TWI739735B - Colored composition, cured film, color filter, method for manufacturing color filter, solid-state imaging device, image display device, and polymer - Google Patents

Abstract

The present invention provides a coloring composition, a cured film, a color filter, a method for manufacturing a color filter, a solid-state imaging element, an image display device, and a polymer that are excellent in heat resistance and solvent resistance. The coloring composition of the present invention includes a polymer TP and a polymerizable compound. The polymer TP includes a repeating unit A having a triarylmethane structure and a repeating unit B having a crosslinkable group. The weight average molecular weight of the polymer TP is 3000 to 500,000, relative to the mass of the polymer TP, the content of the compound A having a triarylmethane structure and a weight average molecular weight of 1500 or less is 20% by mass or less.

Description

Colored composition, cured film, color filter, method for manufacturing color filter, solid-state imaging device, image display device, and polymer

The invention relates to a coloring composition, a cured film, a color filter, a method for manufacturing a color filter, a solid-state imaging element, an image display device, and a polymer.

The colored composition is used in the manufacture of color filters and the like.

In recent years, color filters have tended to be used in liquid crystal display device applications as follows: not only for monitors, but also for televisions. With the trend toward expansion of this use, color filters are required to have high color characteristics in terms of chromaticity, contrast, and the like. In addition, color filters for image sensors (solid-state imaging devices) have also begun to require further improvement in color characteristics such as reduction of color unevenness and improvement of color resolution.

Patent Document 1 and Patent Document 2 disclose a colored composition containing a compound having a triarylmethane structure.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Specification of U.S. Patent Application Publication No. 2013/0141810

[Patent Document 2] International Publication No. 2013/176383

The coloring composition used for color filters and the like needs to be able to form a film with excellent heat resistance and solvent resistance.

However, the heat resistance and solvent resistance of the colored composition disclosed in Patent Document 1 and Patent Document 2 are insufficient.

Therefore, the object of the present invention is to provide a coloring composition, a cured film, a color filter, a method for manufacturing a color filter, a solid-state imaging device, an image display device, and a polymer that are excellent in heat resistance and solvent resistance.

As a result of diligent research based on the above-mentioned situation, the inventors found that the above-mentioned object can be achieved by using the following polymer, which includes a repeating unit A having a triarylmethane structure. , And the repeating unit B having a crosslinkable group, the weight average molecular weight is 3000 to 500,000, and the content of the compound having a triarylmethane structure with a weight average molecular weight of 1500 or less is 20% by mass or less. The present invention provides the following.

<1> A coloring composition comprising a polymer TP and a polymerizable compound, the polymer TP comprising at least one repeating unit having a triarylmethane structure selected from the general formula (TP1) and the general formula (TP2) A, and a repeating unit B with a crosslinkable group, the weight average molecular weight of polymer TP is 3000~500,000, relative to the mass of polymer TP, the content of compound A with a weight average molecular weight of triarylmethane structure of 1500 or less Less than 20% by mass;

In general formula (TP1) and general formula (TP2), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group; Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ and Rtp ₁₁ each independently represent a substitution Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ₇₁ Rtp ₇₂ ; Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group; Rtp ₁₀ represents a hydrogen atom, an alkyl group or an aryl group; a , B, c, and d each independently represent an integer from 0 to 4; when a, b, c, and d are 2 or more, two of Rtp ₅ , Rtp ₆ , Rtp ₈ and Rtp ₉ can be connected to each other to form a ring ; X represents an anion, or X and Rtp absent ₁ ~ Rtp _11, Rtp ₇₁ and Rtp least one contains an anionic _72; Rtp ₁ ~ Rtp _11, any one Rtp _{71 is} and Rtp ₇₂ represents the bond with the repeating unit a Location.

<2> The coloring composition according to <1>, wherein the content of the compound A of the polymer TP is 10% by mass or less relative to the mass of the polymer TP.

<3> The coloring composition as described in <1> or <2>, wherein the weight average molecular weight of the polymer TP is 10,000 to 50,000.

<4> The colored composition according to any one of <1> to <3>, wherein The crosslinking group of the multiple unit B is selected from the group containing ethylenically unsaturated bond, epoxy group, oxetanyl group, oxazoline group, group represented by -COR and carbonate group At least one type; wherein, R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

<5> The coloring composition according to any one of <1> to <4>, wherein X is selected from the group consisting of fluoride anion, chloride anion, bromide anion, iodide anion, cyanide ion, perchlorate anion, boric acid anion, PF ^6- and SbF ^6- least one anion, and is selected from _{^{-SO 3 -, -COO -, -PO}} 4 -, structure represented by the following general formula (A1) represented by the following pass, and Selected from compounds of at least one of the structures represented by formula (A2); general formula (A1)

In the general formula (A1), R ¹ and R ² each independently represent -SO ₂ -or -CO-; the general formula (A2)

In the general formula (A2), R ³ represents -SO ₂ -or -CO-; R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO- or -CN.

<6> The coloring composition according to any one of <1> to <5>, wherein X is a bis(sulfonyl)imide anion, a tris(sulfonyl)methide anion or a sulfonate Anionic compounds.

<7> The colored composition according to any one of <1> to <6>, wherein X is a compound containing a crosslinkable group.

<8> The coloring composition according to any one of <1> to <7>, wherein X is a polymer containing a repeating unit having an anion site.

<9> The coloring composition according to any one of <1> to <4>, wherein in the general formula (TP1) and the general formula (TP2), at least one of _{Rtp 1} to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ Substituted by the group represented by general formula (P); general formula (P)

In the general formula (P), L represents a single bond or a divalent linking group, X ¹ managed from _{^{-SO 3 -, -COO -, -PO}} 4 -, structure represented by the following general formula (A1) represented contained Select from at least one of the group and the group containing the structure represented by the following general formula (A2); general formula (A1)

In the general formula (A1), R ¹ and R ² each independently represent -SO ₂ -or -CO-; the general formula (A2)

In the general formula (A2), R ³ represents -SO ₂ -or -CO-; R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO- or -CN.

<10> The coloring composition according to any one of <1> to <9>, wherein the triarylmethane structure of the repeating unit A is represented by the following general formula (TP3);

In the general formula (TP3), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group with 1 to 6 carbons; Rtp ₂₂ each independently represents an aryl group with 6 to 10 carbons, and Rtp ₇₁ represents an alkyl group or an aryl group; X It represents an anion, or X is absent and at least one of _{Rtp 21} , Rtp ₂₂ and Rtp _{71 includes an anion; any one of Rtp 21} , Rtp ₂₂ and Rtp ₇₁ represents a bonding site with the repeating unit A.

<11> The coloring composition according to any one of <1> to <10>, wherein the repeating unit A is represented by the following general formula (TP3-1);

In the general formula (TP3-1), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbons, Rtp ₂₂ each independently represents an aryl group having 6 to 10 carbons, and Rtp _71a represents an alkylene group or an alkylene group. Aryl group; L ₁ represents a single bond or a divalent linking group, Rtp ₃₁ represents a hydrogen atom or a methyl group; X represents an anion, or X does not exist and at least one of _{Rtp 21} and Rtp _{22 contains an anion.}

<12> The coloring composition according to any one of <1> to <11>, wherein the repeating unit A is represented by the following general formula (TP3-2); [化9]

In the general formula (TP3-2), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group with 1 to 6 carbons, Rtp ₂₄ each independently represents an alkyl group with 1 to 4 carbons, and Rtp ₂₅ each independently represents a hydrogen atom Or an alkyl group with 1 to 3 carbon atoms, Rtp _71a represents an alkylene group or an arylene group; Rtp ₃₁ represents a hydrogen atom or a methyl group; L ₁ represents a single bond or a divalent linking group; X represents an anion, or there is no X In addition, at least one of _{Rtp 21} and Rtp _{22 includes an anion.}

<13> The coloring composition according to any one of <1> to <12>, wherein the polymer TP contains a compound derived from (meth)acrylic acid, (meth)acrylate, and (meth)acrylamide At least one repeating unit.

<14> The coloring composition according to any one of <1> to <13>, which includes a compound selected from the group consisting of xanthene compounds, dipyrromethene-based metal complexes, dioxazine compounds, and phthalocyanine compounds At least one.

<15> The colored composition according to any one of <1> to <14>, which includes Including photopolymerization initiator.

<16> The coloring composition according to any one of <1> to <15>, which includes a bis(trifluoromethanesulfonyl)iminium salt.

<17> The colored composition according to any one of <1> to <16>, which is used to form a colored layer of a color filter.

<18> A cured film formed by curing the colored composition according to any one of <1> to <17>.

<19> A color filter comprising the cured film as described in <18>.

<20> A method for manufacturing a color filter, comprising: using the coloring composition as described in any one of <1> to <17> to form a coloring composition layer; exposing the coloring composition layer to The step of patterning; and the step of developing and removing the unexposed part of the colored composition layer to form a colored pattern.

<21> A method of manufacturing a color filter, comprising: using the coloring composition as described in any one of <1> to <17> to form a coloring composition layer, and curing to form a coloring layer The step of forming a photoresist layer on the colored layer; the step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and the step of using the resist pattern as an etching mask to color The layer is subjected to a step of dry etching.

<22> A solid-state imaging element including the color filter according to <19>.

<23> An image display device including the color filter as described in <19>.

<24> A polymer comprising a repeating unit represented by the following general formula (TP-7), the weight average molecular weight of the polymer is 3000 to 500,000, and the weight of the polymer has a triarylmethane structure relative to the mass of the polymer The content of compound A with an average molecular weight of 1500 or less is 20% by mass or less;

In the general formula (TP-7), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, R ^1a represents an alkylene group or an aryl group, and L ¹¹ represents A single bond or a divalent linking group with 1 to 30 carbons; L ¹² and L ¹³ represent a single bond or a divalent linking group with 1 to 30 ^{carbons; R 2} represents a hydrocarbon group with 1 to 10 carbons; R ³ represents a crosslinkable group; X represents a compound containing bis(sulfonyl)imide anion, tris(sulfonyl)methide anion or sulfonate anion; a~d are the mass ratios of repeating units, a and d represents a number exceeding 0, and b and c each independently represent a number greater than 0.

According to the present invention, a coloring with excellent heat resistance and solvent resistance can be provided Composition, cured film, color filter, color filter manufacturing method, solid-state imaging device, image display device, and polymer.

Hereinafter, the content of the present invention will be described in detail.

In addition, in this specification, "~" is used to include the numerical value described before and after it as the lower limit and the upper limit.

In this specification, the "total solid content" refers to the total mass of the components after removing the solvent from the total composition of the coloring composition.

In the expression of the group (atomic group) in this specification, the expression that does not describe substituted and unsubstituted includes a group (atomic group) not having a substituent, and also includes a group (atomic group) having a substituent. For example, the "alkyl group" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group).

The "radiation" in this specification refers to, for example, the bright-ray spectrum of a mercury lamp, extreme ultraviolet light represented by excimer lasers, extreme ultraviolet light (Extreme Ultraviolet (EUV) light), X-rays, electron beams, and the like. In addition, in the present invention, the term “light” refers to actinic rays or radiation.

Unless otherwise specified, the so-called "exposure" in this manual refers not only to exposure using mercury lamps, extreme ultraviolet light represented by excimer lasers, X-rays, EUV light, etc., but also using particles such as electron beams and ion beams. The description of the beam also includes Included in the exposure.

In this specification, "(meth)acrylate" means both or either of acrylate and methacrylate, and "(meth)acrylic" means both or either of acrylic acid and methacrylic acid, "(Meth)acryloyl group" means both or either of an acryloyl group and a methacryloyl group.

Monomers in this specification are different from oligomers and polymers, and refer to compounds with a weight average molecular weight of 2,000 or less.

In this specification, the term "polymerizable compound" refers to a compound having a polymerizable functional group. The polymerizable functional group refers to a group that participates in a polymerization reaction.

In this specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In this specification, the term "step" not only refers to an independent step, even when it cannot be clearly distinguished from other steps, as long as the step achieves the expected effect, it is also included in this term.

Unless otherwise stated, the weight average molecular weight and the number average molecular weight in the present invention are defined by polystyrene conversion values measured by Gel Permeation Chromatography (GPC).

<Coloring composition>

The coloring composition of the present invention includes a polymer TP and a polymerizable compound. The polymer TP includes a repeating unit A having a triarylmethane structure and a repeating unit B having a crosslinkable group described later. The weight of the polymer TP is average The molecular weight is 3000~500000, relative to the mass of polymer TP, it has the weight average of triarylmethane structure The content of the compound A having an average molecular weight of 1500 or less is 20% by mass or less.

With such a configuration, it is possible to provide a colored composition having excellent heat resistance and solvent resistance. Furthermore, it is also possible to form a film with a good voltage retention rate. As a mechanism for obtaining such an effect, it is considered that by using the polymer TP, the polymer TP is difficult to be eluted from the film when the film is formed, and the solvent resistance and heat resistance are improved. Hereinafter, each component of the colored composition of the present invention will be described in detail.

<<Polymer TP>>

<<<Repeat Unit A>>>

The polymer TP contains a repeating unit A having a triarylmethane structure.

The repeating unit A is preferably a structure represented by the following general formula (A). In all the repeating units of the polymer TP, it is preferable to contain 1% to 99% by mass of the repeating unit A. The upper limit is more preferably 95% by mass or less, and still more preferably 90% by mass or less. The lower limit is more preferably 5% by mass or more. If the content of the repeating unit A is in the above range, the color value becomes more favorable.

In the general formula (A), X ¹ represents the main chain of the repeating unit. L ¹ represents a single bond or a divalent linking group. DyeI represents a triarylmethane structure represented by general formula (TP1) or general formula (TP2) described later.

In the general formula (A), X ¹ represents the main chain of the repeating unit, and generally represents a linking group formed by a polymerization reaction. For example, it is preferably derived from having a (meth)acrylic group, a styryl group, a vinyl group, and an ether The main chain of the base compound. In addition, the form of an alkylene group having a cyclic ring in the main chain is also preferable. Furthermore, the site represented by 2 * is bonded to other repeating units.

X ¹ is not particularly limited as long as it is a linking group formed from a known polymerizable monomer, but it is particularly preferably represented by the following (XX-1) to the following (XX-24) The linking group of is more preferably selected from the (meth)acrylic linking chain represented by (XX-1) and (XX-2), and the styrene series represented by (XX-10)~(XX-17) Linked chains, vinyl-based linked chains represented by (XX-18) and (XX-19) and (XX-24), and more preferably selected from those represented by (XX-1) and (XX-2) The (meth)acrylic linking chain, the styrene linking chain represented by (XX-10)~(XX-17), and the vinyl linking chain represented by (XX-24) are particularly preferred because ( The (meth)acrylic linking chain represented by XX-1) and (XX-2) and the styrene linking chain represented by (XX-11).

In (XX-1)~(XX-24), it means that the part indicated by * is connected to L1. Me represents methyl. In addition, R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

[化12]

When L ¹ represents a divalent linking group, it is preferably an alkylene group, an arylene group, a heterocyclic group, -CH=CH-, -O-, -S-, -CO-, -NR-, -CONR -, -COO-, -OCO-, -SO ₂ -and a linking group formed by combining two or more of these. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

The carbon number of the alkylene group is preferably 1-30. The upper limit is more preferably 25 or less, and still more preferably 20 or less. The lower limit is more preferably 2 or more, and still more preferably 3 or more. The alkylene group may be linear, branched, or cyclic.

The carbon number of the aryl group is preferably 6-20, more preferably 6-12.

L ^{1 is} preferably an alkylene group, an aryl group, -NH-, -CO-, -O-, -COO-, -OCO-, and a linking group formed by combining two or more of these, more preferably Alkylene, aryl and divalent groups formed by combining these with one or more selected from -O-, -COO- and -OCO-, and more preferably alkylene, or alkylene A linking group formed by linking each other through one or more selected from -O-, -COO-, and -OCO-.

L ^{1 is} preferably such that ^{the number of atoms constituting the chain connecting X 1} and DyeI is 1 or more, more preferably 2 or more, still more preferably 3 or more, and particularly preferably 5 or more. The upper limit is preferably 20 or less, for example. According to this aspect, when the polymer TP is synthesized, it is possible to effectively suppress unreacted or insufficiently reacted low-molecular triarylmethane compounds. For example, in the following case, ^{the number of atoms constituting the chain connecting X 1} and DyeI is 10. In addition, the number described together in the structural formula is the number of atoms constituting the chain connecting ^{X 1 and DyeI.}

[化13]

Furthermore, when L ¹ represents a single bond, X ¹ is bonded to any _{of Rtp 1} to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ in the general formula (TP1) and general formula (TP2), preferably with Rtp ₇₁ or Rtp ₇₂ performs bonding.

When L ¹ represents a divalent linking group, L ¹ is bound to any one _{of Rtp 1} to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ in the general formula (TP1) and general formula (TP2), preferably with Rtp ₇₁ or Rtp ₇₂ performs bonding.

<<<<Triarylmethane structure>>>>

Next, the triarylmethane structure of the repeating unit A will be described.

The repeating unit A has a triarylmethane structure selected from the general formula (TP1) and the general formula (TP2).

[化14]

In general formula (TP1) and general formula (TP2), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group; Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ and Rtp ₁₁ each independently represent a substitution Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ₇₁ Rtp ₇₂ ; Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group; Rtp ₁₀ represents a hydrogen atom, an alkyl group or an aryl group; a , B, c, and d each independently represent an integer from 0 to 4; when a, b, c, and d are 2 or more, two of Rtp ₅ , Rtp ₆ , Rtp ₈ and Rtp ₉ can be connected to each other to form a ring ; X represents an anion, or X and Rtp absent ₁ ~ Rtp _11, Rtp ₇₁ and Rtp least one contains an anionic _72; Rtp ₁ ~ Rtp _11, any one Rtp _{71 is} and Rtp ₇₂ represents the bond with the repeating unit a Location.

In the general formula (TP1), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group, or an aryl group. Preferably, any one of Rtp ₁ and Rtp ₂ is an alkyl group, and the other is an aryl group. Preferably, any one of Rtp ₃ and Rtp ₄ is an alkyl group, and the other is an aryl group.

The carbon number of the alkyl group is preferably 1-10, more preferably 1-5, and still more preferably 1-3. The alkyl group may be any of linear, branched, and cyclic, but is preferably linear or branched. The alkyl group is preferably unsubstituted. As a substituent, the substituent mentioned in the term of the substituent group A mentioned later can be mentioned.

