Coloring composition, film, color filter, solid-state imaging element, and image display device
The coloring composition addresses the issue of lightfastness in color filters by incorporating a boron-containing anion to prevent dye decomposition, resulting in films with improved light resistance and adhesiveness for color filters and imaging devices.
Patent Information
- Application Number
- PCT/JP2025/013696
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2024-04-19
- Filing Date
- 2025-04-04
- Publication Date
- 2025-10-23
AI Technical Summary
Existing coloring compositions used in color filters, particularly those containing dyes, suffer from inadequate lightfastness, leading to insufficient light resistance in the resulting films.
A coloring composition comprising a dye, a polymerization initiator, a polymerizable compound, and a specific boron-containing anion with low fluorine content, which forms a film with enhanced light resistance by preventing oxygen interaction with the dye, thereby suppressing dye decomposition.
The composition forms a film with excellent light resistance and adhesiveness, reducing spectral variation and development residues, suitable for use in color filters and solid-state imaging devices.
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Abstract
Description
Coloring composition, film, color filter, solid-state imaging device and image display device
[0001] The present invention relates to a coloring composition containing a dye. The present invention also relates to a film, a color filter, a solid-state imaging device, and an image display device using the coloring composition.
[0002] In recent years, the widespread use of digital cameras and smartphones has led to a significant increase in demand for solid-state imaging devices such as complementary metal-oxide semiconductor (CMOS) image sensors. Color filters are used as key devices in displays and optical elements. Color filters typically have pixels for the three primary colors of red, green, and blue, and serve to separate transmitted light into the three primary colors.
[0003] The pixels of each color of the color filter are manufactured by, for example, forming a pattern by photolithography using a coloring composition containing a colorant. For example, Patent Document 1 describes forming a pattern by photolithography using a coloring composition containing an acid dye, a binder resin, a predetermined ionic compound whose maximum molar absorption coefficient ε in the visible light region is 0 to 3000, and an organic solvent, to form the pixels of the color filter.
[0004] JP 2016-133604 A
[0005] Generally, dyes tend to have lower lightfastness than pigments, and there is room for further improvement in the lightfastness of films obtained using colored compositions containing dyes.
[0006] The present inventors have further studied the colored composition described in Patent Document 1 and have found that even with this colored composition, there is still room for further improvement in the light resistance of the film obtained.
[0007] Therefore, an object of the present invention is to provide a coloring composition capable of forming a film having excellent light resistance. Another object of the present invention is to provide a film, a color filter, a solid-state imaging device, and an image display device.
[0008] The present invention provides the following: <1> A coloring composition comprising: a colorant A containing a dye a; a polymerization initiator B; a polymerizable compound C; and a compound D which is a salt of a cation dx and an anion dz and is represented by formula (Aλ) and has a specific absorbance of 5 or less, wherein the anion dz is an anion containing a boron atom and has a fluorine atom content of 50 mass% or less; 1 =A 1 / (c 1 ×l 1 )...(Aλ) In formula (Aλ), E 1 represents the specific absorbance of compound D at the maximum absorption wavelength in the wavelength range of 400 to 700 nm, and A 1 represents the absorbance of Compound D at the maximum absorption wavelength in the wavelength range of 400 to 700 nm, and 1 represents the cell length in cm, and c 1 represents the concentration of compound D in the solution, expressed in mg / ml. <2> The colored composition according to <1>, wherein the dye a includes a dye a1 having a chemical structure including a cation ax and an anion az, and the ratio of the molar amount of the anion dz of the compound D to the molar amount of the cation ax of the dye a1 is 0.5 to 0.9. <3> The colored composition according to <1> or <2>, wherein the anion dz of the compound D is an anion represented by formula (dz-1); In formula (dz-1), R d1 ~R d4each independently represents an alkyl group, an aryl group, or a heteroaryl group. <4> The colored composition according to any one of <1> to <3>, wherein the anion dz of the compound D is a tetraphenylboron anion. <5> The colored composition according to any one of <1> to <4>, wherein the cation dx of the compound D is an ammonium cation or a potassium cation. <6> The colored composition according to any one of <1> to <5>, wherein the dye a includes a xanthene dye. <7> The colored composition according to any one of <1> to <6>, wherein the dye a includes a dye multimer. <8> The colored composition according to any one of <1> to <7>, wherein the colorant A further includes a pigment. <9> The colored composition according to any one of <1> to <8>, wherein the content of the colorant A in the total solid content of the colored composition is 40 mass% or more. <10> The colored composition according to any one of <1> to <9>, wherein the content of the colorant A is 40 mass% or more in the total solid content of the colored composition. <11> The anion dz of the compound D has a molar absorption coefficient at a wavelength of 248 nm of 200 to 15,000 L mol -1 ・cm -1 <12> The colored composition according to any one of <1> to <11>, which is for use in a color filter. <13> A film obtained using the colored composition according to any one of <1> to <12>. <14> A color filter having the film according to <13>. <15> A solid-state imaging device having the film according to <13>. <16> An image display device having the film according to <13>.
[0009] The present invention can provide a colored composition capable of forming a film having excellent light resistance. The present invention can also provide a film, a color filter, a solid-state imaging device, and an image display device using the colored composition.
[0010] The present invention will be described in detail below. In this specification, the term "to" is used to mean that the numerical values before and after the term are included as the lower and upper limits. In the description of groups (atomic groups) in this specification, a term without specifying whether it is substituted or unsubstituted encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation. As used herein, "(meth)acrylate" refers to either or both of acrylate and methacrylate, "(meth)acrylic" refers to either or both of acrylic and methacrylic, and "(meth)acryloyl" refers to either or both of acryloyl and methacryloyl. In the structural formulae, "Me" refers to a methyl group, "Et" refers to an ethyl group, "Bu" refers to a butyl group, and "Ph" refers to a phenyl group. As used herein, the weight-average molecular weight and number-average molecular weight are polystyrene-equivalent values measured by GPC (gel permeation chromatography). As used herein, the term "total solids" refers to the total mass of all components of a composition excluding the solvent. As used herein, the term "pigment" refers to a colorant that is poorly soluble in a solvent. As used herein, the term "dye" refers to a colorant that is easily soluble in a solvent. As used herein, the term "cation" refers to a positively charged atom or a positively charged atomic group. In this specification, an anion means a negatively charged atom or a negatively charged atomic group. In this specification, symbols (e.g., A, B, C, and D) added before or after a name are terms used to distinguish components, and do not limit the type, number, or superiority of the components.In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved.
[0011] <Coloring composition> The coloring composition of the present invention comprises: a colorant A containing a dye a; a polymerization initiator B; a polymerizable compound C; and a compound D which is a salt of a cation dx and an anion dz and is represented by formula (Aλ) and has a specific absorbance of 5 or less, wherein the anion dz is an anion containing a boron atom and has a fluorine atom content of 50 mass% or less.
[0012] The coloring composition of the present invention can form a film with excellent light resistance. While the detailed reasons for this effect are unclear, it is presumed to be due to the following. Here, the mechanism by which the dye decomposes when a dye-containing film is irradiated with light is presumed to be as follows. Specifically, it is presumed that irradiating a dye-containing film with light excites the dye, transferring energy to nearby oxygen to generate singlet oxygen, which then oxidizes and decomposes the dye. It is presumed that this mechanism causes the dye in the film to be decomposed by light irradiation. The anion dz in the above-described compound D is an anion containing a boron atom, and the fluorine atom content is 50% by mass or less, which facilitates proximity to the dye through π-π interactions with the dye. Furthermore, it is presumed that the anion dz in proximity to the dye can effectively prevent oxygen from approaching the dye. Therefore, even if the dye is excited by light irradiation, the anion dz can prevent oxygen from approaching the dye, thereby suppressing the generation of singlet oxygen. As a result, it is presumed that decomposition of the dye due to light irradiation can be suppressed. For this reason, it is presumed that the colored composition of the present invention can form a film that is excellent in light resistance and in which spectral variation due to light irradiation is suppressed.
[0013] Furthermore, the colored composition of the present invention has good storage stability and can also form a film with excellent adhesiveness.
[0014] Furthermore, the colored composition of the present invention can effectively suppress the generation of development residues when a pattern is formed by photolithography. This is presumably because the anion dz in the above-mentioned compound D has a fluorine atom content of 50 mass% or less, thereby increasing the affinity with the developer.
[0015] The coloring composition of the present invention can be preferably used as a coloring composition for color filters. More specifically, it can be preferably used as a coloring composition for forming pixels of color filters. Examples of types of pixels in color filters include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. The coloring composition of the present invention can also be suitably used for the pixel configuration described in WO 2019 / 102887. Hereinafter, each component used in the coloring composition of the present invention will be described.
[0016] <<Colorant A>> The coloring composition of the present invention contains colorant A (hereinafter referred to as colorant). The colorant contained in the coloring composition of the present invention is one containing dye a (hereinafter referred to as dye). It is preferable that the colorant contained in the coloring composition of the present invention further contains a pigment.
[0017] -Dye- The type of dye is not limited. Known dyes can be used. Examples of the dye include red dyes, blue dyes, green dyes, cyan dyes, magenta dyes, and yellow dyes. One embodiment uses at least one dye selected from the group consisting of cyan dyes, magenta dyes, and yellow dyes.
[0018] The dye is preferably a compound having a dye structure selected from a triarylmethane dye structure, a xanthene dye structure, an anthraquinone dye structure, a cyanine dye structure, a squarylium dye structure, a quinophthalone dye structure, a phthalocyanine dye structure, a subphthalocyanine dye structure, an azo dye structure, a pyrazolotriazole dye structure, a dipyrromethene dye structure, an isoindoline dye structure, a thiazole dye structure, a benzimidazolone dye structure, a perinone dye structure, a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, a diiminium dye structure, a naphthalocyanine dye structure, a rylene dye structure, a dibenzofuranone dye structure, a merocyanine dye structure, a croconium dye structure, and an oxonol dye structure, and The dye is more preferably a compound having a dye structure selected from a triarylmethane dye structure, a xanthene dye structure, an anthraquinone dye structure, a cyanine dye structure, a squarylium dye structure, a quinophthalone dye structure, a phthalocyanine dye structure, a subphthalocyanine dye structure, an azo dye structure, a thiazole dye structure, a pyrazolotriazole dye structure, and a dipyrromethene dye structure, even more preferably a compound having a dye structure selected from a triarylmethane dye structure, a xanthene dye structure, a cyanine dye structure, and a squarylium dye structure, still more preferably a compound having a triarylmethane dye structure or a xanthene dye structure, and particularly preferably a compound having a xanthene dye structure. That is, the dye is preferably a xanthene dye.
[0019] The amount of dye dissolved in 100 g of propylene glycol methyl ether acetate at 25° C. is preferably 0.01 g or more, more preferably 0.5 g or more, and even more preferably 1 g or more.
[0020] The dye used in the present invention is preferably a dye a1 having a chemical structure containing a cation ax and an anion az.
[0021] In dye a1, anion az may exist outside the molecule of cation ax. "Anion az exists outside the molecule of cation ax" refers to a state in which anion az is not bonded to cation ax via a covalent bond and exists as a structural unit independent of cation ax. Examples of the form of dye a1 as described above include salts. Hereinafter, an anion existing outside the molecule of a cation will also be referred to as a counter anion. In dye a1, anion az is preferably bonded to cation ax via a covalent bond. That is, dye a1 preferably takes the form of an intramolecular salt (also called a zwitterion).
[0022] The types of anion az include fluorine anion, chlorine anion, bromine anion, iodine anion, cyanide ion, perchlorate anion, carboxylate anion, sulfonate anion, anion containing a phosphorus atom, imide anion, methide anion, borate anion, and SbF 6 - Examples include imide anions, methide anions, and borate anions, with imide anions and methide anions being more preferred, and imide anions being even more preferred due to their low nucleophilicity. The imide anion is preferably a bis(sulfonyl)imide anion. The methide anion is preferably a tris(sulfonyl)methide anion. The borate anion includes a tetraarylborate anion, a tetracyanoborate anion, a tetrafluoroborate anion, and the like.
[0023] Examples of the type of cation ax include a cation having a xanthene dye structure, a cation having a triarylmethane dye structure, a cation having a cyanine dye structure, and a cation having a squarylium dye structure. Cation ax is preferably a cation having a xanthene dye structure or a cation having a triarylmethane dye structure, and more preferably a cation having a xanthene dye structure because the effects of the present invention are more likely to be obtained significantly.
[0024] Examples of dyes having a cation ax of a xanthene dye structure include compounds represented by formula (XT-1).
[0025]
[0026] In formula (XT-1), R xt1 ~R xt4 each independently represents a hydrogen atom, an alkyl group, or an aryl group; R xt5 represents a substituent, m represents an integer of 0 to 5, Z xt represents a counter anion. xt If there is no xt1 ~R xt5 At least one of the groups comprises an anion.
[0027] R xt1 ~R xt4 The alkyl group and aryl group represented by R may have a substituent. Examples of the substituent include the groups listed as the substituent T described below and polymerizable groups. xt5 Examples of the substituent represented by include the groups exemplified below as the substituent T and polymerizable groups.
[0028] In formula (XT-1), Z xt represents a counter anion. Examples of the counter anion include a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, a carboxylate anion, a sulfonate anion, an anion containing a phosphorus atom, an imide anion, a methide anion, a borate anion, and SbF 6 - Examples include imide anions, methide anions, and borate anions, with imide anions and methide anions being more preferred, and imide anions being even more preferred. As imide anions, bis(sulfonyl)imide anions are preferred. As methide anions, tris(sulfonyl)methide anions are preferred. As borate anions, tetraarylborate anions, tetracyanoborate anions, tetrafluoroborate anions, and the like are included. The molecular weight of the counter anion is preferably 100 to 1,000, more preferably 200 to 500.
[0029] In formula (XT-1), R xt1 ~R xt5 When at least one of the groups contains an anion, examples of the anion include a carboxylate anion, a sulfonate anion, an anion containing a phosphorus atom, an imide anion, a methide anion, and a borate anion. The imide anion, the methide anion, and the borate anion are preferred, the imide anion and the methide anion are more preferred, and the imide anion is even more preferred. The imide anion is preferably a bis(sulfonyl)imide anion. The methide anion is preferably a tris(sulfonyl)methide anion. Specifically, R xt1 ~R xt5 At least one of the is preferably a group containing a partial structure represented by formula (AZ-1) or a group containing a partial structure represented by formula (AZ-2), and more preferably a group containing a partial structure represented by formula (AZ-1).
[0030] The wavy lines in the above formulae represent bonds to other atoms or atomic groups.
[0031] R xt1 ~R xt5 When at least one of R xt1 ~R xt5 It is also preferable that at least one of them has a substituent represented by formula (P-1). In formula (P-1), L 1 represents a single bond or a divalent linking group, and is preferably a single bond. 1 Examples of the divalent linking group represented by L include an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, -O-, -S-, and a group consisting of a combination thereof. 2 is -SO 2 - or -CO-. G represents a carbon atom or a nitrogen atom. n1 represents 2 when G is a carbon atom, and represents 1 when G is a nitrogen atom. R 6 represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom. 6 may be the same or different. 6The number of carbon atoms in the alkyl group containing a fluorine atom represented by R is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. 6 The number of carbon atoms in the fluorine atom-containing aryl group represented by is preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10. The fluorine atom-containing alkyl group and the fluorine atom-containing aryl group may further have a substituent. Examples of the substituent include the substituent T and polymerizable groups described below.
[0032] Examples of dyes having a cation ax of a triarylmethane dye structure include compounds represented by formula (TP-1).
[0033]
[0034] In formula (TP-1), R tp1 ~R tp4 each independently represents a hydrogen atom, an alkyl group, or an aryl group; R tp5 is a hydrogen atom, an alkyl group, an aryl group, or NR tp9 R tp10 (R tp9 and R tp10 represents a hydrogen atom, an alkyl group, or an aryl group, and R tp6 , R tp7 and R tp8 each independently represents a substituent; a, b, and c each independently represent an integer of 0 to 4; when a, b, and c are 2 or more, R tp6 Comrade, R tp7 Peers and R tp8 may be linked to each other to form a ring, tp represents a counter anion, and Z tp If there is no tp1 ~R tp8 At least one of the groups comprises an anion.
[0035] R tp1 ~R tp5 , R tp9 and R tp10 The alkyl group and aryl group represented by R may have a substituent. Examples of the substituent include the groups listed as the substituent T described below and polymerizable groups. tp6 , Rtp7 and R tp8 Examples of the substituent represented by include the groups exemplified below as the substituent T and polymerizable groups.
