JP5224936B2 - Dispersion, black curable composition, production method, production method of light-shielding film or antireflection film for solid-state imaging device, and solid-state imaging device - Google Patents

Description

  The present invention relates to a dispersion containing a black color material, a black curable composition containing the dispersion, a method for producing the same, a light-shielding film or antireflection film for a solid-state image sensor, a method for producing the same, and a solid-state image sensor.

A color filter used in a liquid crystal display device includes a light shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.
Also in the solid-state imaging device, a light shielding film is provided for the purpose of preventing noise generation and improving image quality. Furthermore, an antireflection film may be provided to prevent stray light from outside light and improve color resolution.
As a composition for forming a black matrix for a liquid crystal display device or a light-shielding film for a solid-state imaging device, a photosensitive resin composition containing a black color material such as carbon black or titanium black is known (for example, And Patent Documents 1 to 5).

The black matrix for liquid crystal display devices is mainly required to have a light shielding property in the visible region, while the light shielding film for the solid-state imaging device needs to have a light shielding property in the infrared region in addition to the light shielding property in the visible region. There is.
That is, when a light-shielding film of a wide area is formed using a photosensitive resin composition using a black pigment such as carbon black conventionally used in a black matrix of a liquid crystal display device or the like as a light-shielding film for a solid-state imaging device, In addition to the light shielding property in the visible region, it is necessary to shield light having a wavelength of 800 to 1300 nm in order to prevent noise generation.

  In this case, if carbon black is used for curing by exposure to ultraviolet rays or the like, the transmittance in the wavelength region of 300 to 500 nm is extremely low and curing is difficult. Titanium black has a higher light shielding property in the infrared region than carbon black, and has a transmittance of 300 to 500 nm higher than that of carbon black, but the transmittance is insufficient, resulting in insufficient curing and sensitivity. Lower.

While the black matrix for liquid crystal display devices is required to be miniaturized, the light-shielding film for solid-state imaging device, particularly the surface opposite to the light-receiving element forming surface of the support (hereinafter also referred to as “back surface”) The light shielding film for shielding light is required to uniformly shield light over a larger area than the black matrix for liquid crystal display devices.
However, when a light-shielding film having a large area is formed using the above-described conventional photosensitive resin composition as the light-shielding film for a solid-state imaging device, a region (step) where the film thickness is thinner at the periphery of the light-shielding film than at the central part of the light-shielding film. As a result, the light shielding ability around the light shielding film may be lowered.

Further, when the content of the black color material is increased in order to obtain a high light shielding property, there is a problem that a residue around the light shielding film is easily generated. For the purpose of suppressing the generation of residues, even if the amount of the alkali-soluble resin added is increased, it cannot be sufficiently improved, and there is a problem that the temporal stability is lowered.
Furthermore, a dispersion containing a black color material at a high concentration also has a problem that the dispersibility deteriorates, and it has been awaited for the appearance of a dispersion having a good dispersion state and good dispersion stability.
Japanese Patent Laid-Open No. 10-246955 JP-A-9-54431 Japanese Patent Laid-Open No. 10-46042 JP 2006-36750 A JP 2007-115921 A

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, the present invention provides a black color material-containing dispersion liquid having good dispersibility and good dispersion stability, good temporal stability, reduced light-shielding ability at the periphery, and no residue generation. Providing a black curable composition capable of forming a light-shielding film and an anti-reflective film, particularly a black curable composition for a light-shielding film of a solid-state imaging device and an anti-reflective film, and suppressing a decrease in light-shielding ability at the peripheral portion An object of the present invention is to provide a light-shielding film for a solid-state imaging device, an antireflection film, a manufacturing method thereof, and a solid-state imaging device.

Specific means for solving the above problems are as follows.
<1> (A) A repeating unit represented by the following general formula (I-1) and a repeating unit represented by the following general formula (I-2) are included or represented by the following general formula (II-1). And a resin containing a repeating unit represented by the following general formula (II-2) , (B) a black color material, and (C) a solvent.

Formula (I-1) and (I-2), ^{R 1} and ^{R 2} each independently represent a hydrogen atom, a halogen atom or an alkyl group. a represents an integer of 1 to 5. * Represents a connecting part between repeating units. X represents a group containing any structure selected from structures represented by the following general formula (V-1), general formula (V-2), and general formula (V-3) . Y is represented by the following general formula (III-1) and represents an oligomer chain or a polymer chain having a number average molecular weight of 500 to 1,000,000.

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

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

In general formula (IV), Z is synonymous with Z in general formula (III-1).

In General Formula (V-1) and General Formula (V-2), U represents a single bond or a divalent linking group. d and e each independently represents 0 or 1; In general formula (V-3), Q represents an acyl group or an alkoxycarbonyl group.
<2> The dispersion according to <1>, wherein X in the general formula (I-1) is a group represented by the general formula (V-1).

< 3 > The dispersion liquid according to <1> or <2> , wherein the (B) black color material is titanium black.
< 4 > The dispersion according to any one of <1> to < 3 >, (D) a photopolymerization initiator, and (E) a compound containing an ethylenically unsaturated double bond. A black curable composition characterized.
< 5 > The black curable composition according to < 4 >, wherein the (D) photopolymerization initiator is an oxime photopolymerization initiator.
< 6 > The black curable product according to < 5 >, wherein the content of the oxime photopolymerization initiator is in the range of 3% by mass to 20% by mass of the total solid content of the black curable composition. Sex composition.

< 7 > Prepared by mixing the dispersion according to any one of <1> to < 3 >, (D) a photopolymerization initiator, and (E) a compound containing an ethylenically unsaturated double bond. A method for producing a black curable composition, comprising:
<8> The solid is imaging element black color curable composition according to any one of <4> to <6>.

< 9 > A light-shielding film for a solid-state imaging device, formed using the black curable composition according to any one of <4> to <6> and <8> .
< 10 > An antireflection film for a solid-state imaging device, formed using the black curable composition according to any one of <4> to <6> and <8> .
< 11 > A step of applying the black curable composition according to any one of <4> to <6> and <8> onto a support, exposing through a mask, and developing to form a pattern. A method for producing a light-shielding film for a solid-state imaging device.
<12> A step of applying the black curable composition according to any one of <4> to <6> and <8> on a support, exposing through a mask, and developing to form a pattern. A method for producing an antireflection film for a solid-state imaging device, comprising:
< 13 > A solid-state imaging device comprising the light-shielding film for a solid-state imaging device according to <9> or the antireflection film for a solid-state imaging device according to <10> .

  According to the present invention, it is possible to provide a black color material-containing dispersion liquid having good dispersibility and good dispersion stability, good temporal stability, suppression of a decrease in light shielding ability in the peripheral portion, and generation of residue. A black curable composition capable of forming a light-shielding film and an anti-reflective film, and particularly a black curable composition for a light-shielding film and an anti-reflective film for a solid-state imaging device, and a reduction in light-shielding ability at the peripheral portion can be suppressed. Further, it is possible to provide a light-shielding film for a solid-state imaging device, an antireflection film, a manufacturing method thereof, and a solid-state imaging device.

  Hereinafter, the best mode for carrying out the invention will be described in detail. In addition, in the description of a group (atomic group) in this specification, the description which does not describe substitution and non-substitution means that what has a substituent is included with what does not have a substituent. For example, the expression “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present invention, the “light-shielding color filter” is obtained by exposing and developing a black curable composition containing at least a black color material, an ethylenically unsaturated compound, a resin, a photopolymerization initiator, and a solvent. A light-shielding pattern. The color of the “light-shielding color filter” in the present invention may be an achromatic color such as black or gray, or a black or gray color mixed with a chromatic color.
The “light-shielding color filter” is obtained by exposing and developing a black curable composition containing at least a black color material, an ethylenically unsaturated compound, a resin, a photopolymerization initiator, and a solvent. In other words, it may be a film or a light shielding filter.

The dispersion of the present invention includes (A) the repeating unit represented by the general formula (I-1) and the repeating unit represented by the general formula (I-2), or the general formula (II- 1) a resin containing a repeating unit represented by the general formula (II-2) (hereinafter referred to as “specific resin” as appropriate), (B) a black color material, and (C) It contains a solvent. Details will be described below.

<(A) Specific resin>
Hereinafter, the specific resin will be described in detail.

(I) Main chain portion having nitrogen atom The specific resin of the present invention is composed of (i) a main chain portion having a nitrogen atom. Thereby, the adsorptive power to the pigment surface can be improved and the interaction between the pigments can be reduced.
The specific resin includes the repeating unit represented by the general formula (I-1) and the repeating unit represented by the general formula (I-2), or is represented by the general formula (II-1). The repeating unit and the repeating unit represented by the general formula (II-2) are included.
The number average molecular weight of the main chain in the specific resin of the present invention is preferably 100 to 10,000, more preferably 200 to 5,000, and most preferably 300 to 2,000. The molecular weight of the main chain is determined from the ratio of the terminal group and the hydrogen atom integral value of the main chain measured by nuclear magnetic resonance spectroscopy, or by measuring the molecular weight of the oligomer or polymer containing the amino group as the raw material. Can do.

The specific resin of the present invention has a structure having a repeating unit represented by the general formula (I-1) and a repeating unit represented by the general formula (I-2), or represented by the general formula (II-1). repeating units and formula (II-2) in including a structure containing a repeating unit represented that.

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

In general formulas (I-1) and (I-2), R ¹ and R ² represent a hydrogen atom, a halogen atom, or an alkyl group. a represents an integer of 1 to 5. * Represents a connecting part between repeating units. X represents a group containing a functional group having a pKa of 14 or less. Y is represented by the following general formula (III-1) and represents an oligomer chain or a polymer chain having a number average molecular weight of 500 to 1,000,000.

  In addition to the repeating unit represented by the general formula (I-1) or the general formula (I-2), the specific resin of the present invention further includes a repeating unit represented by the general formula (I-3) as a copolymerization component. It is preferable to have as. By using such a repeating unit in combination, the dispersion performance is further improved when this resin is used as a fine particle dispersant such as a pigment.

In general formula (I-3), R ¹ , R ² and a have the same meaning as in general formula (I-1). Y ′ represents an oligomer chain or a polymer chain having an anionic group and a number average molecular weight of 500 to 1,000,000. The repeating unit represented by the general formula (I-3) is obtained by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amino group in the main chain. It can be formed by reacting.

