TWI565764B - Colored resin composition, cured film using colored resin composition, color filter, method for manufacturing color filter, and solid-state imaging sensing device - Google Patents

Description

Colored resin composition, cured film using the same, color filter, and Manufacturing method, solid-state imaging device, and image display device

The present invention relates to a colored resin composition. In particular, there is a colored resin composition which is preferably used for forming a coloring layer of a color filter. Further, the present invention relates to a cured film, a color filter, a solid-state image sensor, and an image display device using the colored resin composition. Further, the present invention relates to a method of producing a color filter using a colored resin composition.

In recent years, with the development of personal computers, particularly large-screen liquid crystal televisions, there is a tendency for liquid crystal displays (LCDs), particularly color liquid crystal displays, to increase. According to the requirements of further high image quality, the popularity of organic electroluminescence (EL) displays is also desired. On the other hand, demand for solid-state imaging devices such as charge-coupled devices (CCD) image sensors has been increasing due to the spread of digital cameras and mobile phones with cameras.

Used as a key device for these displays or optical components Color filters, along with the need for cost reduction and further high image quality, continue to improve. Such a color filter usually has a coloring pattern of three primary colors of red (R), green (G), and blue (B), and functions to divide the passing light into three primary colors in a display element or an imaging element.

For the coloring agent used in the color filter, the following characteristics are required in common.

That is, the following characteristics are required: better spectral characteristics in terms of color reproducibility; no light scattering that causes a decrease in contrast of the liquid crystal display, or chromatic aberration of the solid-state imaging element. Optical chaos such as unevenness in optical density of color sensation; good fastness under environmental conditions used, such as heat resistance, light resistance, moisture resistance, etc.; and large molar absorption coefficient to achieve film formation, etc. . Therefore, the colorant is usually a pigment.

Patent Document 1 discloses a colored resin composition for a color filter containing a pigment and polyamic acid. Patent Document 2 discloses a polyhalide zinc phthalocyanine pigment composition.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-227921

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-284592

The inventors of the present application conducted research and found that color index (C.I.) Pigment Green 58 (hereinafter also referred to as "PG58") was used as the green color. When the color filter of the pigment is heated at a high temperature, a needle-shaped foreign matter is formed in a boundary region between the green pixel and the adjacent colored pixel.

Patent Document 1 does not describe the use of PG58 as a pigment. The technique described in Patent Document 2 is difficult to suppress needle-shaped foreign matter.

The present invention has been made in view of the above problems, and an object thereof is to provide a colored resin composition capable of suppressing formation of a needle-shaped foreign matter in a boundary region between a green pixel and an adjacent colored pixel when heated at a high temperature.

The inventors of the present invention have conducted research based on the above-mentioned problems, and as a result, have found that the above problems can be solved by using a colored resin composition containing PG58 and a polylysine having a specific structure, and completed the present invention.

Specifically, the above problem is solved by the following means <1>, preferably means <2>~ means <17>.

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

In the formula (1), R ¹ represents a n+2 valent linking group, R ² represents a divalent linking group, and n represents 1 or 2.

<2> The colored resin composition according to <1>, further comprising a diamine compound represented by the following formula (2); H ₂ NR ³ —NH ₂ (2)

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

<3> The colored resin composition as described in <1> or <2> further contains a yellow coloring agent.

<4> The colored resin composition as described in <3>, which contains C.I. Pigment Yellow 129 as a yellow coloring agent.

The colored resin composition according to any one of <1> to <4>, wherein, in the formula (1), R ¹ represents a n+2 valent linking group having 2 to 22 carbon atoms.

The colored resin composition as described in any one of <1> to <4>, wherein, in the formula (1), R ¹ represents a n+2 valent linking group having a cyclic structure.

The coloring resin composition as described in any one of <1> to <6>, wherein, in the formula (1A), R ² represents a divalent linking group having 1 to 22 carbon atoms.

The colored resin composition according to any one of <1> to <6> wherein, in the formula (1), R ² represents a hydrocarbon group or contains a hydrocarbon group and is selected from -Si(R ^2A ) ₂ , a divalent linking group of a group of a combination of at least one of -CO-, -NR-, -O-, -SO ₂ -, and -S-; wherein R ^2A independently represents an alkane having 1 to 6 carbon atoms In the group, 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 <1> to <8>, wherein, in the formula (2), R ³ represents a divalent linking group having 1 to 22 carbon atoms.

The colored resin composition according to any one of <1> to <8>, wherein, in the formula (2), R ³ represents a divalent linking group having a cyclic structure.

<11> The <1> to <8> a colored resin composition described in any one of the general formula (2) contained in R ³ represents the general formula R (1) is the same as the frame ² of the two Price linkage.

<12> The colored resin composition according to any one of <1> to <11> which is used for a solid-state image sensor.

<13> A cured film obtained by curing the colored resin composition according to any one of <1> to <12>.

<14> A color filter comprising a coloring resin composition according to any one of <1> to <12>.

<15> A method of producing a color filter comprising the step of applying a colored resin composition according to any one of <1> to <12> to a substrate to form a colored film; a step of heating at 150 ° C to 350 ° C to cure the photoresist; a step of applying a photoresist on the cured colored film; after pattern exposure of the photoresist, performing alkali development, thereby patterning the photoresist a step of patterning the patterned photoresist as an etch mask, patterning the underlying colored film of the photoresist by dry etching, and removing the patterned photoresist.

<16> A solid-state image sensor having color filter as described in <14> A color filter obtained by the method for producing a color filter according to <15>.

<17> An image display device comprising the color filter according to <14> or a 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 formation of acicular foreign matter in a boundary region between a green pixel and an adjacent colored pixel upon heating at a high temperature. Further, a cured film using the colored resin composition, a color filter, a method of producing a color filter, a solid-state image sensor, and an image display device can be provided.

11‧‧‧1st colored layer

12‧‧‧1st coloring pattern

21‧‧‧Second coloring radiation layer

21A‧‧‧Location corresponding to the first removal group group 121

22‧‧‧2nd coloring pattern

22R‧‧‧ A plurality of second colored pixels provided inside each of the removed portions of the second removal unit group 122

31‧‧‧3rd coloring radiation layer

31A‧‧‧Location corresponding to the second removal group group 122

32‧‧‧3rd coloring pattern

51‧‧‧ photoresist layer

51A‧‧‧Resist Removal Department

52‧‧‧resist pattern (patterned photoresist layer)

100‧‧‧Color filters

120‧‧‧Removal group

121‧‧‧1st removal group

122‧‧‧2nd removal group

Fig. 1 is a schematic cross-sectional view showing a first colored layer.

2 is a schematic cross-sectional view showing a state in which a photoresist layer is formed on a first colored layer.

3 is a schematic cross-sectional view showing a state in which a resist pattern is formed on the first colored layer.

FIG. 4 is a schematic cross-sectional view showing a state in which a first coloring pattern is formed by providing a through hole group in the first colored layer by etching.

Fig. 5 is a schematic cross-sectional view showing a state in which the resist pattern in Fig. 4 is removed.

6 is a schematic cross-sectional view showing a state in which a second colored pattern and a second colored radiation layer are formed.

FIG. 7 is a schematic cross-sectional view showing a state in which a part of the second coloring radiation layer in FIG. 6 and a second coloring element constituting the second coloring pattern are removed.

8 is a schematic cross-sectional view showing a state in which a third colored pattern and a third colored radiation layer are formed.

FIG. 9 is a schematic cross-sectional view showing a state in which the third coloring radiation layer in FIG. 8 is removed.

Hereinafter, the contents of the present invention will be described in detail. In addition, in the specification of the present application, "~" is used in the sense that the numerical values described before and after are included as the lower limit and the upper limit.

In the present specification, the term "total solid content" means the total mass of the components obtained by removing the solvent from the total composition of the composition. In addition, it means a solid component at 25 °C.

In the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). 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, the term "radiation" as used herein means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (Extreme Ultraviolet (EUV) light), an X-ray, an electron beam, or the like. Further, the term "light" as used in the present invention means actinic ray or radiation. The term "exposure" as used in this specification refers not only to the extreme ultraviolet light represented by mercury lamps or excimer lasers, unless otherwise specified. Exposure of lines, X-rays, EUV light, etc., using a beam of electron beams, ion beams, etc., is also included in the exposure.

In the present specification, "(meth)acrylate" means either or both of acrylate and methacrylate, and "(meth)acrylic acid" means either or both of acrylic acid and methacrylic acid," The (meth)acrylonyl group means either or both of an acryloyl group and a methacryl group.

In addition, in this specification, "monomer" and "monomer" have the same meaning. The monomer refers to a compound which is distinguished from an oligomer and a polymer and has 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 "step" refers not only to an independent step, but also to the intended use of the step, as long as the intended effect of the step can be achieved.

In the present specification, the weight average molecular weight and the number average molecular weight are defined by polystyrene equivalent values obtained by gel permeation chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220 (manufactured by Tosoh Corporation) and using TSKgel Super AWM-H (Dongcao) ), manufactured, 6.0 mm ID × 15.0 cm) as a column, and using 10 mmol/L of lithium bromide A solution of N-methyl pyrrolidinone (NMP) was used as the eluent.

The colored resin composition of the present invention (hereinafter sometimes referred to simply as "the composition of the present invention") is characterized by containing polyamic acid and PG58 having a repeating unit represented by the following formula (1).

In the formula (1), R ¹ represents a n+2 valent linking group, R ² represents a divalent linking group, and n represents 1 or 2.

For example, it is known that a color filter using PG58 is heated at a high temperature in a state in which a pixel containing a blue pigment (for example, CI Pigment Blue 15:6 (hereinafter also referred to as "PB15:6") is adjacent to each other. A part of the PG 58 is thermally diffused into the adjacent blue pixel to form a mixed crystal of the thermally diffused PG 58 and the blue pigment, and a needle-shaped foreign matter is formed in the boundary region between the blue pixel and the green pixel. On the other hand, in the present invention, the above problem can be solved by using a colored resin composition containing PG58 and polylysine having a repeating unit represented by the general formula (1). In addition, solvent resistance can also be improved.

Although the mechanism is presumed, the polyamido acid contained in the colored resin composition of the present invention undergoes cyclization of the quinone with a dehydration reaction in the post-baking step after forming the pixel pattern. The polyglycine contained in the colored resin composition of the present invention is cyclized by the quinone imine to form a dense film having a very high film density, so that PG58 can be firmly held in the polyimide film. As a result, the production of acicular foreign matter during high-temperature heating can be suppressed Health.

<Polyuric acid having a repeating unit represented by the general formula (1)>

In the formula (1), R ¹ is a group derived from an acid anhydride, and represents a n+2 valent linking group. The polyamic acid having the repeating unit represented by the formula (1) also functions as a dispersing agent for dispersing PG58 in the colored resin composition. In addition, it also functions as a thermal curing agent.