The carbon number of the aryl group is preferably 6-18, more preferably 6-12, and even more preferably 6. do The substituents that the aryl group may have include the substituents listed in the section of the substituent group A described later.

In the general formula (TP1), Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group, or NRtp ₇₁ Rtp ₇₂ , preferably a hydrogen atom or NRtp ₇₁ Rtp ₇₂ , and more preferably NRtp ₇₁ Rtp ₇₂ .

The carbon number of the alkyl group is preferably 1-10, more preferably 1-5, and still more preferably 1-3. The alkyl group may be any of linear, branched, and cyclic, but is preferably linear. As the substituent which the alkyl group may have, the substituents exemplified in the section of the substituent group A mentioned later can be mentioned. The carbon number of the aryl group is preferably 6-18, more preferably 6-12, and even more preferably 6.

Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and are preferably a hydrogen atom or an alkyl group.

The carbon number of the alkyl group is preferably 1-10, more preferably 1-8, and still more preferably 1-6. The alkyl group may be any of linear, branched, and cyclic, and is preferably cyclic. Alkyl groups can also be substituted. As the substituent which the alkyl group may have, the substituents exemplified in the section of the substituent group A mentioned later can be mentioned.

The carbon number of the aryl group is preferably 6-18, more preferably 6-12, and even more preferably 6. Examples of the substituent that the aryl group may have include the substituents exemplified in the section of the substituent group A described later.

In the general formula (TP1), Rtp ₅ , Rtp ₆ and Rtp ₈ each independently represent a substituent. As a substituent, the substituent mentioned in the term of the substituent group A mentioned later can be mentioned. In particular, it is preferably a linear or branched alkyl group having 1 to 5 carbons, an alkenyl group having 1 to 5 carbons, an aryl group having 6 to 15 carbons, a carboxyl group or a sulfo group, and more preferably a carbon number of 1 to 5. The straight-chain or branched alkyl group, C1-C5 alkenyl group, phenyl group or carboxyl group. In particular, Rtp ₅ and Rtp _{6 are} preferably each independently an alkyl group having 1 to 5 carbon atoms. In addition, Rtp ₈ preferably has two alkenyl groups bonded to each other to form a ring. The ring is preferably a benzene ring.

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

In the general formula (TP2), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group, and the meaning is the _{same as that of Rtp 1} to Rtp ₄ in the general formula (TP1), and the preferred ranges are also the same.

In the general formula (TP2), Rtp ₅ and Rtp ₆ each independently represent a substituent, and their meanings are the _{same as Rtp 5} and Rtp ₆ in the general formula (TP1), and their preferred ranges are also the same.

In the general formula (TP2), Rtp ₉ and Rtp ₁₁ each independently represent a substituent, and the substituents listed in the section of the substituent group A described later can be used.

Rtp _{9 is} preferably an aryl group, more preferably an aryl group having 6 to 12 carbons, and still more preferably a phenyl group.

Rtp _{11 is} preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbons, and still more preferably an alkyl group having 1 to 3 carbons. The alkyl group is preferably linear or branched, and more preferably linear.

In the general formula (TP2), Rtp ₁₀ represents a substituent, and the substituents listed in the section of the substituent group A described later can be used. In particular, Rtp _{10 is more} preferably an aryl group having 6 to 12 carbons, and still more preferably a phenyl group.

In the general formula (TP2), a, b, and d each independently represent an integer of 0 to 4. In particular, a and b preferably represent 0 or 1, and more preferably represent 0. d is preferably a table Shows 0~2, more preferably represents 0.

In general formula (TP1) and general formula (TP2), _{any one of Rtp 1} to Rtp ₁₁ , Rtp _71, and Rtp ₇₂ represents a bonding site with a repeating unit. In particular, it is preferable that Rtp ₇₁ or Rtp ₇₂ is a repeating unit. The bonding part of the unit.

In general formula (TP1) and general formula (TP2), _{at least one of Rtp 1} to Rtp ₁₁ , Rtp _71, and Rtp ₇₂ may contain an anion.

As an anion, preferably _{^{-SO 3 -, -COO -, -PO}} 4 -, bis (sulfo acyl) acyl imide anion, tris (sulfo acyl) methide anion, and tetraarylborate anions, more Preferred are bis(sulfonyl)imide anion, tris(sulfonyl)methide anion and tetraarylborate anion, and more preferably bis(sulfonyl)imide anion and tris(sulfonyl) Radical) methide anion.

Specifically, _{a structure in which at least one of Rtp 1} to Rtp ₁₁ , Rtp _71, and Rtp ₇₂ is substituted with the general formula (P) can be cited.

General formula (P)

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

In the general formula (P), L represents a single bond or a divalent linking group. The divalent linking group preferably represents -NR ¹⁰ -, -O-, -SO ₂ -, a fluorine atom-containing alkylene group, a fluorine atom-containing arylene group, or a group containing a combination of these. In particular, ^{a group containing a combination of -NR 10} -and -SO ₂ -and a fluorine atom-containing alkylene group, a group containing a combination of -O- and a fluorine atom-containing arylene group, or a group containing -NR ¹⁰ -A group combined with -SO ₂ -and a fluorine atom-containing alkylene group.

In -NR ¹⁰ -, R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom.

The carbon number of the alkylene group containing a fluorine atom is preferably from 1 to 10, more preferably from 1 to 6, and even more preferably from 1 to 3. These alkylene groups are more preferably perfluoroalkylene groups. Specific examples of the fluorine-substituted alkylene group include difluoromethylene, tetrafluoroethylene, hexafluoroethylene, and the like.

The carbon number of the arylene group containing a fluorine atom is preferably 6-20, more preferably 6-14, and still more preferably 6-10. Specific examples of the fluorine atom-containing arylene group include tetrafluorophenylene group, hexafluoro-1-naphthylene group, hexafluoro-2-naphthylene group, and the like.

In the general formula (P), X ¹ represents an anion, is preferably managed from _{^{-SO 3 -, -COO -, -PO}} 4 -, containing a structure represented by the following general formula (A1) is represented by the group and containing Select from at least one of the groups of the structure represented by the general formula (A2).

General formula (A1)

In the general formula (A1), R ¹ and R ² each independently represent -SO ₂ -or -CO-.

General formula (A2)

In the general formula (A2), R ³ represents -SO ₂ -or -CO-. R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO-, or -CN.

The group containing the structure represented by the general formula (A1) is preferably a group having a fluorine-substituted alkyl group at the end of one of ^{R 1} and R ^{2 in the general formula (A1), more preferably R 1} and R ² One is directly bonded to the fluorine-substituted alkyl group. The carbon number of the fluorine-substituted alkyl group is preferably from 1 to 10, more preferably from 1 to 6, further preferably from 1 to 3, still more preferably 1 or 2, and particularly preferably 1. These alkyl groups are more preferably perfluoroalkyl groups. As a specific example of the fluorine-substituted alkyl group, a trifluoromethyl group is preferred.

The group containing the structure represented by the general formula (A2) preferably has a fluorine-substituted alkyl group at the end of at least any one of ^{R 3} to R ^{5 in the general formula (A2), more preferably R 3} to R ^{At least any one of 5} is directly bonded to the fluorine-substituted alkyl group. In particular, it is preferable ^{that at least two of R 3} to R ⁵ have a fluorine-substituted alkyl group at the ends, and it is more preferable ^{that at least two of R 3} to R ⁵ are directly bonded to the fluorine-substituted alkyl group. The meaning of the fluorine-substituted alkyl group is the same as that described in the group containing the structure represented by the general formula (A1), and the preferable range is also the same.

Further, as specific examples of X ^1, later-described counter anion include A. In this case, any hydrogen atom or halogen atom constituting the counter anion A is bonded to L in the general formula (P).

In the general formula (TP1) and the general formula (TP2), the part substituted by the general formula (P) may exist at only one site, or may exist at two or more sites. When there are two or more parts substituted by the general formula (P), it is preferable that in the polymer TP, in addition to the cation contained in the triarylmethane structure, there are a number of cations corresponding to the number of anions. .

In general formula (TP1) and general formula (TP2), X represents an anion. In general formula (TP1) and general formula (TP2), X may or may not be present.

In general formula (TP1) and general formula (TP2), when X is present, it means that there is an anion outside the molecule of the triarylmethane structure. In addition, the fact that the triarylmethane structure has an anion outside the molecule means that the triarylmethane structure and the anion are not bonded via a covalent bond but exist as other compounds. Hereinafter, the anion outside the molecule of the triarylmethane structure is also referred to as a counter anion.

As a counter anion, a fluoride anion, a chloride anion, a bromide anion, an iodide anion, a cyanide ion, a perchlorate anion, a borate anion (BF ^4- etc.), PF ^6- , SbF ^6-, etc. are mentioned.

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

The counter anion may be a compound having an anion part. That is, the anion part may be contained as a part of the structure of the compound. When it contains an anion part as a part of the structure of a compound, it may be contained in a part of the polymer (polymer) which has a repeating unit, and may be contained in the so-called low molecular compound with a molecular weight of 2000 or less. In the case of low-molecular-weight compounds, an anion can be exemplified together Part, and at least one form of an alkyl group, an aryl group, and a crosslinkable group. In the present invention, it is preferable that the counter anion is a form of a compound containing a crosslinkable group, and the counter anion is a form of a polymer containing a repeating unit having an anion part.

When the counter anion is an anion portion of the compound having an anionic portion is preferably selected from _{^{-SO 3 -, -COO -, -PO}} 3 -, the structure represented by the following general formula (A1) represented by the following general formula and (A2) At least one of the structures shown.

General formula (A1)

(In the general formula (A1), R ¹ and R ² each independently represent -SO ₂ -or -CO-)

In the general formula (A1), it is preferable that at least one ^{of R 1} and R ² _{represents -SO 2} -, and it is more preferable that both of R ¹ and R ² represent -SO ₂ -.

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

General formula (A1-1)

(In the general formula (A1-1), R ¹ and R ² each independently represent -SO ₂ -or -CO-. X ¹ and X ² each independently represent an alkylene group or an aryl group)

In the general formula (A1-1), R ¹ and R the same meaning as in the general formula (A1) ² in R ¹ and R ^2, preferred ranges are also the same.

When X ¹ represents an alkylene group, the carbon number of the alkylene group is preferably 1-8, more preferably 1-6. When X ¹ represents an aryl extension group, the carbon number of the aryl extension group is preferably 6-18, more preferably 6-12, and even more preferably 6. When X ¹ has a substituent, it is preferably substituted by a fluorine atom.

X ² represents an alkylene group or an arylene group, preferably an alkylene group. The carbon number of the alkylene group is preferably from 1 to 8, more preferably from 1 to 6, still more preferably from 1 to 3, and particularly preferably from 1. When X ² has a substituent, it is preferably substituted by a fluorine atom.

General formula (A2)

(In the general formula (A2), R ³ represents -SO ₂ -or -CO-. R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO- or -CN)

In the general formula (A2), preferably at least one ^{of R 3} to R ⁵ _{represents -SO 2} -, and more preferably at least two ^{of R 3} to R ⁵ _{represents -SO 2} -.

As specific examples of the counter anion is an anion portion when the compound having, also illustrating ^{_{R-SO 3 -, R-}} COO - or R-PO ₄ ^-, and R is a halogen atom, an alkyl group substituted by a halogen atom, a halogen by In the case of atom-substituted aryl groups.

In addition, as specific examples of the compound containing the group represented by the general formula (A1), a compound in which R ¹ is bonded to a halogen atom, an alkyl group substituted with a halogen atom, or an aryl group substituted with a halogen atom can be exemplified. .

In addition, as specific examples of the compound containing the group represented by the general formula (A2), R ⁴ and R ⁵ are each a halogen atom, an alkyl group substituted with a halogen atom, or an aryl group substituted with a halogen atom. Condition.

When the counter anion is a compound having an anion part, the counter anion is preferably a compound containing a bis(sulfonyl)imide anion, a compound containing a tris(sulfonyl)methide anion, or a compound containing a sulfonate anion .

The compound containing the bis(sulfonyl)imide anion may be a monomer or a polymer. The compound containing a bis(sulfonyl)imide anion is preferably represented by the following general formula (AN1).

General formula (AN1)

In the general formula (AN1), R ¹ and R ² each independently represent an alkyl group or an aryl group. X ¹ and X ² may be bonded to form a ring.

R ¹ represents an alkyl group or an aryl group. The alkyl group may be linear, branched, or cyclic. The carbon number of the alkyl group is preferably 1-6, more preferably 1-3. The alkyl group is preferably an alkyl group substituted with a fluorine atom. The number of carbon atoms in the alkyl group substituted with a fluorine atom is preferably from 1 to 6, and more preferably from 1 to 3. The alkyl group may have a substituent. In particular, a perfluoroalkyl group is preferable, and a perfluoromethyl group is more preferable.

The carbon number of the aryl group is preferably 6-18, more preferably 6-12. The aryl group is preferably an aryl group substituted with a fluorine atom.

R ^{2 has} the same meaning as R ¹ and the preferred range is also the same.

As a specific example of the compound containing a bis(sulfonyl)imide anion, a bis(trifluoromethanesulfonyl)imide anion is preferable. With such a configuration, heat resistance can be further improved.

The compound containing a tris(sulfonyl)methide anion is preferably a compound represented by the following general formula (AN2).

General formula (AN2)

In the general formula (AN2), R ³ to R ⁵ each independently represent an alkyl group or an aryl group.

R ³ represents an alkyl group or an aryl group. The alkyl group may be linear, branched, or cyclic. The carbon number of the alkyl group is preferably 1-6, more preferably 1-3. The alkyl group is preferably an alkyl group substituted with a fluorine atom. The number of carbon atoms in the alkyl group substituted with a fluorine atom is preferably from 1 to 6, and more preferably from 1 to 3. The alkyl group may have a substituent. In particular, a perfluoroalkyl group is preferable, and a perfluoromethyl group is more preferable.

The carbon number of the aryl group is preferably 6-18, more preferably 6-12. The aryl group is preferably an aryl group substituted with a fluorine atom.

R ^{4 has} the same meaning as R ³ , and the preferred range is also the same.

R ^{5 has} the same meaning as R ³ , and the preferred range is also the same.

As a specific example of the compound containing a tris(sulfonyl)methide anion, a tris(trifluoromethanesulfonyl)methide anion is preferable.

The compound containing a sulfonate anion is preferably represented by the following general formula (AN3).

Formula (AN3) R-SO ₃ ^-

In the general formula (AN3), R represents an alkyl group or an aryl group. When R represents an alkyl group, it is preferably an alkyl group substituted with a fluorine atom. The carbon number of the alkyl group is preferably 1-6, more preferably 1-3. In particular, a perfluoroalkyl group is preferable, and a perfluoromethyl group is more preferable.

When R represents an aryl group, it is preferably an aryl group substituted with a fluorine atom. The carbon number of the aryl group is preferably 6-18, more preferably 6-12.

As a specific example of the compound containing a sulfonate anion, a trifluoromethanesulfonate anion is preferable.

As specific examples of other counter anions, the following specific examples can be cited, but the present invention is not limited to these specific examples. In this specification, the following specific examples of other counter anions are referred to as "counter anion A".

[化24]

Next, the case where the counter anion is a compound containing a crosslinkable group will be described.

As a crosslinkable group, the well-known polymerizable group which can be crosslinked by radical, acid, and heat is mentioned. Specifically, examples include (meth)acrylic groups, styryl groups, vinyl groups, cyclic ether groups, and groups represented by -COR (where R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). ), preferably at least one selected from (meth)acrylic, styryl, vinyl and cyclic ether groups, more preferably selected from (meth)acrylic, styryl and vinyl One of them is more preferably a (meth)acryloyl group or a styryl group.

The number of crosslinkable groups in the crosslinkable group-containing compound is preferably 1 to 3, more preferably 1.

In addition, the crosslinkable group and the counter anion may be directly bonded or may be bonded via a linking group, but it is preferable to bond via a linking group.

A specific example when the counter anion is a compound containing a crosslinkable group is preferably represented by the following general formula (B).

General formula (B)

(In the general formula (B), P represents a crosslinkable group. L represents a single bond or a divalent linking group. anion represents the counter anion)

In the general formula (B), P represents a crosslinkable group, and the above-mentioned crosslinkable group can be mentioned.

In the general formula (B), when L represents a divalent linking group, it is preferably an alkylene group having 1 to 30 carbons, an arylene group having 6 to 30 carbons, a heterocyclic linking group, and -CH=CH- , -O-, -S-, -C(=O)-, -CO-, -NR-, -CONR-, -OC-, -SO ₂ -and a combination of two or more of these base. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

In particular, the linking group is preferably a combination of two or more of an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -NH-, -CO-, -O-, and -SO _2- Into the link base.

When the counter anion is a compound containing a crosslinkable group, it may have other functional groups other than the crosslinkable group. Examples of other functional groups include acid groups. As an acid group, a carboxyl group, a sulfonic acid group, and a phosphoric acid group can be illustrated. When the counter anion further has an acid group, the number of acid groups in the compound is preferably 1 to 3, more preferably 1.

The following shows specific examples when the counter anion is a compound containing a crosslinkable group, but the present invention is not limited to these specific examples.

[化26]

The molecular weight of the compound containing a crosslinkable group is preferably 200-2000, more preferably 200-500.

Next, the case where the counter anion is a polymer containing a repeating unit having an anion part (hereinafter also referred to as an anion polymer) will be described.

The anionic multimer may have an anion part on the side chain of the repeating unit, may have an anion part on the main chain of the repeating unit, or may have an anion part on both the main chain and the side chain.

The anionic multimer is preferably represented by the following general formula (C) and/or the following general formula (D).

General formula (C)

(In the general formula (C), X ¹ represents the main chain of the repeating unit. L ¹ represents a single bond or a divalent linking group. Anion represents an anion portion)

In the general formula (C), X ¹ represents the main chain of the repeating unit, and generally represents a linking group formed by a polymerization reaction. For example, a (meth)acrylic, styrene, vinyl, etc. are preferred. In addition, the part indicated by 2 * becomes a repeating unit.

When L ¹ represents a divalent linking group, it is preferably an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH=CH-, -O-,- S-, -COO-, -CO-, -NR-, -CONR-, -OCO-, -SO ₂ -and a linking group formed by combining two or more of these. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

L ^{1 is more} preferably a single bond, or a C1-C10 alkylene group, a C6-C12 aryl group, two of -NH-, -CO ₂ -, -O- and -SO _2- The bivalent linking base formed by the above combination.

