WO2016035565A1 - 着色組成物、硬化膜、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子、および画像表示装置 - Google Patents
着色組成物、硬化膜、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子、および画像表示装置 Download PDFInfo
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- WO2016035565A1 WO2016035565A1 PCT/JP2015/073431 JP2015073431W WO2016035565A1 WO 2016035565 A1 WO2016035565 A1 WO 2016035565A1 JP 2015073431 W JP2015073431 W JP 2015073431W WO 2016035565 A1 WO2016035565 A1 WO 2016035565A1
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
- H01L27/1462—Coatings
- H01L27/14621—Colour filter arrangements
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- H—ELECTRICITY
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- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N2209/00—Details of colour television systems
- H04N2209/04—Picture signal generators
- H04N2209/041—Picture signal generators using solid-state devices
- H04N2209/042—Picture signal generators using solid-state devices having a single pick-up sensor
Definitions
- the present invention relates to a coloring composition.
- the present invention relates to a coloring composition suitable for producing a color filter used for a solid-state imaging device, an image display device and the like.
- the present invention also relates to a cured film, a color filter, a solid-state imaging device, and an image display device using the colored composition.
- Color filters are used as key devices for these displays and optical elements, and there is an increasing demand for higher sensitivity and miniaturization.
- Such a color filter normally has a coloring pattern of three primary colors of red (R), green (G), and blue (B), and plays a role of separating transmitted light into the three primary colors.
- Colorants used in color filters are required to have the following properties in common. That is, it is required to have a light absorption characteristic that is favorable for color reproducibility and to have good light resistance.
- Patent Document 1 discloses a quinophthalone dye having 2 to 6 dye structures derived from a quinophthalone dye in one molecule as a quinophthalone dye having excellent solvent solubility and fastness.
- Patent Document 2 discloses a pigment dispersant having 2 to 9 sites having adsorption ability for a pigment in one molecule.
- site having the ability to adsorb to pigment organic dye structure, heterocyclic structure, acid group, group having basic nitrogen atom, urea group, urethane group, group having coordinating oxygen atom, hydrocarbon having 4 or more carbon atoms Groups, alkoxysilyl groups, epoxy groups, isocyanate groups, hydroxyl groups and the like.
- the further improvement of the heat resistance at the time of the heat curing in pattern formation and a color transfer property is calculated
- the present invention has been made in view of such a situation, and an object thereof is to provide a coloring composition having excellent heat resistance and color transfer. Another object of the present invention is to provide a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, and an image display device using such a colored composition.
- the present inventors have found that by introducing a group having 3 or more carbon atoms adjacent to a specific linking group in a branched dye multimer having 2 to 14 dye structures.
- the inventors have found that the heat resistance and color transfer of a coloring composition containing a dye multimer can be improved, and have completed the present invention.
- the above problem has been solved by the following means ⁇ 1>, preferably ⁇ 2> to ⁇ 22>.
- R 1 represents an m + n-valent linking group
- X represents —C ( ⁇ O) O. —, —C ( ⁇ O) —, —C ( ⁇ O) NR 10 —, —O—, —S ( ⁇ O) —, or —SO 2 —
- R 10 represents a hydrogen atom or an alkyl group.
- Y represents an alkylene group
- L 1 represents a single bond or a divalent linking group
- D represents a dye structure
- R 2 represents a monovalent substituent
- 13 represents an integer
- n represents an integer of 2 to 14
- m + n represents an integer of 3 to 15
- a plurality of R 2 may be different from each other
- n is 2
- a plurality of D may be different from each other
- L 1 is a divalent linking group
- L 1 and X are separated by 3 or more carbon atoms by Y
- L 1 is In the case of a single bond, D and X , 3 or more spaced are as number of carbon atoms by Y; at least one of D, L 1, R 1, R 2, X, Y is an acid group.
- D in the general formula (1) is a dye selected from dipyrromethene dyes, triarylmethane dyes, xanthene dyes, cyanine dyes, squarylium dyes, anthraquinone dyes, quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, and azo dyes.
- D in the general formula (1) has a cation moiety and a counter anion, or has a cation moiety and an anion moiety in one molecule, and the counter anion is a sulfonate anion, a sulfonylimide anion, Bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion, carboxylate anion, tetraarylborate anion, BF 4 ⁇ , PF 6 ⁇ , and SbF 6 ⁇
- ⁇ 4> The colored composition according to any one of ⁇ 1> to ⁇ 3>, wherein Y in the general formula (1) is an unsubstituted linear alkylene group.
- Y in the general formula (1) is an unsubstituted linear alkylene group.
- R 2 in the general formula (1) contains a repeating unit derived from a vinyl compound having an acid group.
- R 2 in the general formula (1) contains a repeating unit, and the average number of repeating units is 2 to 20 .
- X is * —C ( ⁇ O) O— #
- * is bonded to Y
- # is bonded to R 1 , any one of ⁇ 1> to ⁇ 6>
- ⁇ 8> The colored composition according to any one of ⁇ 1> to ⁇ 7>, wherein the dye represented by the general formula (1) contains a group having an ethylenically unsaturated bond.
- R 2 in the general formula (1) contains a group having an ethylenically unsaturated bond.
- R 1 in the general formula (1) is A linking group represented by the following general formula (2): A linking group represented by the following general formula (3): A linking group having a main chain composed of a plurality of carbon atoms, wherein the main chain includes at least one portion in which three or more carbon atoms are continuous; A linking group having a main chain composed of one heteroatom and a plurality of carbon atoms, wherein the main chain includes at least one portion in which three or more carbon atoms are continuous; Or A linking group having a main chain composed of at least two heteroatoms and a plurality of carbon atoms, wherein the linking group includes at least one portion in the main chain separated from each other by three or more consecutive carbon atoms; The colored composition according to any one of ⁇ 1 to 9, wherein the general formula (2) In general formula (2), each Z independently represents CR or N, each L 2 independently represents a single bond or a p-valent linking group, R represents a hydrogen atom or a substituent, and a Represents an integer of 1 to 6,
- L 1 in the general formula (1) is Single bond, -S-, A linking group having a main chain composed of a plurality of carbon atoms, wherein the main chain includes at least one portion in which three or more carbon atoms are continuous; A linking group having a main chain composed of one heteroatom and a plurality of carbon atoms, wherein the main chain includes at least one portion in which three or more carbon atoms are continuous; Or A linking group having a main chain composed of at least two heteroatoms and a plurality of carbon atoms, wherein the linking group includes at least one portion in the main chain separated from each other by three or more consecutive carbon atoms; One of the The colored composition according to any one of ⁇ 1> to ⁇ 10>.
- ⁇ 12> The colored composition according to any one of ⁇ 1> to ⁇ 11>, wherein m in the general formula (1) is 1 to 5, and n is 2 to 8.
- ⁇ 13> The colored composition according to any one of ⁇ 1> to ⁇ 12>, wherein the dye represented by the general formula (1) has a weight average molecular weight of 2,000 to 15,000.
- ⁇ 14> The colored composition according to any one of ⁇ 1> to ⁇ 13>, further including a pigment other than the dye represented by the general formula (1).
- ⁇ 15> The colored composition according to any one of ⁇ 1> to ⁇ 14>, further comprising a photopolymerization initiator.
- ⁇ 16> The colored composition according to any one of ⁇ 1> to ⁇ 15>, which is used for forming a colored layer of a color filter.
- ⁇ 17> A cured film obtained by curing the colored composition according to any one of ⁇ 1> to ⁇ 15>.
- ⁇ 18> A color filter using the colored composition according to any one of ⁇ 1> to ⁇ 15>.
- ⁇ 19> a step of applying the colored composition according to any one of ⁇ 1> to ⁇ 15> on a support to form a colored composition layer, a step of exposing the colored composition layer in a pattern, And a step of developing and removing the unexposed portion to form a colored pattern.
- ⁇ 20> a step of applying the colored composition according to any one of ⁇ 1> to ⁇ 15> on a support to form a colored composition layer and curing to form a colored layer; Forming a photoresist layer on the colored layer; Patterning the photoresist layer by exposure and development to obtain a resist pattern; And a step of dry etching the colored layer using the resist pattern as an etching mask.
- a solid-state imaging device having the color filter according to ⁇ 18> or the color filter manufactured by the method for manufacturing a color filter according to ⁇ 19> or ⁇ 20>.
- An image display device having the color filter according to ⁇ 18> or the color filter manufactured by the method for manufacturing a color filter according to ⁇ 19> or ⁇ 20>.
- the present invention it is possible to provide a coloring composition and a dye excellent in heat resistance and color transfer. Moreover, it has become possible to provide a cured film, a color filter, a color filter manufacturing method, a solid-state imaging device, and an image display device using such a colored composition.
- the notation which does not describe substitution and non-substitution includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent.
- 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 rays or “radiation” in this specification refers to, for example, the emission line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV (Extreme Ultraviolet Lithography) light), X-rays, electron beams, etc. Means.
- light means actinic rays or radiation.
- 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.
- 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.
- the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored composition. Solid content means the solid content in 25 degreeC.
- (meth) acrylate represents both and / or acrylate and methacrylate
- (meth) acryl represents both and / or acryl
- (meth) acryloyl represents both and / or acryloyl and methacryloyl.
- 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.
- 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.
- Me in the chemical formula represents a methyl group
- Et represents an ethyl group
- Pr represents a propyl group
- Bu represents a butyl group
- Ph represents a phenyl group
- 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. .
- the weight average molecular weight and the number average molecular weight are defined as polystyrene converted values by gel permeation chromatography (GPC) measurement.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation) and TSKgelgSuper AWM-H (manufactured by Tosoh Corporation, 6) as a column.
- 0 mm ID (inner diameter) ⁇ 15.0 cm) can be obtained by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
- the coloring composition of this invention contains the pigment
- the coloring composition excellent in heat resistance and color transfer property can be provided.
- the dye represented by the general formula (1) described later has a methylene group and an ethylene group as the linking group Y bonded to the group represented by X.
- thermal decomposition at high temperatures was suppressed and heat resistance and color transfer were improved by introducing an alkylene group having 3 or more carbon atoms, because it was easy to thermally decompose.
- the present invention will be described in detail.
- the coloring composition of the present invention contains at least one dye represented by the following general formula (1) (hereinafter sometimes simply referred to as “dye (A)”).
- the dye (A) is a dye multimer having 2 to 14 dye structures in a branched form.
- the coloring matter (A) functions as, for example, a coloring agent in the coloring composition of the present invention.
- R 1 represents an m + n-valent linking group
- X represents —C ( ⁇ O) O—, —C ( ⁇ O) —, —C ( ⁇ O) NR 10 —, —O—, —S ( ⁇ O) —, or —SO 2 —.
- R 10 represents a hydrogen atom or an alkyl group
- Y represents an alkylene group
- L 1 represents a single bond or a divalent linking group
- D represents the dye structure
- R 2 represents a monovalent substituent
- m represents an integer of 1 to 13
- n represents an integer of 2 to 14
- m + n represents an integer of 3 to 15, when m is 2 or more, the plurality of R 2 may be different from each other; when n is 2 or more, the plurality of D may be different from each other;
- L 1 is a divalent linking group
- L 1 and X are separated by 3 or more carbon atoms by Y.
- D and X are carbon atoms by Y. Separated by 3 or more in number, At least one of D, L 1 , R 1 , R 2 , X, and Y has an acid group.
- m represents 1 to 13.
- m is preferably 1 to 5, more preferably an integer of 1 to 4, and particularly preferably 1 to 3.
- n represents 2 to 14.
- n is preferably 2 to 8, more preferably 2 to 7, and particularly preferably 3 to 6.
- m + n represents 3 to 15.
- M and n in one dye (A) are integers, respectively, but the colored composition of the present invention may contain a plurality of dyes having different m and n in the dye (A). Therefore, the average value of m and n in the coloring composition of the present invention may not be an integer.
- m represents an integer of 1 to 13
- n represents an integer of 2 to 14
- m + n preferably represents an integer of 3 to 15.
- the dye (A) is a mixture containing 50% by mass of the dye a1 in which m is 3 and n is 1 in the general formula (1) and 50% by mass of the dye a2 in which m is 2 and n is 2.
- the average value of m is 2.5 and the average value of n is 1.5.
- the dye a2 contained in the mixture has m as an integer of 1 to 13 and n is 2 to 2. Since it satisfies the condition of an integer of 14 and m + n of 3 to 15, it corresponds to the dye (A) of the present invention.
- the dye (A) is a mixture of a plurality of dyes (A)
- the average value of m is preferably 1 to 13
- the average value of n is preferably 2 to 14.
- R 1 represents an m + n-valent linking group.
- m + n satisfies 3 to 15.
- the m + n-valent linking group represented by R 1 includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200 carbon atoms.
- a group consisting of a hydrogen atom and 0 to 20 sulfur atoms is included, which may be unsubstituted or may further have a substituent.
- m + n-valent linking group represented by R 1 include a group formed by combining two or more of the following structural units or the following structural units (which may form a ring structure). Can do.
- the m + n-valent linking group represented by R 1 includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, and 1 to 120 hydrogen atoms. And groups consisting of 0 to 10 sulfur atoms are preferred. More preferably, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 atoms. It is a group consisting of the sulfur atom. More preferably, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 atoms. It is a group consisting of the sulfur atom.
- the m + n-valent linking group represented by R 1 may have a substituent.
- substituents include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, and a sulfonamide group.
- C1-C6 acyloxy groups such as N-sulfonylamido and acetoxy groups, C1-C6 alkoxy groups such as methoxy and ethoxy groups, halogen atoms such as chlorine and bromine, methoxycarbonyl groups and ethoxycarbonyl Group, a C2-C7 alkoxycarbonyl group such as cyclohexyloxycarbonyl group, a cyano group, a carbonic acid ester group such as t-butyl carbonate, and the like.
- a linking group represented by the following general formula (2) A linking group represented by the following general formula (3): A linking group having a main chain composed of a plurality of carbon atoms, wherein the main chain includes at least one portion in which three or more carbon atoms are continuous; A linking group having a main chain composed of one heteroatom and a plurality of carbon atoms, wherein the main chain includes at least one portion in which three or more carbon atoms are continuous; Or A linking group having a main chain composed of at least two heteroatoms and a plurality of carbon atoms, wherein the linking group includes at least one portion in the main chain separated from each other by three or more consecutive carbon atoms; It is preferable that it is either.
- a hetero atom represents an atom having a valence of 2 or more other than a carbon atom, and examples thereof include a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom.
- each Z independently represents CR 20 or N
- each L 2 independently represents a single bond or a p-valent linking group
- R 20 represents a hydrogen atom or a substituent.
- A represents an integer of 1 to 6
- p represents an integer of 2 or more
- L 2 is a linking group having a main chain composed of a plurality of carbon atoms
- the main chain is a linking group containing at least one portion having three or more consecutive carbon atoms, a linking group having a main chain composed of one heteroatom and a plurality of carbon atoms, wherein the main chain has 3 carbon atoms.
- a linking group containing at least one continuous part or a linking group having a main chain composed of at least two heteroatoms and a plurality of carbon atoms, and having three or more consecutive carbon atoms between heteroatoms A linking group comprising at least one moiety separated in the main chain, It is whether the deviation.
- R 20 represents a hydrogen atom or a substituent, and examples of the substituent include those described above as the substituent that R 1 may have.
- L 2 independently represents a single bond or a p-valent linking group so that the valence of the linking group represented by the general formula (2) is m + n, and a is an integer of 1 to 6 P represents an integer of 2 or more.
- each L 3 independently represents a single bond or a q-valent linking group, q represents an integer of 2 or more, and when L 3 is a q-valent linking group, L 3 represents a plurality of A linking group having a main chain consisting of a plurality of carbon atoms, wherein the main chain is a linking group containing at least one portion in which three or more carbon atoms are continuous, a main chain consisting of one heteroatom and a plurality of carbon atoms A linking group having at least one portion in which three or more carbon atoms are continuous, or a linking group having a main chain composed of at least two heteroatoms and a plurality of carbon atoms. And a linking group containing at least one moiety in the main chain in which hetero atoms are separated by three or more consecutive carbon atoms.
- the m + n-valent linking group represented by R 1 is more preferably an alkylene group or a group consisting of a combination of an alkylene group and an ester group, wherein the main chain is a moiety having 3 or more carbon atoms continuous. Or a linking group in which the main chain contains at least one portion in which 5 or more carbon atoms are continuous.
- L 3 each independently represents a single bond or a q-valent linking group so that the valence of the linking group represented by the general formula (3) is m + n, and q is an integer of 2 or more.
- R 1 Specific examples of the m + n-valent linking group represented by R 1 are shown below.
- “#” represents a bond to X or R 2
- p1 to p3, q1 to q4, and r1 to r6 each represents an integer of 0 or more.
- p1 + p2 + p3, q1 + q2 + q3 + q4, r1 + r2 + r3 + r4 + r5 + r6 each represents an integer of 1 or more, and preferably 40 or less.
- the present invention is not limited to these.
- the m + n-valent linking group represented by R 1 is preferably (1) to (14), more preferably (1) to (6), (9) to (11), and (1) to (11) (3), (9) and (11) are particularly preferable.
- X is —C ( ⁇ O) O—, —C ( ⁇ O) —, —C ( ⁇ O) NR 10 —, —O—, —S ( ⁇ O) —, or , —SO 2 —
- R 10 represents a hydrogen atom or an alkyl group.
- X is preferably —C ( ⁇ O) O— or —O—, more preferably —C ( ⁇ O) O—, and —C ( ⁇ O) O— wherein the carbonyl carbon is More preferably, it is bonded to Y. That is, it is more preferable that X is * —C ( ⁇ O) O— #, * is bonded to Y, and # is bonded to R 1 .
- Y represents an alkylene group, and the alkylene group may be linear, branched, or cyclic, and is preferably linear. Further, it may be unsubstituted or may further have a substituent, but is preferably unsubstituted. Examples of the substituent include those described for the substituent that R 1 may have. Y is preferably an unsubstituted linear alkylene group.
- L 1 and X are separated by three or more carbon atoms by Y which is an alkylene group, and when L 1 is a single bond, D and X are Three or more carbon atoms are separated by Y which is an alkylene group.
- the number of carbon atoms indicates the shortest number of carbons present in the main chain connecting L 1 and X (provided that D and X when L 1 is a single bond), and the number of substituted carbons. Is not included. That is, in the following general formulas (B) and (C), the total number of carbon atoms of the alkylene group connecting L 1 and X is 3 as in the following general formula (A), but separates L 1 and X.
- L 1 and X are preferably separated by 3 or more as the number of carbon atoms by Y, more preferably 5 or more. According to this aspect, the heat resistance can be further improved.
- the upper limit is not particularly defined, but is usually 10 or less.
- L 1 represents a single bond or a divalent linking group.
- Divalent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 To 20 sulfur atoms are included, which may be unsubstituted or further substituted.
- divalent linking group examples include the following structural units or groups formed by combining two or more of the following structural units.
- L 1 may be a single bond or 0 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 0 to 100 hydrogen atoms, and A divalent linking group consisting of 0 to 10 sulfur atoms is preferred. More preferably, a single bond or 0 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 0 to 50 hydrogen atoms, and 0 It is a divalent linking group consisting of from 1 to 7 sulfur atoms.
- It is a divalent linking group consisting of from 1 to 5 sulfur atoms. Even more preferably, it is a single bond or a divalent linking group containing at least one sulfur atom in the main chain, that is, containing at least one —S—.
- L 1 is a single bond, —S—, a linking group having a main chain composed of a plurality of carbon atoms, wherein the main chain is a linking group containing at least one portion having three or more consecutive carbon atoms, A linking group having a main chain composed of one heteroatom and a plurality of carbon atoms, wherein the main chain includes at least one moiety having three or more consecutive carbon atoms, or at least two heteroatoms A linking group having a main chain composed of a plurality of carbon atoms, wherein the main chain includes at least one portion in which the heteroatoms are separated by three or more consecutive carbon atoms. Is preferred.
- the divalent linking group represented by L 1 may have a substituent.
- substituents include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, and a sulfonamide group.
- C1-C6 acyloxy groups such as N-sulfonylamido group and acetoxy group
- C1-C6 alkoxy groups such as methoxy group and ethoxy group
- halogen atoms such as chlorine and bromine
- methoxycarbonyl group ethoxy
- alkoxycarbonyl group having 2 to 7 carbon atoms such as a carbonyl group and a cyclohexyloxycarbonyl group
- a carbonic acid ester group such as a cyano group and t-butyl carbonate.
- R 2 represents a monovalent substituent.
- m is 2 or more, a plurality of R 2 may be different from each other.
- R 2 there are two modes: a case where no repeating unit is included and a case where a repeating unit is included.
- R 2 not having a repeating unit Examples of the monovalent substituent having no repeating unit represented by R 2 include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, and a nitro group.
- 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
- a cyclic alkyl group preferably substituted with 3 to 30 carbon atoms
- an unsubstituted cyclic cycloalkyl group such as cyclohexyl and cyclopentyl
- a cyclic alkyl group having a polycyclic structure such as a bicyclic alkyl group (so-called bicycloalkyl group,
- bicyclic cyclic alkyl groups such as bicyclo [1,2,2] hepta -2-yl, bicyclo [2,2,2] octane-3-yl
- tricyclic groups such as tricyclic alkyl groups (so-called tricycloalkyl groups), preferably monocyclic And a bicyclic cyclic alkyl group, and a monocyclic cyclic alkyl group is particularly preferable).
- a linear or branched alkenyl group (a linear or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cyclic An alkenyl group (preferably a substituted or unsubstituted cyclic alkenyl group having 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl).
- alkenyl group such as a bicyclic alkenyl group (preferably a substituted or unsubstituted bicyclic alkenyl group having 5 to 30 carbon atoms such as bicyclo [2,2,1] hept-2- En-1-yl, bicyclo [2,2,2] oct-2-en-4-yl) or a tricyclic alkenyl group, particularly a monocyclic alkenyl group Masui.)
- Alkynyl 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 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
- a heterocyclic group having at least one hetero atom 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.
- alkoxy group preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-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-t-amylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy
- silyloxy group preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy
- a heterocyclic oxy group preferably having a carbon number of 2 to 30 substituted or unsubstituted heterocyclic oxy groups, wherein the heterocyclic moiety is
- 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), an alkoxycarbonyloxy group (preferably having 2 to 30 carbon
- 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
- 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-oc
- Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino)
- 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 substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atom
- alkylthio group preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, ethylthio, n-hexadecylthio
- arylthio group preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms
- the heterocyclic portion described in the above is preferably, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfa Yl, N, N- dimethylsulfamoyl, N- acetyl sulfamoyl, N- benzoylsulfamoy
- 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, phenylsulfinyl, 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, such as methylsulfonyl , Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl
- alkoxycarbonyl group preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, t-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
- a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a 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 a substitution having 3 to 30 carbon atoms) Or an unsubstituted silyl group, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).
- those having a hydrogen atom may have a hydrogen atom portion in the functional group substituted with any of the above groups.
- R 2 having no repeating unit is preferably the following general formula (NR).
- R T is an alkyl group or an aryl group having an acid group or / and a polymerizable group. “*” Represents a bond to R 1 .
- R T preferably has 1 to 5 acid groups.
- polymerizable group examples include known polymerizable groups that can be cross-linked by radicals, acids, or heat, such as groups containing an ethylenically unsaturated bond, cyclic ether groups (epoxy groups, oxetane groups), methylol groups, and the like. Is mentioned. A group containing an ethylenically unsaturated bond is preferred, and a (meth) acryloyl group is more preferred.
- the number of polymerizable groups possessed by RT is preferably 1 to 4.
- RT preferably has an acid group.
- R 2 having a repeating unit a repeating unit derived from a vinyl compound, an ester polymer, an ether polymer, a urethane polymer, an amide polymer, an epoxy polymer, a silicone polymer, And modified products or copolymers thereof (for example, polyether / polyurethane copolymers, copolymers of polyether / vinyl compounds, etc. (random copolymers, block copolymers, graft copolymers) Any of them may be included).
- a repeating unit derived from a vinyl compound it is preferable to have at least one selected from the group consisting of: a repeating unit derived from a vinyl compound, an ester polymer, an ether polymer, a urethane polymer, and a modified product or copolymer thereof. It is more preferable to have at least one kind, and it is particularly preferable to have a repeating unit derived from a vinyl compound.
- R 2 preferably represents a monovalent substituent having 2 to 20 repeating units, more preferably 2 to 15 and even more preferably 2 to 10 repeating units. Represents a monovalent substituent having a unit.
- the average number of m R 2 repeating units is preferably 2 to 20, more preferably 2 to 15, and even more preferably 2 to 10. According to this aspect, the flatness of the coating film is improved.
- the number of repeating units derived from a vinyl compound when m is 1, and the average number of repeating units derived from m R 2 vinyl compounds when m is 2 or more is determined by NMR (Nuclear Magnetic Resonance). Can do.
- m is obtained from the peak area ratio between the m + n-valent linking group represented by R 1 and the dye structure D, and is calculated by dividing the peak area ratio of the repeating unit derived from the vinyl compound by m. Can do.
- (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, Styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl compounds having an acid group, and the like are preferable.
- (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Isobutyl acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, (
- Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.
- Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, and vinyl benzoate.
- Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
- Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
- Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.
- (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N- Methylo Acrylamide, N- hydroxye
- Styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl styrene, Examples thereof include hydroxystyrene, methyl vinylbenzoate, ⁇ -methylstyrene and the like protected with a group deprotectable by an acidic substance (for example, tert-butoxycarbonyl group and the like).
- an acidic substance for example, tert-butoxycarbonyl group and the like.
- vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.
- vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
- olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
- maleimides examples include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide. Also used are (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (eg, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, etc. it can.
- vinyl groups eg, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.
- N-vinylformamide N-vinylacetamide
- N-vinylimidazole N-vinylimidazole
- vinylcaprolactone etc. it can.
- vinyl compounds having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group
- a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group
- the vinyl compound having a urethane group or a urea group can be appropriately synthesized by using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group.
- an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.
- Examples of the vinyl compound having an acid group include a vinyl compound having a carboxyl group, a vinyl compound having a sulfo group, and a vinyl compound having a phosphate group.
- Examples of the vinyl compound having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer.
- an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ⁇ -carboxy-polycaprolactone mono (Meth) acrylate and the like can also be used.
- a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ⁇ -carboxy-polycaprolactone mono (Meth) acrylate and the like
- anhydride containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.
- (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.
- Examples of the vinyl compound having a sulfo group include 2-acrylamido-2-methylpropanesulfonic acid.
- Examples of the vinyl compound having a phosphate group include phosphoric acid mono (2-acryloyloxyethyl ester), phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester), and the like.
- a vinyl compound containing a phenolic hydroxyl group or a vinyl compound containing a sulfonamide group can be used as the vinyl compound having an acid group.
- R 2 preferably contains a repeating unit derived from a vinyl compound having an acid group, more preferably contains more than 30 mol% based on all repeating units contained in R 2, the R 2 More preferably, it is contained in an amount of 30 to 90 mol% with respect to all the repeating units contained.
- R 2 contains a repeating unit derived from a vinyl compound having an acid group, generation of a development residue can be further reduced.
- the acid group a carboxyl group, a sulfo group, and a phosphate group are preferable, and a carboxyl group is more preferable.
- R 2 preferably contains a repeating unit derived from a vinyl compound having a polymerizable group, and more preferably comprises more than 10 mol% based on all repeating units contained in the R 2, R 2 More preferably, it is contained in an amount of 10 to 80 mol% based on the total repeating units contained in.
- R 2 contains a repeating unit derived from a vinyl compound having a polymerizable group, the color transfer property can be further improved.
- the polymerizable group a known polymerizable group that can be crosslinked by a radical, acid, or heat can be used.
- a group containing an ethylenically unsaturated bond a cyclic ether group such as an epoxy group or an oxetane group, or a methylol group Etc.
- a group containing an ethylenically unsaturated bond is preferred, a (meth) acryloyl group is more preferred, and a (meth) acryloyl group derived from glycidyl (meth) acrylate and 3,4-epoxy-cyclohexylmethyl (meth) acrylate is particularly preferred.
- D represents a dye structure.
- the dye structure is preferably a dye structure having a cation moiety and a counter anion, or a dye structure having a cation moiety and an anion moiety in one molecule.
- the counter anion is an anion existing outside the molecule of the dye structure and can form a salt with the cation site of the dye structure. For example, it refers to a case where a cation and an anion are not bonded via a covalent bond but exist as separate compounds.
- having a cation part and an anion part in one molecule means the case where the cation and the anion are couple
- the anion site is preferably a sulfonylimide anion.
- Examples of the dye structure used in the present invention include quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diarylmethane dyes, triarylmethane dyes, xanthene dyes, acridine dyes, etc.), Quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, Dye selected from perinone dye, indigo dye, thioindigo dye, quinoline dye, nitro dye, nitroso dye
- dipyrromethene dyes triarylmethane dyes, xanthene dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, and azo dyes
- a dye structure selected from dipyrromethene dye, triarylmethane dye, xanthene dye, cyanine dye, squarylium dye, anthraquinone dye, quinophthalone dye, phthalocyanine dye, subphthalocyanine dye, and azo dye, and more preferable. More preferred are triarylmethane dyes and xanthene dyes.
- the dye structure preferably used in the present invention will be described in detail.
- Triarylmethane Dye has a partial structure derived from a triarylmethane dye (triarylmethane compound).
- the triarylmethane dye has a partial structure derived from a compound represented by the following formula (TP) as the dye structure.
- TP formula
- a triarylmethane compound is a general term for compounds having a dye moiety containing a triarylmethane skeleton in the molecule.
- Rtp 1 to Rtp 4 each independently represents a hydrogen atom, an alkyl group or an aryl group.
- Rtp 5 represents a hydrogen atom, an alkyl group, an aryl group or NRtp 9 Rtp 10 (Rtp 9 and Rtp 10 represent a hydrogen atom, an alkyl group or an aryl group).
- Rtp 6 , Rtp 7 and Rtp 8 represent a substituent.
- a, b and c each represents an integer of 0 to 4. When a, b and c are 2 or more, Rtp 6 , Rtp 7 and Rtp 8 may be linked to each other to form a ring.
- X ⁇ represents an anion structure. When X ⁇ is not present, at least one of Rtp 1 to Rtp 7 contains an anion.
- Rtp 1 to Rtp 6 are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a phenyl group.
- Rtp 5 is preferably a hydrogen atom or NRtp 9 Rtp 10 , particularly preferably NRtp 9 Rtp 10 .
- Rtp 9 and Rtp 10 are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a phenyl group.
- substituents mentioned in the section of Substituent Group A described later can be used, and in particular, a linear or branched alkyl group having 1 to 5 carbon atoms, Preferred is 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, a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, phenyl A group or a carboxyl group is more preferable.
- Rtp 6 and Rtp 8 are preferably alkyl groups having 1 to 5 carbon atoms, and Rtp 7 is preferably an alkenyl group (particularly a phenyl group in which two adjacent alkenyl groups are linked), a phenyl group or a carboxyl group.
- a, b or c each independently represents an integer of 0 to 4;
- a and b are each preferably 0 or 1, and c is preferably an integer of 0 to 2.
- the compound represented by the formula (TP) is preferably bonded to L 1 of the general formula (1) at any one of Rtp 1 to Rtp 10 .
- Rtp 1 to Rtp 7 When at least one of Rtp 1 to Rtp 7 includes an anion, examples of the anion include a structure in which at least one of Rtp 1 to Rtp 7 is substituted with the general formula (P).
- General formula (P) In the general formula (P), L represents a single bond or a divalent linking group, and X 1 represents —SO 3 ⁇ , —COO ⁇ , —PO 4 ⁇ , a structure represented by the following general formula (A1). It is selected from at least one selected from a group containing and a group containing a structure represented by the following general formula (A2).
- General formula (A1) In general formula (A1), R 1 and R 2 each independently represents —SO 2 — or —CO—.
- R 4 and R 5 each independently represents —SO 2 —, —CO— or —CN.
- L represents a single bond or a divalent linking group.
- the divalent linking group preferably represents a group consisting of —NR 10 —, —O—, —SO 2 —, a fluorine-substituted alkylene group, a fluorine-substituted phenylene group, or a combination thereof.
- a group consisting of a combination of —NR 10 —, —SO 2 and a fluorine-substituted alkylene group a group consisting of a combination of —O— and a fluorine-substituted phenylene group, or —NR 10 —, —SO 2 and a fluorine substitution
- a group consisting of a combination with an alkylene group is preferred.
- R 10 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom.
- the fluorine-substituted alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms. 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.
- the number of carbon atoms of the fluorine-substituted phenylene group is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10.
- fluorine-substituted phenylene group examples include a tetrafluorophenylene group, a hexafluoro-1-naphthylene group, and a hexafluoro-2-naphthylene group.
- X 1 is an anion, including —SO 3 ⁇ , —COO ⁇ , a group including a structure represented by general formula (A1), and a structure represented by general formula (A2). It is preferably selected from at least one selected from the group.
- the group including the structure represented by the general formula (A1) preferably has a fluorine-substituted alkyl group at one terminal of R 1 and R 2 in the general formula (A1) described above, and R 1 and R 2 More preferably, one of these is directly bonded to a fluorine-substituted alkyl group.
- the number of carbon atoms in the fluorine-substituted alkyl group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 1.
- These alkyl groups are more preferably perfluoroalkyl groups.
- a trifluoromethyl group is preferable.
- R 3 ⁇ R 5 preferably has a fluorine-substituted alkyl group
- at least two ends of R 3 ⁇ R 5, preferably has a fluorine-substituted alkyl group, and more preferably at least two of R 3 ⁇ R 5 are melted directly fluorine-substituted alkyl group integration.
- a fluorine-substituted alkyl group is synonymous with what was demonstrated by group containing the structure represented by general formula (A1), and its preferable range is also the same.
- X 1 is preferably a group containing a structure represented by the general formula (A2), more preferably a sulfonylimide anion.
- any hydrogen atom in the dye structure is bonded to L 1 in the general formula (1).
- any halogen atom is detached and bonded to L 1 in the general formula (1).
- a preferred embodiment of the dye structure in the present invention has a partial structure derived from a xanthene dye (xanthene compound).
- the xanthene dye has a partial structure derived from a xanthene compound represented by the following formula (J) as the dye structure.
