TW201506544A - Colored photosensitive resin composition, cured film, color filter, method for manufacturing color filter, solid state image capture device and image display device - Google Patents

Abstract

A colored photosensitive resin composition is provided, which contains a pigment (A), a basic dye derivative (B), a phosphoric acid series dispersing agent (C) represented by the following formula (II), a resin (D) obtained by polymerizating a compound (x) represented by the following formula (IV) with a compound (y) having an ethylenic unsaturated double bond, a photopolymerization initiator (E) and a polymerizable compound (F).

Description

Coloring photosensitive resin composition, cured film, color filter, color Method for manufacturing color filter, solid-state imaging device, and image display device

The invention relates to a liquid crystal display element (Liquid Crystal Display (LCD)) or a solid-state imaging device (Charge-coupled Device (CCD), Complementary Metal Oxide Semiconductor (Complementary Metal- a colored photosensitive resin composition of a color filter used in an Oxide-Semiconductor, CMOS, or the like), a color filter having a colored region formed by the composition, and a color filter having the color filter An image display device such as a solid-state imaging device or a liquid crystal display device for an organic light emitting diode (LED).

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. Due to the demand for further high image quality, the popularity of organic electroluminescence (EL) displays is also desired. On the other hand, due to the digital camera, the mobile phone with the camera Popularization, the demand for solid-state imaging elements such as CCD image sensors is also increasing.

As a key device for these displays or optical components, the use of color filters further increases the requirements for higher image quality and cost reduction. Such a color filter usually has a color pattern of three primary colors of red (R), green (G), and blue (B), and functions to divide the passed light into three primary colors in a display element or an image sensor.

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

That is, the following characteristics are required: there are preferable spectral characteristics in terms of color reproducibility; there is no light scattering which causes a decrease in contrast of the liquid crystal display or color unevenness of the solid-state imaging element. The optical density of the unevenness of the color sensation is optically disordered; the fastness under the environmental conditions to be used, for example, heat resistance, light resistance, moisture resistance, and the like are good; the molar absorption coefficient is large, and thinning can be achieved.

Therefore, the colorant is usually a pigment.

In the case of forming a color filter used in a liquid crystal display device (LCD), a solid-state imaging device (CCD, CMOS, etc.) and a liquid crystal display device for an organic LED, usually after the step of applying a colored photosensitive resin composition on the substrate The step of performing pattern exposure and the step of performing development using an alkaline developer are carried out. At this time, exposure may be performed after the step of applying the colored photosensitive resin composition. Place for a few days during the period before the development step. This post-coating placement is generally referred to as Post Coating Delay (PCD). The reason is that, in the color filter manufacturing process, the substrate coated with the colored photosensitive resin composition is stored in advance, and the exposure is vacant. The developing device is then combined for subsequent exposure. Development step Under, it can be processed effectively.

Due to the background as described above, there is no problem in the formation of the colored pattern after the PCD is required for the colored photosensitive resin composition. Specifically, FIG. 1 is an exposure immediately after coating a colored photosensitive resin composition on a substrate from above the substrate. A schematic view of the colored pattern 1 formed in the case of development is observed. Here, the colored pattern is formed into a rectangular shape. For the colored photosensitive resin composition, it is required to maintain the formation of such a rectangular pattern after the PCD.

However, depending on the type of the coloring photosensitive resin composition, as shown in FIG. 2, the coloring pattern 1 after PCD may be largely collapsed.

For example, Patent Document 1 and Patent Document 2 describe a photosensitive coloring composition containing a resin containing a specific structure of an acrylic monomer as a copolymerization component.

Further, Patent Document 3 and Patent Document 4 disclose a pigment composition containing a triazine ring-containing basic compound having a specific structure and a phosphate-based dispersant having a specific structure.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-101728

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-212654

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-231106

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2007-231107

In Patent Document 1 and Patent Document 2, a coloring composition excellent in dispersion stability and the like can be obtained by using a resin containing a specific structure of an acrylic monomer as a copolymerization component, but when a color filter is used, There is room for further improvement in terms of color unevenness (stain) or temporal stability of the stain. It is considered that the coloring photosensitive resin composition as described in Patent Document 1 and Patent Document 2 is unstable in the adsorption of the pigment particles by the dispersion resin, and is adsorbed to the composition during the long-term passage of the composition. The dispersed resin on the surface of the pigment particles is detached from the surface of the pigment particles. Therefore, it is presumed that during the long-term passage of the composition, the pigment particles cause secondary aggregation and the pigment particle size becomes coarse, resulting in deterioration of the color spot of the color filter after the passage.

In addition, it is described in Patent Document 3 and Patent Document 4 that a pigment composition excellent in dispersion stability and the like can be obtained by using a triazine ring-containing basic compound having a specific structure and a phosphate dispersant having a specific structure. However, in Patent Document 3 and Patent Document 4, the color unevenness (stain), the temporal stability of the stain, and the pattern formation property after PCD are further improved. Room for it. It is considered that the coloring photosensitive resin composition obtained from the pigment composition containing the phosphate-based dispersing agent having a specific structure as described in Patent Document 3 and Patent Document 4 constitutes the phase of each component constituting the composition. Poor capacitance, phase separation of a part of the coating film formed during the post-coating (PCD) process, followed by exposure. The coloring pattern developed by the development collapsed drastically.

The present invention solves the above problems, and is related to a color unevenness (stain) Or a colored photosensitive resin composition having excellent temporal stability of a stain and further pattern formation after PCD, a cured film using the colored photosensitive resin composition, a color filter, and a method of producing a color filter , solid-state imaging device and image display device.

As a result of intensive studies, the inventors of the present invention have found that the problem can be solved by using a predetermined phosphate dispersant and a predetermined resin binder.

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

<1> A colored photosensitive resin composition comprising: (A) a pigment, (B) a basic dye derivative, (C) a phosphate-based dispersant represented by the following formula (II), and (D) a resin obtained by copolymerizing a compound (x) represented by the formula (IV) with a compound (y) having an ethylenically unsaturated double bond, (E) a photopolymerization initiator, and (F) a polymerizable compound,

(In the formula (II), R ³ represents a polyester structure having a number average molecular weight of 400 to 30,000, y represents 1 or 2; and in the case where y is 2, a plurality of R ^{3 's} may be the same or different; In (IV), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 2 or 3 carbon atoms, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring, and n represents 1 An integer of ~15; when n is 2 or more, a plurality of R ^{5 's} may be the same or different).

<2> The colored photosensitive resin composition as described in <1>, wherein (B) the basic dye derivative is a compound having an amine group.

<3> The coloring photosensitive resin composition as described in <1> or <2>, wherein (A) pigment is selected from the group consisting of a red pigment, a green pigment, and a yellow pigment.

<4><1> to <3> in the colored photosensitive resin composition according to any one of the above wherein the general formula (II), R ³ Number-average molecular weight of the polyester structure is indicated by 1900 to 10,000.

<5><1> to <4> The colored photosensitive resin composition according to any one of claims, wherein the general formula (II), R ³ polyester structure is indicated by the two or more different inner The polyester structure obtained by ring-opening polymerization of an ester monomer.

<6> The colored photosensitive resin composition according to any one of <1> to <5> further comprising (G) a resin having a polymerizable double bond in a side chain.

<7> The colored photosensitive resin composition according to <6>, wherein the resin having a polymerizable double bond in the (G) side chain is a resin obtained by reacting the compound (b) with the copolymer (a). The compound (b) has a functional group reactive with a hydroxyl group and an ethylenically unsaturated double bond, and the copolymer (a) is a polymerization having 2 to 6 hydroxyl groups. A copolymer of a monomer (p) and another polymerizable monomer (q).

The coloring photosensitive resin composition of any one of the above-mentioned (A), (D) the compound represented by General formula (IV) with respect to (A) pigment (100). x) The content of the resin copolymerized with the compound (y) having an ethylenically unsaturated double bond is 5 parts by mass to 80 parts by mass.

The coloring photosensitive resin composition of any one of the above-mentioned coloring photosensitive resin composition, (A) pigment, (B) basic pigment derivative, and (C) After dispersing the phosphate-based dispersant represented by the formula (II), the compound (x) represented by the formula (IV) is copolymerized with the compound (y) having an ethylenically unsaturated double bond. Made of resin.

<10> The colored photosensitive resin composition according to any one of <1> to <9> which is a colored region for forming a color filter.

<11> A cured film obtained by curing the colored photosensitive resin composition according to any one of <1> to <10>.

<12> A method of producing a color filter, comprising the step of applying a colored photosensitive resin composition according to any one of <1> to <10> to a support to form a colored photosensitive composition. a step of exposing the colored photosensitive composition layer to a pattern; and a step of developing the unexposed portion to form a colored pattern.

<13> A method of producing a color filter, comprising the step of applying a colored photosensitive resin composition according to any one of <1> to <10> to a support to form a colored photosensitive composition. Layer, hardening it to form a step of coloring a layer; a step of forming a photoresist layer on the colored layer; a step of patterning the photoresist layer by exposure and development to obtain a resist pattern; and using the resist pattern as an etch mask The step of performing a dry etching on the colored layer.

<14> A color filter which is a color filter having a cured film as described in <11>.

<15> A color filter manufactured by the method for producing a color filter according to <12> or <13>.

<16> A solid-state imaging device comprising the color filter according to <14> or <15>.

<17> An image display device comprising the color filter according to <14> or <15>.

According to the present invention, it is possible to provide a colored photosensitive resin composition which is excellent in color unevenness (stain) or color plaque over time and further in pattern formation after PCD, and is hardened by the colored photosensitive resin composition. A film, a color filter, a method of producing a color filter, a solid-state image sensor, and an image display device.

1‧‧‧Coloring pattern

Figure 1 is an exposure immediately after coating a colored photosensitive resin composition on a substrate from above the substrate. Schematic representation of the colored pattern formed in the case of development Figure.

2 is a coating of a colored photosensitive resin composition on a substrate from above the substrate and exposure after PCD. A schematic view of the colored pattern formed in the case of development.

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. Further, the organic EL device of the present invention means an organic electroluminescence device.

In the present specification, the total solid content refers to the total mass of the components obtained by removing the solvent from the total composition of the colored photosensitive resin composition.

In the expression of the group (atomic group) in the present specification, it is not described that the substituted and unsubstituted expression includes a group having no substituent, and also includes a group having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In 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 (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. In the present specification, the term "exposure" is used to describe not only the ultraviolet light, the X-ray, the EUV light, etc., which are represented by mercury lamps or excimer lasers, but also the use of particle beams such as electron beams and ion beams. 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 in the present specification means 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.

The weight average molecular weight and the number average molecular weight can be determined by gel permeation chromatography (GPC).

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.

The term "step" in this specification refers not only to an independent step, but also to a situation where it cannot be clearly distinguished from other steps, as long as the intended effect of the step can be achieved.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a coloring composition excellent in color characteristics.

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

<Coloring photosensitive resin composition>

The colored photosensitive resin composition of the present invention (hereinafter sometimes referred to as "the composition of the present invention" or "colored composition") is characterized by containing (A) a pigment, (B) a basic dye derivative, and (C) a phosphate dispersant represented by the following formula (II), (D) a compound (x) represented by the following formula (IV) and a compound (y) having an ethylenically unsaturated double bond; A resin, (E) a photopolymerization initiator, and (F) a polymerizable compound.

(In the formula (II), R ³ represents a polyester structure having a number average molecular weight of 400 to 30,000, and y represents 1 or 2. When y is 2, a plurality of R ^{3 's} may be the same or different.

In the formula (IV), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 2 or 3 carbon atoms, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring, n Indicates an integer from 1 to 15. When n is 2 or more, a plurality of R ^{5 's} may be the same or different. )

By using the composition of the present invention, the color unevenness (color unevenness) or the temporal stability of the color spots and the pattern formation property after PCD are excellent. Although the reason why the effect of the present invention can be obtained is not certain, the following reason can be presumed.

It is estimated that (C) the phosphate-based dispersant represented by the formula (II) and (D) the compound (x) represented by the formula (IV) and the compound having an ethylenically unsaturated double bond (y) (C) The phosphate-based dispersing agent represented by the formula (II) can obtain the following effects: the dispersing agent strongly adsorbs to the pigment particles, and suppresses the colored spots accompanying the composition over time. Deterioration. Further, it is presumed that (D) a resin obtained by copolymerizing a compound (x) represented by the formula (IV) and a compound (y) having an ethylenically unsaturated double bond as a compatibilizer The function is to inhibit the phase separation of the components constituting the composition during the post-coating (PCD) process. It is considered that the color unevenness (stain) of the present invention, the temporal stability of the stain, and the pattern formation property after PCD are excellent.

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

<<(A) Pigment>>

The composition of the present invention contains (A) a pigment. The pigment used in the present invention is preferably selected from the group consisting of a red pigment, a green pigment, and a yellow pigment, and various conventional inorganic pigments or organic pigments can be used. The pigment is preferably high in transmittance.

Examples of the inorganic pigment include a metal represented by a metal oxide or a metal salt. Specific examples of the compound include black pigments such as carbon black and titanium black, metal oxides of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, cerium, and the like, and composite oxides of the metals. .

Examples of the organic pigment include color index (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, and CI Pigment. Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 167, CI Pigment Yellow 180, CI Pigment Yellow 185, 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 177, CI Pigment Red 209, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, 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 Green 58; CI Pigment Brown 25, CI Pigment Brown 28; C.I. Pigment Black 1 and the like.

The pigment which can be preferably used in the present invention is exemplified below. However, the invention is not limited to the pigments.

CI Pigment Yellow 11, CI Pigment Yellow 24, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 154, CI Pigment Yellow 167, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Orange 36, CI Pigment Orange 71, CI Pigment Red 122, CI Pigment Red 150, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 32, 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 Green 58, CI Pigment Black 1.

These organic pigments may be used singly or in combination for adjusting the spectroscopic or improving the color purity. Specific examples of the combination are shown below. For example, an anthraquinone pigment, an anthraquinone pigment, a diketopyrrolopyrrole pigment as a red pigment, or at least one of the pigments and a disazo yellow pigment or an isoporphyrin yellow pigment may be used. Mixing of a quinophthalone yellow pigment or an anthraquinone red pigment. For example, the lanthanide pigment can be exemplified by C.I. Pigment Red 177, and the lanthanoid pigment can be enumerated C.I. Pigment Red 155, C.I. Pigment Red 224, diketopyrrolopyrrole type pigment C.I. Pigment Red 254, and in terms of color decomposition property, it is preferably mixed with C.I. Pigment Yellow 139. In addition, the quality of the red pigment and the yellow pigment is preferably 100:5 to 100:50. When the mass ratio is 100:4 or less, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and when the mass ratio is 100:51 or more, the main wavelength shifts to a short wavelength, and color decomposition may not be improved. ability. In particular, the mass ratio is preferably in the range of 100:10 to 100:30. Further, in the case where the red pigments are combined with each other, they can be adjusted corresponding to the required spectroscopic light.

Further, as the green pigment, a halogenated phthalocyanine pigment may be used alone, or a halogenated phthalocyanine pigment, a disazo yellow pigment, a quinophthalone yellow pigment, a azomethine yellow pigment or an isoporphyrin yellow pigment may be used. the mix of. For example, such an example is preferably CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, CI Pigment Green 58 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment. Mix of Yellow 180 or CI Pigment Yellow 185. The quality of green and yellow pigments is preferably 100:5~100:150. The mass ratio is particularly preferably in the range of 100:30 to 100:120.

The blue pigment may be a phthalocyanine-based pigment alone or a mixture of the phthalocyanine-based pigment and a dioxazine-based violet pigment. For example, a mixture of C.I. Pigment Blue 15:6 and C.I. Pigment Violet 23 is preferred. The quality of the blue pigment and the purple pigment is preferably from 100:0 to 100:100, more preferably 100:10 or less.

Further, the black pigment may be used singly or in combination of carbon, titanium black, iron oxide, or titanium oxide. When used in the case of mixing these, it is preferably a combination of carbon and titanium black. The carbon and titanium black in this case are preferably in the range of 100:0 to 100:60.

Further, the pigment of the present invention may also be an azo pigment represented by the following formula (A2), a tautomer thereof, or a salt or a hydrate thereof.

(In the formula (A2), G represents a hydrogen atom, an aliphatic group, an aryl group or a heterocyclic group, and R ¹ represents an amine group, an aliphatic oxy group, an aliphatic group, an aryl group or a heterocyclic group which may have a substituent. R ² represents a substituent.

A represents a hetero ring having at least one or more atoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom.

m represents an integer from 0 to 5, and n represents an integer from 1 to 4.

The case of n=2 represents a dimer that mediates R ¹ , R ² , A or G.

The case of n=3 represents a terpolymer that mediates R ¹ , R ² , A or G.

The case of n=4 represents a tetramer interposing R ¹ , R ² , A or G.

Formula (A2) does not have an ionic hydrophilic group)

In the general formula (A2), A preferably represents any one of the following general formulae (A-1) to (A-32). In the general formulae (A-1) to (A-32), R ₅₁ to R ₅₉ each independently represent a hydrogen atom and a substituent, and adjacent substituents may be bonded to each other to form a 5-membered ring to a 6-membered ring. . * indicates a bonding position with an azo group of the formula (A2).

The azo pigment has a specific structure represented by the general formula (A2), whereby it exhibits characteristics excellent in coloring power and color-identical color characteristics, and also exhibits light resistance, Excellent durability such as ozone resistance. For example, the red color pattern of the color filter formed using the coloring composition of the present invention containing the azo pigment represented by the general formula (A2) exhibits better spectral characteristics as red. Here, "the spectral characteristic which is good as red" means, for example, at least one of the following properties. The spectral characteristics that satisfy all of the following three properties are particularly excellent.

. The transmittance in the wavelength range of 650 nm to 750 nm is high.

. In the wavelength range of 540 nm or more, the transmittance curve sharply rises.

. A transmittance in a wavelength range of less than 540 nm (particularly 350 nm to 400 nm) is low.

The substituent of the present invention may be a group which can be substituted, and examples thereof include an aliphatic group, an aryl group, a heterocyclic group, a decyl group, a decyloxy group, a decylamino group, and an aliphatic oxy group. , aryloxy, heterocyclic oxy, aliphatic oxycarbonyl, aryloxycarbonyl, heterocyclooxycarbonyl, amine carbaryl, aliphatic sulfonyl, arylsulfonyl, heterocyclosulfonyl, An aliphatic sulfonyloxy group, an arylsulfonyloxy group, a heterocyclic sulfonyloxy group, an amine sulfonyl group, an aliphatic sulfonylamino group, an arylsulfonylamino group, a heterocyclic sulfonylamino group, Amine, aliphatic amine, arylamine, heterocyclic amine, aliphatic oxycarbonylamino, aryloxycarbonylamino, heterocyclooxycarbonylamino, aliphatic sulfinyl, aryl Sulfosyl, aliphatic thio, arylthio, hydroxy, cyano, sulfo, carboxy, aliphatic oxyamino, aryloxyamino, amine carbylamino, amine sulfonylamino And a halogen atom, an aminesulfonylamine, a mercaptoamine sulfonyl group, a dialiphatic oxyphosphinyl group, a diaryloxyphosphinyl group, or the like. Hereinafter, the term "substituent" "Group" means the substituent.

The aliphatic group represented by G may have a substituent, and may be saturated or unsaturated.

Preferred substituents which the aliphatic group represented by G may have are a hydroxyl group, an aliphatic oxy group, an amine carbaryl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amine group, an aliphatic amine group, a decylamino group. , Aminomethylamino group.

The aliphatic group represented by G is preferably an aliphatic group having 1 to 8 total carbon atoms, more preferably an alkyl group having 1 to 6 total carbon atoms, and examples thereof include a methyl group, an ethyl group, and a cyclohexyl group.