The anionic multimer is preferably represented by the following general formula (AN4).

General formula (AN4)

In the general formula (AN4), X ¹ represents the main chain of the repeating unit. L ¹ represents a single bond or a divalent linking group. R ¹ represents an alkyl group or an aryl group.

^{The meanings of X 1} and L ^{1 are the} same as X ¹ and L ¹ in the general formula (C), and the preferred ranges are also the same.

R ¹ represents an alkyl group or an aryl group. The alkyl group may be linear, branched, or cyclic. The carbon number of the alkyl group is preferably 1-6, more preferably 1-3. The alkyl group is preferably an alkyl group substituted with a fluorine atom. The number of carbon atoms in the alkyl group substituted with a fluorine atom is preferably from 1 to 6, and more preferably from 1 to 3. The alkyl group may have a substituent. In particular, a perfluoroalkyl group is preferable, and a perfluoromethyl group is more preferable. The carbon number of the aryl group is preferably 6-18, more preferably 6-12. The aryl group is preferably an aryl group substituted with a fluorine atom.

General formula (D)

(In the general formula (D), L ² and L ³ each independently represent a single bond or a divalent linking group. Anion represents an anion portion)

In the general formula (D), when L ² and L ³ represent a divalent linking group, they are preferably an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, and- CH=CH-, -O-, -S-, -CO-, -COO-, -NR-, -CONR-, -OCO-, -SO ₂ -and a combination of two or more of these base. Here, R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

L ^{2 is} preferably an arylene group having 6 to 12 carbons (especially a phenylene group). The arylene group having 6 to 30 carbon atoms is preferably substituted with a fluorine atom.

L ^{3 is} preferably a group comprising a combination of an arylene group having 6 to 12 carbons (especially a phenylene group) and -O-, and preferably at least one arylene group having 6 to 12 carbons via a fluorine atom replace.

The anionic multimer may also contain a repeating unit having a polymerizable group. When a repeating unit having a polymerizable group is contained, the amount is preferably 10 mol to 50 mol, and more preferably 10 mol to 30 mol relative to 100 mol of all repeating units.

In addition, the anionic multimer may also contain a repeating unit having an acid group. When containing In the case of a repeating unit having an acid group, the amount is preferably 10 mol to 50 mol, and more preferably 10 mol to 30 mol relative to 100 mol of all repeating units.

The weight average molecular weight of the anionic polymer is preferably 1,000 to 30,000, more preferably 3,000 to 20,000.

When an anionic polymer is formed, a chain transfer agent can also be added. The chain transfer agent is preferably an alkyl mercaptan, more preferably an alkyl mercaptan having a carbon number of 4 or more, and an alkyl mercaptan substituted with a carboxyl group, an ether group, or an ester group.

The content of halogen ions contained in the anionic polymer is preferably 10 ppm to 3000 ppm or less, more preferably 10 ppm to 2000 ppm, and still more preferably 10 ppm to 1000 ppm.

As a specific example of the anionic polymer, the structure described in paragraph 0034 to paragraph 0035 of JP 2015-030742 A can be cited, and the content can be incorporated in this specification.

In the triarylmethane structure represented by the general formula (TP1) and the triarylmethane structure represented by the general formula (TP2), cations exist in a nonlocalized manner as follows, and the following structures have the same meaning, and These are all included in the present invention.

[化30]

The triarylmethane structure is preferably represented by the following general formula (TP3).

In the general formula (TP3), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group with 1 to 6 carbons; Rtp ₂₂ each independently represents an aryl group with 6 to 10 carbons, and Rtp ₇₁ represents an alkyl group or an aryl group; X It represents an anion, or X is absent and at least one of _{Rtp 21} , Rtp ₂₂ and Rtp _{71 includes an anion; any one of Rtp 21} , Rtp ₂₂ and Rtp ₇₁ represents a bonding site with the repeating unit A.

In the general formula (TP3), Rtp _{21 is} preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group may be any of linear, branched, and cyclic, but is preferably linear. The carbon number of the alkyl group is preferably 1 to 4, more preferably 1 to 3. As the substituent which the alkyl group may have, the substituents exemplified in the section of the substituent group A mentioned later can be mentioned. With this structure, the light resistance can be further improved.

In the general formula (TP3), Rtp ₂₂ represents an aryl group having 6 to 10 carbon atoms. Rtp _{22 is} preferably an aryl group having a substituent at least at the ortho position. Examples of the substituent that the aryl group may have include the substituents exemplified in the section of the substituent group A described later, and an alkyl group having 1 to 3 carbon atoms is preferred. With such a configuration, heat resistance can be further improved.

Rtp ₇₁ represents an alkyl group or an aryl group, preferably an alkyl group. The alkyl group may be any of linear, branched, and cyclic, and is preferably cyclic. The carbon number of the alkyl group is preferably 1-8, more preferably 1-6. The carbon number of the aryl group is preferably 6-12, more preferably 6-10.

Any one of Rtp ₂₁ , Rtp ₂₂ and Rtp ₇₁ represents a bonding site with a repeating unit, and _{Rtp 71 is preferably a bonding site with a repeating unit.}

The triarylmethane structure is preferably represented by the following general formula (TP3A).

In the general formula (TP3A), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group with 1 to 6 carbons; Rtp ₂₂ each independently represents an aryl group with 6 to 10 carbons; X represents an anion, or X is absent and Rtp _{At least one of 21} and Rtp ₂₂ contains an anion; * indicates the bonding site with the repeating unit A.

Regarding the details of Rtp ₂₁ and Rtp ₂₂ , their meanings are the _{same as those of Rtp 21} and Rtp _{22 of the} general formula (TP3), and the preferred ranges are also the same.

Substituent group A: Examples of substituents include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, alkoxy groups, aryloxy groups, silalkoxy groups, and heterocyclic oxy groups. , Acyloxy group, carbamoyloxy group, amine group (including alkylamino group, anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, amine Sulfonamide, alkylsulfonylamino or arylsulfonylamino, sulfhydryl, alkylthio group, arylthio, heterocyclic thio, sulfasulfonyl, alkylene Sulfonyl or arylsulfinyl, alkylsulfinyl or arylsulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, carbamethan, arylazo or heterocyclic coupling Nitrogen group, imine group, phosphine group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, etc. For the details of the substituent group A, reference can be made to the descriptions of paragraphs 0174 to 0185 of JP-A-2015-034966, the contents of which can be incorporated into this specification.

<<<<Preferable form of repeating unit A>>>>

The repeating unit A is preferably represented by the following general formula (TP3-1).

[化33]

In the general formula (TP3-1), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbons, Rtp ₂₂ each independently represents an aryl group having 6 to 10 carbons, and Rtp _71a represents an alkylene group or an alkylene group. Aryl group; L ₁ represents a divalent linking group having 2 to 30 carbon _{atoms, Rtp 31} represents a hydrogen atom or a methyl group; X represents an anion, or X does not exist and at least one of _{Rtp 21} and Rtp _{22 contains an anion.}

The meanings of Rtp ₂ 1 and _{Rtp 2 2 are the same as Rtp 21} and Rtp ₂₂ in the general formula (TP3), and the preferred ranges are also the same.

Rtp _71a represents an alkylene group or an arylene group, preferably an alkylene group. The alkylene group may be linear, branched, and cyclic, and is preferably cyclic. The carbon number of the alkylene group is preferably 1-8, more preferably 1-6. The carbon number of the aryl group is preferably 6-12, more preferably 6-10. The alkylene group and the arylene group may have a substituent or may be unsubstituted. It is preferably unsubstituted. As a substituent, the substituent demonstrated in the said substituent group A is mentioned.

L ₁ represents a single bond or a divalent linking group. ¹ L of the same meaning as L ₁ in the general formula (A), preferred ranges are also the same.

In the general formula (TP3-1), the number of atoms in the "-Rtp _71a -L ₁ -" part constituting the chain connecting the main chain of the repeating unit A to the nitrogen atom bonded to _{Rtp 71a of the triarylmethane structure} Preferably it is 1 or more, More preferably, it is 2 or more, More preferably, it is 3 or more, Especially preferably, it is 5 or more. The upper limit is preferably 20 or less, for example. According to this aspect, it is possible to suppress unreacted or insufficiently reacted low molecular triarylmethane compounds when synthesizing the polymer TP. As a result, heat resistance and solvent resistance can be improved.

The repeating unit A is preferably represented by the following general formula (TP3-2).

In the general formula (TP3-2), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group with 1 to 6 carbons, Rtp ₂₄ each independently represents an alkyl group with 1 to 4 carbons, and Rtp ₂₅ each independently represents a hydrogen atom Or an alkyl group with 1 to 3 carbon atoms, Rtp _71a represents an alkylene group or an arylene group; Rtp ₃₁ represents a hydrogen atom or a methyl group; L ₁ represents a single bond or a divalent linking group; X represents an anion, or there is no X In addition, at least one of _{Rtp 21} and Rtp _{22 includes an anion.}

Preferably, Rtp ₂₁ is each independently an alkyl group having 1 to 6 carbon atoms. The alkyl group may be any of linear, branched, and cyclic, but is preferably linear. The carbon number of the alkyl group is preferably 1 to 4, more preferably 1 to 3.

Rtp _{24 is} preferably each independently an alkyl group having 1 or 2 carbon atoms.

When Rtp ₂₅ represents an alkyl group having 1 to 3 carbon atoms, the carbon number of the alkyl group is preferably 1 or 2.

Rtp _71a with the same meaning as in the general formula (TP3-1) Rtp _71a, the preferred ranges are also the same.

₁ the same meaning as L ₁ and L in the general formula (TP3-1), preferred ranges are also the same.

As specific examples of the repeating unit A, the following structures can be cited, but the present invention is not limited to these structures. In addition, the specific example of the repeating unit A also includes a repeating unit derived from a monomer having a triarylmethane structure described later.

[化35]

[化36]

<<<repeat unit B>>>

The polymer TP contains a repeating unit B having a crosslinkable group. In all the repeating units of the polymer TP, it is preferable to contain 1% to 99% by mass of the repeating unit B. The upper limit is more preferably 95% by mass or less, and still more preferably 90% by mass or less. The lower limit is more preferably 2% by mass or more, and still more preferably 3% by mass or more. If the content of the repeating unit B is in the above range, the heat resistance and solvent resistance are particularly excellent.

As the crosslinkable group, a known crosslinkable group that can be crosslinked by radicals, acid, or heat can be used. Examples include groups containing ethylenically unsaturated bonds, cyclic ether groups (epoxy groups). , Oxetanyl), oxazoline group, a group represented by -COR (wherein R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a carbonate group, and the like. As a group containing an ethylenically unsaturated bond, (meth)acryloyl group, a vinyl group, a dicyclopentenyl group, etc. are mentioned. The carbonate group is preferably a cyclic carbonate group.

The crosslinkable group is preferably selected from epoxy group, oxetanyl group, oxazoline group, group represented by -COR (wherein R represents a hydrogen atom or an alkyl group with 1 to 20 carbon atoms), carbonic acid At least one of an ester group, a (meth)acryloyl group, and a vinyl group is more preferably an epoxy group or an oxetanyl group.

Regarding the crosslinkable group possessed by the polymer TP, the crosslinkable group possessed by the polymer TP reacts with each other or with the crosslinkable group possessed by an alkali-soluble binder or a crosslinking agent.

As the repeating unit B, the following specific examples can be given. However, the present invention is not limited to these specific examples.

[化37]

<<<Other repeating units>>>

The polymer TP may further contain other repeating units other than the repeating unit A and the repeating unit B. As other repeating units, for example, repeating units derived from at least one of (meth)acrylic acid, (meth)acrylate, and (meth)acrylamide can be exemplified.

Specifically, a repeating unit having an acid group can be mentioned. As an acid group, a carboxyl group, a sulfonic acid group, and a phosphoric acid group can be illustrated, and a carboxyl group is preferable. When the polymer TP further contains a repeating unit having an acid group, the development performance of the colored composition can be further improved. When the polymer TP further contains a repeating unit having an acid group, among all the repeating units of the polymer TP, the ratio of the repeating unit containing the repeating unit having an acid group is preferably, for example, 10% by mass to 80% by mass, and more Preferably, it is 10% by mass to 60% by mass.

Other repeating units can also have development promoting groups such as lactone groups, acid anhydride groups, amide groups, -COCH ₂ CO-, cyano groups, long-chain alkyl groups and cyclic alkyl groups, aralkyl groups, aryl groups, and polyepoxy groups. Functional groups such as an alkyl group, a hydroxyl group, a maleimide group, and an amine group, such as hydrophilic and hydrophobic adjusting groups.

Specific examples of other repeating units are shown below, but the present invention is not limited to these.

The polymer TP preferably has a structure containing a repeating unit derived from at least one of (meth)acrylic acid, (meth)acrylate, and (meth)acrylamide. For example, the repeating unit A and/or the repeating unit B is a form of a repeating unit derived from at least one of (meth)acrylic acid, (meth)acrylate, and (meth)acrylamide, and the other The repeating unit is in the form of a repeating unit derived from at least one of (meth)acrylic acid, (meth)acrylate, and (meth)acrylamide.

In the present invention, the weight average molecular weight of the polymer TP is preferably 3,000 to 500,000. The lower limit is preferably 4000 or more, more preferably 5000 or more, and even more preferably It is 7000 or more, particularly preferably 10000 or more. The upper limit is preferably 200,000 or less, more preferably 100,000 or less, and particularly preferably 50,000 or less. That is, the weight average molecular weight of the polymer TP is particularly preferably 10,000 to 50,000. By adjusting the weight average molecular weight of the polymer TP to the above range, heat resistance and solvent resistance are good. Furthermore, the voltage characteristics can also be improved.

The number average molecular weight of the polymer TP is preferably 2,000 to 500,000. The lower limit is preferably 2500 or more, more preferably 3000 or more, still more preferably 4000 or more, particularly preferably 5000 or more. The upper limit is preferably 100,000 or less, more preferably 70,000 or less, and particularly preferably 50,000 or less.

The degree of dispersion (weight average molecular weight/number average molecular weight) of the polymer TP is preferably 1.0 to 5.0. The upper limit is preferably 4.0 or less, more preferably 3.5 or less, particularly preferably 2.0 or less.

The weight average molecular weight and number average molecular weight of polymer TP are polystyrene conversion values measured by a gel permeation chromatography (Gel Permeation Chromatograph, GPC), and are specifically measured by the method described in the following examples Value.

In the present invention, relative to the mass of polymer TP, the content of compound A having a triarylmethane structure of polymer TP with a weight average molecular weight of 1500 or less is 20% by mass or less, preferably 10% by mass or less, more preferably It is 5% by mass or less, particularly preferably 1% by mass or less, and it may not be contained substantially. In addition, the so-called "substantially not contained", for example, relative to the mass of the polymer TP, the content of the compound A is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and still more preferably not contained.

By setting the content of compound A to 20% by mass or less, it is possible to effectively inhibit poly The elution of the compound TP from the film, as a result, can improve the solvent resistance or heat resistance of the film.

Compound A is a compound having a triarylmethane structure, and specifically refers to unreacted materials such as raw material monomers having a triarylmethane structure, or impurities containing raw material monomers that do not have a polymerizable group.

The content of the compound A in the polymer TP can be measured by detecting with ultraviolet light in the GPC measurement of the polymer TP.

In the present invention, the content of compound A in the polymer TP is the following value: Using HLC-8020GPC (manufactured by Tosoh Co., Ltd.), two TSKgel α-M (manufactured by Tosoh Co., Ltd., 7.8 mm (Inner diameter)×30cm) as the column, and the measurement condition is set to the sample concentration of 0.35 mass% N-Methyl-2-Pyrrolidone (N-Methyl-2-Pyrrolidone, NMP ) The value of the solution, the flow rate is 0.3 mL/min, the sample injection volume is 10 μL, the measurement temperature is 40° C., and the measurement is performed with an ultraviolet detector.

The polymer TP is preferably a polymer containing a repeating unit represented by the general formula (TP-7).

[化40]

In the general formula (TP-7), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, R ^1a represents an alkylene group or an aryl group, and L ¹¹ represents A single bond or a divalent linking group with 1 to 30 carbons; L ¹² and L ¹³ represent a single bond or a divalent linking group with 1 to 30 ^{carbons; R 2} represents a hydrocarbon group with 1 to 10 carbons; R ³ represents a crosslinkable group; X represents a compound containing bis(sulfonyl)imide anion, tris(sulfonyl)methide anion or sulfonate anion; a~d are the mass ratios of repeating units, a and d represents a number exceeding 0, and b and c each independently represent a number greater than 0.

In the general formula (TP-7), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. The carbon number of the alkyl group is preferably 1 to 3. The alkyl group is preferably linear.

R ² represents a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group may be linear, branched or cyclic, and is preferably linear or cyclic. The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably an alkyl group. In particular, R ^{2 is} preferably a cyclic alkyl group having 5 to 10 carbon atoms, a linear alkyl group having 1 to 8 carbon atoms, or a branched alkyl group having 3 to 8 carbon atoms. The carbon number of the cyclic alkyl group is preferably 6-8, more preferably 6. The carbon number of the linear alkyl group is preferably 1 or 2, more preferably 1. The carbon number of the branched alkyl group is preferably 3-8. The hydrocarbon group may have a substituent, and the substituent is preferably a hydroxyl group. As an example when the hydrocarbon group has a substituent, a hydroxyethyl group is preferred.

R ³ represents a crosslinkable group. Examples of crosslinkable groups include groups selected from ethylenically unsaturated bond-containing groups, epoxy groups, oxetanyl groups, oxazoline groups, and groups represented by -COR (where R represents a hydrogen atom or carbon number). At least one of 1-20 alkyl) and carbonate group. As a group containing an ethylenically unsaturated bond, (meth)acryloyl group, a vinyl group, a dicyclopentenyl group, etc. are mentioned.

R ⁴ represents a hydrogen atom or a methyl group, preferably a methyl group.

R ^1a represents an alkylene group or an arylene group, preferably an alkylene group. The alkylene group may be linear, branched, and cyclic, and is preferably cyclic. The carbon number of the alkylene group is preferably 1-8, more preferably 1-6. The carbon number of the aryl group is preferably 6-12, more preferably 6-10. The alkylene group and the arylene group may have a substituent or may be unsubstituted. It is preferably unsubstituted. As a substituent, the substituent demonstrated in the said substituent group A is mentioned.

