process), and exposure is performed via a predetermined mask pattern, and only the portion of the coating film irradiated with light is hardened ( The exposure process) is developed by a developing solution (developing process) so that a pattern can be formed. Hereinafter, each process will be described.

[Film Forming Process] In the film forming process, the composition of the present invention is applied onto a substrate to form a film. Examples of the substrate include an alkali-free glass, a soda glass, a Pyrex (registered trademark) glass, a quartz glass, a transparent conductive film attached thereto, and the like, and a solid-state image sensor or the like used in a liquid crystal display device or the like. The photoelectric conversion element substrate, for example, a germanium substrate or the like, a complementary metal oxide film semiconductor (CMOS) or the like. Further, an undercoat layer for improving adhesion to the upper layer, preventing diffusion of a substance, or planarizing the surface of the substrate may be applied to the substrates as needed. As a coating method for applying the composition of the present invention on a substrate, various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, spray coating, and screen printing can be employed. Coating method. The coating film thickness of the film is not particularly limited, and is preferably 0.2 μm or more and 50 μm or less, more preferably 0.5 μm or more and 30 μm or less, and more preferably 0.7 μm or more and 20 μm or less from the viewpoint of resolution and developability. good. The composition coated on the substrate is usually dried at a temperature of 70 ° C or higher and 110 ° C or lower for 2 minutes or longer and 4 minutes or shorter to form a film.

[Exposure Process] In the exposure process, the formed film is exposed through a mask, and only the coating film irradiated with light is partially cured. It is preferable that the exposure is performed by irradiation of radiation, and it is preferable to use ultraviolet rays such as g-rays, h-rays, and i-rays as the radiation which can be used for exposure, and a high-pressure mercury lamp is more preferable. ² or more and the irradiation intensity of 1500mJ / cm ² or less is preferred, 10mJ / cm ² or more and 1200mJ / cm ² is more or less good 5mJ / cm, 10mJ / cm ² or more and 1000mJ / cm ² or less is the best.

[Developing Process] After the exposure process, a developing process (an alkaline developing process is preferred) is performed to dissolve the unexposed portion of the light in the alkaline aqueous solution in the exposure process. Thereby, only the portion of the light hardening remains. The developing solution used in the developing process is not particularly limited, and for example, a developing solution containing an alkaline developing solution or an organic solvent can be used. As the developer, an organic alkaline developer which does not cause damage to the substrate circuit or the like is preferable. The development temperature is usually 20° C. or higher and 30° C. or lower, and the development time is 20 seconds or longer and 90 seconds or shorter. As the alkaline developing solution, for example, inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia or the like, a first amine such as ethylamine or n-propylamine, or diethylamine can be used. a second amine such as di-n-amine, a third amine such as triethylamine or methyldiethylamine, an alcohol amine such as dimethylethanolamine or triethanolamine, tetramethylammonium hydroxide or tetraethylammonium hydroxide , tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraamylamine hydroxide, tetrahexylamine hydroxide, tetraoctylamine hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylhydrogen Tetraalkylammonium hydroxide such as amine oxide, methyltrimethanolamine or dibutylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylhydrogen An alkaline aqueous solution such as a quaternary ammonium salt such as ammonium oxide or a cyclic amine such as pyrrole or piperidine. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution for use. The alkaline developer has an alkaline concentration of usually 0.001 to 20% by mass, preferably 0.01 to 10% by mass, more preferably 0.1 to 1% by mass. The pH of the alkaline developer is usually from 10.0 to 15.0. The alkaline concentration and pH of the alkaline developer can be appropriately prepared and used. As the alkaline developing solution, for example, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added in an appropriate amount. Further, in the case of using a developing solution composed of such an alkaline aqueous solution, it is usually washed (rinsed) with pure water after development.

Further, the optical member obtained by the present composition can be incorporated not only in the solid-state imaging device but also in the liquid crystal display device and the organic EL display device. [Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. In addition, there is no special provision, and "parts" and "%" are quality standards. Further, in the examples, the acid value was determined by a potential difference method (solvent tetrahydrofuran/water = 54/6 (volume ratio), titrant solution 0.1 N aqueous sodium hydroxide solution (acid value)). In the measurement of the weight average molecular weight in the following description, HPC-8220GPC (manufactured by TOSOH CORPORATION) was used as the measurement device, TSKguardcolumn SuperHZ-L was used as the guard column, and TSKgel SuperHZM-M, TSKgel SuperHZ4000, TSKgel SuperHZ3000 was used as the column. TSKgel SuperHZ2000 was directly connected to the column, the column temperature was set to 40 ° C, 10 μl of a sample concentration of 0.1% by mass of tetrahydrofuran solution was injected, and tetrahydrofuran was flowed at a flow rate of 0.35 ml per minute as a dissolution solvent, and the peak value of the sample was detected by an RI detecting device. And calculated using a calibration curve made using standard polystyrene.

