JPWO2016031574A1 - Composition, cured film, pattern forming method, color filter, color filter manufacturing method, solid-state imaging device, and image display device - Google Patents

Abstract

The composition is a composition having a triarylmethane compound, a dye having a maximum absorption wavelength in the range of 650 to 750 nm, and a curable compound, and has a maximum absorption wavelength in the range of 650 to 750 nm with respect to the triarylmethane compound. The composition whose mass ratio of the pigment | dye which has is 0.2-1.5.

Description

  The present invention relates to a composition and a cured film using them. The present invention also relates to a pattern forming method, a color filter, a method for manufacturing a color filter, a solid-state imaging device having a color filter, and an image display device.

One of the methods for producing a color filter used for a liquid crystal display device, a solid-state image sensor or the like is a pigment dispersion method. This pigment dispersion method is a method for producing a color filter by a photolithography method using a colored photosensitive composition in which a pigment is dispersed in various photosensitive compositions. That is, a curable composition is applied onto a substrate using a spin coater, a roll coater, or the like, dried to form a coating film, and the coating film is subjected to pattern exposure and development to obtain a colored pixel. By repeating this operation for a desired hue, a color filter is produced.
The method described above is stable against light and heat because it uses a pigment, and the positional accuracy is sufficiently secured because patterning is performed by a photolithographic method, and it is suitable as a method for manufacturing a color filter for a color display. It has been widely used.

  On the other hand, in color filters for solid-state imaging devices such as CCDs (Charge Coupled Devices), further higher image quality and higher sensitivity are recently demanded. Pigment Blue 15: 6 and Pigment Violet 23 are used for the blue pixels, but the combination of these pigments cannot achieve the high light transmission of 400 to 500 nm required for recent image sensors, and a new color material Application is being sought.

As an alternative to the combination of CI Pigment Blue 15: 6 and Pigment Violet 23, application of a triarylmethane compound has been studied (see, for example, Patent Document 1).
On the other hand, Patent Document 2 contains a dye and a polymerizable compound, and is a photosensitive coloring composition, further comprising both a singlet oxygen quencher and an antioxidant. And the use of a triarylmethane dye as the above-mentioned dye is described.
Patent Document 3 discloses (A) a compound that generates radicals by light or heat, (B) a polymer having a phenyl group substituted with a vinyl group in a side chain, and (C) a vinyl group substituted in the molecule. Disclosed is a photosensitive composition comprising a monomer having two or more phenyl groups, (D) an infrared absorber, and (E) a dye having an absorption maximum in the range of 500 nm to 700 nm. It is described that a triarylmethane dye is used as the dye.

JP 2014-80584 A JP 2011-141356 A JP 2005-107389 A

Triarylmethane compounds are known as useful colorants because of their high transmittance in the wavelength range of 400 to 500 nm and low transmittance at 550 to 650 nm. However, triarylmethane compounds usually do not absorb from around 650 nm to the long wave side. For this reason, the composition of patent documents 1-3 cannot be used for the use which has photosensitivity from the vicinity of 650 nm to the long wave side, for example, a solid-state image sensor use. Furthermore, triarylmethane compounds often do not have practical light resistance, and may be difficult to use for applications having photosensitivity on the long wave side from around 650 nm, for example, solid-state imaging device applications.
The present invention has been made in view of the above situation, and is a composition containing a triarylmethane compound, which can be used for applications having photosensitivity from around 650 nm to the long wave side, and has excellent developability. It is an object of the present invention to provide a composition. Another object of the present invention is to provide a cured film, a pattern forming method, a color filter, a color filter manufacturing method, a solid-state imaging device, and an image display device using the composition.

As a result of detailed studies by the present inventors, a composition capable of forming a colored pattern (cured film) having a good hue by mixing a triarylmethane compound and a dye having a specific absorption at an appropriate ratio. Has been found to be able to be provided, and the present invention has been completed.
Specifically, the above problem has been solved by the following means <1>, preferably by <2> to <21>.
<1> a triarylmethane compound, a dye having a maximum absorption wavelength in the range of 650 to 750 nm, and a curable compound,
The composition whose mass ratio of the pigment | dye which has the maximum absorption wavelength in the range of 650-750 nm with respect to a triarylmethane compound is 0.2-1.5.
<2> The composition according to <1>, wherein the triarylmethane compound has a maximum absorption wavelength in a range of 580 to 620 nm.
<3> The composition according to <1> or <2>, wherein the difference between the maximum absorption wavelength of the triarylmethane compound and the dye having the maximum absorption wavelength in the range of 650 to 750 nm is 100 to 150 nm.
<4> The composition according to any one of <1> to <3>, wherein the triarylmethane compound has an ethylenically unsaturated bond group.
<5> The composition according to any one of <1> to <4>, wherein the triarylmethane compound is a multimer.
<6> Any one of <1> to <5>, wherein the dye having a maximum absorption wavelength in the range of 650 to 750 nm is one or more selected from a phthalocyanine compound, a cyanine compound, a squarylium compound, a naphthoquinone compound, and an azo compound. A composition according to claim 1.
The composition in any one of <1>-<6> in which the pigment | dye which has a <7> maximum absorption wavelength in the range of 650-750 nm contains a phthalocyanine compound or a squarylium compound.
The composition in any one of <1>-<7> in which the pigment | dye which has a <8> maximum absorption wavelength in the range of 650-750 nm has an ethylenically unsaturated bond group.
<9> The composition according to any one of <1> to <8>, wherein the dye having a maximum absorption wavelength in the range of 650 to 750 nm is a multimer.
<10> The composition according to any one of <1> to <9>, further including a dye having a maximum absorption wavelength in the range of 500 to 600 nm.
<11> The composition according to any one of <1> to <10>, which is for a color filter.
<12> A cured film obtained by curing the composition according to any one of <1> to <11>.
<13> A step of applying the composition according to any one of <1> to <11> on a support to form a composition layer, a step of exposing the composition layer in a pattern, and a composition layer Forming a colored pattern by developing and removing the unexposed portion of the pattern.
<14> A method for producing a color filter, comprising the pattern forming method according to <13>.
<15> a step of applying the composition according to any one of <1> to <11> on a support to form a composition layer, and curing to form a colored layer;
Forming a photoresist layer on the colored layer;
A method for producing a color filter, comprising: a step of patterning a photoresist layer by exposing and developing the photoresist layer to obtain a resist pattern; and a step of dry etching a colored layer using the resist pattern as an etching mask.
<16> A color filter manufactured using the composition according to any one of <1> to <11>, or a color filter manufactured by the method for manufacturing a color filter according to <14> or <15>.
<17> a triarylmethane compound and a pigment having a maximum absorption wavelength in the range of 650 to 750 nm, the minimum transmittance in the thickness direction in the wavelength range of 450 to 500 nm is 80% or more, and the wavelength is 650 to 700 nm. A color filter having a maximum transmittance in the thickness direction in a range of 25% or less.
<18> A solid-state imaging device having the color filter according to <16> or <17>.
<19> An image display device having the color filter according to <16> or <17>.

<20> The composition according to any one of <1> to <11>, further comprising a polymerization initiator.
<21> The composition according to <20>, wherein the polymerization initiator is an oxime compound.
The mass ratio of the compound having a maximum absorption wavelength of 650 to 750 nm with respect to the <22> triarylmethane compound is 0.3 to 1.4, <1> to <11>, <20> and <21> A composition according to any one of the above.

  According to the present invention, it has become possible to provide a composition excellent in light resistance and heat resistance. In addition, it has become possible to provide a cured film, a pattern forming method, a color filter, a color filter manufacturing method, a solid-state imaging device, and an image display device using the composition.

  In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

  “Actinic light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.

In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition. The density | concentration in this invention says the density | concentration in 25 degreeC.
In the present specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acryloyl” Represents both or one of acryloyl and methacryloyl.
In the present specification, “monomer” and “monomer” are synonymous. The monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by GPC measurement. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh) and TSKgel Super AWM-H (manufactured by Tosoh, 6.0 mm ID × 15.0 cm) as a column. ) Can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.

Composition The composition of the present invention comprises a triarylmethane compound, a dye having a maximum absorption wavelength in the range of 650 to 750 nm, and a curable compound, and has a maximum absorption wavelength in the range of 650 to 750 nm with respect to the triarylmethane compound. The mass ratio of the pigment | dye to have is 0.2-1.5.
By setting it as the said structure, provision of the composition excellent in light resistance is attained. The reason why such an effect is obtained is not yet clear, but the effect of improving the light resistance is estimated as follows. The triarylmethane compound is excited by light and undergoes self-decomposition or decomposition by singlet oxygen when returning to the ground state. However, by using a compound having absorption on the longer wave side than the triarylmethane compound, that is, a dye having a maximum absorption wavelength in the range of 650 to 750 nm, together with the triarylmethane compound, the excited triarylmethane compound can be rapidly Then, energy is supplied to the dye having the maximum absorption wavelength in the range of 650 to 750 nm, and the triarylmethane compound returns to the ground state. As a result, light resistance is improved.
Furthermore, the composition of the present invention can maintain high heat resistance.
In general, triarylmethane compounds tend to agglomerate because they are ionic, and in the current situation where color filters for solid-state imaging devices with smaller pattern sizes are required, development defects May occur or pattern defects may easily occur.
The pattern formability (developability) may not always be sufficient. On the other hand, the composition of the present invention can suppress development defects and pattern defects.

<Triarylmethane compounds>
A triarylmethane compound is a compound containing at least one triarylmethane structure in one molecule. The triarylmethane compound in the present invention may be a triarylmethane monomer containing one triarylmethane structure in one molecule, or a triaryl containing two or more triarylmethane structures in one molecule. It may be a methane multimer or a triarylmethane multimer containing three or more triarylmethane structures in one molecule. The triarylmethane compound is preferably a triarylmethane multimer. The triarylmethane compound preferably has a curable group. Examples of the curable group include an ethylenically unsaturated bond group and a cyclic ether group (such as an epoxy group and an oxetanyl group), and an ethylenically unsaturated bond group is preferable.
In particular, the triarylmethane compound is preferably a multimer or a monomer having an ethylenically unsaturated bond group, more preferably a multimer, having an ethylenically unsaturated bond group. More preferably, it is a multimer. By setting it as such a structure, heat resistance can be improved more.
The composition of the present invention may contain only one type of triarylmethane compound or two or more types. A triarylmethane monomer and a triarylmethane multimer may be used in combination.

The triarylmethane compound in the present invention usually takes the form of a cation. In general, the cation preferably has one or two monovalent and / or divalent cations, and more preferably one monovalent cation, per one triarylmethane structure.
The triarylmethane compound is preferably a dye. In pigment dispersion systems, problems such as the occurrence of scattering due to coarse particles of pigment and the increase in viscosity due to poor dispersion stability are likely to occur, and it may be difficult to further improve contrast and brightness. Such problems can be avoided more effectively.
The dye means a soluble pigment compound that is easily dissolved in a solvent. Here, an arbitrary solvent is mentioned with a solvent, For example, the solvent illustrated in the column of the solvent mentioned later is mentioned. As the solvent used in the present invention, for example, a solvent in which the solubility of the triarylmethane compound in the solvent at 25 ° C. exceeds 0.001 g / 100 g Solvent is preferable.

The maximum absorption wavelength of the triarylmethane compound is preferably in the range of 560 to 620 nm, and more preferably 575 to 610 nm. Further, the maximum absorption wavelength is more preferably the maximum absorption wavelength in the visible region (for example, 380 to 750 nm) of triarylmethane. Furthermore, the triarylmethane compound used in the present invention usually does not have a maximum absorption wavelength in the range of the wavelength of 450 nm to less than 550 nm and the wavelength of 650 nm to 700 nm.
The difference between the maximum absorption wavelength of the triarylmethane compound and the dye having a maximum absorption wavelength described later in the range of 650 to 750 nm is preferably 40 to 150 nm, and more preferably 80 to 120 nm.

  The blending amount of the triarylmethane compound is preferably 10 to 80% by mass, more preferably 20 to 75% by mass, and further preferably 35 to 60% by mass of the solid content of the composition. When blending two or more types of triarylmethane compounds, the total amount is preferably within the above range.

<< Triarylmethane Monomer >>
When the triarylmethane compound is a monomer, the triarylmethane compound contains one triarylmethane structure. The triarylmethane structure includes three aryl groups centered on methane. Each of the three aryl groups is preferably a phenyl group, a naphthyl group, or a ring in which an aryl group and a heterocyclic ring are condensed. Examples of the heterocycle in this case include a nitrogen-containing 5-membered ring or a 6-membered ring.
The triarylmethane compound is preferably a cation represented by the general formula (TP1) and / or a cation represented by the general formula (TP2), and more preferably a cation represented by the general formula (TP1).

In general formulas (TP1) and (TP2), Rtp ^{1 to} Rtp ⁴ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Rtp ⁵ , Rtp ⁶ , Rtp ⁸ , Rtp ⁹ and Rtp ¹¹ each independently represent a substituent. Rtp ⁷ represents a hydrogen atom, an alkyl group, an aryl group, or NRtp ⁷¹ Rtp ⁷² . Rtp ⁷¹ and Rtp ⁷² each independently represent a hydrogen atom, an alkyl group or an aryl group. Rtp ¹⁰ represents a hydrogen atom, an alkyl group or an aryl group. a, b and c each independently represents an integer of 0 to 4; When a, b and c are 2 or more, two of Rtp ⁵ , Rtp ⁶ , Rtp ⁸ and Rtp ⁹ may be linked to each other to form a ring. At least ^{one of} Rtp ^{1 to} Rtp ¹¹ , Rtp ⁷¹ and Rtp ⁷² may contain an anion.

In General Formula (TP1), Rtp ^{1 to} Rtp ⁴ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and preferably a hydrogen atom or an alkyl group.
1-10 are preferable, as for carbon number of an alkyl group, 1-5 are more preferable, and 1-3 are more preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. The alkyl group is preferably unsubstituted. Substituents mentioned in the section of Substituent group A described later can be mentioned.
6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable. Examples of the substituent that the aryl group may have include the substituents mentioned in the section of the substituent group A described later.

In General Formula (TP1), Rtp ⁷ represents a hydrogen atom, an alkyl group, an aryl group, or NRtp ⁷¹ Rtp ⁷² , preferably a hydrogen atom or NRtp ⁷¹ Rtp ⁷² , and more preferably NRtp ⁷¹ Rtp ⁷² .
When Rtp ⁷ represents an alkyl group, the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear. Examples of the substituent that the alkyl group may have include the substituents mentioned in the section of Substituent Group A described later. 6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable.

Rtp ⁷¹ and Rtp ⁷² each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom or an alkyl group. 1-10 are preferable, as for carbon number of an alkyl group, 1-8 are more preferable, 1-6 are more preferable, and 1-3 are especially preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. The alkyl group may be substituted but is preferably unsubstituted. Examples of the substituent that the alkyl group may have include the substituents mentioned in the section of Substituent Group A described later. 6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable. Examples of the substituent that the aryl group may have include the substituents mentioned in the section of the substituent group A described later.

In general formula (TP1), Rtp ⁵ , Rtp ⁶ and Rtp ⁸ each independently represent a substituent. Examples of the substituent include the substituents mentioned in the section of the substituent group A described later. In particular, a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, a carboxyl group, or a sulfo group is preferable, and a linear chain having 1 to 5 carbon atoms. Or a branched alkyl group, a C1-C5 alkenyl group, a phenyl group, or a carboxyl group is more preferable. In particular, Rtp ⁵ and Rtp ⁶ are preferably each independently an alkyl group having 1 to 5 carbon atoms.
Rtp ⁸ preferably has two alkenyl groups bonded to each other to form a ring. The ring is preferably a benzene ring.

  In the general formula (TP1), a, b and c each independently represent an integer of 0 to 4, and a and b preferably represent 0 or 1, and more preferably represent 0. c preferably represents 0 to 2, more preferably 0 or 1.

In general formula (TP2), Rtp ^{1 to} Rtp ⁴ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and are the same as Rtp ^{1 to} Rtp ⁴ in general formula (TP1), and the preferred ranges are also the same. It is.
In general formula (TP2), Rtp ⁵ and Rtp ⁶ each independently represent a substituent, and are synonymous with Rtp ⁵ and Rtp ⁶ in general formula (TP1), and their preferred ranges are also the same.

In General Formula (TP2), Rtp ⁹ and Rtp ¹¹ each independently represent a substituent, and the substituents exemplified in the section of Substituent Group A described later can be used.
Rtp ⁹ is preferably an aryl group, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group.
Rtp ¹¹ is preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group is preferably linear or branched, and more preferably linear.

In General Formula (TP2), Rtp ¹⁰ represents a substituent, and the substituents mentioned in the section of Substituent Group A described later can be used. In particular, Rtp ¹⁰ is more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group.

  In general formula (TP2), a, b and c each independently represent an integer of 0 to 4, and a and b preferably represent 0 or 1, and more preferably represent 0. c preferably represents 0 to 2, and more preferably represents 0.

The dye cation is present in a delocalized manner as follows, and the following two types of structures are included in the triarylmethane compound. The cation moiety may be at any position in the molecule.

The triarylmethane compound preferably contains an ethylenically unsaturated bond group. Such an ethylenically unsaturated bond group is polymerized by, for example, radical polymerization or irradiation with light or heat, or undergoes a crosslinking reaction with other groups. Therefore, when an ethylenically unsaturated bond group is included, the heat resistance tends to be further improved.
The ethylenically unsaturated bond group may consist only of an ethylenically unsaturated bond, or may contain a linking group in addition to the ethylenically unsaturated bond. In particular, ethylenically unsaturated bond group is a group represented by ^-L 0 -P ⁰ is preferable. Here, L ⁰ represents a single bond or a divalent linking group, and P ⁰ represents an ethylenically unsaturated bond.
The divalent linking group includes an alkylene group, an arylene group, a heterocyclic linking group, —CH═CH—, —O—, —S—, —C (═O) —, —CO—, —NR—, and —CONR. —, —OC—, —SO—, —SO ₂ — and a group obtained by combining two or more of these are preferred. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
In particular, the divalent linking group is preferably an arylene group.
The alkylene group may be linear, branched or cyclic. 1-30 are preferable, as for carbon number of an alkylene group, 1-20 are more preferable, 5-20 are more preferable, and 5-10 are especially preferable. Specifically, a methylene group, ethylene group, propylene group, butylene group, hexylene group, heptylene group, cyclopentenylene group, cyclohexylene group and the like are preferable.
6-30 are preferable, as for carbon number of an arylene group, 6-18 are more preferable, and 6-12 are more preferable. Specifically, the arylene group is preferably a phenylene group or a naphthylene group, and more preferably a phenylene group.

Specific examples of the ethylenically unsaturated bond group include a group containing a (meth) acryl group, a group containing a vinyl group, a group containing an allyl group, a group containing a methallyl group, and the like. At least one selected from a group containing a group, a group containing an allyl group, and a group containing a methallyl group is more preferable. Especially, at least 1 sort (s) selected from a (meth) acryl group, an allyl group, and a methallyl group is preferable.
In the above general formula (TP1) or (TP2), the triarylmethane compound preferably includes at least one of Rtp ^{1 to} Rtp ¹¹ , Rtp ⁷¹ and Rtp ⁷² containing an ethylenically unsaturated bond group, and Rtp ⁷ is More preferably, it contains an ethylenically unsaturated bond group, and Rtp ⁷¹ or Rtp ⁷² is more preferably an ethylenically unsaturated bond group.