- R 81 , R 82 , R 83 and R 84 each independently represent a hydrogen atom or a monovalent substituent
- R 85 each independently represents a monovalent substituent
- m Represents an integer of 0 to 5.
- X ⁇ represents a counter anion. When X ⁇ is not present, at least one of R 81 to R 85 contains an anion.
- R 81 to R 85 in formula (J) are the same as the substituents mentioned in the section of Substituent group A described later.
- the compound represented by the formula (J) is preferably bonded to L 1 of the general formula (1) at any one of R 81 to R 85 .
- R 81 and R 82 in formula (J), R 83 and R 84 , and R 85 in the case where m is 2 or more are each independently bonded to each other to form a 5-membered, 6-membered or 7-membered saturated ring. Or a 5-membered, 6-membered or 7-membered unsaturated ring.
- the 5-membered, 6-membered or 7-membered ring formed is a further substitutable group, it may be substituted with the substituents described for R 81 to R 85 and two or more substituents In the case where the substituent is substituted, the substituents may be the same or different.
- R 81 and R 82 , R 83 and R 84 , and R 85 in the case where m is 2 or more are each independently bonded to each other, and have no substituent.
- 5-membered and 7-membered saturated ring or 5-membered, 6-membered and 7-membered unsaturated ring when forming 5-membered, 7-membered saturated ring or 5-membered, 6-membered and 7-membered Examples of the unsaturated ring include pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring and pyridine ring.
- a pyrazine ring and a pyridazine ring preferably a
- R 82 and R 83 are preferably a hydrogen atom or a substituted or unsubstituted alkyl group, and R 81 and R 84 are preferably a substituted or unsubstituted alkyl group or a phenyl group.
- R 85 is preferably a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, a carboxyl group, or an amide group. The sulfo group, the sulfonamide group, the carboxyl group, More preferred is an amide group.
- R 85 is preferably bonded to the adjacent part of carbon linked to the xanthene ring.
- the substituent that the phenyl group of R 81 and R 84 has is particularly preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a sulfo group, a sulfonamide group, or a carboxyl group.
- the compound having a xanthene skeleton represented by the formula (J) can be synthesized by a method described in the literature. Specifically, the methods described in Tetrahedron Letters, 2003, vol. 44, No. 23, pages 4355-4360, Tetrahedron, 2005, vol. 61, No. 12, pages 3097-3106, etc. Can be applied.
- R 81 and R 83 are a group represented by the following general formula (4)
- the other of R 81 and R 83 is a hydrogen atom
- the following general formula (4) Or an aryl group other than the group represented by the general formula (4), or an alkyl group.
- R 82 and R 84 may each independently represent a hydrogen atom, an alkyl group, or an aryl group.
- R 1 and R 2 each independently represents an alkyl group having 3 or more carbon atoms, an aryl group, or a heterocyclic group, and X 1 to X 3 each independently represent a hydrogen atom Alternatively, it represents a monovalent substituent.
- the dye compound represented by the general formula (J) has a counter anion inside and / or outside the molecule.
- R 81 and R 83 are a group represented by General Formula (4), and the other of R 81 and R 83 is a hydrogen atom, represented by General Formula (4) below.
- both R 81 and R 83 may be a group represented by the general formula (4).
- the groups represented by the two general formulas (4) may be the same or different.
- R 1 and R 2 each independently represents an alkyl group having 3 or more carbon atoms, an aryl group, or a heterocyclic group, and a secondary or tertiary alkyl group having 3 to 12 carbon atoms. Or an isopropyl group.
- the alkyl group having 3 or more carbon atoms may be linear, branched or cyclic, may have 3 to 24 carbon atoms, may have 3 to 18 carbon atoms, The number may be 3 to 12.
- propyl group isopropyl group, butyl group (for example, t-butyl group), pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, And cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, It may be a dodecyl group, a cyclopropyl group, a cyclopentyl group or a cyclohexyl group, and may be a propyl group, an isopropyl group, an isoprop
- the aryl group includes a substituted or unsubstituted aryl group.
- the substituted or unsubstituted aryl group may be an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Examples of the substituent are the same as those of the substituent group A described later.
- the heterocycle of the heterocycle group may be a 5-membered or 6-membered ring, and they may be further condensed or not condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle.
- it may be an aromatic heterocyclic group, such as a pyridine ring, pyrazine ring, pyridazine ring, pyrazole ring, imidazole ring, benzimidazole ring, triazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, isothiazole ring, Examples thereof include a benzisothiazole ring and a thiadiazole ring, and may be a pyrazole ring, an imidazole ring, a benzoxazole ring, a thiadiazole ring, a pyrazole ring, a thiadiazole ring (1,3,4-thiadiazole ring, 1,2,4- A thiadiazole ring).
- aromatic heterocyclic group such as a pyridine ring, pyrazine ring, pyridazine ring, pyrazole ring, imidazole ring
- R 1 and R 2 may be an alkyl group having 3 or more carbon atoms, or an alkyl group having 3 to 12 carbon atoms.
- X 1 to X 3 each independently represents a hydrogen atom or a monovalent substituent.
- substituent include the substituent group A described later.
- X 1 to X 3 may be a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an acyl group, an acyloxy group, an alkylthio group, a sulfonamide group, or a sulfamoyl group.
- Examples of the aryl group other than the group represented by the general formula (4) include a phenyl group.
- the phenyl group may or may not have a substituent.
- Examples of the substituent include substituent group A described later, and may be an alkyl group or an aryl group.
- R 82 and R 84 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and the alkyl group and the aryl group may or may not have a substituent.
- the substituted or unsubstituted alkyl group may be an alkyl group having 1 to 30 carbon atoms.
- a substituent the same thing as the substituent group A mentioned later is mentioned.
- the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group (t-butyl group), an n-octyl group, and a 2-ethylhexyl group.
- the substituted or unsubstituted aryl group may be an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Examples of the substituent are the same as those of the substituent group A described later.
- R 82 and R 84 may be a hydrogen atom or an alkyl group, and may be a hydrogen atom.
- R 81 and R 83 may each independently be an aliphatic hydrocarbon group
- R 82 and R 84 may each independently be an aromatic hydrocarbon group.
- R 81 and R 83 each independently represents an aliphatic hydrocarbon group, which may be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a methyl group, It may be an ethyl group, a propyl group or a butyl group, and may be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group or an n-butyl group.
- R 81 and R 83 may be different, but may be the same.
- the alkyl group as R 81 and R 83 may have a substituent, but may have a substituent.
- R 82 and R 84 are each independently an aromatic hydrocarbon group, and may be a phenyl group.
- the aromatic hydrocarbon group as R 82 and R 84 may have a substituent, may be selected from the substituent group A described later, and may be an alkyl group having 1 to 5 carbon atoms. , An ethyl group, a propyl group or a butyl group, or a methyl group, an ethyl group, an n-propyl group or an n-butyl group.
- At least one of R 81 and R 83 and R 82 and R 84 may be represented by the following general formula (A1-1-2).
- R 23 to R 25 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group having 1 to 12 carbon atoms, a carbonyl group, a carbonylamide group, a sulfonyl group.
- R 22 and R 26 each independently represents an alkyl group having 1 to 5 carbon atoms. .
- R 23 to R 25 may be a hydrogen atom or a halogen atom.
- R 22 and R 26 may each independently be an alkyl group having 1 to 5 carbon atoms.
- the alkyl group having 1 to 5 carbon atoms may be a methyl group, an ethyl group, a propyl group, or a butyl group, and is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, or an n-butyl group. Also good.
- Each R 85 may independently be a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a carbonyl group, a nitro group, an amino group, an alkylamino group, an arylamino group, or a sulfonyl group.
- the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, and may be a fluorine atom or a chlorine atom.
- the aliphatic hydrocarbon group may be an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkenyl group, and may be an alkyl group.
- the aromatic hydrocarbon group may be an aryl group or a phenyl group.
- xanthene compounds are shown below, but the present invention is not limited thereto.
- X represents an anion.
- any hydrogen atom in the dye structure is bonded to L 1 in the general formula (1).
- any halogen atom is detached and bonded to L 1 in the general formula (1).
- the cation is delocalized in the dye structure, for example, as shown below, the cation exists on a nitrogen atom or a carbon atom of the xanthene ring.
- Anthraquinone Dye has a partial structure derived from an anthraquinone dye.
- Those having a partial structure derived from an anthraquinone dye are preferably partial structures derived from compounds represented by the following general formulas (AQ-1) to (AQ-3).
- An anthraquinone compound is a general term for compounds having a dye moiety containing an anthraquinone skeleton in the molecule.
- a and B each independently represent an amino group, a hydroxyl group, an alkoxy group or a hydrogen atom.
- Xqa represents ORqa 1 or NRqa 2 Rqa 3.
- Rqa 1 to Rqa 3 each independently represents a hydrogen atom, an alkyl group or an aryl group.
- Rq 1 to Rq 4 represent a substituent.
- the substituents that Rq 1 to Rq 4 can take are the same as the substituents mentioned in the section of Substituent group A described later.
- Ra and Rb each independently represents a hydrogen atom, an alkyl group or an aryl group.
- C and D have the same meanings as A and B in general formula (AQ-1).
- Xqb represents ORqb 1 or NRqb 2 Rqb 3.
- Rqb 1 to Rqb 3 each independently represents a hydrogen atom, an alkyl group or an aryl group.
- Rq 5 to Rq 8 represent a substituent.
- Rq 5 to Rq 8 have the same meanings as Rq 1 to Rq 4 in formula (AQ-1).
- Rc has the same meaning as Ra or Rb in formula (AQ-1).
- E and F have the same meanings as A and B in general formula (AQ-1).
- Xqc represents ORqc 1 or NRqc 2 Rqc 3.
- Rqc 1 to Rqc 3 each independently represents a hydrogen atom, an alkyl group or an aryl group.
- Rq 9 to Rq 12 have the same meanings as Rq 1 to Rq 4 in formula (AQ-1).
- Rd has the same meaning as Ra or Rb in formula (AQ-1).
- anthraquinone dye examples include the following. Further, for example, paragraphs 0049 to 0050 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.
- any hydrogen atom in the structure of the anthraquinone dye is bonded to L 1 in the general formula (1).
- any halogen atom is detached and bonded to L 1 in the general formula (1).
- One of the embodiments of the dye structure used in the present invention has a partial structure derived from a cyanine dye (cyanine compound).
- the partial structure derived from a compound (cyanine compound) represented by the following general formula (PM) is preferred as the one having a partial structure derived from a cyanine dye.
- the cyanine compound is a general term for compounds having a dye moiety containing a cyanine skeleton in the molecule.
- 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 an anion.
- paragraphs 0077 to 0084 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.
- any hydrogen atom in the cyanine dye structure is bonded to L 1 of the general formula (1).
- ⁇ Squarylium dye >>>>
- One embodiment of the dye structure used in the present invention has a partial structure derived from a squarylium dye (squarylium compound).
- squarylium compound As what has a partial structure derived from a squarylium pigment
- the squarylium compound is a general term for compounds having a dye moiety containing a squarylium skeleton in the molecule.
- 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, imidazole, pyrazoyl, thienyl, pyridyl, pyrimidyl, pyridazyl, triazol-1-yl, thienyl, furyl, thiadiazoyl and the like. .
- paragraphs 0088 to 0106 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
- Specific examples of the squarylium dye include the following. Further, for example, paragraph 0105 of JP2013-29760A can be referred to.
- any hydrogen atom in the squarylium dye structure is bonded to L 1 in the general formula (1).
- any halogen atom is detached and bonded to L 1 in the general formula (1).
- One embodiment of the dye structure used in the present invention has a partial structure derived from a quinophthalone dye (quinophthalone compound).
- a partial structure derived from a compound (quinophthalone compound) represented by the following general formula (QP) is preferable.
- the quinophthalone compound is a general term for compounds having a dye moiety containing a quinophthalone skeleton in the molecule.
- Rqp 1 to Rqp 6 each independently represents a hydrogen atom or a substituent. When at least two of Rqp 1 to Rqp 6 are adjacent to each other, they may be bonded to each other to form a ring, and the formed ring may further have a substituent.
- the general formula (QP) for example, paragraphs 0110 to 0114 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
- Specific examples of the quinophthalone dye include the following. Reference can also be made to the description in paragraph 0113 of JP2013-29760A. In the specific example of the quinophthalone dye, any hydrogen atom in the quinophthalone dye structure is bonded to L 1 of the general formula (1). Alternatively, any halogen atom is detached and bonded to L 1 in the general formula (1).
- ⁇ phthalocyanine dye >>>>
- One embodiment of the dye structure used in the present invention has a partial structure derived from a phthalocyanine dye (phthalocyanine compound).
- phthalocyanine compound a phthalocyanine dye represented by the following general formula (F).
- the phthalocyanine compound is a general term for compounds having a dye moiety containing a phthalocyanine skeleton in the molecule.
- M 1 represents a metal
- Z 1 , Z 2 , Z 3 , and Z 4 are each independently composed of an atom selected from a hydrogen atom, a carbon atom, and a nitrogen atom. Represents a group of atoms necessary to form a 6-membered ring.
- the general formula (F) for example, paragraphs 0118 to 0124 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
- Specific examples of the phthalocyanine dye include the following. Further, for example, paragraph 0123 of JP2013-29760A can be referred to. In the specific example of the phthalocyanine dye, any hydrogen atom in the phthalocyanine dye structure is bonded to L 1 in the general formula (1).
- Subphthalocyanine Dye has a partial structure derived from a subphthalocyanine dye (phthalocyanine compound).
- Those having a partial structure derived from a subphthalocyanine dye are preferably those having a partial structure derived from a compound (subphthalocyanine compound) represented by the following general formula (SP).
- SP general formula
- the term “subphthalocyanine compound” is a general term for compounds having a dye moiety containing a subphthalocyanine skeleton in the molecule.
- Z 1 to Z 12 each independently represent a hydrogen atom, an alkyl group, an aryl group, a hydroxy group, a mercapto group, an amino group, an alkoxy group, an aryloxy group, or a thioether group.
- X represents an anion.
- paragraphs 0128 to 0133 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
- Specific examples of the subphthalocyanine dye include the following. For example, the description in paragraph 0132 of JP2013-29760A can be referred to.
- any hydrogen atom in the subphthalocyanine dye structure is bonded to L 1 of the general formula (1).
- any halogen atom is detached and bonded to L 1 in the general formula (1).
- a known azo dye for example, substituted azobenzene
- the description of paragraphs 0084 to 0134 of JP2013-41097A and the description of paragraphs 0029 to 0136 of JP2011-162760A can be referred to as azo dyes, the contents of which are incorporated herein.
- Specific examples of the azo dye include the following. In a specific example of the azo dye, any hydrogen atom in the azo dye structure is bonded to L 1 of the general formula (1). Alternatively, any halogen atom is detached and bonded to L 1 in the general formula (1).
- dipyrromethene dye a dipyrromethene compound and a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound are preferable.
- a dipyrromethene dye the following structure is mentioned, for example.
- the description in paragraphs 0033 to 0136 of JP 2011-95732 A can be referred to, and the contents thereof are incorporated in the present specification.
- Me is a methyl group
- Bu is a butyl group
- Ac is an acetyl group.
- a hydrogen atom in the dye structure D may be substituted with a substituent selected from the following substituent group A.
- substituent group A examples include a halogen atom (eg, fluorine, chlorine, bromine), an alkyl group (preferably a straight chain having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms).
- a branched or cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, butyl group (preferably t-butyl group), pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclo Propyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl, allyl, 3-butene-1 -Yl), an alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably Or an aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, for example, pheny
- a heterocyclic group preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1- Pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl
- a silyl group preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as trimethylsilyl, Triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl
- hydroxyl group cyano group
- a tro group an alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methoxy, ethoxy, 1-butoxy,
- a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N- Ethyl-N-phenylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy group).
- a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms such as N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N- Ethyl-N-phenyl
- alkylsulfonyloxy groups preferably alkylsulfonyloxy groups having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexyl.
- arylsulfo A ruoxy group preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms such as phenylsulfonyloxy
- an acyl group preferably having 1 to 48 carbon atoms, more preferably 1 carbon atom.
- An acyl group having ⁇ 24 for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably having 2 to 24 carbon atoms)
- an alkoxycarbonyl group preferably having 2 to 48 carbon atoms, more preferably having 2 to 24 carbon atoms
- aryloxycarbonyl group preferably having 7 to 32 carbon atoms, Preferably charcoal
- a carbamoyl group preferably a carbamoyl group of 1 to 48
- alkoxycarbonyla Group preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonyl
- alkoxycarbonyla Group preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonyl
- An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonylamino), a sulfonamide group (preferably having 1 to 48 carbon atoms, Preferably a sulfonamide group having 1 to 24 carbon atoms, such as methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexanesulfonamide, sulfamoylamino group (preferably having 1 to 48 carbon atoms, More preferably, it is a sulfamoylamino group having 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably having 1
- a thio group for example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms).
- dodecanesulfinyl an arylsulfinyl group (preferably An arylsulfinyl group having 6 to 32 prime atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfinyl), an alkylsulfonyl group (preferably 1 to 48 carbon atoms, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms).
- an arylsulfinyl group preferably An arylsulfinyl group having 6 to 32 prime atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfinyl
- an alkylsulfonyl group preferably 1 to 48 carbon atoms, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms.
- the counter anion is not particularly limited, but is preferably a non-nucleophilic anion from the viewpoint of heat resistance.
- the non-nucleophilic counter anion known non-nucleophilic anions described in paragraph No. 0075 of JP-A-2007-310315 are preferable.
- the non-nucleophilic property means a property that does not nucleophilic attack the dye by heating.
- Counter anions include sulfonate anion, carboxylate anion, sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion, carboxylate anion, tetraarylborade anion, —CON ⁇ CO—, —CON - SO 2 -, BF 4 - , PF 6 -, SbF 6 -, B - (CN) is preferably at least one selected from 3 OCH 3.
- the counter anion is more preferably a non-nucleophilic anion having a structure represented by the following (AN-1) to (AN-5).
- X 1 and X 2 each independently represent a fluorine atom or a C 1-10 alkyl group having a fluorine atom.
- X 1 and X 2 may be bonded to each other to form a ring.
- X 1 and X 2 each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, More preferred is a perfluoroalkyl group of ⁇ 10, more preferred is a perfluoroalkyl group having 1 to 4 carbon atoms, and a trifluoromethyl group is particularly preferred.
- X 3 , X 4 and X 5 each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms.
- X 3 , X 4 and X 5 are each independently the same as X 1 and X 2 , and the preferred range is also the same.
- X 6 represents an alkyl group having a fluorine atom having 1 to 10 carbon atoms.
- X 6 is preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms.
- X 7 represents an alkylene group having 1 to 10 carbon atoms.
- X 7 is preferably a perfluoroalkylene group having 1 to 10 carbon atoms, and more preferably a perfluoroalkylene group having 1 to 4 carbon atoms.
- Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represents an aryl group.
- Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further an aryl group having 6 to 10 carbon atoms preferable.
- the aryl group represented by Ar 1 , Ar 2 , Ar 3 and Ar 4 may have a substituent.
- a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamide group, a nitro group and the like can be mentioned, and a halogen atom and an alkyl group are preferable, A fluorine atom and an alkyl group are more preferable, and a fluorine atom and a perfluoroalkyl group having 1 to 4 carbon atoms are more preferable.
- Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently more preferably a phenyl group having a halogen atom and / or an alkyl group having a halogen atom, and a phenyl group having a fluorine atom and / or an alkyl group having fluorine. Is more preferable.
- the non-nucleophilic counter anion is also —B (CN) n1 (OR a ) 4-n1 (R a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n1 represents It is preferably an integer of 1 to 4.
- Ra as the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
- R a as the aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group.
- n1 is preferably 1 to 3, and more preferably 1 to 2.
- the non-nucleophilic counter anion is further —PF 6 R P (6-n2) ⁇ (R P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n2 represents an integer of 1 to 6) It is preferable that R P is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a perfluoroalkyl group having 1 to 3 carbon atoms. n2 is preferably an integer of 1 to 4, and more preferably 1 or 2.
- the mass per molecule of the non-nucleophilic counter anion used in the present invention is preferably 100 to 1,000, and more preferably 200 to 500.
- the dye (A) of the present invention may contain only one type of non-nucleophilic counter anion, or may contain two or more types.
- non-nucleophilic counter anion used in the present invention are shown below, but the present invention is not limited thereto.
- the dye (A) preferably has a polymerizable group.
- a known polymerizable group that can be crosslinked by a radical, acid, or heat can be used.
- a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), a methylol group In particular, a group containing an ethylenically unsaturated bond is preferable, a (meth) acryloyl group is more preferable, glycidyl (meth) acrylate and (meth) derived from 3,4-epoxycyclohexylmethyl (meth) acrylate An acryloyl group is particularly preferred.
- R 1 is a linking group selected from (1) to (6) and (9) to (11) described above as an example;
- X is —C ( ⁇ O) O— or —O—,
- Y is an unsubstituted alkylene group,
- L 1 is a divalent linking group containing at least one —S—, and
- R 2 is a substituent containing a repeating unit derived from a vinyl compound having a carboxyl group and a (meth) acryloyl group, The average value of the number of repeating units is 2 to 20,
- D is preferably a dye structure selected from triarylmethane dyes, xanthene dyes, anthraquinone dyes, cyanine dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, azo dyes, and dipyrromethene dyes.
- the weight average molecular weight of the dye (A) is preferably from 2,000 to 15,000, more preferably from 3,000 to 12,500, and even more preferably from 5,000 to 11,000. If the weight average molecular weight is in the above range, the color transfer is better. Furthermore, the developability is improved and the generation of development residues can be further reduced.
- At least one of the dye (A) has an acid group among D, L 1 , R 1 , R 2 , X, and Y.
- the acid value of the dye (A) is preferably 10 mgKOH / g or more, more preferably 20 to 200 mgKOH / g, and particularly preferably 20 to 150 mgKOH / g. If the acid value is 20 mgKOH / g or more, the developability is improved and the generation of development residues can be further reduced.
- the pigment (A) according to the present invention is preferably a dye.
- the dye refers to a pigment having substantial solubility in water or an organic solvent, and is particularly preferably an organic solvent-soluble dye that is soluble in the following organic solvents.
- the organic solvent include esters (eg, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate), ethers (eg, methyl cellosolve acetate, ethyl cellosolve acetate).
- the dye (A) according to the present invention preferably has a turbidity of 2 ppm or less in a cyclohexanone 5 mass% solution.
- dye (A) is the value measured by the method shown in the Example mentioned later.
- the dye (A) according to the present invention is a metal selected from Al, Ca, Cu, Cr, Mg, Fe, Mn, Ni, Co, Cd, Li, Pb, Na, K, Zn, and P, and the dye
- the content of free metal not bonded or coordinated to (A) is preferably 2 ppm or less.
- the total content of the free metals is preferably 2 ppm or less. According to this aspect, it is easy to manufacture a color filter with few defects.
- the content of the free metal in the dye (A) can be measured by appropriately using known analysis means, but is preferably measured by inductively coupled plasma emission spectroscopy as much as possible. .
- the free Br content not bonded or coordinated to the dye (A) is preferably 900 ppm or less, and more preferably 600 ppm or less.
- the content of free Cl not bonded or coordinated to the dye (A) is preferably 900 ppm or less, more preferably 600 ppm or less, and further preferably 300 ppm or less.
- 1500 ppm or less is preferable and, as for the total content of the said free Br and free Cl, 900 ppm or less is more preferable.
- the free Br content and the free Cl content in the dye (A) can be measured by appropriately using known analysis means.
- the halogen content measurement BS The measurement is preferably performed according to the combustion ion chromatograph method according to EN 14582.
- the dye (A) may be used alone or in combination of two or more.
- the mass ratio of the dye to the pigment (dye (A) / pigment) is preferably 0.1 to 5, more preferably 0.2 to 2, and still more preferably 0.3 to 1.
- the content of the coloring matter (A) in the colored composition of the present invention is preferably 1.0 to 50% by mass, more preferably 5.0 to 30% by mass with respect to the total solid content in the colored composition. ⁇ 25% by weight is particularly preferred.
- the dye structure D of the dye (A) of the present invention is a xanthene dye, an azo dye, or a squarylium dye (preferably a xanthene dye), a red colorant (preferably a red pigment) or a yellow colorant (preferably a yellow pigment) )
- a red coloring composition can be formed.
- the total ratio (mass ratio) of the dye (A) of the present invention to the red colorant and the yellow colorant is preferably 10:90 to 90:10.
- the dye represented by the general formula (1) is not particularly limited, but can be synthesized by the following method.
- the synthesis methods (2) to (5) are preferred and the synthesis methods (3) to (5) are more preferred from the viewpoint of ease of synthesis.
- the dye (A) of the present invention has a structure represented by the general formula (2), it is most preferable to synthesize by the synthesis method (5) because of ease of synthesis.
- the synthesis method (5) is preferably a radical polymerization method in the presence of a compound represented by the following general formula (5).
- R 3 represents an m + n-valent linking group
- S represents a sulfur atom
- SH represents Represents a mercapto group
- X represents —C ( ⁇ O) O—, —C ( ⁇ O) —, —C ( ⁇ O) NR 10 —, —O—, —S ( ⁇ O) —, or — SO 2 —
- R 10 represents a hydrogen atom or an alkyl group.
- Y represents an alkylene group
- L 1 represents a single bond or a divalent linking group
- D represents a dye structure
- m represents an integer of 1 to 13
- n represents a number of 2 to 14 M +
- n represents an integer of 3 to 15, and when n is 2 or more, the plurality of D may be different from each other.
- D, L 1 , Y, X, m and n are, D in the general formula (1), respectively, L 1, Y, X, have the same meanings as m and n, the preferred embodiment is also the same is there.
- the compound represented by the general formula (5) can be synthesized by the following method or the like, but the following method (7) is more preferable from the viewpoint of ease of synthesis.
- (6) A method of converting a halide compound having a dye structure into a mercapto compound (a method of reacting with thiourea and hydrolyzing, a method of reacting directly with NaSH, a method of reacting with CH 3 COSNa and hydrolyzing, etc.) )
- (7) A method in which a compound having a dye structure and a functional group capable of reacting with a mercapto group is subjected to an addition reaction or a substitution reaction with a compound having 3 to 15 mercapto groups in one molecule
- Preferred examples of the “functional group capable of reacting with a mercapto group” in the above (7) include acid halides, alkyl halides, aryl halides, isocyanates, and carbon-carbon double bonds.
- the “functional group capable of reacting with a mercapto group” is preferably an aryl halide or an alkyl halide, a substitution reaction, or a carbon-carbon double bond, and the addition reaction is preferably a radical addition reaction.
- the carbon-carbon double bond is more preferably a mono- or di-substituted vinyl group from the viewpoint of reactivity with a mercapto group.
- p1 to p3, q1 to q4, and r1 to r6 each represents an integer of 0 or more.
- p1 + p2 + p3, q1 + q2 + q3 + q4, r1 + r2 + r3 + r4 + r5 + r6 each represents an integer of 1 or more, and preferably 40 or less.
- the present invention is not limited to these.
- substitution reaction product of “a compound having 3 to 15 mercapto groups in one molecule” and “a compound having a dye structure and a functional group capable of reacting with a mercapto group” is, for example, “A compound having 3 to 15 mercapto groups in one molecule” and “a compound having a dye structure and a functional group capable of reacting with a mercapto group” are dissolved in an appropriate solvent, and a base is added thereto. It is obtained using a method of adding and replacing at about 25 ° C. to 100 ° C.
- the radical addition reaction product of “a compound having 3 to 15 mercapto groups in one molecule” and “a compound having a dye structure and a functional group capable of reacting with a mercapto group” is, for example, Of “a compound having 3 to 15 mercapto groups in one molecule” and “a compound having a dye structure and a functional group capable of reacting with a mercapto group” in a suitable solvent, It can be obtained by adding a generator and adding at about 50 ° C. to 100 ° C. (thiol-ene reaction method).
- suitable solvents used in the thiol-ene reaction and the substitution reaction method include “compound having 3 to 15 mercapto groups in one molecule”, “having a dye structure and capable of reacting with a mercapto group” It can be arbitrarily selected depending on the solubility of the “compound having a functional group” and the “reaction product”.
- Examples include formamide, dimethylacetamide, chloroform, toluene, N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), 1,3-dimethyl-2-imidazolidinone (DMI), and pyridine. These solvents may be used as a mixture of two or more.
- radical generators 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate
- An azo compound such as benzoyl peroxide, a peroxide such as benzoyl peroxide, and a persulfate such as potassium persulfate and ammonium persulfate can be used.
- As the base 1,8-diazabicyclo [5.4.0] -7-undecene, triethylamine, diisopropylamine, diisopropylethylamine, sodium hydride and the like can be used.
- the vinyl compound used in the synthesis method of the above (5) is not particularly limited, for example, mentioned in the case R 2 in the general formula (1) is a substituent containing a repeating unit derived from a vinyl compound, The same vinyl compound is used.
- the vinyl compound may be polymerized alone or in combination of two or more.
- the vinyl compound which has 1 or more types of acid groups, and the vinyl compound which does not have 1 or more types of acid groups may be copolymerized. More preferred.
- the dye (A) of the present invention is preferably obtained by polymerizing these vinyl compounds and the compound represented by the general formula (5) by a known method according to a conventional method.
- the compound represented by the general formula (5) functions as a chain transfer agent, and may be simply referred to as “chain transfer agent” hereinafter.
- chain transfer agent a method in which these vinyl compound and chain transfer agent are dissolved in a suitable solvent, a radical polymerization initiator is added thereto, and the mixture is polymerized in a solution at about 50 ° C. to 220 ° C. (solution polymerization method) Can be obtained using
- suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer.
- Examples include formamide, chloroform, toluene, cyclohexanone, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone (DMI). These solvents may be used as a mixture of two or more.
- radical polymerization initiators examples include 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), and 2,2′-azobisisobutyric acid.
- An azo compound such as dimethyl, a peroxide such as benzoyl peroxide, and a persulfate such as potassium persulfate and ammonium persulfate can be used.
- the coloring composition of the present invention contains a curable compound.
- a curable compound a known polymerizable compound that can be cross-linked by radical, acid, or heat can be used.
- polymerizable compounds containing an ethylenically unsaturated bond, cyclic ether (epoxy, oxetane), methylol and the like can be mentioned.
- the polymerizable compound is suitably selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more, from the viewpoint of sensitivity.
- 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.
- Such a group of compounds is widely known, and these can be used without any particular limitation in the present invention. 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.
- Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters, amides, and multimers thereof.
- unsaturated carboxylic acids eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
- esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof.
- a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
- a 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 mercapto, a halogen group or a tosyloxy group is also suitable.
- polymerizable compound a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
- paragraph 0227 of JP2013-29760A can be referred to, the contents of which are incorporated herein.
- Examples of the compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one ethylenically unsaturated group capable of addition polymerization include compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970. Which is incorporated herein by reference.
- dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product); Nippon Kayaku Co., Ltd.
- dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku Co., Ltd.) ), Ethyleneoxy-modified dipentaerythritol hexaacrylate (commercially available A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups are ethylene glycol and propylene glycol residues And via structures (e.g., commercially available from Sartomer Company, SR454, SR499, SR368, SR494) it is preferred. These oligomer types can also be used. Preferred embodiments of the polymerizable compound are shown below.
- the polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. If the polymerizable compound has an unreacted carboxyl group or the like, it can be used as it is. However, if necessary, a non-aromatic carboxylic acid anhydride is reacted with the hydroxyl group of the polymerizable compound. An acid group may be introduced.
- non-aromatic carboxylic acid anhydrides include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like.
- an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
- a polymerizable compound having a group is preferred, 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 Co., Ltd.
- a preferable acid value of the polymerizable compound having an acid group is 0.1 mgKOH / g to 40 mgKOH / g, and particularly preferably 5 mgKOH / g to 30 mgKOH / g.
- the acid value of the polyfunctional monomer is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and when it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability such as the surface smoothness of the pixels is excellent.
- the acid group as the entire polymerizable compound is It is preferable to adjust so that it may enter into the said range.
- polymeric compound which has a caprolactone structure as a polymeric compound.
- the polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.
- a polymerizable compound having a caprolactone structure represented by the following general formula (Z-1) is preferable.
- R 1 represents a hydrogen atom or a methyl group
- m represents a number of 1 or 2
- “*” represents a bond
- R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
- the polymeric compound which has a caprolactone structure can be used individually or in mixture of 2 or more types.
- polymerizable compound a compound represented by the following general formula (Z-4) or (Z-5) can also be used.
- each E independently represents — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O).
- — Each independently represents an integer of 0 to 10
- each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
- the total number of acryloyl groups and methacryloyl groups is 3 or 4
- each m independently represents an integer of 0 to 10
- the total of each m is an integer of 0 to 40 .
- any one of X is a carboxyl group.
- 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 . However, when the total of each n is 0, any one of X is a carboxyl group.
- m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
- the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
- n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
- the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
- — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) — represents oxygen
- a form in which the end on the atom side is bonded to X is preferred.
- the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
- a form in which all six Xs are acryloyl groups is preferable.
- the total content of the compound represented by the general formula (Z-4) or (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
- the compound represented by the general formula (Z-4) or (Z-5) is a conventionally known process, which is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by a 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).
- a pentaerythritol derivative and / or a dipentaerythritol derivative 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)”).
- exemplary compounds (a), (f) b), (e) and (f) are preferred.
- Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
- a compound having an epoxy group can also be used as the polymerizable compound.
- the compound having an epoxy group one having two or more epoxy groups in one molecule is preferable. By using a compound having two or more epoxy groups in one molecule, the effect of the present invention can be achieved more effectively.
- the number of epoxy groups is preferably 2 to 10, more preferably 2 to 5, and particularly preferably 3 in one molecule.
- the compound having an epoxy group preferably has a structure in which two benzene rings are connected by a hydrocarbon group.
- the hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms.
- the epoxy group is connected via a connecting group.
- the linking group include an alkylene group, an arylene group, —O—, —NR ′ — (R ′ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
- R ′ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
- the said effect is acquired by making the upper limit of the epoxy equivalent of the compound which has an epoxy group into 500 g / eq or less.
- the lower limit of the epoxy equivalent of the compound which has an epoxy group shall be 100 g / eq or more.
