JP2017078105A - Curable composition, method for producing cured film, color filter, light-shielding film, solid-state image sensor, and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition capable of forming a cured film exhibiting excellent developability and excellent low reflectivity, a method for producing a cured film using the same, a color filter, a light-shielding film, a solid-state image sensor, and an image display device.SOLUTION: The curable composition contains: a fluorine-containing block copolymer having an A-B block copolymer moiety which comprises an A block having a hydroxyl group or an acid group and a B block having a fluorine atom; a polymerizable compound; a colorant; and a polymer compound selected from the group consisting of a polyacrylate-based polymer having a hydroxyl group or an acid group and a polymethacrylate-based polymer having a hydroxyl group or an acid group.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition, a method for producing a cured film, a color filter, a light shielding film, a solid-state imaging device, and an image display device.

The solid-state imaging device includes a photographing lens, a solid-state imaging device such as a CCD (charge coupled device) and a CMOS (complementary metal oxide semiconductor) disposed behind the photographing lens, and a circuit on which the solid-state imaging device is mounted. A substrate. This solid-state imaging device is mounted on a digital camera, a mobile phone with a camera, a smartphone, or the like.
In a solid-state imaging device, noise may occur due to reflection of visible light. Therefore, the generation of noise is usually suppressed by providing a predetermined light shielding film in the solid-state imaging device.

  Patent Document 1 discloses a resist composition (photosensitive resin composition) including a fluorine-containing resin (random polymer) having a repeating unit containing a fluorine atom and a repeating unit containing a carboxyl group, It is described that a black pigment such as titanium black or carbon black can be added to the composition as a material for forming a light-shielding coating film.

JP 2005-315984 A

By the way, in recent years, various requirements are demanded for the light shielding film.
For example, as the solid-state imaging device becomes smaller, thinner, and more sensitive, there is a demand for further lower reflection of the light shielding film. In particular, it is preferable from an industrial point of view if the low-reflective light-shielding film as described above can be formed by a coating method such as a spin coating method that is excellent in productivity.
The inventors of the present invention studied the production of a light-shielding film using a photosensitive resin composition containing a fluorine-containing resin with reference to Patent Document 1, and found that the photosensitive resin composition had excellent low reflectivity. However, it has been found that further improvement is required for developability.
As this factor, in the coating film formed on the substrate by spin coating using the photosensitive resin composition, the fluorine-containing polymer contained in the composition has a low surface free energy, so that the substrate is It is considered that the surface on the opposite side is unevenly distributed, that is, a high refractive index layer having a high black pigment concentration is formed on the substrate side in the coating film, and a low refractive index layer is formed on the upper layer by a fluoropolymer. It is done. That is, although it was excellent in low reflectivity by the said structure, it was estimated that the development does not advance well by repelling the developing solution to the low refractive index layer containing hydrophobic fluorine atoms during alkali development.

An object of this invention is to provide the curable composition which can form the cured film which shows the outstanding developability and the outstanding low reflectivity in view of the said situation.
The present invention also provides a method for producing a cured film using the curable composition, a color filter and a light-shielding film obtained by curing the curable composition, and a cured film obtained by curing the curable composition. It is another object of the present invention to provide a solid-state imaging device and an image display device.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a curable composition containing a fluorine-containing polymer having a specific structure, and have completed the present invention.
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) a fluorine-containing block copolymer having an AB block copolymer moiety composed of an A block having a hydroxyl group or an acid group and a B block having a fluorine atom;
A polymerizable compound;
A colorant;
A curable composition comprising a polyacrylate polymer having a hydroxyl group or an acid group, and a polymer compound selected from the group consisting of a polymethacrylate polymer having a hydroxyl group or an acid group.
(2) The curability according to (1), wherein the A block is composed of a repeating unit represented by the following formula (A), and the B block is composed of a repeating unit represented by the following formula (B). Composition.
In formula (A), R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a single bond or a divalent linking group, and A ¹ represents a hydrogen atom, a hydroxyl group, a carboxyl group, or a phosphate group. Represents an acid group selected from a phenolic hydroxyl group or a thiol group, or a derivative group thereof.
In formula (B), R ² represents a hydrogen atom or an alkyl group, L ² represents a single bond or a divalent linking group, and R ^f represents a monovalent organic group containing a fluorine atom.
(3) The curable composition according to (2), wherein in the formula (A), L ¹ is a single bond or a divalent linking group having a total number of atoms of 20 or less.
(4) In the above formula (A), L ¹ is a single bond or a linear divalent linking group having a total number of atoms of 10 or less, according to any one of (2) or (3) Curable composition.
(5) The curable composition according to any one of (2) to (4), wherein in the formula (B), ^Rf is a monovalent organic group having 1 to 3 carbon atoms substituted with a fluorine atom. object.
(6) The curable composition according to any one of (1) to (5), wherein the fluorine-containing block copolymer has a hydroxyl value or an acid value of 35 to 150 mgKOH / g.
(7) Curing in any one of (1)-(6) whose content of the said fluorine-containing block copolymer is 1-20 mass% with respect to the total solid in a curable composition. Sex composition.
(8) The curable composition in any one of (1)-(7) whose weight average molecular weights of the said fluorine-containing block copolymer are 5000-50000.
(9) The curable composition according to any one of (1) to (8), wherein the polymer compound has a weight average molecular weight of 10,000 to 50,000.
(10) The curable composition according to any one of (1) to (9), wherein the polymer compound has a polyester structure in the molecule and has a hydroxyl value or an acid value of 20 mgKOH / g or more.
(11) The curable composition according to any one of (1) to (10), wherein a mass ratio between the content of the polymer compound and the content of the fluorine-containing block copolymer is 3 to 8. In addition, the said mass ratio intends the mass of the said high molecular compound / mass of the said fluorine-containing block copolymer.
(12) The curable composition according to any one of (1) to (11), wherein the colorant includes a black pigment.
(13) forming a composition layer of the curable composition according to any one of (1) to (12) on a substrate by spin coating;
A step of exposing the composition layer by irradiating actinic rays or radiation; and
And a step of forming the cured film by alkali development of the composition layer after the exposure.
(14) A color filter obtained by curing the curable composition according to any one of (1) to (11).
(15) A light shielding film obtained by curing the curable composition according to (12).
(16) A solid-state imaging device having a cured film obtained by curing the curable composition according to any one of (1) to (12).
(17) An image display device having a cured film obtained by curing the curable composition according to any one of (1) to (12).

ADVANTAGE OF THE INVENTION According to this invention, while showing the outstanding developability, the curable composition which can form the cured film which shows the outstanding low reflectivity can be provided.
Moreover, according to this invention, the solid-state image sensor and image display apparatus which have a cured film formed by hardening | curing the color filter and light shielding film which harden the said curable composition, and a curable composition are provided. You can also.

The sectional view of the suitable embodiment of the cured film of the present invention is represented. It is a perspective view which shows the solid-state imaging device of 1st Embodiment. It is a disassembled perspective view of the solid-state imaging device of 1st Embodiment. It is sectional drawing which shows the solid-state imaging device of 1st Embodiment. It is sectional drawing which shows the solid-state imaging device of 2nd Embodiment. It is sectional drawing which shows the solid-state imaging device of 3rd Embodiment. It is sectional drawing which shows the solid-state imaging device of 4th Embodiment.

Hereinafter, the curable composition of the present invention (hereinafter also simply referred to as “composition” and “composition of the present invention”), a method for producing a cured film using the curable composition, and curing the curable composition. A preferred embodiment of the solid-state imaging device and the image display device having the color filter and the light-shielding film, and the cured film obtained by curing the curable composition will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “radiation” in the present specification means visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like.
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 represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, “(meth) acryloyl” represents acryloyl and methacryloyl, “ “(Meth) acrylamide” represents acrylamide and methacrylamide. In the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from oligomers and polymers, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.
In the present specification, “hydroxyl group” does not include “phenolic hydroxyl group”.

<Curable composition>
The first feature of the present invention is that a fluorine-containing block copolymer having a predetermined block structure is used. In the following, a guess will be described regarding the reason why the effects of the present invention can be obtained.
First, the curable composition of the present invention is a fluorine-containing block copolymer having an AB block copolymer portion composed of an A block having a hydroxyl group or an acid group and a B block having a fluorine atom (hereinafter simply referred to as “specific polymer”). The specific polymer exhibits a low surface free energy because it contains a fluorine atom. Therefore, for example, in a coating film formed by applying a curable composition on a substrate, the specific polymer is likely to be concentrated in the vicinity of the coating film surface on the side opposite to the substrate. As a result, as shown in FIG. 1, the cured film 10 on the substrate 100 obtained by curing the coating film has a colorant layer (lower layer) 12 containing a colorant (particularly preferably a black pigment) and a specific polymer. It has a two-layer structure with a coating layer (upper layer) 14 that is formed. When such a two-layer structure is formed, the light reflected at the surface of the coating layer and the light reflected at the interface between the coating layer and the colorant layer are canceled out by interference, resulting in excellent low reflectivity. Realized.
The specific polymer has an AB block copolymer site composed of a block composed of a repeating unit having a hydroxyl group or an acid group (A block) and a block composed of a repeating unit having a fluorine atom (B block). It is characterized by having.
That is, in the coating film using the specific polymer, a hydrophilic unit composed of a repeating unit having a hydroxyl group or an acid group is separated from the low refractive index layer of the hydrophobic field formed on the coating film surface by aggregation of fluorine atoms. It is assumed that a field region is formed. With this structure, it is considered that the alkali developer is easily attracted to a hydroxyl group or an acid group, and a penetration path for allowing the alkali developer to penetrate into the film is easily formed, and has excellent developability.
Furthermore, as a second feature of the present invention, a polymer compound selected from the group consisting of a polyacrylate polymer having a hydroxyl group or an acid group and a polymethacrylate polymer having a hydroxyl group or an acid group (hereinafter referred to as “polyacrylate polymer”). , "Referred to as" (meth) acrylic polymer having a hydroxyl group or an acid group ").
The (meth) acrylic polymer having a hydroxyl group or an acid group can be added to the composition as a compound (dispersant) for dispersing a colorant or as a binder.
The (meth) acrylic polymer having a hydroxyl group or an acid group is adsorbed on the surface of a dispersion such as a colorant such as a black pigment and acts to prevent re-aggregation. The combined use with the combination is considered to improve the phase separation between the low refractive index layer and the lower high refractive index layer (hereinafter also referred to as “colored layer”) by the fluorine-containing block copolymer. That is, the low reflectivity that is the effect of the first feature point described above can be further improved. Further, since the structure contains a hydroxyl group or an acid group (particularly preferably a carboxyl group), it contributes to an improvement in developability.
In particular, as described later, by blending a (meth) acrylic polymer having a hydroxyl group or an acid group at a specific ratio (mass ratio) with respect to the fluorine-containing block copolymer, low reflectivity, developability, surface It has been confirmed that the quality can be established with excellent quality.
Hereinafter, first, the composition of the curable composition of the present invention will be described in detail.

(A) Fluorine-containing block copolymer The fluorine-containing block copolymer has an AB block copolymer site composed of an A block having a hydroxyl group or an acid group and a B block having a fluorine atom.
Hereinafter, the A block having a hydroxyl group or an acid group and the B block having a fluorine atom will be described in detail.

  The fluorine-containing block copolymer of the present invention has one or more blocks A and one or more blocks B, and the combination thereof is not particularly limited as long as the effects of the present invention can be obtained. Specifically, A-B, A- (B-A) n, (A-B) m, B-A- (BA) n-B (where n represents an integer of 1 or more, and m represents an integer of 2 or more) ) And the like.

  Among these, n = 1 and m = 2 are preferable for separating the functions to be expressed in order to obtain the effects of the present invention, and among these, AB and ABA are preferable. In particular, those having a structure of AB are more preferable.

  Further, the molecular structure of the fluorine-containing block copolymer of the present invention may be any of linear, branched, radial or any combination thereof, and AB is preferred from the viewpoint of surface uneven distribution. .

Moreover, the molecular structure of the fluorine-containing block copolymer of the present invention may contain a repeating unit other than the repeating units constituting the above A and B. These may contain only one type or two or more types.
Although it does not specifically limit as repeating units other than the repeating unit which comprises the said A and B, As an example, the repeating unit which has a polymeric group is raised. As the polymerizable group, a known polymerizable group that can be cross-linked by a radical, acid or heat can be used. For example, a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), a methylol group, etc. In particular, a group containing an ethylenically unsaturated bond is preferable, a (meth) acryloyl group is more preferable, and (meth) acryloyl derived from glycidyl (meth) acrylate and 3,4-epoxy-cyclohexylmethyl (meth) acrylate The group is particularly preferred.

  Hereinafter, the A block having a hydroxyl group or an acid group and the B block having a fluorine atom will be described in detail.

(Block A)
The A block is a block having a hydroxyl group or an acid group. More specifically, the A block is a block composed of a repeating unit having a hydroxyl group or an acid group (a repeating unit derived from a monomer having a hydroxyl group or an acid group).
The kind of the acid group is not particularly limited, and a known acid group can be used, and examples thereof include a carboxyl group, a phosphoric acid group, a phenolic hydroxyl group, a thiol group, a sulfonic acid group, and a derivative group thereof. The derivative group is chemically derived from the above groups. For example, in the case of a carboxyl group, a base of a carboxyl group and an alkali metal, a base of a carboxyl group and an amine, and the like can be given.

  The A block is not particularly limited as long as it is composed of a repeating unit formed from a monomer having a hydroxyl group or an acid group, but from the viewpoint of developability and low reflectivity, the repeating represented by the following formula (A) It is preferably composed of units.

In formula (A), R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a single bond or a divalent linking group, and A ¹ represents a hydrogen atom, a hydroxyl group, a carboxyl group, or a phosphate group. Represents an acid group selected from a phenolic hydroxyl group or a thiol group, or a derivative thereof.

Hereinafter, the repeating unit represented by the formula (A) will be described.
In the repeating unit represented by the formula (A), R ¹ represents a hydrogen atom or an alkyl group. R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a hydrogen atom or a methyl group. Is particularly preferred.
L ¹ represents a single bond or a divalent linking group.
The divalent linking group is not particularly limited, and examples thereof include those having a total number of atoms of 60 or less. From the viewpoint of not inhibiting formation of a low refractive index layer by aggregation of fluorine atoms expressed by the B block described later, the total number of atoms is preferably 20 or less, more preferably 15 or less, and particularly preferably 10 or less.
Examples of the divalent linking group include an alkylene group, an arylene group, —NR ¹² —, —CONR ¹² —, —CO—, —CO ₂ —, SO ₂ NR ¹² —, —O—, —S—, — Examples thereof include a single group selected from the group consisting of SO ₂ — and a group in which two or more types are combined. R ¹² represents a hydrogen atom or a methyl group.

  As an alkylene group, a C1-C20 alkylene group is mentioned, for example, A C1-C10 alkylene group is preferable, A C1-C6 alkylene group is more preferable, A C1-C3 alkylene The group is particularly preferred. The alkylene group may be linear, branched or cyclic, and may contain a hetero atom.

  As an arylene group, a C6-C20 arylene group is mentioned, for example, It is preferable that it is a C6-C10 arylene group, and a phenylene group is especially preferable.

  The divalent linking group may have any of a cyclic structure and a chain (note that the chain includes a straight chain and a branched chain), but from the viewpoint of developability and low reflectivity. Therefore, it is preferably a chain, and more preferably a straight chain.