R ^{1 is} preferably a n+2 valent linking group having 2 to 22 carbon atoms. Specifically, R ^{1 is} preferably a hydrocarbon group or an n+2 valent linking group containing a combination of a hydrocarbon group and at least one of -CO-, -NR-, -O-, -SO ₂ -, and -S-, more preferably It is a hydrocarbon group or an n+2 valent linking group containing a combination of a hydrocarbon group and -CO-. R ¹ may be an n+2 valent linking group containing a combination of one hydrocarbon group and -CO-, -NR-, -O-, -SO ₂ - or -S-, or may contain two or more hydrocarbon groups and An n+2 valent linking group selected from a combination of two or more groups of -CO-, -NR-, -O-, -SO ₂ -, and -S-. Further, in the case where R ¹ is a n+2 valent linking group containing a combination of a hydrocarbon group and at least one of -CO-, -NR-, -SO ₂ -, -O-, and -S-, it is preferably - CO-, -NR-, -O-, -SO ₂ -, and -S- are not adjacent.

R in the -NR- represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom. The hydrocarbon group of the n+2 valent linking group may be linear, branched or cyclic, and is preferably cyclic.

R ¹ preferably contains a cyclic structure, and preferably contains a cyclic hydrocarbon group. The cyclic structure may be an alicyclic ring or an aromatic ring, and is preferably an aromatic ring. In addition, the ring structure may be a single ring or a multiple ring. The ring structure preferably has a 5-membered ring to 8 membered ring, more preferably a 5-membered ring or a 6-membered ring. Further, the cyclic structure may be a single ring or a heterocyclic ring. When the cyclic structure is a hetero ring, the hetero atom constituting the hetero ring may, for example, be a nitrogen atom, an oxygen atom or a sulfur atom.

Specifically, R ¹ preferably contains an alicyclic hydrocarbon group having 3 to 22 carbon atoms or an aromatic hydrocarbon group having 6 to 22 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 22 carbon atoms, and more preferably contains a carbon number. 6 to 12 aromatic hydrocarbon groups.

In the formula (1), R ² is a group derived from a diamine and represents a divalent linking group. R ^{2 is} preferably a divalent linking group having 1 to 22 carbon atoms. Specifically, R ² preferably contains a hydrocarbon group or contains a hydrocarbon group and at least one selected from the group consisting of -Si(R ^2A ) ₂ -, -CO-, -NR-, -O-, -SO ₂ -, -S- A divalent linking group of a combined group.

R ² may be a divalent linking group containing a combination of one hydrocarbon group and -Si(R ^2A ) ₂ -, -CO-, -NR-, -O-, -SO ₂ - or -S-, or a combination comprising two or more hydrocarbon groups and a combination of two or more groups selected from the group consisting of -Si(R ^2A ) ₂ -, -CO-, -NR-, -O-, -SO ₂ -, and -S- Price linkage.

R ^2A each independently represents an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, 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 any of a linear chain, a branched chain or a cyclic group.

R ² preferably has a cyclic structure, and preferably contains a cyclic hydrocarbon group. The cyclic structure has the same meaning as the cyclic structure which R ¹ in the above formula (1) may contain, 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 further preferably a divalent aromatic hydrocarbon skeleton having 6 to 18 carbon atoms. The linking group is particularly preferably a divalent linking group having a stretching phenyl group.

In the formula (1), n represents 1 or 2, preferably 2. By setting it to 2, the effect of the present invention is exerted more effectively.

The polyamic acid used in the present invention is preferably a repeating unit (repeating unit A) having a cyclic structure of R ² in the formula (1). Further, the polylysine used in the present invention may further have a repeating unit (repeating unit B) in which the R ² in the formula (1) contains a hydrocarbon group and a partial structure of -Si(R ^2A ) ₂ - described above (repeating unit B) ). When the polyamine acid has a repeating unit having a partial structure of -Si(R ^2A ) ₂ -, when the colored resin composition is used to form a cured film, the adhesion to the substrate can be further improved.

When the total amount of the repeating unit represented by the formula (1) is set to 100 mol% (% by mole), the amount of the repeating unit B which may be contained is preferably from 0.5 mol% to 15 mol%, more preferably 1 mol. %~10 mol%, and further preferably from 3 mol% to 7 mol%.

The polyglycolic acid having a repeating unit represented by the formula (1) can be synthesized by a known method, for example, by selectively combining an acid anhydride and a diamine and reacting in a solvent.

As the acid anhydride, a tricarboxylic acid anhydride or a tetracarboxylic acid anhydride can be used, and a tetracarboxylic acid anhydride is preferably used.

The tricarboxylic acid anhydride may, for example, be trimellitic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, 1,2,4-naphthalenetricarboxylic acid-1,2-anhydride, 1, 3,8-naphthalenetricarboxylic acid-1,8-anhydride, and the like.

The tetracarboxylic anhydride may, for example, be 3,3',4,4'-benzophenonetetracarboxylic dianhydride, pyromellitic anhydride, 3,3',4,4'-biphenyltrifluoropropane tetracarboxylic acid Dihydride, 3,4,9,10-decanetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3",4,4"-paired triphenyltetracarboxylic acid Anhydride, 3,3",4,4"-m-phenyltetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentane IV Carboxylic dianhydride, 1,2,3,5-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-dicyclohexene tetracarboxylic acid Anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 4,4'-(hexafluoroisopropylidene) di-o-benzene Dicarboxylic anhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxa-3-furanyl)-naphtho[1,2-c]furan- 1,3-diketone and the like.

Examples of the diamine include 4,4'-diaminodiphenyl ether, 4,4' (or 3,3')-diaminodiphenylanthracene, and 4,4'-diaminobenzoic acid. Aniline, 3,3'-(or 4,4')diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 2,5-diaminotoluene, o-toluidine (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-aminobenzene) Oxy)phenyl]hexafluoropropane 1,3-(or 1,4)diaminocyclohexane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4, 4'-Diamino-3,3'-dimethyldicyclohexyl, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and the like.

With respect to the diamine component, a monomer constituting the repeating unit B (for example, (3-aminopropyl)tetramethyldioxane (halothane dioxide) may be used together with the effect of not impairing the effects of the present invention. amine)). The amount of the siloxane diamine is preferably set to 1 mol% to 20 mol% in all the diamines. The oxirane diamine may be used alone or in combination of two or more.

For the solvent which can be used for the synthesis of the polyamic acid having the repeating unit represented by the general formula (1), the following solvents can be used in combination: N-methyl-2-pyrrolidone, N,N-dimethyl B A guanamine-based polar solvent such as guanamine or N,N-dimethylformamide, and a lactone is a polar solvent. The solvent other than the lactone includes, in addition to the guanamine-based polar solvent, methyl cellosolve, ethyl cellosolve, methyl carbitol, and ethyl carbitol. Wait. The term "lactone" refers to a compound having an aliphatic cyclic ester and having a carbon number of 3 to 12. Specific examples thereof include β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone, but are not limited thereto. In particular, in terms of solubility of polyproline, γ-butyrolactone is preferred.

The polyamic acid having a repeating unit represented by the formula (1) may be adjusted by using the acid anhydride or other acid component other than the diamine or other amine component to adjust the molecular weight of the polyglycolic acid. Examples of the other acid component and other diamine components include monofunctional acid and amine components. Examples of the monofunctional acid or amine component include a monocarboxylic acid, a carboxylic acid dianhydride, and a monoamine. Specific examples thereof include benzoic acid, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, and aniline, but are not limited to these specific examples.

The amount of the other acid component or other amine component is preferably from 0.5 mol% to 5 mol% based on the total number of moles of the carboxylic acid dianhydride and the diamine used for the synthesis of the polyamic acid and other acid components and other amine components. More preferably, it is 0.7 mol% to 3 mol%, and further preferably 0.9 mol% to 2 mol%.

The polyamine acid having a repeating unit represented by the formula (1) preferably has a weight average molecular weight of 5,000 or more, more preferably 6,000 to 100,000, and still more preferably 8,000 to 50,000.

The degree of dispersion (mass average molecular weight / number average molecular weight) of the polyamic acid having the repeating unit represented by the general formula (1) is preferably from 1.1 to 4.0, more preferably from 1.5 to 3.0, still more preferably from 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 with respect to the total solid content of the colored resin composition. The mass % to 50% by mass, more preferably 7% by mass to 40% by mass, and further preferably 9% by mass to 30% by mass.

The amount of the polyamic acid having the repeating unit represented by the general formula (1) may be set to 90% by mass or may be set to 95% by mass based on the total mass of the resin component contained in the colored resin composition. 100% by mass.

The colored resin composition may contain only one polyamino acid having a repeating unit represented by the general formula (1), or may contain two or more polylysines having a repeating unit represented by the general formula (1). In the case of a polyamic acid containing two or more kinds of repeating units represented by the formula (1), it is preferred that the total amount corresponds to the 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 by reference.

The average primary particle size of PG58 used in the present invention is actually 10 nm or more. From the viewpoint of obtaining a better contrast, 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. In addition, as an index indicating the monodispersity of the particles, the ratio (Mv/Mn) of the volume average particle diameter (Mv) to the number average particle diameter (Mn) is used in the present invention unless otherwise specified. The monodispersity of the pigment fine particles (primary particles), that is, Mv/Mn is preferably from 1.0 to 2.0, more preferably from 1.0 to 1.8, still more preferably from 1.0 to 1.5. Further, in the present invention, the average primary particle diameter of the particles is obtained by observing an approximate diameter of the circle based on an image observed by a transmission electron microscope, and is set to 500 average value.

The method for preparing the particles of PG58 may be prepared according to a usual method, for example, by pulverizing by milling (breaking down), or by precipitation using a good solvent and a poor solvent ( Build-up method). Regarding the former (grinding method), the pigment particles can be refined by a usual method using a bead mill or the like. For example, the description described in the item "Mechanical Crushing" of the Japanese Society of Image Society, Vol. 45, No. 5 (2006), pages 12-21 can be referred to. The latter (construction method) is also referred to as a reprecipitation method, and the like, for example, Japanese Patent Laid-Open No. 2011-026452, Japanese Patent Laid-Open No. 2011-012214, Japanese Patent Laid-Open No. 2011-001501, and Japan JP-A-2010-235895, JP-A-2010-2091, JP-A-2010-209160, and the like.

<Other colorants>

The colored resin composition may contain other colorants other than PG58, and may not contain other colorants other than PG58. Other coloring agents may be used alone or in combination of two or more.

The colored resin composition may also contain a yellow coloring agent as another coloring agent. The yellow coloring agent is preferably a yellow pigment, more preferably at least one selected from the group consisting of C.I. Pigment Yellow 129, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, and C.I. Pigment Yellow 185, and further preferably C.I. Pigment Yellow 129. By setting this configuration, the effects of the present invention can be further enhanced.