[0036] In formula (TP-1), Z tp represents a counter anion. tp If there is no tp1 ~R tp8 At least one of the counter anions includes an anion. Examples of the counter anion include the counter anions described above in formula (XT-1). tp1 ~R tp8 When at least one of the groups contains an anion, the anion may be any of the anions described above.
[0037] (Substituent T) Examples of the substituent T include the following groups: an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably an aryl group having 6 to 30 carbon atoms), an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms), a heteroaryloxy group, and an acyl group (preferably an acyl group having 1 to 30 carbon atoms). An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms). a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), a carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), a heteroarylthio group (preferably a group having 1 to 30 carbon atoms), an alkylsulfonyl group (preferably a group having 1 to 30 carbon atoms), an arylsulfonyl group (preferably a group having 6 to 30 carbon atoms), a heteroarylsulfonyl group (preferably a group having 1 to 30 carbon atoms), , alkylsulfinyl groups (preferably having 1 to 30 carbon atoms), arylsulfinyl groups (preferably having 6 to 30 carbon atoms), heteroarylsulfinyl groups (preferably having 1 to 30 carbon atoms), ureido groups (preferably having 1 to 30 carbon atoms), hydroxy groups, carboxy groups, sulfo groups, phosphate groups, carboxylic acid amide groups, sulfonic acid amide groups, imidic acid groups, mercapto groups, halogen atoms, cyano groups, alkylsulfino groups, arylsulfino groups, hydrazino groups, imino groups, and heteroaryl groups (preferably having 1 to 30 carbon atoms). When these groups can be further substituted, they may further have a substituent.Examples of the substituent include the groups explained above as the substituent T, and polymerizable groups.
[0038] Examples of the polymerizable group include ethylenically unsaturated bond-containing groups such as vinyl groups, allyl groups, and (meth)acryloyl groups, epoxy groups, and oxetanyl groups.
[0039] The dye (preferably dye a1) is preferably a compound having a polymerizable group, since this makes it easier to obtain a film with high crosslink density and excellent performance in various aspects.
[0040] Furthermore, the dye (preferably dye a1) is preferably a dye multimer because this tends to reduce the generation of residues during development. A dye multimer is a dye compound having two or more dye structures in one molecule, and preferably has three or more dye structures. There is no particular upper limit, but it can be set to 100 or less. The dye structures in one molecule may be the same dye structure or different dye structures.
[0041] The weight average molecular weight (Mw) of the dye polymer is preferably 2,000 to 50,000. The lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
[0042] Examples of the structure of the dye multimer include dye multimers (A) to (D) described in paragraphs 0047 to 0103 of WO 2016 / 208524. The dye multimer is preferably a dye multimer having a repeating unit represented by formula (A) described below and a dye multimer represented by formula (D) described below. Hereinafter, a dye multimer having a repeating unit represented by formula (A) will also be referred to as dye multimer (A). Furthermore, a dye multimer represented by formula (D) will also be referred to as dye multimer (D).
[0043] The dye multimer (A) preferably contains a repeating unit represented by formula (A). The proportion of the repeating unit represented by formula (A) is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 50% by mass or more, of all repeating units constituting the dye multimer (A). The upper limit can be set to 100% by mass or less, or can be set to 95% by mass or less. In formula (A), X 1 represents a trivalent linking group, L 1 represents a single bond or a divalent linking group; D 1 represents a structure derived from a dye compound.
[0044] X in formula (A) 1 Examples of the trivalent linking group represented by are a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, a polyether linking group, and a polystyrene linking group. A poly(meth)acrylic linking group or a polyalkyleneimine linking group is preferred, and a poly(meth)acrylic linking group is more preferred.
[0045] L 1 represents a single bond or a divalent linking group. 1 Examples of the divalent linking group represented by the formula (I) include an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic group, -CH=CH-, -O-, -S-, -C(=O)-, -COO-, -NR-, -CONR-, -OCO-, -SO-, and -SO 2 - and groups formed by linking two or more of these together, where R represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
[0046] The number of carbon atoms in the alkylene group is preferably 1 to 30. The upper limit is more preferably 25 or less, and even more preferably 20 or less. The lower limit is more preferably 2 or more, and even more preferably 3 or more. The alkylene group may be linear, branched, or cyclic. The alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include the groups exemplified for the substituent T above. The number of carbon atoms in the arylene group is preferably 6 to 20, and more preferably 6 to 12. The arylene group may have a substituent or may be unsubstituted. Examples of the substituent include the groups exemplified for the substituent T above. The heterocyclic group is preferably a 5- or 6-membered ring. The heteroatom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom. The number of heteroatoms in the heterocyclic group is preferably 1 to 3. The heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the groups exemplified for the substituent T above.
[0047] D 1 Examples of the structure derived from a dye compound represented by the formula (I) include a residue in which one or more hydrogen atoms have been removed from a compound having a dye structure selected from a triarylmethane dye structure, a xanthene dye structure, an anthraquinone dye structure, a cyanine dye structure, a squarylium dye structure, a quinophthalone dye structure, a phthalocyanine dye structure, a subphthalocyanine dye structure, an azo dye structure, a pyrazolotriazole dye structure, a dipyrromethene dye structure, an isoindoline dye structure, a thiazole dye structure, a benzimidazolone dye structure, a perinone dye structure, a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, a diiminium dye structure, a naphthalocyanine dye structure, a rylene dye structure, a dibenzofuranone dye structure, a merocyanine dye structure, a croconium dye structure, and an oxonol dye structure. 1 The structure derived from the dye compound represented by formula (XT-1) is preferably a structure derived from the compound represented by formula (XT-1) or a structure derived from the compound represented by formula (TP-1), and more preferably a structure derived from the compound represented by formula (XT-1).
[0048] The dye multimer (A) may contain other repeating units in addition to the repeating unit represented by formula (A). The other repeating units may contain functional groups such as polymerizable groups and acid groups, or may not contain these functional groups. Examples of the polymerizable groups include ethylenically unsaturated bond-containing groups such as vinyl groups and (meth)acryloyl groups. Examples of the acid groups include carboxy groups, sulfo groups, and phosphate groups.
[0049] The proportion of repeating units having a polymerizable group is preferably 0 to 50% by mass of all repeating units constituting the dye multimer (A). The lower limit is preferably 1% by mass or more, more preferably 3% by mass or more. The upper limit is preferably 35% by mass or less, more preferably 30% by mass or less.
[0050] The proportion of repeating units having an acid group is preferably 0 to 50% by mass of all repeating units constituting the dye multimer (A). The lower limit is preferably 1% by mass or more, more preferably 3% by mass or more. The upper limit is preferably 35% by mass or less, more preferably 30% by mass or less.
[0051] The dye multimer (D) is preferably represented by formula (D). In formula (D), L 4 represents a (n+k)-valent linking group, L 41 and L 42 each independently represents a single bond or a divalent linking group; 4 represents a structure derived from a dye compound, and P 4 represents a substituent; n represents 2 to 15, k represents 0 to 13, and n+k is 2 to 15. 4 may be different from each other or may be the same. When k is 2 or more, a plurality of P 4 may be different from each other or may be the same.
[0052] n is preferably 2 to 14, more preferably 2 to 8, particularly preferably 2 to 7, and even more preferably 2 to 6. k is preferably 1 to 13, more preferably 1 to 10, even more preferably 1 to 8, particularly preferably 1 to 7, and even more preferably 1 to 6.
[0053] L 41 and L 42each independently represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, —CH═CH—, —O—, —S—, —CO—, —COO—, —NR—, —CONR—, —OCO—, —SO—, and —SO 2 - and groups formed by linking two or more of these. Here, each R independently represents a hydrogen atom, an alkyl group, or an aryl group. 42 and L 43 are each preferably independently a group containing —S—, and more preferably —S—.
[0054] L 4 The (n+k)-valent linking group represented by includes groups consisting of 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. Examples of the (n+k)-valent linking group include the following structural units or groups consisting of two or more of the following structural units combined together (which may form a ring structure). In the following formulas, * represents a bond.
[0055]
[0056] Specific examples of the (n+k)-valent linking group include the linking groups described in paragraph 0084 of WO 2016 / 208524.
[0057] D 4Examples of the structure derived from a dye compound represented by the formula (I) include a residue in which one or more hydrogen atoms have been removed from a compound having a dye structure selected from a triarylmethane dye structure, a xanthene dye structure, an anthraquinone dye structure, a cyanine dye structure, a squarylium dye structure, a quinophthalone dye structure, a phthalocyanine dye structure, a subphthalocyanine dye structure, an azo dye structure, a pyrazolotriazole dye structure, a dipyrromethene dye structure, an isoindoline dye structure, a thiazole dye structure, a benzimidazolone dye structure, a perinone dye structure, a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, a diiminium dye structure, a naphthalocyanine dye structure, a rylene dye structure, a dibenzofuranone dye structure, a merocyanine dye structure, a croconium dye structure, and an oxonol dye structure. 4 The structure derived from the dye compound represented by formula (XT-1) is preferably a structure derived from the compound represented by formula (XT-1) or a structure derived from the compound represented by formula (TP-1), and more preferably a structure derived from the compound represented by formula (XT-1).
[0058] P 4 Examples of the substituent represented by P include an acid group and a polymerizable group. 4 The substituent represented by may be a monovalent polymer chain having a repeating unit. The monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound. When k is 2 or more, k P 4 may be the same or different.
[0059] - Pigment - The pigment may be either an inorganic pigment or an organic pigment, but from the viewpoints of a wide range of color variations, ease of dispersion, safety, etc., organic pigments are preferred.
[0060] Examples of organic pigments include phthalocyanine pigments, dioxazine pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, azo pigments, azomethine pigments, diketopyrrolopyrrole pigments, pyrrolopyrrole pigments, isoindoline pigments, quinophthalone pigments, triarylmethane pigments, xanthene pigments, cyanine pigments, quinoline pigments, and pteridine pigments.
[0061] The average primary particle diameter of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. In this specification, the primary particle diameter of the pigment can be determined from a photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment. In addition, the average primary particle diameter in the present invention is the arithmetic mean value of the primary particle diameters of 400 primary particles of the pigment. Furthermore, primary particles of the pigment refer to independent particles that are not aggregated.
[0062] The crystallite size of the pigment is preferably 0.1 to 50 nm, more preferably 0.5 to 30 nm, and even more preferably 1 to 15 nm. The crystallite size can be determined from the half-width of the diffraction angle peak using an X-ray diffractometer and calculated using the Scherrer equation. The crystallite size of the pigment can be adjusted by known methods such as adjusting the production conditions or pulverizing the pigment after production.
[0063] The specific surface area of the pigment is 1 to 300 m 2 / g. The lower limit is 10 m 2 / g or more, and 2 / g or more is more preferable. 2 / g or less, and 2 The value of the specific surface area can be determined according to the BET (Brunauer, Emmett and Teller) method in accordance with DIN 66131: Determination of the specific surface area of solids by gas adsorption.
[0064] The amount of pigment dissolved in 100 g of propylene glycol methyl ether acetate at 25° C. is preferably less than 0.01 g, more preferably less than 0.005 g, and even more preferably less than 0.001 g.
[0065] Examples of pigments include yellow pigments, orange pigments, red pigments, green pigments, purple pigments, and blue pigments.
[0066] Examples of the red pigment include diketopyrrolopyrrole pigments, anthraquinone pigments, azo pigments, naphthol pigments, azomethine pigments, xanthene pigments, quinacridone pigments, perylene pigments, and thioindigo pigments, and diketopyrrolopyrrole pigments, anthraquinone pigments, and azo pigments are preferred, and diketopyrrolopyrrole pigments are more preferred. Specific examples of the red pigment include C.I. (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 1 49,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291,294,295,296,297, etc. In addition, as a red pigment, a compound described in paragraph 0034 of WO 2022 / 085485, a brominated diketopyrrolopyrrole compound described in JP-A-2020-085947 can also be used.
[0067] As the red pigment, C.I. Pigment Red 122, 177, 224, 254, 255, 264, 269, and 272 are preferred, C.I. Pigment Red 254, 264, and 272 are more preferred, and C.I. Pigment Red 254 and 272 are even more preferred.
[0068] Examples of green pigments include phthalocyanine pigments and squarylium pigments, with phthalocyanine pigments being preferred. Specific examples of green pigments include C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. Furthermore, halogenated zinc phthalocyanine pigments having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms per molecule can also be used as green pigments. Specific examples include the compounds described in WO 2015 / 118720. Furthermore, as green colorants, compounds described in paragraph 0029 of WO 2022 / 085485, aluminum phthalocyanine compounds described in JP 2020-070426 A, diarylmethane compounds described in JP 2020-504758 A, and the like can also be used.
[0069] As the green pigment, C.I. Pigment Green 7, 36, 58, 62, and 63 are preferred, and C.I. Pigment Green 36 and 58 are more preferred.
[0070] Examples of orange pigments include diketopyrrolopyrrole pigments and azo pigments, and diketopyrrolopyrrole pigments are preferred. Specific examples of orange pigments include C.I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, and 73.
[0071] Examples of the yellow pigment include an azo pigment, an azomethine pigment, an isoindoline pigment, a pteridine pigment, a quinophthalone pigment, and a perylene pigment, and is preferably an isoindoline pigment, a quinophthalone pigment, or an azo pigment. Specific examples of the yellow pigment include C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236, etc.
[0072] Furthermore, as the yellow pigment, an azobarbituric acid nickel complex having the following structure can also be used.
[0073] Examples of purple pigments include dioxazine pigments, quinacridone pigments, perylene pigments, thioindigo pigments, etc. Specific examples of purple pigments include C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.
[0074] Examples of blue pigments include phthalocyanine pigments and squarylium pigments, with phthalocyanine pigments being preferred. Specific examples of blue pigments include C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, and 88. Furthermore, aluminum phthalocyanine compounds having phosphorus atoms can also be used as blue pigments. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A No. 2012-247591 and paragraph 0047 of JP-A No. 2011-157478.
[0075] As colorants, triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in JP 2020-117638 A, phthalocyanine compounds described in WO 2020 / 174991 A, isoindoline compounds or salts thereof described in JP 2020-160279 A, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069442 A, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069730 A, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069730 A, Compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069070, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069067, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069062, halogenated zinc phthalocyanine pigments described in Japanese Patent No. 6809649, isoindoline compounds described in Japanese Patent Application Laid-Open No. 2020-180176, phenothiazine compounds described in Japanese Patent Application Laid-Open No. 2021-187913, halogenated zinc phthalocyanines described in International Publication No. 2022 / 004261, and halogenated zinc phthalocyanines described in International Publication No. halogenated zinc phthalocyanines described in Korean Patent Publication No. 10-2020-0030759, quinophthalone compounds represented by formula 1 in Korean Patent Publication No. 10-2020-0061793, polymeric dyes described in Korean Patent Publication No. 10-2020-0061793, chromatic colorants described in JP 2022-029701, isoindoline compounds described in WO 2022 / 014635, aluminum phthalocyanine compounds described in WO 2022 / 024926, compounds described in JP 2022-045895, and WO 2022 / 05005 Compounds described in JP-A-2020-090676, compounds described in JP-A-2020-055956, compounds described in JP-A-2021-031681, compounds described in JP-A-2022-056354, compounds described in US Patent Application Publication No. 2021 / 0355327, compounds described in WO 2022 / 065357, compounds described in JP-A-2020-045436, compounds described in Korean Patent Publication No. 10-2021-0146726, compounds described in JP-A-2018-178039,Compounds described in Chinese Patent Application Publication No. 113881244, compounds described in Chinese Patent Application Publication No. 113881245, compounds described in Chinese Patent Application Publication No. 113881246, compounds described in JP 2022-104822 A, compounds described in JP 2022-096701 A, compounds described in JP 2020-023652 A, green pigments described in the Journal of the Japan Color Materials Association (published in 2022) pages 80 to 84, compounds described in JP 2022-143135 A, compounds described in JP 2022-140287 A, compounds described in WO 2014 / 014906 Compounds described in Patent Publication No. 2022 / 136308, perylene compounds described in Chinese Patent Application Publication No. 113061349, cyan pigments described in Korean Patent Publication No. 10-2017-0018993, isoindoline compounds described in JP 2020-180176, compounds described in JP 2023-013209, compounds described in JP 2023-013166, xanthene compounds described in WO 2023 / 286526, compounds described in JP 2021-155746, compounds described in JP 2021-155747, JP Compounds described in JP-A-2021-155748, compounds described in JP-A-2021-155749, compounds described in WO 2018 / 051876, compounds described in JP-A-2020-083981, compounds described in JP-A-2023-056463, compounds described in JP-T-2023-515473, dioxane compounds described in JP-T-2022-549530, pigment preparations described in JP-A-2022-061494, diketopyrrolopyrrole pigments described in JP-A-2023-057917, and JP-A-2023-061273 Diketopyrrolopyrrole compounds described in JP-A-2023-519314, phthalocyanines described in JP-A-2023-080419, quinophthalones described in JP-A-2023-103177, phthalocyanine compounds described in JP-A-2023-103177, isoindoline compounds described in JP-A-2020-026521, squarylium compounds described in Korean Patent Publication No. 10-2023-0043000, squarylium compounds described in Korean Patent Publication No. 10-2023-0050069, diketopyrrolopyrrole compounds described in JP-A-2023-127878,Triarylmethane compounds described in JP 2023-150459 A, triarylmethane compounds described in JP 2023-149735 A, core-shell dyes described in JP 2023-123349 A, xanthene compounds described in JP 2023-543717 A, compounds described in Chinese Patent Application Publication No. 116102441 A, compounds described in JP 2023-150459 A, compounds described in JP 2023-167345 A, compounds described in Korean Patent Publication No. 10-2023-0061078, and the like can also be used. The colorant may also be a rotaxane. The dye skeleton may be used in the cyclic structure of the rotaxane, in the rod-shaped structure, or in both structures.