<Example 1> [Preparation of Titanium Dioxide Dispersion 1] A mixed liquid of the following composition was used as a circulation type dispersing device (bead mill) using a ULTRA APEX MILL manufactured by Kotobuki Industries Co., Ltd., and subjected to dispersion treatment as follows. A titanium dioxide dispersion. - Composition - ・ Titanium dioxide (CR-90-2 manufactured by ISHIHARA SANGYO KAISHA, LTD.) (purity: 90% or more): 272.57 parts, dispersant (SOLSPERSE 36000 (dispersion resin with phosphate group)) (30% by mass of PGMEA solution): 136.29 parts propylene glycol-1-monomethyl ether-2-acetate (PGMEA): 241.14 parts

Further, the dispersing device operates under the following conditions.・Ball diameter: φ0.2mm ・Ball filling rate: 65% by volume ・Phase phase speed: 6m/sec ・Pump supply: 10.8kg/hour ・Cooling water: Tap water ・Bead mill ring channel internal volume: 0.15L・Dispersion amount of mixed solution: 0.65kg

After the start of dispersion, the measurement of the average particle diameter was carried out at intervals of 30 minutes. The average particle diameter decreases with the dispersion time, and then the amount of change decreases. The d50 in the particle size distribution is less than 250 nm, and the point at which d90 is less than 350 nm ends. Further, the average particle diameter of the titanium oxide particles in the dispersion was 253 nm. The measurement was a number average particle diameter obtained using a microtrac UPA-EX150 manufactured by Nikkiso Co Ltd.

[Preparation of Titanium Dioxide Dispersion 2] A dispersion liquid was prepared in the same manner as in the preparation of the titanium oxide dispersion liquid 1, except that the composition of the composition and the dispersion liquid to be subjected to the dispersion treatment were changed as follows. Further, the average particle diameter of the titanium oxide particles in the titanium dioxide dispersion 2 was 253 nm. - Composition - ・ Titanium dioxide (CR-90-2 manufactured by ISHIHARA SANGYO KAISHA, LTD.) (purity: 90% or more): 195.91 parts, dispersant (SOLSPERSE 36000 (dispersion resin with phosphate group)) (30% by mass of PGMEA solution): 391.82 parts, propylene glycol-1-monomethyl ether-2-acetate (PGMEA): 62.27 parts ・Dispersion amount of mixed solution: 0.65kg

Using the titanium oxide dispersion liquid 1 obtained above, the components were mixed in such a manner as to have the following composition, whereby the composition of Example 1 was obtained.

- Composition of the composition - ・ Titanium dioxide dispersion prepared as above 1: 8.56 parts ・ The following binder (B-1) 40% by mass PGMEA solution: 40.24 parts Weight average molecular weight (Mw): 11,000, copolymerization ratio (Mo Erbi )as follows.・Monomer (pentaerythritol tetraacrylate): 10.73 parts (A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.; M-1 in the following table) ・Polymerization initiator (K-1): 3.05 parts ・Coloring Anti-detergent (ADEKA stub AO-80, manufactured by ADEKA CORPORATION): 0.17 parts, decane coupling agent-1: (N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane) 1% by mass Cyclohexanone solution: 3.4 parts ・Polymerization inhibitor (p-methoxyphenol): 0.0054 parts ・The following mixture of surfactants (Mw=14000, 0.2% by mass of PGMEA solution) [Chemical Formula 61] : 4.17 copies · PGMEA: 29.68

[Chemical Formula 62]

K-1 (the following compounds)

[Chemical Formula 63]

<Examples 2 to 22> In the same manner as in Example 1, the components were mixed in the following table to obtain the compositions of Examples 2 to 22. The compounds in the table used the following. Polymerization initiator K-2: ADEKA ARKLS NCI831 (manufactured by ADEKA CORPORATION) Hydrane coupling agent-2:

[Chemical Formula 64]

[liquid adjustment table]

[Table 1]

Further, M/B in the following Table 3 indicates the mass ratio of the monomer to the binder in the solid content.

