WO2020080218A1

WO2020080218A1 - Coloring composition, film, color filter, method for manufacturing color filter, solid-state imaging element, and image display device

Info

Publication number: WO2020080218A1
Application number: PCT/JP2019/039780
Authority: WO
Inventors: 宙夢小泉
Original assignee: 富士フイルム株式会社
Priority date: 2018-10-19
Filing date: 2019-10-09
Publication date: 2020-04-23
Also published as: JP7130055B2; TW202028374A; JP7344355B2; JPWO2020080218A1; JP2022180356A

Abstract

Provided is a coloring composition comprising: a coloring agent containing a compound represented by formula (1); a polymerizable monomer having an ethylenically unsaturated bonding group; a photopolymerization initiator; and a resin, wherein the polymerizable monomer in the total solid content of the coloring composition is 0.1-6.0 mass%. Provided are: a film using a coloring composition; a color filter; a method for manufacturing a color filter; a solid-state imaging element; and an image display device.

Description

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

The present invention relates to a coloring composition. The present invention also relates to a film using a coloring composition, a color filter, a method for manufacturing a color filter, a solid-state image sensor, and an image display device.

Demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors has grown significantly with the recent spread of digital cameras and camera-equipped mobile phones. Color filters are used as key devices for displays and optical elements. The color filter usually includes pixels of three primary colors of red, green and blue, and plays a role of separating transmitted light into three primary colors.

The color filter is manufactured, for example, by using a coloring composition containing a coloring agent and performing pattern formation by a photolithography method. Further, in performing pattern formation by the photolithography method, the coloring composition further contains a polymerizable monomer having an ethylenically unsaturated bond group, a photopolymerization initiator, and a resin in addition to the colorant. Things are used.

Also, in recent years, use of a phthalocyanine compound using Al as a central metal (hereinafter, also referred to as an aluminum phthalocyanine compound) as a colorant has been studied (Patent Documents 1 to 3).

[Patent Document 1] JP-A-2005-063593 JP, 2016-170370, A JP, 2013-171063, A

When the present inventor diligently studied a coloring composition containing a coloring agent containing an aluminum phthalocyanine compound, it was found that color unevenness is likely to occur in a film obtained using this coloring composition. In particular, when the compound represented by the formula (1) or the compound represented by the formula (2) described below was used as the aluminum phthalocyanine compound, it was found that color unevenness was likely to occur.

Therefore, an object of the present invention is to provide a coloring composition which is excellent in photolithography and can form a film in which color unevenness is suppressed. Another object of the present invention is to provide a film using a coloring composition, a color filter, a method for manufacturing a color filter, a solid-state image sensor, and an image display device.

The present inventor diligently studied a coloring composition containing a colorant containing an aluminum phthalocyanine compound, a polymerizable monomer having an ethylenically unsaturated bond group, a photopolymerization initiator, and a resin. The reason why the color unevenness is likely to occur in the film obtained using the composition was considered to be due to insufficient compatibility between the aluminum phthalocyanine compound and the polymerizable monomer having an ethylenically unsaturated bond group. Therefore, while using the compound represented by the formula (1) or the compound represented by the formula (2) described below as the aluminum phthalocyanine compound, the content of the polymerizable monomer having an ethylenically unsaturated bond group is within a predetermined range. It was found that a film in which color unevenness is suppressed while having excellent photolithographic properties can be formed by adjusting the amount to be adjusted to, and the present invention has been completed. Therefore, the present invention provides the following.
<1> A coloring composition comprising a coloring agent, a polymerizable monomer having an ethylenically unsaturated bond group, a photopolymerization initiator, and a resin,
The colorant contains at least one selected from the compound represented by the following formula (1) and the compound represented by the following formula (2),
A coloring composition containing a polymerizable monomer in an amount of 0.1 to 6.0% by mass based on the total solid content of the coloring composition;

In formula (1), X ¹ to X ⁴ each independently represent a substituent;
Z ¹ represents a hydroxy group, a halogen atom, —OP (═O) R ¹ R ² , or —O—SiR ³ R ⁴ R ⁵ , and R ¹ to R ⁵ are each independently a hydrogen atom, a hydroxy group, It represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and R ¹ and R ² , and R ³ and R ⁴ may combine with each other to form a ring;
m1 to m4 each independently represent an integer of 0 to 4, and when m1 to m4 are 2 or more, X ¹ to X ⁴ may be the same or different;

In formula (2), X ⁵ to X ¹² each independently represent a substituent;
L ^A represents -O-SiR ⁶ R ⁷ -O-, -O-SiR ⁶ R ⁷ -O-SiR ⁸ R ⁹ -O-, or -OP (= O) R ¹⁰ -O-, R ⁶ to R ¹⁰ each independently represent a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group;
m5 to m12 each independently represent an integer of 0 to 4, and when m5 to m12 are 2 or more, X ⁵ to X ¹² may be the same or different.
<2> The coloring composition according to <1>, wherein the coloring agent contains at least one selected from color index pigment green 62 and color index pigment green 63.
<3> The colorant contains at least one selected from Color Index Pigment Yellow 138, Color Index Pigment Yellow 139, Color Index Pigment Yellow 150, and Color Index Pigment Yellow 231, and is described in <1> or <2>. Coloring composition.
<4> The coloring composition according to any one of <1> to <3>, further containing a compound represented by the following formula (3):

In formula (3), Ry ¹ to Ry ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a sulfo group, a salt of a sulfo group, a carboxyl group, a salt of a carboxyl group, or phthalimidomethyl. Represents a group or a sulfamoyl group;
Two adjacent groups of Ry ¹ to Ry ⁴ may be bonded to each other to form a ring, and two adjacent groups of Ry ¹⁰ to Ry ¹³ may be bonded to each other to form a ring. Good.
<5> Any of <1> to <4>, wherein the total content of the compound represented by formula (1) and the compound represented by formula (2) in the colorant is 30% by mass or more. The coloring composition as described in 1 above.
<6> The coloring composition according to any one of <1> to <5>, in which the resin includes a resin having an ethylenically unsaturated bond group.
<7> The resin is a colored composition according to any one of <1> to <6>, which contains a resin containing a repeating unit derived from a compound represented by the following formula (I):

In the formula, Xi ¹ represents O or NH,
Ri ¹ represents a hydrogen atom or a methyl group,
Li ¹ represents a divalent linking group,
Ri ¹⁰ represents a substituent,
m represents an integer of 0 to 2,
p represents an integer of 0 or more.
<8> The coloring composition according to <7>, wherein the resin containing a repeating unit derived from the compound represented by the formula (I) further contains a repeating unit derived from an alkyl (meth) acrylate.
<9> The ratio M ¹ / B ¹ of the mass M ¹ of the polymerizable monomer contained in the coloring composition to the mass B ^{1 of the} resin contained in the coloring composition is 0.03 to 0.15. The coloring composition according to any one of <1> to <8>.
<10> The polymerizable monomer includes at least one selected from succinic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate, <1> to The coloring composition according to any one of <9>.
<11> A film obtained from the coloring composition according to any one of <1> to <10>.
<12> A color filter having the film according to <11>.
<13> A step of forming a colored composition layer on a support using the colored composition according to any one of <1> to <10>, and a pattern for the colored composition layer by a photolithography method. Forming a color filter.
<14> A solid-state image sensor having the film according to <11>.
<15> An image display device having the film according to <11>.

According to the present invention, it is possible to provide a coloring composition which is excellent in photolithography and can form a film in which color unevenness is suppressed. Further, it is possible to provide a film using a coloring composition, a color filter, a method for manufacturing a color filter, a solid-state image sensor, and an image display device.

Hereinafter, the content of the present invention will be described in detail.
In the present specification, “to” is used to mean that numerical values described before and after the “to” are included as a lower limit value and an upper limit value.
In the description of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not included includes a group (atomic group) having no substituent and a group (atomic group) having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, the term "exposure" includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam, unless otherwise specified. Examples of the light used for exposure include a bright line spectrum of a mercury lamp, deep ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), active rays such as X-rays and electron rays, or radiation.
In the present specification, "(meth) acrylate" represents both acrylate and methacrylate, or either, "(meth) acrylic" represents both acrylic and methacrylic, or "(meth ) "Acryloyl" means both acryloyl and methacryloyl, or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the weight average molecular weight and the number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography) method.
In the present specification, the total solid content refers to the total mass of the components of the composition excluding the solvent.
In the present specification, the pigment means a compound that is difficult to dissolve in a solvent.
In the present specification, the term “process” is included in this term as long as the intended action of the process is achieved not only as an independent process but also when it cannot be clearly distinguished from other processes. .

<Coloring composition>
The coloring composition of the present invention is a coloring composition containing a coloring agent, a polymerizable monomer having an ethylenically unsaturated bond group, a photopolymerization initiator, and a resin, and the coloring agent has the formula ( At least one selected from the compound represented by 1) and the compound represented by the formula (2) is contained, and 0.1 to 6.0 mass% of the polymerizable monomer is contained in the total solid content of the coloring composition. It is characterized by

Since the content of the polymerizable monomer in the total solid content of the coloring composition of the present invention is 0.1 to 6.0% by mass, the compound or formula represented by (1) or the compound represented by the formula (1) is used as the coloring agent. Despite the use of the compound represented by (2), it is possible to effectively suppress the occurrence of color unevenness in the obtained film while maintaining excellent photolithographic properties.

Further, according to the coloring composition of the present invention, since the content of the polymerizable monomer is 0.1 to 6.0% by mass, it is derived from the polymerizable monomer that scatters from the film even if the carbon-carbon bond is broken with time. The amount of the component is small, and it is possible to suppress the film shrinkage of the obtained film over time. In particular, even when the film is exposed to a high humidity environment for a long time, it is possible to effectively suppress the film shrinkage. Therefore, it is possible to suppress the generation of voids between the film formed using the coloring composition of the present invention and the member adjacent to the film. For example, a pixel is formed between pixels of another color by using the coloring composition of the present invention, or a pixel of another color is formed between pixels formed by using the composition of the present invention, and a structure such as a color filter is formed. Even when such a structure is exposed for a long period of time in a high humidity environment during the manufacture of, the generation of voids between adjacent pixels can be suppressed. Further, when the colored composition of the present invention is used to manufacture a structure such as a color filter by forming pixels in a region partitioned by partition walls, such a structure is used for a long period of time in a high humidity environment. Even when exposed, it is possible to suppress the generation of voids between the pixels and the partition walls.

The coloring composition of the present invention can be preferably used as a coloring composition for a color filter. Specifically, it can be preferably used as a coloring composition for forming pixels of a color filter. Further, the coloring composition of the present invention can be preferably used as a coloring composition for a solid-state imaging device, and can be more preferably used as a coloring composition for forming pixels of a color filter used for a solid-state imaging device. The coloring composition of the present invention can also be preferably used as a coloring composition for a display device, and can be more preferably used as a coloring composition for forming pixels of a color filter used for a display device. The coloring composition of the present invention can also be used as a composition for forming color microlenses. Examples of the method for manufacturing a color microlens include the method described in JP-A-2018-010162.

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

<< colorant >>
The coloring composition of the present invention contains a coloring agent. In the present invention, a colorant containing at least one selected from the compound represented by the formula (1) and the compound represented by the formula (2) is used. Hereinafter, the compound represented by the formula (1) is also referred to as the compound (1). The compound represented by the formula (2) is also referred to as the compound (2).

In formula (1), X ¹ to X ⁴ each independently represent a substituent. Examples of the substituent represented by X ¹ to X ⁴ include the substituent T described later. The substituent represented by X ¹ to X ⁴ is preferably a halogen atom, a nitro group, an alkyl group, an aryl group, a heterocyclic group, —ORt ¹ , —SRt ¹ , or —SO ₂ NRt ¹ Rt ^{2 and} is a halogen atom or an alkyl group. Is more preferable, and a halogen atom is still more preferable. Rt ¹ and Rt ² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

In the formula (1), Z ¹ represents a hydroxy group, a halogen atom, —OP (═O) R ¹ R ² , or —O—SiR ³ R ⁴ R ⁵ , and R ¹ to R ⁵ are each independently It represents a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and R ¹ and R ² , and R ³ and R ⁴ may combine with each other to form a ring.

Z ¹ is preferably a hydroxy group, —OP (═O) R ¹ R ² or —O—SiR ³ R ⁴ R ^5, more preferably —OP (═O) R ¹ R ² , and R ¹ and R ² are More preferred is —OP (═O) R ¹ R ² which is each independently an aryl group. Examples of the halogen atom represented by Z ¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl group and the alkoxy group represented by R ¹ to R ⁵ preferably have 1 to 30 carbon atoms, more preferably have 1 to 15 carbon atoms, and further preferably have 1 to 8 carbon atoms. The alkyl group and the alkoxy group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The aryl group and aryloxy group represented by R ¹ to R ⁵ preferably have 6 to 30 carbon atoms, more preferably have 6 to 20 carbon atoms, and further preferably have 6 to 12 carbon atoms. The alkyl group, aryl group, alkoxy group and aryloxy group represented by R ¹ to R ⁵ may further have a substituent. Examples of the substituent include the substituent T described later.

R ¹ and R ² , and R ³ and R ⁴ may combine with each other to form a ring. That is, when Z ¹ is —OP (═O) R ¹ R ² , R ¹ and R ² may combine with each other to form a ring. When Z ¹ is —O—SiR ³ R ⁴ R ⁵ , R ³ and R ⁴ may combine with each other to form a ring. The ring formed by combining these groups may be an aliphatic ring, an aromatic ring, or a heterocycle.

In formula (1), m1 to m4 each independently represent an integer of 0 to 4, preferably 0 or 1, and more preferably 0. When m1 to m4 are 2 or more, X ¹ to X ⁴ may be the same or different.

In formula (2), X ⁵ to X ¹² each independently represent a substituent. Examples of the substituent represented by X ⁵ to X ¹² include the substituent T described later. The substituent represented by X ⁵ to X ¹² is preferably a halogen atom, a nitro group, an alkyl group, an aryl group, a heterocyclic group, —ORt ¹ , —SRt ¹ , or —SO ₂ NRt ¹ Rt ^{2 and} is a halogen atom or an alkyl group. Is more preferable, and a halogen atom is still more preferable. Rt ¹ and Rt ² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

L ^A represents -O-SiR ⁶ R ⁷ -O-, -O-SiR ⁶ R ⁷ -O-SiR ⁸ R ⁹ -O-, or -OP (= O) R ¹⁰ -O-, R ⁶ to R ¹⁰ each independently represent a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group.

L ^A is preferably —O—SiR ⁶ R ⁷ —O— or —OP (═O) R ¹⁰ —O—, more preferably —OP (═O) R ¹⁰ —O—, and R ¹⁰ Is more preferably an aryl group, —OP (═O) R ¹⁰ —O—.

The alkyl group and the alkoxy group represented by R ⁶ to R ¹⁰ preferably have 1 to 30 carbon atoms, more preferably have 1 to 15 carbon atoms, and further preferably have 1 to 8 carbon atoms. The alkyl group and the alkoxy group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The aryl group and the aryloxy group represented by R ⁶ to R ¹⁰ preferably have 6 to 30 carbon atoms, more preferably have 6 to 20 carbon atoms, and further preferably have 6 to 12 carbon atoms. The alkyl group, aryl group, alkoxy group and aryloxy group represented by R ¹ to R ⁵ may further have a substituent. Examples of the substituent include the substituent T described later.