In the formula (A2), the aryl group represented by G may also be condensed or may have a substituent, and the substitutable group may be a group which can be substituted as described in the above-mentioned substituent. Further, it may be any group, and preferred substituents are a nitro group, a halogen atom, an aliphatic oxy group, an amine carbaryl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amine group, an aliphatic amine group, and an anthracene group. Amino group, amine carbenylamine group. The aryl group represented by G is preferably an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms in total, and examples thereof include a phenyl group, a 4-nitrophenyl group, and a 4-ethyl fluorenyl group. Aminophenyl, 4-methanesulfonylphenyl and the like.

In the formula (A2), the heterocyclic group represented by G may have a substituent, and may be saturated or unsaturated, or may be condensed. The substitutable group may be any group as long as it is a group which is described in the above-mentioned substituent and which may be substituted, and a preferred substituent is a halogen atom, a hydroxyl group, an aliphatic oxy group, Aminomethyl thiol, aliphatic oxycarbonyl, aliphatic thio, amine, aliphatic amine, decylamino, amine carbylamino. The heterocyclic group represented by G is preferably a carbon atom-bonded heterocyclic group having 2 to 12 total carbon atoms, more preferably 5 members having 2 to 10 total carbon atoms bonded by a carbon atom. Examples of the heterocyclic group of the 6-membered member include 2-tetrahydrofuranyl group and 2-pyrimidyl group.

G is preferably a hydrogen atom. The reason for this is that it is easy to form intramolecular hydrogen bonds or intramolecular cross hydrogen bonds.

The amine group represented by R ¹ may have a substituent, and the substitutable group may be any group as long as it is a group which can be substituted as described in the above-mentioned substituent, and the substituent is more Examples thereof include an aliphatic group, an aryl group, and a heterocyclic group.

These substituents may further have a substituent, and the substituent is preferably an aliphatic group, a hydroxyl group, a substituent having a guanamine bond, an ether bond, an oxycarbonyl bond, a thioether bond or the like, and an intermolecular hydrogen is easily formed. From the viewpoint of intermolecular interaction such as a bond, a substituent having a bond of a hetero atom and a hydrogen atom is more preferable.

The amine group represented by R ¹ is preferably an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms in total, and a dialkylamino group having 2 to 10 carbon atoms in total (dialkyl groups may also be mutually Bonding to form a 5-membered ring to a 6-membered ring), an arylamine group having a total carbon number of 6 to 12, and a heterocyclic amine group having a total carbon number of 2 to 12 which may be saturated or unsaturated. An unsubstituted amino group, an alkylamino group having 1 to 8 total carbon atoms, a dialkylamino group having 2 to 8 total carbon atoms, an arylamino group having 6 to 10 total carbon atoms, and total carbon The heterocyclic amine group which may be saturated or unsaturated may have an atomic number of 2 to 12, and examples thereof include a methylamino group, an N,N-dimethylamino group, an N-phenylamino group, and an N-(2- Pyrimidinyl)amino group and the like.

Further, an arylamino group having a total carbon number of 6 to 13 and a heterocyclic amino group having a total carbon number of 2 to 12 which may be saturated or unsaturated may be used.

In the case where R ¹ is an arylamine group, the substituent on the aryl group is preferably a substituent having a substituent at a para position relative to a bonding position with an amine group, and preferably has only a para position. The case of a substituent. The substituent may be any group as long as it is a group which can be substituted as described in the above-mentioned substituent, and preferably has a total carbon number of 1 to 7, more preferably a total of An aliphatic group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an allyl group, an (iso)propyl group, a (third) butyl group, etc.), and an aliphatic oxy group having a total carbon number of 1 to 7 ( For example, methoxy, ethoxy, (iso)propoxy, allyloxy, etc.), halogen atom (such as fluorine, chlorine, bromine, etc.), total methyl sulfonyl group having 1 to 7 carbon atoms (such as an amine) Mercapto group, N-phenylamine methyl sulfonyl group, N-methylamine carbhydryl group, etc.), ureido group having a total carbon number of 1 to 7, more preferably 1 to 4 total carbon atoms (for example, guanidine urea) Base, N-methyl ureido group, N,N-dimethyl ureido group, N-4-pyridyl ureido group, N-phenyl ureganyl group, etc., nitro group, total carbon number 1~ a heterocyclic group (for example, an imidazolidinone group) having a condensed ring with an aryl group, a hydroxyl group, an aliphatic thio group having a total carbon number of 1 to 7, more preferably a total carbon number of 1 to 4 (e.g., methylthio group, B) Sulfhydryl, (iso)propylthio, allylthio, (tri)butylthio, etc.), a total of 2 to 7 carbon atoms, more preferably a total of 2 to 4 carbon atoms Such as acetaminophen, propyl decylamino, trimethyl ethylamino, benzhydrylamine, etc.), a total of 2 to 7 carbon atoms, more preferably a total of 2 to 4 carbon atoms Alkoxycarbonylamino group (e.g., methoxycarbonylamino group, propoxycarbonylamino group, etc.), an aliphatic oxycarbonyl group having 2 to 7 total carbon atoms, more preferably 2 to 4 carbon atoms in total (for example) a methoxy group, a ethoxycarbonyl group, or the like), a total of 2 to 7 carbon atoms, more preferably a total of 2 to 4 carbon atoms (which may be an aliphatic carbonyl group or an arylcarbonyl group, or The heterocyclic carbonyl group may have a substituent, and the substitutable group may be any group as long as it is a group which can be substituted as described in the above-mentioned substituent, and is preferably a total carbon atom. The fluorenyl group having 2 to 7 is more preferably a fluorenyl group having 2 to 4 carbon atoms in total, and examples thereof include an ethyl hydrazino group, a propyl fluorenyl group, a benzamidine group, and a 3-pyridinecarbonyl group.

When the substituent on the aryl group of the arylamino group is substituted with the bonding position with the amine group in the para position, since the substituent is located at the end of the molecule, it is easy to form intermolecular hydrogen bonds and the like. Function, so the hue becomes sharp. When the substituent on the aryl group has a substituent, it is preferably an aliphatic group, a hydroxyl group, a substituent having a guanamine bond, an ether bond, an oxycarbonyl bond, a thioether bond or the like, and it is easy to form an intermolecular group. From the viewpoint of intermolecular interaction such as hydrogen bonding, a substituent having a bond of a hetero atom and a hydrogen atom is more preferable.

In the case where R ¹ is a heterocyclic amine group, the substituent may be any group as long as it is a group which can be substituted as described in the above-mentioned substituent, and is preferably a group The substituent in the case of the arylamine group is preferably the same. When the substituent on the heterocyclic group has a substituent, it is preferably an aliphatic group, a hydroxyl group, a decyl bond, an ether bond or an oxycarbonyl group. The substituent such as a bond or a thioether bond is more preferably a substituent having a bond of a hetero atom and a hydrogen atom from the viewpoint of easily forming an intermolecular interaction such as an intermolecular hydrogen bond.

More preferred substituents in the case where R ¹ is an arylamine group or a heterocyclic amine group are an aliphatic group, an aliphatic oxy group, a halogen atom, an amine carbaryl group, a heterocyclic group condensed with an aryl group, and an aliphatic oxygen group. Alkylcarbonyl. The substituent is further preferably an aliphatic group having a total carbon number of 1 to 4, an aliphatic oxy group having a total carbon number of 1 to 4, a halogen atom, a nitro group, an amine group having a total carbon number of 1 to 4, and a total An aliphatic oxycarbonyl group having 2 to 4 carbon atoms.

The aliphatic oxy group represented by R ¹ may have a substituent, and the substituent may be any group as long as it is a group which can be substituted as described in the above-mentioned substituent, and is preferably substituted. The group is a hydroxyl group, an aliphatic oxy group, an amine carbaryl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amine group, an aliphatic amine group, a decylamino group, an amine carbylamino group. The aliphatic oxy group of R ¹ is preferably an alkoxy group having 1 to 8 total carbon atoms, more preferably an alkoxy group having 1 to 4 total carbon atoms, and examples thereof include a methoxy group and an ethoxy group. c) Butoxy, methoxyethoxy, aminecarakimethoxy and the like.

The aliphatic group represented by R ¹ may have a substituent, and the substituent may be any group as long as it is a group which can be substituted as described in the above-mentioned substituent, and a preferred substituent It is a hydroxyl group, an aliphatic oxy group, an amine carbaryl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amine group, an aliphatic amine group, a decylamino group, an amine carbylamino group. The aliphatic group of R ¹ is preferably an alkyl group having a total carbon number of 1 to 8, more preferably an alkyl group having a total carbon number of 1 to 4.

The aryl group represented by R ¹ may have a substituent, and the substituent may be any group as long as it is a group which can be substituted as described in the above-mentioned substituent, and a preferred substituent is An aliphatic group, an aliphatic oxy group, a halogen atom, an amine carbaryl group, a heterocyclic group condensed with an aryl group, or an aliphatic oxycarbonyl group. The aryl group of R ¹ is preferably an aryl group having a total carbon number of 6 to 12, more preferably an aryl group having a total carbon number of 6 to 10, and examples thereof include a phenyl group, a 4-methylphenyl group, and a 3-chlorobenzene group. Base.

The heterocyclic group represented by R ¹ may be a saturated heterocyclic group, may be an unsaturated heterocyclic group, or may have a substituent, and the substituent may be as defined in the above-mentioned substituent and may be substituted. The group may be any group, and a preferred substituent is an aliphatic group, an aliphatic oxy group, an amine carbaryl group, a heterocyclic group condensed with a hetero group, or an aliphatic oxycarbonyl group. The heterocyclic group of R ¹ is preferably a heterocyclic group having 2 to 10 carbon atoms in total, and more preferably a non-aromatic heterocyclic ring of a 5-membered ring to 6-membered ring bonded by a nitrogen atom having 2 to 8 total carbon atoms. Examples of the ring group include 1-piperidinyl group, 4-morpholinyl group, 1-quinoyl group, 2-pyrimidinyl group, 4-pyridyl group and the like.

R ^{1 is} preferably an amine group, an aliphatic oxy group, or a non-aromatic heterocyclic group having a 5-membered ring to a 6-membered ring bonded by a nitrogen atom, more preferably an amine group or an aliphatic oxy group, and further preferably Amine.

R ^{1 is} preferably an amine group.

The substituent represented by R ² may be any group as long as it is a group which can be substituted as described in the above-mentioned substituent, and is preferably an aliphatic group, an aryl group or a heterocyclic group. Aliphatic oxycarbonyl, carboxyl, aminemethanyl, decylamino, sulfonylamino, amine carbylamino, amine sulfonyl, aliphatic oxy, aliphatic thio, cyano, halogen atom More preferably, it is an aliphatic oxycarbonyl group, an amine methyl sulfonyl group, a mercaptoamine group, an amine mercaptoamine group, an aliphatic oxy group, a halogen atom, and particularly preferably an aliphatic oxy group.

In the case where the substituent has a substituent, an aliphatic group, a hydroxyl group, a substituent having a guanamine bond, an ether bond, an oxycarbonyl bond, a thioether bond or the like is preferred, and an intermolecular hydrogen bond is easily formed. From the viewpoint of the intermolecular interaction, a substituent having a bond of a hetero atom and a hydrogen atom is more preferable.

m is preferably in the case of 0 to 3, more preferably in the case of 0 to 1, and further preferably in the case of 0.

n is preferably 1 or 2.

The aliphatic group represented by R ² may have a substituent, and may be saturated or unsaturated, and the substitutable group may be a group which is described in the above-mentioned substituent and which may be substituted. It can be any group. The aliphatic group of R ² is preferably an alkyl group having 1 to 8 total carbon atoms, more preferably an alkyl group having 1 to 6 total carbon atoms, and examples thereof include a methyl group, an ethyl group, an isopropyl group, and a cyclohexyl group. Third butyl and the like.

The aryl group represented by R ² may have a substituent, and the substitutable group may be any group as long as it is a group which can be substituted as described in the above-mentioned substituent. The aryl group of R ² is preferably an aryl group having a total carbon number of 6 to 12, more preferably an aryl group having a total carbon number of 6 to 10, and examples thereof include a phenyl group, a 3-methoxyphenyl group, and a 4-amine. Formylphenyl and the like.

The heterocyclic group represented by R ² may have a substituent, may be saturated or unsaturated, or may be condensed, and the substitutable group may be as described in the above-mentioned substituents and may be carried out. The substituted group may be any group. The heterocyclic group of R ² is preferably a heterocyclic group having 2 to 16 carbon atoms in total, more preferably a heterocyclic group of a 5-membered to 6-membered ring having 2 to 12 total carbon atoms, and examples thereof include 1-pyrrole. Pyridyl, 4-morpholinyl, 2-pyridyl, 1-pyrrolyl, 1-imidazolyl, 1-benzimidazolyl, and the like.

The aliphatic oxycarbonyl group represented by R ² may have a substituent, and may be saturated or unsaturated, and the substitutable group may be a group which can be substituted as described in the above-mentioned substituent. The group can be any group. The aliphatic oxycarbonyl group of R ² is preferably an alkoxycarbonyl group having 1 to 8 total carbon atoms, more preferably an alkoxycarbonyl group having 1 to 6 total carbon atoms, and examples thereof include a methoxycarbonyl group and an isopropyl group. An oxycarbonyl group, an amine formamylmethoxycarbonyl group or the like.

The amine mercapto group represented by R ² may have a substituent, and the substitutable group may be any group as long as it is a group which can be substituted as described in the above-mentioned substituent. Preferred are aliphatic groups, aryl groups, heterocyclic groups and the like. The aminomethyl group of R ² is preferably an amine carbenyl group, an alkylamine carbenyl group having 2 to 9 carbon atoms, a dialkylamine formammonyl group having a total carbon number of 3 to 10, and a total number of carbon atoms. 7 to 13 arylamine carbenyl group, heterocyclic amine carbenyl group having 3 to 12 carbon atoms, more preferably an amine carbenyl group, an alkylamine carbenyl group having 2 to 7 carbon atoms in total, A dialkylamine-methyl group having 3 to 6 carbon atoms, an arylamine-methyl group having 7 to 11 carbon atoms, and a heterocyclic amine-methyl group having 3 to 10 carbon atoms, for example, an amine group Anthracenyl, methylamine, mercapto, dimethylamine, phenylamine, benzylamine, 4-pyridylmethionyl, and the like.

The mercaptoamine group represented by R ² may have a substituent, may be aliphatic, may be aromatic, or may be a heterocyclic ring, and the substitutable group may be as defined in the above-mentioned substituents. The group which can be substituted and described may be any group. The mercaptoamine group of R ² is preferably a mercaptoamine group having a total carbon number of 2 to 12, more preferably a mercaptoamine group having a total carbon number of 1 to 8, and preferably a total carbon number of 1 to 8. Examples of the alkylcarbonylamino group include an ethyl hydrazino group, a benzhydrylamino group, a 2-pyridinecarbonylamino group, a propyl fluorenyl group, and the like.

The sulfonamide group represented by R ² may have a substituent, may be aliphatic, may be aromatic, or may be a heterocyclic ring. The substitutable group may be any group as long as it is a group which is described in the above-mentioned substituent and which can be substituted. The sulfonamide group of R ² is preferably a sulfonylamino group having a total carbon number of 1 to 12, more preferably a sulfonylamino group having a total carbon number of 1 to 8, and preferably a total carbon number of 1 to 8. Examples of the alkylsulfonylamino group include a methanesulfonylamino group, a benzenesulfonylamino group, a 2-pyridinesulfonylamino group, and the like.

The amine mercaptoamine group represented by R ² may have a substituent, and the substitutable group may be any group as long as it is a group which is described in the above-mentioned substituent and which can be substituted. It is preferably an aliphatic group, an aryl group, a heterocyclic group or the like. The amine mercaptoamine group of R ² is preferably an aminomethylamino group, an alkylamine-methylamino group having 2 to 9 carbon atoms, and a dialkylamine formazan having a total carbon number of 3 to 10. An amino group, an arylamine-methylamino group having a total carbon number of 7 to 13, a heterocyclic amine-methylamino group having a total carbon number of 3 to 12, more preferably an aminomethylamino group, and a total carbon An alkylamine-methylamino group having 2 to 7 atoms, a dialkylamine-methylamino group having 3 to 6 carbon atoms, an arylamine-methylamino group having 7 to 11 carbon atoms, Examples of the heterocyclic amine mercaptoamine group having a total carbon number of 3 to 10, for example, an aminomethylamino group, a methylamine, a mercaptoamine group, and an N,N-dimethylamine-methylamino group. And a phenylamine-methylamino group, a 4-pyridylamine-methylamino group, and the like.

The amine sulfonyl group represented by R ² may have a substituent, and the substitutable group may be any group as long as it is a group which is described in the above-mentioned substituent and which can be substituted. Preferred are aliphatic groups, aryl groups, heterocyclic groups and the like. The amine sulfonyl group of R ² is preferably an amine sulfonyl group, an alkylamine sulfonyl group having a total carbon number of 1 to 9, a dialkylamine sulfonyl group having 2 to 10 carbon atoms, and a total number of carbon atoms. 7 to 13 arylamine sulfonyl group, heterocyclic amine sulfonyl group having 2 to 12 carbon atoms, more preferably sulfonyl group, alkylamine sulfonyl group having 1 to 7 carbon atoms, total The dialkylamine sulfonyl group having 3 to 6 carbon atoms, the arylamine sulfonyl group having 6 to 11 carbon atoms, and the heterocyclic amine sulfonyl group having 2 to 10 carbon atoms are exemplified by an amine. Sulfhydryl group, methylamine sulfonyl group, N,N-dimethylamine sulfonyl group, phenylamine sulfonyl group, 4-pyridylamine sulfonyl group and the like.

The aliphatic oxy group represented by R ² may have a substituent, may be saturated or unsaturated, and the substitutable group may be a group which is described in the above-mentioned substituent and which may be substituted. , can be any group. The aliphatic oxy group of R ² is preferably an alkoxy group having 1 to 8 total carbon atoms, more preferably an alkoxy group having 1 to 6 total carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a different oxy group. Propyloxy, cyclohexyloxy, methoxyethoxy, and the like.

The aliphatic thio group represented by R ² may have a substituent, may be saturated or unsaturated, and the substitutable group may be a group which is described in the above-mentioned substituent and which may be substituted. , can be any group. The aliphatic sulfur group of R ² is preferably an alkylthio group having 1 to 8 total carbon atoms, more preferably an alkylthio group having 1 to 6 total carbon atoms, and examples thereof include a methylthio group and an ethylthio group. , Aminomethylthiomethyl, Tributylthio and the like.

The halogen atom represented by R ² is preferably a fluorine atom, a chlorine atom or a bromine atom, and more preferably a chlorine atom. In terms of the effects of the present invention, R ^{2 is} preferably an aliphatic oxycarbonyl group or an amine carbaryl group. In the aspect of the effect of the present invention, m is preferably a case of 0 or 1, more preferably a case of 0.

The general formula (A-1) to the general formula (A-32) represented by A will be described. The portion represented by the formula (A-1) to the formula (A-32) is preferably a total of 2 to 15 carbon atoms, more preferably 2 to 12 carbon atoms.

The substituent represented by R ₅₁ to R ₅₄ may be any group as long as it is a group which can be substituted as described in the above-mentioned substituent. The substituent of R ₅₁ to R ₅₄ is preferably an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an amine carbaryl group, a decylamino group, a sulfonylamino group, an aliphatic oxy group, or an aliphatic group. The thio group, the cyano group and the like are more preferably an aliphatic group, an aliphatic oxycarbonyl group, an amine carbaryl group, an aliphatic oxy group, a cyano group or the like.

In terms of the effects of the present invention, R ₅₁ to R _{54 are} preferably a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an amine carbaryl group, a decylamino group or a sulfonium sulfonate. In the case of an amine group, an aliphatic oxy group, an aliphatic thio group or a cyano group, a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group, an amine carbaryl group, an aliphatic oxy group or a cyano group is more preferable.