<Example 23> The composition of Example 23 was obtained by mixing the components in the following composition.・2:12.16 parts of the titanium dioxide dispersion prepared as above ・The following adhesive (B-2) 40% by mass PGMEA solution: 36.01 parts The weight average molecular weight (Mw) was 14,000, and the copolymerization ratio (mol ratio) was as follows.・Monomer (pentaerythritol tetraacrylate): 9.90 parts (A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.) ・Polymerization initiator (K-1): 2.82 parts ・Coloring inhibitor (ADEKA Sake made by ADEKA CORPORATION) AO-80): 0.18 parts, decane coupling agent-1: (N-2-(aminoethyl)-3-aminopropylmethyldimethoxy decane) 1% by mass of cyclohexanone solution: 1.75 parts Polymerization inhibitor (p-methoxyphenol): 0.0050 parts, the following UV absorber 1: 0.35 parts, the following surfactants, 0.2% by mass, PGMEA solution: 4.17 parts, PGMEA: 32.66 parts

[Chemical Formula 65]

<Preparation of Pigment Dispersion 2-1 to 2-7> A bead mill using a zirconia bead having a diameter of 0.3 mm (a high pressure disperser NANO-3000-10 with a pressure reducing mechanism (Nippon Bee Chemical Co., Ltd.) ()) A mixture of the following composition was mixed for 3 hours and dispersed to prepare a pigment dispersion. The amount of use of the respective components (unit: parts by mass) is shown in Table 2.

[Table 2]

[Colorant] ・PR254 : CIPigment Red 254 ・PB15:6 :CIPigment Blue 15:6 ・PG58 :CIPigment Green58 ・PY139 :Pigment Yellow 139 ・PV23 :Pigment Violet 23 ・PB7 :Pigment Black 7 ・Irgaphor Black [ BASF company system]

[Dispersion Resin] ・Dispersion Resin A: The following structure (Mw: 24000)

[Chemical Formula 66]

[Organic Solvent] PGMEA: Propylene Glycol Monomethyl Ether Acetate

<Composition of Example 24> Each component was mixed so as to have the following composition, whereby the composition of Example 24 was obtained.・2:12.10 parts of the titanium dioxide dispersion prepared above ・The pigment dispersion liquid prepared as above 2-1: 0.44 parts ・ The above-mentioned binder (B-2) 40% by mass PGMEA solution: 35.90 parts/monomer (pentaerythritol tetraacrylate) : 9.90 parts (A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.) ・Polymerization initiator (K-1): 2.82 parts, coloring inhibitor (ADEKA stub AO-80, manufactured by ADEKA CORPORATION): 0.18 parts·decane Coupling agent-1: (N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane) 1% by mass cyclohexanone solution: 1.75 parts ・Polymerization inhibitor (p-methoxyphenol) ): 0.0050 parts, the above-mentioned UV absorber 1: 0.35 parts, the above surfactant 1: 1.17 parts, PGMEA: 32.40 parts

<Example 25> A composition was obtained in the same manner as in Example 24 except that the pigment dispersion liquid 2-1 was changed to the pigment dispersion liquid 2-2.

<Composition of Example 26> A composition was obtained in the same manner as in Example 24 except that the pigment dispersion liquid 2-1 was changed to the pigment dispersion liquid 2-3.

<Composition of Example 27> A composition was obtained in the same manner as in Example 24, except that the pigment dispersion liquid 2-1 was changed to the pigment dispersion liquid 2-4.

<Composition of Example 28> A composition was obtained in the same manner as in Example 24, except that the pigment dispersion liquid 2-1 was changed to the pigment dispersion liquid 2-5.

<Composition of Example 29> A composition was obtained in the same manner as in Example 24, except that the pigment dispersion liquid 2-1 was changed to the pigment dispersion liquid 2-6.

<Composition of Example 30> A composition was obtained in the same manner as in Example 24, except that the pigment dispersion liquid 2-1 was changed to the pigment dispersion liquid 2-7.

<Composition of Example 31> The components of Example 31 were obtained by mixing the components in such a manner as to have the following composition.・2:12.10 parts of the titanium dioxide dispersion prepared as above ・2-4: 0.22 parts of the pigment dispersion prepared as above ・2-5: 0.22 parts of the pigment dispersion prepared as above ・The above-mentioned binder (B-2) 40% by mass PGMEA Solution: 35.90 parts, monomer (pentaerythritol tetraacrylate): 9.90 parts (A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.) ・Polymerization initiator (K-1): 2.82 parts, coloring inhibitor (ADEKA) CORPORATION ADEKA stub AO-80): 0.18 parts decane coupling agent-1: (N-2-(aminoethyl)-3-aminopropylmethyldimethoxy decane) 1% by mass cyclohexanone solution : 1.75 parts ・Polymerization inhibitor (p-methoxyphenol): 0.0050 parts ・The above UV absorber 1: 0.35 parts ・The above surfactant 1:4.17 parts ・PGMEA: 32.40 parts

<Composition of Example 32> The same procedure as in Example 31 was carried out except that the pigment dispersion liquid 2-4 was changed to the pigment dispersion liquid 2-1, and the pigment dispersion liquid 2-5 was changed to the pigment dispersion liquid 2-3. Obtain the composition.