Substituent group A:
Substituents include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups Silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfa Moylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group Groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl or heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, silyl groups, etc. It is done. Details are described below.

  A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms) For example, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably having 3 to 30 carbon atoms substituted or Examples thereof include unsubstituted cycloalkyl groups such as cyclohexyl and cyclopentyl, and polycycloalkyl groups such as bicycloalkyl groups (preferably substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms such as bicyclo [ 1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3 Yl) or group of polycyclic structures such as tricycloalkyl groups. Preferably monocyclic cycloalkyl group, a bicycloalkyl group, a monocyclic cycloalkyl group is particularly preferred.)

  Linear or branched alkenyl group (straight or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl Group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and a polycycloalkenyl group such as bicyclo An alkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] Octo-2-en-4-yl) and tricycloalkenyl groups, with monocyclic cycloalkenyl groups being particularly preferred. Cycloalkenyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, e.g., ethynyl, propargyl, trimethylsilylethynyl group),

  An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 to 5 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably the ring-constituting atom is selected from carbon atom, nitrogen atom and sulfur atom And a heterocyclic group having at least one heteroatom of any one of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydride Hexyl group, a nitro group, a carboxyl group,

  An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably Is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, tert-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 to 2 carbon atoms) 30 substituted or unsubstituted heterocyclic oxy groups Heterocyclic portion is preferably described in the heterocyclic portion described above heterocyclic group, e.g., 1-phenyl-5-oxy, 2-tetrahydropyranyloxy),

  An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably having 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted group having 7 to 30 carbon atoms). Substituted aryloxycarbonyloxy groups such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

  An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms); For example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino), acylamino group (preferably formylamino group, carbon number A substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3, 4,5-tri-n-octyloxyphenylcarbonylamino), amino A rubonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl- Methoxycarbonylamino),

  Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) A sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino Sulfonylamino), alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methyl Sulfonyla Bruno, butyl sulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenyl sulfonylamino, p- methylphenyl sulfonylamino), a mercapto group,

  An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms). , For example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, wherein the heterocyclic portion is the above-described heterocyclic group The heterocyclic moiety described in the above is preferable, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfa Yl, N, N- dimethylsulfamoyl, N- acetyl sulfamoyl, N- benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), a sulfo group,

  An alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenyl Sulfinyl, p-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, Methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted group having 7 to 30 carbon atoms) Arylka Bonyl group, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), aryloxycarbonyl group (preferably substituted or unsubstituted aryl having 7 to 30 carbon atoms) An oxycarbonyl group, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl),

  An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably having a carbon number) 1-30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl or hetero A ring azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocycle portion is the heterocycle described in the above heterocyclic group); Ring portion is preferred), for example, phenyl Zo group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms, such as N -Succinimide group, N-phthalimide group), phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably Is a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),

  A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group ( Preferably, it is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably substituted with 3 to 30 carbon atoms) Or an unsubstituted silyl group, for example, trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl).

At least ^{one of} Rtp ^{1 to} Rtp ¹¹ , Rtp ⁷¹ and Rtp ⁷² may contain an anion. When these groups contain an anion, the anion is preferably —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , bis (sulfonyl) imide anion, tris (sulfonyl) methide anion and tetraarylborate anion. ) Imide anion, tris (sulfonyl) methide anion and tetraarylborate anion are more preferred, and bis (sulfonyl) imide anion and tris (sulfonyl) methide anion are more preferred.
Specific examples include a structure in which at least one of Rtp ^{1 to} Rtp ¹¹ , Rtp ⁷¹ and Rtp ⁷² is substituted with the general formula (P).
General formula (P)

In general formula (P), L represents a single bond or a divalent linking group, and X ¹ represents an anion.

In general formula (P), L represents a single bond or a divalent linking group. The divalent linking group preferably represents —NR ¹⁰ —, —O—, —SO ₂ —, an alkylene group containing a fluorine atom, an arylene group containing a fluorine atom, or a combination thereof. In particular, a group consisting of a combination of —NR ¹⁰ —, —SO ₂ and an alkylene group containing a fluorine atom, and a group consisting of a combination of —O— and an arylene group containing a fluorine atom are preferred.
In —NR ¹⁰ —, R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and preferably a hydrogen atom.
1-10 are preferable, as for carbon number of the alkylene group containing a fluorine atom, 1-6 are more preferable, and 1-3 are more preferable. These alkylene groups are more preferably perfluoroalkylene groups. Specific examples of the fluorine-substituted alkylene group include a difluoromethylene group, a tetrafluoroethylene group, and a hexafluoropropylene group.
6-20 are preferable, as for carbon number of the arylene group containing a fluorine atom, 6-14 are more preferable, and 6-10 are more preferable. Specific examples of the arylene group containing a fluorine atom include a tetrafluorophenylene group, a hexafluoro-1-naphthylene group, and a hexafluoro-2-naphthylene group.

In General Formula (P), X ¹ represents an anion, and is selected from —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , bis (sulfonyl) imide anion, tris (sulfonyl) methide anion and tetraarylborate anion. Species are preferred, one kind selected from bis (sulfonyl) imide anion, tris (sulfonyl) methide anion and tetraarylborate anion is more preferred, and bis (sulfonyl) imide anion or tris (sulfonyl) methide anion is still more preferred.

When at least one of Rtp ^{1 to} Rtp ¹¹ , Rtp ⁷¹ and Rtp ⁷² contains an anion, at least one of Rtp ^{1 to} Rtp ¹¹ , Rtp ⁷¹ and Rtp ⁷² has a structure substituted with the general formula (P-1) It is also preferable.
Formula (P-1)

In General Formula (P-1), L ¹ represents a single bond or a divalent linking group, and is preferably a single bond. Examples of the divalent linking group represented by L ¹ include a group consisting of an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, —O—, —S—, or a combination thereof.
L ² represents —SO ₂ — or —CO—.
G represents a carbon atom or a nitrogen atom.
n1 represents 2 when G is a carbon atom, and represents 1 when G is a nitrogen atom.
R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom. When n1 is 2, two R ⁶ may be the same or different.
The number of carbon atoms in the alkyl group containing a fluorine atom R ⁶ represents preferably 1 to 10, more preferably 1 to 6, 1 to 3 is more preferable.
R ⁶ carbon atoms in the aryl group containing represents fluorine atom, preferably 6 to 20, more preferably 6 to 14, 6 to 10 is more preferable.

  In the case of a triarylmethane monomer, the molecular weight of the triarylmethane compound is preferably 300 to 1,000, and more preferably 500 to 1,000.

  Specific examples of the triarylmethane monomer are shown below, but the present invention is not limited thereto.

<< Triarylmethane Multimer >>
When the triarylmethane compound is a multimer (also referred to as a triarylmethane multimer), it is a compound containing two or more triarylmethane structures, preferably three or more triarylmethane structures. The triarylmethane multimer includes at least one repeating unit represented by the following general formula (A) and general formula (C), or the counter anion includes a repeating unit having a counter anion. Or represented by the general formula (D) described later.

  The triarylmethane multimer preferably has a repeating unit represented by the following general formula (A).

Formula (A)

(In general formula (A), X ¹ represents the main chain of the repeating unit. L ¹ represents a single bond or a divalent linking group. Dye represents a triarylmethane structure.)
In the general formula (A), X ¹ represents a main chain of repeating units. Two sites represented by * are repeating units. X ¹ is preferably —CH ₂ —CH ₂ — or —CH ₂ —C (CH ₃ ) —.

When L ¹ represents a divalent linking group, an alkylene group having 1 to 30 carbon atoms (methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), an arylene group having 6 to 30 carbon atoms (phenylene group, Naphthalene group, etc.), heterocyclic linking group, -CH = CH-, -O-, -S-, -C (= O)-, -CO-, -NR-, -CONR-, -OC-, -SO Examples include —, —SO ₂ —, a linking group in which two or more of these are combined, and a group represented by the following formula (L-1). Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.

In the formula, it is linked to X ¹ of formula (A) at the site indicated by * 1, and is linked to Dye of formula (A) at the site indicated by * 2.

L ¹¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 18 carbon atoms, —O—, —CO—, —S—, —SO ₂ —, —NR ^A R ^B —, or Examples include groups composed of these combinations. The alkylene group may be linear, branched or cyclic. The arylene group may be monocyclic or polycyclic. In —NR ^A R ^B —, R ^A and R ^B each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^A and R ^B are bonded to each other to form a ring. Also good.
L ¹² represents —SO ₂ — or —CO—.
L ¹³ represents a divalent linking group. Examples of the divalent linking group include the groups described for L ¹¹ , and an arylene group having 6 to 18 carbon atoms (preferably a phenylene group), —O—, —CO—, —S—, —NR ^A R ^B A group consisting of-or a combination thereof is preferred, and a group consisting of a combination of a phenylene group, -O- and -CO- is more preferred.
G represents a carbon atom or a nitrogen atom.
n2 represents 1 when G is a carbon atom, and represents 0 when G is a nitrogen atom.
R ^7A represents an alkylene group containing a fluorine atom or an arylene group containing a fluorine atom. 1-10 are preferable, as for carbon number of an alkylene group, 1-6 are more preferable, and 1-3 are more preferable. 6-20 are preferable, as for carbon number of an arylene group, 6-14 are more preferable, and 6-10 are more preferable.
R ^7B represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom. 1-10 are preferable, as for carbon number of an alkyl group, 1-6 are more preferable, and 1-3 are more preferable. 6-20 are preferable, as for carbon number of an aryl group, 6-14 are more preferable, and 6-10 are more preferable.

L ¹ is a single bond or an alkylene group having 1 to 30 carbon atoms (preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 5 to 20 carbon atoms, still more preferably, _{- (CH 2) n - (} n is an integer of from 1 to 10)), an arylene group having 6 to 12 carbon atoms (preferably a phenylene group, a naphthylene group), - NH -, - CO -, - O- , and -SO _A divalent linking group in which two or more _2- are combined is preferable. Moreover, group represented by the said (L-1) is also preferable. In particular, L ¹ is preferably — (CH ₂ ) _n — (n is an integer of 5 to 10) or an arylene group having 6 to 12 carbon atoms (preferably a phenylene group or a naphthylene group), and —COO— or a phenylene group is preferable. More preferably, it is a linking group.

When L ¹ represents a single bond, X ¹ is preferably bonded to any ^one of Rtp ^{1 to} Rtp ¹¹ , Rtp ⁷¹ and Rtp ^{72 in} the general formulas (TP1) and (TP2), and Rtp ⁷¹ or Rtp ⁷² is more preferable.
When L ¹ represents a divalent linking group, L ¹ is preferably bonded to any _one of Rtp _{1 to} Rtp ₁₁ , Rtp ₇₁ and Rtp _{72 in} the general formulas (TP1) and (TP2), and Rtp More preferably, it is bound to ₇₁ or Rtp ₇₂ .

Specific examples of combinations of X ¹ and L ¹ are shown below, but the present invention is not limited to these.
In particular, (XX), (XX-2), (XX-25) and (XX-26) (meth) acrylic linkage chains represented by (XX-10) to (XX-17), ( It is more preferably selected from styrene-based linking chains represented by (XX-27) and (XX-28) and vinyl-based linking chains represented by (XX-24), and styrene-based linking chains are more preferable.
In (XX-1) to (XX-24), it is connected to the triarylmethane structure at the site indicated by *. Me represents a methyl group. R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

Moreover, the following is also preferable as a specific example of the combination of X ¹ and L ¹ . In the following specific examples, n represents an integer of 1 to 9. Moreover, it represents connecting with a triarylmethane structure at a site indicated by *.

Dye represents a triarylmethane structure, a cation represented by the general formula (TP1) or a cation represented by the general formula (TP2) is preferable, and a cation represented by the general formula (TP1) is more preferable. Dye is preferably bonded to L ¹ via at least one of Rtp ^{1 to} Rtp ¹¹ , Rtp ⁷¹ and Rtp ^{72 in} the above general formula (TP1) or (TP2), and via Rtp ⁷ More preferably, it is bonded to L ^1, and more preferably is bonded to L ¹ via Rtp ⁷¹ or Rtp ⁷² .

  Specific examples of the repeating unit containing a triarylmethane structure include the following structures, but the present invention is not limited thereto.

  The triarylmethane multimer may consist only of repeating units having triarylmethane, but may contain other repeating units. Specifically, other repeating units that the triarylmethane multimer may contain include repeating units containing an alkali-soluble group such as an acid group, repeating units containing a polymerizable group, and the like. The multimer preferably contains at least a repeating unit containing an alkali-soluble group such as an acid group. The triarylmethane multimer may contain only one type of these repeating units, or may contain two or more types. Hereinafter, these repeating units will be described in detail.

<<< Repeating unit containing a polymerizable group >>>
As the polymerizable group contained in the repeating unit containing a polymerizable group, a known polymerizable group that can be crosslinked by a radical, an acid, or heat can be used. For example, a group containing an ethylenically unsaturated bond, a cyclic ether group (Epoxy group, oxetane group), methylol group and the like are mentioned, but a group containing an ethylenically unsaturated bond is particularly preferable, (meth) acryloyl group is more preferable, glycidyl (meth) acrylate and 3,4-epoxycyclohexyl. A (meth) acryloyl group derived from methyl (meth) acrylate is more preferred.

  Examples of the method for introducing a polymerizable group include (1) a method in which a repeating unit is modified and introduced with a polymerizable group-containing compound, and (2) a method in which a repeating unit and a polymerizable group-containing compound are copolymerized and introduced. is there. Details of these can be referred to the descriptions in paragraphs 0334 to 0342 of JP 2013-225112 A, and the contents thereof are incorporated in the present specification.

When the triarylmethane multimer includes a repeating unit containing a polymerizable group, the polymerizable group amount is preferably 0.1 to 2.0 mmol with respect to 1 g of the dye structure, and is 0.2 to 1.5 mmol. More preferably, it is particularly preferably 0.3 to 1.0 mmol.
Moreover, when a triarylmethane multimer contains the repeating unit containing a polymeric group, the amount is 5-40 mol% with respect to all the repeating units, for example, and 5-35 mol% is more preferable.

  Specific examples of the repeating unit containing the polymerizable group include the following. However, the present invention is not limited to these.

<<< Repeating unit containing acid group >>>
Examples of the acid group of the repeating unit containing an acid group include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. A carboxylic acid group and a sulfonic acid group are preferable, and a carboxylic acid group is more preferable. Only one type of acid group may be contained in the repeating unit containing an acid group, or two or more types may be used.
When the triarylmethane multimer contains a repeating unit containing an acid group, the ratio of the repeating unit containing a repeating unit having an acid group is preferably from 1 to 80 mol% based on all repeating units, and from 10 to 65 % Mol is more preferred.

<<< Repeating unit containing other alkali-soluble groups >>>
Examples of the repeating unit containing an alkali-soluble group other than the acid group include a repeating unit containing a phenolic hydroxyl group.
The triarylmethane multimer contains a repeating unit having a group consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains in the side chain (hereinafter sometimes referred to as “(b) repeating unit”). Is also preferable.
(B) The number of repeating alkyleneoxy chains in the repeating unit is preferably 2 to 10, more preferably 2 to 15, and still more preferably 2 to 10.
One alkyleneoxy chain is represented by — (CH ₂ ) _n O—, and n is an integer, but n is preferably 1 to 10, more preferably 1 to 5, and further preferably 2 or 3.
In the group consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, only one kind of alkyleneoxy chain may be contained, or two or more kinds may be contained.
(B) The repeating unit is preferably represented by the following general formula.

(In the formula, X ₁ represents a linking group formed by polymerization, L ₁ represents a single bond or a divalent linking group, and P represents a group containing a group consisting of repeating alkyleneoxy chains.)
_{X 1} and _{L 1} in the general formula (P), have the same meanings as _{X 1} and _{L 1} in formula (A), and preferred ranges are also the same.
P represents a group containing a group consisting of repeating alkyleneoxy chains, more preferably a group consisting of repeating alkyleneoxy chains-terminal atom or terminal group.
The terminal atom or terminal group is preferably a hydrogen atom, an alkyl group, an aryl group or a hydroxyl group, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a hydroxyl group, a hydrogen atom, a methyl group, a phenyl group and A hydroxyl group is more preferred, and a hydrogen atom is particularly preferred.

As a method for introducing an alkali-soluble group into a dye multimer, the description in paragraph 0351 of JP2013-225112A can be referred to, and the contents thereof are incorporated herein.
When the triarylmethane multimer contains repeating units containing other alkali-soluble groups, for example, 1 to 80 mol% is preferable and 10 to 65 mol% is more preferable with respect to all repeating units.
Moreover, the ratio of the repeating unit containing all the alkali-soluble groups containing an acid group or another alkali-soluble group is preferably, for example, 1 to 80 mol%, more preferably 10 to 65 mol% with respect to all repeating units.

  The amount of alkali-soluble group possessed by the dye is preferably 0.3 mmol to 2.0 mmol, more preferably 0.4 mmol to 1.5 mmol, and 0.5 mmol to 1.0 mmol with respect to 1 g of the dye. Is particularly preferred.

<<< other repeating units >>>
The triarylmethane multimer may have a repeating unit other than the repeating units described above. Specifically, development accelerators such as lactones, acid anhydrides, amides, —COCH ₂ CO—, cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups, hydroxyl groups, maleimides Examples thereof include a repeating unit containing at least one selected from a hydrophilic group such as a group and an amino group.
These may be included in only one type, or may be included in two or more types.
Examples of the introduction method include a method of introducing the dye structure in advance, and a method of copolymerizing a monomer having the above group.
When the triarylmethane multimer contains other repeating units, the ratio is preferably 40 to 80 mol% of all repeating units.

  Although the specific example of the repeating unit containing the acid group mentioned above or other repeating units is shown, this invention is not limited to this.

The triarylmethane multimer also preferably contains a repeating unit represented by the following general formula (C).

In general formula (C), L ³ represents a single bond or a divalent linking group. DyeIII represents a triarylmethane structure. m represents 0 or 1;

In general formula (C), L ³ represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L ³ include an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, —CH═CH—, —O—, and —S—. , —C (═O) —, —CO ₂ —, —NR—, —CONR—, —O ₂ C—, —SO—, —SO ₂ — and a linking group formed by linking two or more thereof. Are preferable. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
m represents 0 or 1, but is preferably 1.

As for carbon number of an alkyl group and an alkylene group, 1-30 are preferable. The upper limit is more preferably 25 or less, and still more preferably 20 or less. The lower limit is more preferably 2 or more, and still more preferably 3 or more. The alkyl group and alkylene group may be linear, branched or cyclic.
6-20 are preferable and, as for carbon number of an aryl group and an arylene group, 6-12 are more preferable.
The heterocyclic linking group and the heterocyclic group are preferably a 5-membered ring or a 6-membered ring. The hetero atom contained in the heterocyclic linking group and the heterocyclic group is preferably an oxygen atom, a nitrogen atom or a sulfur atom. The number of heteroatoms contained in the heterocyclic linking group and the heterocyclic group is preferably 1 to 3.

  The dye multimer having a repeating unit represented by the general formula (C) may contain other repeating units described above. Moreover, the repeating unit represented by general formula (A) mentioned above may further be included.

  The dye multimer having the repeating unit represented by the general formula (C) can be synthesized by sequential polymerization. Sequential polymerization means polyaddition (for example, reaction of diisocyanate compound and diol, reaction of diepoxy compound and dicarboxylic acid, reaction of tetracarboxylic dianhydride and diol, etc.) and polycondensation (for example, dicarboxylic acid). And a diol, a reaction of a dicarboxylic acid and a diamine, and the like. Among these, synthesis by polyaddition reaction is particularly preferable because the reaction conditions can be moderated and the dye skeleton is not decomposed. Known reaction conditions can be applied to the sequential polymerization.