Preferable examples of the divalent linking group include an alkylene group which may contain an ester bond, —CONR ¹² —, —O— and the like. The alkylene group may contain a hetero atom.

Among them, L ¹ is preferably a single bond or a divalent linking group having a total number of atoms of 20 or less, more preferably a single bond or a linear divalent linking group having a total number of atoms of 10 or less. A linear alkylene group having a total number of atoms of 10 or less that may contain a single bond or an ester bond is more preferred.

A ¹ represents a hydrogen atom, a hydroxyl group, an acid group selected from a carboxyl group, a phosphate group, a phenolic hydroxyl group or a thiol group, or a derivative thereof. The case where A ¹ is a hydrogen atom is a form that can be taken when L ¹ represents a single bond, and the repeating unit represented by the formula (A) is acrylic acid or α-alkyl-substituted acrylic acid (for example, Methacrylic acid).
A ¹ is preferably non-hydrophobic from the viewpoint of more excellent developability, and therefore it may be a hydrogen atom, a hydroxyl group, an acid group selected from a carboxyl group, a phosphate group, or a thiol group, or a derivative group thereof. From the viewpoint of more excellent developability, a hydrogen atom, a carboxyl group or a phosphate group is more preferable, and a hydrogen atom or a carboxyl group is still more preferable.

  Commercially available monomers that can be the repeating unit represented by the formula (A) include HO-MS and HOA-MS manufactured by Kyoeisha Chemical Co., Ltd., Hosmer M manufactured by Unichemical Co., Ltd., Shin Nakamura Chemical Co., Ltd. NK ester CB36 manufactured by

  Specific examples of the repeating unit represented by the above formula (A) include structural units having the following structure. However, the present invention is not limited to these. In the following structural units, R represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. More preferably, a hydrogen atom or a methyl group is more preferable.

  In the fluorine-containing block copolymer, the ratio of the repeating units constituting the A block is preferably 5 to 80 mol%, more preferably 10 to 50 mol%, based on all repeating units in the fluorine-containing block copolymer. Preferably, 15 to 40 mol% is most preferable. When the ratio of the repeating unit constituting the A block is within the above range, it is effective in that the solubility in an organic solvent is good and the residual monomer is reduced.

(B block)
The B block is a block having a fluorine atom. More specifically, the B block is a block composed of a repeating unit having a fluorine atom (a repeating unit derived from a monomer having a fluorine atom). Compared to the random structure, the block structure promotes the aggregation of fluorine atoms and facilitates the formation of a hydrophobic field on the surface of the coating film. Therefore, it is composed of repeating units formed from monomers having fluorine atoms. In addition to increasing the selection range (option) of the unit structure, the selection range of the structure of the repeating unit other than the monomer having a fluorine atom is also increased.
The B block is not particularly limited as long as it is composed of a repeating unit formed from a monomer having a fluorine atom, but from the viewpoint of developability and low reflectivity, the repeating unit represented by the following formula (B) It is preferable that it is comprised.

In formula (B), R ² represents a hydrogen atom or an alkyl group, L ² represents a single bond or a divalent linking group, and R ^f represents a monovalent organic group containing a fluorine atom.

In the repeating unit represented by the formula (B), R ² represents a hydrogen atom or an alkyl group. R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a hydrogen atom or a methyl group. Particularly preferred.
L ² represents a single bond or a divalent linking group. However, when L ² represents a divalent linking group, it is preferable that L ² does not contain a fluorine atom.
Examples of the divalent linking group include an alkylene group, an arylene group, —NR ¹² —, —CONR ¹² —, —CO—, —CO ₂ —, SO ₂ NR ¹² —, —O—, —S—, — Examples thereof include a single group selected from the group consisting of SO ₂ — and a group in which two or more types are combined. R ¹² represents a hydrogen atom or a methyl group.
As the preferable range of alkylene and arylene groups are the same as preferred ranges of the groups described in the divalent linking group represented by L ¹ described above.

Among these, from the viewpoint of excellent developability and suppression of residues after lower development, L ² is preferably a single bond or an alkylene group, and moreover, from the viewpoint of having a wide design range of reflectance reduction, L ² is preferably a single bond or an alkylene group having 1 to 3 carbon atoms.

R ^f represents a monovalent organic group containing a fluorine atom.
Examples of the monovalent organic group containing a fluorine atom include an alkyl group substituted with a fluorine atom and an aryl group substituted with a fluorine atom.
The alkyl group substituted with a fluorine atom is preferably a linear, branched or cyclic alkyl group in which at least one hydrogen atom is substituted with a fluorine atom from the viewpoint of achieving both low reflection and developability. Furthermore, from the viewpoint of having a wide merit in the design range for reducing the reflectivity, the alkyl group substituted with a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. It is particularly preferred that
The number of carbon atoms of the alkyl group substituted with a fluorine atom is preferably 1-20, more preferably 1-10, and even more preferably 1-5.

In the aryl group substituted with a fluorine atom, the aryl group is preferably directly substituted with a fluorine atom. The aryl group substituted with a fluorine atom preferably has 6 to 20 carbon atoms, and more preferably a phenyl group.
The alkyl group substituted with a fluorine atom and the aryl group substituted with a fluorine atom may further have a substituent other than the fluorine atom.
As examples of the alkyl group substituted with a fluorine atom and the aryl group substituted with a fluorine atom, for example, paragraphs 0266 to 0272 of JP2011-100089A can be referred to, and the contents thereof are described in this specification. Incorporated.

Specific examples of the repeating unit represented by the formula (B) include the following, but the present invention is not limited thereto. In specific examples, X ¹ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. A hydrogen atom or a methyl group is preferable.

Among them, R ^f is a monovalent organic group having 1 to 3 total carbon atoms substituted with fluorine atoms from the viewpoint of excellent surface uneven distribution and achieving both excellent developability and low reflectivity. Of these, —C (CF ₃ ) ₂ is more preferable.

  Examples of commercially available monomers that can be the repeating unit represented by the formula (B) include HFIP-M and HFIP-A manufactured by Central Glass Co., Ltd., Biscoat 13F, and Biscoat 8FM manufactured by Osaka Organic Chemical Industry Co., Ltd. .

  In the fluorine-containing block copolymer, the proportion of the repeating units constituting the B block is preferably 20 to 95 mol%, more preferably 50 to 90 mol%, based on all repeating units in the fluorine-containing block copolymer. Preferably, 60 to 85 mol% is most preferable. When the ratio of the repeating units constituting the B block is within the above range, it is effective in terms of being excellent in low reflection.

  The ratio of the content of the repeating unit constituting the A block and the content of the repeating unit constituting the B block is not particularly limited, and the molar ratio (molar amount of the repeating unit constituting the A block / B block constituting The molar amount of the repeating unit is 1/99 to 99/1, and 15/85 to 85/15 is preferable in terms of more excellent developability and low reflectivity.

(Hydroxyl value, acid value)
The hydroxyl value and acid value of the fluorine-containing block copolymer are not particularly limited, but are often in the range of 10 to 200 mgKOH / g.
Especially, it is preferable that it is the range of 35-150 mgKOH / g, and it is more preferable that it is the range of 35-100 mgKOH / g.
When the hydroxyl value and acid value of the fluorine-containing block copolymer are in the above ranges, better low reflectivity, developability, and linearity can be achieved. That is, if the hydroxyl group value and acid value of the fluorine-containing block copolymer are 150 mgKOH / g or less, good low reflectivity, developability and linearity can be obtained, and if it is 35 mgKOH / g or more, alkali developability is obtained. Better.
Note that the hydroxyl value or acid value of the fluorine-containing block copolymer is within a predetermined range means that, for example, the hydroxyl value of the fluorine-containing block copolymer having a hydroxyl group is within a predetermined range, or an acid group is The acid value of the fluorine-containing block copolymer having is in a predetermined range.

  In the present invention, the hydroxyl value and acid value of the fluorine-containing block copolymer can be calculated from, for example, the average content of hydroxyl groups and the average content of acid groups in the polymer. Moreover, the polymer which has a desired hydroxyl value can be obtained by changing content of the structural unit containing the hydroxyl group which is a structural component of a fluorine-containing block copolymer. Regarding the acid value, a polymer having a desired acid value can be obtained by changing the content of the structural unit containing an acid group which is a constituent component of the fluorine-containing block copolymer.

The acid value can be calculated according to a known method.
The hydroxyl value can be calculated according to the method described in JIS K0070. That is, the hydroxyl value is represented by the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The same applies to the hydroxyl value of the phenolic hydroxyl group.

(Weight average molecular weight)
The weight average molecular weight (Mw: in terms of polystyrene) of the fluorinated block copolymer is preferably 5000 to 50000, and more preferably 5,000 to 15000. By setting it as the said range, it is excellent in surface uneven distribution property and developability and surface property are improved more.
The dispersity (weight average molecular weight / number average molecular weight) is preferably 1.80 to 3.00, and more preferably 1.80 to 2.00.
The GPC (gel permeation chromatography) method is based on the method described later in the Examples section.

The fluorine-containing block copolymer can be synthesized by a known method. In recent years, a method for producing a block copolymer by living radical polymerization has been developed, and various polymerization methods that can easily control the structure and molecular weight using the same have been developed. (JP 2013-237862)
Examples include atom transfer radical polymerization (ATRP method) in which a heavy metal such as copper, ruthenium, nickel, and iron, and a ligand that forms a complex therewith are used to polymerize a halogen compound as an initiation compound. The polymerization initiator to be used is not particularly limited as long as it has a function of initiating polymerization of monomers, and various block copolymers can be synthesized with a wide selection range of monomer species.

(Content in curable composition)
The content of the fluorine-containing block copolymer in the curable composition is preferably 1 to 50% by mass, more preferably 1 to 20% by mass with respect to the total solid content in the curable composition. More preferred is mass%.
The curable composition may contain one type of fluorine-containing block copolymer, or may contain two or more types. When a composition contains 2 or more types of fluorine-containing block copolymers, the total should just be in the said range.

(B) Polymerizable compound The polymerizable compound is preferably a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C or higher at normal pressure. In particular, the polymerizable compound preferably contains 2 to 10 ethylenically unsaturated groups, and is preferably a so-called polyfunctional polymerizable compound.
Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ester Ter, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and then (meth) acrylated after addition of ethylene oxide or propylene oxide, poly ((pentaerythritol) or poly (pentaerythritol) (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49- Examples include polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, as described in JP-B 43191 and JP-B 52-30490. it can. Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, those introduced as photocurable monomers and oligomers can also be used.
In addition, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol described in JP-A-10-62986 as general formula (1) and general formula (2) together with specific examples thereof and then (meth) acrylated Can also be used.
Of these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and structures in which these acryloyl groups are linked to dipentaerythritol via ethylene glycol and propylene glycol residues are preferred. These oligomer types can also be used.
Also, 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. Depending on the situation, a photopolymerizable composition having an extremely excellent photosensitive speed can be obtained. Commercially available products include urethane oligomers UAS-10, UAB-140 (trade name, manufactured by Nippon Paper Chemicals Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (trade name, Nippon Kasei). Medicinal Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
In addition, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned. The polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound. Examples of the tetrafunctional or higher acrylate compound include KAYARD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd.).

A polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.
When using in combination of 2 or more types of polymeric compounds, the combination aspect can be suitably set according to the physical property etc. which are requested | required of a composition. As one suitable combination aspect of a polymeric compound, the aspect which combines 2 or more types of polymeric compounds selected from the polyfunctional acrylate compound mentioned above is mentioned, for example, As an example, dipentaerythritol hexaacrylate is mentioned. And a combination of pentaerythritol triacrylate.
It is preferable that content of a polymeric compound is contained so that it may become 3 mass%-55 mass% with respect to the total solid in the curable composition of this invention, and 10 mass%-50 mass%. More preferred.

Moreover, the mass ratio (polymerizable compound / (fluorinated block copolymer)) of the polymerizable compound and the above-mentioned fluorine-containing block copolymer in the composition of the present invention is 0.1 to 20. preferable.
When the fluorine-containing block copolymer contained in the composition of the present invention is unevenly distributed on the surface, the lower layer of the coating film by the composition of the present invention has a high concentration of a polymerizable compound, a coloring material, and an initiator. Although it is difficult for the radiation of the time to reach the lower layer, even in this case, a value of 0.1 to 20 is preferable because the sensitivity of the composition is high and the composition can be cured uniformly. Further, the linearity of the pattern portion becomes better during pattern formation. The mass ratio to the fluorinated block copolymer (polymerizable compound / (fluorinated block copolymer)) is more preferably 0.5 to 15, and particularly preferably 1.0 to 10.

(C) Colorant Various known color pigments and color dyes can be used as the colorant.
As a coloring dye, for example, in the case of use in the manufacture of a color filter, chromatic dyes (chromatic dyes) such as R (red), G (green), and B (blue) that form color pixels of the color filter In addition, colorants described in paragraphs 0027 to 0200 of JP 2014-42375 can also be used. Moreover, the black dye (black dye) generally used for black matrix formation or light-shielding film system formation can be used.
From the viewpoint of constituting the two-layer structure shown in FIG. 1, it is preferable to use a color pigment.
Examples of the color pigment include chromatic pigments (chromatic pigments such as R (red), G (green), and B (blue)) that form the color pixels of the color filter if used in the manufacture of color filters. ), And black pigments (black pigments) generally used for forming a black matrix or forming a light-shielding film system.

  As the chromatic pigment, various conventionally known inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a finer one as much as possible, and considering the handling properties, the average primary particle diameter of the pigment is 0.01 μm. ˜0.1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable.

In addition, the average primary particle diameter of a pigment can be measured using a transmission electron microscope (Transmission Electron Microscope, TEM). As the transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
Maximum length of particle image obtained using transmission electron microscope (Dmax: maximum length at two points on the contour of the particle image) and maximum length vertical length (DV-max: two straight lines parallel to the maximum length) The shortest length connecting two straight lines perpendicularly) was measured, and the geometric mean value (Dmax × DV-max) ^1/2 was taken as the particle diameter. The particle diameter of 100 particles was measured by this method, and the arithmetic average value was taken as the average particle diameter to obtain the average primary particle diameter of the pigment. The “average primary particle size” in the examples of the present specification is also the same as the arithmetic average value.

  Examples of inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And metal oxides of the above metals.

[Pigment]
Examples of the pigment include conventionally known various inorganic pigments or organic pigments.
Examples of the inorganic pigment include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.
The following can be mentioned as an organic pigment. 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, 72,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc.,
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. ,
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
C. I. Pigment Green 7, 10, 36, 37, 58, 59
C. I. Pigment Violet 1,19,23,27,32,37,42
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80
These organic pigments can be used alone or in various combinations in order to increase color purity.

(Black pigment)
In the present invention, a black pigment can also be used as the pigment. Hereinafter, the black pigment will be described in more detail.
Various known black pigments can be used as the black pigment. In particular, carbon black, titanium black, titanium oxide, iron oxide, manganese oxide, graphite and the like are preferable from the viewpoint of realizing a high optical density in a small amount, and in particular, at least one of carbon black and titanium black is included. In particular, titanium black is preferred from the viewpoint of low absorption in the light absorption wavelength region of the initiator related to the curing efficiency by exposure. Specific examples of carbon black are commercially available C.I. I. Pigment Black 1 and other organic pigments C.I. I. Examples thereof include, but are not limited to, inorganic pigments such as CI Pigment Black 7.