L ¹¹ represents a single bond or a divalent linking group having 1 to 30 carbon atoms. Examples of divalent linking groups include: alkylene groups having 1 to 30 carbon atoms, arylene groups having 6 to 12 carbon atoms, and these are selected from -CO-, -OCO-, -O-, -NH- and -SO ₂ -is a combination of bases. The divalent linking group is preferably an alkylene group or a linking group in which alkylene groups are connected via one or more selected from -O-, -COO-, and -OCO-.

L ¹² and L ¹³ represent a single bond or a bivalent linking group having 1 to 30 carbon atoms. Examples of the divalent linking group include alkylene groups having 1 to 30 carbon atoms, arylene groups having 6 to 12 carbon atoms, and these are selected from the group consisting of -CO-, -OCO-, -O-, -NH- and- SO ₂ -a combination of bases. The alkylene group and the arylene group may have a substituent or may be unsubstituted. Examples of the substituent include the above-mentioned substituent group A. Among them, a hydroxyl group is preferred.

In the general formula (TP-7), the number of atoms in the ^{"-L 11} -R ^1a -" part constituting the chain connecting the main chain of the repeating unit A to ^{the nitrogen atom bonded to R 1a of the triarylmethane structure} Preferably it is 1 or more, More preferably, it is 2 or more, More preferably, it is 3 or more, Especially preferably, it is 5 or more. The upper limit is preferably 20 or less, for example.

In the general formula (TP-7), X represents a compound containing bis(sulfonyl)imide anion, tris(sulfonyl)methide anion or sulfonate anion, preferably containing bis(sulfonyl) The compound of the imine anion.

The compound containing the bis(sulfonyl)imide anion may be a single body or a multimer. The compound containing a bis(sulfonyl)imide anion is preferably a compound represented by the general formula (AN1).

The compound containing a tris(sulfonyl)methide anion is preferably a compound represented by the general formula (AN2).

The compound containing a sulfonate anion is preferably a compound represented by the general formula (AN3).

a to d are the mass ratios of the repeating units, a and d represent a number exceeding 0, and b and c each independently represent a number of 0 or more. When the total of a to d is set to 1, a is preferably 0.01 to 0.99. b represents an integer of 0 or more, preferably 0 to 90. c represents an integer of 0 or more, preferably 0 to 90. d is preferably 0.01 to 0.99.

The following shows specific examples of the polymer TP in the present invention, but it is not limited to these specific examples.

[化41]

[化42]

[化43]

[化44]

[化45]

<Manufacturing method of polymer TP>

The polymer TP of the present invention can be produced by polymerizing raw material monomers containing at least a triaryl group represented by at least one selected from general formula (TP1a) and general formula (TP2a) A triarylmethane monomer of a methane structure and a monomer having a crosslinkable group. The raw material monomer may further include a monomer having an acid group or a monomer having a functional group described in the other repeating unit.

[化46]

In general formula (TP1a) and general formula (TP2a), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group; Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ and Rtp ₁₁ each independently represent a substitution Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ₇₁ Rtp ₇₂ ; Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group; Rtp ₁₀ represents a hydrogen atom, an alkyl group or an aryl group; a , B, c, and d each independently represent an integer from 0 to 4; when a, b, c, and d are 2 or more, two of Rtp ₅ , Rtp ₆ , Rtp ₈ and Rtp ₉ can be connected to each other to form a ring ; X represents an anion, or X and absent Rtp ₁ ~ Rtp _11, Rtp ₇₁ and at least one contains an anionic Rtp _{72; Rtp 1 ~ Rtp 11, Rtp} 71 Rtp and having at least one polymerizable group _72.

_{Rtp 1 ~ Rtp 11, Rtp 71} , Rtp meaning as the general formula (TP1a) Rtp _72, and X, and the general formula (TP2a) of _{1 ~ Rtp 11, Rtp 71,} Rtp 72 and the same as X, preferred ranges are also the same .

In general formula (TP1a) and general formula (TP2a), _{at least one of Rtp 1} to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ has a polymerizable group. It is preferable _{that at least one of Rtp 71} and Rtp ₇₂ has a polymerizable group. As a polymerizable group, a vinyl group, a (meth)acryloyl group, a styryl group, etc. are mentioned, Preferably it is a (meth)acryloyl group.

Specific examples of triarylmethane monomers are shown below. One of the structures shown below Among them, from the viewpoint of polymerization, D-42 to D-44 are preferred.

The polymerization temperature is preferably 40°C to 90°C, more preferably 50°C to 70°C. By increasing the polymerization temperature within the range where the crosslinkable group in the polymer does not react, the polymerization of the triarylmethane monomer can be facilitated. For example, by performing polymerization within the temperature range, the reaction between the epoxy group and the carboxyl group in the polymer is suppressed and the increase in the molecular weight can be suppressed. As a result, a polymer excellent in brightness and heat resistance can be obtained. In addition, the residual amount of triarylmethane monomer can be reduced, and solvent resistance or voltage retention can be improved.

The polymerization is preferably performed in a solution containing 30% to 60% by mass of the raw material monomers in total. The content of the raw material monomer in the solution is more preferably 35% by mass to 55% by mass, and still more preferably 40% by mass to 55% by mass. If the content of the raw material monomer is within the above range, the polymerization of the triarylmethane monomer can be facilitated. As a result, the content of the compound A in the polymer TP can be reduced.

Examples of the solvent used in the preparation of the reaction solution of the raw material monomer include solvents that can be contained in the coloring composition described later.

A chain transfer agent can also be added during polymerization. The chain transfer agent is preferably an alkyl mercaptan, and more preferably an alkyl mercaptan having 4 or more carbons or an alkyl mercaptan substituted with a carboxyl group, an ether group, or an ester group. In particular, from the viewpoint of odor, dodecyl mercaptan and dipentaerythritol hexa-3-mercaptopropionate are preferred, and from the viewpoint of promoting developability, thiomalic acid and mercapto are preferred. Propionic acid.

After the polymerization is completed, a refining treatment can also be carried out. Thereby, the content of compound A can be reduced.

In the coloring composition of the present invention, relative to the coloring composition of the present invention As for the total solid content, the content of the polymer TP is preferably 10% by mass to 60% by mass, more preferably 10% by mass to 40% by mass.

<<Other coloring compounds>>

The coloring composition of the present invention may also contain one or two or more other coloring compounds other than the polymer TP. Examples of other coloring compounds include dye compounds, pigment compounds, and dispersions of these.

When the pigment compound is formulated as a dispersion, it can be prepared in accordance with the description in Japanese Patent Laid-Open No. 9-197118 and Japanese Patent Laid-Open No. 2000-239544.

Examples of dye compounds include azo series (for example, Solvent Yellow 162), anthraquinone series (for example, the anthraquinone compound described in Japanese Patent Laid-Open No. 2001-10881), and phthalocyanine series (for example, U.S. Patent 2008/ 0076044A1), xanthene series (e.g. CI Acid Red 289 (CIAcid.Red 289)), triarylmethane series (e.g. CI Acid Blue 7 (CIAcid Blue 7), CI Acid Blue 83 ( CIAcid Blue 83), CI Acid Blue 90 (CIAcid Blue 90), CI Solvent Blue 38 (CISolvent Blue 38), CI Acid Violet 17 (CIAcid Violet 17), CI Acid Violet 49 (CIAcid Violet 49), CI Acid Green 3 (CIAcid Green 3)), methine dyes, xanthene dyes (e.g. Japanese Patent Laid-Open No. 2010-32999), dipyrromethene-based metal complex compounds (e.g., Japanese Patent Laid-Open No. 2012- Communiqué No. 237985) and so on.

Examples of the pigment compound include perylene, perylene, quinacridone, quinacridone quinone, anthraquinone, anthracenanthrone, benzimidazolone, bisazo condensation, bisazo, Azo, indanthrene, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, indigo, thioindigo, isoindoline, isoindolinone, pyranthrone Or isoviolanthrone and so on. In more detail, for example, perylene compound pigments such as Pigment Red 190, Pigment Red 224, and Pigment Violet 29; perylene compound pigments such as Pigment Orange 43 or Pigment Red 194; Pigment Violet 19, Pigment Violet 42, and Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 207, or Pigment Red 209 and other quinacridone compound pigments, Pigment Red 206, Pigment Orange 48, or Pigment Orange 49 and other quinacridone quinone compound pigments, Pigment Yellow 147 Anthraquinone compound pigments, pigment red 168 and other anthraquinone compound pigments, Pigment Brown 25, Pigment Violet 32, Pigment Orange 36, Pigment Yellow 120, Pigment Yellow 180, Pigment Yellow 181, Pigment Orange 62, or Pigment Red 185, etc. Benzimidazolone compound pigments, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 166, Pigment Orange 34, Pigment Orange 13, Pigment Orange 31, Pigment Red 144, Pigment Red 166, Pigment Red 220 , Pigment Red 221, Pigment Red 242, Pigment Red 248, Pigment Red 262, or Pigment Brown 23 and other disazo condensed compound pigments, Pigment Yellow 13, Pigment Yellow 83, or Pigment Yellow 188 and other disazo compound pigments, Pigment Red 187, Pigment Red 170, Pigment Yellow 74, Pigment Yellow 150, Pigment Red 48, Pigment Red 53, Pigment Orange 64, or Pigment Red 247 and other azo compound pigments, Pigment Blue 60 and other indanthrene compound pigments, Pigment Green 7 , Pigment Green 36, Pigment Green 37, Pigment Green 58, Pigment Blue 16, Pigment Blue 75, or Pigment Blue 15 and other phthalocyanine compound pigments, Pigment Blue 56, or Pigment Blue 61 and other triarylcarbonium compound pigments, Pigment Violet 23 , Or Dioxazine compound pigments such as Pigment Violet 37, Aminoanthraquinone compound pigments such as Pigment Red 177, Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 272, Pigment Orange 71, or Pigment Orange 73 and other diketones Pyrrolopyrrole Compound pigments, thioindigo compound pigments such as Pigment Red 88, isoindolinone compound pigments such as Pigment Yellow 139 and Pigment Orange 66, isoindolinone compound pigments such as Pigment Yellow 109 or Pigment Orange 61, Pigment Orange 40, or pigment Pianthrone compound pigments such as Red 216, or isoviolanthrone compound pigments such as Pigment Violet 31.

In the present invention, it is preferably a color material of green to cyan, preferably a phthalocyanine compound such as Pigment Green 7, Pigment Green 36, Pigment Green 37, Pigment Green 58, Pigment Blue 16, Pigment Blue 75, or Pigment Blue 15 Pigments, triarylcarbonium compound pigments such as Pigment Blue 56, or Pigment Blue 61, dioxazine compound pigments such as Pigment Violet 23, or Pigment Violet 37, Aminoanthraquinone compound pigments such as Pigment Red 177, Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 272, Pigment Orange 71, or Pigment Orange 73 and other diketopyrrolopyrrole compound pigments, Pigment Red 88 and other thioindigo compound pigments, Pigment Yellow 139, Pigment Orange 66 and other isoindoline compound pigments , Pigment Yellow 109, or Pigment Orange 61 and other isoindolinone compound pigments, Pigment Orange 40, or Pigment Red 216 and other pyranthrone compound pigments, or Pigment Violet 31 and other isoviolanthrone compound pigments.

In particular, as other coloring compounds, it is preferable to contain at least one selected from xanthene compounds, dipyrromethene-based metal zirconium compounds, oxazine compounds, and phthalocyanine compounds, and it is more preferable to contain at least one selected from xanthene compounds and two At least one of pyrromethene-based metal aluminum compounds.

<Xanthene Compound>

A xanthene compound is a compound having a xanthene skeleton in the molecule. Examples of xanthene compounds include: Dye Index (Colour Index, C.I.) Acid Red 51 (hereinafter, the description of C.I. Acid Red is omitted, and only the number is described. Others are the same), 52, 87, 92, 94, 289, 388, CI Acid Violet 9, 30, 102, CI Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, CI Basic Red 10 (Rhodamine B), 11 , CI Basic Violet 10, 11, 25, CI Solvent Red 218, CI Medium Red 27, CI Reactive Red 36 (Rose Bengal B), Sulfo-Rhodamine G, Japanese Patent Laid-Open No. 2010-32999 The described xanthene compound, the xanthene compound described in Japanese Patent No. 4492760, and the like.

The xanthene compound preferably contains a compound represented by general formula (1a) (hereinafter, sometimes referred to as "compound (1a)"). Compound (1a) may also be its tautomer. When the compound (1a) is used, the content of the compound (1a) in the xanthene compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. In particular, as the xanthene compound, it is preferable to use only the compound (1a).

General formula (1a)

In the general formula (1a), R ¹ to R ⁴ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbons that may have a substituent, or a monovalent saturated hydrocarbon group with 6 to 10 carbons that may have a substituent _{The -CH 2} -contained in the saturated hydrocarbon group can be substituted by -O-, -CO- or -NR ¹¹ -; R ¹ and R ² can be bonded to each other to form a ring containing a nitrogen atom, R ³ and R ⁴ may be bonded to each other to form a ring containing a nitrogen atom; R ⁵ represents _{^{-OH, -SO 3 -, -SO 3}} H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z + , -CO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ ; R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 6 carbon atoms; m1 represents an integer of 0 to 5. When m1 is 2 or more, multiple R ⁵ may be the same or different; m2 and m3 each independently represent an integer of 0-3. When m2 and m3 are independently 2 or 3, a plurality of R ⁶ and R ⁷ may be the same or different independently; a represents 0 or 1; when a represents 0, any one of ^{R 1} to R ⁷ The group has an anion; X ^- represents an anion; Z ⁺ represents N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , four R ¹¹ can be the same or different; R ⁸ represents a monovalent saturated with carbon number of 1-20 Hydrocarbon group, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom; R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group with 1 to 20 carbon atoms, and the saturated hydrocarbon group contains- CH ₂ -may be substituted by -O-, -CO-, -NH- or -NR ⁸ -, R ⁹ and R ¹⁰ may be bonded to each other to form a 3-membered to 10-membered heterocyclic ring containing a nitrogen atom; R ¹¹ It represents a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbons, or an aralkyl group with 7 to 10 carbons.

Examples of the monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms in R ¹ to R ^{4 include phenyl, tolyl, xylyl, mesityl, propylphenyl, and butylbenzene.} Base and so on. Among them, tolyl, xylyl, mesityl, and propylphenyl are preferred, especially tolyl and xylyl, and among them, 2,6-disubstituted xylyl is preferred. .

Examples of substituents that the aromatic hydrocarbon group may have include halogen atoms, -R ⁸ , -OH, -OR ⁸ , -SO ₃ -, -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, and- CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ or -SO ₂ NR ⁹ R ¹⁰ . Among these, the substituents are preferably -SO ₃ -, -SO ₃ H, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ , more preferably -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ . _{As -SO 3} ^- Z ^{+ in} this case, -SO ₃ ^- N ⁺ (R ¹¹ ) _{4 is} preferable.

When R ¹ to R ^{4 are} these groups, a color filter with more excellent heat resistance can be formed.

Examples of the ring formed by bonding R ¹ and R ^{2 to} each other and the ring formed by bonding R ³ and R ^{4 to each other include the following.}

Among these, from the viewpoint of compound stability, the structure shown below is preferable.

[化51]

Examples of monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms in R ⁸ to R ¹¹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, Linear alkyl groups such as decyl, dodecyl, hexadecyl, and eicosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; ring Alicyclic saturated hydrocarbon groups with 3 to 20 carbon atoms such as propyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl.

Among them, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl are preferred, and propyl, isopropyl, and butyl are particularly preferred. , Hexyl, 2-ethylhexyl.

The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.

Examples of -OR ⁸ include: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, and diethylhexyloxy. Decaoxy and so on. Among them, methoxy, ethoxy, propoxy, and butoxy are preferred.

Examples of -CO ² R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tertiary butoxycarbonyl group, a hexyloxycarbonyl group, and an eicosyloxycarbonyl group. Among them, a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group are preferred.

Examples of -SR ⁸ include methylthio, ethylthio, butylthio, hexylthio, decylthio, and icosylthio.

Examples of -SO ₂ R ⁸ include methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl, and eicosylsulfonyl.

Examples of -SO ₃ R ⁸ include: methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl, and oxacin Oxysulfonyl and so on.

Examples of -SO ₂ NR ⁹ R ¹⁰ include: sulfasulfonyl; N-methylsulfasulfonyl, N-ethylsulfasulfonyl, N-propylsulfasulfonyl, and N-isopropyl Sulfamoyl, N-Butyl Sulfamoyl, N-Isobutyl Sulfamoyl, N-Second Butyl Sulfamoyl, N-Third Butyl Sulfamoyl, N-Pentyl Sulfamyl, N-(1-ethylpropyl)sulfamethonyl, N-(1,1-dimethylpropyl)sulfamethonyl, N-(1,2-dimethylpropyl) ) Sulfonamide, N-(2-Ethylhexyl) Sulfonyl, N-(2,2-Dimethylpropyl) Sulfonyl, N-(1-methylbutyl) Sulfonyl Aceyl, N-(2-methylbutyl)sulfasulfonyl, N-(3-methylbutyl)sulfasulfonyl, N-cyclopentylsulfasulfonyl, N-hexylsulfasulfonyl , N-(1,3-dimethylbutyl)sulfasulfonyl, N-(3,3-dimethylbutyl)sulfasulfonyl, N-heptylsulfasulfonyl, N-(1 -Methylhexyl) Sulfonyl, N-(1,4-Dimethylpentyl) Sulfonyl, N-octyl Sulfonyl, N-(2-Ethylhexyl) Sulfonyl , N-(1,5-dimethyl)hexylsulfasulfonyl, N-(1,1,2,2-tetramethylbutyl)sulfasulfonyl and other N-1 substituted sulfasulfonyl groups; N , N-Dimethylsulfasulfonyl, N,N-Ethylmethylsulfasulfonyl, N,N-Diethylsulfasulfonyl, N,N-propylmethylsulfasulfonyl, N A Group) N,N-2 substituted sulfasulfonyl, N,N-heptylmethylsulfasulfonyl, etc.

Among them, preferred are N-methylsulfasulfonyl, N-ethylsulfasulfonyl, N-propylsulfasulfonyl, N-isopropylsulfasulfonyl, and N-butylsulfasulfonyl , N-pentylsulfasulfonyl, N-(2-ethylhexyl)sulfasulfonyl, more preferably N-methylsulfasulfonyl, N-ethylsulfasulfonyl, N-propylamine Sulfonyl, N-butylsulfasulfonyl, N-(2-ethylhexyl)sulfasulfonyl.