The substituent represented by R ₅₅ may be any group as long as it is a group which is described in the above-mentioned substituent and which can be substituted. The substituent of R ₅₅ is preferably an aliphatic group, an aryl group, a heterocyclic group or the like, more preferably an aliphatic group, an aryl group, or an aromatic member having a nitrogen atom at a position adjacent to a bonding site of a nitrogen atom. ~6 member heterocyclic group.

In the aspect of the effect of the present invention, R _{55 is} preferably an aliphatic group, an aryl group or a heterocyclic group, more preferably an aliphatic group, an aryl group or a contiguous position to a bond site with a nitrogen atom. In the case of an aromatic 5-membered to 6-membered heterocyclic group containing a nitrogen atom, it is preferable to use an aromatic 5-membered to 6-membered heterocyclic group containing a nitrogen atom at a position adjacent to a bonding site of a nitrogen atom. R ₅₅ is an aromatic 5-membered to 6-membered heterocyclic group containing a nitrogen atom at a position adjacent to a bonding site of a nitrogen atom, and it is easy to firmly form an intermolecular interaction of a dye molecule, and is easily formed firmly. Intramolecular interactions. Therefore, it is easy to form a pigment having a stable molecular arrangement, and it is preferable in that it exhibits a good hue and high fastness (light resistance, gas, heat, water, etc.).

In the aspect of the effects of the present invention, the aromatic 5-membered to 6-membered heterocyclic group which preferably contains a nitrogen atom at a position adjacent to the bonding site of the nitrogen atom as R ₅₅ may have a substituent. The substituted group may be any group as long as it is a group which is described in the above-mentioned substituent and which can be substituted. Preferred substituents are hydroxy, aliphatic oxy, carbamoyl, aliphatic oxycarbonyl, aliphatic thio, amine, aliphatic amine, decylamino, amine carbylamino The saturated heterocyclic group may be an unsaturated heterocyclic group or a condensed heterocyclic group, and preferably has a total carbon number of 2 to 12 and a nitrogen atom at a position adjacent to a bonding site of the nitrogen atom. The aromatic 5-membered to 6-membered heterocyclic group is more preferably an aromatic 5-membered to 6-membered heterocyclic group having a nitrogen atom at a position adjacent to a bonding site of a nitrogen atom having 2 to 10 carbon atoms in total. For example, 2-thiazolyl, 2-benzothiazolyl, 2-oxazolyl, 2-benzoxazolyl, 2-pyridyl, 2-pyrazinyl, 3-pyridazinyl, 2-pyrimidine Further, 2-pyrimidinyl, 4-pyrimidinyl, 2-imidazolyl, 2-benzimidazolyl, 2-triazinyl or the like may be a tautomeric structure together with a substituent.

In terms of the effects of the present invention, the aryl group which is preferable as R ₅₅ may have a substituent, and the substitutable group is only a group which can be substituted as described in the above-mentioned substituent. The group may be any group, and preferred substituents are a hydroxyl group, a nitro group, an aliphatic group, an aliphatic oxy group, an amine carbaryl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amine group, an aliphatic group. Amine, mercaptoamine, amine mercaptoamine. The aryl group of R ₅₅ is preferably an aryl group having a total carbon number of 6 to 12, more preferably an aryl group having a total carbon number of 6 to 10, and examples thereof include a phenyl group, a 3-methoxyphenyl group, and a 4-amine. A mercaptophenyl group or the like is preferably a phenyl group.

In terms of the effect of the present invention, the aliphatic group which is preferable as R ₅₅ may have a substituent, and the substitutable group may be as described in the above-mentioned substituent and may be substituted. The group may be any group, and preferred substituents are a hydroxyl group, a nitro group, an aliphatic oxy group, an amine carbaryl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amine group, an aliphatic amine group, Mercaptoamine, amine mercaptoamine. The aliphatic group of R ₅₅ is preferably an alkyl group having 1 to 6 total carbon atoms, more preferably an aliphatic group having 1 to 4 total carbon atoms, and examples thereof include a methyl group, an ethyl group, and a methoxyethyl group. Aminomethylaminomethyl or the like is preferably a methyl group.

In the general formula (A2), R _{55 is} preferably any one of the following (Y-1) to (Y-13), and in order to easily obtain an intramolecular hydrogen bond structure, it is more preferably a 6-membered ring as follows ( In the case of any of Y-1) to (Y-6), it is preferable to use any of the following (Y-1), (Y-3), (Y-4), and (Y-6). It is especially preferable to the case of the following (Y-1) or (Y-4). * in the general formula (Y-1) to the general formula (Y-13) represents a bonding site with the N atom of the pyrazole ring. Y ₁ to Y ₁₁ represent a hydrogen atom or a substituent. G ₁₁ in (Y-13) represents a non-metal atom group which can constitute a 5- to 6-membered heterocyclic ring, and the hetero ring represented by G ₁₁ may be unsubstituted or may have a substituent, and the heterocyclic ring may be a single ring. It can also be a shrink ring. The formula (Y-1) to the formula (Y-13) may be a tautomeric structure together with the substituent.

[Chemistry 7]

The substituent represented by Y ₁ to Y ₁₁ may be any group as long as it is a group which can be substituted as described in the above-mentioned substituent. The substituent of Y ₁ to Y ₁₁ is preferably an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an amine carbaryl group, a decylamino group, a sulfonylamino group, an aliphatic oxy group, an aliphatic group. A sulfur group, a cyano group or the like is more preferably an aliphatic group, an aliphatic oxy group, an aliphatic thio group or a cyano group. In Y ₁ to Y ₁₁ , two adjacent substituents may form a 5-membered ring to a 6-membered ring.

In terms of the effects of the present invention, Y ₁ to Y _{11 are} preferably a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an amine carbaryl group, a decylamino group or a sulfonium sulfonate. In the case of an amine group, an aliphatic oxy group, an aliphatic thio group or a cyano group, a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group, an amine carbaryl group, an aliphatic oxy group or a cyano group is more preferable.

In terms of the effect of the present invention, the A in the general formula (A2) is the side of the hue The surface is preferably a 5-membered ring heterocyclic ring, more preferably a nitrogen-containing or sulfur-containing 5-membered heterocyclic ring, and further preferably a 5-membered heterocyclic ring containing two or more hetero atoms.

The substituent represented by R ₅₆ to R ₅₇ and R ₅₉ may be any group as long as it is a group which can be substituted as described in the above-mentioned substituent. The substituent of R ₅₆ to R ₅₇ and R ₅₉ is preferably an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an amine carbaryl group, a decylamino group, a sulfonylamino group or an aliphatic oxy group. An aliphatic thio group, a cyano group or the like is more preferably an aliphatic group, an aliphatic oxy group, an aliphatic thio group or a cyano group.

In terms of the effects of the present invention, R ₅₆ to R ₅₇ and R _{59 are} preferably an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an amine carbaryl group, a decylamino group or a sulfonium sulfonate. In the case of an amine group, an aliphatic oxy group, an aliphatic thio group or a cyano group, it is more preferably an aliphatic group, an aliphatic oxy group, an aliphatic thio group or a cyano group.

The substituent represented by R ₅₈ may be any group as long as it is a group which is described in the above-mentioned substituent and which can be substituted. In terms of the effects of the present invention, R _{58 is} preferably a heterocyclic group, a Hammert's substituent constant σp value of 0.2 or more electron withdrawing groups, and more preferably a σp value of 0.3 or more. Electronic basis. The upper limit is an electron withdrawing group having a σp value of 1.0 or less.

Specific examples of R _{58 which is} an electron withdrawing group having a σp value of 0.2 or more include an anthracenyl group, a mercaptooxy group, an aminomethyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, and a second group. Alkylphosphinyl, diarylphosphonium, diarylphosphinyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfonyloxy Base, mercaptothio, sulfonyl, thiocyanate, thiocarbonyl, alkyl halide, halogenated alkoxy, halogenated aryloxy, alkyl halide, halogenated alkylthio, σp An aryl group, a heterocyclic group, a halogen atom, an azo group, or a selenocyanate group substituted with another electron-donating group having a value of 0.20 or more.

Further, in terms of the effects of the present invention, R _{58 is} preferably the case of (Y-1) to (Y-13), and in order to easily obtain an intramolecular hydrogen bond structure, it is more preferably a 6-membered ring. In the case of any of (Y-1) to (Y-6), it is preferable that any of the above (Y-1), (Y-3), (Y-4), and (Y-6) The case is particularly preferably the case of (Y-1) or (Y-4).

The heterocyclic ring of (A-1) to (A-32) exemplified as A in the general formula (A2) is lightly strong as long as the atom adjacent to the carbon atom bonded to the azo group is a hetero atom. The tendency of the property and the thermal fastness to become high is preferable because a pigment having such a structural feature is used for a color filter to obtain a color filter exhibiting high contrast.

In terms of the effect of the present invention, the azo pigment represented by the formula (A2) is preferably a case where G is a hydrogen atom, and R ¹ is an amine group or a saturated heterocyclic group bonded with a nitrogen atom, m When it is 0 or 1, when m is 1, R ² is an aliphatic oxycarbonyl group, an amine carbenyl group or an aliphatic oxy group, and A is (A-1), (A-10) to (A-17). And (A-20) to (A-23), (A-27), (A-28), (A-30) to (A-32), and n is 1 or 2.

More preferably, it is the case where G is a hydrogen atom, R ¹ is an amine group or a saturated heterocyclic group bonded with a nitrogen atom, m is 0 or 1, and in the case where m is 1, R ² is an aliphatic oxycarbonyl group. , Aminomethyl or alkoxy, A is (A-1), (A-10), (A-11), (A-13) to (A-17), (A-20), A-22) Any of (A-23), (A-27), (A-28), (A-30) to (A-32), and n is 1 or 2.

Further preferably, the case is as follows: G is a hydrogen atom, R ¹ is an amine group or a saturated heterocyclic group bonded with a nitrogen atom, m is 0, and A is (A-10), (A-11), (A-13) )~(A-17), (A-20), (A-22)~(A-23), (A-27), (A-28), (A-30)~(A-32) Either, and n is 1 or 2.

It is particularly preferable that G is a hydrogen atom, R ¹ is an amine group, m is 0, and A is (A-16) to (A-17), (A-20), (A-28), (A- Any one of 32), n is 1 or 2; particularly preferably, G is a hydrogen atom, R ¹ is an amine group, m is 0, A is (A-16), and n is 1 or 2.

In the aspect of the effect of the present invention, the azo pigment represented by the formula (A2) is more preferably an azo pigment represented by the following formula (A3).

With respect to the azo pigment represented by the general formula (A3), Z or R ₅₅ forms a cross hydrogen bond with the hydroxyl group of the naphthalene ring by an azo group, thereby improving the planarity of the pigment structure, and the intramolecular and intermolecular interactions are changed. Strong, as a result, light fastness, heat fastness, solvent resistance, and the like are greatly improved, which is preferable.

Hereinafter, the azo pigment, the tautomer, the salt or the hydrate represented by the formula (A3) will be described in detail.

General formula (A3) [Chemical 8]

(In the formula (A3), R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ , m and n are respectively the same as R ¹ , R ² , R ₅₅ , R ₅₉ , m and n defined in the formula (A2). Meaning Z. The Hammer's σp value is an electron withdrawing group of 0.2 or more. The case of n=2 represents a dimer interposing R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ or Z. The case of n=3 represents interposed _{R 21, R 22, R 55} , R 59 or Z trimer .n = 4 represents the case interposed _{R 21, R 22, R 55} , R 59 or Z tetramer of general formula ( A3) does not have an ionic hydrophilic group)

The substituent having a σp value of 0.2 or more of Hammett represented by Z is exemplified by the group described in the description of R ₅₈ of the above formula (A2).

Preferred substituents and ranges of R ₂₁ , R ₂₂ , R ₅₅ , R ₅₉ , m and n of the azo pigment represented by the formula (A3) and R ¹ , R ² and R _{55 of the} formula (A2) , R ₅₉ , m, and n are the same.

In terms of the effect of the present invention, Z is preferably an anthracenyl group, an aminomethyl fluorenyl group, an alkoxycarbonyl group, a cyano group, an alkylsulfonyl group, an amine sulfonyl group, more preferably an amine carbaryl group or an alkane. The case of an oxycarbonyl group or a cyano group, particularly preferably a cyano group.

In terms of the effect of the present invention, the azo pigment represented by the formula (A3) is preferably a case where R ₂₁ is an amine group which may have a substituent, m is 0 or 1, and when m is 1. When R ₂₂ is an aliphatic oxycarbonyl group, an amine carbaryl group or an aliphatic oxy group, and R ₅₅ is an aromatic 5-membered to 6-membered heterocyclic group having a nitrogen atom at a position adjacent to the bonding site, and R ₅₉ is A hydrogen atom or an aliphatic group, Z is a mercapto group, an amine mercapto group, an alkoxycarbonyl group, a cyano group, an alkylsulfonyl group or an aminesulfonyl group, and n is 1 or 2.

More preferably, R ₂₁ is an amine group which may have a substituent, m is 0, R ₅₅ is any one of (Y-1) to (Y-13), and R ₅₉ is a hydrogen atom or an aliphatic group, Z It is an aminomethyl group, an alkoxycarbonyl group or a cyano group, and n is 1 or 2.

Further, it is preferably the case where R ₂₁ is an amine group which may have a substituent, m is 0, R ₅₅ is any one of (Y-1) to (Y-6), and R ₅₉ is a hydrogen atom or an aliphatic group, Z It is an aminomethyl group, an alkoxycarbonyl group or a cyano group, and n is 1 or 2.

More preferably, R ₂₁ is an amine group which may have a substituent, m is 0, R ₅₅ is (Y-1), (Y-4) or (Y-6), R ₅₉ is a hydrogen atom, and Z is Cyano group, and n is 1 or 2.

In the aspect of the effect of the present invention, the azo pigment represented by the formula (A2) or the formula (A3) preferably has a "total number of carbon atoms/number of azo groups" of 40 or less, more preferably 30. the following. In the aspect of the effect of the present invention, the azo pigment represented by the formula (A2) or the formula (A3) preferably has a "molecular weight/number of azo groups" of 700 or less. In the aspect of the effect of the present invention, the azo pigment represented by the formula (A2) or the formula (A3) is preferably substituted without an ionic substituent such as a sulfo group or a carboxyl group.

In other aspects of the azo compound represented by the above formula (A2), it is preferred that A is (A-1) to (A-9), (A-11) to (A-13), (A). -17), (A-20)~(A-23), (A-27), (A-28), (A-30)~(A-32), more preferably (A-11)~( A-13), (A-17), (A-20)~(A-23), (A-27), (A-28), (A-30) ~(A-32), and thus better (A-17), (A-20), (A-22)~(A-23), (A-27), (A-28), (A-31), (A-32), and further Jia Wei (A-20), (A-28), (A-32), and especially good (A-20). Further, it is preferable that R ₅₆ of (A-20) is R ₅₉ .

In the present invention, the tautomer of the azo pigment represented by the formula (A2) or the formula (A3) is also included in the range. The general formula (A2) or the general formula (A3) is represented by a limit structural formula in a plurality of tautomeric forms which are preferable from the chemical structure, and may be a tautomer other than the described structure, and may also contain It is used in the form of a mixture of various tautomers.

For example, the azo pigment represented by the following formula (A1') is considered to be an azo-oxime tautomer represented by the following formula (A1').

In the present invention, the pigment represented by the following formula (A1') which is a tautomer of the azo pigment represented by the formula (A2) is also included in the range.

(In the formula (A1'), G, R ₁ , R ₂ , m, n and A have the same meanings as G, R ¹ , R ² , m and n in the formula (A2), respectively)

In the azo pigment represented by the formula (A2), the general formula of the azo pigment which is more preferably as described above may be represented by the following formula (A4-1) to formula (A4-4). Azo pigment. The azo pigment represented by the above formula (A2) is preferably an azo pigment represented by the following formula (A4-1) to formula (A4-4).

Hereinafter, the azo pigments represented by the general formulae (A4-1) to (A4-4), the tautomers thereof, and the salts or hydrates thereof will be described in detail.

(In the general formula (A4-1) to the general formula (A4-4), R ₁ , R ₂ , m and n have the same meanings as R ¹ , R ² , m and n in the formula (A2), respectively. A carbon atom or a nitrogen atom is represented, and Ax forms an aromatic 5 member to 6 membered heterocyclic group together with X and an adjacent carbon atom, and Bx forms an aromatic 5 member to 6 membered heterocyclic group together with an adjacent carbon atom. And represents a corresponding group in (A-1) to (A-32) defined by A of the formula (A2). Yx forms a heterocyclic group together with a nitrogen atom and an adjacent carbon atom, and represents a general formula ( A2) the corresponding group in the heterocyclic group defined by R _55. R ₂₃ represents a substituent such as R ₅₁ , R ₅₄ , R ₅₇ or R ₅₈ defined by the formula (A2), which corresponds to the corresponding substitution. a substituent of the group obtained by removing a carbonyl group from the group. R' ₁ represents a corresponding substituent from which the -NH- group is removed from the amine group of R ¹ defined by the formula (A2)

A variety of tautomers are conceivable for the azo pigments represented by the above formula (A2), formula (A3), and formula (A4-1) to formula (A4-4).

Further, in the present invention, the azo pigment represented by the formula (A2) preferably has a substituent which forms an intramolecular hydrogen bond or an intramolecular cross hydrogen bond. More preferably, it has at least one or more substituents which form intramolecular hydrogen bonds, and it is more preferable to have at least one or more substituents which form intramolecular cross hydrogen bonds.

The factor of the structure is preferably a nitrogen atom of a heterocyclic group or a hydroxyl group of a naphthalene substituent which is contained in the azo pigment structure as represented by the general formulae (A4-1) to (A4-4). a hydrogen atom and an oxygen atom, an azo group or a nitrogen atom of a mercapto group as a tautomer thereof, or a carbonyl group substituted with an azo group contained in an azo pigment structure, a hydrogen atom of a hydroxyl group of a naphthalene substituent, and oxygen The atom, and the azo group or the nitrogen atom of the thiol group as its tautomer easily form a cross hydrogen bond in the molecule.

As a result, the planarity of the molecule is increased, intramolecular. Further, the intermolecular interaction is further improved, and the crystallinity of the azo pigment represented by the general formulae (A4-1) to (A4-4) becomes high (it is easy to form a high-order structure), and the required performance as a pigment is light fastness. Further, thermal stability, wet heat stability, water resistance, gas resistance, and/or solvent resistance are greatly improved, which is a more preferable example.

From this point of view, the azo pigment represented by the formula (A2) is preferably a formula (A3), the pigment represented by the formula (A4-1) to the formula (A4-4), more preferably represented by the formula (A3), the formula (A4-1) or the formula (A4-2) The pigment is particularly preferably an azo pigment represented by the formula (A3).

Specific examples of the azo pigment used in the present invention can be referred to, for example, the compounds described in paragraphs 0094 to 0116 of JP-A-2011-162760, the contents of which are incorporated herein by reference.

Further, the pigment of the present invention may be a quinophthalone compound selected from the following general formula (1A), general formula (1B), and general formula (1C) (hereinafter sometimes referred to as "specific quinophthalone compound"). More than one pigment. By using a quinophthalone compound, the effect is high, the contrast is high, and the coloring power is excellent, and the color filter is excellent in the low viscosity of the coloring composition.

