WO2015122284A1

WO2015122284A1 - Colored resin composition, cured film using same, color filter and production method therefor, solid-state imaging element, and image display device

Info

Publication number: WO2015122284A1
Application number: PCT/JP2015/052489
Authority: WO
Inventors: 陽樹稲部
Original assignee: 富士フイルム株式会社
Priority date: 2014-02-14
Filing date: 2015-01-29
Publication date: 2015-08-20
Also published as: TWI565764B; KR101752269B1; JP2015151465A; TW201533178A; KR20160104651A; JP6019050B2

Abstract

Provided are: a colored resin composition capable of suppressing the formation of needle-shaped contaminants in a boundary area between green pixels and adjacent colored pixels during high-temperature heating; a cured film using same; a color filter and a production method therefor; a solid-state imaging element; and an image display device. The colored resin composition includes polyamic acid having a repeated unit indicated by general formula (1) and a C.I. pigment green 58. In the general formula (1), R¹ indicates an n + 2-valent linking group, R² indicates a divalent linking group, and n indicates 1 or 2.

Description

COLORED RESIN COMPOSITION AND CURED FILM USING THE SAME, COLOR FILTER AND METHOD FOR MANUFACTURING THE SAME

The present invention relates to a colored resin composition. In particular, the present invention relates to a colored resin composition preferably used for forming a colored layer of a color filter. Furthermore, the present invention relates to a cured film, a color filter, a solid-state imaging device, and an image display device using the colored resin composition. The present invention also relates to a method for producing a color filter using a colored resin composition.

In recent years, with the development of personal computers, particularly large-screen liquid crystal televisions, the demand for liquid crystal displays (LCD), especially color liquid crystal displays, has been increasing. The spread of organic EL displays is also awaited due to the demand for higher image quality. On the other hand, with the widespread use of digital cameras and camera-equipped mobile phones, the demand for solid-state imaging devices such as CCD image sensors has greatly increased.
Color filters are used as key devices for these displays and optical elements, and the demand for cost reduction is increasing along with the demand for higher image quality. Such a color filter is usually provided with a coloring pattern of three primary colors of red (R), green (G), and blue (B), and in a display device or an image sensor, light passing therethrough is divided into three primary colors. It plays a role to draw.

The colorant used in the color filter is commonly required to have the following characteristics.
In other words, it has optical characteristics that are favorable for color reproducibility, optical scattering such as light scattering that causes a decrease in contrast of a liquid crystal display, and unevenness in optical density that causes color unevenness and roughness of a solid-state imaging device. There is a need for it to be free, toughness under the environmental conditions used, for example, heat resistance, light resistance, moisture resistance, etc., to have a large molar extinction coefficient and to be thin. For this reason, it is common to use a pigment as a colorant.
Patent Document 1 discloses a colored resin composition for a color filter containing a pigment and a polyamic acid. Patent Document 2 discloses a polyhalogenated zinc phthalocyanine pigment composition.

Japanese Patent Laid-Open No. 2003-227921 JP 2007-284592 A

When this inventor examined, as a green pigment, C.I. I. It has been found that a color filter using Pigment Green 58 (hereinafter also referred to as “PG58”) forms needle-like foreign matters in the boundary region between the green pixel and the adjacent colored pixel when heated at a high temperature.
Patent Document 1 does not describe the use of PG58 as a pigment. With the technique described in Patent Document 2, it is difficult to suppress needle-like foreign matters.
This invention solves this subject, and it aims at providing the colored resin composition which can suppress that a needle-like foreign material is formed in the boundary area | region of the color pixel adjacent to the green pixel at the time of high temperature heating. And

As a result of investigations by the inventors of the present invention based on the above problems, it has been found that the above problems can be solved by using a colored resin composition containing PG58 and a polyamic acid having a specific structure. It came to complete.
Specifically, the above problem has been solved by the following means <1>, preferably by means <2> to <17>.
<1> A polyamic acid having a repeating unit represented by the following general formula (1) and C.I. I. A colored resin composition comprising CI Pigment Green 58;

In general formula (1), R ¹ represents an n + divalent linking group, R ² represents a divalent linking group, and n represents 1 or 2.
<2> The colored resin composition according to <1>, further including a diamine compound represented by the following general formula (2);

In general formula (2), R ³ represents a divalent linking group.
<3> The colored resin composition according to <1> or <2>, further including a yellow colorant.
<4> C.I. I. The colored resin composition according to <3>, comprising Pigment Yellow 129.
<5> The colored resin composition according to any one of <1> to <4>, wherein R ¹ in formula (1) represents an n + divalent linking group having 2 to 22 carbon atoms.
<6> The colored resin composition according to any one of <1> to <4>, wherein R ¹ in formula (1) represents an n + divalent linking group including a cyclic structure.
<7> The colored resin composition according to any one of <1> to <6>, wherein R ² represents a divalent linking group having 1 to 22 carbon atoms in the general formula (1A).
<8> In the general formula (1), R ² represents a hydrocarbon group, or a hydrocarbon group and —Si (R ^2A ) ₂ , —CO—, —NR—, —O—, —SO ₂ —, and — The colored resin composition according to any one of <1> to <6>, which represents a divalent linking group containing a group consisting of a combination with at least one selected from S-; wherein R ^2A is independently Represents an alkyl group having 1 to 6 carbon atoms, and R in —NR— represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
<9> The colored resin composition according to any one of <1> to <8>, wherein R ³ represents a divalent linking group having 1 to 22 carbon atoms in the general formula (2).
<10> The colored resin composition according to any one of <1> to <8>, wherein R ³ represents a divalent linking group including a cyclic structure in the general formula (2).
R ³ in <11> general formula (2) represents a divalent linking group containing the same skeleton and R ² in general formula (1), according to any one of <1> to <8> Colored resin composition.
<12> The colored resin composition according to any one of <1> to <11>, which is used for a solid-state imaging device.
<13> A cured film obtained by curing the colored resin composition according to any one of <1> to <12>.
<14> A color filter having a colored layer using the colored resin composition according to any one of <1> to <12>.
<15> a step of forming a colored film by applying the colored resin composition according to any one of <1> to <12> on a substrate;
Heating and curing the colored film at 150 to 350 ° C.,
Applying a photoresist on the cured colored film;
Patterning the photoresist by pattern development of the photoresist, followed by alkali development,
Using the patterned photoresist as an etching mask, patterning a colored film under the photoresist by dry etching,
Removing the photoresist after patterning;
A method for producing a color filter, comprising:
<16> A solid-state imaging device having a color filter according to <14> or a color filter obtained by the method for producing a color filter according to <15>.
<17> An image display device having the color filter according to <14> or the color filter obtained by the method for producing a color filter according to <15>.

According to the present invention, it is possible to provide a colored resin composition capable of suppressing the formation of needle-like foreign matters in the boundary region between the green pixel and the adjacent colored pixel during high-temperature heating. In addition, it has become possible to provide a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, and an image display device using the colored resin composition.

It is a schematic sectional drawing of a 1st colored layer. It is a schematic sectional drawing which shows the state in which the photoresist layer was formed on the 1st colored layer. It is a schematic sectional drawing which shows the state in which the resist pattern was formed on the 1st colored layer. It is a schematic sectional drawing which shows the state in which the 1st colored pattern was formed by providing a through-hole group in the 1st colored layer by etching. It is a schematic sectional drawing which shows the state from which the resist pattern in FIG. 4 was removed. It is a schematic sectional drawing which shows the state in which the 2nd coloring pattern and the 2nd coloring radiation sensitive layer were formed. It is a schematic sectional drawing which shows the state from which the 2nd coloring radiation sensitive layer in FIG. 6 and a part of 2nd coloring pixel which comprises a 2nd coloring pattern were removed. It is a schematic sectional drawing which shows the state in which the 3rd coloring pattern and the 3rd coloring radiation sensitive layer were formed. It is a schematic sectional drawing which shows the state from which the 3rd coloring radiation sensitive layer in FIG. 8 was removed.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition. The solid content at 25 ° C.

In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes a group (atomic group) having a substituent together with a group (atomic group) having no substituent. To do. 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 addition, “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.

In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic” ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, “monomer” and “monomer” are synonymous. A monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.

In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm ID × 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.

The colored resin composition of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) includes a polyamic acid having a repeating unit represented by the following general formula (1) and PG58. To do.

In general formula (1), R ¹ represents an n + divalent linking group, R ² represents a divalent linking group, and n represents 1 or 2.
For example, when a color filter using PG58 is heated at a high temperature in a state where pixels containing a blue pigment (for example, CI Pigment Blue 15: 6 (hereinafter also referred to as “PB15: 6”)) are adjacent to each other. , A part of PG 58 is thermally diffused to the adjacent blue pixel, a mixed crystal of the thermally diffused PG 58 and the blue pigment is formed, and needle-like foreign matters are formed in the boundary region between the blue pixel and the green pixel. all right. On the other hand, in this invention, the said subject can be solved by using the coloring resin composition containing PG58 and the polyamic acid which has a repeating unit represented by General formula (1). Moreover, solvent resistance can also be improved.
Although this mechanism is presumed, the polyamic acid contained in the colored resin composition of the present invention causes imide cyclization accompanied by a dehydration reaction in the post-baking step after the pixel pattern is formed. Since the polyamic acid contained in the colored resin composition of the present invention forms a dense film having a very high film density by the imide cyclization, PG58 can be firmly held in the polyimide film. As a result, it is possible to suppress the occurrence of acicular foreign matters during high temperature heating.