- the compound having an epoxy group 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 macromolecule (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more).
- the weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000.
- a compound represented by the following general formula (E1) is preferably used as the compound having an epoxy group having a structure in which two benzene rings are connected by a hydrocarbon group.
- R 1 to R 13 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and L 1 represents a single bond or a divalent linking group.
- R 1 to R 13 in the general formula (E1) each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom.
- the alkyl group in R 1 to R 13 is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.
- the alkyl group is not limited to any of linear, branched and cyclic, but is preferably linear or branched, and particularly preferably linear.
- the alkyl group may have a substituent or may be unsubstituted. Unsubstituted is preferred.
- alkyl group may have examples of the substituent that the alkyl group may have include an alkyl group (preferably a linear, branched, or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, , Methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), alkenyl A group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl, allyl, 3-buten-1-yl), an alkynyl group (preferably having 2 to 20 carbon atoms,
- a heterocyclic group having 1 to 18 carbon atoms such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzo Triazol-1-yl), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as trimethylsilyl, triethylsilyl, tributylsilyl, tert-butyldimethylsilyl, tert-hexyl) Dimethylsilyl), hydroxyl group, cyano group, nitro group, alkoxy group (preferably carbon 1 to 48, more preferably an alkoxy group having 1 to 24 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy,
- a silyloxy group such as trimethylsilyloxy, tert-butyldimethylsilyloxy, diphenylmethylsilyloxy
- an acyloxy group preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms such as acetoxy, Pivaloyloxy, 2-ethylhexanoyloxy, 2-methylpropanoyloxy, octanoyloxy, butanoyloxy, 2-methylbutanoyloxy, benzoyloxy, dodecanoyloxy
- alkoxycarbonyloxy preferably Is an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as ethoxycarbonyloxy, tert-butoxycarbonyloxy, or a cyclic alkyloxycarbonyloxy group.
- aryloxycarbonyloxy groups preferably aryloxycarbonyloxy groups having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonyloxy
- carbamoyloxy groups preferably carbon atoms
- a sulfamoyloxy group preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy, N-propylsulfa Moyloxy
- alkylsulfonylo Si group alkylsulf
- alkoxycarbonyl group preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, methoxycarbonyl , Ethoxycarbonyl, oct Tadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl
- aryloxycarbonyl group preferably having 7 to 32 carbon atoms, more preferably aryl having 7 to 24 carbon atoms
- An oxycarbonyl group such as phenoxycarbonyl
- a carbamoyl group preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms such as carbamoyl, N, N-diethylcar
- N, N-dimethylureido, N-phenylureido imide group (preferably an imide group having 36 or less carbon atoms, more preferably 24 or less carbon atoms, for example, N-succinimide, N-phthalimide), alkoxycarbonyl An amino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyloxycarbonyl; Amino), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonylamino), a sulfonamide group (preferably carbon A sulfonamide group having 1 to 48
- Alkylthio groups such as methylthio, ethylthio, octylthio, cyclohexyl Thio), an arylthio group (preferably an arylthio group having 6 to 48 carbon atoms, more preferably an arylthio group having 6 to 24 carbon atoms, such as phenylthio), a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a carbon number).
- heterocyclic thio groups such as 2-benzothiazolylthio, 2-pyridylthio, 1-phenyltetrazolylthio
- alkylsulfinyl groups preferably having 1 to 32 carbon atoms, more preferably having 1 to 32 carbon atoms
- 24 alkylsulfinyl groups such as dodecanesulfinyl
- arylsulfinyl groups preferably arylsulfinyl groups having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms such as phenylsulfinyl
- alkylsulfonyl groups preferably Is an alkylsulfo having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms.
- arylsulfonyl groups (preferably having 6 to 48 carbon atoms, An arylsulfonyl group having 6 to 24 carbon atoms, such as phenylsulfonyl, 1-naphthylsulfonyl), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as sulfamoyl, N, N-dipropylsulfamoyl
- the alkoxy group in R 1 to R 13 is preferably an alkoxy group having 1 to 30 carbon atoms, and particularly preferably an alkoxy group having 1 to 12 carbon atoms.
- the alkoxy group may have a substituent or may be unsubstituted. Unsubstituted is preferred. Specific examples of the substituent include the same substituents that the alkyl group may have.
- Examples of the halogen atom in R 1 to R 13 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- R 1 to R 13 are preferably each independently a hydrogen atom, a methyl group, an ethyl group or a methoxy group.
- R 13 is preferably a methyl group.
- R 1 to R 12 are preferably hydrogen atoms.
- L 1 in the general formula (E1) represents a single bond or a divalent linking group.
- a divalent linking group is preferred.
- the divalent linking group include an alkylene group, an arylene group, —O—, —NR′— (R ′ may be a hydrogen atom, an alkyl group which may have a substituent, or a substituent. And a group containing at least one selected from a structure represented by —SO 2 —, —CO—, —O— and —S—. These may have a substituent.
- the substituent include the same as those described above for the substituent that the alkyl group in R 1 to R 13 may have.
- the number of carbon atoms of the alkylene group is preferably 1-30, and more preferably 1-12.
- the number of carbon atoms in the arylene group is preferably 6 to 30, and more preferably 6 to 12.
- the compound represented by the general formula (E1) is more preferably a compound represented by the following general formula (E1a).
- R 1 to R 19 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom.
- R 1 to R 19 in the general formula (E1a) have the same meanings as R 1 to R 13 in the general formula (E1).
- R 1 to R 19 are preferably each independently a hydrogen atom, a methyl group, an ethyl group or a methoxy group. More preferably, at least one selected from R 13 , R 18 and R 19 is a methyl group. More preferably, R 13 , R 18 and R 19 are methyl groups, and R 1 to R 12 and R 14 to R 17 are hydrogen atoms.
- Examples of the compound represented by the general formula (E1a) include 1- [4- (1-hydroxy-1-methyl-ethyl) -phenyl] ethanone and phenols (unsubstituted or having 1 to 12 carbon atoms).
- the compound obtained as a main component by reaction of this is mentioned.
- Examples of commercially available products include VG-3101L manufactured by Printec Co., Ltd., NC-6000 and NC-6300 manufactured by Nippon Kayaku Co., Ltd.
- R EP1 to R EP3 each represent a hydrogen atom, a halogen atom, or an alkyl group, and the alkyl group may have a cyclic structure, and may have a substituent. Also good. R EP1 and R EP2 and R EP2 and R EP3 may be bonded to each other to form a ring structure.
- alkyl group may have include a hydroxyl group, a cyano group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an alkylthio group, an alkylsulfone group, an alkylsulfonyl group, and an alkylamino group.
- QEP represents a single bond or an nEP- valent organic group.
- R EP1 ⁇ R EP3 combines with Q EP may form a ring structure.
- nEP represents an integer of 2 or more, preferably 2 to 10, and more preferably 2 to 6. However, n EP is 2 when Q EP is a single bond.
- QEP is an nEP- valent organic group
- a linear or cyclic nEP- valent saturated hydrocarbon group preferably having 2 to 20 carbon atoms
- nEP- valent aromatic ring group preferably having 6 to 30 carbon atoms
- a chain or cyclic saturated hydrocarbon or aromatic hydrocarbon such as an ether group, an ester group, an amide group, a sulfonamide group, an alkylene group (preferably having 1 to 4 carbon atoms, more preferably a methylene group), etc.
- a divalent linking group, a trivalent linking group such as —N (—) 2, or an nEP valent organic group having a structure in which a combination thereof is linked is preferable.
- an oligomer or polymer having an epoxy group in the side chain can also be preferably used.
- examples of such compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and aliphatic epoxy resins. These compounds may be used as commercial products or can be obtained by introducing an epoxy group into the side chain of the polymer.
- bisphenol A type epoxy resin JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), etc.
- bisphenol F type epoxy resin is JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835.
- EPICLON N-695 manufactured by DIC Corporation
- EOCN-1020 manufactured by Nippon Kayaku Co., Ltd.
- aliphatic epoxy resins include ADEKA RESIN EP-4080S, E -4085S, EP-4088S (above, manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEEAD PB 3600, PB 4700 (above, manufactured by Daicel Chemical Industries), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation).
- ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), JER1031S (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.
- Commercially available compounds having an epoxy group include JER1031S (Mitsubishi Chemical Corporation), JER1032H60 (Mitsubishi Chemical Corporation), EPICLON HP-4700.
- EPICLON N-695 made by DIC Corporation
- EPICLON840 made by DIC Corporation
- EPICLON N660 made by DIC Corporation
- EPICLON HP7200 DIC Corporation Etc.
- the introduction reaction may be, for example, a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride.
- a tertiary amine such as triethylamine or benzylmethylamine
- dodecyltrimethylammonium chloride tetramethylammonium chloride
- tetraethylammonium chloride tetraethylammonium chloride.
- the amount of the alicyclic epoxy unsaturated compound introduced is preferably controlled so that the acid value of the obtained polymer is in a range satisfying 5 to 200 KOH ⁇ mg / g.
- the epoxy unsaturated compound those having a glycidyl group as an epoxy group such as glycidyl (meth) acrylate and allyl glycidyl ether can be used, but an unsaturated compound having an alicyclic epoxy group is preferable. As such a thing, the following compounds can be illustrated, for example.
- the compound which has an epoxy group may be used independently, and may be used in combination of 2 or more type.
- the coloring composition of this invention contains the compound which has an epoxy group, as a total content of the compound which has an epoxy group in a coloring composition, it is 0 with respect to the total solid (mass) of a coloring composition. 1 to 20% by mass is preferable, 0.1 to 10% by mass is more preferable, and 0.5 to 5% by mass is particularly preferable.
- the polymerizable compound is described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765.
- Urethane acrylates and urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. is there.
- addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 as polymerizable compounds.
- a compound having an oxetane group can also be used as the polymerizable compound.
- the compound having an oxetane group include the compounds described in paragraphs 0134 to 0145 of JP-A-2008-224970, the contents of which are incorporated herein.
- Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX can be used.
- polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
- the coloring composition of this invention contains coloring agents other than the pigment
- the colorant other than the pigment (A) include dyes and pigments, and pigments are preferable.
- the pigment means an insoluble coloring compound that is difficult to dissolve in a solvent. Typically, it means a dye compound that exists in a dispersed state as particles in the composition.
- an arbitrary solvent is mentioned with a solvent, For example, the solvent illustrated in the column of the solvent mentioned later is mentioned.
- the pigment used in the present invention preferably has a solubility at 25 ° C. of 0.1 g / 100 g Solvent or less, for example, for both propylene glycol monomethyl ether acetate and water.
- Suitable dyes other than the above-mentioned pigment (A) include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, No. 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No. 5,667,920, U.S. Pat.No. 505950, U.S. Pat.
- the dyes disclosed in JP-A-6-51115 and JP-A-6-194828 can be used.
- the chemical structure includes pyrazole azo, pyromethene, anilinoazo, triarylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, etc.
- Dyes can be used.
- a dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.
- Pigment As the pigment other than the dye (A) described above, conventionally known various inorganic pigments or organic pigments can be used, and organic pigments are preferably used.
- the pigment preferably has a high transmittance.
- inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And black pigments such as the above-described metal complex oxides, carbon black, and titanium black.
- 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; I. Pigment brown 25, 28; C. I. Pigment black 1; and the like.
- 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.
- 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.
- 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
- an anthraquinone pigment C.I. I. Pigment red 177
- 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 from 100: 5 to 100: 50, and more preferably from 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the desired spectrum.
- 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.
- a disazo yellow pigment e.g., a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment
- C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83 e. 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, and more preferably 100: 30 to 100: 120.
- a phthalocyanine pigment can be used alone, or a mixture of this with a dioxazine purple pigment can be used.
- 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 to the violet pigment is preferably 100: 0 to 100: 100.
- 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 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.
- the pigment is preferably a pigment selected from anthraquinone pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinophthalone pigments, isoindoline pigments, azomethine pigments, and dioxazine pigments.
- 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
- the content of the pigment is preferably 10 to 70% by mass, and preferably 25 to 65% by mass with respect to all components excluding the solvent contained in the colored composition. More preferred is 35 to 55% by mass.
- the coloring composition of the present invention may contain only one type of pigment or two or more types of pigments. When two or more types are included, the total amount is preferably within the above range.
- Pigment dispersant When the coloring composition of this invention contains a pigment, it is preferable to contain a pigment dispersant.
- the pigment dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic. -Based copolymers, naphthalenesulfonic acid formalin condensates], surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
- the polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.
- Examples of the terminal-modified polymer having an anchor site to the pigment surface include a polymer having a phosphate group at the terminal described in JP-A-3-112992, JP-A-2003-533455, and the like. Examples thereof include polymers having a sulfonic acid group at the terminal end described in JP-A-273191 and the like, and polymers having a partial skeleton of an organic dye and a heterocyclic ring described in JP-A-9-77994. In addition, polymers having two or more pigment surface anchor sites (acid groups, basic groups, organic dye partial skeletons, heterocycles, etc.) introduced at the polymer ends described in JP-A-2007-277514 are also available. It is preferable because of excellent dispersion stability.
- Examples of the graft polymer having an anchor site to the pigment surface include a polyester-based dispersant, and specific examples thereof include JP-A-54-37082, JP-A-8-507960, Reaction products of poly (lower alkyleneimine) and polyester described in JP-A-2009-258668, etc., reaction products of polyallylamine and polyester described in JP-A-9-169821, etc., JP-A-10-339949 A copolymer of a macromonomer and a nitrogen atom monomer described in JP-A-2004-37986, JP-A-2003-238837, JP-A-2008-9426, JP-A-2008-81732, etc.
- a graft type polymer having a partial skeleton or a heterocyclic ring of the organic dye described in JP 2010-106268 A Copolymer of a macromonomer and acid group-containing monomer of the mounting thereof.
- the amphoteric dispersion resin having a basic group and an acid group described in JP-A-2009-203462 has the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersion. From the viewpoint of
- Macromonomer AA-6 (terminal) manufactured by Toa Gosei Co., Ltd. Polymethyl methacrylate having a methacryloyl group), AS-6 (polystyrene having a methacryloyl group at the end group), AN-6S (a copolymer of styrene and acrylonitrile having a methacryloyl group at the end group), AB-6 ( Polybutyl acrylate whose end group is a methacryloyl group), Plaxel FM5 manufactured by Daicel Chemical Industries, Ltd.
- a polyester-based macromonomer that is particularly excellent in flexibility and solvophilicity is particularly preferable from the viewpoint of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the coloring composition using the pigment dispersion
- a polyester macromonomer represented by a polyester macromonomer described in JP-A-2-272009 is particularly preferable.
- block polymers having an anchor site to the pigment surface block polymers described in JP-A Nos. 2003-49110 and 2009-52010 are preferable.
- the pigment dispersant is also available as a commercial product. Specific examples thereof include “DA-7301” manufactured by Kashiwagi Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate)” manufactured by BYK Chemie, and 107 (carbon carboxylate).
- Acid ester 110 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), “BYK-P104, P105 (high Molecular weight unsaturated polycarboxylic acid), manufactured by EFKA “EFKA 4047, 4050 to 4010 to 4165 (polyurethane type), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (High molecular weight polycarboxylate), 6220 (fatty acid Reester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd.,
- the pigment dispersant 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 a terminal-modified polymer, a graft polymer, or a 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.
- the acid cellulose derivative examples include a resin having a hydroxyl group modified with an acid anhydride, and a (meth) acrylic acid copolymer is particularly preferable.
- a resin having a hydroxyl group modified with an acid anhydride examples include a resin having a hydroxyl group modified with an acid anhydride, and a (meth) acrylic acid copolymer is particularly preferable.
- An alkali-soluble resin containing is also preferred.
- an alkali-soluble resin: benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer is exemplified.
- n 20.
- the total content of the pigment dispersant is preferably 1 to 80 parts by mass with respect to 100 parts by mass of the pigment, and 5 to 70 parts by mass. Is more preferably 10 to 60 parts by mass.
- the amount used is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass with respect to 100 parts by mass of the pigment.
- the amount of the pigment derivative used is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and particularly preferably 5 to 15 parts by mass with respect to 100 parts by mass of the pigment.
- the total content of the colorant and the dispersant component is 50% by mass or more with respect to the total solid content constituting the colored composition of the present invention. It is preferably at most mass%, more preferably at least 55 mass% and at most 85 mass%, further preferably at least 60 mass% and at most 80 mass%.
- the coloring composition of the present invention may further contain an alkali-soluble resin.
- 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 include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group.
- the group is soluble in an organic solvent and developed with a weak alkaline aqueous solution. Possible are preferable, and (meth) acrylic acid is particularly preferable.
- These acid groups may be used alone or in combination of two or more.
- Examples of the monomer that can give an acid group after 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 (meth). And monomers having an isocyanate group such as acrylate. Only one type of monomer for introducing these acid groups may be used, or two or more types may be used. In order to introduce an acid group into the alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of giving an acid group after polymerization may be polymerized as a monomer component.
- 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.
- 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.
- 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.
- 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,
- 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, ⁇ -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfury
- 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.
- 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 in JP 2010-168539 A can be referred to.
- the coloring composition of this invention can form the cured coating film which was very excellent also in transparency with heat resistance.
- the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R 1 and R 2 is not particularly limited, and examples thereof include methyl, ethyl, n Linear or branched alkyl groups such as -propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butylcyclohexyl Alicyclic groups such as dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-eth
- ether dimer examples include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene).
- 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.
- the alkali-soluble resin may contain a structural unit derived from an ethylenically unsaturated compound represented by the 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 which may contain a benzene ring. And represents an alkyl group of 20. n represents an integer of 1 to 15.)
- the alkylene group of R 2 preferably has 2 to 3 carbon atoms.
- the alkyl group of R 3 has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R 3 may contain 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.
- an alkali-soluble resin having a polymerizable group may be used.
- an 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.
- the alkali-soluble resin containing the above-mentioned polymerizable group include: Dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer.
- Diamond Shamrock Co.Ltd. Biscoat R- H.264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like.
- an alkali-soluble resin containing these polymerizable groups an isocyanate group 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; Urethane-modified polymerizable double bond-containing acrylic resin obtained by the above reaction, unsaturated group-containing acrylic obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule Resin, acid pendant type epoxy acrylate resin, OH group-containing acrylic resin and polymerizable double bond-containing acrylic resin obtained by reacting a polymerizable double bond, OH group-containing acrylic resin and isocyanate Resin obtained by reacting compound having polymerizable group, JP 2002-229207 A Resin obtained by basic treatment of a resin having an ester group having a leaving group such as a halogen atom or a sulf
- 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. .
- 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.
- alkali-soluble resin descriptions from paragraphs 0558 to 0571 of JP2012-208494A (corresponding to ⁇ 0685> to ⁇ 0700> of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof can be referred to. Is incorporated herein.
- 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 to 2020 of JP 2012-208474 A
- 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.
- 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.
- the content of the alkali-soluble resin is preferably 1 to 15% by mass, more preferably 2 to 2%, based on the total solid content of the colored composition. It is 12% by mass, and particularly preferably 3 to 10% by mass.
- the colored composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
- the colored composition of the present invention preferably further contains a photopolymerization initiator.
- the photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
- the photopolymerization initiator preferably contains at least one compound having a 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).
- the photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives.
- Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.
- trihalomethyltriazine compounds trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -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.
- trihalomethyltriazine compound More preferred are trihalomethyltriazine compound, ⁇ -aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, ⁇ -aminoketone
- the colored composition of the present invention when used for the production of a color filter for 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.
- an oxime compound as the photopolymerization initiator.
- 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.
- an oxime compound can improve the color transfer.
- paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
- hydroxyacetophenone compounds 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.
- hydroxyacetophenone-based initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
- aminoacetophenone initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
- 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.
- acylphosphine initiator commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
- photopolymerization initiator examples include oxime compounds.
- oxime compounds 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 can be used.
- oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Examples thereof include compounds described in 202-232, JP-A No. 2000-66385, JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
- IRGACURE-OXE01 manufactured by BASF
- IRGACURE-OXE02 manufactured by BASF
- TRONLY TR-PBG-304 TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arcles NC 831 and Adeka Arcles NCI-930 (manufactured by ADEKA) can also be used.
- 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. 2009-292039, in which a nitro group is introduced into the dye moiety, ketoxime compounds described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule A compound described in US Pat. No.
- the oxime compound is preferably a compound represented by the following formula (OX-1).
- the oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .
- R and B each independently represent a monovalent substituent
- A represents a divalent organic group
- Ar represents an aryl group.
- the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
- 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.
- these groups may have one or more substituents.
- the substituent mentioned above may be further substituted by another substituent.
- the substituent examples 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 monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
- the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
- an oxime compound having a fluorine atom can also be used as a photopolymerization initiator.
- Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP-A 2013-164471 ( C-3). This content is incorporated herein.
- the oxime compound has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 405 nm.
- the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
- a known method can be used. Specifically, for example, an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) is used and an ethyl acetate solvent is used. It is preferable to measure at a concentration of 0.01 g / L. You may use the photoinitiator used for this invention in combination of 2 or more type as needed.
- the content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5%, based on the total solid content of the colored composition. -30% by mass, more preferably 1-20% by mass. 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.
- the coloring composition of the present invention is a polyfunctional mercapto compound, an organic solvent, a crosslinking agent, a polymerization inhibitor, a surfactant, an organic carboxylic acid, as long as the effects of the present invention are not impaired.
- Other components such as an organic carboxylic acid anhydride may be included.
- the colored composition of the present invention may contain a polyfunctional mercapto compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound.
- the polyfunctional mercapto compound is preferably a secondary alkane mercapto, particularly preferably a compound having a structure represented by the following general formula (T1).
- T1 In the formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.
- 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 mercapto 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 mercapto compounds can be used alone or in combination.
- the blending amount of the polyfunctional mercapto compound in the colored composition of the present invention is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass with respect to the total solid content excluding the solvent. preferable.
- the polyfunctional mercapto compound may contain only 1 type and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range. Further, the polyfunctional mercapto compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.
- the coloring composition of the present invention may contain an organic solvent.
- the organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied. Is preferably selected. Moreover, when preparing the coloring composition in this invention, it is preferable that at least 2 type of organic solvent is included.
- organic solvents examples include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate.
- Alkyl oxyacetates eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)
- alkyl 3-oxypropionate Esters eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.
- 2-oxypropionic acid alkyl esters eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.
- the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
- the content of the organic solvent in the colored composition is preferably such that the total solid concentration of the colored composition is 5% to 80% by mass, and more preferably 5 to 60% by mass, from the viewpoint of applicability. 10 to 50% by mass is particularly preferable.
- the coloring composition of the present invention may contain only one type of organic solvent or two or more types of organic solvents. When two or more types are included, the total amount is preferably within the above range.
- crosslinking agent By containing a crosslinking agent, the hardness of the cured film obtained can be further increased.
- 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.
- the content of the crosslinking agent is not particularly defined, but is preferably 2 to 30% by mass, and preferably 3 to 20% by mass based on the total solid content of the composition. More preferred.
- the coloring 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 colored 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 colored composition.
- the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
- the content of the polymerization inhibitor is preferably about 0.01 to 5% by mass relative to the mass of the coloring composition.
- the coloring 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.
- ⁇ surfactant Various surfactants may be added to the colored composition of the present invention from the viewpoint of further improving coatability.
- 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.
- the coloring composition of the present invention contains a fluorosurfactant, so that liquid properties (particularly fluidity) when prepared as a coating solution are further improved.
- Liquidity can be further improved. That is, in the case of forming a film using a coating liquid to which a coloring composition containing a fluorosurfactant is applied, wetting the coated surface by reducing the interfacial tension between the coated surface and the coating liquid. The coating property is improved and the coating property to the coated surface is improved. For this reason, even when a thin film of about several ⁇ m 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 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 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 a colored composition.
- fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781F (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.
- a fluorosurfactant described in JP 2010-32698 A can also be used.
- a block polymer can be used as the fluorosurfactant, and specific examples include compounds described in JP2011-89090A.
- the fluorosurfactant has 2 or more (preferably 5 or more) repeating units derived from a (meth) acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group and / or a propyleneoxy group) (A fluorine-containing polymer compound containing a repeating unit derived from a (meth) acrylate compound can also be preferably used.
- 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 JP-A 2010-164965, paragraphs 0050 to 0090 and paragraphs 0289 to 0295, such as MegaFac RS-101, RS-102, and RS-718K manufactured by DIC.
- nonionic surfactant examples 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 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1) Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like. Also, NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can be used.
- cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
- phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
- organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
- (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
- W001 manufactured by Yusho Co., Ltd.
- anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
- silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
- the coloring composition of the present invention contains a surfactant
- the addition amount of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.001%, based on the total mass of the coloring composition. 005 to 1.0% by 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.
- the coloring 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.
- organic carboxylic acid and the organic carboxylic acid anhydride for example, paragraphs 0338 to 0340 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.
- the amount of the organic carboxylic acid and / or organic carboxylic acid anhydride is usually 0.01 to 10% by weight based on the total solid content.
- the range is preferably 0.03 to 5% by weight, more preferably 0.05 to 3% by weight.
- the coloring composition of the present invention may contain only one type or two or more types of organic carboxylic acids and / or organic carboxylic anhydrides. When two or more types are included, the total amount is preferably within the above range.
- additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be blended with the coloring composition as necessary.
- these additives include those described in JP-A No. 2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein.
- the coloring 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.
- a resin containing a monomer represented by the general formula (1) of JP-A-2006-215453 as a copolymer component can be contained as a binder.
- the colored composition of the present invention it is bonded or arranged to each component in the colored composition such as a dye, pigment, pigment dispersant, solvent, alkali-soluble resin, polymerizable compound, surfactant, photopolymerization initiator, and epoxy compound.
- a metal selected from free Al, Ca, Cu, Cr, Mg, Fe, Mn, Ni, Co, Cd, Li, Pb, Na, K, Zn, and P is not more than 25 ppm. Is preferred.
- the total content of the free metals is preferably 70 ppm or less, and more preferably 60 ppm or less. According to this aspect, it is easy to manufacture a color filter with few defects.
- content of the said free metal in a coloring composition can be measured using a known analysis means suitably, it is preferable to measure by inductively coupled plasma emission spectroscopy as much as possible.
- means for avoiding contamination of these metals include purity control of raw materials, selection of a non-metallic reaction vessel (for example, glass), selection of an appropriate purification and storage method, and the like.
- the colored composition of the present invention it is bonded or arranged to each component in the colored composition such as a dye, pigment, pigment dispersant, solvent, alkali-soluble resin, polymerizable compound, surfactant, photopolymerization initiator, and epoxy compound.
- the unrestricted free Br content is preferably 900 ppm or less, and more preferably 600 ppm or less. Moreover, 900 ppm or less is preferable and, as for free Cl content, 600 ppm or less is more preferable.
- the total content of free Br and free Cl is preferably 1500 ppm or less, and more preferably 900 ppm or less. According to this aspect, it is easy to manufacture a color filter with few defects.
- the free Br content and free Cl content in the colored composition can be measured by appropriately using known analysis means, but in accordance with the halogen content measurement BS EN 14582 as much as possible. It is preferable to measure in accordance with the combustion ion chromatograph method.
- the coloring composition of the present invention is prepared by mixing the aforementioned components.
- the components constituting the colored composition may be mixed together, or may be sequentially added after each component is dissolved and dispersed in a solvent.
- 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 colored composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects.
- 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)
- PTFE polytetrafluoroethylene
- nylon eg nylon-6, nylon-6,6
- PP polypropylene
- the pore size of the filter is suitably about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 3.0 ⁇ m, more preferably about 0.05 to 0.5 ⁇ m.
- a fiber-shaped filter medium examples include polypropylene fiber, nylon fiber, glass fiber, and the like. , TPR005, etc.) and SHPX type series (SHPX003 etc.) filter cartridges can be used.
- the filtering by the first filter may be performed only once or may be performed twice or more.
- the pore diameter here can refer to the nominal value of the filter manufacturer.
- a commercially available filter for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
- the second filter a filter formed of the same material as the first filter described above can be used.
- 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 colored composition of the present invention can be suitably used for forming a colored layer of a color filter because it can form a cured film having good heat resistance and color transfer.
- the coloring composition of the present invention is a coloring pattern such as a color filter used in an image display device such as a solid-state imaging device (for example, CCD, CMOS (Complementary Metal-Oxide ⁇ Semiconductor)) or a liquid crystal display device (LCD). It can be suitably used for forming. Furthermore, it can be suitably used as a production application for printing ink, inkjet ink, paint, and the like. Especially, it can use suitably for manufacture of the color filter for solid-state image sensors, such as CCD and CMOS.
- the cured film of the present invention is formed by curing the colored composition of the present invention. Such a cured film is preferably used for a color filter.
- the first aspect of the method for producing a color filter of the present invention includes a step of applying the colored composition of the present invention on a support to form a colored composition layer, and a step of exposing the colored composition layer in a pattern-like manner. And a step of developing and removing the unexposed portion to form a colored pattern. Furthermore, you may provide the process (prebaking process) of baking a colored composition layer, and the process (post-baking process) of baking the developed coloring pattern as needed. Hereinafter, these steps may be collectively referred to as a pattern forming step.
- the second aspect of the method for producing a color filter of the present invention includes a step of applying the colored composition of the present invention on a support to form a colored composition layer and curing to form a colored layer; A step of forming a photoresist layer on the colored layer, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and forming a colored pattern by dry etching the colored layer using the resist pattern as an etching mask Including the step of.
- the color filter of the present invention can be suitably obtained by the above production method. These details are described below.
- the colored composition layer is formed by applying the colored composition of the present invention on the support.
- a solid-state imaging element substrate in which an imaging element (light receiving element) such as a CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used.
- 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.
- 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.
- various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied.
- the drying (pre-baking) of the colored composition layer coated on the support can be performed at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, oven or the like.
- the colored composition layer formed in the colored composition layer forming step is exposed in a pattern.
- pattern exposure can be performed by exposing the colored 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.
- radiation light
- ultraviolet rays such as g-line and i-line are preferable (particularly preferably i-line).
- the irradiation amount (exposure amount) is, for example, 0.03 to 2.
- the oxygen concentration at the time of exposure can be appropriately selected.
- 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).
- 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 illuminance can be set as appropriate, and can usually be selected from the range of 1000 W / m 2 to 100,000 W / m 2 (eg, 5000 W / m 2 , 15000 W / m 2 , 35000 W / m 2 ). .
- 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 thickness of the cured film is preferably 1.0 ⁇ m or less, more preferably 0.1 ⁇ m to 0.9 ⁇ m, and further preferably 0.2 ⁇ m to 0.8 ⁇ m. It is preferable to set the film thickness to 1.0 ⁇ m or less because high resolution and high adhesion can be obtained.
- a cured film having a thin film thickness of 0.7 ⁇ m 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.
- the coloring pattern excellent in developability, surface roughness suppression, and pattern shape can be obtained.
- the colored composition layer of the light non-irradiated portion in the exposure step is eluted in the alkaline aqueous solution, and only the photocured portion 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 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.
- alkaline agent used in the developer examples include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide.
- Organic alkaline compounds such as choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, and the concentration of these alkaline agents is 0.001 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.
- 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.
- a surfactant may be used for the developer.
- the surfactant examples include the surfactant described in the above-described composition, and a nonionic surfactant is preferable.
- the amount is preferably 0.001 to 2.0% by weight, more preferably 0.01 to 1.0% by weight, based on the total weight of the developer.
- the developing solution which consists of such alkaline aqueous solution, generally it is preferable to wash
- post-bake heat treatment after drying. If a multicolor coloring pattern is formed, a cured film can be produced by sequentially repeating the process for each color. Thereby, a color filter is obtained.
- the 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 coating film after development is in the above-described condition. be able to.
- the dry etching can be performed using the etching gas with the colored layer as a mask using the patterned photoresist layer as a mask.
- a positive or negative radiation sensitive composition is applied onto the colored layer and dried to form a photoresist layer.
- the photoresist for example, a positive type radiation sensitive composition is used.
- the positive type radiation sensitive composition includes a positive type photoresist which is sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer laser, electron beams, ion beams and X rays.
- a positive resist composition suitable for use can be used.
- the radiation g-line, h-line and i-line are preferable, and i-line is particularly preferable.
- 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 ICs and LSIs.
- 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 from 0.1 to 3 ⁇ m, preferably from 0.2 to 2.5 ⁇ m, and more preferably from 0.3 to 2 ⁇ m.
- the application of the photoresist layer can be suitably performed using the above-described application method in the colored 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.
- a resist through hole group in the photoresist layer 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 does not affect the colored layer containing the colorant and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist.
- a combination of various organic solvents or an alkaline aqueous solution can be used.
- 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.
- alkaline compounds 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, 1,8-diazabicyclo [5.4.0] -7-undecene.
- alkaline aqueous solution is used as a developing solution, generally a washing process is performed with water after development.
- the resist pattern as an etching mask, patterning is performed by dry etching so that a 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.
- the dry etching is preferably performed in the following manner from the viewpoint of forming the pattern cross section closer to a rectangle and reducing the damage to the support.
- 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.
- N 2 nitrogen gas
- O 2 oxygen gas
- 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.
- 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.
- 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) The overetching time is calculated with respect to the total time of (3) and (4) described above, and overetching is performed.
- the mixed gas used in the first-stage etching process 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.
- 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 stage etching process and the over etching process after the etching is performed up to the region where the support is not exposed by the mixed gas of fluorine-based gas and oxygen gas in the first stage etching process, damage to the support is avoided. From the viewpoint, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.
- the ratio between 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.
- the 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 preferably 5 to 25% from the viewpoint of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.
- the resist pattern that is, the etching mask
- 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.
- time to make stripping solution or a solvent stagnant It is preferable that it is several dozen seconds to several minutes.
- examples of the step of removing the resist pattern using the cleaning water include a step of removing the resist pattern by spraying the cleaning water onto the resist pattern from a spray type or shower type spray nozzle.
- the washing water pure water can be preferably used.
- 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 an organic solvent, but may further contain an inorganic solvent.
- organic solvents include 1) hydrocarbon compounds, 2) halogenated hydrocarbon compounds, 3) alcohol compounds, 4) ether or acetal compounds, 5) ketones or aldehyde compounds, and 6) ester 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.
- Specific examples include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, and triethanolamine.