General formula (1B) [Chemical 12]

(In the general formulae (1A) to (1C), R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ and R ⁴⁴ to R ⁶⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and Alkoxy group having a substituent, an aryl group which may have a substituent, -SO ₃ H; -COOH; and a monovalent to trivalent metal salt of the acidic group; an alkylammonium salt, a substituent which may have a substituent Benzoquinone imine methyl, or aminesulfonyl group which may have a substituent)

Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

Further, the alkyl group which may have a substituent includes, in addition to a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a n-hexyl group, an n-octyl group, a stearyl group, Other than a straight or branched alkyl group such as 2-ethylhexyl, trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2,2 may be mentioned. ,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl A substituted alkyl group such as a 4-methoxybenzyl group, a 4-nitrobenzyl group or a 2,4-dichlorobenzyl group.

Further, the alkoxy group having a substituent is methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, neopentyloxy, 2, Other than a linear or branched alkoxy group such as 3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy or 2-ethylhexyloxy, trichloromethoxy , trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2-di-trifluoromethylpropoxy, 2- Alkoxy groups having a substituent such as an ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, or a benzyloxy group.

Further, the aryl group which may have a substituent may be, for example, a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group or a p-methoxyphenyl group, in addition to an aryl group such as a phenyl group, a naphthyl group or a fluorenyl group. 2,4-Dichlorophenyl, pentafluorophenyl, 2-aminophenyl, 2-methyl-4-chlorophenyl, 4-hydroxy-1-naphthyl, 6-methyl-2-naphthyl An aryl group having a substituent such as 4,5,8-trichloro-2-naphthyl, anthraquinonyl or 2-aminoindenyl.

Further, examples of the acidic group include -SO ₃ H and -COOH, and the monovalent to trivalent metal salt of the acidic group may, for example, be a sodium salt, a potassium salt, a magnesium salt, a calcium salt, an iron salt or an aluminum salt. Further, examples of the acid group alkylammonium salt include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, palmityl trimethylammonium and dilauryldimethylammonium. A quaternary alkyl ammonium salt such as distearyl dimethyl ammonium salt.

a phthalic acid imine methyl group (C ₆ H ₄ (CO) ₂ N-CH ₂ -) which may have a substituent, and an amine sulfonyl group (H ₂ NSO ₂ -) which may have a substituent Examples of the substituent include a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, and the like.

Further, from the viewpoint of low viscosity of the dispersion, the quinophthalone compound is more preferably R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ , R ⁴⁴ to R ⁶⁰ of the formula (1A) to the formula (1C). It is a hydrogen atom or a halogen atom.

Specific examples of the quinophthalone compound include the quinophthalone compound (a) to the quinophthalone compound (r) shown below, but the present invention is not limited to these compounds.

[Chemistry 14]

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[Chemistry 16]

In addition, the phthalocyanine dye represented by the following general formula (1) (hereinafter sometimes referred to as "specific phthalocyanine dye") may be used as the pigment of the present invention.

(In the formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent or an aryl group which may have a substituent. R ¹ and R ² are each independently A hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent or -OR ³ , and R ¹ and R ² may be bonded to each other to form a ring. R ³ is an alkyl group which may have a substituent Or an aryl group which may have a substituent)

Specific examples of the specific phthalocyanine dye which can be used in the present invention are listed below, but are not limited to these specific examples.

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[Chemistry 19]

The diketopyrrolopyrrole pigment represented by the following formula (2) can also be used as the pigment of the present invention.

[Chemistry 20]

(In the formula (2), A and B are each independently a hydrogen atom, a fluorine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, -CF ₃ , -OR ¹ , -SR ² , -N(R ³ )R ⁴ , -COOR ⁵ , -CONH ₂ , -CONHR ⁶ , -CON(R ⁷ )R ⁸ , -SO ₂ NH ₂ , -SO ₂ NHR ⁹ or -SO ₂ N(R ¹⁰ )R ¹¹ , R ¹ to R ¹¹ are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent or an aralkyl group which may have a substituent. Is a hydrogen atom)

In the specific heterodiketopyrrolopyrrole pigment represented by the formula (2) used in the pigment of the present invention, in terms of brightness, contrast, and effect of suppressing crystallization, the formula (2-1) is preferred. , formula (2-2), formula (2-3), and formula (2-4). Further, R ⁶ to R ^{8 in the} formula (2-3) and the formula (2-4) are preferably an alkyl group having 4 or more carbon atoms or a substituent group in terms of contrast and effect of suppressing crystallization. Phenyl. The reason why these effects are exhibited in terms of high contrast and suppression of crystallization is considered to be due to the large volume substitution of a carboamide group having a carbon number of 4 or more, a phenyl group, a third butyl group or the like. The steric hindrance effect of the base suppresses the aggregation of the pigment. Further, the specific heterodiketopyrrolopyrrole pigment having a carboguanamine group, a phenyl group or a tert-butyl group is excellent in color characteristics, so that the excellent brightness of the brominated diketopyrrolopyrrole pigment is not impaired.

(In the formulae (2-3) and (2-4), R ⁶ to R ⁸ are each independently an alkyl group having 1 to 12 carbon atoms or a phenyl group having a substituent)

Specific examples of the specific heterodiketopyrrolopyrrole pigment of the formula (2) which can be used in the present invention are listed below, but are not limited to these specific examples.

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[Chem. 24]

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When the primary particle size of the pigment is used as a color filter, it is preferably 100 nm or less from the viewpoint of color unevenness or contrast, and is preferably from the viewpoint of dispersion stability. 5nm or more. The primary particle size of the pigment is preferably from 5 nm to 75 nm, more preferably from 5 nm to 55 nm, and particularly preferably from 5 nm to 35 nm. The specific dispersion resin of the present invention can be in a range of from 5 nm to 35 nm. A particularly good effect is achieved when the primary particle size pigment combination.

The primary particle size of the pigment can be measured by a known method such as an electron microscope.

The pigment is preferably selected from the group consisting of an anthraquinone pigment, a diketopyrrolopyrrole pigment, a phthalocyanine pigment, a quinophthalone pigment, an isoporphyrin pigment, a carbamide pigment, and a dioxazine pigment. Pigments. Especially preferred are CI Pigment Red 122, CI Pigment Red 177 (anthraquinone pigment), CI Pigment Red 254 (diketopyrrolopyrrole pigment), CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15:6 (phthalocyanine pigment), CI Pigment Yellow 138 (quinacridone pigment), CI Pigment Yellow 139, CI Pigment Yellow 185 (isoporphyrin pigment), CI Pigment Yellow 150 (Kia Amine pigment), CI Pigment Violet 23 (dioxazine pigment).

Further, the composition of the present invention may contain a known dye other than the pigment (A). For example, Japanese Patent Laid-Open Publication No. Sho 64-90403, Japanese Patent Laid-Open No. Hei 64-91102, Japanese Patent Laid-Open No. Hei No. Hei 1-94301, Japanese Patent Laid-Open No. Hei 6-11614, Japanese Patent Registration No. 2592207 , U.S. Patent No. 4,808, 510, U.S. Patent No. 5,679, 920, U.S. Patent No. 5, 560, 950, U.S. Patent No. 5, 505, 950, Japanese Patent Laid-Open No. Hei No. Hei 5- 333 207, Japanese Patent Laid-Open No. Hei 6-35183, Japanese Patent Laid-Open No. Hei 6-51115, Japan The pigment disclosed in Japanese Laid-Open Patent Publication No. Hei 6-194928 or the like. The chemical structure can be used: pyrazole azo, pyrromethylene, aniline azo, triphenylmethane, lanthanide, benzylidene, oxonium, pyrazolotriazole azo A dye such as a pyridone azo, a cyanine, a phenothiazine or a pyrrolopyrazine.

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 the pigment in the composition of the present invention is preferably 10% by mass to 70% by mass, and more preferably 20% by mass, based on the total component (solid content) other than the solvent contained in the coloring photosensitive resin composition. 60% by mass, and more preferably 30% by mass to 60% by mass.

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

<<(B) Alkaline Pigment Derivatives>>

The composition of the present invention contains (B) a basic dye derivative. The basic dye derivative is a compound having a structure in which a part of the pigment is substituted with a basic group.

Examples of the pigment constituting the basic dye derivative include a quinoline pigment, a benzimidazolone pigment, an isoporphyrin pigment, a diketopyrrolopyrrole pigment, an azo pigment, and a phthalocyanine pigment. , anthraquinone pigment, quinacridone pigment, dioxazine pigment, piperidone pigment, anthraquinone pigment, thioindole pigment, isoindolinone pigment, quinophthalone pigment, reduction Threne) is a pigment, a metal complex pigment, and the like.

The basic dye derivative is preferably a quinoline-based, benzimidazolone-based or isoporphyrin-based basic dye derivative, and more preferably a benzimidazolone-based basic dye derivative.

Specifically, the compound described in JP-A-60-88185, and the compound described in JP-A-2000-239554, The compound having a pigment core structure and an amine group in the molecule described in Japanese Laid-Open Patent Publication No. 2009-86375 is incorporated herein by reference.

The basic group which the basic dye derivative has is preferably an amine group.

Among them, the basic dye derivative is preferably a dye derivative represented by the following formula (P1) or (I).

A-N=N-X-Y (P1)

In the formula (P1), A represents a component which can form an azo pigment together with X-Y. The above A may be arbitrarily selected as long as it is a compound which can be coupled with a diazonium compound to form an azo pigment. Specific examples of the above A are shown below, but the present invention is not limited to these specific examples.

In the above formula (P1), X represents a single bond (meaning that Y is directly bonded to -N=N-) or a group selected from a divalent linking group represented by the following structural formula.

In the above formula (P1), Y represents a group represented by the following formula (P2).

In the formula (P2), Z represents a lower alkyl group. Z represents -(CH ₂ ) _b -, and b represents an integer of 1 to 5, and preferably b represents 2 or 3. In the formula (P2), -NR ₂ represents a lower alkylamino group or a saturated heterocyclic ring of 5 or 6 members containing a nitrogen atom. In the case where -NR ₂ represents a lower alkylamino group, the above -NR ₂ represents -N(C _n H _2n+1 ) ₂ , n represents an integer of 1 to 4, and preferably n represents 1 or 2. On the other hand, when -NR ₂ represents a saturated heterocyclic ring of 5 or 6 members containing a nitrogen atom, the above -NR _{2 is} preferably a heterocyclic ring represented by the following structural formula.

In the above formula (P2), Z and -NR ₂ each may have a lower alkyl group or an alkoxy group as a substituent. In the above formula (P2), a represents 1 or 2, and preferably a represents 2.

Specific examples (specific examples 1 to 22) of the compound represented by the above formula (P1) are shown below, but the present invention is not limited to these specific examples.

In the general formula (I), Dye represents an n-valent organic dye residue, and X represents a single bond, -CONH-Y ² -, -SO ₂ NH-Y ² - or -CH ₂ NHCOCH ₂ NH-Y ² - (Y ² represents an alkylene group or an aryl group which may have a substituent), Y ¹ represents -NH- or -O-, and when n represents 1, Z represents a hydroxyl group, an alkoxy group, and the following formula (III) The group represented by -NH-X-Dye (X is the same as X in the formula (I)), and when n represents an integer of 2 to 4, Z represents a hydroxyl group, an alkoxy group or a lower group, respectively. In the group represented by the above formula (III), R ¹ and R ² each represent an alkyl group which may have a substituent, and R ¹ and R ² may be bonded to each other to form a hetero ring containing a nitrogen atom. m represents an integer from 1 to 6, and n represents an integer from 1 to 4. When n is 2 or more, a plurality of X, Y ¹ , R ¹ and R ² may be the same or different.

In the formula (III), Y ³ represents -NH- or -O-. R ¹ and R ² each represent an alkyl group which may have a substituent, and R ¹ and R ² may be bonded to each other to form a hetero ring containing a nitrogen atom. m represents an integer from 1 to 6.

Dye represents an n-valent organic pigment residue. The organic dye residue may, for example, be a chromogenic atomic group in the pigment as described above, a similar structure or a partial structure thereof, and specifically includes a skeleton selected from the group consisting of a skeleton having an azo group, a skeleton having a urea structure, and a skeleton having a mercapto structure. a structure having a cyclic guanamine structure, an aromatic ring having a 5-membered ring containing a hetero atom, and a partial structure having one or more aromatic rings having a 6-membered ring containing a hetero atom, and Dye contains the structure. Substituents for some organic pigment residues.

Dye 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 bonded to the pigment directly or through a linking group. Any of a core structure, an aromatic ring, a nitrogen-containing aromatic ring, an oxygen-containing aromatic ring, or a sulfur-containing aromatic ring. Specific examples thereof include a quinoline-based residue, a benzimidazolone-based residue, an isoporphyrin-based residue, a diketopyrrolopyrrole-based residue, an azo-based residue, a phthalocyanine-based residue, and an anthracene. Residue, quinacridone residue, dioxazine Residue, piperine residue, lanthanide residue, thioindole residue, isoindolone residue, quinacridone residue, reducing residue, metal complex residue, etc. .

Specific examples of the organic dye residue represented by Dye include a copper phthalocyanine residue and the following organic dye residue. In the formula, * represents a bonding site with X in the formula (I).

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Among these, a monoazo dye having a benzimidazolone skeleton is preferred.

X represents a single bond, -CONH-Y ² -, -SO ₂ NH-Y ² - or -CH ₂ NHCOCH ₂ NH-Y ² -, preferably a single bond.

Y ² represents an alkylene group or an extended aryl group which may have a substituent. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. Specific examples thereof include a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. The alkylene group may have a substituent, and the substituent may be a group described in the item of the substituent.

The aryl group is preferably a aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Specific examples thereof include a stretching phenyl group, a stretching naphthyl group, and a stretching group.

The alkylene group and the extended aryl group may have a substituent, and the substituent may be a group described in the item of the substituent.

Y ¹ represents -NH- or -O-, preferably -NH-.

R ¹ and R ² each represent an alkyl group which may have a substituent, and R ¹ and R ² may be bonded to each other to form a hetero ring containing a nitrogen atom.

The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a n-hexyl group, and an n-octyl group. The alkyl group may have a substituent, and the substituent may be a group described in the item of the substituent.

R ¹ and R ² preferably represent the same alkyl group which may have a substituent.

m represents an integer of 1 to 6, preferably 1 to 4, more preferably 1 to 3.

n represents an integer of 1 to 4, preferably 1 to 3, more preferably 1 or 2.

In the case where n represents 1, the Z represents a hydroxyl group, an alkoxy group, a group represented by the above formula (III) or -NH-X-Dye (X has the same meaning as X in the formula (I)) In the case where n represents an integer of 2 to 4, Z represents a hydroxyl group, an alkoxy group or a group represented by the above formula (III).

In the case where n represents 1, Z is preferably a group represented by the above formula (III) or -NH-X-Dye, more preferably a group represented by the above formula (III).

When n represents an integer of 2 to 4, Z is preferably a group represented by the above formula (III).

In the formula (III), Y ³ represents -NH- or -O-, preferably -NH-. Y ³ preferably represents the same group as Y ¹ in the formula (I).

R ¹ and R ² in the formula (III) each represent an alkyl group which may have a substituent, and have the same meanings as R ¹ and R ² in the formula (I), and the preferred range is also the same. R ¹ and R ² in the formula (III) are preferably an alkyl group which may have the same substituent. Further, R ¹ and R ² in the formula (III) are preferably an alkyl group which may have the same substituent as R ¹ and R ² in the formula (I).

m represents an integer of 1 to 6, preferably 1 to 4, more preferably 1 to 3. m preferably represents the same integer as m in the formula (I).

Specific examples of the basic dye derivative used in the present invention are shown below, but the present invention is not limited to these specific examples.

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The content of the (B) basic dye derivative in the present invention is preferably 0.5% by mass or more and 40% by mass or less, and more preferably 1% by mass or more and 15% by mass or less based on the total solid content.

In addition, the content of the (B) basic dye derivative is preferably 0.5 parts by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the (A) pigment.

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

<<(C) Phosphate dispersant represented by the general formula (II)>>

The composition of the present invention contains (C) a phosphate-based dispersant represented by the formula (II). By containing the phosphate-based dispersant, the dispersant is strongly adsorbed to the pigment particles, and deterioration of the stain accompanying the composition over time can be suppressed. In addition, when the pigment composition described in Patent Document 3 and Patent Document 4 is used as it is for coloring a photosensitive resin composition, the compatibility of the component (C) with other components is inferior, and the color spot is slightly enlarged over time. , The pattern formation property after PCD is very poor, but in the present invention, this problem is eliminated by using it in combination with the component (D).

(In the formula (II), R ³ represents a polyester structure having a number average molecular weight of 400 to 30,000, and y represents 1 or 2. When y is 2, a plurality of R ^{3 's} may be the same or different)

R ³ represents a polyester structure having a number average molecular weight of 400 to 30,000, and when y is 2, a plurality of R ^{3 's} may be the same or different. The number average molecular weight of the polyester structure is preferably from 1900 to 10,000, more preferably from 400 to 3,000, and particularly preferably from 2,000 to 3,000. In the case of less than 400, the pigment dispersibility is lacking and it cannot be used.

The polyester structure may be a polyester structure obtained by ring-opening polymerization of a lactone monomer, and having a polyester structure such as a styryl group, an acrylonitrile group, a cyanoacryl fluorenyl group, a methacryl fluorenyl group or a vinyl ether group. A polyester group obtained by ring-opening polymerization of a lactone monomer is preferred.

The phosphate-based dispersant represented by the formula (II) may be a single type of phosphate ester of R ³ or a plurality of phosphate esters containing different R ³ . Further, the phosphate dispersant having y = 1 may be used alone or in a mixture of a phosphate dispersant of y = 1 and a phosphate dispersant of y = 2.

When the phosphate ester represented by the formula (II) has a ratio of the phosphate dispersant of y=1 to the phosphate dispersant of y=2 of 100:0 to 100:30, the pigment dispersibility is improved. good.

In addition, when R ³ of the phosphate-based dispersant represented by the formula (II) is a polyester structure having a number average molecular weight of 400 to 10,000, the pigment dispersibility is improved, which is preferable. More preferably 400~3000.

Further, when R ³ of the phosphate-based dispersant represented by the formula (II) is a polyester structure obtained by ring-opening polymerization of two or more different lactone monomers, the effects of the present invention are excellent, and it is very preferable.

Further, R ³ of the phosphate-based dispersant represented by the formula (II) is preferably represented by the following formula (11).

General formula (11) R ¹² -OR ¹³ -(OR ¹⁴ ) _S

(wherein R ¹² represents an alkylene group, R ¹³ represents a trihydric or higher polyhydric alcohol structure, R ¹⁴ represents an acrylonitrile group, a cyanoacryl fluorenyl group, a methacryl fluorenyl group, and s represents 2 or more)

R ^{12 is} preferably an alkylene group having a carbon number of 8 or less. Further, from the viewpoint of pigment dispersibility, s is preferably 2 or more. In this case, R ¹⁴ may also use groups different from each other. s is better for 2~5, especially better 2.

Examples of the trivalent or higher polyhydric alcohol used in R ¹³ include glycerin, propanol, pentaerythritol, and dipentaerythritol. Especially good is ternary to six-membered alcohol.

The acid value of the phosphate-based dispersant is preferably from 10 mgKOH/g to 300 mgKOH/g, more preferably from 30 mgKOH/g to 200 mgKOH/g, and still more preferably from 40 mgKOH/g to 150 mgKOH/g.

The production of the phosphate-based dispersant can be carried out by a known method. For example, the description of paragraphs 0037 to 0051 of JP-A-2007-231107 can be incorporated into the present specification.

The content of the phosphate-based dispersant in the composition of the present invention is preferably from 1% by mass to 30% by mass, more preferably from 2% by mass to 20% by mass, and further preferably from 4% by mass to 15% by mass based on the total solid content. %.

In addition, the content of the (C) phosphate-based dispersant is preferably from 5 parts by mass to 60 parts by mass, more preferably from 9 parts by mass to 40 parts by mass, per 100 parts by mass of the (A) pigment.