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

  The specific resin of the present invention is a lower group containing a primary or tertiary amino group in addition to the repeating units represented by the general formula (I-1), general formula (I-2) and general formula (I-3). An alkyleneimine may be contained as a repeating unit. In addition, the group shown by said X, Y, or Y 'may couple | bond with the nitrogen atom in such a lower alkyleneimine repeating unit. Resins containing both a repeating unit having a group represented by X and a repeating unit having Y bonded to such a main chain structure are also included in the specific resin of the present invention.

The repeating unit represented by the general formula (I-1) is a repeating unit having a group containing a functional group having a pKa of 14 or less. Such a repeating unit is from the viewpoint of storage stability and developability. The total repeating unit contained in the resin of the present invention preferably contains 1 to 80 mol%, and most preferably 3 to 50 mol%.
The repeating unit represented by the general formula (I-2) is a repeating unit having an oligomer chain or a polymer chain having a number average molecular weight of 500 to 1,000,000, and such a repeating unit has storage stability. From this viewpoint, it is preferable to contain 10 to 90 mol%, and most preferably 30 to 70 mol% in all repeating units of the resin of the present invention.
In order to examine the content ratio between the two, from the viewpoint of the balance between dispersion stability and hydrophilicity / hydrophobicity, the repeating unit (I-1) :( I-2) has a molar ratio in the range of 10: 1 to 1: 100. And is more preferably in the range of 1: 1 to 1:10.

In addition, the repeating unit represented by the general formula (I-3) used in combination has a partial structure including an oligomer chain or a polymer chain having a number average molecular weight of 500 to 1,000,000 as a main chain nitrogen atom. From the viewpoint of the effect, it is preferably contained in an amount of 0.5 to 20 mol%, and preferably 1 to 10 mol% in all repeating units of the resin of the present invention. Most preferred.
It can be confirmed that the polymer chain “Y” is ionically bonded by infrared spectroscopy or base titration.

<Repeating unit represented by general formula (II-1) and repeating unit represented by (II-2)>
The repeating unit represented by the general formula (II-1) and the repeating unit represented by the general formula (II-2), which are other preferable constituent components of the specific resin of the present invention, will be described in detail.

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

  In addition to the repeating unit represented by the general formula (II-1) and the repeating unit represented by the general formula (II-2), the resin of the present invention is further represented by the general formula (II-3). Preferably, the unit is included in the copolymer component. By using such a repeating unit in combination, the dispersion performance is further improved when this resin is used as a fine particle dispersant such as a pigment.

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

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

The general formula (II-1) is a repeating unit having a group containing a functional group having a pKa of 14 or less. Such a repeating unit is included in the resin of the present invention from the viewpoint of storage stability and developability. It is preferable to contain 1-80 mol% in all the repeating units to be contained, and it is most preferable to contain 3-50 mol%.
The general formula (II-2) is a repeating unit having an oligomer chain or a polymer chain having a number average molecular weight of 500 to 1,000,000, and such a repeating unit is selected from the viewpoint of storage stability. It is preferable to contain 10-90 mol% in all the repeating units of resin, and it is most preferable to contain 30-70 mol%.

In order to examine the content ratio of both, from the viewpoint of dispersion stability and hydrophilicity / hydrophobicity balance, the repeating unit (II-1) :( II-2) is in the range of 10: 1 to 1: 100 in molar ratio. And is more preferably in the range of 1: 1 to 1:10.
The repeating unit represented by the general formula (II-3) used in combination is preferably contained in an amount of 0.5 to 20 mol%, preferably 1 to 10 mol%, in all the repeating units of the resin of the present invention. Is most preferred.
In the specific resin of the present invention, from the viewpoint of dispersibility, it is most preferable to include both the repeating unit represented by the general formula (I-1) and the repeating unit represented by the general formula (I-2). .

<(Ii) Group “X” containing a functional group with pKa of 14 or less>
X is a group containing a functional group represented by the following general formula (V-1), general formula (V-2) or general formula (V-3), and having a pKa at a water temperature of 25 ° C. of 14 or less. Represent. Here, “pKa” has the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.).
The “functional group whose pKa is 14 or less” may be any functional group as long as it is included in the group represented by the following general formula (V-1), general formula (V-2), or general formula (V-3) . functional groups are preferred pKa of 12 or less, especially, the functional group is most preferably a pKa of 11 or less. Specifically, mosquito carboxylic acid (about pKa 3 to 5), sulfonic acid (about pKa _-3~-2), - a COCH 2 CO- (about pKa 8 to 10).
The group “X” containing a functional group having a pKa of 14 or less is usually bonded directly to a nitrogen atom contained in the main chain structure. In addition to the covalent bond, they may be linked in a form that forms a salt by ionic bond.

The group "X" containing a functional group having a pKa of 14 or less in the present invention, are represented by a general formula (V-1), formula (V-2) or general formula (V-3) Structure and it has a.

  In General Formula (V-1) and General Formula (V-2), U represents a single bond or a divalent linking group. d and e each independently represents 0 or 1; In general formula (V-3), Q represents an acyl group or an alkoxycarbonyl group.

Examples of the divalent linking group represented by U include alkylene (more specifically, for example, —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CHMe—, — (CH ₂ ) ₅ —. , —CH ₂ CH (n—C ₁₀ H ₂₁ ) —, etc.), oxygen-containing alkylene (more specifically, for example, —CH ₂ OCH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ —, etc.) , Arylene groups (for example, phenylene, tolylene, biphenylene, naphthylene, furylene, pyrrolylene, etc.), alkyleneoxy (for example, ethyleneoxy, propyleneoxy, phenyleneoxy, etc.), etc. Alternatively, an arylene group having 6 to 20 carbon atoms is preferable, and an alkylene having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms is most preferable. Further, from the viewpoint of productivity, d is preferably 1, and e is preferably 0.

  Q represents an acyl group or an alkoxycarbonyl group. As the acyl group in Q, an acyl group having 1 to 30 carbon atoms (for example, formyl, acetyl, n-propanoyl, benzoyl, etc.) is preferable, and acetyl is particularly preferable. As the alkoxycarbonyl group in Q, Q is particularly preferably an acyl group, and an acetyl group is preferable from the viewpoint of easy production and availability of a raw material (precursor X ′ of X).

  “X” in the present invention is characterized by being bonded to a nitrogen atom in the main chain. Thereby, the dispersibility and dispersion stability of the pigment are dramatically improved. The reason for this is unknown, but it is thought as follows. That is, the nitrogen atom in the main chain part exists in the structure of an amino group, an ammonium group or an amide group, and these are adsorbed by interacting with the acidic part on the pigment surface, such as a hydrogen bond or an ionic bond. Conceivable. Furthermore, since “X” of the present invention functions as an acid group, it can interact with a basic part (such as a nitrogen atom) or a metal atom (such as copper of copper phthalocyanine) of the pigment. In other words, since the resin of the present invention can adsorb both the basic part and the acidic part of the pigment with nitrogen atoms and “X”, the adsorbing ability is improved, and the dispersibility and storage stability are dramatically improved. It is thought to have improved.

  Furthermore, since “X” includes a functional group having a pKa of 14 or less as a partial structure, it functions as an alkali-soluble group. Accordingly, when this resin is used for a curable composition, energy is applied to the coating film to be partially cured, and the unexposed part is dissolved and removed to form a pattern. In a black curable composition using a pigment dispersion containing an ultrafine pigment, a pigment dispersion having a high pigment content, and a black curable composition, the dispersibility / dispersion is improved. It seems that stability and developability can be established.

  The content of the functional group having a pKa of 14 or less in X is not particularly limited, but is preferably 0.01 to 5 mmol, most preferably 0.05 to 1 mmol with respect to 1 g of the specific resin of the present invention. . Within this range, the dispersibility and dispersion stability of the pigment are improved, and when the resin is used in the curable composition, the developability of the uncured portion is excellent. In addition, from the viewpoint of acid value, the amount of the acid value of the specific resin being about 5 to 50 mgKOH / g is included in the development when the specific resin of the present invention is used for a pattern-forming curable composition. From the viewpoint of sex.

<(Iii) Oligomer chain or polymer chain “Y” having a number average molecular weight of 500 to 100,000>
“Y” is represented by the following general formula (III-1) and represents an oligomer chain or a polymer chain having a number average molecular weight of 500 to 100,000 . Binding site of the specific resin of Y is Ru terminal der.

Y is preferably bonded to a nitrogen atom in the main chain. The bonding mode between Y and the main chain is covalent bond, ionic bond, or a mixture of covalent bond and ionic bond. The ratio of the binding mode between Y and the main chain is covalent bond: ionic bond = 100: 0 to 0: 100, preferably 95: 5 to 5:95, and most preferably 90:10 to 10:90. Outside this range, the dispersibility / dispersion stability deteriorates and the solvent solubility decreases.
Y is preferably ionically bonded to the nitrogen atom in the main chain portion as an amide bond or carboxylate.

The number average molecular weight of Y can be measured by the polystyrene conversion value by GPC method. The number average molecular weight of Y is particularly preferably 1,000 to 50,000, and most preferably 1,000 to 30,000 from the viewpoints of dispersibility, dispersion stability, and developability.
It is preferable that two or more side chain structures represented by Y are connected to the main chain in one molecule of resin, and most preferably five or more are connected.

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

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

In general formula (IV), Z is synonymous with Z in general formula (III-1).
When specific resin contains the repeating unit represented by general formula (I-3) or (II-3), it is preferable that Y 'is general formula (III-2).

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

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

(IV-1) The carboxylic acid used in the polycondensation reaction of the carboxylic acid and the lactone is preferably an aliphatic carboxylic acid (a linear or branched carboxylic acid having 1 to 30 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, Valeric acid, n-hexanoic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, palmitic acid, 2-ethylhexanoic acid, cyclohexane acid, etc.), hydroxy group-containing carboxylic acid (C1-C30 direct) A chain or branched hydroxy group-containing carboxylic acid is preferable, for example, glycolic acid, lactic acid, 3-hydroxypropionic acid, 4-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, ricinoleic acid, 12-hydroxydodecanoic acid, 12-hydroxystearic acid. Acid, 2,2-bis (hydroxymethyl) butyric acid, etc.), in particular, straight chain fat having 6 to 20 carbon atoms. Hydroxy group-containing carboxylic acid of the carboxylic acid or 1 to 20 carbon atoms are preferred. These carboxylic acids may be used as a mixture. As the lactone, a known lactone can be used, for example, β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-hexanolactone, γ-octanolactone, δ-valerolactone, δ-hexalanolactone. , Δ-octanolactone, ε-caprolactone, δ-dodecanolactone, α-methyl-γ-butyrolactone, and the like, and ε-caprolactone is particularly preferable from the viewpoint of reactivity and availability.
These lactones may be used as a mixture of plural kinds.
The charging ratio at the time of the reaction between the carboxylic acid and the lactone cannot be uniquely determined because it depends on the molecular weight of the target polyester chain, but is preferably carboxylic acid: lactone = 1: 1 to 1: 1,000, and 1: 3 to 1: 500 is most preferred.

