WO2017056901A1

WO2017056901A1 - Composition, cured film, pattern, pattern manufacturing method, optical sensor, and imaging element

Info

Publication number: WO2017056901A1
Application number: PCT/JP2016/076408
Authority: WO
Inventors: 大貴瀧下; 翔一中村; 嶋田　和人
Original assignee: 富士フイルム株式会社
Priority date: 2015-09-29
Filing date: 2016-09-08
Publication date: 2017-04-06
Also published as: TW201715308A; JPWO2017056901A1; JP6598868B2

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 device

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

In recent years, a white resist is required for appearance adjustment of various sensors and optical members. These white resists require high resistance and adhesion in order to withstand processes such as sensor assembly. In addition, the white resist is required to be lithographic in order to form a pattern only in a necessary place. Further, since the white resist uses light scattering, relatively large particles having a particle size of 50 nm or more are used, and there is a concern about stability. For this reason, storage stability and redispersibility are also important points.
For example, Patent Document 1 describes a white photosensitive resin composition that uses a selenium-based blue dye to obtain a cured product that suppresses discoloration due to thermal history, but requires the addition of a colorant. There was a problem with the resolution of the pattern.

Patent Document 2 discloses a white photosensitive resin composition using an oxime ester photopolymerization initiator and describes that a pattern latent image can be accurately formed. However, there is a problem with coloring resistance. It was.

JP 2012-150461 A JP 2008-134621 A

The present invention has been made in view of the above-described problems of the prior art, and has high in-plane uniformity, flat transmittance in the visible region, resistance, lithographic properties, storage stability, adhesion, and redispersibility. The present invention provides a composition capable of forming a cured film excellent in coating uniformity, a cured film, a pattern, a method for producing the pattern, an optical sensor, and an imaging device.

Specific means for solving the above problems are as follows.
(1) A composition containing (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 (1) to (3), wherein the average particle size of (D) is 150 nm or more.
(5) The composition according to any one of (1) to (4), further comprising (F) a coloring inhibitor.
(6) The composition according to (5), wherein the anti-coloring agent (F) is a phenol compound.
(7) The composition according to (6), wherein the anti-coloring agent (F) is a phenol compound having a substituent at 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-based 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 oxime compound.
(12) The composition according to any one of (1) to (11), further comprising a coloring material.
(13) A cured film formed using the composition according to any one of (1) to (12).
(14) A step of applying the composition according to any one of (1) to (12) on a substrate;
A method for producing a pattern, comprising: a step of exposing through a mask; and a step of developing the exposed film to form a pattern.
(15) A pattern manufactured by the manufacturing method according to (14).
(16) An optical sensor using a cured film formed using the composition according to any one of (1) to (12).
(17) An imaging device using a cured film formed using the composition according to any one of (1) to (12).

According to the present invention, a cured film having high in-plane uniformity, flat transmittance in the visible region, and excellent resistance, lithographic properties, storage stability, adhesion, redispersibility, and coating uniformity is formed. Composition, cured film, pattern, pattern manufacturing method, optical sensor, and image sensor can be provided.

In the notation of a group (atomic group) in this specification, a notation that does not indicate substitution or non-substitution refers to a group (atomic group) having a substituent together with a group (atomic group) having no substituent. Is also included. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl. In the present specification, “monomer” is synonymous with “monomer.” “Monomer” in the present invention is a compound having a weight average molecular weight of 2,000 or less, distinguished from oligomers and polymers. In the present specification, the “polymerizable compound” means a compound having a polymerizable group, and may be a monomer or a polymer. A group that participates in the 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 size of 50 nm or more, and (E) a solvent. This has a white appearance derived from particle scattering.

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

[(A) Binder]
The composition of the present invention contains a binder from the viewpoint of improving film properties.
It is preferable to use a linear organic polymer as the binder. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such a linear organic polymer include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. No. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a monomer having a carboxyl group alone or in combination. Polymerized resin, acid anhydride monomer alone or copolymerized, acid anhydride unit hydrolyzed, half-esterified or half-amidated, epoxy resin modified with unsaturated monocarboxylic acid and acid anhydride And epoxy acrylate. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene. Examples of the monomer having an acid anhydride include maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful. The binder of the composition of the present invention is preferably soluble in an alkaline developer.

In the present invention, when a copolymer is used as a binder, a monomer other than the above-mentioned monomers can be used as a compound to be copolymerized. Examples of other monomers 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 methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as
(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- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate;
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.
(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in JP-A-2002-309057, JP-A-2002-311569 and the like can be mentioned.

In the present invention, these monomers can be applied to the synthesis of a copolymer by combining them without particular limitation within the scope of the present invention. For example, although an example of the copolymer formed by polymerizing the monomer component containing these monomers is shown below, this invention is not limited to this. The composition ratio of the exemplary compounds shown below is mol%.

The binder preferably contains a repeating unit obtained by polymerizing a monomer component of a compound represented by the following general formula (ED) (hereinafter sometimes referred to as “ether dimer”).

(In General Formula (ED), R ₁ and R ₂ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)

Thereby, the composition of this invention can form the cured film which is excellent in the coloring resistance with respect to heating, such as heating for 15 minutes at 265 degreeC, for example. In the general formula (ED) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, and examples thereof include methyl, Linear or branched alkyl groups such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t -Alicyclic groups such as butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; alkyl substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl Group; an alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance.

Specific examples of the ether dimer include specific examples of the ether dimer described in paragraph <0565> of JP2012-208494A (corresponding to <0694> of the corresponding US Patent Application Publication No. 2012/235099). The contents of which are incorporated herein by reference.
Specific examples of ether dimers include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl- 2,2 ′-[oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be used alone or in combination of two or more. Moreover, the structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

Other monomers that can be copolymerized with the ether dimer include, for example, a monomer for introducing an acid group, a monomer for introducing a radical polymerizable double bond, and an epoxy group. Monomers and other copolymerizable monomers other than these may be mentioned. Only 1 type may be used for such a monomer and it may use 2 or more types.

Examples of the monomer for introducing an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid, monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride, and anhydride. And monomers having a carboxylic anhydride group such as itaconic acid. Among these, (meth) acrylic acid is particularly preferable.
The monomer for introducing an acid group may be a monomer that can give an acid group after polymerization, such as a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, Examples thereof include monomers having an epoxy group such as glycidyl (meth) acrylate, and monomers having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate. In the case of using a monomer for introducing a radical polymerizable double bond, when using a monomer capable of imparting an acid group after polymerization, it is preferable to perform a treatment for imparting an acid group after polymerization. The treatment for adding an acid group after polymerization varies depending on the type of monomer, and examples thereof include the following treatment. When using the monomer which has a hydroxyl group, the process which adds acid anhydrides, such as a succinic anhydride, a tetrahydrophthalic anhydride, a maleic anhydride, is mentioned, for example. When using a monomer having an epoxy group, for example, a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or, for example, (meth) acrylic acid For example, a treatment of adding an acid anhydride such as succinic acid anhydride, tetrahydrophthalic acid anhydride, maleic acid anhydride to the hydroxyl group generated after adding such an acid can be mentioned. When a monomer having an isocyanate group is used, for example, a treatment of adding a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid can be mentioned.

When the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) contains a monomer for introducing an acid group, the content ratio is not particularly limited, In the monomer component, the content is preferably 5 to 70% by mass, more preferably 10 to 60% by mass.

Examples of the monomer for introducing a radical polymerizable double bond include, for example, monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride Monomers having a group; monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether; . When using a monomer for introducing a radical polymerizable double bond, it is preferable to perform a treatment for imparting a radical polymerizable double bond after polymerization. The treatment for imparting a radical polymerizable double bond after polymerization differs depending on the type of monomer that can impart a radical polymerizable double bond to be used, and examples thereof include the following treatment. When using a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl The process which adds the compound which has epoxy groups and radically polymerizable double bonds, such as glycidyl ether, is mentioned. In the case of using a monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride, a treatment of adding a compound having a hydroxyl group and a radically polymerizable double bond such as 2-hydroxyethyl (meth) acrylate can be mentioned. . When using a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzylglycidyl ether, (meth) acrylic acid, etc. The process which adds the compound which has the acid group of this and a radically polymerizable double bond is mentioned.

When the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) contains a monomer for introducing a radical polymerizable double bond, the content ratio is particularly limited. However, it is preferably 5 to 70% by mass, more preferably 10 to 60% by mass in the total monomer components.

Examples of the monomer for introducing an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. Can be mentioned.
When the polymer formed by polymerizing the monomer component containing the compound represented by the general formula (ED) contains a monomer for introducing an epoxy group, the content ratio is not particularly limited, In the monomer component, the content is preferably 5 to 70% by mass, more preferably 10 to 60% by mass.

Other copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n (meth) acrylate -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy (meth) acrylate (Meth) acrylic acid esters such as ethyl; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadienes such as butadiene and isoprene Or substituted butadiene compounds; ethylene, propylene, vinyl chloride, Ethylene or substituted ethylene compound such Rironitoriru; vinyl esters such as vinyl acetate; and the like. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance.

When the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) contains another copolymerizable monomer, the content ratio is not particularly limited, and is 95% by mass. The following is preferable, and 85 mass% or less is more preferable.
The weight average molecular weight of the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) is not particularly limited, and the viscosity of the composition and the heat resistance of the coating film formed by the composition. From the viewpoint of properties, it is preferably 2000 to 200000, more preferably 5000 to 100,000, and still more preferably 5000 to 20000.
When the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) has an acid group, the acid value is preferably 30 to 500 mgKOH / g, more preferably 50 ~ 400 mg KOH / g.

A polymer obtained by polymerizing a monomer component containing a compound represented by the general formula (ED) can be easily obtained by polymerizing at least a monomer containing an ether dimer. At this time, the cyclization reaction of the ether dimer proceeds simultaneously with the polymerization to form a tetrahydropyran ring structure.
The polymerization method applied to the synthesis of the polymer obtained by polymerizing the monomer component containing the compound represented by the general formula (ED) is not particularly limited, and various conventionally known polymerization methods can be adopted. In particular, the solution polymerization method is preferred. Specifically, for example, in accordance with the synthesis method of the polymer (a) described in JP-A-2004-300204, a polymerization product obtained by polymerizing a monomer component containing a compound represented by the general formula (ED). A coalescence can be synthesized.

Hereinafter, although the exemplary compound of the polymer formed by polymerizing the monomer component containing the compound represented by the general formula (ED) is shown, the present invention is not limited to these. The composition ratio of the exemplary compounds shown below is mol%.

In the present invention, in particular, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as “DM”), benzyl methacrylate (hereinafter referred to as “BzMA”), methyl methacrylate (hereinafter referred to as “MMA”). ), Methacrylic acid (hereinafter referred to as “MAA”), and 2-hydroxypropylene glycol dimethacrylate (hereinafter referred to as “X”). In particular, the molar ratio of DM: BzMA: MMA: MAA: X is preferably 5 to 15:40 to 50: 5 to 15: 5 to 15:20 to 30. It is preferable that 95% by mass or more of the components constituting the copolymer used in the present invention is these components. The weight average molecular weight of such a polymer is preferably 9000 to 20000.
The polymer used in the present invention has a weight average molecular weight (polystyrene conversion value measured by GPC method) of preferably 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and more preferably 5000 to More preferably, it is 5 × 10 ⁴ .

The weight average molecular weight of the binder used in the composition of the present invention (polystyrene conversion value measured by GPC method) 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, and more preferably 2,000 or more and 250,000 or less. The dispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 or more and 10 or less.
These binders may be any of random polymers, block polymers, graft polymers 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, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include -2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used when synthesizing the binder used in the composition of the present invention include known compounds such as an azo initiator and a peroxide initiator.

In the composition of this invention, a binder can be used individually by 1 type or in combination of 2 or more types.
The content of the binder is preferably 1% by mass to 90% by mass, more preferably 5% by mass to 80% by mass, and more preferably 10% by mass to 70% by mass with respect to the total solid content of the composition. It is particularly preferable that the content is not more than mass%.

[(B) Monomer]
(B) As the monomer, an addition polymerizable compound having at least one ethylenically unsaturated double bond is preferably used, and a compound having at least one terminal ethylenically unsaturated bond, preferably two or more is used. More preferably. Such compounds are widely known in the technical field, and can be used without particular limitation in the present invention.