<Polyamic acid having a repeating unit represented by the general formula (1)>
In general formula (1), R ¹ is a group derived from an acid anhydride and represents an n + divalent linking group. The polyamic acid having a repeating unit represented by the general formula (1) also functions as a dispersant for dispersing PG58 in the colored resin composition. It also functions as a thermosetting agent.
R ¹ is preferably an n + divalent linking group having 2 to 22 carbon atoms. Specifically, R ¹ is n + 2 consisting of a hydrocarbon group or a combination of a hydrocarbon group and at least one of —CO—, —NR—, —O—, —SO ₂ —, and —S—. A valent linking group is preferable, and a hydrocarbon group or an n + divalent linking group composed of a combination of a hydrocarbon group and —CO— is more preferable. R ¹ may be an n + divalent linking group comprising a combination of one hydrocarbon group and —CO—, —NR—, —O—, —SO ₂ —, or —S—, N + divalent linking group comprising a combination of two or more hydrocarbon groups and two or more groups selected from —CO—, —NR—, —O—, —SO ₂ —, and —S—. May be. When R ¹ is an n + divalent linking group comprising a combination of a hydrocarbon group and at least one of —CO—, —NR—, —SO ₂ —, —O— and —S—, -, -NR-, -O-, -SO _2- , and -S- are preferably not adjacent to each other.
R in —NR— represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and preferably a hydrogen atom. The hydrocarbon group contained in the n + divalent linking group may be linear, branched or cyclic, but is preferably cyclic.
R ¹ preferably includes a cyclic structure, and preferably includes a cyclic hydrocarbon group. The cyclic structure may be an alicyclic ring or an aromatic ring, but is preferably an aromatic ring. The cyclic structure may be monocyclic or polycyclic. The cyclic structure preferably contains a 5- to 8-membered ring, and more preferably contains a 5- or 6-membered ring. Further, the cyclic structure may be monocyclic or heterocyclic. When the cyclic structure is a heterocyclic ring, examples of the hetero atom constituting the heterocyclic ring include a nitrogen atom, an oxygen atom, and a sulfur atom.
Specifically, R ¹ preferably has an alicyclic hydrocarbon group having 3 to 22 carbon atoms or an aromatic hydrocarbon group having 6 to 22 carbon atoms, and preferably has an aromatic hydrocarbon group having 6 to 22 carbon atoms. And more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms.

In general formula (1), R ² is a group derived from diamine and represents a divalent linking group. R ² is preferably a divalent linking group having 1 to 22 carbon atoms. Specifically, R ² is selected from a hydrocarbon group, or a hydrocarbon group and —Si (R ^2A ) ₂ —, —CO—, —NR—, —O—, —SO ₂ —, —S—. A divalent linking group containing a group composed of a combination with at least one kind is preferred.
R ² is a divalent linkage comprising a combination of one hydrocarbon group and —Si (R ^2A ) ₂ —, —CO—, —NR—, —O—, —SO ₂ —, or —S—. Or a group selected from two or more hydrocarbon groups and —Si (R ^2A ) ₂ —, —CO—, —NR—, —O—, —SO ₂ —, and —S—. It may be a divalent linking group comprising a combination of two or more groups.
R ^2A each independently represents an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group. R in —NR— represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The hydrocarbon group may be linear, branched or cyclic.
R ² preferably contains a cyclic structure, and preferably contains a cyclic hydrocarbon group. The cyclic structure is synonymous with the cyclic structure that R ¹ in the general formula (1) may have, and the preferred range is also the same.
R ² is more preferably a divalent linking group having an alicyclic hydrocarbon skeleton having 3 to 22 carbon atoms or an aromatic hydrocarbon skeleton having 6 to 22 carbon atoms, and an aromatic hydrocarbon skeleton having 6 to 18 carbon atoms. A divalent linking group having a phenylene group is particularly preferable.
In general formula (1), n represents 1 or 2, and 2 is preferable. By setting it to 2, the effect of the present invention is more effectively exhibited.

The polyamic acid used in the present invention preferably has a repeating unit (repeating unit A) in which R ² in the general formula (1) includes a cyclic structure. In addition, the polyamic acid used in the present invention further has a repeating unit (repeating unit B) in which R ² in the general formula (1) includes a hydrocarbon group and the partial structure of —Si (R ^2A ) ₂ — described above. You may do it. When the polyamic acid has a repeating unit including a partial structure of —Si (R ^2A ) ₂ —, the adhesion to the substrate can be further improved when a cured film is formed using the colored resin composition. it can.
When the total amount of the repeating unit represented by the general formula (1) is 100 mol%, the amount of the repeating unit B that may be contained is preferably 0.5 to 15 mol%, more preferably 1 to 10 mol%. Preferably, 3 to 7 mol% is more preferable.

The polyamic acid having a repeating unit represented by the general formula (1) can be synthesized by a known method, for example, by selectively combining an acid anhydride and a diamine and reacting them in a solvent.
As the acid anhydride, tricarboxylic acid anhydride or tetracarboxylic acid anhydride can be used, and tetracarboxylic acid anhydride is preferably used.
Tricarboxylic acid anhydrides include trimellitic acid anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, 1,2,4-naphthalene tricarboxylic acid-1,2-anhydride, 1, 3,8-naphthalenetricarboxylic acid-1,8-anhydride and the like.
Examples of tetracarboxylic acid anhydrides include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltrifluoropropanetetracarboxylic acid Anhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ″, 4,4 ″ -para-phenyltetracarboxylic Acid dianhydride, 3,3 ″, 4,4 ″ -metha-phenyltetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclo Pentanetetracarboxylic dianhydride, 1,2,3,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexene tetracarboxylic dianhydride, 1,2,4,5- Cyclohexanetetracarboxylic dianhydride, 2,3,5-tri Carboxycyclopentyl acetic acid dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3- Furanyl) -naphtho [1,2-C] furan-1,3-dione.

Examples of diamines include 4,4'-diaminodiphenyl ether, 4,4 '(or 3,3')-diaminodiphenyl sulfone, 4,4'-diaminobenzanilide, 3,3'- (or 4,4 ' ) Diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 2,5-diaminotoluene, o-tolidine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-bis (4-aminophenoxy) ) Biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] ether, 2,2-bis [4- (4-aminophenoxy) ) Phenyl] hexafluoropropane 1,3- (or 1,4) diaminocyclohexane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane 4,4'-diamino-3,3'-dimethyl dicyclohexyl, 3,3'-diaminodiphenyl ether, 3,4' like diaminodiphenyl ether and the like.

As the diamine component, a monomer constituting the above-mentioned repeating unit B (for example, (3-aminopropyl) tetramethyldisiloxane (siloxane diamine)) may be used in combination as long as the effects of the present invention are not impaired. The amount of siloxane diamine is preferably 1 to 20 mol% in the total diamine. Siloxane diamine may be used individually by 1 type, and may use 2 or more types.

Examples of the solvent that can be used for synthesizing the polyamic acid having the repeating unit represented by the general formula (1) include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and the like. These amide polar solvents and lactone polar solvents can be used in admixture. Examples of solvents other than lactones include methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol and the like in addition to the amide polar solvent. Lactones are aliphatic cyclic esters having 3 to 12 carbon atoms. Specific examples include, but are not limited to, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and the like. In particular, γ-butyrolactone is preferred from the viewpoint of solubility of polyamic acid.

The polyamic acid having the repeating unit represented by the general formula (1) may be prepared by using the acid anhydride or diamine other than the above-described acid anhydride or other amine component to adjust the molecular weight of the polyamic acid. . Examples of the other acid component and the other diamine component include a monofunctional acid and an amine component. Examples of the monofunctional acid or amine component include monocarboxylic acid, carboxylic dianhydride, monoamine and the like. Specific examples include, but are not limited to, benzoic acid, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, aniline, and the like.
The amount of the other acid component or other amine component is 0.5 to 5 based on the total number of moles of carboxylic dianhydride and diamine and other acid components and other amine components used in the synthesis of the polyamic acid. The mol% is preferable, 0.7 to 3 mol% is more preferable, and 0.9 to 2 mol% is more preferable.

The weight average molecular weight of the polyamic acid having a repeating unit represented by the general formula (1) is preferably 5000 or more, more preferably 6,000 to 100,000, and further preferably 8,000 to 50,000.
The dispersity (mass average molecular weight / number average molecular weight) of the polyamic acid having a repeating unit represented by the general formula (1) is preferably 1.1 to 4.0, more preferably 1.5 to 3.0, More preferably, it is 1.7 to 2.5.

The content of the polyamic acid having the repeating unit represented by the general formula (1) in the colored resin composition is preferably 5 to 50% by mass, and preferably 7 to 40% by mass with respect to the total solid content of the colored resin composition. % Is more preferable, and 9 to 30% by mass is further preferable.
The amount of the polyamic acid having the repeating unit represented by the general formula (1) with respect to the total mass of the resin components contained in the colored resin composition can be 90% by mass, or 95 to 100% by mass. You can also.
The colored resin composition may contain only one type of polyamic acid having a repeating unit represented by the general formula (1), or may contain two or more types. When 2 or more types are included, the total amount thereof preferably corresponds to the above content.