(IV-2) The hydroxy group-containing carboxylic acid in the polycondensation of the hydroxy group-containing carboxylic acid is the same as the hydroxy group-containing carboxylic acid in (IV-1), and the preferred range is also the same.
(IV-3) As a dihydric alcohol in a polycondensation reaction of a dihydric alcohol and a dihydric carboxylic acid (or cyclic acid anhydride), a linear or branched aliphatic diol (a diol having 2 to 30 carbon atoms is preferable, For example, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, etc. In particular, aliphatic diols having 2 to 20 carbon atoms are preferred.
As the divalent carboxylic acid, a linear or branched divalent aliphatic carboxylic acid (preferably a divalent aliphatic carboxylic acid having 1 to 30 carbon atoms is preferable. For example, succinic acid, maleic acid, adipic acid, sebacic acid, Dodecanedioic acid, glutaric acid, suberic acid, tartaric acid, oxalic acid, malonic acid, etc.), and in particular, a divalent carboxylic acid having 3 to 20 carbon atoms is preferred. Further, acid anhydrides equivalent to these divalent carboxylic acids (for example, succinic anhydride, glutaric anhydride, etc.) may be used.
The divalent carboxylic acid and the dihydric alcohol are preferably charged at a molar ratio of 1: 1. This makes it possible to introduce a carboxylic acid at the terminal.

The polycondensation during the production of the polyester is preferably performed by adding a catalyst. As the catalyst, a catalyst that functions as a Lewis acid is preferable. For example, a Ti compound (eg, Ti (OBu) ₄ , Ti (O—Pr) _4, etc.), a Sn compound (eg, tin octylate, dibutyltin oxide, dibutyltin laurate) , Monobutyltin hydroxybutyl oxide, stannic chloride, etc.), protonic acids (for example, sulfuric acid, paratoluenesulfonic acid, etc.) and the like. The catalyst amount is preferably from 0.01 to 10 mol%, most preferably from 0.1 to 5 mol%, based on the number of moles of all monomers. The reaction temperature is preferably 80 to 250 ° C, and most preferably 100 to 180 ° C. Although reaction time changes with reaction conditions, it is 1 to 24 hours in general.

  The number average molecular weight of the polyester can be measured as a polystyrene converted value by the GPC method. The number average molecular weight of the polyester is 1,000 to 1,000,000, preferably 2,000 to 100,000, and most preferably 3,000 to 50,000. When the molecular weight is in this range, both dispersibility and developability can be achieved.

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

Specific embodiments of the specific resin of the present invention [(A-1) to (A-19), (A-21) to (A-48), (A-52), (A-55) to (A-57 the)], are shown below by specific structures and combinations of the repeating units having the resin, the present invention is not limited thereto. In the following formula, k, l, m, and n each represent a polymerization molar ratio of repeating units, k is 1-80, l is 10-90, m is 0-80, n is 0-70, and k + l + m + n = 100. p and q represent the number of linked polyester chains, and each independently represents 5 to 100,000. R ′ represents a hydrogen atom or an alkoxycarbonyl group.

In order to synthesize the specific resin of the present invention, (1) a method of reacting a resin having a primary or secondary amino group with a precursor x of X and a precursor y of Y, (2) containing X Although it is possible to produce by a method by polymerization of a monomer and a macromonomer containing Y, first, a resin having a primary or secondary amino group in the main chain is synthesized, and then the resin of X is added to the resin. The precursor x and the precursor y of Y are preferably reacted and introduced into a nitrogen atom present in the main chain by a polymer reaction.
Examples of the resin having a primary or secondary amino group include an oligomer or a polymer containing a primary or secondary amino group constituting the main chain portion having the nitrogen atom. For example, poly (lower alkylene imine), poly (polymer) Examples include allylamine, polydiallylamine, metaxylenediamine-epichlorohydrin polycondensate, and polyvinylamine. Of these, oligomers or polymers composed of poly (lower alkyleneimine) or polyallylamine are preferred.

The precursor x of the group “X” having a functional group having a pKa of 14 or less represents a compound capable of reacting with the resin having the primary or secondary amino group and introducing X into the main chain.
Examples of x are cyclic carboxylic acid anhydrides (cyclic carboxylic acid anhydrides having 4 to 30 carbon atoms are preferred, such as succinic acid anhydride, glutaric acid anhydride, itaconic acid anhydride, maleic acid anhydride, allyl succinic acid. Anhydride, butyl succinic anhydride, n-octyl succinic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n-docosenyl succinic anhydride, (2- (Hexene-1-yl) succinic anhydride, (2-methylpropen-1-yl) succinic anhydride, (2-dodecen-1-yl) succinic anhydride, n-octenyl succinic anhydride, (2, 7-octanedien-1-yl) succinic anhydride, acetylmalic anhydride, diacetyltartaric anhydride, het acid anhydride, cyclohexane-1,2-dicarboxylic acid Water, 3 or 4-methylcyclohexane-1,2-dicarboxylic anhydride, tetrafluorosuccinic anhydride, 3 or 4-cyclohexene-1,2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1 , 2-dicarboxylic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, naphthalic anhydride, naphthalic anhydride, bicyclo [2.2.2] oct-7-ene-2,3,5 6-tetracarboxylic dianhydride, pyromellitic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, 1,2,3,4-cyclopentanecarboxylic dianhydride Etc.), halogen atom-containing carboxylic acids (for example, chloroacetic acid, bromoacetic acid, iodoacetic acid, 4-chloro-n-butyric acid, etc.), sultone (for example, propane sultone, 1,4-butanthol) Etc.), diketene, cyclic sulfocarboxylic anhydride (for example, 2-sulfobenzoic acid anhydride, etc.), - COCH ₂ COCl compounds containing (e.g., ethyl malonyl chloride, etc.), or a cyano acetic acid chloride, and the like, In particular, cyclic carboxylic acid anhydride, sultone, and diketene are preferable from the viewpoint of productivity.

The precursor y of the oligomer chain or polymer chain “Y” having a number average molecular weight of 500 to 1,000,000 is reacted with the resin having the primary or secondary amino group to introduce “Y”. Represents a possible compound.
y is preferably a number average molecular weight of 500 to 1,000,000 oligomer or polymer having a group capable of covalent bonding or ionic bonding with a nitrogen atom of a specific resin at the end, and in particular, a number average molecular weight having a free carboxyl group at one end. Most preferred are 500 to 1,000,000 oligomers or polymers.
Examples of y include a polyester represented by the general formula (IV) having a free carboxylic acid at one end, a polyamide having a free carboxylic acid at one end, and a poly (meth) having a free carboxylic acid at one end. Examples thereof include acrylic resins, and polyesters containing a free carboxylic acid at one end represented by the general formula (IV) are most preferable.

  y can be synthesized by a known method. For example, as described above, a polyester containing a free carboxylic acid at one end represented by the general formula (IV) can be synthesized between (IV-1) carboxylic acid and lactone. Examples thereof include polycondensation, (IV-2) polycondensation of a hydroxy group-containing carboxylic acid, and (IV-3) polycondensation of a dihydric alcohol and a divalent carboxylic acid (or a cyclic acid anhydride). A polyamide containing a free carboxylic acid at one end can be produced by self-condensation of an amino group-containing carboxylic acid (for example, glycine, alanine, β-alanine, 2-aminobutyric acid, etc.). A poly (meth) acrylic acid ester having a free carboxylic acid at one end is obtained by radical polymerization of a (meth) acrylic acid monomer in the presence of a carboxyl group-containing chain transfer agent (for example, 3-mercaptopropionic acid). Can be manufactured.

  The specific resin of the present invention includes (a) a method in which a resin having a primary or secondary amino group and x and y are simultaneously reacted, and (b) a reaction between a resin having a primary or secondary amino group and x, and then y And (c) a method in which a resin having a primary or secondary amino group is reacted with y and then reacted with x. In particular, (c) a method in which a resin having a primary or secondary amino group is reacted with y and then reacted with x is preferable.

  Although reaction temperature can be suitably selected according to conditions, 20-200 degreeC is preferable and 40-150 degreeC is the most preferable. The reaction time is preferably 1 to 48 hours, and more preferably 1 to 24 hours from the viewpoint of productivity.

The reaction may be performed in the presence of a solvent. Examples of the solvent include water, sulfoxide compounds (for example, dimethyl sulfoxide), ketone compounds (for example, acetone, methyl ethyl ketone, cyclohexanone, etc.), ester compounds (for example, ethyl acetate, butyl acetate, ethyl propionate, propylene glycol 1-monomethyl ether). 2-acetate, etc.), ether compounds (eg, diethyl ether, dibutyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbon compounds (eg, pentane, hexane, etc.), aromatic hydrocarbon compounds (eg, toluene, xylene, mesitylene, etc.) Nitrile compounds (eg, acetonitrile, propiononitrile, etc.), amide compounds (eg, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc.), carboxylated compounds (Eg, acetic acid, propionic acid, etc.), alcohol compounds (eg, methanol, ethanol, isopropanol, n-butanol, 3-methylbutanol, 1-methoxy-2-propanol, etc.), halogenated solvents (eg, chloroform, 1, 2-dichloroethane etc.).
When using a solvent, it is preferable to use 0.1-100 mass times with respect to a substrate, and it is most preferable to use 0.5-10 mass times.
The specific resin of the present invention may be purified by a reprecipitation method. By removing the low molecular weight component by the reprecipitation method, the dispersion performance when the obtained specific resin is used as a pigment dispersant is improved.
For reprecipitation, it is preferable to use a hydrocarbon meter solvent such as hexane and an alcohol solvent such as methanol.