The (B) monomer is also preferably a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol ( (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso Isocyanurate and can mixtures thereof, is preferably pentaerythritol tetra (meth) acrylate.

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

In the general formula, n is an integer of 0 to 14, and m is an integer of 1 to 8. A plurality of R and T present in one molecule may be the same or different.
In each of the radical polymerizable monomers represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of R is —OC (═O) CH═CH ₂ , or A group represented by —OC (═O) C (CH ₃ ) ═CH ₂ is represented.
Specific examples of the radically polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraphs 0248 to 0251 of JP-A-2007-26979. Can also be suitably used.
In addition, in Japanese Patent Application Laid-Open No. 10-62986, compounds represented by general formulas (1) and (2), together with specific examples thereof, are compounds (meth) acrylated after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol. Can also be used as a monomer.

Among them, as the monomer, pentaerythritol tetraacrylate (commercially available product is A-TMMT; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available product is KAYARAD D-330; Nippon Kayaku Co., Ltd.) Dipentaerythritol tetraacrylate (commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available product is KAYARAD D-310; Nippon Kayaku Co., Ltd.) Company-made), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) is preferable, and pentaerythritol tetraacrylate is more preferable.

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

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

These monomers may be used individually by 1 type, and since it is difficult to use a single compound on manufacture, 2 or more types may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the developing dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

Moreover, it is preferable to contain the polyfunctional monomer which has a caprolactone structure as a monomer.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipenta Ε-caprolactone modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone Can be mentioned. Among these, a polyfunctional monomer having a caprolactone structure represented by the following formula (1) is preferable.

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

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

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

Such polyfunctional monomers having a caprolactone structure are 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, wherein the compound number = 2, R ¹ are all hydrogen atoms of the group represented by (2)), DPCA-30 (the above formulas (1) to the (3), m = 1, equation (2) in compound number = 3, R ¹ are all hydrogen atoms of the group represented by), the DPCA-60 (the above formula (1) ~ (3), m = 1, the group represented by the formula (2) Number = 6, a compound in which R ¹ is all hydrogen atoms), DPCA-120 (in the above formulas (1) to (3), m = 2, the number of groups represented by formula (2) = 6, R ¹ Are compounds in which all are hydrogen atoms).
In this invention, the polyfunctional monomer which has a caprolactone structure can be used individually or in mixture of 2 or more types.

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

In the general formula (i) and (ii), E are each _{_{independently, - ((CH 2) y}} CH 2 O) -, or _{_{- ((CH 2) y CH}} (CH 3) O) - represents, Each y independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In the general formula (i), the total number of acryloyl groups and methacryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. However, when the total of each m is 0, any one of X is a carboxyl group.
In general formula (ii), the total number of acryloyl groups and methacryloyl groups is 5 or 6, and n 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 general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In general formula (ii), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In addition, — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) — in general formula (i) or general formula (ii) is a terminal on the oxygen atom side. Is preferred in which X is bonded to X.
The compound represented by general formula (i) or (ii) may be used individually by 1 type, and may be used together 2 or more types. In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.
Moreover, as a total content in the monomer of the compound represented by general formula (i) or (ii), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

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

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

Examples of commercially available compounds represented by the general formula (i) or (ii) include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and pentylene manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the monomer include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and JP-B-58- Urethane compounds having an ethylene oxide skeleton described in JP-A-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used as monomers. Thus, a curable composition having an extremely excellent photosensitive speed can be obtained.
Commercially available monomers include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp), U-4HA, U-6LPA, UA-32P, U-10HA, U-10PA, UA-122P, UA- 1100H, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) UA-9050, UA-9048 (manufactured by BASF) and the like.

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

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

In general formula (a), X is a hydrogen atom or an organic group, and preferably an organic group having at least one polymerizable group and having an amino group. Y ¹ , Y ² , and Y ³ are each independently an alkyl group, alkenyl group, alkynyl group, aryl group, hydroxyl group, alkoxy group, halogen atom, aryloxy group, amino group, silyl group, heterocyclic group, or hydrogen Represents an atom, and is preferably an alkyl group or an alkoxy group.
In general formula (a), X, Y ¹ , Y ² , and Y ³ have a polymerizable group (for example, (meth) acrylic acid ester group, (meth) acrylamide group, styryl group, etc.). Also good.
Examples of the silyl compound include silyl compounds having a polymerizable group in paragraphs 0056 to 0066 of JP2009-242604A.
As the polymerizable compound, thio (meth) acrylate compounds described in Paragraphs 0024 to 0031 of US Pat. No. 4,176,717 (paragraphs 0027 to 0033 of US2005 / 0261406A) can also be used. Incorporated.

The monomer or the like is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix series M-305, M-510, and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. When two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is essential that the acid value of the entire polyfunctional monomer is within the above range. It is.

About these monomers, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of a composition. For example, it is selected from the following viewpoints. In the composition of the present invention, the monomers can be used singly or in combination of two or more.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
In addition, the compatibility and dispersibility with other components (for example, polymerization initiator, titanium dioxide particles, etc.) contained in the composition are also important factors in selecting and using the monomer. The compatibility may be improved by using a low-purity compound or using two or more other components in combination. In addition, a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a substrate.

The content of the monomer (B) with respect to the total solid content of the composition is preferably in the range of 1% by mass to 50% by mass, more preferably in the range of 3% by mass to 40% by mass, The range of 5% by mass to 30% by mass is more preferable.
Within this range, it is preferable because coloring is prevented and curability 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 the polymerization of monomers, and can be appropriately selected from known polymerization initiators. The polymerization initiator is preferably a photopolymerization initiator. As the photopolymerization initiator, for example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compound described in JP-A-62-258241, compound described in JP-A-5-281728, compound described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums Compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

More preferred are trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, α-aminoketone Particularly preferred is at least one compound selected from the group consisting of compounds, oxime compounds, triallylimidazole dimer, and benzophenone compounds.

In particular, when the composition of the present invention is used for the production of a color filter of a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape, so that development is possible with no residue in the unexposed area. It is preferred that From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen. For this reason, it is necessary to keep the addition amount of the photopolymerization initiator low. Considering these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device. Further, the use of an oxime compound can improve the color transfer.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used.
As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

More preferred examples of the photopolymerization initiator include oxime compounds.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane Examples include -2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Examples thereof include compounds described in 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166, and the like.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used.

Further, as oxime compounds other than those described above, compounds described in JP-T-2009-519904 in which oxime is linked to carbazole N position, and compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety A nitro group introduced into the dye moiety, a compound described in JP 2010-15025 A and US Patent Application Publication No. 2009-292039, a ketoxime compound described in International Publication No. 2009-131189, and a triazine skeleton And the compound described in US Pat. No. 7,556,910 containing the oxime skeleton in the same molecule, the compound described in JP2009-221114A having an absorption maximum at 405 nm and good sensitivity to a g-ray light source , Etc. may be used.
Preferably, for example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

In general 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), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In General Formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.

In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP-A 2013-164471 ( C-3). This content is incorporated herein.
In the present invention, the oxime compound may be an oxime compound having a nitro group. Specific examples of oxime compounds having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, ADEKA Acruz NCI-831 (made by ADEKA) is mentioned.

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

In the formula (1), R ¹ and R ² are each independently 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 When an arylalkyl group having 7 to 30 carbon atoms is represented and R ¹ and R ² are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R ³ and R ⁴ are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, wherein X is a direct bond or carbonyl Indicates a group.

In the formula ^(2), R ^1, R 2, ^{R 3} and ^{R 4} have the same meanings as ^R ^1, R 2, ^{R 3} and ^{R 4} in Formula (1), ^{R 5} ^is -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 R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms; X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 5.

In the above formulas (1) and (2), R ¹ and R ² are preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl 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. X is preferably a direct bond.
Specific examples of the compounds represented by formula (1) and formula (2) include, for example, compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.

Specific examples of oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited thereto.

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 455 nm.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
For the molar extinction coefficient of the compound, a known method can be used. For example, in a UV-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian), an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure.

The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1 to 20% by mass with respect to the total solid content of the composition. . Within this range, better sensitivity and pattern formability can be obtained. The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

[(D) Particles with an average particle size of 50 nm or more]
The particles in the present invention preferably have a high refractive index and scatter light. The particles are not particularly limited as long as they scatter light, but metal particles are preferable, titanium dioxide and zirconium dioxide are more preferable, and titanium dioxide particles are particularly preferable.
The titanium dioxide particles can be represented by the chemical formula TiO ₂ , and the purity is preferably 70% or more, more preferably 80% or more, and further preferably 85% or more. Low-order titanium oxide, titanium oxynitride and the like represented by the general formula Ti _n O _2n-1 (n represents a number of 2 to 4) are preferably 30% by mass or less, and 20% by mass or less. More preferably, the content is 15% by mass or less.
The titanium dioxide particles in the present invention are not particularly limited as long as the average particle diameter is 50 nm or more. For example, the titanium dioxide particles can be appropriately selected from commercially available titanium dioxide particles.
The average particle diameter (number average particle diameter) of the titanium dioxide particles is preferably 50 nm or more, more preferably 100 nm or more, and more preferably 150 nm or more, in that light is scattered to make it appear white. Particularly preferred. When the average particle diameter of the titanium dioxide particles is less than 50 nm, the reflectance may decrease.
There is no restriction | limiting in particular as an upper limit of the average particle diameter of a titanium dioxide particle, It is preferable that it is 1000 nm or less, and it is more preferable that it is 500 nm or less.
The “average particle size” here means the average particle size of secondary particles in which primary particles are aggregated. In addition, the particle size distribution of the secondary particles that can be used (hereinafter also simply referred to as “particle size distribution”) is 70% by mass or more of the secondary particles falling into (average particle size ± 100) nm. Preferably it is 80 mass% or more. The particle size distribution of the secondary particles can be measured using a dynamic light scattering method (scattering intensity distribution). The average particle size of the primary particles is observed with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and 100 particle sizes are measured at a portion where the particles are not aggregated, and an average value is calculated. Can be determined by

In the present invention, the refractive index of the titanium dioxide particles is not particularly limited, and is preferably 1.75 to 2.70, more preferably 1.90 to 2.70 from the viewpoint of obtaining a high refractive index. .
The specific surface area of the titanium dioxide particles is preferably 10 m ² / g to 400 m ² / g, more preferably 10 m ² / g to 200 m ² / g, and 10 m ² / g to 150 m ² / g. More preferably, it is more preferably 10 m ² / g to 40 m ² / g.
The shape of the titanium dioxide particles is not particularly limited. For example, it can be a rice grain shape, a spherical shape, a cubic shape, a spindle shape, or an indefinite shape.

The titanium dioxide particles in the present invention may have been surface-treated with an organic compound. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, silane coupling agents are preferred. The titanium dioxide particles in the present invention are preferably those treated with Al (aluminum), Si (silicon) and organic matter.
The surface treatment may be carried out by using a single surface treatment agent or a combination of two or more surface treatment agents.
It is also preferable that the surface of the titanium dioxide particles is covered with an oxide such as aluminum, silicon, or zirconia. Thereby, a weather resistance improves more.

As a titanium dioxide particle in this invention, what is marketed can be used preferably.
Commercially available titanium dioxide particles include, for example, trade names of Taipei R-550, R-580, R-630, R-670, R-680, R-780, R-780-2 manufactured by Ishihara Sangyo Co., Ltd. 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-5 1A, PT-501R, UT771, trade names R-3L, R-5N, R-7E, R-11P, R-21, R-25, R-32, R-42, R manufactured by Sakai Chemical Industry Co., Ltd. -44, R-45M, R-62N, R-310, R-650, SR-1, D-918, GTR-100, FTR-700, TCR-52, trade names 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, T-150W, MT-300HD, MT-500B, MT-500SA, MT-500HD, MT-600B, MT-600SA, MT-700B, MT-700HD, trade names KR-310, KR- manufactured by Titanium Industry Co., Ltd. 380, KR-380N, trade names TR-600, TR-700, TR-750, TR-840, TR-900 manufactured by Fuji Titanium Industry Co., Ltd. .
In the present invention, the particles (D) may be used singly or in combination of two or more.