(Other pigments)
In the present invention, pigments having infrared absorptivity other than the pigments described as black pigments can also be used.
As the pigment having infrared absorptivity, a tungsten compound, a metal boride and the like are preferable, and among them, a tungsten compound is preferable from the viewpoint of excellent light-shielding property at wavelengths in the infrared region. In particular, a tungsten compound is preferable from the viewpoint of excellent light absorption wavelength region of an initiator related to curing efficiency by exposure and excellent translucency in the visible light region.

  Two or more of these pigments may be used in combination, or may be used in combination with a dye described later. In order to adjust the color tone and improve the light-shielding property in a desired wavelength region, for example, chromatic pigments such as black, red, green, yellow, orange, purple, and blue described above for pigments having infrared light-shielding properties or black The aspect which mixes the dye mentioned later is mentioned. The pigment having black or infrared light shielding properties preferably contains a red pigment or dye and a purple pigment or dye, and the pigment having black or infrared light shielding properties particularly preferably contains a red pigment.

The black pigment preferably contains titanium black.
Titanium black is black particles containing titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and treatment with a water repellent material as disclosed in JP-A-2007-302836 is also possible. Is possible.

The specific surface area of titanium black is not particularly limited, but 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 becomes 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 titanium black commercial products include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade names: manufactured by Mitsubishi Materials Corporation), Tilack D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.

Furthermore, it is also preferable to contain titanium black as a dispersion containing titanium black and Si atoms.
In this embodiment, titanium black is contained as a dispersion in the composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more in terms of mass. Is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is more preferable.
Here, the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
In order to change the Si / Ti of the object to be dispersed (for example, 0.05 or more), the following means can be used.
First, titanium oxide and silica particles are dispersed using a disperser to obtain a dispersion, and this dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.), thereby mainly producing titanium black particles. A dispersed material containing Si and Ti as components can be obtained. The reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia.
Examples of titanium oxide include TTO-51N (trade name: manufactured by Ishihara Sangyo).
Examples of commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name: manufactured by Evonik).
A dispersing agent may be used for the dispersion of titanium oxide and silica particles. Examples of the dispersant include those described in the section of the dispersant described later.
The dispersion may be performed in a solvent. Examples of the solvent include water and organic solvents. What is demonstrated in the column of the organic solvent mentioned later is mentioned.
Titanium black whose Si / Ti is adjusted to 0.05 or more, for example, is produced by the method described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of Japanese Patent Application Laid-Open No. 2008-266045 can do.

The composition containing this dispersion by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a suitable range (for example, 0.05 or more). When a light shielding film is formed using an object, the residue derived from the composition outside the region where the light shielding film is formed is reduced. In addition, a residue contains the component derived from compositions, such as a titanium black particle and a resin component.
The reason why the residue is reduced is not yet clear, but the above-mentioned dispersed material tends to have a small particle size (for example, a particle size of 30 nm or less). By increasing the amount of components contained, the adsorptivity of the entire film with the underlying layer is reduced, and this is presumed to contribute to the improvement of the development removal property of the uncured composition (particularly titanium black) in the formation of the light shielding film Yes.
In addition, titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light. Therefore, the above-described dispersion containing titanium black and Si atoms (preferably Si / Ti is in terms of mass) The light-shielding film formed by using a material having a thickness of 0.05 or more exhibits excellent light-shielding properties.
The content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A. ).
Whether the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more with respect to the dispersion to be contained in the light-shielding film obtained by curing the composition Is determined using the method (2) described in paragraph 0035 of JP2013-249417A.

In the dispersion containing titanium black and Si atoms, the above-described titanium black can be used.
Further, in this dispersion, in addition to titanium black, for the purpose of adjusting dispersibility, colorability, etc., complex oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline You may use together the black pigment which consists of black etc. by combining 1 type (s) or 2 or more types as a to-be-dispersed body.
In this case, it is preferable that 50% by mass or more of the total dispersion is occupied by the dispersion made of titanium black.
In addition, in this dispersion, for the purpose of adjusting the light shielding property, other colorants (such as organic pigments and dyes) may be used in combination with titanium black as long as the effects of the present invention are not impaired. Good.
Hereinafter, materials used for introducing Si atoms into the dispersion will be described. When Si atoms are introduced into the dispersion, a Si-containing material such as silica may be used.
Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used.
Furthermore, if the particle size of the silica particles is smaller than the film thickness when the light shielding film is formed, the light shielding property is more excellent. Therefore, it is preferable to use fine particle type silica as the silica particles. Examples of the fine particle type silica include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.

Further, as the pigment, a tungsten compound and a metal boride can also be used.
Below, a tungsten compound and a metal boride are explained in full detail.
The curable composition of the present invention can use a tungsten compound and / or a metal boride.
Tungsten compounds and metal borides have high absorption with respect to infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, they have high light blocking properties (shielding properties) with respect to infrared rays) and absorption with respect to visible light. It is a low infrared shielding material. For this reason, the curable composition of this invention can form a pattern with high light-shielding property in an infrared region, and high translucency in a visible light region by containing a tungsten compound and / or a metal boride.
In addition, the tungsten compound and the metal boride have a small absorption even for light having a shorter wavelength than that in the visible range used for exposure of a high-pressure mercury lamp, KrF, ArF, and the like used for image formation. For this reason, by combining with the polymeric compound, alkali-soluble resin, and photoinitiator which are mentioned later, while being able to obtain the outstanding pattern, a development residue can be suppressed more in pattern formation.

Examples of the tungsten compound include a tungsten oxide compound, a tungsten boride compound, a tungsten sulfide compound, and the like, and a tungsten oxide compound represented by the following general formula (composition formula) (I) is preferable.
M _x W _y O _z (I)
M represents a metal, W represents tungsten, and O represents oxygen.
0.001 ≦ x / y ≦ 1.1
2.2 ≦ z / y ≦ 3.0

  As the metal of M, for example, alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and the like can be mentioned, and an alkali metal is preferable. 1 type or 2 types or more may be sufficient as the metal of M.

  M is preferably an alkali metal, more preferably Rb or Cs, and still more preferably Cs.

When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, generation of an impurity phase in the tungsten compound can be more reliably avoided. it can.
When z / y is 2.2 or more, chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide compound represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like. Cs _0.33 WO ₃ or Rb _0.33 WO ₃ is preferable, and Cs _0.33 WO ₃ is more preferable.

  The tungsten compound is preferably fine particles. The average particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. When the average particle diameter is in such a range, the tungsten fine particles are less likely to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding photoacid disturbance, the average particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average particle size of the tungsten fine particles is usually 1 nm or more.

  Two or more tungsten compounds can be used.

Tungsten compounds are commercially available, but when the tungsten compound is, for example, a tungsten oxide compound, the tungsten oxide compound is obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere. (See Japanese Patent No. 4096205).
The tungsten oxide compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

In addition, as the metal boride, lanthanum boride (LaB ₆ ), praseodymium boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), boride Titanium (TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), boride One or more of molybdenum (MoB ₂ , Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ), and the like can be exemplified, and lanthanum boride (LaB ₆ ) is preferable.

  The metal boride is preferably fine particles. The average particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and still more preferably 100 nm or less. When the average particle diameter is in such a range, it becomes difficult for the metal boride fine particles to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding photoacid disturbance, the average particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average particle size of the metal boride fine particles is usually 1 nm or more.

  Two or more metal borides can be used.

  The metal boride is available as a commercial product, for example, as a dispersion of metal boride fine particles such as KHF-7 manufactured by Sumitomo Metal Mining Co., Ltd.

〔dye〕
Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Tokuho 2592207, and U.S. Pat. No. 4,808,501. U.S. Pat. No. 5,667,920, U.S. Pat. No. 505950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-51115. The pigment | dye currently disclosed by 194828 gazette etc. can be used. When classified as chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.

In the present invention, a colorant having an absorption maximum in the wavelength range of 800 to 900 nm can be used as the colorant.
Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, and quaterylenes. Compounds, dithiol metal complex compounds, croconium compounds and the like.
As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squalium compound, and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP-A No. 2010-1111750 may be used. Incorporated. As the cyanine compound, for example, “functional pigment, Shin Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, Kodansha Scientific”, the contents of which are incorporated herein.

  As the colorant having the above spectral characteristics, compounds disclosed in paragraphs 0004 to 0016 of JP-A-07-164729, compounds disclosed in paragraphs 0027 to 0062 of JP-A-2002-146254, JP-A-2011-16483 It is also possible to use near-infrared absorbing particles that are composed of oxide crystallites containing Cu and / or P disclosed in paragraphs 0034 to 0067 of the publication and have a number average aggregate particle diameter of 5 to 200 nm.

In the present invention, the colorant having an absorption maximum in the wavelength range of 800 to 900 nm is preferably a pyrrolopyrrole compound. The pyrrolopyrrole compound may be a pigment or a dye, but a pigment is preferred because it is easy to obtain a curable composition capable of forming a film having excellent heat resistance.
For details of the pyrrolopyrrole compound, the description of paragraphs 0017 to 0047 of JP-A-2009-263614 can be referred to, and the contents thereof are incorporated in the present specification. Specific examples thereof include compounds described in paragraph numbers 0049 to 0058 of JP-A-2009-263614, and the contents thereof are incorporated in the present specification.

  In addition, dye multimers described in paragraphs 0027 to 0200 of JP-A-2014-199436 can also be suitably used. In addition, a salt-forming compound obtained by reacting a resin having a cationic group in the side chain described in JP-A-2011-242752 with paragraphs 0018 to 0078 and an anionic dye is preferably used as a dye multimer. Can do.

Furthermore, the curable composition of this invention may contain the extender as needed. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments can be used alone or in admixture of two or more. The amount of the extender is usually 0 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the colorant. In the present invention, the colorant and extender can be used by modifying their surface with a polymer in some cases.
In addition to black pigments or pigments that excel in light transmission in the visible light region and have a function of blocking light in the infrared light region, red, blue, yellow, green, purple, etc. as required The above-mentioned colored organic pigments or dyes may be included. When using in combination with colored organic pigments, or dyes and black pigments, or pigments that excel in light transmission in the visible wavelength range and have the ability to block light in the infrared wavelength range, use red pigments or dyes. Is preferably used in an amount of 1 to 40% by mass with respect to a black pigment or a pigment excellent in light transmittance in the visible wavelength region and excellent in the function of blocking light in the infrared wavelength range, Pigment Red 254 is preferable.

  The content of the colorant (particularly preferably black pigment) in the composition is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and more preferably 35 to 60% by mass with respect to the total solid content in the composition. % Is more preferable.

(D) (Meth) acrylic polymer having a hydroxyl group or an acid group The composition of the present invention contains a (meth) acrylic polymer having a hydroxyl group or an acid group (hereinafter also referred to as “polymer compound”). To do. The (meth) acrylic polymer is a compound different from the above-described fluorine-containing block copolymer.
The (meth) acrylic polymer having a hydroxyl group or an acid group can be added to the composition as a compound (dispersant) used for dispersing the colorant or as a binder. In the composition of the present invention, a (meth) acrylic polymer having a hydroxyl group or an acid group is preferably added as a dispersant, and a (meth) acrylic polymer dispersant having a hydroxyl group or an acid group, and a hydroxyl group or It is more preferable to use in combination with a (meth) acrylic polymer binder having an acid group.
The compound (dispersant) used for dispersing the colorant is used when the colorant is dispersed (for example, when preparing a dispersion of a pigment or a dye that is hardly soluble in a solvent). Corresponds to a compound that is added as a post-addition when the colorant is not dispersed (for example, a dye solution) or after the colorant is dispersed (for example, after the pigment dispersion or the dye liquid is prepared).
The (meth) acrylic polymer having a hydroxyl group or an acid group contributes to improving the dispersibility of the above-described coloring pigment such as titanium black, and also contributes to developability because the hydroxyl group or acid group is included in the structure. . Moreover, by using together with the fluorine-containing block copolymer mentioned above, the phase separation of the low refractive index layer and the colored layer is improved, and the low reflectivity is further improved.
In particular, the mass ratio of the (meth) acrylic polymer having a hydroxyl group or an acid group to the fluorine-containing block copolymer (the (meth) acrylic polymer having a hydroxyl group or an acid group / the fluorine-containing block copolymer) is 2 10 is preferable, 3-8 is more preferable, and 3-6 is more preferable. By adding a (meth) acrylic polymer having a hydroxyl group or an acid group to the fluorine-containing block copolymer in the above numerical range, the effect of the present invention can be further enhanced, and low reflectivity and developability. In addition, the surface property can be established with excellent quality.

  The polymer compound contains a repeating unit derived from a (meth) acrylate monomer as a main component, but may contain other repeating units as long as the effects of the present invention are not impaired. . The polymer compound preferably contains 50 mol% or more of a repeating unit derived from a (meth) acrylate monomer, more preferably 80 mol% or more, and even more preferably 90 mol% or more. .

(Hydroxyl value, acid value)
The hydroxyl value and acid value of the polymer compound are preferably 20 mgKOH / g or more. When the hydroxyl value and acid value of the polymer compound are 20 mgKOH / g or more, the alkali developability becomes better, and the pigment containing a black pigment or the like (particularly titanium black), or a dispersion containing titanium black and Si atoms. Sedimentation of the body can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the composition can be further improved.
The upper limit of the polymer compound hydroxyl value and acid value is not particularly limited, but if it is 160 mgKOH / g or less, pattern peeling during development when forming a colored layer can be more effectively suppressed.
The hydroxyl value and acid value of the polymer compound are more preferably in the range of 20 mgKOH / g to 140 mgKOH / g, and still more preferably in the range of 20 mgKOH / g to 120 mgKOH / g.
The hydroxyl value or acid value of the polymer compound is within a predetermined range, for example, whether the hydroxyl value of a polyacrylate polymer having a hydroxyl group (or a polymethacrylate polymer) is within a predetermined range, Or the acid value of the polyacrylate polymer (or polymethacrylate polymer) having an acid group is within a predetermined range.

  In the present invention, the hydroxyl value and acid value of the polymer compound can be calculated, for example, from the average content of hydroxyl groups and the average content of acid groups in the polymer compound. Moreover, the resin which has a desired hydroxyl value can be obtained by changing content of the structural unit containing the hydroxyl group which is a structural component of a high molecular compound. Regarding the acid value, a resin having a desired acid value can be obtained by changing the content of the structural unit containing an acid group which is a constituent component of the polymer compound.

The acid value can be calculated according to a known method.
The hydroxyl value can be calculated according to the method described in JIS K0070. That is, the hydroxyl value is represented by the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The same applies to the hydroxyl value of the phenolic hydroxyl group.

(Weight average molecular weight)
The weight average molecular weight of the polymer compound in the present invention is 4,000 as a polystyrene conversion value by GPC (gel permeation chromatography) method from the viewpoint of pattern peeling inhibition during development and developability when forming a colored layer. It is preferably 300 or more and 300 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferred.
In particular, when a polymer compound is introduced into the composition as a dispersant, the dispersibility is further improved by setting the weight average molecular weight to 10,000 or more and 50,000 or less.
The GPC method uses HLC-8020 GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).