[0076] The content of the colorant in the total solid content of the coloring composition is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, and the upper limit is preferably 80% by mass or less, and more preferably 75% by mass or less.
[0077] The content of the dye in the total solid content of the coloring composition is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and particularly preferably 15% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, particularly preferably 40% by mass or less, and most preferably 30% by mass or less. Furthermore, the content of the dye in the colorant contained in the coloring composition is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, and particularly preferably 25% by mass or more. The upper limit can be 100% by mass or less, or can be 90% by mass or less, or can be 80% by mass or less, or can be 70% by mass or less, or can be 60% by mass or less, or can be 50% by mass or less.
[0078] When the colorant contained in the coloring composition of the present invention further contains a pigment, the content of the pigment is preferably 10 to 1,000 parts by mass relative to 100 parts by mass of the dye. The lower limit is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, and even more preferably 200 parts by mass or more. The upper limit is preferably 600 parts by mass or less, more preferably 400 parts by mass or less.
[0079] <<Polymerization initiator B>> The coloring composition of the present invention contains a polymerization initiator B (hereinafter referred to as a polymerization initiator). The polymerization initiator is preferably a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet to visible regions is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.
[0080] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a hexaarylbiimidazole compound, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, or a 3-aryl-substituted coumarin compound, more preferably a compound selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound. Further, as the photopolymerization initiator, compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, photopolymerization initiators described in WO 2018 / 221177, photopolymerization initiators described in WO 2018 / 110179, photopolymerization initiators described in JP-A-2019-043864, photopolymerization initiators described in JP-A-2019-044030, peroxide-based initiators described in JP-A-2019-167313, oxazolidinyl compounds described in JP-A-2020-055992, Aminoacetophenone-based initiators having an amine group, oxime-based photopolymerization initiators described in JP-A-2013-190459, polymers described in JP-A-2020-172619, compounds represented by formula 1 described in WO 2020 / 152120, compounds described in JP-A-2021-181406, photopolymerization initiators described in JP-A-2022-013379, compounds represented by formula (1) described in JP-A-2022-015747,Fluorine-containing fluorene oxime ester photoinitiators described in JP-T-2021-507058, initiators described in Chinese Patent Application Publication No. 110764367, initiators described in JP-T-2022-518535, initiators described in WO 2021 / 175855, compounds described in Taiwan Patent Application Publication No. 202200534, compounds described in JP-A-2022-078550, Korean Patent Publication No. Compounds described in Patent Publication No. 10-2017-0087330, compounds described in International Publication No. 2022 / 075452, oxime ester compounds described in Chinese Patent Application Publication No. 110066225, compounds described in Korean Patent Publication No. 10-2022-0076157, compounds having a triarylamine or N-arylcarbazole skeleton described in paragraphs 0042 to 00 of International Publication No. 2019 / 013112 62, an oxime ester-based photopolymerization initiator described in Japanese Patent No. 7219378, a photopolymerization initiator described in Korean Patent Publication No. 10-2021-0146174, a photopolymerization initiator described in International Publication No. 2019 / 013112, a photopolymerization initiator described in JP-A-2023-033731, an initiator described in JP-T-2022-515524, an initiator described in JP-T-2023-517304 , initiators described in Chinese Patent Application Publication No. 114149517, aminoketone compounds described in Chinese Patent Application Publication No. 115925596, compounds described in Japanese Patent Application Publication No. 2023-159489, compounds described in Japanese Patent Application Publication No. 2023-159487, compounds described in Taiwan Patent Application Publication No. 202336003, and compounds described in Chinese Patent Application Publication No. 113527138.
[0081] Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.
[0082] Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (all manufactured by BASF), etc. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (all manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (all manufactured by BASF), etc.
[0083] Examples of the oxime compound include the compounds described in paragraph 0142 of WO 2022 / 085485, the compounds described in Japanese Patent No. 5430746, the compounds described in Japanese Patent No. 5647738, the compounds represented by the general formula (1) of JP-A-2021-173858, and the compounds described in paragraphs 0022 to 0024, and the compounds represented by the general formula (1) of JP-A-2021-170089 and the compounds described in paragraphs 0117 to 0120. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04, Irgacure OXE05 (all manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-3054, TR-PBG-3057, TR-PBG-314, TR-PBG-327, TR-PBG-345, TR-PBG-346, TR- Examples of suitable oxime compounds include PBG-358, TR-PBG-365, TR-PBG-380, TR-PBG-610, TR-PBG-A, and TR-PBG-B (all manufactured by TRONLY Corporation), and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation; photopolymerization initiator 2 described in JP 2012-014052 A). Furthermore, it is also preferable to use, as the oxime compound, a compound that is not colorable or a compound that is highly transparent and does not easily discolor. Commercially available products include ADEKA ARCLES NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).
[0084] As the photopolymerization initiator, an oxime compound having a fluorene ring, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, an oxime compound having a fluorine atom, an oxime compound having a nitro group, an oxime compound having a benzofuran skeleton, an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton, or a compound described in paragraphs 0143 to 0149 of WO 2022 / 085485 can also be used.
[0085] As the photopolymerization initiator, a compound represented by formula (OX-1) can also be used.
[0086] In formula (OX-1), X 1a represents a divalent linking group containing at least one ring selected from the group consisting of an aromatic ring and a heterocyclic ring; 1a represents a hydrogen atom or an acyl group; R 2a represents an alkyl group or an aryl group; R 3a and R 4a each independently represents a hydrogen atom or an alkyl group; Alk 1 and Alk 2 each independently represents an alkyl group; R 3a and R 4a may be bonded to form a ring, Alk 1 and Alk 2 may be bonded to form a ring, and n represents 0 or 1.
[0087] X in formula (OX-1) 1a Examples of the divalent linking group represented by include a divalent aromatic ring group, a divalent heterocyclic group, a divalent group in which two or more aromatic rings are bonded via a single bond or a linking group, a divalent group in which two or more heterocycles are bonded via a single bond or a linking group, and a divalent group in which an aromatic ring and a heterocycle are bonded via a single bond or a linking group. Examples of the linking group that bonds the above-mentioned aromatic rings, heterocyclic groups, or aromatic rings and heterocycles include -CH 2 -, -O-, -CO-, -S-, -NR x - and groups combining these. xrepresents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
[0088] X in formula (OX-1) 1a is preferably a group represented by any one of formulas (X-1) to (X-13), more preferably a group represented by formula (X-1), formula (X-2), formula (X-4), formula (X-6) or formula (X-8), and further preferably a group represented by formula (X-2) or formula (X-6). In the formula R X1 ~R X9 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and * represents a bond.
[0089] R X1 ~R X9 The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heterocyclic group.
[0090] R X1 ~R X9 The number of carbon atoms in the alkenyl group represented by is preferably 2 to 15, and more preferably 2 to 10. The alkenyl group may be linear, branched, or cyclic. The alkenyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heterocyclic group.
[0091] R X1 ~R X9 The number of carbon atoms in the alkynyl group represented by is preferably 2 to 15, and more preferably 2 to 10. The alkynyl group may be linear, branched, or cyclic. The alkynyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heterocyclic group.
[0092] R X1 ~R X9The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heterocyclic group.
[0093] R X1 ~R X9 The heterocyclic group represented by is preferably a 5-membered or 6-membered ring. The heteroatoms contained in the heterocyclic group are preferably oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms contained in the heterocyclic group is preferably 1 to 3. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.
[0094] R in formula (OX-1) 1a represents a hydrogen atom or an acyl group, and is preferably an acyl group. 1a The acyl group represented by is —C(O)—R 101 It is preferable that R 101 represents an aryl group or a heterocyclic group, and is preferably an aryl group.
[0095] R 101 The number of carbon atoms in the aryl group represented by R is preferably 6 to 20, and more preferably 6 to 12. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heterocyclic group. 101 The aryl group represented by is preferably a phenyl group, a methylphenyl group or a naphthyl group, more preferably a methylphenyl group or a naphthyl group.
[0096] R 101 The heterocyclic group represented by is preferably a 5-membered or 6-membered ring. The heteroatoms contained in the heterocyclic group are preferably oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms contained in the heterocyclic group is preferably 1 to 3. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.
[0097] R in formula (OX-1)2a represents an alkyl group or an aryl group, and is preferably an alkyl group because the reactivity of the generated radical is high. 2a The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent, but is preferably an unsubstituted alkyl group. R 2a The alkyl group represented by R is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group. 2a The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6. The aryl group may have a substituent, but is preferably an unsubstituted aryl group.
[0098] R in formula (OX-1) 3a and R 4a R each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom. 3a and R 4a The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent, but is preferably an unsubstituted alkyl group. R 3a and R 4a may be bonded to form a ring. The ring formed is preferably a 5- or 6-membered ring, and more preferably a 5- or 6-membered aliphatic hydrocarbon ring.
[0099] Alk of formula (OX-1) 1 and Alk 2each independently represents an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent, but is preferably an unsubstituted alkyl group. Alk 1 and Alk 2 may be bonded to form a ring, and preferably form a ring. The ring formed is preferably a 5- or 6-membered ring, more preferably a 5- or 6-membered aliphatic hydrocarbon ring, and more preferably a cyclopentane ring or a cyclohexane ring.
[0100] In formula (OX-1), n represents 0 or 1, and is preferably 0.
[0101] Specific examples of the compound represented by formula (OX-1) include the compounds described in paragraphs 0092 to 0096 of JP-A No. 2012-113104 and the compound described in paragraph 0041 of JP-A No. 2012-189997.
[0102] As the photopolymerization initiator, a compound represented by formula (OX-2) can also be used.
[0103] In formula (OX-2), R 1b and R 2b each independently represents a substituent, R 3b ~R 7b each independently represents a hydrogen atom or a substituent, Ar 1b represents an aromatic ring group or a heterocyclic group which may have a substituent; n represents 0 or 1;
[0104] R 1b and R 2bExamples of the substituent represented by include an alkyl group and an aryl group, and an alkyl group is preferred. The alkyl group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkenyl group, an alkynyl group, and a heterocyclic group. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, even more preferably 6 to 10 carbon atoms, and particularly preferably 6 carbon atoms. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heterocyclic group.
[0105] R 3b ~R 7b Examples of the substituent represented by R include a halogen atom, an alkyl group, and an aryl group. Examples of the alkyl group and the aryl group include those described above. 3b ~R 7b is preferably a hydrogen atom.
[0106] Ar 1b represents an aromatic ring group or a heterocyclic group which may have a substituent, Ar 1b is preferably an aromatic ring group which may have a substituent. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a nitro group, and an acyl group, and an acyl group is preferred. Examples of the acyl group include the acyl groups described above.
[0107] As the photopolymerization initiator, a compound represented by formula (OX-3) can also be used.
[0108] In formula (OX-3), Ar 1c represents a (k+m+1)-valent aromatic ring group or a (k+m+1)-valent heterocyclic group; Ar 2c represents a (k+2)-valent aromatic ring group or a (k+2)-valent heterocyclic group; R 1c ~R 3ceach independently represents a substituent; 1c is a single bond or CR 11c R 12c represents R 11c and R 12c each independently represents a hydrogen atom, an alkyl group, or an aryl group; 1c Ha-CH 2 represents --, --O-- or --S--; k represents 0 or 1; m represents an integer of 0 to 4; and n represents 0 or 1.
[0109] R 1c and R 2c Examples of the substituent represented by include an alkyl group and an aryl group, and an alkyl group is preferred. The alkyl group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkenyl group, an alkynyl group, and a heterocyclic group. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, even more preferably 6 to 10 carbon atoms, and particularly preferably 6 carbon atoms. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heterocyclic group. R 2c is preferably an alkyl group having a branched or cyclic structure.
[0110] R 3c Examples of the substituent represented by include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an acyl group, and an acyl group is preferred. Examples of the acyl group include the acyl groups described above.
[0111] L 1c is a single bond or CR 11c R 12c represents R 11c and R 12c R each independently represents a hydrogen atom, an alkyl group, or an aryl group. 11c and R 12c The alkyl group and aryl group in R 1c and R 2cWhen k is 1, L 1c is preferably a single bond.
[0112] X 1c is -CH 2 It represents -, -O- or -S-, and is preferably -O- or -S-.
[0113] Ar 1c represents a (k+m+1)-valent aromatic ring group or a (k+m+1)-valent heterocyclic group, and is preferably a (k+m+1)-valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.
[0114] Ar 2c represents a (k+2)-valent aromatic ring group or a (k+2)-valent heterocyclic group, and is preferably a (k+2)-valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.
[0115] k represents 0 or 1, and is preferably 0. m represents an integer of 0 to 4, and is preferably 0 or 1, and more preferably 1. n represents 0 or 1, and is preferably 0.
[0116] Specific examples of the oxime compound include the compounds shown below.
[0117]
[0118]
[0119]
[0120]
[0121]
[0122] The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. Furthermore, from the viewpoint of sensitivity, the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1,000 to 300,000, even more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure using a spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.
[0123] As the photopolymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thereby obtaining good sensitivity. Furthermore, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in solvents and the like is improved, making it less likely to precipitate over time, and improving the stability of the coloring composition over time. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include the compounds described in paragraph 0148 of WO 2022 / 065215.
[0124] The content of the polymerization initiator in the total solid content of the colored composition is preferably 0.1 to 30% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less. In the colored composition of the present invention, only one type of polymerization initiator may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.
[0125] <<Polymerizable Compound C>> The coloring composition of the present invention contains a polymerizable compound C (hereinafter referred to as a polymerizable compound). Examples of the polymerizable compound include a compound having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. The polymerizable compound used in the present invention is preferably a radically polymerizable compound.
[0126] The polymerizable compound may be in any chemical form, such as a monomer, prepolymer, or oligomer, but is preferably a monomer. The molecular weight of the polymerizable compound is preferably 100 to 3,000. The upper limit is more preferably 2,000 or less, and even more preferably 1,500 or less. The lower limit is more preferably 150 or more, and even more preferably 250 or more.
[0127] The polymerizable compound is preferably a compound containing two or more ethylenically unsaturated bond-containing groups, more preferably a compound containing three or more ethylenically unsaturated bond-containing groups, even more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and particularly preferably a compound containing 3 to 6 ethylenically unsaturated bond-containing groups. Furthermore, the polymerizable compound is preferably a trifunctional to 15-functional (meth)acrylate compound, more preferably a trifunctional to hexafunctional (meth)acrylate compound. Specific examples of the polymerizable compound include the compounds described in paragraphs 0075 to 0083 of WO 2022 / 065215 and the compounds described in Taiwan Patent Application Publication No. 201832008.