The triarylmethane multimer is also preferably represented by the general formula (D).

In general formula (D), L ⁴ represents a (n + k) -valent linking group. n represents an integer of 2 to 20, and k represents an integer of 0 to 20. DyeIV represents a triarylmethane structure, and P represents a substituent. When n is 2 or more, the plurality of DyeIVs may be different from each other, and when k is 2 or more, the plurality of P may be different from each other. n + k represents an integer of 2 to 20.

In general formula (D), 2-15 are preferable, as for n, 2-14 are more preferable, 2-8 are still more preferable, 2-7 are especially preferable, and 2-6 are more preferable.
2-20 are preferable, 2-15 are more preferable, 2-14 are still more preferable, 2-8 are still more preferable, 2-7 are especially preferable, and 2-6 are still more preferable.
Note that n and k in one multimer are integers, respectively, but in the present invention, a plurality of multimers having different n and k in the general formula (D) may be included. Therefore, the average value of n and k in the composition of the present invention may not be an integer.

(N + k) -valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and Groups consisting of 0 to 20 sulfur atoms are included.
Specific examples of the (n + k) -valent linking group include a group composed of a combination of two or more of the following structural units or the following structural units (which may form a ring structure). .

  Specific examples of the (n + k) -valent linking group are shown below. However, the present invention is not limited to these. Moreover, the coupling group described in paragraph number 0071-0072 of Unexamined-Japanese-Patent No. 2008-222950 and the coupling group described in paragraph number 0176 of Unexamined-Japanese-Patent No. 2013-029760 are mentioned.

In general formula (D), P represents a substituent. Examples of the substituent include an acid group and a curable group. Examples of the curable group include a radical polymerizable group such as a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetanyl group), an oxazoline group, and a methylol group. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
The substituent represented by P may be a monovalent polymer chain having a repeating unit. The monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound. When k is 2 or more, the k Ps may be the same or different.
When P is a monovalent polymer chain having a repeating unit and k is 1, P has 2 to 20 repeating units derived from a vinyl compound (preferably 2 to 15, more preferably 2 to 10). Are preferable. When P is a monovalent polymer chain having repeating units and k is 2 or more, the average number of repeating units derived from k P vinyl compounds is 2 to 20 (preferably 2 to 15 and more preferably 2 to 10).
When P is a monovalent polymer chain having repeating units, the number of repeating units of P when k is 1 and the average number of repeating units of P when k is 2 or more are expressed as It can be determined by resonance (NMR).

In the case where P is a monovalent polymer chain having a repeating unit, examples of the repeating unit constituting P include the other repeating units described above. It is preferable that another repeating unit has 1 or more types chosen from the repeating unit which has the acid group mentioned above, and the repeating unit which has a sclerosing | hardenable group. When the repeating unit having an acid group is contained, the developability can be improved. When a repeating unit having a curable group is included, color mixing with other colors and spectral fluctuation after development can be further suppressed.
When P contains a repeating unit containing an acid group, the ratio of the repeating unit containing an acid group is preferably from 10 to 80 mol%, more preferably from 10 to 65 mol%, based on all the repeating units of P.
When P includes a repeating unit having a curable group, the ratio of the repeating unit having a curable group is preferably 10 to 80 mol%, more preferably 10 to 65 mol%, based on all repeating units of P. .

In general formula (D), DyeIV represents a triarylmethane structure.
In the general formula (D), the triarylmethane structure represented by DyeIV is a structure in which one or more arbitrary hydrogen atoms of the triarylmethane monomer are removed, and a part of the triarylmethane monomer is L ⁴ may be formed. Further, it may be a polymer chain containing a repeating unit having a triarylmethane structure in the main chain or side chain. The polymer chain is not particularly defined as long as it contains a triarylmethane structure, but is one kind selected from a (meth) acrylic resin, a styrene resin, and a (meth) acrylic / styrene resin. Preferably there is. The repeating unit of the polymer chain is not particularly defined, and examples thereof include the repeating unit represented by the general formula (A) described above and the repeating unit represented by the general formula (C) described above. The total number of repeating units having a triarylmethane structure in all repeating units constituting the polymer chain is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, and more preferably 20 to 40 mol%. Is more preferable.
The polymer chain may contain other repeating units described above in addition to the repeating unit having a triarylmethane structure. As other repeating units, it is preferable to have one or more selected from repeating units having an acid group and repeating units having a curable group.
When the polymer chain includes a repeating unit having a curable group, the ratio of the repeating unit having a curable group is preferably, for example, 5 to 50 mol, and 10 to 40 mol with respect to 100 mol of all repeating units of the polymer chain. Is more preferable.
When the polymer chain includes a repeating unit having an acid group, the ratio of the repeating unit having an acid group is preferably, for example, 5 to 50 mol, more preferably 10 to 40 mol, based on 100 mol of all repeating units of the polymer chain. preferable.

The multimer represented by the general formula (D) can be synthesized by the following method or the like.
(1) A compound in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group, etc. is introduced at the end, an acid halide having a triarylmethane structure, an alkyl halide having a triarylmethane structure, or a triarylmethane structure A method of polymerizing the isocyanate and the like.
(2) A method in which a compound in which a carbon-carbon double bond is introduced at a terminal and a thiol compound having a triarylmethane structure are subjected to a Michael addition reaction.
(3) A method in which a compound in which a carbon-carbon double bond is introduced at a terminal and a thiol compound having a triarylmethane structure are reacted in the presence of a radical generator.
(4) A method of reacting a polyfunctional thiol compound having a plurality of thiol groups introduced at its terminal with a compound having a carbon-carbon double bond and a triarylmethane structure in the presence of a radical generator.
(5) A method in which a vinyl compound is radically polymerized in the presence of a thiol compound having a triarylmethane structure.

When the triarylmethane compound is a multimer, the weight average molecular weight is preferably 1,000 to 100,000, and more preferably 5,000 to 50,000.
A triarylmethane compound can be contained individually by 1 type or in combination of 2 or more types.

<< Counter anion >>
When the triarylmethane compound is in the form of a cation, it contains a counter anion. The counter anion is not particularly defined, and a known counter anion can be employed. The counter anion is determined according to the number of cations that the triarylmethane compound has.
The counter anion may be in the same molecule as the triarylmethane compound or may be outside the same molecule. The counter anion is in the same molecule means a case where the cation and the counter anion are bonded via a covalent bond.
The counter anion may consist of only the anion part paired with the cation part of the triarylmethane compound, or may have other sites in addition to the anion part. The counter anion may be a multimer (hereinafter also referred to as an anion multimer). When the triarylmethane compound is a multimer, the counteranion may also be contained in the triarylmethane compound multimer as a repeating unit having a counteranion.
Hereinafter, examples of the counter anion used in the present invention will be described.

Examples of the case consisting only of a counter anion include fluorine anion, chlorine anion, bromine anion, iodine anion, cyanide ion, perchlorate anion, borate anion (BF ⁴⁻ etc.), PF ⁶⁻ and SbF ^6−. .

The borate anion is a group represented by B (R ¹⁰ ) ⁴⁻ , and R ¹⁰ is exemplified by a fluorine atom, a cyano group, a fluorinated alkyl group, an alkoxy group, an aryloxy group, and the like.

The counter anion is also at least one selected from —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , a structure represented by the following general formula (A1), and a structure represented by the following general formula (A2). May be included.

General formula (A1)

(In general formula (A1), R ¹ and R ² each independently represent —SO ₂ — or —CO—.)
In formula (A1), at least one of ^{R 1} and ^{R 2} -SO ₂ - preferably represents an, both ^{R 1} and ^{R 2} are -SO ₂ - and more preferably represents.

The general formula (A1) is more preferably represented by the following general formula (A1-1).
Formula (A1-1)

(In General Formula (A1-1), R ¹ and R ² each independently represent —SO ₂ — or —CO—, and X ¹ and X ² each independently represent an alkylene group or an arylene group. )
In formula (A1-1), ^{R 1} and ^{R 2} of the general formula (A1) in the same meaning as ^{R 1} and ^{R 2,} and preferred ranges are also the same.
When X ¹ represents an alkylene group, the carbon number of the alkylene group is 1 to 8 are preferred, 1-6 is more preferable. When X ¹ represents an arylene group, the carbon number of the arylene group is preferably 6 to 18, more preferably 6 to 12, 6 is more preferable. When X ¹ has a substituent, it is preferably substituted with a fluorine atom.
X ² represents an alkylene group or an arylene group, and an alkylene group is preferable. 1-8 are preferable, as for carbon number of an alkylene group, 1-6 are more preferable, 1-3 are more preferable, and 1 is especially preferable. When X ² has a substituent, it is preferably substituted with a fluorine atom.

General formula (A2)

(In General Formula (A2), R ³ represents —SO ₂ — or —CO—. R ⁴ and R ⁵ each independently represent —SO ₂ —, —CO—, or —CN).
Preferably representing the at ^least two R 3 to R ⁵ is -SO ₂ - - In formula ^(A2), at least one of R 3 to R ⁵ -SO ₂ more preferably represents.

Specific examples of the counter ^{_{anion, R-SO 3 -, R}} -COO - or R-PO ₄ ^- in a, R is a halogen atom, an alkyl group which may be substituted by a halogen atom, substituted with a halogen atom Examples of the aryl group that may be used are also exemplified.
The general formula Specific examples of the counter anion include a group represented by (A1) is, R ¹ is a halogen atom, an alkyl group which may be substituted by a halogen atom, an aryl group which may be substituted with a halogen atom The case where it couple | bonds with is illustrated.
As specific examples of the counter anion containing the group represented by the general formula (A2), R ⁴ and R ⁵ are each substituted with a halogen atom, an alkyl group which may be substituted with a halogen atom, or a halogen atom. The case where it is an aryl group that may be present is exemplified.
Specific examples of other counter anions include the following, but the present invention is not limited thereto.

The counter anion may contain a radical polymerizable group.
Examples of the radical polymerizable group that the counter anion may contain include known polymerizable groups that can be crosslinked by radicals, acids, and heat. Specific examples include a (meth) acryl group, a styrene group, a vinyl group, a cyclic ether group, and a methylol group, and at least one selected from a (meth) acryl group, a styrene group, a vinyl group, and a cyclic ether group. Preferably, one selected from a (meth) acryl group, a styrene group, and a vinyl group is more preferable, and a (meth) acryl group or a styrene group is more preferable.
1-3 are preferable and, as for the number of the radically polymerizable groups which the counter anion may contain, 1 is more preferable.

In addition, between the radical polymerizable group and the above-described —SO ₃ ^— , —COO ⁻ , —PO ₄ ^— , the structure represented by the general formula (A1), and the structure represented by the general formula (A2), They may be directly bonded or may be bonded via a linking group, but are preferably bonded via a linking group.
The counter anion containing a radical polymerizable group is preferably represented by the following general formula (b), for example.

General formula (b)

(In general formula (B), P represents a radical polymerizable group. L represents a single bond or a divalent linking group. Anion represents —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , and the above general formula. (The structure represented by (A1) and the structure represented by the general formula (A2) are represented.)

In general formula (b), P represents a radical polymerizable group, and examples thereof include the radical polymerizable group described above.
In the general formula (b), when L represents a divalent linking group, an alkylene group having 1 to 30 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, a butylene group, etc.), a carbon number of 6 to 30 arylene groups, heterocyclic linking groups, —CH═CH—, —O—, —S—, —C (═O) —, —CO—, —NR—, —CONR—, —OC—, —SO -, - SO ₂ - and linking group combining two or more. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
In particular, the linking group includes an alkylene group having 1 to 10 carbon atoms (preferably — (CH ₂ ) _n — (n is an integer of 1 to 10)), an arylene group having 6 to 12 carbon atoms (preferably a phenylene group, naphthylene group), - NH -, - CO -, - O- and -SO ₂ - two or more combined linking group.

  Although the specific example of the counter anion containing a radically polymerizable group is shown below, this invention is not limited to these.

  300-1,000 are preferable and, as for the molecular weight of the counter anion containing a radically polymerizable group, 500-1,000 are more preferable.

When the counter anion is a multimer, the counter anion includes an oligomer, and is preferably a multimer including a repeating unit including an anion portion. As an embodiment in the case where the counter anion is a multimer, as an embodiment in which the counter anion is a multimer including a repeating unit having a triarylmethane structure and a repeating unit having a counter anion and / or a triarylmethane compound, The aspect which is a multimer containing the repeating unit which has an anion is mentioned. The triarylmethane compound in the case where the counter anion is a multimer corresponds to the triarylmethane multimer.
The counter anion including a multimeric structure preferably has a structure represented by the following general formula (c) and / or the following general formula (d).

Formula (c)

(In the general formula (c), X ¹ represents a main chain of a repeating unit. L ¹ represents a single bond or a divalent linking group. Anion represents —SO ₃ ^— , —COO ⁻ , —PO ₄ ^—. Represents a structure represented by the general formula (A1) and a structure represented by the general formula (A2).

In the general formula (c), X ¹ represents a main chain of repeating units, usually represents a linking group formed by polymerization reaction, for example, (meth) acrylic, styrene, vinyl and the like are preferable. Two sites represented by * are repeating units.

When L ¹ represents a divalent linking group, an alkylene group having 1 to 30 carbon atoms (methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), an arylene group having 6 to 30 carbon atoms (phenylene group, Naphthylene group, etc.), heterocyclic linking group, —CH═CH—, —O—, —S—, —C (═O) —, —CO—, —NR—, —CONR—, —OC—, —SO -, - SO ₂ - and linking group combining two or more. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
In particular, L ¹ is a single bond or an alkylene group having 1 to 10 carbon atoms (preferably — (CH ₂ ) _n — (n is an integer of 1 to 10)), an arylene group having 6 to 12 carbon atoms ( A divalent linking group in which two or more of phenylene group, naphthylene group), —NH—, —CO—, —O— and —SO ₂ — are combined is preferable.

Specific examples of the combination of X ¹ and L ¹ include (XX-1) to (XX-24) described above, but are not limited thereto. In addition, the anion multimer is connected with the above anion at a site indicated by * in (XX-1) to (XX-24).

General formula (d)

(In General Formula (d), L ² and L ³ each independently represent a single bond or a divalent linking group. Anion represents —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , (The structure represented by (A1) and the structure represented by the general formula (A2) are represented.)

In General Formula (d), when L ² and L ³ represent a divalent linking group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, —CH═CH— , —O—, —S—, —C (═O) —, —CO—, —NR—, —CONR—, —O ₂ C—, —SO—, —SO ₂ — and combinations of two or more thereof A linking group is preferred. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
L ² is preferably an arylene group having 6 to 12 carbon atoms (particularly a phenylene group). The arylene group having 6 to 30 carbon atoms is preferably substituted with a fluorine atom.
L ³ is preferably a group comprising a combination of an arylene group having 6 to 12 carbon atoms (particularly a phenylene group) and —O—, and at least one arylene group having 6 to 12 carbon atoms is substituted with a fluorine atom. It is preferable.

  As the molecular weight of the anionic multimer, the weight average molecular weight is preferably 3,000 to 30,000, and the molecular weight distribution is preferably 0.8 to 3.0 in terms of Mw / Mn, more preferably the weight average molecular weight is 5, The molecular weight distribution is 1 to 2.5 in terms of Mw / Mn.

When forming an anionic multimer, a chain transfer agent may be added. The chain transfer agent is preferably an alkyl mercaptan, more preferably an alkyl mercaptan having 10 or less carbon atoms or an alkyl mercaptan substituted with an ether group / ester group. In particular, an alkyl mercaptan having a log P value of 5 or less is more preferable.
The amount of the anionic monomer compound having a radical polymerizable group that is a raw material of the anionic multimer contained in the anionic multimer is preferably 5% or less, more preferably 1% or less.
The halogen ion content contained in the anionic multimer is preferably 10 to 3000 ppm, more preferably 10 to 2000 ppm, and still more preferably 10 to 1000 ppm.
Specific examples of the anion multimer are shown below, but the present invention is not limited thereto.

The following specific examples show a state in which the counter anion is not dissociated, but it goes without saying that the state in which the counter anion is dissociated is also within the scope of the present invention.

  When the counter anion is a multimer, it may contain other repeating units in addition to the repeating unit having a counter anion. Examples of the other repeating units include other repeating units that may be included in the case where the triarylmethane compound is a multimer, and the preferred range is also synonymous.

<(B) Dye having a maximum absorption wavelength in the range of 650 to 750 nm>
A dye having a maximum absorption wavelength in the range of 650 to 750 nm (hereinafter also referred to as dye (B)) has a maximum absorption wavelength in the range of 650 to 750 nm. Moreover, it is preferable that a pigment | dye (B) does not have a maximum absorption wavelength in the wavelength range of 450-500 nm.
The structure of the dye (B) can be any known one without particular limitation, but phthalocyanine compounds, cyanine compounds, squarylium compounds, naphthoquinone compounds and azo compounds are preferred, and phthalocyanine compounds, cyanine compounds, squarylium compounds and azo compounds are more preferred. More preferred are phthalocyanine compounds, cyanine compounds and squarylium compounds, particularly preferred are phthalocyanine compounds and squarylium compounds, and more preferred are phthalocyanine dyes.
In particular, when an ionic compound (phthalocyanine compound or the like) is added, pattern defects due to poor development or poor curing can be further suppressed. The reason for this is presumed, but it is presumed that the interaction between the ionic triarylmethane compound and the ionic compound can further suppress aggregation in the same molecule and suppress pattern defects.

The mass ratio of the pigment (B) to the triarylmethane compound (the mass of the pigment having a maximum absorption wavelength in the range of 650 to 750 nm / the mass of the triarylmethane compound) is 0.2 to 1.5. It is more preferably 3 to 1.4, still more preferably 0.4 to 1.2, and particularly preferably 0.5 to 0.8. When 2 or more types of pigment | dye (B) are mix | blended, said total amount becomes said range. With such a configuration, pattern defects can be further suppressed.
The difference in maximum absorption wavelength between the triarylmethane compound and the compound having a maximum absorption wavelength of 650 to 750 nm is preferably 50 to 200 nm, more preferably 70 to 180 nm, and still more preferably 100 to 150 nm.

<< phthalocyanine compound >>
As the phthalocyanine compound, a compound represented by the following general formula (PC) is preferable.
General formula (PC)

In the general formula (PC), M represents a metal. R ^{1 to} R ¹⁶ represent a hydrogen atom, a halogen atom, an alkoxy group, an arylalkoxy group, a heterocyclic alkoxy group, an amino group, an alkylthio group, an arylthio group, and a heterocyclic thio group. However, at least one of R ^{1 to} R ¹⁶ is an alkylalkoxy group, an arylalkoxy group, a heterocyclic alkoxy group, an amino group, an alkylthio group, an arylthio group, and a heterocyclic thio group.

Examples of metals represented by M include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe metal atoms, AlCl, InCl, and FeCl. , TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl ₂ and other metal chlorides, TiO and VO and other metal oxides, and Si (OH) _{2 and} other metal hydroxides, particularly Cu, VO and Zn Is preferable, and Cu is more preferable.