- Preferred are monoethanolamine, diethanolamine, and triethanolamine, and more preferred is monoethanolamine (H 2 NCH 2 CH 2 OH).
- cyclic nitrogen-containing compounds include isoquinoline, imidazole, N-ethylmorpholine, ⁇ -caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, ⁇ -picoline, ⁇ -picoline, ⁇ -picoline, 2- Preferred examples include pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, and 2,6-lutidine.
- NMP N-methyl-2-pyrrolidone
- NMP N-methyl-2-pyrrolidone
- the stripping solution preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.
- acyclic nitrogen-containing compound at least one selected from monoethanolamine, diethanolamine, and triethanolamine, and cyclic
- the nitrogen-containing compound preferably includes at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine, and more preferably includes monoethanolamine and N-methyl-2-pyrrolidone.
- a deposit means an etching product deposited and deposited on the side wall of a colored layer.
- 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.
- the method for producing a color filter of the present invention may have a step known as a method for producing a color filter for a solid-state imaging device as a step other than the above, if necessary.
- a curing step of curing the formed colored pattern by heating and / or exposure may be included as necessary.
- the solvent for the colored composition of the present invention is used to efficiently clean the nozzles and pipes of the discharge unit of the coating apparatus, contamination due to adhesion, sedimentation, and drying of the colored composition and pigment in the coating machine.
- the cleaning liquids described in JP2007-2101A, JP2007-2102A, JP2007-281523A, and the like can be suitably used.
- 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, more preferably from 20/80 to 80/20.
- PGMEA propylene glycol monomethyl ether acetate
- PGME propylene glycol monomethyl ether
- the ratio is particularly preferably 60/40.
- the above-described surfactant relating to the colored composition of the present invention may be added to the cleaning liquid.
- the color filter of the present invention uses the colored composition of the present invention, the color filter is excellent in heat resistance and color transfer.
- 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.
- the film thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 ⁇ m or less, more preferably 1.0 ⁇ m or less, and even more preferably 0.7 ⁇ m or less. Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less, and particularly preferably 1.7 ⁇ m or less.
- the solid-state imaging device of the present invention includes 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 solid-state imaging device CCD image sensor, CMOS image sensor, etc.
- a transfer electrode made of polysilicon, etc.
- the photodiode is placed on the transfer electrode.
- the color filter for a solid-state image sensor according to the present invention is provided.
- a light collecting means for example, a micro lens, etc., the same applies hereinafter
- the color filter of the present invention can be used not only for solid-state imaging devices 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.
- display devices For the definition of display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Industrial Books Co., Ltd.) Issued in the first year).
- the liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 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 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.)”.
- the present invention is applied to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
- the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system.
- COA Color-filter On Array
- 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.
- the COA method has high resolution and excellent long-term durability.
- a liquid crystal display device can be provided.
- a resin film may be provided on the color filter layer.
- the color filter of the present invention can be preferably used for a micro O red type (micro OLED) display.
- 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.
- 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) ”.
- backlighting SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Are listed.
- the color filter according to the present invention When the color filter according to the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and further, red, green and blue LED light sources (RGB-LED).
- RGB-LED red, green and blue LED light sources
- the dye (A) used in the following examples is a mixture in which m and n in the general formula (1) take a plurality of different values with a certain distribution, and m and n described in Table 1 below are used.
- the value of n is an average value for each dye.
- the weight average molecular weight was measured in terms of polystyrene by GPC (Gel Permeation Chromatography) measurement. Specifically, HLC-8220 (manufactured by Tosoh) was used, TSKgel Super AWM-H (manufactured by Tosoh, 6.0 mm ID (inner diameter) ⁇ 15.0 cm) was used as a column, and 10 mmol / L lithium bromide NMP (N -Methylpyrrolidinone) solution.
- GPC Gel Permeation Chromatography
- A 56.11 ⁇ Vs ⁇ 0.1 ⁇ f / w
- Vs Amount of 0.1 mol / l sodium hydroxide aqueous solution required for titration (mL)
- f Potency of 0.1 mol / l sodium hydroxide aqueous solution
- w Mass of measurement sample (g) (solid content conversion)
- DCSF Spiro [3H-2,1-benzoxathiole-3,9 '-[9H] xanthene], 3', 6'-dichloro-, 1,1-dioxide, manufactured by Chugai Kasei
- 31 parts, 2,6-diisopropyl 67 parts of aniline, 17 parts of zinc chloride and 120 parts of sulfolane were placed in a flask and stirred at an external temperature of 200 ° C. for 8 hours. Thereafter, the mixture was allowed to cool to room temperature, the reaction solution was added dropwise to 600 parts of 2N aqueous hydrochloric acid, and the precipitated crystals were filtered off.
- reaction solution was concentrated under reduced pressure, dehydrated methanol was added, and 19 parts of sodium methoxide (28% methanol solution) was added.
- reaction solution was added dropwise to 120 parts of 1N aqueous hydrochloric acid while cooling in an ice bath, and 200 parts of ethyl acetate was added to carry out a liquid separation operation.
- organic layer was washed with 200 parts of 1N hydrochloric acid water, 200 parts of water, and 200 parts of saturated saline.
- Sodium sulfate was added to the obtained organic layer, followed by filtration, and the filtrate was concentrated under reduced pressure to obtain 13 parts of (S-4).
- reaction solution was dropped into a mixed solvent of 250 parts of 1N aqueous hydrochloric acid, reprecipitated and filtered, and the solid obtained by suspension was placed in 250 parts of acetonitrile, washed in suspension, and filtered again. B-1) 7.4 parts were obtained. It was confirmed that the ratio of the dye portion to the R portion in the NMR measurement was 3.5.
- the solid obtained by suspension in 250 parts of acetonitrile is suspended and washed, and then filtered again to obtain the present invention shown below.
- 6.0 parts of the dye (Po-1) was obtained.
- the weight average molecular weight of Po-1 (polystyrene equivalent value) was 8900, and the acid value was 60 mgKOH / g by titration with a 0.1N aqueous sodium hydroxide solution. From the NMR, the molar ratio of the dye structure / MAA / BBEM HBr desorber was 3.5 / 6 / 4.5, and the number of repetitions of the P part was calculated to be 4 on average.
- the turbidity of Po-1 at 5% by mass of cyclohexanone was 0.5 ppm.
- Al, Ca, Cu, Cr, Mg, Fe, Mn, Ni, Co, Cd, Li, Pb, Na, K, Zn, and P, which are not bound or coordinated to Po-1, are free All of the aforementioned metals were 2 ppm or less.
- the free Br content not bound or coordinated to Po-1 was 500 ppm, and the free Cl content was 100 ppm.
- the weight average molecular weight (Polystyrene conversion value) of Po-7 was 7200, and the acid value was 44 mgKOH / g by titration with 0.1N sodium hydroxide aqueous solution. From the NMR, the molar ratio of the adduct of dye structure / MAA / ICA / ICA and GMA was 3.5 / 3.5 / 2. The turbidity of Po-7 at 5% by mass of cyclohexanone was 1.5 ppm.
- R 1 represents the structure of the mercapto compound before the reaction.
- m + n corresponds to the number of mercapto groups in the mercapto compound, and m and n represent the average values of m and n in the resulting dye.
- BBEM and CEEMA in the synthesis method mean that they were synthesized using these compounds.
- R 2 represents the average number of repeating units contained in the resulting dye.
- An acid value shows the acid value of the pigment
- Mw is the weight average molecular weight of the dye obtained, and is obtained by the GPC measurement method.
- ⁇ Example 1> 1 Preparation of Resist Solution After the components having the following composition were mixed and dissolved, the resist solution for undercoat layer was prepared by filtering with a 0.45 ⁇ m nylon filter.
- Composition of resist solution for undercoat layer Solvent: propylene glycol monomethyl ether acetate 19.20 parts Solvent: ethyl lactate 36.67 parts
- Ethylenically unsaturated double bond-containing compound dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Sartomer) 12.20 parts ⁇ Polymerization inhibitor: p-methoxyphenol 0.0061 parts ⁇ Fluorine surfactant: F-475, manufactured by DIC Corporation 0.83 parts ⁇ Photopolymerization initiator: trihalomethyltriazine-based photopolymerization Initiator 0.586 parts (TAZ-107, manufactured by Midori Chemical Co., Ltd.)
- Pigment Blue 15: 6 (blue pigment; hereinafter also referred to as “PB15: 6”) 19.4 parts by mass (average primary particle size 55 nm), and pigment dispersant Disperbyk-161 (by BYK Chemie) 2.95 parts by mass , Alkali-soluble resin J1 (benzyl methacrylate / methacrylic acid copolymer, 30% PGMEA solution) in a solid content equivalent of 2.95 parts by mass (solution 9.93 parts by mass) and PGMEA 165.3 parts by mass Were mixed and dispersed for 3 hours using a beads mill (zirconia beads 0.3 mm diameter).
- the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism.
- This dispersion treatment was repeated 10 times to obtain C.I. I. Pigment Blue 15: 6 dispersion was obtained.
- the obtained C.I. I. Pigment Blue 15: 6 dispersion, the average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), and was found to be 24 nm. .
- Production of color filter (colored pattern) 4-1 Production of color filter using colored composition by photolithography method The colored composition prepared above is applied to the undercoat layer of the silicon wafer with an undercoat layer prepared above. To form a colored layer (coating film). 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 1 ⁇ m. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at an exposure dose of 50 to 1200 mJ / cm 2 through an Island pattern mask having a pattern of 1.0 ⁇ m square at a wavelength of 365 nm.
- FPA-3000i5 + manufactured by Canon Inc.
- 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 Co., Ltd.), and CD-2000 (Fuji Film). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the undercoat layer of the silicon wafer with the undercoat layer.
- the silicon wafer on which the colored pattern is formed is fixed to a horizontal rotary table by a vacuum chuck method, and pure water is sprayed from the jet nozzle from above the rotation center while rotating the silicon wafer at a rotation speed of 50 rpm by a rotating device.
- a silicon wafer with a colored pattern having a structure in which a colored pattern (color filter) was provided on the undercoat layer of the silicon wafer with an undercoat layer was obtained.
- ⁇ Heat resistance evaluation >> The colored composition prepared above was applied to a glass substrate using a spin coater to form a coating film.
- the glass substrate on which the colored layer was formed was placed on a hot plate at 280 ° C. so as to be in contact with the substrate surface and heated for 1 hour to conduct a heat resistance test.
- the color difference ( ⁇ E * ab) before and after heating was measured using a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). Based on the measured color difference ( ⁇ E * ab value), the heat resistance was evaluated according to the following evaluation criteria. A smaller ⁇ E * ab value indicates better heat resistance.
- the ⁇ E * 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).
- ⁇ E * ab is 3 or less
- Example 2 to 40 Comparative Examples 1 to 3>
- Example 3 Preparation of colored composition
- pigment dispersion P1, dye C-1, photopolymerization initiator I-2, alkali-soluble resin 1, and polymerizable compound Z-3 are shown in the table below.
- a colored composition was prepared in the same manner as in Example 1 except that the change was made as described above, and the heat resistance and the color transfer property were evaluated in the same manner as in Example 1.
- Example 41 In “3-2. Preparation of colored composition” in Example 1, a colored composition was prepared in the same manner as in Example 1, except that the following components were mixed. The heat resistance and the color transfer were evaluated.
- Organic solvent cyclohexanone: 17.12 parts Alkali-soluble resin 1 (J1): 1.23 parts (solid 0.37 parts, solid content concentration 30%)
- Alkali-soluble resin 2 Alkali-soluble resin 2 (Acrycure-RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)): 0.23 part
- Photopolymerization initiator I-2 (IRGACURE OXE-02): 0.975 part
- a cyclohexanone solution of dye Po-1 Solid content 12.3%
- Pigment dispersion P1 CI Pigment Blue 15: 6 dispersion, PGMEA solution, solids concentration 12.8%
- Polymerizability Compound Z-1 ethyleneoxy-modified dipentaerythritol hexaacrylate, NK ester
- pigment dispersion P3 (CI Pigment Blue 15: 6 dispersion)
- a pigment dispersion P3 was prepared by the same operation except that the following dispersant D2 was used as the pigment dispersant.
- Mw 20000
- x / y 15/85 (mass ratio)
- n 20
- acid value 100 mgKOH / g
- pigment dispersion P4 (dispersion of CI Pigment Red254)
- C.I. I A pigment dispersion P4 was prepared in the same manner as the pigment dispersion P1, except that Pigment Red254 was used.
- the average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.))) to be 26 nm.
- pigment dispersion P5 (dispersion of CI Pigment Green 58)
- C.I. I A pigment dispersion P5 was prepared in the same manner as in the preparation of the pigment dispersion P1, except that Pigment Green 58 was used.
- the average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), and was 30 nm.
- pigment dispersion P6 (dispersion of CI Pigment Yellow 139)
- C.I. I A pigment dispersion P6 was prepared in the same manner as the pigment dispersion P1, except that Pigment Yellow 139 was used.
- the average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)), and was 27 nm.
- Alkali-soluble resin 1 following structure
- Polymerizable compound Z1 ethyleneoxy-modified dipentaerythritol hexaacrylate, NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)
- Z2 Dipentaerythritol hexaacrylate, KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
- Z3 Ethoxylation (4) Pentaerythritol tetraacrylate, SR494 (manufactured by Sartomer)
- Z4 Ethoxylation (3) Trimethylolpropane triacrylate, SR454 (manufactured by Sartomer)
- Z5 Ethoxylation (6) Trimethylolpropane triacrylate, SR499 (manufactured by Sartomer)
- Z6 KAYARAD DPCA-60 (Nippon Kayaku Co., Ltd.)
- Z7 Tris (2-hydroxyethyl)
- Example 42 The following components were mixed, dispersed and dissolved, and filtered through a 0.45 ⁇ m nylon filter to obtain a colored composition. Using the obtained colored composition, heat resistance and color transfer were evaluated in the same manner as in Example 1.
- Organic solvent cyclohexanone: 25.22 parts
- Alkali-soluble resin 2 (Acrycure-RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)): 0.12 part (0.05 part solid, solid content concentration 41.7%)
- Photopolymerization initiator I-7 0.59 parts ⁇ Cyclohexanone solution of dye Po-1 (solid content concentration 12.3%): 23.04 parts
- Pigment dispersion P1 (CI Pigment Blue 15: 6 dispersion) Liquid, PGMEA solution, solid content concentration 12.8%): 45.66 parts, polymerizable compound Z-4 ethoxy
- Example 43 In the preparation of the colored composition in Example 42, the dye Po-1, the pigment dispersion P-1, the photopolymerization initiator I-7, the alkali-soluble resin 1, the polymerizable compound Z-4, and the epoxy compound E1 are shown in the following table.
- a colored composition was prepared in the same manner as in Example 42 except that the above was changed. Using the obtained colored composition, heat resistance and color transfer were evaluated in the same manner as in Example 1.
- the colored compositions of Examples 42 to 58 were excellent in heat resistance and color transfer.
- Example 59 The following components were mixed, dispersed and dissolved, and filtered through a 0.45 ⁇ m nylon filter to obtain a colored composition. Using the obtained colored composition, heat resistance and color transfer were evaluated in the same manner as in Example 1.
- Organic solvent cyclohexanone: 14.69 parts
- Alkali-soluble resin 1 J1: 0.29 parts (solid 0.09 parts, solid content concentration 30%)
- Alkali-soluble resin 2 Acrycure-RD-F8 (manufactured by Nippon Shokubai Co., Ltd.)): 0.05 part
- Photopolymerization initiator I-2 (IRGACURE OXE-02): 0.78 part Cyclohexanone solution of dye Po-1 1 (solid content concentration 12.3%): 28.45 parts ⁇ Cyclohexanone solution of dye Po-12 2 (solid content concentration 12.3%): 51.23 parts ⁇
- Example 60 In the preparation of the coloring composition in Example 59, the dye Po-1, dye Po-12, photopolymerization initiator I-2, alkali-soluble resin 1, polymerizable compound Z-3, and epoxy compound E-1 are shown in the following table.
- a colored composition was prepared in the same manner as in Example 59 except that the above was changed. Using the obtained colored composition, heat resistance and color transfer were evaluated in the same manner as in Example 1.
- the colored compositions of Examples 59 to 70 were excellent in heat resistance and color transfer.
- the colored composition obtained above was applied on a 7.5 cm ⁇ 7.5 cm glass substrate using a spin coater so that the film thickness was 0.5 ⁇ m, and using a hot plate at 200 ° C. Heating was performed for 5 minutes, the coating film was cured, and a colored layer was produced. The thickness of this colored layer was 0.5 ⁇ m.
- a positive photoresist “FHi622BC” manufactured by FUJIFILM Electronics Materials
- the photoresist layer was subjected to pattern exposure using an i-line stepper (manufactured by Canon Inc.) at an exposure amount of 350 mJ / cm 2 for 1 minute at a temperature at which the temperature of the photoresist layer or the atmospheric temperature becomes 90 ° C.
- the heat treatment was performed.
- 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 ⁇ m in consideration of etching conversion difference (pattern width reduction by etching).