The colored resin composition of the present invention may further contain one or more phthalocyanine pigments selected from the group consisting of aluminum (Al), titanium (Ti), iron (Fe), and the like. One of a group consisting of tin (Sn), lead (Pb), gallium (Ga), vanadium (V), molybdenum (Mo), tantalum (Ta), and niobium (Nb) as a central metal halide phthalocyanine pigment And halogenated phthalocyanine pigments without a central metal. By setting such a configuration, the effect of the present invention is excellent, and a cured film which is less likely to cause color mixing of other colors can be formed. The content of the phthalocyanine pigment is preferably 5% by mass or less, and more preferably 0.5% by mass to 2% by mass based on the content of PG58 in the colored resin composition.

As the other organic pigment which can be appropriately added to the colored resin composition of the present invention, other organic pigments, inorganic pigments, dyes and the like other than the PG58 and yellow pigment can be used.

Other organic pigments which can be appropriately added to the colored resin composition of the present invention include, for example, CI Pigment Yellow 11, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 53, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 99, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 147, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 167, CI Pigment Yellow 180, CI Pigment Yellow 199; CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 43, CI Pigment Orange 71; CI Pigment Red 81, CI Pigment Red 105, CI Pigment Red 122, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 155, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 209, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 270; CI pigment violet 19, CI pigment violet 23, CI pigment violet 32, CI pigment violet 39; CI pigment blue 1, CI pigment blue 2, CI pigment blue 15, CI pigment blue 15: 1, CI pigment blue 15: 3, CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 66; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37; CI Pigment Brown 25, CI Pigment Brown 28 ; CI Pigment Black 1 and so on.

The inorganic pigment which can be appropriately added to the colored resin composition of the present invention may be a metal compound represented by a metal oxide or a metal salt or a salt, and specific examples thereof include iron, cobalt, aluminum, cadmium, lead, copper, titanium, and magnesium. a metal oxide such as chromium, zinc or bismuth or a composite oxide of the metal, or a black pigment such as carbon black or titanium black.

A known dye which can be appropriately added to the coloring resin composition of the present invention can be used, for example, in Japanese Patent Laid-Open Publication No. SHO 64-90403, Japanese Patent Laid-Open No. Hei 64-91102, and Japanese Patent Laid-Open No. Hei No. 1-94301 Japanese Patent Laid-Open No. Hei 6-11614, Japanese Patent Registration No. 2592207, U.S. Patent No. 4,808,501, U.S. Patent No. 5,567,920, U.S. Patent No. 5,505,950, U.S. Patent No. 5,567,920, Japanese Patent Laid-Open No. 5-333207 The pigment disclosed in Japanese Laid-Open Patent Publication No. Hei 6-35183, Japanese Patent Application Laid-Open No. Hei No. Hei. If distinguished by chemical structure, pyrazole azo compounds, pyrrolemethylene compounds, anilino azo compounds, triphenylmethane compounds, hydrazine compounds, benzylidene compounds, oxonium compounds, pyrazoles can be used. And triazole azo compounds, pyridone azo a compound, a cyanine compound, a phenothiazine compound, a pyrrolopyrazole azomethine compound, and the like. Further, a dye polymer can also be used as the dye. The compound described in Japanese Laid-Open Patent Publication No. 2011-041097, and the Japanese Patent Publication No. 2013-041097.

The content of PG58 in the colored resin composition is preferably from 20% by mass to 80% by mass, more preferably from 30% by mass to 70% by mass, even more preferably from 40% by mass to 60% by mass based on the total solid content of the colored resin composition. quality%.

In the case where the colored resin composition further contains a yellow coloring agent, the content of the yellow coloring agent in the colored resin composition is preferably from 10 parts by mass to 100 parts by mass, more preferably PG58 (100 parts by mass). 20 parts by mass to 85 parts by mass. Further, the amount of CI Pigment Yellow 129, CI Pigment Yellow 150, and CI Pigment Yellow 185 is preferably 85% by mass or more, and more preferably 90% by mass or more based on the total amount of the yellow coloring agent contained in the colored resin composition. Further, it is preferably 95% by mass to 100% by mass.

<Pigment Derivative>

The composition of the present invention may further contain a pigment derivative. The pigment derivative is preferably a compound (hereinafter also referred to as a specific pigment derivative) having a pigment core structure and an amine group in the molecule.

By using a specific pigment derivative, an interaction between the pigment core structure in the specific pigment derivative and PG58 can be formed, and the adsorptivity of both can be more effectively ensured.

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

In the 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 or unsaturated carbon group having 3 to 20 carbon atoms. Cycloalkyl or aryl. These organic groups may also have more substituents. Further examples of the substituent which may be mentioned include a halogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, and an aromatic group. Oxygen, thioalkoxy, thioaryloxy, carboxy, alkoxycarbonyl, sulfo, sulfonylamino, ureido, thioureido, amine, amidino, carbonyl, nitro or Substituents for these groups.

Further, R ¹ and R ² may be bonded to each other to form a ring.

In particular, the compound represented by the formula (A) is preferably a compound having at least one of a guanamine structure and a urea structure in the molecule. Further, the compound represented by the formula (A) is preferably a compound having a heterocyclic structure.

In the formula (A), X is an m-valent group containing a pigment core structure. Here, the pigment mother core structure is a chromogenic atomic group in an organic pigment, a similar structure or a partial structure thereof, and specifically includes a skeleton having an azo group, a skeleton having a urea structure, a skeleton having a guanamine structure, and a ring. The structure of the guanamine structure, the aromatic ring having a 5-membered ring containing a hetero atom, and the structure of one or more partial structures of an aromatic ring having a 6-membered ring containing a hetero atom. X is a substituent containing the core structure of the pigments.

X in the general formula (A) preferably has a pigment core structure or a pigment core structure and an aromatic ring, or a nitrogen-containing aromatic ring, or an oxygen-containing aromatic ring, or a sulfur-containing aromatic ring, and the amine group is directly or by The linking group is bonded to any one of a pigment core structure, an aromatic ring, a nitrogen-containing aromatic ring, an oxygen-containing aromatic ring, and a sulfur-containing aromatic ring. It is particularly preferred to have a pigment core structure and an aromatic ring, or a nitrogen-containing aromatic ring, and to bond with an amine group by a divalent linking group.

In the general formula (A), m is an integer of from 1 to 8, and from the viewpoint of dispersibility and storage stability of the dispersion, it is preferably from 1 to 6, more preferably from 1 or 2.

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

Cu-cp: copper phthalocyanine residue

Particularly, the pigment derivative used in the composition of the present invention is preferably the following compound.

The pigment derivative shown below is preferably a metal salt having a carboxylic acid group or a sulfonic acid group or the acid groups. An ammonium salt as a pigment derivative of a substituent. Specifically, among the pigment derivatives shown below, it is preferred to use the pigment derivatives represented by (A) to (I), and more preferably the pigments represented by (A), (B), and (I). derivative.

CuPc: copper phthalocyanine skeleton

The content of the pigment derivative is preferably from 0.5 part by mass to 50 parts by mass, more preferably 100 parts by mass of all the pigments containing PG58 in the colored resin composition. It is 1 part by mass to 25 parts by mass, and more preferably 5 parts by mass to 15 parts by mass.

The pigment derivative may be contained alone or in combination of two or more kinds in the colored resin composition. When two or more cases are contained, it is preferable that the total amount is the said range.

<Diamine compound represented by the general formula (2)>

The composition of the present invention preferably further contains a diamine compound represented by the formula (2).

H ₂ NR ³ -NH ₂ (2)

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

By setting the above configuration, the effects of the present invention can be more effectively achieved. Although the mechanism is presumed, in general, when a coating film containing polyamic acid is heated at a high temperature, the polyaminic acid undergoes quinone cyclization accompanied by a dehydration reaction by a reaction mechanism represented by the following formula (a). , the film hardens. In this case, when an amine compound is contained in the coating film, the amine compound (R ³ -NH ₂ in the following formula (b)) functions as a base catalyst by a reaction mechanism represented by the following formula (b). Promotes hardening of the coating film caused by cyclization of quinone imine. In this way, by promoting the hardening of the coating film, PG58 is more firmly held in the polyimide film, so that generation of needle-shaped foreign matter during high-temperature heating of the obtained color filter can be suppressed.

In the formula (2), R ³ is a group derived from a 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 divalent linking group containing a hydrocarbon group or a group containing a combination of a hydrocarbon group and -CO-, -NR-, -O-. R in -NR- represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The hydrocarbon group may be any of a linear chain, a branched chain or a cyclic group.

R ³ preferably has a cyclic structure, and preferably contains a cyclic hydrocarbon group. The cyclic structure has the same meaning as the cyclic structure which R ² in the above formula (1) may contain. Further, the same as the preferred range of R ³ in the general formula (1) R ^2.

Further, R ³ in the formula (2) is preferably a divalent linking group containing the same skeleton as R ² in the formula (1). Compatible containing polyamide acid having the general formula (2) in the diamine compound of the general formula R (1) ³ represented by the general formula linked to the same skeleton ² R (1) is a divalent group Since it is excellent in the properties, it is more effective as a catalyst for the thermosetting reaction of polylysine represented by the formula (1), and the effects of the present invention can be more effectively achieved.

Here, the same skeleton as R ² means that at least a part of the atoms constituting the divalent linking group are common. For example, when R ² is a phenylene group, R ³ may be a phenyl group, may be substituted by a phenyl group, or may be a group containing a combination of a phenyl group and -O-. In particular, R ³ preferably has the same partial structure as R ² in the formula (1), and more preferably has the same structure as R ² in the formula (1).

Specific examples of the diamine compound represented by the formula (2) include diamines which can be used in the synthesis of the polyamic acid.

The content of the diamine compound represented by the formula (2) in the colored resin composition is preferably from 0.01% by mass to 10% by mass, more preferably from 0.1% by mass to 2% by mass based on the total solid content of the colored resin composition. %, further preferably 0.3% by mass to 0.8% by mass, particularly preferably 0.4% by mass to 0.7% by mass.

The diamine compound represented by the formula (2) may be used alone or in combination of two or more. When two or more cases are used, it is preferred that the total amount thereof corresponds to the content.

<organic solvent>

The composition of the present invention may further contain an organic solvent.

The organic solvent is not particularly limited as long as it satisfies the solubility of each component or the coatability of the colored resin composition.