The ^{monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 9} and R ¹⁰ may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom.

R ⁵ is preferably ^{_{-CO 2 H, -CO 2 - Z}} +, -CO 2 R 8, -CO 2 NHR 9, -SO 3 -, -SO 3 - Z +, -SO 3 H, -SO 2 R ^8, or -SO ₂ NHR ^9, more preferably _{^{-SO 3 -, -SO 3 - Z}} +, -SO 3 H or -SO ₂ NHR ^9.

m1 is preferably an integer of 1 to 4, more preferably 1 or 2.

R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 6 carbon atoms.

m2 and m3 each independently represent an integer of 0 to 3, and 0 is preferred.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ^{11 include benzyl, phenylethyl, and phenylbutyl.}

a represents 0 or 1. When a represents 0, ^{any one of R 1} to R ⁷ has an anion, preferably R ⁵ has an anion.

X ^- is contained corresponding to the valence of the cation contained in the general formula (1a), and is usually monovalent or divalent, preferably monovalent. Examples of the anion X ^{− include} : fluoride anion, chloride anion, bromide anion, iodide anion, cyanide ion, perchlorate anion, etc. or low nucleophilic anion, preferably fluoride anion, chloride anion, bromide anion, or iodide anion . The low nucleophilic anion means an anion structure in which an organic acid having a pKa lower than that of sulfuric acid is dissociated. Examples of the anion include the low nucleophilic anion described in paragraph 0075 of JP 2007-310315, and the anion described in paragraph 0016 to paragraph 0025 of JP 2012-173399 , Japanese Patent Laid-Open No. 2013-037316, the anion part described in paragraph 0025 to paragraph 0033, etc., the content of which can be incorporated into this specification.

Z ⁺ is N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably N ⁺ (R ¹¹ ) ₄ .

N ⁺ (R ¹¹ ) _{4 is} preferably a monovalent saturated hydrocarbon group having 5 to 20 carbons at least two of the 4 R ^11. In addition, ^{the total carbon number of the four R 11} is preferably 20 to 80, and more preferably 20 to 60.

Compound (1a) is preferably a compound represented by general formula (3a) (hereinafter may be referred to as "compound (3a)"). Compound (3a) may also be its tautomer.

In the general formula (3a), R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. The hydrogen atoms contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted by an alkoxy group having 1 to 3 carbon atoms, and the -CH ₂ -contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may also be replaced by- O-, -CO- or -NR ¹¹ -replacement.

R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 4 carbons, an alkyl sulfanyl group having 1 to 4 carbons, or an alkyl sulfanyl group having 1 to 4 carbons.

R ³¹ and R ³³ may be bonded to each other to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be bonded to each other to form a ring containing a nitrogen atom.

p and q each independently represent an integer of 0-5. When p is 2 or more, a plurality of R ³³ may be the same or different. When q is 2 or more, a plurality of R ³⁴ may be the same or different.

The same meaning as R ¹¹ in the general formula (1a) in R ^11.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbons in R ³¹ and R ³² include the number of carbons in the monovalent saturated hydrocarbon group having 1 to 10 carbons described in ^{R 8 in the general formula (1a)} A monovalent saturated hydrocarbon group of 1-10. Among them, methyl, ethyl, propyl, butyl, hexyl, and 2-ethylhexyl are preferred. The aromatic hydrocarbon group having 6 to 10 carbon atoms which may be possessed as a substituent includes the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms described in R ¹ in the general formula (1a).

Examples of the alkoxy group having 1 to 3 carbon atoms that can replace the hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

Preferably, R ³¹ and R ³² are each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, second butyl, tertiary butyl, etc. . Among them, methyl, ethyl, and propyl are preferred.

Examples of the alkylthio group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include methylthio, ethylthio, propylthio, butylthio, isopropylthio, and the like.

Examples of the alkylsulfonyl groups having 1 to 4 carbon atoms in R ³³ and R ^{34 include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, and isopropyl.} Sulfonyl and so on.

p and q are preferably an integer of 0-2, more preferably 0 or 1.

As a specific example of the compound (1a), the compound represented by formula (1-1) to formula (1-43) described in paragraph number 0039 to paragraph number 0046 of JP 2014-005451 A can be cited , Its content can be incorporated into this manual.

As the xanthene compound, commercially available xanthene dyes (for example, "Chugai Aminol Fast Pink R-H/C" manufactured by Chugai Chemicals Co., Ltd., and "Rhodamin 6G" manufactured by Taoka Chemical Industry Co., Ltd.) can be used. In addition, a commercially available xanthene dye can also be used as a starting material and synthesized with reference to Japanese Patent Laid-Open No. 2010-32999, the content of which can be incorporated in this specification.

<Dipyrromethene based metal complexes>

Examples of the dipyrromethene-based metal aluminum compound include compounds in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound.

General formula (I) [化53]

In the general formula (I), R ¹ to R ⁶ each independently represent a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Examples of the substituent include the above-mentioned substituent group A. When the substituent is a group that may be further substituted, it may be further substituted by any of the above-mentioned substituents. Furthermore, when it has two or more substituents, these substituents may be the same or different.

In the general formula (I), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ may be independently bonded to each other to form a 5-member, 6-member or 7-member ring . As the ring to be formed, a saturated ring or an unsaturated ring can be mentioned. Examples of the 5-membered, 6-membered, or 7-membered saturated ring or unsaturated ring include pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, A pyrrolidine ring, a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, Preferably, a benzene ring and a pyridine ring are mentioned.

Furthermore, when the formed 5-membered, 6-membered, and 7-membered rings are groups that may be further substituted, they may be substituted by any one of the substituent group A, and when they are substituted by two or more substituents, These substituents may be the same or different.

In the general formula (I), R ¹ and R ^{6 are} preferably alkylamino groups, arylamino groups, carbamide groups, ureido groups, amide groups, alkoxycarbonylamino groups, and sulfonamide groups, It is more preferably a carbamido group, a ureido group, an alkoxycarbonylamino group, and a sulfonamido group, and still more preferably a carbamido group, a ureido group, an alkoxycarbonylamino group, and a sulfonamido group, and particularly preferably Carbamide group, urea group.

In the general formula (I), R ² and R ^{5 are} preferably an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamethan group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imino group, The carbamate sulfonyl group, more preferably an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamate group, an alkylsulfonyl group, a nitrile group, an imino group, a carbamate sulfonyl group, and even more Preferred are alkoxycarbonyl, aryloxycarbonyl, carbamethan, nitrile, amido, carbamate sulfonyl groups, particularly preferably alkoxycarbonyl, aryloxycarbonyl, carbamate .

In the general formula (I), R ³ and R ^{4 are} preferably an alkyl group, an aryl group or a heterocyclic group, and more preferably an alkyl group or an aryl group.

In the general formula (I), when R ³ and R ⁴ represent an alkyl group, the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, for example: methyl , Ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, and benzyl. In addition, it is more preferably a branched or cyclic alkyl group having 1 to 12 carbon atoms, for example, isopropyl, cyclopropyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, and cyclo Hexyl. More preferably, it is a secondary or tertiary alkyl group having 1 to 12 carbon atoms, and examples thereof include isopropyl, cyclopropyl, isobutyl, tertiary butyl, cyclobutyl, and cyclohexyl.

In the general formula (I), when R ³ and R ⁴ represent an aryl group, the aryl group is preferably a phenyl group and a naphthyl group, and more preferably a phenyl group.

When R ³ and R ⁴ represent a heterocyclic group, the heterocyclic group is preferably 2-thienyl, 4-pyridyl, 3-pyridyl, 2-pyridyl, 2-furyl, 2-pyrimidyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl or benzotriazol-1-yl, more preferably 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl or 1-pyridyl.

Next, the metal atom or metal compound forming the dipyrromethene-based metal aluminous compound will be described.

The metal atom or metal compound can be any metal atom or metal compound as long as it can form a complex compound, including divalent metal atoms, divalent metal oxides, and divalent metal hydrogens. Oxide, or divalent metal chloride. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, it also includes AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl ₂ and other metal chlorides, TiO, VO and other metal oxides, Si(OH) ₂ and other metal hydroxides.

Among these, from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and manufacturing suitability of the complex compound, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn are preferred. , Cu, Ni, Co, TiO, B, or VO, more preferably Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO, particularly preferably Fe, Zn, Cu, Co , B, or VO (V=O). Among these, Zn is particularly preferred.

The preferred form of the dipyrromethene-based metal complex compound formed by the compound represented by the general formula (I) coordinated on a metal atom or a metal compound can refer to paragraph 0153~ of Japanese Patent Laid-Open No. 2012-237985 The content of the complex compound represented by general formula (I-1), general formula (I-2), or general formula (I-3) described in paragraph 0176 can be incorporated into this specification.

As a specific example of the dipyrromethene-based metal complex compound, refer to the description of paragraph 0179 to paragraph 0186 of JP 2012-237985 A, the content of which can be incorporated into this specification.

When the coloring composition of the present invention contains other coloring compounds, the total solid content of the coloring composition of the present invention is preferably 0.5% by mass to 70% by mass. In addition, it is preferable to add to the coloring composition so that the absorption intensity ratio (absorption at 450 nm/absorption at 650 nm) is in the range of 0.95 to 1.05.

<<Polymerizable compound>>

The colored composition of the present invention contains a polymerizable compound. As a polymerizable compound, the addition polymerizable compound which has at least one ethylenically unsaturated double bond is mentioned, for example.

Specifically, it is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Such a group of compounds is widely known in the industrial field, and these compounds can be used in the present invention without particular limitation. These compounds may be monomers, prepolymers, ie, dimers, trimers, and oligomers, or mixtures of these compounds, and (co)polymers of these compounds. Preferably it is a monomer.

Examples of monomers and (co)polymers thereof include: unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters , Amides, and these (co)polymers, preferably esters of unsaturated carboxylic acids and aliphatic polyol compounds, amides of unsaturated carboxylic acids and aliphatic polyamine compounds, and these The (co)polymer. in addition, The addition reactants of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amine groups, and mercapto groups with monofunctional or polyfunctional isocyanates or epoxies, or with monofunctional Or the dehydration condensation reaction product of polyfunctional carboxylic acid, etc. In addition, addition reactants of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and further have halogens Substitution reactants of unsaturated carboxylic acid esters or amides with detachable substituents such as sulfonyloxy group or tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. In addition, as another example, a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether, etc. may be used instead of the unsaturated carboxylic acid.

As specific examples of these compounds, refer to paragraphs 0156 to 0159 of JP 2014-208808 A, the contents of which can be incorporated into this specification.

In addition, as polymerizable compounds, dipentaerythritol triacrylate (commercially available product is Kayarad (KAYARAD) D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available product is Kayara (KAYARAD) D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product is Kayarad (KAYARAD) D-310; manufactured by Nippon Kayaku Co., Ltd.) , Dipentaerythritol hexa(meth)acrylate (commercially available product is Kayarad (KAYARAD) DPHA; manufactured by Nippon Kayaku Co., Ltd.), and these (meth)acrylic acid groups are through ethylene glycol residues , Propylene glycol residues and bonded structures are also preferred. These oligomer types can also be used.

The structure of these polymerizable compounds, whether to be used alone or in combination, and the amount of addition The details of the usage method can be arbitrarily set according to the final performance design of the coloring composition. For example, from the viewpoint of sensitivity, a structure having a large amount of unsaturated groups per molecule is preferred, and in many cases, it is preferably bifunctional or higher. In addition, from the viewpoint of improving the strength of the cured film, it is preferably trifunctional or higher, and furthermore, the number of functional groups is different by using in combination. For polymerizable compounds having different polymerizable groups (for example, acrylate, methacrylate, styrene-based compound, and vinyl ether-based compound), the method of adjusting both sensitivity and strength is also effective. In addition, in terms of compatibility and dispersibility with other ingredients contained in the colored composition (such as photopolymerization initiators, colorants (pigments), binder polymers, etc.), the choice of polymerizable compounds. The method of use is also an important factor. For example, sometimes low-purity compounds can be used or two or more of them can be used in combination to improve compatibility. In addition, from the viewpoint of improving the adhesion to a hard surface of a substrate or the like, a specific structure can also be selected.

From the viewpoint of more effectively obtaining the effects of the present invention, the content of the polymerizable compound in the total solid content of the coloring composition is preferably 10% by mass to 80% by mass, more preferably 15% by mass to 75% by mass, Particularly preferred is 20% by mass to 60% by mass.

The composition of the present invention may contain only one type of polymerizable compound, or two or more types. When two or more are contained, it is preferable that the total amount thereof falls within the above-mentioned range.

<<Photopolymerization initiator>>

The coloring composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, and it is preferably selected from the viewpoints of characteristics, initial efficiency, absorption wavelength, availability, cost, and the like.

As the photopolymerization initiator, for example, at least one active halogen compound selected from the group consisting of halomethyl oxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl substituted coumarin compounds, and dichlorophene Polymers, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, oxime compounds, etc. Specific examples of the photopolymerization initiator include those described in paragraph [0070] to paragraph [0077] of JP 2004-295116 A. Among them, from the viewpoint of rapid polymerization reaction, etc., an oxime compound or a biimidazole-based compound is preferred.

The oxime-based compound (hereinafter, also referred to as "oxime-based photopolymerization initiator") is not particularly limited, and examples thereof include: Japanese Patent Laid-Open No. 2000-80068, WO02/100903A1, and Japanese Patent Laid-Open 2001- The oxime compound described in 233842 gazette and others.

As a specific example of the oxime-based compound, reference can be made to the description of paragraph 0053 of JP 2013-182215 A, the content of which can be incorporated into this specification.

In the present invention, from the viewpoints of sensitivity, stability over time, and coloration during post-heating, the oxime compound is more preferably a compound represented by the following general formula (1) or (2) .

(In the general formula (1), R and X each represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1 to 5)

As R, from the viewpoint of high sensitivity, an acyl group is preferable, and specifically, an acetyl group, a propyl group, a benzyl group, and a tolyl group are preferable.

As A, from the viewpoint of improving sensitivity and suppressing coloration with heating with time, an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tertiary butyl group, a dodecyl group) is preferred. Substituted alkylene, alkylene substituted with alkenyl (e.g. vinyl, allyl), aryl (e.g. phenyl, p-tolyl, xylyl, cumyl, naphthyl, anthryl) , Phenanthryl, styryl) substituted alkylene.

As Ar, a substituted or unsubstituted phenyl group is preferable from the viewpoint of improving sensitivity and suppressing coloration with heating with time. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, for example.

X is preferably an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkylthiooxy group, and an aryloxy group from the viewpoint of improving solvent solubility and absorption efficiency in a long wavelength region Group thiooxy group or amino group. In addition, n in the general formula (1) is preferably an integer of 1-2.

[化55]

In the general formula (2), R ¹⁰¹ represents an alkyl group, an alkanoyl group, an alkenoyl group, an arylalanyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, an alkylthiocarbonyl group, an arylthiocarbonyl group , Heterocyclic thiocarbonyl or CO-CO-Rf. Rf represents a carbocyclic aromatic group or a heterocyclic aromatic group.

R ¹⁰² represents an alkyl group, an aryl group, or a heterocyclic group, and these may be substituted.

R ¹⁰³ and R ¹⁰⁴ each independently represent an alkyl group, an aryl group, or a heterocyclic group, and these groups may be further substituted with a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylcarbonyl group, and the like.

R ¹⁰⁵ to R ¹¹¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryl group, a heteroaryl group, an alkylthio group, an arylthio group, and a heteroaryl group. Amino groups, alkylcarbonyl groups, arylcarbonyl groups, heterocyclic carbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heterocyclic oxycarbonyl groups, nitro groups, amino groups, sulfonic acid groups, hydroxyl groups, carboxylic acid groups, amide groups , Carboxamide or cyano.

When ^{one or two of R 105} to R ¹¹¹ are electron-withdrawing substituents, that is, a nitro group, a cyano group, an alkyl carbonyl group, or an aryl carbonyl group, a coloring composition with higher curability can be obtained, so Better.

As a specific example of the compound having a chrysanthemum structure represented by the general formula (2), Paragraph No. 0087 of Japanese Patent Laid-Open No. 2014-177502 can be cited ~ The content of the compound described in paragraph number 0088 can be incorporated into this specification.

The compound having a tea structure represented by the general formula (2) can be synthesized in accordance with the synthesis method described in WO2014-050738, for example.

Commercially available oxime-based photopolymerization initiators can be used: IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), TR-PBG -304 (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), Adeka Arkls NCI-831 (manufactured by ADEKA), Adeka Arkls NCI-930 (manufactured by ADEKA), etc.

As a specific example of the biimidazole-based compound, reference can be made to the description of paragraph 0061 to paragraph 0070 of JP 2013-182213 A, the content of which can be incorporated into this specification.

In addition, in the coloring composition of the present invention, in addition to the photopolymerization initiator, other known photopolymerization initiators described in paragraph 0079 of JP 2004-295116 A can also be used.

In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include: the compound described in Japanese Patent Laid-Open No. 2010-262028, the compound 24 described in the Japanese Patent Publication No. 2014-500852, the compound 36 to the compound 40, and the Japanese Patent Special The compound (C-3) and the like described in the Publication No. 2013-164471. Its content can be incorporated into this manual.

From the viewpoint of obtaining the effects of the present invention more effectively, the initiation of photopolymerization The content of the agent in the total solid content of the coloring composition is preferably 3% by mass to 20% by mass, more preferably 4% by mass to 19% by mass, and particularly preferably 5% by mass to 18% by mass.

The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more are contained, it is preferable that the total amount thereof falls within the above-mentioned range.

<<Organic Solvent>>

The coloring composition of the present invention preferably contains an organic solvent.

The organic solvent is basically not limited as long as it can satisfy the solubility of the coexisting components or the coatability of the colored composition. It is particularly preferable to consider the solubility, coatability, and safety of the adhesive. choose.

As the organic solvent, esters, ethers, ketones, and aromatic hydrocarbons can be used, and specifically, those described in paragraphs 0161 to 0162 of JP 2012-032754 A can be exemplified.

From the viewpoint of the solubility of each component, etc., it is also preferable to mix two or more of these organic solvents. In this case, particularly preferred is the following mixed solution, which contains selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, Diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, Two or more of propylene glycol methyl ether and propylene glycol methyl ether acetate.