[0128] Preferred polymerizable compounds include dipentaerythritol tri(meth)acrylate (commercially available product: KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product: KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product: KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., and NK Ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds having a structure in which the (meth)acryloyl group is bonded via an ethylene glycol and / or propylene glycol residue (e.g., SR454, SR499, commercially available from Sartomer).Examples of polymerizable compounds include diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available product: M-460, manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (NK Ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (KAYARAD, manufactured by Nippon Kayaku Co., Ltd.). HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1 006, 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), Aronix MT-3041, 3042 (manufactured by Toagosei Co., Ltd., polymerizable compounds containing amines), Aronix M-510, 520 (manufactured by Toagosei Co., Ltd., polymerizable compounds having an acidic group), Etercure 6361-100 (Eternal Materials, polymerizable compound having a hyperbranched structure), EBECRYL80 (amine-containing tetrafunctional monomer, manufactured by Daicel-Olknes Co., Ltd.), EBECRYL7100 (amine-containing bifunctional monomer, manufactured by Daicel-Olknes Co., Ltd.), CN371NS (amine-containing bifunctional monomer, manufactured by Arkema), HOA-MPL (2-acryloyloxyethyl-phthalic acid: manufactured by Kyoeisha Chemical Co., Ltd.), HOA-MPE (2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid: manufactured by Kyoeisha Chemical Co., Ltd.), polymerizable compounds having a dendrimer structure or hyperbranched structure described in JP 2023-043479 A, polymerizable compounds described in JP 2023-529984 A, polymerizable compounds described in WO 2023 / 190562, and the like can also be used.
[0129] As the polymerizable compound, a polymerizable compound having a fluorene skeleton can also be used. The polymerizable compound having a fluorene skeleton is preferably a bifunctional polymerizable compound. Commercially available polymerizable compounds having a fluorene skeleton include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).
[0130] The content of the polymerizable compound in the total solid content of the coloring composition is preferably 1 to 35% by mass, and more preferably 5 to 30% by mass. The upper limit is preferably 25% by mass or less, and more preferably 20% by mass or less. The lower limit is preferably 8% by mass or more, and more preferably 10% by mass or more. The coloring composition of the present invention may contain only one type of polymerizable compound, or may contain two or more types. When two or more types of polymerizable compounds are contained, the total amount thereof preferably falls within the above range.
[0131] <<Compound D>> The coloring composition of the present invention contains compound D, which is a salt of cation dx and anion dz and is represented by formula (Aλ) and has a specific absorbance of 5 or less. The anion dz is an anion containing a boron atom, and has a fluorine atom content of 50 mass% or less.
[0132] E 1 =A 1 / (c 1 ×l 1 )...(Aλ) In formula (Aλ), E 1 represents the specific absorbance of compound D at the maximum absorption wavelength in the wavelength range of 400 to 700 nm, and A 1 represents the absorbance of Compound D at the maximum absorption wavelength in the wavelength range of 400 to 700 nm, and 1 represents the cell length in cm, and c 1 represents the concentration of Compound D in solution, expressed in mg / ml.
[0133] The specific absorbance of compound D represented by formula (Aλ) is 5 or less, preferably 3 or less, and more preferably 1 or less. The specific absorbance represented by formula (Aλ) is an index showing the degree to which compound D absorbs light in the visible range. The smaller the specific absorbance represented by formula (Aλ), the lower the absorbance of light in the visible range. There is no lower limit for the specific absorbance. When a lower limit for the specific absorbance is set, the specific absorbance represented by formula (Aλ) may be determined to be 0.001 or more.
[0134] In the formula (Aλ), “A 1 The absorbance represented by " is measured by the following method. A measurement sample is prepared using compound D and a solvent in which compound D is sufficiently soluble. When compound D has sufficient solubility in 1-methoxy-2-propanol, 1-methoxy-2-propanol is used as the solvent. When compound D does not have sufficient solubility in 1-methoxy-2-propanol, cyclohexanone is used as the solvent. The absorbance of the measurement sample at 25°C (room temperature) is measured using a cell with an optical path length of 1 cm.
[0135] The molecular weight of compound D is preferably 80 to 5000. The upper limit is preferably 3000 or less, more preferably 2000 or less, even more preferably 1500 or less, and particularly preferably 1200 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 250 or more.
[0136] Compound D may have a polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated bond-containing group such as a vinyl group, an allyl group, or a (meth)acryloyl group, an epoxy group, or an oxetanyl group, and an ethylenically unsaturated bond-containing group is preferred. When compound D has a polymerizable group, cation dx may have a polymerizable group, an anion dz may have a polymerizable group, or each of cation dx and anion dz may have a polymerizable group.
[0137] The amount of Compound D dissolved in 100 g of 1-methoxy-2-propanol at 25° C. is preferably 0.1 g or more, more preferably 0.5 g or more, and even more preferably 1 g or more.
[0138] The amount of Compound D dissolved in 100 g of cyclohexanone at 25° C. is preferably 0.1 g or more, more preferably 0.5 g or more, and even more preferably 1 g or more.
[0139] The molar absorption coefficient of Compound D at a wavelength of 248 nm is 300 to 20,000 L mol because it can promote film curing by exposure. -1 ・cm -1 It is preferable that the concentration is 400 to 5000 L mol -1 ・cm -1 More preferably, it is 700 to 2000 L mol -1 ・cm -1 It is more preferable that:
[0140] Specific examples of Compound D include Compounds D-1 to D-24 shown in the Examples below.
[0141] (Anion dz) In compound D, anion dz that forms a salt with cation dx is an anion containing a boron atom and has a fluorine atom content of 50 mass % or less.
[0142] The fluorine atom content of the anion dz is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. It is particularly preferable that the anion dz does not contain fluorine atoms.
[0143] The molecular weight of the anion dz is preferably 100 to 800, more preferably 200 to 600, and even more preferably 300 to 500.
[0144] The molar absorption coefficient of the anion dz at a wavelength of 248 nm is 200 to 15,000 L mol -1 ・cm -1 It is preferable that the concentration is 500 to 5000 L mol -1 ・cm -1More preferably, it is 800 to 2000 L mol -1 ・cm -1 It is more preferable that:
[0145] The anion dz is preferably a monovalent or divalent anion, more preferably a monovalent anion.
[0146] Examples of the anion dz include anions represented by formula (dz-1) and anions represented by formula (dz-2), and the anion represented by formula (dz-1) is preferred.
[0147]
[0148] R in formula (dz-1) d1 ~R d4 each independently represents an alkyl group, an aryl group, or a heteroaryl group.
[0149] R d1 ~R d4 The number of carbon atoms in the alkyl group represented by R is preferably 1 to 10, and more preferably 1 to 6. d1 ~R d4 The alkyl group represented by may be linear, branched or cyclic. d1 ~R d4 The alkyl group represented by may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, an aryl group, an aryloxy group, an acyl group, and an acyloxy group, and an alkoxy group, an aryl group, an aryloxy group, an acyl group, or an acyloxy group is preferred. d1 ~R d4 The alkyl group represented by is preferably an unsubstituted alkyl group.
[0150] R d1 ~R d4 The aryl group represented by R preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. d1 ~R d4 The aryl group represented by R is preferably a phenyl group. d1 ~R d4The aryl group represented by may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group, and an acyloxy group, and an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group, or an acyloxy group is preferred. d1 ~R d4 The aryl group represented by is preferably an unsubstituted aryl group.
[0151] R d1 ~R d4 The heteroaryl group represented by is preferably a 5-membered or 6-membered ring. The heteroatom contained in the heteroaryl group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom. The number of heteroatoms contained in the heteroaryl group is preferably 1 to 3. The heteroaryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group, and an acyloxy group, and the alkyl group, alkoxy group, aryl group, aryloxy group, acyl group, or acyloxy group is preferred. R d1 ~R d4 The heteroaryl group represented by is preferably an unsubstituted heteroaryl group.
[0152] R in formula (dz-1) d1 ~R d4 are each independently preferably an alkyl group or an aryl group, more preferably an aryl group.
[0153] R in formula (dz-2) d11 ~R d14 each independently represents —O—, —CO—, —COO—, or —OCO—; L d11 and L d12 each independently represents a single bond or a hydrocarbon group. d11 and L d12 The hydrocarbon group represented by may be linear, branched or cyclic. d11 and L d12 The hydrocarbon group represented by may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
[0154] Specific examples of the anion dz include anions dz1 to dz16 described in the examples below, and the anion dz1 (tetraphenylboron anion) is preferred.
[0155] (Cation dx) In compound D, examples of the cation dx that forms a salt with the anion dz include a cation of a single typical metal atom, a carbocation, an ammonium cation, a phosphonium cation, and a sulfonium cation. A cation of a single typical metal atom or an ammonium cation is preferred, and an ammonium cation or a potassium cation is more preferred because it can improve the storage stability of the colored composition.
[0156] The cation of a simple substance of a typical metal atom is preferably a cation of a metal element contained in Group 1A (alkali metal), Group 2A (alkaline earth metal), Group 2B (zinc group), Group 3B (boron group), Group 4B (carbon group), or Group 5B (nitrogen group) of the periodic table. Specific examples include lithium (Li) cation, beryllium (Be) cation, sodium (Na) cation, magnesium (Mg) cation, aluminum (Al) cation, potassium (K) cation, calcium (Ca) cation, zinc (Zn) cation, gallium (Ga) cation, rubidium (Rb) cation, strontium (Sr) cation, cadmium (Cd) cation, indium (In) cation, tin (Sn) cation, cesium (Cs) cation, barium (Ba) cation, mercury (Hg) cation, thallium (Tl) cation, lead (Pb) cation, bismuth (Bi) cation, francium (Fr) cation, and radium (Ra) cation. Among these, lithium (Li) cation, sodium (Na) cation, magnesium (Mg) cation, aluminum (Al) cation, potassium (K) cation, calcium (Ca) cation, zinc (Zn) cation, gallium (Ga) cation, rubidium (Rb) cation, strontium (Sr) cation, indium (In) cation, cesium (Cs) cation, and barium (Ba) cation are preferred, lithium (Li) cation, sodium (Na) cation, magnesium (Mg) cation, aluminum (Al) cation, potassium (K) cation, calcium (Ca) cation, and zinc (Zn) cation are more preferred, and lithium (Li) cation, sodium (Na) cation, and potassium (K) cation are even more preferred.
[0157] Examples of the ammonium cation include cations represented by the following formula (dx-1). In formula (dx-1), R AN1 ~R AN4 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group, and the hydrogen atoms contained therein are not represented by -OH, -CH=CH 2 or -CH=CHR bIn addition, between the carbon-carbon bonds of the alkyl group and the alkenyl group, there may be substituted with —O—, —S—, —CO—, —NH— or —NR b - may be inserted. AN1 ~R AN4 may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom. In this case, a hydrogen atom contained in the heterocyclic ring may be substituted by -R b , may be substituted with —OH. b represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms.
[0158] The molecular weight of the ammonium cation is preferably 80 to 600, more preferably 90 to 400, and even more preferably 100 to 300.
[0159] Specific examples of ammonium cations include tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, tetrabutylammonium cation, monoethyltrimethylammonium cation, monopropyltrimethylammonium cation, monobutyltrimethylammonium cation, monostearyltritylammonium cation, distearyldimethylammonium cation, tristearylmonomethylammonium cation, stearyltrimethylammonium cation, trioctylmethylammonium cation, dioctyldimethylammonium cation, monolauryltrimethylammonium cation, dilauryldimethylammonium cation, trilaurylmethylammonium cation, triamylbenzylammonium cation, trihexylbenzylammonium cation, trioctylbenzylammonium cation, trilaurylbenzylammonium chloride cation, benzyldimethylstearylammonium cation, benzyldimethyloctylammonium cation, dialkyl (alkyl is C14 to C18)dimethylammonium cation, cations of the structures shown below, and cations dx1 to dx4 listed in the examples.
[0160] The cation dx is preferably a monovalent to trivalent cation, more preferably a monovalent or trivalent cation, and even more preferably a monovalent cation.
[0161] The content of compound D in the total solid content of the coloring composition is preferably 0.1 to 15% by mass. The upper limit is preferably 12% by mass or less, and more preferably 10% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more.
[0162] The ratio of the molar amount of compound D to the molar amount of the dye is preferably 0.1 to 2, more preferably 0.3 to 1.2, and even more preferably 0.5 to 0.9, because this ratio allows the effects of the present invention to be more significantly exhibited.
[0163] When a dye a1 having a chemical structure containing a cation ax and an anion az is used as the dye, the ratio of the molar amount of the anion dz of the compound D to the molar amount of the cation ax of the dye a1 is preferably 0.1 to 2, more preferably 0.3 to 1.2, and even more preferably 0.5 to 0.9, because this ratio allows the effects of the present invention to be more significantly exhibited.
[0164] Only one type of compound D may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is in the above range.
[0165] <<Polyalkyleneoxy Compound>> The colored composition of the present invention preferably contains a polyalkyleneoxy compound. Examples of the polyalkyleneoxy compound include compounds represented by formula (PAO-1).
[0166] In formula (PAO-1), R ao1 and R ao2 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a group having 1 to 6 carbon atoms containing an acid group, or a group having 1 to 6 carbon atoms containing an amino group; X ao1 represents a linear or branched alkylene group, n represents an integer of 1 or more, and when n is 2 or more, a plurality of X ao1may be the same or different.
[0167] R ao1 and R ao2 The number of carbon atoms in the alkyl group represented by is preferably 1 to 3, and more preferably 1 or 2. The alkyl group is preferably a methyl group or an ethyl group, and more preferably a methyl group.
[0168] R ao1 and R ao2 The aryl group having 6 to 12 carbon atoms represented by is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
[0169] R ao1 and R ao2 With regard to the group having 1 to 6 carbon atoms containing an acid group represented by the formula (I), examples of the acid group include a carboxy group, a sulfo group, and a phosphate group.
[0170] R ao1 and R ao2 The amino group may be any of the following: -NRa 1 Ra 2 Examples include those represented by the formula: Ra 1 and Ra 2 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
[0171] R ao1 and R ao2 are each preferably independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ao1 and R ao2 and the other is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably a hydrogen atom). ao1 and R ao2 At least one of the groups is an alkyl group (preferably a methyl group).
[0172] X ao1represents a linear or branched alkylene group, and is preferably a linear alkylene group. The alkylene group preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms. X ao1 is preferably an ethylene group.
[0173] When n is 2 or more, multiple X ao1 may be the same or different, but are preferably the same. ao1 At least one of X is preferably an ethylene group. ao1 is more preferably an ethylene group.
[0174] In formula (PAO-1), n represents an integer of 1 or more. The upper limit of n is preferably 500 or less, more preferably 50 or less, and even more preferably 15 or less. The lower limit of n is preferably 2 or more, and more preferably 4 or more.
[0175] The molecular weight of the polyalkyleneoxy compound is preferably 100 to 30,000, more preferably 100 to 10,000, even more preferably 100 to 5,000, and particularly preferably 150 to 2,000. The upper limit of the molecular weight is preferably 1,000 or less, more preferably 800 or less, and even more preferably 500 or less. In this specification, the molecular weight of the polyalkyleneoxy compound refers to the value calculated from the structural formula of the polyalkyleneoxy compound when the molecular weight can be calculated from the structural formula, and when it is difficult to calculate from the structural formula, it refers to the number average molecular weight. The number average molecular weight of the polyalkyleneoxy compound is a polystyrene-equivalent value measured by GPC (gel permeation chromatography) method.
[0176] The boiling point of the polyalkyleneoxy compound is preferably 150°C to 1000°C, more preferably 250°C to 900°C, even more preferably 300°C to 800°C, and particularly preferably 320°C to 700°C.
[0177] Specific examples of the polyalkyleneoxy compound include polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 1000, polyethylene glycol 20000, polyethylene glycol monomethyl ether 550, polyethylene glycol dimethyl ether 550, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monobutyl ether, polypropylene glycol 400, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, diethylene glycol monophenyl ether, (2-butoxyethoxy)acetic acid, and 2-[2-(2-aminoethoxy)ethoxy]ethanol.
[0178] The content of the polyalkyleneoxy compound in the coloring composition is preferably 0.01 to 5.0% by mass. The upper limit is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1.0% by mass or less. The lower limit is preferably 0.05% by mass or more. Only one type of polyalkyleneoxy compound may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
[0179] <<Resin>> The coloring composition of the present invention preferably further contains a resin. The resin is blended, for example, for the purpose of dispersing particles such as pigments in the coloring composition or for the purpose of using as a binder. Note that a resin used mainly for dispersing particles such as pigments is also called a dispersant. However, such a use of the resin is merely an example, and the resin can also be used for purposes other than the above.
[0180] The weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.