  The content of the polymer compound in the composition is preferably from 1 to 70% by mass, more preferably from 5 to 50% by mass, with respect to the total solid content in the composition, from the point that the effects of the present application are remarkably obtained. 10 to 40% by mass is more preferable.

  In particular, when the polymer compound is introduced into the composition as a dispersant, the content of the polymer compound in the composition is 0.1 to 50 mass with respect to the total solid content in the composition. % Is preferable, 0.3 to 40% by mass is more preferable, and 0.5 to 30% by mass is further preferable from the viewpoint that the effects of the present application are remarkably obtained. By setting the content in the above range, the dispersibility is also improved.

  Hereinafter, for the (meth) acrylic polymer (polymer compound) having a hydroxyl group or an acid group, a dispersant (hereinafter also referred to as “polymer compound C”) and a binder (hereinafter also referred to as “polymer compound D”). Each of these forms is classified and explained.

(Polymer Compound C)
As the (meth) acrylic polymer dispersant (polymer compound C) having a hydroxyl group or an acid group, for example, a known pigment dispersant can be appropriately selected and used, for example, a modification having a hydroxyl group or an acid group. Examples thereof include poly (meth) acrylates and (meth) acrylic copolymers.
The polymer compound C can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer based on its structure.

The polymer compound C is adsorbed on the surface of a colorant such as a black pigment and a dispersion object such as a pigment used in combination as desired, and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.
On the other hand, the adsorptivity of the polymer compound C to these can be promoted by modifying the surface of titanium black or the above-mentioned dispersion material containing titanium black and Si atoms.

The polymer compound C preferably has a structural unit having a graft chain. In the present specification, “structural unit” is synonymous with “repeating unit”.
Since the polymer compound C having a structural unit having such a graft chain has an affinity for a solvent by the graft chain, it is excellent in dispersibility of a color pigment such as a black pigment and dispersion stability after aging. Is. In addition, since the composition has an affinity with a polymerizable compound or other resin that can be used in combination due to the presence of the graft chain, a residue is hardly generated by alkali development.
When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility is improved. On the other hand, when the graft chain is too long, the adsorptive power to a colored pigment such as a black pigment is lowered and the dispersibility tends to be lowered. For this reason, the graft chain preferably has a number of atoms excluding hydrogen atoms in the range of 40 to 10,000, more preferably a number of atoms excluding hydrogen atoms of 50 to 2000, and atoms excluding hydrogen atoms. More preferably, the number is 60 to 500.
Here, the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.

The graft chain preferably has a polymer structure.
Examples of the polymer structure include a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, and a polyether structure.
Examples of the polymer compound C include a modified poly (meth) acrylate having the polymer structure in the side chain. In order to improve the interaction between the graft chain and the solvent, thereby increasing the dispersibility, the polymer structure in the graft chain is preferably at least one of a polyester structure and a polyether structure, and is a polyester structure. It is preferable.

  The structure of the macromonomer having such a polymer structure as a graft chain is not particularly limited, but a macromonomer having a reactive double bond group can be preferably used.

  Corresponding to the structural unit having a graft chain of the polymer compound C, commercially available macromonomers suitably used for the synthesis of the polymer compound C include AA-6 (trade name, Toa Gosei Co., Ltd.), AA- 10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AW-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, Manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.), Blemmer PP-100 (trade name, NOF Corporation )), Blemmer PP-500 (trade name, manufactured by NOF Corporation), BREMMER PP-800 (trade name, manufactured by NOF Corporation), Blemmer PP-1000 (trade name, manufactured by NOF Corporation) ), Blemmer 55-PET-800 (trade name, manufactured by NOF Corporation), Blemmer P E-4000 (trade name, manufactured by NOF Corporation), BREMMER PSE-400 (trade name, manufactured by NOF Corporation), BREMMER PSE-1300 (trade name, manufactured by NOF Corporation), Blemmer 43PAPE- 600B (trade name, manufactured by NOF Corporation) is used. Among these, AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.) Bremermer PME-4000 (trade name, manufactured by NOF Corporation) and the like are used.

  The polymer compound C preferably includes a structural unit represented by any one of the following formulas (1) to (4) as a structural unit having a graft chain. The following formula (1A) and the following formula (2A) More preferably, it includes a structural unit represented by any of the following formula (3A), the following formula (3B), and the following (4).

In formulas (1) to ^{(4), W 1, W} 2, W 3, and ^{W 4} represents an oxygen atom.
In the formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms from the viewpoint of synthesis constraints. Further, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.

In Formula (1) to Formula (4), Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly limited in structure. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ , and Y ⁴ include the following (Y-1) to (Y-21) linking groups. . In the structure shown below, A and B each represent a binding site with the left terminal group and the right terminal group in Formulas (1) to (4). Of the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.

In the formulas (1) to (4), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, and specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. Is mentioned. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ , and Z ⁴ , those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms. Of these, a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is particularly preferable. The alkyl group contained in the alkoxy group may be linear, branched or cyclic.

In Formula (1)-Formula (4), n, m, p, and q are the integers of 1 to 500 each independently.
Moreover, in Formula (1) and Formula (2), j and k represent the integer of 2-8 each independently. J and k in Formula (1) and Formula (2) are preferably integers of 4 to 6, and most preferably 5, from the viewpoints of dispersion stability and developability.

In Formula (3), R ³ represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ³ may be the same as or different from each other.
In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure. R ⁴ preferably includes a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

Moreover, the high molecular compound C can have a structural unit which has the graft chain from which 2 or more types of structures differ. That is, the molecule of the polymer compound C may contain structural units represented by the formulas (1) to (4) having different structures, and in the formulas (1) to (4), n, When m, p, and q each represent an integer of 2 or more, in Formula (1) and Formula (2), j and k may include structures different from each other in the side chain, and Formula (3) In Formula (4), R ³ , R ⁴ and X ⁵ present in a molecule may be the same as or different from each other.

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

Wherein ^(1A), X ^1, Y 1, ^{Z 1} and n are as defined ^{X 1,} Y 1, ^{Z 1} and n in Formula (1), and preferred ranges are also the same. Wherein ^(2A), X ^2, Y 2, ^{Z 2} and m are as defined ^{X 2,} Y 2, ^{Z 2} and m in the formula (2), and preferred ranges are also the same.

  Moreover, as a structural unit represented by Formula (3), it is more preferable that it is a structural unit represented by following formula (3A) or Formula (3B) from a viewpoint of dispersion stability and developability.

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

  The polymer compound C more preferably has a structural unit represented by the formula (1A) as a structural unit having a graft chain.

  In the polymer compound C, the structural unit having a graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90 with respect to the total mass of the polymer compound C in terms of mass. % Is preferably included, and more preferably 5 to 30%. When the structural unit having a graft chain is contained within this range, the dispersibility of a colored pigment such as a black pigment (particularly titanium black particles) is high, and the developability when forming a colored layer is good.

  The polymer compound C preferably has a hydrophobic structural unit that is different from the structural unit having a graft chain (that is, does not correspond to the structural unit having a graft chain). However, in the present invention, the hydrophobic structural unit is a structural unit having no hydroxyl group or acid group (for example, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).

  The hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.

ClogP values are available from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.
A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B. Taylor and C.M. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. et al. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. et al. Leo. Calculating logPoch from structure. Chem. Rev. , 93, 1281-1306, 1993.

log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
logP = log (Coil / Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
When the logP value increases to a positive value across 0, the oil solubility increases. When the logP value increases to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating aqueous properties.

  The polymer compound C preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulas (i) to (iii) as hydrophobic structural units.

In the above formulas (i) to (iii), R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or a carbon atom number of 1-6. An alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.).
R ¹ , R ² , and R ³ are more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom or a methyl group. R ² and R ³ are particularly preferably a hydrogen atom.
X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.

L is a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (for example, arylene group) , Substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR ³¹ —, where R ³¹ Is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), or a combination thereof.

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for the carbon atom number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.

  6-20 are preferable, as for the carbon atom number of a bivalent aromatic group, 6-15 are more preferable, and 6-10 are still more preferable. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid. Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group, or heterocyclic group.

L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. Polyoxyethylene structure, - _(OCH 2 _CH 2) represented by n-, n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

Z is an aliphatic group (eg, alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (eg, aryl group, substituted aryl group, arylene group, substituted arylene group). , A heterocyclic group, or a combination thereof. These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR ³¹ —, wherein R ³¹ is an aliphatic group, an aromatic group. Group or heterocyclic group) or a carbonyl group (—CO—) may be contained.

The aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for the carbon atom number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4-cyclohexyl. A phenyl group and the like are included. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon ring, homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclic hydrocarbon ring such as tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [4 .4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have a hydroxyl group or an acid group as a substituent.

  6-20 are preferable, as for the carbon atom number of an aromatic group, 6-15 are more preferable, and 6-10 are still more preferable. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have a hydroxyl group or an acid group as a substituent.

The heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid. Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group does not have a hydroxyl group or an acid group as a substituent.

In the above formula (iii), R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms ( For example, a methyl group, an ethyl group, a propyl group, etc.), Z, or -LZ is represented. Here, L and Z are as defined above. As R < ⁴ >, R < ⁵ > and R < ⁶ >, a hydrogen atom or a C1-C3 alkyl group is preferable, and a hydrogen atom is more preferable.

In the present invention, as the monomer represented by the general formula (i), R ¹ , R ² , and R ³ are a hydrogen atom or a methyl group, and L is a single bond, an alkylene group, or an oxyalkylene structure. A compound in which X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
Further, as the monomer represented by the general formula (ii), R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group or an aromatic group. Is preferred. Further, as the monomer represented by the general formula (iii), R ⁴ , R ⁵ , and R ⁶ are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Certain compounds are preferred.

Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
As examples of typical compounds represented by formulas (i) to (iii), the compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Incorporated into.

  In the polymer compound C, the hydrophobic structural unit is preferably contained in a range of 10 to 90% and more preferably in a range of 20 to 80% with respect to the total mass of the polymer compound C in terms of mass. preferable. When the content is in the above range, sufficient pattern formation can be obtained.

The polymer compound C has a hydroxyl group or an acid group as a functional group capable of forming an interaction with a colored pigment such as a black pigment (particularly titanium black). When a hydroxyl group or an acid group is introduced into the polymer compound C, a structural unit having a hydroxyl group or an acid group may be introduced into the polymer compound C. In particular, by having an alkali-soluble group such as a carboxylic acid group as the acid group, the polymer compound C can be imparted with better developability for pattern formation by alkali development.
That is, by introducing an alkali-soluble group into the polymer compound C, in the composition of the present invention, the polymer compound C as a dispersant that contributes to the dispersion of a colored pigment such as a black pigment has alkali solubility. . Such a composition containing the polymer compound C has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
Moreover, when the high molecular compound C has a structural unit having a hydroxyl group or an acid group, the high molecular compound C becomes easily compatible with the solvent, and the coating property tends to be improved.
This is because a hydroxyl group or an acid group in a structural unit having a hydroxyl group or an acid group easily interacts with a colored pigment such as a black pigment, and the polymer compound C stably disperses the colored pigment such as a black pigment. This is presumed to be because the viscosity of the polymer compound C in which the colored pigments are dispersed is low and the polymer compound C itself is easily dispersed stably.

  However, the structural unit having a hydroxyl group or an acid group may be the same structural unit as the above-described structural unit having a graft chain or a different structural unit, but the structural unit having a hydroxyl group or an acid group is It is a structural unit different from the hydrophobic structural unit described above (that is, it does not correspond to the hydrophobic structural unit described above).

Examples of the acid group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and preferably a carboxylic acid Group, sulfonic acid group, and phosphoric acid group, and particularly preferred is a carboxylic acid group that has good adsorptive power to colored pigments such as black pigments and has high dispersibility. .
That is, the polymer compound C preferably further has a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound C may have one or more structural units having a hydroxyl group or an acid group.
The content of the structural unit having a hydroxyl group or an acid group in the polymer compound C is preferably 5 to 80% with respect to the total mass of the polymer compound C in terms of mass, and more preferably by alkali development. From the viewpoint of suppressing damage of image strength, it is 10 to 60%.

  Although how a hydroxyl group or an acid group is introduced into the polymer compound C in the present invention is not particularly limited, the polymer compound C is a single monomer represented by the following general formulas (iv) to (vi). It is preferable to have one or more structural units selected from structural units derived from the body.

In general formula (iv) to general formula (vi), R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon atom. An alkyl group having 1 to 6 numbers (for example, a methyl group, an ethyl group, a propyl group, etc.) is represented.
In general formula (iv) to general formula (vi), R ¹¹ , R ¹² and R ¹³ are more preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably Are each independently a hydrogen atom or a methyl group. In general formula (iv), R ¹² and R ¹³ are each particularly preferably a hydrogen atom.

X ₁ in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Y in the general formula (v) represents a methine group or a nitrogen atom.

Moreover, L < ₁ > in general formula (iv)-general formula (v) represents a single bond or a bivalent coupling group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene group and substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino bond (—NR ³¹ ′ — Here, R ³¹ ′ includes an aliphatic group, an aromatic group, or a heterocyclic group), a carbonyl bond (—CO—), or a combination thereof.

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for the carbon atom number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

  6-20 are preferable, as for the carbon atom number of a bivalent aromatic group, 6-15 are more preferable, and 6-10 are the most preferable. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid. Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.

L ₁ is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L ₁ may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. Polyoxyethylene structure, - _(OCH 2 _CH 2) represented by n-, n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In General Formula (iv) to General Formula (vi), Z ₁ represents a hydroxyl group or an acid group, and more preferably a carboxylic acid group.

In the general formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (for example, , methyl group, ethyl group, propyl group, etc.), - represents a _{Z 1,} or _-L 1 -Z _1. Wherein _{L 1} and _{Z 1} are the same meaning as _{L 1} and _{Z 1} in the above, it is the preferable examples. R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

In the present invention, as the monomer represented by the general formula (iv), R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom or a methyl group, and L ₁ is an alkylene group or an oxyalkylene structure. A compound in which X ₁ is an oxygen atom or an imino group and Z ₁ is a carboxylic acid group is preferable.
Further, as the monomer represented by the general formula (v), R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is methine. Compounds that are groups are preferred.
Furthermore, as the monomer represented by the general formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom or a methyl group, and L ₁ is a single bond or an alkylene group, A compound in which Z is a carboxylic acid group is preferred.

Below, the typical example of the monomer (compound) represented by general formula (iv)-general formula (vi) is shown.
Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride, Examples include acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, and 4-vinylbenzoic acid.

Furthermore, for the purpose of improving various performances such as image strength, the polymer compound C has a structural unit having a graft chain, a hydrophobic structural unit, and a hydroxyl group or an acid group as long as the effects of the present invention are not impaired. Other structural units different from the structural units and having various functions (for example, structural units having a functional group having affinity with the dispersion medium used in the dispersion) may be further included.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
The polymer compound C can use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or more based on the total mass of the polymer compound C in terms of mass. % Or less, and particularly preferably 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.

  The polymer compound C can be synthesized based on a known method, and examples of the solvent used in the synthesis of the polymer compound C include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene. Glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, Examples include toluene, ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.

Specific examples of the polymer compound C that can be used in the present invention include “EFKA 4400 to 4402 (modified polyacrylate) manufactured by EFKA Corporation,“ Polyflow No. 50E and No. 300 (acrylic copolymer) ”manufactured by Ajinomoto Fan Techno Co., Ltd. Etc.
These polymer compounds C may be used alone or in combination of two or more.