- a photoresist stripping solution “MS230C” manufactured by FUJIFILM Electronics Materials Co., Ltd.
- washing with pure water and spin drying were performed, and then a dehydration baking process was performed at 100 ° C. for 2 minutes. As a result, a color filter was obtained.
- Example 72 to 81 Comparative Examples 4 to 6>
- a colored composition was prepared in the same manner as in Example 71 except that the dye Po-1, the pigment dispersion P1, and the epoxy compound E5 were changed as shown in the following table.
- heat resistance and color transfer were evaluated.
- Example 82 The following components were mixed, dispersed and dissolved, and filtered through a 0.45 ⁇ m nylon filter to obtain a colored composition. Using the obtained colored composition, heat resistance and color transfer were evaluated in the same manner as in Example 71.
- Example 83 to 88> A colored composition was prepared in the same manner as in Example 82 except that the dye Po-1, dye Po-12, and epoxy compound E5 were changed as shown in the following table in the preparation of the colored composition in Example 82. . Using the obtained colored composition, heat resistance and color transfer were evaluated in the same manner as in Example 71.
- the examples were excellent in heat resistance and color transfer.
- the comparative example was inferior in heat resistance and color transfer.
- the epoxy compound E4 described in Tables 5 and 6 is EPICLON HP7200 (manufactured by DIC), and E5 is JER1031S (manufactured by Mitsubishi Chemical Corporation).
- the reaction solution was cooled to 65 ° C., stirred for 12 hours, and added with 109 parts of anhydrous magnesium chloride, 294 parts of tripotassium phosphate, and 788 parts of 2,6-diethylaniline.
- the reaction solution was heated to 140 ° C., stirred for 22 hours, and then cooled to 50 ° C.
- 7828 parts of acetonitrile was added dropwise and stirred at 50 ° C. for 3 hours.
- the reaction solution was cooled to room temperature and stirred for 2 hours, and the resulting crystals were collected by filtration and washed with 2817 parts of acetonitrile.
- the crystals were added to 2466 parts of methanol while washing with 274 parts of methanol at room temperature, and stirred at 50 ° C. for 3 hours.
- the reaction solution was cooled to room temperature, 3716 parts of 2N hydrochloric acid was added dropwise, and the mixture was stirred at room temperature for 2 hours.
- the obtained crystals were separated by filtration and washed successively with 3334 parts of ion exchange water and 798 parts of acetonitrile.
- the crystals were dried under reduced pressure at 60 ° C. for 14 hours to obtain 250 parts of intermediate 4.
- the obtained crystal was separated by filtration and washed successively with a mixture of 1113 parts of acetonitrile, 1412 parts of ion-exchanged water, 4236 parts of ion-exchanged water, and 1059 parts of acetonitrile to obtain 238 parts of intermediate 5.
- reaction solution was concentrated under reduced pressure at 35 ° C., cooled to 5 ° C., and stirred for 30 minutes.
- the obtained solid was filtered and washed with 450 parts of ion exchange water, followed by vacuum drying at 45 ° C. for 12 hours to obtain 107 parts of intermediate 6.
- the reaction solution was cooled to 5 ° C., and the resulting crystals were filtered and washed with 505 parts of methanol.
- the crystals were placed in a flask, 909 parts of methanol was added, and the mixture was heated to reflux for 1 hour. This was cooled to 5 ° C., the crystals were filtered, washed with 505 parts of methanol, and dried under reduced pressure at 45 ° C. for 12 hours to obtain 194 parts of (A-xt-23).
- NEP solution V-601: 0.694 parts, NEP: 6.19 parts
- V-601 2,2′-azobis (isobutyric acid) dimethyl [V-601; manufactured by Wako Pure Chemical Industries]
- 0.69 part of NEP was added and stirred at 80 ° C. for 30 minutes, and then a V-601 NEP solution (V-601: 0.694 part, NEP: 1.15 part) was added.
- the reaction solution was stirred at 80 ° C. for 1.5 hours, and then a V-601 NEP solution (V-601: 0.694 parts, NEP: 1.15 parts) was added.
- the reaction solution was stirred at 80 ° C.
- V-601 NEP solution V-601: 0.694 parts, NEP: 1.15 parts
- V-601: 0.694 parts, NEP: 1.15 parts V-601 NEP solution
- NEP 1.15 parts
- this reaction solution was added dropwise to a mixed solvent of 543 parts of methanol, 686 parts of ultrapure water and 0.478 parts of p-methoxyphenol, and the mixture was stirred at room temperature for 1 hour.
- the reaction solution was heated to 47.5 ° C., stirred for 1 hour, and then cooled to room temperature.
- the obtained solid was filtered and washed with a mixed solvent of 272 parts of methanol and 343 parts of ultrapure water.
- This solid was reslurried with a mixed solvent of 136 parts of methanol, 172 parts of ultrapure water, and 0.478 parts of p-methoxyphenol, and the resulting solid was filtered and washed with 136 parts of methanol and 172 parts of ultrapure water.
- This solid was blown and dried at 45 ° C. for 2 days to obtain 45.7 parts of the dye (Po-28) according to the present invention shown below.
- the weight average molecular weight (polystyrene equivalent value) of Po-28 was 8900, and the acid value was 61 mgKOH / g by titration with a 0.1N sodium hydroxide aqueous solution.
- the molar ratio of the dye structure / MAA / BBEM HBr desorber was 3.5 / 6 / 4.5, and the number of repetitions of the P part was calculated to be 4 on average.
- the turbidity of Po-28 at 5% by mass of cyclohexanone was 1.0 ppm.
- Al, Ca, Cu, Cr, Mg, Fe, Mn, Ni, Co, Cd, Li, Pb, Na, K, Zn, and P, which are not bound or coordinated to Po-28, are free All of the aforementioned metals were 2 ppm or less.
- the free Br content not bound or coordinated to Po-28 was 400 ppm and the free Cl content was 100 ppm.
- A-xt-23 to A-xt-26 have the following structures.
- Example 1 ⁇ Examples 89 to 96>
- the dye, the pigment dispersion, the photopolymerization initiator, the alkali-soluble resin 1, the polymerizable compound, and the epoxy compound were changed to the raw materials described in Table 8 below, in the same manner as in Example 1, A colored composition was prepared. Using the obtained colored composition, heat resistance and color transfer were evaluated in the same manner as in Example 1.
- the colored compositions of Examples 89 to 96 were excellent in heat resistance and color transfer.
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Abstract
Description
本発明者らが、特許文献1に開示された色素を含む着色組成物について検討したところ、加熱硬化時に分解が生じ、耐熱性や色移り性に劣ることが分かった。
具体的には、下記手段<1>により、好ましくは、<2>~<22>により、上記課題は解決された。
<1>下記一般式(1)で示される色素および硬化性化合物を含有する着色組成物;一般式(1)
(D―L1―Y―X―) n―R1―(R2) m一般式(1)中、R1は、m+n価の連結基を表し、Xは、―C(=O)O―、―C(=O)―、―C(=O)NR10―、―O―、―S(=O)―、または、―SO2―を表し、R10は水素原子またはアルキル基を表し、Yは、アルキレン基を表し、L1は、単結合または2価の連結基を表し、Dは、色素構造を表し、R2は、1価の置換基を表す;mは、1~13の整数を表し、nは、2~14の整数を表し、m+nは、3~15の整数を表す;mが2以上の場合、複数のR2は互いに異なっていても良く、nが2以上の場合、複数のDは互いに異なっていても良い;L1が2価の連結基の場合は、L1とXとは、Yにより炭素原子数として3以上隔てられており、L1が単結合の場合はDとXとは、Yにより炭素原子数として3以上隔てられている;D、L1、R1、R2、X、Yのうち少なくとも1つは酸基を有する。
<2>一般式(1)におけるDが、ジピロメテン色素、トリアリールメタン色素、キサンテン色素、シアニン色素、スクアリリウム色素、アントラキノン色素、キノフタロン色素、フタロシアニン色素、サブフタロシアニン色素、およびアゾ色素から選ばれる色素に由来する、<1>に記載の着色組成物。
<3>一般式(1)におけるDが、カチオン部位と対アニオンとを有するか、または、一分子内にカチオン部位とアニオン部位とを有し、対アニオンが、スルホン酸アニオン、スルホニルイミドアニオン、ビス(アルキルスルホニル)イミドアニオン、トリス(アルキルスルホニル)メチドアニオン、カルボン酸アニオン、テトラアリールボレートアニオン、BF4 -、PF6 -、およびSbF6 -から選ばれる少なくとも1種であり、アニオン部位が、スルホニルイミドアニオンである、<1>または<2>に記載の着色組成物。
<4>一般式(1)におけるYが、無置換の直鎖アルキレン基である、<1>~<3>のいずれかに記載の着色組成物。
<5>一般式(1)におけるR2が、酸基を有するビニル化合物由来の繰り返し単位を含有する、<1>~<4>のいずれかに記載の着色組成物。
<6>一般式(1)におけるR2が、繰り返し単位を含有し、繰り返し単位の個数の平均値が2~20個である、<1>~<5>のいずれかに記載の着色組成物。
<7>一般式(1)におけるXが、*―C(=O)O―#であり、*はYに結合し#はR1に結合する、<1>~<6>のいずれかに記載の着色組成物。
<8>一般式(1)で示される色素が、エチレン性不飽和結合を有する基を含有する、<1>~<7>のいずれかに記載の着色組成物。
<9>一般式(1)におけるR2が、エチレン性不飽和結合を有する基を含有する、<1>~<8>のいずれかに記載の着色組成物。
<10>一般式(1)におけるR1が、
下記一般式(2)で示される連結基、
下記一般式(3)で示される連結基、
複数の炭素原子からなる主鎖を有する連結基であって、主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、
1つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって、主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、
または、
少なくとも2つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって連続した3つ以上の炭素原子によってヘテロ原子間が隔てられた部分を主鎖中に少なくとも1つ含む連結基、のいずれかである、<1~9のいずれかに記載の着色組成物;一般式(2)
一般式(2)中、Zは、それぞれ独立に、CRまたはNを表し、L2は、それぞれ独立に、単結合またはp価の連結基を表し、Rは水素原子または置換基を表し、aは1~6の整数を表し、pは2以上の整数を表し、L2がp価の連結基の場合、L2は複数の炭素原子からなる主鎖を有する連結基であって、主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、1つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって、主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、または、少なくとも2つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって連続した3つ以上の炭素原子によってヘテロ原子間が隔てられた部分を主鎖中に少なくとも1つ含む連結基、のいずれかである;一般式(3)
一般式(3)中、L3は、それぞれ独立に、単結合またはq価の連結基を表し、qは2以上の整数を表し、L3がq価の連結基の場合、L3は複数の炭素原子からなる主鎖を有する連結基であって、主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、1つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって、主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、または、少なくとも2つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって連続した3つ以上の炭素原子によってヘテロ原子間が隔てられた部分を主鎖中に少なくとも1つ含む連結基、のいずれかである。
<11>一般式(1)におけるL1が、
単結合、
―S―、
複数の炭素原子からなる主鎖を有する連結基であって、主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、
1つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって、主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、
または、
少なくとも2つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって連続した3つ以上の炭素原子によってヘテロ原子間が隔てられた部分を主鎖中に少なくとも1つ含む連結基、のいずれかである、
<1>~<10>のいずれかに記載の着色組成物。
<12>一般式(1)におけるmが1~5であり、nが2~8である、<1>~<11>のいずれかに記載の着色組成物。
<13>一般式(1)で示される色素の重量平均分子量が、2000~15000である、<1>~<12>のいずれかに記載の着色組成物。
<14>さらに、一般式(1)で示される色素以外の顔料を含む、<1>~<13>のいずれかに記載の着色組成物。
<15>さらに、光重合開始剤を含む、<1>~<14>のいずれかに記載の着色組成物。
<16>カラーフィルタの着色層形成用である、<1>~<15>のいずれかに記載の着色組成物。
<17><1>~<15>のいずれかに記載の着色組成物を硬化して得られた硬化膜。
<18><1>~<15>のいずれかに記載の着色組成物を用いてなるカラーフィルタ。<19><1>~<15>のいずれかに記載の着色組成物を支持体上に適用して着色組成物層を形成する工程と、着色組成物層をパターン状に露光する工程と、未露光部を現像除去して着色パターンを形成する工程と、を含むカラーフィルタの製造方法。
<20><1>~<15>のいずれかに記載の着色組成物を支持体上に適用して着色組成物層を形成し、硬化して着色層を形成する工程と、
着色層上にフォトレジスト層を形成する工程と、
露光および現像することによりフォトレジスト層をパターニングしてレジストパターンを得る工程と、
レジストパターンをエッチングマスクとして着色層をドライエッチングする工程と、を含むカラーフィルタの製造方法。
<21><18>に記載のカラーフィルタ、または、<19>もしくは<20>に記載のカラーフィルタの製造方法によって製造したカラーフィルタを有する固体撮像素子。
<22><18>に記載のカラーフィルタ、または、<19>もしくは<20>に記載のカラーフィルタの製造方法によって製造したカラーフィルタを有する画像表示装置。
本明細書における基(原子団)の表記に於いて、置換および無置換を記していない表記は、置換基を有さない基(原子団)と共に置換基を有する基(原子団)をも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
本明細書において、全固形分とは、着色組成物の全組成から溶剤を除いた成分の総質量をいう。
固形分とは、25℃における固形分をいう。
本発明の着色組成物は、後述する一般式(1)で示される色素および硬化性化合物を含有する。
このような効果が得られる理由については、未だ明確ではないが、後述する一般式(1)で表される色素は、Xで表される基に結合する連結基Yとして、メチレン基及びエチレン基では熱分解しやすかったところ、炭素原子数3以上を隔てるアルキレン基を導入したことによって、高温における熱分解が抑制され、耐熱性ならびに色移り性が良好になったものと推測される。以下、本発明について詳細に説明する。
本発明の着色組成物は、下記一般式(1)で表される色素(以下、単に「色素(A)」ということがある。)の少なくとも1種を含有する。
(D―L1―Y―X―) n―R1―(R2) m
一般式(1)中、R1は、m+n価の連結基を表し、
Xは、―C(=O)O―、―C(=O)―、―C(=O)NR10―、―O―、―S(=O)―、または、―SO2―を表し、R10は水素原子またはアルキル基を表し、
Yは、アルキレン基を表し、
L1は、単結合または2価の連結基を表し、
Dは、色素構造を表し、
R2は、1価の置換基を表し、
mは、1~13の整数を表し、
nは、2~14の整数を表し、
m+nは、3~15の整数を表し、
mが2以上の場合、複数のR2は互いに異なっていても良く、nが2以上の場合、複数のDは互いに異なっていても良く、
L1が2価の連結基の場合は、L1とXとは、Yにより炭素原子数として3以上隔てられており、L1が単結合の場合はDとXとは、Yにより炭素原子数として3以上隔てられており、
D、L1、R1、R2、X、Yのうち少なくとも1つは酸基を有する。
一般式(1)中、nは2~14を表す。nとしては、2~8が好ましく、2~7がより好ましく、3~6が特に好ましい。
一般式(1)中、m+nは、3~15を表す。
本発明において、1つの色素(A)における、mは1~13の整数を表し、nは2~14の整数を表し、m+nは、3~15の整数を表すことが好ましい。
例えば、色素(A)が、一般式(1)におけるmが3で、nが1の色素a1を50質量%と、mが2で、nが2の色素a2を50質量%含有する混合物である場合、mの平均値は、2.5で、nの平均値は、1.5となるが、この混合物に含まれる上記色素a2は、mが1~13の整数で、nが2~14の整数で、m+nが3~15の整数の条件を満たすので、本発明の色素(A)に該当する。
また、色素(A)が、複数の色素(A)の混合物である場合は、mの平均値が1~13で、nの平均値が2~14であることが好ましい。
一般式(1)中、R1は、m+n価の連結基を表す。m+nは3~15を満たす。
R1で表されるm+n価の連結基としては、1から100個までの炭素原子、0個から10個までの窒素原子、0個から50個までの酸素原子、1個から200個までの水素原子、および0個から20個までの硫黄原子から成り立つ基が含まれ、無置換でも置換基を更に有していてもよい。
下記一般式(2)で示される連結基、
下記一般式(3)で示される連結基、
複数の炭素原子からなる主鎖を有する連結基であって、主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、
1つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって、主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、
または、
少なくとも2つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって連続した3つ以上の炭素原子によってヘテロ原子間が隔てられた部分を主鎖中に少なくとも1つ含む連結基、
のいずれかであることが好ましい。
但し、本発明においては、これらに制限されるものではない。
一般式(1)中、Xは、―C(=O)O―、―C(=O)―、―C(=O)NR10―、―O―、―S(=O)―、または、―SO2―を表し、R10は水素原子またはアルキル基を表す。Xが、―C(=O)O―、または―C(=O)NR10―の場合、結合の向きはどちらでも良い。つまり、カルボニル炭素は、Yに結合してもよいし、R1に結合してもよい。
Xは、―C(=O)O―または―O―であることが好ましく、―C(=O)O―であることがより好ましく、―C(=O)O―であってカルボニル炭素がYに結合することが更に好ましい。つまり、Xは、*―C(=O)O―#であり、*はYに結合し#はR1に結合することが更に好ましい。
一般式(1)中、Yは、アルキレン基を表し、アルキレン基は、直鎖状、分岐状、または環状のいずれであっても良く、直鎖状であることが好ましい。また、無置換でもあってもよく、置換基を更に有していてもよいが、無置換が好ましい。置換基としては、R1が有していてもよい置換基で説明したものが挙げられる。Yは、無置換の直鎖アルキレン基であることが好ましい。
L1とX(但し、L1が単結合の場合はDとX)は、Yにより炭素原子数として3以上隔てられていることが好ましく、5以上隔てられていることが更に好ましい。この態様によれば、より耐熱性を向上できる。上限値については、特に定めるものでは無いが、通常、10以下である。
一般式(1)中、L1は、単結合または2価の連結基を表す。
2価の連結基としては、1から100個までの炭素原子、0個から10個までの窒素原子、0個から50個までの酸素原子、1個から200個までの水素原子、および0個から20個までの硫黄原子から成り立つ基が含まれ、無置換でも置換基を更に有していてもよい。
一般式(1)中、R2は、1価の置換基を表し、mが2以上の場合、複数のR2は互いに異なっていても良い。R2としては、繰り返し単位を有さない場合と、繰り返し単位を有する場合の2つの態様がある。
R2により表される、繰り返し単位を有さない1価の置換基としては、例えば、ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、カルボキシル基、アルコキシ基、アリールオキシ基、シリルオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アミノ基(アルキルアミノ基、アニリノ基を含む)、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキル又はアリールスルホニルアミノ基、メルカプト基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルファモイル基、スルホ基、アルキル又はアリールスルフィニル基、アルキル又はアリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、アリール又はヘテロ環アゾ基、イミド基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、シリル基などが挙げられる。以下詳細に記述する。
*-X-Y-L1-RT
R2により表される、繰り返し単位を有する1価の置換基としては、ビニル化合物由来の繰り返し単位、エステル系ポリマー、エーテル系ポリマー、ウレタン系ポリマー、アミド系ポリマー、エポキシ系ポリマー、シリコーン系ポリマー、およびこれらの変性物、または共重合体〔例えば、ポリエーテル/ポリウレタン共重合体、ポリエーテル/ビニル化合物の重合体の共重合体など(ランダム共重合体、ブロック共重合体、グラフト共重合体のいずれであってもよい。)を含む。〕からなる群より選択される少なくとも一種を有することが好ましく、ビニル化合物由来の繰り返し単位、エステル系ポリマー、エーテル系ポリマー、ウレタン系ポリマー、およびこれらの変性物または共重合体からなる群より選択される少なくとも一種を有することがより好ましく、ビニル化合物由来の繰り返し単位を有することが特に好ましい。
mが1の場合におけるビニル化合物由来の繰り返し単位の数、mが2以上の場合、m個のR2のビニル化合物由来の繰り返し単位の個数の平均値は、NMR(Nuclear Magnetic Resonance)により求めることができる。具体的には例えば、R1で表されるm+n価の連結基と色素構造Dとのピーク面積比からmを求め、ビニル化合物由来の繰り返し単位のピーク面積比をmで割ることにより算出することができる。
クロトン酸エステル類としては、クロトン酸ブチル、およびクロトン酸ヘキシル等が挙げられる。
ビニルエステル類としては、ビニルアセテート、ビニルクロロアセテート、ビニルプロピオネート、ビニルブチレート、ビニルメトキシアセテート、および安息香酸ビニルなどが挙げられる。
マレイン酸ジエステル類としては、マレイン酸ジメチル、マレイン酸ジエチル、およびマレイン酸ジブチルなどが挙げられる。
フマル酸ジエステル類としては、フマル酸ジメチル、フマル酸ジエチル、およびフマル酸ジブチルなどが挙げられる。
イタコン酸ジエステル類としては、イタコン酸ジメチル、イタコン酸ジエチル、およびイタコン酸ジブチルなどが挙げられる。
(メタ)アクリルアミド類としては、(メタ)アクリルアミド、N-メチル(メタ)アクリルアミド、N-エチル(メタ)アクリルアミド、N-プロピル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド、N-n-ブチルアクリル(メタ)アミド、N-t-ブチル(メタ)アクリルアミド、N-シクロヘキシル(メタ)アクリルアミド、N-(2-メトキシエチル)(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N-フェニル(メタ)アクリルアミド、N-ニトロフェニルアクリルアミド、N-エチル-N-フェニルアクリルアミド、N-ベンジル(メタ)アクリルアミド、(メタ)アクリロイルモルホリン、ジアセトンアクリルアミド、N-メチロールアクリルアミド、N-ヒドロキシエチルアクリルアミド、ビニル(メタ)アクリルアミド、N,N-ジアリル(メタ)アクリルアミド、N-アリル(メタ)アクリルアミドなどが挙げられる。
スチレン類としては、スチレン、メチルスチレン、ジメチルスチレン、トリメチルスチレン、エチルスチレン、イソプロピルスチレン、ブチルスチレン、ヒドロキシスチレン、メトキシスチレン、ブトキシスチレン、アセトキシスチレン、クロロスチレン、ジクロロスチレン、ブロモスチレン、クロロメチルスチレン、酸性物質により脱保護可能な基(例えば、tert-ブトキシカルボニル基など)で保護されたヒドロキシスチレン、ビニル安息香酸メチル、およびα-メチルスチレンなどが挙げられる。
ビニルエーテル類としては、メチルビニルエーテル、エチルビニルエーテル、2-クロロエチルビニルエーテル、ヒドロキシエチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、ヘキシルビニルエーテル、オクチルビニルエーテル、メトキシエチルビニルエーテルおよびフェニルビニルエーテルなどが挙げられる。
ビニルケトン類の例としては、メチルビニルケトン、エチルビニルケトン、プロピルビニルケトン、フェニルビニルケトンなどが挙げられる。
オレフィン類の例としては、エチレン、プロピレン、イソブチレン、ブタジエン、イソプレンなどが挙げられる。
マレイミド類の例としては、マレイミド、ブチルマレイミド、シクロヘキシルマレイミド、フェニルマレイミドなどが挙げられる。
(メタ)アクリロニトリル、ビニル基が置換した複素環式基(例えば、ビニルピリジン、N-ビニルピロリドン、ビニルカルバゾールなど)、N-ビニルホルムアミド、N-ビニルアセトアミド、N-ビニルイミダゾール、ビニルカプロラクトン等も使用できる。
カルボキシル基を有するビニル化合物として、(メタ)アクリル酸、ビニル安息香酸、マレイン酸、マレイン酸モノアルキルエステル、フマル酸、イタコン酸、クロトン酸、桂皮酸、アクリル酸ダイマーなどが挙げられる。また、2-ヒドロキシエチル(メタ)アクリレートなどの水酸基を有するモノマーと、無水マレイン酸や無水フタル酸、シクロヘキサンジカルボン酸無水物のような環状無水物との付加反応物、ω-カルボキシ-ポリカプロラクトンモノ(メタ)アクリレートなども利用できる。また、カルボキシル基の前駆体として無水マレイン酸、無水イタコン酸、無水シトラコン酸などの無水物含有モノマーを用いてもよい。これらの内では、共重合性やコスト、溶解性などの観点から(メタ)アクリル酸が特に好ましい。
スルホ基を有するビニル化合物として、2-アクリルアミド-2-メチルプロパンスルホン酸などが挙げられる。
リン酸基を有するビニル化合物として、リン酸モノ(2-アクリロイルオキシエチルエステル)、リン酸モノ(1-メチル-2-アクリロイルオキシエチルエステル)などが挙げられる。
酸基としては、カルボキシル基、スルホ基、リン酸基が好ましく、より好ましくはカルボキシル基である。
重合性基としては、ラジカル、酸、熱により架橋可能な公知の重合性基を用いることができ、例えば、エチレン性不飽和結合を含む基、エポキシ基やオキセタン基などの環状エーテル基、メチロール基等が挙げられる。エチレン性不飽和結合を含む基が好ましく、(メタ)アクリロイル基がさらに好ましく、(メタ)アクリル酸グリシジルおよび3,4-エポキシ-シクロヘキシルメチル(メタ)アクリレート由来の(メタ)アクリロイル基が特に好ましい。
一般式(1)中、Dは色素構造を表す。nが2以上の場合、複数のDは互いに異なっていても良い。色素構造としては、カチオン部位と対アニオンとを有する色素構造、または、一分子内にカチオン部位とアニオン部位とを有する色素構造が好ましい。なお、対アニオンとは、色素構造の分子外に存在するアニオンであって、色素構造のカチオン部位と塩を形成しうるアニオンである。例えば、カチオンとアニオンが共有結合を介して結合せず、別化合物として存在している場合をいう。また、一分子内にカチオン部位とアニオン部位とを有するとは、カチオンとアニオンが共有結合を介して結合している場合をいう。一分子内にカチオン部位とアニオン部位とを有する場合、アニオン部位はスルホニルイミドアニオンであることが好ましい。
色素構造を形成しうる具体的な色素化合物については「新版染料便覧」(有機合成化学協会編;丸善、1970)、「カラーインデックス」(The Society of Dyers and colourists)、「色素ハンドブック」(大河原他編;講談社、1986)などに記載されている。
これらの色素構造の中でも、色分離性、耐光性の観点から、ジピロメテン色素、トリアリールメタン色素、キサンテン色素、アントラキノン色素、シアニン色素、スクアリリウム色素、キノフタロン色素、フタロシアニン色素、サブフタロシアニン色素、およびアゾ色素から選ばれる色素構造が好ましく、ジピロメテン色素、トリアリールメタン色素、キサンテン色素、シアニン色素、スクアリリウム色素、アントラキノン色素、キノフタロン色素、フタロシアニン色素、サブフタロシアニン色素、およびアゾ色素から選ばれる色素構造がより好ましく、トリアリールメタン色素およびキサンテン色素が更に好ましい。
以下、本発明で好ましく用いられる色素構造について具体的に説明する。
本発明に用いられる色素構造の態様の一つは、トリアリールメタン色素(トリアリールメタン化合物)に由来する部分構造を有するものである。トリアリールメタン色素としては、下記式(TP)で表される化合物に由来する部分構造を、色素構造として有する。トリアリールメタン化合物とは、分子内にトリアリールメタン骨格を含む色素部位を有する化合物を総称するものである。
a、bまたはcは、それぞれ独立に0~4の整数を表す。特にaおよびbは、それぞれ、0または1が好ましく、cは0~2の整数が好ましい。
式(TP)で表される化合物は、Rtp1~Rtp10のいずれか1つの部位で一般式(1)のL1と結合していることが好ましい。
一般式(P)
一般式(P)中、Lは単結合または2価の連結基を表し、X1は、-SO3 -、-COO-、-PO4 -、下記一般式(A1)で表される構造を含む基および下記一般式(A2)で表される構造を含む基から選択される少なくとも1種から選択される。
一般式(A1)
一般式(A1)中、R1およびR2はそれぞれ独立して-SO2-または-CO-を表す。
一般式(A2)
一般式(A2)中、R3は、-SO2-または-CO-を表す。R4およびR5はそれぞれ独立して-SO2-、-CO-または-CNを表す。
-NR10-において、R10は、水素原子または炭素数1~5のアルキル基を表し、水素原子が好ましい。
フッ素置換アルキレン基の炭素数は、1~10が好ましく、1~6がより好ましく、1~3がさらに好ましい。これらのアルキレン基は、パーフルオロアルキレン基がより好ましい。フッ素置換アルキレン基の具体例としては、ジフルオロメチレン基、テトラフルオロエチレン基、ヘキサフルオロプロピレン基などが挙げられる。
フッ素置換フェニレン基の炭素数は、6~20が好ましく、6~14がより好ましく、6~10がさらに好ましい。フッ素置換フェニレン基の具体例としては、テトラフルオロフェニレン基、ヘキサフルオロ-1-ナフチレン基、ヘキサフルオロ-2-ナフチレン基などが挙げられる。
一般式(A1)で表される構造を含む基は、上述した一般式(A1)中、R1およびR2の一方の末端に、フッ素置換アルキル基を有することが好ましく、R1およびR2の一方が直接フッ素置換アルキル基と結合していることがより好ましい。フッ素置換アルキル基の炭素数は、1~10が好ましく、1~6がより好ましく、1~3がさらに好ましく、1または2がよりさらに好ましく、1が特に好ましい。これらのアルキル基は、パーフルオロアルキル基がより好ましい。フッ素置換アルキル基の具体例としては、トリフルオロメチル基が好ましい。
一般式(A2)で表される構造を含む基は、上述した一般式(A2)中、R3~R5の少なくともいずれかの末端に、フッ素置換アルキル基を有することが好ましく、R3~R5の少なくとも2つが直接フッ素置換アルキル基と結合していることがより好ましい。特に、R3~R5の少なくとも2つの末端に、フッ素置換アルキル基を有することが好ましく、R3~R5の少なくとも2つが直接フッ素置換アルキル基とけ統合していることがより好ましい。フッ素置換アルキル基は、一般式(A1)で表される構造を含む基で説明したものと同義であり、好ましい範囲も同様である。
X1は、一般式(A2)で表される構造を含む基であることが好ましく、スルホニルイミドアニオンがより好ましい。
本発明における色素構造の好ましい態様は、キサンテン色素(キサンテン化合物)に由来する部分構造を有するものである。キサンテン色素としては、下記式(J)で表されるキサンテン化合物に由来する部分構造を、色素構造として有する。
式(J)で表される化合物は、R81~R85のいずれか1つの部位で、一般式(1)のL1と結合していることが好ましい。
上記式(J)中のR81とR82、R83とR84、およびmが2以上の場合のR85同士は、各々独立に、互いに結合して、置換基を有しない5員、6員並びに7員の飽和環または5員、6員並びに7員の不飽和環を形成する場合、置換基を有しない5員、6員並びに7員の飽和環または5員、6員並びに7員の不飽和環としては、例えば、ピロール環、フラン環、チオフェン環、ピラゾール環、イミダゾール環、トリアゾール環、オキサゾール環、チアゾール環、ピロリジン環、ピペリジン環、シクロペンテン環、シクロヘキセン環、ベンゼン環、ピリジン環、ピラジン環、ピリダジン環が挙げられ、好ましくは、ベンゼン環、ピリジン環が挙げられる。
また、X-が存在せず、R81、R82、R83およびR84の少なくとも1つがアニオンを含む場合、対アニオンが同一構成単位内にある場合の記載を参酌できる。
(式(J)で表される化合物の第1の態様)
式(J)で表される化合物は、R81およびR83の一方が下記一般式(4)で表される基であり、R81およびR83の他方が水素原子、下記一般式(4)で表される基または一般式(4)で表される基以外のアリール基、アルキル基を表してもよい。また、R82およびR84は、それぞれ独立に、水素原子、アルキル基、または、アリール基を表してもよい。
一般式(4)
一般式(4)中、R1およびR2は、それぞれ独立に、炭素数3以上のアルキル基、アリール基、または、ヘテロ環基を表し、X1~X3は、それぞれ独立に、水素原子または1価の置換基を表す。一般式(J)で表される色素化合物は、分子内および/または分子外に対アニオンを有する。