Inorganic fine particles may be used as the particles (D). As the inorganic fine particles, not only those composed of a single inorganic substance, but also particles combined with other materials may be used. For example, from the viewpoint of improving sedimentation properties, it is composed of particles having pores or other materials inside, particles in which a large number of inorganic particles are attached to core particles, core particles composed of polymer particles, and a shell layer composed of inorganic nanoparticles. It is preferable to use core-shell composite particles.
As the core-shell composite particles composed of the core particles composed of the polymer particles and the shell layer composed of inorganic nanoparticles, the description in paragraphs 0012 to 0042 of JP-A-2015-47520 can be referred to, for example. The contents of which are incorporated herein.

As content of the titanium dioxide particle in the composition of this invention, it is preferable that it is 1 mass% or more with respect to a composition total solid, It is more preferable that it is 3 mass% or more, It is 5 mass% or more. It is particularly preferred.
There is no restriction | limiting in particular as an upper limit of content, It is more preferable that it is 70 mass% or less with respect to a composition total solid, It is more preferable that it is 60 mass% or less, It is most 50 mass% or less. preferable. Further, when used as a material for an optical sensor or an optical member, the content is preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

[Dispersant]
The composition of the present invention preferably contains a dispersant from the viewpoint of improving the dispersibility of the particles (D) in the composition, and more preferably contains a polymer dispersant having an adsorption site.
In the present invention, the site having the ability to adsorb the particles (D) is collectively referred to as “adsorption site” as appropriate.
Examples of the adsorption site in the present invention include 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 alkyloxycarbonyl group, an alkylaminocarbonyl group, and a carboxylic acid. And monovalent substituents having at least one group selected from the group consisting of a base, a sulfonamide group, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group.

Preferred examples of the “acid group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphorus atom-containing group (such as a phosphate group, a monophosphate group, and a polyphosphate group), and a boric acid group. Carboxylic acid groups, sulfonic acid groups, monosulfate groups, and phosphorus atom-containing groups (such as phosphate groups, monophosphate ester groups, and polyphosphate ester groups) are more preferable, and carboxylic acid groups or phosphorus atom-containing groups are particularly preferable. .
As the “urea group”, for example, —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, 6 or more carbon atoms) And an aryl group having a carbon number of 7 or more is given as a preferred example, and —NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom or a group having 1 carbon atom). An alkyl group having up to 10 atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms are more preferred, and —NHCONHR ¹⁷ (wherein R ¹⁷ is a hydrogen atom or having 1 to 10 carbon atoms) An alkyl group, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms are particularly preferred.
As the “urethane group”, for example, —NHCOOR ¹⁸ , —NR ¹⁹ COOR ²⁰ , —OCONHR ²¹ , —OCONR ²² R ²³ (wherein R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are each Independently, preferred examples include 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.) -NHCOOR ¹⁸ , -OCONHR ²¹ (where , R ¹⁸ and R ²¹ 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, or the like, more preferably —NHCOOR ¹⁸ , — OCONHR ²¹ ^(wherein, each independently R ^{18, R 21} is an alkyl group having 6 or more aryl groups of carbon atoms of from 1 to 10 carbon atoms Represents a number of 7 or more aralkyl group having a carbon.), Etc. are particularly preferred.
Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a crown ether.

Examples of the “group having a basic nitrogen atom” include an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following formula (a1), a formula (a2 And the like.

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

Among these, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently a group having 1 to 10 carbon atoms. An alkyl group, a phenyl group, and a benzyl group.), A guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms, Represents a phenyl group and a benzyl group. ] An amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. ] Is more preferable.
In particular, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms. , A phenyl group and a benzyl group.), A guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 5 carbon atoms, a phenyl group Represents a benzyl group. ] An amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group. Etc. are preferably used.
The alkyl group moiety in the “alkyloxycarbonyl 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 moiety in the “alkylaminocarbonyl group” is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
Examples of the “carboxylic acid group” include groups composed of ammonium salts of carboxylic acids.
In the “sulfonamide group”, a hydrogen atom bonded to a nitrogen atom may be substituted with an alkyl group (such as a methyl group), an acyl group (such as an acetyl group or a trifluoroacetyl group), and the like.

Examples of the “heterocyclic structure” include 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, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, imide groups, hydantoin, indole, quinoline, carbazole, acridine, acridone Anthraquinone is a preferred example.

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 and an ethyl group, a phenyl group, and a naphthyl group. Such as an aryloxy group having 6 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamido group, an N-sulfonylamido group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, etc. Alkoxy groups having 1 to 20 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate And carbonic acid ester groups.

The “alkoxysilyl group” may be any of monoalkoxysilyl group, dialkoxysilyl group, trialkoxysilyl group, but is preferably trialkoxysilyl group, such as trimethoxysilyl group, triethoxysilyl group, etc. Is mentioned.
Examples of the “epoxy group” include a substituted or unsubstituted oxirane group (ethylene oxide group).
The adsorption site is preferably an acid-based adsorption site. An acid group etc. are mentioned as an acid type adsorption site. Especially, it is preferable that an acid type adsorption site is 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 general formula (1).

In the general 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 is 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 alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group Represents a monovalent substituent having at least one group selected from the group consisting of an alkoxysilyl 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. The m P ¹ may be the same or different.
As the polymer compound represented by the general formula (1), the description after paragraph 0039 of Japanese Patent Application Laid-Open No. 2007-277514 (corresponding to <0053> of US Patent Application Publication No. 2010/0233595) can be referred to. The contents of which are incorporated herein by reference.

Since the substituent A ¹ which the polymer dispersant represented by the general formula (1) has can interact with the particles (D), the number of the dispersant represented by the general formula (1) is n (1 By having (˜9) substituents A ¹ , it is possible to strongly interact with the particles (D). In addition, m polymer chains P ¹ of the polymer dispersant represented by the general formula (1) can function as a steric repulsion group, and by having m, the particles exhibit a good steric repulsion force ( D) can be uniformly dispersed. Further, it is estimated that the polymer dispersant represented by the general formula (1) does not cause aggregation of particles due to cross-linking between particles, which can be generated by a conventional graft random structure dispersant, in terms of molecular structure. The

Hereinafter, each group in General formula (1) is demonstrated in detail. The polymer dispersant represented by the general formula (1) is also disclosed in Japanese Patent Application Laid-Open No. 2007-277514 (Japanese Patent Application No. 2006-269707), and is described in the description. The contents and the preferred structure can be applied in the following description, and repeated descriptions will be omitted as appropriate.
A ¹ represents a monovalent substituent having at least one functional group having an adsorption ability for the particle (D) and at least one structure that can have an adsorption ability for the particle (D) such as a heterocyclic structure.
In addition, the site | part (the said functional group and structure) which has the adsorption ability with respect to this particle | grain (D) is equivalent to the said "adsorption site | part."

Adsorption sites in one A ^1, may be contained at least one, may contain two or more kinds.
Acid groups, urea groups for A ^1, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a heterocyclic group, an alkyloxycarbonyl group, alkylaminocarbonyl group, carboxylate, sulfonamide For details of the monovalent substituent having at least one group selected from the group consisting of a group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group, 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 alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfonamide group, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group As described above as a monovalent substituent having at least one group selected from the group consisting of is there.
In the present invention, the “monovalent substituent having at least one kind of adsorption site” includes the aforementioned adsorption site, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to It is a monovalent substituent formed by bonding up to 100 oxygen atoms, 1 to 400 hydrogen atoms, and a linking group consisting of 0 to 40 sulfur atoms. In the case where adsorption sites themselves may constitute a monovalent substituent, adsorption sites themselves may also be a monovalent substituent represented by A ^1.

The linking group bonded to the adsorption site may be a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200. And a linking group consisting of 0 to 20 sulfur atoms is preferred, and this organic linking group may be unsubstituted or may further have a substituent.

Among the above, as A ¹ , a monovalent substitution having at least one group selected from the group consisting of an acid group, a urea group, a urethane group, a sulfonamide group, an imide group and a group having a coordinating oxygen atom It is preferably a group.
In particular, from the viewpoint of improving the interaction with the particles (D), improving the refractive index, and reducing the viscosity of the composition, A ¹ is a monovalent substitution having at least one functional group of pKa5-14. More preferably, it is a group.
Here, “pKa” has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
Examples of the functional group of pKa5 to 14 include a urea group, a urethane group, a sulfonamide group, an imide group, and a group having a coordinating oxygen atom.
Specifically, for example, a urea group (about pKa 12 to 14), a urethane group (about pKa 11 to 13), —COCH ₂ CO— (about pKa 8 to 10) as a coordinating oxygen atom, a sulfonamide group (About pKa 9 to 11).

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

In the general 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, an alkyloxycarbonyl group, an alkylaminocarbonyl group) , Carboxylate group, sulfonamide group, heterocyclic group, alkoxysilyl group, epoxy group, isocyanate group or hydroxyl group), and R ²⁴ represents a single bond or a (a + 1) -valent linking group. a represents an integer of 1 to 10, and B ¹ existing in the general formula (4) may be the same or different.

Examples of the adsorption site represented by B ¹ include those similar to the adsorption site constituting A ¹ in the general formula (1) described above, and preferred examples are also the same.
Among them, an acid group, a urea group, a urethane group, a sulfonamide group, an imide group or a group having a coordinating oxygen atom is preferable, and a urea group, a functional group having a pKa of 5 to 14 is more preferable. It is more preferably a urethane group, a sulfonamide group, an imide 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. Preferably, a is 1 to 7, more preferably a is 1 to 5, and particularly preferably a is 1 to 3.
(A + 1) valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and Groups consisting of 0 to 20 sulfur atoms are included and may be unsubstituted or further substituted.

R ²⁴ may be a single bond, or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and (A + 1) valent linking groups consisting of 0 to 10 sulfur atoms are preferred, single bonds or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 More preferred are (a + 1) valent linking groups consisting of up to oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond, or 1 to 10 carbons (A + 1) valent linkage consisting of atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms The group is particularly preferred.

Among the above, when the (a + 1) -valent linking group has a substituent, examples of the substituent include carbon such as a methyl group and an ethyl group such as an ethyl group having 1 to 20 carbon atoms, a phenyl group, and a naphthyl group. Carbon number such as aryloxy group having 6 to 16 carbon atoms, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group and the like, acyloxy group having 1 to 6 carbon atoms, methoxy group, ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate And carbonic acid ester groups.

In general formula (1), R ² represents a single bond or a divalent linking group. n R ² may be the same or different.
Divalent linking groups include 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 are included, which may be unsubstituted or further substituted.

R ² includes a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and Divalent linking groups consisting of 0 to 10 sulfur atoms are preferred, single bonds, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 More preferred are divalent linking groups consisting of oxygen atoms, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond or 1 to 10 carbon atoms, 0 Particularly preferred are divalent linking groups consisting of from 1 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms.

Among the above, when the divalent linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon number of 6 such as a phenyl group and a naphthyl group. From 1 to 16 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups and the like, acyloxy groups having 1 to 6 carbon atoms, methoxy groups, ethoxy groups and the like. Alkoxy groups up to 6, halogen atoms such as chlorine and bromine atoms, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate, etc. Examples include carbonate ester groups.

In general 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, and 1 to 200. Groups consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or may further have a substituent.

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

In the general formula (1), P ¹ represents a polymer chain and can be selected from known polymers according to the purpose. The m P ¹ may be the same or different.
Among the polymers, a vinyl monomer polymer or copolymer, an ester polymer, an ether polymer, a urethane polymer, an amide polymer, an epoxy polymer, a silicone polymer, and modifications thereof are used to form a polymer chain. Or copolymer [for example, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer polymer, etc. (any of random copolymer, block copolymer, graft copolymer, etc. May also be included). At least one selected from the group consisting of vinyl monomers, selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferred, and a polymer or copolymer of vinyl monomers is particularly preferred.

The polymer chain P ¹ preferably contains at least one repeating unit.
The number k of at least one repeating unit in the polymer chain P ¹ is preferably 3 or more, more preferably 5 or more, from the viewpoint of exhibiting steric repulsion and improving dispersibility.
In addition, from the viewpoint of suppressing bulkiness of the polymer dispersant represented by the general formula (1) and causing the particles (D) to be densely present in the cured film, the number of repeating units k of at least one repeating unit is: It is preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less.

The polymer chain is preferably soluble in an organic solvent. When the affinity with the organic solvent is low, the affinity with the dispersion medium is weakened, and it may be impossible to secure an adsorption layer sufficient for stabilizing the dispersion.