  As specific examples of the polymer compound C, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated herein.

  In the composition of the present invention, when a (meth) acrylic polymer having a hydroxyl group or an acid group is contained as a dispersant (polymer compound C), the content of the polymer compound C is the total solid content of the composition. On the other hand, 0.1-50 mass% is preferable and 0.5-30 mass% is more preferable.

In addition to the polymer compound C described above, a graft copolymer of paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 of US2011 / 0124824) can be used as the dispersant, These contents can be incorporated and are incorporated herein.
In addition to the above, it has a side chain structure in which acidic groups in paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding to paragraphs 0075 to 0133 of US 2011/0279759) are bonded via a linking group. Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.

(Polymer Compound D)
Examples of the (meth) acrylic polymer binder (polymer compound D) having a hydroxyl group or an acid group include a modified poly (meth) acrylate having a hydroxyl group or an acid group, a (meth) acrylic copolymer, and the like. Can do.
As the polymer compound D, it is also preferable to use a polymer having a structural unit having a graft chain and a structural unit having a hydroxyl group or an acid group (alkali-soluble group).
The definition of the structural unit which has a graft chain is synonymous with the structural unit which has the graft chain which the dispersing agent mentioned above has, and its suitable range is also the same.
Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. Particularly preferred are carboxylic acid groups.

  The structural unit having a hydroxyl group or an acid group preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulas (vii) to (ix).

In the general formula (vii) to general formula (ix), R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon atom. An alkyl group having a number of 1 to 6 (for example, methyl group, ethyl group, propyl group, etc.)
In general formula (vii) to general formula (ix), R ²¹ , R ²² , and R ²³ are more preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably Are each independently a hydrogen atom or a methyl group. In general formula (vii), R ²¹ and R ²³ are each particularly preferably a hydrogen atom.

X ₂ in the general formula (vii) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Y in the general formula (viii) represents a methine group or a nitrogen atom.

Moreover, L < ₂ > in general formula (vii)-general formula (ix) represents a single bond or a bivalent coupling group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene group and substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino bond (—NR ⁴¹ ′ — Here, R ⁴¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), or a combination thereof.

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for the carbon atom number of an aliphatic group, 1-15 are more preferable, and 1-10 are still more preferable. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

  6-20 are preferable, as for the carbon atom number of a bivalent aromatic group, 6-15 are more preferable, and 6-10 are the most preferable. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ⁴² , where R ⁴² is a fatty acid. Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.

L ₂ is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L ₂ may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) n—, and n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In General Formula (vii) to General Formula (ix), Z ₂ is a hydroxyl group or an acid group, and is preferably a carboxylic acid group.

In the general formula (ix), R ²⁴ , R ²⁵ , and R ²⁶ are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (for example, , methyl group, ethyl group, propyl group, etc.), - represents a _{Z 2,} or _-L 2 -Z _2. Here _{L 2} and _{Z 2} has the same meaning as _{L 2} and _{Z 2} in the above, and preferred examples are also the same. R ²⁴ , R ²⁵ , and R ²⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

In the present invention, as the monomer represented by the general formula (vii), R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom or a methyl group, and L ₂ is an alkylene group or an oxyalkylene structure. A compound in which X ₂ is an oxygen atom or an imino group and Z ₂ is a carboxylic acid group is preferable.
Further, as the monomer represented by the general formula (vii), R ²¹ is a hydrogen atom or a methyl group, L ₂ is an alkylene group, Z ₂ is a carboxylic acid group, and Y is methine. The group is preferably a compound.
Furthermore, as the monomer represented by the general formula (ix), a compound in which R ²⁴ , R ²⁵ , and R ²⁶ are each independently a hydrogen atom or a methyl group and Z ₂ is a carboxylic acid group is preferable.

  The polymer compound D can be synthesized by the same method as that for the pigment dispersant having a structural unit having a graft chain described above.

In particular, among the polymer compounds D, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomer as required] copolymer, and [allyl (meth) acrylate / (meth) acrylic] The acid / other addition-polymerizable vinyl monomer as required] copolymer is preferable because of its excellent balance of film strength, sensitivity and developability.
Examples of commercially available products include Acrybase FF-187, FF-426 (manufactured by Fujikura Kasei Co., Ltd.), AcryCure-RD-F8 (Nippon Shokubai Co., Ltd.), and Cyclomer P (ACA) 230AA manufactured by Daicel Ornex Co., Ltd. Is mentioned.

  The polymer compound D may have one or more structural units having a hydroxyl group or an acid group.

The polymer compound D can also be used as a colorant dispersant. Moreover, you may use together with the high molecular compound C.
The content of the structural unit having a hydroxyl group or an acid group is preferably 5 to 95%, in terms of mass, with respect to the total mass of the binder polymer, and more preferably from the viewpoint of suppressing damage of image strength due to alkali development. From 10 to 90%.

  In the composition of the present invention, when a (meth) acrylic polymer having a hydroxyl group or an acid group is contained as a binder (polymer compound D), the content of the polymer compound D is based on the total solid content of the composition. 0.1 to 30% by mass is preferable, and 0.3 to 25% by mass is more preferable.

<Other optional components>
In the composition of this invention, other components other than each main component mentioned above may be contained.
Hereinafter, various optional components will be described in detail.

(Polymerization initiator)
The composition of the present invention may contain a polymerization initiator.
There is no restriction | limiting in particular as a polymerization initiator, It can select suitably from well-known polymerization initiators, For example, what has photosensitivity (what is called a photoinitiator) is preferable.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. 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 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds 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 curable composition of the present invention is used for the production of a light-shielding film of a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is important that it is developed without any problems. 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, and the amount of photopolymerization initiator added must be kept low. Therefore, in view of 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 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. In particular, an oxime initiator is preferable because it has high sensitivity and high polymerization efficiency, can be cured regardless of the color material concentration, and can be easily designed with a high color material concentration. In particular, when the curable composition of the present invention is used, since the fluorine-containing block copolymer is unevenly distributed on the surface, the color material in the lower layer of the formed layer may be high in concentration. It is preferable because it can be cured regardless of the concentration, and it is easy to design a high color material concentration.
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-propionyloxyimibutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane 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, JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166.
IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used as commercial products. TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (made by ADEKA) can also be used.

Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904, in which an oxime is linked to the carbazole N position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292209, in which a nitro group is introduced into the dye moiety, a ketoxime compound described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule A compound described in U.S. Pat. No. 7,556,910, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like 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 N—O bond of the oxime 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 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 general formula (OX-1), as a bivalent organic group represented by A, a C1-C12 alkylene group, a cycloalkylene group, and an alkynylene group are preferable. 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 2013-164471 A ( C-3). This content is incorporated herein.

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

In 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, and 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 Represents an atom or a hydroxyl group, and 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 4.

In the above formulas (1) and (2), R ¹ and R ² are preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl, cyclohexyl group or 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 the oxime compound 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 a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. 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.
You may use the photoinitiator used for this invention in combination of 2 or more type as needed.

  As for content of a polymerization initiator, 0.1-50 mass% is preferable with respect to the total solid of a curable composition, More preferably, it is 0.5-30 mass%, More preferably, it is 1-20 mass%. is there. Within this range, better sensitivity and pattern formability can be obtained. The curable composition of the present invention may contain only one type of polymerization initiator or two or more types of polymerization initiators. When two or more types are included, the total amount is preferably within the above range.

  The content of the polymerization initiator in the composition of the present invention is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, based on the total solid content in the composition, More preferably, it is 1-10 mass%.

〔Silane coupling agent〕
The composition of the present invention may contain a silane coupling agent.
A silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. Note that a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
In order to improve the adhesion between the substrate and the cured film, the silane coupling agent preferably does not contain a fluorine atom and a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded). Includes silicon atoms (excluding silicon atoms bonded with hydrolyzable groups), alkylene groups substituted with silicon atoms, straight chain alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms Desirably not.

The silane coupling agent preferably has a group represented by the following formula (Z). * Represents a bonding position.
Formula (Z) * -Si- (R _Z1 ) ₃
In the formula (Z), R _Z1 represents a hydrolyzable group, and the definition thereof is as described above.

The silane coupling agent preferably has one or more curable functional groups selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group. The curable functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group.
In addition, a radically polymerizable group is also mentioned as a suitable aspect of the curable functional group contained in the said silane coupling agent.

  The molecular weight of the silane coupling agent is not particularly limited, and is preferably 100 to 1000 from the viewpoint of handleability, and is preferably 270 or more and more preferably 270 to 1000 in terms of more excellent effects of the present invention.

One preferred embodiment of the silane coupling agent is a silane coupling agent X represented by the formula (W).
Formula _{(W) R Z2 -Lz-Si-} (R Z1) 3
R _z1 represents a hydrolyzable group, and the definition is as described above.
R _z2 represents a curable functional group, the definition is as described above, and the preferred range is also as described above.
Lz represents a single bond or a divalent linking group. If Lz represents a divalent linking group, the divalent As the linking group, an alkylene group optionally substituted with a halogen atom, an arylene group optionally halogen atoms substituted, -NR 12 ^{-, -} CONR _{^{12 -, - CO -, -}} CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof. Especially, at least 1 sort (s) selected from the group which consists of the alkylene group which the C2-C10 halogen atom may substitute, and the arylene group which the C6-C12 halogen atom may substitute, or , At least selected from the group consisting of these groups and —NR ¹² —, —CONR ¹² —, —CO—, —CO ₂ —, SO ₂ NR ¹² —, —O—, —S—, and SO ₂ —. A group consisting of a combination with one kind of group is preferable, an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms, —CO ₂ —, —O—, —CO—, —CONR ¹² —, or A group consisting of a combination of these groups is more preferred. Here, R ¹² represents a hydrogen atom or a methyl group.

  As the silane coupling agent X, N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-trimethoxy Silane (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 (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (trade name manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-503), glycidoxyoctyltrimethoxysilane (trade name KBM-48, manufactured by Shin-Etsu Chemical Co., Ltd.) 3), and the like.

As another preferred embodiment of the silane coupling agent, a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule and having a hydrolyzable group bonded to the silicon atom is provided. Can be mentioned.
The silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different. Atoms and substituents that can be bonded are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an alkyl group and / or an aryl group, a silyl group Group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group, and the like. These substituents further include amino groups, halogen atoms, sulfonamide groups, which can be substituted with silyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, thioalkoxy groups, alkyl groups and / or aryl groups, It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxyl group, a salt thereof, a sulfo group, or a salt thereof.
Note that at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above.
The silane coupling agent Y may contain a group represented by the formula (Z).

The silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is used as a substituent. It preferably has at least one organic group. The amino group structure may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may exist as a substituted amino group such as aniline.
Here, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent, and examples of the substituent that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, and a sulfonamide. Group, alkoxycarbonyl group, carbonyloxy group, amide group, urea group, alkyleneoxy group ammonium group, alkylammonium group, carboxyl group, or a salt thereof, sulfo group and the like.
Moreover, it is preferable that the nitrogen atom is couple | bonded with the curable functional group through arbitrary organic coupling groups. Preferred examples of the organic linking group include the above-described nitrogen atom and a substituent that can be introduced into the organic group bonded thereto.

The definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above.
The silane coupling agent Y only needs to have at least one curable functional group in one molecule, but it is also possible to adopt an embodiment having two or more curable functional groups, sensitivity, stability. From the viewpoint, it is preferable to have 2 to 20 curable functional groups, more preferably 4 to 15 and most preferably 6 to 10 curable functional groups in the molecule.

  The molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, but include the above-described ranges (preferably 270 or more).

The content of the silane coupling agent in the composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on the total solid content in the composition. 0-6 mass% is further more preferable.
Moreover, it is preferable that the mass ratio of the silane coupling agent in a composition and the fluorine-containing block copolymer mentioned above is 0.1-20, and 0.2 from a viewpoint of making low reflectance and linearity compatible. It is more preferable that it is -15, and it is especially preferable that it is 0.3-10.

  The composition of the present invention may contain one silane coupling agent or two or more silane coupling agents. When a composition contains 2 or more types of silane coupling agents, the sum should just be in the said range.

〔resin〕
The composition of the present invention preferably contains a resin. The resin does not include the above-described fluorine-containing block copolymer, silane coupling agent, (meth) acrylic polymer having a hydroxyl group or an acid group. That is, the resin is a resin different from the fluorine-containing block copolymer, the silane coupling agent, the (meth) acrylic polymer having a hydroxyl group or an acid group.
Examples of the resin include a binder polymer (hereinafter sometimes referred to as an alkali-soluble resin). In addition, the alkali-soluble resin mentioned later may be contained as a pigment dispersant.

(Binder polymer)
The composition of the present invention may contain a binder polymer.
As the binder polymer, a linear organic polymer is preferably used. 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. Among these, as the binder polymer, an alkali-soluble resin (a resin having a group that promotes alkali-solubility) is particularly preferable.
The binder polymer is a linear organic high molecular polymer, and an alkali-soluble resin having at least one group that promotes alkali solubility in a molecule (preferably a molecule having a styrene copolymer as a main chain). It can be suitably selected from the inside. From the viewpoint of heat resistance, polyhydroxystyrene resins and polysiloxane resins are preferred.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. The group is soluble in an organic solvent and developed with a weak alkaline aqueous solution. What is possible is preferred. These acid groups may be used alone or in combination of two or more.

Examples of the binder 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, JP-B-54-25957, Those described in Kaisho 54-92723, JP-A-59-53836, and JP-A-59-71048, that is, resins having a carboxyl group alone or copolymerized, having acid anhydrides Examples thereof include resins obtained by hydrolyzing, half-esterifying, or half-amidating acid anhydride units by copolymerizing monomers alone or by copolymerization, and epoxy acrylates obtained by modifying epoxy resins with unsaturated monocarboxylic acids and acid anhydrides. Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and examples of monomers having an acid anhydride include maleic anhydride. An acid etc. are mentioned. Similarly, an acidic cellulose derivative having a carboxylic acid group in the side chain is also exemplified. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in each of publications such as European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463 has an excellent balance of film strength and developability. It is preferable.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

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

  The content of the binder polymer in the composition of the present invention is preferably 0.1 to 30% by mass and more preferably 0.3 to 25% by mass with respect to the total solid content of the composition.

〔solvent〕
The composition of the present invention may contain a solvent.
Examples of the solvent include water and organic solvents.
Examples of organic solvents include, for example, 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, cyclopentanone, 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 Nomethyl 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, acetic acid Examples include, but are not limited to, ethyl, butyl acetate, methyl lactate, and ethyl lactate.

A solvent may be used individually by 1 type and may be used in combination of 2 or more type.
When two or more solvents are used in combination, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, It is composed of two or more selected from the group consisting of 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
As a quantity of the solvent contained in the composition of this invention, it is preferable that it is 10-90 mass% with respect to the total mass of a composition, and it is more preferable that it is 20-85 mass%.

[Others]
The composition of the present invention may contain an ultraviolet absorber. Thereby, the shape of a pattern can be made more excellent (fine).
As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. As specific examples of these, compounds of paragraphs 0137 to 0142 (corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
In addition, a diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) is also preferably used.
Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP 2012-32556 A.
The composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is preferably 0.001 to 15% by mass relative to the total solid content of the composition. 0.01 to 10 mass% is more preferable, and 0.1 to 5 mass% is still more preferable.