The phosphate-based dispersant may be contained in the composition of the present invention alone or in combination of two or more. When two or more cases are contained, it is preferable that the total amount is the said range.

In addition to the above, other dispersing agents may be contained, and the dispersing agents described in JP-A-2013-073104, No. 0333 to 0338 may be contained, and these contents are incorporated in the specification of the present application.

<<(D) Resin obtained by copolymerizing a compound (x) represented by the formula (IV) with a compound (y) having an ethylenically unsaturated double bond >>

The composition of the present invention contains (D) a resin obtained by copolymerizing a compound (x) represented by the formula (IV) and a compound (y) having an ethylenically unsaturated double bond (hereinafter also referred to as a specific resin binder). ). In Patent Document 1 or Patent Document 2, the component (D) functions as a so-called dispersant. On the other hand, in the invention of this application, the component (D) functions as a compatibilizer. The reason can be presumed as follows. That is, with respect to the component (C) of the present invention (phosphoric acid dispersant), the polyester residues thereof are easily agglomerated with each other. The crystals tend to be phase-separated from other components constituting the composition (for example, (E) a polymerization initiator or (F) a polymerizable compound), and only the component (C) tends to aggregate and crystallize. When the component (D) is added thereto, the sterically bulky aromatic ring moiety contained in the component (D) is represented by -Ph-R ⁶ of the compound (x) represented by the formula (IV). Partially) entering the polyester residue portion of component (C) to prevent condensation of polyester residues with each other. Crystallization results in an effect of suppressing phase separation of the component (C).

In the case where the pigment composition described in Patent Document 3 or Patent Document 4 is directly used for coloring the photosensitive resin composition, as described above, there are (C) a phosphate-based dispersant and other constituent materials. The component tends to phase separate, but in the present invention, the problem is eliminated by blending the component (D), and the phase separation of each component constituting the composition during the post-coating (PCD) process can be effectively suppressed. Happening.

(In the formula (IV), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 2 or 3 carbon atoms, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. n represents an integer from 1 to 15. When n is 2 or more, a plurality of R ^{5 's} may be the same or different)

R ⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. The alkyl group represented by R ⁶ is an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R ⁶ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group.

The benzene ring-containing alkyl group represented by R ⁶ may, for example, be 1-phenylethyl, 1-phenylpropyl, 1-phenylbutyl, 1-phenylpentyl, 1-phenylhexyl, 1- Phenylheptyl, 1-phenyloctyl, 1-phenylindenyl, 1-phenylindenyl, benzyl, 2-phenyl(iso)propyl, and the like.

Among these, a benzyl group and a 2-phenyl (iso)propyl group are preferable.

The compound (x) may be exemplified by an ethylene oxide (Ethylene Oxide, EO) modified (meth) acrylate of phenol, an EO of p-cumylphenol or a propylene oxide (Propylene Oxide, PO) modified (methyl). Acrylate, EO modified (meth) acrylate of nonylphenol, PO modified (meth) acrylate of nonylphenol, and the like. Among these compounds, in terms of sufficiently obtaining the function of the resin (D) as a compatibilizer, EO or PO-modified (meth) acrylate of p-cumylphenol is particularly preferable.

The compound (y) having an ethylenically unsaturated double bond may, for example, be (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, (iso)propyl (meth)acrylate, (a) (iso)butyl acrylate, (iso)pentyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate Ester Base) cyclohexyl acrylate, glycidyl (meth)acrylate, isobornyl (meth)acrylate, acid phosphonium oxyethyl (meth)acrylate, acid phosphonium propyl methacrylate And (meth)acrylic acid-3-chloro-2-acid phosphonium oxyethyl ester, acidic phosphoniumoxy polyethylene glycol mono(meth)acrylate, and the like.

The ratio of the compound (x) in the (D) resin of the present invention is from 0.1% by mass to 50% by mass, more preferably from 10% by mass to 35% by mass. When the ratio of the compound (x) is less than 10% by mass, the effect of the resin (D) as a compatibilizer is lowered, and if it is less than 0.1% by mass, the effect of the resin (D) as a compatibilizer is further lowered. Therefore, it is not good. In addition, when the amount is more than 35% by mass, the hydrophobicity is increased, and the developability of the colored photosensitive resin composition may be lowered or the residue may be formed. Further, if it is more than 50% by mass, the composition of the colored photosensitive resin composition may be different. The compatibility of the components is remarkably lowered, sometimes causing precipitation of a monomer or a photopolymerization initiator.

The weight average molecular weight (Mw) of the (D) resin (copolymer) of the present invention is preferably from 5,000 to 100,000, more preferably from 10,000 to 50,000.

In addition, in order to increase the sensitivity of the coloring photosensitive resin composition by reacting a monomer or a resin, an ethylenic double bond can be introduced into the side chain of the (D) resin (copolymer) of the present invention. Specifically, when the resin has a reactive functional group such as a hydroxyl group, the glycidyl (meth)acrylate, 2-(meth)acryloxylated isocyanate or the like has a reaction with the reactive functional group. The functional group and the ethylenically unsaturated group are reacted, and an ethylenic double bond is introduced into the side chain.

(D) The production of the resin can be produced by a known method. For example, reference can be made to paragraphs 0041 to 0045 of JP-A-2004-101728. The contents are incorporated into this specification.

The content of the (D) resin of the composition of the present invention is preferably from 1% by mass to 50% by mass, more preferably from 3% by mass to 40% by mass, even more preferably from 5% by mass to 30% by mass based on the total solid content. .

Further, the content of the (D) resin is preferably from 5 parts by mass to 80 parts by mass, more preferably from 10 parts by mass to 70 parts by mass, per 100 parts by mass of the (A) pigment. The content of the (D) resin is set to 5 parts by mass to 80 parts by mass based on 100 parts by mass of the (A) pigment, and the (D) resin functions effectively as a compatibilizer instead of functioning as a dispersing agent, and the present invention The effect is excellent.

(D) The resin may be contained in the composition of the present invention alone or in combination of two or more. When two or more cases are contained, it is preferable that the total amount is the said range.

<(E) Photopolymerization initiator>

The composition of the present invention contains a photopolymerization initiator in terms of further improving the sensitivity.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound described later, and can be appropriately selected from known photopolymerization initiators. For example, it is preferred to have a sensitivity to ultraviolet light to visible light. Further, it may be an active agent which generates a living radical by some action with a photo-excited sensitizer, or may be an initiator which initiates cationic polymerization depending on the kind of the monomer.

Further, the photopolymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm, more preferably 330 nm to 500 nm.

Examples of the photopolymerization initiator include a halogenated hydrocarbon derivative (for example, a triazine skeleton, a oxadiazole skeleton, etc.), a decylphosphine oxide such as acyl phosphine oxide, or a hexaaryl group. An anthracene compound such as a biimidazole or an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, or a hydroxyacetophenone.

Further, from the viewpoint of exposure sensitivity, it is preferably selected from the group consisting of a trihalomethyltriazine compound, a benzoin dimethyl ketal compound, an α-hydroxyketone compound, an α-amino ketone compound, and a mercaptophosphine. Compound, phosphine oxide compound, metallocene compound, hydrazine compound, triaryl imidazole dimer, hydrazine compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivative thereof, cyclopentadiene-benzene- A compound of the group consisting of an iron complex and a salt thereof, a halogenated methyl oxadiazole compound, and a 3-aryl-substituted coumarin compound.

A commercially available product can also be used as the trihalomethyltriazine compound, and for example, TAZ-107 (manufactured by Midori Chemical Co., Ltd.) can also be used.

In particular, when the composition of the present invention is used for producing a color filter provided in a solid-state image sensor, it is necessary to form a fine pattern in a sharp shape. Therefore, it is important that the hardenability is in the unexposed portion. Development was carried out without residue. From this point of view, a photopolymerization initiator is particularly preferably a ruthenium compound. In particular, when a fine pattern is formed in a solid-state image sensor, stepwise exposure is used for exposure for curing, but the exposure machine may be damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator to be low. Therefore, in consideration of these aspects, it is particularly preferable to use a ruthenium compound as the (E) photopolymerization initiation when forming a fine pattern such as a solid-state image sensor. Agent.

The halogenated hydrocarbon derivative having a triazine skeleton, the ketone compound, and the photopolymerization initiator other than the above can be referred to the compound described in paragraphs 0074 to 0077 of JP-A-2013-077009. The content is incorporated into this specification.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be preferably used. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969 and a cerium oxide-based phosphine-based initiator described in Japanese Patent No. 4,258,899 can be used.

The hydroxyacetophenone-based initiator can be used: IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, Yanjiagu (IRGACURE)-127 (trade name: all manufactured by BASF). Amino acetophenone-based initiators can be used: IRGACURE-907, IRGACURE-369 and IRGACURE-379, IRGACURE, which are commercially available products. - OXE379 (trade name: all manufactured by BASF). The amine acetophenone-based initiator may also be a compound described in JP-A-2009-191179, which has an absorption wavelength matched to a long-wavelength light source such as 365 nm or 405 nm. Further, as the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by BASF) can be used as a commercial product.

More preferably, the photopolymerization initiator is a ruthenium compound. Specific examples of bismuth compounds A compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and a compound described in JP-A-2006-342166 can be used. In addition, examples of ruthenium compounds include: "Journal of the Chemical Society (JCS) Perkin II (1979) pp. 1653-1660, "Journal of the Chemical Society, JCS) Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, The compound described in each of the publications of JP-A-2000-66385, JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166 Wait.

Commercially available products are also preferably used in IRGACURE-OXE01 (BASF), IRGACURE-OXE02 (BASF), TR-PBG-304 (Changzhou) Made by Powerful New Materials Co., Ltd.).

The ruthenium compound such as an anthracene derivative which can be preferably used as the photopolymerization initiator of the present invention can be referred to the compound described in paragraph 0080 to paragraph 0116 of JP-A-2013-077009, the contents of which are incorporated herein. In the manual.

The ruthenium compound has a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength range of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 455 nm.

From the viewpoint of sensitivity, the cerium compound is at 365 nm or 405 nm. The molar absorption coefficient is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, and particularly preferably from 5,000 to 200,000.

The molar absorption coefficient of the compound can be determined by a known method. Specifically, for example, an ultraviolet-visible spectrophotometer (Carry-5) spectrophotometer manufactured by Varian Co., Ltd. is preferably used. (spectrophotometer)) was measured at a concentration of 0.01 g/L using an ethyl acetate solvent.

The photopolymerization initiator used in the present invention may be used in combination of two or more kinds as needed.

When the (E) photopolymerization initiator is contained in the composition of the present invention, the content of the (E) photopolymerization initiator is preferably 0.1% by mass or more and 50% by mass based on the total solid content of the composition. In the following, it is more preferably 0.5% by mass or more and 30% by mass or less, and still more preferably 1% by mass or more and 20% by mass or less. Better sensitivity and pattern formation can be obtained within this range.

<<(F) Polymeric Compound>>

The composition of the present invention contains (F) a polymerizable compound. In the present invention, a known polymerizable compound which can be crosslinked by a radical, an acid or a heat can be used, and examples thereof include an ethylenically unsaturated bond and a cyclic ether (epoxy or oxetane). A polymerizable compound such as a methylol group. From the viewpoint of sensitivity, the (F) polymerizable compound is preferably selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds. Among them, a polyfunctional polymerizable compound having four or more functional groups is preferable, and a polyfunctional polymerizable compound having five or more functional groups is more preferable.

Such a compound group is widely known in the industry, and can be used in the present invention. These compounds are used without particular limitation. These may be, for example, any of the following chemical forms: a monomer, a prepolymer, that is, a dimer, a trimer, and an oligomer, or a mixture thereof, and the like. The polymerizable compounds of the present invention may be used alone or in combination of two or more.

More specifically, examples of the monomer and the prepolymer thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methacrylic acid, maleic acid, etc.) or esters thereof. The guanamines and the polymers thereof are preferably esters of an unsaturated carboxylic acid and an aliphatic polyol compound, and guanamines of an unsaturated carboxylic acid and an aliphatic polyamine compound, and the like. Things. Further, it is also preferred to use the following reactants: an unsaturated carboxylic acid ester having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, or an addition of a monofunctional or polyfunctional isocyanate or epoxy group. a reactant, or a dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid, or the like. Further, the following reactants are also preferred: an unsaturated carboxylic acid ester or a guanamine having an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol. The reactants further include a substituted carboxylic acid ester of a detachable substituent such as a halogen group or a tosyloxy group, or a substituted reactant of a monofunctional or polyfunctional alcohol, an amine or a thiol. Further, as another example, a compound group of a vinylbenzene derivative such as an unsaturated phosphonic acid or styrene, a vinyl ether or an allyl ether may be used instead of the unsaturated carboxylic acid.

As the specific compound, the compound described in Paragraph No. [0095] to Paragraph No. [0108] of JP-A-2009-288705 is preferably used in the present invention.

Further, the polymerizable compound is also preferably a compound having an ethylenically unsaturated group having at least one vinyl group capable of undergoing addition polymerization and having a boiling point of 100 ° C or higher at normal pressure. For the examples, the compounds described in paragraph 0124 of JP-A-2013-077009, the contents of which are incorporated herein by reference.

Further, a compound having a boiling point of 100 ° C or higher and having at least one ethylenically unsaturated group capable of undergoing addition polymerization under normal pressure is also preferably a paragraph number [0254] of JP-A-2008-292970. The compound described in paragraph No. [0257].

In addition to the above, the radical polymerizable monomer represented by the general formula (MO-1) to the general formula (MO-5) described in paragraphs 0126 to 0129 of JP-A-2013-077009, The contents thereof are incorporated in this specification.

In addition, the following compounds can also be used as the above-mentioned polyfunctional compound as described in the general formula (1) and the general formula (2) in the Japanese Patent Publication No. Hei 10-62986. A compound obtained by adding (meth)acrylic acid to ethylene after adding ethylene oxide or propylene oxide.

Among them, the polymerizable compound is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available product) KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercial product is KAYARAD D-310; Nippon Chemical Co., Ltd. Made by the company), dipentaerythritol hexa(meth) acrylate (commercial product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; The structure of the (Methylene) propylene sulfhydryl group interspersed with ethylene glycol residues and propylene glycol residues, manufactured by Shin-Nakamura Chemical Co., Ltd.). These types of oligomers can also be used. The preferred aspect of the polymerizable compound is shown below.

The polymerizable compound may be a polyfunctional monomer, and may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. When the ethylenic compound has an unreacted carboxyl group as in the case of the mixture as described above, it can be used as it is, and if necessary, a non-aromatic carboxylic anhydride can be reacted with a hydroxyl group of the ethylenic compound to introduce an acid group. In this case, specific examples of the non-aromatic carboxylic anhydride to be used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and alkylated six. Hydrogen phthalic anhydride, succinic anhydride, maleic anhydride.

In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and preferably has a non-aromatic carboxylic anhydride reacting with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. The polyfunctional monomer is particularly preferably those in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. Commercially available products include M-510 and M-520 which are polybasic acid-modified acrylic oligomers manufactured by East Asia Synthetic Co., Ltd., for example.

These monomers may be used singly, but it is difficult to use a single compound in terms of production, and it is also possible to use two or more kinds in combination. Further, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as a monomer, as needed.

The preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mgKOH/g to 40 mgKOH/g, particularly preferably from 5 mgKOH/g to 30 mgKOH/g. If the polyfunctional monomer is acid When the value is too low, the development and dissolution characteristics are lowered. If the value is too high, the production or handling becomes difficult, and the photopolymerization performance is lowered, and the curability such as surface smoothness of the pixel is deteriorated. Therefore, in the case where two or more kinds of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is preferred that the acid group of the entire polyfunctional monomer is in the The way the range is adjusted.

Further, a polyfunctional monomer having a caprolactone structure is also preferred as a polymerizable monomer.

The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in its molecule, and examples thereof include ε-caprolactone-modified polyfunctional (meth) acrylate, and ε- Caprolactone modified polyfunctional (meth) acrylate by trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, two Polyols such as pentaerythritol, tripentaerythritol, glycerin, diglycerin, and trimethylol melamine are obtained by esterification with (meth)acrylic acid and ε-caprolactone. Among them, the compounds described in paragraphs 0135 to 0153 of JP-A-2013-077009 can be referred to in the present specification.

A commercially available product of such a polymerizable compound is, for example, a tetrafunctional acrylate SR-494 having four ethylene oxide chains manufactured by Sartomer Co., Ltd., which is manufactured by Nippon Kayaku Co., Ltd. Six pentyloxylated hexafunctional acrylates DPCA-60, three trifunctional acrylates TPA-330 having an extended isobutoxy chain, and the like.

Further, the polymerizable compound is also preferably a Japanese Patent Publication No. Sho 48-41708, a Japanese Patent Laid-Open No. 51-37193, and a Japanese Patent. Japanese Patent Publication No. Sho. A urethane-based compound having an ethylene oxide-based skeleton described in Japanese Patent Publication No. Sho 62-39417. In addition, the intramolecular structure having an amine structure or a thioether structure as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. As the polymerizable compound, an addition polymerizable compound can obtain a curable composition having a very excellent photospeed.

Commercial products of the polymerizable compound include urethane oligomer UAS-10, urethane oligomer UAB-140 (manufactured by Shanyang Guoce Pulp Co., Ltd.), and "UA-7200" (new Made by Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha), Trihydroxyl Propane triacrylate (commercially available as A-TMPT; manufactured by Shin-Nakamura Chemical Co., Ltd.).

Regarding a cyclic ether (epoxy or oxetane), for example, as an epoxy group, the bisphenol A type epoxy resin is JER-827, JER-828, JER-834, JER-1001, JER-1002. , JER-1003, JER-1055, JER-1007, JER-1009, JER-1010 (above is made by Japan Epoxy Resin Co., Ltd.), Epiclon 860, Epiclon 1050, Ai Epiclon 1051, Epiclon 1055 (above is manufactured by Di Aisheng (DIC) Co., Ltd.); bisphenol F epoxy resin is JER-806, JER-807, JER-4004, JER -4005, JER-4007, JER-4010 (above is made by Japan Epoxy Resin Co., Ltd.), Abilon (EPICLON) 830, Epiclon 835 (above is manufactured by Di Aisheng (DIC) Co., Ltd.), LCE -21, RE-602S (above is manufactured by Nippon Kayaku Co., Ltd.); phenol novolac type epoxy resin is JER-152, JER-154, JER-157S70, JER-157S65 (above is Japanese epoxy resin ( () manufacturing), Abilon (EPICLON) N-740, Epiclon (EPICLON) N-770, Epiclon (EPICLON) N-775 (above produced by Di Aisheng (DIC) (share)); The phenol novolac type epoxy resin is EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, Abby Cloning (EPICLON) N-680, EPICLON N-690, EPICLON N-695 (above), EOCN-1020 (above is Japanese chemical) (manufacturing); aliphatic epoxy resin can be listed as: ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, ADEKA RESIN EP-4088S ( The above is made by ADEKA (shares), Celloxide 2021P, competition Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE-3150 (1,2-ring of 2,2-bis(hydroxymethyl)-1-butanol Oxy-4-(2-oxopropyl)cyclohexane adduct), EPOLEAD PB 3600, EPOLEAD PB 4700 (above is Daicel Chemical Industry) ))), Denacol EX-211L, Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Dina test Denacol EX-321L, Denacol EX-850L (above manufactured by Nagase Chemtex), ADEKA RESIN EP-4000S, Adico resin (ADEKA RESIN) EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA), JER-1031S (manufactured by Nippon Epoxy Co., Ltd.), and the like. Such a polymerizable compound is suitable for the case where a pattern is formed by dry etching.