In formula (2), m5 to m12 each independently represent an integer of 0 to 4, preferably 0 or 1, and more preferably 0. When m5 to m12 are 2 or more, X ⁵ to X ¹² may be the same or different.

(Substituent T)
Examples of the substituent T include a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, -ORt ¹ , -CORt ¹ , -COORt ¹ , -OCORt ¹ , -NRt ¹ Rt ² , -NHCORt ¹ , -CONRt ¹ Rt ² , -NHCONRt ¹ Rt ² , -NHCOORt ¹ , -SRt ¹ , -SO ₂ Rt ¹ , -SO ₂ ORt ¹ , -NHSO ₂ Rt ¹ or -SO ₂ NRt ¹ Rt ² may be mentioned. Rt ¹ and Rt ² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rt ¹ and Rt ² may combine to form a ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably has 1 to 15 carbon atoms, and further preferably has 1 to 8 carbon atoms. The alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
The alkenyl group preferably has 2 to 30 carbon atoms, more preferably has 2 to 12 carbon atoms, and particularly preferably has 2 to 8 carbon atoms. The alkenyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
The alkynyl group preferably has 2 to 30 carbon atoms, and more preferably has 2 to 25 carbon atoms. The alkynyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear.
The aryl group preferably has 6 to 30 carbon atoms, more preferably has 6 to 20 carbon atoms, and further preferably has 6 to 12 carbon atoms.
The heterocyclic group may be a monocyclic ring or a condensed ring. The heterocyclic group is preferably a single ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The hetero atom forming the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described above for the substituent T.

Specific examples of the compound (1) and the compound (2) include compounds having the following structures, compounds described in paragraph Nos. 0046 to 0053 of JP-A-2005-063593, paragraphs No. 0151 to JP-A-2013-171063. And the compounds described in paragraph Nos. 0251 to 0258 of JP-A-2016-170370. In the compounds having the following structures, PG62 is color index pigment green 62, and PG63 is color index pigment green 63.

The total content of the compound (1) and the compound (2) in the colorant is preferably 30% by mass or more, more preferably 40% by mass or more, and 50% by mass or more. Is more preferable. The upper limit can be 100% by mass, 90% by mass or less, and 80% by mass or less.

The colorant used in the present invention preferably contains a yellow colorant in addition to the compound (1) and the compound (2) described above. According to this aspect, it is easy to form a film having a spectral characteristic suitable for a green pixel. Further, the content of the yellow colorant in the coloring composition is preferably 5 to 60 parts by mass based on 100 parts by mass of the total amount of the compound (1) and the compound (2) described above. The upper limit is preferably 55 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 45 parts by mass or less. The lower limit is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more.

Examples of yellow colorants include azo compounds, quinophthalone compounds, isoindolinone compounds, isoindoline compounds, anthraquinone compounds and the like. The yellow colorant may be a pigment or a dye.

Examples of the yellow pigment include color index (CI) pigment yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31. , 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81. , 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126. , 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 16 , And the like 170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,231,232.

As the yellow pigment, the pigment described in JP-A-2017-201003 and the pigment described in JP-A-2017-197719 can be used.

As the yellow colorant, the quinophthalone compounds described in paragraphs 0011 to 0034 of JP2013-054339A and the quinophthalone compounds described in paragraphs 0013 to 0058 of JP2014-026228A can be used. .

The colorant used in the present invention is selected from Color Index Pigment Yellow 138, Color Index Pigment Yellow 139, Color Index Pigment Yellow 150, and Color Index Pigment Yellow 231 in addition to the above-described compound (1) and compound (2). It is preferable to include at least one of When these colorants are contained, the content is preferably 5 to 60 parts by mass based on 100 parts by mass of the total amount of the compound (1) and the compound (2) described above. The upper limit is preferably 55 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 45 parts by mass or less. The lower limit is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more.

The colorant used in the present invention preferably contains a compound represented by the following formula (3) (hereinafter, also referred to as compound (3)) in addition to the above-described compound (1) and compound (2). The compound (3) can be preferably used as a yellow colorant.

In formula (3), Ry ¹ to Ry ¹³ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a sulfo group, a salt of a sulfo group, a carboxyl group, a salt of a carboxyl group, or phthalimidomethyl. Group or sulfamoyl group, and preferably a halogen atom.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable. The carbon number of the alkyl group and the alkoxy group is preferably 1 to 30, more preferably 1 to 15, and further preferably 1 to 8. The alkyl group and the alkoxy group may be linear, branched or cyclic, preferably linear or branched, and more preferably linear. The aryl group preferably has 6 to 30 carbon atoms, more preferably has 6 to 20 carbon atoms, and further preferably has 6 to 12 carbon atoms. Regarding the salt of a sulfo group and the salt of a carboxyl group, an atom or an atomic group constituting the salt is an alkali metal ion (Li ⁺ , Na ⁺ , K ^+, etc.), an alkaline earth metal ion (Ca ²⁺ , Mg ^2+). Etc.), ammonium ion, imidazolium ion, pyridinium ion, phosphonium ion and the like.

In formula (3), two adjacent groups of Ry ¹ to Ry ⁴ may be bonded to each other to form a ring, and two adjacent groups of Ry ¹⁰ to Ry ¹³ may be bonded to each other to form a ring. May be formed. Among them, at least one set of two adjacent groups of Ry ¹ to Ry ⁴ and Ry ¹⁰ to Ry ¹³ is preferably bonded to form a ring. The ring formed may be an aliphatic ring, an aromatic ring, or a heterocycle, and is preferably an aromatic ring. Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocycle, and an aromatic hydrocarbon ring is preferable. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring and a phenanthrene ring, and a benzene ring is preferable.

The compound (3) is preferably a compound represented by any of the following formulas (3a) to (3c).

In formulas (3a) to (3c), Ry ¹ to Ry ¹³ and Ry ¹⁰¹ to Ry ¹⁰⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a sulfo group or a sulfo group. It represents a salt, a carboxyl group, a salt of a carboxyl group, a phthalimidomethyl group, or a sulfamoyl group, and preferably represents a halogen atom.

Specific examples of the compound (3) include the compounds described in Examples described later and the compound described in paragraph No. 0073 of International Publication No. 2012/128233.

When the colorant used in the present invention further contains the compound (3), the content thereof is 5 to 60 parts by mass based on 100 parts by mass of the total of the compound (1) and the compound (2) described above. Is preferred. The upper limit is preferably 55 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 45 parts by mass or less. The lower limit is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more.

The colorant used in the present invention may further contain a colorant other than the above-mentioned compounds (hereinafter, also referred to as other colorant). Examples of other colorants include the following.

C. I. Pigment Orange 2, 5, 13, 16, 17, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Above, orange pigment),
C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48: 1,48: 2,48: 3,48: 4 49,49: 1,49: 2,52: 1,52: 2,53: 1,57: 1,60: 1,63: 1,66,67,81: 1,81: 2,81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184. 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, 294, etc. , Red pigment ,
C. I. Pigment Green 7, 10, 36, 37, 58, 59 etc. (above, green pigment),
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, 61 etc. (above, purple pigment),
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 22, 29, 60, 64, 66, 79, 80, 87, 88 etc. , Blue pigment).

Further, as a green pigment, a halogenated zinc phthalocyanine pigment having an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms of 8 to 12 and an average number of chlorine atoms of 2 to 5 Can also be used. Specific examples include the compounds described in WO 2015/118720. Further, the compound described in CN1069009027A, a phthalocyanine compound having a phosphoric acid ester as a ligand, or the like can be used as a green pigment.

As the red pigment, a diketopyrrolopyrrole pigment in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, a diketopyrrolopyrrole pigment described in paragraph Nos. 0016 to 0022 of Patent No. 6248838. A pigment or the like can also be used. As the red pigment, it is also possible to use a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom bonded to the aromatic ring is introduced is bound to a diketopyrrolopyrrole skeleton. it can.

Also, dyes can be used as other colorants. The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo type, anilino azo type, triaryl methane type, anthraquinone type, anthrapyridone type, benzylidene type, oxonol type, pyrazolotriazole azo type, pyridone azo type, cyanine type, phenothiazine type, pyrrolopyrazole azomethine type, xanthene type, Examples thereof include phthalocyanine-based dyes, benzopyran-based dyes, indigo-based dyes, and pyrromethene-based dyes. Further, the thiazole compound described in JP 2012-158649 A, the azo compound described in JP 2011-18449 A, and the azo compound described in JP 2011-145540 A can also be preferably used. Further, the intramolecular imide type xanthene dye described in JP-A-2018-012863 can also be used.

Also, a dye multimer can be used as another colorant. The dye multimer is preferably a dye used by being dissolved in a solvent, but the dye multimer may form particles, and when the dye multimer is particles, it is usually in a state of being dispersed in a solvent. Used. The dye multimer in the form of particles can be obtained, for example, by emulsion polymerization, and specific examples thereof include the compounds and production methods described in JP-A-2015-214682. The dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The plurality of dye structures contained in one molecule may be the same dye structure or different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000. The lower limit is more preferably 3,000 or more, still more preferably 6000 or more. The upper limit is more preferably 30,000 or less, further preferably 20,000 or less. Dye multimers are described in JP2011-213925A, JP2013-041097A, JP2015-028144A, JP2005-030742A, WO2016 / 031442 and the like. Compounds can also be used.

The content of the colorant is preferably 35% by mass or more, more preferably 40% by mass or more, further preferably 45% by mass or more, particularly preferably 50% by mass or more, based on the total solid content of the coloring composition. The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less.

In the colored composition of the present invention, the total content of the compound (1) and the compound (2) is preferably 25% by mass or more, and more preferably 30% by mass or more based on the total solid content of the colored composition. , 35% by mass or more is more preferable, and 40% by mass or more is particularly preferable. The upper limit is preferably 65% by mass or less, and more preferably 60% by mass or less.

<< Pigment derivative >>
The coloring composition of the present invention may contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the chromophore is substituted with an acid group, a basic group or a phthalimidomethyl group. The chromophore constituting the pigment derivative, quinoline skeleton, benzimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthraquinone skeleton, quinacridone skeleton, dioxazine skeleton, perinone skeleton, perylene skeleton, thioindigo skeleton, iso Indoline skeleton, isoindolinone skeleton, quinophthalone skeleton, slene skeleton, metal complex-based skeleton, etc. are mentioned, and quinoline skeleton, benzimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, quinophthalone skeleton, isoindoline skeleton and phthalocyanine skeleton are included. The azo skeleton and the benzimidazolone skeleton are more preferable. The acid group contained in the pigment derivative is preferably a sulfo group or a carboxyl group, more preferably a sulfo group. As the basic group contained in the pigment derivative, an amino group is preferable, and a tertiary amino group is more preferable.

In the present invention, a pigment derivative having excellent visible transparency (hereinafter, also referred to as a transparent pigment derivative) may be contained as the pigment derivative. The maximum value of the molar extinction coefficient in the wavelength region of 400 ~ 700 nm of the transparent pigment derivative (.epsilon.max) is that it is preferable, 1000L ^· mol ^-1 ^· ^cm -1 or less is not more than 3000L ^· mol ^-1 ^· ^cm -1 Is more preferable, and 100 L · mol ⁻¹ · cm ⁻¹ or less is further preferable. The lower limit of εmax is, for example, 1 L · mol ⁻¹ · cm ⁻¹ or more, and may be 10 L · mol ⁻¹ · cm ⁻¹ or more.

Specific examples of the pigment derivative include the compounds described in paragraph Nos. 0162 to 0183 of JP 2011-252065 A and the compounds described in JP 2003-081972 A. In addition, specific examples of the transparent pigment derivative include compounds having the following structures.

The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the total amount of the compound (1) and the compound (2). The total content of the pigment derivative and the colorant is preferably 35% by mass or more, more preferably 40% by mass or more, further preferably 45% by mass or more, and 50% by mass based on the total solid content of the coloring composition. A mass% or more is particularly preferable. The upper limit is preferably 70% by mass or less, more preferably 65% by mass or less. As the pigment derivative, only one kind may be used, or two or more kinds may be used in combination.

<< resin >>
The coloring composition of the present invention contains a resin. The resin is blended, for example, for the purpose of dispersing particles such as a pigment in the composition and for the use of a binder. The resin mainly used to disperse particles and the like in the composition is also referred to as a dispersant. However, such an application of the resin is an example, and the resin may be used for the purpose other than such an application.

Examples of the resin include (meth) acrylic resin, (meth) acrylamide resin, epoxy resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene. Examples thereof include ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and siloxane resin.

The weight average molecular weight (Mw) of the resin is preferably 2000 to 2000000. The upper limit is preferably 1,000,000 or less, more preferably 500000 or less. The lower limit is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more.

In the colored composition of the present invention, a resin having an acid group can be used as the resin. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like. The resin having an acid group can be used as an alkali-soluble resin or a dispersant. The acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, further preferably 70 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.

The colored composition of the present invention is a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) as a resin (hereinafter, these compounds may be referred to as “ether dimer”). A resin containing a repeating unit derived from can be used.

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms, which may have a substituent.

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

For specific examples of ether dimers, reference can be made to paragraph number 0317 of JP2013-029760A, the contents of which are incorporated herein.

In the colored composition of the present invention, a resin having a maleimide structure can be used as the resin. In addition, in this specification, a maleimide structure is a structure derived from a maleimide compound. Examples of the maleimide compound include maleimide and N-substituted maleimide. Examples of the N-substituted maleimide include cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, n-butyl maleimide, lauryl maleimide and the like.

The resin having a maleimide structure is preferably a resin containing a repeating unit having a maleimide structure. The maleimide structure may be contained in the main chain of the repeating unit or may be contained in the side chain of the repeating unit. The maleimide structure is preferably contained in the main chain of the repeating unit because it is easy to form a film with suppressed color unevenness.

The colored composition of the present invention contains a resin i (hereinafter, also referred to as resin i) containing a repeating unit derived from the compound represented by the formula (I) (hereinafter, also referred to as repeating unit i1-1) as a resin. Is also preferable. When the coloring composition of the present invention contains the resin i, it is easy to obtain a film in which color unevenness is suppressed. The content of the repeating unit i1-1 in all repeating units of the resin i is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more.

In the formula, Xi ¹ represents O or NH, and is preferably O.
Ri ¹ represents a hydrogen atom or a methyl group.
Li ¹ represents a divalent linking group. Examples of the divalent linking group include a hydrocarbon group, a heterocyclic group, —NH—, —SO—, —SO ₂ —, —CO—, —O—, —COO—, —OCO—, —S— and these. And a group formed by combining two or more of the above. Examples of the hydrocarbon group include an alkyl group and an aryl group. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Examples of the kind of hetero atom that constitutes the heterocyclic group include a nitrogen atom, an oxygen atom and a sulfur atom. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a monocyclic ring or a condensed ring. The hydrocarbon group and the heterocyclic group may have a substituent. Examples of the substituent include an alkyl group, an aryl group, a hydroxy group, a halogen atom and the like.
Ri ¹⁰ represents a substituent. Examples of the substituent represented by Ri ¹⁰ include the following substituent Ti, which is preferably a hydrocarbon group, and more preferably an alkyl group which may have an aryl group as a substituent.
m represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
p represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 3, still more preferably 0 to 2, even more preferably 0 or 1, and particularly preferably 1.