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. Here, the fluorine-containing block copolymer of the present invention is not included in the surfactant. In particular, the composition of the present invention can further improve the uniformity of coating thickness and the liquid-saving property because the liquid property (particularly fluidity) is further improved by containing a fluorine-based surfactant. it can.
Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781F (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (above, manufactured by Asahi Glass Co., Ltd.).
Here, the fluorine-containing block copolymer of the present invention is not included in the above-mentioned fluorine-based surfactant.
Specific examples of other surfactants include, for example, surfactants described in paragraphs 0174 to 0177 of JP2013-249417A, the contents of which are incorporated herein.
Only one type of surfactant may be used, or two or more types may be combined.
0.001-2.0 mass% is preferable with respect to the total mass of a composition, and, as for the addition amount of surfactant, 0.005-1.0 mass% is more preferable.

In addition to the above components, the following components may be further added to the composition of the present invention. Examples include sensitizers, co-sensitizers, cross-linking agents, curing accelerators, fillers, thermosetting accelerators, polymerization inhibitors, plasticizers, diluents, sensitizers, and the like. Adhesion promoters and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) These known additives may be added as necessary.
These components include, for example, paragraph numbers 0183 to 0228 of JP2012-003225A (corresponding US Patent Application Publication No. 2013/0034812 [0237] to [0309]), JP2008-250074. Paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, paragraph numbers 0159 to 0184 of JP 2013-195480 A, and the like can be referred to, and the contents thereof are incorporated in the present specification. .

  The solid content concentration of the composition of the present invention is preferably 5 to 50% by mass, and more preferably 15 to 40% by mass in terms of the balance between the thickness of the formed colored layer and the light shielding property.

<Method for preparing composition>
The composition of the present invention can be prepared by mixing the above-described various components by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser).
The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, a filter made of fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon, polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP), and the like can be given. Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The filter has a pore size of about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and still more preferably 0.3 to 0.0 μm. 7 μm. By setting it within this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filtration clogging of the pigment.
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. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering. 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. (formerly Japan 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. The pore size of the second filter is suitably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm.

<Hardened film and manufacturing method thereof>
A cured film can be formed by using the composition described above.
The cured film to be formed is, as described with reference to FIG. 1 described above, a coating layer formed by including a colored layer (lower layer) containing a colorant (particularly a black pigment) and a fluorine-containing block copolymer. It has a two-layer structure with (upper layer). In addition, a coating layer is a layer normally arrange | positioned on the opposite side (air side) from the board | substrate in the cured film arrange | positioned on a board | substrate.
The colored layer mainly contains a colorant such as the black pigment described above.
A coating layer is a layer formed mainly by the fluorine-containing block copolymer unevenly distributed in the surface vicinity of the coating film obtained by apply | coating a composition. In the coating layer, the fluorine-containing block copolymer may react with other components (for example, a polymerizable compound). The coating layer does not contain a colorant.
The refractive index of the cured film is preferably lower than the refractive index of the colored layer.

The thickness of the cured film is not particularly limited, but is preferably 0.2 to 25 μm, more preferably 1.0 to 10 μm, from the viewpoint that the effect of the present invention is more excellent.
The above thickness is an average thickness, and is a value obtained by measuring the thicknesses of five or more arbitrary points of the cured film and arithmetically averaging them.

Although the manufacturing method in particular of a cured film is not restrict | limited, The method of apply | coating the curable composition mentioned above on a board | substrate, forming a coating film, performing a hardening process with respect to a coating film, and manufacturing a cured film is mentioned. .
The method of the curing treatment is not particularly limited, and examples thereof include a photocuring treatment or a thermosetting treatment, and a photocuring treatment (particularly a curing treatment by irradiation with actinic rays or radiation) is preferable from the viewpoint of easy pattern formation. .
The type of substrate used is not particularly limited. In particular, when a cured film is disposed in a solid-state imaging device, various members in the solid-state imaging device (for example, an infrared light cut filter, an outer peripheral portion of a solid-state imaging device, an outer peripheral portion of a wafer level lens, a solid-state imaging) The element back surface etc. are mentioned preferably.

A preferred embodiment in the case of producing a patterned cured film is a step of applying a composition of the present invention on a substrate by spin coating to form a composition layer (hereinafter referred to as “composition layer forming step” as appropriate). Abbreviated), a step of exposing the composition layer by irradiation with actinic rays or radiation (hereinafter abbreviated as “exposure step” as appropriate), and a cured film obtained by alkali development of the exposed composition layer. And a step of forming (hereinafter abbreviated as “development step” where appropriate).
Specifically, the composition of the present invention is applied onto a substrate directly or via another layer by spin coating to form a composition layer (composition layer forming step), and through a predetermined mask pattern. Then, exposure is performed by irradiating actinic rays or radiation, and only the coating film portion irradiated with light is cured (exposure process), and development is performed with an alkaline developer (development process), thereby producing a patterned cured film. be able to.
Hereinafter, each process in the said aspect is demonstrated.

[Composition layer forming step]
In the composition layer forming step, a composition layer is formed by applying the composition of the present invention on a substrate.
The type of the substrate is not particularly limited, but when a cured film is disposed in the solid-state imaging device, for example, various members in the solid-state imaging device (for example, infrared light cut filter, outer peripheral portion of the solid-state imaging device, wafer level lens) And the like, and the like.
As a coating method of the composition of the present invention on the substrate, various coating methods such as spin coating, slit coating, ink jet method, spray coating, spin coating, cast coating, roll coating, screen printing method, etc. are applied. However, spin coating is particularly preferred.
The composition coated on the substrate is usually dried at 70 ° C. to 110 ° C. for about 2 minutes to 4 minutes to form a composition layer.

[Exposure process]
In the exposure step, the composition layer formed in the composition layer forming step is exposed by irradiating actinic rays or radiation through a mask, and only the coating film portion irradiated with the light is cured.
The exposure is preferably performed by irradiation with radiation. 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 preferred as a light source. The irradiation intensity is preferably 5 mJ / cm ² or more 1500 mJ / cm ² or less, 10 mJ / cm ² or more 1000 mJ / cm ² or less being more preferred.

[Development process]
Subsequent to the exposure step, development processing (development step) is performed to elute the light non-irradiated portion in the exposure step into the developer. Thereby, only the photocured part remains.
As the developer, it is desirable to use an organic alkali developer. 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 alkaline aqueous solution include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate as the inorganic developer, ammonia water, ethylamine, diethylamine as the organic alkali developer. , Dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4 , 0] -7-undecene and the like, an alkaline aqueous solution in which the concentration is 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass, is mentioned. It is. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution. In the case of using a developer composed of such an alkaline aqueous solution, it is generally washed (rinsed) with pure water after development.

  In addition, after performing a composition layer formation process, an exposure process, and a image development process, you may implement the hardening process which hardens | cures the formed pattern-shaped light shielding film by heating and / or exposure as needed.

<Infrared light cut filter with light shielding film, solid-state imaging device>
When a black pigment is used as the colorant, the above-described cured film can be suitably applied as a so-called light shielding film. Such a light shielding film can be suitably applied to a solid-state imaging device.
In the following, a first embodiment of a solid-state imaging device having a light shielding film of the present invention will be described in detail.
As shown in FIGS. 2 and 3, the solid-state imaging device 2 includes a CMOS sensor 3 as a solid-state imaging device, a circuit board 4 on which the CMOS sensor 3 is mounted, and a ceramic ceramic substrate 5 that holds the circuit board 4. And. The solid-state image pickup device 2 is held on a ceramic substrate 5, an IR cut filter 6 that cuts infrared light (IR) toward the CMOS sensor 3, a photographing lens 7, and a lens holder 8 that holds the photographing lens 7. And a holding cylinder 9 that holds the lens holder 8 movably. Further, instead of the CMOS sensor 3, a CCD sensor or an organic CMOS sensor may be provided.
The ceramic substrate 5 has an opening 5 a into which the CMOS sensor 3 is inserted, has a frame shape, and surrounds the side surface of the CMOS sensor 3. In this state, the circuit board 4 on which the CMOS sensor 3 is mounted is fixed to the ceramic substrate 5 with an adhesive (for example, an epoxy adhesive, the same applies hereinafter). Various circuit patterns are formed on the circuit board 4.

In the IR cut filter 6, a reflection film that reflects infrared light is formed on a plate-like glass or blue glass, and the surface on which the reflection film is formed becomes the incident surface 6a. The IR cut filter 6 is formed in a size slightly larger than the opening 5a, and is fixed to the ceramic substrate 5 with an adhesive so as to cover the opening 5a.
A CMOS sensor 3 is disposed behind the photographing lens 7 (downward in FIGS. 3 and 4), and an IR cut filter 6 is disposed between the photographing lens 7 and the CMOS sensor 3. The subject light enters the light receiving surface of the CMOS sensor 3 through the photographing lens 7 and the IR cut filter 6. At this time, the infrared light is cut by the IR cut filter 6.
The circuit board 4 is connected to a control unit provided in an electronic device (for example, a digital camera) on which the solid-state imaging device 2 is mounted, and power is supplied from the electronic device to the solid-state imaging device 2. In the CMOS sensor 3, a large number of color pixels are two-dimensionally arranged on the light receiving surface, and each color pixel photoelectrically converts incident light and accumulates generated signal charges.

  As shown in FIGS. 3 and 4, the light shielding film (light shielding layer) 11 described above is arranged over the entire circumference at the end of the incident surface 6 a of the IR cut filter 6, and infrared light with a light shielding film is provided. A cut filter is formed. The reflected light R1 emitted from the photographing lens 7 and reflected by the front surface (the upper surface in FIGS. 3 and 4) of the ceramic substrate 5 is incident on the CMOS sensor 3 after being repeatedly reflected and refracted in the device, When the reflected light R2 reflected from the inner wall surface of the lens holder 8 emitted from the lens 7 enters the CMOS sensor 3, flare occurs in the captured image. The light shielding film 11 shields harmful light such as reflected light R <b> 1 and R <b> 2 toward the CMOS sensor 3. The light shielding film 11 is applied by, for example, spin coating or spray coating. 3 and 4, the thickness of the light shielding film 11 is exaggerated.

FIG. 5 shows a solid-state imaging device 20 according to the second embodiment. In addition, the same code | symbol is attached | subjected to the structural member similar to the thing of 1st Embodiment, and the detailed description is abbreviate | omitted.
The solid-state imaging device 20 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9. The above-described light shielding film (light shielding layer) 21 is formed on the side end face of the IR cut filter 6 over the entire circumference. When the reflected light R3 emitted from the photographing lens 7 and reflected by the front surface of the ceramic substrate 5 is incident on the CMOS sensor 3 after being repeatedly reflected and refracted in the apparatus, it causes flare in the photographed image. . The light shielding film 21 shields harmful light such as reflected light R <b> 3 directed toward the CMOS sensor 3.

FIG. 6 shows a solid-state imaging device 30 according to the third embodiment. In addition, the same code | symbol is attached | subjected to the structural member similar to the thing of 1st Embodiment, and the detailed description is abbreviate | omitted.
The solid-state imaging device 30 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9. The light-shielding film (light-shielding layer) 31 described above is formed on the end and side end surfaces of the incident surface 6a of the IR cut filter 6 over the entire circumference. That is, the first and second embodiments are combined. In this embodiment, since the light shielding performance is higher than in the first and second embodiments, the occurrence of flare is reliably suppressed.

FIG. 7 shows a solid-state imaging device 40 according to the fourth embodiment. In addition, the same code | symbol is attached | subjected to the structural member similar to the thing of 1st Embodiment, and the detailed description is abbreviate | omitted.
The solid-state imaging device 40 includes a CMOS sensor 3, a circuit board 4, a ceramic substrate 5, an IR cut filter 6, a photographing lens 7, a lens holder 8, and a holding cylinder 9. The light-shielding film (light-shielding layer) 31 described above is formed on the end and side end surfaces of the incident surface 6a of the IR cut filter 6 over the entire circumference.
A light shielding film (light shielding layer) 41 is formed on the inner wall surface of the ceramic substrate 5. When reflected light that is emitted from the photographing lens 7, passes through the IR cut filter 6, and is reflected by the inner wall surface of the ceramic substrate 5 enters the CMOS sensor 3, flare of the photographed image occurs. Since the light shielding film 41 has a light shielding performance higher than that of the inner wall surface of the ceramic substrate 5, the occurrence of flare is reliably suppressed.

<Color filter>
Moreover, the cured film of this invention can be used also for a color filter.

  The color filter can be suitably used for a solid-state imaging device such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor), and is particularly suitable for a high-resolution CCD or CMOS that exceeds 1 million pixels. It is. For example, the color filter can be used by being disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

  The color filter can be preferably used for an organic electroluminescence (organic EL) element. As the organic EL element, a white organic EL element is preferable. The organic EL element preferably has a tandem structure. Regarding the tandem structure of organic EL elements, Japanese Patent Application Laid-Open No. 2003-45676, supervised by Akiyoshi Mikami, “The Forefront of Organic EL Technology Development-High Brightness, High Accuracy, Long Life, Know-how Collection”, Technical Information Association, 326-328 pages, 2008, etc. Examples of the tandem structure of the organic EL element include a structure in which an organic EL layer is provided between a lower electrode having light reflectivity and an upper electrode having light transmittance on one surface of a substrate. The lower electrode is preferably made of a material having a sufficient reflectance in the visible light wavelength region. The organic EL layer preferably includes a plurality of light emitting layers and has a stacked structure (tandem structure) in which the plurality of light emitting layers are stacked. For example, the organic EL layer may include a red light emitting layer, a green light emitting layer, and a blue light emitting layer in the plurality of light emitting layers. And it is preferable that they have a some light emission auxiliary layer for light-emitting a light emitting layer together with a some light emitting layer. The organic EL layer can have, for example, a stacked structure in which light emitting layers and light emitting auxiliary layers are alternately stacked. An organic EL element having an organic EL layer having such a structure can emit white light. In that case, the spectrum of white light emitted from the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm) and the yellow region (580 nm to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable. By combining an organic EL element that emits white light (white organic EL element) and the color filter of the present invention, a spectrum excellent in color reproducibility can be obtained, and a clearer image or image can be displayed.

The film thickness of the colored pattern (colored pixel) in the color filter is preferably 2.0 μm or less, more preferably 1.0 μm or less, and even more preferably 0.7 μm or less. The lower limit can be, for example, 0.1 μm or more, and can also be 0.2 μm or more.
Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less. The lower limit can be, for example, 0.1 μm or more, and can also be 0.2 μm or more.

<Image display device>
The cured film (color filter, light-shielding film, etc.) of the present invention can be used for image display devices such as liquid crystal display devices and organic electroluminescence display devices.

  For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter in the present invention may be used for a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention relates to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), a STN (Super-Twist Nematic). ), TN (Twisted Nematic), VA (Vertical Alignment), OCS (On-chip spacer), FFS (Fringe field switching), and R-OCB (Reflective Optical Compensated).
In addition, the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system. In the COA type liquid crystal display device, the required characteristics for the color filter require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the stripping solution resistance, in addition to the normal required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

The liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter in the present invention. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. Regarding these components, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlighting, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Yukiaki Yagi), etc. Have been described.

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

<Synthesis Example 1: Synthesis of fluorinated block copolymer 1>
First, the fluorinated block copolymer 1 was synthesized by the following method.