<Comparative Example 1> The same procedure as in the preparation of the titanium oxide dispersion 1 was carried out except that TTO-55N (trade name: ISHIHARA SANGYO KAISHA, LTD., rutile type, Ti atom content: 99 atm%) was used as the titanium dioxide pigment. The way to get the dispersion. The average particle diameter of the titanium dioxide particles in the dispersion was 30 nm. The composition of Comparative Example 1 was obtained in the same manner as in Example 1 using this dispersion.

A cured film was formed using the prepared composition, and [transmittance], [in-plane uniformity], and [spectral flatness] were evaluated.

[Formation of Cured Film] The compositions of Examples 1 to 32 and Comparative Example 1 were applied to an 8-inch glass wafer (manufactured by EAGLE XG CORNING. Incorporated, thickness: 1.1 mm) by spin coating, followed by heating. The plate was heated at a temperature of 100 ° C for 2 minutes to obtain a coated film. The coated film was exposed at 500 mJ/cm ² by an ultrahigh pressure mercury lamp "USH-500BY" manufactured by USHIO INC. Further, it was heated on a hot plate at a temperature of 200 ° C for 5 minutes to obtain a cured film.

[Spectrophotometry (Transmittance)] The spectroscopic (transmittance) of the above-mentioned cured film was measured by "MCPD-3700" manufactured by Otsuka Electronics Co., Ltd. The transmittance at 400 nm is shown in Table 3 below.

[In-Plane Uniformity] The film surface was scratched every 1 cm from the center to the end of the glass wafer, and 10 film thicknesses in the wafer surface were measured by a stylus film thickness meter DEKTAK XT (manufactured by BRUKER). . Thereafter, the film thickness unevenness was calculated according to the following formula. Unevenness of film thickness = (maximum film thickness - minimum value of film thickness) ÷ (measured as average value of film thickness at 10 points) × 100 The unevenness of the calculated film thickness was evaluated based on the following criteria. A case where the film thickness is not more than 2% is regarded as 4, a case where more than 2% and 3% or less is regarded as 3, a case where more than 3% and 5% or less is regarded as 2, and a case where more than 5% is regarded as 1 is regarded as 1.

[Spectroscopic flatness] The spectroscopic (transmittance) of the above-mentioned cured film was measured by "MCPD-3700" manufactured by Otsuka Electronics Co., Ltd., and the transmittance of the lowest transmittance and the highest transmittance between 400 nm and 700 nm was evaluated in the following manner. difference. A case where the difference in transmittance is 20% or less is regarded as 3, and a case where more than 20% and 30% or less is regarded as 2, and a case where more than 30% is regarded as 1 is regarded as 1.

Evaluation form

[table 3]

Further, in the above examples, the same properties were exhibited even if the monomer, the binder, the polymerization initiator, and the particles were changed within the above preferred range. Further, two or more kinds of monomers, two or more kinds of binders, and two or more kinds of polymerization initiators are also included, and the same performance is also exhibited. In addition, in place of the inorganic particles (titanium dioxide) used in the above examples, the core particles composed of polymer particles and the shell composed of inorganic nanoparticles are described in paragraphs 0012 to 0942 of JP-A-2015-47520. In the case of a layered core/shell composite particle, the same result as described above can also be obtained.

no

no

Claims (17)

A composition comprising (A) a binder, (B) a monomer, (C) a polymerization initiator, (D) particles having an average particle diameter of 50 nm or more, and (E) a solvent. The composition of claim 1, wherein the particles of (D) are metal particles. The composition of claim 2, wherein the particles of (D) are titanium dioxide. The composition according to any one of claims 1 to 3, wherein the particles of (D) have an average particle diameter of 150 nm or more. The composition according to any one of claims 1 to 3, further comprising (F) a coloring preventive agent. The composition according to claim 5, wherein the (F) coloring preventing agent is a phenol compound. The composition according to claim 6, wherein the (F) coloring preventing agent is a phenol compound having a substituent in the ortho position of the phenolic hydroxyl group. The composition according to any one of claims 1 to 3, further comprising a dispersant, wherein the dispersant is a polymer dispersant having an adsorption site. The composition according to claim 8, wherein the adsorption site is an acid adsorption site. The composition according to claim 9, wherein the acid-based adsorption site is at least one of a phosphorus atom-containing group and a carboxylic acid group. The composition according to claim 1, wherein the (C) polymerization initiator is an anthracene compound. The composition according to any one of claims 1 to 3, further comprising a color material. A cured film formed by using the composition according to any one of claims 1 to 12. A method for producing a pattern, comprising: a process of coating a composition according to any one of claims 1 to 12 on a substrate; a process of performing exposure through a mask; and a film after exposure A process of developing to form a pattern. A pattern produced by the manufacturing method described in claim 14. An optical sensor using a cured film formed by using the composition according to any one of claims 1 to 12. An image pickup element using a cured film formed by using the composition according to any one of claims 1 to 12.