When R ^{1 to} R ¹⁶ represent a halogen atom, the halogen atom is preferably a chlorine atom or a fluorine atom.
When R < ¹ > -R < ¹⁶ > represents an alkoxy group, 1-18 are preferable, as for carbon number of an alkoxy group, 1-15 are more preferable, and 1-12 are more preferable. The alkyl chain portion of the alkoxy group is preferably a straight chain or branched chain. The alkoxy group may have a substituent, and the substituent is preferably an ethylenically unsaturated bond group, and more preferably a vinyl group.
If R ¹ to R ¹⁶ represents an arylalkoxy group, the number of carbon atoms of the aryl alkoxy group is preferably 7 to 18, 7 to 12 is more preferable.
When R ^{1 to} R ¹⁶ represent a heterocyclic alkoxy group, the heterocyclic ring may be monocyclic or polycyclic, and may be aromatic or non-aromatic. The number of heteroatoms constituting the heterocycle is preferably 1 to 3. The hetero atom is preferably a nitrogen atom.
When R < ¹ > -R < ¹⁶ > represents an alkylthio group, 1-18 are preferable, as for carbon number of an alkylthio group, 1-15 are more preferable, and 1-12 are more preferable.
When R < ¹ > -R < ¹⁶ > represents an arylthio group, 6-18 are preferable and, as for carbon number of an arylthio group, 6-12 are more preferable.
When R ^{1 to} R ¹⁶ represent a heterocyclic thio group, the heterocyclic ring has the same meaning as the heterocyclic ring described above for the heterocyclic alkoxy group.

R ^{1 to} R ¹⁶ are one or two of R ^{1 to} R ⁴ , one or two of R ^{5 to} R ⁸ , one or two of R ^{9 to} R ¹² , one of R ^{13 to} R ¹⁶ . One or two are each independently an alkoxy group, an arylalkoxy group, a heterocyclic alkoxy group, an amino group, an alkylthio group, an arylthio group and a heterocyclic thio group, and the rest are preferably a hydrogen atom or a halogen atom. R ⁴ , R ⁸ , R ¹² and R ¹⁶ are an alkoxy group, an arylalkoxy group, a heterocyclic alkoxy group, an amino group, an alkylthio group, an arylthio group or a heterocyclic thio group, and the remainder is a hydrogen atom or a halogen atom Is preferred. In particular, it is preferable that R ⁴ , R ⁸ , R ¹² and R ¹⁶ are alkoxy groups, and the rest are hydrogen atoms.
R ³ , R ⁷ , R ¹¹ and R ¹⁵ are an alkoxy group, an arylalkoxy group, a heterocyclic alkoxy group, an amino group, an alkylthio group, an arylthio group or a heterocyclic thio group, and the rest are hydrogen atoms or halogen atoms. It is also preferable that there is.
R ¹ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹² , R ¹³ and R ¹⁶ are an alkoxy group, an arylalkoxy group, a heterocyclic alkoxy group, an amino group, an alkylthio group, an arylthio group or a heterocyclic thio group. It is also preferred that the group is a hydrogen atom or a halogen atom.
R ¹ , R ⁵ , R ⁹ , and R ¹³ are an alkoxy group, an arylalkoxy group, a heterocyclic alkoxy group, an amino group, an alkylthio group, an arylthio group, or a heterocyclic thio group, and the remainder is a hydrogen atom or a halogen atom It is also preferable.
R ² , R ⁶ , R ¹⁰ , and R ¹⁴ are an alkoxy group, an arylalkoxy group, a heterocyclic alkoxy group, an amino group, an alkylthio group, an arylthio group, or a heterocyclic thio group, and the remainder is a hydrogen atom or a halogen atom It is also preferable.

Although the example of the phthalocyanine compound used by this invention is shown below, it cannot be overemphasized that this invention is not limited to these.

<< cyanine compound >>
As the cyanine compound, a compound represented by the following general formula (PM) is preferable.
General formula (PM)

In general formula (PM), ring Z1 and ring Z2 each independently represent a heterocyclic ring which may have a substituent. l represents an integer of 0 or more and 3 or less. X ⁻ represents a counter anion.

Each of the ring Z1 and the ring Z2 is preferably a nitrogen-containing heterocyclic ring having a substituent, more preferably a nitrogen-containing condensed complex ring having a substituent, and more preferably an indole ring having a substituent.
Examples of the ring Z1 and the ring Z2 include oxazole, benzoxazole, oxazoline, thiazole, thiazoline, benzothiazole, indolenine, benzoindolenine, 1,3-thiadiazine, and benzoindolenine is preferable. The substituents that the ring Z1 and the ring Z2 may have are the same as the substituents exemplified in the substituent group A, and preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. And an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 4 carbon atoms is more preferable.
l represents an integer of 0 or more and 3 or less, preferably 1 or 2, and more preferably 1.
Examples of X ⁻ include the counter anions mentioned for the triarylmethane compound, and the preferred range is also the same. X < ^- > may be linked to the dye skeleton of the cyanine compound, or may be linked to a part of the dye multimer (polymer chain or the like).

The general formula (PM) is preferably represented by the following general formula (PM-2).
General formula (PM-2)

In the formula, each of the ring Z ⁵ and the ring Z ⁶ independently represents a benzene ring which may have a substituent or a naphthalene ring which may have a substituent, and an unsubstituted benzene ring is more preferable. .
Y ^- is, represents a counter anion. The counter anion is preferably selected from the anions described above.
n represents an integer of 0 or more and 3 or less, and the same preferable range as l in the general formula (PM-1).
A ¹ and A ² each independently represent an oxygen atom, a sulfur atom, a selenium atom, a carbon atom or a nitrogen atom. A carbon atom, a nitrogen atom or a sulfur atom is preferable, and a carbon atom is more preferable.
R ¹ and R ² each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and an alkyl group having 1 to 6 carbon atoms or 2 to 2 carbon atoms. 6 alkenyl groups are preferable, and an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 4 carbon atoms is more preferable.
R ³ and R ⁴ each independently represents a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a divalent group formed by combining one R ³ and one R ⁴ together. Represents an aliphatic hydrocarbon group having 2 to 6 carbon atoms, and a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms is preferable. The aliphatic hydrocarbon group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.
a and b each independently represent an integer of 0 or more and 2 or less. 1 or 2 is preferable and 2 is more preferable.

Although the example of the cyanine compound used by this invention is shown below, it cannot be overemphasized that this invention is not limited to these.

<< Squarylium Compound >>
As the squarylium compound, a compound represented by the general formula (K) is preferable.
General formula (K)

In the general formula (K), A and B each independently represent an aryl group or a heterocyclic group. The aryl group is preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and examples thereof include phenyl and naphthyl. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group, and examples thereof include pyroyl, imidazoyl, pyrazoyl, thienyl, pyridyl, pyrimidyl, pyridazyl, triazol-1-yl, thienyl, furyl, thiadiazoyl and the like. .
In particular, A and B are preferably an aryl group having a substituent, and more preferably a phenyl group having a substituent. The substituent is preferably a hydroxyl group and —NR ¹ R ² . ^{R 1} and ^{R 2} in -NR ¹ R ² is preferably an aryl group having 6 to 12 carbon atoms, a phenyl group is more preferable.

Although the example of the squarylium compound used by this invention is shown below, it cannot be overemphasized that this invention is not limited to these.

<< Naphthoquinone compound >>
As the naphthoquinone compound, a compound represented by the general formula (NQ) is preferable.

General formula (NQ)

  In general formula (NQ), Ra to Rh are each independently a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, An alkoxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, and an amino group are represented. Ra and Rb, Re and Rf, Rd and Re, and Rf and Rg may be connected to each other to form a ring. Ra and Rb are particularly preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group and an alkoxy group, and more preferably a hydrogen atom, a halogen atom and an alkenyl group. Rf and Re are preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an arylthio group and a carbamoyl group, and more preferably a hydrogen atom, a halogen atom, an arylthio group and a carbamoyl group. Rc, Rd, Rg and Rh are preferably a hydrogen atom, an alkyl group and an aryl group, Rc and Rh are a hydrogen atom, and Rd and Rg are preferably a hydrogen atom, an alkyl group and an aryl group.

Although the example of the naphthoquinone compound used by this invention is shown below, it cannot be overemphasized that this invention is not limited to these.

<< Azo compound >>
The azo compound is not particularly defined, but examples thereof include compounds represented by the following general formula (Az).
General formula (Az)

In general formula (Az), R ^{1 to} R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl. Represents a group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group, and A represents an aryl group or a heterocyclic group, particularly an aryl group having an amino group, and a phenyl group and a naphthyl group having an amino group Is more preferable.

Although the example of the azo compound used by this invention is shown below, it cannot be overemphasized that this invention is not limited to these. Of the compounds described in JP-A-2013-225112, paragraphs 0142 to 0183, compounds having a maximum absorption wavelength in a predetermined range can also be preferably employed.

  (B) It is preferable that the pigment | dye which has maximum absorption wavelength in the range of 650-750 nm has an ethylenically unsaturated bond group. By having an ethylenically unsaturated bond group, curability increases, and durability (light resistance, heat resistance, solvent resistance, developer resistance, etc.) can be further improved. As an ethylenically unsaturated bond group, it is synonymous with the ethylenically unsaturated bond group in the above-mentioned triarylmethane compound, and its preferable range is also the same.

<< When Dye (B) is a Multimer >>
The dye (B) is also preferably a multimer. When the dye (B) is a multimer, the weight average molecular weight is preferably 2,000 to 20,000, and more preferably 6,000 to 15,000.
Moreover, it is preferable that ratio [(Mw) / (Mn)] of the weight average molecular weight (Mw) of a pigment | dye (B) and a number average molecular weight (Mn) is 1.0-3.0, and is 1.6. It is more preferable that it is -2.5, and it is especially preferable that it is 1.6-2.0.

The glass transition temperature (Tg) of the dye (B) is preferably 50 ° C. or higher, and more preferably 100 ° C. or higher. Further, the 5% weight loss temperature by thermogravimetric analysis (TGA measurement) is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and further preferably 200 ° C. or higher. By being in this region, when applying the composition of the present invention to the production of a color filter or the like, it becomes possible to reduce the concentration change caused by the heating process.
When the dye (B) is a multimer, a dye multimer containing a repeating unit represented by the general formula (A-1) or a repeating unit represented by the general formula (C-1), or a general formula (D- The dye multimer represented by 1) is exemplified, and the structure represented by the general formula (D-1) is more preferable.

<<< Repeating unit represented by formula (A-1) >>>
Formula (A-1)

(In General Formula (A-1), X ¹ represents a group forming a main chain, L ¹ represents a single bond or a divalent linking group, and Dye I represents a dye structure of dye (B).)
Hereinafter, Formula (A-1) will be described in detail.

In General Formula (A-1), X ¹ represents a group that forms a main chain. That is, it refers to a portion that forms a repeating unit corresponding to the main chain formed by the polymerization reaction. X ¹ has the same meaning as X ^{1 in} the general formula (A) of the triarylmethane compound described above, and is preferably a linking group represented by the above (XX-1) to (XX-24). (Meth) acrylic linking chains represented by 1) and (XX-2), styrene linking chains represented by (XX-10) to (XX-17), and (XX-24) More preferably selected from vinyl-based linking chains, (meth) acrylic linking chains represented by (XX-1) and (XX-2) and styrene-based linking chains represented by (XX-11) More preferred.

In General Formula (A-1), L ¹ represents a single bond or a divalent linking group. When L ¹ represents a divalent linking group, the divalent linking group includes a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, methylene group, ethylene group, trimethylene group, propylene group, butylene). Group), a substituted or unsubstituted arylene group having 6 to 30 carbon atoms (eg, phenylene group, naphthylene group, etc.), substituted or unsubstituted heterocyclic linking group, —CH═CH—, —O—, —S —, —C (═O) —, —CO ₂ —, —NR—, —CONR—, —O ₂ C—, —SO—, —SO ₂ — and a linkage formed by linking two or more thereof. Represents a group. L ¹ is more preferably a single bond or an alkylene group, and more preferably a single bond or — (CH ₂ ) _n — (n is an integer of 1 to 5). Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
The divalent linking group represented by L ¹ may be a group capable of ionic bonding or coordination bonding with DyeI. In this case, either an anionic group or a cationic group may be used.
Examples of the anionic group include —COO ⁻ , —PO ₃ H ⁻ , —SO ₃ ⁻ , —SO ₃ NH ⁻ , —SO ₃ N ^— CO—, and the like, —COO ⁻ , —PO ₃ H ⁻ , — SO ₃ ^- is preferred.
Examples of the cationic group include substituted or unsubstituted onium cations (for example, ammonium, pyridinium, imidazolium, phosphonium and the like), and ammonium cations are particularly preferable.
When L ¹ has a group capable of ionic bond or coordinate bond with Dye I, L ¹ is an anion part (—COO ⁻ , —SO ₃ ⁻ , —O ⁻ etc.) or a cation part (such as the above) that Dye I has. An onium cation, a metal cation, etc.).

  In General Formula (A-1), DyeI represents the dye structure of the dye (B) described above.

The dye multimer having the repeating unit represented by the general formula (A-1) is, for example, (1) a method of synthesizing a monomer having a dye structure by addition polymerization, (2) an isocyanate group, an acid anhydride group or an epoxy. Synthesized by a method in which a polymer having a highly reactive functional group such as a group is reacted with a dye having a functional group (hydroxyl group, primary or secondary amino group, carboxyl group, etc.) capable of reacting with the highly reactive functional group it can.
Known addition polymerizations (radical polymerization, anionic polymerization, cationic polymerization) can be applied to the addition polymerization, but among these, synthesis by radical polymerization is particularly preferable because the reaction conditions can be moderated and the dye structure is not decomposed. Known reaction conditions can be applied to the radical polymerization.
Among them, the dye multimer having the repeating unit represented by formula (A-1) is obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond group from the viewpoint of heat resistance. A radical polymer is preferred.

<<< Repeating unit represented by formula (C-1) >>>
Next, details of the dye multimer represented by formula (C-1) will be described.
Formula (C-1)

(In General Formula (C-1), L ³ represents a single bond or a divalent linking group. DyeIII represents the dye structure of dye (B). M represents 0 or 1)

In the general formula (C-1), L ³ represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L ³ include a substituted or unsubstituted linear, branched or cyclic alkylene group having 1 to 30 carbon atoms (eg, methylene group, ethylene group, trimethylene group, propylene group, butylene group). Etc.), a substituted or unsubstituted arylene group having 6 to 30 carbon atoms (eg, phenylene group, naphthylene group, etc.), substituted or unsubstituted heterocyclic linking group, —CH═CH—, —O—, —S—. , -NR- (R is each independently a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,.), - C (= O) -, - SO -, - SO 2 -, and these Preferable examples include a linking group formed by linking two or more.
m represents 0 or 1, but is preferably 1.

Setting forth specific examples to be preferably used as the divalent linking group represented by L ³ in formula (C-1) below, but is not limited to these as L ³ of the present invention . In addition, the site | part shown by * represents the connection site | part with DyeIII etc.

  The dye multimer having the repeating unit represented by formula (C-1) is synthesized by sequential polymerization. Sequential polymerization means polyaddition (for example, reaction of diisocyanate compound and diol, reaction of diepoxy compound and dicarboxylic acid, reaction of tetracarboxylic dianhydride and diol, etc.) and polycondensation (for example, dicarboxylic acid). And a diol, a reaction of a dicarboxylic acid and a diamine, and the like. Among these, synthesis by polyaddition reaction is particularly preferable because the reaction conditions can be moderated and the dye structure is not decomposed. Known reaction conditions can be applied to the sequential polymerization.

<<< other repeating units >>>
When the dye (B) is a multimer containing the general formula (A-1) or the general formula (C-1), the dye (B) may further contain another repeating unit.
Examples of the other repeating unit include a repeating unit containing an alkali-soluble group such as an acid group, a repeating unit containing a polymerizable group, and the like, and preferably includes at least a repeating unit containing an alkali-soluble group such as an acid group. Each of these repeating units may contain only one type or two or more types. Hereinafter, the details of these repeating units are synonymous with those described in the above triarylmethane multimer, and the preferred ranges are also the same.

In the dye (B), the ratio of the repeating units containing all alkali-soluble groups, including acid groups or other alkali-soluble groups, is preferably, for example, 1 to 80 mol%, preferably 10 to 65 mol%, based on all repeating units. Is more preferable.
The amount of the alkali-soluble group containing an acid group contained in the dye (B) is preferably 0.3 mmol to 2.0 mmol, more preferably 0.4 mmol to 1.5 mmol, based on 1 g of the dye. It is especially preferable that it is 0.5 mmol-1.0 mmol.
The amount of the polymerizable group possessed by the dye (B) is preferably 0.1 to 2.0 mmol, more preferably 0.2 to 1.5 mmol, relative to 1 g of the dye (B), and 0.3 to Particularly preferred is 1.0 mmol.
Moreover, 5-50 mol is preferable with respect to 100 mol of all the repeating units, and, as for the ratio of the repeating unit in which the pigment | dye (B) contains the repeating unit which has a polymeric group, 10-20 mol is more preferable.

<<< Dye Multimer Represented by Formula (D-1) >>>
Next, the dye multimer represented by the general formula (D-1) will be described in detail.
Formula (D-1)

(In General Formula (D-1), L ⁴ represents an (n + m) -valent linking group. N represents an integer of 2 to 20. m represents an integer of 0 to 20. DyeIV represents a dye structure. W is an acid group or a group having an acid group.)

In general formula (D-1), n becomes like this. Preferably it is 2-15, More preferably, it is 3-15, Most preferably, it is 3-6.
When n is 2 or more, each DyeIV may be the same or different.

In general formula (D-1), m is preferably 1 to 15, particularly preferably 2 to 6.
W is an acid group or a group having an acid group. For example, carboxyl group, sulfo group, phosphono group, phosphonoxy group, carboxymethyl group, 1-carboxyethyl group, 2-carboxyethyl group, 1-carboxypropyl group, 3- Carboxypropyl group, 4-carboxybutyl group, 5-carboxypentyl group, 6-carboxyhexyl group, 1,2-dicarboxyethyl group, 1,3-dicarboxypropyl group, 2,3-dicarboxypropyl group, 2 -Carboxyphenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 2,4-dicarboxyphenyl group, 2,5-dicarboxyphenyl group, 2-carboxynaphthyl group, sulfomethyl group, 4-sulfobutyl group, 2 -Sulfophenyl group, 3-sulfophenyl group, phosphonomethyl group, phosphono Shimechiru groups, polymethacrylic acid, poly (methacrylic acid-methyl methacrylate group), but can be mentioned, and particularly preferably a group having a carboxyl group.
When m is 2 or more, W may be one type or two or more types.
In the general formula (D-1), when n is 2, the divalent linking group represented by L ⁴ is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (for example, a methylene group or an ethylene group). , Trimethylene group, propylene group, butylene group, etc.), substituted or unsubstituted arylene groups having 6 to 30 carbon atoms (for example, phenylene group, naphthylene group, etc.), substituted or unsubstituted heterocyclic linking groups, -CH = CH -, -O-, -S-, -NR- (R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group), -C (= O)-, -SO-. , —SO ₂ —, and a linking group formed by linking two or more of these are preferable.

The (n + m) -valent linking group in which (n + m) is 3 or more is a substituted or unsubstituted arylene group (1,3,5-phenylene group, 1,2,4-phenylene group, 1,4,5,8- A linking group formed by substituting the divalent linking group with a central nuclei such as a naphthylene group), a heterocyclic linking group (eg, 1,3,5-triazine group), an alkylene linking group, etc. Can be mentioned.
In particular, a group composed of a combination of an unsubstituted alkylene group having 1 to 6 carbon atoms, —O—, —C (═O) —, and —S— is preferable.
Specific examples of the (n + m) -valent linking group represented by L ⁴ are shown below, but are not limited thereto.