(Substituent Ti)
Examples of the substituent Ti include a halogen atom, a cyano group, a nitro group, a hydrocarbon group, a heterocyclic group, —ORti ¹ , —CORti ¹ , —COORti ¹ , —OCORti ¹ , —NRti ¹ Rti ² , —NHCORti ¹ , — CONRti ¹ Rti ² , —NHCONRti ¹ Rti ² , —NHCOORti ¹ , —SRti ¹ , —SO ₂ Rti ¹ , —SO ₂ ORti ¹ , —NHSO ₂ Rti ¹ or —SO ₂ NRti ¹ Rti ² may be mentioned. Rti ¹ and Rti ² each independently represent a hydrogen atom, a hydrocarbon group or a heterocyclic group. Rti ¹ and Rti ² may combine to form a ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group and an aryl group. The alkyl group preferably has 1 to 30 carbon atoms, more preferably has 1 to 15 carbon atoms, and further preferably has 1 to 8 carbon atoms. The alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably branched.
The alkenyl group preferably has 2 to 30 carbon atoms, more preferably has 2 to 12 carbon atoms, and particularly preferably has 2 to 8 carbon atoms. The alkenyl group may be linear, branched or cyclic, preferably linear or branched.
The alkynyl group preferably has 2 to 30 carbon atoms, and more preferably has 2 to 25 carbon atoms. The alkynyl group may be linear, branched or cyclic, preferably linear or branched.
The aryl group preferably has 6 to 30 carbon atoms, more preferably has 6 to 20 carbon atoms, and further preferably has 6 to 12 carbon atoms.
The heterocyclic group may be a monocyclic ring or a condensed ring. The heterocyclic group is preferably a single ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3. The hetero atom forming the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.
The hydrocarbon group and the heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described for the above-mentioned substituent Ti.

The compound represented by the formula (I) is preferably a compound represented by the following formula (I-1).

Xi ¹ represents O or NH, and is preferably O.
Ri ¹ represents a hydrogen atom or a methyl group.
Ri ² , Ri ³ and Ri ¹¹ each independently represent a hydrocarbon group.
The hydrocarbon group represented by Ri ² and Ri ³ is preferably an alkylene group or an arylene group, and more preferably an alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms. The hydrocarbon group represented by Ri ¹¹ is preferably an alkyl group which may have an aryl group as a substituent, and more preferably an alkyl group having an aryl group as a substituent. The alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 10 carbon atoms, and further preferably has 1 to 5 carbon atoms. When the alkyl group has an aryl group as a substituent, the carbon number of the alkyl group means the carbon number of the alkyl moiety.
Ri ¹² represents a substituent. Examples of the substituent represented by Ri ¹² include the above-described substituent Ti.
n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.
m represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
p1 represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 3, further preferably 0 to 2, further preferably 0 to 1, and particularly preferably 0.
q1 represents an integer of 1 or more, preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2, and particularly preferably 1.

The compound represented by the formula (I) is preferably a compound represented by the following formula (III).

In the formula, Ri ¹ represents a hydrogen atom or a methyl group, Ri ²¹ and Ri ²² each independently represent an alkylene group, and n represents an integer of 0 to 15. The alkylene group represented by Ri ²¹ and Ri ²² preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms. preferable. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and further preferably an integer of 0 to 3.

Examples of the compound represented by the formula (I) include ethylene oxide- or propylene oxide-modified (meth) acrylate of paracumylphenol. Examples of commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).

The resin i preferably further contains a repeating unit derived from an alkyl (meth) acrylate (hereinafter, also referred to as a repeating unit i1-2). When the resin i further has the repeating unit i1-2, the effect of improving the solvent solubility is obtained. The alkyl moiety of the alkyl (meth) acrylate preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and further preferably 3 to 6 carbon atoms. Preferable specific examples of the alkyl (meth) acrylate include n-butyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl acrylate, etc., and n-butyl (meth) acrylate is preferable because it is easy to obtain more excellent solvent solubility. Butyl (meth) acrylate is preferred. The content of the repeating unit i1-2 in all the repeating units of the resin i is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 15 mol% or more.

The resin i preferably further contains a repeating unit having an acid group. According to this aspect, the effect of improving the developability can be obtained. The content of the repeating unit having an acid group in all the repeating units of the resin i is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more. The upper limit is preferably 60 mol% or less, and more preferably 50 mol% or less.

The resin i preferably further contains a repeating unit having an ethylenically unsaturated bond group. Examples of the repeating unit having an ethylenically unsaturated bond group include a repeating unit represented by the formula (A-1-1) described later. The content of the repeating unit having an ethylenically unsaturated bond group in all repeating units of the resin i is preferably 5 mol% or more, more preferably 10 mol% or more, and 15 mol% or more. Is more preferable. The upper limit is preferably 50 mol% or less, and more preferably 40 mol% or less.

The coloring composition of the present invention may contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups accounts for 70 mol% or more, when the total amount of acid groups and basic groups is 100 mol%, A resin consisting only of acid groups is more preferable. The acid group contained in the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH / g. Further, the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%. The basic group contained in the basic dispersant is preferably an amino group.

The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin used as the dispersant contains a repeating unit having an acid group, generation of a development residue can be further suppressed when forming a pattern by the photolithography method.

The resin used as the dispersant is also preferably a graft resin. Details of the graft resin can be referred to the descriptions in paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.

It is also preferable that the resin used as the dispersant is a polyimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine-based dispersant has a main chain having a partial structure having a functional group of pKa14 or less and a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain has a basic nitrogen atom. The resin having is preferable. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. Regarding the polyimine dispersant, the description in paragraph numbers 0102 to 0166 of JP 2012-255128 A can be referred to, and the contents thereof are incorporated in the present specification.

It is also preferable that the resin used as the dispersant has a structure in which a plurality of polymer chains are bonded to the core part. Examples of such resins include dendrimers (including star polymers). In addition, specific examples of the dendrimer include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A-2013-043962.

The resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond group in its side chain. The content of the repeating unit having an ethylenically unsaturated bond group in its side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and more preferably 20 to 70 mol, based on all repeating units of the resin. % Is more preferable.

The dispersant is also available as a commercially available product, and specific examples thereof include Disperbyk series manufactured by Big Chemie (for example, Disperbyk-111, 2001) and Sols Perth series manufactured by Nippon Lubrizol Co., Ltd. ( For example, Sols Perth 20000, 76500, etc.), Ajinomoto Fine Techno Co., Ltd. Azisper series, etc. are mentioned. The product described in paragraph No. 0129 of JP2012-137564A and the product described in paragraph No. 0235 of JP2017-194662A can be used as a dispersant.

The resin used in the present invention preferably contains a resin having an ethylenically unsaturated bond group (hereinafter, also referred to as a polymerizable resin). According to this aspect, it is possible to more effectively suppress the film shrinkage over time.

The ethylenically unsaturated bond group value (hereinafter, also referred to as C = C value) of the polymerizable resin is preferably 0.05 to 5.0 mmol / g. The upper limit is more preferably 4.0 mmol / g or less, further preferably 3.0 mmol / g or less, even more preferably 2.0 mmol / g or less, and 1.0 mmol / g or less. It is particularly preferable that The lower limit is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more. The C = C value of the polymerizable resin is a numerical value representing the molar amount of C = C groups per 1 g of the solid content of the polymerizable resin. The C = C value of the polymerizable resin is obtained by extracting the low molecular weight component (a) at the C = C group site from the polymerizable resin by alkali treatment and measuring the content by high performance liquid chromatography (HPLC). It can be calculated. When the C = C group site cannot be extracted from the polymerizable resin by alkali treatment, the value measured by the NMR method (nuclear magnetic resonance) is used.
C = C value of polymerizable resin [mmol / g] = (content of low molecular component (a) [ppm] / molecular weight of low molecular component (a) [g / mol]) / (measured value of polymerizable resin) [G] x (solid content concentration of polymerizable resin [mass%] / 100) x 10)

The polymerizable resin preferably contains a repeating unit having an ethylenically unsaturated bond group in its side chain, and more preferably contains a repeating unit represented by the following formula (A-1-1). Further, in the polymerizable resin, the repeating unit having an ethylenically unsaturated bond group is preferably contained in an amount of 10 mol% or more, more preferably 10 to 80 mol%, based on the total repeating units of the polymerizable resin, 20 It is more preferable that the content is up to 70 mol%.

In formula (A-1-1), X ¹ represents a main chain of a repeating unit, L ¹ represents a single bond or a divalent linking group, and Y ¹ represents an ethylenically unsaturated bond group.

In formula (A-1-1), the main chain of the repeating unit represented by X ¹ is not particularly limited. There is no particular limitation as long as it is a linking group formed of a known polymerizable monomer. For example, poly (meth) acrylic linking group, polyalkyleneimine linking group, polyester linking group, polyurethane linking group, polyurea linking group, polyamide linking group, polyether linking group, polystyrene linking group, etc. The poly (meth) acrylic linking group and the polyalkyleneimine linking group are preferable, and the poly (meth) acrylic linking group is more preferable, from the viewpoints of availability and production suitability of the raw material.

In the formula (A-1-1), the divalent linking group represented by L ¹ is an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkylene group having 1 to 12 carbon atoms). An oxy group), an oxyalkylene carbonyl group (preferably an oxyalkylene carbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), —NH—, —SO—, —SO ₂ — , —CO—, —O—, —COO—, —OCO—, —S— and groups formed by combining two or more of these. The alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may be linear, branched, or cyclic, and are preferably linear or branched. Further, the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group, and a hydroxy group is preferable from the viewpoint of production suitability.

In the formula (A-1-1), examples of the ethylenically unsaturated bond group represented by Y ¹ include a vinyl group, an allyl group, a methallyl group, a (meth) acryloyl group and a styrene group, and a (meth) acryloyl group, A styrene group is preferable, a (meth) acryloyl group is more preferable, and an acryloyl group is particularly preferable.

Specific examples of the repeating unit represented by the formula (A-1-1) include repeating units represented by the following formula (A-1-1a) and repeating units represented by the following formula (A-1-1b). Units are included.

In formula (A-1-1a), R ^a1 to R ^a3 each independently represent a hydrogen atom or an alkyl group, and Q ^1a represents —CO—, —COO—, —OCO—, —CONH— or phenylene. Represents a group, L ¹ represents a single bond or a divalent linking group, and Y ¹ represents an ethylenically unsaturated bond group. The alkyl group represented by R ^a1 to R ^a3 preferably has 1 to 10 carbon atoms, more preferably 1 to 3, and still more preferably 1. Q ^1a is preferably —COO— or —CONH—, and more preferably —COO—.

In formula (A-1-1b), R ^a10 and R ^a11 each independently represent a hydrogen atom or an alkyl group, m1 represents an integer of 1 to 5, and L ¹ represents a single bond or a divalent linkage. Represents a group, and Y ¹ represents an ethylenically unsaturated bond group. The alkyl group represented by R ^a10 and R ^a11 preferably has 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms.

The polymerizable resin preferably further contains a repeating unit having a graft chain. When the polymerizable resin contains a repeating unit having a graft chain, it is possible to more effectively suppress aggregation of the compound (1) or the compound (2) due to steric hindrance due to the graft chain. Further, at the time of forming the cured film, the polymerizable resin may be polymerized in the vicinity of the compound (1) or the compound (2) to firmly hold the compound (1) or the compound (2) in the film, It is also possible to more effectively suppress thermal diffusion of these compounds due to heating and form a cured film having excellent heat resistance. The polymerizable resin preferably contains a repeating unit having a graft chain in an amount of 1.0 to 60 mol%, more preferably 1.5 to 50 mol%, based on all repeating units of the polymerizable resin. A polymerizable resin containing a repeating unit having a graft chain is preferably used as a dispersant.

In the present invention, the graft chain means a polymer chain branched and extended from the main chain of the repeating unit. The length of the graft chain is not particularly limited, but the longer the graft chain, the higher the steric repulsion effect, and the higher the dispersibility of the compound (1) or the compound (2). The graft chain preferably has 40 to 10000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and has 60 to 60 atoms excluding hydrogen atoms. It is more preferably 500.

The graft chain preferably contains a repeating unit having at least one structure selected from polyester repeating units, polyether repeating units, poly (meth) acrylic repeating units, polyurethane repeating units, polyurea repeating units and polyamide repeating units. It is more preferable to include a repeating unit having at least one structure selected from a repeating unit, a polyether repeating unit and a poly (meth) acrylic repeating unit, and it is further preferable to include a polyester repeating unit. Examples of the polyester repeating unit include a repeating unit having a structure represented by the following formula (G-1), formula (G-4) or formula (G-5). Further, examples of the polyether repeating unit include a repeating unit having a structure represented by the following formula (G-2). Examples of the poly (meth) acrylic repeating unit include a repeating unit having a structure represented by the following formula (G-3).

In the above formula, R ^G1 and R ^G2 each represent an alkylene group. The alkylene group represented by R ^G1 and R ^G2 is not particularly limited, but a linear or branched alkylene group having 1 to 20 carbon atoms is preferable, and a linear or branched alkylene group having 2 to 16 carbon atoms. A group is more preferable, and a linear or branched alkylene group having 3 to 12 carbon atoms is further preferable.
In the above formula, R ^G3 represents a hydrogen atom or a methyl group.
In the above formula, Q ^G1 represents —O— or —NH—, and L ^G1 represents a single bond or a divalent linking group. The divalent linking group includes an alkylene group (preferably having 1 to 12 carbon atoms), an alkyleneoxy group (preferably having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably having 1 carbon atom). To 12 oxyalkylenecarbonyl groups), arylene groups (preferably arylene groups having 6 to 20 carbon atoms), —NH—, —SO—, —SO ₂ —, —CO—, —O—, —COO—, OCO. —, —S—, and groups formed by combining two or more of these.
R ^G4 represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group and a heteroarylthioether group.

The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group and a heteroarylthioether group. Among them, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable, from the viewpoint of improving dispersibility of the pigment and the like. The alkyl group and the alkoxy group may be linear, branched or cyclic, with linear or branched being preferred.

In the present invention, the graft chain has a structure represented by the following formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a) or formula (G-5a). Preferably there is.

In the above formula, R ^G1 and R ^G2 each represent an alkylene group, R ^G3 represents a hydrogen atom or a methyl group, Q ^G1 represents —O— or —NH—, and L ^G1 represents a single bond or It represents a divalent linking group, R ^G4 represents a hydrogen atom or a substituent, and W ¹⁰⁰ represents a hydrogen atom or a substituent. n1 to n5 each independently represent an integer of 2 or more. For ^{^{^{R G1 ~ R G4, Q G1}}} , L G1 , Formula (G1) ~ (G-5 ) has the same meaning as ^{^{^{R G1 ~ R G4, Q G1}}} , L G1 described in, the preferred range is also the same is there.

In formulas (G-1a) to (G-5a), W ¹⁰⁰ is preferably a substituent. Examples of the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group and a heteroarylthioether group. Among them, a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable, from the viewpoint of improving dispersibility of the pigment and the like. The alkyl group and the alkoxy group may be linear, branched or cyclic, with linear or branched being preferred.

In formulas (G-1a) to (G-5a), n1 to n5 are each preferably an integer of 2 to 100, more preferably an integer of 2 to 80, even more preferably an integer of 8 to 60.

In the formula (G-1a), R ^G1s in each repeating unit when n1 is 2 or more may be the same or different. Moreover, when R ^G1 contains two or more kinds of repeating units having different R ^G1 , the arrangement of each repeating unit is not particularly limited, and may be random, alternating, or block. The same applies to the formulas (G-2a) to (G-5a).

Examples of the repeating unit having a graft chain include a repeating unit represented by the following formula (A-1-2).