The details of the use of the polymerizable compound, such as the structure, the use alone or in combination, and the amount of addition, can be arbitrarily set depending on the final performance design of the colored photosensitive resin composition. For example, from the viewpoint of sensitivity, it is preferred that the structure has a large content of unsaturated groups per molecule, and in many cases, it is preferably a difunctional or higher. In addition, from the viewpoint of improving the strength of the cured film formed of the colored photosensitive resin composition, it is preferable to use a trifunctional or higher functional group, and further, the number of functional groups is different. A method of adjusting both sensitivity and strength by using a polymerizable group (for example, an acrylate, a methacrylate, a styrene compound, or a vinyl ether compound) is also effective. Further, it is preferable to use a polymerizable compound having a trifunctional or higher functional group and a different ethylene oxide chain length in order to adjust the developability of the colored photosensitive resin composition, and to obtain excellent pattern forming ability.

In addition, compatibility and dispersion with other components (for example, a photopolymerization initiator, a dispersion, an alkali-soluble resin, and the like) contained in the colored photosensitive resin composition Selective, polymeric compounds. The use method is also an important factor. For example, it is sometimes possible to improve the compatibility by using a low-purity compound or a combination of two or more. Further, from the viewpoint of improving the adhesion to the hard surface of the support or the like, a specific structure may be selected.

The content of the (F) polymerizable compound in the composition of the present invention is preferably from 0.1% by mass to 90% by mass, and more preferably from 1.0% by mass to 50% by mass, based on the total solid content of the coloring photosensitive resin composition. More preferably, it is 2.0% by mass to 30% by mass.

<<Other ingredients>>

In addition to the above-described respective components, the composition of the present invention may further contain (G) a resin having a polymerizable double bond in a side chain, an organic solvent, a crosslinking agent, etc., insofar as the effects of the present invention are not impaired. ingredient.

- (G) a resin having a polymerizable double bond in a side chain -

In the present invention, a resin having a polymerizable double bond in the side chain (G) (hereinafter also referred to as "(G) resin") may be further contained. The composition of the present invention can be more effectively cured by further containing a resin having a polymerizable double bond in the (G) side chain. The polymerizable double bond is preferably a (meth) acrylate.

(G) The resin having a polymerizable double bond in the side chain is not particularly limited as long as it has a polymerizable double bond in the side chain, and it is preferred to have a functional group reactive with a hydroxyl group and an ethylenically unsaturated double bond. A compound (b) and a resin obtained by reacting a polymerizable monomer (p) having two to six hydroxyl groups with a copolymer (a) of another polymerizable monomer (q).

The polymerizable monomer (p) having two to six hydroxyl groups in the resin having a polymerizable double bond in the side chain of (G) is a compound having two or more and six or less hydroxyl groups and an ethylenically unsaturated double bond. For example, a monomer represented by the following formula (1) can be used.

(wherein R ¹ and R ⁴ each independently represent a hydrogen atom, a substituted alkyl group having 1 to 5 carbon atoms, R ² represents an alkylene group having 1 to 4 carbon atoms, and R ³ represents a carbon number of 1 to 4; An alkyl group or a single bond, and n represents an integer of 2 or more and 6 or less)

The monomer represented by the above formula (1) may, for example, be a monoester of a polyhydric alcohol having an ethylenically unsaturated double bond, and is preferably a mono(meth)acrylate.

The other polymerizable monomer (q) is a polymerizable monomer copolymerizable with the polymerizable monomer (p) having 2 to 6 hydroxyl groups, and examples thereof include (meth)acrylic acid and (meth)acrylic acid. Ester, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylic acid Tributyl ester, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethyl (meth) acrylate Hexyl ester, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl) propyl (meth)acrylates such as tetrahydrofurfuryl ester; N-vinylpyrrolidone; styrene and its derivatives, styrenes such as α-methylstyrene; (meth) acrylamide, hydroxy Acrylamide such as methyl (meth) acrylamide, alkoxy hydroxymethyl (meth) acrylamide, diacetone (meth) acrylamide; (meth) acrylonitrile, ethylene, propylene, Other vinyl compounds such as butene, vinyl chloride, and vinyl acetate; and macromonomers such as polymethyl methacrylate macromonomers and polystyrene macromonomers. These monomers may be used alone or in combination of two or more.

Further, the copolymerization of the polymerizable monomer (p) having 2 to 6 hydroxyl groups and the other polymerizable monomer (q) is preferably 5% by mass to 95% by mass: 95% by mass to 5% by mass, more preferably It is 30% by mass to 70% by mass: 70% by mass to 30% by mass. When the copolymerization ratio of the polymerizable monomer (p) is less than 5% by mass, the number of ethylenically unsaturated double bonds which can be introduced is small, and the value of the double bond equivalent (the double bond equivalent defined by the following formula) becomes large. , can not get full sensitivity. When the copolymerization ratio of the polymerizable monomer (p) exceeds 95% by mass, a large amount of ethylenically unsaturated double bonds can be introduced, but the ratio of the polymerizable monomer (q) becomes low, so that it is difficult to maintain dispersion stability. Physical properties such as solubility and chemical resistance.

The production of the copolymer (a) having a polymerizable monomer (p) having 2 to 6 hydroxyl groups and another polymerizable monomer (q) can be produced by a known method, and for example, refer to Japanese Patent Laid-Open No. 2005-156930. The description of paragraph 0013 of the Gazette is incorporated into the present specification.

(G) a resin having a polymerizable double bond in a side chain by copolymerizing the compound (b) having a functional group reactive with a hydroxyl group and an ethylenically unsaturated double bond Obtained by the reaction of the substance (a). Examples of the functional group capable of reacting with a hydroxyl group of the compound (b) having a functional group reactive with a hydroxyl group and an ethylenically unsaturated double bond include an isocyanate group and a carboxyl group, and particularly preferably in terms of reactivity. Isocyanate group.

Specific examples of the compound having an isocyanate group and an ethylenically unsaturated double bond include 2-propenylethyl isocyanate and 2-methylpropenylethyl isocyanate. Further, specific examples of the compound having a carboxyl group and an ethylenically unsaturated double bond include acrylic acid, methacrylic acid, and maleic anhydride.

The amount of the ethylenically unsaturated double bond introduced into the copolymer (a) via a hydroxyl group is represented by the "double bond equivalent" of the obtained resin. The double bond equivalent is a standard for the amount of double bonds contained in the molecule. When the photosensitive resin having the same molecular weight is used, the smaller the value of the double bond equivalent is, the larger the amount of introduction of the double bond is.

[double bond equivalent] = [molecular weight of repeating structural unit] / [number of double bonds in repeating structural unit]

The (G) resin of the present invention preferably has a double bond equivalent weight of from 200 to 2,000, more preferably from 300 to 900. When the double bond equivalent of the (G) resin is less than 200, the ratio of the polymerizable monomer (p) into which the ethylenically unsaturated double bond is introduced becomes high, and a sufficient amount of the polymerizable monomer which maintains various properties cannot be obtained (q) ) Copolymerization. In the case of more than 2,000, the number of ethylenically unsaturated double bonds is small, so that sufficient sensitivity cannot be obtained.

Further, the weight average molecular weight (Mw) of the (G) resin is preferably from 2,000 to 200,000, more preferably from 5,000, in terms of good dispersibility of the composition of the present invention. ~50000.

The reaction of the copolymer (a) with the compound (b) having a functional group reactive with a hydroxyl group and an ethylenically unsaturated double bond can be carried out by a known method, and for example, refer to JP-A-2005-156930. The description of paragraph 0016 is incorporated into the present specification.

The content of the resin having a polymerizable double bond in the (G) side chain in the composition of the present invention is preferably from 0.1% by mass to 50% by mass, more preferably from 0.3% by mass to 40% by mass, based on the total solid content. Further preferably, it is 0.5% by mass to 30% by mass.

(G) The resin having a polymerizable double bond in the side chain may be contained in the composition of the present invention alone or in combination of two or more. When two or more cases are contained, it is preferable that the total amount is the said range.

- alkali soluble resin -

The composition of the present invention may further contain an alkali-soluble resin as a binder. Further, the alkali-soluble resin described herein does not include a component contained in the composition of the present invention as a dispersant component.

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). There is at least one group that promotes alkali solubility. From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, or an acrylic acid/acrylamide copolymer resin is preferred in terms of controlling developability. In particular, an acrylic resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin is preferable.

The alkali-soluble resin can be referred to, for example, the alkali-soluble resin described in paragraphs 0179 to 0208 of JP-A-2013-077009, the contents of which are incorporated herein by reference.

In addition, 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]). These are incorporated into the specification of the present application.

Further, it is preferable to use the copolymer (B) described in Paragraph No. 0029 to Paragraph No. 0063 described in JP-A-2012-32767, and the alkali-soluble resin used in the examples, and Japanese Patent Laid-Open No. 2012-208474 The adhesive resin described in Paragraph No. 0088 to Paragraph No. 0098 of the publication and the adhesive resin described in the example, and the adhesive resin described in Paragraph No. 0022 to Paragraph No. 0032 of JP-A-2012-137531 The adhesive resin used in the example, the adhesive resin described in Paragraph No. 0132 to Paragraph No. 0143 of the Japanese Patent Laid-Open Publication No. 2013-024934, and the adhesive resin used in the Example, Japanese Patent Laid-Open No. 2011-242752 Paragraph No. 0092 to Paragraph No. 0098 and the adhesive resin described in the examples, and the adhesive resin described in Paragraph No. 0030 to Paragraph No. 0072 of JP-A-2012-032770. This is incorporated into the specification of the present application.

The acid value of the alkali-soluble resin is preferably from 30 mgKOH/g to 200 mgKOH/g, more preferably from 50 mgKOH/g to 150 mgKOH/g, most preferably from 70 mgKOH/g to 120 mgKOH/g.

Further, the weight average molecular weight (Mw) of the alkali-soluble resin is preferably from 2,000 to 50,000, more preferably from 5,000 to 30,000, most preferably from 7,000 to 20,000.

When the alkali-soluble resin is contained in the coloring composition, the content of the alkali-soluble resin in the coloring composition is preferably from 1% by mass to 15% by mass, more preferably 2% by mass, based on the total solid content of the coloring composition. ~12% by mass, particularly preferably 3% by mass to 10% by mass.

The composition of the present invention may contain only one alkali-soluble resin, or may contain two or more kinds. When two or more cases are contained, it is preferable that the total amount is the said range.

-Organic solvents-

The composition of the present invention may also 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 coloring photosensitive resin composition, and it is particularly preferable to consider the solubility and coating of an ultraviolet absorber, an alkali-soluble resin, a dispersant, and the like. Choose sex and safety. The organic solvent may be one type or two or more types.

The organic solvent may preferably be exemplified as esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, butyrate B. Ester, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg methyl methoxyacetate, A) Ethyl oxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate (eg methyl 3-oxypropionate) , 3-oxypropionic acid ethyl ester, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ester, etc.)), 2- Alkyl oxypropionates (for example, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (for example, methyl 2-methoxypropionate, 2 -ethyl methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-oxy-2-methyl Methyl propionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc. ), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutanoate, etc.; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol single Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.; Such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; and as an aromatic hydrocarbon such as toluene Xylene, cyclopentanone and the like.

From the viewpoint of improving the solubility of the ultraviolet absorber and the alkali-soluble resin, the surface state of the coating, and the like, it is preferred to mix the organic solvents in two or more kinds. In this case, a mixed solution composed of two or more selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl cellosolve is particularly preferred. Acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Kikabi alcohol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate.

From the viewpoint of coating properties, the content of the organic solvent in the composition is preferably set so that the total solid content concentration of the composition becomes 5 to 80% by mass. The amount is preferably from 5% by mass to 60% by mass, particularly preferably from 10% by mass to 50% by mass.

-crosslinker -

It is also possible to supplement the use of the crosslinking agent in the composition of the present invention to further increase the hardness of the cured film obtained by curing the composition.

The crosslinking agent is not particularly limited as long as it can be cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin; and (b) a selected from the group consisting of a methylol group, an alkoxymethyl group, and an anthracene oxygen group. a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent in the methyl group; (c) at least one selected from the group consisting of a methylol group, an alkoxymethyl group and a decyloxymethyl group A substituted phenol compound, a naphthol compound or a hydroxy hydrazine compound. Among them, a polyfunctional epoxy resin is preferred.

For details of specific examples of the crosslinking agent, the descriptions of paragraphs 0134 to 0147 of JP-A-2004-295116 can be referred to.

When the crosslinking agent is contained in the composition of the present invention, the amount of the crosslinking agent to be added is not particularly limited, but is preferably 2% by mass to 30% by mass, and more preferably 3% by mass, based on the total solid content of the composition. ~20% by mass.

The composition of the present invention may contain only one type of crosslinking agent, and may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

- Polymerization inhibitors -

In the composition of the present invention, in order to prevent unnecessary thermal polymerization of the polymerizable compound during or during storage of the composition, it is desirable to add a small amount of a polymerization inhibitor.

The polymerization inhibitor which can be used in the present invention may, for example, be hydroquinone or p-methoxy. Phenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol ), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine sulfonium salt, and the like.

In the case where the composition of the present invention contains a polymerization inhibitor, the amount of the polymerization inhibitor added is preferably from about 0.01% by mass to about 5% by mass based on the mass of all the components.

The composition of the present invention may contain only one polymerization inhibitor, and may contain two or more types. When two or more cases are contained, it is preferable that the total amount is the said range.

- surfactant -

In the composition of the present invention, various surfactants may be added from the viewpoint of further improving coatability. In the present invention, when the (C) component and the (D) component are used in combination by blending a surfactant, the effect of the present invention excellent in PCD resistance can be more effectively exhibited. Regarding the reason, the following mechanism can be presumed. In other words, the reason why the PCD resistance of the composition of the present invention is excellent is as described above, and it is considered that the reason is that the (D) component contains a sterically bulky aromatic ring moiety (general formula (IV) The portion of the compound (x) represented by -Ph-R ⁶ is introduced into the polyester residue portion of the component (C) to prevent aggregation of the polyester residues with each other. As a result of the crystallization, phase separation of the component (C) is suppressed. It is presumed that when a surfactant is added thereto, an interfacial activity effect is exhibited between the sterically bulky aromatic ring portion contained in the component (D) and the polyester residue portion of the component (C), and the component (D) The sterically bulky portion smoothly enters into the polyester residue portion of the component (C).

Surfactants can be used: fluorine-based surfactants, nonionic surfactants, Various surfactants such as a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant.

In particular, since the composition of the present invention contains a fluorine-based surfactant, the solution characteristics (especially fluidity) at the time of preparation of the coating liquid are further improved, so that the uniformity of the coating thickness or the liquid-saving property can be further improved.

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 of the surface to be coated and the coating liquid is lowered to wet the coated surface. It is improved and the coating property to the coated surface is improved. Therefore, even when a film having a thickness of about several 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 from 5% by mass to 30% by mass, even more preferably from 7% by 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, Meijia Method (Megafac) F781 (above is made by Di Aisheng (DIC)), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above Sumitomo 3M) Manufacturing), 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) Made for Asahi Glass Co., Ltd.).

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates (for example, propoxylated glycerin, ethoxylated glycerin). Etc.), polyoxyethylene ethyl lauryl ether, polyoxyethylene ethyl stearyl ether, polyoxyethylene ethyl oleyl ether, polyoxyethyl octyl phenyl ether, polyoxyethyl phenyl benzene Ethyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10 manufactured by BASF), Pluronic L31, Pluronic L61, Pluronic L62, Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tetronic 701 , Tetronic 704, Tetronic 901, Tetronic 904, Tetronic 150R1), Solsperse 20000 (Lubrizol, Japan) (shares)) and so on.

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: Efka (EFKA)-745, manufactured by Morishita Industries Co., Ltd.), and an organic oxirane. Polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No. 75, Polyflow No. 90, Boliflo (Polyflow) No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), etc.

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" manufactured by Momentive Performance Materials "TSF-4460", "TSF-4452", "KP341", "KF6001" and "KF6002" manufactured by Shin-Etsu Chemical Co., Ltd., BYK Chemie, BYK 307, "BYK 323", "BYK" 330, etc.

The surfactant may be used alone or in combination of two or more.

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

The composition of the present invention may contain only one surfactant, and may also contain two on. When two or more cases are contained, it is preferable that the total amount is the said range.

-Other additives -

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

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

Specifically, the ultraviolet absorber is preferably the following compound.

--Organic carboxylic acid, organic carboxylic anhydride --

The composition of the present invention may also contain an organic carboxylic acid having a molecular weight of 1,000 or less and/or an organic carboxylic anhydride.

Specific examples of the organic carboxylic acid compound include an aliphatic carboxylic acid or an aromatic carboxylic acid. Examples of the aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, glycolic acid, acrylic acid, and methacrylic acid, and oxalic acid and propylene glycol. Dicarboxylic acids such as acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, etc. , a tricarboxylic acid such as 1,2,3-propanetricarboxylic acid or aconitic acid. Further, examples of the aromatic carboxylic acid include a carboxylic acid in which a carboxyl group such as benzoic acid or phthalic acid is directly bonded to a phenyl group, and a carboxylic acid in which a carboxyl group is bonded to a carboxyl group via a phenyl group. Among these, a molecular weight of 600 or less, particularly a molecular weight of 50 to 500 is particularly preferable, and specific examples thereof include maleic acid, malonic acid, succinic acid, and itaconic acid.

Examples of the organic carboxylic acid anhydride include an aliphatic carboxylic acid anhydride and an aromatic carboxylic acid anhydride. Specific examples thereof include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, and Malay. An aliphatic carboxylic acid such as an acid anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride Anhydride. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, a molecular weight of 600 or less, particularly a molecular weight of 50 to 500 is particularly preferable, and specific examples thereof include maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride.

When the organic carboxylic acid or the organic carboxylic acid anhydride is contained in the composition of the present invention, the amount of the organic carboxylic acid and/or the organic carboxylic acid anhydride is usually 0.01% by mass to 10% by mass based on the total solid content. It is in the range of 0.03 mass% to 5% by mass, more preferably 0.05 mass% to 3% mass%.

By adding these organic carboxylic acids and/or organic carboxylic anhydrides having a molecular weight of 1,000 or less, high pattern adhesion can be maintained, and the residual of the composition can be further reduced.

<Method for Preparing Colored Photosensitive Resin Composition>

The composition of the present invention is prepared by mixing the ingredients described above.

Furthermore, in the preparation of the composition, the components constituting the composition may be formulated at one time, or the components may be dissolved. Disperse in a solvent and then mix them one by one. In addition, the order of input or the working conditions at the time of preparation are not particularly limited. For example, all ingredients can be dissolved at the same time. The composition is prepared by dispersing in a solvent, and if necessary, the components may be appropriately prepared into two or more kinds of solutions. The dispersion was mixed and prepared at the time of use (at the time of coating) to prepare a composition.

In the present invention, it is preferred to disperse the (A) pigment, (B) the basic dye derivative, and (C) the phosphate dispersant represented by the formula (II), and then formulate (D) the formula ( IV) A resin obtained by copolymerizing a compound (x) represented by a compound (y) having an ethylenically unsaturated double bond.

The composition prepared as described above can be used by filtration using a filter having a pore diameter of preferably 0.01 μm to 3.0 μm, more preferably a pore diameter of 0.05 μm to 0.5 μm.

Since the composition of the present invention can form a cured film excellent in heat resistance and color characteristics, it can be preferably used for forming a colored pattern (colored layer) of a color filter. Further, the composition of the present invention can be preferably used for forming a coloring pattern such as a color filter used in an image display device such as a solid-state imaging device (for example, CCD, CMOS, or the like) or a liquid crystal display device (LCD). Further, it can also be preferably used for production of printing inks, inkjet inks, paints, and the like. Among them, it can be preferably used for the production of color filters for solid-state imaging devices such as CCDs and CMOSs.

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

Next, the cured film, pattern forming method, and color filter of the present invention will be described in detail.