<PG58>
The colored resin composition contains PG58. PG58 can be synthesized, for example, by the method described in paragraphs 0084 to 0085 of JP-A-2007-284592, the contents of which are incorporated herein.
The average primary particle size of PG58 used in the present invention is practically 10 nm or more. The upper limit is preferably 1 μm or less, more preferably 500 nm or less, further preferably 200 nm or less, further preferably 100 nm or less, and particularly preferably 50 nm or less from the viewpoint of obtaining better contrast. In the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used as an index representing the monodispersity of the particles unless otherwise specified. The monodispersity of the pigment fine particles (primary particles), that is, Mv / Mn, is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and 1.0 to 1. 5 is particularly preferred. In the present invention, the average primary particle diameter of the particles is obtained by obtaining the equivalent circle diameter from an image observed with a transmission electron microscope, and taking the average value of the 500 particles.

The PG58 particles may be prepared by ordinary methods, for example, by pulverizing by milling (breakdown method) or by precipitation using a good solvent and a poor solvent (buildup method). May be. About the former (breakdown method), a pigment particle can be refined | miniaturized by a usual method using bead mill etc. For example, it is possible to refer to the description described in the section “Mechanical Disintegration” in Journal of the Imaging Society of Japan, Vol. 45, No. 5 (2006), pages 12-21. The latter (build-up method) is also referred to as a reprecipitation method and the like. For example, JP 2011-026452 A, JP 2011-012214 A, JP 2011-001501 A, JP 2010-235895 A, Reference can be made to JP 2010-2091 A, JP 2010-209160 A, and the like.

<Other colorants>
The colored resin composition may or may not contain a colorant other than PG58. Other colorants may be used alone or in combination of two or more.
The colored resin composition is used as another colorant. It may contain a yellow colorant. As the yellow colorant, a yellow pigment is preferable. I. Pigment yellow 129, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. More preferably at least one selected from CI Pigment Yellow 185; I. Pigment Yellow 129 is more preferable. By setting it as such a structure, the effect of this invention can be improved more.
The colored resin composition of the present invention includes a halogenated phthalocyanine pigment having, as a central metal, one selected from the group consisting of Al, Ti, Fe, Sn, Pb, Ga, V, Mo, Ta, and Nb, and One or more phthalocyanine pigments selected from halogenated phthalocyanine pigments having no central metal may be further included. By setting it as such a structure, while being excellent in the effect of this invention, the hardened | cured film which cannot produce other color mixing easily can be formed. The content of the phthalocyanine pigment is preferably 5% by mass or less, more preferably 0.5 to 2% by mass with respect to the content of PG58 in the colored resin composition.

As other organic pigments that can be appropriately added to the colored resin composition of the present invention, organic pigments other than the above-described PG58 and yellow pigments, inorganic pigments, dyes, and the like can be used.
Examples of other organic pigments that can be appropriately added to the colored resin composition of the present invention include:
C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,147,151,154,155,167,180,199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81,105,122,149,150,155,171,175,176,209,220,224,242,255,264,270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1;
Etc.

Examples of the inorganic pigment that can be appropriately added to the colored resin composition of the present invention include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper And metal oxides such as titanium, magnesium, chromium, zinc, and antimony, and black pigments such as composite oxides of the above metals, carbon black, and titanium black.

Known dyes that can be appropriately added to the colored resin composition of the present invention include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614. No. 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No. 5,667,920, U.S. Pat.No. 505950, U.S. Pat. The dyes disclosed in JP-A-6-51115 and JP-A-6-194828 can be used. When classified as a chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.

The content of PG58 in the colored resin composition is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and further preferably 40 to 60% by mass with respect to the total solid content of the colored resin composition.
When the colored resin composition further contains a yellow colorant, the content of the yellow colorant in the colored resin composition is preferably 10 to 100 parts by mass, preferably 20 to 85 parts with respect to PG58 (100 parts by mass). Part by mass is more preferable. Moreover, C.I. with respect to the total amount of the yellow colorant contained in the colored resin composition. I. Pigment yellow 129, C.I. I. Pigment yellow 150 and C.I. I. The amount of CI Pigment Yellow 185 is preferably 85% by mass or more, more preferably 90% by mass or more, and further preferably 95 to 100% by mass.

<Pigment derivative>
The composition of the present invention may further contain a pigment derivative. As the pigment derivative, it is preferable to use a compound having a pigment mother nucleus structure and an amino group in the molecule (hereinafter also referred to as a specific pigment derivative).
By using the specific pigment derivative, an interaction is formed between the pigment core structure in the specific pigment derivative and PG58, and the adsorptivity of both can be more effectively ensured.

The specific pigment derivative is preferably a compound represented by the following general formula (A).

In the general formula (A), R ¹ and R ² each independently represent a hydrogen atom or a monovalent organic group, preferably a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, or a saturated group having 3 to 20 carbon atoms. Or an unsaturated cycloalkyl group or an aryl group. These organic groups may further have a substituent. Further, the substituents that may have are halogen atoms, hydroxyl groups, alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, aryl groups, heterocyclic groups, cyano groups, alkoxy groups. , Aryloxy group, thioalkoxy group, thioaryloxy group, carboxyl group, alkoxycarbonyl group, sulfo group, sulfonamido group, urea group, thiourea group, amino group, amide group, carbonyl group, nitro group or these groups A substituent is mentioned.
R ¹ and R ² may be bonded to each other to form a ring.

In particular, the compound represented by the general formula (A) is preferably a compound having at least one of an amide structure and a urea structure in the molecule. Moreover, it is preferable that the compound represented by general formula (A) is a compound which has a heterocyclic structure.

In general formula (A), X is an m-valent group containing a pigment mother nucleus structure. Here, the pigment mother nucleus structure is a chromogenic group in an organic pigment, a similar structure, or a partial structure. Specifically, a skeleton having an azo group, a skeleton having a urea structure, a skeleton having an amide structure, Examples thereof include a structure containing one or more partial structures selected from a skeleton having a cyclic amide structure, an aromatic ring having a heteroatom-containing 5-membered ring, and an aromatic ring having a heteroatom-containing 6-membered ring. X is a substituent containing these pigment mother nucleus structures.
X in the general formula (A) has a pigment mother nucleus structure or a pigment mother nucleus structure and an aromatic ring, a nitrogen-containing aromatic ring, an oxygen-containing aromatic ring, or a sulfur-containing aromatic ring, and an amino group is a pigment mother structure. It is preferably bonded directly or via a linking group to any one of the core structure, aromatic ring, nitrogen-containing aromatic ring, oxygen-containing aromatic ring and sulfur-containing aromatic ring. In particular, it preferably has a pigment mother nucleus structure and an aromatic ring or a nitrogen-containing aromatic ring and is bonded to an amino group by a divalent linking group.
In the general formula (A), m is an integer of 1 to 8, preferably 1 to 6, and more preferably 1 or 2, from the viewpoint of dispersibility and storage stability of the dispersion.

Hereinafter, preferred specific examples of the pigment derivative used in the present invention are shown, but the invention is not limited thereto. Among the pigment derivatives shown below, derivatives having a benzimidazole skeleton as the pigment nucleus structure are preferable. Specifically, among the pigment derivatives shown below, pigment derivatives containing a benzimidazole skeleton represented by (1) to (12) are preferable, and those containing a benzimidazole skeleton containing (7) to (12) are preferable. Pigment derivatives are particularly preferred.

In particular, the following compounds are preferred as the pigment derivative used in the composition of the present invention.
Among the pigment derivatives shown below, a pigment derivative having a carboxylic acid group or a sulfonic acid group or a metal salt / ammonium salt thereof as a substituent is preferable. Specifically, among the pigment derivatives shown below, the pigment derivatives represented by (A) to (I) are preferably used, and the pigment derivatives represented by (A), (B), and (I) are preferably used. Particularly preferred.

The content of the pigment derivative is preferably 0.5 to 50 parts by mass, more preferably 1 to 25 parts by mass, and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the total pigment including PG58 in the colored resin composition. Further preferred.
Only 1 type of pigment derivative may be contained in the colored resin composition, and may be contained 2 or more types. When two or more types are included, the total amount is preferably within the above range.

<Diamine compound represented by the general formula (2)>
It is preferable that the composition of this invention further contains the diamine compound represented by General formula (2).

In general formula (2), R ³ represents a divalent linking group.

By setting it as the said structure, the effect of this invention can be achieved more effectively. Although this mechanism is presumed, generally, when a coating film containing polyamic acid is heated at a high temperature, the polyamic acid undergoes imide cyclization accompanied by a dehydration reaction by the reaction mechanism represented by the following formula (a), and the coating film is cured. . In this case, if the amine compound is contained in the coating film, the amine compound (R ³ —NH ₂ in the following formula (b)) acts as a base catalyst by the reaction mechanism shown in the following formula (b), and the imide Curing of the coating film by cyclization is promoted. Thus, since hardening of a coating film is accelerated | stimulated, since PG58 is hold | maintained more firmly in a polyimide film, generation | occurrence | production of the acicular foreign material at the time of high temperature heating of the color filter obtained can be suppressed.