<<< Other pigment multimers >>>
In addition, the polymer compound represented by the general formula (1) according to claim 1 of JP 2007-277514 A, wherein A ¹ is a dye having a maximum absorption wavelength in the range of 650 to 750 nm Can also be used preferably, the contents of which are incorporated herein. More specifically, the polymer compound represented by the general formula (1) according to claim 1 of JP 2007-277514 A, wherein A ¹ is a phthalocyanine compound, a cyanine compound, a squarylium compound, and an azo compound. It is preferably a group in which one hydrogen atom of a compound selected from is removed.

<Curable compound>
The composition of the present invention contains a curable compound. Examples of the curable compound include a polymerizable compound, a thermosetting compound, and an alkali-soluble resin. 1-80 mass% of solid content of the composition of this invention is preferable, and, as for the total amount of these sclerosing | hardenable compounds, 2-30 mass% is more preferable.

<Polymerizable compound>
The composition of the present invention preferably contains a polymerizable compound.
As the polymerizable compound, a known polymerizable compound that can be cross-linked by a radical, acid, or heat can be used. For example, a polymerizable compound containing an ethylenically unsaturated bond group, a cyclic ether (epoxy, oxetane), methylol, or the like. Compounds. The polymerizable compound is preferably selected from compounds having at least one terminal ethylenically unsaturated bond group, preferably two or more, from the viewpoint of sensitivity. Among them, a polyfunctional polymerizable compound having 4 or more functional groups is preferable, and a polyfunctional polymerizable compound having 5 or more functional groups is more preferable. The polymerizable compound is preferably a radical polymerizable compound.

  Such compound groups are widely known in this industrial field, and in the present invention, these compounds can be used without any particular limitation. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers or mixtures thereof and multimers thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together. The polymerizable compound is preferably a monomer. 100-3000 are preferable and, as for the molecular weight of a polymeric compound, 200-2000 are more preferable.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable 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 compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be suitably used in the present invention.

Further, as the polymerizable compound, a compound having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylene group is also preferable. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol ( (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylates obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as nurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A Urethane (meth) acrylates as described in JP-A-51-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof.
A polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group can also be used.
Other preferable polymerizable compounds include a fluorene ring described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and the like, and an ethylenically unsaturated group. It is also possible to use a compound having two or more functions, a cardo resin.

  Moreover, as a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group, paragraph numbers [0254] to [0257] of JP-A-2008-292970 are disclosed. Also suitable are the compounds described in.

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

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
In each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), at least one of a plurality of Rs is —OC (═O) CH═CH ₂ or —OC. A group represented by (═O) C (CH ₃ ) ═CH ₂ is represented.
Specific examples of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5) include the compounds described in paragraph numbers 0248 to 0251 of JP-A-2007-26979. It can be suitably used in the invention.

  Moreover, the compound which (meth) acrylate-ized after adding ethylene oxide and propylene oxide to the said polyfunctional alcohol described with the specific example as general formula (1) and (2) in Unexamined-Japanese-Patent No. 10-62986 is also, It can be used as a polymerizable compound.

  Among them, as a polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; manufactured by Nippon Kayaku), Dipentaerythritol penta (meth) acrylate (as a commercially available product, KAYARAD D-310; manufactured by Nippon Kayaku), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; manufactured by Nippon Kayaku), ethyleneoxy modified di Pentaerythritol hexaacrylate (A-DPH-12E as a commercial product; manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are via ethylene glycol and propylene glycol residues are preferred. These oligomer types can also be used.

  As a polymeric compound, it is a polyfunctional monomer, Comprising: You may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. If the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. Non-aromatic carboxylic acid anhydrides may be reacted to introduce acid groups. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei.

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

Moreover, it is also a preferable aspect to contain the polyfunctional monomer which has a linear ester structure derived from caprolactone as a polymeric compound.
The polyfunctional monomer having a linear ester structure derived from caprolactone is not particularly limited as long as it has a linear ester structure derived from caprolactone in its molecule. For example, trimethylolethane , Ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, and other esters, (meth) acrylic acid and ε-caprolactone An ε-caprolactone-modified polyfunctional (meth) acrylate obtained by converting into a cation can be mentioned. Among these, a polyfunctional monomer having a linear ester structure derived from caprolactone represented by the following general formula (Z-1) is preferable.

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

In General Formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.

In General Formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.

Such polyfunctional monomers having a linear ester structure derived from caprolactone are commercially available, for example, from Nippon Kayaku as KAYARAD DPCA series, and DPCA-20 (formulas (Z-1) to ( Z-3), m = 1, the number of groups represented by formula (Z-2) = 2, a compound in which R ¹ is all hydrogen atoms, DPCA-30 (same formula, m = 1, formula (Z -2) = number of groups represented by 3 = compound in which R ¹ is all hydrogen atoms), DPCA-60 (formula, m = 1, number of groups represented by formula (Z-2) = 6) , Compounds in which R ¹ is all hydrogen atoms), DPCA-120 (in the same formula, m = 2, the number of groups represented by formula (Z-2) = 6, compounds in which R ¹ is all hydrogen atoms), etc. Can be mentioned.
In the present invention, the polyfunctional monomer having a linear ester structure derived from caprolactone can be used alone or in admixture of two or more.

  The specific monomer in the present invention is preferably at least one selected from the group of compounds represented by the following general formula (Z-4) or (Z-5).

In the general formulas (Z-4) and (Z-5), each E independently represents — ((CH ₂ ) yCH ₂ O) — or — ((CH ₂ ) yCH (CH ₃ ) O) —. Y represents each independently an integer of 0 to 10, and X each independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In said general formula (Z-4), the sum total of acryloyl group and methacryloyl group is 3 or 4, m represents the integer of 0-10 each independently, and the sum of each m is an integer of 0-40. is there. However, when the total of each m is 0, any one of X is a carboxyl group.
In the general formula (Z-5), the total number of acryloyl groups and methacryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. is there. However, when the total of each n is 0, any one of X is a carboxyl group.

In the general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable as the sum total of each m.
In the general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Further, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
In general formula (Z-4) or general formula (Z-5) in the _{- ((CH 2) yCH 2} O) - or _{- ((CH 2) yCH (} CH 3) O) - , the oxygen atom side A form in which the terminal of X is bonded to X is preferred.

  The compound represented by the general formula (Z-4) or the general formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (Z-5), a form in which all six Xs are acryloyl groups is preferable.

  Moreover, as a total content in the polymeric compound of the compound represented by general formula (Z-4) or general formula (Z-5), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

  The compound represented by the above general formula (Z-4) or general formula (Z-5) is a conventionally known process, in which ethylene oxide or propylene oxide is ring-opened to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by an addition reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”), and among them, exemplary compounds (a) and ( b), (e) and (f) are preferred.

  As a commercial item of the polymerizable compound represented by the general formula (Z-4) or (Z-5), for example, SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 as polymerizable compounds. By using the compounds, it is possible to obtain a curable composition having an extremely excellent photosensitive speed.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp), UA-7200 (manufactured by Shin-Nakamura Chemical), DPHA-40H (manufactured by Nippon Kayaku), UA-306H, UA -306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoei) and the like.

  Examples of the cyclic ether (epoxy, oxetane) include those having an epoxy group such as JER-827, JER-828, JER-834, JER-1001, JER-1002, and JER-1003 as bisphenol A type epoxy resins. , JER-1055, JER-1007, JER-1009, JER-1010 (above made by Japan Epoxy Resin), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (above, made by DIC), etc. -806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (above, made by Japan Epoxy Resin), EPICLON830, EPICLON8 5 (above, manufactured by DIC), LCE-21, RE-602S (above, manufactured by Nippon Kayaku Co., Ltd.), etc., and phenol novolac type epoxy resins such as JER-152, JER-154, JER-157S70, JER-157S65 ( Above, made by Japan Epoxy Resin), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, made by DIC), etc. N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above made by DIC), EOCN-1020 (above made by Nippon Kayaku), ADEKA RE as an aliphatic epoxy resin SIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE-3150 (2,2-bis (hydroxymethyl) -1-butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct), EPOLEEAD PB 3600, PB 4700 (above, manufactured by Daicel Chemical Industries), Denacol EX-211L, EX-212L, EX-214L, EX- 216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (above, manufactured by ADEKA), NC-2000, N -3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA), JER-1031S (manufactured by Japan Epoxy Resins), and the like. Such a polymerizable compound is suitable for forming a pattern by a dry etching method.

About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, addition amount, etc. can be arbitrarily set according to the final performance design of a composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, from the viewpoint of increasing the strength of the cured film formed from the composition, those having 3 or more functional groups are preferable, and further, different functional groups / different polymerizable groups (for example, acrylic ester, methacrylic ester, styrene compound, vinyl ether). It is also effective to adjust both sensitivity and strength by using a compound of a compound type). Further, it is preferable to use a trifunctional or higher functional polymerizable compound having a different ethylene oxide chain length in that the developability of the composition can be adjusted and an excellent pattern forming ability can be obtained.
In addition, selection and use of polymerizable compounds are important for compatibility and dispersibility with other components (eg photopolymerization initiators, dispersions, alkali-soluble resins, etc.) contained in the composition. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a support.

The content of the polymerizable compound in the composition of the present invention is preferably 0.1 to 70% by mass, more preferably 1 to 50% by mass, and 2 to 30% by mass with respect to the total solid content in the composition. Further preferred.
The composition of the present invention may contain only one type of polymerizable compound or two or more types. When two or more types are included, the total amount is preferably within the above range.

<Photopolymerization initiator>
When the composition of this invention contains a polymeric compound, it is preferable to contain a photoinitiator further.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime. Examples include oxime compounds such as derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like, with oxime compounds being preferred.

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

More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, triarylimidazole compounds, benzimidazole compounds, onium compounds, benzophenone compounds, and acetophenone compounds. At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole compound, a benzophenone compound, a triarylimidazole compound, and a benzimidazole compound is particularly preferable. The triarylimidazole compound may be a mixture with benzimidazole.
Specifically, examples of the trihalomethyltriazine compound include the following compounds. Note that Ph is a phenyl group.


Examples of the triarylimidazole compound and the benzimidazole compound include the following compounds.

A commercially available product can be used as the trihalomethyltriazine compound, for example, TAZ-107 (manufactured by Midori Chemical) can also be used.
In particular, when the composition of the present invention is used for the production of a color filter included in a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is important that it be developed. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Therefore, in view of these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3333724, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), a compound described in JP-A-62-258241, a compound described in JP-A-5-281728, a compound described in JP-A-5-34920, and U.S. Pat. No. 4,221,976. Examples thereof include compounds described in the specification, in particular, compounds described in paragraph No. 0075 of JP2013-077009A.

  Moreover, an acridine derivative is illustrated as photoinitiators other than the above. Specific examples include the compounds described in paragraph No. 0076 of JP2013-077009A, the contents of which are incorporated herein.

  Examples of the ketone compound include compounds described in paragraph No. 0077 of JP2013-077709A, the contents of which are incorporated herein.

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

  More preferred examples of the photopolymerization initiator include oxime compounds. Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.

  Examples of oxime compounds such as oxime derivatives that are suitably used as photopolymerization initiators in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660, J. MoI. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE (registered trademark) -OXE01 (manufactured by BASF) and IRGACURE (registered trademark) -OXE02 (manufactured by BASF) are also preferably used as commercial products.
Examples of oxime compounds include TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arc. Commercial products such as NCI-831 and Adeka Arcles NCI-930 (manufactured by ADEKA) can also be used.

  Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904, in which an oxime is linked to the carbazole N position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292209, in which a nitro group is introduced into the dye moiety, and ketoxime compounds described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are the same molecule A compound described in U.S. Pat. No. 7,556,910, a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.

Preferably, it can also be suitably used for the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744. Among the cyclic oxime compounds, the cyclic oxime compounds fused to the carbazole dyes described in JP2010-32985A and JP2010-185072A in particular have high light absorptivity from the viewpoint of high sensitivity. preferable.
Further, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can be preferably used because it can achieve high sensitivity by regenerating active radicals from polymerization inert radicals. it can.

Particularly preferred are oxime compounds having a specific substituent as disclosed in JP-A-2007-269979 and oxime compounds having a thioaryl group as described in JP-A-2009-191061.
Specifically, the oxime compound that is a photopolymerization initiator is preferably a compound represented by the following general formula (OX-1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

In General Formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In General Formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

  The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has a maximum absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm. .

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, in an ultraviolet-visible spectrophotometer (Varian's Carry-5 spectrophotometer), 0.01 g It is preferable to measure at a concentration of / L.

  Specific examples (C-4) to (C-13) of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.

  In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP 2013-164471 A ( C-3). This content is incorporated herein.

  The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has a maximum absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm. .

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

<Thermosetting compound>
As the thermosetting compound, for example, a compound having a thermosetting functional group can be used. The thermosetting compound refers to a compound that can be cured by heating, and generally refers to a compound that is cured by heating at 180 ° C. or higher.
As the thermosetting functional group, for example, those having at least one group selected from an epoxy group, a methylol group, an alkoxymethyl group, an acyloxymethyl group, an isocyanate group, a vinyl ether group, and a mercapto group are preferable. As the thermosetting compound, those having two or more thermosetting functional groups in one molecule are more preferable, and compounds having two or more epoxy groups in one molecule are more preferable.
Thermosetting compounds include epoxy compounds, melamine compounds (eg, alkoxymethylated, acyloxymethylated melamine compounds), urea compounds (eg, alkoxymethylated, acyloxymethylated urea compounds), phenolic compounds ( For example, preferred examples include hydroxymethylated or alkoxymethylated phenolic compounds or resins, and alkoxymethyletherified phenolic compounds). Epoxy compounds and melamine compounds are more preferred, and epoxy compounds are more preferred.

The thermosetting compound may be a low molecular weight compound (for example, a molecular weight of less than 2000, or a molecular weight of less than 1000), or a high molecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, the weight average molecular weight is 1000 or more). Either of these may be used. In the present invention, those having a molecular weight of 1000 or more are preferred, and those having a molecular weight of 2000 to 100,000 are more preferred. In the present invention, a compound having 2 or more epoxy groups in one molecule and a molecular weight of 1000 or more is particularly preferable.
Specific examples of these compounds include the compounds described in paragraphs 0085 to 0125 of JP2014-089408A, the contents of which are incorporated herein. Moreover, what corresponds to a thermosetting compound among the said polymeric compounds is illustrated as a preferable example of the thermosetting compound of this invention.

<Other colorant other than triarylmethane compound and dye (B)>
The composition of the present invention may contain a colorant other than the triarylmethane compound and the dye (B). As the other colorant, a dye having a maximum absorption wavelength in the range of 500 to 600 nm (hereinafter also referred to as a dye (C)) is preferable. The transmittance of 490 to 510 nm can be adjusted, and the image quality is improved.
Examples of the dye (C) include a xanthene dye, a dipyrromethene dye, and an anthraquinone dye, and a xanthene dye is preferable. These dyes may be monomeric or multimeric.

  The xanthene dye is preferably represented by a xanthene compound represented by the following formula (J).

In formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represent a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, and m represents 0 Represents an integer of ~ 5. X ⁻ represents a counter anion. When X ⁻ is not present, at least one of R ^{81 to} R ⁸⁵ contains an anion.
In formula (J), R ^{81 to} R ⁸⁵ are each independently preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and even more preferably an alkyl group. When X ⁻ is not present, at least one of R ^{81 to} R ⁸⁵ contains an anion. When at least one of R ^{81 to} R ⁸⁵ contains an anion, examples of the anion include the structure described in the above-described triarylmethane compound, and the preferred range is also the same.
1-10 are preferable, as for carbon number of an alkyl group, 1-5 are more preferable, and 1-3 are more preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. The alkyl group is preferably unsubstituted.
6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable.
In the formula (J), m is preferably an integer of 1 to 3, and more preferably 1 or 2.
In formula (J), X ⁻ represents a counter anion. The counter anion is synonymous with the counter anion described in the above-described triarylmethane compound, and the preferred range is also the same.
When the xanthene dye is a multimer, any one of R ^{81 to} R ⁸⁵ is preferably bonded to another part of the multimer, and more preferably, the other part of the multimer is bonded via R ^85. Are connected.

  Specific examples of xanthene compounds are shown below, but the present invention is not limited thereto.

The dipyrromethene dye is preferably a dipyrromethene dye represented by the following general formula (I).

In general formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, halogen, An atom, an alkyl group, an aryl group, or a heterocyclic group is represented. The description of these substituents can be referred to the descriptions in paragraphs 0047 to 0056 of JP-A No. 2014-132348, the contents of which are incorporated herein.
When the dipyrromethene dye is a multimer, any one of R ^{1 to} R ⁷ is preferably bonded to another part of the multimer, and more preferably, the other part of the multimer is bonded via R ^3. Are connected.

Next, the metal atom or metal compound that forms the dipyrromethene-based metal complex compound will be described.
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or 2 Valent metal chlorides are included. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ Further, metal chlorides such as GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are also included.
Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, and the like from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex B or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO (V = O) Is most preferred. Among these, Zn is particularly preferable.
Examples of the dipyrromethene dye include the following compounds. Details of the dipyrromethene dye can be referred to the descriptions in paragraphs 0045 to 0095 of JP-A No. 2014-132348, the contents of which are incorporated herein.

The dye (C) preferably contains an ethylenically unsaturated group and / or is a multimer.
When the dye (C) contains an ethylenically unsaturated group, details thereof are described in the case where the triarylmethane monomer has an ethylenically unsaturated group, and the triarylmethane has a maximum absorption wavelength of 500 to 600 nm. A preferred example is a compound substituted with a dye structure in the above range. For example, in the case of the dipyrromethene dye represented by the general formula (I), R ³ preferably contains an ethylenically unsaturated group.
When the dye (C) is a multimer, it is preferably a multimer containing a repeating unit containing a dye structure. In the repeating unit represented by the general formula (A) described in the triarylmethane multimer described above, As Dye, a multimer having a dye structure having a maximum absorption wavelength in the range of 500 to 600 nm is more preferable.
In the general formula (D) described in the triarylmethane multimer described above, DyeIV is preferably a multimer having a dye structure having a maximum absorption wavelength in the range of 500 to 600 nm.
The dye structure is preferably a dye structure derived from a xanthene compound or a dye structure derived from a dipyrromethene compound, more preferably a dye structure derived from a xanthene compound represented by the general formula (J), and R ⁸⁵ in the general formula (J) or L ^{1 of the} repeating unit represented by the general formula (A) described in the above-described triarylmethane multimer or the general formula described in the above-described triarylmethane multimer via R ³ in the general formula (I) It is preferably bonded to L ⁴ in (D).
When the dye (C) is a multimer, it may contain other repeating units in addition to the repeating unit containing the dye structure. Specifically, a repeating unit containing an alkali-soluble group such as an acid group, a repeating unit containing a polymerizable group, and the like are exemplified, and preferably includes at least a repeating unit containing an alkali-soluble group such as an acid group. Each of these repeating units may contain only one type or two or more types. The details of these repeating units are synonymous with the description of the repeating unit containing an alkali-soluble group such as an acid group described in the above triarylmethane multimer, the repeating unit containing a polymerizable group, etc., and the preferred range is also synonymous. is there.

Specific examples when the dye (C) is a multimer include the following.