The organic solvent may preferably be exemplified by esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, and isopropyl butyrate. Ester, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg methoxy) Methyl acetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-oxopropane Base esters (eg methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxyl) Methyl propionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-oxopropionate (eg methyl 2-oxypropionate, ethyl 2-oxypropionate, 2- Propyl oxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -ethyl ethoxypropionate)), methyl 2-oxy-2-methylpropanoate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2-methyl) Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl acetate, 2 - methyl oxobutanoate, ethyl 2-oxobutanoate, γ-butyrolactone, etc.; and as ethers such as 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, etc.; and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; and as aromatic hydrocarbons, for example Toluene, xylene; and, for example, 3-methyl-3-methoxybutanol as an alcohol.

From the viewpoint of the coating property, the content of the organic solvent in the colored resin composition is preferably such that the total solid content concentration of the composition is from 5% by mass to 80% by mass, more preferably from 5% by mass to 60% by mass. The mass% is particularly preferably 10% by mass to 50% by mass.

The composition of the present invention may contain only one organic solvent, and may contain two or more organic solvents. In the case of containing two or more organic solvents, it is preferred to The measurement is in the range.

<Other ingredients>

The colored resin composition of the present invention may contain a pigment dispersant, a polymerizable compound, a polymerization initiator, an alkali-soluble resin, a surfactant, an alkaline earth metal ion or the like as a component other than the above components.

(pigment dispersant)

In the composition of the present invention, since the polyamic acid also functions as a pigment dispersant, it may be substantially free of a pigment dispersant or may further contain a pigment dispersant.

Examples of the pigment dispersant include polymer dispersants [for example, polyamine-amines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified Poly(meth)acrylate, (meth)acrylic copolymer, sulfamic acid naphthalenesulfonate condensate], and polyoxyalkylene alkyl phosphate, polyoxyethylene ethylamine, alkanolamine Such as surfactants, 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 according to the structure thereof.

For the pigment dispersant, for example, the description of paragraphs 0216 to 0022 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated into the specification of the present application.

When the pigmented resin composition further contains a pigment dispersant, the total content of the pigment dispersant may be set to 1 part by mass to 80 parts by mass, or may be set to 5 parts by mass, based on 100 parts by mass of the pigment containing PG58. 70 parts by mass may be set to 10 parts by mass 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 may be set to 5 parts by mass or less, or may be set to 1 part by mass or less, based on 100 parts by mass of the pigment containing PG58. Can be set to 0 parts by mass.

(polymerizable compound)

In the composition of the present invention, since the polyamic acid also functions as a thermosetting agent, it may not substantially contain a polymerizable compound, and may further contain a polymerizable compound.

The polymerizable compound can be referred to, for example, the description of paragraphs 0129 to 0136 of JP-A-2011-137125, which is incorporated herein by reference.

When the composition of the present invention contains a polymerizable compound, the content of the polymerizable compound may be set to 1% by mass to 10% by mass based on the total solid content of the composition of the present invention, and may be set to 0.1% by mass. 3 mass%.

When the composition of the present invention contains substantially no polymerizable compound, the content of the polymerizable compound may be set to 1% by mass or less, or may be set to 0.1% by mass or less based on the total solid content of the composition of the present invention. It can also be set to 0% by mass.

(polymerization initiator)

The composition of the present invention may contain a polymerization initiator, and may be substantially free of a polymerization initiator. Particularly in the case where the composition of the present invention is used in a dry etching process, it is preferably substantially free of a photopolymerization initiator.

The polymerization initiator can be appropriately selected, for example, from a known photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more.

Examples of the polymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton, a oxadiazole skeleton, etc.), a mercaptophosphine compound such as a mercaptophosphine oxide, and a hexaaryl group. An anthracene compound such as an imidazole or an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a ketoxime, an aminoacetophenone compound, or hydroxyacetophenone.

For the ruthenium compound, for example, the formula (OX-1) or the formula (OX-2) after the paragraph 0513 of the Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to [0632] of the specification of the U.S. Patent Application Publication No. 2012/235099) can be referred to. The description of the compounds indicated is incorporated herein by reference.

In addition, the polymerization initiator can use TRONLY TR-PBG-304, TRONLY TR-PBG-309, and TRONLY TR-PBG-305 (CHANGZHOU TRONLY NEW) Commercial products such as manufactured by ELECTRONIC MATERIALS CO., LTD).

When the composition of the present invention contains a polymerization initiator, the content of the polymerization initiator may be set to 1% by mass to 5% by mass based on the total solid content of the composition of the present invention, and may be set to 0.1 mass. %~1% by mass.

When the composition of the present invention contains substantially no polymerization initiator, the content of the polymerization initiator may be set to 1% by mass or less, or may be set to 0.1 mass, based on the total solid content of the composition of the present invention. Below %, it can also be set to 0% by mass.

(alkali soluble resin)

The alkali-soluble resin can be appropriately selected from the following alkali-soluble resins, which are linear organic high molecular polymers, and are molecules (preferably molecules having an acrylic copolymer or a styrene copolymer as a main chain). It has at least one group that promotes alkali solubility.

The alkali-soluble resin can be referred to the following paragraphs 0558 to 5571 of the Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to U.S. Patent Application Publication No. 2012/0235099, the specification of [0685] to [0700]). The content is incorporated into the specification of the present application.

When the colored resin composition of the present invention contains an alkali-soluble resin, the content of the alkali-soluble resin in the total solid content of the composition of the present invention may be set to 0.01% by mass to 10% by mass, or may be set to 1 mass. %~5 mass%.

(surfactant)

The composition of the present invention may further contain various surfactants from the viewpoint of further improving coatability.

As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used. In particular, the composition of the present invention can further improve the solution characteristics (particularly fluidity) when the coating liquid is prepared by containing a fluorine-based surfactant, and can further improve the uniformity of the coating thickness or the liquid-saving property.

In other words, when the film formation is carried out using a coating liquid using a composition containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the surface to be coated is wetted. The properties are improved, and the coatability to the coated surface is improved. Therefore, even when a film having a thickness of a few micrometers (μm) is formed with a small amount of liquid, it is possible to more preferably form a film having a uniform thickness having a small thickness unevenness, which is effective in this respect.

The fluorine content in the fluorine-based surfactant is preferably from 3% by mass to 40% by mass, more Preferably, it is 5 mass% to 30 mass%, and particularly preferably 7 mass% to 25% by mass. The fluorine-containing surfactant is effective in the uniformity of the thickness of the coating film or the liquid-saving property in the range of the fluorine-based surfactant, and the solubility in the composition is also good.

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

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates of such compounds (for example, propoxylated glycerol, ethoxylation). Glycerin, etc., polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethyl octyl phenyl ether, polyoxyethyl thiol Phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearyl Acid esters, sorbitan fatty acid esters (Pluronic L10, Pluronic L31, Pluronic L61, Pluronic L62, Pluronic, manufactured by BASF) 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tetronic 701, Tetronic 704, Tetronic 901, Trow Tetronic 904, Tetronic 150R1), Solsperse 20000 (Lubrizol Japan).

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: Efka (EFKA)-745, manufactured by Morishita Industries Co., Ltd.), and an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). , (meth)acrylic (co)polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (Common Chemicals ( () manufacturing), W001 (Yu Shang (share) manufacturing) and so on.

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusei Co., Ltd.).

Examples of the fluorenone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, and East, manufactured by Toray-Dow Corning Co., Ltd. Toray Silicone DC11PA", "Toray Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Dong Lizhen" Toray Silicone SH30PA", "Toray Silicone" SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452" manufactured by Momentive Performance Materials, Inc. "KP341", "KF6001" and "KF6002" manufactured by the company, "BYK 307", "BYK 323" and "BYK" 330 manufactured by BYK Chemie "Wait.

When the surfactant is contained in the composition of the present invention, the content of the surfactant is preferably from 0.001% by mass to 2.0% by mass, more preferably from 0.005% by mass to 1.0%, based on the total mass of the composition of the present invention. quality%.

The composition of the present invention may contain only one surfactant and may contain two or more surfactants. In the case where two or more kinds of surfactants are contained, it is preferred that the total amount thereof is in the above range.

(alkaline earth metal ion)

The colored resin composition of the present invention may further contain an alkaline earth metal ion (for example, calcium ion or the like). By setting such a configuration, the effect of the present invention is excellent, and the generation of acicular foreign matter due to the mixed crystal of molten zinc phthalocyanine and copper phthalocyanine can be more effectively suppressed. For example, the content of the alkaline earth metal ions can be set to 30 ppm by mass to 300 ppm by mass with respect to the mass of the PG58.

In addition to the above, various additives such as a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomerating agent, and the like may be blended as needed in the colored resin composition. The additives described in paragraphs 0155 to 0156 of JP-A-2004-295116 may be incorporated into the specification of the present application.

The composition of the present invention may contain the sensitizer or light stabilizer described in paragraph 0078 of JP-A-2004-295116, and the heat-resistant polymerization agent described in paragraph 0081 of the publication.

<Method for Producing Colored Resin Composition>

The composition of the present invention can be prepared by mixing the above components.

Further, in the preparation of the composition of the present invention, the components constituting the colored resin composition may be blended together, or the respective components may be dissolved and dispersed in a solvent and then sequentially formulated. In addition, the order of input or the working conditions at the time of preparation are not particularly limited. For example, all the components may be simultaneously dissolved and dispersed in a solvent to prepare a colored resin composition, and if necessary, each component may be appropriately prepared into two or more kinds of solutions and dispersions, and when used (at the time of coating), These solutions and dispersions were mixed to prepare a composition.

The composition of the present invention is preferably prepared by dispersing a dispersion of PG58 by a dispersing agent into other components.

The composition of the present invention is preferably filtered by a filter to remove foreign matter or to reduce defects and the like.

The filter used for the filtration of the filter is not particularly limited as long as it is a filter that can be used for filtration purposes and the like.

Examples of the material of the filter include fluororesins such as polytetrafluoroethylene (PTFE); polyamine-based resins such as nylon-6 and nylon-6,6; and polycondensation of polyethylene and polypropylene (PP). Olefin resin (including high density, ultra high molecular weight) and the like. Among these raw materials, polypropylene (including high density polypropylene) is preferred.

The pore diameter of the filter is not particularly limited, and is, for example, about 0.01 μm to 20.0 μm, preferably about 0.01 μm to 5 μm, and more preferably about 0.01 μm to 2.0 μm.

By setting the pore diameter of the filter to the above range, fine particles can be removed more effectively, and the turbidity can be further reduced.

Here, the pore size of the filter can be referred to the nominal value of the filter manufacturer. Commercially available filters are available, for example, from Pall Co., Ltd., Advantec Toyo Co., Ltd., and Entegris Co., Ltd. (formerly Japan, Mykrolis) )))) or various filters provided by KITZ Micro Filter Co., Ltd., etc.

When the filter is filtered, two or more types of filters may be used in combination.

For example, the first filter may be used for filtration, and then the second filter having a different pore size than the first filter may be used for filtration.