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

In the general formula (2), A ² represents an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, an alkyloxycarbonyl group, an alkylaminocarbonyl group, or a carboxylate group. , A monovalent substituent having at least one group selected from the group consisting of a sulfonamide group, a heterocyclic group, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group. The n A ² may be the same or different.
Incidentally, ^{A 2} has the same meaning as ^{A 1} in the general formula (1), a preferable embodiment thereof is also the same.

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

In the general formula (2), R ³ represents a (m + n) -valent linking group. m + n satisfies 3 to 10.
The (m + n) -valent linking group represented by R ³ includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 100 carbon atoms. Groups consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or may further have a substituent.
Specifically, as the (m + n) -valent linking group represented by R ³ , those similar to those exemplified as the (m + n) -valent linking group represented by R ¹ in the general formula (1) are used. The preferred embodiments are also the same.

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

Further, P ² of the general formula (2) represents a polymer chain, can be selected according to the purpose or the like from such known polymers. the m P ² can be the same or different. The preferred embodiment of the polymer is the same as P ¹ in the general formula (1).

Of the polymer dispersants represented by the general formula (2), those satisfying all of R ³ , R ⁴ , R ⁵ , P ² , m, and n shown below are most preferable.
R ³ : Specific examples (1), (2), (10), (11), (16), or (17) described in paragraphs 0082 to 0083 of JP-A-2007-277514
R ⁴ : a single bond or the following structural unit or a combination of the structural units: “1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 carbon atoms A divalent linking group comprising an oxygen atom, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms (which may have a substituent, for example, methyl Group, alkyl group having 1 to 20 carbon atoms such as ethyl group, aryl group having 6 to 16 carbon atoms such as phenyl group and naphthyl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide group , An acyloxy group having 1 to 6 carbon atoms such as an acetoxy group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom such as a chlorine atom and a bromine atom, and a methoxycarbonyl group An ethoxycarbonyl group, an alkoxycarbonyl group having from 2 to 7 carbon atoms such as cyclohexyl oxycarbonyl group, a cyano group, such as carbonic acid ester group such as t- butyl carbonate.)

R ⁵ : single bond, ethylene group, propylene group, the following group (a), or the following group (b)
In the following groups, R ¹² represents a hydrogen atom or a methyl group, and l represents 1 or 2.

P ² : Polymer or copolymer of vinyl monomer, ester polymer, ether polymer, urethane polymer, and modified products thereof m: 1 to 3
n: 3-6

The acid value of the polymer dispersant represented by the general formula (1) or (2) is not particularly limited, and from the viewpoint of dispersibility, the acid value is preferably 400 mgKOH / g or less, and 300 mgKOH / g or less. More preferably, it is particularly preferably 250 mgKOH / g or less.
In addition, there is no restriction | limiting in particular as a lower limit of an acid value, It is preferable that it is 5 mgKOH / g or more from a viewpoint of the dispersion stability of titanium dioxide particle, and it is more preferable that it is 10 mgKOH / g or more.

Here, the acid value of the polymer dispersant represented by the general formula (1) or (2) is a solid content acid value.
In the present invention, the acid value of the polymer dispersant represented by the general formula (1) or (2) is, for example, the average content of acid groups in the dispersant represented by the general formula (1) or (2). It can be calculated from the quantity.
The molecular weight of the polymer dispersant represented by formula (1) or (2) is preferably 1000 to 50000, more preferably 3000 to 30000, and particularly preferably 3000 to 20000 in terms of weight average molecular weight. When the weight average molecular weight is within the above range, the effects of the plurality of adsorption sites introduced at the ends of the polymer are sufficiently exhibited, and the performance excellent in the adsorptivity to the titanium dioxide particle surface can be exhibited.
Specific examples of the polymer compound represented by the above general formula (1) include the steps after JP-A-2007-277514, paragraph 0266 (corresponding to <0389> in US 2010/0233595). The description of compounds C-1 to C-57 synthesized in the examples can be referred to, and the contents thereof are incorporated herein.

(Method for synthesizing polymer dispersant represented by formula (1) or (2))
The polymer dispersant represented by the general formula (1) or (2) is not particularly limited, and may be synthesized according to the synthesis method described in paragraphs 0114 to 0140 and 0266 to 0348 of JP-A-2007-277514. Can do.

As the dispersant, a resin described below (hereinafter, appropriately referred to as “dispersion resin 2”) may be used. The dispersion resin 2 has a repeating unit having a group X having a functional group of pKa 14 or less, an oligomer chain or a polymer chain Y having 40 to 10,000 atoms in the side chain, and contains a basic nitrogen atom. .

As will be described in detail later, both the nitrogen atom in the dispersion resin 2 and the functional group of pKa14 or less possessed by the group X interact with the particles (D), and the dispersion resin 2 is an oligomer having 40 to 10,000 atoms. In order to have the chain or polymer chain Y, for example, when the oligomer chain or polymer chain Y functions as a steric repulsion group, good dispersibility can be exhibited and the particles (D) can be uniformly dispersed. Even when the composition is stored for a long time at room temperature or the like, the precipitation of the particles (D) can be suppressed for a long time by the interaction between the oligomer chain or polymer chain Y and the solvent. Further, since the oligomer chain or polymer chain Y functions as a steric repulsion group, aggregation of the particles (D) is prevented. Therefore, even if the content of the particles (D) is increased, dispersibility and Dispersion stability is not easily lost.

Here, the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom, and the dispersion resin 2 preferably contains a structure having a nitrogen atom of pKb14 or less, and has a nitrogen atom of pKb10 or less. More preferably, it contains a structure.
In the present invention, “base strength pKb” refers to pKb at a water temperature of 25 ° C., which is one of the indexes for quantitatively representing the strength of the base, and is synonymous with the basicity constant. The base strength pKb and the acid strength pKa are in a relationship of pKb = 14−pKa.
The group X having a functional group of pKa14 or less has the same meaning as the group X 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 is also synonymous with the oligomer chain or polymer chain Y having 40 to 10,000 atoms described later for the dispersion resin 2-1. is there.
As the dispersion resin 2, a repeating unit having a group X having a functional group of pKa14 or less represented by the following formula, a repeating unit having a basic nitrogen atom represented by the following formula, and the number of atoms represented by the following formula Examples thereof include a resin containing a repeating unit having an oligomer chain or polymer chain Y of 40 to 10,000 (corresponding in order from the left of the structure of the following repeating unit).

In the above formula, x, y, and z each represent a polymerization molar ratio of repeating units, and x is preferably 5 to 50, y is 5 to 60, and z is 10 to 90. l represents the number of linked polyester chains, and is an integer capable of forming an oligomer chain or polymer chain having 40 to 10,000 atoms, preferably 70 to 2000.
The dispersion resin 2 is a resin having a repeating unit containing a nitrogen atom to which a group X having a functional group of pKa14 or less is bonded, and an oligomer chain or polymer chain Y having 40 to 10,000 atoms in the side chain. Is preferred.
The dispersion resin 2 is selected from (i) a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit. At least one repeating unit containing a nitrogen atom, the repeating unit having a group X bonded to the nitrogen atom and having a functional group of pKa14 or less, and (ii) 40 to 40 atoms in the side chain A resin 2-1 having 10,000 oligomer chains or polymer chains Y (hereinafter, appropriately referred to as “dispersion resin 2-1”) is particularly preferable.

((I) at least one selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit. Repeating unit containing a species of nitrogen atom)
The dispersion resin 2-1 is selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit. A repeating unit (i) containing at least one nitrogen atom. Thereby, the adsorption | suction force to the particle | grain (D) surface improves, and the interaction between the said particle | grains (D) can be reduced.
The poly (lower alkyleneimine) may be a chain or a network.
At least one nitrogen atom selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit The number average molecular weight of the main chain obtained by polymerizing the repeating unit (i) containing, that is, the number average molecular weight of the portion excluding the oligomer chain or polymer chain Y portion of the side chain from the dispersion resin 2-1, 100 to 10,000 are preferred, 200 to 5,000 are more preferred, and 300 to 2,000 are most preferred. The number average molecular weight of the main chain part is obtained from the ratio of the hydrogen atom integral value of the terminal group and main chain part measured by nuclear magnetic resonance spectroscopy, or by measuring the molecular weight of an oligomer or polymer containing an amino group as a raw material. Can be sought.

The repeating unit (i) containing a nitrogen atom is particularly preferably a poly (lower alkyleneimine) -based repeating unit or a polyallylamine-based repeating unit. In the present invention, the term “lower” in the poly (lower alkyleneimine) means that it has 1 to 5 carbon atoms, and the term “lower alkyleneimine” means an alkyleneimine having 1 to 5 carbon atoms. To clarify this structure, the dispersion resin 2-1 has a structure having a repeating unit represented by the general formula (I-1) and a repeating unit represented by the general formula (I-2), or a general formula ( It preferably includes a structure having a repeating unit represented by II-1) and a repeating unit represented by formula (II-2).

(Repeating unit represented by general formula (I-1) and repeating unit represented by general formula (I-2))
The repeating unit represented by the general formula (I-1) and the repeating unit represented by the general formula (I-2), which are preferable components of the dispersion resin 2-1, will be described in detail.

In the above general formulas (I-1) and (I-2),
R ¹ and R ² each independently represents a hydrogen atom, a halogen atom or an alkyl group. a independently represents an integer of 1 to 5; * Represents a connecting part between repeating units.
X represents a group having a functional group of pKa14 or less.
Y represents an oligomer chain or a polymer chain having 40 to 10,000 atoms.

In addition to the repeating unit represented by the general formula (I-1) or the general formula (I-2), the dispersion resin 2-1 further includes a repeating unit represented by the general formula (I-3) as a copolymerization component. It is preferable to have as. By using such repeating units in combination, the dispersion performance of the particles (D) is further improved.

In the general formula (I-3),
*, R ¹ , R ² and a are as defined in formula (I-1).
Y ′ represents an oligomer chain or polymer chain having an anion group and having 40 to 10,000 atoms.
The repeating unit represented by the general formula (I-3) is obtained by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amino group in the main chain. It can be formed by reacting.

In general formula (I-1), general formula (I-2), and general formula (I-3), R ¹ and R ² are particularly preferably hydrogen atoms. a is preferably 2 from the viewpoint of obtaining raw materials.

The dispersion resin 2-1 may contain a lower alkyleneimine as a repeating unit in addition to the repeating units represented by the general formula (I-1), the general formula (I-2), and the general formula (I-3). Good. As described above, the lower alkyleneimine represents an alkyleneimine having 1 to 5 carbon atoms. The dispersion resin 2-1 may or may not contain such a lower alkyleneimine repeating unit. When it is contained, the lower alkyleneimine repeating unit contains all of the lower alkyleneimine repeating units contained in the dispersion resin 2-1. It is preferable to contain 1 to 70 mol% in the repeating unit. In addition, the group shown by X, Y, or Y 'may couple | bond with the nitrogen atom in such a lower alkylene imine repeating unit. Resins containing both a repeating unit having a group represented by X and a repeating unit having Y bonded to the main chain structure are also included in the dispersion resin 2-1.

The repeating unit represented by the general 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 such a repeating unit containing a nitrogen atom is preserved. From the viewpoint of stability and developability, the content is preferably 1 to 80 mol% in all repeating units contained in the dispersion resin 2-1.
The repeating unit represented by the general formula (I-2) is a repeating unit having an oligomer chain or a polymer chain having 40 to 10,000 atoms, and such a repeating unit is dispersed from the viewpoint of storage stability. The content is preferably 10 to 90 mol% in all repeating units of the resin 2-1.
Regarding the content ratio of the two, from the viewpoint of the balance between dispersion stability and hydrophilicity / hydrophobicity, the repeating unit (I-1) :( I-2) is preferably in the range of 10: 1 to 1: 100 in molar ratio. .

The repeating unit represented by the general formula (I-3) used in combination optionally has a partial structure containing an oligomer chain or a polymer chain having 40 to 10,000 atoms ionically bonded to the nitrogen atom of the main chain. In view of the effect, it is preferable to contain 0.5 to 20 mol% in all repeating units of the dispersion resin 2-1.

(Repeating unit represented by general formula (II-1) and repeating unit represented by (II-2))
The repeating unit represented by the general formula (II-1) and the repeating unit represented by the general formula (II-2), which are other preferable constituents of the dispersion resin 2-1, will be described in detail.