As the content of the organic solvent in the coloring composition, it is preferable that the total solid content concentration in the composition becomes 10% by mass to 80% by mass, and it is more preferable that the total solid content concentration in the composition becomes 15% by mass to 60% by mass. The amount of mass%.

The coloring composition of the present invention may contain only one organic solvent or two above. When two or more are contained, it is preferable that the total amount thereof falls within the above-mentioned range.

<<Alkali-soluble binder>>

The colored composition of the present invention preferably contains an alkali-soluble binder. The alkali-soluble binder is not particularly limited except that it has alkali solubility, but it is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

The alkali-soluble binder is preferably a linear organic polymer polymer that is soluble in an organic solvent and can be developed by a weakly alkaline aqueous solution. Examples of such linear organic polymer polymers include polymers having a carboxylic acid in the side chain, such as Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-34327, and Japanese Patent Publication No. 58- No. 12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 59-53836, Japanese Patent Publication No. 59-71048, methacrylic acid copolymers, acrylic copolymers, and itaconic Acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, etc., and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

In addition to the above, as the alkali-soluble binder in the present invention, an acid anhydride is added to a polymer having a hydroxyl group, etc., or polyhydroxystyrene-based resin, polysiloxane-based resin, poly((formaldehyde) Base) 2-hydroxyethyl acrylate), polyvinylpyrrolidone or polyethylene oxide, polyvinyl alcohol, etc. are also useful. In addition, the linear organic polymer may be obtained by copolymerizing a monomer having hydrophilicity. Examples thereof include: alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, glycerol (meth)acrylate, (meth)acrylamide, and N-methylol Acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth)acrylate, methacrylamide Phloline (meth)acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth)acrylate, ethyl (meth)acrylate, Branched or linear propyl (meth)acrylate, branched or linear butyl (meth)acrylate, or phenoxyhydroxypropyl (meth)acrylate, etc. In addition, as hydrophilic monomers, it includes tetrahydrofurfuryl, phosphoric acid, phosphate, quaternary ammonium salt groups, ethoxylated chains, propyleneoxy chains, sulfonic acid groups, and those derived from their salts. Monomers such as phenyl group, morpholinoethyl group, etc. are also useful.

As the alkali-soluble binder, a copolymer of maleimide and ethylene oxide represented by formula (b1) or formula (b2) can also be preferably used.

(In formula (b1), R ¹ represents a hydrogen atom, an aryl group, or an alkyl group)

Examples of the alkyl group when R ¹ represents an alkyl group include a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms.

The alkyl group may have a substituent, and examples of the substituent that can be introduced into the alkyl group include a phenyl group, a carbonyl group, an alkoxy group, a hydroxyl group, an amino group, and the like.

Examples of the aryl group when R ¹ represents an aryl group include a monocyclic aryl group, a polycyclic aryl group, a condensed ring structure aryl group, and a heteroatom-containing heteroaryl group. More specifically, a phenyl group, a naphthyl group, a biphenyl group, a benzimidazolyl group, a pyridyl group, a furyl group, etc. can be mentioned.

The aryl group may have a substituent. Examples of the substituent that can be introduced into the aryl group include alkyl groups such as methyl, ethyl, tertiary butyl, and cyclohexyl, alkoxy groups such as methoxy, carboxyl, and hydroxyl. Amino, nitro, chloro, bromo, etc.

(In formula (b2), R ² represents a hydrogen atom or a methyl group. R ³ is an alkylene group having 2 or 3 carbon atoms, R ⁴ represents a hydrogen atom, an aryl group, or an alkyl group, and m represents an integer of 1-15)

Examples of the alkyl group when R ⁴ represents an alkyl group include a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 1 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms.

The alkyl group may have a substituent, and examples of the substituent that can be introduced into the alkyl group include a phenyl group, a carbonyl group, and an alkoxy group.

Examples of the aryl group when R ⁴ represents an aryl group include a monocyclic aryl group, a polycyclic aryl group, a condensed ring structure aryl group, and a heteroatom-containing heteroaryl group. More specifically, phenyl, naphthyl, anthracenyl, biphenyl, benzimidazolyl, indolyl, imidazolyl, oxazolyl, carbazolyl, pyridyl, furyl, etc. can be mentioned.

The aryl group may have a substituent. Examples of the substituent that can be introduced into the aryl group include: Alkyl groups such as nonyl, methyl, ethyl, tertiary butyl, cyclohexyl, alkoxy such as methoxy, carboxyl, hydroxyl, amino, nitro, chloro, bromo, etc.

In addition, the alkali-soluble binder may have a polymerizable group on the side chain, and for example, polymers containing an allyl group, a (meth)acrylic group, an allyloxyalkyl group, etc., on the side chain are also useful. Examples of polymers containing the polymerizable group include: commercially available KS RESIST-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (Daicel Chemical Co., Ltd.) Industrial (stock) manufacturing), etc. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin, etc. are also useful.

Among these various alkali-soluble adhesives, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic/acrylamide resins are preferred. The copolymer resin is preferably an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin from the viewpoint of controlling developability.

In particular, it is preferably a copolymer having a repeating unit represented by the following general formula (2) and an acidic group, and more preferably, in addition to the general formula (2) and the acidic group, it is represented by the general formula (3) The structural unit of the copolymer.

(In the general formula (2), R ²⁰ represents a hydrogen atom or a methyl group, and R ²¹ to R ²⁵ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an aryl group)

(In the general formula (3), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² and R ¹³ each independently represent a hydrogen atom or a carbonyl group with 3 to 20 carbon atoms containing an unsaturated double bond as a partial structure. R ^{12 does not exist} And R ¹³ are both hydrogen atoms. When ^{at least one of R 12} and R ¹³ represents a carbonyl group with 3 to 20 carbons containing an unsaturated double bond as a partial structure, it may further contain a carboxyl group as a partial structure)

The acrylic resin is preferably a copolymer containing a monomer selected from benzyl (meth)acrylate, (meth)acrylic acid, hydroxyethyl (meth)acrylate, (meth)acrylamide, and the like, Or commercially available KS RESIST-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (manufactured by Daicel Chemical Industry Co., Ltd.), etc.

In addition, the alkali-soluble binder may contain a structural unit derived from a compound represented by the following general formula (X).

General formula (X) [化60]

In the general formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms that may contain a benzene ring. n represents an integer of 1-15.

In the general formula (X), the carbon number of the alkylene group of _{R 2 is preferably 2-3.} Moreover, _{the carbon number of the alkyl group of R 3} is 1-20, More preferably, it is 1-10, and _{the alkyl group of R 3} may contain a benzene ring. Examples of the benzene ring-containing alkyl group represented by R ₃ include a benzyl group, a 2-phenyl(iso)propyl group, and the like.

From the viewpoints of developability, liquid viscosity, etc., the weight average molecular weight of the alkali-soluble adhesive (a polystyrene conversion value measured by the GPC method) is preferably 1,000 to 200,00, more preferably 2,000 to 100,000, Especially preferred is 5,000~50,000.

The acid value of the alkali-soluble adhesive is preferably 10mg/KOH~1000mg/KOH, more preferably 50mg/KOH~300mg/KOH, still more preferably 50mg/KOH~200mg/KOH, particularly preferably 105mg/KOH~200mg/ KOH.

The content of the alkali-soluble binder is preferably 10% by mass to 80% by mass of the total solid content of the coloring composition, and more preferably 20% by mass to 60% by mass.

The composition of the present invention may contain only one kind of alkali-soluble binder, or two or more kinds. When two or more are contained, it is preferable that the total amount thereof falls within the above-mentioned range.

<<Crosslinking agent>>

The coloring composition of the present invention may further contain a crosslinking agent.

The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) epoxy resin, (b) selected from methylol, alkoxymethyl A melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent in the oxymethyl group, and (c) selected from the group consisting of methylol, alkoxymethyl, and oxymethyl A phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one substituent in the methyl group. Among them, multifunctional epoxy resins are preferred.

For the details of specific examples and the like of the crosslinking agent, reference can be made to the description of paragraphs 0134 to 0147 of JP 2004-295116 A, and the contents can be incorporated into this specification.

When the coloring composition of the present invention contains a crosslinking agent, the content of the crosslinking agent is preferably 0.01% by mass to 50% by mass, and more preferably 0.5% by mass to 30% by mass relative to the total solid content of the coloring composition.

<<Surface Active Agent>>

The colored composition of the present invention may also contain a surfactant. The surfactant may be any of nonionic, cationic, and anionic, but it is preferably a surfactant having an ethylene oxide structure or a fluorine-based surfactant. Particularly preferred is a surfactant having an ethylene oxide structure with a Hydrophil-Lipophile Balance (HLB) value in the range of 9.2 to 15.5 or a fluorine-based interfacial activity described in Japanese Patent Laid-Open No. 2-54202 Agent.

When the coloring composition of the present invention contains a surfactant, compared to the coloring composition The total solid content of the substance, the content of the surfactant is preferably 0.0001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass.

The composition of the present invention may contain only one type of surfactant, or may contain two or more types. When two or more are contained, it is preferable that the total amount thereof falls within the above-mentioned range.

<<Dye stabilizer>>

The coloring composition of the present invention may also contain a dye stabilizer. As the dye stabilizer, a polymer surfactant (polymer dispersant) is preferred. Examples of polymer dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid, and (parts) Ammonium salts or (part of) alkylamine salts; (co)polymers of hydroxyl-containing unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylates or modified products thereof; sulfonic acid or Phosphoric acid polymers, etc. As the crosslinkable group, a known polymerizable group that can be crosslinked by radicals, acid, and heat can be used. Specifically, examples include (meth)acrylic groups, styryl groups, vinyl groups, cyclic ether groups, and methylol groups, preferably (meth)acrylic groups, styryl groups, and vinyl groups, and more preferably (Meth) acrylic group and styryl group.

In addition, as a dye stabilizer, it is also effective to add salts of the following anions (lithium salt, sodium salt, potassium salt, etc.).

When the coloring composition of the present invention contains a dye stabilizer, the content of the dye stabilizer is preferably 0.01% by mass to 50% by mass, and more preferably 0.5% by mass to 30% by mass relative to the total solid content of the coloring composition.

[化61]

<<Antioxidant>>

The colored composition of the present invention may also contain an antioxidant. Examples of antioxidants include radical scavengers, peroxide decomposers, ultraviolet absorbers, singlet oxygen quenchers, and the like.

As a radical scavenger, a phenolic antioxidant, a hindered amine antioxidant, etc. are mentioned, for example. Examples of phenol-based antioxidants include hydroxyphenyl propionate-based compounds, hydroxybenzyl-based compounds, thiobisphenol-based compounds, thiomethylphenol-based compounds, and alkanediylphenol-based compounds. Among them, from the viewpoint of the stability of the color characteristics, a hydroxyphenyl propionate-based compound is preferred.

For example, the compounds described in paragraphs 0013 to 0034 of JP 2012-155243 A, and paragraphs 0030 to 0042 of JP 2013-14748 A can be preferably used.

The peroxide decomposer is a compound that decomposes peroxide generated by exposure to light or the like into harmless substances and does not generate new free radicals, and examples thereof include phosphorus-based antioxidants and sulfur-based antioxidants. Among them, from the viewpoint of stability of color characteristics, sulfur-based antioxidants are preferred.

Examples of ultraviolet absorbers include salicylate-based antioxidants and benzophenone-based antioxidants.

Singlet oxygen quenchers are compounds that can deactivate singlet oxygen by the energy movement of oxygen from the singlet state. For example, in addition to ethylenic compounds such as tetramethylethylene and cyclopentene, diethylamine, tris Ethylamine, 1,4-Diazabicyclooctane (1,4-Diazabicyclooctane, DABCO), N-ethylimidazole and other amines, substituted naphthalene, dimethylnaphthalene, dimethoxyanthracene, Condensed polycyclic aromatic compounds such as anthracene and diphenylanthracene; 1,3-diphenylisobenzofuran, 1,2,3,4-tetraphenyl-1,3-cyclopentadiene, pentaphenyl In addition to aromatic compounds such as cyclopentadiene, examples include: Harry H. wasserman, "Singlet Oxygen", Chapter 5, Academic Press (1979), Nicholas J. Turro, "Modern "Modern Molecular Photochemistry", Chapter 14, The Benjamin Cummings Publishing Co., Inc. (1978), and "High-functional Chemistry for Color Photo Sensitive Materials" issued by CMC ", a compound exemplified as a singlet oxygen quencher in Chapter 7 (2002).

In addition to these, metal complexes in which a compound having a sulfur atom is used as a ligand can be cited. Examples of such compounds include nickel complexes, cobalt complexes, and copper complexes with bisdithio-α-diketone, bisphenyldithiol, and thiobisphenol as ligands , Manganese complexes, platinum complexes and other transition metal chelate compounds.

Examples of sulfur-based antioxidants include thiopropionate-based compounds and mercaptobenzimidazole-based compounds. Among them, from the viewpoint of the stability of the color characteristics, a thiopropionate-based compound is preferred.

In the present invention, the antioxidant can be used alone or in combination of two or more. With respect to 100 parts by mass of the coloring agent, the content of the antioxidant is preferably 0.01 parts by mass to 20 parts by mass, and particularly preferably 0.1 parts by mass to 10 parts by mass.

<<hardening accelerator>>

The colored composition of the present invention may contain a compound that functions as a hardening accelerator.

For example, it can be used: selected from the group consisting of aromatic amine compounds, tertiary amine compounds, amine salts, phosphonium salts, amidine salts, amide compounds, thiol compounds, blocked isocyanate compounds, and compounds containing imidazole rings At least one compound.

When the colored composition contains a hardening accelerator, the low-temperature hardening of the colored composition can be achieved more effectively. Moreover, the storage stability of the colored composition can be further improved.

As a commercially available product of the hardening accelerator, Karenz MT series (manufactured by Showa Denko Co., Ltd.) such as Karenz MTBD-1 and the like can be cited.

In the present invention, the hardening accelerator can be used alone or in combination of two or more. The content of the hardening accelerator is preferably 0.01 parts by mass to 20 parts by mass, and particularly preferably 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound.

<<Anti-reducing agent>>

The colored composition of the present invention may also contain an anti-reduction agent. As the anti-reduction agent, a quinone compound is preferred, and a quinone compound having the following structure having a molecular weight of about 100 to 800 is more preferred.

<<Acid Generator>>

The coloring composition of the present invention may also contain an acid generator. The acid generator can be photoacid The generator may also be a thermal acid generator, but is preferably a thermal acid generator. If a thermal acid generator is used, the heat resistance of the cured film tends to be further improved.

Thermal acid generator refers to an acid generator that generates acid when heated at 100°C to 250°C at 1013.25 hPa. As the acid to be generated, an acid having a pKa of 5 or less is preferred. As specific examples of the generated acid, sulfonic acid, carboxylic acid, phosphoric acid, etc. can be exemplified, and sulfonic acid is more preferable.

As the photoacid generator, reference can be made to the description of paragraph 0103 to paragraph 0113 of JP 2006-259002 A, and these contents can be incorporated into this specification.

The thermal acid generator includes ionic compounds (onium salts) and nonionic compounds.

The ionic compound (onium salt) is preferably one that does not contain heavy metals or halogen ions, and is preferably an onium salt of sulfonic acid.

Specific examples of ionic thermal acid generators include triphenyl sulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, 1-dimethylthio-4, 7-dihydroxynaphthalene, 4-hydroxyphenyldimethyl sulfonium, benzyl-4-hydroxyphenylmethyl sulfonium, 2-methylbenzyl-4-hydroxyphenylmethyl sulfonium, 2-methylbenzyl -4-Acetylphenylmethylsulfonate, 2-methylbenzyl-4-benzyloxyphenylmethylsulfonate, methanesulfonate of these, triflate, camphorsulfonic acid Salt, p-toluenesulfonate, hexafluorophosphonate, etc.

<<Other ingredients>>

The coloring composition of the present invention may further contain a bis(trifluoromethanesulfonyl)imide salt. By containing bis(trifluoromethanesulfonyl)imide salt, heat resistance can be improved. As double (Trifluoromethanesulfonyl) iminium salt, including: bis(trifluoromethanesulfonyl) iminium potassium, bis(trifluoromethanesulfonyl) iminium sodium, bis(trifluoromethanesulfonyl) (Alkyl) Lithium imide and the like. The content of the bis(trifluoromethanesulfonyl)imide salt is preferably 0.1 mol to 2 mol, more preferably 0.3 mol relative to 1 mol of the triarylmethane repeating unit of the polymer TP ~0.8 mol.

The coloring composition of the present invention may further contain various additives such as fillers, ultraviolet absorbers, anti-agglomeration agents, sensitizers, and light stabilizers, if necessary.

<Preparation method of coloring composition>

The coloring composition of the present invention can be prepared by mixing the above-mentioned components with arbitrary components as needed.

When preparing the coloring composition, the components of the coloring composition can be mixed at one time, and the components can also be dissolved. Disperse in a solvent and then deploy them in sequence. In addition, there are no particular restrictions on the order of input or working conditions at the time of deployment. For example, all ingredients can be dissolved at the same time. Disperse in a solvent to prepare the composition. If necessary, each component can also be prepared into two or more solutions. Dispersion, these solutions when in use (during coating). The dispersion liquid is mixed and prepared as a composition.

In order to remove foreign matter or reduce defects, etc., the colored composition of the present invention is preferably filtered with a filter. As the filter, as long as it is a filter that has been used for filtering purposes, etc., it can be used without particular limitation. Examples include the use of fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6, nylon-6, and 6, and polyolefin resins (including high-density resins such as polyethylene and polypropylene). Density, ultra-high molecular weight) and other filters. These raw materials Among them, polypropylene (including high-density polypropylene) is preferred.

The pore size of the filter is suitably about 0.01 μm to 7.0 μm, preferably about 0.01 μm to 3.0 μm, and more preferably about 0.05 μm to 0.5 μm. By setting it as this range, the fine foreign matter which hinders the preparation of a uniform and smooth colored composition in a subsequent step can be reliably removed.

When using filters, different filters can also be combined. At this time, the filtration by the first filter may be performed only once, or may be performed twice or more.

In addition, it is also possible to combine first filters having different pore diameters within the above-mentioned range. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, available from Pall Co., Ltd., Advantec Toyo Co., Ltd., Nihon Entegris Co., Ltd. (formerly Nihon Entegris) Co., Ltd. Choose from various filters provided by Mykrolis Co., Ltd. or Kitz Microfilter Co., Ltd. etc.