炭素数3以上のアルキル基としては、具体的には、直鎖、分岐鎖、又は環状いずれでも良く、炭素数3~24であってもよく、炭素数3~18であってもよく、炭素数3~12であってもよい。具体的には、例えば、プロピル基、イソプロピル基、ブチル基(例えばt-ブチル基)、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、2-エチルヘキシル基、ドデシル基、ヘキサデシル基、シクロプロピル基、シクロペンチル基、シクロヘキシル基、1-ノルボルニル基、1-アダマンチル基が挙げられ、プロピル基、イソプロピル基、ブチル基、t-ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、2-エチルヘキシル基、ドデシル基、シクロプロピル基、シクロペンチル基、シクロヘキシル基であってもよく、プロピル基、イソプロピル基、ブチル基(t-ブチル基)、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、2-エチルヘキシル基であってもよく、イソプロピル基、t-ブチル基、2-エチルヘキシル基であってもよい。
アリール基としては置換もしくは無置換のアリール基が含まれる。置換もしくは無置換のアリール基としては、炭素数6~30のアリール基であってもよく、例えば、フェニル基、ナフチル基が挙げられる。置換基の例としては、後述する置換基群Aと同じである。
ヘテロ環基のヘテロ環としては、5員又は6員環であってもよく、それらは更に縮環していてもよいし、縮環していなくてもよい。また、芳香族ヘテロ環であっても非芳香族ヘテロ環であっても良い。例えば、ピリジン環、ピラジン環、ピリダジン環、キノリン環、イソキノリン環、キナゾリン環、シンノリン環、フタラジン環、キノキサリン環、ピロール環、インドール環、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピラゾール環、イミダゾール環、ベンズイミダゾール環、トリアゾール環、オキサゾール環、ベンズオキサゾール環、チアゾール環、ベンゾチアゾール環、イソチアゾール環、ベンズイソチアゾール環、チアジアゾール環、イソオキサゾール環、ベンズイソオキサゾール環、ピロリジン環、ピペリジン環、ピペラジン環、イミダゾリジン環、チアゾリン環などが挙げられる。中では芳香族ヘテロ環基であってもよく、ピリジン環、ピラジン環、ピリダジン環、ピラゾール環、イミダゾール環、ベンズイミダゾール環、トリアゾール環、ベンズオキサゾール環、チアゾール環、ベンゾチアゾール環、イソチアゾール環、ベンズイソチアゾール環、チアジアゾール環が挙げられ、ピラゾール環、イミダゾール環、ベンズオキサゾール環、チアジアゾール環であってもよく、ピラゾール環、チアジアゾール環(1,3,4-チアジアゾール環、1,2,4-チアジアゾール環)であってもよい。それらは置換基を有していても良く、置換基の例としては、後述するアリール基の置換基と同じである。
R1およびR2は、炭素数3以上のアルキル基であってもよく、炭素数3~12のアルキル基であってもよい。
置換又は無置換のアルキル基は、炭素原子数が1~30のアルキル基であってもよい。置換基の例としては、後述する置換基群Aと同じものが挙げられる。アルキル基の例には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基(t-ブチル基)、n-オクチル基、2-エチルヘキシル基を挙げることができる。
置換もしくは無置換のアリール基としては、炭素数6~30のアリール基であってもよく、例えば、フェニル基、ナフチル基が挙げられる。置換基の例としては、後述する置換基群Aと同じである。
R82およびR84は、水素原子またはアルキル基であってもよく、水素原子であってもよい。
式(J)で表される化合物は、R81およびR83がそれぞれ独立に、脂肪族炭化水素基であり、R82およびR84がそれぞれ独立に、芳香族炭化水素基であってもよい。
R82およびR84はそれぞれ独立に芳香族炭化水素基であり、フェニル基であってもよい。R82およびR84としての芳香族炭化水素基は、置換基を有していても良く、後述する置換基群Aから選択され、炭素数1~5のアルキル基であってもよく、メチル基、エチル基、プロピル基、ブチル基であってもよく、メチル基、エチル基、n-プロピル基、n-ブチル基であってもよい。
R81およびR83ならびにR82およびR84の少なくとも1つが、下記一般式(A1-1-2)で表されてもよい。
一般式(A1-1-2)
一般式(A1-1-2)において、R23~R25は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、アルコキシ基、炭素数1~12のアルキル基、カルボニル基、カルボニルアミド基、スルホニル基、スルホニルアミド基、ニトロ基、アミノ基、アミノカルボニル基、アミノスルホニル基、スルホニルイミド基またはカルボニルイミド基を表し、R22およびR26は、それぞれ独立に炭素数1~5のアルキル基を表す。
一般式(A1-1-2)において、R23~R25は、水素原子またはハロゲン原子であってもよい。
一般式(A1-1-2)において、R22およびR26は、それぞれ独立に炭素数1~5のアルキル基であってもよい。炭素数1~5のアルキル基は、メチル基、エチル基、プロピル基、ブチル基であってもよく、メチル基、エチル基、n-プロピル基、iso-プロピル基、n-ブチル基であってもよい。
R85はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アリール基、カルボニル基、ニトロ基、アミノ基、アルキルアミノ基、アリールアミノ基、または、スルホニル基であってもよい。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子が例示され、フッ素原子または塩素原子であってもよい。脂肪族炭化水素基は、炭素数1~10の脂肪族炭化水素基であってもよい。また、脂肪族炭化水素基は、アルキル基、アルケニル基、アルケニル基が例示され、アルキル基であってもよい。芳香族炭化水素基は、アリール基であってもよく、フェニル基であってもよい。
また、色素構造中、カチオンは、非局在化しているため、例えば以下に示すように、窒素原子またはキサンテン環の炭素原子上に存在してする。
本発明に用いられる色素構造の態様の一つは、アントラキノン色素に由来する部分構造を有するものである。アントラキノン色素(アントラキノン化合物)に由来する部分構造を有するものとしては、下記一般式(AQ-1)~(AQ-3)で表される化合物に由来する部分構造が好ましい。アントラキノン化合物とは、分子内にアントラキノン骨格を含む色素部位を有する化合物を総称するものである。
一般式(AQ-1)、(AQ-2)及び(AQ-3)の好ましい範囲としては、例えば、特開2013-29760号公報の段落0045~0047を参酌することができ、この内容は本願明細書に組み込まれる。
本発明に用いられる色素構造の態様の一つは、シアニン色素(シアニン化合物)に由来する部分構造を有するものである。シアニン色素に由来する部分構造を有するものとしては、下記一般式(PM)で表される化合物(シアニン化合物)に由来する部分構造が好ましい。本発明においてシアニン化合物とは、分子内にシアニン骨格を含む色素部位を有する化合物を総称するものである。
一般式(PM)の好ましい範囲としては、例えば、特開2013-29760号公報の段落0077~0084を参酌することができ、この内容は本願明細書に組み込まれる。なお、特開2013-29760号公報の段落0077~0084に記載のシアニン色素の具体例において、シアニン色素構造中のいずれかの水素原子が、一般式(1)のL1と結合する。
本発明に用いられる色素構造の態様の一つは、スクアリリウム色素(スクアリリウム化合物)に由来する部分構造を有するものである。スクアリリウム色素に由来する部分構造を有するものとしては、下記一般式(K)で表される化合物(スクアリリウム化合物)に由来する部分構造が好ましい。本発明においてスクアリリウム化合物とは、分子内にスクアリリウム骨格を含む色素部位を有する化合物を総称するものである。
一般式(K)の好ましい範囲としては、例えば、特開2013-29760号公報の段落0088~0106を参酌することができ、この内容は本願明細書に組み込まれる。
スクアリリウム色素の具体例としては、例えば、以下が挙げられる。また、例えば、特開2013-29760号公報の段落0105を参酌することができる。なお、スクアリリウム色素の具体例において、スクアリリウム色素構造中のいずれかの水素原子が、一般式(1)のL1と結合する。もしくは、いずれかのハロゲン原子が脱離して、一般式(1)のL1と結合する。
本発明に用いられる色素構造の態様の一つは、キノフタロン色素(キノフタロン化合物)に由来する部分構造を有するものである。キノフタロン色素に由来する部分構造を有するものとしては、下記一般式(QP)で表される化合物(キノフタロン化合物)に由来する部分構造が好ましい。本発明においてキノフタロン化合物とは、分子内にキノフタロン骨格を含む色素部位を有する化合物を総称するものである。
一般式(QP)の好ましい範囲としては、例えば、特開2013-29760号公報の段落0110~0114を参酌することができ、この内容は本願明細書に組み込まれる。
キノフタロン色素の具体例としては、例えば、以下が挙げられる。また、特開2013-29760号公報の段落0113の記載を参照することができる。キノフタロン色素の具体例において、キノフタロン色素構造中のいずれかの水素原子が、一般式(1)のL1と結合する。もしくは、いずれかのハロゲン原子が脱離して、一般式(1)のL1と結合する。
本発明に用いられる色素構造の態様の一つは、フタロシアニン色素(フタロシアニン化合物)に由来する部分構造を有するものである。フタロシアニン色素に由来する部分構造を有するものとしては、下記一般式(F)で表される化合物(フタロシアニン化合物)に由来する部分構造を有するものが好ましい。本発明においてフタロシアニン化合物とは、分子内にフタロシアニン骨格を含む色素部位を有する化合物を総称するものである。
一般式(F)の好ましい範囲としては、例えば、特開2013-29760号公報の段落0118~0124を参酌することができ、この内容は本願明細書に組み込まれる。
フタロシアニン色素の具体例としては、例えば、以下が挙げられる。また、例えば、特開2013-29760号公報の段落0123を参酌することができる。なお、フタロシアニン色素の具体例において、フタロシアニン色素構造中のいずれかの水素原子が、一般式(1)のL1と結合する。
本発明に係る色素構造を有するカチオンの態様の一つは、サブフタロシアニン色素(フタロシアニン化合物)に由来する部分構造を有するものである。サブフタロシアニン色素に由来する部分構造を有するものとしては、下記一般式(SP)で表される化合物(サブフタロシアニン化合物)に由来する部分構造を有するものが好ましい。本発明においてサブフタロシアニン化合物とは、分子内にサブフタロシアニン骨格を含む色素部位を有する化合物を総称するものである。
一般式(SP)の好ましい範囲としては、例えば、特開2013-29760号公報の段落0128~0133を参酌することができ、この内容は本願明細書に組み込まれる。
サブフタロシアニン色素の具体例としては、例えば、以下が挙げられる。また、例えば、特開2013-29760号公報の段落0132に記載を参照できる。サブフタロシアニン色素の具体例において、サブフタロシアニン色素構造中のいずれかの水素原子が、一般式(1)のL1と結合する。もしくは、いずれかのハロゲン原子が脱離して、一般式(1)のL1と結合する。
本発明に係る色素構造の一つは、アゾ色素(アゾ化合物)に由来する部分構造を有するものである。本発明においてアゾ化合物とは、分子内にN=N基を含む色素部位を有する化合物を総称するものである。アゾ色素としては、公知のアゾ色素(例えば、置換アゾベンゼン等)から適宜選択して適用することができる。例えば、アゾ色素としては、特開2013-41097号公報の段落0084~0134の記載、及び特開2011-162760号公報の段落0029~0136の記載を参酌でき、この内容は本明細書に組み込まれる。アゾ色素の具体例としては、例えば、以下が挙げられる。アゾ色素の具体例において、アゾ色素構造中のいずれかの水素原子が、一般式(1)のL1と結合する。もしくは、いずれかのハロゲン原子が脱離して、一般式(1)のL1と結合する。
本発明に係る色素構造の態様の一つは、ジピロメテン色素に由来する部分構造を有するものである。ジピロメテン色素としては、ジピロメテン化合物、および、ジピロメテン化合物と金属または金属化合物とから得られるジピロメテン金属錯体化合物が好ましい。例えば、ジピロメテン色素としては、例えば、下記構造が挙げられる。また、特開2011-95732号公報の段落0033~0136の記載を参酌することができ、この内容は本願明細書に組み込まれる。以下の式中Meはメチル基であり、Buはブチル基であり、Acはアセチル基である。
(置換基群A)
色素構造Dが置換されていてもよい置換基としては、ハロゲン原子(例えば、フッ素、塩素、臭素)、アルキル基(好ましくは炭素数1~48、より好ましくは炭素数1~24の、直鎖、分岐鎖、又は環状のアルキル基で、例えば、メチル、エチル、プロピル、イソプロピル、ブチル基(好ましくは、t-ブチル基)、ペンチル、ヘキシル、ヘプチル、オクチル、2-エチルヘキシル、ドデシル、ヘキサデシル、シクロプロピル、シクロペンチル、シクロヘキシル、1-ノルボルニル、1-アダマンチル)、アルケニル基(好ましくは炭素数2~48、より好ましくは炭素数2~18のアルケニル基で、例えば、ビニル、アリル、3-ブテン-1-イル)、アルキニル基(好ましくは炭素数2~20、より好ましくは炭素数2~12、特に好ましくは炭素数2~8であり、例えばプロパルギル、3-ペンチニル等が挙げられる。)、アリール基(好ましくは炭素数6~48、より好ましくは炭素数6~24のアリール基で、例えば、フェニル、ナフチル)、ヘテロ環基(好ましくは炭素数1~32、より好ましくは炭素数1~18のヘテロ環基で、例えば、2-チエニル、4-ピリジル、2-フリル、2-ピリミジニル、1-ピリジル、2-ベンゾチアゾリル、1-イミダゾリル、1-ピラゾリル、ベンゾトリアゾール-1-イル)、シリル基(好ましくは炭素数3~38、より好ましくは炭素数3~18のシリル基で、例えば、トリメチルシリル、トリエチルシリル、トリブチルシリル、t-ブチルジメチルシリル、t-ヘキシルジメチルシリル)、ヒドロキシル基、シアノ基、ニトロ基、アルコキシ基(好ましくは炭素数1~48、より好ましくは炭素数1~24のアルコキシ基で、例えば、メトキシ、エトキシ、1-ブトキシ、2-ブトキシ、イソプロポキシ、t-ブトキシ、ドデシルオキシ、環状のアルキルオキシ基で、例えば、シクロペンチルオキシ、シクロヘキシルオキシ)、アリールオキシ基(好ましくは炭素数6~48、より好ましくは炭素数6~24のアリールオキシ基で、例えば、フェノキシ、1-ナフトキシ)、ヘテロ環オキシ基(好ましくは炭素数1~32、より好ましくは炭素数1~18のヘテロ環オキシ基で、例えば、1-フェニルテトラゾール-5-オキシ、2-テトラヒドロピラニルオキシ)、シリルオキシ基(好ましくは炭素数1~32、より好ましくは炭素数1~18のシリルオキシ基で、例えば、トリメチルシリルオキシ、t-ブチルジメチルシリルオキシ、ジフェニルメチルシリルオキシ)、アシルオキシ基(好ましくは炭素数2~48、より好ましくは炭素数2~24のアシルオキシ基で、例えば、アセトキシ、ピバロイルオキシ、ベンゾイルオキシ、ドデカノイルオキシ)、アルコキシカルボニルオキシ基(好ましくは炭素数2~48、より好ましくは炭素数2~24のアルコキシカルボニルオキシ基で、例えば、エトキシカルボニルオキシ、t-ブトキシカルボニルオキシ、環状のアルキルオキシカルボニルオキシ基で、例えば、シクロヘキシルオキシカルボニルオキシ)、アリールオキシカルボニルオキシ基(好ましくは炭素数7~32、より好ましくは炭素数7~24のアリールオキシカルボニルオキシ基で、例えば、フェノキシカルボニルオキシ)、
これらの置換基は更に置換されてもよい。また置換基が二つ以上ある場合は、同一でも異なっていても良い。また、可能な場合には互いに連結して環を形成していてもよい。
詳細については、例えば、特開2013-29760号公報の段落0027~0038を参酌することもでき、この内容は本願明細書に組み込まれる。
一般式(1)の色素構造Dが、カチオン部位と対アニオンとで構成される場合、対アニオンとしては特に制限は無いが、耐熱性の観点で非求核性のアニオンであることが好ましい。非求核性の対アニオンとしては、特開2007-310315号公報の段落番号0075等に記載の公知の非求核性アニオンが好ましい。ここで、非求核性とは、加熱により色素を求核攻撃しない性質を意味する。
対アニオンとしては、スルホン酸アニオン、カルボン酸アニオン、スルホニルイミドアニオン、ビス(アルキルスルホニル)イミドアニオン、トリス(アルキルスルホニル)メチドアニオン、カルボン酸アニオン、テトラアリールボレードアニオン、-CON-CO-、-CON-SO2-、BF4 -、PF6 -、SbF6 -、B-(CN)3OCH3から選ばれる少なくとも一種であることが好ましい。より好ましくは、スルホン酸アニオン、スルホニルイミドアニオン、ビス(アルキルスルホニル)イミドアニオン、トリス(アルキルスルホニル)メチドアニオン、カルボン酸アニオン、テトラアリールボレートアニオン、BF4 -、PF6 -、およびSbF6 -から選ばれる少なくとも一種である。
これらの中でも、対アニオンとしては、下記(AN-1)~(AN-5)で表される構造を有する非求核性アニオンであることがより好ましい。
X1およびX2は、それぞれ独立に、フッ素原子またはフッ素原子を有する炭素数1~10のアルキル基を表し、フッ素原子またはフッ素原子を有する炭素数1~10のアルキル基が好ましく、炭素数1~10のペルフルオロアルキル基であることがより好ましく、炭素数1~4のペルフルオロアルキル基であることがさらに好ましく、トリフルオロメチル基が特に好ましい。
X3、X4およびX5は、それぞれ独立に、X1およびX2と同義であり、好ましい範囲も同義である。
X6は、炭素数1~10のペルフルオロアルキル基であることが好ましく、炭素数1~4のペルフルオロアルキル基であることがさらに好ましい。
X7は、炭素数1~10のペルフルオロアルキレン基であることが好ましく、炭素数1~4のペルフルオロアルキレン基であることがさらに好ましい。
Ar1、Ar2、Ar3およびAr4は、それぞれ独立に、炭素数6~20のアリール基が好ましく、炭素数6~14のアリール基がより好ましく、炭素数6~10のアリール基がさらに好ましい。
Ar1、Ar2、Ar3およびAr4が表わすアリール基は、置換基を有しても良い。置換基を有する場合、ハロゲン原子、アルキル基、アリール基、アルコキシ基、カルボニル基、カルボニルオキシ基、カルバモイル基、スルホ基、スルホンアミド基、ニトロ基等が挙げられ、ハロゲン原子およびアルキル基が好ましく、フッ素原子、アルキル基がより好ましく、フッ素原子、炭素数1~4のペルフルオロアルキル基がさらに好ましい。
Ar1、Ar2、Ar3およびAr4は、それぞれ独立に、ハロゲン原子および/またはハロゲン原子を有するアルキル基を有するフェニル基がより好ましく、フッ素原子および/またはフッ素を有するアルキル基を有するフェニル基がさらに好ましい。
n1は、1~3が好ましく、1~2がより好ましい。
n2は、1~4の整数が好ましく、1または2がより好ましい。
本発明の色素(A)は、非求核性対アニオンを1種類のみ含んでいても良いし、2種類以上を含んでいても良い。
重合性基としては、ラジカル、酸、熱により架橋可能な公知の重合性基を用いることができ、例えば、エチレン性不飽和結合を含む基、環状エーテル基(エポキシ基、オキセタン基)、メチロール基等が挙げられるが、特にエチレン性不飽和結合を含む基が好ましく、(メタ)アクリロイル基がさらに好ましく、(メタ)アクリル酸グリシジルおよび3,4-エポキシーシクロヘキシルメチル(メタ)アクリレート由来の(メタ)アクリロイル基が特に好ましい。
R1が、例として上述した(1)~(6)、および(9)~(11)から選ばれる連結基であり、
Xが、―C(=O)O―または―O―であり、
Yが、無置換のアルキレン基であり、
L1が、―S―を少なくとも1個含む、2価の連結基であり、R2が、カルボキシル基および(メタ)アクリロイル基を有するビニル化合物由来の繰り返し単位を含有する置換基であって、繰り返し単位の個数の平均値が、2~20個であり、
Dが、トリアリールメタン色素、キサンテン色素、アントラキノン色素、シアニン色素、スクアリリウム色素、キノフタロン色素、フタロシアニン色素、サブフタロシアニン色素、アゾ色素およびジピロメテン色素から選ばれる色素構造であることが好ましい。
色素(A)の重量平均分子量は、2000~15000が好ましく、3000~12500がより好ましく、5000~11000がさらに好ましい。重量平均分子量が上記範囲であれば、色移り性がより良好である。さらには、現像性が向上して、現像残渣の発生をより低減できる。
有機溶剤としては、エステル類(例えば、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、乳酸エチル、酢酸ブチル、3-メトキシプロピオン酸メチル等)、エーテル類(例えばメチルセロソルブアセテート、エチルセロソルブアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等)、ケトン類(メチルエチルケトン、シクロヘキサノン、2-ヘプタノン、3-ヘプタノン等)、芳香族炭化水素類(例えば、トルエン、キシレン等)が挙げられ、これら溶剤に対し、1~50質量%溶解することが好ましく、5~40質量%溶解することがより好ましく、10~30質量%溶解することが特に好ましい。この範囲にあることで、本発明の着色組成物をカラーフィルタ等の作製に適用する際に、好適な塗布面状や、他色塗布後の溶出による濃度低下をより低減できる。
本発明に係る色素(A)は、Al、Ca、Cu、Cr、Mg、Fe、Mn、Ni、Co、Cd、Li、Pb、Na、K、ZnおよびPから選ばれる金属であって、色素(A)に結合または配位していない遊離の金属の含有量が2ppm以下であることが好ましい。また、上記遊離の金属の合計含有量は、2ppm以下であることが好ましい。この態様によれば、欠陥の少ないカラーフィルタを製造しやすい。なお、色素(A)中における上記遊離の金属の含有量は、既知の解析手段を適宜用いて測定することが可能であるが、可能な限りにおいて、誘導結合プラズマ発光分光により測定することが好ましい。
本発明に係る色素(A)は、色素(A)に結合または配位していない遊離のBr含有量は、900ppm以下が好ましく、600ppm以下がより好ましい。また、色素(A)に結合または配位していない遊離のCl含有量は、900ppm以下が好ましく、600ppm以下がより好ましく、300ppm以下が更に好ましい。また、上記遊離のBrと遊離のClとの合計含有量は、1500ppm以下が好ましく、900ppm以下がより好ましい。この態様によれば、欠陥の少ないカラーフィルタを製造しやすい。なお、色素(A)中における上記遊離のBr含有量および上記遊離のCl含有量は、既知の解析手段を適宜用いて測定することが可能であるが、可能な限りにおいては、ハロゲン量測定BS EN 14582に準拠した燃焼イオンクロマトグラフ法に準拠して測定することが好ましい。
顔料に対する色素の質量比(色素(A)/顔料)としては、0.1~5が好ましく、0.2~2がよりに好ましく、0.3~1がさらに好ましい。
本発明の着色組成物中における色素(A)の含有量は、着色組成物中の全固形分に対して1.0~50質量%が好ましく、5.0~30質量%がさらに好ましく、10~25質量%が特に好ましい。
本発明の色素(A)の色素構造Dが、キサンテン色素、アゾ色素、スクアリリウム色素(好ましくはキサンテン色素)である場合は、赤色着色剤(好ましくは赤色顔料)や黄色着色剤(好ましくは黄色顔料)との併用により、赤色着色組成物をなすことができる。この場合、本発明の色素(A)と、赤色着色剤及び黄色着色剤の合計の比率(質量比)は、10:90~90:10であることが好ましい。
上記一般式(1)で表される色素は、特に制限されないが、下記方法などにより合成することができる。
(1)カルボキシル基、ヒドロキシル基、アミノ基等から選択される官能基を末端に導入したポリマーと、色素構造を有する酸ハライド、色素構造を有するアルキルハライド、あるいは色素構造を有するイソシアネート等と、を高分子反応させる方法。
(2)末端に炭素-炭素二重結合を導入したポリマーと、色素構造を有するメルカプトと、をマイケル付加反応させる方法。
(3)末端に炭素-炭素二重結合を導入したポリマーと、色素構造を有するメルカプトと、をラジカル発生剤存在下で反応させる方法。
(4)末端に複数のメルカプトを導入したポリマーと、炭素-炭素二重結合および色素構造とを有する化合物と、をラジカル発生剤存在下で反応させる方法。
(5)色素構造を有するメルカプト化合物存在下で、ビニル化合物をラジカル重合する方法。
(D―L1―Y―X―)n-R3-(SH)m一般式(3)中、R3は、m+n価の連結基を表し、Sは、硫黄原子を表し、SHは、メルカプト基を表し、Xは、―C(=O)O―、―C(=O)―、―C(=O)NR10―、―O―、―S(=O)―、または、―SO2―を表し、R10は水素原子またはアルキル基
を表す。Yは、アルキレン基を表し、L1は、単結合または2価の連結基を表し、Dは、色素構造を表し、mは、1~13の整数を表し、nは、2~14の数を表し、m+nは、3~15の整数を表し、nが2以上の場合、複数のDは互いに異なっていても良い。
(6)色素構造を有するハライド化合物からメルカプト化合物に変換する方法(チオ尿素と反応させ、加水分解する方法、NaSHと直接反応させる方法、CH3COSNaと反応させ、加水分解させる方法などが挙げられる)
(7)一分子中に3~15個のメルカプト基を有する化合物に、色素構造を有し、かつメルカプト基と反応可能な官能基を有する化合物を付加反応もしくは置換反応させる方法
「メルカプト基と反応可能な官能基」がアリールハライドもしくはアルキルハライドであり、置換反応である、もしくは炭素-炭素二重結合であり、付加反応がラジカル付加反応であることが好ましい。なお、炭素-炭素二重結合としては、メルカプト基との反応性の点で、1置換もしくは2置換のビニル基がより好ましい。
例えば、メタノール、エタノール、プロパノール、イソプロパノール、1-メトキシ-2-プロパノール、1-メトキシ-2-プロピルアセテート、アセトン、メチルエチルケトン、メチルイソブチルケトン、メトキシプロピルアセテート、乳酸エチル、酢酸エチル、アセトニトリル、テトラヒドロフラン、ジメチルホルムアミド、ジメチルアセトアミド、クロロホルム、トルエン、N-メチルピロリドン(NMP)、N-エチルピロリドン(NEP)、1,3-ジメチル-2-イミダゾリジノン(DMI)、ピリジンが挙げられる。これらの溶媒は、二種以上を混合して使用してもよい。
ビニル化合物は一種のみで重合させてもよいし、二種以上を併用して共重合させてもよい。
また、アルカリ現像処理が必要な光硬化性組成物に適用する場合、1種以上の酸基を有するビニル化合物と、1種以上の酸基を有さないビニル化合物と、を共重合させることがより好ましい。
例えば、これらのビニル化合物、および連鎖移動剤を適当な溶媒中に溶解し、ここにラジカル重合開始剤を添加して、約50℃~220℃で、溶液中で重合させる方法(溶液重合法)を利用して得られる。
<<<重合性化合物>>>
本発明の着色組成物は、硬化性化合物を含有する。硬化性化合物としては、ラジカル、酸、熱により架橋可能な公知の重合性化合物を用いることができる。例えば、エチレン性不飽和結合、環状エーテル(エポキシ、オキセタン)、メチロール等を含む重合性化合物が挙げられる。重合性化合物は、感度の観点から、末端エチレン性不飽和結合を少なくとも1個、好ましくは2個以上有する化合物から好適に選ばれる。中でも、4官能以上の多官能重合性化合物が好ましく、5官能以上の多官能重合性化合物がさらに好ましい。
これらの具体的な化合物としては、特開2009-288705号公報の段落番号〔0095〕~〔0108〕に記載されている化合物を本発明においても好適に用いることができる。
酸基を有する重合性化合物の好ましい酸価としては、0.1mgKOH/g~40mgKOH/gであり、特に好ましくは5mgKOH/g~30mgKOH/gである。多官能モノマーの酸価が0.1mgKOH/g以上であれば、現像溶解特性が良好であり、40mgKOH/g以下であれば、製造や取扱い上、有利である。さらには、光重合性能が良好で、画素の表面平滑性等の硬化性に優れる。従って、異なる酸基の重合性化合物を2種以上併用する場合、或いは酸基を有しない重合性化合物と酸基を有する重合性化合物とを併用する場合、全体の重合性化合物としての酸基が上記範囲に入るように調整することが好ましい。
カプロラクトン構造を有する重合性化合物としては、分子内にカプロラクトン構造を有する限り特に限定されるものではないが、例えば、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール、トリメチロールメラミン等の多価アルコールと、(メタ)アクリル酸及びε-カプロラクトンをエステル化することにより得られる、ε-カプロラクトン変性多官能(メタ)アクリレートを挙げることができる。なかでも下記一般式(Z-1)で表されるカプロラクトン構造を有する重合性化合物が好ましい。
本発明において、カプロラクトン構造を有する重合性化合物は、単独で又は2種以上を混合して使用することができる。
一般式(Z-4)中、アクリロイル基及びメタクリロイル基の合計は3個又は4個であり、mは各々独立に0~10の整数を表し、各mの合計は0~40の整数である。但し、各mの合計が0の場合、Xのうちいずれか1つはカルボキシル基である。
一般式(Z-5)中、アクリロイル基及びメタクリロイル基の合計は5個又は6個であり、nは各々独立に0~10の整数を表し、各nの合計は0~60の整数である。但し、各nの合計が0の場合、Xのうちいずれか1つはカルボキシル基である。
また、各mの合計は、2~40の整数が好ましく、2~16の整数がより好ましく、4~8の整数が特に好ましい。
一般式(Z-5)中、nは、0~6の整数が好ましく、0~4の整数がより好ましい。
また、各nの合計は、3~60の整数が好ましく、3~24の整数がより好ましく、6~12の整数が特に好ましい。
また、一般式(Z-4)又は一般式(Z-5)中の-((CH2)yCH2O)-又は-((CH2)yCH(CH3)O)-は、酸素原子側の末端がXに結合する形態が好ましい。
具体的には、下記式(a)~(f)で表される化合物(以下、「例示化合物(a)~(f)」とも称する。)が挙げられ、中でも、例示化合物(a)、(b)、(e)、(f)が好ましい。
また、エポキシ基は、連結基を介して連結していることが好ましい。連結基としては、アルキレン基、アリーレン基、-O-、-NR’-(R’は、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表し、水素原子が好ましい)で表される構造、-SO2-、-CO-、-O-および-S-から選ばれる少なくとも一つを含む基が挙げられる。
アルキル基は、直鎖、分岐及び環状の何れにも限定されないが、直鎖または分岐が好ましく、直鎖が特に好ましい。
アルキル基は、置換基を有していてもよく、無置換であってもよい。無置換が好ましい。
アルキル基が有してもよい置換基としては、例えば、アルキル基(好ましくは炭素数1~48、より好ましくは炭素数1~24の、直鎖、分岐鎖、または環状のアルキル基で、例えば、メチル、エチル、プロピル、イソプロピル、n-ブチル、tert-ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、2-エチルヘキシル、ドデシル、ヘキサデシル、シクロプロピル、シクロペンチル、シクロヘキシル、1-ノルボルニル、1-アダマンチル)、アルケニル基(好ましくは炭素数2~48、より好ましくは炭素数2~18のアルケニル基で、例えば、ビニル、アリル、3-ブテン-1-イル)、アルキニル基(好ましくは炭素数2~20、より好ましくは炭素数2~12、特に好ましくは炭素数2~8であり、例えばプロパルギル、3-ペンチニル等が挙げられる。)、アリール基(好ましくは炭素数6~48、より好ましくは炭素数6~24のアリール基で、例えば、フェニル、ナフチル)、ヘテロ環基(好ましくは炭素数1~32、より好ましくは炭素数1~18のヘテロ環基で、例えば、2-チエニル、4-ピリジル、2-フリル、2-ピリミジニル、1-ピリジル、2-ベンゾチアゾリル、1-イミダゾリル、1-ピラゾリル、ベンゾトリアゾール-1-イル)、シリル基(好ましくは炭素数3~38、より好ましくは炭素数3~18のシリル基で、例えば、トリメチルシリル、トリエチルシリル、トリブチルシリル、tert-ブチルジメチルシリル、tert-ヘキシルジメチルシリル)、ヒドロキシル基、シアノ基、ニトロ基、アルコキシ基(好ましくは炭素数1~48、より好ましくは炭素数1~24のアルコキシ基、さらに好ましくは炭素数1~3のアルコキシ基で、例えば、メトキシ、エトキシ、1-ブトキシ、2-ブトキシ、イソプロポキシ、tert-ブトキシ、ドデシルオキシ、環状のアルキルオキシ基で、例えば、シクロペンチルオキシ、シクロヘキシルオキシ)、アリールオキシ基(好ましくは炭素数6~48、より好ましくは炭素数6~24のアリールオキシ基で、例えば、フェノキシ、1-ナフトキシ)、ヘテロ環オキシ基(好ましくは炭素数1~32、より好ましくは炭素数1~18のヘテロ環オキシ基で、例えば、1-フェニルテトラゾール-5-オキシ、2-テトラヒドロピラニルオキシ)、シリルオキシ基(好ましくは炭素数1~32、より好ましくは炭素数1~18のシリルオキシ基で、例えば、トリメチルシリルオキシ、tert-ブチルジメチルシリルオキシ、ジフェニルメチルシリルオキシ)、アシルオキシ基(好ましくは炭素数2~48、より好ましくは炭素数2~24のアシルオキシ基で、例えば、アセトキシ、ピバロイルオキシ、2-エチルヘキサノイルオキシ基、2-メチルプロパノイルオキシ基、オクタノイルオキシ基、ブタノイルオキシ基、2-メチルブタノイルオキシ基、ベンゾイルオキシ、ドデカノイルオキシ)、アルコキシカルボニルオキシ基(好ましくは炭素数2~48、より好ましくは炭素数2~24のアルコキシカルボニルオキシ基で、例えば、エトキシカルボニルオキシ、tert-ブトキシカルボニルオキシ、環状のアルキルオキシカルボニルオキシ基で、例えば、シクロヘキシルオキシカルボニルオキシ)、アリールオキシカルボニルオキシ基(好ましくは炭素数7~32、より好ましくは炭素数7~24のアリールオキシカルボニルオキシ基で、例えば、フェノキシカルボニルオキシ)、カルバモイルオキシ基(好ましくは炭素数1~48、よりこの好ましくは炭素数1~24のカルバモイルオキシ基で、例えば、N,N-ジメチルカルバモイルオキシ、N-ブチルカルバモイルオキシ、N-フェニルカルバモイルオキシ、N-エチル-N-フェニルカルバモイルオキシ)、スルファモイルオキシ基(好ましくは炭素数1~32、より好ましくは炭素数1~24のスルファモイルオキシ基で、例えば、N,N-ジエチルスルファモイルオキシ、N-プロピルスルファモイルオキシ)、アルキルスルホニルオキシ基(好ましくは炭素数1~38、より好ましくは炭素数1~24のアルキルスルホニルオキシ基で、例えば、メチルスルホニルオキシ、ヘキサデシルスルホニルオキシ、シクロヘキシルスルホニルオキシ)、アリールスルホニルオキシ基(好ましくは炭素数6~32、より好ましくは炭素数6~24のアリールスルホニルオキシ基で、例えば、フェニルスルホニルオキシ)、アシル基(好ましくは炭素数1~48、より好ましくは炭素数1~24のアシル基で、例えば、ホルミル、アセチル、ピバロイル、ベンゾイル、テトラデカノイル、シクロヘキサノイル)、アルコキシカルボニル基(好ましくは炭素数2~48、より好ましくは炭素数2~24のアルコキシカルボニル基で、例えば、メトキシカルボニル、エトキシカルボニル、オクタデシルオキシカルボニル、シクロヘキシルオキシカルボニル、2,6-ジ-tert-ブチル-4-メチルシクロヘキシルオキシカルボニル)、アリールオキシカルボニル基(好ましくは炭素数7~32、より好ましくは炭素数7~24のアリールオキシカルボニル基で、例えば、フェノキシカルボニル)、カルバモイル基(好ましくは炭素数1~48、より好ましくは炭素数1~24のカルバモイル基で、例えば、カルバモイル、N,N-ジエチルカルバモイル、Nーエチル-N-オクチルカルバモイル、N,N-ジブチルカルバモイル、N-プロピルカルバモイル、N-フェニルカルバモイル、N-メチルN-フェニルカルバモイル、N,N-ジシクロへキシルカルバモイル)、アミノ基(好ましくは炭素数32以下、より好ましくは炭素数24以下のアミノ基で、例えば、アミノ、メチルアミノ、N,N-ジブチルアミノ、テトラデシルアミノ、2-エチルへキシルアミノ、シクロヘキシルアミノ)、アニリノ基(好ましくは炭素数6~32、より好ましくは6~24のアニリノ基で、例えば、アニリノ、N-メチルアニリノ)、ヘテロ環アミノ基(好ましくは炭素数1~32、より好ましくは1~18のヘテロ環アミノ基で、例えば、4-ピリジルアミノ)、カルボンアミド基(好ましくは炭素数2~48、より好ましくは2~24のカルボンアミド基で、例えば、アセトアミド、ベンズアミド、テトラデカンアミド、ピバロイルアミド、シクロヘキサンアミド)、ウレイド基(好ましくは炭素数1~32、より好ましくは炭素数1~24のウレイド基で、例えば、ウレイド、N,N-ジメチルウレイド、N-フェニルウレイド)、イミド基(好ましくは炭素数36以下、より好ましくは炭素数24以下のイミド基で、例えば、N-スクシンイミド、N-フタルイミド)、アルコキシカルボニルアミノ基(好ましくは炭素数2~48、より好ましくは炭素数2~24のアルコキシカルボニルアミノ基で、例えば、メトキシカルボニルアミノ、エトキシカルボニルアミノ、tert-ブトキシカルボニルアミノ、オクタデシルオキシカルボニルアミノ、シクロヘキシルオキシカルボニルアミノ)、アリールオキシカルボニルアミノ基(好ましくは炭素数7~32、より好ましくは炭素数7~24のアリールオキシカルボニルアミノ基で、例えば、フェノキシカルボニルアミノ)、スルホンアミド基(好ましくは炭素数1~48、より好ましくは炭素数1~24のスルホンアミド基で、例えば、メタンスルホンアミド、ブタンスルホンアミド、ベンゼンスルホンアミド、ヘキサデカンスルホンアミド、シクロヘキサンスルホンアミド)、スルファモイルアミノ基(好ましくは炭素数1~48、より好ましくは炭素数1~24のスルファモイルアミノ基で、例えば、N、N-ジプロピルスルファモイルアミノ、N-エチル-N-ドデシルスルファモイルアミノ)、アゾ基(好ましくは炭素数1~32、より好ましくは炭素数1~24のアゾ基で、例えば、フェニルアゾ、3-ピラゾリルアゾ)、アルキルチオ基(好ましくは炭素数1~48、より好ましくは炭素数1~24のアルキルチオ基で、例えば、メチルチオ、エチルチオ、オクチルチオ、シクロヘキシルチオ)、アリールチオ基(好ましくは炭素数6~48、より好ましくは炭素数6~24のアリールチオ基で、例えば、フェニルチオ)、ヘテロ環チオ基(好ましくは炭素数1~32、より好ましくは炭素数1~18のヘテロ環チオ基で、例えば、2-ベンゾチアゾリルチオ、2-ピリジルチオ、1-フェニルテトラゾリルチオ)、アルキルスルフィニル基(好ましくは炭素数1~32、より好ましくは炭素数1~24のアルキルスルフィニル基で、例えば、ドデカンスルフィニル)、アリールスルフィニル基(好ましくは炭素数6~32、より好ましくは炭素数6~24のアリールスルフィニル基で、例えば、フェニルスルフィニル)、アルキルスルホニル基(好ましくは炭素数1~48、より好ましくは炭素数1~24のアルキルスルホニル基で、例えば、メチルスルホニル、エチルスルホニル、プロピルスルホニル、ブチルスルホニル、イソプロピルスルホニル、2-エチルヘキシルスルホニル、ヘキサデシルスルホニル、オクチルスルホニル、シクロヘキシルスルホニル)、アリールスルホニル基(好ましくは炭素数6~48、より好ましくは炭素数6~24のアリールスルホニル基で、例えば、フェニルスルホニル、1-ナフチルスルホニル)、スルファモイル基(好ましくは炭素数32以下、より好ましくは炭素数24以下のスルファモイル基で、例えば、スルファモイル、N,N-ジプロピルスルファモイル、N-エチル-N-ドデシルスルファモイル、N-エチル-N-フェニルスルファモイル、N-シクロヘキシルスルファモイル)、スルホ基、ホスホニル基(好ましくは炭素数1~32、より好ましくは炭素数1~24のホスホニル基で、例えば、フェノキシホスホニル、オクチルオキシホスホニル、フェニルホスホニル)、ホスフィノイルアミノ基(好ましくは炭素数1~32、より好ましくは炭素数1~24のホスフィノイルアミノ基で、例えば、ジエトキシホスフィノイルアミノ、ジオクチルオキシホスフィノイルアミノ)、等が挙げられる。これらの置換基はさらに置換されてもよい。また置換基が二つ以上ある場合は、同一でも異なっていても良い。また、可能な場合には互いに連結して環を形成していてもよい。
アルコキシ基は、置換基を有していてもよく、無置換であってもよい。無置換が好ましい。置換基の具体例としては、アルキル基が有していてもよい置換基と同様のものが挙げられる。
2価の連結基としては、アルキレン基、アリーレン基、-O-、-NR’-(R’は、水素原子、置換基を有していてもよいアルキル基または置換基を有していてもよいアリール基を表し、水素原子が好ましい)で表される構造、-SO2-、-CO-、-O-および-S-から選ばれる少なくとも一つを含む基が挙げられる。これらは、置換基を有してもよい。置換基としては、上述したR1~R13におけるアルキル基が有していてもよい置換基で説明したものと同様のものが挙げられる。
アルキレン基の炭素数は、1~30が好ましく、1~12がより好ましい。
アリーレン基の炭素数は、6~30が好ましく、6~12がより好ましい。
一般式(E1a)のR1~R19は、上記一般式(E1)のR1~R13と同義である。
特に、R1~R19は、それぞれ独立に水素原子、メチル基、エチル基またはメトキシ基のいずれかが好ましい。また、より好ましくは、R13、R18およびR19から選ばれる1以上がメチル基である。更に好ましくは、R13、R18およびR19がメチル基で、R1~R12、R14~R17が水素原子である。
QEPは単結合若しくはnEP価の有機基を表す。REP1~REP3は、QEPとも結合して環構造を形成していても良い。
nEPは2以上の整数を表し、好ましくは2~10、更に好ましくは2~6である。但しQEPが単結合の場合、nEPは2である。
これらの化合物は、市販品を用いてもよいし、ポリマーの側鎖へエポキシ基を導入することによっても得られる。
また、エポキシ基を有する化合物の市販品としては、JER1031S(三菱化学(株)製)、JER1032H60(三菱化学(株)製)、EPICLON HP-4700
(DIC(株)社製)、EPICLON N-695(DIC(株)社製)、EPICLON840(DIC(株)社製)、EPICLON N660(DIC(株)社製)、EPICLON HP7200(DIC(株)社製)等も好ましく用いることができる。