5-100 mass% is preferable with respect to a triarylmethane compound, and, as for content of the pigment | dye (C) in the composition of this invention, 20-60 mass% is more preferable.
5-100 mass% is preferable with respect to a pigment | dye (B), and, as for content of the pigment | dye (C) in the composition of this invention, 10-80 mass% is more preferable.
The composition of the present invention may contain only one type of dye (C), or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Other colorant other than triarylmethane compound, dye (B) and dye (C)>
The composition of the present invention contains other pigments and / or dyes as colorants other than the triarylmethane compound, the dye (B) and the dye (C) without departing from the spirit of the present invention. Also good. However, it is also possible to adopt a configuration that does not substantially contain a colorant other than the triarylmethane compound, the dye (B), and the dye (C). “Substantially free” means, for example, 1% by mass or less of the total colorant.
As the pigment, various conventionally known inorganic pigments or organic pigments can be used, and organic pigments are preferably used. The pigment preferably has a high transmittance.

  Examples of inorganic pigments include black pigments such as carbon black and titanium black, metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, Mention may be made of metal oxides such as titanium, magnesium, chromium, zinc and antimony, and composite oxides of the above metals.

As an organic pigment, for example,
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,179,209,220,224,242,254,255,264,270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37, 58, 59;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1;
Etc.

  Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

C. I. Pigment yellow 11,24,108,109,110,138,139,150,151,154,167,180,185;
C. I. Pigment orange 36, 71;
C. I. Pigment Red 122,150,171,175,177,209,224,242,254,255,264;
C. I. Pigment violet 19, 23, 32;
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37, 58, 59;
C. I. Pigment Black 1.

These organic pigments can be used alone or in various combinations in order to adjust the spectrum and increase the color purity.
Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment , Etc. can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. When the ratio is 100: 4 or less, it is difficult to suppress the light transmittance from 400 nm to 500 nm. When the ratio is 100: 51 or more, the main wavelength tends to be closer to the short wavelength, and the color resolution may not be improved. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the required spectrum.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment and the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 10 or less.

  Further, as the pigment for the black matrix, carbon, titanium black, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium black is preferable. The mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60.

  The composition of the present invention preferably contains a colorant other than black, and more preferably contains a blue colorant. The colorant other than black is preferably a pigment, and more preferably a blue pigment.

When used for a color filter, the primary particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability. The primary particle size of the pigment is more preferably 5 to 75 nm, further preferably 5 to 55 nm, and particularly preferably 5 to 35 nm.
The primary particle size of the pigment can be measured by a known method such as an electron microscope.

Among these, the pigment is preferably a pigment selected from anthraquinone pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinophthalone pigments, isoindoline pigments, azomethine pigments, and dioxazine pigments. In particular, C.I. I. Pigment red 177 (anthraquinone pigment), C.I. I. Pigment red 254 (diketopyrrolopyrrole pigment), C.I. I. Pigment green 7, 36, 58, C.I. I. Pigment Blue 15: 6 (phthalocyanine pigment), C.I. I. Pigment yellow 138 (quinophthalone pigment), C.I. I. Pigment yellow 139,185 (isoindoline pigment), C.I. I. Pigment yellow 150 (azomethine pigment), C.I. I. Pigment violet 23 (a dioxazine pigment) is particularly preferable.
Other dyes include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, JP 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 505950, US Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-51115 The pigment | dye currently disclosed by 6-194828 gazette etc. can be used. The chemical structure uses dyes such as pyrazole azo, anilino azo, triphenylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine. it can.
Other dyes may use pigment multimers. Examples of the dye multimer include compounds described in JP2011-213925A, JP2013-041097A, and the like.

When the composition of this invention contains another pigment and / or dye, 10 mass%-70 mass% are preferable with respect to all the components except the solvent contained in a composition, More preferably, 20 mass% It is -60 mass%, More preferably, it is 25 mass%-50 mass%.
The composition of the present invention may contain only one type or two or more types of other pigments and / or dyes. When two or more types are included, the total amount is preferably within the above range.

<Alkali-soluble resin>
The composition of the present invention preferably further contains an alkali-soluble resin.
The molecular weight of the alkali-soluble resin is not particularly defined, but it is preferable that Mw is 5000 to 100,000. Moreover, it is preferable that Mn is 1000-20,000.

  The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.

  Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, but are soluble in a solvent and can be developed with a weak alkaline aqueous solution. Of these, (meth) acrylic acid is particularly preferred. These acid groups may be used alone or in combination of two or more.

Examples of the monomer capable of imparting an acid group after the polymerization include, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types. In order to introduce an acid group into an alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component.
In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.

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

  As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer. , Maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolak resins, etc., acid cellulose derivatives having a carboxylic acid in the side chain, and acid anhydrides added to polymers having a hydroxyl group. Can be mentioned. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, as N-position-substituted maleimide monomer described in JP-A-10-300922, may be mentioned N- phenylmaleimide, an N- cyclohexyl maleimide and the like. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

  As the alkali-soluble resin, a compound represented by the following general formula (ED) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”) are essential. It is also preferable to include a polymer (a) obtained by polymerizing the monomer component.

In General Formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
General formula (ED2)

In General Formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the general formula (ED2), the description of JP 2010-168539 A can be referred to.

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

  Specific examples of the ether dimer include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-amyl) -2,2 ′-[oxybis (methylene)] bis-2-prope , Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2- Ethylhexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxy) Ethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene) )] Bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-butyl) Cyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclo Decanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ′ -[Oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate and the like. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

  Moreover, in order to improve the crosslinking efficiency of the composition in the present invention, an alkali-soluble resin having a polymerizable group may be used. By having a polymerizable group, heat resistance and light resistance tend to be further improved. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful. Examples of the polymer containing the above-mentioned polymerizable group include: NR series (manufactured by Mitsubishi Rayon), Photomer 6173 (manufactured by COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd.), Biscote R-264, KS resist. 106 (all manufactured by Osaka Organic Chemical Industry), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries), Ebecryl 3800 (manufactured by Daicel UCB), and the like. As the alkali-soluble resin containing these polymerizable groups, an isocyanate resin and an OH group are reacted in advance to leave one unreacted isocyanate group, and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group. Unsaturation obtained by reaction of urethane-modified polymerizable double bond-containing acrylic resin obtained by reaction with acryl, acrylic resin containing carboxyl group and compound having both epoxy group and polymerizable double bond in the molecule Group-containing acrylic resin, acid pendant epoxy acrylate resin, polymerizable double bond-containing acrylic resin obtained by reacting OH group-containing acrylic resin and dibasic acid anhydride having polymerizable double bond, OH group A resin obtained by reacting an acrylic resin containing an isocyanate with a compound having a polymerizable group, A resin having a side chain with an ester group having a leaving group such as a halogen atom or a sulfonate group at the α-position or β-position described in JP-A-229207 and JP-A-2003-335814; The resulting resin is preferred.

Moreover, alkali-soluble resin may contain the structural unit derived from the ethylenically unsaturated monomer shown by following formula (X).
Formula (X)

(In Formula (X), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 10 carbon atoms, and R ³ represents a hydrogen atom or a benzene ring that may contain a benzene ring. Represents an alkyl group of 20. n represents an integer of 1 to 15.)
In the formula (X), the number of carbon atoms of the alkylene group R ² is preferably 2-3. Although the carbon number of the alkyl group of R ³ is 1 to 20, more preferably 1 to 10, alkyl group of R ³ may include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ³ include a benzyl group and a 2-phenyl (iso) propyl group.

  As the alkali-soluble resin, in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer or a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers is suitable. . In addition, benzyl (meth) acrylate / (meth) acrylic acid / (meth) acrylic acid-2-hydroxyethyl copolymer copolymerized with 2-hydroxyethyl methacrylate, 2 described in JP-A-7-140654 -Hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl Methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Gerare, particularly preferred examples include a copolymer of benzyl methacrylate / methacrylic acid.

As the alkali-soluble resin, paragraphs 0558 to 0571 of JP 2012-208494 A (corresponding to US Patent Application Publication No. 2012/0235099, [0685] to [0700]) and the following descriptions can be referred to. Are incorporated herein.
Furthermore, the copolymer (B) described in paragraph Nos. 0029 to 0063 described in JP 2012-32767 A and the alkali-soluble resin used in Examples, paragraph Nos. 0088 of JP 2012-208474 A The binder resin described in 0098 and the binder resin used in Examples, the binder resin described in Paragraph Nos. 0022 to 0032 of JP 2012-137531 B, and the binder resin used in Examples, No. 024934, paragraph numbers 0132 to 0143 described in paragraphs 0132 to 0143 and the binder resins used in the examples, JP 2011-242752A paragraphs 0092 to 0098 and the binder resins used in the examples, Paragraph No. of Kokai 2012-032770 It preferred to use a binder resin according to 030-0072. These contents are incorporated herein. More specifically, the following resins are preferable.

The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and particularly preferably 70 mgKOH / g to 120 mgKOH / g.
Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.

When the alkali-soluble resin is contained in the composition, the content of the alkali-soluble resin is preferably 0.1% by mass to 15% by mass, more preferably 0.1% by mass with respect to the total solid content of the composition. They are mass%-12 mass%, Most preferably, they are 1 mass%-10 mass%.
The composition of the present invention may contain only one kind of alkali-soluble resin, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.

<Solvent>
The composition of the present invention may contain a solvent.
The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the composition, but in particular the solubility, applicability, and safety of ultraviolet absorbers, alkali-soluble resins and dispersants, etc. It is preferable to select in consideration. Moreover, when preparing the composition in this invention, it is preferable that at least 2 type of solvent is included.

  Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate (Eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)) ), 2-Oki Propionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropion) Propyl acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, 2-methoxy-2-methyl Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. As ethers, For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Examples of propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and aromatic hydrocarbons For example, toluene, xylene and the like are preferable.

  It is also preferable to mix two or more of these solvents from the viewpoints of the solubility of the ultraviolet absorber and the alkali-soluble resin, the improvement of the coated surface, and the like. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

The content of the solvent in the composition is preferably such that the total solid concentration of the composition is 5% by mass to 80% by mass, more preferably 5% by mass to 60% by mass, from the viewpoint of applicability. The amount of 10% by mass to 60% by mass is more preferable.
The composition of the present invention may contain only one type of solvent or two or more types of solvents. When two or more types are included, the total amount is preferably within the above range.

<Multifunctional thiol compound>
The composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound. The polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following general formula (T1).
General formula (T1)

(In the formula (T1), n represents an integer of 2 to 4, and L represents a 2 to 4 valent linking group.)

  In the general formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and a compound represented by the formula (T2) is particularly preferable. These polyfunctional thiols can be used alone or in combination.

  When the composition of this invention contains a polyfunctional thiol compound, 0.3-8.9 mass% is preferable with respect to the total solid content except a solvent, and 0.8-6.4 mass% is more preferable.

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

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

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.

Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (above DIC), Florard FC430, FC431, FC171 (above, Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104 SC-105, SC1068, SC-381, SC-383, S393, S393, KH-40 (made by Asahi Glass), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA), etc. . A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. Moreover, the fluoropolymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant. Specific examples thereof include compounds described in JP2010-164965A paragraphs 0050-0090 and 0289-0295, such as MegaFac RS-101, RS-102 and RS-718K manufactured by DIC.

  Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5 manufactured by BASF) 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1), SO Sparse 20000 (Lubrizol), and the like. Further, NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. . 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical), W001 (manufactured by Yusho) and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho) and the like.

Examples of the silicone-based surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Toray Silicone SH21PA”, “Toray Silicone SH28PA”, “Toray Silicone SH29PA” manufactured by Toray Dow Corning. , “Tole Silicone SH30PA”, “Tole Silicone SH8400”, Momentive Performance Materials “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF-4442”, Examples include “KP341”, “KF6001”, “KF6002” manufactured by Shin-Etsu Silicone, “BYK307”, “BYK323”, “BYK330” manufactured by BYK Chemie.
When the composition of the present invention contains a surfactant, the addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably 0.001% by mass with respect to the total mass of the composition. It is 005 mass%-1.0 mass%.
The composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.

<Other ingredients>
In addition to the components described above, the composition of the present invention is within the range not impairing the effects of the present invention, and in addition to pigment dispersants, crosslinking agents, polymerization inhibitors, organic carboxylic acids, organic carboxylic acid anhydrides, etc. May be included.

<< Pigment dispersant >>
When the composition of the present invention has a pigment, a pigment dispersant can be used in combination as desired.
Examples of pigment dispersants that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth) acrylates. , (Meth) acrylic copolymers, naphthalenesulfonic acid formalin condensates], and surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, and pigment derivatives, etc. Can do.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.
Details of the dispersant can be referred to the descriptions in paragraphs 0098 to 0102 of JP-A-2014-130344, and the contents thereof are incorporated in the present specification.

  These pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. The pigment dispersant may be used in combination with an alkali-soluble resin together with the terminal-modified polymer, graft polymer, or block polymer having an anchor site to the pigment surface. Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples thereof include acidic cellulose derivatives, and (meth) acrylic acid copolymers are particularly preferable. Further, N-substituted maleimide monomer copolymers described in JP-A-10-300902, ether dimer copolymers described in JP-A-2004-300204, and polymerizable groups described in JP-A-7-319161. An alkali-soluble resin containing is also preferred. Specifically, an alkali-soluble resin: benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer is exemplified.

In the composition, when the pigment dispersant is contained, the total content of the pigment dispersant is preferably 1 part by weight to 80 parts by weight with respect to 100 parts by weight of the pigment, and 5 parts by weight to 70 parts by weight. Is more preferable, and it is more preferable that it is 10 mass parts-60 mass parts. The specific dispersion resin is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, among the dispersant components contained in the composition.
The composition of the present invention may contain only one type of pigment dispersant, or two or more types of pigment dispersants. When two or more types are included, the total amount is preferably within the above range.

Specifically, if a polymer dispersant is used, the amount used is preferably in the range of 5 to 100 parts by mass in terms of mass with respect to 100 parts by mass of the pigment, and 10 to 80 parts by mass. More preferably, it is in the range of parts by mass.
Moreover, when using together a pigment derivative, it is preferable that it is in the range of 1 mass part-30 mass parts in conversion of mass as a usage-amount of a pigment derivative with respect to 100 mass parts of pigments, 3 mass parts-20 mass parts. More preferably, it is in the range, and particularly preferably in the range of 5 to 15 parts by mass.

  In the composition, from the viewpoint of curing sensitivity and color density, the total content of the colorant and the dispersant component is preferably 50% by mass or more and 90% by mass or less with respect to the total solid content constituting the composition. 55 mass% or more and 85 mass% or less is more preferable, and 60 mass% or more and 80 mass% or less is further more preferable.

<< Crosslinking agent >>
It is also possible to supplement the composition of the present invention with a crosslinking agent to further increase the hardness of a cured film obtained by curing the composition.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, substituted with one substituent, Phenol compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are preferred.
The details of paragraphs 0134 to 0147 of JP-A No. 2004-295116 can be referred to for details such as specific examples of the crosslinking agent.
When the crosslinking agent is contained in the composition of the present invention, the blending amount of the crosslinking agent is not particularly defined, but is preferably 2 to 30% by mass, more preferably 3 to 20% by mass based on the total solid content of the composition. preferable.
The composition of the present invention may contain only one type of cross-linking agent, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Polymerization inhibitor >>
In the composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition.
Examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
When a polymerization inhibitor is contained in the composition of the present invention, 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 entire composition.
The composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<< Organic carboxylic acid, organic carboxylic anhydride >>
The composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid anhydride.
Specific examples of the organic carboxylic acid compound include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, Examples thereof include dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricarbaryl acid and aconitic acid. Examples of the aromatic carboxylic acid include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and carboxylic acids in which a carboxyl group is bonded to the phenyl group through a carbon bond. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically maleic acid, malonic acid, succinic acid, and itaconic acid are preferred.

  Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specific examples include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, and tetrahydrophthalic anhydride. Succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. An aliphatic carboxylic acid anhydride is mentioned. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.

When the composition of the present invention contains an organic carboxylic acid or an organic carboxylic anhydride, the amount of the organic carboxylic acid and / or organic carboxylic anhydride added is usually 0.01 to 10% by weight in the total solid content, Preferably it is 0.03 to 5 weight%, More preferably, it is the range of 0.05 to 3 weight%.
The composition of the present invention may contain only one type of organic carboxylic acid and / or organic carboxylic acid anhydride, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
By adding these organic carboxylic acids and / or organic carboxylic acid anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the remaining undissolved material of the composition while maintaining high pattern adhesion.

In addition to the above, the composition may contain various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like, if necessary. Examples of these additives include those described in paragraphs 0155 to 0156 of JP-A No. 2004-295116, the contents of which are incorporated herein.
The composition of the present invention may contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116, and a thermal polymerization inhibitor described in paragraph 0081 of the same publication.
The composition of the present invention may contain only one type of the above components, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

<Method for preparing composition>
The composition of the present invention is prepared by mixing the aforementioned components.
In preparing the composition, the components constituting the composition may be combined at once, or may be sequentially combined after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
The composition prepared as described above can be used after being filtered off using a filter or the like.
The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. If it is conventionally used for the filtration use etc., it can use without being specifically limited. For example, fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight) For example). Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The filter has a pore diameter of about 0.01 to 7.0 μm, preferably about 0.01 to 2.5 μm, and more preferably about 0.01 to 2.0 μm. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of a uniform and smooth composition in a post process. Further, it is also preferable to use a fiber-like filter medium, and examples of the filter medium include polypropylene fiber, nylon fiber, glass fiber, and the like. Specifically, SBP type series (SBP008 etc.), TPR type series (TPR002) manufactured by Loki Techno Co., Ltd. , TPR005, etc.) and SHPX type series (SHPX003 etc.) filter cartridges can be used.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. The pore diameter here can refer to the nominal value of the filter manufacturer. The commercially available filter can be selected from various filters provided by, for example, Nippon Pole, Advantech Toyo, Japan Integris (formerly Japan Microlith) or Kitz Microfilter.
As the second filter, a filter formed of the same material as the first filter described above can be used.
For example, the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

  The composition of the present invention is preferably used as a composition for a color filter. That is, it is preferably used for forming a colored layer of a color filter. More specifically, since the composition of the present invention can form a cured film having excellent heat resistance and color characteristics, it is suitably used for forming a color pattern (colored layer) of a color filter. In addition, the composition of the present invention forms a colored pattern such as a color filter used in a solid-state imaging device (for example, CCD, CMOS (Complementary Metal-Oxide Semiconductor), etc.) and an image display device such as a liquid crystal display device (LCD). It can be suitably used for use. Furthermore, it can be suitably used as a production application for printing ink, inkjet ink, paint, and the like. Especially, it can use suitably as a production use of the color filter for solid-state image sensors, such as CCD and CMOS.

<Curing film, pattern forming method, color filter, and color filter manufacturing method>
Next, the cured film, the pattern forming method, and the color filter in the present invention will be described in detail through the manufacturing method.
The cured film of the present invention is formed by curing the composition of the present invention. Such a cured film is preferably used for a color filter.