  The thus obtained new resin of the present invention preferably has a weight average molecular weight measured by GPC method of 3,000 to 100,000, and more preferably 5,000 to 50,000. . When the molecular weight is in the above range, there is an advantage that high developability and high storage stability can be achieved. Further, (i) the presence of a nitrogen atom in the main chain portion in the specific resin of the present invention can be confirmed by a method such as acid titration, (ii) the presence of a functional group having a pKa of 14 or less, and The fact that the functional group is bonded to the nitrogen atom present in the main chain can be confirmed by methods such as base titration, nuclear magnetic resonance spectroscopy, and infrared spectroscopy. (Iii) The point having an oligomer chain or polymer chain “Y” having a number average molecular weight of 500 to 1,000,000 in the side chain should be confirmed by a method such as nuclear magnetic resonance spectroscopy / GPC method. Can do.

  Below, the specific example of specific resin of this invention is described with the molecular weight.

<(B) Black color material>
As the black color material that can be used in the present invention, various known black pigments and black dyes can be used. In particular, from the viewpoint of realizing a high optical density in a small amount, carbon black, titanium black, iron oxide, oxidation Manganese, graphite, and the like are preferable. Among them, carbon black and titanium black are preferable, and titanium black is most preferable.

The average primary particle size (average primary particle size) of the black pigment is preferably small from the viewpoint of foreign matter generation and the influence on the yield in the production of a solid-state imaging device. The average primary particle size is preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm or less.
The average particle diameter can be measured by applying a pigment to a suitable substrate and observing with a scanning electron microscope.

The content of the black color material in the black curable composition is not particularly limited, but is preferably as high as possible in order to obtain a high optical density with a thin film, and is 5 in the total solid content of the curable composition. -95 mass% is preferable, 10-95 mass% is still more preferable, 15-85 mass% is especially preferable.
If the amount of the black color material is too small, it is necessary to increase the film thickness in order to obtain a high optical density. If the amount of the black color material is too large, the photocuring does not proceed sufficiently and the strength as a film decreases, In some cases, the development latitude tends to narrow.

  The carbon black in the present invention is black fine particles including carbon fine particles, and preferred particles include carbon fine particles having a diameter of about 3 to 1000 nm. Further, the surface of the fine particles can have functional groups containing various carbon atoms, hydrogen atoms, oxygen atoms, sulfur atoms, nitrogen atoms, halogen atoms, inorganic atoms, and the like. Carbon black can be changed in its properties by variously changing the particle diameter (particle size), structure (particle connection), and surface properties (functional group) according to the intended application. It is also possible to change the blackness and affinity with the paint, or to provide conductivity.

  Carbon blacks suitable for the present invention include, for example, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 900 manufactured by Mitsubishi Chemical Corporation. 850, MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Rack N339, Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LP . Carbon black thermax N990, N991, N907, N908, N990, N991, N908 made by Cancarb. Carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa's carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2, ColorBlack Fw1, ColorBlack 170, BlackBlack, BlackBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printex140U, Printex140V Show Black Cabot Show Black N134, Show Black N110, Show Black N234, Show Black N220, Show Black N219, Show Black N285, Show Black N339, Show Black N330, Show Black N326, Show Black N351, Show Black N330T, Show Black IP200 , Show Black IP300, Show Black MAF, Show Black N500, Show Black N762, Nippon Kayaku Niteron # 300, Niteron # 200, Niteron # 200H, Niteron # 200IS, Niteron # 200L, Tokai Carbon Seast 9H, Seast 9 Seast 7HM, Seast 6, Seast 600, Seast 5H, Seast KH, Seast 3H, Seast 3, Seast 00, Seast NH, Seast N, Seast 3M, Seast SVH, Seast 116HM, Seast 116, Seast SO, Seast F, Seast FM, Seast V, Seast S, VULCAN10H made by Cabot, VULCAN9, VULCAN7H, VULCAN6, VULCAN6LM, LUGAL300VU M, VULCAN 3H, VULCAN 4H, VULCAN J, VULCAN 3, VULCAN 299, STERLING-SO, STERLING V, STERLING VH, STERLING 142, STERLING-NS, REGAL-SRF, and others Examples include carbon black Can.

  In addition, the carbon black in the present invention may preferably have insulating properties. The carbon black having an insulating property is a carbon black exhibiting an insulating property when the volume resistance as a powder is measured by the following method. For example, an organic substance is adsorbed, coated, or coated on the surface of the carbon black particles. It has an organic compound on the surface of carbon black particles, such as chemically bonded (grafted).

A method for measuring the volume resistance will be described below. For example, carbon black is dispersed in propylene glycol monomethyl ether so as to have a 20:80 mass ratio with benzyl methacrylate-methacrylic acid copolymer (molar ratio 70:30, weight average molecular weight 30,000) to prepare a coating solution. After coating on a chromium substrate having a thickness of 1.1 mm and 10 cm × 10 cm to prepare a coating film having a dry film thickness of 3 μm, the coating film was further heated in a hot plate at 220 ° C. for about 5 minutes, and then JIS. A volume resistivity value is measured in an environment of 23 ° C. and a relative humidity of 65% by applying with a high resistivity meter manufactured by Mitsubishi Chemical Co., Ltd., Hirestor UP (MCP-HT450) conforming to K6911.
Carbon black having a volume resistance value of 10 ⁵ Ω · cm or more, more preferably 10 ⁶ Ω · cm or more, and particularly preferably 10 ⁷ Ω · cm or more is preferable.

  As the carbon black as described above, for example, JP-A-11-60988, JP-A-11-60989, JP-A-10-330634, JP-A-11-80583, JP-A-11-80584, Carbon black whose surface is coated with a resin as disclosed in JP-A-9-124969, JP-A-9-95625 and the like can be used.

The titanium black of the present invention is black particles having 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, zirconium oxide, and can also be treated with a water repellent material as disclosed in JP-A-2007-302836. .
Further, the titanium black of the present invention is a black pigment such as a complex oxide such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline black, etc. for the purpose of adjusting dispersibility, colorability and the like. May be contained in one kind or a combination of two or more kinds. In this case, the titanium black particles occupy 50% by mass or more of the pigment.

In addition, for the purpose of controlling the light-shielding property at a desired wavelength, it is also possible to add existing colorants such as pigments such as red, blue, green, yellow, cyan, magenta, violet and orange, or dyes. .
The pigment used in combination is preferably used in the range of 2 to 50 parts by mass, more preferably 2 to 30 parts by mass of the combined pigment, with respect to 100 parts by mass of the sum of the black pigment and the combined pigment. The combined pigment is preferably 2 to 10 parts by mass.

  Examples of commercially available titanium black products include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, Ako Kasei Co., Ltd., and Tilac D manufactured by Mitsubishi Materials Corporation.

  Titanium black is produced by heating a mixture of titanium dioxide and metal titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No. Sho 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), etc. is not.

The primary particle size of the titanium black particles is not particularly limited, but is preferably 3 to 150 nm, more preferably 10 to 100 nm, from the viewpoint of dispersibility and colorability.
The specific surface area of the titanium black is not particularly limited, but the water repellency after the surface treatment of the titanium black with a water repellent agent has a predetermined performance. Therefore, the value measured by the BET method is usually 5 to 150 m. ² / g approximately, it is preferably Among them, 20 to 100 m ² / g approximately.

In the present invention, the black color material is preferably a black dispersion composition before the black curable composition. The black dispersion composition can be obtained by preparing the above-described black pigment or the above-described combination pigment by dispersing it with a dispersant and a solvent.
As the dispersant, a dispersant described later is preferably used. Further, it may be added at the time of pigment processing to be used as a pigment coating type dispersant, or may be added as a dispersant when a pigment such as titanium black is dispersed by a dispersing machine such as a bead mill.

  The preparation mode of the dispersion composition of the present invention is not particularly limited. For example, the pigment, the dispersant, and the solvent are mixed with a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, or the like. It can be obtained by carrying out fine dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 to 1 mm.

Before performing bead dispersion, knead and disperse using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder while applying strong shearing force. It is also possible to perform processing.
For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

<(C) Solvent>
The dispersion of the present invention has at least one (C) solvent. (C) As a solvent, in consideration of the solubility of each component contained in the pigment dispersion and the applicability when applied to a curable composition, one or more organic solvents shown below are used. Basically, it is not particularly limited as long as these desired physical properties are satisfied, but it is preferably selected in consideration of safety.

  Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl oxyacetate, and ethyl oxyacetate. , Butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3-methoxypropion Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methoxypropion Ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2 -Methyl methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

  Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate (ethylene glycol monomethyl ether acetate), ethyl cellosolve acetate (ethylene glycol monoethyl ether acetate), diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, pro Glycol propyl ether acetate; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; and aromatic hydrocarbons, e.g., toluene, xylene and the like; are preferred.

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate (PGMEA) and the like are more preferable.

  As content of the (C) solvent in the dispersion liquid of this invention, 2-90 mass% is preferable, 2-80 mass% is more preferable, 5-70 mass% is the most preferable.

<Black curable composition>
By further adding (D) a photopolymerization initiator and (E) a compound containing an ethylenically unsaturated double bond to the dispersion of the present invention, resolution, color characteristics, coatability, developability, etc. It is possible to provide a black curable composition excellent in the above.

<(D) Photopolymerization initiator>
The black curable composition of the present invention contains a photopolymerization initiator.
The photopolymerization initiator in the present invention is a compound that is decomposed by light and starts and accelerates polymerization of a compound containing an ethylenically unsaturated double bond described later (E), and has an absorption in a wavelength region of 300 to 500 nm. It is preferable. Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

  Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaaryls. Examples include rubiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62 -212401, JP-A-63-70243, JP-A-63-298339, M.S. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and in particular, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

Oki The source diazole compounds include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxadiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) , Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl methyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, and methyl o-benzoyl benzoate.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaful Lophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

As the biimidazole compound, for example, a hexaarylbiimidazole compound (rophine dimer compound) is preferable.
Examples of the hexaarylbiimidazole compound include lophine dimers described in JP-B-45-37377 and JP-B-44-86516, JP-B-6-29285, U.S. Pat. No. 3,479,185, and the like. Various compounds described in each specification such as 4,311,783 and 4,622,286, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) vididazole, 2, 2'-bis (o , O′-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5 Examples include '-tetraphenylbiimidazole.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, and Kunz, Martin “Rad Tech'98. Proceeding April 19-22, 1998, Chicago”. The organic borate described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, or organic boron oxosulfonium complex, JP-A-6-175554 No. 6, JP-A-6-175553 Organoboron iodonium complexes described in JP-A-9-188710, organoboron phosphonium complexes described in JP-A-9-348710, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

  Examples of oxime photopolymerization initiators include J. Org. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Japanese Patent Application Laid-Open No. 2000-66385, Japanese Patent Application Laid-Open No. 2000-80068, Japanese Patent Application Publication No. 2004-534797 Compounds and the like.