In general formula (2), R ³ is a group derived from diamine and represents a divalent linking group. R ³ is preferably a divalent linking group having 1 to 22 carbon atoms. Specifically, R ³ is preferably a hydrocarbon group or a divalent linking group containing a group composed of a combination of a hydrocarbon group and —CO—, —NR—, and —O—. R in —NR— represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The hydrocarbon group may be linear, branched or cyclic.
R ³ preferably includes a cyclic structure, and preferably includes a cyclic hydrocarbon group. The cyclic structure is synonymous with the cyclic structure that R ² in the general formula (1) may have. Further, preferred ranges of R ³ is the same as R ² of the above-mentioned general formula (1).
In addition, R ³ in the general formula (2) is preferably a divalent linking group containing the same skeleton as R ² in the general formula (1). As R ³ in the general formula (2), a diamine compound having a divalent linking group containing the same skeleton as R ² in the general formula (1) is a polyamic acid represented by the general formula (1). Since it is excellent in compatibility, it becomes more effective as a catalyst for the thermosetting reaction of the polyamic acid represented by the general formula (1), and the effects of the present invention can be achieved more effectively.
Here, the same skeleton as R ² means that at least a part of atoms constituting the divalent linking group is common. For example, when R ² is a phenylene group, R ³ may be a phenylene group, a phenylene group may be substituted, or a group consisting of a combination of a phenylene group and —O—. Good. In particular, R ³ preferably has the same partial structure as R ² in general formula (1), and more preferably has the same structure as R ² in general formula (1).
Specific examples of the diamine compound represented by the general formula (2) include diamines that can be used when synthesizing the polyamic acid described above.

The content of the diamine compound represented by the general formula (2) in the colored resin composition is preferably 0.01 to 10% by mass, and preferably 0.1 to 2% by mass with respect to the total solid content of the colored resin composition. % Is more preferable, 0.3 to 0.8% by mass is further preferable, and 0.4 to 0.7% by mass is particularly preferable.
The diamine compound represented by the general formula (2) may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the total amount corresponds to the said content.

<Organic solvent>
The composition of the present invention may further contain an organic solvent.
The organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the colored resin composition are satisfied.

Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )) 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy- Methyl 2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2-oxobutanoic acid Ethyl, γ-butyrolactone, etc. As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether , Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like, and ketones, for example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like, and aromatic hydrocarbons, Example If, toluene, xylene, and, as alcohols, such as 3-methyl-3-methoxybutanol and the like are preferably exemplified.

The content of the organic solvent in the colored resin composition is preferably such that the total solid concentration of the composition is 5% by mass to 80% by mass from the viewpoint of applicability. Is more preferable, and 10% by mass to 50% by mass is particularly preferable.
The composition of the present invention may contain only one type of organic solvent or two or more types of organic solvents. When two or more types are included, the total amount is preferably within the above range.

<Other ingredients>
The colored resin composition of the present invention contains a pigment dispersant, a polymerizable compound, a polymerization initiator, an alkali-soluble resin, a surfactant, an alkaline earth metal ion, and the like as components other than the components described above. Also good.

(Pigment dispersant)
In the composition of the present invention, since the above-described polyamic acid also functions as a pigment dispersant, the pigment dispersant may not be substantially contained, but may further contain a pigment dispersant.
Examples of the pigment dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic. -Based copolymers, naphthalenesulfonic acid formalin condensates], surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like. The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.
With respect to the pigment dispersant, for example, the description in paragraphs 0216 to 0222 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
When the colored resin composition further contains a pigment dispersant, the total content of the pigment dispersant may be 1 to 80 parts by mass with respect to 100 parts by mass of the pigment containing PG58. The mass may be from 70 parts by mass, and may be from 10 to 60 parts by mass.
When the composition of the present invention does not substantially contain a pigment dispersant, the content of the pigment dispersant can be 5 parts by mass or less with respect to 100 parts by mass of the pigment containing PG58, and 1 part by mass or less. Or 0 parts by mass.
(Polymerizable compound)
Since the polyamic acid mentioned above functions also as a thermosetting agent, the composition of this invention does not need to contain a polymeric compound substantially, but may contain a polymeric compound further.
As for the polymerizable compound, for example, the description in paragraphs 0129 to 0136 of JP2011-137125A can be referred to, and the contents thereof are incorporated in the present specification.
When the composition of the present invention contains a polymerizable compound, the content of the polymerizable compound can be 1 to 10% by mass with respect to the total solid content of the composition of the present invention, 0.1 to 3 It can also be made into the mass%.
When the composition of the present invention does not substantially contain a polymerizable compound, the content of the polymerizable compound can be 1% by mass or less based on the total solid content of the composition of the present invention. It can also be made into the mass% or less, and can also be 0 mass%.

(Polymerization initiator)
Although the composition of this invention may contain a polymerization initiator, it does not need to contain a polymerization initiator substantially. In particular, when the composition of the present invention is used in a dry etching process, it is preferable that the photopolymerization initiator is not substantially contained.
As a polymerization initiator, it can select suitably from well-known photoinitiators, for example. Only one type of photopolymerization initiator may be used, or two or more types may be used in combination.
Examples of the polymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like.
Examples of the oxime compound include those represented by the following formula (OX-1) or (OX-2) in paragraph 0513 of JP2012-208494A (corresponding US Patent Application Publication No. 2012/235099, [0632]). Reference may be made to the description of the compounds represented, the contents of which are incorporated herein.
In addition, as polymerization initiators, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD) Commercial products such as can also be used.
When the composition of the present invention contains a polymerization initiator, the content of the polymerization initiator can be 1 to 5% by mass relative to the total solid content of the composition of the present invention, and 0.1 to It can also be 1 mass%.
When the composition of the present invention does not substantially contain a polymerization initiator, the content of the polymerization initiator can be 1% by mass or less based on the total solid content of the composition of the present invention. It can also be made into the mass% or less, and can also be 0 mass%.

(Alkali-soluble resin)
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group.
For the alkali-soluble resin, paragraphs 0558 to 0571 of JP2012-208494A (corresponding to [0685] to [0700] of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof can be referred to. It is incorporated herein.
When the colored resin composition of the present invention contains an alkali-soluble resin, the content of the alkali-soluble resin can be 0.01 to 10% by mass in the total solid content of the composition of the present invention. It can also be 5 mass%.

(Surfactant)
The composition of the present invention may further contain various surfactants from the viewpoint of further improving applicability.
As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. In particular, the composition of the present invention can further improve liquid properties (particularly fluidity) when it is prepared as a coating solution by containing a fluorosurfactant, and can improve uniformity of coating thickness and saving. Liquidity can be further improved.
That is, when a film is formed using a coating liquid to which a composition containing a fluorosurfactant is applied, the wettability to the coated surface is reduced by reducing the interfacial tension between the coated surface and the coating liquid. Is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.

Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) and the like.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1) Solsperse 20000 (Lubrizol Japan Co., Ltd.), and the like.

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

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

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.
When a surfactant is contained in the composition of the present invention, the content of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably based on the total mass of the composition of the present invention. Is 0.005 mass% to 1.0 mass%.
The composition of the present invention may contain only one type of surfactant or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

(Alkaline earth metal ions)
The colored resin composition of the present invention may further contain alkaline earth metal ions (such as calcium ions). With such a configuration, the effects of the present invention are excellent, and the generation of needle-like foreign matters due to a mixed crystal of molten zinc phthalocyanine and copper phthalocyanine can be more effectively suppressed. For example, the content of alkaline earth metal ions relative to the mass of PG58 can be 30 to 300 ppm by mass.

In addition to the above, various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be blended with the colored resin composition as necessary. Examples of these additives include those described in JP-A No. 2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein.
The composition of the present invention may contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph 0081 of the publication.

<Method for producing colored resin composition>
The composition of this invention can be prepared by mixing each component mentioned above.
In preparing the composition of the present invention, the components constituting the colored resin composition may be combined at once, or may be sequentially mixed after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, a colored resin composition may be prepared by simultaneously dissolving and dispersing all components in a solvent, and if necessary, each component may be suitably used as two or more solutions / dispersions at the time of use ( These may be mixed at the time of application) to prepare as a composition.
In the composition of the present invention, it is preferable that PG58 dispersed with a dispersant is blended with other components.

The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects.
As a filter used for filter filtration, if it is a filter conventionally used for the filtration use etc., it can use without being specifically limited.
Examples of filter materials include: fluororesins such as PTFE (polytetrafluoroethylene); polyamide resins such as nylon-6 and nylon-6, 6; polyolefin resins such as polyethylene and polypropylene (PP) (high density, super Including high molecular weight); Among these materials, polypropylene (including high density polypropylene) is preferable.

The pore size of the filter is not particularly limited, but is, for example, about 0.01 to 20.0 μm, preferably about 0.01 to 5 μm, and more preferably about 0.01 to 2.0 μm.
By setting the pore diameter of the filter in the above range, fine particles can be more effectively removed and turbidity can be further reduced.
Here, the pore size of the filter can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .

In filter filtration, two or more filters may be used in combination.
For example, filtration can be performed first using a first filter, and then using a second filter having a pore diameter different from that of the first filter.
At that time, the filtering by the first filter and the filtering by the second filter may be performed only once or twice or more, respectively.
As the second filter, a filter formed of the same material as the first filter described above can be used.

<Application>
The cured film obtained by curing the composition of the present invention is preferably used for forming a colored pattern of a color filter because other colors are unlikely to be mixed on the surface. In addition, the composition of the present invention is preferably used for forming a colored pattern such as a color filter used in a solid-state imaging device (for example, CCD, CMOS, etc.) or an image display device such as a liquid crystal display device (LCD). it can. In particular, a color filter for a solid-state imaging device such as a CCD and a CMOS can be suitably used as a production application. Further, the composition of the present invention can be preferably used as a colored resin composition for dry etching.