(Step 1) Synthesis of PMAA-Br by living radical polymerization Cuprous chloride (6.23 g, 46.4 mmol), 4,4′-dinonyl-2,2′-bipyridine (37.9 g, 92. 8 mmol), ethyl 2-bromoisobutyrate (4.52 g, 23.2 mmol) as a polymerization initiator was added to perform nitrogen substitution. 70 ml of anisole bubbled with nitrogen for 30 minutes and methacrylic acid (150 g, 1.74 mol) from which the polymerization inhibitor had been removed through an alumina column were added so that the molar ratio of the monomer to the initiator was 75/1. The polymerization was started by immersion in a hot water bath at 0 ° C. After 10 hours, the temperature was returned to room temperature and the polymerization was stopped by contacting with air. The polymer solution was purified through an alumina column. The solution was poured into methanol to precipitate a polymer, and then vacuum dried at 100 ° C. The number average molecular weight Mn of the obtained polymer was 1500 g / mol, and the molecular weight distribution Mw / Mn was 1.17.

(Step 2) Synthesis Method of PMAA-b-Pi6F by Living Radical Polymerization Cuprous bromide (1.2 g, 8.4 mmol), Me ₆ TREN ((Tris [2- (dimethylamino) ethyl] amine) in a 1 L flask 3.87 g, 16.8 mmol), PMAA-Br (7.86 g, 5.2 mmol) synthesized in Step 1 as a polymerization initiator was added to perform nitrogen substitution. After adding 200 ml of anisole bubbled with nitrogen for 30 minutes and i6FMA (49.5 g, 0.21 mol) from which the polymerization inhibitor had been removed through an alumina column, the flask was immersed in a 90 ° C. hot water bath to initiate polymerization. After 10 hours, the temperature was returned to room temperature and the polymerization was stopped by contacting with air. The polymer solution was purified through an alumina column. This solution was poured into methanol to precipitate a polymer, and then vacuum dried at 140 ° C. to obtain a fluorinated block copolymer 1 (PMAA-b-Pi6F). The number average molecular weight Mn was 11700 g / mol, and the molecular weight distribution Mw / Mn was 1.36.

<Synthesis Examples 2 to 11: Synthesis of fluorinated block copolymers 2 to 11>
The synthesis example 1 (fluorine-containing block copolymer) was used except that the monomers used in the synthesis of the fluorine-containing block copolymer 1 and the addition amount of the polymerization initiator were adjusted as described in Table 1 below. Fluorine-containing block copolymers 2 to 11 were obtained by the same procedure as in Synthesis method 1 of Polymer 1.

Table 1 summarizes the monomer composition of the fluorinated block copolymers 1 to 11 and the amount of the polymerization initiator used for the synthesis of the fluorinated block copolymers 1 to 11, respectively.
In Table 1 below, the units of “amount” of monomer 1, monomer 2 and initiator are all “g”. The “amount” in the initiator column means the initial addition amount “g” when the initiator is mixed with the monomer.

Various monomers listed in Table 1 are shown below.
(Block A composition)
MAA: Methacrylic acid (monomer having a carboxylic acid group)
HO-MS: 2-methacryloyloxyethyl succinic acid (manufactured by Kyoeisha Chemical Co., Ltd.) (monomer having a carboxylic acid group)
M5300: <ω-carboxy-polycaprolactone (n≈2) monoacrylate> (manufactured by Toagosei Co., Ltd.) (monomer having a carboxylic acid group)
Phosmer M: Acid phosphooxyethyl methacrylate (manufactured by Unichemical Co., Ltd.) (monomer having a phosphate group)
PHS: Parahydroxystyrene (monomer having a phenolic hydroxyl group)
NK ester CB36: (manufactured by Shin-Nakamura Chemical Co., Ltd.) (monomer having a carboxylic acid group)
(Block B composition)
i6FMA: Methacrylic acid 1,1,1,3,3,3-hexafluoroisopropyl C6FMA: 2- (perfluorohexyl) -ethyl methacrylate

<Synthesis Example 12: Synthesis of Comparative Fluoro Resin 1>
-Composition 1-
・ MAA [monomer] 1.40 g
I6FMA [monomer] 16.1 g
・ 2,2′-azobis (methyl 2-methylpropionate) [polymerization initiator] 0.325 g
・ Propylene glycol monomethyl ether acetate [solvent] 35.0 g

The monomer solution for dropping obtained by mixing the components shown in the above composition 1 was dropped into 17.5 g of propylene glycol monomethyl ether acetate heated to 80 ° C. in a nitrogen atmosphere over 3 hours.
Thereafter, 0.325 g of 2,2′-azobis (methyl 2-methylpropionate) was added, heated to 90 ° C., heated for 2 hours, and a comparative fluorine-containing resin shown below as a 30% by mass solution. 1 was obtained. The obtained fluororesin 1 for comparison corresponds to a so-called random polymer.

<Synthesis Example 13: Synthesis of comparative fluorine-containing resin 2>
-Composition 2-
・ I6FMA [monomer] 13.3 g
-NK ester CB36 [manufactured by Shin-Nakamura Chemical Co., Ltd., monomer] 4.20 g
・ 2,2′-azobis (methyl 2-methylpropionate) [polymerization initiator] 0.270 g
・ Propylene glycol monomethyl ether acetate [solvent] 30.6 g

The monomer solution for dropping obtained by mixing the components shown in the above composition 2 was dropped into 10.2 g of propylene glycol monomethyl ether acetate heated to 80 ° C. in a nitrogen atmosphere over 3 hours.
Thereafter, 0.270 g of 2,2′-azobis (methyl 2-methylpropionate) was added, heated to 90 ° C., heated for 2 hours, and a comparative fluorine-containing resin shown below as a 30 mass% solution. 2 was obtained. The obtained fluororesin 2 for comparison corresponds to a so-called random polymer.

  Summarizes the structure, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), and acid value of the fluorine-containing resins (fluorinated block copolymers 1 to 11, comparative fluorine-containing resins 1 and 2) prepared above. Table 2 below shows.

In this example, the obtained fluorine-containing block copolymers 1 to 11 (including intermediates thereof) and comparative fluorine-containing resins 1 and 2 have a weight average molecular weight (Mw), a number average molecular weight (Mn), and a molecular weight distribution. (Mw / Mn) was calculated by GPC (Gel Permeation Chromatography) measurement under the following measurement conditions.
Apparatus: HLC-8220GPC [manufactured by Tosoh Corporation]
Detector: Differential refractometer (RI detector)
Precolumn TSKGUARDCOLUMN MP (XL) 6 mm x 40 mm [manufactured by Tosoh Corporation]
Sample side column: Directly connect the following 4 columns (all manufactured by Tosoh Corporation)
TSK-GEL Multipore-HXL-M 7.8mm x 300mm
Reference side column: Same as sample side column Temperature chamber temperature: 40 ° C
Mobile phase: Tetrahydrofuran Sample-side mobile bed flow rate: 1.0 mL / min Reference-side mobile bed flow rate: 0.3 mL / min Sample concentration: 0.1% by mass
Sample injection volume: 100 μL
Data collection time: 16 minutes to 46 minutes after sample injection Sampling pitch: 300 msec

  In Table 2, the acid value was determined by neutralization titration using an aqueous sodium hydroxide solution. Specifically, the solution obtained by dissolving the fluororesin in a solvent is titrated with an aqueous sodium hydroxide solution using a potentiometric method, and the number of millimoles of acid contained in 1 g of the fluororesin solid is calculated. The value was then determined by multiplying the molecular weight of KOH by 56.1.

  In addition, about the fluorine-containing coblock copolymer of Example 5 shown in Table 2, the hydroxyl value was calculated | required. Specifically, the hydroxyl value was calculated according to the method described in JIS K0070. That is, the hydroxyl value is represented by the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated.

<Preparation of titanium black dispersion>
-Composition 3-
・ (A) Titanium black (average primary particle size 30 nm, TTO-51N trade name, manufactured by Ishihara Sangyo)
45 parts- (B) Dispersant ((Meth) acrylic polymer dispersant (polymer compound C) containing an acid group described later) 13.5 parts

  The components shown in composition 3 were mixed and subjected to a dispersion treatment to obtain a dispersion. When the molecular weight of the dispersant described later is in the range of 10,000 to 50,000, good dispersibility of titanium black was obtained.

[Example 1: Preparation of black curable composition M-1]
Using the titanium black dispersion prepared above, various components and cyclohexanone were mixed so as to have the composition shown in Table 3 to obtain a black curable composition M-1 having a solid content of 32% by mass.

(Synthesis of polymer compound D)
According to the production method described in paragraphs 0338 to 0340 of JP 2010-106268 A (see specific resin 4 in the literature), a polymer compound D was obtained. The polymer compound D had a skeleton of the following formula (T), where x was 90% by mass, y was 0% by mass, and z was 10% by mass. The weight average molecular weight of the polymer compound D was 40,000, the acid value was 100 mgKOH / g, and the number of graft chain atoms (excluding hydrogen atoms) was 117.

(Synthesis of polymer compound C)
The polymer compound C was synthesized by referring to the description in paragraphs 0219 to 0223 of JP 2013-249417 A (see the specific resin 9 in the literature). The polymer compound C had a skeleton of the following formula (T), where x was 43% by mass, y was 49% by mass, and z was 8% by mass. The weight average molecular weight of the polymer compound C was 30000, the acid value was 60 mgKOH / g, and the number of graft chain atoms (excluding hydrogen atoms) was 117.

Formula (T)

[Examples 2-11, Comparative Examples 1-2]
In the preparation of the black curable composition M-1, the same method except that the fluorinated block copolymer 1 was changed to the fluorinated block copolymers 2 to 11 and the comparative fluorinated resins 1 and 2, Black curable compositions M-2 to M-13 were respectively prepared.

<Preparation and evaluation of light-shielding color filter for solid-state image sensor>
[Black curable composition layer forming step]
The spin coat coating rotation speed is adjusted so that the film thickness after coating and heat treatment is 2.0 μm, and the black curable compositions M-1 to M-13 are formed on the silicon wafer [support]. Any one of these was uniformly applied and heat-treated for 120 seconds with a hot plate having a surface temperature of 120 ° C. In this way, a coating film [black curable composition layer] having a thickness of 2.0 μm was obtained.

[Exposure process]
Next, using an i-line stepper, FPA-3000iS + [manufactured by Canon Inc.], irradiation (exposure) was performed at an exposure amount of 200 mJ / cm ² through a mask having a linear 300 μm (width 300 μm, length 4 mm). .

[Development process]
After irradiation (exposure), paddle development was performed at 23 ° C. for a predetermined time using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH).

[Post-baking process]
Further, heat treatment was performed at 220 ° C. for 300 seconds using a clean oven CLH-21CDH (manufactured by Koyo Thermo Co., Ltd.).

[Evaluation]
The coating film and pattern obtained as described above were evaluated as follows.

<Developability>
About the coating film obtained by making it above, the developability was evaluated by the following evaluation criteria about the coating film which was not exposed after a black curable composition layer formation process. Development was performed under the conditions described in [Development step] above.
“A”: developed in 30 seconds or less (all dissolved).
“B”: Development was possible, but development required more than 30 seconds and within 60 seconds.
“C”: developed, but required more than 60 seconds for development.
“D”: Development was not possible due to repelling of the developer.
The evaluation results are shown in Table 4 below. In addition, the weight average molecular weight (Mw) of the fluorine-containing resin described in Table 4 is the same as that described in Table 2.

<Reflectance>
For the evaluation of reflectance, light of 400 to 800 nm was incident on the prepared cured film at an incident angle of 5 °, and the transmittance at a wavelength of 750 nm was measured with a spectrometer UV4100 manufactured by Hitachi High Technology. In addition, the cured film used for reflectance evaluation was produced by performing similarly to the [post-baking process] except having made [exposure process] full exposure in the said preparation method.
“A”: less than 3% reflectivity “B”: 3% to 5% reflectivity
“C”: greater than 5% reflectivity Table 4 shows the evaluation results.

<Surface shape>
About the pattern obtained through the said [post-baking process], it observed by visual observation and evaluated surface condition by the following evaluation criteria.
“A”: no foreign matter in appearance.
“B”: There is almost no foreign matter.
“C”: There are many foreign substances.
The evaluation results are shown in Table 4 below.

As is apparent from Table 4 above, the black curable composition M- having fluorine-containing block copolymers 1 to 11 each having an AB block copolymer portion composed of an A block having an acid group and a B block having a fluorine atom. It was confirmed that the cured film (Examples 1-11) formed by 1-11 has the outstanding developability and low reflectivity.
Further, when Example 3 and Example 1 are compared, the reflectance, planarity is reduced by setting the total number of atoms of the linking group of the A block having an acid group (corresponding to L ¹ in Formula (A)) to 10 or less. It was confirmed that the property becomes better.
Further, in contrast to Example 5 and Example 1, Example 5 is highly hydrophobic because the A block is formed of a repeating unit containing a phenolic hydroxyl group, and a black curable composition using this is used. When the cured film formed and Example 1 were compared, the developability of Example 1 was more excellent.

In Example 9, the developability, low reflectivity, and surface property were good, but the linearity evaluation was low. In addition, with linearity, about the pattern obtained through the said [post-baking process], it observes visually with an electron microscope, and evaluates the linearity of the edge part (boundary part of an exposed part and an unexposed part) of a pattern. It is a test to do.
From the comparison of Example 9, Example 1 and Example 8, by making the acid value of the fluorine-containing block copolymer 35 to 150 mgKOH / g, it can be more excellent in developability, surface property, and linearity. confirmed.

Moreover, from the results of Example 10, it was found that the developability and planarity were more excellent when the weight average molecular weight of the fluorine-containing block copolymer was 50000 or less.
In addition, from the results of Example 11, it was found that when the acid group in the A block of the fluorine-containing block copolymer is linked with a linking group not containing a cyclic structure, the developability and low reflectivity are more excellent.

On the other hand, in Comparative Example 1 (the fluorine-containing block copolymer of Example 1 having a random structure), the developability did not satisfy the desired level.
Further, in Comparative Example 2 (the fluorine-containing block copolymer of Example 11 having a random structure), aggregation occurred in the alicyclic structure portion, and the aggregation of fluorine atoms in the B block was inhibited. Evaluation was low in both developability and low reflectivity.

[Examples 1-a, 1-b, 1-c: Preparation of black curable compositions M-1-a, M-1-b, M-1-c]
Various components and cyclohexanone were mixed so that the composition of Table 3 in Example 1 became the composition shown in Table 5, and black curable compositions M-1-a to M-1-c having a solid content of 32% by mass were obtained. Obtained.

  Using the obtained black curable compositions M-1-a to M-1-c, a coating film [black curable composition layer] is formed so that the film thickness after coating and heat treatment becomes 3.0 μm. Except for this, pattern formation and evaluation were carried out in the same manner as in Example 1 from [Black curable composition layer forming step] to [Post-baking step].

<Evaluation of developability and reflectance of Examples 1-a to 1-c>
The coatability and pattern obtained as described above were evaluated for developability, low reflectivity, and surface property. The various evaluation methods are the same as the evaluation methods in Example 1.
The results are shown in Table 6.