  Specific examples of oxime initiators suitable for the present invention are shown below.

  As a more preferable oxime-based photopolymerization initiator, the following formula (3) is more preferable from the viewpoints of sensitivity, diameter stability, and coloring during post-heating.

In the general formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. r is an integer of 1-5.
Although the specific example of General formula (3) is shown below, it is not limited to these structures.
X in the general formula (3) is preferably an alkyl group having 1 to 10 carbon atoms or a halogen atom, and most preferably an alkyl group having 1 to 5 carbon atoms. R is preferably an acyl group having 1 to 20 carbon atoms, and most preferably an acyl group having 1 to 5 carbon atoms. A is preferably an alkylene group having 1 to 10 carbon atoms, and most preferably an alkylene group having 1 to 5 carbon atoms. Ar is preferably a phenyl group or a halogen atom-containing aryl group, and most preferably a halogen atom-containing aryl group. n is preferably 1 to 3, and most preferably 1.

  Specific examples of the oxime compound include the following compounds, preferably the compound of the general formula (3). Moreover, it is not limited to the compound illustrated below.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. . In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  As the photopolymerization initiator (D) used in the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, phosphine Oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxa Compounds selected from the group consisting of diazole compounds and 3-aryl substituted coumarin compounds are preferred.

  More preferably, they are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

  In particular, when the curable composition of the present invention is used for the production of a solid-state imaging device of a color filter, it is necessary to form fine pixels with a sharp shape, and therefore, a fine unexposed portion with curable properties. It is important to develop without residue. From such a viewpoint, an oxime compound is particularly preferable. In particular, when fine pixels are 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 can be said that the use of an oxime compound as a photopolymerization initiator (F) is most preferable for forming a finely colored pattern such as a solid-state imaging device.

  The content of the (D) photopolymerization initiator contained in the curable composition of the present invention is preferably 0.1 to 50% by mass, more preferably 0, based on the total solid content of the curable composition. 0.5 to 30% by mass, particularly preferably 1 to 20% by mass. Within this range, good sensitivity and pattern formability can be obtained.

<(E) Compound containing ethylenically unsaturated double bond>

  The compound (E) containing an ethylenically unsaturated double bond that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least a terminal ethylenically unsaturated bond. It is selected from compounds having one, preferably two or more. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof.

  Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. Those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Furthermore, monomers containing acid groups can also be used, for example, (meth) acrylic acid, pentaerythritol triacrylate succinic acid monoester, dipentaerythritol pentaacrylate succinic acid monoester, pentaerythritol triacrylate maleic acid monoester, dipenta Erythritol pentaacrylate maleic acid monoester, pentaerythritol triacrylate phthalic acid monoester, dipentaerythritol pentaacrylate phthalic acid monoester, pentaerythritol triacrylate tetrahydrophthalic acid monoester, dipentaerythritol pentaacrylate tetrahydrophthalic acid monoester It is done. In these, pentaerythritol triacrylate succinic acid monoester etc. are mentioned.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group in a compound represented by the following general formula to a polyisocyanate compound having two or more isocyanate groups. Etc.

Formula ^{_{CH 2 = C (R 10)}} COOCH 2 CH (R 11) OH
(However, R ¹⁰ and R ¹¹ represent H or CH _3. )

  Further, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56-17654 Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Furthermore, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238 Can obtain a photopolymerizable composition having an excellent photosensitive speed.

  Other examples include reacting polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. And polyfunctional acrylates and methacrylates such as epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 are also included. be able to. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these addition polymerizable compounds, the details of usage methods such as the structure, single use or combined use, addition amount and the like can be arbitrarily set according to the performance design of the curable composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image area, that is, the cured film, those having three or more functionalities are preferable. Further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether type). A method of adjusting both sensitivity and strength by using a compound) is also effective. From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. preferable. Moreover, it is preferable to contain an EO modified body from a viewpoint of hardening sensitivity and the developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.

  In addition, the selection and use method of the addition polymerization compound is also an important factor for compatibility and dispersibility with other components in the curable composition (for example, resin, photopolymerization initiator, black color material). For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion with a substrate or the like.

  From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Manufactured), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoei), UA-7200 (Shin Nakamura Chemical Co., Ltd.) And TO-1382 (manufactured by Toagosei Co., Ltd.) are preferable.

  Among them, bisphenol A diacrylate EO modified, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, di Examples of commercially available modified products such as pentaerythritol hexaacrylate EO include DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 ( Kyoeisha) is more preferable.

  The content of the compound (E) containing an ethylenically unsaturated double bond in the present invention is preferably 1% by mass to 90% by mass in the solid content of the black curable composition of the present invention. It is more preferably from 80% by mass to 80% by mass, and further preferably from 10% by mass to 70% by mass.

  In particular, when the black curable composition of the present invention is used for forming a coloring pattern of a color filter, the content of the compound (E) containing an ethylenically unsaturated double bond is 5% by mass to 50% in the above range. The mass is preferably 7% by mass, more preferably 7% by mass to 40% by mass, and still more preferably 10% by mass to 35% by mass.

The black curable composition of this invention may further contain the arbitrary components explained in full detail below as needed.
Hereinafter, optional components that the black curable composition of the present invention may contain will be described.

<Sensitizer>
The black curable composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength.
As the sensitizer that can be used in the present invention, those sensitized by an electron transfer mechanism or an energy transfer mechanism are preferable.

Examples of the sensitizer used in the black curable composition of the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
That is, for example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), Thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, Toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squaryu (Eg, squalium), acridine orange, coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes Carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, etc. Examples include aromatic ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

  More preferable examples of the sensitizer in the black curable composition of the present invention include compounds represented by the following general formulas (e-1) to (e-4).

(In formula (e-1), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ¹ represents the basicity of the dye in combination with adjacent A ¹ and the adjacent carbon atom. Represents a nonmetallic atomic group forming a nucleus, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of a dye. W may represent an oxygen atom or a sulfur atom.)

(In Formula (e-2), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ² —, where L ² represents —O— or —S—. In addition, W is synonymous with that shown in Formula (e-1).)

(In the formula (e-3), A ² represents a sulfur atom or NR ⁵⁹ , L ³ represents a nonmetallic atomic group that forms a basic nucleus of the dye in combination with adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent non-metallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.)

(In Formula (e-4), A ³ and A ⁴ each independently represent —S— or —NR ⁶² , R ⁶² represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and L ⁴ and L ⁵ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in cooperation with adjacent A ³ and A ⁴ and adjacent carbon atoms, and R ⁶⁰ and R ⁶¹ each independently represent a monovalent group. And can be bonded to each other to form an aliphatic or aromatic ring.)

The content of the sensitizer in the black curable composition of the present invention is preferably 0.1 to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency. 0.5-15 mass% is more preferable.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

Moreover, as a preferable sensitizer which can be contained in the black curable composition of the present invention, in addition to the above sensitizer, a compound represented by the following general formula (II), and a general formula (III) described later are used. And at least one selected from the following compounds.
These may be used individually by 1 type, and may use 2 or more types together.

In general formula (II), R ¹¹ and R ¹² each independently represents a monovalent substituent, and R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. Represent. s ¹ represents an integer of 0 to 5, s ² represents an integer of 0 to 5, and s ¹ and s ² are not both 0. When s ¹ is 2 or more, a plurality of R ¹¹ may be the same or different. When s ² is 2 or more, a plurality of R ¹² may be the same or different. In the general formula (II), the isomer by the double bond is not limited to either.

The compound represented by the general formula (II) preferably has a molar extinction coefficient ε at a wavelength of 365 nm of 500 mol ⁻¹ · L · cm ⁻¹ or more, and ε at a wavelength of 365 nm of 3000 mol ⁻¹ · L · cm ^{−. 1} or more is more preferable, and ε at a wavelength of 365 nm is most preferably 20000 mol ⁻¹ · L · cm ⁻¹ or more. It is preferable that the value of the molar extinction coefficient ε at each wavelength is in the above range because the sensitivity improvement effect is high from the viewpoint of light absorption efficiency.

Although the preferable specific example of a compound represented by general formula (II) is illustrated below, this invention is not limited to these.
Note that in this specification, a chemical formula may be described by a simplified structural formula, and a solid line or the like that does not clearly indicate an element or a substituent particularly represents a hydrocarbon group.

In General Formula (III), B ¹ represents an aromatic ring or a hetero ring that may have a substituent, X ² represents an oxygen atom, a sulfur atom, or —N (R ²³ ) —, and B ² represents oxygen atom, a sulfur atom, or -N ^{(R 23)} - represents a. R ²¹ , R ²² , and R ²³ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, and B ¹ , R ²¹ , R ²² , and R ²³ are bonded to each other to form an aliphatic group Or aromatic rings may be formed.

In the general formula (III), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group. When R ²¹ , R ²² and R ²³ represent a monovalent nonmetal atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group It is preferably a heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

In the compound represented by the general formula (III), B ² is preferably an oxygen atom or —N (R ²³ ) — from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator. R ²³ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group. Further, B ² is most preferably —N (R ²³ ) —.

  Hereinafter, although the preferable specific example of a compound represented by general formula (III) is shown, this invention is not limited to this. Further, it is not clear about an isomer by a double bond connecting an acidic nucleus and a basic nucleus, and the present invention is not limited to either isomer.

[(G) Co-sensitizer]
The black curable composition of the present invention preferably further contains (G) a co-sensitizer.
In the present invention, the co-sensitizer further improves the sensitivity of the photopolymerization initiator and (F) sensitizer to actinic radiation, or suppresses polymerization inhibition of the (E) ethylenically unsaturated compound by oxygen, etc. Has an effect.

  Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these co-sensitizers is 0.1 to 30 mass with respect to the mass of the total solid content of the black curable composition of the present invention, from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. % Is preferable, a range of 1 to 25% by mass is more preferable, and a range of 0.5 to 20% by mass is further preferable.