In this case, the filtration by the first filter and the filtration by the second filter may be performed only once or twice or more.

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

<Use>

The cured film obtained by hardening the composition of the present invention is preferably used for forming a colored pattern of a color filter because other colors are not easily mixed on the surface. In addition, the composition of the present invention can be preferably used to form solid-state imaging elements (for example, CCD, mutual A coloring pattern such as a color filter used in an image display device such as a metal oxide semiconductor (CMOS) or a liquid crystal display (LCD). Among them, it can be preferably used for the production of color filters for solid-state imaging devices such as CCDs and CMOSs. Further, the composition of the present invention can be preferably used as a colored resin composition for dry etching.

<Method for Producing Cured Film, Pattern Forming Method, Color Filter, and Color Filter>

Next, the cured film, the pattern forming method, and the color filter of the present invention will be described in detail by a method for producing the same. Further, a method of manufacturing a color filter using the pattern forming method of the present invention will also be described.

The cured film of the present invention is obtained by hardening the composition of the present invention. The cured film can be preferably used for a color filter.

The pattern forming method of the present invention applies the composition of the present invention to a support to form a colored resin composition layer, and removes an unnecessary portion to form a colored pattern.

The pattern forming method of the present invention can be preferably used to form a color pattern (pixel) which the color filter has.

The colored resin composition of the present invention can be patterned by dry etching, or a color filter can be produced by pattern formation by a so-called photolithography method.

That is, the first embodiment of the pattern forming method of the present invention can exemplify a pattern forming method including the following steps: forming a colored resin composition on a support to form a step of coloring the resin composition layer to form a colored layer; forming a photoresist layer on the colored layer; and 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 etch mask.

Further, the second embodiment of the pattern forming method of the present invention can exemplify a pattern forming method including the steps of applying a colored resin composition to a support to form a colored resin composition layer, and forming a colored resin composition layer by a step of performing exposure in a pattern; and a step of developing and removing the unexposed portion to form a colored pattern.

Such a pattern forming method can be used to fabricate a colored layer of a color filter. That is, in the present invention, a method of manufacturing a color filter including the pattern forming method of the present invention is also disclosed.

Hereinafter, the methods will be described in detail.

Hereinafter, each step in the pattern forming method of the present invention will be described in detail by a method of producing a color filter for a solid-state image sensor, but the present invention is not limited to this method. Hereinafter, the color filter for a solid-state imaging device may be simply referred to as a "color filter".

Preferably, the method for producing a color filter of the present invention comprises the steps of: applying a colored resin composition onto a substrate to form a colored film (colored layer); and applying a colored film coated on the substrate at 150 ° C a step of heating to cure at ~350 ° C; a step of applying a photoresist on the cured colored film; after pattern exposure of the photoresist, performing alkali development, thereby patterning the photoresist a step of using a patterned photoresist as an etch mask to dry the underlying layer of the photoresist by dry etching a step of patterning the film; and a step of removing the patterned photoresist.

Hereinafter, a method of manufacturing the color filter of the present invention will be described with reference to specific examples using FIGS. 1 to 9.

<<<Steps for forming the first coloring pixel>>>

In the step of forming the first colored pixel, the first colored pixel is preferably formed by dry etching.

In the method of producing a color filter of the present invention, first, as shown in the schematic cross-sectional view of FIG. 1, the first colored layer 11 is formed as a first colored resin composition as a colored resin composition (step (A) ). The coloring resin composition of the present invention can be used as the first colored resin composition.

The first colored layer 11 is preferably a green transparent layer. By setting the first colored layer 11 as a green transparent layer, the color sensitivity can be further improved.

The first colored layer 11 can be formed, for example, by a rotary coating, a slit coating, a spray coating, a spin coating method, a rotary coating, a cast coating, or the like. A coating method such as roll coating applies a colored resin composition onto a support and dries it to form a colored layer. It is particularly preferred to carry out the coating by a spin coating method.

The support is not particularly limited as long as it is a support used for the color filter, and examples thereof include soda glass, borosilicate glass, and quartz glass used in liquid crystal display elements and the like. A support for a transparent conductive film or a substrate for a photoelectric conversion element used in a solid-state image sensor or the like, such as an oxide film or tantalum nitride, is attached to the glass. In addition, as long as the invention is not damaged, the An intermediate layer or the like is disposed between the support and the color filter.

The thickness of the first colored layer 11 after drying is preferably in the range of 0.3 μm to 2.0 μm, more preferably in the range of 0.35 μm to 1.5 μm, and still more preferably in the range of 0.35 μm to 1.2 μm.

The first colored layer 11 is preferably hardened by heating by a heating means such as a hot plate or an oven. The heating temperature is preferably from 90 ° C to 250 ° C, more preferably from 100 ° C to 230 ° C. The heating time varies depending on the heating mechanism. When heating is performed on a hot plate, it is usually about 2 minutes to 30 minutes. When heating in an oven, it is usually about 30 minutes to 90 minutes.

Further, it is preferable that the first colored layer 11 is further subjected to heat treatment (post-baking). The heating temperature for post-baking is preferably from 150 ° C to 350 ° C, more preferably from 200 ° C to 250 ° C. The heating time varies depending on the heating mechanism, and is usually about 20 minutes to 90 minutes.

Then, patterning is performed by dry etching so that the removed portion group is formed in the first colored layer 11 (step (B)). Thereby, the first coloring pattern is formed. According to this method, the first colored layer is formed by the first colored resin composition, and the removal portion is grouped by exposure and development of the first colored layer, so that the required portion can be more reliably provided. A group of removal portions of a shape (especially a rectangular shape).

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

Specifically, a positive or negative photoresist is applied onto the first colored layer 11 and dried to form a photoresist layer. When the photoresist layer 51 is formed, Jia is further implementing pre-baking treatment. In particular, the formation process of the photoresist is preferably a form in which heat treatment (Post exposure bake (PEB)) after exposure and heat treatment (post-baking treatment) after development are performed.

As the photoresist, for example, a positive photoresist can be used. The positive type resist can be used: a positive type resist suitable for inducing ultraviolet rays (g rays, h rays, i rays), far ultraviolet rays including excimer lasers, electron beams, ion beams, and X-rays. A positive resist composition for the agent. In the radiation, it is preferably g-ray, h-ray, or i-ray, and among them, i-ray is preferable.

Specifically, the positive type resist is preferably a composition containing a quinonediazide compound and an alkali-soluble resin. The quinonediazide compound may be a naphthoquinonediazide compound.

The thickness of the dried photoresist layer 51 is preferably from 0.1 μm to 3 μm, preferably from 0.2 μm to 2.5 μm, and more preferably from 0.3 μm to 2 μm. Further, the application of the photoresist layer 51 can be preferably carried out by using the coating method of the first colored layer 11.

Then, as shown in the schematic cross-sectional view of FIG. 3, the photoresist layer 51 is exposed and developed, thereby forming a resist pattern (patterned photoresist layer) provided with the resist removal portion group 51A. ) 52.

The formation of the resist pattern 52 is not particularly limited, and a conventionally known photolithography technique can be used. The resist removal portion group 51A is provided in the photoresist layer 51 by exposure and development, whereby the resist pattern 52 as an etching mask used in the subsequent etching is provided on the first colored layer 11. .

The exposure of the photoresist layer 51 can be performed by interposing a predetermined mask pattern, using g-rays, h-rays, i-rays, etc., preferably i-rays, positive or negative. The type of photoresist is exposed. After the exposure, the developing treatment is performed by the developing solution, whereby the photoresist is removed corresponding to the region where the colored pattern is to be formed.

The developer 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. For example, various organic solvents can be used. Combination or alkaline aqueous solution.

The alkaline aqueous solution is preferably an alkaline aqueous solution prepared by dissolving a basic compound in a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass. Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and hydroxide. Tetraethylammonium, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]- 7-undecene and the like. Further, when an alkaline aqueous solution is used as the developer, the cleaning treatment is usually carried out using water after development.

Then, as shown in the schematic cross-sectional view of FIG. 4, the resist pattern 52 is used as an etching mask, and patterned by dry etching so that the removed 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 the first removal unit group 121 and the second removal unit group 122.

The removal portion group 120 is provided in the first colored layer 11 in a checkerboard pattern. Therefore, the first colored pattern 12 in which the removed portion group 120 is provided in the first colored layer 11 has a plurality of square-shaped first colored pixels in a checkerboard pattern.

Specifically, in the dry etching, the first colored layer 11 is dry etched using the resist pattern 52 as an etching mask. A representative example of dry etching can be listed Japanese Patent Laid-Open No. 59-126506, Japanese Patent Laid-Open No. Sho 59-46628, Japanese Patent Laid-Open No. Sho 58-9108, Japanese Patent Laid-Open No. Sho 58-2809, Japanese Patent Laid-Open No. 57-148706 The method described in the gazettes of Japanese Patent Laid-Open No. 61-41102, etc., is incorporated herein by reference.

From the viewpoint of forming the pattern cross section closer to a rectangular shape or further reducing the damage to the support, the dry etching is preferably carried out in the following form.

It is preferable to include a form of etching in which the first-stage etching is performed by using a mixed gas of a fluorine-based gas and oxygen (O ₂ ) until a region (depth) in which the support is not exposed; and the second-stage etching is performed. After the etching in the first stage, etching is performed using a mixed gas of nitrogen (N ₂ ) and oxygen (O ₂ ) until it is preferably near the region (depth) where the support is exposed; and after the support is exposed Etching. Hereinafter, a specific method of dry etching, etching in the first stage, etching in the second stage, and over etching will be described.

Dry etching can be performed by previously obtaining etching conditions by the following method.

(1) The etching rate (nm/min) in the etching in the first step and the etching rate (nm/min) in the etching in the second step were respectively calculated.

(2) The time required for the etching in the first-stage etching and the time required for the etching in the second-stage etching are calculated.

(3) The first-stage etching is performed in accordance with the etching time calculated in the above (2).

(4) The second-stage etching is performed in accordance with the etching time calculated in the above (2). Alternatively, the end point can be used to determine the etching time and The second-stage etching is performed in accordance with the determined etching time.

(5) The over-etching time is calculated with respect to the total time of the above (3) and (4), and over-etching is performed.

The mixed gas used in the first-stage etching step preferably contains a fluorine-based gas and oxygen (O ₂ ) from the viewpoint of processing the organic material as the film to be processed into a rectangular shape. Further, by setting the etching step of the first step to a form that is etched to a region where the support is not exposed, damage of the support can be avoided.

Further, in the second etching step and the over-etching step, it is preferable to use a mixed gas of a fluorine-based gas and oxygen in the first-stage etching step from the viewpoint of avoiding damage of the support. After etching is performed until the region where the support is not exposed, the etching treatment is performed using a mixed gas of nitrogen gas and oxygen gas.