As the second filter, a filter formed of the same material as the first filter can be used.

For example, the filtration by the first filter may be performed only in the dispersion, and after mixing other components, the second filtration may be performed.

Since the coloring composition of the present invention can form a cured film with excellent hue and contrast, it can be suitably used as a coloring layer formation (coloring pixel formation) of color filters used in image display devices or solid-state imaging devices. Use) a coloring composition, and can be suitably used for the production of printing inks, inkjet inks, paints, and the like.

<Cure film, color filter, color filter manufacturing method>

The cured film of the present invention is formed by curing the colored composition of the present invention. The cured film can be preferably used for color filters.

Any method can be used to form the color filter of the present invention as long as it is a method that can form a colored region (colored pattern) formed by applying the coloring composition of the present invention to a substrate and then hardening. It is preferably produced using the coloring composition of the present invention.

In addition, when the coloring composition of the present invention is used to manufacture a color filter for a solid-state imaging element, the manufacturing method described in paragraphs 0359 to 0371 of Japanese Patent Laid-Open No. 2011-252065 can also be used.

The manufacturing method of the color filter of the present invention preferably includes: a step of forming a coloring composition layer using the coloring composition of the present invention, a step of exposing the coloring composition layer into a pattern, and a step of exposing the coloring composition layer The step of developing and removing the unexposed part to form a colored pattern. Furthermore, if necessary, a step of baking the colored composition layer (pre-baking step) and a step of baking the developed colored pattern (post-baking step) may be provided.

<<Steps of forming a colored composition layer>>

In the step of forming the coloring composition layer, the coloring composition of the present invention is applied to the substrate to form the coloring composition layer.

Examples of substrates include alkali-free glass used in liquid crystal display elements, soda glass, Pyrex (registered trademark) glass, quartz glass, and a transparent conductive film attached to these glasses. , Or solid-state imaging element, etc. The photoelectric conversion element substrates used in the substrates, such as silicon substrates or plastic substrates. In addition, on these substrates, a black matrix that separates each pixel may be formed, or a transparent resin layer may be provided in order to promote adhesion or the like. In addition, in order to improve the adhesion with the upper layer, to prevent the diffusion of substances, or to flatten the surface, if necessary, an undercoat layer may be provided on the substrate.

In addition, the plastic substrate preferably has a gas barrier layer and/or a solvent resistant layer on its surface.

In addition, as the substrate, a thin film transistor (TFT) type color liquid crystal display device (hereinafter referred to as a "TFT type liquid crystal driving substrate") arranged with a thin film transistor (TFT) type color liquid crystal display device is used. The coloring pattern formed by using the coloring composition of the present invention can also be formed on the driving substrate to produce a color filter.

Examples of the substrate in the TFT-based liquid crystal drive substrate include glass, silicone, polycarbonate, polyester, aromatic polyamide, polyimide, and polyimide. If necessary, appropriate pretreatments such as chemical treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, and vacuum evaporation may be performed on these substrates in advance. For example, a substrate obtained by forming a passivation film such as a silicon nitride film on the surface of a TFT-type liquid crystal drive substrate can be used.

As an application method of the colored composition, coating is preferred, and coating is preferably performed by methods such as spin coating, slit coating, cast coating, roll coating, bar coating, and inkjet.

The coloring composition layer formed on the substrate is preferably dried (pre-baked bake). The pre-baking can be performed using a hot plate, oven, etc., in a temperature range of 50°C to 140°C, preferably about 70°C to 110°C, in a condition of 10 seconds to 300 seconds. Furthermore, pre-baking may also be used in combination with high frequency processing. High frequency processing can also be used alone. If necessary, vacuum treatment can also be performed before pre-baking. Regarding the conditions of vacuum drying, the degree of vacuum is preferably 13Pa~133Pa, more preferably 26Pa~66.5Pa.

The thickness of the colored composition layer formed by the colored composition is appropriately selected according to the purpose. In the case of a color filter for an image display device, it is preferably in the range of 0.2 μm to 5.0 μm, more preferably in the range of 1.0 μm to 4.0 μm, and most preferably in the range of 1.5 μm to 3.5 μm. In addition, in the case of a color filter for a solid-state imaging element, it is preferably in the range of 0.2 μm to 5.0 μm, more preferably in the range of 0.3 μm to 2.5 μm, and most preferably in the range of 0.3 μm to 1.5 μm. In addition, the thickness of the colored composition layer is the film thickness after prebaking.

<<Steps to Exposure>>

Then, in the manufacturing method of the color filter of this invention, the film (coloring composition layer) containing a coloring composition formed on a board|substrate in the said way is exposed via, for example, a photomask. As light or radiation that can be applied to exposure, g-ray, h-ray, i-ray, j-ray, KrF light, and ArF light are preferred, and i-ray is particularly preferred. When i-rays are used for irradiating light, it is preferable to irradiate with an exposure amount of ^{100 mJ/cm 2} to 10000 mJ/cm ^2.

In addition, as other exposure light, various mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, visible and ultraviolet laser light sources, fluorescent lamps of ultra-high pressure, high pressure, medium pressure, and low pressure can also be used. Tungsten lamps, sunlight, etc.

Exposure procedure using laser light source

In the exposure method using a laser light source, as the light source, it is preferable to use an ultraviolet laser. The irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, and more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm. Specifically, the third harmonic (355nm) of Nd: YAG (yttrium aluminum garnet) laser, or XeCl of excimer laser, which is a solid laser with high output power and is relatively inexpensive, can be suitably used. (308nm), XeF (353nm).

The exposure amount of the object (pattern) to be exposed is in the range of 1 mJ/cm ² to 100 mJ/cm ² , more preferably in the range of 1 mJ/cm ² to 50 mJ/cm ² . If the exposure amount is in this range, it is preferable from the viewpoint of the productivity of pattern formation.

The exposure device is not particularly limited. As a commercially available exposure device, Callisto (manufactured by V-Technology Co., Ltd.), EGIS (manufactured by V-Technology Co., Ltd.), or DF2200G (Dainippon Network) can be used. Screen (Dainippon Screen) (manufactured by shares), etc. In addition, devices other than those described above can also be suitably used.

When manufacturing color filters for liquid crystal display devices, a proximity exposure machine or a mirror projection exposure machine can be preferably used, and exposure using h-rays and i-rays is mainly used. In addition, when manufacturing color filters for solid-state imaging devices, it is preferable to use a stepping exposure machine and mainly use i-rays. Furthermore, when using a TFT-based liquid crystal drive substrate to manufacture a color filter, the mask used is not only provided with a pattern to form pixels (coloring patterns), but also provided with a pattern to form recesses such as through holes. Patterned photomask.

The coloring composition layer exposed in this manner can be heated.

In addition, in order to suppress oxidation and fading of the color material in the color composition layer, exposure may be performed while flowing nitrogen gas into the reaction chamber.

<<Steps to form colored patterns>>

Then, the coloring composition layer after exposure is developed with a developing solution. Thereby, a negative or positive colored pattern (resist pattern) can be formed. In the development step, the unhardened part of the coated film after exposure is eluted into the developing solution, and only the hardened part remains on the substrate.

As long as the developer is a coating film (coloring composition layer) that dissolves the coloring composition in the unhardened portion, and does not dissolve the hardened portion, any developer can be used. For example, a combination of various organic solvents or alkaline aqueous solutions can be used.

Examples of the organic solvent used for development include the solvents described above that can be used when preparing the coloring composition of the present invention.

Examples of the alkaline aqueous solution include: tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, benzyltrimethylammonium hydroxide, hydrogen Sodium oxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl hydroxide Alkaline ammonium, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5,4,0]-7-undecene and other basic compounds are changed to a concentration of 0.001% to 10% by mass, preferably It is an alkaline aqueous solution dissolved in a way that becomes 0.01% by mass to 1% by mass. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted so that the pH becomes 11-13, and more preferably the pH becomes 11.5-12.5.

In the alkaline aqueous solution, for example, an appropriate amount of water-soluble organic solvents such as methanol and ethanol, or surfactants, etc. may be added.

The development temperature is usually 20°C to 30°C, and the development time is 20 seconds to 90 seconds.

The development can be any of dipping, spraying, spraying, etc., and it can also be combined with shaking, rotating, ultrasonic, etc. It is also possible to wet the surface to be developed with water or the like before contact with the developer solution to prevent uneven development. In addition, the substrate may be tilted for development.

In addition, when manufacturing color filters for solid-state imaging elements, liquid-impregnated development can also be used.

After the development process, a rinsing process for washing and removing the remaining developer solution is performed, and after drying, in order to achieve complete curing, a heating process (post-baking) is performed.

The rinsing treatment is usually performed with pure water, but in order to save liquid, the following methods can also be used: use pure water in the final cleaning, use the used pure water in the initial stage of the cleaning, or tilt the substrate for cleaning, or And irradiate with ultrasound.

After the rinsing treatment, dehydration and drying are carried out, and then a heating treatment is usually carried out at about 200°C to 250°C. This heating treatment (post-baking) can use a heating mechanism such as a heating plate, a convection oven (hot air circulation dryer), a high-frequency heating machine, etc., in order to meet the above conditions, by continuous or batch type of post-development The coating film is carried out.

By combining the desired number of hues and repeating the above steps for each color in turn, a colored cured film (coloring pattern) with multiple colors can be produced. Made of color filters.

In the manufacturing method of the color filter of the present invention, in particular, the coloring pattern (pixel) formed using the coloring composition may be irradiated with ultraviolet rays for post-exposure.

It is preferable to further heat-treat the colored pattern that has been post-exposed as described above. By heating the formed colored pattern (so-called post-baking treatment), the colored pattern can be further hardened. This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, and the like.

The temperature during the heat treatment is preferably 100°C to 300°C, more preferably 150°C to 250°C. In addition, the heating time is preferably about 10 minutes to 120 minutes.

The colored pattern obtained in the manner described constitutes the pixels in the color filter. When fabricating a color filter with pixels of multiple hues, it is only necessary to repeat the steps described above in combination with the desired number of colors.

Furthermore, the post-exposure and/or post-baking treatment can be performed after the formation, exposure, and development of each single-color coloring composition layer (one color at a time), and it can also be used in all desired colors. After the formation, exposure, and development of several colored composition layers are completed, the post-exposure and/or post-baking treatments are performed at one time.

In addition, the coloring composition of the present invention can also be applied to a method of manufacturing a color filter including a dry etching step. As an example of such a manufacturing method, a manufacturing method including the steps of forming a coloring layer using the coloring composition of the present invention, forming a photoresist layer on the coloring layer, and performing exposure and development The step of patterning the photoresist layer to obtain a resist pattern, and the resist The etching agent pattern is used as an etching mask to dry-etch the colored layer.

The color filter (color filter of the present invention) obtained by the method of manufacturing the color filter of the present invention uses the coloring composition of the present invention, and therefore has excellent hue and contrast.

The color filter of the present invention can be used in image display devices or solid-state imaging devices, and is particularly suitable for use in liquid crystal display devices. When used in a liquid crystal display device, a good hue can be achieved while displaying images with excellent spectral characteristics and contrast.

As the use of the coloring composition of the present invention, the above description mainly focuses on the use of forming the coloring pattern of the color filter, but it can also be applied to the coloring pattern (pixel) that constitutes the color filter. Formation of isolated black matrix.

The black matrix on the substrate can be formed by the following method: using a colored composition containing black pigments such as carbon black, titanium black, etc., processed pigments, after coating, exposure, and development steps, post-baking as needed .

<Image display device>

The image display device of the present invention is provided with the color filter of the present invention. Examples of the image display device include a liquid crystal display device, an organic electroluminescence (organic EL (Electroluminescence)) display device, and the like. Especially suitable for the use of liquid crystal display devices. The liquid crystal display device including the color filter of the present invention can display a high-quality image with good color and luster of the displayed image and excellent display characteristics.

For the definition of image display devices or the details of each display device, please refer to "Electronic Display Components (by Sasaki Akio, Kogyo Chosakai Publishing (Stock) 1990 Issued)", "Display Components (Ibuki Junaki) NS, Industrial Books (Sangyo Tosho) (shares) issued in 1989)" and so on. In addition, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, issued by the Industrial Research Council (Stock) 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, it can be applied to various types of liquid crystal display devices described in the "Next Generation Liquid Crystal Display Technology".

Among them, the color filter of the present invention is particularly effective for a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT liquid crystal display device is described in, for example, "Color TFT Liquid Crystal Display (published by Kyoritsu Publishing Co., Ltd. in 1996)". Furthermore, the present invention can also be applied to a liquid crystal display with enlarged viewing angles such as in-plane switching (IPS) and other lateral electric field drive methods, multi-domain vertical alignment (Multi-domain Vertical Alignment, MVA) and other pixel division methods, etc. Device, or Super-Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), on-chip spacer (OCS), fringe field switching (fringe field switching, FFS), and Reflective Optically Compensated Bend (R-OCB), etc.

In addition, the color filter of the present invention can also be used in a bright and high-definition color-filter-on-array (COA) method.

If the color filter of the present invention is used in an image display device, it can achieve high contrast when combined with a three-wavelength tube of a previously known cold cathode tube. Furthermore, by combining red, green, and blue light-emitting diodes The volume light source (RGB-LED (Light Emitting Diode)) as the backlight source can provide high brightness, high color purity and good color reproducibility Good image display device.

<Solid-state imaging device>

The solid-state imaging element of the present invention includes the color filter of the present invention. The configuration of the solid-state imaging element of the present invention is not particularly limited as long as it includes the color filter of the present invention and functions as a solid-state imaging element. For example, the following configurations can be cited.

The structure is as follows: a solid-state imaging element (Charge Coupled Device (CCD) image sensor, complementary metal oxide semiconductor (Complementary Metal Oxide Semiconductor, CMOS) image sensor, etc.) is provided on the support. A plurality of photodiodes in the light receiving area and transfer electrodes containing polysilicon, etc., on the photodiodes and the transfer electrodes, there are light-shielding films containing tungsten, etc. that open only to the light-receiving part of the photodiodes to shield light The film has an element protection film including silicon nitride and the like formed so as to cover the entire surface of the light-shielding film and the light receiving portion of the photodiode, and the element protection film has the color filter for solid-state imaging elements of the present invention piece.

Furthermore, it may also be a configuration that has a condensing mechanism (for example, a microlens, etc.) on the element protection film and under the color filter (on the side close to the support), or The color filter has a condensing mechanism.

[Example]

Hereinafter, the present invention will be explained more specifically by referring to examples. As long as they do not deviate from the gist of the present invention, the materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed. Therefore, the scope of the present invention is not limited It is determined by the specific example shown below. Furthermore, as long as there is no special explanation in advance, "%" and "parts" are the quality standards.

<Method for measuring weight average molecular weight (Mw) (GPC measurement)>

Remove the solvent from the sample, dilute the obtained solid content to 0.1% by mass with tetrahydrofuran, and use HLC-8020GPC (manufactured by Tosoh Co., Ltd.) to make 2 TSKgel α-M (manufactured by Tosoh Co., Ltd.) 7.8 mm (inner diameter) × 30 cm) connected in series as a column for measurement. The weight average molecular weight (Mw) is determined by setting the measurement conditions as N-methyl-2-pyrrolidone (NMP) with a sample concentration of 0.35 mass%, a flow rate of 0.3 mL/min, a sample injection volume of 10 μL, and a measurement temperature of 40°C, and use an ultraviolet detector to measure the value obtained.

<The content of the compound (compound A) with a weight average molecular weight of 1500 or less having a triarylmethane structure>

Based on the data obtained by GPC measurement, estimate and calculate the amount of compounds with a weight average molecular weight of 1500 or less.

<Synthesis Example 1>

(Synthesis of TAM1)

TAM1 is synthesized according to the following route.

[化62]

(Synthesis of synthetic intermediate (compound 2))

Add 25.1 g of 4,4'-dichlorobenzophenone (compound 1), 200 mL of xylene, 28.8 g of tertiary butoxy sodium, and 1,3,5- mesitylene amine into a three-necked flask and proceed After 1 hour of nitrogen bubbling, 22.5 mg of palladium(II) acetate and 78.1 mg of dicyclohexyl(1,1-diphenyl-1-propen-2-yl)phosphine were added, and the mixture was stirred at 110°C for 3 hours.

After cooling to room temperature, add a mixed solution of 200 mL of ion-exchanged water and 40 mL of 2-propanol. After filtering, a mixed solution of 160 mL of toluene and 20 mL of 2-propanol, 200 mL of ion-exchanged water, and 200 mL of 2-propanol are added. Washing was performed sequentially to obtain 39.3 g (yield 87.6%) of compound 2.

(Synthesis of synthetic intermediate (compound 3))

N-methylpyrrolidone 150mL and sodium hydride 8.0g were added by flowing nitrogen gas in a three-necked flask, and 30.0g of compound 2 dissolved in 100mL of N-methylpyrrolidone was added dropwise over 30 minutes. After stirring for 3 hours, it lasted 30 minutes 27.4 g of methyl p-toluenesulfonate was added dropwise. After stirring for 2 hours, a mixed solution of 220 mL of ion-exchanged water and 50 mL of 2-propanol was slowly added dropwise, and then 70 mL of 1 mol/L hydrochloric acid water was added dropwise, followed by filtration. Washing was performed in the order of a mixed solvent of 200 mL of ion-exchanged water, 200 mL of methanol, 160 mL of hexane, and 20 mL of 2-propanol to obtain 31.6 g (99.0%) of compound 3.

(Synthesis of synthetic intermediate (compound 5))

Add 110 mL of acetonitrile, 24.5 g of 1-naphthylamine (compound 4) and 3.2 g of zinc perchlorate hexahydrate to a three-necked flask, and heat to 40°C. Add 1,2-epoxycyclohexane dropwise over 30 minutes After 23.5 g, it was stirred for 5 hours. 110 mL of acetonitrile was added, 170 mL of ion-exchanged water was added dropwise, and after stirring for 20 minutes, it was cooled to room temperature, and after stirring for 1 hour, it was filtered. It was washed twice with 50 mL of ion-exchange water to obtain 32.3 g (yield 71.2%) of compound 5.