<Alkali-soluble resin>
The alkali-soluble resin that can be used in the present invention is a linear organic polymer, and at least 1 in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having two groups that promote alkali solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group, hydroxyl group, etc.).
More preferable as the alkali-soluble resin is a polymer having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid, as described in Japanese Unexamined Patent Publication Nos. 59-53836 and 59-71048. Acrylic copolymers such as acid copolymers, partially esterified maleic acid copolymers, etc., acidic cellulose derivatives having carboxylic acids in the side chains, and polymers having hydroxyl groups with acid anhydrides added. Can be mentioned.
As an acid value, the range of 30-150 mgKOH / g is preferable, and the range of 35-120 mgKOH / g is the most preferable.

As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Examples of the alkyl (meth) acrylates and aryl (meth) ^{_{acrylate, CH 2 = C (R 1}} ) (COOR 3) [wherein, ^{R 1} represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, ^{R 2} Represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) ) Acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl is an alkyl group having 1 to 8 carbon atoms) ), Hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate and the like.

A resin having a polyalkylene oxide chain in the molecular side chain is also preferred. The polyalkylene oxide chain may be a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or a combination thereof, and the terminal is a hydrogen atom or a linear or branched alkyl group.
1-20 are preferable and, as for the repeating unit of a polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable. Acrylic copolymers having a polyalkylene oxide chain in these side chains are, for example, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate , Poly (ethylene glycol-propylene glycol) mono (meth) acrylate and the like, and compounds in which these terminal OH groups are alkyl-blocked, such as methoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, methoxypoly (ethylene glycol) -An acrylic copolymer having propylene glycol) mono (meth) acrylate or the like as a copolymerization component.

In addition, as the vinyl compound, CH ₂ = CR ¹ R ² [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms. R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. Specific examples include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like.
These other copolymerizable monomers can be used singly or in combination of two or more. Other preferable copolymerizable monomers are alkyl (meth) acrylate (alkyl is an alkyl group having 2 to 4 carbon atoms), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene.
Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.

The acrylic copolymer has an acid value in the range of 20 to 200 mgKOH / g, as already described. When the acid value exceeds 200, the acrylic copolymer becomes too soluble in alkali and the appropriate development range (development latitude) becomes narrow. On the other hand, if it is too small, such as less than 20, the solubility in alkali is small and it takes too much time for development, which is not preferable.
Moreover, the mass average molecular weight Mw (polystyrene conversion value measured by GPC method) of the acrylic copolymer is used to realize a viscosity range that is easy to use in a process such as applying a color resist, and to ensure film strength. Therefore, it is preferably 2,000 to 100,000, more preferably 3,000 to 50,000.
In order to make the acid value of an acrylic copolymer into the range specified above, it can carry out easily by adjusting the copolymerization ratio of each monomer appropriately. Moreover, the range of the weight average molecular weight can be easily achieved by using an appropriate amount of a chain transfer agent according to the polymerization method in the copolymerization of the monomers.
The acrylic copolymer can be produced, for example, by a known radical polymerization method. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an acrylic copolymer by radical polymerization can be easily set by those skilled in the art. Condition setting is possible.

  The addition amount when adding the alkali-soluble resin to the black curable composition of the present invention is preferably 5 to 90% by mass, more preferably 10 to 60% by mass, based on the total solid content of the composition. . When the amount of the alkali-soluble resin is less than 5% by mass, the film strength is lowered. When the amount is more than 90% by mass, the acid content increases, so that it becomes difficult to control the solubility and the pigment is relatively reduced. Therefore, sufficient image density cannot be obtained. If it is in this range, it is preferable in that it becomes easy to obtain a coating film having an appropriate thickness that provides a necessary color density. In particular, the yield is high with respect to slit coating suitable for coating on a wide substrate having a large area, and a good coating film can be obtained.

In order to improve the crosslinking efficiency of the black curable composition in the present invention, a resin having a polymerizable group in an alkali-soluble resin may be used alone or in combination with an alkali-soluble resin having no polymerizable group, Polymers containing an aryl group, a (meth) acryl group, an aryloxyalkyl group or the like in the side chain are useful.
The alkali-soluble resin having a polymerizable double bond can be developed with an alkali developer, and is further provided with photocurability and thermosetting.
Examples of polymers containing these polymerizable groups are shown below, but are not limited to the following as long as alkali-soluble groups such as COOH groups and OH groups and carbon-carbon unsaturated bonds are included.
(1) Urethane modification obtained by reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and reacting at least one (meth) acryloyl group with an acrylic resin containing a carboxyl group Polymerizable double bond-containing acrylic resin, (2) unsaturated group-containing acrylic resin obtained by reaction of an acrylic copolymer containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule ,
(3) Acid pendant type epoxy acrylate resin,
(4) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic copolymer containing an OH group with a dibasic acid anhydride having a polymerizable double bond.
Among the above, the resins (1) and (2) are particularly preferable.

  The acid value of the alkali-soluble resin having a polymerizable double bond in the present invention is preferably in the range of 30 to 150 mgKOH / g, more preferably 35 to 120 mgKOH / g, and the weight average molecular weight Mw is preferably 2 1,000 to 100,000, more preferably 3,000 to 50,000.

  As a specific example, a copolymer of an OH group such as 2-hydroxyethyl acrylate, a COOH group such as methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable with these, an OH group A compound obtained by reacting an epoxy ring having reactivity with a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used. In the reaction with the OH group, a compound having an acid anhydride, an isocyanate group, or an acryloyl group in addition to the epoxy ring can be used. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used.

  Examples of the compound having both an alkali solubilizing group such as a COOH group and an intercarbon unsaturated group include, for example, Dynar NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Ltd .; Biscort R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel) And UCB Co., Ltd.).

<Other polymers>
The black curable composition of the present invention has other polymer materials [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid from the viewpoint of improving dispersion stability and developing property control. Ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], and polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine A dispersant such as can be further added. Such other polymer materials can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.

  The above-mentioned polymer material that can be used in combination acts on the surface of the pigment 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. Specific examples of other polymer materials that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group)”, 130, manufactured by BYK Chemie. (Polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, manufactured by EFKA Corporation ” 4010, 4165 (polyurethane-based), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (Phthalocyanine derivative), 6750 ( "Zo pigment derivative)", "Ajisper PB821, PB822" manufactured by Ajinomoto Fine Techno Co., Ltd., "Floren TG-710 (urethane oligomer)" manufactured by Kyoeisha, "Polyflow No. 50E, No. 300 (acrylic copolymer)", Enomoto “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Kasei Corporation, manufactured by Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," acetamine 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft-type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) "manufactured by Nikko Chemical Co., Ltd. Alternatively, methacrylic acid / benzyl methacrylate, preferably, methacrylic acid / benzyl methacrylate having an acid value of 20 to 150 mgKOH can be used.

These polymer materials may be used alone or in combination of two or more. When the polymer material is used in combination, the content of the polymer material in the present invention is preferably 1% by mass to 100% by mass with respect to the specific resin of the present invention, and 3% by mass to 80% by mass. More preferably, 5% by mass to 50% by mass is even more preferable.
Since the pigment dispersion of the present invention uses the specific resin of the present invention as a pigment dispersant, the pigment dispersion is excellent in pigment dispersibility and dispersion stability even when a fine pigment is contained at a high concentration.

<Polymerization inhibitor>
In the present invention, a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the black curable composition. Is desirable.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

  The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the black curable composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

<Other additives>
Furthermore, in the present invention, in order to improve the physical properties of the cured film, a known additive such as an inorganic filler, a plasticizer, or a substrate adhesive that can improve the substrate adhesion may be added.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and a binder.

When the black curable composition of the present invention is applied to the surface of a hard material such as a substrate, an additive for improving the adhesion to the surface of the hard material (hereinafter referred to as “substrate adhesion agent”). May be added.
As the substrate adhesion agent, known materials can be used, but it is particularly preferable to use a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane and phenyltrimethoxysilane are preferred, and γ-methacryloxypropyltrimethoxysilane is most preferred.

  Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite). ) Titanate, tetra (2,2-diallyloxymethyl) bis (di-tridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldi Methacrylic isostearoyl titanate, isopropyl isostearoyl diacryl titanate, Li isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- amidoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.

  The content of the substrate adhesive is 0.1% by mass or more and 30% or more based on the total solid content of the curable composition of the present invention, from the viewpoint of leaving no residue in the unexposed portion of the black curable composition. It is preferably at most mass%, more preferably at least 0.5 mass% and at most 20 mass%, particularly preferably at least 1 mass% and at most 10 mass%.

<Color filter and manufacturing method thereof>
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of the present invention is characterized by having a colored pattern formed on the support using the black curable composition for a color filter of the present invention.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

  The method for producing a color filter of the present invention comprises a step of applying a black curable composition for a color filter of the present invention on a support to form a black curable composition layer (hereinafter appropriately referred to as “black curable composition”). Abbreviated as “layer forming step”), a step of exposing the black curable composition layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and the black curable composition after exposure. And a step of developing the layer to form a colored pattern (hereinafter abbreviated as “development step” as appropriate).

Specifically, the black curable composition for a color filter of the present invention is applied on a support (substrate) directly or via another layer to form a black curable composition layer (black curable composition). Composition layer forming step), exposing through a predetermined mask pattern, curing only the light-irradiated coating film portion (exposure step), and developing with a developer (developing step), each color (three colors or The color filter of the present invention can be manufactured by forming a patterned film composed of (four colors) pixels.
Hereinafter, each process in the manufacturing method of the color filter of this invention is demonstrated.

[Black curable composition layer forming step]
In the black curable composition layer forming step, the black curable composition layer for a color filter of the present invention is applied on a support to form a black curable composition layer.

As the support that can be used in this step, for example, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these glasses, imaging elements, etc. Examples of the photoelectric conversion element substrate include a silicon substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  As a coating method of the black curable composition for a color filter of the present invention on a support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like are applied. be able to.

The coating thickness of the black curable composition for color filters is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm, still more preferably 0.2 μm to 3 μm, in terms of the film thickness after pre-baking. .
Moreover, when manufacturing the color filter for solid-state image sensors, as a coating film thickness of the black curable composition for color filters, it converts into the film thickness after a prebaking from a viewpoint of resolution and developability, and is 0. .35 μm to 1.5 μm is preferable, and 0.40 μm to 1.0 μm is more preferable.