In formula (A-1-2), X ² represents a main chain of a repeating unit, L ² represents a single bond or a divalent linking group, and W ¹ represents a graft chain.

Examples of the main chain of the repeating unit represented by X ² in formula (A-1-2) include the structures described for X ¹ in formula (A-1-1), and the preferred ranges are also the same. The divalent linking group represented by L ² in formula (A-1-2) includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) and an arylene group (preferably an arylene group having 6 to 20 carbon atoms). , —NH—, —SO—, —SO ₂ —, —CO—, —O—, —COO—, OCO—, —S— and groups formed by combining two or more of these. Examples of the graft chain represented by W ¹ in the formula (A-1-2) include the above-mentioned graft chains.

Specific examples of the repeating unit represented by the formula (A-1-2) include repeating units represented by the following formula (A-1-2a) and repeating units represented by the following formula (A-1-2b). Units are included.

In the formula (A-1-2a), R ^b1 to R ^b3 each independently represent a hydrogen atom or an alkyl group, and Q ^b1 represents —CO—, —COO—, —OCO—, —CONH— or phenylene. Represents a group, L ² represents a single bond or a divalent linking group, and W ¹ represents a graft chain. The alkyl group represented by R ^b1 to R ^b3 preferably has 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1. Q ^b1 is preferably —COO— or —CONH—, and more preferably —COO—.

In formula (A-1-2b), R ^b10 and R ^b11 each independently represent a hydrogen atom or an alkyl group, m2 represents an integer of 1 to 5, and L ² represents a single bond or a divalent linkage. Represents a group, and W ¹ represents a graft chain. The alkyl group represented by R ^b10 and R ^b11 preferably has 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms.

When the polymerizable resin contains a repeating unit having a graft chain, the repeating unit having a graft chain has a weight average molecular weight (Mw) of preferably 1000 or more, more preferably 1000 to 10000, and more preferably 1000 to 7500. Is more preferable. In the present invention, the weight average molecular weight of the repeating unit having a graft chain is a value calculated from the weight average molecular weight of the raw material monomer used for the polymerization of the repeating unit. For example, the repeating unit having a graft chain can be formed by polymerizing a macromonomer. Here, the macromonomer means a polymer compound having a polymerizable group introduced at the polymer end. When a repeating unit having a graft chain is formed using a macromonomer, the weight average molecular weight of the macromonomer corresponds to the repeating unit having a graft chain.

The polymerizable resin preferably further contains a repeating unit having an acid group. When the polymerizable resin further contains a repeating unit having an acid group, the dispersibility of the compound (1) or the compound (2) can be further improved. Furthermore, the developability can be improved. Examples of the acid group include a carboxyl group, a sulfo group and a phosphoric acid group.

Examples of the repeating unit having an acid group include a repeating unit represented by the following formula (A-1-3).

In formula (A-1-3), X ³ represents a main chain of a repeating unit, L ³ represents a single bond or a divalent linking group, and A ¹ represents an acid group. The main chain of the repeating unit represented by X ³ in formula (A-1-3) includes the structure described for X ¹ in formula (A-1-1), and the preferred range is also the same. The divalent linking group represented by L ³ in formula (A-1-3) includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) and an alkenylene group (preferably an alkenylene group having 2 to 12 carbon atoms). An alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms) ), —NH—, —SO—, —SO ₂ —, —CO—, —O—, —COO—, OCO—, —S— and groups formed by combining two or more of these. The alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may be linear, branched, or cyclic, and are preferably linear or branched. Further, the alkylene group, the alkylene group in the alkyleneoxy group, and the alkylene group in the oxyalkylenecarbonyl group may have a substituent or may be unsubstituted. A hydroxy group etc. are mentioned as a substituent. Examples of the acid group represented by A ¹ in the formula (A-1-3) include a carboxyl group, a sulfo group and a phosphoric acid group.

Specific examples of the repeating unit represented by the formula (A-1-3) include a repeating unit represented by the following formula (A-1-3a) and a repeating unit represented by the following formula (A-1-3b). Units are included.

In the formula (A-1-3a), R ^c1 to R ^c3 each independently represent a hydrogen atom or an alkyl group, and Q ^c1 is —CO—, —COO—, —OCO—, —CONH— or phenylene. Represents a group, L ³ represents a single bond or a divalent linking group, and A ¹ represents an acid group. The alkyl group represented by R ^c1 to R ^c3 preferably has 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 carbon atoms. Q ^c1 is preferably —COO— or —CONH—, and more preferably —COO—.

In the formula (A-1-3b), R ^c10 and R ^c11 each independently represent a hydrogen atom or an alkyl group, m3 represents an integer of 1 to 5, and L ³ represents a single bond or a divalent linkage. Represents a group, and A ¹ represents an acid group. The alkyl group represented by R ^c10 and R ^c11 preferably has 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms.

When the polymerizable resin contains a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 80 mol% or less in all repeating units of the polymerizable resin, and 10 to 80 mol% is preferable. More preferable. When the polymerizable resin contains a repeating unit having an acid group, the acid value of the polymerizable resin is preferably 20 to 150 mgKOH / g. The upper limit is more preferably 100 mgKOH / g or less. The lower limit is preferably 30 mgKOH / g or more, and more preferably 35 mgKOH / g or more. When the acid value of the polymerizable resin is within the above range, particularly excellent dispersibility is likely to be obtained. Furthermore, excellent developability is easily obtained.

The polymerizable resin is also preferably a resin containing a repeating unit represented by the formula (b-10).

In formula (b-10), Ar ¹⁰ represents a group containing an aromatic carboxyl group, L ¹¹ represents —COO— or —CONH—, L ¹² represents a trivalent linking group, and P ¹⁰ represents ( It represents a polymer chain having a (meth) acryloyl group.

Examples of the group containing an aromatic carboxyl group represented by Ar ¹⁰ in the formula (b-10) include a structure derived from an aromatic tricarboxylic acid anhydride and a structure derived from an aromatic tetracarboxylic acid anhydride. Examples of aromatic tricarboxylic acid anhydrides and aromatic tetracarboxylic acid anhydrides include compounds having the following structures.

In the above formula, Q ¹ represents a single bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, or a formula (Q-1) shown below. Or a group represented by the following formula (Q-2).

Specific examples of the aromatic tricarboxylic acid anhydride include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzenetricarboxylic acid anhydride], etc.) , Naphthalene tricarboxylic acid anhydride (1,2,4-naphthalene tricarboxylic acid anhydride, 1,4,5-naphthalene tricarboxylic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, 1,2,8-naphthalene Tricarboxylic acid anhydride, etc.), 3,4,4'-benzophenone tricarboxylic acid anhydride, 3,4,4'-biphenyl ether tricarboxylic acid anhydride, 3,4,4'-biphenyl tricarboxylic acid anhydride, 2,3 , 2'-biphenyl tricarboxylic acid anhydride, 3,4,4'-biphenylmethane tricarboxylic acid anhydride, or 3,4,4'- Phenyl sulfonic tricarboxylic acid anhydrides. Specific examples of the aromatic tetracarboxylic acid anhydrides include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, and 3,3. ', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyl sulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid Acid dianhydride, 3,3 ', 4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan Tracarboxylic acid dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4 , 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3', 4,4 ' -Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride , Bis (triphenylphthalic acid) -4,4'-diphenylether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane Anhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,4- Dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic acid dianhydride Anhydrous etc. are mentioned.

Specific examples of the group containing an aromatic carboxyl group represented by Ar ¹⁰ include a group represented by the formula (Ar-1), a group represented by the formula (Ar-2), and a group represented by the formula (Ar-3). Group.

In formula (Ar-1), n1 represents an integer of 1 to 4, preferably an integer of 1 to 2, and more preferably 2.
In the formula (Ar-2), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 to 2, and even more preferably 2.
In formula (Ar-3), n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 to 2, and most preferably 1. More preferable. However, at least one of n3 and n4 is an integer of 1 or more.
In formula (Ar-3), Q ¹ represents a single bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, or the above formula (Q— It represents a group represented by 1) or a group represented by the above formula (Q-2).

In formula (b-10), L ¹¹ represents —COO— or —CONH—, and preferably —COO—.

Examples of the trivalent linking group represented by L ¹² in the formula (b-10) include a hydrocarbon group, —O—, —CO—, —COO—, —OCO—, —NH—, —S— and 2 of these. Examples thereof include groups in which two or more species are combined. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably has 1 to 20 carbon atoms, and further preferably has 1 to 15 carbon atoms. The aliphatic hydrocarbon group may be linear, branched or cyclic. The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably has 6 to 20 carbon atoms, and further preferably has 6 to 10 carbon atoms. The hydrocarbon group may have a substituent. A hydroxy group etc. are mentioned as a substituent. The trivalent linking group represented by L ¹² is preferably a group represented by the following formula (L12-1), and more preferably a group represented by the formula (L12-2).

L ^12a and L ^12b each represent a trivalent linking group, X ¹ represents S, * 1 represents a bonding position with L ¹¹ in formula (b-10), and * 2 represents formula (b-10). Represents the bonding position with P ¹⁰ .

The trivalent linking group represented by L ^12a and L ^12b is selected from a hydrocarbon group; a hydrocarbon group and —O—, —CO—, —COO—, —OCO—, —NH— and —S—. Examples thereof include groups in which at least one type is combined.

In formula (b-10), P ¹⁰ represents a polymer chain having a (meth) acryloyl group. The polymer chain represented by P ¹⁰ preferably has at least one repeating unit selected from poly (meth) acrylic repeating units, polyether repeating units, polyester repeating units and polyol repeating units. The weight average molecular weight of the polymer chain P ¹⁰ is preferably 500 to 20,000. The lower limit is preferably 600 or more, more preferably 1000 or more. The upper limit is preferably 10,000 or less, more preferably 5000 or less, still more preferably 3000 or less. When the weight average molecular weight of P ¹⁰ is in the above range, the dispersibility of the pigment in the composition is good. This resin is preferably used as a dispersant.

In the formula (b-10), the polymer chain represented by P ¹⁰ is preferably a polymer chain containing repeating units represented by the following formulas (P-1) to (P-5), and (P-5) A polymer chain containing a repeating unit represented by is more preferable.

In the above formula, R ^P1 and R ^P2 each represent an alkylene group. As the alkylene group represented by R ^P1 and R ^P2 , a linear or branched alkylene group having 1 to 20 carbon atoms is preferable, and a linear or branched alkylene group having 2 to 16 carbon atoms is more preferable. Further, a linear or branched alkylene group having 3 to 12 carbon atoms is more preferable.
In the above formula, R ^P3 represents a hydrogen atom or a methyl group.
In the above formula, L ^P1 represents a single bond or an arylene group, and L ^P2 represents a single bond or a divalent linking group. L ^P1 is preferably a single bond. The divalent linking group represented by L ^P2 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), —NH—, —SO—, Examples include —SO ₂ —, —CO—, —O—, —COO—, —OCO—, —S—, —NHCO—, —CONH—, and groups formed by combining two or more of these.
R ^P4 represents a hydrogen atom or a substituent. As the substituent, a hydroxy group, a carboxyl group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, (meth) acryloyl Groups and the like.

Further, the polymer chain represented by P ¹⁰ is more preferably a polymer chain having a repeating unit containing a (meth) acryloyl group in its side chain. In addition, the proportion of repeating units containing a (meth) acryloyl group in the side chain in all repeating units constituting P ¹⁰ is preferably 5% by mass or more, more preferably 10% by mass or more, It is more preferably 20% by mass or more. The upper limit may be 100% by mass, preferably 90% by mass or less, and more preferably 60% by mass or less.

Further, the polymer chain represented by P ¹⁰ also preferably has a repeating unit containing an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfo group and a phenolic hydroxy group. According to this aspect, the dispersibility of the pigment in the composition can be further improved. Furthermore, the developability can be further improved. The proportion of the repeating unit containing an acid group is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and further preferably 3 to 10% by mass.

The resin containing a repeating unit represented by the formula (b-10) is obtained by reacting at least one acid anhydride selected from aromatic tetracarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides with a hydroxy group-containing compound. Can be manufactured. Examples of the aromatic tetracarboxylic acid anhydride and aromatic tricarboxylic acid anhydride include those mentioned above. The hydroxy group-containing compound is not particularly limited as long as it has a hydroxy group in the molecule, but is preferably a polyol having two or more hydroxy groups in the molecule. It is also preferable to use a compound having two hydroxy groups and one thiol group in the molecule as the hydroxy group-containing compound. Examples of the compound having two hydroxy groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2- Propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1- Examples thereof include mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like. Examples of other hydroxy group-containing compounds include the compounds described in JP-A-2018-101039, paragraphs 0084 to 0095, the contents of which are incorporated herein.

The molar ratio of the acid anhydride group in the acid anhydride to the hydroxy group in the hydroxy group-containing compound (acid anhydride group / hydroxy group) is preferably 0.5 to 1.5.

The weight average molecular weight of the resin containing the repeating unit represented by the formula (b-10) is preferably 2000 to 35,000. The upper limit is preferably 25,000 or less, more preferably 20,000 or less, and further preferably 15,000 or less. The lower limit is preferably 4000 or more, more preferably 6000 or more, and further preferably 7000 or more.

The acid value of the resin containing the repeating unit represented by the formula (b-10) is preferably 5 to 200 mgKOH / g. The upper limit is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, and further preferably 80 mgKOH / g or less. The lower limit is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, and further preferably 20 mgKOH / g or more.

As the polymerizable resin, it is also preferable to use a compound represented by the following formula (OP1).

In the formula, Rp ⁴ has a number average molecular weight of 400 to 30000, represents a polyether residue and / or a polyester residue having an ethylenically unsaturated bond group, and y represents a number of 1 to 2.

The number average molecular weight of Rp ⁴ is more preferably 400 to 10000, further preferably 400 to 3000. When the number average molecular weight of Rp ⁴ is in the above range, the dispersibility of the pigment is good, and such a resin is preferably used as a dispersant.

Examples of the polyether residue and / or polyester residue having an ethylenically unsaturated bond group represented by Rp ⁴ include a polyether residue having a styrene group, a (meth) acryloyl group, a cyanoacryloyl group, a vinyl ether group and / or the like. Examples include polyester residues.

Rp ⁴ is preferably a group represented by the following formula (Rp-1).
^{^{-Rp 12 -O-Rp 13 - (}} O-Rp 14) S
In the formula, Rp ¹² represents an alkylene group, Rp ¹³ represents a trivalent or higher polyhydric alcohol residue, Rp ¹⁴ represents a (meth) acryloyl group or a cyanoacryloyl group, and s represents 2 or more.

Rp ¹² is preferably an alkylene group having 8 or less carbon atoms. Further, s is preferably 2 or more from the viewpoint of pigment dispersibility. In this case, Rp ¹⁴ may use different groups from each other. s is more preferably 2 to 5, and particularly preferably 2.

Examples of the trihydric or higher polyhydric alcohol used for Rp ¹³ include glycerin, propyl alcohol, pentaerythritol, and dipentaerythritol. Particularly, trivalent to hexavalent ones are preferable.

Compounds of formula (OP1) is to Rp ⁴ may be a single species of phosphoric acid esters may be used more phosphoric acid esters of different Rp ^4. Further, the compound of y = 1 may be used alone, or a mixture of the compound of y = 1 and the compound of y = 2 may be used. In the compound represented by the formula (OP1), when the abundance ratio of the compound of y = 1 and the compound of y = 2 is 100: 0 to 100: 30, the pigment dispersibility becomes good, which is preferable. Further, when Rp ^{4 of the} compound represented by the formula (OP1) is a polycaprolactone residue having a number average molecular weight of 400 to 10000 (more preferably 400 to 3000), the pigment dispersibility becomes good, which is preferable.