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

In the pattern forming method of the present invention, the colored resin composition layer is formed by applying the composition of the present invention on a support, and unnecessary portions are removed to form a colored pattern.
The pattern forming method of the present invention can be suitably applied to the formation of a colored pattern (pixel) included in a color filter.
The colored resin composition of the present invention may form a pattern by a dry etching method, or may produce a color filter by pattern formation by a so-called photolithography method.
That is, as a first embodiment of the pattern forming method of the present invention, a step of applying a colored resin composition on a support to form a colored resin composition layer and curing to form a colored layer, on the colored layer A pattern forming method includes a step of forming a photoresist layer on the substrate, a step of patterning the photoresist layer by exposure and development to obtain a resist pattern, and a step of dry etching the colored layer using the resist pattern as an etching mask. Is done.
In addition, as a second embodiment of the pattern forming method of the present invention, a step of forming a colored resin composition layer by applying the colored resin composition on a support, and exposing the colored resin composition layer in a pattern shape The pattern formation method including a process and the process of developing and removing an unexposed part and forming a colored pattern is illustrated.
Such a pattern forming method is used for manufacturing a colored layer of a color filter. That is, the present invention also discloses a method for manufacturing a color filter including the pattern forming method of the present invention.
These details will be described below.

Hereinafter, although each process in the pattern formation method of this invention is demonstrated in detail through the manufacturing method of the color filter for solid-state image sensors, this invention is not limited to this method. Hereinafter, the color filter for the solid-state imaging device may be simply referred to as “color filter”.
The method for producing a color filter of the present invention comprises a step of applying a colored resin composition onto a substrate to form a colored film (colored layer), and heating the colored film applied on the substrate at 150 to 350 ° C. to cure. A step of applying a photoresist on the cured colored film, a step of patterning the photoresist after pattern exposure, and a step of patterning the photoresist by alkali development, and a photo process using the patterned photoresist as an etching mask. It is preferable to include a step of patterning the colored film under the resist by dry etching and a step of removing the patterned photoresist.
Hereinafter, the manufacturing method of the color filter of the present invention will be described with reference to specific examples with reference to FIGS.

<<< Step of Forming First Colored Pixel >>>
In the step of forming the first colored pixel, it is preferable to form the first colored pixel by dry etching.
In the method for producing a color filter of the present invention, first, as shown in the schematic cross-sectional view of FIG. 1, a first colored layer 11 is formed from a first colored resin composition as a colored resin composition (step ( A)). As the first colored resin composition, the above-described colored resin composition of the present invention can be used.
The first colored layer 11 is preferably a green transmission layer. By making the first colored layer 11 a green transmissive layer, color sensitivity can be further improved.

The first colored layer 11 is applied, for example, by applying a colored resin composition onto a support by a coating method such as spin coating, slit coating, spray coating, spin coating, spin coating, cast coating, roll coating, and the like. And forming a colored layer. In particular, it is preferable to apply by spin coating.
The support is not particularly limited as long as it is used for a color filter in addition to a silicon substrate. For example, soda glass, borosilicate glass, quartz glass, and a transparent conductive film attached to these are used for liquid crystal display elements. And a photoelectric conversion element substrate used for a solid-state imaging device, such as an oxide film or silicon nitride. Further, an intermediate layer or the like may be provided between the support and the color filter as long as the present invention is not impaired.
The thickness of the first colored layer 11 after drying is preferably in the range of 0.3 to 2.0 μm, more preferably in the range of 0.35 to 1.5 μm, and more preferably in the range of 0.35 to 1.2 μm. preferable.

The first colored layer 11 is preferably cured by heating with a heating device such as a hot plate or an oven. The heating temperature is preferably 90 ° C to 250 ° C, more preferably 100 ° C to 230 ° C. The heating time varies depending on the heating means, but when heated on a hot plate, it is usually about 2 to 30 minutes, and when heated in an oven, it is usually about 30 to 90 minutes.
The first colored layer 11 is preferably further subjected to heat treatment (post-bake). The heating temperature for post baking is preferably 150 ° C. to 350 ° C., more preferably 200 ° C. to 250 ° C. The heating time varies depending on the heating means, but is usually about 20 to 90 minutes.

Next, patterning is performed by dry etching so that a removal portion group is formed in the first colored layer 11 (step (B)). Thereby, a first colored pattern is formed. According to this technique, the first colored layer is formed with the first colored resin composition, and a desired shape (as compared with the case where the removal portion group is provided by exposing and developing the first colored layer) In particular, the removal portion group having a rectangular shape can be provided more reliably.

Dry etching can be performed on the first colored layer 11 using an etching gas using the patterned photoresist layer as a mask. For example, as shown in the schematic sectional view of FIG. 2, first, a photoresist layer 51 is formed on the first colored layer 11.

Specifically, a positive or negative photoresist is applied on the first colored layer 11 and dried to form a photoresist layer. In forming the photoresist layer 51, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming a photoresist, a mode in which heat treatment after exposure (PEB) and heat treatment after development (post-bake treatment) are desirable.

As the photoresist, for example, a positive type photoresist is used. This positive photoresist is suitable for positive photoresists sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer lasers, electron beams, ion beams and X rays. A positive resist composition can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.
Specifically, a composition containing a quinonediazide compound and an alkali-soluble resin is preferable as a positive photoresist. Examples of the quinonediazide compound include a naphthoquinonediazide compound.
The thickness of the dried photoresist layer 51 is preferably 0.1 to 3 μm, more preferably 0.2 to 2.5 μm, and still more preferably 0.3 to 2 μm. Note that the application of the photoresist layer 51 can be suitably performed using the application method for the first colored layer 11.

Next, as shown in the schematic cross-sectional view of FIG. 3, the photoresist layer 51 is exposed and developed to form a resist pattern (patterned photoresist layer) 52 provided with a resist removal portion group 51A.
The formation of the resist pattern 52 is not particularly limited, and a conventionally known photolithography technique can be used. By providing the resist removal portion group 51 </ b> A in the photoresist layer 51 by exposure and development, a resist pattern 52 as an etching mask used in the next etching is provided on the first colored layer 11.
The exposure of the photoresist layer 51 can be performed by exposing a positive or negative photoresist to g-line, h-line, i-line, etc., preferably i-line, through a predetermined mask pattern. . After the exposure, the photoresist is removed in accordance with a region where a colored pattern is to be formed by developing with a developer.
As the developer, any can be used as long as it does not affect the first colored layer containing the colorant and dissolves the exposed portion of the positive resist and the uncured portion of the negative resist. Combinations of various organic solvents and alkaline aqueous solutions can be used.
As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass is suitable. Alkaline compounds include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl Examples thereof include ammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like. In addition, when alkaline aqueous solution is used as a developing solution, generally a washing process is performed with water after development.

Next, as shown in the schematic cross-sectional view of FIG. 4, the resist pattern 52 is used as an etching mask, and patterning is performed by dry etching so that the removal portion group 120 is formed in the first colored layer 11. Thereby, the 1st coloring pattern 12 is formed. Here, the removal unit group 120 includes a first removal unit group 121 and a second removal unit group 122.
The removal unit group 120 is provided on the first colored layer 11 in a checkered pattern. Therefore, the 1st coloring pattern 12 in which the removal part group 120 is provided in the 1st coloring layer 11 has a some square 1st coloring pixel in checkered form.
Specifically, in the dry etching, the first colored layer 11 is dry etched using the resist pattern 52 as an etching mask. Representative examples of dry etching include JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, JP-A-61-41102, and the like. And the contents thereof are incorporated herein by reference.

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

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

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

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

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

Next, as shown in the schematic cross-sectional view of FIG. 5, the resist pattern (that is, etching mask) 52 remaining after the etching is removed. The removal of the resist pattern 52 includes a step of applying a stripping solution or a solvent to the resist pattern 52 so that the resist pattern 52 can be removed, and a step of removing the resist pattern 52 using cleaning water. Is preferred. For example, a step of applying a stripping solution or a solvent on at least the resist pattern 52 and stagnating for a predetermined time to perform paddle development can be included. Although there is no restriction | limiting in particular as time to make stripping solution or a solvent stagnant, It is preferable that it is several dozen seconds to several minutes. Further, for example, the resist pattern 52 may be removed by spraying cleaning water onto the resist pattern 52 from a spray type or shower type spray nozzle.
As the washing water, pure water can be preferably used. Further, examples of the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle that is a movable injection nozzle and in which the movable range includes the entire support.

<<< Step of Forming Second Colored Pixel >>>
In the step of forming the second colored pixel, the second colored pixel adjacent to the first colored pixel is formed by photolithography using the second colored radiation-sensitive composition. In the present invention, by forming the second colored pixel by photolithography, the number of steps can be reduced as compared with the case where all steps are performed by dry etching.