エポキシ不飽和化合物としては、グリシジル(メタ)アクリレートやアリルグリシジルエーテル等のエポキシ基としてグリシジル基を有するものも使用可能であるが、脂環式エポキシ基を有する不飽和化合物であることが好ましい。このようなものとしては、例えば以下の化合物を例示することができる。
本発明の着色組成物が、エポキシ基を有する化合物を含有する場合、着色組成物中におけるエポキシ基を有する化合物の総含量としては、着色組成物の全固形分(質量)に対して、0.1~20質量%が好ましく、0.1~10質量%がより好ましく、0.5~5質量%が特に好ましい。
また、本発明では重合性化合物としてオキセタン基を有する化合物を用いることもできる。オキセタン基を有する化合物としては、特開2008-224970号公報の段落0134~0145記載の化合物が挙げられ、その内容は本明細書に組み込まれる。具体例としては、アロンオキセタンOXT-121、OXT-221、OX-SQ、PNOX(以上、東亞合成(株)製)を用いることができる。
重合性化合物の市販品としては、ウレタンオリゴマーUAS-10、UAB-140(山陽国策パルプ社製)、UA-7200」(新中村化学社製、DPHA-40H(日本化薬社製)、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600(共栄社製)などが挙げられる。
本発明において、顔料とは、溶剤に溶解しにくい不溶性の色素化合物を意味する。典型的には、組成物中に粒子として分散された状態で存在する色素化合物を意味する。ここで、溶剤とは、任意の溶剤が挙げられ、例えば後述する溶剤の欄で例示する溶剤が挙げられる。本発明に用いられる顔料は、例えば、プロプレングリコールモノメチルエーテルアセテ-トおよび水のいずれに対しても、25℃における溶解度が0.1g/100gSolvent以下が好ましい。
上述した色素(A)以外の公知の染料としては、例えば特開昭64-90403号公報、特開昭64-91102号公報、特開平1-94301号公報、特開平6-11614号公報、特登2592207号、米国特許4808501号明細書、米国特許5667920号明細書、米国特許505950号明細書、米国特許5667920号明細書、特開平5-333207号公報、特開平6-35183号公報、特開平6-51115号公報、特開平6-194828号公報等に開示されている色素を使用できる。化学構造としては、ピラゾールアゾ系、ピロメテン系、アニリノアゾ系、トリアリールメタン系、アントラキノン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系等の染料を使用できる。
また、染料としては色素多量体を用いてもよい。色素多量体としては、特開2011-213925号公報、特開2013-041097号公報に記載されている化合物が挙げられる。
上述した色素(A)以外の顔料としては、従来公知の種々の無機顔料または有機顔料を用いることができ、有機顔料を用いることが好ましい。顔料としては、高透過率であることが好ましい。
C.I.ピグメントイエロー11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199,;
C.I.ピグメントオレンジ36,38,43,71;
C.I.ピグメントレッド81,105,122,149,150,155,171,175,176,177,179,209,220,224,242,254,255,264,270;
C.I.ピグメントバイオレット19,23,32,39;
C.I.ピグメントブルー1,2,15,15:1,15:3,15:6,16,22,60,66;
C.I.ピグメントグリーン7,36,37,58,59;C.I.ピグメントブラウン25,28;
C.I.ピグメントブラック1;等を挙げることができる。
C.I.ピグメントイエロー11,24,108,109,110,138,139,150,151,154,167,180,185,
C.I.ピグメントオレンジ36,71,
C.I.ピグメントレッド122,150,171,175,177,209,224,242,254,255,264,
C.I.ピグメントバイオレット19,23,32,
C.I.ピグメントブルー15:1,15:3,15:6,16,22,60,66,
C.I.ピグメントグリーン7,36,37,58,59;
C.I.ピグメントブラック1,7
顔料の一次粒子サイズは、電子顕微鏡等の公知の方法で測定することができる。
中でも、顔料としては、アントラキノン系顔料、ジケトピロロピロール系顔料、フタロシアニン系顔料、キノフタロン系顔料、イソインドリン系顔料、アゾメチン系顔料、およびジオキサジン系顔料から選ばれる顔料であることが好ましい。特に、C.I.ピグメントレッド177(アントラキノン系顔料),C.I.ピグメントレッド254(ジケトピロロピロール系顔料)、C.I.ピグメントグリーン7,36,58、C.I.ピグメントブルー15:6(フタロシアニン系顔料)、C.I.ピグメントイエロー138(キノフタロン系顔料)、C.I.ピグメントイエロー139,185(イソインドリン系顔料)、C.I.ピグメントイエロー150(アゾメチン系顔料)、C.I.ピグメントバイオレット23(ジオキサジン系顔料)が特に好ましい。
本発明の着色組成物は、顔料を、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。
本発明の着色組成物は、顔料を含む場合、顔料分散剤を含有することが好ましい。
顔料分散剤としては、高分子分散剤〔例えば、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ(メタ)アクリレート、(メタ)アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物〕、及び、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、アルカノールアミン等の界面活性剤、及び、顔料誘導体等を挙げることができる。
高分子分散剤は、その構造から更に直鎖状高分子、末端変性型高分子、グラフト型高分子、ブロック型高分子に分類することができる。
具体的には、高分子分散剤を用いる場合であれば、その使用量としては、顔料100質量部に対して、5~100質量部が好ましく、10~80質量部がより好ましい。
また、顔料誘導体を併用する場合、顔料誘導体の使用量としては、顔料100質量部に対し、1~30質量部が好ましく、3~20質量部がより好ましく、5~15質量部が特に好ましい。
本発明の着色組成物は、さらに、アルカリ可溶性樹脂を含有してもよい。
アルカリ可溶性樹脂としては、線状有機高分子重合体であって、分子(好ましくは、アクリル系共重合体、スチレン系共重合体を主鎖とする分子)中に少なくとも1つのアルカリ可溶性を促進する基を有するアルカリ可溶性樹脂の中から適宜選択することができる。耐熱性の観点からは、ポリヒドロキシスチレン系樹脂、ポリシロキサン系樹脂、アクリル系樹脂、アクリルアミド系樹脂、アクリル/アクリルアミド共重合体樹脂が好ましく、現像性制御の観点からは、アクリル系樹脂、アクリルアミド系樹脂、アクリル/アクリルアミド共重合体樹脂が好ましい。
一般式(ED2)
一般式(ED2)中、Rは、水素原子または炭素数1~30の有機基を表す。一般式(ED2)の具体例としては、特開2010-168539号公報の記載を参酌できる。
]ビス-2-プロペノエート、ジ(n-プロピル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジ(イソプロピル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジ(n-ブチル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジ(イソブチル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジ(tert-ブチル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジ(tert-アミル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジ(ステアリル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジ(ラウリル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジ(2-エチルヘキシル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジ(1-メトキシエチル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジ(1-エトキシエチル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジベンジル-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジフェニル-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジシクロヘキシル-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジ(tert-ブチルシクロヘキシル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジ(ジシクロペンタジエニル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジ(トリシクロデカニル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジ(イソボルニル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジアダマンチル-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジ(2-メチル-2-アダマンチル)-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート等が挙げられる。これらの中でも特に、ジメチル-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジエチル-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジシクロヘキシル-2,2'-[オキシビス(メチレン)]ビス-2-プロペノエート、ジベンジル-2,2'-[オキシビス
(メチレン)]ビス-2-プロペノエートが好ましい。これらエーテルダイマーは、1種のみであってもよいし、2種以上であってもよい。一般式(ED)で示される化合物由来の構造体は、その他のモノマーを共重合させてもよい。
一般式(X)
(式(X)において、R1は、水素原子またはメチル基を表し、R2は炭素数2~10のアルキレン基を表し、R3は、水素原子またはベンゼン環を含んでもよい炭素数1~20のアルキル基を表す。nは1~15の整数を表す。)
さらに、特開2012-32767号公報に記載の段落番号0029~0063に記載の共重合体(B)および実施例で用いられているアルカリ可溶性樹脂、特開2012-208474号公報の段落番号0088~0098に記載のバインダー樹脂および実施例で用いられているバインダー樹脂、特開2012-137531号公報の段落番号0022~0032に記載のバインダー樹脂および実施例で用いられているバインダー樹脂、特開2013-024934号公報の段落番号0132~0143に記載のバインダー樹脂および実施例で用いられているバインダー樹脂、特開2011-242752号公報の段落番号0092~0098および実施例で用いられているバインダー樹脂、特開2012-032770号公報の段落番号0030~0072の記載のバインダー樹脂を用いること好ましい。これらの内容は本願明細書に組み込まれる。より具体的には、下記の樹脂が好ましい。
また、アルカリ可溶性樹脂の重量平均分子量(Mw)としては、2,000~50,000が好ましく、5,000~30,000がさらに好ましく、7,000~20,000が特に好ましい。
本発明の着色組成物は、アルカリ可溶性樹脂を、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。
本発明の着色組成物は、さらに光重合開始剤を含有することが好ましい。
光重合開始剤としては、重合性化合物の重合を開始する能力を有する限り、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視の光線に対して感光性を有するものが好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよく、モノマーの種類に応じてカチオン重合を開始させるような開始剤であってもよい。
また、光重合開始剤は、約300nm~800nm(330nm~500nmがより好ましい。)の範囲内に少なくとも約50の分子吸光係数を有する化合物を、少なくとも1種含有していることが好ましい。
本発明に用いられる光重合開始剤の具体例としては、例えば、特開2013-29760号公報の段落0265~0268を参酌することができ、この内容は本願明細書に組み込まれる。
ヒドロキシアセトフェノン系開始剤としては、IRGACURE-184、DAROCUR-1173、IRGACURE-500、IRGACURE-2959,IRGACURE-127(商品名:いずれもBASF社製)を用いることができる。アミノアセトフェノン系開始剤としては、市販品であるIRGACURE-907、IRGACURE-369、及び、IRGACURE-379(商品名:いずれもBASF社製)を用いることができる。アミノアセトフェノン系開始剤として、365nm又は405nm等の長波光源に吸収波長がマッチングされた特開2009-191179公報に記載の化合物も用いることができる。また、アシルホスフィン系開始剤としては市販品であるIRGACURE-819やDAROCUR-TPO(商品名:いずれもBASF社製)を用いることができる。
市販品ではIRGACURE-OXE01(BASF社製)、IRGACURE-OXE02(BASF社製)も好適に用いられる。また、TRONLY TR-PBG-304、TRONLY TR-PBG-309、TRONLY TR-PBG-305(常州強力電子新材料有限公司社(CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO.,LTD)製)、アデカアークルズNCI-831およびアデカアークルズNCI-930(ADEKA社製)も用いることができる。
好ましくは、例えば、特開2013-29760号公報の段落0274~0275を参酌することができ、この内容は本願明細書に組み込まれる。
具体的には、オキシム化合物としては、下記式(OX-1)で表される化合物が好ましい。なお、オキシムのN-O結合が(E)体のオキシム化合物であっても、(Z)体のオキシム化合物であっても、(E)体と(Z)体との混合物であってもよい。
一般式(OX-1)中、Rで表される一価の置換基としては、一価の非金属原子団であることが好ましい。
一価の非金属原子団としては、アルキル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環基、アルキルチオカルボニル基、アリールチオカルボニル基等が挙げられる。また、これらの基は、1以上の置換基を有していてもよい。また、前述した置換基は、さらに他の置換基で置換されていてもよい。
置換基としてはハロゲン原子、アリールオキシ基、アルコキシカルボニル基またはアリールオキシカルボニル基、アシルオキシ基、アシル基、アルキル基、アリール基等が挙げられる。
一般式(OX-1)中、Bで表される一価の置換基としては、アリール基、複素環基、アリールカルボニル基、又は、複素環カルボニル基が好ましい。これらの基は1以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
一般式(OX-1)中、Aで表される二価の有機基としては、炭素数1~12のアルキレン基、アルキニレン基が好ましい。これらの基は1以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
化合物のモル吸光係数の測定は、公知の方法を用いることができるが、具体的には、例えば、紫外可視分光光度計(Varian社製Cary-5 spectrophotometer)にて、酢酸エチル溶媒を用い、0.01g/Lの濃度で測定することが好ましい。
本発明に用いられる光重合開始剤は、必要に応じて2種以上を組み合わせて使用しても良い。
本発明の組成物は、光重合開始剤を、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。
本発明の着色組成物は、上述の各成分に加えて、本発明の効果を損なわない範囲で、さらに、多官能メルカプト化合物、有機溶剤、架橋剤、重合禁止剤、界面活性剤、有機カルボン酸、有機カルボン酸無水物などの他の成分を含んでいてもよい。
本発明の着色組成物は、重合性化合物の反応を促進させることなどを目的として、分子内に2個以上のメルカプト基を有する多官能メルカプト化合物を含んでいてもよい。多官能メルカプト化合物は、2級のアルカンメルカプト類であることが好ましく、特に下記一般式(T1)で表される構造を有する化合物であることが好ましい。
一般式(T1)
(式(T1)中、nは2~4の整数を表し、Lは2~4価の連結基を表す。)
本発明の着色組成物は、有機溶剤を含有してもよい。
有機溶剤は、各成分の溶解性や着色組成物の塗布性を満足すれば基本的には特に制限はないが、色素(A)、硬化性化合物等の溶解性、塗布性、安全性を考慮して選ばれることが好ましい。また、本発明における着色組成物を調製する際には、少なくとも2種類の有機溶剤を含むことが好ましい。
本発明において、有機溶剤は、過酸化物の含有率が0.8mmol/L以下であることが好ましく、過酸化物を実質的に含まないことがより好ましい。
本発明の着色組成物は、有機溶剤を、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。
本発明の着色組成物に架橋剤を含有させてもよい。架橋剤を含有させることにより、得られる硬化膜の硬度をより高めることもできる。
架橋剤としては、架橋反応により膜硬化を行なえるものであれば、特に限定はなく、例えば、(a)エポキシ樹脂、(b)メチロール基、アルコキシメチル基、及びアシロキシメチル基から選ばれる少なくとも1つの置換基で置換された、メラミン化合物、グアナミン化合物、グリコールウリル化合物又はウレア化合物、(c)メチロール基、アルコキシメチル基、及びアシロキシメチル基から選ばれる少なくとも1つの置換基で置換された、フェノール化合物、ナフトール化合物又はヒドロキシアントラセン化合物、が挙げられる。中でも、多官能エポキシ樹脂が好ましい。
架橋剤の具体例などの詳細については、特開2004-295116号公報の段落0134~0147の記載を参照することができ、この内容は本願明細書に組み込まれる。
本発明の着色組成物中に架橋剤を含有する場合、架橋剤の含有量は、特に定めるものではないが、組成物の全固形分の2~30質量%が好ましく、3~20質量%がより好ましい。
本発明の着色組成物は、架橋剤を、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。
本発明の着色組成物においては、着色組成物の製造中又は保存中において、重合性化合物の不要な熱重合を阻止するために、少量の重合禁止剤を添加することが望ましい。
本発明に用いうる重合禁止剤としては、ハイドロキノン、p-メトキシフェノール、ジ-t-ブチル-p-クレゾール、ピロガロール、t-ブチルカテコール、ベンゾキノン、4,4'-チオビス(3-メチル-6-t-ブチルフェノール)、2,2'-メチレンビス(4-メチル-6-t-ブチルフェノール)、N-ニトロソフェニルヒドロキシアミン第一セリウム塩等が挙げられる。
本発明の着色組成物が重合禁止剤を含有する場合、重合禁止剤の含有量は、着色組成物の質量に対して、約0.01~5質量%が好ましい。
本発明の着色組成物は、重合禁止剤を、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。
本発明の着色組成物には、塗布性をより向上させる観点から、各種の界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。
即ち、フッ素系界面活性剤を含有する着色組成物を適用した塗布液を用いて膜形成する場合においては、被塗布面と塗布液との界面張力を低下させることにより、被塗布面への濡れ性が改善され、被塗布面への塗布性が向上する。このため、少量の液量で数μm程度の薄膜を形成した場合であっても、厚みムラの小さい均一厚の膜形成をより好適に行える点で有効である。
フッ素系界面活性剤は、特開2010-32698号公報に記載のフッ素系界面活性剤を用いることもできる。
また、フッ素系界面活性剤としてブロックポリマーを用いることもでき、具体例としては、例えば特開2011-89090号公報に記載された化合物が挙げられる。
フッ素系界面活性剤は、フッ素原子を有する(メタ)アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基(好ましくはエチレンオキシ基および/またはプロピレンオキシ基)を2以上(好ましくは5以上)有する(メタ)アクリレート化合物に由来する繰り返し単位と、を含む含フッ素高分子化合物も好ましく用いることができる。
また、エチレン性不飽和基を側鎖に有する含フッ素重合体をフッ素系界面活性剤として用いることもできる。具体例としては、特開2010-164965号公報0050~0090段落および0289~0295段落に記載された化合物、例えばDIC社製のメガファックRS-101、RS-102、RS-718K等が挙げられる。
本発明の着色組成物に界面活性剤を含有する場合、界面活性剤の添加量は、着色組成物の全質量に対して、0.001~2.0質量%が好ましく、より好ましくは0.005~1.0質量%である。
本発明の組成物は、界面活性剤を、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。
本発明の着色組成物は、分子量1000以下の有機カルボン酸、及び/又は有機カルボン酸無水物を含有していてもよい。有機カルボン酸及び有機カルボン酸無水物の具体例としては、例えば、特開2013-29760号公報の段落0338~0340を参酌することができ、この内容は本願明細書に組み込まれる。
本発明の着色組成物に有機カルボン酸、有機カルボン酸無水物を含有する場合、有機カルボン酸および/または有機カルボン酸無水物の添加量は、通常、全固形分中0.01~10重量%、好ましくは0.03~5重量%、より好ましくは0.05~3重量%の範囲である。
本発明の着色組成物は、有機カルボン酸および/または有機カルボン酸無水物を、それぞれ、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。
本発明の着色組成物においては、特開2004-295116号公報の段落0078に記載の増感剤や光安定剤、同公報の段落0081に記載の熱重合防止剤を含有することができる。また、バインダーとして特開2006-215453号公報の一般式(1)で示される単量体を共重合成分として含む樹脂を含有することができる。
本発明の着色組成物において、色素、顔料、顔料分散剤、溶剤、アルカリ可溶性樹脂、重合性化合物、界面活性剤、光重合開始剤、エポキシ化合物等の着色組成物中の各成分に結合または配位していない遊離のBr含有量は、900ppm以下が好ましく、600ppm以下がより好ましい。また、遊離のCl含有量は、900ppm以下が好ましく、600ppm以下がより好ましい。また、遊離のBrと遊離のClとの合計含有量は、1500ppm以下が好ましく、900ppm以下がより好ましい。この態様によれば、欠陥の少ないカラーフィルタを製造しやすい。なお、着色組成物中における遊離のBr含有量および遊離のCl含有量は、既知の解析手段を適宜用いて測定することが可能であるが、可能な限りにおいて、ハロゲン量測定BS EN 14582に準拠した燃焼イオンクロマトグラフ法に準拠して測定することが好ましい。
本発明の着色組成物は、前述の成分を混合することで調製される。
なお、着色組成物の調製に際しては、着色組成物を構成する各成分を一括配合してもよいし、各成分を溶剤に溶解・分散した後に逐次配合してもよい。また、配合する際の投入順序や作業条件は特に制約を受けない。例えば、全成分を同時に溶剤に溶解・分散して組成物を調製してもよいし、必要に応じては、各成分を適宜2つ以上の溶液・分散液としておいて、使用時(塗布時)にこれらを混合して組成物として調製してもよい。
本発明の着色組成物は、異物の除去や欠陥の低減などの目的で、フィルタで濾過することが好ましい。従来からろ過用途等に用いられているものであれば特に限定されることなく用いることができる。例えば、PTFE(ポリテトラフルオロエチレン)等のフッ素樹脂、ナイロン(例えばナイロン-6、ナイロン-6,6)等のポリアミド系樹脂、ポリエチレン、ポリプロピレン(PP)等のポリオレフィン樹脂(高密度、超高分子量を含む)等によるフィルタが挙げられる。これら素材の中でもポリプロピレン(高密度ポリプロピレンを含む)およびナイロンが好ましい。
フィルタの孔径は、0.01~7.0μm程度が適しており、好ましくは0.01~3.0μm程度、さらに好ましくは0.05~0.5μm程度である。この範囲とすることにより、後工程において均一及び平滑な着色組成物の調製を阻害する、微細な異物を確実に除去することが可能となる。また、ファイバ状のろ材を用いることも好ましく、ろ材としては例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられ、具体的にはロキテクノ社製のSBPタイプシリーズ(SBP008など)、TPRタイプシリーズ(TPR002、TPR005など)、SHPXタイプシリーズ(SHPX003など)のフィルタカートリッジを用いることができる。
また、上述した範囲内で異なる孔径の第1のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール株式会社、アドバンテック東洋株式会社、日本インテグリス株式会社(旧日本マイクロリス株式会社)又は株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択することができる。
第2のフィルタは、上述した第1のフィルタと同様の材料等で形成されたものを使用することができる。
例えば、第1のフィルタでのフィルタリングは、分散液のみで行い、他の成分を混合した後で、第2のフィルタリングを行ってもよい。
次に、本発明における硬化膜、カラーフィルタについて、その製造方法を通じて詳述する。また、本発明のカラーフィルタの製造方法についても説明する。
本発明の硬化膜は、本発明の着色組成物を硬化してなる。かかる硬化膜はカラーフィルタに好ましく用いられる。
また、本発明のカラーフィルタの製造方法の第二の態様は、本発明の着色組成物を支持体上に適用して着色組成物層を形成し、硬化して着色層を形成する工程と、着色層上にフォトレジスト層を形成する工程と、露光および現像することによりフォトレジスト層をパターニングしてレジストパターンを得る工程と、レジストパターンをエッチングマスクとして着色層をドライエッチングして着色パターンを形成する工程とを含む。
本発明のカラーフィルタは、上記製造方法により好適に得ることができる。以下これらの詳細を述べる。
着色組成物層を形成する工程では、支持体上に、本発明の着色組成物を適用して着色組成物層を形成する。
本発明における着色パターンは、固体撮像素子用基板の撮像素子形成面側(おもて面)に形成されてもよいし、撮像素子非形成面側(裏面)に形成されてもよい。
固体撮像素子における着色パターンの間や、固体撮像素子用基板の裏面には、遮光膜が設けられていてもよい。
また、支持体上には、必要により、上部の層との密着改良、物質の拡散防止或いは基板表面の平坦化のために下塗り層を設けてもよい。
<<<露光工程>>>
露光工程では、着色組成物層形成工程において形成された着色組成物層を、パターン状に露光する。例えば、支持体上に形成した着色組成物層に対し、ステッパー等の露光装置を用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン露光することができる。これにより、露光部分を硬化することができる。
露光に際して用いることができる放射線(光)としては、g線、i線等の紫外線が好ましく(特に好ましくはi線)用いられる。照射量(露光量)は、例えば、0.03~2.
5J/cm2が好ましく、0.05~1.0J/cm2がより好ましく、0.08~0.5J/cm2が最も好ましい。
露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば酸素濃度が19体積%以下の低酸素雰囲気下(例えば、15体積%、5体積%、実質的に無酸素)で露光してもよく、酸素濃度が21体積%を超える高酸素雰囲気下(例えば、22体積%、30体積%、50体積%)で露光してもよい。また、露光照度は適宜設定することが可能であり、通常1000W/m2~100000W/m2(例えば、5000W/m2、15000W/m2、35000W/m2)の範囲から選択することができる。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度10体積%で照度10000W/m2、酸素濃度35体積%で照度20000W/m2などとすることができる。
膜厚を、1.0μm以下とすることにより、高解像性、高密着性を得られるため、好ましい。
また、本工程においては、0.7μm以下の薄い膜厚を有する硬化膜も好適に形成することができ、得られた硬化膜を、後述するパターン形成工程にて現像処理することで、薄膜でありながらも、現像性、表面荒れ抑制、およびパターン形状に優れた着色パターンを得ることができる。
次いでアルカリ現像処理を行うことにより、露光工程における光未照射部分の着色組成物層がアルカリ水溶液に溶出し、光硬化した部分だけが残る。
現像液としては、下地の撮像素子や回路などにダメージを起さない、有機アルカリ現像液が望ましい。現像温度としては通常20℃~30℃であり、現像時間は、従来20秒~90秒であった。より残渣を除去するため、近年では120秒~180秒実施する場合もある。さらには、より残渣除去性を向上するため、現像液を60秒ごとに振り切り、さらに新たに現像液を供給する工程を数回繰り返す場合もある。
また、現像液には無機アルカリを用いてもよく、無機アルカリとしては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、硅酸ナトリウム、メタ硅酸ナトリウムなどが好ましい。
また、現像液には、界面活性剤を用いてもよい。界面活性剤の例としては、前述した組成物で説明した界面活性剤が挙げられ、ノニオン系界面活性剤が好ましい。現像液が界面活性剤を含有する場合、現像液の全質量に対して、0.001~2.0質量%が好ましく、より好ましくは0.01~1.0質量%である。
なお、このようなアルカリ性水溶液からなる現像液を使用した場合には、一般に現像後純水で洗浄(リンス)することが好ましい。
ポストベークは、硬化を完全なものとするための現像後の加熱処理であり、通常100℃~240℃、好ましくは200℃~240℃の熱硬化処理を行う。
このポストベーク処理は、現像後の塗布膜を、上記条件になるようにホットプレートやコンベクションオーブン(熱風循環式乾燥機)、高周波加熱機等の加熱手段を用いて、連続式あるいはバッチ式で行うことができる。
ドライエッチングは、着色層を、パターニングされたフォトレジスト層をマスクとしてエッチングガスを用いて行うことができる。具体的には、着色層上にポジ型またはネガ型の感放射線性組成物を塗布し、これを乾燥させることによりフォトレジスト層を形成する。フォトレジスト層の形成においては、さらにプリベーク処理を施すことが好ましい。特に、フォトレジストの形成プロセスとしては、露光後の加熱処理(PEB)、現像後の加熱処理(ポストベーク処理)を実施する形態が望ましい。
具体的には、ポジ型の感放射線性組成物として、キノンジアジド化合物およびアルカリ可溶性樹脂を含有する組成物が好ましい。キノンジアジド化合物およびアルカリ可溶性樹脂を含有するポジ型の感放射線性組成物は、500nm以下の波長の光照射によりキノンジアジド基が分解してカルボキシル基を生じ、結果としてアルカリ不溶状態からアルカリ可溶性になることを利用するものである。このポジ型フォトレジストは解像力が著しく優れているので、ICやLSI等の集積回路の作製に用いられている。キノンジアジド化合物としては、ナフトキノンジアジド化合物が挙げられる。市販品としては例えばFHi622BC」(富士フイルムエレクトロニクスマテリアルズ社製)などが挙げられる。
フッ素系ガスと酸素ガス(O2)との混合ガスを用い、支持体が露出しない領域(深さ)までエッチングを行なう第1段階のエッチングと、この第1段階のエッチングの後に、窒素ガス(N2)と酸素ガス(O2)との混合ガスを用い、好ましくは支持体が露出する領域(深さ)付近までエッチングを行なう第2段階のエッチングと、支持体が露出した後に行なうオーバーエッチングとを含む形態が好ましい。以下、ドライエッチングの具体的手法、並びに第1段階のエッチング、第2段階のエッチング、およびオーバーエッチングについて説明する。
(1)第1段階のエッチングにおけるエッチングレート(nm/min)と、第2段階のエッチングにおけるエッチングレート(nm/min)とをそれぞれ算出する。
(2)第1段階のエッチングで所望の厚さをエッチングする時間と、第2段階のエッチングで所望の厚さをエッチングする時間とをそれぞれ算出する。
(3)上述した(2)で算出したエッチング時間に従って第1段階のエッチングを実施する。
(4)上述した(2)で算出したエッチング時間に従って第2段階のエッチングを実施する。あるいはエンドポイント検出でエッチング時間を決定し、決定したエッチング時間に従って第2段階のエッチングを実施してもよい。
(5)上述した(3)および(4)の合計時間に対してオーバーエッチング時間を算出し、オーバーエッチングを実施する。
上記のうち、アルキレングリコールモノアルキルエーテルカルボキシレートおよびアルキレングリコールモノアルキルエーテルが好ましい。
これら溶媒は、単独で用いても2種以上を混合して用いてもよい。2種以上を混合する場合、水酸基を有する溶剤と水酸基を有しない溶剤とを混合することが好ましい。水酸基を有する溶剤と水酸基を有しない溶剤との質量比は、1/99~99/1、好ましくは10/90~90/10、さらに好ましくは20/80~80/20である。プロピレングリコールモノメチルエーテルアセテート(PGMEA)とプロピレングリコールモノメチルエーテル(PGME)の混合溶剤で、その比率が60/40であることが特に好ましい。なお、汚染物に対する洗浄液の浸透性を向上させるために、洗浄液には上述した本発明の着色組成物に関する界面活性剤を添加してもよい。
本発明のカラーフィルタは、CCD、CMOS等の固体撮像素子に好適に用いることができ、特に100万画素を超えるような高解像度のCCDやCMOS等に好適である。本発明の固体撮像素子用カラーフィルタは、例えば、CCDまたはCMOSを構成する各画素の受光部と、集光するためのマイクロレンズと、の間に配置されるカラーフィルタとして用いることができる。
また、着色パターン(着色画素)のサイズ(パターン幅)としては、2.5μm以下が好ましく、2.0μm以下がより好ましく、1.7μm以下が特に好ましい。
本発明の固体撮像素子は、既述の本発明のカラーフィルタを備える。本発明の固体撮像素子の構成としては、本発明におけるカラーフィルタが備えられた構成であり、固体撮像素子として機能する構成であれば特に限定はないが、例えば、以下のような構成が挙げられる。
さらに、デバイス保護膜上であってカラーフィルタの下(支持体に近い側)に集光手段(例えば、マイクロレンズ等。以下同じ)を有する構成や、カラーフィルタ上に集光手段を有する構成等であってもよい。
本発明のカラーフィルタは、固体撮像素子のみならず、液晶表示装置や有機EL表示装置などの、画像表示装置に用いることができ、特に液晶表示装置の用途に好適である。本発明のカラーフィルタを備えた液晶表示装置は、表示画像の色合いが良好で表示特性に優れた高画質画像を表示することができる。
また、本発明におけるカラーフィルタは、明るく高精細なCOA(Color-filter On Array)方式にも供することが可能である。COA方式の液晶表示装置にあっては、カラーフィルタ層に対する要求特性は、前述のような通常の要求特性に加えて、層間絶縁膜に対する要求特性、すなわち低誘電率および剥離液耐性が必要とされることがある。本発明のカラーフィルタにおいては、色相に優れた色素を用いることから、色純度、光透過性などが良好で着色パターン(画素)の色合いに優れるので、解像度が高く長期耐久性に優れたCOA方式の液晶表示装置を提供することができる。なお、低誘電率の要求特性を満足するためには、カラーフィルタ層の上に樹脂被膜を設けてもよい。
また、本発明のカラーフィルタは、マイクロオーレッド方式(マイクロOLED)のディスプレイにも好ましく用いることができる。
これらの画像表示方式については、例えば、「EL、PDP、LCDディスプレイ-技術と市場の最新動向-(東レリサーチセンター調査研究部門 2001年発行)」の43ページなどに記載されている。
バックライトに関しては、SID meeting Digest 1380(2005)(A.Konno et.al)や、月刊ディスプレイ 2005年12月号の18~24ページ(島 康裕)、同25~30ページ(八木隆明)などに記載されている。
また、以下の実施例で用いた色素(A)は、一般式(1)におけるm及びnが、ある分布をもって異なる複数の値をとっている混合物であり、以下の表1で記載したmおよびnの値は各色素での平均値の値である。
重量平均分子量は、GPC(Gel Permeation Chromatography)測定によるポリスチレン換算値にて測定した。具体的には、HLC-8220(東ソー製)を用い、カラムとしてTSKgel Super AWM―H(東ソー製、6.0mmID(内径)×15.0cm)を、溶離液として10mmol/L リチウムブロミドNMP(N-メチルピロリジノン)溶液を用いることによって求めた。
酸価は、固形分1gあたりの酸性成分を中和するのに要する水酸化カリウムの質量を表わしたものである。具体的には、測定サンプルをテトラヒドロフラン/水=9/1(質量比)混合溶液に溶解し、電位差滴定装置(商品名:AT-510、京都電子工業製)を用いて、得られた溶液を25℃において、0.1mol/l水酸化ナトリウム水溶液で中和滴定した。滴定pH曲線の変曲点を滴定終点として、次式により酸価を算出した。
A=56.11×Vs×0.1×f/w
A:酸価(mgKOH/g)
Vs:滴定に要した0.1mol/l水酸化ナトリウム水溶液の使用量(mL)
f:0.1mol/l水酸化ナトリウム水溶液の力価
w:測定サンプル質量(g)(固形分換算)
色素2.5gをシクロヘキサノン47.5gに溶解させ、得られた液を濁度測定装置(三菱化学株式会社製SEP-PT-760D型、光路長10mm、252.2ppmの標準板使用)を用いて測定した。
色素を、MEK(メチルエチルケトン)/NMP(N-メチルピロリドン)=1/9の1質量%溶液とし、誘導結合プラズマ発光分光(ICP-OES)で、遊離金属量を測定した。
ハロゲン量測定BS EN 14582に準拠した燃焼イオンクロマトグラフ法にて、遊離ハロゲン量を測定した。
特開2000-162429号公報に記載の方法と同様にして、トリアリールメタン化合物(A-tp-1)~(A-tp-4)を合成した。
以下の合成は、ガラス製フラスコを使用して実施した。また、DCSFは、NMP溶解後にセライトろ過して晶析した、HPLC(液体クロマトグラフィ)測定で純度95%以上のものを使用した。また、2,6-ジイソプロピルアニリンは、塩酸塩とした後、水酸化ナトリウムで処理して精製した、HPLC測定で純度95%以上のものを使用した。
DCSF(Spiro[3H-2,1-benzoxathiole-3,9'-[9H]xanthene], 3',6'-dichloro-, 1,1-dioxide、中外化成製)31部、2,6-ジイソプロピルアニリン67部、塩化亜鉛17部、スルホラン120部をフラスコへ入れ外温200度にて8時間攪拌した。その後、室温まで放冷し、2N塩酸水600部へ反応液を滴下し、析出した結晶をろ別した。結晶を、40度のアセトニトリル600部で分散洗浄し、ろ取し、送風乾燥を10時間行い、中間体1を42.5部(収率:82%)得た。
<<中間体2の合成>>
中間体1を11部およびオキシ塩化リン50部をフラスコへ入れ60℃で4時間攪拌した。室温まで放冷し、氷水150部へ反応液を滴下し、30分攪拌した。得られた結晶をろ別し、水20部で洗浄した後、得られた結晶をクロロホルム150部に溶かし、セライトろ過を行った。ろ液を5%食塩水100部、15%食塩水100部で分液洗浄した。硫酸ナトリウム乾燥の後、減圧濃縮し、中間体2を12.1部(収率:91%)得た。
<<中間体3の合成>>
ペンタフルオロベンゼンスルホニルクロリド15部、テトラヒドロフラン(THF)300部をフラスコに入れ、内温を-10℃に冷却した。そこに28%アンモニア水6.8部を、反応液が0℃以下を維持するように滴下した。滴下後1時間0℃で攪拌したのち、反応液をろ過した。得られたろ液を減圧濃縮し、THFを除いた後、水100部を添加し、攪拌した。得られた固体をろ過し、水洗した後に送風乾燥を10時間行い、中間体3を11.7部(収率:84%)得た。
<<キサンテン化合物(A-xt-1)の合成>>
中間体3を5部、中間体2を18.0部、塩化メチレンを50部フラスコに加え、室温で攪拌した。そこにトリエチルアミン(TEA)6.1部をフラスコに加え、室温で2時間攪拌した。反応終了後、反応液をクロロホルム/酢酸エチル溶媒を用いてカラムクロマトグラフィーにより精製することで、A-xt-1を11.1部(収率:60%)得た。<キサンテン化合物(A-xt-2)~(A-xt-5)の合成例>
上記キサンテン化合物(A-xt-1)と同様に合成した。
以下に示すように、一分子中に3~15個のメルカプト基を有する化合物(S-6)、(S-4)を合成した。(S-1)~(S-3)、(S-5)、(S-7)~(S-19)も同様の手法にて合成した。
<<(S-6)の合成>>
ジペンタエリスリトール5部、ジメチルアセトアミド80部を三口フラスコに加え、窒素雰囲気下20℃の水浴中で攪拌した。6-ブロモヘキサノイルクリド31部を温度が30℃をこえないように滴下した後、室温で2時間攪拌した。反応液を1N塩酸水350部に少しずつ加え反応を停止した後、酢酸エチル500部を加え分液操作を行った。続いて、有機層を飽和重曹水250部、水250部、飽和食塩水150部で洗浄した。得られた有機層に硫酸ナトリウムを加えた後、ろ別し、ろ液を減圧濃縮することで中間体1を24部得た。