The content of the resin in the total solid content of the coloring composition is preferably 25 to 60% by mass. The upper limit is preferably 55% by mass or less, and more preferably 50% by mass or less. The lower limit is preferably 30% by mass or more, and more preferably 35% by mass or more.

Further, in the present invention, the content of the resin having an ethylenically unsaturated bond group in the total amount of the resin contained in the coloring composition of the present invention is preferably 50 to 100% by mass, and 60 to 100% by mass. Is more preferable, and 70 to 100% by mass is further preferable.

In the present invention, it is also preferable to use a resin having an ethylenically unsaturated bond group and a resin having no ethylenically unsaturated bond group together. According to this aspect, color unevenness can be suppressed more effectively. In this case, the mass ratio of the resin having an ethylenically unsaturated bond group and the resin having no ethylenically unsaturated bond group is a resin having an ethylenically unsaturated bond group: a resin having an ethylenically unsaturated bond group. No resin = 1: 0.001 to 0.800 is preferable, 1: 0.002 to 0.700 is more preferable, and 1: 0.003 to 0.600 is further preferable.

<< polymerizable monomer >>
The colored composition of the present invention contains a polymerizable monomer having an ethylenically unsaturated bond group (hereinafter referred to as a polymerizable monomer). Examples of the ethylenically unsaturated bond group include a vinyl group, a (meth) allyl group and a (meth) acryloyl group. The polymerizable monomer is preferably a compound that can be polymerized by radicals (radical polymerizable monomer).

The polymerizable monomer is preferably a compound containing three or more ethylenically unsaturated bond groups. The upper limit of the ethylenically unsaturated bond group is preferably 15 or less, more preferably 10 or less, and further preferably 6 or less. The polymerizable monomer is preferably a tri- or higher functional (meth) acrylate compound, more preferably a 3- to 15-functional (meth) acrylate compound, and a 3- to 10-functional (meth) acrylate compound. It is more preferable that the (meth) acrylate compound having a functionality of 3 to 6 is used.

The molecular weight of the polymerizable monomer is preferably 100 to 2000. The upper limit is preferably 1500 or less, more preferably 1000 or less, further preferably 450 or less, and particularly preferably 400 or less. The lower limit is preferably 150 or more.

The ethylenically unsaturated bond group value of the polymerizable monomer (hereinafter referred to as C = C value) is 2 to 14 mmol / g from the viewpoint of stability of the composition over time, color fastness of the obtained film, and the like. Is preferred. The lower limit is preferably 3 mmol / g or more, more preferably 4 mmol / g or more, and further preferably 5 mmol / g or more. The upper limit is preferably 12 mmol / g or less, more preferably 10 mmol / g or less, and further preferably 8 mmol / g or less. The C = C value of the polymerizable monomer was calculated by dividing the number of ethylenically unsaturated bond groups contained in one molecule of the polymerizable monomer by the molecular weight of the polymerizable monomer.

The polymerizable monomer used in the present invention is also preferably a compound having 3 or more ethylenically unsaturated bond groups and having a molecular weight of 450 or less, and a compound having 3 ethylenically unsaturated bond groups and having a molecular weight of 450 or less. Is more preferable, and a trifunctional (meth) acrylate compound having a molecular weight of 450 or less is further preferable. According to this aspect, the solvent resistance of the obtained film can be further improved. Although the detailed reason why such an effect is obtained is not clear, it is presumed that it is because a highly dense network structure could be formed by exposure. Examples of the polymerizable monomer having three ethylenically unsaturated bond groups and having a molecular weight of 450 or less include trimethylolpropane tri (meth) acrylate.

The polymerizable monomer used in the present invention is also preferably a compound having an isocyanurate skeleton. Specific examples of the polymerizable monomer having an isocyanurate skeleton include tris (2-acryloyloxyethyl) isocyanurate and ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate. Commercially available products include Fancryl FA-731A (manufactured by Hitachi Chemical Co., Ltd.), NK ester A9300, A9300-1CL, A9300-3CL (manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-315 (Toagosei Co., Ltd.). ) And the like.

In the present invention, as the polymerizable monomer, dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Japanized) Yakuhin Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd., and these (meth) acryloyl groups bound to each other via ethylene glycol and / or propylene glycol residues. A compound with a structure such as a sartomer Commercially available from, may SR454, SR499) be used. It is also preferable to use Aronix M-402 (manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as the polymerizable monomer.

In the present invention, it is also preferable to use a polymerizable monomer having an acid group as the polymerizable monomer. By using the polymerizable monomer having an acid group, the coloring composition layer in the unexposed area can be easily removed during development, and the development residue can be suppressed. Examples of the acid group include a carboxyl group, a sulfo group and a phosphoric acid group, and a carboxyl group is preferable. Examples of the polymerizable monomer having an acid group include succinic acid-modified dipentaerythritol penta (meth) acrylate. Examples of commercially available polymerizable monomers having an acid group include Aronix M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) and the like. The acid value of the polymerizable monomer having an acid group is preferably 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable monomer is 0.1 mgKOH / g or more, the solubility in the developing solution is good, and when it is 40 mgKOH / g or less, it is advantageous in production and handling.

In the present invention, it is also preferable to use a compound having a caprolactone structure as the polymerizable monomer. The polymerizable monomer having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.

The polymerizable monomer is a compound described in JP-A-2017-048367, JP-A-6057891, JP-A-6031807, a compound described in JP-A-2017-194662, 8UH-1006, 8UH. It is also preferable to use -1012 (all manufactured by Taisei Fine Chemicals Co., Ltd.) and light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.).

The polymerizable monomer used in the present invention contains at least one selected from succinic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate. preferable. According to this aspect, more excellent photolithographic property can be easily obtained.

The content of the polymerizable monomer in the total solid content of the coloring composition is 0.1 to 6.0% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and further preferably 1.5% by mass or more. The upper limit is preferably 5.5% by mass or less, more preferably 5.0% by mass or less, and further preferably 4.5% by mass or less.

Further, the total content of the resin and the polymerizable monomer in the total solid content of the coloring composition is preferably 25.5 to 65.5 mass%. The upper limit is preferably 60.0 mass% or less, more preferably 54.5 mass% or less. The lower limit is preferably 31.0 mass% or more, and more preferably 36.5 mass% or more.

Further, the total content of the photopolymerization initiator and the polymerizable monomer in the total solid content of the coloring composition is preferably 1.4 to 12.5% by mass. The upper limit is preferably 11.0% by mass or less, and more preferably 9.5% by mass or less. The lower limit is preferably 2.2% by mass or more, and more preferably 3.0% by mass or more.

Further, the ratio (M ¹ / B ¹ ) of the mass M ¹ of the polymerizable monomer contained in the coloring composition to the mass B ^{1 of the} resin contained in the coloring composition is 0.03 to 0.15. Is preferred. The lower limit of the ratio value is preferably 0.035 or more, more preferably 0.040 or more, and further preferably 0.045 or more. The upper limit is preferably 0.13 or less, more preferably 0.11 or less, and further preferably 0.9 or less. If the above-mentioned ratio is 0.03 or more, the pattern formability by the photolithography method is good, and if it is 0.15 or less, the generation of residues during the pattern formation by the photolithography method can be suppressed more effectively. .

Further, the ratio (M ¹ / I ¹ ) of the mass M ¹ of the polymerizable monomer contained in the coloring composition and the mass I ¹ of the photopolymerization initiator contained in the coloring composition is 0.013 to 12,000. Is preferred. The lower limit of the ratio value is preferably 0.071 or more, more preferably 0.167 or more, still more preferably 0.300 or more. The upper limit is preferably 6.111 or less, more preferably 4.167 or less, still more preferably 3,000 or less. If the above-mentioned ratio is 0.013 or more, the line width sensitivity is good, and if it is 12.000 or less, the pattern formability by the photolithography method is good.

In the colored composition of the present invention, the polymerizable monomer may be used alone or in combination of two or more. Moreover, when two or more polymerizable monomers are used, it is preferable that the total amount thereof be within the above range.

<< photopolymerization initiator >>
The coloring composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light rays in the ultraviolet region to the visible region are preferable. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thiols. Examples thereof include compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds and phenylglyoxylate compounds. From the viewpoint of exposure sensitivity, the photopolymerization initiator is more preferably a compound selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and further preferably an oxime compound. . Regarding the photopolymerization initiator, the descriptions in paragraphs 0065 to 0111 and JP 6301489 of JP-A-2014-130173 can be referred to, and the contents thereof are incorporated in the present specification.

Examples of commercially available α-hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (all manufactured by BASF). Commercially available α-aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (all manufactured by BASF). Examples of commercially available acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (above, manufactured by BASF).

Examples of the oxime compound include the compounds described in JP 2001-233842 A, the compounds described in JP 2000-080068 A, the compounds described in JP 2006-342166 A, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compound described in J. C. S. Compounds described in Perkin II (1979, pp.156-162), Compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in Japanese Patent Laid-Open No. 2000-066385, Compounds described in JP-A-2004-534797, JP-A-2006-342166, JP-A-2017-0197766, JP-A-6065596, and WO 2015 / 152153, the compound described in WO2017 / 051680, the compound described in JP-A-2017-198865, and the paragraphs 0025 to 0038 of WO2017 / 164127. Such compounds, and the like. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy Examples thereof include imino-1-phenylpropan-1-one. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tengden Electronic New Materials Co., Ltd.), and ADEKA OPTOMER N-1919. (Photopolymerization initiator 2 described in JP 2012-014052, manufactured by ADEKA Corporation) can be used. As the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and being resistant to discoloration. Examples of commercially available products include ADEKA ARKUL'S NCI-730, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation).

In the present invention, an oxime compound having a fluorene ring can be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include the compounds described in JP-A-2014-137466. This content is incorporated herein.

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

In the present invention, an oxime compound having a nitro group can be used as the photopolymerization initiator. The oxime compound having a nitro group is also preferably dimerized. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, The compounds described in paragraph Nos. 0007 to 0025 of Japanese Patent No. 4223071 are ADEKA ARCRUZ NCI-831 (manufactured by ADEKA Corporation).

In the present invention, an oxime compound having a benzofuran skeleton can be used as the photopolymerization initiator. Specific examples thereof include OE-01 to OE-75 described in WO 2015/036910.

Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited thereto.

In the present invention, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photopolymerization initiator. By using such a photo-radical polymerization initiator, two or more radicals are generated from one molecule of the photo-radical polymerization initiator, so that good sensitivity can be obtained. Further, when a compound having an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, it becomes difficult to deposit over time, and the stability over time of the coloring composition can be improved. . Specific examples of the bifunctional or trifunctional or more photoradical polymerization initiators include those disclosed in Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675. Dimers of oxime compounds described in paragraphs Nos. 0421 to 0417 and International Publication No. 2017/033680, paragraphs 0039 to 0055, compounds (E) and compounds described in JP-A No. 2013-522445. G), Cmpd 1 to 7 described in International Publication No. 2016/034963, and oxime ester photoinitiator described in paragraph No. 0007 of JP-A-2017-523465, JP-A-2017-167399. The photoinitiator described in paragraphs 0020 to 0033, JP-A-20 Photopolymerization initiators described in paragraphs 0017 to 0026 of JP-7-151342 (A), and the like.

In the present invention, as the photopolymerization initiator, the photopolymerization initiator 1 having an absorption coefficient at a wavelength of 365 nm in methanol of 1.0 × 10 ⁴ mL / gcm or more, and the absorption coefficient at a wavelength of 365 nm in methanol of 1. It is also preferable to use together with the photopolymerization initiator 2 having a light absorption coefficient of 0 × 10 ² mL / gcm or less and a wavelength of 254 nm of 1.0 × 10 ³ mL / gcm or more. According to this aspect, it is easy to sufficiently cure the coloring composition by exposure, and it is easy to obtain more excellent photolithographic property. As the photopolymerization initiator 1 and the photopolymerization initiator 2, it is preferable to select and use a compound having the above extinction coefficient from the above compounds.

In addition, in this invention, the light absorption coefficient in the said wavelength of a photoinitiator is the value measured as follows. That is, it was calculated by dissolving the photopolymerization initiator in methanol to prepare a measurement solution and measuring the absorbance of the above-mentioned measurement solution. Specifically, the above-mentioned measurement solution was placed in a glass cell having a width of 1 cm, and the absorbance was measured using a UV-Vis-NIR spectrometer (Cary5000) manufactured by Agilent Technologies, and the absorbance was applied to the following formula to obtain a wavelength of 365 nm and a wavelength. The extinction coefficient (mL / gcm) at 254 nm was calculated.

In the above equation, ε is the extinction coefficient (mL / gcm), A is the absorbance, c is the concentration of the photopolymerization initiator (g / mL), and 1 is the optical path length (cm).

The extinction coefficient of the photopolymerization initiator 1 in methanol at a wavelength of 365 nm is preferably 1.1 × 10 ⁴ mL / gcm or more, and 1.2 × 10 ⁴ to 1.0 × 10 ⁵ mL / gcm. It is more preferable that it is 1.3 × 10 ⁴ to 5.0 × 10 ⁴ mL / gcm, and it is still more preferable that it is 1.5 × 10 ⁴ to 3.0 × 10 ⁴ mL / gcm. Particularly preferred.
The absorption coefficient of light having a wavelength of 254 nm in the photopolymerization initiator 1 in methanol is preferably 1.0 × 10 ⁴ to 1.0 × 10 ⁵ mL / gcm, and 1.5 × 10 ⁴ to It is more preferably 9.5 × 10 ⁴ mL / gcm, further preferably 3.0 × 10 ⁴ to 8.0 × 10 ⁴ mL / gcm.

As the photopolymerization initiator 1, an oxime compound, an α-aminoketone compound and an acylphosphine compound are preferable, an oxime compound and an acylphosphine compound are more preferable, an oxime compound is further preferable, an oxime compound containing a fluorine atom and an oxime having a benzofuran skeleton. Compounds are particularly preferred.
Specific examples of the photopolymerization initiator 1 include (C-13) and (C-15) shown in the above specific examples of the oxime compound.

The absorption coefficient of light having a wavelength of 365 nm in methanol of the photopolymerization initiator 2 is preferably 10 to 1.0 × 10 ² mL / gcm, and 20 to 1.0 × 10 ² mL / gcm. Is more preferable. Further, the absorption coefficient of light having a wavelength of 254 nm in methanol of the photopolymerization initiator 2 is preferably 1.0 × 10 ³ to 1.0 × 10 ⁶ mL / gcm, and 5.0 × 10 ³ to It is more preferably 1.0 × 10 ⁵ mL / gcm. The photopolymerization initiator 2 is preferably an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound or a phenylglyoxylate compound, more preferably an α-hydroxyketone compound or a phenylglyoxylate compound, and a hydroxyalkylphenone compound. Is more preferable. Specific examples of the photopolymerization initiator 2 include 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available products are, for example, IRGACURE-184, manufactured by BASF), 1- [4- (2-hydroxyethoxy) -phenyl. ] -2-Hydroxy-2-methyl-1-propan-1-one (commercially available products include, for example, IRGACURE-2959, manufactured by BASF).