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

The dispersion resin 2-1 is represented by the general formula (II-3) in addition to the repeating unit represented by the general formula (II-1) and the repeating unit represented by the general formula (II-2). It is preferable to include a repeating unit as a copolymerization component. By using such repeating units in combination, the dispersion performance of the particles (D) is further improved.

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

In the general formulas (II-1), (II-2) and (II-3), R ³ , R ⁴ , R ⁵ and R ⁶ are preferably hydrogen atoms from the viewpoint of availability of raw materials.

The general formula (II-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 such a repeating unit containing a nitrogen atom is a viewpoint of storage stability and developability. Therefore, the content is preferably 1 to 80 mol% in all repeating units contained in the dispersion resin 2-1.
The general formula (II-2) is a repeating unit having an oligomer chain or a polymer chain Y having an atom number of 40 to 10,000, and such a repeating unit is selected from all of the dispersion resins 2-1 from the viewpoint of storage stability. It is preferable to contain 10 to 90 mol% in the repeating unit.

Regarding the content ratio of the two, from the viewpoint of the balance between dispersion stability and hydrophilicity / hydrophobicity, the repeating unit (II-1) :( II-2) is preferably in the range of 10: 1 to 1: 100 in molar ratio. .
It is preferable that the repeating unit represented by the general formula (II-3) used in combination is contained in an amount of 0.5 to 20 mol% in all the repeating units of the dispersion resin 2-1.
From the viewpoint of dispersibility, the dispersion resin 2-1 particularly preferably includes both the repeating unit represented by the general formula (I-1) and the repeating unit represented by the general formula (I-2). .

<Group X having functional group of pKa14 or less>
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 satisfy this condition, and examples thereof include a known functional group having a pKa that satisfies the above range. Particularly, the pKa is 12 or less. The functional group is preferably, and the functional group having a pKa of 11 or less is most preferable. Specifically, carboxylic acid (about pKa 3-5), sulfonic acid (about pKa -3-2), -COCH ₂ CO- (about pKa 8-10), -COCH ₂ CN (about pKa 8-11) ), —CONHCO—, phenolic hydroxyl group, —R _F CH ₂ OH or — (R _F ) ₂ CHOH (R _F represents a perfluoroalkyl group; about pKa 9 to 11), sulfonamide group (about pKa 9 to 11) ) And the like.
When the pKa of the functional group of the group X is 14 or less, the interaction with the particle (D) can be achieved.
The group X having a functional group of pKa14 or less is preferably directly bonded to the nitrogen atom in the repeating unit containing a nitrogen atom. However, if the nitrogen atom and X in the repeating unit containing a nitrogen atom are only covalent bonds, Instead, they may be linked in such a manner that a salt is formed by ionic bonding.

As the group X containing a functional group of pKa14 or less in the present invention, those having a structure represented by general formula (V-1), general formula (V-2) or general formula (V-3) are particularly preferable. .

In the general formula (V-1) and general formula (V-2),
U represents a single bond or a divalent linking group.
d and e each independently represents 0 or 1;
In the general formula (V-3), Q represents an acyl 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 (N-C ₁₀ H ₂₁ )-, etc.), an oxygen-containing alkylene group (eg, —CH ₂ OCH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ —, etc.), an arylene group (eg, phenylene, tolylene, Biphenylene, naphthylene, furylene, pyrrolylene, etc.), alkyleneoxy groups (for example, ethyleneoxy, propyleneoxy, phenyleneoxy, etc.), alkenylene groups (for example, vinylene groups), and the like. Further, from the viewpoint of productivity, d is preferably 1, and e is preferably 0.

Q represents an acyl group or an alkoxycarbonyl group. Q is particularly preferably an acyl group, and is preferably an acetyl group from the viewpoint of ease of production and availability of the raw material (precursor X ′ of X).

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

Furthermore, since the group X contains a functional group having a pKa of 14 or less as a partial structure, it also functions as an alkali-soluble group. As a result, the developability of the uncured region into an alkaline developer is improved, and it is considered that the dispersibility, dispersion stability, and developability can be established.

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 with respect to 1 g of the dispersion resin 2. In this range, the dispersibility and dispersion stability of the particles (D) are improved, and the developability of the uncured part is excellent. Further, from the viewpoint of the developability, it is preferable that the acid value of the dispersion resin 2 is included in an amount such that the acid value is about 5 to 50 mgKOH / g.

(Oligomer chain or polymer chain Y having 40 to 10,000 atoms)
Examples of Y include known polymer chains such as polyester, polyamide, polyimide, and poly (meth) acrylate that can be connected to the main chain portion of the dispersion resin 2. The binding site of Y to the dispersion resin 2 is preferably the terminal of the oligomer chain or polymer chain Y.

Y is at least one selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit. It is preferably bonded to the nitrogen atom of the repeating unit containing the nitrogen atom. At least one nitrogen atom selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit The bonding mode between the main chain portion such as a repeating unit containing bismuth and Y is covalent bond, ionic bond, or a mixture of covalent bond and ionic bond. The ratio of the bonding mode between Y and the main chain is covalent bond: ionic bond = 100: 0 to 0: 100, preferably 95: 5 to 5:95. Outside this range, the dispersibility / dispersion stability deteriorates and the solvent solubility decreases.
Y is preferably ion-bonded to a nitrogen atom of a repeating unit containing a nitrogen atom as an amide bond or carboxylate.

The number of atoms of the oligomer chain or polymer chain Y is preferably 50 to 5,000, more preferably 60 to 3,000, from the viewpoint of dispersibility, dispersion stability, and developability.
If the number of atoms per oligomer chain or polymer chain Y is less than 40, the graft chain is short, so that the steric repulsion effect is reduced and the dispersibility may be lowered. On the other hand, if the number of atoms per oligomer chain or polymer chain Y exceeds 10,000, the oligomer chain or polymer chain Y becomes too long, and the adsorptive power to the particles (D) may be reduced, resulting in reduced dispersibility. .
Moreover, the number average molecular weight of Y can be measured by the polystyrene conversion value by GPC method. The number average molecular weight of Y is particularly preferably 1,000 to 50,000, and most preferably 1,000 to 30,000 from the viewpoints of dispersibility, dispersion stability, and developability.
It is preferable that two or more side chain structures represented by Y are connected to the main chain in one molecule of the resin, and most preferably five or more are connected.

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

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

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

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

Polyester having a carboxyl group at one end (polyester represented by the general formula (IV)) includes (IV-1) polycondensation of carboxylic acid and lactone, (IV-2) polycondensation of hydroxy group-containing carboxylic acid, ( IV-3) It can be obtained by polycondensation of a dihydric alcohol and a divalent carboxylic acid (or cyclic acid anhydride).

(IV-1) The carboxylic acid used in the polycondensation reaction between the 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 are used in combination. As the lactone, a known lactone can be used.
These lactones may be used as a mixture of plural kinds.
The charged molar ratio at the time of the reaction between the carboxylic acid and the lactone cannot be uniquely determined because it depends on the molecular weight of the target polyester chain, but is preferably carboxylic acid: lactone = 1: 1 to 1: 1,000, and preferably 1: 3 to 1 : 500 is most preferable.

(IV-2) The hydroxy group-containing carboxylic acid in the polycondensation of the hydroxy group-containing carboxylic acid is the same as the hydroxy group-containing carboxylic acid in (IV-1), and the preferred range is also the same.
(IV-3) As the dihydric alcohol in the polycondensation reaction between the dihydric alcohol and the divalent carboxylic acid (or cyclic acid anhydride), a linear or branched aliphatic diol (more preferably having 2 to 30 carbon atoms) is used. Diol) is preferred.
The divalent carboxylic acid is preferably a linear or branched divalent aliphatic carboxylic acid (more preferably a divalent aliphatic carboxylic acid having 1 to 30 carbon atoms).
The divalent carboxylic acid and the dihydric alcohol are preferably charged at a molar ratio of 1: 1. This makes it possible to introduce a carboxylic acid at the terminal.

Polycondensation during polyester production is preferably performed by adding a catalyst. The catalyst is preferably a catalyst that functions as a Lewis acid.

The number average molecular weight of the polyester can be measured as a polystyrene converted value by the GPC method. The number average molecular weight of the polyester is 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 in this range, both dispersibility and developability can be achieved.

The polyester partial structure forming the polymer chain in Y is in particular a polyester obtained by (IV-1) polycondensation of a carboxylic acid and a lactone and (IV-2) polycondensation of a hydroxy group-containing carboxylic acid. Is preferable from the viewpoint of ease of production.

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

As a method for synthesizing the dispersion resin 2, the dispersion resin 2 can be synthesized by the method described in Japanese Patent Application No. 2011-190180.

The dispersion resin 2 in the present invention preferably has a weight average molecular weight measured by GPC method of 3,000 to 100,000, and more preferably 5,000 to 55,000. When the molecular weight is in the above range, there is an advantage that high developability and high storage stability can be achieved. Moreover, the presence of the 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, and the presence of a functional group having a pKa of 14 or less, and its functional The fact that the group is bonded to the nitrogen atom of the repeating unit can be confirmed by methods such as base titration, nuclear magnetic resonance spectroscopy, and infrared spectroscopy. Further, (ii) the point of having an oligomer chain or polymer chain Y having 40 to 10,000 atoms in the side chain can be confirmed by a method such as nuclear magnetic resonance spectroscopy or GPC method.

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

(Dispersant other than the polymer dispersant represented by the general formula (1) or (2) and the dispersion resin 2)
The composition of the present invention contains a polymer dispersant represented by the general formula (1) or (2) and a dispersant other than the dispersion resin 2 (hereinafter sometimes referred to as “other dispersant”). It may be.
Other dispersants that can be used in the present invention include polymer dispersants (for example, polymer dispersants having acid groups such as phosphorus atom-containing groups or carboxylic acids as acid-based adsorption sites, polyamidoamines and their salts, Polycarboxylic acid and salts thereof, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkyl Examples thereof include phosphoric acid esters, polyoxyethylene alkylamines, alkanolamines, and pigment derivatives. Among these, from the viewpoint of satisfactorily forming a fine hole pattern, a polymer dispersant having at least one of a phosphorus atom-containing group or a carboxylic acid group as an acid adsorption site is preferable. 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 linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
Other dispersants adsorb on the surface of the titanium dioxide particles and act to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the surface of the titanium dioxide particles can be cited as preferred structures.
On the other hand, the other dispersant has an effect of promoting the adsorption of the dispersant by modifying the surface of the titanium dioxide particles.

Specific examples of other dispersants include “DISPERBYK101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110, 180 (copolymer containing an acid group), 130 (polyamide), 161, manufactured 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 series) manufactured by EFKA ), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (Azo pigment derivative ) ”,“ Ajisper PB821, PB822 ”manufactured by Ajinomoto Fintechno Co., Ltd.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd.,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ”, Enomoto Chemical “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725”, manufactured by Kao Corporation DEMAL RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate), “homogenol L-18 (polymer polycarboxylic acid)”, “Emulgen 920 , 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," acetamine 86 Stearylamine acetate) ", Lubrizol" Solsperse 5000 (SOLSPERSE 5000) (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end). , 24000, 26000, 28000, 32000, 36000, 38500 (graft type polymer), 41000 "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical Co., Ltd. Etc.
In the present invention, Solsperse 26000 (SOLPERSE 26000), 36000, or 41000 can be suitably used as the polymer dispersant having a phosphorus atom-containing group (for example, a phosphoric acid group) as an acid-based adsorption site.
In the composition of the present invention, the dispersant can be used alone or in combination of two or more.

From the viewpoint of dispersibility, the content of the dispersant with respect to the total solid content of the composition of the present invention is preferably 1 to 40% by mass, more preferably 1.3 to 30% by mass, and 1.5 to A range of 20% by weight is more preferred, a range of 2-10% by weight is particularly preferred, and a range of 2-6% by weight is most preferred.
In addition, when the composition of the present invention contains a dispersant, if the amount of the dispersant is too much, it may cause peeling, so the mass of the dispersant in the composition is more than the mass of the particles (D). The mass ratio in the composition of the dispersant and the particles (D) is preferably small, more preferably dispersant / particle (D) = 0.01 to 0.8, and the dispersant / particle (D). = 0.03 to 0.5 is more preferable, and dispersant / particle (D) = 0.05 to 0.3 is particularly preferable.
Further, the total content of the binder (A) and the dispersant (sometimes referred to as polymer content) greatly contributes to the resolution, and the polymer content is 10 to 80 mass in the total solid content of the composition. % Is preferable, a range of 20 to 80% by mass is more preferable, and a range of 30 to 75% by mass is particularly preferable. In this case, a binder having an acid group is preferable as the binder, and a dispersant having an acidic group and / or a basic group is preferable as the dispersant.