[0181] Examples of resins include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, and styrene resins. Further, examples of the resin include the resins described in paragraphs 0091 to 0099 of WO 2022 / 065215, the blocked polyisocyanate resins described in JP 2016-222891 A, the resins described in JP 2020-122052 A, the resins described in JP 2020-111656 A, the resins described in JP 2020-139021 A, the resins described in JP 2017-138503 A containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain, the resins described in paragraphs 0199 to 0233 of JP 2020-186373 A, the alkali-soluble resins described in JP 2020-186325 A, and the resins described in Korean Patent Publication No. Resins represented by formula 1 described in JP-A-2020-0078339, copolymers containing epoxy groups and acid groups described in WO 2022 / 030445, resins described in JP-A-2018-135514, copolymers described in JP-A-2020-041046, resins described in JP-A-2023-033156, resins described in JP-A-2023-030386, resins described in JP-A-2023-027753, resins described in JP-A-2020-139021, resins described in JP-A-2023-074038, resins described in JP-A-2023-079666, and cardo resins described in Chinese Patent Application Publication No. 115947929 can also be used.
[0182] The resin preferably has an acid group. The acid group can be used as an alkali-soluble resin. Examples of the acid group include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxy group.
[0183] The acid value of the resin having acid groups is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, even more preferably 300 mgKOH / g or less, and particularly preferably 200 mgKOH / g or less. The weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, and more preferably 5,000 to 50,000. The number average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.
[0184] The resin having an acid group preferably contains a repeating unit having an acid group on a side chain, and more preferably contains 5 to 70 mol% of the repeating units having an acid group on a side chain based on all repeating units of the resin. The upper limit of the content of repeating units having an acid group on a side chain is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of repeating units having an acid group on a side chain is preferably 10 mol% or more, more preferably 20 mol% or more.
[0185] For resins having acid groups, please refer to the descriptions in paragraphs
[0558] to
[0571] of JP 2012-208494 A (corresponding to paragraphs
[0685] to
[0700] of U.S. Patent Application Publication No. 2012 / 0235099 A) and paragraphs
[0076] to
[0099] of JP 2012-198408 A, the contents of which are incorporated herein by reference. Commercially available resins having acid groups can also be used. There are no particular limitations on the method for introducing acid groups into the resin, and examples include the method described in Japanese Patent No. 6,349,629 A. Furthermore, examples of methods for introducing acid groups into the resin include a method in which an acid anhydride is reacted with a hydroxy group generated by a ring-opening reaction of an epoxy group to introduce the acid group.
[0186] The coloring composition of the present invention also preferably contains a resin having a basic group. The resin having a basic group is preferably a resin containing a repeating unit having a basic group in a side chain, more preferably a copolymer having a repeating unit having a basic group in a side chain and a repeating unit not containing a basic group, and even more preferably a block copolymer having a repeating unit having a basic group in a side chain and a repeating unit not containing a basic group. The resin having a basic group can also be used as a dispersant. The amine value of the resin having a basic group is preferably 5 to 300 mgKOH / g. The lower limit is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more. The upper limit is preferably 200 mgKOH / g or less, more preferably 100 mgKOH / g or less.
[0187] Commercially available resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, and BYK-LPN6919 (all manufactured by BYK-Chemie), and Solsperse 112. 00, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by The Lubrizol Group, Japan), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like. In addition, the resin having a basic group may be the block copolymer (B) described in paragraphs 0063 to 0112 of JP-A-2014-219665, the block copolymer A1 described in paragraphs 0046 to 0076 of JP-A-2018-156021, or the vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP-A-2019-184763, the contents of which are incorporated herein by reference.
[0188] The coloring composition of the present invention also preferably contains a resin having an acid group and a resin having a basic group. According to this embodiment, the storage stability of the coloring composition can be further improved. When a resin having an acid group and a resin having a basic group are used in combination, the content of the resin having a basic group is preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 50 to 200 parts by mass, per 100 parts by mass of the resin having an acid group.
[0189] It is also preferable to use a resin having an aromatic carboxy group as the resin. In a resin having an aromatic carboxy group, the aromatic carboxy group may be contained in the main chain of the repeating unit or may be contained in a side chain of the repeating unit. It is preferable that the aromatic carboxy group is contained in the main chain of the repeating unit. In this specification, an aromatic carboxy group refers to a group having a structure in which one or more carboxy groups are bonded to an aromatic ring. In the aromatic carboxy group, the number of carboxy groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2. Examples of resins having an aromatic carboxy group include the resins described in paragraphs 0082 to 0107 of WO 2021 / 166858.
[0190] The coloring composition of the present invention preferably contains a resin as a dispersant. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the term "acidic dispersant (acidic resin)" refers to a resin in which the amount of acid groups is greater than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol% or more when the total amount of acid groups and basic groups is taken as 100 mol%. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH / g. Furthermore, the term "basic dispersant (basic resin)" refers to a resin in which the amount of basic groups is greater than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups is greater than the amount of acid groups when the total amount of acid groups and basic groups is taken as 100 mol%. The basic group possessed by the basic dispersant is preferably an amino group.
[0191] The resin used as the dispersant is preferably a graft resin. For details of the graft resin, please refer to paragraphs 0025 to 0094 of JP 2012-255128 A, the contents of which are incorporated herein by reference.
[0192] The resin used as the dispersant is preferably a resin having an aromatic carboxy group, such as those mentioned above.
[0193] The resin used as the dispersant is preferably a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine-based dispersant is preferably a resin having a main chain with a partial structure having a functional group with a pKa of 14 or less, and a side chain having 40 to 10,000 atoms, and having a basic nitrogen atom in at least one of the main chain and the side chain. There are no particular restrictions on the basic nitrogen atom, as long as it is a nitrogen atom that exhibits basicity. For details about polyimine-based dispersants, please refer to the descriptions in paragraphs 0102 to 0166 of JP 2012-255128 A, the contents of which are incorporated herein by reference.
[0194] The resin used as a dispersant is preferably a resin having a structure in which multiple polymer chains are bonded to a core portion. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.
[0195] The resin used as a dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in a side chain. The content of the repeating unit having an ethylenically unsaturated bond-containing group in a side chain is preferably 10 mol % or more, more preferably 10 to 80 mol %, and even more preferably 20 to 70 mol %, of all repeating units of the resin.
[0196] As the dispersant, the resin described in JP 2018-087939 A, the block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077 A, polyethyleneimine having a polyester side chain described in WO 2016 / 104803, block copolymers described in WO 2019 / 125940 A, block polymers having an acrylamide structural unit described in JP 2020-066687 A, block polymers having an acrylamide structural unit described in JP 2020-066688 A, dispersants described in WO 2016 / 104803, and the like can also be used.
[0197] Dispersants are also available as commercially available products, and specific examples thereof include the DISPERBYK series manufactured by BYK Chemie, the SOLSPERSE series manufactured by Lubrizol Japan, the Efka series manufactured by BASF, and the AJISPER series manufactured by Ajinomoto Fine-Techno Co., Ltd. In addition, the products described in paragraph 0129 of JP 2012-137564 A and the products described in paragraph 0235 of JP 2017-194662 A can also be used as dispersants.
[0198] The content of the resin in the total solid content of the coloring composition is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and even more preferably 30% by mass or less. The lower limit can be 0% by mass or more, or 1% by mass or more, or even 2% by mass or more. The content of the resin having an acid group in the total solid content of the coloring composition is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, and even more preferably 30% by mass or less. The lower limit can be 0% by mass or more, or 1% by mass or more, or even 2% by mass or more. The content of the resin having an acid group in the total amount of resin is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, because excellent developability is easily obtained. The upper limit can be 100% by mass, or can be 95% by mass or more, or can be 90% by mass or less. The colored composition of the present invention may contain only one type of resin, or may contain two or more types of resins. When two or more types of resins are contained, the total amount thereof is preferably within the above range.
[0199] <<Compound Having a Cyclic Ether Group>> The coloring composition of the present invention may contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The epoxy group may be an alicyclic epoxy group. The alicyclic epoxy group refers to a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed. The compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups contained in the epoxy compound is preferably 2 or more.
[0200] Examples of compounds having a cyclic ether group include the compounds described in paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, and paragraphs 0085 to 0092 of JP-A-2014-089408, compounds described in JP-A-2017-179172, xanthene-type epoxy resins described in JP-A-2021-195421, and xanthene-type epoxy resins described in JP-A-2021-195422.
[0201] The compound having a cyclic ether group may be a low molecular weight compound (for example, a molecular weight of less than 2000, or even less than 1000) or a high molecular weight compound (macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). The weight average molecular weight of the compound having a cyclic ether group is preferably 200 to 100,000, and more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.
[0202] Commercially available examples of compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all manufactured by NOF Corporation, epoxy group-containing polymers).
[0203] The content of the compound having a cyclic ether group in the total solid content of the coloring composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. Only one type of compound having a cyclic ether group may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is in the above range.
[0204] <<Pigment Derivative>> The coloring composition of the present invention may contain a pigment derivative. The pigment derivative is used, for example, as a dispersing aid. A dispersing aid is a material that enhances the dispersibility of a pigment or the like in a coloring composition.
[0205] Examples of the pigment derivative include a compound having at least one structure selected from the group consisting of a dye structure and a triazine structure, and an acid group or a basic group.
[0206] Examples of the dye structure include a quinoline dye structure, a benzimidazolone dye structure, a benzisoindole dye structure, a benzothiazole dye structure, an iminium dye structure, a squarylium dye structure, a croconium dye structure, an oxonol dye structure, a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, an azo dye structure, an azomethine dye structure, a phthalocyanine dye structure, a naphthalocyanine dye structure, an anthraquinone dye structure, a quinacridone dye structure, a dioxazine dye structure, a perinone dye structure, a perylene dye structure, a thiazineindigo dye structure, a thioindigo dye structure, an isoindoline dye structure, an isoindolinone dye structure, a quinophthalone dye structure, a dithiol dye structure, a triarylmethane dye structure, and a pyrromethene dye structure.
[0207] Examples of the acid group possessed by the pigment derivative include a carboxy group, a sulfo group, a phosphate group, a boronic acid group, an imidic acid group, and salts thereof. Examples of the atom or atomic group constituting the salt include an alkali metal ion (Li + , Na + , K. + etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ Examples of the imide acid group include an ammonium ion, an imidazolium ion, a pyridinium ion, and a phosphonium ion. 2 NHSO 2 R X1 , -CONHSO 2 R X2 , -CONHCOR X3 or -SO 2 NHCOR X4 is preferred, and —SO 2 NHSO2 R X1 , -CONHSO 2 R X2 , or -SO 2 NHCOR X4 is more preferred, and —SO 2 NHSO 2 R X1 or -CONHSO 2 R X2 is more preferred. X1 ~R X4 R each independently represents an alkyl group or an aryl group. X1 ~R X4 The alkyl group and aryl group represented by R may have a substituent. The substituent is preferably a halogen atom, and more preferably a fluorine atom. X1 ~R X4 are each independently preferably an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and more preferably an alkyl group containing a fluorine atom. The number of carbon atoms in the alkyl group containing a fluorine atom is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The number of carbon atoms in the aryl group containing a fluorine atom is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6.
[0208] Examples of basic groups possessed by the pigment derivative include amino groups, pyridinyl groups and their salts, ammonium salts, and phthalimidomethyl groups. Examples of atoms or atomic groups that constitute the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
[0209] The amino group is —NR x11 R x12 and a cyclic amino group.
[0210] -NR x11 R x12 In the group represented by x11 and R x12are each independently a hydrogen atom, an alkyl group, or an aryl group, and are preferably an alkyl group. That is, the amino group is preferably a dialkylamino group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent. The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have a substituent.
[0211] Examples of the cyclic amino group include a pyrrolidine group, a piperidine group, a piperazine group, a morpholine group, etc. These groups may further have a substituent.
[0212] The pigment derivative may be a pigment derivative having excellent visible transparency (hereinafter also referred to as a transparent pigment derivative). The maximum molar absorption coefficient (εmax) of the transparent pigment derivative in the wavelength range of 400 to 700 nm is 3000 L mol -1 ・cm -1 It is preferable that the concentration is 1000 L mol or less. -1 ・cm -1 More preferably, it is 100 L mol or less. -1 ・cm -1 The lower limit of εmax is, for example, 1 L mol -1 ・cm -1 or more, and 10 L mol -1 ・cm -1 More than that is fine.
[0213] Specific examples of pigment derivatives include the compounds described in the examples below, the compounds described in paragraph 0124 of WO 2022 / 085485, the benzimidazolone compounds or salts thereof described in JP 2018-168244 A, compounds having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6996282, compounds described in JP 2019-172968 A, and compounds described in the specification of Chinese Patent Application Publication No. 115124889.
[0214] When the coloring composition of the present invention contains a pigment derivative, the content of the pigment derivative in the total solid content of the coloring composition is preferably 0.3 to 20% by mass. The lower limit is preferably 0.6% by mass or more, and more preferably 0.9% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 12.5% by mass or less, and even more preferably 10% by mass or less. The content of the pigment derivative is preferably 1 to 30 parts by mass per 100 parts by mass of the pigment. The lower limit is preferably 2 parts by mass or more, and more preferably 3 parts by mass or more. The upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less. The coloring composition of the present invention may contain only one type of pigment derivative, or may contain two or more types. When two or more types of pigment derivatives are contained, the total amount thereof preferably falls within the above range.
[0215] <<Polyalkyleneimine>> The coloring composition of the present invention may also contain a polyalkyleneimine. The polyalkyleneimine is used, for example, as a dispersing aid for pigments. The polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine. The polyalkyleneimine is preferably a polymer having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group. The alkyleneimine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
[0216] The molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less. Regarding the molecular weight value of the polyalkyleneimine, if the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, if the molecular weight of the specific amine compound cannot be calculated from the structural formula or calculation is difficult, the number average molecular weight value measured by the boiling point elevation method is used. If the number average molecular weight cannot be measured by the boiling point elevation method or is difficult to measure, the number average molecular weight value measured by the viscosity method is used. If the number average molecular weight cannot be measured by the viscosity method or is difficult to measure, the number average molecular weight value measured in terms of polystyrene by GPC (gel permeation chromatography) is used.
[0217] The amine value of the polyalkyleneimine is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and even more preferably 15 mmol / g or more.
[0218] Specific examples of alkyleneimines include ethyleneimine, propyleneimine, 1,2-butyleneimine, and 2,3-butyleneimine, with ethyleneimine or propyleneimine being preferred, and ethyleneimine being more preferred. It is particularly preferred that the polyalkyleneimine be polyethyleneimine. Furthermore, the polyethyleneimine preferably contains primary amino groups in an amount of 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total of primary amino groups, secondary amino groups, and tertiary amino groups. Commercially available polyethyleneimines include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).
[0219] The content of the polyalkyleneimine in the total solid content of the coloring composition is preferably 0.1 to 5% by mass. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. The content of the polyalkyleneimine is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. The upper limit is preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less. Only one type of polyalkyleneimine may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is in the above-mentioned range.
[0220] <<Silane Coupling Agent>> The coloring composition of the present invention may contain a silane coupling agent. Examples of the silane coupling agent include silane compounds having a hydrolyzable group, and preferably silane compounds having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, and an alkoxy group is preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. In addition, examples of functional groups other than the hydrolyzable group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, and a phenyl group, and an amino group, a (meth)acryloyl group, and an epoxy group are preferred. Specific examples of the silane coupling agent include the compound described in paragraph 0177 of WO 2022 / 085485 and the compound described in JP 2019-183020 A. The content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.01 to 15% by mass. The upper limit is preferably 10% by mass or less, and more preferably 5% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The silane coupling agent may be one type, or two or more types. When two or more types are used, it is preferable that the total amount is in the above range.
[0221] <<Solvent>> The coloring composition of the present invention preferably contains a solvent. Examples of the solvent include organic solvents. The type of solvent is basically not particularly limited as long as the solubility of each component and the coatability of the composition are satisfied. Examples of organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For details of these, please refer to paragraph
[0223] of WO 2015 / 166779, the contents of which are incorporated herein by reference. Furthermore, ester-based solvents substituted with a cyclic alkyl group and ketone-based solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether ... Examples of suitable ethylene glycol monomethyl ether acetate include 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol.However, it may be preferable to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, the amount may be 50 ppm by mass (parts per million) or less, 10 ppm by mass or less, or 1 ppm by mass or less, relative to the total amount of organic solvents).
[0222] The metal content of the organic solvent is preferably low. The metal content of the organic solvent is preferably, for example, 10 parts per billion (ppb) by mass or less. If necessary, an organic solvent having a metal content of ppt (parts per trillion) by mass may be used. Such organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (The Chemical Daily, November 13, 2015).