  The black curable composition for a color filter applied on the support is usually dried at 70 ° C. to 110 ° C. for about 2 minutes to 4 minutes to form a black curable composition layer.

[Exposure process]
In the exposure step, the black curable composition layer formed in the black curable composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is preferably from ^{5mJ / cm 2 ~1500mJ / cm 2} , more preferably ^{10mJ / cm 2 ~1000mJ / cm 2} , 10mJ / cm 2 ~800mJ / cm 2 being most preferred. In particular, 100 to 800 mJ / cm ² is preferable for solid-state imaging device applications, and 50 to 500 mJ / cm ² is most preferable for LCD applications.

[Development process]
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part remains.
As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

  As the alkali used in the developer, for example, an inorganic developer such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metaoxalate or the like can be used, but preferably an organic developer. Specifically, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0]- An alkaline aqueous solution obtained by diluting an organic alkaline compound such as 7-undecene with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  In addition, in the manufacturing method of the color filter of this invention, after performing the black curable composition layer formation process mentioned above, an exposure process, and the image development process, the formed colored pattern is heated and / or exposed as needed. It may include a curing step for curing.

  By repeating the black curable composition layer forming step, the exposure step, and the developing step (and the curing step if necessary) described above for the desired number of hues, a color filter having a desired hue is produced.

Since the color filter of the present invention uses the black curable composition for a color filter of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition is resistant to development. Since it is excellent, it is possible to form a high-resolution pattern that has excellent exposure sensitivity, good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape. Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. That is, the color filter of the present invention is preferably applied to a solid-state image sensor.
The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these. Unless otherwise specified, “part” is based on mass.
In the examples, acid value and amine value are determined by potentiometric method (solvent tetrahydrofuran / water = 100/10 (volume ratio), titrant 0.01N aqueous sodium hydroxide solution (acid value), 0.01N hydrochloric acid (amine value). ).

(Synthesis Example 1) Synthesis of Polyester (i-1) 6.4 g of n-octanoic acid, 200 g of ε-caprolactone and 5 g of titanium (IV) tetrabutoxide were mixed, heated at 160 ° C. for 8 hours, and then cooled to room temperature. Polyester (i-1) was obtained.
The scheme is shown below.

(Synthesis Examples 2 to 10)
Polyesters (i-2) to (i-10) were obtained in the same manner as in Synthesis Example 1 except that the carboxylic acid and lactone were changed as shown in Table 1 in Synthesis Example 1 and the amount of carboxylic acid charged was changed. It was. The number average molecular weight and weight average molecular weight of the resins obtained in these synthesis examples were measured by the GPC method described above. The results are shown in Table 1 below. The number of lactone repeating units calculated from the raw material charging ratio is shown in Table 1 below.

(Synthesis Example 11) Synthesis of Polyester (i-11) Under a nitrogen stream, 100 g of 12-hydroxystearic acid, 0.1 g of titanium (IV) tetrabutoxide and 300 g of xylene are mixed, and water generated at an external temperature of 160 ° C. is dean. The reaction was conducted while distilling off with a Stark tube. When the number average molecular weight in GPC measurement was 8,000 and the weight average molecular weight was 12,000, the heating was stopped to obtain polyester (i-11).

(Synthesis Example 12) Synthesis of Polyester (i-12) The same experiment as in Synthesis Example 11 was performed, and when the number average molecular weight in GPC measurement was 6,000 and the weight average molecular weight was 11,000, heating was stopped, Polyester (i-12) was obtained.

(Synthesis Example 13) Synthesis of Polyester (i-13) Dean Stark tube was used to generate water that produces 307 g of adipic acid, 110 g of neopentyl glycol, 57 g of 1,4-butanediol and 26 g of ethylene glycol at an external temperature of 160 ° C. under a nitrogen stream. The reaction was carried out while distilling off. When the number average molecular weight in GPC measurement was 8,000 and the weight average molecular weight was 13,000, the reaction was stopped to obtain polyester (i-13).

Synthesis Example 14 Synthesis of Macromonomer (i-14) 50 g (500 mmol) of methyl methacrylate, 100 g of propylene glycol monomethyl ether, and 2.5 g (23.6 mmol) of 2-mercaptopropionic acid were heated to 80 ° C. in a nitrogen stream. did. Next, 0.1 g of V-601 (azobis (isobutyric acid) dimethyl Wako Pure Chemical Industries, Ltd.) was added, and after 3 hours, 0.1 g of V-601 was further added and heated for 4 hours. Thereafter, 3.35 g (23.6 mmol) of glycidyl methacrylate and 0.5 g of tetrabutylammonium bromide were added and heated at 80 ° C. for 5 hours. After cooling, reprecipitation was performed using a mixed solvent of 200 mL of water and 800 mL of methanol, and after drying, 55 g of macromonomer (i-14) was obtained.

(Synthesis Example 15)
[Synthesis of Resin (J-1)]
10 g of polyethyleneimine (SP-018, number average molecular weight 1,800, manufactured by Nippon Shokubai) and 100 g of polyester (i-1) as Y precursor y were mixed and heated at 120 ° C. for 3 hours to obtain an intermediate (J -1B) was obtained. Thereafter, the mixture is allowed to cool to 65 ° C., and 200 g of propylene glycol 1-monomethyl ether 2-acetate (hereinafter sometimes referred to as PGMEA) containing 3.8 g of succinic anhydride as the X precursor x is slowly added and stirred for 2 hours. did. Thereafter, PGMEA was added to obtain a 10 mass% PGMEA solution of the resin (J-1). Resin (J-1) has a side chain derived from polyester (i-1) and a group having a functional group (carboxyl group) having a pKa derived from succinic anhydride of 14 or less.
A synthesis scheme is shown below.

When acid value titration of the intermediate (J-1B) was performed, it was confirmed that the acid value was 0.11 mmol / g. Moreover, when the amine titration and acid titration of resin (J-1) were performed, the acid value was 0.31 mmol / g and the amine value was 0.83 mmol / g. That is, from the difference between the acid value of the resin (J-1) and the acid value of the intermediate (J-1B), the mol% of the repeating unit corresponding to the general formula (J-1)) is the resin (J-1). (L ₁ + l ₂ ) (= mol% of the repeating unit corresponding to the general formula (I-2)) is an acid of the intermediate (J-1B) from the difference between the amine value of the resin and the number of nitrogen atoms of the resin before the reaction The mol% of (m ₁ + m ₂ ) (= the repeating unit corresponding to the general formula (I-3)) can be calculated from the valence, k / (l ₁ + l ₂ ) / (m ₁ + m ₂ ) / n = 10 / 50/5/35.
That is, in the repeating unit represented by the general formula (I-1), 10 mol% of the repeating unit in which X is —COCH ₂ CH ₂ CO ₂ H, and the repeating unit represented by the general formula (I-2) , Y is a resin containing 50 mol% of poly (ε-caprolactone). Moreover, the weight average molecular weight by GPC method was 24,000.

(Synthesis Examples 16 to 31)
[Synthesis of Resins (J-2) to (J-13)]
As shown in Table 2 and Table 3, the synthesis was performed in the same manner as in Synthesis Example 15 except that the amino group-containing resin, the X precursor x, and the polyester obtained in Synthesis Examples 1 to 13 were used. PGMEA 10 mass% solutions of resins (J-2) to (J-13) were obtained. Resin (J-13) was prepared by reprecipitation of the reaction solution with water, drying, and making a 10% by mass solution with PEGMA.
The amino group-containing resin used for the synthesis is as shown below.
SP-003 (polyethyleneimine (made by Nippon Shokubai) number average molecular weight 300)
SP-006 (polyethyleneimine (made by Nippon Shokubai) number average molecular weight 600)
SP-012 (polyethyleneimine (made by Nippon Shokubai) number average molecular weight 1,200)
SP-018 (polyethyleneimine (made by Nippon Shokubai) number average molecular weight 1,800)

(Synthesis Example 32)
[Synthesis of Resin (J-14)]
In a reactor equipped with a Dean-Stark tube, 100 g of polyallylamine (PAA-03, weight average molecular weight 3,000, manufactured by Nippon Shokubai) aqueous solution and 500 g of toluene were refluxed at an external temperature of 130 ° C. until distillation of water stopped, Thereafter, it was concentrated to remove toluene. Next, 100 g of polyester (i-1) was mixed and heated at 120 ° C. for 3 hours. Then, it stood to cool to 65 degreeC, PGMEA200g containing 3.8g of succinic anhydrides (X precursor x) was added slowly, and it stirred for 2 hours. Then, PGMEA was added and the 10 mass% solution of PGMEA of resin (J-14) was obtained.

(Synthesis Examples 33 to 40)
[Synthesis of Resins (J-15) to (J-26)]
As shown in Table 2 and Table 3, the synthesis was performed in the same manner as in Synthesis Example 32 except that the amino group-containing resin, the X precursor x, and the polyester obtained in Synthesis Examples 1 to 13 were used. A 10 mass% solution of PGMEA of resins (J-15) to (J-26) was obtained.
The amino group-containing resin used for the synthesis is as shown below.
PAA-01 (polyallylamine (manufactured by Nittobo) weight average molecular weight 1,000)
PAA-03 (polyallylamine (manufactured by Nittobo) weight average molecular weight 3,000)
PAA-05 (polyallylamine (manufactured by Nittobo) weight average molecular weight 5,000)
PAA-08 (polyallylamine (manufactured by Nittobo) weight average molecular weight 8,000)

( Reference Synthesis Example 41 )
[Synthesis of Resin (J-27)]
Monomer (B) 0.50 g (3.5 mmol), macromonomer (i-14) 55 g (23 mmol), methacrylate 2- (N, N-dimethylaminoethyl) (9.6 mmol) 1.50 g, dodecanethiol 0 0.2 g (1.0 mmol) was dissolved in a mixed solvent of 200 g of dimethyl sulfoxide and 100 g of N-methylpyrrolidone. After heating to 80 ° C., 0.1 g of V-601 was added and stirred for 3 hours. Thereafter, 0.1 g of V-601 was added, and the mixture was stirred for 3 hours and then allowed to cool. The obtained solution was dropped into 4000 L of water over 1 hour, and the precipitated resin was collected by filtration. After drying, it was dissolved in 1-methoxy-2-propanol to obtain a 10% by mass solution.
A synthesis scheme is shown below.