The pattern forming method of the present invention comprises a step of applying the composition of the present invention on a support to form a composition layer, a step of exposing the composition layer in a pattern, and an unexposed portion of the composition layer. And a pattern forming method including a step of forming a colored pattern by development and removal. The pattern forming method of the present invention can be suitably applied to the formation of a colored pattern (pixel) included in a color filter.
The method for producing a color filter of the present invention includes the pattern forming method of the present invention.
The composition of the present invention may produce a color filter by pattern formation by a so-called photolithography method, or may form a pattern by dry etching.
That is, as a first production method of the color filter of the present invention, a step of applying a composition on a support to form a composition layer, a step of exposing the composition layer in a pattern, and a composition layer And a step of forming a colored pattern by developing and removing the unexposed portion of the film.
In addition, as a second production method of the color filter of the present invention, a step of applying the composition of the present invention on a support to form a composition layer and curing to form a colored layer; Illustrated is a method including a step of forming a resist layer, a step of patterning the photoresist layer by exposing and developing the photoresist layer to obtain a resist pattern, and a step of dry etching the colored layer using the resist pattern as an etching mask The
In the present invention, it is more preferable to manufacture by photolithography.
These details are described below.

  Hereinafter, although each process in the pattern formation method of this invention is demonstrated in detail through the manufacturing method of the color filter for solid-state image sensors, this invention is not limited to this method. Hereinafter, the color filter for the solid-state imaging device may be simply referred to as “color filter”.

<< Step of Forming Composition Layer >>
In the step of forming the composition layer, the composition layer is formed on the support by applying the composition of the present invention.

As a support that can be used in this step, for example, a solid-state imaging device substrate in which an imaging device (light receiving device) such as a CCD (Charge Coupled Device) or CMOS is provided on a substrate (for example, a silicon substrate) is used. it can.
The colored pattern in the present invention may be formed on the imaging element forming surface side (front surface) of the solid-state imaging element substrate, or may be formed on the imaging element non-forming surface side (back surface).
A light shielding film may be provided between the colored patterns in the solid-state image sensor or on the back surface of the substrate for the solid-state image sensor.
Further, if necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface. In the undercoat layer, a solvent, an alkali-soluble resin, a polymerizable compound, a polymerization inhibitor, a surfactant, a photopolymerization initiator, and the like can be blended. Each of these components is derived from the components blended in the above-described composition of the present invention. It is preferable to select appropriately.

  As a method for applying the composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied.

  The composition layer coated on the support can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, oven, or the like.

<< Process for forming pattern by photolithography >>
<<< Step of Exposure >>>
In the exposure step, the composition layer formed in the composition layer forming step is exposed in a pattern. For example, pattern exposure can be performed by exposing the composition layer formed on the support using a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line). Irradiation dose (exposure dose), for example, preferably 0.03~2.5J / cm ^2, more preferably 0.05~1.0J / cm ^2, and most preferably 0.08~0.5J / cm ² .
The oxygen concentration at the time of exposure can be appropriately selected. In addition to being performed in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free). ), Or in a high oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume). The exposure intensity is can be set appropriately, usually ^{1000W / m 2 ~100000W / m 2} ( ^{e.g., 5000W / m 2, 15000W /} m 2, 35000W / m 2) can be selected from the range of . Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / ^{m 2} at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / ^{m 2.}

The film thickness of the cured film (colored film) is preferably 1.0 μm or less, more preferably 0.1 μm to 0.9 μm, and still more preferably 0.2 μm to 0.8 μm.
It is preferable to set the film thickness to 1.0 μm or less because high resolution and high adhesion can be obtained.
In addition, in this step, a cured film having a thin film thickness of 0.7 μm or less can also be suitably formed, and the obtained cured film is developed in a pattern forming process described later, thereby forming a thin film. Although it exists, the coloring pattern excellent in developability, surface roughness suppression, and pattern shape can be obtained.

<<< Development process >>>
Next, by performing an alkali development treatment, the composition layer of the light non-irradiated part in the exposure step is eluted in the alkaline aqueous solution, and only the photocured part remains.
The developer is preferably an organic alkali developer that does not cause damage to the underlying image sensor or circuit. The development temperature is usually 20 ° C. to 30 ° C., and the development time is conventionally 20 seconds to 90 seconds. In order to remove the residue more, in recent years, it may be carried out for 120 seconds to 180 seconds. Furthermore, in order to further improve residue removability, the process of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.

Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide. , Choline, pyrrole, piperidine, organic alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene, and the concentration of these alkaline agents is 0.001% by mass to 10% by mass, An alkaline aqueous solution diluted with pure water so as to be preferably 0.01% by mass to 1% by mass is preferably used as the developer.
In addition, an inorganic alkali may be used for the developer, and as the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metaoxalate and the like are preferable.
Further, a surfactant may be used for the developer. Examples of the surfactant include the surfactant described in the above-described composition, and a nonionic surfactant is preferable. When a developing solution contains surfactant, 0.001-2.0 mass% is preferable with respect to the total mass of a developing solution, More preferably, it is 0.01-1.0 mass%.
In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it is preferable to wash | clean (rinse) with a pure water after image development.

Next, it is preferable to perform heat treatment (post-bake) after drying. If a multicolor coloring pattern is to be formed, a cured film can be produced by sequentially repeating the above steps for each color. Thereby, a color filter is obtained.
Post-baking is a heat treatment after development for complete curing, and a heat curing treatment is usually performed at 100 ° C. to 240 ° C., preferably 200 ° C. to 240 ° C.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coated film after development is in the above-described condition be able to.

<< When pattern is formed by dry etching method >>
Dry etching can be performed by using an etching gas for the colored layer with the patterned photoresist layer as a mask. Specifically, a positive or negative radiation sensitive composition is applied onto the colored layer and dried to form a photoresist layer. In the formation of the photoresist layer, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming the photoresist layer, a mode in which heat treatment after exposure (PEB) and heat treatment after development (post-bake treatment) are desirable.

As the photoresist, for example, a positive type radiation sensitive composition is used. This positive type radiation sensitive composition includes a positive type photosensitive material sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer lasers, electron beams, ion beams and X rays. A positive resist composition suitable for resist can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.
Specifically, as the positive radiation sensitive composition, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable. A positive radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin indicates that a quinonediazide group is decomposed by irradiation with light having a wavelength of 500 nm or less to produce a carboxyl group, resulting in alkali-solubility from an alkali-insoluble state. It is what you use. Since this positive photoresist has remarkably excellent resolution, it is used for manufacturing integrated circuits such as IC (integrated circuit) and LSI (Large Scale Integration). Examples of the quinonediazide compound include a naphthoquinonediazide compound. Examples of commercially available products include “FHi622BC” (manufactured by FUJIFILM Electronics Materials).

  The thickness of the photoresist layer is preferably 0.1 to 3 μm, preferably 0.2 to 2.5 μm, and more preferably 0.3 to 2 μm. In addition, the application of the photoresist layer can be suitably performed using the above-described application method in the colored layer.

  Next, by exposing and developing the photoresist layer, a resist pattern (patterned photoresist layer) provided with a group of resist through holes is formed. The formation of the resist pattern is not particularly limited, and can be performed by appropriately optimizing a conventionally known photolithography technique. By providing a resist through hole group in the photoresist layer by exposure and development, a resist pattern as an etching mask used in the next etching is provided on the colored layer.

  The exposure of the photoresist layer is performed by exposing the positive-type or negative-type radiation-sensitive composition with g-line, h-line, i-line, etc., preferably i-line, through a predetermined mask pattern. Can do. After the exposure, the photoresist is removed in accordance with a region where a colored pattern is to be formed by developing with a developer.

  Any developer can be used as long as it dissolves the exposed portion of the positive resist and the uncured portion of the negative resist without affecting the colored layer containing the colorant. Or an alkaline aqueous solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable. Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include pyrrole, piperidine, and 1,8-diazabicyclo [5,4,0] -7-undecene. In addition, when alkaline aqueous solution is used as a developing solution, generally a washing process is performed with water after development.

  Next, using the resist pattern as an etching mask, patterning is performed by dry etching so that the through hole group is formed in the colored layer. Thereby, a colored pattern is formed. The through hole group is provided in a checkered pattern in the colored layer. Therefore, the first colored pattern in which the through hole group is provided in the colored layer has a plurality of square-shaped first colored pixels in a checkered pattern.

  Specifically, in the dry etching, the colored layer is dry etched using the resist pattern as an etching mask. Representative examples of dry etching include JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61-41102, etc. There are methods described in the publications.

Dry etching is preferably performed in the following manner from the viewpoint of forming a pattern cross section closer to a rectangle and reducing damage to the support.
Using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ), the first stage etching is performed up to a region (depth) where the support is not exposed, and after this first stage etching, nitrogen gas ( N ₂ ) and oxygen gas (O ₂ ), and a second stage etching is preferably performed to the vicinity of the region (depth) where the support is exposed, and over-etching is performed after the support is exposed. The form containing these is preferable. Hereinafter, a specific method of dry etching and the first stage etching, second stage etching, and over-etching will be described.

Dry etching is performed by obtaining etching conditions in advance by the following method.
(1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are calculated respectively. (2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated. (3) The first stage etching is performed according to the etching time calculated in (2) above. (4) The second stage etching is performed according to the etching time calculated in (2) above. Alternatively, the etching time may be determined by endpoint detection, and the second stage etching may be performed according to the determined etching time. (5) Overetching time is calculated with respect to the total time of (3) and (4) above, and overetching is performed.

The mixed gas used in the first stage etching step preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing the organic material that is the film to be etched into a rectangular shape. In addition, the first stage etching process can avoid damage to the support body by etching to a region where the support body is not exposed. The second etching step and the over-etching step are performed in the first etching step after etching to a region where the support is not exposed by the mixed gas of fluorine-based gas and oxygen gas. From the viewpoint of avoidance, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.

  It is important to determine the ratio between the etching amount in the first stage etching process and the etching amount in the second stage etching process so as not to impair the rectangularity due to the etching process in the first stage etching process. It is. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching process and the etching amount in the second-stage etching process) is preferably in the range of more than 0% and not more than 50%. 10 to 20% is more preferable. The etching amount is an amount calculated from the difference between the remaining film thickness to be etched and the film thickness before etching.

  Etching preferably includes an over-etching process. The overetching process is preferably performed by setting an overetching ratio. Moreover, it is preferable to calculate the overetching ratio from the etching process time to be performed first. The over-etching ratio can be arbitrarily set, but it is preferably 30% or less of the etching processing time in the etching process, and 5 to 25% in terms of maintaining the etching resistance of the photoresist and the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.

  Next, the resist pattern (that is, the etching mask) remaining after the etching is removed. The removal of the resist pattern preferably includes a step of applying a stripping solution or a solvent on the resist pattern so that the resist pattern can be removed, and a step of removing the resist pattern using cleaning water.

  Examples of the step of applying a stripping solution or solvent on the resist pattern so that the resist pattern can be removed include, for example, a step of applying a stripping solution or solvent on at least the resist pattern and stagnating for a predetermined time to perform paddle development Can be mentioned. Although there is no restriction | limiting in particular as time to make stripping solution or a solvent stagnant, It is preferable that it is several dozen seconds to several minutes.

  Examples of the process of removing the resist pattern using the cleaning water include a process of removing the resist pattern by spraying the cleaning water onto the resist pattern from a spray type or shower type spray nozzle. As the washing water, pure water can be preferably used. Further, examples of the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support. When the spray nozzle is movable, the resist pattern is more effectively removed by moving the support pattern from the center of the support to the end of the support more than twice during the process of removing the resist pattern and spraying the cleaning water. be able to.

  The stripping solution generally contains a solvent, but may further contain an inorganic solvent. Examples of the solvent include 1) a hydrocarbon compound, 2) a halogenated hydrocarbon compound, 3) an alcohol compound, 4) an ether or acetal compound, 5) a ketone or aldehyde compound, 6) an ester compound, 7) Polyhydric alcohol compounds, 8) Carboxylic acid or acid anhydride compounds thereof, 9) Phenol compounds, 10) Nitrogen compounds, 11) Sulfur compounds, and 12) Fluorine compounds. The stripping solution preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specifically, for example, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, triethanolamine, etc. Preferred are monoethanolamine, diethanolamine and triethanolamine, and more preferred is monoethanolamine (H ₂ NCH ₂ CH ₂ OH). Examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, α-picoline, β-picoline, γ-picoline, 2- Preferred examples include pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, 2,6-lutidine and the like. Are N-methyl-2-pyrrolidone and N-ethylmorpholine, more preferably N-methyl-2-pyrrolidone (NMP).

  The stripping solution preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound. Among these, as the acyclic nitrogen-containing compound, at least one selected from monoethanolamine, diethanolamine, and triethanolamine, and cyclic The nitrogen-containing compound preferably contains at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably contains monoethanolamine and N-methyl-2-pyrrolidone.

  When removing with the stripping solution, it is sufficient that the resist pattern 52 formed on the first colored pattern 12 is removed, and a deposit as an etching product adheres to the side wall of the first colored pattern 12 However, the deposit may not be completely removed. A deposit means an etching product deposited and deposited on the side wall of a colored layer.

  As the stripping solution, the content of the non-cyclic nitrogen-containing compound is 9 parts by weight or more and 11 parts by weight or less with respect to 100 parts by weight of the stripping solution, and the content of the cyclic nitrogen-containing compound is 100 parts by weight of the stripping solution. On the other hand, what is 65 to 70 mass parts is desirable. Further, the stripping solution is preferably obtained by diluting a mixture of an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound with pure water.

  In addition, the manufacturing method of this invention may have a well-known process as a manufacturing method of the color filter for solid-state image sensors as processes other than the above as needed. For example, after performing the composition layer forming step, the exposure step, and the pattern forming step described above, a curing step of curing the formed colored pattern by heating and / or exposure may be included as necessary.

Further, when the composition according to the present invention is used, for example, clogging of a nozzle or a pipe part of a coating apparatus discharge unit, contamination due to adhesion, sedimentation, or drying of the composition or pigment in the coating machine may occur. Therefore, in order to efficiently clean the contamination caused by the composition of the present invention, it is preferable to use the solvent related to the present composition as the cleaning liquid. JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP2007-2101A, JP2007-2102A, JP2007-281523A, and the like can also be suitably used for cleaning and removing the composition according to the present invention.
Of the above, alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoalkyl ethers are preferred.
These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 80/20. In a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), the ratio is particularly preferably 60/40. In addition, in order to improve the permeability of the cleaning liquid with respect to contaminants, a surfactant related to the present composition may be added to the cleaning liquid.

<Color filter>
Since the color filter of the present invention uses the composition of the present invention, exposure with excellent exposure margin can be achieved, and the formed colored pattern (colored pixel) has excellent pattern shape, and the surface of the pattern is rough and developed. Since the residue in the portion is suppressed, the color characteristics are excellent.
The color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels. The color filter for a solid-state imaging device of the present invention can be used as a color filter disposed between, for example, a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

In addition, as a film thickness of the coloring pattern (color pixel) in the color filter of this invention, 2.0 micrometers or less are preferable, 1.0 micrometer or less is more preferable, and 0.7 micrometer or less is further more preferable.
Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.
The color filter of the present invention includes a triarylmethane compound, a dye having a maximum absorption wavelength in the range of 650 to 750 nm, and a curable compound, and the minimum transmittance in the thickness direction in the wavelength range of 450 to 500 nm is 80%. The maximum value of the transmittance in the thickness direction in the wavelength range of 650 to 700 nm is preferably 25% or less.
In the color filter of the present invention, the minimum transmittance in the thickness direction in the wavelength range of 450 to 500 nm is preferably 84% or more, and more preferably 90% or more.
In the color filter of the present invention, the maximum transmittance in the thickness direction in the wavelength range of 650 to 700 nm is preferably 20% or less, and more preferably 15% or less.
In the color filter of the present invention, the mass ratio of the dye having a maximum absorption wavelength in the range of 650 to 750 nm with respect to the triarylmethane compound is preferably 0.2 to 1.5.
Here, the transmittance of the color filter refers to a glass substrate coated with the composition of the present invention so that the dry film thickness is 0.6 μm, an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation, UV3600 ) Measured with a spectrophotometer (ref. Glass substrate).

<Solid-state imaging device>
The solid-state imaging device of the present invention has the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is a configuration provided with the color filter in the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. .

A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on a support, and the photodiode and the transfer electrode are provided on the support. A light-shielding film made of tungsten or the like having an opening only in the light-receiving portion of the photodiode, and a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion. It is the structure which has the color filter for solid-state image sensors of this invention on a device protective film.
Further, a configuration having light collecting means (for example, a microlens, etc., the same applies hereinafter) on the device protective film and below the color filter (on the side close to the support), or a structure having the light collecting means on the color filter Etc.

<Image display device>
The color filter of the present invention can be used not only for the solid-state imaging device but also for image display devices such as liquid crystal display devices and organic EL display devices, and is particularly suitable for use in liquid crystal display devices. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good display image color and excellent display characteristics.

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

The color filter of the present invention may be used in a color TFT (thin film transistor) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention relates to a liquid crystal display device with a wide viewing angle, such as a lateral electric field drive method such as IPS (In-Place-Switching), a pixel division method such as MVA, STN (Super-twisted nematic), TN (Twisted). Nematic), VA (Virtical Alignment), OCS (Optically Compensated. Splay), FFS (fringe field switching), and R-OCB (R-Optically Compensated Bend).
In addition, the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system. In the case of a COA type liquid crystal display device, the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the stripping solution, in addition to the normal required characteristics as described above. Sometimes. In the color filter of the present invention, since a dye multimer excellent in hue is used, the color purity, light transmittance, etc. are good and the color pattern (pixel) is excellent in color, so the resolution is high and the long-term durability is excellent. A COA liquid crystal display device can be provided. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".
Moreover, in this invention, it can use preferably also for the display of a micro O red system (micro OLED). These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

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

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

<Synthesis example>
<< Synthesis of Triarylmethane (T-1) >>

  5.15 g (10 mmol) of C.I. I. Basic Blue 7 was added to a mixed solution of 50 mL of methylene chloride and 10 mL of water and stirred. Next, 3.19 g (10 mmol) of potassium bis (trifluoromethanesulfonyl) imide was added thereto and stirred for 2 hours. Thereafter, the aqueous layer was removed from this solution, and the methylene chloride layer was concentrated to obtain 7.2 g of (T-1).

<< Synthesis of Triarylmethane (T-2) >>

(T-2a) was synthesized according to Synthesis Example 1 of JP-A No. 2000-162429. (T-2a) 6.0 g (10 mmol) was added to a mixture of 50 mL of methylene chloride and 10 mL of water and stirred. Next, 3.19 g (10 mmol) of potassium bis (trifluoromethanesulfonyl) imide was added thereto and stirred for 2 hours. Thereafter, the aqueous layer was removed from this solution, and the methylene chloride layer was concentrated to obtain 8.2 g of (T-2).

<< Synthesis of Triarylmethane (T-3) >>

  (T-2) 10.0 g, methacrylic acid 2.1 g, 2,2′-azobis (methyl isobutyrate) 0.5 g, and 1-dodecanethiol 0.8 g were dissolved in cyclohexanone 28.2 g. This solution was added dropwise to 10.0 g of cyclohexanone heated to 75 ° C. under a nitrogen stream over 2 hours, stirred for 2 hours, and then heated at 90 ° C. for 2 hours. After allowing to cool to 50 ° C., 1.4 g of glycidyl methacrylate, 0.01 g of tetrabutylammonium bromide and 0.01 g of p-methoxyphenol were added to this solution and heated at 100 ° C. for 24 hours in an air atmosphere. After allowing to cool, this solution was added dropwise to a mixed solution of 50 mL of methanol and 250 mL of ion exchange water. The obtained solid was collected by filtration and dried at 40 ° C. to obtain 12.5 g of (T-3). The obtained (T-3) had a weight average molecular weight of 9,000 and an acid value of 65 mgKOH / g.