[(E) Solvent]
The composition of the present invention contains a solvent. The solvent can be composed of various organic solvents.
Organic solvents that can be used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, 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 Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, Examples include ethyl lactate.
These organic solvents can be used alone 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. Furthermore, 30 mass% or less is the most preferable from a viewpoint of application | coating uniformity.

In the present invention, it is preferable to use a solvent having a low metal content. For example, the metal content is preferably 10 ppb or less. A ppt level solvent may be used as necessary, and such a high-purity solvent is provided by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter of the filter used for filtration 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 number of atoms and different structures). Moreover, only 1 type may be included and the isomer may be included multiple types.

The composition of the present invention may further contain optional components described in detail below, if necessary.
The composition of the present invention can contain a color material, and examples of the color material include a chromatic colorant or an organic black colorant.

(Chromatic colorant)
In the present invention, the chromatic colorant is preferably a colorant selected from a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant.

In the present invention, the chromatic colorant may be a pigment or a dye. A pigment is preferable.
The average particle diameter (r) of the pigment is preferably 20 nm ≦ r ≦ 300 nm, more preferably 25 nm ≦ r ≦ 250 nm, and still more preferably 30 nm ≦ r ≦ 200 nm. The “average particle size” here means the average particle size of secondary particles in which primary particles of the pigment are aggregated.
Further, the particle size distribution of the secondary particles of the pigment that can be used (hereinafter, also simply referred to as “particle size distribution”) is 70% by mass or more of the secondary particles falling within (average particle size ± 100) nm. It is preferable that it is 80 mass% or more. The particle size distribution of the secondary particles can be measured using the scattering intensity distribution.

As a method for preparing a pigment having the above average particle size (secondary particle size) and particle size distribution of secondary particles, the following methods may be mentioned. First, a commercially available pigment is preferably mixed with a resin and an organic solvent to prepare a pigment mixture. If necessary, other pigments (the average particle diameter of secondary particles usually exceeds 300 nm) may be mixed together. Thereafter, for example, by using a pulverizer such as a bead mill or a roll mill, the pigment in the pigment mixed solution is pulverized and mixed and dispersed to prepare a pigment having predetermined characteristics. The pigment thus obtained is usually in the form of a pigment dispersion.

The pigment is preferably an organic pigment, and examples thereof include the following. However, the present invention is not limited to these.
Color 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 like (or more, and yellow pigment),
C. I. Pigment 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. (Orange pigment)
C. I. Pigment 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)
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (above, green pigment),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (above, purple pigment),
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc. (above, blue pigment),
These organic pigments can be used alone or in various combinations.

The dye is not particularly limited, and a known dye can be used. The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Dyes such as xanthene, phthalocyanine, benzopyran, indigo, and pyromethene can be used. Moreover, you may use the multimer of these dyes. Further, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.

As the dye, an acid dye and / or a derivative thereof can be preferably used.
In addition, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, an oil-soluble dye, a food dye, and / or a derivative thereof can be usefully used.

Specific examples of the acid dye are shown below, but are not limited thereto. Examples thereof include the following dyes and derivatives of these dyes.
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 chroma 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

Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Acidic dyes such as Solvent orange 45; Rhodamine B, Rhodamine 110, and derivatives of these dyes are also preferably used.

Among them, as the dye, triarylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazoleazo And at least one selected from anilinoazo, pyrazolotriazole azo, pyridone azo, anthrapyridone, and pyromethene.
Further, pigments and dyes may be used in combination.

(Organic black colorant)
In the present invention, examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, and bisbenzofuranone compounds and perylene compounds are preferable.
Examples of the bisbenzofuranone compounds include those described in JP-T 2010-534726, JP-2012-515233, JP-2012-515234, and the like, for example, “Irgaphor Black” manufactured by BASF It is available.
Examples of perylene compounds include C.I. I. Pigment Black 31, 32 and the like.
Examples of the azomethine compound include those described in JP-A-1-170601, JP-A-2-34664, etc., and can be obtained, for example, as “Chromofine Black A1103” manufactured by Dainichi Seika Co., Ltd.

[Blue pigment or purple pigment]
From the viewpoint of improving the color resistance of the cured film formed by the composition of the present invention, the composition of the present invention can contain a blue pigment or a violet pigment.
Examples of blue pigments or purple pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, and C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 It is preferable.

-Pigment preparation- (Color matching)
These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below.
As the blue pigment, a single phthalocyanine pigment or a mixture of this and a dioxazine purple pigment can be used. As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

It is preferable to contain a dispersant when dispersing the blue pigment or purple pigment. The type of the dispersant is not particularly limited, and a polymer dispersant is preferably used. Dispersor BYK-101, DisperBYK-102, DisperBYK-103, DisperBYK-106, DisperBYK-111, DisperBYK-161, DisperBYK-162, DisperBYK-164D, DisperBYK-164D, DisperBYK-164D , DisperBYK-168, DisperBYK-170, DisperBYK-171, DisperBYK-174, DisperBYK-182 (manufactured by BYK Chemie), EFKA4010, EFKA4046, EFKA5080, EFKA5504, EFKA5504, EFKA5204E 62, EFKA7500, EFKA7570, EFKA7575, EFKA7580 (manufactured by Fuka Additive), disperse aid 6, disperse aid 8, disperse aid 15, disperse aid 9100 (manufactured by San Nopco); Solsperse 3000 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, 32000, 36000, 39000, 41000, 71000, and other various Solsperse dispersants (manufactured by Geneca); Adeka Pluronic L31, F38, L42, L44 , L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka Co., Ltd.) and Iso S-20 (manufactured by Sanyo Chemical Co., Ltd.) “Disparon KS-860, 873SN, 874 (polymer dispersing agent), # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester) manufactured by Enomoto Kasei Co., Ltd. Type) ”.
In addition, pigment derivatives such as phthalocyanine derivatives (trade name: EFKA-745 (manufactured by Efka)), Solsperse 5000, 12000, Solsperse 22000 (manufactured by Zeneca) can also be used.

In addition, a composition may contain a black pigment as a coloring material.
The black pigment is not particularly limited, and known ones can be used. For example, carbon black, titanium black, graphite, etc. are mentioned, carbon black and titanium black are preferable, and titanium black is more preferable. Titanium black is black particles containing titanium atoms, and low-order titanium oxide and titanium oxynitride are preferable.
The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. For example, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, treatment with a water-repellent substance as disclosed in JP 2007-302836 A is also possible. Specific examples of black pigments include C.I. I. Pigment Black 1, 7, titanium black pigment and the like.

Titanium black is typically titanium black particles, and it is preferable that both the primary particle size and the average primary particle size of each particle are small. Specifically, the average primary particle size is preferably in the range of 10 nm to 45 nm. In the present invention, the particle diameter, that is, the particle diameter is 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 can be obtained by measuring the area obtained by photographing with an electron micrograph and correcting the photographing magnification.

The specific surface area of titanium black is not particularly limited, and the value measured by the BET (Brunauer, Emmett, Teller) method is used in order that the water repellency after the surface treatment of titanium black with a water repellent agent has a predetermined performance. It is preferably 5 m ² / g or more and 150 m ² / g or less, and more preferably 20 m ² / g or more and 120 m ² / g or less. Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilack D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.

Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms to Ti atoms in the dispersion is adjusted to a range of 0.20 to 0.50, and the like can be mentioned. Regarding the dispersion, the description in paragraphs 0020 to 0105 of JP2012-169556A can be referred to, and the contents thereof are incorporated in the present specification.

The addition amount of the color material is preferably 50 parts by mass or less, more preferably 20 parts by mass or less, and more preferably 10 parts by mass when the total of the particles having an average particle diameter of 50 nm or more and the color material is 100 parts by mass. Part or less is more preferable, and 5 parts by mass or less is particularly preferable. If it is in the above-mentioned range, the function as color adjustment can be appropriately achieved without affecting the dispersion stability of the composition. As a minimum, 0.01 mass part or more is preferable and 0.1 mass part or more is more preferable.
If the amount is within the above range, the amount is not excessively decreased, and the performance is stabilized.

[Silane coupling agent]
A silane coupling agent can be used for the composition of this invention from a viewpoint of the adhesive improvement with the further board | substrate.
The silane coupling agent preferably has an alkoxysilyl group as a hydrolyzable group that can be chemically bonded to an inorganic material. In addition, it preferably has a group that interacts or forms a bond with an organic resin and exhibits an affinity, and such a group has a (meth) acryloyl group, a phenyl group, a mercapto group, a glycidyl group, and an oxetanyl group. Those having a (meth) acryloyl group or glycidyl group are more preferable.
That is, the silane coupling agent used in the present invention is preferably a compound having an alkoxysilyl group and a (meth) acryloyl group or an epoxy group, and specifically, a (meth) acryloyl-tri having the following structure. Examples include methoxysilane compounds and glycidyl-trimethoxysilane compounds.

In addition, the silane coupling agent in the present invention is also preferably a silane compound having at least two types of functional groups having different reactivity in one molecule, and particularly preferably having an amino group and an alkoxy group as functional groups. As such a silane coupling agent, for example, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane) (Shin-Etsu Chemical Co., Ltd.) Product name KBM-602), N-β-aminoethyl-γ-aminopropyl-trimethoxysilane (trade name KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ -Aminopropyl-triethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-trimethoxysilane (trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-triethoxysilane ( Shin-Etsu Chemical Co., Ltd. trade name KBE-903).
As the silane coupling agent, a compound having two or more alkoxysilyl groups can also be suitably used. Examples of the compound having two or more alkoxysilyl groups include 1,6-bis (trimethoxysilyl) hexane, tris- (3-trimethoxysilylpropyl) isocyanurate, 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 Chemical Co., Ltd.).

When the silane coupling agent is used, the addition amount is preferably in the range of 0.01% by mass to 15.0% by mass in the total solid content of the composition, and 0.05% by mass to 10.0% by mass. % Is more preferable. In the composition of the present invention, the silane coupling agent can be used alone or in combination of two or more.

[(F) Anti-coloring agent]
The composition of the present invention preferably contains a coloring inhibitor.
The coloring inhibitor in the present invention is preferably a polymerization inhibitor, a phenol compound, and a phosphite compound or a thioether compound known as an antioxidant, a phenol compound having a molecular weight of 500 or more, and a molecular weight of 500. It is more preferable that it is the above phosphite compound or thioether compound. You may use these in mixture of 2 or more types. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. Preferable phenolic compounds include hindered phenolic compounds. In particular, it is preferable to have a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group. In this case, the substituted group is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group. Group, t-pentyl group, hexyl group, octyl group, isooctyl group and 2-ethylhexyl group are more preferable. Moreover, the stabilizer which has a phenol group and a phosphite group in the same molecule is also mentioned as a preferable material.

Also, phosphorus antioxidants can be suitably used as coloring inhibitors. Phosphorus antioxidants include tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine-6. -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2-yl And at least one compound selected from the group consisting of) oxy] ethyl] amine and ethyl bis (2,4-ditert-butyl-6-methylphenyl) phosphite.

These are readily available as commercial products and are sold by the following manufacturers. From Asahi Denka Kogyo Co., Ltd., ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, ADK STAB AO-80 Available as 330.
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.
Two or more colorants may be mixed and used.

[Sensitizer]
The composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of (C) the polymerization initiator and increasing the photosensitive wavelength.
As a sensitizer that can be used in the present invention, a sensitizer that is sensitized by an electron transfer mechanism or an energy transfer mechanism to (C) the polymerization initiator is preferable.