In the step of forming the second colored pixels, as shown in the schematic cross-sectional view of FIG. 6, the second colored radiation-sensitive property is formed inside each removed portion in the first removed portion group 121 and the second removed portion group 122. The composition is embedded, and the second colored radiation-sensitive composition is used to form the first colored layer (that is, the first colored pattern 12 in which the removal portion group 120 is formed on the first colored layer 11). Two colored radiation-sensitive layers 21 are laminated (step (C)). Thereby, the 2nd coloring pattern 22 which has a some 2nd coloring pixel in the removal part group 120 of the 1st coloring layer 11 is formed. Here, the second colored pixel is preferably a square pixel. The second colored radiation sensitive layer 21 can be formed in the same manner as the method for forming the first colored layer 11 described above.
The thickness of the second colored radiation-sensitive layer 21 after post-baking is preferably 0.1 to 1.5 μm, and more preferably 0.1 to 1.0 μm.

Then, the second colored radiation-sensitive layer 21 is exposed and developed at a position 21A corresponding to the first removal portion group 121 provided in the first colored layer 11 of the second colored radiation-sensitive layer 21. 21 and the plurality of second colored pixels 22R provided inside each removal portion of the second removal portion group 122 are removed (step (D)) (see the schematic cross-sectional view of FIG. 7).
As radiation (light) that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferable (particularly preferably i-line). Irradiation dose (exposure dose) is more preferably ^{30mJ / cm 2 ~ 3000mJ / cm} 2 is preferably ^{50mJ / cm 2 ~ 2500mJ / cm} 2, 100mJ / cm 2 ~ 500mJ / cm 2 is particularly preferred.
The developer is synonymous with the developer described in the step of forming the first colored pixels described above.
As a development method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) The paddle method is particularly preferable.
The development time is not particularly limited as long as the colored layer in the unexposed area is sufficiently dissolved, and is usually 10 seconds to 300 seconds. Preferably, it is 20 seconds to 120 seconds.
The temperature of the developer is preferably from 0 ° C to 50 ° C, more preferably from 15 ° C to 35 ° C.

<<< Step of Forming Third Colored Pixel >>>
The method for manufacturing a color filter of the present invention may further include a step of forming a third colored pixel after the step of forming the second colored pixel.
In the step of forming the third colored pixel, as shown in the schematic cross-sectional view of FIG. 8, the third colored radiation-sensitive composition is embedded in each removed portion in the second removed portion group 122, The first colored layer (that is, the first colored pattern 12 in which the second colored pattern 22 is formed in the first removal portion group 121) so that a plurality of third colored pixels are formed. A third colored radiation-sensitive layer 31 is formed on the third colored radiation-sensitive composition (step (E)). Thereby, the 3rd coloring pattern 32 which has a some 3rd coloring pixel in the 2nd removal part group 122 of the 1st coloring layer 11 is formed. Here, the third colored pixel is preferably a square pixel. The formation of the third colored radiation-sensitive layer 31 can be performed in the same manner as the step of forming the colored layer using the colored resin composition in the first embodiment described above.
The thickness of the third colored resin composition layer 31 after post-baking is preferably in the range of 0.1 to 1 μm, more preferably in the range of 0.2 to 0.8, and in the range of 0.3 to 0.6 μm. Is more preferable.

Then, the third colored radiation-sensitive layer 31 is exposed and developed at a position 31A corresponding to the second removal portion group 122 provided in the first colored layer 11 of the third colored radiation-sensitive layer 31. By removing 31, as shown in the schematic cross-sectional view of FIG. 9, the color filter 100 having the first colored pattern 12, the second colored pattern 22, and the third colored pattern 32 is manufactured. (Step (F)).

The second colored radiation-sensitive composition and the third colored radiation-sensitive composition described above each contain a colorant. Examples of the colorant may include those described above in the coloring composition of the present invention, but one of the second colored pixel and the third colored pixel is a blue transmissive portion, and the other is a red transmissive portion. preferable. The colorant contained in the coloring composition for forming the blue transmission part is C.I. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, and C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 or more It is preferable. The colorant contained in the coloring composition for forming the red transmitting part is preferably at least one selected from those described in paragraph numbers 0037 and 0039 of JP2012-172003A. Is incorporated herein by reference.

In each of the second colored radiation-sensitive composition and the third colored radiation-sensitive composition, the content of the colorant composition with respect to the total solid content is preferably 30% by mass or more, and 35% by mass. More preferably, it is more preferably 40% by mass or more. Moreover, content with respect to the total solid of the composition of a coloring agent is 90 mass% or less normally, and it is preferable that it is 80 mass% or less.

Also, it is preferable that a negative radiation sensitive composition is used for each of the second colored radiation sensitive composition and the third colored radiation sensitive composition. This negative radiation sensitive composition includes negative radiation sensitive to radiation such as ultraviolet rays (g rays, h rays, i rays), deep ultraviolet rays including excimer laser, electron beams, ion beams and X rays. Sex compositions can be used. Of the radiation, g-line, h-line and i-line are preferable, and i-line is particularly preferable.

Specifically, the negative radiation-sensitive composition is preferably a composition containing a photopolymerization initiator, a polymerization component (polymerizable compound), a binder resin (alkali-soluble resin, etc.) and the like. Examples described in paragraph Nos. 0017 to 0064 of Kaikai 2005-326453 may be mentioned, the contents of which are incorporated herein. Such a negative radiation sensitive composition utilizes the fact that the photopolymerization initiator initiates the polymerization reaction of the polymerizable compound upon irradiation with radiation, and as a result, the alkali soluble state becomes alkali insoluble. To do.

<Method for patterning colored resin composition layer by wet etching>
In the method for producing a color filter of the present invention, a pattern can be formed by a wet etching method. An example of a method for forming a pattern by the wet etching method is shown below.
On the substrate, the colored resin composition described above is applied to form a colored film.
As the substrate, soda glass, alkali-free glass, borosilicate glass, quartz glass, or the like can be usually used. For the coating, methods such as spinner, spray coating, dipping, roll coating, bar coating, and die coating are used. The applied colored resin composition is preferably dried in the range of 50 to 180 ° C. for several seconds to several hours using an oven, a hot plate, and infrared rays.
A photoresist for pattern formation is applied on the colored film to form a photoresist layer. The thickness of the photoresist layer is preferably from 0.1 to 3 μm, preferably from 0.2 to 2.5 μm, more preferably from 0.3 to 2 μm. Subsequently, using an exposure apparatus, a mask is formed on the photoresist layer coating. Place, irradiate with actinic radiation and expose. Examples of actinic rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays and visible rays are preferable. When a positive photoresist is used, after the exposure, the development of the photoresist layer and the etching of the colored film are simultaneously performed with a positive photoresist developer. The photoresist layer that has become unnecessary after etching is removed. Usually, a solvent such as acetone or cellosolve is used for peeling. The colored film is heat-treated to finish the patterning of the colored film. The heat treatment is performed for 5 minutes to 5 hours while selecting the temperature and raising the temperature stepwise or selecting a temperature range and continuously raising the temperature. The heat treatment temperature is preferably 180 to 400 ° C, and more preferably 180 to 350 ° C. For example, heat treatment is performed at 130 ° C., 200 ° C., and 300 ° C. for 30 minutes. Further, the temperature may be increased linearly from room temperature to 300 ° C. over 2 hours.
The above steps are repeated for red, green, and blue colored compositions, or yellow, cyan, magenta, and optionally a black matrix (black). A color filter can be formed by forming an overcoat film made of acrylic polymer, polysiloxane, polyimide, or the like as necessary, and sputtering a metal oxide film such as ITO.

<Method for patterning colored resin composition layer by photolithography>
In the method for producing a color filter of the present invention, the colored resin composition layer can be patterned by a photolithography method. For details of the photolithography method, reference can be made to paragraph numbers 0173 to 0185 of JP2013-227497A, the contents of which are incorporated herein.

Since the color filter of the present invention is formed of a colored resin composition having a high colorant concentration, the thickness of the colored pattern can be extremely reduced (for example, 0.7 μm or less). In addition, since other colors hardly remain on the surface and color mixing does not easily occur, a color filter in which crosstalk (light color mixing) is suppressed can be obtained.

The color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD or CMOS, and is particularly suitable for a CCD or CMOS having a high resolution exceeding 1 million pixels. The color filter for a solid-state imaging device of the present invention can be used as a color filter disposed between, for example, a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light.

The thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably from 0.1 to 1.0 μm, more preferably from 0.1 to 0.8 μm.
Further, the size (pattern width) of the colored pattern (colored pixel) can be 2.5 μm or less, can be 2.0 μm or less, and can be 0.9 to 1.4 μm. In particular, by using a dry etching method, a colored pattern having the above size can be efficiently produced.

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

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

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

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

The color filter of the present invention may be used in a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
In addition, the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system. In the case of a COA type liquid crystal display device, the required characteristics for the color filter layer require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the stripping solution, in addition to the normal required characteristics as described above. Sometimes. In the color filter of the present invention, since a dye having excellent hue is used, the color purity, light transmittance, etc. are good and the color of the colored pattern (pixel) is excellent. Therefore, the COA method has high resolution and excellent long-term durability. A liquid crystal display device can be provided. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends (issued in 2001 by Toray Research Center Research Division)".

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

When the color filter according to the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and further, red, green and blue LED light sources (RGB-LED). By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “%” and “parts” are based on mass.