The content of the photopolymerization initiator in the total solid content of the coloring composition is preferably 0.5 to 8.0% by mass. The lower limit is preferably 0.9% by mass or more, more preferably 1.2% by mass or more, still more preferably 1.5% by mass or more. The upper limit is preferably 7.0 mass% or less, more preferably 6.0 mass% or less, and further preferably 5.0 mass% or less. In the colored composition of the present invention, the photopolymerization initiator may be used alone or in combination of two or more. When two or more kinds are used, the total amount thereof is preferably within the above range.

<< Compound Having Epoxy Group >>
The colored composition of the present invention can contain a compound having an epoxy group (hereinafter, also referred to as an epoxy compound). Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferable. The epoxy compound preferably has 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups may be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups is preferably 2 or more. Epoxy compounds are described in paragraph numbers 0034 to 0036 of JP2013-011869A, paragraphs 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0092 of JP2014-0889408A. Compounds, compounds described in JP-A-2017-179172 can also be used. These contents are incorporated herein.

The epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 2,000, further less than 1,000), or a macromolecular compound (for example, a molecular weight of 1,000 or more, and in the case of a polymer, a weight average molecular weight of 1,000 or more). Any of The weight average molecular weight of the epoxy compound is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, still more preferably 3000 or less.

Examples of commercially available epoxy compounds include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), and the like.

The content of the epoxy compound in the total solid content of the coloring composition is preferably 0.1 to 20% by mass. The lower limit is, for example, preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, preferably 15% by mass or less, and more preferably 10% by mass or less. The epoxy compound contained in the coloring composition may be only one kind or two or more kinds. When two or more kinds are used, the total amount thereof is preferably within the above range.

<< silane coupling agent >>
The coloring composition of the present invention may contain a silane coupling agent. According to this aspect, the adhesion of the obtained film to the support can be further improved. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and a functional group other than that. Further, the hydrolyzable group means a substituent which is directly bonded to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl group, (meth) allyl group, (meth) acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group, and isocyanate group. , A phenyl group and the like, and an amino group, a (meth) acryloyl group and an epoxy group are preferable. Specific examples of the silane coupling agent include the compounds described in JP-A 2009-288703, paragraphs 0018 to 0036, and the compounds described in JP-A 2009-242604, paragraphs 0056 to 0066. Are incorporated herein by reference.

The content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.1 to 5% by mass. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The silane coupling agent may be only one kind or two or more kinds. When two or more kinds are used, the total amount is preferably within the above range.

<< organic solvent >>
The coloring composition of the present invention contains an organic solvent. The organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents and the like. For details of these, reference can be made to paragraph No. 0223 of WO 2015/166779, the content of which is incorporated herein. Further, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, and 2 -Heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N , N-dimethylpropanamide and the like. However, it may be better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as the organic solvent due to environmental reasons (for example, 50 mass ppm (parts relative to the total amount of the organic solvent). per million) or less, 10 mass ppm or less, or 1 mass ppm or less).

In the present invention, it is preferable to use an organic solvent having a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent having a mass ppt (parts per trilion) level may be used, and such an organic solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015). Examples of methods for removing impurities such as metals from the organic solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The content of the organic solvent in the coloring composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and further preferably 30 to 90% by mass.

<< Curing accelerator >>
A curing accelerator may be added to the colored composition of the present invention for the purpose of promoting the reaction of the polymerizable compound or lowering the curing temperature. The curing accelerator is a methylol compound (for example, a compound exemplified as a cross-linking agent in paragraph No. 0246 of JP-A-2005-034963), amines, phosphonium salts, amidine salts, amide compounds (above, for example, JP-A- Curing agent described in paragraph No. 0186 of 2013-041165, base generator (for example, ionic compound described in JP-A-2014-055114), cyanate compound (for example, JP-A-2012-150180) Paragraph No. 0071), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in JP 2011-253054 A), an onium salt compound (for example, Paragraph Nos. JP 2005-034963 A). Compounds exemplified as acid generators in 0216 , Compounds described in JP-A-2009-180949) or the like can be used.

When the coloring composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9% by mass based on the total solid content of the coloring composition, and 0.8 to 6.4. Mass% is more preferable.

<< polymerization inhibitor >>
The coloring composition of the present invention may contain a polymerization inhibitor. As the polymerization inhibitor, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, cerous salt, etc.) can be mentioned. Of these, p-methoxyphenol is preferable. The content of the polymerization inhibitor in the total solid content of the coloring composition is preferably 0.0001 to 5% by mass.

<< Surfactant >>
The coloring composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used. Regarding the surfactant, paragraph numbers 0238 to 0245 of WO 2015/166779 can be referred to, and the contents thereof are incorporated herein.

In the present invention, the surfactant is preferably a fluorinated surfactant. By including a fluorine-based surfactant in the coloring composition, liquid characteristics (particularly fluidity) can be further improved, and liquid saving can be further improved. It is also possible to form a film having a small thickness unevenness.

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

Examples of the fluorinated surfactant include surfactants described in paragraphs 0060 to 0064 of JP-A-04041318 (corresponding paragraphs 0060 to 0064 of WO 2014/017669) and JP-A-2011-2011. Examples thereof include the surfactants described in paragraph Nos. 0117 to 0132 of Japanese Patent No. 132503, the contents of which are incorporated herein. Examples of commercially available fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS. -330 (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, Examples include SC-1068, SC-381, SC-383, S-393, KH-40 (above Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above OMNOVA). .

Further, as the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Regarding such a fluorine-based surfactant, the description in JP-A-2016-216602 can be referred to, and the contents thereof are incorporated in the present specification.

A block polymer can also be used as the fluorine-based surfactant. For example, the compounds described in JP 2011-089090 A may be mentioned. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the ratio of repeating units is mol%.

Also, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond group in its side chain can be used. As specific examples, the compounds described in JP-A-2010-164965, paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295, such as Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation. , RS-72-K and the like. As the fluorine-based surfactant, the compounds described in paragraph Nos. 0015 to 0158 of JP-A-2005-117327 can be used.

The content of the surfactant in the total solid content of the coloring composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass. The surfactant may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.

<< UV absorber >>
The coloring composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound or the like can be used. For details of these, please refer to paragraphs 0052 to 0072 of JP2012-208374A, paragraphs 0317 to 0334 of JP2013-068814A, and paragraphs 0061 to 0080 of JP2016-162946A. Reference may be made to these contents, which are incorporated herein. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.). Examples of the benzotriazole compound include MYUA series manufactured by Miyoshi Oil & Fats (Chemical Industry Daily, February 1, 2016). Further, as the ultraviolet absorber, compounds described in paragraph Nos. 0049 to 0059 of Japanese Patent No. 6268967 can also be used. The content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. In the present invention, the ultraviolet absorber may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.

<< Antioxidant >>
The coloring composition of the present invention may contain an antioxidant. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferable phenol compounds include hindered phenol compounds. A compound having a substituent at the site (ortho position) adjacent to the phenolic hydroxy group is preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. The antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used.

The content of the antioxidant in the total solid content of the coloring composition is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass. As the antioxidant, only one kind may be used, or two or more kinds may be used. When two or more kinds are used, the total amount is preferably within the above range.

<< Other ingredients >>
The coloring composition of the present invention, if necessary, a sensitizer, a curing accelerator, a filler, a thermal curing accelerator, a plasticizer and other auxiliaries (for example, conductive particles, a filler, a defoaming agent, Flame retardant, leveling agent, peeling accelerator, perfume, surface tension adjusting agent, chain transfer agent, etc.) may be contained. Properties such as film physical properties can be adjusted by appropriately incorporating these components. These components are described, for example, in paragraph No. 0183 or later (corresponding U.S. Patent Application Publication No. 2013/0034812, paragraph No. 0237) of JP 2012-003225 A, or paragraphs of JP 2008-250074 A. References such as numbers 0101 to 0104 and 0107 to 0109 can be referred to, and the contents thereof are incorporated in this specification. Moreover, the coloring composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site functioning as an antioxidant is protected by a protecting group, and the compound is heated at 100 to 250 ° C or heated at 80 to 200 ° C in the presence of an acid / base catalyst. As a result, compounds in which the protecting group is eliminated to function as an antioxidant can be mentioned. Examples of the latent antioxidant include the compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Examples of commercially available products include ADEKA ARCRUZ GPA-5001 (manufactured by ADEKA). Further, the coloring composition of the present invention may contain a light resistance improver.

The water content of the coloring composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

The viscosity of the colored composition of the present invention can be adjusted for the purpose of adjusting the film surface condition (flatness, etc.) and adjusting the film thickness. The value of the viscosity can be appropriately selected as necessary, but for example, at 25 ° C., 0.3 mPa · s to 50 mPa · s is preferable, and 0.5 mPa · s to 20 mPa · s is more preferable. As a method for measuring the viscosity, for example, a Toki Sangyo viscometer RE85L (rotor: 1 ° 34 ′ × R24, measuring range: 0.6 to 1200 mPa · s) is used, and the temperature is adjusted to 25 ° C. Can be measured.

The coloring composition of the present invention can be preferably used as a coloring composition for forming colored pixels in a color filter. Examples of the colored pixel include a green pixel and a blue pixel, which can be more preferably used as a coloring composition for forming a green pixel or a blue pixel, and are more preferably used as a coloring composition for forming a green pixel. it can.

When the colored composition of the present invention is used as a color filter for a liquid crystal display device, the voltage holding ratio of the liquid crystal display device provided with the color filter is preferably 70% or more, more preferably 90% or more. . Known means for obtaining a high voltage holding ratio can be incorporated as appropriate, and typical means include the use of highly pure materials (for example, reduction of ionic impurities) and the control of the amount of acidic functional groups in the composition. Is mentioned. The voltage holding ratio can be measured by, for example, the method described in paragraph 0243 of JP 2011-008004 A, paragraphs 0123 to 0129 of JP 2012-224847 A, or the like.

The container for the colored composition of the present invention is not particularly limited, and a known container can be used. In addition, as the container, for the purpose of suppressing the mixing of impurities into the raw materials and the composition, a multi-layer bottle in which the inner wall of the container is composed of 6 types of 6 layers of resin or a bottle of 6 types of resin having 7 layers structure is used. It is also preferable to use. As such a container, for example, the container described in JP-A-2015-123351 can be mentioned. Further, the coloring composition of the present invention and the composition used for producing the image sensor are contained for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the composition, and suppressing the component deterioration. It is also preferable that the inner wall of the container is made of glass or stainless steel.

<Method for preparing coloring composition>
The coloring composition of the present invention can be prepared by mixing the above components. In the preparation of the coloring composition, all the components may be dissolved and / or dispersed in an organic solvent at the same time to prepare the coloring composition. If necessary, each component may be appropriately used in two or more solutions or dispersions. Alternatively, the coloring composition may be prepared by mixing these at the time of use (at the time of application).

Also, it is preferable to include a process of dispersing the pigment in the preparation of the coloring composition. In the process of dispersing the pigment, the mechanical force used to disperse the pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high speed impeller, a sand grinder, a flow jet mixer, a high pressure wet atomization, and an ultrasonic dispersion. Further, in the pulverization of the pigment in the sand mill (bead mill), it is preferable to use the beads having a small diameter, and to increase the filling rate of the beads to perform the treatment under the condition that the pulverization efficiency is increased. Further, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. In addition, the process and disperser for dispersing the pigments are described in "Dispersion Technology Taizen, Information Technology Co., Ltd., July 15, 2005" and "Dispersion technology centering on suspension (solid / liquid dispersion system) and industrial application. In fact, the process and disperser described in Paragraph No. 0022 of JP-A-2015-157893, "Comprehensive reference materials, published by the Management Development Center Publishing Department, October 10, 1978" can be suitably used. Further, in the process of dispersing the pigment, the particles may be refined in the salt milling step. The materials, equipment, processing conditions, etc. used in the salt milling process can be referred to, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629.

When preparing the colored composition, it is preferable to filter the colored composition with a filter for the purpose of removing foreign matters and reducing defects. The filter can be used without particular limitation as long as it is a filter that has been conventionally used for filtration and the like. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight). (Including the polyolefin resin), and the like. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, still more preferably 0.05 to 0.5 μm. If the pore size of the filter is within the above range, fine foreign matter can be removed more reliably. Regarding the pore size value of the filter, the nominal value of the filter manufacturer can be referred to. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used.

Also, it is preferable to use a fibrous filter medium as the filter. Examples of the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Examples of commercially available products include SBP type series (SBP008 etc.), TPR type series (TPR002, TPR005 etc.) and SHPX type series (SHPX003 etc.) manufactured by Loki Techno.

When using filters, different filters (eg, first filter and second filter) may be combined. At that time, the filtration with each filter may be performed only once, or may be performed twice or more. Further, filters having different pore sizes within the above range may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after the other components are mixed, the filtration with the second filter may be performed.

<Membrane>
The film of the present invention is a film obtained from the coloring composition of the present invention described above. The film of the present invention can be preferably used as a colored pixel of a color filter. Examples of the colored pixel include a green pixel and a blue pixel, and a green pixel is more preferable. The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention has the above-mentioned film of the present invention. More preferably, the pixel of the color filter has the film of the present invention. The color filter of the present invention can be used for a solid-state imaging device such as CCD (charge coupled device) or CMOS (complementary metal oxide semiconductor), an image display device, or the like.

In the color filter of the present invention, the film thickness of the film of the present invention can be appropriately adjusted according to the purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.3 μm or more.

The pixel width of the color filter of the present invention is preferably 0.5 to 20.0 μm. The lower limit is preferably 1.0 μm or more, and more preferably 2.0 μm or more. The upper limit is preferably 15.0 μm or less, more preferably 10.0 μm or less. The Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.

Each pixel included in the color filter of the present invention preferably has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and further preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example. The surface roughness of a pixel can be measured using, for example, AFM (atomic force microscope) Dimension 3100 manufactured by Veeco. The contact angle of water on the pixel can be set to a suitable value as appropriate, but is typically in the range of 50 to 110 °. The contact angle can be measured using, for example, a contact angle meter CV-DT • A type (manufactured by Kyowa Interface Science Co., Ltd.). Further, it is preferable that the volume resistance value of the pixel is high. Specifically, the volume resistance value of the pixel is preferably 10 ⁹ Ω · cm or more, and more preferably 10 ¹¹ Ω · cm or more. The upper limit is not specified, but it is preferably 10 ¹⁴ Ω · cm or less, for example. The volume resistance value of the pixel can be measured using, for example, an ultra-high resistance meter 5410 (manufactured by Advantest).

In addition, the color filter of the present invention may be provided with a protective layer on the surface of the film of the present invention. Providing the protective layer can impart various functions such as oxygen blocking, low reflection, hydrophilicity / hydrophobicity, and blocking of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.). The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Examples of the method of forming the protective layer include a method of applying a resin composition dissolved in an organic solvent to form the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. As a component constituting the protective layer, (meth) acrylic resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide Resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine resins, polycarbonate resins, polyacrylonitrile resins, cellulose _{_{resins, Si, C, W, Al}} 2 O 3, Mo, etc. SiO 2, _Si 2 _{N 4,} and the like, two kinds of these components It may contain above. For example, in the case of a protective layer for the purpose of blocking oxygen, it is preferable that the protective layer contains a polyol resin, SiO ₂ , and Si ₂ N ₄ . Further, in the case of the protective layer aiming at low reflection, the protective layer preferably contains a (meth) acrylic resin or a fluororesin.