Examples of the sensitizer include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
As the sensitizer, specifically, description in paragraphs 0231 to 0253 of JP 2010-106268 A (corresponding to <0256> to <0273> in US 2011/0124824 of the corresponding specification) can be referred to. The contents of which are incorporated herein by reference.
The content of the sensitizer in the composition is preferably 0.1% by mass or more and 20% by mass or less in terms of solid content from the viewpoint of light absorption efficiency in the deep part and decomposition efficiency of the initiator. More preferably, the content is 5% by mass or more and 15% by mass or less.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

[Co-sensitizer]
The composition of the present invention preferably further contains a co-sensitizer.
In the present invention, the co-sensitizer has functions such as (C) further improving the sensitivity of the polymerization initiator and the sensitizer to actinic radiation, or suppressing the polymerization inhibition of the monomer (B) by oxygen.
As the co-sensitizer, specifically, refer to the description of JP-A 2010-106268, paragraphs 0254 to 0257 (corresponding to <0277> to <0279> in US Patent Application Publication No. 2011/0124824). The contents of which are incorporated herein by reference.
The content of these co-sensitizers is in the range of 0.1% by mass or more and 30% by mass or less with respect to the total solid content of the composition from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and chain transfer. Is preferable, the range of 1 mass% or more and 25 mass% or less is more preferable, and the range of 1.5 mass% or more and 20 mass% or less is still more preferable. These may be used alone or in combination of two or more.

[Polymerization inhibitor]
In the present invention, it is preferable to add a polymerization inhibitor in order to prevent unnecessary polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the composition.
Polymerization inhibitors that can be used in the present invention include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium Examples include compounds, and cationic dyes, sulfide group-containing compounds, nitro group-containing compounds, and transition metal compounds such as FeCl ₃ and CuCl ₂ .

Further preferred embodiments are as follows.
The phenolic hydroxyl group-containing compound is hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t-butylphenol), Selected from the group consisting of 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol (BHT), phenolic resins, and cresol resins It is preferable that it is a compound.
N-oxide compounds include 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picoline A compound selected from the group consisting of acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide is preferred.
Piperidine 1-oxyl free radical compounds include piperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1 -Oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimide A compound selected from the group consisting of -2,2,6,6-tetramethylpiperidine 1-oxyl free radical and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical Is preferred.
The pyrrolidine 1-oxyl free radical compounds are preferably 3-carboxyproxyl free radicals (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical).
The N-nitrosophenylhydroxylamines are preferably compounds selected from the group consisting of N-nitrosophenylhydroxylamine cerium salts and N-nitrosophenylhydroxylamine aluminum salts.
The diazonium compound is selected from the group consisting of 4-diazophenyldimethylamine hydrogen sulfate, 4-diazodiphenylamine tetrafluoroborate, and 3-methoxy-4-diazodiphenylamine hexafluorophosphate Is preferred.

Examples of suitable polymerization inhibitors that can be used in the present invention are illustrated below, but the present invention is not limited thereto. Examples of phenolic polymerization inhibitors include the following exemplified compounds (P-1) to (P-24).

Examples of amine polymerization inhibitors include the following exemplary compounds (N-1) to (N-7).

Examples of sulfur polymerization inhibitors include the following exemplary compounds (S-1) to (S-5).

Examples of phosphite polymerization inhibitors include the following exemplary compounds (R-1) to (R-5).

Furthermore, each compound shown below can also be used as a suitable polymerization inhibitor.

Among the above exemplified compounds, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t-) are preferable. Butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol) phenolic hydroxyl group-containing compounds, piperidine 1-oxyl, free radical compounds, or 2,2,6,6-tetramethylpiperidine 1- Oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido- 2,2,6,6-tetramethylpiperidine 1-oxylf -Piperidine 1-oxyl free radical, 4-maleimido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical A radical compound, or an N-nitrosophenylhydroxylamine compound of N-nitrosophenylhydroxylamine primary cerium salt and N-nitrosophenylhydroxylamine aluminum salt, more preferably 2,2,6,6-tetramethylpiperidine 1 -Oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamide -2,2, , 6-tetramethylpiperidine 1-oxyl free radical, 4-maleimido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1 A piperidine 1-oxyl free radical compound of an oxyl free radical, or an N-nitrosophenyl hydroxylamine compound of an N-nitrosophenylhydroxylamine cerium salt and an N-nitrosophenylhydroxylamine aluminum salt, more preferably a -nitroso N-nitrosophenylhydroxylamine compounds of phenylhydroxylamine primary cerium salt and N-nitrosophenylhydroxylamine aluminum salt.

A preferable addition amount of the polymerization inhibitor is preferably 0.01 parts by weight or more and 10 parts by weight or less, and 0.01 parts by weight or more and 8 parts by weight or less with respect to 100 parts by weight of the polymerization initiator (C). More preferably, it is most preferably in the range of 0.01 to 5 parts by mass.
By setting it as the said range, the curing reaction suppression in a non-image part and the curing reaction acceleration in an image part are fully performed, and image forming property and a sensitivity become favorable.
In the composition of the present invention, the polymerization inhibitor can be used alone or in combination of two or more.

[Surfactant]
Various surfactants may be added to the composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, since the composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved. Sex can be improved more.
That is, when a film is formed using a coating liquid to which a composition containing a fluorosurfactant is applied, the wettability to the coated surface is reduced by reducing the interfacial tension between the coated surface and the coating liquid. Is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

The fluorine content of the fluorosurfactant is preferably 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-described range, it is effective in terms of uniformity of coating film thickness and liquid-saving properties, and good solubility.
Specific examples of the fluorosurfactant include surfactants described in paragraphs 0060 to 0064 of JP-A-2014-41318 (paragraphs 0060 to 0064 of the corresponding international publication 2014/17669 pamphlet) and the like. The contents of which are incorporated herein by reference. Examples of commercially available fluorosurfactants include Megafuck F-171, Megafuck F-172, Megafuck F-173, Megafuck F-176, Megafuck F-177, Megafuck F-141, Mega Fuck F-142, Mega Fuck F-143, Mega Fuck F-144, Mega Fuck R30, Mega Fuck F-437, Mega Fuck F-475, Mega Fuck F-479, Mega Fuck F-482, Mega Fuck F-554 , MegaFuck F-780 (above, manufactured by DIC Corporation), FLORARD FC430, FLORARD FC431, FLORARD 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 (manufactured by Asahi Glass Co., Ltd.) and the like. As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 can also be used.
The following compounds are also exemplified as the fluorosurfactant used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
Moreover, the fluoropolymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant. Specific examples include compounds described in JP-A 2010-164965, paragraphs 0050 to 0090 and 0289 to 0295, such as MegaFac RS-101, RS-102, and RS-718K manufactured by DIC.

Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Pi Nin 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 Yushi Co., Ltd.), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.) and the like.
Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.
Only one type of surfactant may be used, or two or more types may be combined.

The composition may or may not contain a surfactant. When it is contained, the addition amount of the surfactant is 0.001% by mass to 2.0% by mass with respect to the total mass of the composition. Preferably, it is 0.005% by mass to 1.0% by mass.

[Other additives]
Furthermore, you may add well-known additives, such as a plasticizer and a fat-sensitizing agent, in order to improve the physical property of a cured film with respect to a composition.
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of a monomer and a binder.

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

In the general formula (I), R ¹ and R ² each independently represents 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 or different from each other and do not represent a hydrogen atom at the same time.
R ¹ and R ² may form a cyclic amino group together with the nitrogen atom to which R ¹ and R ² are bonded. Examples of the cyclic amino group include piperidino group, morpholino group, pyrrolidino group, hexahydroazepino group, piperazino group and the like.
R ³ and R ⁴ represent an electron withdrawing group. Here, the electron withdrawing group is an electron withdrawing group having a Hammett's substituent constant σ _p value (hereinafter simply referred to as “σ _p value”) of 0.20 or more and 1.0 or less. Preferably, it is an electron withdrawing group having a σ _p value of 0.30 or more and 0.8 or less. R ³ and R ⁴ may combine with each other to form a ring.
Moreover, at least one of the above R ¹ , R ² , R ³ , and R ⁴ may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may be a copolymer with another monomer.
For the description of the substituent of the ultraviolet absorber represented by the formula (I), refer to the description in WO2009 / 123109A paragraphs 0024 to 0033 (corresponding to US Patent Application Publication No. 2011/0039195 <0040> to <0059>). These contents are incorporated herein by reference. Preferable specific examples of the compound represented by the formula (I) are exemplified compounds (1) to (1) to (2009) in paragraphs 0034 to 0037A (corresponding to <0060> of US Patent Application Publication No. 2011/0039195). 14) can be referred to, and the contents thereof are incorporated in the present specification.

The composition of the present invention may or may not contain an ultraviolet absorber. When it is contained, the content of the ultraviolet absorber is 0.1% by mass to 10% by mass with respect to the total solid content of the composition. %, More preferably 0.1% to 5% by weight, and particularly preferably 0.1% to 3% by weight.
Moreover, in this invention, various ultraviolet absorbers may be used individually by 1 type, and may be used in combination of 2 or more type.
The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. If it is conventionally used for the filtration use etc., it can use without being specifically limited. For example, fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon-6 and nylon-6,6, polyolefin resin such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), etc. Filter. Among these materials, polypropylene (including high density polypropylene) is preferable.
The filter has a pore diameter of 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 becomes possible to reliably remove fine foreign matters that are mixed in the dissolved pigment and the like and inhibit the preparation of a uniform and smooth composition in the subsequent step.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter 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 Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (former Nihon Microlith Co., Ltd.), or Kitz Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as the first filter described above can be used. For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

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

<Curing film>
The present invention has been made in view of the above-described problems of the prior art, and has high in-plane uniformity, flat transmittance in the visible region, resistance, lithographic properties, storage stability, adhesion, and redispersibility. Since a cured film excellent in coating uniformity can be formed, it can be suitably used as an appearance adjusting material for various optical sensors and optical members.
That is, the composition of the present invention is preferably used for forming a cured film.
The present invention also 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, a step of applying the above-described composition on a substrate by a spray method, a roll coating method, a spin coating method (spin coating method), a bar coating method,
Followed by a first heating step and a subsequent curing step which cures by a second heating and / or exposure at a higher temperature.
As conditions in the first heating step, it is preferable that the drying be performed under a condition of 70 ° C. or higher and 110 ° C. or lower and about 2 minutes or longer and 4 minutes or shorter.

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

<Pattern and manufacturing method thereof>
Hereinafter, the pattern of this invention is explained in full detail through the manufacturing method.
The method for producing a pattern of the present invention is abbreviated as an “exposure step” as appropriate, a step of applying a composition of the present invention on a substrate to form a film, and a step of exposing the film through a mask. And a step of developing the exposed film to form a pattern (hereinafter abbreviated as “development step” as appropriate).
In the pattern manufacturing method of the present invention, it is preferable to have a curing step of curing the formed pattern by heating and / or exposure after performing the above-described film forming step, exposure step, and development step. .
Specifically, the composition of the present invention is applied directly or via another layer to a substrate to form a film (film forming process), exposed through a predetermined mask pattern, and irradiated with light. The pattern can be formed by curing only the coated film portion (exposure process) and developing with a developer (development process).
Hereinafter, each step will be described.

[Film formation process]
In the film forming step, a film is formed by applying the composition of the present invention on a substrate.
As the substrate, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like in which a transparent conductive film is attached thereto, a solid-state imaging device, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS).
Further, if necessary, an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.
As a coating method of the composition of the present invention on the substrate, various coating methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, spray coating, and screen printing can be applied.
The coating 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 further preferably 0.7 μm or more and 20 μm or less from the viewpoint of resolution and developability.
The composition coated on the substrate is usually dried under conditions of 70 ° C. or higher and 110 ° C. or lower and about 2 minutes or longer and 4 minutes or shorter to form a film.

[Exposure process]
In the exposure step, the formed film is exposed through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is more preferable. Irradiation intensity 5 mJ / cm ² or more 1500 mJ / cm ² or less is preferably 10 mJ / cm ² or more 1200 mJ / cm ² and more preferably less, 10 mJ / cm ² or more 1000 mJ / cm ² or less is most preferable.