<< Synthesis of Triarylmethane (T-4) >>

(T-2) 8.47 g (10 mmol), 1.30 g (10 mmol) itaconic acid, 2.61 g (3.3 mmol) of dipentaerythritol hexakis (2-mercaptopropionate) (DPMP) and 1-methoxy- 22.1 g of 2-propanol was heated to 90 ° C. under a nitrogen stream. Next, 0.10 g of 2,2′-azobis (isobutyric acid) dimethyl was added three times in total every 2 hours. The reaction liquid was dripped at the solution of methanol 50mL and ion-exchange water 250mL after standing_to_cool, 8.5 g of (T-4) was obtained by extract | collecting the obtained solid by filtration and drying at 40 degreeC. The obtained (T-4) had a weight average molecular weight of 4,800 and an acid value of 89 mgKOH / g.
In the compound (T-4), A represents the following structure (L4-11). In the following structure, * represents a linking site.

<< Synthesis of Triarylmethane (T-5) >>

(T-2) 8.47 g (10 mmol), dipentaerythritol hexakis (2-mercaptopropionate) (DPMP) 2.61 g (3.3 mmol) and 1-methoxy-2-propanol 22.1 g Under heating to 90 ° C. Next, 0.10 g of 2,2′-azobis (isobutyric acid) dimethyl was added three times every 2 hours, and heated at 100 ° C. for 3 hours to contain 1-methoxy-2-containing (t-1). A propanol solution was obtained. After allowing to cool, 1.72 g (20 mmol) of methacrylic acid was added and heated to 80 ° C. under a nitrogen stream. Next, 0.10 g of 2,2′-azobis (isobutyric acid) dimethyl was added three times every 2 hours, and heated at 100 ° C. for 3 hours to contain 1-methoxy-2-containing (t-2). A propanol solution was obtained. After standing to cool, 1.42 g (10 mmol) of glycidyl methacrylate, 0.01 g of tetrabutylammonium bromide, and 0.01 g of p-methoxyphenol were added and heated at 100 ° C. for 24 hours in an air atmosphere. After standing to cool, it was added dropwise to a solution of 50 mL of methanol and 250 mL of ion-exchanged water, and the resulting solid was collected by filtration and dried at 40 ° C. to obtain 13.2 g (T-5). The obtained (T-5) had a weight average molecular weight of 7,200 and an acid value of 40 mgKOH / g. In the compound (T-5), A represents the structure (L4-11).
<< Synthesis of Triarylmethane (T-6) >>

  (T-2) 8.47 g (10 mmol), 3-mercapto-1,2-propanediol 0.24 g (20 mmol) and 1-methoxy-2-propanol 22.1 g were heated to 90 ° C. in a nitrogen stream. Next, 0.10 g of 2,2′-azobis (isobutyric acid) dimethyl was added three times every 2 hours, and the mixture was heated at 100 ° C. for 3 hours. After allowing to cool, the obtained reaction solution was concentrated using an evaporator. The concentrate was separated with chloroform and a 5% by weight aqueous sodium bicarbonate solution, and then the organic layer was concentrated with an evaporator. The resulting concentrate was subjected to column purification (filler: silica gel, eluent: liquid for mixing chloroform and methanol) to obtain 7.12 g of (t-3). (T-3) 6.71 g (7 mmol), pyromellitic anhydride 2.18 g (10 mmol), 2,3-dihydroxypropyl methacrylate 3 mmol (0.48 g) and N-methylpyrrolidone 18.1 g were added, and nitrogen was added. Heated to 100 ° C. under a stream of air. Next, 0.010 g of monobutyltin oxide was added and stirred for 24 hours. After standing to cool, it was added dropwise to 200 mL of 1 mol / l hydrochloric acid and filtered. The obtained filtrate was washed with 200 mL of a 50% by weight aqueous methanol solution and dried to obtain 6.33 g of (T-6). The obtained (T-6) had a weight average molecular weight of 9,600 and an acid value of 120 mgKOH / g.

<< Synthesis of Dye (D-5) >>

(D-2) 8.15 g (10 mmol), 1.30 g (10 mmol) itaconic acid, 2.61 g (3.3 mmol) of dipentaerythritol hexakis (2-mercaptopropionate) (DPMP) and 1-methoxy- 22.1 g of 2-propanol was mixed and the solution was heated to 90 ° C. under a nitrogen stream. Next, 0.10 g of 2,2′-azobis (isobutyric acid) dimethyl was added to the solution three times in total every 2 hours. After allowing to cool, this solution was added dropwise to a mixed solution of 50 mL of methanol and 250 mL of ion exchange water. The obtained solid was collected by filtration and dried at 40 ° C. to obtain 8.5 g of (D-5). The obtained (D-5) had a weight average molecular weight of 4,200 and an acid value of 92 mgKOH / g.
In the compound (D-5), A represents the structure (L4-11).

<< Synthesis of Dye (A-1) >>

  Monomer (X-1) 16.4 g, methacrylic acid 1.60 g, dodecyl mercaptan 0.51 g, propylene glycol 1-monomethyl ether 2-acetate (hereinafter also referred to as “PGMEA”) 46.6 g are mixed and this solution is mixed. Was added to a three-necked flask and heated to 80 ° C. under a nitrogen atmosphere. To the remaining solution, 0.58 g of 2,2'-azobis (isobutyric acid) dimethyl was added and dissolved, and this was added dropwise to the above-mentioned three-necked flask over 2 hours. After stirring for 3 hours, the temperature was raised to 90 ° C., and the mixture was stirred for 2 hours. Next, 1.60 g of glycidyl methacrylate and 0.10 g of tetrabutylammonium bromide were added to the reaction solution and heated at 90 ° C. for 10 hours. After cooling to room temperature, this reaction solution was added dropwise to a mixed solvent of methanol / ion exchange water = 100 mL / 10 mL to reprecipitate. After filtration, blow drying at 40 ° C. for 2 days, 15.6 g of a dye multimer (A-1) was obtained. The obtained (A-1) had a weight average molecular weight of 7,500 and an acid value of 30 mgKOH / g.

<Measurement method of maximum absorption wavelength>
100 mg of the dye was dissolved in 200 mL of tetrahydrofuran, and tetrahydrofuran was added to 2 mL of this solution to make 200 mL. This solution was measured from 400 to 800 nm using a Cary 5000 UV-Vis-NIR spectrophotometer (manufactured by Agilent Technologies), and the maximum absorption wavelength was measured.

1. Preparation of resist solution Components of the following composition were mixed and dissolved to prepare an undercoat layer resist solution.
<Composition of resist solution for undercoat layer>
Solvent: propylene glycol monomethyl ether acetate (PGMEA) 19.20 parts Solvent: ethyl lactate 36.67 parts Alkali-soluble resin: benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer (molar ratio = 60/22/18, weight average molecular weight 15,000, number average molecular weight 9,000) 40% PGMEA solution
30.51 parts ・ Dipentaerythritol hexaacrylate (KAYARAD DPHA (manufactured by Nippon Kayaku)) 12.20 parts ・ Polymerization inhibitor: 0.0061 part of p-methoxyphenol ・ Fluorosurfactant: F-475, manufactured by DIC 0.83 parts, photopolymerization initiator: trihalomethyltriazine photopolymerization initiator (TAZ-107, manufactured by Midori Chemical) 0.586 parts

2. Production of silicon wafer substrate with undercoat layer A 6-inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so that the dry film thickness is 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. A substrate was obtained.

3. Preparation of Composition <Compositions of Examples 1-33 and Comparative Examples 1-3>
The following components were mixed, dispersed and dissolved, and filtered through a 0.45 μm nylon filter to obtain compositions of Examples 1-33 and Comparative Examples 1-3.
Triarylmethane compound (triarylmethane (A)) described in Table 4 Dye (B) described in Table 4 The total of the triarylmethane compound and the dye (B) is 60 parts.
-Dye (C) When blended, 10 parts-Cyclohexanone 100 parts-Alkali-soluble resin (the following J1 or J2: compounds described in the following table) 5 parts-Solsperse 20000
(1% cyclohexane solution, manufactured by Nippon Lubrizol) 1 part Photopolymerization initiator (the following (I-1) to (I-8): compounds described below) 1 part dipentaerythritol hexaacrylate (KAYARAD DPHA ( Nippon Kayaku))) 10 parts ・ Glycerol propoxylate (1% cyclohexane solution) 0.1 part

(I-1) is IRGACURE (registered trademark) -OXE01, (I-2) is IRGACURE (registered trademark) -OXE02 (manufactured by BASF), (I-3) is IRGACURE (registered trademark) -379, (I- 4) is DAROCUR (registered trademark) -TPO (all of which are manufactured by BASF).

Alkali-soluble resin

In the compound (D-5), A represents the following structure (L4-11). In the following structure, * represents a linking site.

Dye (A-2), Dye (A-3)

In the above (A-2), the molar ratio of the repeating unit containing a dye structure, the repeating unit containing an acid group, and the repeating unit containing a polymerizable group is 51:19:30, and Mw is 8500.

Dye (A-4)
Synthesized by the method described in JP-A-2014-199436.
Acid value = 1.01 mmol / g
a / b / c / d = 36/12/32/20 (mol%)
Mw = 13,000

Dye (A-5)
Synthesized by the method described in JP-A-2014-199436.

4). Preparation of color filter by composition <Pattern formation>
Each of the compositions of Examples and Comparative Examples prepared as described above was applied onto the undercoat layer of a silicon wafer substrate with an undercoat layer obtained in “2. Production of silicon wafer substrate with an undercoat layer” above. A physical layer (coating film) was formed. Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.6 μm.

Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon), exposure was performed at various exposure amounts of 50 to 1200 mJ / cm ² through an Island pattern mask having a pattern of 1.0 μm square at a wavelength of 365 nm.
Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics Materials). The product was subjected to paddle development at 23 ° C. for 60 seconds to form a colored pattern on the silicon wafer substrate.

The silicon wafer on which the colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 r. p. m. While being rotated, pure water was supplied from the upper side of the rotation center in a shower form to perform a rinsing treatment, and then spray-dried.
As described above, a monochromatic color filter having a colored pattern formed by the composition of the example or the comparative example was produced.
Thereafter, the size of the colored pattern was measured using a length measuring SEM (scanning electron microscope) “S-9260A” (manufactured by Hitachi High-Technologies). The exposure amount at which the pattern size was 1.0 μm was determined as the optimum exposure amount.

5. Performance evaluation 5-1. Light Resistance As an index for evaluating light resistance (light fastness), a color difference (ΔE * ab value) before and after light irradiation was measured. Specifically, the composition obtained above was applied onto a glass substrate so that the dry film thickness was 0.6 μm, thereby forming a coating film. This coating film was irradiated with a xenon lamp at 100,000 lux for 20 hours (equivalent to 2 million lux · h), and the color difference (ΔE * ab value) before and after irradiation was measured. A chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.) was used for measuring the color difference (ΔE * ab value). A smaller ΔE * ab value indicates better light resistance. The ΔE * ab value is a value obtained from the following color difference formula based on the CIE 1976 (L *, a *, b *) space color system (New Color Science Handbook edited by the Japan Color Society (1985) p. 60). 266).
ΔE * ab = {(ΔL *) 2+ (Δa *) 2+ (Δb *) 2} 1/2

5-2. Heat resistance As an index for evaluating heat resistance (heat fastness), a color difference (ΔE * ab value) before and after heating was measured. Specifically, the composition obtained above was applied onto a glass substrate so that the dry film thickness was 0.6 μm, thereby forming a coating film. This coating film was placed on a 200 ° C. hot plate so as to be in contact with the glass substrate surface, heated for 1 hour, and the color difference (ΔE * ab value) before and after heating was measured. A chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.) was used for measuring the color difference (ΔE * ab value). A smaller ΔE * ab value indicates better heat resistance.

5-3. Transmittance The composition obtained above was applied onto a glass substrate so that the dry film thickness was 0.6 μm, thereby forming a coating film. Using a spectrophotometer (ref. Glass substrate) of an ultraviolet visible near-infrared spectrophotometer UV3600 (manufactured by Shimadzu Corporation), the transmittance of this coating film is measured in the wavelength range of 400 nm to 450 nm, 500 nm, and 650 nm to 700 nm. did. For the transmittance in the wavelength range of 400 nm to 450 nm and 650 nm to 700 nm, the average value of the transmittances every 5 nm was defined as the transmittance.

5-4. Development defects 200 colored patterns obtained by the above pattern formation were observed by SEM to confirm the presence or absence of development defects. The more development defects, the worse the yield.

  As is apparent from the above table, it was found that when a color filter was produced with a photoresist using the composition of the present invention, it was excellent in light resistance, heat resistance, spectral characteristics, and development defect suppression.

  In the above “3. Preparation of composition”, dipentaerythritol hexaacrylate was changed to A-DPH-12E (made by Shin-Nakamura Chemical Co., Ltd.) with the same mass, and a composition was prepared. Similar results were obtained when evaluated.

6). Preparation of pattern forming composition to which dry etching method was applied The following components were mixed and dissolved to obtain compositions of Examples 34 to 60 and Comparative Examples 4 to 6.
-Triarylmethane compound described in Table 5-Dye (B) described in Table 5 The total of the triarylmethane compound and the dye (B) is 60 parts.
-Dye (C) When blended, 10 parts-Cyclohexanone 100 parts-Solsperse 20000
(1% cyclohexane solution, Nippon Lubrizol 1 part, thermosetting compound (EHPE-3150 (manufactured by Daicel Chemical Industries, 1,2-epoxy-4- (2,2-bis (hydroxymethyl) -1-butanol)) -Oxiranyl) cyclohexane adduct)) 15 parts glycerol propoxylate (1% cyclohexane solution) 0.048 parts

7). Performance Evaluation A colored pattern was formed as described below, and pattern defects were evaluated for this colored pattern. On the glass substrate, the said composition was apply | coated using the spin coater so that the film thickness after drying might be set to 0.6 micrometer, and the heat processing (prebaking) were performed for 120 second using a 100 degreeC hotplate. Next, a heat treatment (post-bake) was performed for 300 seconds using a 220 ° C. hot plate to prepare a colored film.
A positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials) was applied on the colored film and prebaked to form a 0.8 μm-thick photoresist layer. Subsequently, the photoresist layer is subjected to pattern exposure using an i-line stepper (manufactured by Canon) at an exposure amount of 350 mJ / cm ² , and heat treatment is performed at a temperature at which the temperature of the photoresist layer or the atmospheric temperature becomes 90 ° C. for 1 minute. Was done. Thereafter, development processing was performed with a developer “FHD-5” (manufactured by FUJIFILM Electronics Materials) for 1 minute, and further post-baking processing was performed at 110 ° C. for 1 minute to form a resist pattern. The resist pattern was formed with a side of 1.0 μm in consideration of etching conversion difference (pattern width reduction by etching).
Next, dry etching was performed according to the following procedure.

RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, etching chamber internal pressure: 4.0 Pa, substrate temperature: 50 ° C., mixed gas with dry etching equipment (Hitachi High Technologies, U-621) The gas type and flow rate were set to CF ₄ : 80 mL / min. , O ₂ : 40 mL / min. , Ar: 800 mL / min. As a result, the first stage etching process of 80 seconds was performed.

Next, in the same etching chamber, RF power: 600 W, antenna bias: 100 W, wafer bias: 250 W, chamber internal pressure: 2.0 Pa, substrate temperature: 50 ° C., gas mixture type and flow rate of N ₂ : 500 mL / min. , O ₂ : 50 mL / min. , Ar: 500 mL / min. (N ₂ / O ₂ / Ar = 10/1/10), and the second-stage etching process for 28 seconds was performed.

  After dry etching under the above conditions, the resist is removed by using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials) for 120 seconds to remove the resist, followed by washing with pure water, spin Drying was performed. Thereafter, a dehydration baking process was performed at 100 ° C. for 2 minutes. In this way, a colored pattern was formed on the glass substrate.

  200 colored patterns formed as described above were observed with an SEM to confirm the presence or absence of development defects. The more development defects, the worse the yield.

  As is apparent from the above table, it was found that when a color filter was produced by dry etching using the composition of the present invention, it was excellent in suppressing pattern defects. Furthermore, about Example 34-60, when the light resistance, heat resistance, and the transmittance | permeability were measured according to the above-mentioned method, the same tendency as Examples 1-33 was seen. Moreover, when Comparative Example 4-6 measured light resistance, heat resistance, and the transmittance | permeability according to the above-mentioned method, the same tendency as Comparative Examples 4-6 was seen.

Claims (19)

Triarylmethane compounds,
A dye having a maximum absorption wavelength in the range of 650 to 750 nm, and a curable compound,
Including
The composition whose mass ratio of the pigment | dye which has the said maximum absorption wavelength in the range of 650-750 nm with respect to the said triarylmethane compound is 0.2-1.5.   The composition according to claim 1, wherein the triarylmethane compound has a maximum absorption wavelength in a range of 580 to 620 nm.   The composition of Claim 1 or 2 whose difference of the maximum absorption wavelength of the said triarylmethane compound and the pigment | dye which has the said maximum absorption wavelength in the range of 650-750 nm is 100-150 nm.   The composition according to any one of claims 1 to 3, wherein the triarylmethane compound has an ethylenically unsaturated bond group.   The composition according to any one of claims 1 to 4, wherein the triarylmethane compound is a multimer.   The pigment | dye which has the said maximum absorption wavelength in the range of 650-750 nm is 1 or more types selected from a phthalocyanine compound, a cyanine compound, a squarylium compound, a naphthoquinone compound, and an azo compound in any one of Claims 1-5. The composition as described.   The composition according to any one of claims 1 to 6, wherein the dye having the maximum absorption wavelength in a range of 650 to 750 nm contains a phthalocyanine compound or a squarylium compound.   The composition of any one of Claims 1-7 in which the pigment | dye which has the said maximum absorption wavelength in the range of 650-750 nm has an ethylenically unsaturated bond group.   The composition according to any one of claims 1 to 8, wherein the dye having the maximum absorption wavelength in a range of 650 to 750 nm is a multimer.   The composition according to any one of claims 1 to 9, further comprising a dye having a maximum absorption wavelength in a range of 500 to 600 nm.   The composition according to any one of claims 1 to 10, which is used for a color filter.   The cured film formed by hardening | curing the composition of any one of Claims 1-11. Applying the composition according to any one of claims 1 to 11 on a support to form a composition layer;
Exposing the composition layer in a pattern;
Developing and removing unexposed portions of the exposed composition layer to form a colored pattern; and
A pattern forming method including:   A method for producing a color filter, comprising the pattern forming method according to claim 13. Applying the composition according to any one of claims 1 to 11 on a support to form a composition layer, and curing to form a colored layer;
Forming a photoresist layer on the colored layer;
Patterning the photoresist layer by exposing and developing the photoresist layer to obtain a resist pattern;
Dry etching the colored layer using the resist pattern as an etching mask;
A method for producing a color filter, comprising:   The color filter manufactured using the composition of any one of Claims 1-11, or the color filter manufactured by the manufacturing method of the color filter of Claim 14 or 15. A triarylmethane compound, and a dye having a maximum absorption wavelength in the range of 650 to 750 nm,
Including
A color filter having a minimum thickness direction transmittance of 80% or more in a wavelength range of 450 to 500 nm and a maximum thickness direction transmittance of 25% or less in a wavelength range of 650 to 700 nm.   A solid-state imaging device having the color filter according to claim 16.   An image display device comprising the color filter according to claim 16.