When the resin composition is applied to form the protective layer, known methods such as a spin coating method, a casting method, a screen printing method, and an inkjet method can be used as a method for applying the resin composition. As the organic solvent contained in the resin composition, a known organic solvent (eg, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used. When the protective layer is formed by the chemical vapor deposition method, known chemical vapor deposition methods (thermochemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method) are known as the chemical vapor deposition method. Can be used.

The protective layer is an additive such as organic / inorganic fine particles, an absorber of light of a specific wavelength (for example, ultraviolet rays, near infrared rays, etc.), a refractive index adjusting agent, an antioxidant, an adhesive agent, a surfactant, etc., if necessary. May be included. Examples of organic / inorganic particles include polymer particles (eg, silicone resin particles, polystyrene particles, melamine resin particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride. , Magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate and the like. A known absorber can be used as the absorber having a specific wavelength. Examples of the ultraviolet absorber and the near infrared absorber include the materials described above. The content of these additives can be adjusted appropriately, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total weight of the protective layer.

As the protective layer, the protective layer described in paragraph Nos. 0073 to 0092 of JP-A-2017-151176 may be used.

The color filter may have a structure in which each colored pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. In this case, the partition wall preferably has a lower refractive index than each colored pixel. Further, the partition wall may be formed with the configuration described in US2018 / 0040656.

<Method of manufacturing color filter>
Next, a method for manufacturing the color filter of the present invention will be described. The color filter of the present invention comprises a step of forming a coloring composition layer on a support using the coloring composition of the present invention described above, and a step of forming a pattern on the coloring composition layer by a photolithography method, Can be manufactured through.

Pattern formation by a photolithography method includes a step of forming a colored composition layer on a support using the colored composition of the present invention, a step of exposing the colored composition layer to a pattern, and a step of forming the colored composition layer. And a step of developing and removing the exposed portion to form a pattern (pixel). If necessary, a step of baking the colored composition layer (pre-bake step) and a step of baking the developed pattern (pixel) may be provided (post-bake step).

In the step of forming a coloring composition layer, the coloring composition layer of the present invention is used to form a coloring composition layer on a support. The support is not particularly limited and can be appropriately selected depending on the application. For example, a glass substrate, a silicon substrate, etc. are mentioned, and a silicon substrate is preferable. Further, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film and the like may be formed on the silicon substrate. In addition, a black matrix that isolates each pixel may be formed on the silicon substrate. Further, the silicon substrate may be provided with an undercoat layer for the purpose of improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the substrate surface.

As a method for applying the coloring composition, a known method can be used. For example, a dropping method (drop casting); a slit coating method; a spraying method; a roll coating method; a spin coating method (spin coating); a cast coating method; a slit and spin method; a pre-wet method (for example, JP 2009-145395A). Methods described in the publication); inkjet (for example, on-demand method, piezo method, thermal method), ejection-type printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Examples include various printing methods; transfer methods using molds and the like; nanoimprint methods and the like. The method for applying the inkjet method is not particularly limited, and for example, the method described in “Expanding and Usable Inkjet-Infinite Possibilities Seen in Patents”, issued by Sumi Betechno Research, February 2005 (especially from page 115) (See page 133), Japanese Patent Application Laid-Open No. 2003-262716, Japanese Patent Application Laid-Open No. 2003-185831, Japanese Patent Application Laid-Open No. 2003-261827, Japanese Patent Application Laid-Open No. 2012-126830, Japanese Patent Application Laid-Open No. 2006-169325, and the like. Can be mentioned. Regarding the method for applying the coloring composition, the descriptions in International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and the contents thereof are incorporated in the present specification.

The colored composition layer formed on the support may be dried (prebaked). If the film is produced by a low temperature process, prebaking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150 ° C or lower, more preferably 120 ° C or lower, and further preferably 110 ° C or lower. The lower limit may be, for example, 50 ° C. or higher, and may be 80 ° C. or higher. The prebake time is preferably 10 to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 2200 seconds. Prebaking can be performed with a hot plate, an oven, or the like.

Next, the colored composition layer is exposed in a pattern (exposure step). For example, the colored composition layer can be exposed in a pattern by using a stepper exposure device, a scanner exposure device, or the like through a mask having a predetermined mask pattern. Thereby, the exposed portion can be cured.

Radiation (light) that can be used at the time of exposure includes g rays, i rays, and the like. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of light having a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm) are preferable. Also, a long-wavelength light source of 300 nm or more can be used.

Irradiation dose (exposure dose), for example, preferably 0.03 ~ 2.5J / cm ^2, more preferably 0.05 ~ 1.0J / cm ^2. The oxygen concentration at the time of exposure can be appropriately selected. In addition to performing in the air, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially The exposure may be carried out under oxygen-free conditions or under a high oxygen atmosphere in which the oxygen concentration exceeds 21% by volume (for example, 22% by volume, 30% by volume or 50% by volume). The exposure intensity is can be set appropriately, usually ^{^{1000W / m 2 ~ 100000W / m}} 2 ( ^{e.g., 5000W / m 2, 15000W /} m 2, or, 35000W / ^{m 2)} selected from the range of You can Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / ^{m 2} at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / ^{m 2.}

Next, the unexposed portion of the colored composition layer is developed and removed to form a pattern (pixel). The development removal of the unexposed part of the coloring composition layer can be performed using a developing solution. As a result, the unexposed portion of the colored composition layer in the exposure step is eluted into the developing solution, and only the photocured portion remains. As the developing solution, an organic alkaline developing solution that does not damage the underlying device or circuit is desirable. The temperature of the developer is preferably 20 to 30 ° C., for example. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the process of shaking off the developing solution every 60 seconds and further supplying a new developing solution may be repeated several times.

The developer is preferably an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water. Examples of the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide. Organic compounds such as, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene Alkaline compounds, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate Um, and inorganic alkaline compound such as sodium metasilicate. As the alkaline agent, a compound having a large molecular weight is preferable in terms of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Further, the developing solution may further contain a surfactant. Examples of the surfactant include the above-mentioned surfactants, and nonionic surfactants are preferable. The developer may be produced once as a concentrated solution and diluted to a required concentration at the time of use, from the viewpoint of convenience of transportation and storage. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times. Further, it is also preferable to wash (rinse) with pure water after the development. In addition, the rinsing is preferably performed by supplying a rinse liquid to the colored composition layer after development while rotating the support on which the colored composition layer after development is formed. It is also preferable that the nozzle for discharging the rinse liquid is moved from the central portion of the support to the peripheral portion of the support. At this time, when moving from the central portion of the support body of the nozzle to the peripheral edge portion, the movement speed of the nozzle may be gradually reduced. By performing the rinse in this manner, it is possible to suppress the in-plane variation of the rinse. Further, the same effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center of the support to the peripheral portion.

After development, it is preferable to carry out additional exposure processing and heat processing (post-baking) after drying. The additional exposure process and the post-baking are curing processes after development to complete the curing. The heating temperature in the post-baking is preferably 100 to 240 ° C, more preferably 200 to 240 ° C. Post-baking can be performed in a continuous or batch manner by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so that the film after development can meet the above conditions. . When the additional exposure process is performed, the light used for the exposure is preferably light having a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in KR1020170122130A.

<Solid-state image sensor>
The solid-state image sensor of the present invention has the above-mentioned film of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it includes the film of the present invention and functions as a solid-state imaging device, but examples thereof include the following configurations.

On the substrate, there are provided a plurality of photodiodes forming a light receiving area of a solid-state image pickup device (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and transfer electrodes made of polysilicon or the like. A device protection film made of silicon nitride or the like, which has a light-shielding film that is opened only on the photodiode and the light-receiving portion of the photodiode on the transfer electrode and covers the entire light-shielding film and the photodiode light-receiving portion on the light-shielding film. And has a color filter on the device protective film. Further, a structure having a condensing unit (for example, a microlens, etc., below) on the device protective film and below the color filter (the side close to the substrate), or a structure having a condensing unit on the color filter, etc. It may be. Further, the color filter may have a structure in which each colored pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the partition wall preferably has a low refractive index for each colored pixel. Examples of the imaging device having such a structure include the devices described in JP2012-227478A, JP2014-179577A, and International Publication No. 2018/043654. The image pickup apparatus provided with the solid-state image pickup element of the present invention can be used not only for digital cameras and electronic devices (such as mobile phones) having an image pickup function, but also for vehicle-mounted cameras and surveillance cameras.

<Image display device>
The image display device of the present invention has the above-mentioned film of the present invention. Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device. For the definition of the image display device and the details of each image display device, see, for example, "Electronic Display Device (Akio Sasaki, Industrial Research Institute, 1990)", "Display Device (Junsho Ibuki, Industrial Books ( (Published in 1989) ”etc. Further, the liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Institute Co., Ltd., published in 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, liquid crystal display devices of various systems described in the above-mentioned “next-generation liquid crystal display technology”.

The present invention will be described more specifically with reference to the following examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Further, in the structural formulas described in the following examples, Me represents a methyl group.

<Measurement of weight average molecular weight (Mw)>
The weight average molecular weight (Mw) of the measurement sample was measured by gel permeation chromatography (GPC) according to the following conditions.
Column type: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 are connected to each other. Developing solvent: Tetrahydrofuran Column temperature: 40 ° C
Flow rate (sample injection amount): 1.0 μL (sample concentration 0.1% by mass)
Device name: Tosoh Corp. HLC-8220GPC
Detector: RI (refractive index) detector Calibration curve Base resin: Polystyrene resin

<Method of measuring acid value>
The measurement sample was dissolved in a mixed solvent of tetrahydrofuran / water = 9/1 (mass ratio), and the obtained solution was used at 25 ° C. using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Manufacturing Co., Ltd.). Neutralization titration with a 0.1 mol / L sodium hydroxide aqueous solution. Using the inflection point of the titration pH curve as the titration end point, the acid value was calculated by the following formula.
A = 56.11 × Vs × 0.5 × f / w
A: Acid value (mgKOH / g)
Vs: Amount of 0.1 mol / L sodium hydroxide aqueous solution used for titration (mL)
f: titer of 0.1 mol / L sodium hydroxide aqueous solution w: measured sample mass (g) (solid content conversion)

<Preparation of dispersion>
After mixing the raw materials described in the table below, and mixing and dispersing for 3 hours using a bead mill (zirconia beads 0.1 mm diameter), a high pressure disperser with a pressure reducing mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) ) Was used to perform a dispersion treatment under a pressure of 2000 kg / cm ³ and a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a dispersion liquid. In addition, in the following table, the numerical value described in the column of the mass part of the dispersant is a value in terms of solid content. Moreover, the numerical value described in the column of the mass part of the solvent is a value including the amount of the solvent contained in the dispersant.

The raw materials described in the above table are as follows.
(Colorant)
Colorant A1: C.I. I. Pigment Green 62 (aluminum phthalocyanine compound, a compound represented by the formula (1))
Colorants A2 to A4: Compounds of the following structures Colorant A5: C.I. I. Pigment Green 63 (aluminum phthalocyanine compound, which is a compound represented by the formula (1))

Colorant B1: C.I. I. Pigment Yellow 138
Colorant B2: C.I. I. Pigment Yellow 139
Colorant B3: C.I. I. Pigment Yellow 150
Colorant B4: C.I. I. Pigment Yellow 231
Colorants B5 to B7: compounds having the following structures

Colorant C1: C.I. I. Pigment Red 254

(Pigment derivative)
Derivative N1: compound having the following structure

(Dispersant)
Dispersant D1: Dispersant (phosphate ester) produced by the following method
A reaction vessel equipped with an air inlet tube, a condenser, and a stirrer was charged with 300 g of 2-hydroxyethyl methacrylate, 1315 g of ε-caprolactone monomer, 0.33 g of methylhydroquinone, and 0.01 g of monobutyltin oxide, and heated to 120 ° C while flowing dry air. The temperature was raised and maintained for 2 hours. After confirming the disappearance of the caprolactone monomer, the mixture was cooled to 40 ° C. or lower, 111 g of polyphosphoric acid having an orthophosphoric acid content of 118% was mixed, gradually heated, and heated at 80 ° C. for 6 hours while stirring, A phosphoric acid ester (dispersant D1) having a number average molecular weight of Rp ⁴ of the following formula of 700 and an abundance ratio of y = 1 and y = 2 of 100: 12 was obtained. The acid value of the obtained phosphoric acid ester was 100 mgKOH / g.

Dispersant D2: Dispersant produced by the following method In a reaction vessel equipped with a gas introduction tube, thermometer, condenser, and stirrer, 108 parts by mass of 1-thioglycerol, 174 parts by mass of pyromellitic dianhydride, propylene glycol monomethyl. 650 parts by mass of ether acetate (PGMEA) and 0.2 parts by mass of monobutyltin oxide as a catalyst were charged, and after substituting with nitrogen gas, they were reacted at 120 ° C. for 5 hours (first step). It was confirmed by measuring the acid value that 95% or more of the acid anhydride was half-esterified. Next, 160 parts by mass of the compound obtained in the first step in terms of solid content, 200 parts by mass of 2-hydroxypropyl methacrylate, 200 parts by mass of ethyl acrylate, 150 parts by mass of t-butyl acrylate, 200 parts by mass of 2-methoxyethyl acrylate. Parts, 200 parts by weight of methyl acrylate, 50 parts by weight of methacrylic acid, 663 parts by weight of PGMEA, and heated to 80 ° C. in a reaction vessel to obtain 1.2 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile). Parts were added and reacted for 12 hours (second step). Solid content measurement confirmed that 95% had reacted. Finally, 500 parts by mass of a 50% PGMEA solution of the compound obtained in the second step, 27.0 parts by mass of 2-methacryloyloxyethyl isocyanate (MOI) and 0.1 part by mass of hydroquinone were charged, and 2270 cm based on the isocyanate group was charged. ^The reaction was performed until the disappearance of the ^-1 peak was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled, PGMEA was added to adjust the solid content concentration to 50 mass%, the acid value was 68 mgKOH / g, the C = C value was 0.62 mmol / g, and the weight average molecular weight (Mw). A resin solution (dispersant D2) of 13,000 resins was obtained.
Dispersant D3: Resin having the following structure (the numerical value attached to the main chain is the molar ratio of repeating units, and the numerical value attached to the side chain is the number of repeating units. Mw: 20000, acid value: 70 mgKOH / g, C = C value: 0.4 mmol / g)

Dispersant D4: Resin having the following structure (the numerical value attached to the main chain is the molar ratio of repeating units, the numerical value attached to the side chain is the number of repeating units, Mw: 20000, acid value: 75 mgKOH / g)

(solvent)
Solvent J1: Propylene glycol monomethyl ether acetate (PGMEA)
Solvent J2: Cyclohexanone Solvent J3: Cyclohexyl acetate

<Preparation of coloring composition>
The raw materials shown in the following table are mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare G compositions 1 to 25, P compositions 1, 2 and R compositions. No. 1 coloring composition was prepared. The R composition 1 is a coloring composition for reliability evaluation.

The raw materials listed in the above table are as follows.

(Dispersion liquid)
Dispersions K1 to K9, L1 to L8, M1: Dispersions K1 to K9, L1 to L8, M1 described above

(resin)
Resin E1: Resin having the following structure (the numbers attached to the main chain are the molar ratios of repeating units, and the numbers attached to the side chains are the number of repeating units, Mw: 10000).