[Development process]
Subsequent to the exposure step, a development step (preferably an alkali development step) is performed to elute the non-light-irradiated portion in the exposure step into an alkaline aqueous solution. Thereby, only the photocured part remains.
The developer used in the development step is not particularly limited, and for example, an alkali developer or a developer containing an organic solvent can be used.
As the developer, an organic alkali developer that does not damage the underlying circuit or the like is preferable. The development temperature is usually from 20 ° C. to 30 ° C., and the development time is from 20 seconds to 90 seconds.
Examples of the alkali developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium Hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyl Tetraalkylammonium hydroxide such as methylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, etc. Alkaline aqueous solutions such as quaternary ammonium salts, cyclic amines such as pyrrole and pihelidine can be used. Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution. The alkali concentration of the alkali developer is usually from 0.001 to 20% by mass, preferably from 0.01 to 10% by mass, and more preferably from 0.1 to 1% by mass. The pH of the alkali developer is usually from 10.0 to 15.0. The alkali concentration and pH of the alkali developer can be appropriately adjusted and used. For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like may be added to the alkali developer.
In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

Note that the optical member obtained from the present composition may be incorporated not only in a solid-state imaging device but also in a liquid crystal display device or an organic EL display device.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. Unless otherwise specified, “part” and “%” are based on mass.
In the examples, the acid value was determined by a potentiometric method (solvent tetrahydrofuran / water = 54/6 (volume ratio), titrant 0.1N aqueous sodium hydroxide solution (acid value)).
In addition, the weight average molecular weight is measured using HPC-8220GPC (manufactured by Tosoh Corp.) as a measuring device, TSKguardcolumn SuperHZ-L as a guard column, TSKgel SuperHZM-M as a column, TSKgel SuperHZ4000, TSKgel SuperHZ3000 column, and KSK SuperHZ3000 column. Use a column temperature of 40 ° C., inject 10 μl of a 0.1% by mass tetrahydrofuran solution with a sample concentration of 0.1%, flow tetrahydrofuran at a flow rate of 0.35 ml per minute as the eluting solvent, and detect the sample peak with the RI detector. And calculated using a calibration curve prepared using standard polystyrene.

<Example 1>
[Preparation of titanium dioxide dispersion 1]
Using a Ultra Apex mill manufactured by Kotobuki Industries Co., Ltd. as a circulation type dispersion device (bead mill), a mixture treatment having the following composition was dispersed as follows to obtain a titanium dioxide dispersion.
~ Composition ~
・ Titanium dioxide (CR-90-2 manufactured by Ishihara Sangyo Co., Ltd.) (Purity 90% or more)
: 272.57 parts ・ Dispersant (SOLSPERSE36000 (dispersion resin having a phosphate group))
(30% by mass PGMEA solution): 136.29 parts, propylene glycol-1-monomethyl ether-2-acetate (PGMEA)
: 241.14 parts

The dispersing device was operated under the following conditions.
・ Bead diameter: φ0.2mm
・ Bead filling rate: 65% by volume
・ Peripheral speed: 6m / sec ・ Pump supply: 10.8kg / hour ・ Cooling water: Tap water ・ Bead mill annular passage volume: 0.15L
・ Amount of liquid mixture to be dispersed: 0.65 kg

After the start of dispersion, the average particle size was measured at 30 minute intervals.
The average particle diameter decreased with the dispersion time, but the amount of change gradually decreased. Dispersion was terminated when d50 in the particle size distribution was less than 250 nm and d90 was less than 350 nm. The average particle diameter of the titanium dioxide particles in this dispersion was 253 nm. This measurement is the number average particle diameter obtained using Nikkiso Co., Ltd. Microtrac UPA-EX150.

[Preparation of titanium dioxide dispersion 2]
A dispersion was prepared in the same manner as the preparation of the titanium dioxide dispersion 1 except that the composition and the amount of the mixture to be dispersed were changed as follows. The average particle diameter of the titanium dioxide particles in the titanium dioxide dispersion 2 was 253 nm.
~ Composition ~
・ Titanium dioxide (CR-90-2 manufactured by Ishihara Sangyo Co., Ltd.) (Purity 90% or more)
195.91 parts Dispersant (SOLSPERSE 36000 (dispersion resin having a phosphate group))
(30% by mass PGMEA solution): 391.82 parts, propylene glycol-1-monomethyl ether-2-acetate (PGMEA)
: 62.27 parts-Volume of liquid mixture to be dispersed: 0.65 kg

Using the titanium dioxide dispersion 1 obtained above, the components of Example 1 were obtained by mixing the components so as to have the following composition.

~ Composition of composition ~
-Titanium dioxide dispersion 1 prepared above: 8.56 parts-Binder (B-1) 40% by mass PGMEA solution: 40.24 parts The weight average molecular weight (Mw) is 11000, and the copolymerization ratio (molar ratio) ) Is as follows.
Monomer (pentaerythritol tetraacrylate): 10.73 parts (A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd .; M-1 in the table below)
-Polymerization initiator (K-1): 3.05 parts-Anti-coloring agent (Adeka Stub AO-80 manufactured by Adeka Co., Ltd.): 0.17 parts-Silane coupling agent-1: (N-2- (aminoethyl) ) -3-Aminopropylmethyldimethoxysilane) 1% by mass cyclohexanone solution: 3.4 parts / polymerization inhibitor (p-methoxyphenol): 0.0054 parts / surfactant The following mixture (Mw = 14000, 0.2 mass) % PGMEA solution)

: 4.17 parts ・ PGMEA: 29.68 parts

K-1 (hereinafter referred to as compound)

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

[Preparation table]

In addition, M / B in Table 3 below represents the mass ratio of the monomer and binder in the solid content.

<Example 23>
Each component was mixed so that it might become the following compositions, and the composition of Example 23 was obtained.
-Titanium dioxide dispersion prepared as above 2: 12.16 parts-Binder (B-2) 40 mass% PGMEA solution: 36.01 parts The weight average molecular weight (Mw) is 14000, and the copolymerization ratio (molar ratio) ) Is 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 TAB AO-80 manufactured by Adeka Co., Ltd.): 0.18 parts Silane coupling agent-1: (N-2- (aminoethyl) ) -3-Aminopropylmethyldimethoxysilane) 1% by weight cyclohexanone solution: 1.75 parts ・ Polymerization inhibitor (p-methoxyphenol): 0.0050 parts ・ The following UV absorber: 1.0.35 parts ・ The following surface activity Agent 1 0.2% by mass PGMEA solution: 4.17 parts PGMEA: 32.66 parts

<Preparation of pigment dispersions 2-1 to 2-7>
Using 0.3 mm diameter zirconia beads, a mixture of the following composition was mixed and dispersed for 3 hours with a bead mill (high pressure disperser NANO-3000-10 with a decompression mechanism manufactured by Nippon BEE Co., Ltd.) A pigment dispersion was prepared. Table 2 shows the usage amount (unit: parts by mass) of the corresponding component.

[Colorant]
PR254: C.I. I. Pigment Red 254
-PB15: 6: C.I. I. Pigment Blue 15: 6
PG58: C.I. I. Pigment Green 58
・ PY139: Pigment Yellow 139
・ PV23: Pigment Violet 23
・ PB7: Pigment Black 7
・ Irgaphor Black [manufactured by BASF]

[Dispersion resin]
-Dispersing resin A: the following structure (Mw: 24000)

[Organic solvent]
PGMEA: Propylene glycol monomethyl ether acetate

<Composition of Example 24>
Each component was mixed so that it might become the following compositions, and the composition of Example 24 was obtained.
-Titanium dioxide dispersion prepared above 2: 12.10 parts-Pigment dispersion 2-1 prepared above-0.44 parts-Binder (B-2) 40 wt% 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 TAB AO-80 manufactured by Adeka Co., Ltd.): 0.18 parts Silane coupling agent-1: (N-2- (aminoethyl) ) -3-Aminopropylmethyldimethoxysilane) 1 mass% cyclohexanone solution: 1.75 parts Polymerization inhibitor (p-methoxyphenol): 0.0050 parts UV absorber 1: 0.35 parts Above surface activity Agent 1: 4.17 parts PGMEA: 32.40 parts

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

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

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

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

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

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

<Composition of Example 31>
Each component was mixed so that it might become the following compositions, and the composition of Example 31 was obtained.
-Titanium dioxide dispersion prepared above 2: 12.10 parts-Pigment dispersion 2-4 prepared above: 0.22 parts-Pigment dispersion prepared 2-5: 0.22 parts above-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 TAB AO-80 manufactured by Adeka Co., Ltd.): 0.18 parts Silane coupling agent-1: (N-2- (aminoethyl) ) -3-Aminopropylmethyldimethoxysilane) 1 mass% cyclohexanone solution: 1.75 parts Polymerization inhibitor (p-methoxyphenol): 0.0050 parts UV absorber 1: 0.35 parts Above surface activity Agent 1: 4.17 parts PGMEA: 32.40 parts

<Composition of Example 32>
A composition was obtained according to the same procedure as Example 31 except that the pigment dispersion 2-4 was changed to the pigment dispersion 2-1, and the pigment dispersion 2-5 was changed to the pigment dispersion 2-3.

<Comparative Example 1>
A dispersion was obtained in the same manner as the preparation of titanium dioxide dispersion 1, except that TTO-55N (trade name, manufactured by Ishihara Sangyo Co., Ltd., rutile type, content of Ti atom: 99 atm%) was used as the titanium dioxide pigment. . 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 Example 1 using this dispersion.

Using the prepared composition, a cured film was formed, and [transmissivity], [in-plane uniformity], and [spectral flatness] were evaluated.

[Formation of cured film]
Each of the compositions of Examples 1 to 32 and Comparative Example 1 was applied by spin coating on an 8-inch glass wafer (Eagle XG Corning, thickness 1.1 mm), and then heated at 100 ° C. on a hot plate. A coating film was obtained by heating for a minute. This coating film was exposed at 500 mJ / cm ² with an ultrahigh pressure mercury lamp “USH-500BY” manufactured by USHIO INC. Furthermore, it heated on the hotplate for 5 minutes at 200 degreeC, and the cured film was obtained.

[Spectroscopic measurement (transmittance)]
The spectrum (transmittance) of the cured film was measured using “MCPD-3700” manufactured by Otsuka Electronics Co., Ltd. Table 3 below shows the transmittance at 400 nm.

[In-plane uniformity]
The film surface was scratched every 1 cm from the center to the edge of the glass wafer, and the film thickness in the wafer surface was measured at 10 points using a stylus type film thickness meter DEKTAK XT (manufactured by BRUKER). And the dispersion | variation in the film thickness was computed based on the following formula.
Variation in film thickness = (maximum value of film thickness−minimum value of film thickness) ÷ (average value of film thickness measured at 10 points) × 100
The calculated film thickness variation was evaluated based on the following criteria. The film thickness variation was 2% or less, 4 was greater than 2%, 3% or less, 3 was greater than 3%, and 5% was less than 2%.

[Spectral flatness]
The spectrum (transmittance) of the cured film was measured with “MCPD-3700” manufactured by Otsuka Electronics Co., Ltd., and the difference in transmittance between the minimum transmittance and the maximum transmittance between 400 nm and 700 nm was evaluated as follows. A transmittance difference of 20% or less was 3 or more than 20%, a transmittance difference of 30% or less was 2 or more than 30%, and 1.

Evaluation list

In the above examples, the same performance is exhibited even when the monomer, binder, polymerization initiator, and particles are changed within the above-mentioned preferred ranges. The same performance is exhibited even when two or more monomers, two or more binders and two or more polymerization initiators are contained.
In place of the inorganic particles (titanium dioxide) used in the above examples, core particles made of polymer particles and a shell layer made of inorganic nanoparticles are described in paragraphs 0012 to 0042 of JP-A-2015-47520. The same results as above were obtained when the core-shell composite particles made of

Claims

(A) A composition containing 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 according to claim 1, wherein the particles (D) are metal particles.
The composition according to claim 2, wherein the particles of (D) are titanium dioxide.
The composition according to any one of claims 1 to 3, wherein the average particle diameter of the particles of (D) is 150 nm or more.
The composition according to any one of claims 1 to 4, further comprising (F) a coloring inhibitor.
The composition according to claim 5, wherein the anti-coloring agent (F) is a phenol compound.
The composition according to claim 6, wherein the anti-coloring agent (F) is a phenol compound having a substituent at the ortho position of the phenolic hydroxyl group.
The composition according to any one of claims 1 to 7, 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-based 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 polymerization initiator (C) is an oxime compound.
The composition according to any one of claims 1 to 11, further comprising a coloring material.
A cured film formed using the composition according to any one of claims 1 to 12.
Applying a composition according to any one of claims 1 to 12 on a substrate;
A method for producing a pattern, comprising: a step of exposing through a mask; and a step of developing the exposed film to form a pattern.
A pattern manufactured by the manufacturing method according to claim 14.
An optical sensor using a cured film formed using the composition according to any one of claims 1 to 12.
An imaging device using a cured film formed using the composition according to any one of claims 1 to 12.