The ratio of the amount of etching in the etching step in the first step to the amount of etching in the etching step in the second step is determined to be such that the rectangularity obtained by the etching treatment in the etching step of the first step is not impaired. . Further, the ratio of the latter in the total etching amount (the total amount of etching in the etching step in the first step and the etching amount in the etching step in the second step) is preferably in a range of more than 0% and 50% or less. More preferably 10% to 20%. The amount of etching refers to an amount calculated from the difference between the film thickness remaining in the film to be etched and the film thickness before etching.

In addition, the etching preferably includes an overetching process. The overetching treatment is preferably performed by setting an overetch ratio. Further, the overetch ratio is preferably calculated based on the etching processing time performed first. The overetch ratio can be arbitrarily set, and in terms of maintaining the etching resistance of the photoresist and the rectangularity of the etched pattern, it is preferably in the etching step. The etching treatment time is 30% or less, more preferably 5% to 25%.

Then, as shown in the schematic cross-sectional view of FIG. 5, the resist pattern (ie, the etching mask) 52 remaining after the etching is removed. The removal of the resist pattern 52 preferably includes the steps of: applying a stripping liquid or a solvent to the resist pattern 52, adjusting the resist pattern 52 to a removable state; and using the cleaning water to remove the resist The step of pattern 52 removal. For example, a step of applying a peeling liquid or a solvent to at least the resist pattern 52 and stopping it for a predetermined period of time to carry out liquid-coating development may be mentioned. The time for stopping the stripping solution or the solvent is not particularly limited, and is preferably from several tens of seconds to several minutes. Further, for example, washing water may be sprayed onto the resist pattern 52 from a spray or spray type spray nozzle to remove the resist pattern 52.

Pure water can be preferably used for the washing water. Further, the injection nozzle may be an injection nozzle including the entire support in the injection range thereof, or an injection nozzle which is a movable injection nozzle and whose movable range includes the entire support.

<<<Steps for forming the second coloring 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 linear composition. In the present invention, the second colored pixel is formed by photolithography, whereby 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 pixel, as shown in the schematic cross-sectional view of FIG. 6, the second coloring-sensitive radiation composition is embedded in each of the first removal unit group 121 and the second removal unit group 122. The inside of the portion is on the first colored layer (that is, the first colored pattern 12 in which the removed portion group 120 is formed in the first colored layer 11) The second coloring sensitizing radiation layer 21 is laminated by the second coloring sensitizing radiation composition (step (C)). Thereby, the second colored pattern 22 having the plurality of second colored pixels is formed in the removed portion group 120 of the first colored layer 11. Here, the second colored pixel is preferably a quadrangular pixel. The formation of the second coloring radiation layer 21 can be performed in the same manner as the method of forming the first coloring layer 11.

The thickness of the second coloring radiation layer 21 after post-baking is preferably from 0.1 μm to 1.5 μm, more preferably from 0.1 μm to 1.0 μm.

Then, the second coloring radiation layer 21 is exposed and developed at a position 21A corresponding to the first removal portion group 121 provided in the first coloring layer 11, whereby the second coloring radiation layer 21 is formed. And a plurality of second colored pixels 22R provided in the respective removed portions of the second removal unit group 122 are removed (step (D)) (see a schematic cross-sectional view of FIG. 7).

In particular, it is preferable to use ultraviolet rays (especially i-rays) such as g-rays and i-rays for radiation (light) which can be used for exposure. Irradiation amount (exposure amount) is preferably ^{30mJ / cm 2 ~ 3000mJ / cm} 2, more preferably ^{50mJ / cm 2 ~ 2500mJ / cm} 2, particularly preferably ^{100mJ / cm 2 ~ 500mJ / cm} 2.

The developer has the same meaning as the developer described in the step of forming the first colored pixel.

The developing method can be applied, for example, to a method of immersing a substrate in a bath filled with a developing solution for a certain period of time (dipping method), and a method of developing the developing solution by stacking the developing solution on the surface of the substrate and holding it for a certain period of time. Liquid method); a method of spraying a developing solution on a surface of a substrate (spraying method); and scanning a developing solution at a certain speed The nozzle is a method of continuously ejecting the developer onto the substrate rotating at a constant speed (dynamic dispensing method), etc., and particularly preferably a liquid-coated side.

The development time is not particularly limited as long as the coloring layer of the unexposed portion is sufficiently dissolved, and is usually from 10 seconds to 300 seconds. It is preferably from 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.

<<<Steps for forming the third coloring pixel>>>

The method of producing a color filter of the present invention may further include the 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 coloring-sensitive radiation composition is embedded in each of the removed portions of the second removed portion group 122 to form a plurality of The third coloring element is formed by the third coloring sensation in the first coloring layer (that is, the first coloring pattern 12 in which the second coloring pattern 22 is formed in the first removing portion group 121). The third coloring radiation layer 31 is formed (step (E)). Thereby, the third coloring pattern 32 having a plurality of third colored pixels is formed in the second removal portion group 122 of the first colored layer 11. Here, the third colored pixel is preferably a quadrangular pixel. The formation of the third coloring-sensitive radiation layer 31 can be performed in the same manner as the step of forming a coloring layer using the colored resin composition in the first embodiment.

The thickness of the third colored resin composition layer 31 after post-baking is preferably in the range of 0.1 μm to 1 μm, more preferably in the range of 0.2 to 0.8, and still more preferably in the range of 0.3 μm to 0.6 μm.

Then, the third coloring radiation layer 31 is placed on the first The position 31A corresponding to the second removal portion group 122 in the color layer 11 is exposed and developed, whereby the third color-sensing radiation layer 31 is removed, whereby the manufacturing is performed as shown in the schematic cross-sectional view of FIG. 1 coloring pattern 12, second coloring pattern 22, and color filter 100 of third coloring pattern 32 (step (F)).

The second coloring sensitizing radiation composition and the third coloring sensitizing radiation composition each contain a coloring agent. The coloring agent can be similarly described in the coloring composition of the present invention. It is preferable that one of the second coloring element and the third coloring element is a blue transmitting portion and the other is a red transmitting portion. The coloring agent contained in the colored composition for forming the blue transmissive portion is preferably selected from the group consisting of CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 27, CI Pigment Violet 32, and CI Pigment Violet 37. , CI Pigment Violet 42 and CI Pigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 15, CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI One or more of Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64, CI Pigment Blue 66, CI Pigment Blue 79, and CI Pigment Blue 80. The coloring agent contained in the colored composition for forming the red transmissive portion is preferably one or more selected from the coloring agents described in paragraph number 0037 and paragraph number 0039 of JP-A-2012-172003. The content is incorporated into the specification of the present application.

In each of the second coloring sensitizing radiation composition and the third coloring sensitizing radiation composition, the content of the coloring agent with respect to the total solid content of the composition is preferably 30% by mass or more, more preferably 35% by mass or more, and further Good is 40% by mass or more. Further, the content of the colorant relative to the total solid content of the composition is usually 90% by mass. Next, it is preferably 80% by mass or less.

Further, it is preferable that each of the second coloring radiation composition and the third coloring radiation composition is a negative radiation sensitive composition. The negative-type radiation-sensitive linear composition can use negative-inductance radiation that induces ultraviolet rays (g-rays, h-rays, and i-rays), far-ultraviolet rays including excimer lasers, electron beams, ion beams, and X-rays. Composition. In the radiation, it is preferably g-ray, h-ray, or i-ray, and among them, i-ray is 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. The composition described in paragraph number 0017 to paragraph number 0064 of the publication No. 2005-326453 is incorporated in the specification of the present application. Such a negative-type radiation-sensitive linear composition utilizes a phenomenon in which a photopolymerization initiator initiates a polymerization reaction of a polymerizable compound by irradiation of radiation, and as a result, it changes from an alkali-soluble state to an alkali-insoluble property.

<Method of Patterning Colored Ceramic Composition Layer by Wet Etching Method>

In the method of producing a color filter of the present invention, pattern formation may be performed by a wet etching method. An example of a method of pattern formation using a wet etching method is shown below.

The colored resin composition is applied onto a substrate to form a colored film.

As the substrate, soda glass, alkali-free glass, borosilicate glass, quartz glass or the like can be usually used. Coating can use rotator, spray coating, dipping, roll coating, bar coating, die coating, etc. method. The drying of the applied colored resin composition is preferably carried out in the range of 50 ° C to 180 ° C for several seconds to several hours using an oven, a hot plate, or infrared rays.

A photoresist for pattern formation is applied onto the colored film to form a photoresist layer. The thickness of the photoresist layer is preferably from 0.1 μm to 3 μm, preferably from 0.2 μm to 2.5 μm, and more preferably from 0.3 μm to 2 μm.

Then, using a exposure device, a mask is placed on the photoresist layer film, and the chemical line is irradiated to perform exposure. Examples of the chemical line include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays and visible rays are preferable. In the case of using a positive type resist, the development of the photoresist layer and the etching of the colored film are simultaneously performed by the developer using the positive photoresist after the exposure. The photoresist layer which becomes unnecessary after etching is peeled off. Usually, a solvent such as acetone or a cellosolve is used for the peeling. The colored film is subjected to heat treatment to complete patterning of the colored film. The heat treatment is performed for 5 minutes to 5 hours while selecting the temperature and increasing the temperature stepwise, or selecting a certain temperature range and continuously increasing the temperature. The heat treatment temperature is preferably from 180 ° C to 400 ° C, more preferably from 180 ° C to 350 ° C. For example, heat treatment is performed for 30 minutes at 130 ° C, 200 ° C, and 300 ° C, respectively. In addition, it is also possible to linearly raise the temperature to 300 ° C from room temperature in 2 hours.

The above steps are repeated for the red, green, and blue colored compositions or yellow, cyan, magenta, and optionally black matrices (black). If necessary, an overcoat film containing an acrylic polymer, a polycrystalline siloxane, a polyimine or the like is formed, and a metal oxide film such as indium tin oxide (ITO) is sputtered, whereby a color filter can be produced.

<The patterning of the colored resin composition layer by photolithography Method>

In the method of producing a color filter of the present invention, the colored resin composition layer may be patterned by photolithography. For details of the photolithography method, reference may be made to the specification of the present application by referring to Paragraph No. 0173 to Paragraph No. 0185 of Japanese Patent Laid-Open No. 2013-227497.

Since the color filter of the present invention is formed of a colored resin composition having a high concentration of a colorant, the thickness of the colored pattern can be made extremely thin (for example, 0.7 μm or less). Further, since other colors are less likely to remain on the surface and color mixing is less likely to occur, a color filter in which crosstalk (mixing of light) is suppressed can be obtained.