<Synthesis of polyamic acids PA-1 to PA-3>
<< Synthesis Example 1 >>
In a reaction vessel equipped with a thermometer, a nitrogen gas inlet tube and a stirrer in a three-necked round bottom flask, 15.0 g (75 mmol) of 4,4′-diaminodiphenyl ether and 5.0 g (20 mmol) of 3,3′-diaminodiphenylsulfone Bis-3- (aminopropyl) tetramethyldisiloxane 1.2 g (5 mmol) was charged together with 280 g of γ-butyrolactone, and 16.1 g (50 mmol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride Then, 10.7 g (49 mmol) of pyromellitic anhydride was added and reacted at 60 ° C. for 5 hours, then 0.2 g (2 mmol) of maleic anhydride was added, and further reacted at 60 ° C. for 1 hour. A polyamic acid solution PA-1 having a solid content concentration of 20% by mass was obtained.

<< Synthesis Examples 2 to 3 >>
Polyamic acid PA-2 to PA having a solid content concentration of 20% by mass in the same manner as in Synthesis Example 1 except that the type and amount of raw materials used in the synthesis of polyamic acid are changed as shown in Table 1 below. -3 was obtained.

Each abbreviation in Table 1 means the following.
DAE: 4,4′-diaminodiphenol ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
DDS: 3,3′-diaminodiphenol sulfone (manufactured by Wako Pure Chemical Industries, Ltd.)
DBA: 4,4′-diaminobenzanilide (manufactured by Tokyo Chemical Industry Co., Ltd.)
HAD: Hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
Si-DA: Bis (3-aminopropyl) tetramethyldisiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.)
BTDA: 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (Wako Pure Chemical Industries, Ltd.)
PMDA: pyromellitic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.)
BTCA: 1,2,3,4-butanetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid BT-100)
MA: Maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)
PA: phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Preparation of Green Colored Resin Compositions G-1 to G-34>
A mixture having the following composition was uniformly stirred and mixed, and then mixed and dispersed by a bead mill for 3 hours to prepare a green colored resin composition G-1.
Polyhalogenated zinc phthalocyanine pigment (CI Pigment Green 58, manufactured by DIC Corporation) 7.70 parts by mass Nickel azo yellow pigment (CI Pigment Yellow 150) 6.30 parts by mass Polyamic acid PA-1 6.00 Part by mass (as non-volatile content)
γ-butyrolactone 40.00 parts by mass 3-methyl-3-methoxybutanol 40.00 parts by mass

The green colored resin compositions G-2 to G- were prepared in the same manner as the green colored resin composition G-1, except that the composition of the green colored resin composition G-1 was changed to the composition shown in Table 2 below. 34 was prepared.

Each abbreviation in Table 2 indicates the following compound.
PG58: C.I. I. Pigment Green 58 (polyhalogenated zinc phthalocyanine green pigment, manufactured by DIC Corporation)
PY129: C.I. I. Pigment Yellow 129 (copper azomethine yellow pigment)
PY150: C.I. I. Pigment Yellow 150 (Nickel azo yellow pigment)
PY185: C.I. I. Pigment Yellow 185 (isoindoline-based yellow pigment)
D-1: Pigment derivative having the following structural formula (manufactured by FUJIFILM Corporation)

D-2: Pigment derivative having the following structural formula (manufactured by FUJIFILM Corporation)

D-3: Pigment derivative having the following structural formula (manufactured by FUJIFILM Corporation)

C-1: p-phenylenediamine (manufactured by Wako Pure Chemical Industries, Ltd.)
C-2: 4,4′-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-3: 4,4′-diaminobenzanilide (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-4: Hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
F-1: Made by DIC, MegaFuck F-781F (fluorine-based surfactant)
BL: γ-butyrolactone MMB: 3-methyl-3-methoxybutanol dispersant A: polymer dispersant having the following structural formula (manufactured by FUJIFILM Corporation), where a = 3.5, b = 2. 5 and an acid value of 30 mg KOH / g and a weight average molecular weight of 20,000 was used)

Epoxy resin A: Epoxy resin having the following structural formula (manufactured by Daicel Chemical Industries, EHPE3150)

<Evaluation of green colored resin composition>
<< Evaluation of solvent resistance >>
The green colored resin compositions G-1 to G-34 obtained above were applied onto a glass substrate using a spin coater so that the film thickness after drying was 0.6 μm, and prebaked at 100 ° C. for 120 seconds. A colored film was obtained. The obtained colored film was further heated (post-baked) at 240 ° C. for 30 minutes in a nitrogen atmosphere, and the coating film was cured. In this process, the polyamic acid in the coating film undergoes a dehydration condensation reaction and is converted to polyimide.
The cured coating film obtained by the curing treatment was immersed in N-methylpyrrolidone for 60 seconds, and the change in spectral transmittance of the cured coating film before and after immersion was measured with MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). The solvent resistance was evaluated by the obtained color difference ΔEab. The smaller ΔEab, the smaller the change in spectral transmittance before and after immersion in the solvent, and the better the solvent resistance. Table 2 summarizes the evaluation results of solvent resistance.

<< Evaluation of acicular foreign matter >>
(Preparation of blue pigment dispersion B1)
As a pigment, C.I. I. Pigment blue 15: 6 (9.5 parts), C.I. I. A mixture of Pigment Violet 23 (2.4 parts), BYK-161 (5.6 parts made by BYK) as a pigment dispersant, and PGMEA (82.5 parts) was mixed for 15 hours using a bead mill. Dispersion was carried out to prepare a blue pigment dispersion B1.

(Preparation of blue resin composition Ba)
Pigment dispersion: 51.2 parts of the above blue pigment dispersion B1 Photopolymerization initiator: IRGACURE OX-01 (manufactured by BASF Corporation)
0.87 parts Polymerizable compound: KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.)
4.7 parts / Binder: ACA230AA (manufactured by Daicel Chemical Industries, Ltd.)
7.4 parts ・ Polymerization inhibitor: p-methoxyphenol 0.002 parts ・ Nonionic surfactant: Pionine D-6112-W (manufactured by Takemoto Yushi Co., Ltd.) 0.19 parts ・ Silane coupling agent: KBM- 10.8 parts of cyclohexanone 0.9% solution of 602 (manufactured by Shin-Etsu Chemical Co., Ltd.), organic solvent: 14.3 parts of PGMEA, organic solvent: 6.4 parts of cyclohexanone, fluorosurfactant: F-781 (DIC) 4.2 parts solution of cyclohexanone (manufactured by Co., Ltd.)

<Green pixel pattern formation process by dry etching>
(Formation of green layer)
After applying the above-mentioned green colored resin composition on a silicon wafer with a spin coater, drying on a hot plate at 100 ° C. for 180 seconds, and then performing a heat treatment (post bake) at 240 ° C. for 30 minutes in a nitrogen atmosphere. A green colored film was formed. The thickness of this green colored film was 0.6 μm.

(Application of mask resist)
On the obtained green colored film, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials) was applied and prebaked to form a 0.8 μm-thick photoresist layer.

(Mask resist pattern exposure and development)
The obtained photoresist layer was subjected to pattern exposure using an i-line stepper (manufactured by Canon Inc.) and subjected to heat treatment for 1 minute at a temperature at which the temperature of the photoresist layer or the atmospheric temperature was 90 ° C. Thereafter, development processing was performed with a developer “FHD-5” (manufactured by FUJIFILM Electronics Materials) for 1 minute, and further post-baking processing was performed at 110 ° C. for 1 minute to form a resist pattern. This resist pattern is a pattern in which square-shaped resist films formed with a side of 1.25 μm are arranged in a checkered pattern in consideration of etching conversion difference (pattern width reduction by etching).

(Dry etching)
Using the obtained resist pattern as an etching mask, dry etching of the green colored film was performed according to the following procedure.
RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, chamber internal pressure: 4.0 Pa, substrate temperature: 50 ° C., mixed gas in dry etching apparatus (Hitachi High Technologies, U-621) The gas type and flow rate were CF ₄ : 80 mL / min. , O ₂ : 40 mL / min. , Ar: 800 mL / min. As a result, the first stage etching process of 80 seconds was performed.
Under this etching condition, the amount of green layer scraping was 534 nm (89% etching amount), and there was a remaining film of about 58 nm.
Next, in the same etching chamber, RF power: 600 W, antenna bias: 100 W, wafer bias: 250 W, chamber internal pressure: 2.0 Pa, substrate temperature: 50 ° C., gas mixture type and flow rate of N ₂ : 500 mL / min. , O ₂ : 50 mL / min. , Ar: 500 mL / min. (N ₂ / O ₂ / Ar = 10/1/10), and the second etching process and the over-etching process were performed with the over-etching rate in the total etching being 20%.
The etching rate of the green layer under the second stage etching conditions was 600 nm / min or more, and it took about 10 seconds to etch the remaining film of the green layer. The sum of 80 seconds of the first stage etching time and 10 seconds of the second stage etching time was calculated as the etching time. As a result, the etching time was 80 + 10 = 90 seconds, the over-etching time was 90 × 0.2 = 18 seconds, and the total etching time was set to 90 + 18 = 108 seconds.
After performing dry etching under the above conditions, the resist pattern is removed for 120 seconds using a photoresist stripping solution “MS230C” (manufactured by FUJIFILM Electronics Materials), and the resist pattern is removed, followed by washing with pure water. Spin drying was performed. Thereafter, a dehydration baking process was performed at 100 ° C. for 2 minutes. As described above, a green pattern in which square green pixels having a side of 1.2 μm are arranged in a checkered pattern was obtained. Thus, it was confirmed that a fine pixel pattern suitable for a color filter for a solid-state imaging device can be formed by processing the green colored film formed from the green resin composition of the present invention by dry etching.