[0223] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter. The pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.
[0224] The organic solvent may contain isomers (compounds having the same number of atoms but different structures). The organic solvent may contain only one type of isomer or multiple types of isomers.
[0225] The organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
[0226] The content of the solvent in the coloring composition is preferably from 10 to 95% by mass, more preferably from 20 to 90% by mass, and even more preferably from 30 to 90% by mass.
[0227] In addition, from the viewpoint of environmental regulations, it is preferable that the colored composition of the present invention is substantially free of environmentally restricted substances. In the present invention, "substantially free of environmentally restricted substances" means that the content of environmentally restricted substances in the colored composition is 50 mass ppm or less, preferably 30 mass ppm or less, more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Examples of environmentally restricted substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These substances are registered as environmentally restricted substances under the REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulations, the PRTR (Pollutant Release and Transfer Register) Act, the VOC (Volatile Organic Compounds) regulations, etc., and their usage amounts and handling methods are strictly regulated. These compounds may be used as solvents when producing each component used in the coloring composition, and may be mixed into the coloring composition as a residual solvent. From the viewpoint of human safety and environmental considerations, it is preferable to reduce these substances as much as possible. Examples of methods for reducing environmentally restricted substances include a method in which the system is heated or depressurized to a temperature above the boiling point of the environmentally restricted substance, thereby distilling off the environmentally restricted substance from the system. Furthermore, when distilling off a small amount of environmentally regulated substances, it is useful to perform azeotropy with a solvent having a boiling point equivalent to that of the solvent in question in order to increase efficiency. Furthermore, when a radically polymerizable compound is contained, a polymerization inhibitor or the like may be added before distillation under reduced pressure to prevent intermolecular crosslinking due to the progress of a radical polymerization reaction during distillation under reduced pressure. These distillation methods can be used at any stage, such as the stage of raw materials, the stage of a product obtained by reacting the raw materials (for example, a resin solution or a polyfunctional monomer solution after polymerization), or the stage of a colored composition prepared by mixing these compounds.
[0228] <<Polymerization Inhibitor>> The coloring composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.), and 2,2,6,6-tetramethylpiperidine 1-oxyl. Among these, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the coloring composition is preferably 0.0001 to 5% by mass. The polymerization inhibitor may be used alone or in combination with two or more types. When two or more types are used, the total amount preferably falls within the above range.
[0229] <<Surfactant>> The coloring composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant. For the surfactant, reference can be made to the surfactants described in paragraphs 0238 to 0245 of WO 2015 / 166779, the contents of which are incorporated herein by reference.
[0230] As the fluorine-based surfactant, the compounds described in paragraphs 0167 to 0173 of WO 2022 / 085485 can be used.
[0231] Examples of nonionic surfactants include the compounds described in paragraph 0174 of WO 2022 / 085485.
[0232] Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419. OIL (all manufactured by Dow Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (all manufactured by BYK-Chemie). As the silicone surfactant, compounds having the following structure can also be used.
[0233] The content of the surfactant in the total solid content of the coloring composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass. The surfactant may be one type or two or more types. When two or more types are used, it is preferable that the total amount is in the above range.
[0234] <<UV Absorber>> The coloring composition of the present invention may contain an UV absorber. Examples of UV absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and dibenzoyl compounds. Specific examples of such compounds include the compound described in paragraph 0179 of WO 2022 / 085485, the reactive triazine UV absorber described in JP 2021-178918 A, the UV absorber described in JP 2022-007884 A, the compound described in Korean Patent Publication No. 10-2022-0014454, and the compound described in JP 2023-013321 A. The content of the UV absorber in the total solid content of the coloring composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. In the present invention, the ultraviolet absorber may be used alone or in combination of two or more kinds. When two or more kinds are used, it is preferable that the total amount is in the above range.
[0235] <<Antioxidant>> The coloring composition of the present invention may contain an antioxidant. Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of the phenolic antioxidant include hindered phenol compounds. The phenolic antioxidant is preferably a compound having a substituent at a position adjacent to the phenolic hydroxy group (ortho position). The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite, and tris(2,4-di-tert-butylphenyl)phosphite. Commercially available antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, ADK STAB AO-330 (manufactured by ADEKA Corporation), and JP-650 (manufactured by Johoku Chemical Industry Co., Ltd.). Antioxidants include the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, the compounds described in WO 2017 / 006600, the compounds described in WO 2017 / 164024, and the compounds described in Korean Patent Publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the coloring composition is preferably 0.01 to 20 mass%, more preferably 0.3 to 15 mass%. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is in the above range.
[0236] <<Curing Accelerator>> The coloring composition of the present invention may contain a curing accelerator. Examples of the curing accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, and onium salt compounds. Specific examples of the curing accelerator include the compounds described in paragraph 0164 of WO 2022 / 085485 and the compounds described in JP 2021-181406 A. The content of the curing accelerator in the total solid content of the coloring composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.
[0237] <<Other Components>> The coloring composition of the present invention may contain, as necessary, a sensitizer, a plasticizer, and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling promoters, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately incorporating these components, properties such as film physical properties can be adjusted. As these components, the compounds described in paragraph 0182 of WO 2022 / 085485 can be used.
[0238] The coloring composition of the present invention may contain a metal oxide in order to adjust the refractive index of the resulting film. Examples of the metal oxide include TiO 2 , ZrO 2 , Al 2 O 3 , SiO 2 The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and even more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. In this case, the core may be hollow.
[0239] The coloring composition of the present invention may contain a light resistance improver. Examples of the light resistance improver include the compounds described in paragraph 0183 of WO 2022 / 085485.
[0240] It is also preferable that the coloring composition of the present invention is substantially free of terephthalic acid ester. Here, "substantially free of" means that the content of terephthalic acid ester in the total amount of the coloring composition is 1000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero.
[0241] In view of environmental regulations, the colored composition of the present invention preferably has a melamine content of 10,000 ppm by mass or less.
[0242] The coloring composition of the present invention preferably has a free metal content of 100 ppm by mass or less, more preferably 50 ppm by mass or less. The free halogen content is preferably 100 ppm by mass or less, more preferably 50 ppm by mass or less. The chloride ion concentration in the coloring composition is preferably 100 ppm by mass or less, more preferably 50 ppm by mass or less. Examples of methods for reducing free metals and halogens in the coloring composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.
[0243] From the viewpoint of environmental regulations, the use of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts may be restricted. In the colored composition of the present invention, when the content of the above-mentioned compounds is reduced, the content of perfluoroalkyl sulfonic acids (particularly perfluoroalkyl sulfonic acids having a perfluoroalkyl group of 6 to 8 carbon atoms) and their salts, and perfluoroalkyl carboxylic acids (particularly perfluoroalkyl carboxylic acids having a perfluoroalkyl group of 6 to 8 carbon atoms) and their salts is preferably in the range of 0.01 ppb to 1,000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, relative to the total solids content of the colored composition. The colored composition of the present invention may be substantially free of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts. For example, by using a compound that can replace perfluoroalkyl sulfonic acid and its salt, and a compound that can replace perfluoroalkyl carboxylic acid and its salt, a coloring composition that is substantially free of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt may be selected. Examples of compounds that can replace regulated compounds include compounds that are exempt from regulation due to the difference in the number of carbon atoms in the perfluoroalkyl group. However, the above content does not preclude the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt. The coloring composition of the present invention may contain perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt within the maximum allowable range.
[0244] The water content of the colored composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.
[0245] The colored composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface state (flatness, etc.), adjusting the film thickness, etc. The viscosity value can be appropriately selected as needed, but for example, it is preferably 0.3 mPa·s to 50 mPa·s, and more preferably 0.5 mPa·s to 20 mPa·s at 25°C. The viscosity can be measured, for example, using a cone-plate type viscometer, with the temperature adjusted to 25°C.
[0246] <<Storage Container>> The container for storing the coloring composition is not particularly limited, and any known container can be used. In addition, the container described in paragraph 0187 of WO 2022 / 085485 can be used as the storage container.
[0247] <Method for preparing colored composition> The colored composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the colored composition, all components may be simultaneously dissolved and / or dispersed in a solvent to prepare the colored composition, or, if necessary, each component may be prepared as two or more appropriate solutions or dispersions, which may be mixed at the time of use (at the time of application) to prepare the colored composition.
[0248] The preparation of the coloring composition preferably includes a process for dispersing the pigment. In the process for dispersing the pigment, mechanical forces used to disperse the pigment include compression, squeezing, impact, shear, and cavitation. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high-speed impeller, a sand grinder, a flow jet mixer, high-pressure wet atomization, and ultrasonic dispersion. Furthermore, when grinding the pigment in a sand mill (bead mill), it is preferable to use small-diameter beads, increase the bead packing ratio, or otherwise increase the grinding efficiency under such conditions. Furthermore, it is preferable to remove coarse particles after the grinding process by filtration, centrifugation, or the like. In addition, the process and disperser for dispersing pigments can be suitably used, for example, the process and disperser described in "Dispersion Technology Encyclopedia," published by Joho Kiko Co., Ltd., July 15, 2005, or "Dispersion Technology and Industrial Applications Focused on Suspension (Solid / Liquid Dispersion System) - Comprehensive Data Collection," published by the Management Development Center Publishing Department, October 10, 1978, or paragraph 0022 of JP 2015-157893 A. In addition, in the process for dispersing pigments, particle refinement may be performed in a salt milling process. For details on the materials, equipment, processing conditions, etc. used in the salt milling process, see, for example, JP 2015-194521 A and JP 2012-046629 A. Examples of materials for beads used in dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. The beads may also be made of an inorganic compound having a Mohs hardness of at least 2. The coloring composition may contain 1 to 10,000 ppm of the beads.
[0249] In preparing the colored composition, it is preferable to filter the colored composition with a filter for the purpose of removing foreign matter, reducing defects, etc. Examples of the type of filter and filtration method used for filtration include the filters and filtration methods described in paragraphs 0196 to 0199 of WO 2022 / 085485.
[0250] <Film> The film of the present invention is a film obtained from the coloring composition of the present invention described above. The film of the present invention can be used for color filters, etc. Specifically, it can be preferably used as a colored layer (pixel) of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. The film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.
[0251] <Color filter> Next, the color filter of the present invention will be described. The color filter of the present invention has the above-mentioned film of the present invention. More preferably, the film of the present invention is used as a pixel of the color filter. The color filter of the present invention can be used in solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal-oxide semiconductors), image display devices, etc.
[0252] In the color filter of the present invention, the film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.
[0253] The width of the pixels included in the color filter is preferably 0.5 to 20.0 μm. The lower limit is preferably 1.0 μm or more, and more preferably 2.0 μm or more. The upper limit is preferably 15.0 μm or less, and more preferably 10.0 μm or less. The Young's modulus of the pixels is preferably 0.5 to 20 GPa, and more preferably 2.5 to 15 GPa.
[0254] It is preferable that each pixel included in the color filter has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. There is no specified lower limit, but it is preferably 0.1 nm or more, for example. The surface roughness of the pixel can be measured using, for example, a Veeco Dimension 3100 AFM (atomic force microscope). The contact angle of water on the pixel can be set to an appropriate preferred value, but is typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT Type A (Kyowa Interface Science Co., Ltd.). It is also preferable that the volume resistance of the pixel is high. Specifically, the volume resistance of the pixel is 10 9 It is preferable that the resistance is Ω·cm or more, and 10 11 It is more preferable that the resistivity is Ω·cm or more. 14 The volume resistance of the pixel can be measured using, for example, an Ultra High Resistance Meter 5410 (manufactured by Advantest Corporation).
[0255] In the color filter, a protective layer may be provided on the surface of the film of the present invention. By providing a protective layer, various functions can be imparted, such as oxygen blocking, low reflectivity, hydrophilicity / hydrophobicity, and blocking of light of specific wavelengths (ultraviolet rays, near-infrared rays, etc.). The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Methods for forming the protective layer include a method of applying a resin composition dissolved in an organic solvent, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. Components constituting the protective layer include (meth)acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al 2 O 3 , Mo, SiO 2 , Si 2 N 4 For example, in the case of a protective layer intended to block oxygen, the protective layer may contain a polyol resin and SiO 2 and Si 2 N 4 In the case of a protective layer intended to reduce reflection, the protective layer preferably contains a (meth)acrylic resin and a fluorine resin.
[0256] When forming a protective layer by applying a resin composition, known methods such as spin coating, casting, screen printing, and inkjet printing can be used as the method for applying the resin composition. Known organic solvents (e.g., propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used as the organic solvent contained in the resin composition. When forming the protective layer by chemical vapor deposition, known chemical vapor deposition methods (thermal chemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition) can be used as the chemical vapor deposition method.
[0257] The protective layer may contain additives such as organic or inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet light, near-infrared light, etc.), refractive index adjusters, antioxidants, adhesives, and surfactants, as needed. Examples of organic or inorganic fine particles include polymeric fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, and barium sulfate. Known absorbers for light of specific wavelengths can be used. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass, and more preferably 1 to 60% by mass, of the total mass of the protective layer.
[0258] In addition, as the protective layer, the protective layers described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.
[0259] The color filter may have a structure in which each pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.
[0260] <Method for producing a color filter> Next, a method for producing a color filter using the colored composition of the present invention will be described. The method for producing a color filter preferably includes a step of forming a colored composition layer on a support using the colored composition of the present invention, a step of patternwise exposing the colored composition layer, and a step of developing and removing the unexposed areas of the colored composition layer to form a pattern (pixels). If necessary, a step of baking the colored composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.
[0261] In the step of forming a coloring composition layer, a coloring composition layer is formed on a support using the coloring composition of the present invention. The support is not particularly limited and can be appropriately selected depending on the application. Examples include a glass substrate and a silicon substrate, with a silicon substrate being preferred. The silicon substrate may also be formed with a charge-coupled device (CCD), a complementary metal-oxide semiconductor (CMOS), a transparent conductive film, or the like. A black matrix is sometimes formed on the silicon substrate to isolate each pixel. The silicon substrate may also be provided with a base layer to improve adhesion with an upper layer, prevent diffusion of substances, or flatten the substrate surface. The surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane. It is also preferably 30 to 80° when measured with water.
[0262] As the coating method of the coloring composition, known methods can be used. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a rotary coating method (spin coating); a casting coating method; a slit and spin method; a pre-wetting method (for example, a method described in JP-A-2009-145395); inkjet (for example, an on-demand method, a piezo method, a thermal method), various printing methods such as nozzle jet and other ejection printing, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; a transfer method using a mold or the like; a nanoimprint method, etc. can be mentioned. In addition, the coating method described in paragraph 0207 of WO 2022 / 085485 can also be used.
[0263] The colored composition layer formed on the support may be dried (prebaked). When a film is produced by a low-temperature process, prebaking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, or can also be 80°C or higher. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Prebaking can be performed using a hot plate, an oven, or the like.
[0264] Next, the coloring composition layer is exposed to light in a pattern (exposure step). For example, the coloring composition layer can be exposed to light in a pattern by using a stepper exposure machine, a scanner exposure machine, or the like, through a mask having a predetermined mask pattern. This allows the exposed portion to be cured.
[0265] Examples of radiation (light) that can be used for exposure include g-rays and i-rays. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm), with KrF rays (wavelength 248 nm) being preferred. Long-wave light sources of 300 nm or more can also be used. As the light source, an electrodeless ultraviolet lamp system or a hybrid curing method using ultraviolet and infrared rays can be used.
[0266] The exposure may be performed by continuous irradiation with light or by pulsed irradiation (pulse exposure), which is an exposure method in which light irradiation and pauses are repeated in short cycles (for example, milliseconds or less).
[0267] The irradiation amount (exposure amount) is, for example, 0.03 to 2.5 J / cm 2 is preferred, and 0.05 to 1.0 J / cm 2The oxygen concentration during exposure can be appropriately selected. In addition to being performed in the atmosphere, exposure may be performed in a low-oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration of more than 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). The exposure illuminance can be appropriately set, and is usually 1000 W / m 2 ~100000W / m 2 (For example, 5000 W / m 2 , 15000W / m 2 , or 35,000 W / m 2 The oxygen concentration and exposure illuminance may be appropriately combined. For example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W / m 2 , oxygen concentration 35% by volume, illuminance 20,000 W / m 2 etc.