  In Example 1-a and Example 1-c, the same developability and planarity results as in Example 1 were obtained. From a comparison between Example 1-a and Example 1-b, it was found that Example 1-a, which has an excellent surface shape, can obtain the desired curing more significantly. From a comparison between Example 1-a and Example 1-c, it was found that the desired effect of the present application was remarkably obtained when the amount of the fluorine-containing block copolymer was large.

[Evaluation of applicability of black curable composition M-1 (Example 1)]
When the black curable composition M-1 (Example 1) obtained above was applied using an inkjet method and a spray coating method, and the same evaluation was performed, the same result was obtained for each evaluation. . After that, when repeated evaluation was performed, there were cases where ejection bending was caused by the ink jet method and nozzle clogging at the time of restart was caused by the spray coating method, but it recovered immediately after maintenance. Repeated evaluation revealed that spray application was easier to handle.

[Example 1-A: Preparation and pattern formation of black curable composition M-1-A]
In Example 1, the addition amount of the fluorinated block copolymer 1 was 3.0 parts, and the mass ratio of the polymerizable compound to the fluorinated block copolymer 1 (polymerizable compound / fluorinated block copolymer 1). The black curable composition M-1-A was prepared in the same manner except that the solid content was adjusted to 0.7 and the amount of cyclohexanone was adjusted (total solid in the black curable composition M-1-A). Content of fluorine-containing block copolymer 1 with respect to the content: 3.7% by mass).
Except having formed the coating film [black curable composition layer] so that the film thickness after application | coating and heat processing might be set to 3.0 micrometers using the obtained black curable composition M-1-A, Example 1 [Black curable composition layer forming step] to [Post-baking step] were performed in the same manner as in No. 1, and pattern formation and evaluation were performed.

[Example 1-B: Preparation and pattern formation of black curable composition M-1-B]
In Example 1, the addition amount of the fluorinated block copolymer 1 was 3.0 parts, and the mass ratio of the polymerizable compound to the fluorinated block copolymer 1 (polymerizable compound / fluorinated block copolymer 1). The black curable composition M-1-B was prepared in the same manner except that the solid was adjusted with the amount of cyclohexanone (total solid in the black curable composition M-1-B). Content of fluorine-containing block copolymer 1 with respect to the content: 3.5% by mass).
Except having formed the coating film [black curable composition layer] so that the film thickness after application | coating and heat processing might be set to 3.0 micrometers using the obtained black curable composition M-1-B, Example 1 [Black curable composition layer forming step] to [Post-baking step] were performed in the same manner as in No. 1, and pattern formation and evaluation were performed.

[Example 1-C: Preparation and pattern formation of black curable composition M-1-C]
In Example 1, the addition amount of the fluorinated block copolymer 1 was 3.0 parts, and the mass ratio of the polymerizable compound to the fluorinated block copolymer 1 (polymerizable compound / fluorinated block copolymer 1). The black curable composition M-1-C was prepared in the same manner except that the solid was adjusted with the amount of cyclohexanone (based on the total solid content in the black curable composition M-1-C). Content of fluorine-containing block copolymer 1: 2.7% by mass).
Except having formed the coating film [black curable composition layer] so that the film thickness after application | coating and heat processing might be set to 3.0 micrometers using the obtained black curable composition M-1-C, Example 1 [Black curable composition layer forming step] to [Post-baking step] were performed in the same manner as in No. 1, and pattern formation and evaluation were performed.

[Example 1-1: Pattern formation of black curable composition M-1]
Moreover, Example 1 except having formed the coating film [black curable composition layer] so that the film thickness after application | coating and heat processing might be set to 3.0 micrometers using the black curable composition of Example 1. The method from [Black curable composition layer forming step] to [Post-baking step] was carried out in the same manner as above to perform pattern formation and evaluation.

<Evaluation of developability / linearity and reflectance of Examples 1-A to C and Example 1-1>
Linearity was evaluated according to the following criteria.
<Linearity>
The pattern obtained through the above [post-baking step] was evaluated by visually observing with an electron microscope whether or not the pattern edge portion (boundary portion between the exposed portion and the unexposed portion) could be developed with a clean straight line. .
In Example 1-1 and Examples 1-A to C, the same results (developability and low reflectivity) as in Example 1 were obtained. In Example 1-1 and Examples 1-A to C, clean straight lines could be developed in the linearity evaluation. However, about Example 1-A and Example 1-C, in the evaluation of linearity, the edge part of the pattern became a straight line with a slightly rough shape.
When Example 1-A and Example 1-C were evaluated in the same manner with a film thickness of 2.0 μm, the same results (developability / linearity, low reflectivity) as in Example 1 were obtained. It was.

[Example 1-D]
In Example 1, instead of titanium black, carbon black (trade name “Color Black S170”, manufactured by Degussa, average primary particle diameter of 17 nm, BET specific surface area of 200 m ² / g, carbon black manufactured by gas black method) A black curable composition M-1-D was prepared in the same manner except that was used.
Using the obtained black curable composition M-1-D, the process from [Black curable composition layer forming step] to [Post-baking step] is performed in the same manner as in Example 1 to perform pattern formation and evaluation. It was.
In Example 1-D, the same results as in Example 1 were obtained with respect to developability and low reflectivity. However, when Example 1 and Example 1-D were compared in the evaluation of linearity, the results were as follows. It was found that the linearity of Example 1 was better.

[Example 1-E]
In the preparation of the titanium black dispersion liquid of Example 1, pigment dispersion liquid R1 was obtained in the same manner except that Pigment Red 254 (trade name BK-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) was used instead of titanium black. Thereafter, a black curable composition M-1-E was prepared in the same manner except that the titanium black of Example 1 was changed to the pigment dispersion R1.
Using the obtained black curable composition M-1-E, the process from [Black curable composition layer forming step] to [Post-baking step] is performed in the same manner as in Example 1 to perform pattern formation and evaluation. It was.
In Example 1-E, the same results as in Example 1 were obtained with respect to developability and linearity. However, when Example 1 and Example 1-E were compared in evaluation of low reflection, Example 1 1 was found to be more excellent in point reflectivity.

[Example 1-F]
Except for changing 45 parts of titanium black of Example 1 into 40 parts of titanium black and 5 parts of pigment dispersion R, a pigment dispersion R2 was obtained in the same manner, and then the titanium black of Example 1 was used as a pigment dispersion. A black curable composition M-1-F was prepared by the same method except that it was changed to R2. Using the obtained black curable composition M-1-F, the process from [Black curable composition layer forming step] to [Post-baking step] is performed in the same manner as in Example 1 to perform pattern formation and evaluation. It was.
Example 1-F was evaluated in the same manner as in Example 1. As a result, the same results as in Example 1 (developability / linearity, low reflectivity) were obtained.
Moreover, compared with Example 1, it turned out that the reflectance and transmittance | permeability of light are low in the wavelength of an infrared region, and it is excellent in light-shielding property.

[Example 1-G]
In the preparation of the titanium black dispersion of Example 1, a dye dispersion R3 was obtained in the same manner except that the xanthene dye polymer (Xa) shown in the following Production Example was used instead of titanium black. A curable composition M-1-G was prepared in the same manner except that the titanium black was changed to the dye dispersion R3.
Using the obtained curable composition M-1-G, the process from [Black curable composition layer forming step] to [Post-baking step] was performed in the same manner as in Example 1 to perform pattern formation and evaluation. .
In Example 1-G, the same results as in Example 1 were obtained with respect to developability and linearity. However, when Example 1 and Example 1-G were compared, Example 1 was more point reflective. It turned out to be excellent.

<Production example>
Synthesis of Xanthene Dye Polymer A dye multimer (xanthene Xa) was obtained according to the method for producing a salt-forming compound (A-1) described in paragraph 0165 of JP2011-242752. In addition, the structure of the used polymer and a pigment | dye is shown below. The weight average molecular weight (Mw) of the dye multimer (xanthene Xa) confirmed by GPC measurement was 10,500.

[Example 1-H]
In the same manner as in Example 1 except that 45 parts of titanium black was changed to 40 parts of titanium black and 5 parts of dye dispersion R3 to obtain a pigment / dye mixed dispersion R4. A black curable composition M-1-H was prepared in the same manner except that the pigment / dye mixed dispersion R4 was used. Using the obtained black curable composition M-1-H, the process from [Black curable composition layer forming step] to [Post-baking step] is performed in the same manner as in Example 1 to perform pattern formation and evaluation. It was.
When Example 1-H was evaluated in the same manner as in Example 1, the same results (developability / linearity, low reflectivity) as in Example 1 were obtained.

  From the above results, it is presumed that the desired effect can be obtained even when the colorant is changed or when a plurality of colorants are used in combination.

Example 1-I
A black curable composition M-1-I was prepared in the same manner except that the polymerization initiator of Example 1 was changed to IRGACURE-907 (manufactured by BASF Japan).
Using the obtained black curable composition M-1-I, the process from [Black curable composition layer forming step] to [Post-baking step] is performed in the same manner as in Example 1 to perform pattern formation and evaluation. It was.
In Example 1-1, the same results as in Example 1 were obtained with respect to developability and low reflectivity, but when Example 1 was compared with Example 1-1, the linearity of Example 1 was I found it better.

[Example 1-J]
A black curable composition M-1-J was prepared by the same method except that the solvent in Example 1 was changed from cyclohexanone to 1: 1 by mass ratio of cyclohexanone and propylene glycol monomethyl ether acetate.
Using the obtained black curable composition M-1-J, the process from [Black curable composition layer forming step] to [Post-baking step] is performed in the same manner as in Example 1 to perform pattern formation and evaluation. It was.
For Example 1-J, the same results (developability / linearity, low reflectivity) as in Example 1 were obtained.

[Example 1-K]
7. The polymerizable compound of Example 1 was KAYARAD DPHA (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 10.0 parts, and PET-30 (pentaerythritol triacrylate, manufactured by Nippon Kayaku Co., Ltd.). A black curable composition M-1-K was prepared in the same manner except that the amount was changed to 5 parts.
Using the obtained black curable composition M-1-K, the process from [Black curable composition layer forming step] to [Post-baking step] is performed in the same manner as in Example 1 to perform pattern formation and evaluation. It was.
For Example 1-K, the same results (developability / linearity, low reflectivity) as in Example 1 were obtained.

<Synthesis Example 14: Synthesis of fluorinated block copolymer 12>
Synthesis Method of PMAA-b-Pi6F-b-PMAA by Living Radical Polymerization Cuprous bromide (1.2 g, 8.4 mmol), Me ₆ TREN ((Tris [2- (dimethylamino) ethyl] amine) in a 1 L flask 3.87 g, 16.8 mmol), and PMAA-b-Pi6F (60.8 g, 5.2 mmol) synthesized in Synthesis Example 1 was added as a polymerization initiator to perform nitrogen substitution. After adding 350 ml of anisole bubbled with nitrogen for 30 minutes and MAA (49.5 g, 0.21 mol) from which the polymerization inhibitor had been removed through an alumina column, the flask was immersed in a 90 ° C. hot water bath to initiate polymerization. After 10 hours, the temperature was returned to room temperature and the polymerization was stopped by contacting with air. The polymer solution was purified through an alumina column. This solution was poured into methanol to precipitate a polymer, and then vacuum dried at 140 ° C. to obtain a fluorinated block copolymer 12 (PMAA-b-Pi6F-b-PMAA). The number average molecular weight Mn was 17700 g / mol, and the molecular weight distribution Mw / Mn was 1.42. The acid value was 55 mg / KOH.

Example 12
A black curable composition M-14 was prepared in the same manner as in the preparation of the black curable composition M-1, except that the fluorinated block copolymer 1 was changed to the fluorinated block copolymer 12. . Using the obtained black curable composition M-14, the process from [Black curable composition layer forming step] to [Post-baking step] was performed in the same manner as in Example 1 to perform pattern formation and evaluation. When Example 1 and Example 12 were compared, since the surface uneven distribution property was AB, it turned out that the reflectance of Example 1 is more excellent (reflectance evaluation is B). As for developability, the same results as in Example 1 were obtained.

2, 20, 30, 40 Solid-state imaging device 3 CMOS sensor 4 Circuit board 5 Ceramic substrate 5a Opening 5b Inner wall 6 IR cut filter 7 Shooting lens 8 Lens holder 9 Holding cylinder 10 Cured film 11, 21, 31, 41 Light-shielding film ( Light shielding layer)
12 Colored layer 14 Covering layer 100 Substrate

Claims (17)

A fluorine-containing block copolymer having an AB block copolymer portion composed of an A block having a hydroxyl group or an acid group and a B block having a fluorine atom;
A polymerizable compound;
A colorant;
A curable composition comprising a polyacrylate polymer having a hydroxyl group or an acid group, and a polymer compound selected from the group consisting of a polymethacrylate polymer having a hydroxyl group or an acid group. The curable composition according to claim 1, wherein the A block is composed of a repeating unit represented by the following formula (A), and the B block is composed of a repeating unit represented by the following formula (B).
In formula (A), R ¹ represents a hydrogen atom or an alkyl group, L ¹ represents a single bond or a divalent linking group, and A ¹ represents a hydrogen atom, a hydroxyl group, a carboxyl group, or a phosphate group. Represents an acid group selected from a phenolic hydroxyl group or a thiol group, or a derivative group thereof.
In formula (B), R ² represents a hydrogen atom or an alkyl group, L ² represents a single bond or a divalent linking group, and R ^f represents a monovalent organic group containing a fluorine atom. The curable composition according to claim 2, wherein L ¹ in the formula (A) is a single bond or a divalent linking group having a total number of atoms of 20 or less. The curable composition according to claim 2 or 3, wherein L ¹ in the formula (A) is a single bond or a linear divalent linking group having a total number of atoms of 10 or less. The curable composition according to any one of claims 2 to 4, wherein, in the formula (B), ^Rf is a monovalent organic group having 1 to 3 carbon atoms substituted with a fluorine atom.   The curable composition of any one of Claims 1-5 whose hydroxyl value or acid value of the said fluorine-containing block copolymer is 35-150 mgKOH / g.   The curable composition according to any one of claims 1 to 6, wherein the content of the fluorine-containing block copolymer is 1 to 20% by mass relative to the total solid content in the curable composition. .   The curable composition of any one of Claims 1-7 whose weight average molecular weights of the said fluorine-containing block copolymer are 5000-50000.   The curable composition of any one of Claims 1-8 whose weight average molecular weights of the said high molecular compound are 10000-50000.   The curable composition according to any one of claims 1 to 9, wherein the polymer compound has a polyester structure in the molecule and has a hydroxyl value or an acid value of 20 mgKOH / g or more.   The curable composition of any one of Claims 1-10 whose mass ratio of content of the said high molecular compound and content of the said fluorine-containing block copolymer is 3-8. In addition, the said mass ratio intends the mass of the said high molecular compound / mass of the said fluorine-containing block copolymer.   The curable composition according to claim 1, wherein the colorant includes a black pigment. Forming a composition layer of the curable composition according to any one of claims 1 to 12 on a substrate by spin coating;
Exposing the composition layer by irradiating actinic rays or radiation; and
And a step of forming the cured film by alkali development of the composition layer after the exposure.   The color filter formed by hardening | curing the curable composition of any one of Claims 1-11.   The light shielding film formed by hardening | curing the curable composition of Claim 12.   The solid-state image sensor which has a cured film formed by hardening | curing the curable composition of any one of Claims 1-12.   The image display apparatus which has a cured film formed by hardening | curing the curable composition of any one of Claims 1-12.