(Synthesis Examples 42 to 44)
[Synthesis of Comparative Resins (J-28) to (J-30)]
In Synthesis Examples 15 to 17, the same operation was performed except that succinic anhydride as the X precursor x was not added, and comparative resins (J-28) to (J-30) were obtained.

(Measurement of acid value and amine value)
The acid values and amine values of the obtained resins (J-1) to (J-27) and comparative resin resins (J-28) to (J-30) were measured by the methods described above. The results are shown in Tables 2 and 3.
From these measurement results, it was confirmed that a functional group having a pKa of 14 or less was present in the side chain of the intermediate acid value and the target resin acid value.

[Preparation of dispersion]
[Example 1]
A black color material (described in Table 4), a dispersion resin, an alkali-soluble resin (benzyl methacrylate / methacrylic acid copolymer (= 70/30 molar ratio, Mw: 30000) in a propylene glycol monomethyl acetate solution (solid content: 40% by mass) The mixture was mixed according to Table 4 and subjected to a high-viscosity dispersion treatment with two rolls, and the viscosity at this time was designated as viscosity A. Next, an alkali-soluble resin (coordinating benzyl methacrylate / methacrylic acid) was added to the obtained dispersion. 10 parts of a polymer propylene glycol monomethyl acetate solution) and 200 parts of propylene glycol monomethyl ether acetate were added and stirred for 3 hours using a homogenizer under the condition of 3000 rpm, and the resulting mixed solution was mixed with 0.3 mm diameter zirconia beads. Using a disperser (trade name Dispermat GETZM Subjected to 5 hours finely dispersed by NN Co.), dispersion (L-1) was prepared. To the viscosity at this time is the viscosity B.

The viscosity of the obtained dispersion was measured, and the dispersion stability (storage temperature 25 ° C.) was evaluated.
-Evaluation criteria-
○: After one month of dispersion, the viscosity increase was 0 to less than 5%.
Δ: After one month of dispersion, an increase in viscosity of 5% or more and less than 10% was observed.
X: An increase in viscosity of 10% or more was observed after one month of dispersion.

In the “black color material” in Table 4, A and B are as follows.
A: Titanium black 13M-T (manufactured by Gemco) (average primary particle size 60 nm)
B: Carbon black (Pigment Black 7) (average primary particle diameter 15 nm).
In Table 4, the numbers in parentheses in the columns of the black color material, the dispersion resin, and the alkali-soluble resin represent the mass parts of each material used (in the case of a solution, the mass part of solid content).

  Table 4 shows the following. In the examples using the dispersion resins J-1 to J-26, which are specific resins of the present invention, the viscosity of the dispersion (viscosity B) is low, and even when the dispersion is stored for 1 month, almost no increase in viscosity is observed. There wasn't. On the other hand, in the comparative example not using the specific resin of the present invention, the dispersion had a high viscosity, and the viscosity increased greatly upon storage, so that the storage stability was poor and could not be used.

[Examples 2 to 26, Reference Example 27 , and Comparative Examples 28 to 30]
In Example 1 except that the type of black color material, the amount thereof, the type of dispersion resin, and the amount of alkali-soluble resin were changed as shown in Table 4 in the high-viscosity dispersion treatment with two rolls in Example 1. In the same manner as in No. 1, a dispersion was obtained and evaluated. The results are shown in Table 4. As a result of the evaluation, it is clear that the specific resin of the present invention has better dispersion stability than the resin of the comparative example.

[Example 28]
[Preparation of black curable composition]
The following components were mixed to obtain a black curable composition M-1.

Alkali-soluble resin (propylene glycol monomethyl acetate solution of benzyl methacrylate / methacrylic acid copolymer (= 70/30, Mw: 30000, solid content 40% by mass) 1.6 parts) Compound containing ethylenically unsaturated double bond (Dipentaerythritol hexaacrylate) 2.3 parts-Compound containing ethylenically unsaturated double bond (ethoxylated pentaerythritol tetraacrylate) 0.8 parts-Dispersion liquid (L- 1) described in Table 4 30 parts- Propylene glycol monomethyl ether acetate 10 parts, ethyl-3-ethoxypropionate 8 parts, initiator: listed in Table 5 0.8 parts

[Production and evaluation of light-shielding film for solid-state image sensor]
Using the above black curable composition M-1, the coating rotation speed of the spin coat was adjusted so that the film thickness after coating with a hot plate at a surface temperature of 120 ° C. for 120 seconds after coating was 1.0 μm. The film was uniformly coated on a silicon wafer to obtain a 1.0 μm coating film.
Then, i-line stepper, FPA-3000iS + through a photomask having a pattern of 3mm square using (Canon Co., Ltd.), the exposure amount in the range of 100~5000mJ / cm ^2, of 100 mJ / cm ² Irradiated by changing in increments.
After the irradiation, paddle development is performed for 60 seconds at 23 ° C. using a 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH), and then rinse is performed using pure water for 20 seconds in a spin shower. Washed with pure water. Thereafter, the adhering water droplets were removed with high-level air, and the substrate was naturally dried to obtain a black image pattern.

[Evaluation]
The following evaluation was performed using said black curable composition M-1. The results are shown in Table 5.

-Exposure sensitivity evaluation-
The minimum exposure amount in which the film thickness after development of the region irradiated in the exposure step was 95% or more with respect to 100% of the film thickness before exposure was measured, and this was evaluated as the exposure sensitivity.

-Evaluation of storage stability (stability over time)-
Moreover, the following method evaluated the temporal stability (storage stability) of the black curable composition M-1 obtained as mentioned above.
That is, after the black curable composition M-1 was stored at room temperature for 1 month, the degree of viscosity change was evaluated according to the following criteria.
-Criteria-
○: Viscosity change of less than 3%.
Δ: Viscosity change of 3% or more and less than 10%.
X: Viscosity change of 10% or more.

-Residue evaluation-
Furthermore, the developability of the black curable composition M-1 obtained as described above was evaluated by the following method.
That is, in the exposure process in the above sensitivity evaluation, the presence or absence of a residue in an area not irradiated with light (unexposed portion) was observed to evaluate developability. The evaluation criteria are as follows.
-Evaluation criteria-
○: Residue was not confirmed at all in the unexposed area. Δ: Residue was slightly confirmed at the unexposed area, but there was no practical problem. ×: Residue was remarkably confirmed at the unexposed area. It was done.
-Step evaluation-
The obtained light shielding film pattern was image | photographed with the optical microscope, and the width | variety of the step area | region was measured. It shows that the narrower the width of the step region, the better the light shielding ability of the central part and the peripheral part.

(Examples 29-53 , Reference Example 54, Comparative Examples 4-6)
A black curable composition was obtained in the same manner as in Example 28 except that the dispersions and initiators listed in Table 5 were used, and the same evaluation as in Example 28 was performed. The results are shown in Table 5.

A to E in the column of “Initiator” in Table 5 indicate the following compounds.
A: IRGACURE OXE02 (Ciba Specialty Chemicals)
B: IRGACURE 379 (Ciba Specialty Chemicals)
C: DAROCURE TPO (Ciba Specialty Chemicals)
D: the following compound E: the following compound The chemical structures of A, B, C, D and E are shown below.

  Table 5 shows the following. All the examples using the specific resin of the present invention have high sensitivity, good stability over time when used as a curable composition, little residue when developed, small step width, small pattern size But a good pattern was achieved. On the other hand, the comparative example not using the specific resin of the present invention has low sensitivity, requires a large exposure amount, and the aging composition has poor stability over time, a residue is generated during development, and the step width is further increased. It turns out that it is not suitable for the light shielding film of the solid-state image sensor which requires a large and small pattern size.

Claims (13)

(A) A repeating unit represented by the following general formula (I-1) and a repeating unit represented by the following general formula (I-2), or a repeating unit represented by the following general formula (II-1) A dispersion containing a resin containing a unit and a repeating unit represented by the following general formula (II-2) , (B) a black color material, and (C) a solvent.

In general formulas (I-1) and (I-2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or an alkyl group. a represents an integer of 1 to 5. * Represents a connecting part between repeating units. X represents a group having any structure selected from structures represented by the following general formula (V-1), general formula (V-2), and general formula (V-3). Y is represented by the following general formula (III-1) and represents an oligomer chain or a polymer chain having a number average molecular weight of 500 to 1,000,000.

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

In general formula (III-1), Z represents a polymer chain or an oligomer chain having a polyester chain as a partial structure.

In General Formula (V-1) and General Formula (V-2), U represents a single bond or a divalent linking group. d and e each independently represents 0 or 1; In general formula (V-3), Q represents an acyl group or an alkoxycarbonyl group. The dispersion according to claim 1, wherein X in the general formula (I-1) is a group represented by the general formula (V-1). The dispersion liquid according to claim 1 or 2 , wherein the (B) black color material is titanium black. A dispersion liquid according to any one of claims 1 to 3 , (D) a photopolymerization initiator, and (E) a compound containing an ethylenically unsaturated double bond. Black curable composition. The black curable composition according to claim 4 , wherein the photopolymerization initiator (D) is an oxime photopolymerization initiator. 6. The black curable composition according to claim 5 , wherein the content of the oxime photopolymerization initiator is in the range of 3% by mass to 20% by mass of the total solid content of the black curable composition. . It is prepared by mixing the dispersion according to any one of claims 1 to 3 , (D) a photopolymerization initiator, and (E) a compound containing an ethylenically unsaturated double bond. A method for producing a black curable composition. Black color curable composition according to any one of the preceding claims 6 a solid-state imaging device. The light-shielding film for solid-state image sensors formed using the black curable composition of any one of Claims 4-6 and Claim 8 . The antireflection film for solid-state image sensors formed using the black curable composition of any one of Claims 4-6 and Claim 8 . It has the process of apply | coating the black curable composition of any one of Claims 4-6, and Claim 8 on a support body, exposing through a mask, and developing, and forming a pattern. A method for producing a light-shielding film for a solid-state imaging device. It has the process of apply | coating the black curable composition of any one of Claims 4-6, and Claim 8 on a support body, exposing through a mask, and developing, and forming a pattern. A method for producing an antireflection film for a solid-state imaging device. A solid-state imaging device comprising the light-shielding film for a solid-state imaging device according to claim 9 or the antireflection film for the solid-state imaging device according to claim 10 .