The color filter of the present invention can be preferably used for a solid-state imaging device such as a CCD or a CMOS, and is particularly suitable for a high-resolution CCD or CMOS of more than one million pixels. The color filter for a solid-state image sensor of the present invention can be used, for example, as a color filter disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for collecting light.

The coloring pattern (coloring pixel) of the color filter of the present invention preferably has a film thickness of 0.1 μm to 1.0 μm, more preferably 0.1 μm to 0.8 μm.

Further, the size (pattern width) of the colored pattern (colored pixel) may be set to 2.5 μm or less, or may be set to 2.0 μm or less, or may be set to 0.9 μm to 1.4 μm. In particular, by using a dry etching method, a colored pattern of the above size can be efficiently produced.

<Solid image sensor>

The solid-state imaging element of the present invention is provided with the color filter of the present invention described above sheet. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has a configuration that functions as a solid-state imaging device, and the configuration is as follows.

The solid-state imaging device has a configuration in which a plurality of photodiodes constituting a light receiving region of a solid-state imaging device (a CCD image sensor, a CMOS image sensor, or the like) and a transmission electrode including a polysilicon or the like are provided on the support. The photodiode and the transfer electrode have a light-shielding film containing tungsten or the like only having a light-receiving portion of the photodiode, and the light-shielding film has a surface covering the entire surface of the light-shielding film and the photodiode light-receiving portion. An element protective film containing tantalum nitride or the like is formed, and the color filter for a solid-state imaging device of the present invention is provided on the element protective film.

Furthermore, it may be configured to have a light collecting means (for example, a microlens or the like, the same below) on the element protective layer and under the color filter (on the side close to the support), or may have a color filter. The composition of the concentrating mechanism, and the like.

<Image display device>

The color filter of the present invention can be used not only for the solid-state imaging device but also for an image display device such as a liquid crystal display device or an organic EL display device, and is particularly suitable for use in a liquid crystal display device. The liquid crystal display device including the color filter of the present invention can display a high-quality image in which the hue of the display image is good and the display characteristics are excellent.

In the case of the definition of the display device or the details of each display device, for example, it is described in "Electronic display device (Sasaki Sasaki, Industrial Research Association (share), issued in 1990)", "Display device (Ibuki Shunzhang, industry) Books (shares), 1989 Annual release) and so on. In addition, the liquid crystal display device is described, for example, in "Next-Generation Liquid Crystal Display Technology (Editor Uchida Ronjin, Industrial Research Association, issued in 1994)". The liquid crystal display device to which the present invention is 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 can also be used in a liquid crystal display device of a Thin Film Transistor (TFT) type. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)". Furthermore, the present invention can also be applied to an enlarged liquid crystal display such as a transverse electric field driving method such as In-Plane Switching (IPS) or a pixel division method such as multi-domain vertical alignment (MVA). Device or Super Twisted Nematic (STN), Twisted Nematic (TN), Vertical Alignment (VA), Optically Compensated Splay (OCS), Fringe Field Switching, FFS) and Reflective-Optically Compensated Bend (R-OCB).

In addition, the color filter of the present invention can also be used in a bright and high-definition Color-filter On Array (COA) mode. In the COA liquid crystal display device, in addition to the usual required characteristics as described above, the required characteristics of the color filter layer may require characteristics of the interlayer insulating film, that is, low dielectric constant and peeling resistance. Liquid. In the color filter of the present invention, since a coloring matter excellent in color tone is used, color purity, light transmittance, and the like are good, and a coloring pattern (pixel) is obtained. Since the color tone is excellent, it is possible to provide a COA liquid crystal display device having high resolution and excellent long-term durability. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin coating film may be provided on the color filter layer.

These image display methods are described, for example, in "Electroluminescence (EL), Plasma Display Panel (PDP), Liquid Crystal Display (LCD) displays - technology and market. Trends - (Toray Research Center, Research and Research Department, issued in 2001), 43 pages, etc.

The liquid crystal display device including 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 securing film, in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device composed of such known members. For example, the "94 liquid crystal display peripheral materials and chemicals market (Ichishima Kentaro, CMC (share), issued in 1994)", "2003 liquid crystal related market status and future prospects (volume) (Former Liangji, Fuji Kamelai Institute (share), issued in 2003).

The backlight is recorded on the 18th page of the December 2005 issue of the "SID meeting Digest" (1380 (2005)) (A. Konno et al.) or the monthly display. 24 pages (Island Kang Yu) and the document 25 to 30 pages (Yamu Longming) and so on.

When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a three-wavelength tube of a conventionally known cold cathode tube, and By setting the red, green, and blue LED light sources (RGB-LEDs) as backlights, it is possible to provide a liquid crystal display device having high brightness and high color reproducibility.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "%" and "parts" are quality standards unless otherwise specified.

<Synthesis of polyglycine PA-1~polyproline PA-3>

<<Synthesis example 1>>

To a three-neck round bottom flask, a reaction vessel equipped with a thermometer, a nitrogen gas introduction tube, and a chopper was placed, and 15.0 g (75 mmol) of 4,4'-diaminodiphenyl ether was added together with 280 g of γ-butyrolactone. 3,3'-Diaminodiphenylphosphonium 5.0g (20mmol), bis-3-(aminopropyl)tetramethyldioxane 1.2g (5mmol), added 3,3',4,4 '- benzophenone tetracarboxylic dianhydride 16.1 g (50 mmol), and pyromellitic anhydride 10.7 g (49 mmol), after reacting at 60 ° C for 5 hours, adding 0.2 g (2 mmol) of maleic anhydride, and further to 60 The reaction was carried out at ° C for 1 hour to obtain a polyaminic acid solution PA-1 having a solid concentration of 20% by mass.

<<Synthesis Example 2 to Synthesis Example 3>>

A polyglycine having a solid content concentration of 20% by mass was obtained by the same method as in the above Synthesis Example 1 except that the type and amount of the raw material used in the synthesis of the polyamic acid were changed as shown in the following Table 1. PA-2~polyglycolic acid PA-3.

Each of the abbreviations in Table 1 is as follows.

DAE: 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)

DDS: 3,3'-diaminodiphenyl hydrazine (manufactured by Wako Pure Chemical Co., Ltd.)

DBA: 4,4'-diaminobenzimidamide (manufactured by Tokyo Chemical Industry Co., Ltd.)

HAD: hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

Si-DA: bis(3-aminopropyl)tetramethyldioxane (manufactured by Tokyo Chemical Industry Co., Ltd.)

BTDA: 3,3',4,4'-benzophenone tetracarboxylic dianhydride (manufactured by Wako Pure Chemical Co., Ltd.)

PMDA: pyromellitic anhydride (manufactured by Wako Pure Chemical Co., Ltd.)

BTCA: 1,2,3,4-butane tetracarboxylic dianhydride (manufactured by Nippon Chemical and Chemical Co., Ltd., Rikacid 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 Composition G-1 to Green Colored Resin Composition G-34>

The mixture of 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.

The green colored resin composition G-2 was prepared by the same method 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 described in the following Table 2. Green colored resin composition G-34.

Each of the abbreviations in Table 2 refers to the following compounds.

PG58: C.I. Pigment Green 58 (polyhalide zinc phthalocyanine green pigment, manufactured by Di Ai Sheng (DIC) Co., Ltd.)

PY129: C.I. Pigment Yellow 129 (copper azomethine yellow pigment)

PY150: C.I. Pigment Yellow 150 (nickel azo yellow pigment)

PY185: C.I. Pigment Yellow 185 (isoporphyrin yellow pigment)

D-1: a pigment derivative of the following structural formula (manufactured by Fujifilm Co., Ltd.)

D-2: a pigment derivative of the following structural formula (manufactured by Fujifilm Co., Ltd.)

D-3: Pigment derivative of the following structural formula (Fujifilm) Manufacturing)

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'-diaminobenzimidil (manufactured by Tokyo Chemical Industry Co., Ltd.)

C-4: hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

F-1: Megafac F-781F (fluorine-based surfactant) manufactured by Diane Health (DIC) Co., Ltd.

BL: γ-butyrolactone

MMB: 3-methyl-3-methoxybutanol

Dispersant A: a polymer dispersant of the following structural formula (manufactured by Fujifilm Co., Ltd.), using a = 3.5, b = 2.5, an acid value of 30 mgKOH/g, and a weight average molecular weight of the following formula: 20,000)

Epoxy Resin A: Epoxy resin of the following structural formula (Daicel Chemical Industry, EHPE3150)

<Evaluation of Green Colored Resin Composition>

<<Evaluation of solvent resistance>>

The obtained green colored resin composition G-1 to green colored resin composition G-34 was applied onto a glass substrate to a thickness of 0.6 μm after drying, and was applied at 100 ° C for 120 seconds. The bell is prebaked to obtain a colored film. The obtained colored film was further heated (post-baking) at 240 ° C for 30 minutes under a nitrogen atmosphere to carry out a hardening treatment of the coating film. In this process, the polylysine in the coating film undergoes a dehydration condensation reaction to be converted into a polyimine.

The hardened coating film obtained by the hardening treatment was immersed in N-methylpyrrolidone for 60 seconds, and the spectral transmittance change of the cured coating film before and after immersion was measured by MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). The obtained color difference ΔEab was used to evaluate solvent resistance. The smaller the ΔEab, the smaller the variation in the spectral transmittance before and after the solvent immersion, which means that the solvent resistance is more excellent. The evaluation results of the solvent resistance are collectively shown in Table 2.

<<Evaluation of needle-shaped foreign bodies>>

(Preparation of Blue Pigment Dispersion B1)

C.I. Pigment Blue 15:6 (9.5 parts) and C.I. containing as a pigment by a bead mill. Pigment Violet 23 (2.4 parts), BYK-161 as a pigment dispersant (5.6 parts by BYK), and Propyleneglycol monomethyl ether acetate (PGMEA) ( The mixture of 82.5 parts) was mixed and dispersed for 15 hours to prepare a blue pigment dispersion B1.

(Preparation of blue resin composition B-a)

<Step of Forming Green Pixel Pattern Using Dry Etching>

(formation of green layer)

The green colored resin composition was applied onto a wafer by a spin coater, dried at 100 ° C for 180 seconds on a hot plate, and then heat treated at 240 ° C for 30 minutes in a nitrogen atmosphere (post-baking) Bake), thereby forming a green colored film. The green colored film had a film thickness of 0.6 μm.

(Coating of mask resist)

A positive photoresist "FHi622BC" (manufactured by Fujifilm Electronics Materials Co., Ltd.) was applied onto the obtained green colored film, and prebaking was performed to form a photoresist layer having a film thickness of 0.8 μm.