Resin E2: Resin having the following structure (the numbers attached to the main chain are molar ratios of repeating units, Mw: 14000, acid value: 78 mgKOH / g)

Resin E3: 50 parts by mass of methyl methacrylate, 50 parts by mass of n-butyl methacrylate, and 45.4 parts by mass of PGMEA (propylene glycol monomethyl ether acetate) were charged into a reaction vessel, and the atmosphere gas was replaced with nitrogen gas. The inside of the reaction vessel is heated to 70 ° C., 6 parts by mass of 3-mercapto-1,2-propanediol is added, 0.12 parts by mass of AIBN (azobisisobutyronitrile) is further added, and the reaction is performed for 12 hours. Let Solid content measurement confirmed that 95% had reacted. Next, 9.7 parts by mass of pyromellitic dianhydride, 70.3 parts by mass of PGMEA, and 0.20 parts by mass of DBU (1,8-diazabicyclo- [5.4.0] -7-undecene) as a catalyst were added. And reacted at 120 ° C. for 7 hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated to obtain a resin having the following structure. The obtained resin had an acid value of 43 mgKOH / g and a weight average molecular weight (Mw) of 9000.

Resin E4: Resin having the following structure (the numbers attached to the main chain are molar ratios of repeating units, Mw: 30,000, acid value: 110 mgKOH / g)

Resin E5: Resin having the following structure (numerals attached to the main chain are molar ratios of repeating units, Mw: 11,000, acid value: 30 mgKOH / g)

(Polymerizable monomer)
Polymerizable monomer F1: a mixture of compounds having the following structures (containing 30 to 40 mol% of the right side compound)

Polymerizable monomer F2: compound having the following structure

Polymerizable monomer F3: succinic acid-modified dipentaerythritol pentaacrylate

(Photopolymerization initiator)
Initiators G1 to G3: compounds having the following structures

Initiator G4: IRGACURE OXE01 (manufactured by BASF)

(Surfactant)
Surfactant H1: BYK-379 (manufactured by BYK Chemie)

(Polymerization inhibitor)
Polymerization inhibitor I1: p-methoxyphenol

(solvent)
Solvent J1: Propylene glycol monomethyl ether acetate Solvent J2: Cyclohexanone Solvent J3: Cyclohexyl acetate

<Evaluation of color unevenness>
CT-4000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied on a glass substrate by spin coating to a film thickness of 0.1 μm, and heated at 220 ° C. for 1 hour using a hot plate. The formation was formed. Each colored composition (G composition or P composition) was applied onto this glass substrate with an underlayer by a spin coating method, and then heated at 100 ° C. for 2 minutes using a hot plate to a thickness of 0. A composition layer of 5 μm was obtained.
This composition layer was irradiated with light having a wavelength of 365 nm and exposed at an exposure amount of 500 mJ / cm ² . Then, post baking was performed at 220 ° C. for 300 seconds using a hot plate to form a film. Using a glass substrate (evaluation substrate) on which this film was formed, the luminance distribution was analyzed by the following method, and color unevenness was evaluated based on the number of pixels whose deviation from the average was ± 10% or more.
A method of measuring the brightness distribution will be described. An evaluation substrate is installed between the observation lens and the light source of the optical microscope to irradiate the observation lens with light, and the transmitted light state is measured with an optical microscope MX-50 (manufactured by Olympus). And observed. The film surface was photographed for five arbitrarily selected regions. The brightness of the photographed image was digitized and stored as a density distribution of 256 gradations from 0 to 255. The luminance distribution was analyzed from this image, and the color unevenness was evaluated by the number of pixels whose deviation from the average exceeds ± 10%. The evaluation criteria are as follows.
5: The number of pixels whose deviation from the average exceeds ± 10% is 1000 or less.
4: The number of pixels whose deviation from the average exceeds ± 10% is more than 1000 and 3000 or less.
3: The number of pixels whose deviation from the average exceeds ± 10% exceeds 3000 and is 5000 or less.
2: The number of pixels whose deviation from the average exceeds ± 10% exceeds 5000 and is 15000 or less.
1: The number of pixels whose deviation from the average exceeds ± 10% exceeds 15,000.

<Evaluation of photolithography (adhesion)>
CT-4000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied on a silicon wafer by a spin coating method to a film thickness of 0.1 μm, and heated at 220 ° C. for 1 hour using a hot plate. The formation was formed. Each colored composition (G composition or P composition) was applied onto this silicon wafer with an underlayer by a spin coating method, and then heated at 100 ° C. for 2 minutes using a hot plate to a thickness of 0. A composition layer of 5 μm was obtained.
Using an i-line stepper exposure device (FPA-3000i5 +, manufactured by Canon Inc.) for this composition layer, a mask in which square pixels each having a side of 1.1 μm are arranged in an area of 4 mm × 3 mm on the substrate Light having a wavelength of 365 nm was irradiated through the pattern to perform exposure with an exposure amount of 500 mJ / cm ² .
The composition layer after exposure was subjected to paddle development at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide. After that, a spin shower was used to rinse with water, and then pure water was used for washing. After that, water droplets were blown off with high-pressure air to naturally dry the silicon wafer, and then post baking was performed at 220 ° C. for 300 seconds using a hot plate to form a pattern. The obtained pattern was observed using an optical microscope, and the closely attached patterns were counted in all the patterns to evaluate the photolithography property.
5: All patterns are in close contact.
4: 90% or more and less than 100% of all patterns are in close contact with each other.
3: 80% or more and less than 90% of all patterns are in close contact with each other.
2: The contact pattern is 70% or more and less than 80% of all patterns.
1: The pattern in close contact is less than 70% of all patterns.

<Reliability evaluation>
CT-4000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied onto a silicon wafer by a spin coating method so that the film thickness was 0.1 μm. Then, it heated at 100 degreeC for 2 minutes using the hot plate. Furthermore, it heated at 230 degreeC for 2 minutes using the hot plate, and formed the base layer. Each colored composition (G composition or P composition) was applied onto this silicon wafer with an underlayer by a spin coating method, and then heated at 100 ° C. for 2 minutes using a hot plate to a thickness of 0. A composition layer of 5 μm was obtained.
This composition layer was irradiated with light having a wavelength of 365 nm through an i-line stepper exposure device (FPA-3000i5 +, manufactured by Canon Inc.) through a mask having a Bayer pattern of 1.0 μm on each side. , 150 mJ / cm ² exposure amount.
The composition layer after exposure was subjected to paddle development at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide. After that, a spin shower was used to rinse with water, and then pure water was used for washing. After that, water droplets were blown off with high-pressure air to naturally dry the silicon wafer, and then post baking was performed at 220 ° C. for 300 seconds using a hot plate to form a green pixel.
Subsequently, similar processing was performed on the R composition 1, and a red pixel was formed in a void portion of the green pixel to form a structure in which the green pixel and the red pixel were adjacent to each other.
The manufactured structure was incorporated into a solid-state image sensor, and a constant temperature and constant humidity test was performed for 2000 hours in a constant temperature and constant humidity chamber at a temperature of 85 ° C. and a humidity of 85%. The above structure is taken out from the solid-state image sensor after the constant temperature and humidity test, and the cross section (20 places) of the structure is observed using a transmission electron microscope (magnification: 40,000 times) to check for the presence of voids (voids) between pixels. Observation was performed to check the occurrence rate of voids (voids) between pixels, and the reliability was judged according to the following criteria.
The occurrence rate of voids (voids) was calculated by the following formula for each combination of pixels in contact with each other.
Occurrence rate of voids (gap) = [number of boundaries with voids (voids) among observed boundaries] / [number of boundaries observed]
In addition, in the present example, by selecting 20 cross sections at random from the structure and observing the presence or absence of voids (voids) in 10 boundary groups arranged in succession for each cross section, 200 boundaries were observed.
5: Occurrence rate of voids (voids) = 0
4: 0 <Void (Void) Occurrence Rate ≤ 0.1
3: 0.1 <occurrence rate of voids (voids) ≤ 0.2
2: 0.2 <occurrence rate of voids (voids) ≤ 0.5
1: 0.5 <occurrence rate of voids (voids) ≤ 1.0

As shown in the above table, in the examples, the evaluation of color unevenness and photolithography (adhesion) was good. Furthermore, the evaluation of reliability was also good. On the other hand, in the comparative example, one of the color unevenness and the photolithographic property was insufficiently evaluated. The numerical value of the content of the polymerizable monomer in the above table is the value of the content of the polymerizable monomer in the total solid content of the coloring composition. The M / B ratio is the ratio of the mass M of the polymerizable monomer contained in the coloring composition to the mass B of the resin contained in the coloring composition. The mass M of the polymerizable monomer is the total mass of the polymerizable monomers F1 to F3 contained in the coloring composition. The mass B of the resin is the total mass of the dispersants D1 to D4 and the resins E1 to E5 contained in the coloring composition.

(Example 100)
The Green composition was applied onto a silicon wafer by spin coating so that the film thickness after film formation was 1.0 μm. Then, using a hot plate, it heated at 100 degreeC for 2 minutes. Then, using an i-line stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed through a mask having a dot pattern of 2 μm square with an exposure amount of 1000 mJ / cm ² . Next, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it rinsed with a spin shower and further washed with pure water. Next, the Green composition was patterned by heating at 200 ° C. for 5 minutes using a hot plate. Similarly, the Red composition and the Blue composition were sequentially patterned to form green, red, and blue coloring patterns (Bayer patterns).
The coloring composition of G composition 1 was used as the Green composition.
The Red composition and the Blue composition will be described later.
The Bayer pattern is, as disclosed in U.S. Pat. No. 3,971,065, one red element, two green elements, and one blue element. ) Element and a 2 × 2 array of color filter elements are repeated. The obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had a suitable image recognition ability.

-Red composition-
The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a Red composition.
Red pigment dispersion: 51.7 parts by mass Resin 101: 0.6 parts by mass Polymerizable compound 102: 0.6 parts by mass Photopolymerization initiator 101: 0.3 parts by mass Surfactant 101: 4.2 parts by mass PGMEA : 42.6 parts by mass

-Blue composition-
The components below were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 μm to prepare a Blue composition.
Blue pigment dispersion: 44.9 parts by mass 40% by mass PGMEA solution of resin 101: 2.1 parts by mass Polymerizable compound 101: 1.5 parts by mass Polymerizable compound 102: 0.7 parts by mass Photopolymerization initiator 101: 0.8 parts by mass Surfactant 101: 4.2 parts by mass PGMEA: 45.8 parts by mass

The raw materials used for the Red composition and the Blue composition are as follows.

Red pigment dispersion C.I. I. Pigment Red 254, 9.6 parts by mass, C.I. I. Pigment Yellow 139 (4.3 parts by mass), a dispersant (Disperbyk-161, manufactured by BYK Chemie) 6.8 parts by mass, and PGMEA (79.3 parts by mass) were mixed with a bead mill (zirconia beads 0.3 mm diameter). ), And mixed and dispersed for 3 hours. Thereafter, a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) equipped with a decompression mechanism was further used to perform dispersion treatment under a pressure of 2000 kg / cm ³ at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a Red pigment dispersion liquid.

Blue pigment dispersion C.I. I. Pigment Blue 15: 6, 9.7 parts by mass, C.I. I. Pigment Violet 23 (2.4 parts by mass), Dispersant (Disperbyk-161, manufactured by BYK Chemie) 5.5 parts by mass, PGMEA (82.4 parts by mass) was mixed with a beads mill (zirconia beads 0.3 mm diameter). And mixed and dispersed for 3 hours. Thereafter, a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) equipped with a decompression mechanism was further used to perform dispersion treatment under a pressure of 2000 kg / cm ³ at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion liquid.

Resin 101: 40% by mass PGMEA solution of resin having the following structure (numerals attached to the main chain are molar ratios, Mw = 14000)

Polymerizable compound 101: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
Polymerizable compound 102: compound having the following structure

Photopolymerization initiator 101: IRGACURE OXE02 (manufactured by BASF)
Surfactant 101: 1% by mass PGMEA solution of the following mixture (Mw = 14000). In the following formula,% indicating the proportion of repeating units is mol%.

Claims

A coloring composition comprising a colorant, a polymerizable monomer having an ethylenically unsaturated bond group, a photopolymerization initiator, and a resin,
The colorant contains at least one selected from the compound represented by the following formula (1) and the compound represented by the following formula (2),
A coloring composition containing 0.1 to 6.0% by mass of the polymerizable monomer in the total solid content of the coloring composition;

In formula (1), X 1 to X 4 each independently represent a substituent;
Z 1 represents a hydroxy group, a halogen atom, —OP (═O) R 1 R 2 , or —O—SiR 3 R 4 R 5 , and R 1 to R 5 are each independently a hydrogen atom, a hydroxy group, It represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and R 1 and R 2 , and R 3 and R 4 may combine with each other to form a ring;
m1 to m4 each independently represent an integer of 0 to 4, and when m1 to m4 are 2 or more, X 1 to X 4 may be the same or different;

In formula (2), X 5 to X 12 each independently represent a substituent;
L A represents -O-SiR 6 R 7 -O-, -O-SiR 6 R 7 -O-SiR 8 R 9 -O-, or -OP (= O) R 10 -O-, R 6 to R 10 each independently represent a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group;
m5 to m12 each independently represent an integer of 0 to 4, and when m5 to m12 are 2 or more, X 5 to X 12 may be the same or different.
The coloring composition according to claim 1, wherein the coloring agent includes at least one selected from color index pigment green 62 and color index pigment green 63.
The coloring composition according to claim 1 or 2, wherein the colorant includes at least one selected from color index pigment yellow 138, color index pigment yellow 139, color index pigment yellow 150, and color index pigment yellow 231.
The coloring composition according to any one of claims 1 to 3, wherein the coloring agent further contains a compound represented by the following formula (3):

In formula (3), Ry 1 to Ry 13 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a sulfo group, a salt of a sulfo group, a carboxyl group, a salt of a carboxyl group, or phthalimidomethyl. Represents a group or a sulfamoyl group;
Two adjacent groups of Ry 1 to Ry 4 may be bonded to each other to form a ring, and two adjacent groups of Ry 10 to Ry 13 may be bonded to each other to form a ring. Good.
5. The colorant according to claim 1, wherein a total content of the compound represented by the formula (1) and the compound represented by the formula (2) is 30% by mass or more. The coloring composition according to the item.
The coloring composition according to any one of claims 1 to 5, wherein the resin contains a resin having an ethylenically unsaturated bond group.
The coloring composition according to any one of claims 1 to 6, wherein the resin contains a resin containing a repeating unit derived from a compound represented by the following formula (I):

In the formula, Xi 1 represents O or NH,
Ri 1 represents a hydrogen atom or a methyl group,
Li 1 represents a divalent linking group,
Ri 10 represents a substituent,
m represents an integer of 0 to 2,
p represents an integer of 0 or more.
The coloring composition according to claim 7, wherein the resin containing a repeating unit derived from the compound represented by the formula (I) further contains a repeating unit derived from an alkyl (meth) acrylate.
The ratio M 1 / B 1 of the mass M 1 of the polymerizable monomer contained in the coloring composition to the mass B 1 of the resin contained in the coloring composition is 0.03 to 0.15. Item 9. The colored composition according to any one of items 1 to 8.
10. The polymerizable monomer comprises at least one selected from succinic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate. The coloring composition according to any one of items.
A film obtained from the coloring composition according to any one of claims 1 to 10.
A color filter having the film according to claim 11.
A step of forming a coloring composition layer on a support using the coloring composition according to any one of claims 1 to 10, and a step of forming a pattern on the coloring composition layer by a photolithography method. And a method for manufacturing a color filter having:
A solid-state image sensor having the film according to claim 11.
An image display device having the film according to claim 11.