(Synthesis of synthetic intermediate (R-2))

Add 20 mL of acetonitrile, 4.8 g of 2-methacryloxyethyl succinic acid, 5.3 g of p-toluenesulfonyl chloride, and 4.8 g of compound 5 into a three-necked flask, and drip it over 30 minutes while cooling to below 10°C. After adding 4.6 g of 1-methylimidazole, the mixture was stirred for 5 hours. After the temperature was raised to room temperature, 30 mL of toluene and 30 mL of ion-exchange water were added for liquid separation, _{washed twice with 30 mL of a 5% NaHCO 3} aqueous solution, and then concentrated under reduced pressure to obtain an oily compound.

8.9 g of the obtained oily compound, 20 mL of acetonitrile, 9.1 g of compound 3, and 6.4 g of phosphorus oxychloride were added to a three-necked flask, stirred at 90°C for 3 hours, and after cooling to room temperature, 110 mL of ethyl acetate was added It was separated with 60 mL of ion-exchanged water. After washing with a 5% NaHCO ₃ aqueous solution, 7.3 g of lithium bis(trifluoromethanesulfonyl) imide was added and stirred for 30 minutes, 60 mL of ion-exchanged water was added for liquid separation, and the 5% NaHCO ₃ aqueous solution was used for washing. After being concentrated under reduced pressure, it was purified by a silica gel column to obtain 8.9 g (yield of 98.0%) of compound R-2.

<Synthesis of TAM1 (polymerization step)>

Add 1.9 g of propylene glycol-1-monomethyl ether-2-acetate into the three-necked flask, heat to 60°C while flowing nitrogen gas, and add propylene glycol-1-monomethyl ether-2-acetic acid dropwise over 1 hour Esters 4.5g, dodecyl mercaptan 0.24g, 5.0g R-2, cyclohexyl methacrylate 0.56g, glycidyl methacrylate 0.67g, methacrylic acid 0.43g, and 2,2'-co A solution of 0.16 g of azobis(2,4-dimethylvaleronitrile) was stirred for 1 hour, and 0.08 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added and stirred for 5 hours. After cooling to room temperature, 35 mL of hexane was added, and after stirring for 1 hour, filtration was performed to obtain 6.7 g (96.6% yield) of TAM1.

<TAM2~TAM6>

It was synthesized in the same manner as in Synthesis Example 1 except that the amount of dodecyl mercaptan in the polymerization step was changed.

<TAM7~TAM15>

It was synthesized in the same manner as TAM3 except that the amount of each monomer in the polymerization step was changed.

<TAM16~TAM22>

It was synthesized in the same manner as TAM3 except that the monomers in the polymerization step were changed.

<TAM23>

Except changing compound 3 to N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone Otherwise, it was synthesized in the same manner as TAM3.

<TAM24>

It was synthesized in the same manner as TAM3 except that the lithium bis(trifluoromethanesulfonyl)imidide was changed to potassium tris(trifluoromethanesulfonyl)methide.

<TAM25>

It was synthesized in the same manner as TAM3 except that the lithium bis(trifluoromethanesulfonyl)imidide was changed to lithium trifluoromethanesulfonate.

<R-1>

Basic Blue 7 (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

<R-3, R-5>

It was synthesized in the same manner as in Synthesis Example 1 except that the amount of dodecyl mercaptan in the polymerization step was changed.

<R-4>

It was synthesized in the same manner as in Synthesis Example 1 except that the amount of each monomer in the polymerization step was changed.

[Test Example 1]

<Example 1 to Example 25, Comparative Example 1 to Comparative Example 5>

(Preparation of coloring composition)

The raw materials of the following composition are mixed to prepare a coloring composition.

-composition-

. Coloring agent...5.1 parts by mass

. Polymerizable compound (T-1)... 6.0 parts by mass

. Alkali-soluble binder (U-2)...5.3 parts by mass

. Photopolymerization initiator (V-4)...0.3 parts by mass

. Hardening accelerator (V-5)...0.2 parts by mass

. Solvent (X-1)…71 parts by mass

. Solvent (X-3)…13 parts by mass

. Surfactant (Z-1)...0.01 parts by mass

Coloring agent: the following structure. In the following formulae, the numerical value described together in the repeating unit is the mass ratio of the added raw materials.

[化63]

[化64]

[化65]

[化66]

Polymerizable compound (T-1): KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)

Alkali-soluble adhesive (U-2): Allyl methacrylate/methacrylic acid (77/23 "mass ratio" copolymer, weight average molecular weight 37,000, acid value 137mgKOH/g)

Photopolymerization initiator (V-4): IRGACURE OXE-02 (BASF Japan)

Hardening accelerator (V-5): Karenz MTBD-1 (Showa Denko Co., Ltd.)

Solvent (X-1): Propylene glycol monomethyl ether acetate

Solvent (X-3): (Methyl Ethyl Diglycol (MEGD) manufactured by Japan Emulsifier Co., Ltd.)

Surfactant (Z-1): the following mixture (Mw=14000)

<Production of hardened film>

The colored curable resin composition obtained above was coated on a 100mm×100mm glass substrate (1737, manufactured by Corning Corporation) by a spin coating method, and dried at room temperature for 30 minutes to volatilize the volatile components. Colored layer. The full-exposed i-ray (wavelength: 365 nm) is irradiated to the colored layer without interposing a photomask to form a latent image. The light source of the i-ray uses an ultra-high pressure mercury lamp, which is irradiated after turning into parallel light. At this time, the amount of irradiated light was set to 40 mJ/cm ² . Then, at 26°C, a sodium carbonate/sodium bicarbonate aqueous solution (concentration of 2.4% by mass) was used to develop the colored layer on which the latent image was formed for 45 seconds, and then rinsed with running water for 20 seconds, and then sprayed Come for drying. The dried film was calcined at 230°C for 20 minutes in a clean oven to obtain a cured film.

The following evaluation was performed on the cured film obtained above.

<Heat resistance>

Calculate the transmission spectrum of the cured film obtained above and compare it to the above at 230℃ The obtained cured film was additionally subjected to the color difference ΔEab of the transmission spectrum when firing for 80 minutes. A small ΔEab value indicates excellent heat resistance.

ΔEab is less than 2…6

ΔEab is 2 or more, less than 3…5

ΔEab is 3 or more, less than 4...4

ΔEab is 4 or more, less than 5…3

ΔEab is 5 or more, less than 10...2

ΔEab is 10 or more...1

<Solvent resistance (difference in chromaticity)>

After heating the cured film obtained above at 230°C for 30 minutes, immerse it in Propylene Glycol Monomethyl Ether Acetate (PGMEA) at 25°C for 10 minutes, and measure the color before and after immersion. And calculate the color change index ΔEab. The ΔEab value was calculated from the transmission spectra of the cured film before and after immersion in PGMEA. In addition, when the value of ΔEab is 3 or less, it is assumed that there is little hue change and excellent solvent resistance.

ΔEab is 1.5 or more, less than 2...5

ΔEab is 2 or more, less than 3.5…4

ΔEab is 3.5 or more, less than 4…3

ΔEab is 4 or more, less than 5...2

ΔEab is 5 or more...1

<Voltage retention rate>

The coloring composition was coated on a glass substrate (trade name: 1737 Corning Co.) with indium tin oxide (ITO) electrodes so that the film thickness after drying became 2.0 μm, and the temperature was maintained at 100°C. Dry in an oven for 60 seconds (pre-baking). ^{After that, exposure of 100mJ/cm 2} (illuminance of 20mW/cm ² ) was performed without a mask, and then an alkaline developer (trade name: CDK-1, Fujifilm Electronic Materials) (Stock The 1% aqueous solution produced by) was developed at 25° C., and the coated film after washing and drying was heated in an oven at 230° C. for 20 minutes (post-baking) to form a cured film. Then, the substrate on which the cured film was formed and the substrate in which only the ITO electrode was vapor-deposited into a predetermined shape were bonded together using a sealant mixed with 5 μm glass beads, and then the liquid crystal MJ971189 (MJ971189 manufactured by Merck) was injected between the substrates. Trade name), and make a liquid crystal cell.

Then, after placing the liquid crystal cell in a constant temperature layer of 60°C for 24 hours, the liquid crystal voltage retention measurement system VHR-1A (trade name) manufactured by TOYO Corporation was used as follows: The measurement conditions were used to measure the voltage holding ratio of the liquid crystal cell, and to evaluate it based on the scores shown in the following criteria. The higher the score, the better the voltage retention.

Measurement conditions

. Distance between electrodes: 5μm~15μm

. Applied voltage pulse amplitude: 5V

. Pulse frequency of applied voltage: 60Hz

. Applied voltage pulse width: 16.67msec

*Voltage retention rate: the potential difference of the liquid crystal cell after 16.7 milliseconds/the value of the applied voltage within 0 milliseconds

*Judgment method

Above 90%: 5

More than 85% but less than 90%: 4

Above 80% but less than 85%: 3

Above 75% but less than 80%: 2

Less than 75%: 1

According to the above results, the examples can form a cured film excellent in heat resistance and solvent resistance. Furthermore, the voltage retention rate of the cured film is excellent.

On the other hand, the comparative example cannot coexist heat resistance and solvent resistance.

[Test Example 2]

<Example 26~Example 48>

(Preparation of coloring composition)

The raw materials of the following composition are mixed to prepare a coloring composition.

-composition-

. Coloring agent...5.1 parts by mass

. Polymerizable compound (T-1)... 6.0 parts by mass

. Alkali-soluble binder (U-2)...5.3 parts by mass

. Photopolymerization initiator (V-4)...0.3 parts by mass

. Hardening accelerator (V-5)...0.2 parts by mass

. Additive (W-1)...0.5 parts by mass

. Solvent (X-1)…71 parts by mass

. Solvent (X-3)…13 parts by mass

. Surfactant (Z-1)...0.01 parts by mass

Coloring agent: the coloring agent described in the following table

Polymerizable compound (T-1), alkali-soluble binder (U-2), photopolymerization initiator (V-4), hardening accelerator (V-5), solvent (X-1), solvent (X- 3) Surfactant (Z-1): the polymerizable compound (T-1), alkali-soluble binder (U-2), photopolymerization initiator (V-4), hardening accelerator (V- 5), solvent (X-1), solvent (X-3), surfactant (Z-1)

Additive (W-1): Potassium bis(trifluoromethanesulfonyl) imide (Mitsubishi Materials Corporation manufacture)

The heat resistance, solvent resistance, and voltage retention were evaluated in the same manner as in Test Example 1. The results are shown in the following table.

According to the above results, the examples can form a cured film excellent in heat resistance and solvent resistance. Furthermore, the voltage retention rate of the cured film is excellent.

Claims (23)

A coloring composition comprising a polymer TP and a polymerizable compound, the polymer TP comprising a repeating unit A having a triarylmethane structure represented by the general formula (TP1), and a repeating unit B having a crosslinkable group , The crosslinkable group of the repeating unit B is selected from the group consisting of ethylenically unsaturated bond-containing groups, epoxy groups, oxetanyl groups, oxazoline groups, groups represented by -COR, and carbonates At least one of the group; wherein R represents a hydrogen atom or an alkyl group with 1 to 20 carbons, the weight average molecular weight of the polymer TP is 3000 to 500000, and relative to the mass of the polymer TP, it has triarylmethane The content of the compound A having a weight average molecular weight of 1500 or less is 20% by mass or less, and the compound A is an unreacted material of a raw material monomer having a triarylmethane structure, or a raw material monomer that does not have a polymerizable group Impurity

In the general formula (TP1), Rtp ₁ to Rtp ₄ each independently represent a hydrogen atom, an alkyl group or an aryl group; Rtp ₅ , Rtp ₆ and Rtp ₈ each independently represent a substituent; Rtp ₇ represents NRtp ₇₁ Rtp ₇₂ ; Rtp ₇₁ And Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group, or an aryl group; a, b, and c each independently represent an integer from 0 to 4; when a, b, and c are 2 or more, Rtp ₅ , Rtp ₆ and Rtp ₈ the two may be mutually connected to form a ring; X represents an anion, or X and Rtp absent ₁ ~ Rtp _8, Rtp ₇₁ and Rtp least one contains an anionic _72; Rtp ₁ ~ Rtp _8, any Rtp _{71 is} and Rtp ₇₂ One represents the bonding site with the repeating unit A. The coloring composition according to claim 1, wherein the content of the compound A in the polymer TP is 10% by mass or less relative to the mass of the polymer TP. The coloring composition according to item 1 or item 2 of the scope of patent application, wherein the weight average molecular weight of the polymer TP is 10,000 to 50,000. The coloring composition according to item 1 or item 2 of the scope of patent application, wherein the X is selected from the group consisting of fluoride anion, chloride anion, bromide anion, iodide anion, cyanide ion, perchlorate anion, borate anion , PF ^6- and SbF ^6- least one anion, and is selected from ^{_{-SO 3 -, -COO -, -PO}} 4 -, structure represented by the following general formula (A1) and represented by the following formula ( A2) Select from compounds of at least one structure among the represented structures;

In the general formula (A1), R ¹ and R ² each independently represent -SO ₂ -or -CO-; the general formula (A2)

In the general formula (A2), R ³ represents -SO ₂ -or -CO-; R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO- or -CN. The coloring composition according to item 1 or item 2 of the scope of patent application, wherein the X is a compound containing bis(sulfonyl)imide anion, tris(sulfonyl)methide anion or sulfonate anion Compound. The coloring composition according to item 1 or item 2 of the scope of patent application, wherein the X is a compound containing a crosslinkable group. The coloring composition according to item 1 or item 2 of the scope of patent application, wherein the X is a polymer containing a repeating unit having an anionic site. Such as the coloring composition described in item 1 or item 2 of the scope of patent application, wherein in the general formula (TP1) and the general formula (TP2), _{at least one of Rtp 1} to Rtp ₁₁ , Rtp ₇₁ and Rtp ₇₂ has the general formula ( P) Substitution of the group represented;

In the general formula (P), L represents a single bond or a divalent linking group, X ¹ managed from _{^{-SO 3 -, -COO -, -PO}} 4 -, structure represented by the following general formula (A1) represented contained Select from at least one of a group and a group containing a structure represented by the following general formula (A2);

In the general formula (A1), R ¹ and R ² each independently represent -SO ₂ -or -CO-;

In the general formula (A2), R ³ represents -SO ₂ -or -CO-; R ⁴ and R ⁵ each independently represent -SO ₂ -, -CO- or -CN. The coloring composition according to item 1 or item 2 of the scope of patent application, wherein the triarylmethane structure of the repeating unit A is represented by the following general formula (TP3);

In the general formula (TP3), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group with 1 to 6 carbons; Rtp ₂₂ each independently represents an aryl group with 6 to 10 carbons, and Rtp ₇₁ represents an alkyl group or an aryl group; X It represents an anion, or X is absent and at least one of _{Rtp 21} , Rtp ₂₂ and Rtp _{71 includes an anion; any one of Rtp 21} , Rtp ₂₂ and Rtp ₇₁ represents a bonding site with the repeating unit A. The coloring composition according to item 1 or item 2 of the scope of patent application, wherein the repeating unit A is represented by the following general formula (TP3-1);

In the general formula (TP3-1), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbons, Rtp ₂₂ each independently represents an aryl group having 6 to 10 carbons, and Rtp _71a represents an alkylene group or an alkylene group. Aryl group; L ₁ represents a single bond or a divalent linking group, Rtp ₃₁ represents a hydrogen atom or a methyl group; X represents an anion, or X does not exist and at least one of _{Rtp 21} and Rtp _{22 contains an anion.} The coloring composition according to item 1 or item 2 of the scope of patent application, wherein the repeating unit A is represented by the following general formula (TP3-2);

In the general formula (TP3-2), Rtp ₂₁ each independently represents a hydrogen atom or an alkyl group with 1 to 6 carbons, Rtp ₂₄ each independently represents an alkyl group with 1 to 4 carbons, and Rtp ₂₅ each independently represents a hydrogen atom Or an alkyl group with 1 to 3 carbon atoms, Rtp _71a represents an alkylene group or an arylene group; Rtp ₃₁ represents a hydrogen atom or a methyl group; L ₁ represents a single bond or a divalent linking group; X represents an anion, or X is absent In addition, at least one of _{Rtp 21} and Rtp _{22 includes an anion.} The coloring composition according to item 1 or item 2 of the scope of patent application, wherein the polymer TP contains at least one of (meth)acrylic acid, (meth)acrylate and (meth)acrylamide The repeating unit. The coloring composition according to item 1 or item 2 of the scope of patent application includes at least one selected from the group consisting of xanthene compounds, dipyrromethene-based metal complexes, dioxazine compounds, and phthalocyanine compounds. The coloring composition described in item 1 or item 2 of the scope of patent application includes a photopolymerization initiator. The coloring composition as described in item 1 or item 2 of the scope of patent application, which includes a bis(trifluoromethanesulfonyl)imide salt. The colored composition described in item 1 or item 2 of the scope of patent application is used to form the colored layer of a color filter. A hardened film formed by hardening the colored composition described in item 1 or item 2 of the scope of patent application. A color filter includes the hardened film as described in item 17 of the scope of patent application. A method for manufacturing a color filter, comprising: using the coloring composition as described in item 1 or item 2 of the scope of patent application to form a coloring composition layer; exposing the coloring composition layer into a pattern的 step; and the step of developing and removing the unexposed portion of the colored composition layer to form a colored pattern. A method for manufacturing a color filter, comprising: using the coloring composition described in item 1 or item 2 of the scope of the patent application to form a coloring composition layer, and curing to form the coloring layer; A step of forming a photoresist layer on the colored layer; a step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and using the resist pattern as an etching mask The step of dry etching the colored layer. A solid-state imaging element, which includes the 18th item in the scope of patent application The color filter. An image display device comprising the color filter as described in item 18 of the scope of patent application. A polymer comprising a repeating unit represented by the following general formula (TP-7), the weight average molecular weight of the polymer is 3000 to 500000, relative to the mass of the polymer, having a triarylmethane structure The content of Compound A with a weight average molecular weight of 1500 or less is 20% by mass or less;

In the general formula (TP-7), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or a methyl group, R ^1a represents an alkylene group or an aryl group, and L ¹¹ represents A single bond or a divalent linking group with 1 to 30 carbons; L ¹² and L ¹³ represent a single bond or a divalent linking group with 1 to 30 ^{carbons; R 2} represents a hydrocarbon group with 1 to 10 carbons; R ³ represents a crosslinkable group; X represents a compound containing bis(sulfonyl)imide anion, tris(sulfonyl)methide anion or sulfonate anion; a~d are the mass ratios of repeating units, a and d represents a number exceeding 0, and b and c each independently represent a number greater than 0.