(pattern exposure and development of resist with mask)

The obtained photoresist layer was subjected to pattern exposure using an i-ray stepper (manufactured by Canon), and heat treatment was performed for 1 minute at a temperature at which the temperature of the photoresist layer or the ambient temperature became 90 °C. Thereafter, the developing solution "FHD-5" (manufactured by Fujifilm Electronics Materials Co., Ltd.) was subjected to development treatment for 1 minute, and further subjected to post-baking treatment at 110 ° C for 1 minute to form a resist pattern. This resist pattern is a pattern in which square-shaped resist films formed on one side of 1.25 μm are arranged in a checkerboard shape in consideration of an etching transition difference (reduction in pattern width due to etching).

(dry etching)

Using the obtained resist pattern as an etching mask, dry etching of the green colored film was performed in the following order.

Using a dry etching device (manufactured by Hitachi High-technologies, U-621), RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, internal pressure of the chamber: 4.0 Pa, The substrate temperature: 50 ° C, the gas type and flow rate of the mixed gas were set to CF ₄ : 80 mL / min., O ₂ : 40 mL / min., Ar: 800 mL / min., the first stage of 80 seconds was carried out. Etching process.

The amount of removal of the green layer under the etching conditions was 534 nm (etching amount of 89%), and it was in a state of having a residual film of about 58 nm.

Then, in the same etching chamber, under the conditions of RF power: 600 W, antenna bias: 100 W, wafer bias: 250 W, internal pressure of the chamber: 2.0 Pa, substrate temperature: 50 ° C, the mixed gas The gas type and flow rate were set to N ₂ : 500 mL/min., O ₂ : 50 mL/min., Ar: 500 mL/min. (N ₂ /O ₂ /Ar = 10/1/10), and the total amount of etching was The overetch rate was set to 20%, and the second etching process and the overetch process were performed.

The etching rate of the green layer in the etching conditions of the second stage is 600 nm/min or more, and it takes about 10 seconds to etch the residual film of the green layer. The etching time was calculated by adding 80 seconds of the etching time of the first stage to the etching time of the second stage of 10 seconds. The result was an etching time of 80 + 10 = 90 seconds, an overetching time of 90 x 0.2 = 18 seconds, and a total etching time of 90 + 18 = 108 seconds.

After the dry etching was carried out under the above conditions, the photoresist stripping liquid "MS230C" (manufactured by Fujifilm Electronics Materials Co., Ltd.) was subjected to a peeling treatment for 120 seconds to remove the resist pattern, and the pure resist was used. Washing and spin drying of water. Thereafter, a dehydration baking treatment was performed at 100 ° C for 2 minutes. By the above operation, a green pattern in which square green-shaped pixels of 1.2 μm on one side were arranged in a checkerboard pattern was obtained. In this way, it was confirmed that the green colored film formed of the green resin composition of the present invention was processed by dry etching to form a fine pixel pattern suitable for a color filter for a solid-state image sensor.

In the <Step of Forming a Green Pixel Pattern by Dry Etching>, a square having a side of 1.2 μm prepared by using each of the green colored resin composition G-1 to the green colored resin composition G-34 was prepared. A green pattern in which a green pixel is arranged in a checkerboard pattern, in which a blue resin composition Ba is embedded in each of the through holes of the green pattern, and the thickness after drying and post-baking is 0.40 μm. In a method, a blue resin composition Ba is applied onto the green pattern to obtain a laminated color filter in which a blue radiation-sensitive layer is formed on a green layer.

The blue radiation-sensitive layer of the thus obtained laminated color filter was subjected to pattern exposure using an i-ray stepper (manufactured by Canon). Here, the exposure area is a region corresponding to the through holes located in the even rows in the checkerboard pattern of the green pattern.

Then, the exposed multi-layer color filter is placed on the rotation. On a horizontal rotary table of a spray developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), a 60% dilution of CD-2000 (Fujifilm Electronics Materials Co., Ltd.) was used. The solution development was carried out at 23 ° C for 60 seconds. Thereafter, the color filter is fixed on the horizontal rotating table by a vacuum chuck, and the color filter is rotated by 50 rpm by a rotating device. The surface was ejected from the discharge nozzle from the upper side of the rotation center to supply pure water in a shower form, and then spray-dried.

By the above operation, it is obtained that the blue pixel set in the through-holes of the odd-numbered rows in the blue-sensitive radiation layer in the laminated color filter and the checkerboard pattern of the green pattern is removed. Color filter precursors.

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 by a scanning electron microscope (manufactured by Hitachi, S-9260) to confirm whether or not needle-shaped foreign matter was generated in the boundary region between the green pixel and the blue pixel. As a result of the confirmation, it was evaluated according to the following method based on the occurrence of needle-shaped foreign matter. The evaluation results are summarized in Table 2.

A: No needle-shaped foreign matter is produced at all.

B: A small acicular foreign body having a length of less than 0.1 μm was slightly observed, but it was a problem-free level.

C: A needle-like foreign matter having a length of 0.1 μm to 0.2 μm was slightly observed, but it was a problem-free level.

D: Large acicular foreign bodies longer than 0.2 μm were observed in large numbers.

Comparative Example 2 (Verification of the effect of the case of using PG36 as a green pigment)

The mixture of the following composition was uniformly stirred and mixed, and then mixed and dispersed by a bead mill for 3 hours, whereby CI Pigment Green 36 was used as a green pigment, and the polyamic acid PA-1 was used as a hardening resin. Green colored resin composition G36-PA.

Further, the mixture of the following composition was uniformly stirred and mixed, and then mixed and dispersed by a bead mill for 3 hours, thereby preparing a green colored resin using CI Pigment Green 36 as a green pigment and using an epoxy resin as a hardening resin. Composition G36-EP.

The green colored resin composition G36-PA and the green colored resin composition G36-EP were each evaluated by the same method as the evaluation method of the solvent resistance and the needle-shaped foreign matter. As a result, there was no difference in the evaluation results of solvent resistance and needle-like foreign matter between G36-PA and G36-EP. From the results, it is known that when PG36 is used as the green pigment, even if the poly-proline used in the present invention is used as the hardening The resin also does not exhibit the effects of the present invention.

<Formation of Green Pixel Pattern by Wet Etching>

(formation of green layer)

The green colored resin composition G-1 was applied onto a glass wafer by a spin coater, and then dried at 100 ° C for 180 seconds using a hot plate to form a green colored film.

(Coating of mask resist)

Then, a positive photoresist "FHi622BC" (manufactured by Fujifilm Electronics Materials Co., Ltd.) was applied onto the green colored film, and prebaking was performed to form a photoresist layer having a film thickness of 0.8 μm.

(pattern exposure of mask with resist and wet etching by alkali development)

Then, the photoresist layer was subjected to pattern exposure using an i-ray stepper (manufactured by Canon), and heat treatment was performed for 1 minute at a temperature at which the temperature of the photoresist layer or the ambient temperature became 90 °C. Thereafter, the developing solution "FHD-5" (manufactured by Fujifilm Electronics Materials Co., Ltd.) was immersed on the photoresist, and development of the photoresist and the underlying green colored film was carried out simultaneously (this operation is equivalent to The upper photoresist film serves as a wet etching step of the underlying green colored film of the mask). After etching, the undesired photoresist layer is peeled off using methyl cellosolve acetate. The polyimine precursor green colored film thus obtained was subjected to heating (post-baking) treatment at 240 ° C for 30 minutes in a nitrogen atmosphere to obtain a green pixel pattern having a film thickness of 1.2 μm. It was confirmed by a scanning electron microscope (manufactured by Hitachi, S-9260) that the green pixel pattern had a pixel size of 120 μm × 80 μm.

Green colored resin composition G-2 to green by the same method as described above The coloring resin composition G-30 was also attempted to form a pattern by wet etching, and as a result, it was confirmed that the green pixel pattern could be formed without any problem by any of the compositions.

From the above, it has been confirmed that a green colored film formed of the green colored resin composition of the present invention can be formed by wet etching, and a color filter suitable for various display devices such as a liquid crystal display device or an organic LED display device can be formed. A pixel pattern of a size of several tens to several hundreds of micrometers (μm) of a light sheet.

12‧‧‧1st coloring pattern

22‧‧‧2nd coloring pattern

32‧‧‧3rd coloring pattern

100‧‧‧Color filters

Claims (17)

A colored resin composition comprising a poly-proline and a CI pigment green 58 having a repeating unit represented by the following formula (1); In the formula (1), R ¹ represents a n+2 valent 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 formula (2); H ₂ NR ³ -NH ₂ (2) in the formula (2), R ³ Indicates a divalent linking group. The colored resin composition as described in claim 1 or 2 further contains a yellow coloring agent. The colored resin composition according to claim 3, which contains C.I. Pigment Yellow 129 as the yellow coloring agent. The coloring resin composition according to the first or second aspect of the invention, wherein in the formula (1), R ¹ represents a n+2 valent linking group having 2 to 22 carbon atoms. The colored resin composition according to the first or second aspect of the invention, wherein, in the formula (1), R ¹ represents an n+2 valent linking group having a cyclic structure. The colored resin composition according to the first or second aspect of the invention, wherein, in the formula (1), R ² represents a divalent linking group having 1 to 22 carbon atoms. The colored resin composition according to claim 1 or 2, wherein in the formula (1), R ² represents a hydrocarbon group or a hydrocarbon group and is selected from the group consisting of -Si(R ^2A ) ₂ -, a divalent linking group of a group of a combination of at least one of CO-, -NR-, -O-, -SO ₂ -, and -S-; wherein R ^2A independently represents an alkyl group having 1 to 6 carbon atoms R in -NR- represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The colored resin composition according to the first or second aspect of the invention, wherein, in the formula (2), R ³ represents a divalent linking group having 1 to 22 carbon atoms. The colored resin composition according to Item 1 or 2, wherein in the above formula (2), R ³ represents a divalent linking group having a cyclic structure. The colored resin composition according to Item 1 or 2, wherein R ³ in the general formula (2) represents a skeleton containing the same skeleton as R ² in the general formula (1) Price linkage. A colored resin composition as described in claim 1 or 2, which is used for a solid-state image sensor. A cured film obtained by hardening a coloring resin composition according to any one of claims 1 to 12. A color filter having a coloring layer using the coloring resin composition according to any one of claims 1 to 12. A method of manufacturing a color filter, comprising: The step of applying a colored resin composition according to any one of claims 1 to 12 to a substrate to form a colored film; and heating the colored film at 150 ° C to 350 ° C to cause the coloring film to be heated at 150 ° C to 350 ° C a step of hardening; applying a photoresist on the hardened color film; and performing a base exposure on the photoresist to perform alkali development, thereby patterning the photoresist; a step of patterning the colored film of the lower layer of the photoresist by dry etching using the patterned photoresist as an etch mask; and removing the patterned photoresist step. A solid-state image sensor having a color filter as described in claim 14 of the patent application. An image display device having the color filter of claim 14 of the patent application.