[0268] Next, the unexposed portions of the coloring composition layer are developed and removed to form a pattern (pixels). The unexposed portions of the coloring composition layer can be developed and removed using a developer. As a result, the unexposed portions of the coloring composition layer in the exposure step are dissolved into the developer, leaving only the photocured portions. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, to improve residue removability, the process of shaking off the developer every 60 seconds and then supplying fresh developer may be repeated several times.
[0269] Examples of the developer include organic solvents and alkaline developers, and alkaline developers are preferably used. Regarding the developer and the washing (rinsing) method after development, the developer and washing method described in paragraph 0214 of WO 2022 / 085485 can be used.
[0270] After development and drying, it is preferable to perform additional exposure treatment or heating treatment (post-baking). The additional exposure treatment or post-baking is a post-development curing treatment to ensure complete curing. The heating temperature in post-baking is, for example, preferably 100 to 300°C, more preferably 200 to 270°C. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to achieve the above conditions for the developed film. When additional exposure treatment is performed, it is preferable that the light used for exposure has a wavelength of 400 nm or less. The additional exposure treatment may also be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
[0271] <Solid-state imaging device> The solid-state imaging device of the present invention has the above-described film of the present invention. The configuration of the solid-state imaging device is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device, but examples thereof include the following configurations.
[0272] The substrate includes a plurality of photodiodes constituting a light-receiving area of a solid-state imaging device (such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor) and transfer electrodes made of polysilicon or the like. A light-shielding film is formed on the photodiodes and transfer electrodes, with only the light-receiving portions of the photodiodes exposed. A device protection film made of silicon nitride or the like is formed on the light-shielding film so as to cover the entire light-shielding film and the light-receiving portions of the photodiodes. A color filter is also provided on the device protection film. Furthermore, the device protection film may include a light-collecting means (e.g., a microlens, etc.; the same applies hereinafter) below the color filter (on the side closer to the substrate), or on the color filter. The color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. In this case, the partition walls preferably have a lower refractive index than the color pixels. Examples of imaging devices having such a structure include those described in JP 2012-227478 A, JP 2014-179577 A, and WO 2018 / 043654 A. Furthermore, as shown in JP 2019-211559 A, an ultraviolet absorbing layer may be provided within the structure of the solid-state imaging element to improve light resistance. An imaging device equipped with the solid-state imaging element of the present invention can be used for digital cameras, electronic devices with imaging functions (such as mobile phones), as well as in-vehicle cameras and surveillance cameras.
[0273] <Image Display Device> The image display device of the present invention has the above-described film of the present invention. Examples of image display devices include liquid crystal display devices and organic electroluminescence display devices. Definitions of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Nobuaki Ibuki, published by Sangyo Tosho Co., Ltd. in 1989). Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994). There are no particular limitations on the liquid crystal display device to which the present invention can be applied, and the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology."
[0274] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the structural formulas shown below, Me represents a methyl group, Et represents a methyl group, and i-Pr represents an isopropyl group. n Bu represents a normal butyl group.
[0275] <Synthesis Examples of Compounds> (Synthesis Example of Compound D-1) 10 g of sodium tetraphenylborate (Kalibor, manufactured by Dojindo Laboratories, Inc.) and 100 g of ion-exchanged water were placed in a three-necked flask, and a stirring blade and a thermometer were installed. The mixture was stirred at 200 rpm using a Three-One motor to dissolve the contents. A separately prepared aqueous solution of 8.12 g of tetrabutylammonium chloride and 100 g of ion-exchanged water was added dropwise to the flask using a dropping funnel over 30 minutes. After stirring for 1 hour after the addition, the mixture was filtered using a Kiriyama funnel. The residue was washed with ion-exchanged water and air-dried for 30 minutes. The residue was transferred to a petri dish and dried for 12 hours to a constant weight using a blower dryer set at 40°C, yielding Compound D-1. Analysis using an X-ray fluorescence analyzer (XRF) revealed that the residual Na ions were 1000 ppm and the residual Cl ions were 1000 ppm.
[0276] (Synthesis Example of Compound D-5) 10 g of sodium tetraphenylborate (Kalibor, manufactured by Dojindo Laboratories, Inc.) and 100 g of methanol were placed in a three-necked flask, and a stirring blade and a thermometer were installed. The mixture was stirred at 200 rpm using a Three-One motor to dissolve the compound. A separately prepared aqueous solution of 3.15 g of potassium acetate and 100 g of methanol was added dropwise to the flask using a dropping funnel over 30 minutes. After the dropwise addition, the mixture was stirred for 1 hour and then filtered using a Kiriyama funnel. The residue was washed with ion-exchanged water and air-dried for 30 minutes. The residue was transferred to a petri dish and dried for 12 hours to a constant weight using a blower dryer set at 40°C to obtain Compound D-5. 1 g of the obtained Compound D-5 was dissolved in 30 g of acetone, and 50 g of ion-exchanged water was added to precipitate Compound D-5. The solvent was then removed using a rotary evaporator at 45 torr and 30°C for 30 minutes. The filtrate was collected using a Kiriyama funnel and a filter bell, and ion-exchanged water was added to bring the total amount to 100 g. The resulting liquid was analyzed by ion chromatography, and the analytical results were converted into the residual amounts in Compound D-5. The residual amount of Na was 100 ppm, and the amount of acetate anion was below the lower detection limit (10 ppm).
[0277] (Synthesis Example of Compound D-8) 2.4 g of magnesium and 10 ml of ultra-dehydrated tetrahydrofuran (THF) were added to a three-neck flask. A stirring blade, a nitrogen inlet tube, a condenser, and a thermometer were installed via a Y-shaped tube, and nitrogen was flowed at 20 ml / min. A calcium chloride tube filled with calcium chloride as a desiccant was installed in the condenser. The mixture was heated in a water bath to an internal temperature of 30°C, and stirred at 200 rpm using a three-one motor. 0.2 g of 1,2-dibromoethane was added to the reaction solution, and the generation of fine bubbles was confirmed. Separately, 14.1 g of 4-bromotoluene was dissolved in 140 g of THF and 40 g of diethyl ether, and the solution was added dropwise to the reaction solution using a dropping funnel at a rate such that the internal temperature remained below 35°C. After the dropwise addition, the mixture was stirred at 30°C for 1 hour to prepare a Grignard reagent. Subsequently, 1.7 g of sodium tetrafluoroborate was added, and the mixture was stirred for 24 hours. The completion of the reaction was confirmed using nuclear magnetic resonance analysis (NMR). 33 g of sodium carbonate and 330 g of ion-exchanged water were added to a 1 L glass beaker and stirred with a stirrer until dissolved, after which the reaction solution was slowly poured into it. After stirring for 20 minutes, the remaining magnesium was removed by filtration through Celite. An extraction operation was performed using diethyl ether, and the resulting organic layer was washed with saturated saline. 5 g of sodium sulfate was added to the organic layer and allowed to stand overnight. The sodium sulfate was removed by filtration, and the solvent was distilled off using an evaporator. When crystals precipitated, toluene was added, and white crystals were obtained by filtration. The residue was transferred to a petri dish and dried for 12 hours to a constant weight using a blower dryer set at 40°C to obtain sodium tetra(p-tolyl)borate. Salt exchange was performed in the same manner as for Compound D-1, except that a reslurry step using ion-exchanged water was introduced, to obtain Compound D-8. Analysis was performed in the same manner as for Compound D-5, and the residual Na content was 200 ppm and the residual Cl content was 30 ppm. Furthermore, analysis using high performance liquid chromatography (HPLC) revealed that the area % purity at 210 nm was 99.1%.
[0278] (Synthesis Example of Compound D-20) 2 g of orthoboric acid, 12 g of 1-hydroxyl-2-naphthalenecarboxylic acid, 50 g of methanol, and 20 g of ion-exchanged water were added to a three-necked flask, and a stirring blade, a nitrogen inlet tube, a condenser, and a thermometer were installed via a Y-shaped tube. Nitrogen was flowed at 20 ml / min. A calcium chloride tube filled with calcium chloride as a desiccant was installed in the condenser. After stirring at 200 rpm for 30 minutes using a Three-One motor, 35 g of a 5% by mass aqueous potassium hydroxide solution was added, and the mixture was heated in a water bath so that the internal temperature reached 80°C. After stirring for 5 hours, the crystals were filtered out using a Kiriyama funnel. The crystals were washed with a mixture of ion-exchanged water and methanol, air-dried for 30 minutes, transferred to a petri dish, and dried in a 50°C air dryer for 30 hours until a constant weight was obtained, thereby obtaining Compound D-20.
[0279] <Preparation of Dispersion> After mixing the raw materials listed in the table below, 230 parts by mass of zirconia beads with a diameter of 0.3 mm were added, and the mixture was dispersed for 5 hours using a paint shaker. The zirconia beads were then separated by filtration to obtain a dispersion. The solids concentration (% by mass) of the dispersion and the pigment concentration (% by mass) of the dispersion are also listed in the table.
[0280] The details of the materials indicated by the abbreviations in the table above are as follows: (Pigments) PG-1: C.I. Pigment Blue 15:6 PG-2: C.I. Pigment Red 254 PG-3: C.I. Pigment Yellow 139 PG-4: C.I. Pigment Yellow 150 PG-5: C.I. Pigment Violet 23 PG-6: C.I. Pigment Green 36
[0281] (Derivatives) PS-1: BYK-SYNERGIST 2100 (BYK Corporation) PS-2: BYK-SYNERGIST 2105 (BYK Corporation) PS-3, PS-4, PS-5, PS-8, PS-9: Compounds with the following structures
[0282] (Dispersant) DS-1: DISPERBYK-161 (manufactured by BYK-Chemie) DS-2: 30% by mass propylene glycol monomethyl ether acetate solution of a resin having the following structure (the number attached to the main chain is the molar ratio. The weight average molecular weight of the resin is 11,000) DS-3: A 30% by mass propylene glycol monomethyl ether acetate solution of a resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. The weight-average molecular weight of the resin is 7,000.) DS-4: 30% by mass solution of Plysurf A215C (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) in propylene glycol monomethyl ether acetate
[0283] (Solvent) S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-3: 1-methoxy-2-propanol (PGME)
[0284] <Production of Colored Composition> The raw materials other than the solvent shown in the table below were mixed with 0.0007 parts by mass of a polymerization inhibitor (p-methoxyphenol), and 0.05 parts by mass of a silicone surfactant (KF-6000, manufactured by Shin-Etsu Chemical Co., Ltd.), and then the solvent shown in the table below was added so that the solids concentration was 12% by mass, thereby obtaining a colored composition. In the table, the blend amounts of ingredients other than the solvent are parts by mass in terms of solids content, and the solvent ratios are mass ratios. The ratio of the molar amount of the specific compound to the molar amount of the dye is shown in the column "Molar Ratio 1," and the ratio of the molar amount of the anion of the specific compound to the molar amount of the dye cation is shown in the column "Molar Ratio 1."
[0285]
[0286]
[0287] Details of the materials indicated by the abbreviations in the table above are as follows:
[0288] (Dispersion) Dispersion 1 to 8: Dispersion 1 to 8 described above
[0289] (Dye Solution) A-1: A cyclohexanone solution (solid content: 12.3% by mass) of a dye (cyanine dye, molecular weight 510) having the following structure.
[0290] A-2: A cyclohexanone solution (solid content: 12.3% by mass) of a dye having the following structure (xanthene dye, weight-average molecular weight 7000, m: 3, n: 3)
[0291] A-3: A cyclohexanone solution (solid content: 12.3% by mass) of a dye having the following structure (xanthene dye, molecular weight 704)
[0292] A-4: A cyclohexanone solution (solid content: 12.3% by mass) of a dye having the following structure (xanthene dye, weight-average molecular weight: 10,000).
[0293] A-5: A cyclohexanone solution (solid content: 12.3% by mass) of a dye having the following structure (xanthene dye, molecular weight: 1115)
[0294] A-6: A cyclohexanone solution (solid content: 12.3% by mass) of a dye having the following structure (triarylmethane dye, molecular weight: 1,165).
[0295] A-7: A cyclohexanone solution (solid content: 12.3% by mass) of a dye having the following structure (cyanine dye, molecular weight 774)
[0296] A-8: C.I. Acid Red 289 (xanthene dye, molecular weight 676) cyclohexanone solution (solid content: 12.3% by mass)
[0297] A-9: A cyclohexanone solution (solid content: 12.3% by mass) of a colored polymer (xanthene dye, weight average molecular weight: 9000) having the following structure:
[0298] A-10: A cyclohexanone solution (solid content: 12.3% by mass) of a dye having the following structure (squarylium dye, molecular weight: 324)
[0299] A-11: A cyclohexanone solution (solid content: 12.3% by mass) of a dye having the following structure (cyanine dye, molecular weight: 374)
[0300] A-12: Cyclohexanone solution of Acid Green 27 (solid content: 12.3% by mass) A-13: Cyclohexanone solution of Acid Yellow 23 (solid content: 12.3% by mass) A-14: Cyclohexanone solution of Solvent Blue 25 (solid content: 12.3% by mass) A-15: Cyclohexanone solution of Acid Red 52 (solid content: 12.3% by mass)
[0301] (Specific Compounds) D-1 to D-24, DC-1, DC-2: The compounds shown below. The values in the ε column in the table below are the molar absorption coefficients of the respective anions at 248 nm. The specific absorbances of the respective compounds, represented by the following formula (Aλ), were all 5 or less. The specific absorbances of the respective compounds were measured using 1-methoxy-2-propanol as a solvent. E 1 =A 1 / (c 1 ×l 1 ) ...(Aλ) E 1 : Specific absorbance of the compound at the maximum absorption wavelength in the wavelength range of 400 to 700 nm A 1 : Absorbance of the compound at the maximum absorption wavelength in the wavelength range of 400 to 700 nm 1 : Cell length expressed in cm 1 : concentration of the compound in solution, expressed in mg / ml
[0302] In the above table, dx1 to dx9 are the cations shown below.
[0303] In the above table, dz1 to dz16, dzc1 and dzc2 are the anions shown below.
[0304] (Resin) P-1: 30% by mass propylene glycol monomethyl ether acetate solution of a resin having the following structure (the number attached to the main chain is the molar ratio of the repeating unit. The weight average molecular weight of the resin is 11,000.) P-2: 40% by mass propylene glycol monomethyl ether acetate solution of a resin having the following structure (the number next to the main chain is the molar ratio of the repeating unit. The weight-average molecular weight of the resin is 11,000.) P-3: A 30% by mass propylene glycol monomethyl ether acetate solution of a resin having the following structure (the number next to the main chain is the molar ratio of the repeating unit, and the number next to the side chain is the number of repeating units. The weight-average molecular weight of the resin is 11,000.) P-4: 40% by mass propylene glycol monomethyl ether acetate solution of a resin having the following structure (the number next to the main chain is the molar ratio of the repeating unit. The weight-average molecular weight of the resin is 11,000.)
[0305] (Polymerizable Compounds) M-1: KAYARAD DPHA (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.) M-2, M-3: Compounds having the following structure M-4: Aronix MT-3041 (manufactured by Toagosei Co., Ltd.)
[0306] (Photopolymerization initiators) I-1 to I-5: Compounds having the following structures
[0307] (Additives) E-1: Compound having the following structure (ultraviolet absorber) E-2: Compound having the following structure (weight average molecular weight 3500, compound having a cyclic ether group) E-3: Compound having the following structure (weight average molecular weight 2300, compound having a cyclic ether group) E-4: Compound having the following structure (silane coupling agent) E-5: Compound having the following structure (silane coupling agent) E-6: Compound having the following structure (silane coupling agent) E-7: Compound having the following structure (antioxidant) E-8: Compound having the following structure (multifunctional thiol compound) E-9: Compound having the following structure (multifunctional thiol compound) E-10: Polyethylene glycol (PEG-400, manufactured by Sanyo Chemical Industries, Ltd.)