In the above <Green pixel pattern forming step by dry etching>, square green pixels having a side of 1.2 μm, which are created by using the green colored resin compositions G-1 to G-34, are arranged in a checkered pattern. Each green pattern is prepared, so that the blue resin composition Ba is embedded in each through hole of the green pattern, and the thickness after drying and post-baking is 0.40 μm. Blue resin composition Ba was applied on the green pattern to obtain a laminated color filter in which a blue radiation-sensitive layer was formed on the green layer.
The blue radiation sensitive layer of the multilayer color filter thus obtained was subjected to pattern exposure using an i-line stepper (manufactured by Canon Inc.). Here, an exposure area | region is an area | region corresponding to the through-hole located in an even number row | line | column in the checkered pattern of the said green pattern.
Next, the layered color filter after exposure was placed on a horizontal rotating table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (manufactured by FUJIFILM Electronics Materials Co., Ltd.). ) Was used for 60 seconds at 23 ° C. After that, the color filter is fixed to the horizontal rotary table by a vacuum chuck method, and the color filter is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is supplied from the ejection nozzle in a shower shape from above the rotation center to rinse. Treatment was followed by spray drying.
As described above, a color filter precursor obtained by removing the blue radiation-sensitive layer in the laminated color filter and the blue pixels provided in the through holes located in the odd rows in the checkered pattern of the green pattern was obtained.
The color filter precursor thus obtained was subjected to heat treatment at 230 ° C. for 300 seconds on a hot plate. The color filter precursor after the heat treatment was observed using a scanning electron microscope (Hitachi, S-9260), and it was confirmed whether needle-like foreign matters were generated in the boundary region between the green pixel and the blue pixel. As a result of the confirmation, the evaluation was performed in the following manner according to the state of occurrence of acicular foreign matter. The evaluation results are summarized in Table 2.
A: No acicular foreign matter is generated at all B: Small acicular foreign matters with a length of less than 0.1 μm are slightly observed, but there is no problem C: Acicular foreign matters with a length of 0.1 to 0.2 μm Slightly observed, but no problem level D: Many large needle-like foreign objects exceeding 0.2 μm in length were observed

Comparative Example 2 (Verification of effects when PG36 is used as a green pigment)
A mixture having the following composition was stirred and mixed uniformly, and then mixed and dispersed by a bead mill for 3 hours, whereby C.I. I. Using Pigment Green 36, a green colored resin composition G36-PA using the above-described polyamic acid PA-1 as a cured resin was prepared.
Polyhalogenated copper phthalocyanine pigment (CI Pigment Green 36) 7.70 parts by mass Nickel azo yellow pigment (CI Pigment Yellow 150)
6.30 parts by mass Polyamic acid PA-1 6.00 parts by mass (as non-volatile content)
γ-butyrolactone 40.00 parts by mass 3-methyl-3-methoxybutanol 40.00 parts by mass

Further, a mixture having the following composition was uniformly stirred and mixed, and then mixed and dispersed by a bead mill for 3 hours, whereby C.I. I. A green colored resin composition G36-EP using Pigment Green 36 and an epoxy resin as a cured resin was prepared.
Polyhalogenated copper phthalocyanine pigment (CI Pigment Green 36) 7.70 parts by mass Nickel azo yellow pigment (CI Pigment Yellow 150)
6.30 parts by mass Dispersant A 4.20 parts by mass Epoxy resin A (manufactured by Daicel Chemical Industries, EHPE 3150)
1.80 parts by mass γ-butyrolactone 40.00 parts by mass 3-methyl-3-methoxybutanol 40.00 parts by mass

Each of the above green colored resin compositions G36-PA · G36-EP was evaluated by the same method as the solvent resistance and needle foreign matter evaluation methods described above. As a result, there was no difference between G36-PA and G36-EP in the solvent resistance and the evaluation results of needle-like foreign matters. From this result, it was found that when PG36 was used as the green pigment, the effect of the present invention could not be found even when the polyamic acid used in the present invention was used as the cured resin.

<Formation of green pixel pattern by wet etching>
(Formation of green layer)
The above-mentioned green colored resin composition G-1 was applied onto a glass wafer with a spin coater and then dried on a hot plate at 100 ° C. for 180 seconds to form a green colored film.
(Application of mask resist)
Next, a positive photoresist “FHi622BC” (manufactured by FUJIFILM Electronics Materials) was applied on the green colored film and prebaked to form a 0.8 μm-thick photoresist layer.
(Pattern exposure of mask resist and wet etching by alkali development)
Subsequently, the photoresist layer was subjected to pattern exposure using an i-line stepper (manufactured by Canon Inc.), and heat treatment was performed for 1 minute at a temperature at which the temperature of the photoresist layer or the atmospheric temperature was 90 ° C. Thereafter, a developer “FHD-5” (manufactured by FUJIFILM Electronics Materials Co., Ltd.) was immersed in the photoresist, and the photoresist and the lower green colored film were developed at the same time (this is the upper photoresist film). This is equivalent to a wet etching process of the underlying green colored film using the After etching, the unnecessary photoresist layer was peeled off with methyl cellosolve acetate. The polyimide precursor green colored film thus obtained was heated (post-baked) at 240 ° C. for 30 minutes in a nitrogen atmosphere to obtain a green pixel pattern having a film thickness of 1.2 μm. The green pixel pattern was confirmed to have a pixel size of 120 μm × 80 μm with a scanning electron microscope (Hitachi, S-9260).
As a result of trying the pattern formation by wet etching for the green colored resin compositions G-2 to G-30 by the same method as above, it was confirmed that the green pixel pattern was formed from any composition without any problem. .
From the above, by producing a green colored film formed from the green colored resin composition of the present invention by wet etching, several tens to several numbers suitable for color filters for various display devices such as liquid crystal display devices and organic LED display devices. It was confirmed that a pixel pattern having a size of about 100 μm can be formed.

11 1st colored layer, 12 1st colored pattern, 21 2nd colored radiation sensitive layer, 21A, position corresponding to 1st

removal part group

121, 22 2nd coloring pattern, 22R 2nd removal part group A plurality of second colored pixels provided in each removal portion of 122, 31 third colored radiation-sensitive layer, 31A position corresponding to second

removal portion group

122, 32 third coloring pattern, 51 photo Resist layer, 51A resist removal portion, 52 resist pattern (patterned photoresist layer), 120 removal portion group, 121 first removal portion group, 122 second removal portion group

Claims

A polyamic acid having a repeating unit represented by the following general formula (1) and C.I. I. A colored resin composition comprising CI Pigment Green 58;

In general formula (1), R 1 represents an n + divalent linking group, R 2 represents a divalent linking group, and n represents 1 or 2.
The colored resin composition according to claim 1, further comprising a diamine compound represented by the following general formula (2);

In general formula (2), R 3 represents a divalent linking group.
The colored resin composition according to claim 1 or 2, further comprising a yellow colorant.
As the yellow colorant, C.I. I. The colored resin composition according to claim 3, comprising Pigment Yellow 129.
The colored resin composition according to any one of claims 1 to 4, wherein, in the general formula (1), R 1 represents an n + divalent linking group having 2 to 22 carbon atoms.
The colored resin composition according to any one of claims 1 to 4, wherein in the general formula (1), R 1 represents an n + divalent linking group containing a cyclic structure.
The colored resin composition according to any one of claims 1 to 6, wherein R 2 in the general formula (1A) represents a divalent linking group having 1 to 22 carbon atoms.
In the general formula (1), R 2 is a hydrocarbon group, or a hydrocarbon group and —Si (R 2A ) 2 —, —CO—, —NR—, —O—, —SO 2 —, and —S—. The colored resin composition according to any one of claims 1 to 6, which represents a divalent linking group containing a group consisting of a combination with at least one selected from: R 2A independently Represents an alkyl group having 1 to 6 carbon atoms, and R in —NR— represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
The colored resin composition according to any one of claims 1 to 8, wherein in the general formula (2), R 3 represents a divalent linking group having 1 to 22 carbon atoms.
The colored resin composition according to any one of claims 1 to 8, wherein, in the general formula (2), R 3 represents a divalent linking group containing a cyclic structure.
The colored resin composition according to any one of claims 1 to 8, wherein R 3 in the general formula (2) represents a divalent linking group containing the same skeleton as R 2 in the general formula (1). object.
The colored resin composition according to any one of claims 1 to 11, which is used for a solid-state imaging device.
A cured film obtained by curing the colored resin composition according to any one of claims 1 to 12.
A color filter having a colored layer using the colored resin composition according to any one of claims 1 to 12.
Applying the colored resin composition according to any one of claims 1 to 12 on a substrate to form a colored film;
Heating and curing the colored film at 150 to 350 ° C .;
Applying a photoresist on the cured colored film;
A step of patterning the photoresist by performing alkali exposure after pattern exposure of the photoresist,
Patterning the colored film under the photoresist by dry etching using the patterned photoresist as an etching mask;
Removing the patterned photoresist.
A method for producing a color filter, comprising:
The solid-state image sensor which has a color filter obtained by the manufacturing method of the color filter of Claim 14, or the color filter of Claim 15.
An image display device comprising the color filter according to claim 14 or the color filter obtained by the method for producing a color filter according to claim 15.