The pattern forming method of the present invention includes the steps of: coloring the photosensitive composition layer forming step, and applying the colored photosensitive resin composition of the present invention to the support to form a colored photosensitive composition layer (hereinafter also referred to as "coloring composition" An exposure step of exposing the colored composition layer in a pattern; and a pattern forming step of developing and removing the unexposed portion to form a colored pattern.

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

The support for forming a pattern by the pattern forming method of the present invention is not particularly limited as long as it is a support that can be applied to pattern formation, other than a plate-like material such as a substrate.

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.

The method for producing a color filter of the present invention employs the pattern forming method of the present invention, comprising the step of forming a colored pattern on a support using the pattern forming method of the present invention.

That is, the method of producing a color filter of the present invention is applied to the pattern forming method of the present invention, and is characterized by comprising the steps of: coloring the photosensitive composition of the present invention a step of applying a colored photosensitive composition layer on the support; a step of exposing the colored photosensitive composition layer in a pattern; and a step of developing the colored portion by developing and removing the unexposed portion.

Further, a step of baking the colored composition layer (prebaking step) and a step of baking the developed colored pattern (post baking step) may be provided as needed. Hereinafter, these steps are collectively referred to as a pattern forming step.

The color filter of the present invention can be preferably obtained by the above manufacturing method.

Hereinafter, the color filter for a solid-state imaging device may be simply referred to as a "color filter".

Hereinafter, each step of the pattern forming method of the present invention will be described in detail by the method of producing the color filter of the present invention.

<Step of Forming Colored Photosensitive Composition Layer>

In the step of forming the colored photosensitive composition layer, the composition of the present invention is applied to a support to form a colored photosensitive composition layer.

For the support which can be used in this step, for example, a substrate (for example, a germanium substrate) may be provided with a charge coupled device (CCD) or a complementary metal-oxide semiconductor (CMOS). A substrate for a solid-state image sensor of an element (light receiving element).

The colored pattern of the present invention can be formed on the imaging element forming surface side (surface) of the solid-state imaging device substrate, or can be formed on the surface side (back surface) where the imaging element is not formed.

It can also be used between the color patterns of solid-state imaging elements or the base of solid-state imaging elements. A light-shielding film is provided on the back of the board.

Further, on the support, an undercoat layer may be provided as needed to improve adhesion to the upper layer, to prevent diffusion of substances, or to planarize the surface of the substrate.

Various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, and screen printing can be applied to the method of applying the composition of the present invention to a support.

The drying (prebaking) of the colored photosensitive composition layer coated on the support can be carried out at a temperature of 50 ° C to 140 ° C for 10 seconds to 300 seconds using a hot plate, an oven or the like.

<<Step of Exposing a Coloring Photosensitive Composition Layer in a Pattern (When Patterning Is Performed by Photolithography)>>

- Exposure step -

In the exposure step, for example, a mask having a predetermined mask pattern is interposed by using an exposure device such as a stepper, and the coloring photosensitive composition layer formed in the coloring photosensitive composition layer forming step is subjected to pattern exposure. Thereby, a cured film can be obtained.

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 ~ 1500mJ / cm} 2, more preferably ^{50mJ / cm 2 ~ 1000mJ / cm} 2, most preferably ^{80mJ / cm 2 ~ 500mJ / cm} 2.

The film thickness of the cured film is preferably 1.0 μm or less, more preferably 0.1 μm to 0.9 μm, still more preferably 0.2 μm to 0.8 μm.

By setting the film thickness to 1.0 μm or less, high resolution and high adhesion can be obtained. Therefore, it is better.

Further, in this step, a cured film having a thin film thickness of 0.7 μm or less can be preferably formed, and the obtained cured film can be developed by a pattern forming step to be described later, thereby obtaining developability even for a film. A coloring pattern excellent in surface roughness suppression and pattern shape.

<<<Steps for forming a colored pattern>>>

Then, an alkali development treatment is performed, whereby the colored photosensitive composition layer of the portion which is not irradiated with light in the exposure step is eluted into the alkaline aqueous solution, and only the photocured portion remains.

The developer is desirably an organic alkali developer which does not cause damage to the underlying imaging element or circuit. The development temperature is usually 20 ° C to 30 ° C, and the development time is 20 seconds to 90 seconds. In order to further remove the residue, in recent years, it has been carried out for 120 seconds to 180 seconds. Further, in order to further improve the residue removal property, the following steps may be repeated several times: the developer is removed every 60 seconds, and the developer is further supplied again.

Examples of the alkaline agent used in the developing solution include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. An organic basic compound such as a amide, a benzyltrimethylammonium hydroxide, a choline, a pyrrole, a piperidine or a 1,8-diazabicyclo-[5.4.0]-7-undecene, preferably An alkaline aqueous solution obtained by diluting the alkali agent so as to have a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass, is used as a developing solution.

Further, an inorganic base may be used in the developer. The inorganic base is preferably, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate or sodium metasilicate.

Further, in the case of using a developing solution containing such an alkaline aqueous solution, it is usually washed (rinsed) with pure water after development.

Then, it is preferred to carry out heat treatment (post-baking) after drying. If a color pattern of a plurality of colors is formed, the steps may be repeated one by one for each color to produce a hardened film. Thereby, a color filter can be obtained.

The post-baking is a heat treatment after development for complete hardening, and is usually performed at 100 ° C to 240 ° C, preferably 200 ° C to 240 ° C.

The post-baking of the developed coating film may be carried out in a continuous or batch manner by using a heating mechanism such as a hot plate or a convection oven (hot air circulation dryer) or a high-frequency heating machine in such a manner as to achieve the above conditions. Baked.

<<Step of Forming Photoresist Layer, Step of Obtaining Resist Pattern, and Step of Performing Dry Etching (When Patterning Is Performed by Dry Etching)>>

Dry etching can be performed using the patterned photoresist layer as a mask using an etching gas. Specifically, a positive or negative radiation sensitive composition is applied onto the colored layer obtained by curing the colored photosensitive composition layer, and dried to form a photoresist layer. At the time of formation of the photoresist layer, it is preferred to further carry out the prebaking treatment. The formation process of the photoresist layer is particularly preferably a form in which heat treatment (Post-Exposure Bake (PEB)) after exposure and heat treatment (post-baking treatment) after development are performed.

For the photoresist, for example, a positive type radiation sensitive composition can be used. The sense of positive The radiation-linear composition can be used for positive-type photoresists such as induced ultraviolet rays (g-rays, h-rays, and i-rays), and far-ultraviolet rays including an excimer laser, electron beams, ion beams, and X-rays. Resist composition. In the radiation, it is preferably g-ray, h-ray, or i-ray, and among them, i-ray is preferable.

Specifically, the positive radiation sensitive composition is preferably a composition containing a quinonediazide compound and an alkali-soluble resin. A positive-type radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin is obtained by decomposing a quinonediazide group by light irradiation at a wavelength of 500 nm or less to produce a carboxyl group, and the result is changed from an alkali-insoluble state. Alkali soluble. Since the positive resist has an excellent resolving power, it can be used to form an integrated circuit such as an integrated circuit (IC) or a large scale integrated circuit (LSI). The quinonediazide compound may be a naphthoquinonediazide compound. For example, "FHi622BC" (made by Fujifilm Electronic Materials Co., Ltd.), etc. are mentioned as a commercial item.

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. Furthermore, the formation of the coated photoresist layer can be preferably carried out using the coating method of the coloring layer described above.

Then, the photoresist layer is exposed and developed to form a resist pattern (patterned photoresist layer) provided with a resist through-hole group. The formation of the resist pattern is not particularly limited, and the conventionally known photolithography technique can be appropriately optimized. A resist through-hole group is provided in the photoresist layer by exposure and development, whereby a resist pattern as an etching mask used for subsequent etching is provided on the colored layer.

The exposure of the photoresist layer can be performed by interposing a predetermined mask pattern, and using a g-ray, an h-ray, an i-ray, or the like, preferably an i-ray, for a positive or negative radiation sensitive composition. exposure. After the exposure, the photoresist is removed by performing development processing using a developer to correspond to a region where the colored pattern is to be formed.

The developer may be used as long as it does not affect the coloring layer containing the coloring agent, and the exposed portion of the positive resist and the uncured portion of the negative resist may be used. For example, various organic solvents may 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 from 0.001% by mass to 10% by mass, preferably from 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, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and the like. Further, when an alkaline aqueous solution is used as the developing solution, the cleaning treatment is usually performed by water after development.

Then, the resist pattern is used as an etching mask, and patterning is performed by dry etching so that the through-hole group is formed in the colored layer. Thereby a colored pattern is formed. The through hole group is disposed in the colored layer in a checkerboard pattern. Therefore, the first colored pattern in which the through-hole group is provided in the colored layer has a plurality of square-shaped first colored pixels in a checkerboard pattern.

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

It is preferable to include a first-stage etching, a second-stage etching, and an over-etching. The first-stage etching uses a mixed gas of a fluorine-based gas and oxygen (O ₂ ), and etching is performed until the support is not exposed. In the region (depth), the second-stage etching is performed after the etching in the first step, and etching is performed using a mixed gas of nitrogen (N ₂ ) and oxygen (O ₂ ) until it is preferable that the support is exposed. The over-etching is performed after the support is exposed, in the vicinity of (depth). 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 is performed by previously obtaining etching conditions by the following method.

(1) The etching rate (nm/min) of the etching in the first stage and the etching rate (nm/min) in the etching in the second stage were respectively calculated. (2) Calculate the time required for etching in the etching of the first stage and the time required to etch the required thickness in the etching of the second stage. (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 etching time is determined by end point detection, and the second etching is performed in accordance with the determined etching time. (5) The overetching time is calculated for 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, the etching step of the first step can be prevented from being damaged by the support so as to be etched until the region where the support is not exposed. Further, from the viewpoint of avoiding damage of the support, the etching step and the over-etching step in the second step are preferably performed by a mixed gas of a fluorine-based gas and oxygen in the etching step of the first-stage etching step. After 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 important in such a manner as not to impair the squareness obtained by the etching treatment in the etching step of the first step. . Further, the ratio of the latter in the total etching amount (the total of the etching amount 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 not more than 50%. 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 that is initially performed. The overetching ratio can be arbitrarily set, and it is preferably 30% or less, more preferably 5% to 25%, of the etching treatment time in the etching step in terms of maintaining the etching resistance of the photoresist and the rectangularity of the etching pattern. , especially good for 10% to 15%.

Then, the resist pattern remaining after the etching (ie, the etching mask) is removed. The removal of the resist pattern preferably includes the steps of: applying a stripping liquid or a solvent to the resist pattern to adjust the resist pattern to a removable state; and removing the resist pattern using the washing water. step.

The step of applying a peeling liquid or a solvent to the resist pattern to adjust the resist pattern to a removable state includes, for example, applying a peeling liquid or a solvent to at least the resist pattern, and stopping the film for a predetermined period of time. The step of immersing the development. 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, the step of removing the resist pattern using the washing water may, for example, be a step of ejecting the washing water from the resist pattern by a spray type or a spray type spray nozzle to remove the resist pattern. Pure water can be preferably used for the washing water. Further, the injection nozzle may be an injection nozzle that includes the entire support in the injection range thereof, or an injection nozzle that is a movable injection nozzle and whose movable range includes the entire support. When the ejection nozzle is movable, the cleaning water can be sprayed two times or more from the center of the support to the end of the support in the step of removing the resist pattern, thereby more effectively removing the resist pattern. .

The stripping solution usually contains an organic solvent, and may further contain an inorganic solvent. Examples of the organic solvent include 1) a hydrocarbon-based compound, 2) a halogenated hydrocarbon-based compound, 3) an alcohol-based compound, 4) an ether or an acetal-based compound, 5) a ketone or an acid-based compound, and 6) an ester-based compound, and 7) A polyol compound, 8) a carboxylic acid or an anhydride thereof, 9) a phenol compound, 10) a nitrogen-containing compound, 11) a sulfur-containing compound, and 12) a fluorine-containing compound. The stripper preferably contains a nitrogen-containing compound, and more preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The acyclic nitrogen-containing compound is preferably an acyclic nitrogen-containing compound having a hydroxyl group. Specific examples thereof include monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N,N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, and the like. Diethanolamine, triethanolamine or the like is preferably monoethanolamine, diethanolamine or triethanolamine, more preferably monoethanolamine (H ₂ NCH ₂ CH ₂ OH). Further, examples of the cyclic nitrogen-containing compound include isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, and α-A. Pyridine, β-methylpyridine, γ-methylpyridine, 2-methylpiperidine, 3-methylpiperidine, 4-methylpiperidine, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-dimethylpyridine, 2,6-lutidine, etc., preferably N-methyl-2-pyrrolidone N-ethylmorpholine, more preferably N-methyl-2-pyrrolidone (NMP).

The stripping liquid preferably contains an acyclic nitrogen-containing compound and a cyclic nitrogen-containing compound, and more preferably contains at least one selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine as acyclic nitrogen-containing compound. The nitrogen-containing compound is at least one selected from the group consisting of N-methyl-2-pyrrolidone and N-ethylmorpholine, and further preferably contains monoethanolamine and N-methyl-2-pyrrolidone.

When the removal is performed by the peeling liquid, the resist pattern formed on the first colored pattern may be removed, and deposits (precipitates) as etching products may be adhered to the side walls of the first colored pattern. In this case, the deposit may not be completely removed. The term "deposited material" means that the etching product adheres to the side wall of the colored layer.

The content of the stripping liquid is preferably 9 parts by mass or more and 11 parts by mass or less based on 100 parts by mass of the stripping liquid, and the content of the cyclic nitrogen-containing compound is 65 parts by mass based on 100 parts by mass of the stripping liquid. More than or equal to 70 parts by mass. Further, the peeling liquid is preferably one obtained by diluting a mixture of the acyclic nitrogen-containing compound and the cyclic nitrogen-containing compound with pure water.

Furthermore, the manufacturing method of the present invention may include a step known as a method of producing a color filter for a solid-state image sensor as a step other than the above. For example, performing the coloring photosensitive composition layer forming step, the exposing step, and After the pattern forming step, a hardening step of hardening the formed coloring pattern by heating and/or exposure may be included as needed.

Further, in the case of using the composition of the present invention, for example, clogging of the nozzle or the piping portion of the coating device discharge portion or adhesion of the coloring composition or pigment to the coater may occur. settlement. Pollution caused by drying, etc. Therefore, in order to efficiently clean the contamination caused by the composition of the present invention, it is preferred to use a solvent related to the present composition described above as a cleaning liquid. In addition, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The cleaning liquids described in the Japanese Patent Publication No. 2007-291191, the Japanese Patent Publication No. 2007-2101, the Japanese Patent Publication No. 2007-2102, and the Japanese Patent Publication No. 2007-281523 can also be used. It is preferably used for cleaning and removal of the composition of the present invention.

Among them, an alkylene glycol monoalkyl ether carboxylate and an alkylene glycol monoalkyl ether are preferred.

These solvents may be used singly or in combination of two or more. In the case of mixing two or more kinds, it is preferred to mix a solvent having a hydroxyl group with a solvent having no hydroxyl group. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. More preferably, it is a mixed solvent of Propyleneglycol monomethylether acetate (PGMEA) and Propyleneglycol monomethylether (PGME) in a ratio of 60/40. Furthermore, in order to increase the permeability of the cleaning fluid to the contaminants, A surfactant associated with the present composition described above may also be added to the cleaning solution.

Since the color filter of the present invention uses the composition of the present invention, it is possible to perform exposure with excellent exposure margin, and the pattern shape of the formed color pattern (colored pixel) is excellent, and the surface of the pattern is rough or developed. Since the residue of the portion is suppressed, the color characteristics are excellent.

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 the CCD or CMOS and a microlens for collecting light.

In addition, the thickness of the colored pattern (colored pixel) of the color filter of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less, and still more preferably 0.7 μm or less.

Further, the size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and still more preferably 1.7 μm or less.

[Solid image sensor]

The solid-state imaging device of the present invention includes the color filter of the present invention described above. 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 light receiving region constituting a solid-state imaging device (a CCD image sensor, a CMOS image sensor, or the like) is provided on a support. a plurality of photodiodes of the domain and a transfer electrode including a polysilicon or the like, wherein the photodiode and the transfer electrode have a light-shielding film containing tungsten or the like, and only a light-receiving portion of the photodiode is opened, An element protective film containing tantalum nitride or the like formed to cover the entire surface of the light-shielding film and the photodiode light-receiving portion is provided on the light-shielding film, and the color filter for solid-state imaging device of the present invention is provided on the element protective film. sheet.

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.

The definition of the display device or the details of each display device is described in, for example, "Electronic display device (Sasaki Sasaki, Industrial Research Association, stocks, issued in 1990)", "Display elements (Ibuki Shun, industrial books) (shares), issued in 1989) 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. The liquid crystal display device of the color TFT type is described, for example, in "Color TFT Liquid Crystal Display (Kyoritsu Publishing Co., Ltd., 1996)". Furthermore, the present invention can also be applied to a liquid crystal display device or a super-twisting direction having a viewing angle such as a transverse electric field driving method such as coplanar switching (IPS) or a pixel division method such as multi-domain vertical alignment (MVA). 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) and the like.

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 liquid crystal display device of the COA type, 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 resistance. Stripping liquidity. In the color filter of the present invention, since a dye multimer having excellent hue is used, color purity, light transmittance, and the like are excellent, and color tone (pixel) is excellent in color tone, so that high resolution and long-term durability can be provided. A COA liquid crystal display device excellent in properties. Further, in order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.

These image display methods are described, for example, in "Electroluminescence (EL), plasma display panels (Plasma Display) Panel, PDP), Liquid Crystal Display (LCD) display - the latest trends in technology and market - (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 comprises, in addition to the color filter of the present invention, an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle securing film. . 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 - 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 "Monitor"~ 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 the red, green, and blue LED light source can be realized. (RGB-LED) is set as a backlight, and can provide a liquid crystal display device with high brightness and high color reproducibility.

[Examples]

The invention is specifically illustrated by the following examples. The following examples The materials, the amounts used, the ratios, the contents of the treatment, the order of the treatment, and the like can be appropriately changed as long as they do not deviate from the gist of the 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.

<(C) Synthesis of a phosphate dispersant> (Synthesis Example 1)

In a reaction vessel equipped with a condenser tube, a nitrogen gas introduction tube, and a stirrer in a three-neck round bottom flask, 18.6 g of lauryl alcohol (manufactured by Nacalai Tesque Co., Ltd.) and ε-caprolactone monomer 57.1 were added. g (manufactured by Wako Pure Chemical Co., Ltd.) and tetrabutyl titanate (0.06 g (manufactured by Tokyo Chemical Industry Co., Ltd.), and the inside of the reaction vessel was replaced with nitrogen, and then the mixture was heated and stirred at 120 ° C for 3 hours. The disappearance of the lactone monomer was confirmed by ¹ H-NMR (Nuclear Magnetic Resonance, NMR). After the reaction solution was cooled to room temperature, it was mixed with 8.45 g of polyphosphoric acid having an orthophosphoric acid content of 116%, and the temperature was gradually raised, and the mixture was heated and stirred at 80 ° C for 6 hours to obtain a compound of the formula (II). The number average molecular weight of R ³ is 760, y = 1 and y = 2 is a phosphate dispersant (C-1) having a ratio of 100:12. The obtained phosphate-based dispersant had an acid value of 166.

(Synthesis Example 2 to Synthesis Example 4)

The type of monohydric alcohol used was changed as shown in Table 1 below. The amount added and the type of lactone monomer used. A phosphate dispersant (C-2) to a phosphate dispersant (C-4) was obtained by the same method as in the above Synthesis Example 1 except for the addition.

In the above Table 1, the number average molecular weight of R ³ represents the number average molecular weight of the general formula (II).