[0308] (Solvents) S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Cyclohexanone S-3: 1-methoxy-2-propanol (PGME) S-4: Cyclopentanone
[0309] <Performance Evaluation> (Evaluation of Lightfastness) A colored composition was applied onto a glass substrate by spin coating, and then heat-treated (pre-baked) using a hot plate at 120°C for 120 seconds. The resulting coating film was exposed to light (KrF line) with a wavelength of 248 nm at an illuminance of 35,000 W / m using a KrF scanner exposure machine. 2 , exposure dose 100 mJ / cm 2The exposure was performed by irradiating under the conditions of . The glass substrate on which the exposed coating film was formed was placed on the horizontal rotating table of a spin-shower developer (DW-30 model, Chemitronics Corporation) and then treated for 60 seconds at 23°C using a 60% diluted solution of CD-2000 (Fujifilm Electronic Materials Co., Ltd.). The glass substrate on which the film was formed after the above treatment was fixed to the horizontal rotating table using a vacuum chuck. While rotating the glass substrate at 50 rpm using a rotation device, pure water was supplied in a shower from a spray nozzle from above the center of rotation to perform a rinse treatment, and then spray-dried. Next, a heat treatment (post-bake) was performed for 300 seconds using a hot plate at 200°C to form a film with a thickness of 0.45 μm. The light transmittance (transmittance) of the obtained film was measured using a spectrometer (MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.) in the wavelength range of 400 to 700 nm. Next, the film was irradiated with 100,000 Lux light for 2,000 hours (total irradiation dose: 200 million Lux hr) using a light resistance tester (Super Xenon Weather Meter SX75, manufactured by Suga Test Instruments Co., Ltd.). The transmittance of the film after light irradiation was measured, and the light resistance was evaluated according to the following criteria. -Evaluation criteria- A: The integrated value of the transmittance of the film at wavelengths of 400 to 700 nm after light irradiation is 98% or more of the integrated value of the transmittance of the film at wavelengths of 400 to 700 nm before light irradiation. B: The integrated value of the transmittance of the film at wavelengths of 400 to 700 nm after light irradiation is 96% or more and less than 98% of the integrated value of the transmittance of the film at wavelengths of 400 to 700 nm before light irradiation. C: The integrated value of the transmittance of the film at wavelengths of 400 to 700 nm after light irradiation is 94% or more and less than 96% of the integrated value of the transmittance of the film at wavelengths of 400 to 700 nm before light irradiation. D: The integrated value of the transmittance of the film at wavelengths of 400 to 700 nm after light irradiation is 90% or more and less than 94% of the integrated value of the transmittance of the film at wavelengths of 400 to 700 nm before light irradiation. E: The integrated value of the transmittance of the film after light irradiation at wavelengths of 400 to 700 nm is less than 90% of the integrated value of the transmittance of the film before light irradiation at wavelengths of 400 to 700 nm.
[0310] (Evaluation of Adhesion) An underlayer-forming composition (CT-4000L, Fujifilm Electronic Materials Co., Ltd.) was applied to an 8-inch (20.32 cm) silicon wafer by spin coating, and heated at 220°C for 300 seconds using a hot plate to form an underlayer having a thickness of 0.1 μm, thereby obtaining a silicon wafer (support) with an underlayer. A coloring composition was applied onto the underlayer of the silicon wafer with an underlayer using a spin coater, and then heated (pre-baked) at 100°C for 120 seconds using a hot plate to obtain a coating film having a thickness of 0.45 μm. Next, the coating film was exposed to light (KrF line) with a wavelength of 248 nm through a patterned mask (0.5 μm x 0.5 μm) using a KrF scanner exposure machine at an illuminance of 35,000 W / m 2 , exposure dose 100 mJ / cm 2 The coating film was then exposed to light under the following conditions. The exposed coating film was then shower-developed at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as the developer. The coating film was then rinsed with pure water by spin shower and heated at 230°C for 2 minutes to form pixels (patterns). The resulting pixels were observed at a magnification of 20,000x using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Tech Corporation). The number of peeled pixels out of the total number of pixels (1071 x 1071) formed in the observed partial region was counted, and the adhesion was evaluated based on the following evaluation criteria. -Evaluation criteria- A: The number of peeled pixels was 10 or less. B: The number of peeled pixels was more than 10 but not more than 20. C: The number of peeled pixels was more than 20 but not more than 50. D: The number of peeled pixels was more than 50 but not more than 200. E: The number of peeled pixels was more than 200.
[0311] (Evaluation of developability) A colored composition was applied onto a glass substrate by spin coating, and then heat-treated (pre-baked) at 120°C for 120 seconds using a hot plate. The resulting coating film was exposed to light (KrF line) with a wavelength of 248 nm through a patterned mask (0.5 µm x 0.5 µm) using a KrF scanner exposure machine at an illuminance of 35,000 W / m 2 , exposure dose 100 mJ / cm 2The glass substrate on which the exposed coating film was formed was placed on the horizontal rotating table of a spin-shower developer (DW-30 model, Chemitronics Corporation), and then puddle development was performed for 60 seconds at 23°C using a 60% diluted solution of CD-2000 (Fujifilm Electronic Materials Co., Ltd.), forming a colored pattern on the glass substrate. The glass substrate on which the colored pattern was formed was fixed to the horizontal rotating table using a vacuum chuck system, and then, while rotating the glass substrate at a rotation speed of 50 rpm using a rotation device, pure water was supplied in a shower-like manner from a spray nozzle from above the center of rotation to perform a rinse treatment, followed by spray drying. Next, a heat treatment (post-bake) was performed for 300 seconds using a hot plate at 200°C, forming a colored pattern (pixels) with a thickness of 0.45 μm. The glass substrate on which the pixels were formed was observed using a scanning electron microscope, and the developability was evaluated according to the following evaluation criteria. -Evaluation criteria- A: There was very little residue between pixels, and there was no practical problem. B: There was little residue between pixels, and there was no practical problem. C: There was a little amount of residue between pixels, but there was no practical problem. D: There was a lot of residue between pixels. E: It was not possible to form pixels.
[0312] (Evaluation of storage stability) The initial viscosity (V0) of the colored composition was measured using "RE-85L" manufactured by Toki Sangyo Co., Ltd. Next, the colored composition was left to stand at 45°C for 7 days, and then the viscosity (V1) was measured. The viscosity increase rate (%) of the colored composition after standing was calculated based on the following formula, and the storage stability was evaluated. The smaller the viscosity increase rate (%), the better the storage stability. The viscosity of the colored composition was measured in a state where the temperature was adjusted to 25°C. Viscosity increase rate (%) = [(viscosity after standing (V1) - initial viscosity (V0)) / initial viscosity (V0)] × 100 - Evaluation criteria - A: Viscosity increase rate is less than 1% B: Viscosity increase rate is 1% or more but less than 3% C: Viscosity increase rate is 3% or more but less than 5% D: Viscosity increase rate is 5% or more but less than 10%
[0313]
[0314] As shown in the above table, the examples had better light resistance evaluations than the comparative examples. In each evaluation, the same effect was obtained even when the exposure light source was changed to i-line (wavelength 365 nm).
[0315] The same effects can be obtained even if part or all of the resins, polymerizable compounds, photopolymerization initiators and solvents used in the colored compositions of the examples are replaced with materials described in this specification.
[0316] (Examples 501 to 510) A green pixel-forming composition was applied to a silicon wafer by spin coating so that the film thickness after formation would be 1.0 μm. Then, the wafer was heated at 100° C. for 2 minutes using a hot plate. Next, an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon Inc.) was used to apply a 1000 mJ / cm 2 The wafer was exposed to light through a mask with a 2 μm square dot pattern at an exposure dose of 1000 μm. Next, puddle development was performed using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) at 23°C for 60 seconds. The wafer was then rinsed with a spin shower and further washed with pure water. The green pixel-forming composition was then patterned on the silicon wafer by heating at 200°C for 5 minutes using a hot plate. Similarly, the red pixel-forming composition and the blue pixel-forming composition were sequentially patterned to form red, green, and blue colored patterns (Bayer patterns). In Examples 501 to 510, the compositions listed in the table below were used for the blue pixel-forming composition, green pixel-forming composition, and red pixel-forming composition. The Bayer pattern is a repeated 2 × 2 array of color filter elements each having one red element, two green elements, and one blue element, as disclosed in U.S. Pat. No. 3,971,065. The obtained color filter was incorporated into a solid-state imaging device according to a known method. By using the colored compositions prepared in Examples 1 to 10, solid-state imaging devices having suitable image recognition functions and light resistance were obtained.
[0317]
[0318] [Green Composition 1] The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pall Corporation) with a pore size of 0.45 μm to prepare Green Composition 1. Green pigment dispersion: 73.7 parts by mass Resin 4 (40% by mass PGMEA solution): 0.3 parts by mass Polymerizable compound 1: 1.2 parts by mass Photopolymerization initiator 1: 0.6 parts by mass Surfactant 1: 4.2 parts by mass UV absorber 1: 0.5 parts by mass PGMEA: 19.5 parts by mass
[0319] [Green Composition 2] The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pall Corporation) with a pore size of 0.45 μm to prepare Green Composition 2. Green pigment dispersion: 73.7 parts by mass Yellow pigment dispersion 1: 5.3 parts by mass Resin 4 (40% by mass PGMEA solution): 0.3 parts by mass Polymerizable compound 1: 1.2 parts by mass Photopolymerization initiator 2: 0.6 parts by mass Surfactant 1: 4.2 parts by mass UV absorber 1: 0.5 parts by mass PGMEA: 9.2 parts by mass Cyclopentanone: 5.0 parts by mass
[0320] [Red Composition 1] The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) with a pore size of 0.45 μm to prepare Red Composition 1. Red pigment dispersion 1: 51.7 parts by mass Resin 4 (40% by mass PGMEA solution): 0.6 parts by mass Polymerizable compound 4: 0.6 parts by mass Photopolymerization initiator 1: 0.3 parts by mass Surfactant 1: 4.2 parts by mass PGMEA: 42.6 parts by mass
[0321] [Red Composition 2] The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pall Corporation) with a pore size of 0.45 μm to prepare Red Composition 2. Red pigment dispersion 2: 31.3 parts by mass Yellow pigment dispersion 2: 21.8 parts by mass Resin 4 (40% by mass PGMEA solution): 3.7 parts by mass Polymerizable compound 1: 0.7 parts by mass Photopolymerization initiator 1: 0.3 parts by mass Additive E-4: 1.2 parts by mass Surfactant 1: 0.001 parts by mass PGMEA: 8.2 parts by mass PGME: 15.2 parts by mass Cyclopentanone: 17.6 parts by mass
[0322] The raw materials used for Green Composition 1, Green Composition 2, Red Composition 1, and Red Composition 2 are as follows.
[0323] Green pigment dispersion A mixture consisting of 6.4 parts by mass of C.I. Pigment Green 36, 5.3 parts by mass of C.I. Pigment Yellow 150, 5.2 parts by mass of a dispersant (DISPERBYK-161, BYK-Chemie), and 83.1 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.3 mm diameter) to prepare a pigment dispersion. Thereafter, a high-pressure disperser NANO-3000-10 (Japan BYE Co., Ltd.) equipped with a pressure reducing mechanism was used to disperse the mixture at 2000 kg / cm. 2 The dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 1000 psi. This dispersion treatment was repeated 10 times to obtain a green pigment dispersion.
[0324] Red pigment dispersion 1 A mixture consisting of 9.6 parts by mass of C.I. Pigment Red 254, 4.3 parts by mass of C.I. Pigment Yellow 139, 6.8 parts by mass of a dispersant (DISPERBYK-161, BYK Chemie), and 79.3 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.3 mm diameter) to prepare a pigment dispersion. Thereafter, a high-pressure disperser NANO-3000-10 (Japan BYE Co., Ltd.) equipped with a pressure reducing mechanism was used to mix and disperse the mixture at 2000 kg / cm. 2 This dispersion treatment was repeated 10 times to obtain a red pigment dispersion liquid.
[0325] Red pigment dispersion 2 A mixture consisting of 11.5 parts by mass of C.I. Pigment Red 264, 2.5 parts by mass of pigment derivative 1 described below, 4.9 parts by mass of dispersant 1 described below, 68.6 parts by mass of PGMEA, and 12.5 parts by mass of PGME was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.3 mm diameter) to prepare a pigment dispersion. Thereafter, the mixture was further mixed at 2000 kg / cm using a high-pressure disperser NANO-3000-10 equipped with a pressure reducing mechanism (Japan BEE Co., Ltd.). 2This dispersion treatment was repeated 10 times to obtain Red pigment dispersion liquid 2.
[0326] Yellow pigment dispersion 1 A mixture consisting of 11.4 parts by mass of C.I. Pigment Yellow 129, 1.6 parts by mass of the pigment derivative 1 described below, 4.0 parts by mass of dispersant 1 described below, and 83.0 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.3 mm diameter) to prepare a pigment dispersion. Thereafter, a high-pressure disperser equipped with a pressure reducing mechanism, NANO-3000-10 (Japan BEE Co., Ltd.), was used to mix and disperse the mixture at 2000 kg / cm. 2 This dispersion treatment was repeated 10 times to obtain Yellow pigment dispersion liquid 1.
[0327] Yellow Pigment Dispersion 2 A mixture consisting of 11.4 parts by mass of C.I. Pigment Yellow 139, 1.6 parts by mass of the pigment derivative 1 described below, 4.0 parts by mass of dispersant 1 described below, and 83.0 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.3 mm diameter) to prepare a pigment dispersion. Thereafter, a high-pressure disperser equipped with a pressure reduction mechanism, NANO-3000-10 (Japan BEE Co., Ltd.), was used to mix and disperse the mixture at 2000 kg / cm. 2 This dispersion treatment was repeated 10 times to obtain Yellow pigment dispersion liquid 2.
[0328] Dispersant 1: Resin having the following structure (weight average molecular weight: 24,000; the number attached to the main chain is the number of moles, and the number attached to the side chain is the number of repeating units): Pigment derivative 1: Compound having the following structure (basic pigment derivative)
[0329] Polymerizable compound 1: KAYARAD DPHA (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, Nippon Kayaku Co., Ltd.) Polymerizable compound 4: a compound having the following structure Resin 4: Resin having the following structure (the numbers attached to the main chain indicate the molar ratio of repeating units. The weight-average molecular weight of the resin is 11,000, and the acid value is 70 mgKOH / g.) Photopolymerization initiator 1: Irgacure OXE01 (BASF) Photopolymerization initiator 2: TR-PBG-314 (Tronly) Surfactant 1: 1 mass % PGMEA solution of the following mixture (weight average molecular weight 14,000). In the following formulas, the units of % (62% and 38%) indicating the proportion of repeating units are % by mass. Ultraviolet absorber 1 (UV-503, manufactured by Daito Chemical Co., Ltd.)
Claims
1. A coloring composition comprising a colorant A containing a dye a, a polymerization initiator B, a polymerizable compound C, and a compound D which is a salt of a cation dx and an anion dz and is represented by the formula (Aλ) and has a specific absorbance of 5 or less, wherein the anion dz is an anion containing a boron atom and has a fluorine atom content of 50 mass% or less; E 1 =A 1 / (c 1 ×l 1 )...(Aλ) In formula (Aλ), E 1 represents the specific absorbance of compound D at the maximum absorption wavelength in the wavelength range of 400 to 700 nm, and A 1 represents the absorbance of Compound D at the maximum absorption wavelength in the wavelength range of 400 to 700 nm, and 1 represents the cell length in cm, and c 1 represents the concentration of Compound D in solution, expressed in mg / ml.
2. The coloring composition according to claim 1, wherein the dye a comprises a dye a1 having a chemical structure containing a cation ax and an anion az, and the ratio of the molar amount of the anion dz of the compound D to the molar amount of the cation ax of the dye a1 is 0.5 to 0.
9.
3. The coloring composition according to claim 1 or 2, wherein the anion dz of the compound D is an anion represented by formula (dz-1). In formula (dz-1), R d1 ~R d4 each independently represents an alkyl group, an aryl group, or a heteroaryl group.
4. The coloring composition according to claim 1 or 2, wherein the anion dz of said compound D is a tetraphenylboron anion.
5. The coloring composition according to claim 1 or 2, wherein the cation dx of the compound D is an ammonium cation or a potassium cation.
6. The coloring composition according to claim 1 or 2, wherein dye a comprises a xanthene dye.
7. The coloring composition according to claim 1 or 2, wherein the dye a comprises a dye multimer.
8. The coloring composition according to claim 1 or 2, wherein said colorant A further comprises a pigment.
9. The colored composition according to claim 1 or 2, wherein the content of the colorant A in the total solid content of the colored composition is 40 mass % or more.
10. The coloring composition according to claim 1 or 2, further comprising a polyalkyleneoxy compound.
11. The anion dz of the compound D has a molar absorption coefficient at a wavelength of 248 nm of 200 to 15,000 L mol -1 ・cm -1 The coloring composition according to claim 1 or 2, 12. The coloring composition according to claim 1 or 2, which is for use in a color filter.
13. A film obtained using the coloring composition according to claim 1 or 2.
14. A color filter comprising the film according to claim 13.
15. A solid-state imaging device having the film according to claim 13.
16. An image display device comprising the film according to claim 13.
Citation Information
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