続いて20部の中間体1、チオウレア8.9部、エタノール200部、ヨウ化カリウム17.6部を三口フラスコに加え、窒素雰囲気下加熱還流で18時間反応させた。その後、20%炭酸カリウム水溶液81部を加え、70℃で3時間反応させた後、冷却した。続いて、1N塩酸水150部とクロロホルム300部を加え分液操作を行った。飽和食塩水150部で2回洗浄し、有機層に硫酸ナトリウムを加えた後、ろ別し、ろ液を減圧濃縮することで(S-6)を14.7部得た。
ジペンタエリスリトール15部、脱水DMF(N,N-ジメチルホルムアミド)270部、アリルブロミド86部を三口フラスコに加え、窒素雰囲気下20℃の水浴中で攪拌した。水素化ナトリウム(60%のオイルディスパージョン)計35部を温度が35℃をこえないように添加した後、室温で2時間攪拌した。反応液を1N塩酸水200部に少しずつ加え反応を停止した後、酢酸エチル200部を加え分液操作を行った。続いて、有機層を1N塩酸水200部、水200部、飽和食塩水200部で洗浄した。得られた有機層に硫酸ナトリウムを加えた後、ろ別し、ろ液を減圧濃縮することで中間体2を28部得た。
続いて25部の中間体2、チオ酢酸58部を脱水THF(テトラヒドロフラン)125部に溶かし、窒素雰囲気下70℃で30分攪拌した後、アゾビスイソブチロニトリル2部を添加し、70℃4時間攪拌した。 得られた反応液を減圧濃縮した後、脱水メタノールを加え、ナトリウムメトキシド(28%メタノール溶液)19部を加えた。一時間後に反応溶液を1N塩酸水120部に氷浴で冷やしながら滴下した後、酢酸エチル200部を加え分液操作を行った。続いて、有機層を1N塩酸水200部、水200部、飽和食塩水200部で洗浄した。得られた有機層に硫酸ナトリウムを加えた後、ろ別し、ろ液を減圧濃縮することで(S-4)を13部得た。
以下に示すように、色素構造を有するメルカプト化合物を合成した。
<<合成例>>
<<<(B-1)の合成>>>
一分子中に3~15個のメルカプト基を有する化合物(S-6)2.0部、キサンテン化合物(A-xt-1)6.2部、ジアザビシクロウンデセン1.03部を、ジメチルホルムアミド(DMF)39.8部に溶解させ25℃2時間攪拌した。反応後、1N塩酸水250部の混合溶媒に反応溶液を滴下して再沈しろ過して得られた固体をアセトニトリル250部に入れ懸濁洗浄し、再度ろ過することにより以下に示すメルカプト化合物(B-1)7.4部を得た。NMR測定でのR部位に対する色素部位の比率が3.5であることを確認した。
(B-1)と同様に、(A-xt-1)を対応する色素に、(S-6)を対応するメルカプト基を有する化合物に変更し、表1に示すm、n数となるように合成した。
なお、表1における(A-xt-1)~(A-xt-5)、(A-tp-1)~(A-tp-5)、(A-aq-1)、(A-az-1)、(A-sq-1)、(A-Pc-1)、(A-subPc-1)、(A-Qu-1)、(A-pm-1)は、上述した構造の色素である。
(Po-1)の合成
メルカプト化合物(B-1)を5.0部、メタクリル酸(MAA)0.62部、エチレングリコールモノ2-ブロモイソブチレートモノメタクリレート(BBEM)1.07部およびN-エチルピロリドン9.0部の混合溶液を窒素気流下、90℃に加熱した。これに2,2’-アゾビス(イソ酪酸)ジメチル〔V-601;和光純薬製〕を0.087部添加した後、90℃で1.5時間加熱攪拌した。さらにV-601を0.087部添加した後、90℃で1.5時間加熱攪拌し、さらにV-601を0.087部添加した後、90℃で2時間加熱攪拌した。室温まで冷却した後、ジアザビシクロウンデセン(DBU)10.0部をゆっくり加え、室温で14時間攪拌した。その後、氷浴で5度以下に冷却し、メタンスルホン酸6.3部をゆっくり加えた。反応後、1規定塩酸水250部の混合溶媒に反応溶液を滴下して再沈しろ過して得られた固体をアセトニトリル250部に入れ懸濁洗浄し、再度ろ過することにより以下に示す本発明に係る色素(Po-1)を6.0部得た。Po-1の重量平均分子量(ポリスチレン換算値)は8900であり、0.1N水酸化ナトリウム水溶液を用いた滴定により、酸価は60mgKOH/gであった。また、NMRより、色素構造/MAA/BBEMのHBr脱離体のモル比率は、3.5/6/4.5であり、P部の繰り返し数は平均4と計算された。
また、Po-1のシクロヘキサノン5質量%での濁度は0.5ppmであった。
また、Al、Ca、Cu、Cr、Mg、Fe、Mn、Ni、Co、Cd、Li、Pb、Na、K、ZnおよびPであって、Po-1に結合または配位していない、遊離した前述の金属量はすべて2ppm以下であった。さらに、Po-1に結合または配位していない、遊離したBr含有量は500ppmで、遊離したCl含有量は100ppmであった。
メルカプト化合物(B-7)を5.0部、イタコン酸(ICA)0.41部およびN-エチルピロリドン9.0部の混合溶液を窒素気流下、90℃に加熱した。これに2,2’-アゾビス(イソ酪酸)ジメチル〔V-601;和光純薬製〕を0.022部添加した後、90℃で1.5時間加熱攪拌した。さらにV-601を0.022部添加した後、90℃で1.5時間加熱攪拌し、さらにV-601を0.022部添加した後、90℃で2時間加熱攪拌した。室温まで冷却した後、N-エチルピロリドン30.0部、テトラブチルアンモニウムブロミド(TBAB)0.05部、メタクリル酸グリシジル(GMA)0.27部を添加し、80℃18時間加熱攪拌した。室温まで冷却した後、ヘキサン/酢酸エチル250部の混合溶媒に反応溶液を滴下して再沈し、以下に示す本発明に係る色素(Po-7)を5.1部得た。Po-7の重量平均分子量(ポリスチレン換算値)は7200であり、0.1N水酸化ナトリウム水溶液を用いた滴定により、酸価は44mgKOH/gであった。また、NMRより、色素構造/MAA/ICA/ICAとGMAの付加体のモル比率は、3.5/3.5/2であった。
また、Po-7のシクロヘキサノン5質量%での濁度は1.5ppmであった。
また、Al、Ca、Cu、Cr、Mg、Fe、Mn、Ni、Co、Cd、Li、Pb、Na、K、ZnおよびPであって、Po-7に結合または配位していない、遊離した前述の金属量はすべて2ppm以下であった。さらに、Po-7に結合または配位していない、遊離したBr含有量は400ppmで、遊離したCl含有量は100ppmであった。
使用するメルカプト化合物やモノマー等を表1に記載の通りにし、上記(Po-1)、(Po-7)の合成と同様の手法にて合成した。
上記表1において、R1は、反応前のメルカプト化合物の構造を示す。m+nは、メルカプト化合物のメルカプト基の数に対応し、m、nは得られる色素における、m、nの平均値を示す。下記表中、合成方法における、BBEM、CEEMAは、これらの化合物を用いて合成したことを意味する。R2は得られる色素が有する繰り返し単位の平均個数を示す。酸価は、得られる色素の酸価を示す(単位:mgKOH/g)。Mwは得られる色素の重量平均分子量で、GPC測定法により得られる。
1.レジスト液の調製
下記組成の成分を混合して溶解した後、0.45μmナイロンフィルタでろ過することにより、下塗り層用レジスト液を調製した。
下塗り層用レジスト液の組成
・溶剤:プロピレングリコールモノメチルエーテルアセテート 19.20部
・溶剤:乳酸エチル 36.67部
・アルカリ可溶性樹脂:メタクリル酸ベンジル/メタクリル酸/メタクリル酸-2-ヒドロキシエチル共重合体(モル比=60/22/18、重量平均分子量15,000、数平均分子量9,000)の40%PGMEA溶液 30.51部
・エチレン性不飽和二重結合含有化合物:ジペンタエリスリトールヘキサアクリレート(KAYARAD DPHA、サートマー社製)
12.20部
・重合禁止剤:p-メトキシフェノール 0.0061部
・フッ素系界面活性剤:F-475、DIC(株)製 0.83部
・光重合開始剤:トリハロメチルトリアジン系の光重合開始剤 0.586部
(TAZ-107、みどり化学社製)
6inchシリコンウエハをオーブン中で200℃のもと30分加熱処理した。次いで、このシリコンウエハ上に、下塗り層用レジスト液を乾燥膜厚が1.5μmになるように塗布し、更に220℃のオーブン中で1時間加熱乾燥させて下塗り層を形成し、下塗り層付シリコンウエハ基板を得た。
3-1.青色顔料分散液の調製(顔料分散液P1)
(顔料分散液P1(C.I.Pigment Blue15:6分散液)の調製)
以下のようにして、顔料分散液P1(C.I.Pigment Blue15:6分散液)を調製した。
即ち、C.I.Pigment Blue15:6(青色顔料;以下、「PB15:6」とも称する)を19.4質量部(平均一次粒子径55nm)、及び顔料分散剤Disperbyk-161(BYKChemie社製)を2.95質量部、アルカリ可溶性樹脂J1(メタクリル酸ベンジル/メタクリル酸の共重合体、30%PGMEA溶液)を固形分換算で2.95質量部(溶液9.93質量部)、PGMEA165.3質量部からなる混合液を、ビーズミル(beads mill)(ジルコニアビーズ0.3mm径)により3時間混合・分散した。その後、さらに、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、2000kg/cm3の圧力下で流量500g/minとして分散処理を行なった。この分散処理を10回繰り返し、顔料分散液として、C.I.Pigment Blue15:6分散液を得た。得られたC.I.Pigment Blue15:6分散液について、顔料の平均一次粒子径を動的光散乱法(Microtrac Nanotrac UPA-EX150(日機装社(Nikkiso Co.,)td.)製))により測定したところ、24nmであった。
下記の各成分を混合して分散、溶解し、0.45μmナイロンフィルタでろ過することにより着色組成物を得た。
・有機溶剤(シクロヘキサノン):14.69部
・アルカリ可溶性樹脂1(J1):0.29部(固形0.09部、固形分濃度30%)
・アルカリ可溶性樹脂2(アクリキュア-RD-F8(日本触媒社製)):0.05部
・光重合開始剤I-2(IRGACURE OXE-02):0.78部
・色素Po-1のシクロヘキサノン溶液(固形分濃度12.3%):28.45部
・顔料分散液P1(C.I.Pigment Blue15:6分散液、PGMEA溶液、固形分濃度12.8%):51.23部
・重合性化合物Z-3 エトキシ化(4)ペンタエリスリトールテトラアクリレート、SR494(サートマー社製):1.61部
・エポキシ化合物E-1(EHPE3150、ダイセル(株)製):0.39部
・重合禁止剤(p-メトキシフェノール):0.0007部
・フッ素系界面活性剤(DIC社製F475、1%PGMEA溶液):2.50部
4-1:フォトリソグラフィ法による着色組成物を用いたカラーフィルタの作製
上記で調製された着色組成物を、上記で作製された下塗り層付シリコンウエハの下塗り層上に塗布し、着色層(塗布膜)を形成した。そして、この塗布膜の乾燥膜厚が1μmになるように、100℃のホットプレートを用いて120秒間加熱処理(プリベーク)を行なった。
次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して365nmの波長でパターンが1.0μm四方のIslandパターンマスクを通して50~1200mJ/cm2の露光量で露光した。
その後、照射された塗布膜が形成されているシリコンウエハ基板をスピン・シャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、CD-2000(富士フイルムエレクトロニクスマテリアルズ(株)製)を用いて23℃で60秒間パドル現像を行ない、下塗り層付シリコンウエハの下塗り層上に着色パターンを形成した。
着色パターンが形成されたシリコンウエハを、真空チャック方式で水平回転テーブルに固定し、回転装置によってシリコンウエハを回転数50rpmで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理を行ない、その後スプレー乾燥し、200℃で300秒間、ホットプレートでポストベークを行い、シリコンウエハ上の膜厚1μmの着色パターン(カラーフィルタ)を得た。
以上により、下塗り層付シリコンウエハの下塗り層上に着色パターン(カラーフィルタ)が設けられた構成の着色パターン付シリコンウエハを得た。
上記で調製された着色組成物をガラス基板にスピンコーターを用いて塗布し、塗膜を形成した。着色層を形成したガラス基板を、基板面で接するように280℃のホットプレートに載置して1時間加熱して、耐熱性試験を実施した。
加熱前後での色差(ΔE*ab)を色度計MCPD-1000(大塚電子(株)製)を用いて測定した。測定された色差(ΔE*ab値)に基づき、下記評価基準に従って耐熱性を評価した。ΔE*ab値は、値の小さい方が、耐熱性が良好なことを示す。なお、ΔE*ab値は、CIE1976(L*,a*,b*)空間表色系による以下の色差公式から求められる値である(日本色彩学会編 新編色彩科学ハンドブック(昭和60年)p.266)。
A:ΔE*abが3以下
B:ΔE*abが3より大きく5以下
C:ΔE*abが5より大きく10以下
D:ΔE*abが10より大きい
各カラーフィルタにおける着色パターンの吸光度を、MCPD-3000(大塚電子(株)製)にて測定した(吸光度A)。
カラーフィルタの着色パターン形成面に、乾燥膜厚が1μmとなるようにCT-2000L溶液(富士フイルムエレクトロニクスマテリアルズ(株)製;透明下地剤)を塗布し、乾燥させて、透明膜を形成した後、280℃で30分間加熱処理を行なった。
加熱終了後、着色パターンに隣接する透明膜の吸光度を、MCPD-3000(大塚電子(株)製)にて測定した(吸光度B)。
得られた透明膜の吸光度Bの値について、加熱前に測定した着色パターンの吸光度Aの値に対する割合[%]を算出した〔下記(式A)〕。これを隣接ピクセルへの色移りを評価する指標とした。
(式A) 色移り(%)=(吸光度B/吸光度A)×100
A:1%未満
B:1%以上3%未満
C:3%以上5%未満
D:5%以上
実施例1における「3-2.着色組成物の調製」において、顔料分散液P1、色素C-1、光重合開始剤I-2、アルカリ可溶性樹脂1、重合性化合物Z-3を下記表のように変更したこと以外は、実施例1と同様にして、着色組成物を調製し、実施例1と同様にして、耐熱性、色移り性を評価した。
実施例1における「3-2.着色組成物の調製」において、下記の各成分を混合したこと以外は、実施例1と同様にして、着色組成物を調製し、実施例1と同様にして、耐熱性、色移り性を評価した。
・有機溶剤(シクロヘキサノン):17.12部
・アルカリ可溶性樹脂1(J1):1.23部(固形0.37部、固形分濃度30%)
・アルカリ可溶性樹脂2(アクリキュア-RD-F8(日本触媒社製)):0.23部
・光重合開始剤I-2(IRGACURE OXE-02):0.975部
・色素Po-1のシクロヘキサノン溶液(固形分濃度12.3%):24.57部
・顔料分散液P1(C.I.Pigment Blue15:6分散液、PGMEA溶液、固形分濃度12.8%):51.40部
・重合性化合物Z-1(エチレンオキシ変性ジペンタエリスリトールヘキサアクリレート、NKエステル A-DPH-12E(新中村化学社製)):1.96部
・重合禁止剤(p-メトキシフェノール):0.0007部
・フッ素系界面活性剤(DIC社製F475、1%PGMEA溶液):2.50部
一方、比較例1~3は、耐熱性、色移り性に劣っていた。
(顔料分散液P2(C.I.Pigment Blue15:6分散液)の調製)
顔料分散液P1の調製において、顔料分散剤として、下記分散剤D1を用いる以外は同様の操作により顔料分散液P2を調製した。
Mw=20000、x/y=50/50(質量比)、n=20、酸価=100mgKOH/g
顔料分散液P1の調製において、顔料分散剤として、下記分散剤D2を用いる以外は同様の操作により顔料分散液P3を調製した。
Mw=20000、x/y=15/85(質量比)、n=20、酸価=100mgKOH/g
顔料分散液P1の調製において、顔料としてPB15:6の代わりに、C.I.Pigment Red254を使用する以外は顔料分散液P1の調製と同様にして顔料分散液P4を調製した。顔料の平均一次粒子径を動的光散乱法(Microtrac Nanotrac UPA-EX150(日機装社(Nikkiso Co.,)td.)製))により測定したところ、26nmであった。
顔料分散液P1の調製において、顔料としてPB15:6の代わりに、C.I.Pigment Green58を使用する以外は顔料分散液P1の調製と同様にして顔料分散液P5を調製した。顔料の平均一次粒子径を動的光散乱法(Microtrac Nanotrac UPA-EX150(日機装社(Nikkiso Co.,)td.)製))により測定したところ、30nmであった。
顔料分散液P1の調製において、顔料としてPB15:6の代わりに、C.I.Pigment Yellow139を使用する以外は顔料分散液P1の調製と同様にして顔料分散液P6を調製した。顔料の平均一次粒子径を動的光散乱法(Microtrac Nanotrac UPA-EX150(日機装社(Nikkiso Co.,)td.)製))により測定したところ、27nmであった。
Z1:エチレンオキシ変性ジペンタエリスリトールヘキサアクリレート、NKエステル A-DPH-12E(新中村化学社製)
Z2:ジペンタエリスリトールヘキサアクリレート、KAYARAD DPHA(日本化薬社製)
Z3:エトキシ化(4)ペンタエリスリトールテトラアクリレート、SR494(サートマー社製)
Z4:エトキシ化(3)トリメチロールプロパントリアクリレート、SR454(サートマー社製)
Z5:エトキシ化(6)トリメチロールプロパントリアクリレート、SR499(サートマー社製)
Z6:KAYARAD DPCA-60(日本化薬社製)
Z7:トリス(2-ヒドロキシエチル)イソシアヌレートトリアクリレート、SR368(サートマー社製)
エポキシ化合物
E1:EHPE3150、ダイセル(株)製
E2:EPICLON840(DIC製)
E3:EPICLEPICLON N660(DIC製)
E4:EPICLON HP7200(DIC製)
下記の各成分を混合して分散、溶解し、0.45μmナイロンフィルタでろ過することにより着色組成物を得た。得られた着色組成物を用い、実施例1と同様にして、耐熱性、色移り性を評価した。
(組成)
・有機溶剤(シクロヘキサノン):25.22部
・アルカリ可溶性樹脂1(J1):0.62部(固形0.19部、固形分濃度30.6%)
・アルカリ可溶性樹脂2(アクリキュア-RD-F8(日本触媒社製)):0.12部(固形0.05部、固形分濃度41.7%)
・光重合開始剤I-7:0.59部
・色素Po-1のシクロヘキサノン溶液(固形分濃度12.3%):23.04部
・顔料分散液P1(C.I.Pigment Blue15:6分散液、PGMEA溶液、固形分濃度12.8%):45.66部
・重合性化合物Z-4 エトキシ化(3)トリメチロールプロパントリアクリレート、SR454(サートマー社製):1.90部
・エポキシ化合物E-1(EHPE3150、ダイセル(株)製):0.35部
・重合禁止剤(p-メトキシフェノール):0.0009部
・フッ素系界面活性剤(メガファックF781F、DIC製(メガファックF781Fはアルキレンオキシ鎖を有するフッ素系界面活性剤である)、1%PGMEA溶液):2.50部
実施例42における着色組成物の調製において、色素Po-1、顔料分散液P-1、光重合開始剤I-7、アルカリ可溶性樹脂1、重合性化合物Z-4、エポキシ化合物E1を下記表のように変更したこと以外は、実施例42と同様にして、着色組成物を調製した。得られた着色組成物を用い、実施例1と同様にして、耐熱性、色移り性を評価した。
下記の各成分を混合して分散、溶解し、0.45μmナイロンフィルタでろ過することにより着色組成物を得た。得られた着色組成物を用い、実施例1と同様にして、耐熱性、色移り性を評価した。
(組成)
・有機溶剤(シクロヘキサノン):14.69部
・アルカリ可溶性樹脂1(J1):0.29部(固形0.09部、固形分濃度30%)
・アルカリ可溶性樹脂2(アクリキュア-RD-F8(日本触媒社製)):0.05部
・光重合開始剤I-2(IRGACURE OXE-02):0.78部
・色素Po-1のシクロヘキサノン溶液1(固形分濃度12.3%):28.45部
・色素Po-12のシクロヘキサノン溶液2(固形分濃度12.3%):51.23部
・重合性化合物Z-3 エトキシ化(4)ペンタエリスリトールテトラアクリレート、SR494(サートマー社製):1.61部
・エポキシ化合物E-1(EHPE3150、ダイセル(株)製):0.39部
・重合禁止剤(p-メトキシフェノール):0.0007部
・フッ素系界面活性剤(DIC社製F475、1%PGMEA溶液):2.50部
実施例59における着色組成物の調製において、色素Po-1、色素Po-12、光重合開始剤I-2、アルカリ可溶性樹脂1、重合性化合物Z-3、エポキシ化合物E-1を下記表のように変更したこと以外は、実施例59と同様にして、着色組成物を調製した。得られた着色組成物を用い、実施例1と同様にして、耐熱性、色移り性を評価した。
<実施例71>
下記の各成分を混合して分散、溶解し、0.45μmナイロンフィルタでろ過することにより着色組成物を得た。
(組成)
・有機溶剤(シクロヘキサノン):17.12部
・エポキシ化合物E5:JER1031S(三菱化学(株)製、エポキシ当量:180-220(g/eq.)):4.395部
・色素Po-1のシクロヘキサノン溶液(固形分濃度12.3%):24.57部
・顔料分散液P1(C.I.Pigment Blue15:6分散液、PGMEA溶液、固形分濃度12.8%):51.40部
・重合禁止剤(p-メトキシフェノール):0.0007部
・フッ素系界面活性剤(DIC社製F475、1%PGMEA溶液):2.50部
上記で得られた着色組成物を、7.5cm×7.5cmのガラス基板上に膜厚が0.5μmになるようにスピンコーターを用いて塗布し、ホットプレートを使用して、200℃で5分間、加熱を行い、塗布膜を硬化して着色層を作製した。この着色層の膜厚は、0.5μmであった。
次いで、ポジ型フォトレジスト「FHi622BC」(富士フイルムエレクトロニクスマテリアルズ社製)を塗布し、90℃で1分間、プリベーク処理を実施し、膜厚0.8μmのフォトレジスト層を形成した。
続いて、フォトレジスト層を、i線ステッパー(キャノン(株)製)を用い、350mJ/cm2の露光量でパターン露光し、フォトレジスト層の温度又は雰囲気温度が90℃となる温度で1分間、加熱処理を行なった。その後、現像液「FHD-5」(富士フイルムエレクトロニクスマテリアルズ社製)で1分間の現像処理を行ない、さらに110℃で1分間のポストベーク処理を実施して、レジストパターンを形成した。このレジストパターンのサイズは、エッチング変換差(エッチングによるパターン幅の縮小)を考慮して、一辺1.0μmで形成した。
次に、得られたガラス基板を、直径8インチ(1インチ=25.4mm)のシリコンウェハに貼り付け、ドライエッチング装置(U-621、日立ハイテクノロジーズ社製)にて、RFパワー:800W、アンテナバイアス:400W、ウエハバイアス:200W、チャンバーの内部圧力:4.0Pa、基板温度:50℃、混合ガスのガス種及び流量をCF4:80mL/分、O2:40mL/分、Ar:800mL/min.として、80秒の第1段階のエッチング処理を実施した。
次いで、同一のエッチングチャンバーにて、RFパワー:600W、アンテナバイアス:100W、ウエハバイアス:250W、チャンバーの内部圧力:2.0Pa、基板温度:50℃、混合ガスのガス種及び流量をN2:500mL/分、O2:50mL/分、Ar:500mL/分とし(N2/O2/Ar=10/1/10)、28秒の第2段階エッチング処理、オーバーエッチング処理を実施した。
上記条件でドライエッチングを行った後、フォトレジスト剥離液「MS230C」(富士フイルムエレクトロニクスマテリアルズ社製)を使用して、50℃で120秒間、剥離処理を実施してレジストを除去し、着色パターンを形成した。更に純水による洗浄、スピン乾燥を実施し、その後、100℃で2分間の脱水ベーク処理を行った。以上により、カラーフィルタを得た。
実施例71における着色組成物の調製において、色素Po-1、顔料分散液P1、エポキシ化合物E5を下記表のように変更したこと以外は、実施例71と同様にして、着色組成物を調製し、実施例71と同様にして、耐熱性、色移り性を評価した。
下記の各成分を混合して分散、溶解し、0.45μmナイロンフィルタでろ過することにより着色組成物を得た。得られた着色組成物を用い、実施例71と同様にして、耐熱性、色移り性を評価した。
(組成)
・有機溶剤(シクロヘキサノン):17.12部
・エポキシ化合物E5:JER1031S(三菱化学(株)製、エポキシ当量:180-220(g/eq.)):4.395部
・色素Po-1のシクロヘキサノン溶液1(固形分濃度12.3%):24.57部
・色素Po-12のシクロヘキサノン溶液2(固形分濃度12.3%):51.40部
・重合禁止剤(p-メトキシフェノール):0.0007部
・フッ素系界面活性剤(DIC社製F475、1%PGMEA溶液):2.50部
実施例82における着色組成物の調製において、色素Po-1、色素Po-12、エポキシ化合物E5を下記表のように変更したこと以外は、実施例82と同様にして、着色組成物を調製した。得られた着色組成物を用い、実施例71と同様にして、耐熱性、色移り性を評価した。
上記表に示す通り、実施例は、耐熱性および色移り性に優れていた。
これに対し、比較例は、耐熱性および色移り性が劣っていた。
なお、表5、6に記載のエポキシ化合物E4は、EPICLON HP7200(DIC製)であり、E5は、JER1031S(三菱化学(株)製)である。
下記の実験はガラス製フラスコを使用して実施した。
DCSF204部(NMP溶解後にセライトろ過して晶析した、HPLC測定で純度95%以上のものを使用。)、スルホラン1408部、2,6-ジイソプロピルアニリン(塩酸塩とした後、水酸化ナトリウムで処理して精製した、HPLC測定で純度95%以上のものを使用。)295部、1-ブトキシ-2-プロパノール108部をフラスコへ入れ、80℃で4.5時間攪拌した。この反応液を65℃へ降温し、12時間攪拌し、無水塩化マグネシウム109部、リン酸三カリウム294部、2,6-ジエチルアニリン788部を添加した。この反応液を140℃まで昇温し、22時間攪拌した後、50℃へ降温した。この反応液にアセトニトリル7828部を滴下し、50℃にて3時間攪拌した。この反応液を室温まで降温して2時間攪拌した後、得られた結晶をろ別し、アセトニトリル2817部で洗浄した。メタノール2466部に、室温にてこの結晶をメタノール274部で洗いながら添加し、50℃にて3時間攪拌した。この反応液を室温まで降温し、2N塩酸3716部を滴下し、室温にて2時間攪拌した。得られた結晶をろ別し、イオン交換水3334部、アセトニトリル798部で順次洗浄した。この結晶を60℃にて14時間減圧乾燥し、中間体4を250部得た。
DMF105部、スルホラン1068部、中間体1を282部、およびアセトニトリル222部を室温にてフラスコに入れ、85℃まで昇温して5分攪拌した。この反応液にオキシ塩化リン285部を滴下した後、110℃で3.5時間攪拌した。60℃まで放冷し、アセトニトリル222部を加え、-2℃まで放冷した。この反応液が-2℃から7℃の間になるようにイオン交換水2824部を滴下した後、1時間攪拌した。得られた結晶をろ別し、アセトニトリル1113部、イオン交換水1412部の混合液およびイオン交換水4236部、アセトニトリル1059部で順次洗浄して中間体5を238部得た。
ペンタフルオロベンゼンスルホニルクロリド150部、テトラヒドロフラン(THF)2668部をフラスコに入れ、内温を-10℃に冷却した。そこに28%アンモニア水54.8部を、反応液が-5℃以下を維持するように滴下した。滴下後-10℃で10分間攪拌した後、28%アンモニア水6.85部を反応液が-5℃以下を維持するように滴下した。さらに滴下後-10℃で10分攪拌したのち、28%アンモニア水1.14部を反応液が-5℃以下を維持するように滴下した。この反応液に塩化リチウム3.58部を添加した後、室温まで昇温し、10分間攪拌した。この反応液をろ過し、THF400部で洗浄した。ろ液と洗液を合わせてフラスコに入れ、室温にてイオン交換水1005部を滴下した。この反応液を35℃で2時間攪拌し、室温まで冷却した後、酢酸ナトリウム7.39部を添加し、室温で10分攪拌した。この反応液を35℃で減圧濃縮した後、5℃まで冷却して30分間攪拌した。得られた固体をろ過し、イオン交換水450部で洗浄した後に45℃で真空乾燥12時間を行い、中間体6を107部得た。
DMI(1,3-ジメチル-2-イミダゾリジノン)508部をフラスコに入れ、中間体6を86.4部、中間体5を208部をDMI 127部で洗浄しながらフラスコに加えた。室温で5分間攪拌した後、1℃まで冷却し、そこにジイソプロピルエチルアミン113部を1~5℃で加え、1~5℃で2時間攪拌した。反応終了後、1~5℃で反応液に酢酸35.0部を添加して、室温まで昇温し、エキネンF6(変性アルコール、日本アルコール販売(株))788部を添加した。この反応液を室温にて10分間攪拌した後、セライトろ過をおこない、エキネンF6 265部で洗浄した。ろ液と洗液を合わせてフラスコに入れ、エキネンF6を1194部、イオン交換水250部を室温にて滴下した後、キサンテン化合物(A-xt-23)の種結晶0.03部を室温にて加えて13時間攪拌した。この反応液を5℃まで冷却して、得られた結晶をろ過し、メタノール505部で洗浄した。この結晶をフラスコに入れ、メタノール909部を添加し、1時間加熱還流した。これを5℃まで冷却して、結晶をろ過し、メタノール505部で洗浄した後、45℃にて12時間減圧乾燥をおこない、(A-xt-23)を194部得た。
一分子中に3~15個のメルカプト基を有する化合物(S-6)22.0部とDMI(1,3-ジメチル-2-イミダゾリジノン)317部をフラスコ入れ、窒素雰囲気下、室温にて5分間攪拌した。これに、キサンテン化合物(A-xt-23)66.0部をDMI34.0部で洗いこみながら徐々に添加して、室温にて30分攪拌した。この反応液にDBU(ジアザビシクロウンデセン)11.3部を、DMI1.13部で洗いこみながら30℃を超えないように添加し、室温にて1時間攪拌した。この反応液に酢酸13.4部をDMI1.3部で洗いこみながら30℃を超えないように添加した後、室温にて5分攪拌した。メタノール720部と超純水303部の混合溶媒にこの反応溶液を滴下して再沈し、得られた固体をろ過し、メタノール360部と超純水151部の混合溶媒で洗浄した。得られた固体を45℃で2日間送風乾燥することにより、以下に示すメルカプト化合物(B-28)86.5部を得た。NMR測定でのR部位に対する色素部位の比率が3.5であることを確認した。
メルカプト化合物(B-28)を37.1部(固形分94.40%)、4-OH TEMPO(4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン1-オキシル フリーラジカル)0.082部、メタクリル酸(MAA)5.44部、エチレングリコールモノ2-ブロモイソブチレートモノメタクリレート(BBEM)10.4部およびNEP(N-エチルピロリドン)56.4部の混合溶液を窒素気流下、80℃に加熱した。この反応液に2,2’-アゾビス(イソ酪酸)ジメチル〔V-601;和光純薬製〕のNEP溶液(V-601:0.694部、NEP:6.19部)を3時間かけて滴下した。滴下終了後、NEP0.69部を添加して80℃で30分攪拌し、さらにV-601のNEP溶液(V-601:0.694部、NEP:1.15部)を添加した。この反応液を80℃で1.5時間攪拌した後、さらにV-601のNEP溶液(V-601:0.694部、NEP:1.15部)を添加した。この反応液を80℃で1.5時間攪拌した後、さらにV-601のNEP溶液(V-601:0.694部、NEP:1.15部)を添加し、90℃まで昇温して2時間攪拌した。室温まで冷却した後、系内の窒素置換を止めて空気下とし、4-OH TEMPOの0.204部、NEPの26.7部を添加し、続けて30℃を超えないようにDBU(ジアザビシクロウンデセン)42.7部をNEP3.04部で洗いながらゆっくり加え、室温で14時間攪拌した。その後、NEP62.6部を添加し、氷浴で5度以下に冷却し、15℃を超えないようにメタンスルホン酸27.0部をNEP1.99部で洗いこみながらゆっくり加えた。添加終了後、メタノール543部、超純水686部、p-メトキシフェノール0.478部の混合溶媒にこの反応溶液を滴下して再沈し、室温にて1時間攪拌した。この反応液を47.5℃まで昇温し、1時間攪拌した後、室温まで冷却した。得られた固体をろ過し、メタノール272部、超純水343部の混合溶媒で洗浄した。この固体をメタノール136部、超純水172部、p-メトキシフェノール0.478部の混合溶媒でリスラリーし、得られた固体をろ過してメタノール136部、超純水172部で洗浄した。この固体を45℃で2日間送風乾燥することにより、以下に示す本発明に係る色素(Po-28)を45.7部得た。Po-28の重量平均分子量(ポリスチレン換算値)は8900であり、0.1N水酸化ナトリウム水溶液を用いた滴定により、酸価は61mgKOH/gであった。また、NMRより、色素構造/MAA/BBEMのHBr脱離体のモル比率は、3.5/6/4.5であり、P部の繰り返し数は平均4と計算された。
Po-28のシクロヘキサノン5質量%での濁度は1.0ppmであった。また、Al、Ca、Cu、Cr、Mg、Fe、Mn、Ni、Co、Cd、Li、Pb、Na、K、ZnおよびPであって、Po-28に結合または配位していない、遊離した前述の金属量はすべて2ppm以下であった。さらに、Po-28に結合または配位していない、遊離したBr含有量は400ppmで、遊離したCl含有量は100ppmであった。
((B-29)~(B-33)の合成)
(B-28)と同様に、(A-xt-23)を対応する色素に、(S-6)を対応するメルカプト基を有する化合物に変更し、表に示すm、n数となるように合成した。
実施例1において、色素、顔料分散液、光重合開始剤、アルカリ可溶性樹脂1、重合性化合物およびエポキシ化合物を、下記表8に記載の原料に変更した以外は、実施例1と同様にして、着色組成物を調製した。得られた着色組成物を用い、実施例1と同様にして、耐熱性および色移り性を評価した。
Claims (22)
- 下記一般式(1)で示される色素および硬化性化合物を含有する着色組成物;
一般式(1) (D―L1―Y―X―) n―R1―(R2) m
一般式(1)中、R1は、m+n価の連結基を表し、Xは、―C(=O)O―、―C(=O)―、―C(=O)NR10―、―O―、―S(=O)―、または、―SO2―を表し、R10は水素原子またはアルキル基を表し、Yは、アルキレン基を表し、L1は、単結合または2価の連結基を表し、Dは、色素構造を表し、R2は、1価の置換基を表す;mは、1~13の整数を表し、nは、2~14の整数を表し、m+nは、3~15の整数を表す;mが2以上の場合、複数のR2は互いに異なっていても良く、nが2以上の場合、複数のDは互いに異なっていても良い;L1が2価の連結基の場合は、L1とXとは、Yにより炭素原子数として3以上隔てられており、L1が単結合の場合はDとXとは、Yにより炭素原子数として3以上隔てられている;D、L1、R1、R2、X、Yのうち少なくとも1つは酸基を有する。 - 前記一般式(1)におけるDが、ジピロメテン色素、トリアリールメタン色素、キサンテン色素、シアニン色素、スクアリリウム色素、アントラキノン色素、キノフタロン色素、フタロシアニン色素、サブフタロシアニン色素、およびアゾ色素から選ばれる色素に由来する、請求項1に記載の着色組成物。
- 前記一般式(1)におけるDが、カチオン部位と対アニオンとを有するか、または、一分子内にカチオン部位とアニオン部位とを有し、前記対アニオンが、スルホン酸アニオン、スルホニルイミドアニオン、ビス(アルキルスルホニル)イミドアニオン、トリス(アルキルスルホニル)メチドアニオン、カルボン酸アニオン、テトラアリールボレートアニオン、BF4 -、PF6 -、およびSbF6 -から選ばれる少なくとも1種であり、前記アニオン部位が、スルホニルイミドアニオンである、請求項1または2に記載の着色組成物。
- 前記一般式(1)におけるYが、無置換の直鎖アルキレン基である、請求項1~3のいずれか1項に記載の着色組成物。
- 前記一般式(1)におけるR2が、酸基を有するビニル化合物由来の繰り返し単位を含有する、請求項1~4のいずれか1項に記載の着色組成物。
- 前記一般式(1)におけるR2が、繰り返し単位を含有し、前記繰り返し単位の個数の平均値が2~20個である、請求項1~5のいずれか1項に記載の着色組成物。
- 前記一般式(1)におけるXが、*―C(=O)O―#であり、*はYに結合し#はR1に結合する、請求項1~6のいずれか1項に記載の着色組成物。
- 前記一般式(1)で示される色素が、エチレン性不飽和結合を有する基を含有する、請求項1~7のいずれか1項に記載の着色組成物。
- 前記一般式(1)におけるR2が、エチレン性不飽和結合を有する基を含有する、請求項1~8のいずれか1項に記載の着色組成物。
- 前記一般式(1)におけるR1が、
下記一般式(2)で示される連結基、
下記一般式(3)で示される連結基、
複数の炭素原子からなる主鎖を有する連結基であって、該主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、
1つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって、該主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、
または、
少なくとも2つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって連続した3つ以上の炭素原子によって前記ヘテロ原子間が隔てられた部分を該主鎖中に少なくとも1つ含む連結基、のいずれかである、請求項1~9のいずれか1項に記載の着色組成物;一般式(2)
一般式(2)中、Zは、それぞれ独立に、CR20またはNを表し、L2は、それぞれ独立に、単結合またはp価の連結基を表し、R20は水素原子または置換基を表し、aは1~6の整数を表し、pは2以上の整数を表し、L2がp価の連結基の場合、L2は複数の炭素原子からなる主鎖を有する連結基であって、該主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、1つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって、該主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、または、少なくとも2つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって連続した3つ以上の炭素原子によって前記ヘテロ原子間が隔てられた部分を該主鎖中に少なくとも1つ含む連結基、のいずれかである;一般式(3)
一般式(3)中、L3は、それぞれ独立に、単結合またはq価の連結基を表し、qは2以上の整数を表し、L3がq価の連結基の場合、L3は複数の炭素原子からなる主鎖を有する連結基であって、該主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、1つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって、該主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、または、少なくとも2つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって連続した3つ以上の炭素原子によって前記ヘテロ原子間が隔てられた部分を該主鎖中に少なくとも1つ含む連結基、のいずれかである。 - 一般式(1)におけるL1が、
単結合、
―S―、
複数の炭素原子からなる主鎖を有する連結基であって、該主鎖は炭素原子3つ以上連続している部分を少なくとも1つ含む連結基、
1つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって、該主鎖は炭素原子が3つ以上連続している部分を少なくとも1つ含む連結基、
または、
少なくとも2つのヘテロ原子と複数の炭素原子からなる主鎖を有する連結基であって連続した3つ以上の炭素原子によって前記ヘテロ原子間が隔てられた部分を該主鎖中に少なくとも1つ含む連結基、のいずれかである、
請求項1~10のいずれか1項に記載の着色組成物。 - 前記一般式(1)におけるmが1~5であり、nが2~8である、請求項1~11のいずれか1項に記載の着色組成物。
- 前記一般式(1)で示される色素の重量平均分子量が、2000~15000である、請求項1~12のいずれか1項に記載の着色組成物。
- さらに、前記一般式(1)で示される色素以外の顔料を含む、請求項1~13のいずれか1項に記載の着色組成物。
- さらに、光重合開始剤を含む、請求項1~14のいずれか1項に記載の着色組成物。
- カラーフィルタの着色層形成用である、請求項1~15のいずれか1項に記載の着色組成物。
- 請求項1~15のいずれか1項に記載の着色組成物を硬化して得られた硬化膜。
- 請求項1~15のいずれか1項に記載の着色組成物を用いてなるカラーフィルタ。
- 請求項1~15のいずれか1項に記載の着色組成物を支持体上に適用して着色組成物層を形成する工程と、前記着色組成物層をパターン状に露光する工程と、未露光部を現像除去して着色パターンを形成する工程と、を含むカラーフィルタの製造方法。
- 請求項1~15のいずれか1項に記載の着色組成物を支持体上に適用して着色組成物層を形成し、硬化して着色層を形成する工程と、
前記着色層上にフォトレジスト層を形成する工程と、
露光および現像することにより前記フォトレジスト層をパターニングしてレジストパターンを得る工程と、
前記レジストパターンをエッチングマスクとして前記着色層をドライエッチングする工程と、を含むカラーフィルタの製造方法。 - 請求項18に記載のカラーフィルタ、または、請求項19もしくは20に記載のカラーフィルタの製造方法によって製造したカラーフィルタを有する固体撮像素子。
- 請求項18に記載のカラーフィルタ、または、請求項19もしくは20に記載のカラーフィルタの製造方法によって製造したカラーフィルタを有する画像表示装置。
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JP6339208B2 (ja) | 2018-06-06 |
JPWO2016035565A1 (ja) | 2017-08-10 |
TW201609992A (zh) | 2016-03-16 |
KR20170031747A (ko) | 2017-03-21 |
US10444625B2 (en) | 2019-10-15 |
US20170146904A1 (en) | 2017-05-25 |
TWI656178B (zh) | 2019-04-11 |
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