<(D) Synthesis of specific resin binder> (Synthesis Example 5)

A propylene glycol monomethyl ether acetate was placed in a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas introduction tube, and a stirring device, and heated to 80 ° C while introducing nitrogen gas into the reaction vessel. 123.3 g of benzyl methacrylate, 17.2 g of methacrylic acid, and p-cumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd.) were added dropwise from the dropping tube at the same temperature for 2 hours. (Aronix) M110") A mixture of 31.0 g and 10.0 g of azobisisobutyronitrile was subjected to a polymerization reaction.

After the obtained resin solution was cooled to room temperature, about 3 g of the sample was sampled and dried by heating at 180 ° C for 20 minutes, and then the nonvolatile matter was measured, and propylene glycol B was added in a resin solution prepared in advance so that the nonvolatile content was 40% by mass. The acid ester was obtained as a solution of the resin binder (D-1).

<Synthesis of Resin Adhesive 1> (Synthesis Example 6)

A propylene glycol monomethyl ether acetate was placed in a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas introduction tube, and a stirring device, and heated to 100 ° C while introducing nitrogen gas into the reaction vessel. A mixture of 123.3 g of benzyl methacrylate, 25.8 g of methacrylic acid, and 10.0 g of azobisisobutyronitrile was added dropwise from the dropping tube at the same temperature for 1 hour to carry out a polymerization reaction.

After the obtained resin solution was cooled to room temperature, about 3 g of the sample was sampled and dried by heating at 180 ° C for 20 minutes, and then the nonvolatile matter was measured, and propylene glycol B was added in a resin solution prepared in advance so that the nonvolatile content was 40% by mass. The acid ester was obtained as a solution of the resin binder 1.

<(G) Resin Synthesis> (Synthesis Example 7)

A propylene glycol monomethyl ether acetate was placed in a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas introduction tube, and a stirring device, and heated to 80 ° C while introducing nitrogen gas into the reaction vessel. A mixture of 123.3 g of benzyl methacrylate, 17.2 g of methacrylic acid, 14.6 g of Glycerol monomethacrylate, and 10.0 g of azobisisobutyronitrile was added dropwise from the dropping tube at the same temperature for 2 hours. , carrying out a polymerization reaction.

23.3 g of 2-methylpropenylethyl isocyanate ("Karenz MOI" manufactured by Showa Denko Co., Ltd.) and dibutyltin laurate 0.3 were added dropwise to the obtained resin solution at 70 ° C for 3 hours. g, a mixture of cyclohexanone 90g.

After the obtained resin solution was cooled to room temperature, about 3 g of the sample was sampled and dried by heating at 180 ° C for 20 minutes, and then the nonvolatile content was measured, and propylene glycol B was added in a resin solution of the first synthesis so that the nonvolatile content was 40% by mass. The acid ester was obtained as a solution of the resin binder (G-1).

<Manufacture of Red Pigment Dispersion Composition>

The mixture of the following composition is uniformly stirred and mixed, and then mixed by a bead mill. The red pigment dispersion composition (R-a) was prepared by dispersing for 3 hours.

The red pigment dispersion composition (Rb) to the red pigment dispersion composition was prepared by the same method as the preparation of the red pigment dispersion composition (Ra) except that the composition was changed to the composition described in the following Table 2. (Rp).

In the above Table 2, each symbol means the following compound.

PR254...diketopyrrolopyrrole red pigment (C.I. Pigment Red 254)

PY139...Isoporphyrin yellow pigment (C.I. Pigment Yellow 139)

PR177...蒽醌 red pigment (C.I. Pigment Red 177)

PR122...quinacridone red pigment (C.I. Pigment Red 122)

PO71...diketopyrrolopyrrole orange pigment (C.I. Pigment Orange 71)

Red-a: azo red pigment Red-a of the following structural formula

Pigment derivative (B-2): a compound of the following structural formula

Pigment derivative (B-3): a compound of the following structural formula

Pigment derivative (B-4): a compound of the following structural formula

<Preparation of Green Pigment Dispersion Composition>

The mixture of the following composition is uniformly stirred and mixed, and then mixed by a bead mill. The green pigment dispersion composition (G-a) was prepared by dispersing for 3 hours.

The green pigment dispersion composition (Gb) to the green pigment dispersion composition was prepared by the same method as the preparation of the green pigment dispersion composition (Ga) except that the composition was changed to the composition of Table 3 below. Go).

In the above Table 3, each symbol means the following compound.

PG7...Copper chloride phthalocyanine green pigment (C.I. Pigment Green 7)

PG36...Brass Copper Phthalocyanine Green Pigment (C.I. Pigment Green 36)

PG58...zinc halide phthalocyanine green pigment (C.I. Pigment Green 58)

PY139...Isoporphyrin yellow pigment (C.I. Pigment Yellow 139)

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

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

Pigment derivative (B-5): a compound of the following structural formula

<Preparation of yellow pigment dispersion composition>

The mixture of the following composition is uniformly stirred and mixed, and then mixed by a bead mill. The yellow pigment dispersion composition (Y-a) was prepared by dispersing for 3 hours.

<Preparation of Blue Pigment Dispersion Composition>

The mixture of the following composition is uniformly stirred and mixed, and then mixed by a bead mill. The blue pigment dispersion composition (B-a) was prepared by dispersing for 3 hours.

[化58]

The content of the composition is changed to the composition of the following Table 4, except that the blue pigment dispersion composition (Bb) to the blue pigment dispersion composition is prepared by the same method as the preparation of the blue pigment dispersion composition (Ba). (Bg).

In the above Table 4, each symbol means the following compound.

PB15: 6...copper phthalocyanine blue pigment (C.I. Pigment Blue 15:6)

PV23...dioxazine-based violet pigment (C.I. Pigment Violet 23)

Pigment derivative (B-7): a compound of the following structural formula

<Preparation of Red Photosensitive Resin Composition>

The mixture of the following composition was uniformly stirred and mixed to prepare a red photosensitive resin composition (RR-a).

Propylene glycol monomethyl ether acetate (PGMEA) 42.2 parts by mass

Photopolymerization initiator (E-1): 1.2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzhydrylhydrazine)] (Manufactured by BASF) IRGACURE OXE01)

Ethylene unsaturated compound (F-1): ethylene oxide modified product of dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-DPH-12E)

Fluorine-based surfactant: (Manufactured by Dainippon Ink Co., Ltd., Megafac F-781F)

The red photosensitive resin composition (RR-b) was prepared by the same method as the preparation of the red photosensitive resin composition (RR-a) except that the composition was changed to the composition of the following Table 5. Red photosensitive resin composition (RR-v).

<evaluation> (Evaluation of pattern formation after PCD)

(1) Preparation of transparent resist solution A (negative type)

The following components were mixed and dissolved to prepare a transparent resist solution A.

(Benzyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate copolymer molar ratio = 60:20:20, average molecular weight of 30200 (in terms of polystyrene), 41% cyclohexanone solution)

(2) Fabrication of a glass substrate with an undercoat layer

The glass substrate (Corning 1737) was ultrasonically washed with 0.5% NaOH water, and then washed with water and dehydrated (200 ° C / 20 minutes). Then, the transparent resist solution A obtained in the above (1) was applied onto the cleaned glass substrate so as to have a film thickness after drying of 2 μm by a spin coater, and dried by heating at 220 ° C for 1 hour. An undercoat layer is formed, thereby preparing a glass substrate with an undercoat layer.

(3) Exposure of coloring photosensitive resin composition. Development (coloring pattern formation)

Two sheets of the following substrate were prepared: the red photosensitive resin composition (RR-a) to the red photosensitive resin composition (RR-v) obtained above was applied by a spin coater so that the film thickness after drying was 0.6 μm. A substrate obtained by prebaking at 100 ° C for 120 seconds on the undercoat layer of the undercoated glass substrate obtained in the above (2).

For one of the substrates, an i-ray stepwise exposure apparatus FPA-i5+ (manufactured by Canon) was used immediately after application of the red photosensitive resin composition, and a mask having a line width of 1.1 μm was used. The coating film was irradiated with an optimum exposure amount of a checkerboard pattern having a length of 1.1 μm on one side at a wavelength of 365 nm. After exposure, use developer CD-2000 (Fujifilm Electronic Materials) Materials) (manufacturing)) Development was carried out at 25 ° C for 40 seconds. Thereafter, the mixture was rinsed with running water for 30 seconds, and then spray-dried to obtain a colored pattern.

Then, after applying the red photosensitive resin composition to the other of the substrates, after standing for 72 hours (PCD) in a clean room at room temperature, coloring was obtained by the same method as described above. pattern.

The two coloring patterns thus obtained were observed by a scanning electron microscope (SEM), and exposed immediately after coating (without PCD). The coloring pattern obtained by development is exposed after PCD. The shapes of the colored patterns obtained by the development were compared and evaluated according to the following criteria.

A: Compared with the shape of the colored pattern without PCD, the shape of the colored pattern after PCD is completely unchanged.

B: The shape of the colored pattern after PCD is slightly changed, but no problem

C: The shape of the colored pattern after PCD collapses, there is a problem

D: The shape of the colored pattern after PCD collapses drastically

The PCD evaluation results are collectively shown in Table 5 below.

(Evaluation of color unevenness (color unevenness))

The red photosensitive resin composition (RR-a) to the red photosensitive resin composition (RR-v) obtained above was applied onto a glass substrate so that the film thickness after drying was 0.6 μm, using a spin coater. The colored coating film 1 was obtained by prebaking at 100 ° C for 120 seconds.

Further, the red photosensitive resin composition (RR-a) to the red photosensitive resin composition (RR-v) obtained in the above manner were used at room temperature for 6 months, and then used. The spin coater was applied onto a glass substrate so that the film thickness after drying became 0.6 μm, and prebaked at 100 ° C for 120 seconds to obtain a colored coating film 2 .

Each of the obtained colored coating films was placed between an observation lens of an optical microscope and a light source, and the light was irradiated toward the observation lens, and the transmitted light state was observed using an optical microscope provided with a digital camera having a magnification of 1,000. A CCD of 1.28 million pixels was mounted on a digital camera provided in an optical microscope, and the surface of the colored coating film in a transmitted light state was imaged by the digital camera. The captured image is stored as a digital image (digital image) which is digitally converted in the form of a bit map of 8 bits.

Further, the photographing of the surface of the colored coating film was performed on 20 regions selected arbitrarily. Further, regarding the digitally converted data, the luminance of each of the RGB three primary colors is quantized and stored for the captured image with a density distribution of 256 levels of 0 to 255.

Then, the stored digital image is divided into a lattice shape so that one grid size corresponds to 0.5 μm square on the actual substrate, and the luminance in one block is averaged. In the present embodiment, a digital camera of 1.28 million pixels is used to capture an image 1000 times optically, so 0.5 μm on the actual substrate becomes 0.5 mm on the captured image, and the image size on the display is 452 mm × 352 mm. Therefore, the total number of blocks in a region is 636,416.

For all blocks of each region, the average brightness of any one block and all adjacent blocks adjacent thereto is measured. The block having a difference of 5 or more from the average luminance of the adjacent blocks is regarded as a significant difference block, and the average total number of significant difference blocks in the entire area is calculated. The smaller the value, the smaller the difference in concentration from adjacent blocks, and the less the color spots, the table The more excellent the characteristics shown as a color filter.

The average total number of stains of the colored coating film 1 is taken as the value of the stain immediately after preparation, and the average number of stains of the colored coating film 2 is taken as the value of the stain after 6 months at room temperature. The stain growth rate at which the value of the stain immediately after preparation was divided after 6 months at room temperature was shown in Table 5 below.

In the above Table 5, each symbol means the following compound.

Photopolymerization initiator (E-2): ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O - 乙醯基肟) (Manufactured by BASF, IRGACURE OXE02)

Photopolymerization initiator (E-3): 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl ]-1-butanone (made by BASF), IRGACURE 379)

Ethylene unsaturated compound (F-2): a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA)

Ethylene unsaturated compound (F-3): Trimethylolpropane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMPT)

UV absorber: a compound of the following structural formula

According to the results shown in Table 5, the red photosensitive resin composition (RR-r) and the red photosensitive resin composition (RR-t) of Comparative Example 1 and Comparative Example 3 contained the composition of the present invention. (C) a phosphate dispersant as an essential component, but Since the resin of the specific structure is not contained (D), the pattern formation property after PCD is largely deteriorated, and the increase in the time of the stain is also slightly large. In addition, the red photosensitive resin composition (RR-s) and the red photosensitive resin composition (RR-u) of Comparative Example 2 and Comparative Example 4 contain the (D) specific structure as an essential component in the composition of the present invention. The resin does not contain (C) a phosphate dispersant, so the color plaque increases greatly with time, and there is room for improvement in pattern formation after PCD.

In contrast, for example, the red photosensitive resin composition (RR-a) of the present invention shown in the first embodiment contains the (C) phosphate-based dispersant as an essential component in the composition of the present invention, and further contains (D). The resin of a specific structure is suppressed by the increase in color plaque over time, and the pattern formation property after PCD is also greatly improved.

Further, in Examples 6 to 20 in which the resin (G-1) having a polymerizable double bond in the side chain was used as the (G) resin binder, the increase rate of the color spots was further suppressed.

It was found that Example 12 and Example 19 using the phosphate dispersant (C-3) were more excellent in pattern formability after PCD than the examples using the other phosphate dispersant.

It is known that in Example 5 in which the content of the resin of (D) specific structure is more than 80 parts by mass of the pigment dispersion composition (Rc) with respect to 100 parts by mass of the (A) pigment, although the increase rate of the stain and the PCD The pattern formation property after the latter was superior to the comparative example, but it was slightly inferior to the other examples.

It was found that the (A) pigment, the (B) basic dye derivative, and the (C) phosphate dispersant were dispersed as shown in Example 4 to obtain a red pigment dispersion composition, and then blended (D). The resin composition was used to prepare a red photosensitive resin composition, whereby the color spot was further increased over time, and the pattern formation property after PCD was further improved.

<Preparation of Green Photosensitive Resin Composition>

The mixture of the following composition was uniformly stirred and mixed to prepare a green photosensitive resin composition (GR-a).

The green photosensitive resin composition (GR-b) to green photosensitive was prepared by the same method as the preparation of the green photosensitive resin composition (GR-a) except that the composition was changed to the contents of Table 6. Resin composition (GR-u).

The obtained green photosensitive resin composition (GR-a) to green photosensitive resin composition (GR-u) was subjected to the same method as in Example 1 and immediately after preparation and at room temperature for 6 months. The value of the subsequent stain and the evaluation of the pattern formation after PCD. The results are summarized in Table 6 below.

According to the results shown in Table 6, the green photosensitive resin composition (GR-r) and the green photosensitive resin composition (GR-t) of Comparative Example 5 and Comparative Example 7 contained the composition of the present invention as Since the (C) phosphate-based dispersant of the essential component does not contain the resin of the specific structure (D), the pattern formation property after PCD is largely deteriorated, and the increase in the time of the stain is also slightly large. In addition, the green photosensitive resin composition (GR-s) and the green photosensitive resin composition (GR-u) of Comparative Example 6 and Comparative Example 8 contain the (D) specific structure as an essential component in the composition of the present invention. The resin binder does not contain the (C) phosphate dispersant, so the color plaque increases greatly with time, and there is room for improvement in pattern formation after PCD.

With respect to these comparative examples, for example, the green photosensitive resin composition (GR-a) of the present invention shown in Example 21 contains the (C) phosphate-based dispersant as an essential component in the composition of the present invention, and further Since the resin of (D) specific structure is contained, the increase in color plaque over time is suppressed, and the pattern formation property after PCD is greatly improved.

Further, in Examples 26 to 39 in which the resin (G-1) having a polymerizable double bond in the side chain was used as the (G) resin binder, the increase rate of the stain was further suppressed.

It was found that Example 32 and Example 39 using the phosphate-based dispersant (C-3) were more excellent in pattern formability after PCD than the examples using the other phosphate-based dispersant.

It is known that in Example 25, which uses 100 parts by mass of the (A) pigment and (D) the content of the resin exceeds 80 parts by mass of the pigment dispersion composition (Gc), although the increase rate of the color spots and the pattern after the PCD Formability is better than the comparative example, but with other The example is slightly worse.

After the (A) pigment, the (B) basic dye derivative, and the (C) phosphate dispersant were dispersed as shown in Example 24, the (D) resin was blended to prepare a colored photosensitive resin composition. The increase in color plaque over time is further suppressed, and the pattern formation after PCD is further improved.

<Preparation of Blue Photosensitive Resin Composition>

The mixture of the following composition was uniformly stirred and mixed to prepare a blue photosensitive resin composition (BR-a).

A blue photosensitive resin composition (BR-b) was prepared by the same method as the preparation of the blue photosensitive resin composition (BR-a) except that the content of the composition was changed to the following Table 7. ) ~ Blue photosensitive resin composition (BR-m).

The obtained blue photosensitive resin composition (BR-a) to blue photosensitive resin composition (BR-m) was subjected to the same method as in Example 1 to carry out the rigid method. The value of the stain after 6 months elapsed at room temperature and the pattern formation property after PCD were evaluated. The results are summarized in Table 7 below.

According to the results shown in Table 7, the blue photosensitive resin composition (BR-1) of Comparative Example 9 contains the (C) phosphate-based dispersant as an essential component in the composition of the present invention, but does not contain ( D) Since the resin binder of a specific structure is degraded, the pattern formation property after PCD is largely deteriorated, and the time-lapse of the stain is also slightly larger. Further, the blue photosensitive resin composition (BR-m) of Comparative Example 10 contains the (D) specific structure resin as an essential component in the composition of the present invention, but does not contain the (C) phosphate-based dispersant. The color plaque increases greatly over time, and there is room for improvement in pattern formation after PCD.

With respect to these comparative examples, for example, the blue photosensitive resin composition (BR-a) of the present invention shown in Example 40 contains the (C) phosphate-based dispersant as an essential component in the composition of the present invention. Further, since (D) a resin binder having a specific structure is contained, the increase in stain after 6 months at room temperature is suppressed, and the pattern formation property after PCD is greatly improved.

Further, in Examples 45 to 52 in which the resin (G-1) having a polymerizable double bond in the side chain was used as the (G) resin binder, the increase rate of the color spots was further suppressed.

It was found that Example 43 and Example 51 using the phosphate dispersant (C-3) were more excellent in pattern formability after PCD than the examples using the other phosphate dispersant.

It is known that in Example 44, which uses 100 parts by mass of the (A) pigment and (D) the content of the resin exceeds 80 parts by mass of the pigment dispersion composition (Rc), although the increase rate of the stain and the pattern after the PCD Formability is better than the comparative example, but with other The example is slightly worse.

When the (A) pigment, the (B) basic dye derivative, and the (C) phosphate dispersant are dispersed as shown in Example 43, the (D) resin is blended to prepare a colored photosensitive resin composition. The increase in color plaque over time is further suppressed, and the pattern formation after PCD is further improved.

The colored photosensitive resin was prepared in the same manner except that the (B) basic dye derivative in each of the above examples was replaced by the compound 7 (reproduced below) of paragraph 0223 of JP-A-2011-162760. Composition. The pattern formation property of the obtained coloring photosensitive resin composition was evaluated, and it was confirmed that a favorable pattern was formed.

1‧‧‧Coloring pattern

Claims (18)

A colored photosensitive resin composition comprising: (A) a pigment, (B) a basic dye derivative, (C) a phosphate-based dispersant represented by the following formula (II), and (D) a general formula a resin obtained by copolymerizing a compound (x) represented by (IV) with a compound (y) having an ethylenically unsaturated double bond, (E) a photopolymerization initiator, and (F) a polymerizable compound, In the formula (II), R ³ represents a polyester structure having a number average molecular weight of 400 to 30,000, y represents 1 or 2; and in the case where y is 2, a plurality of R ^{3 's} may be the same or different; In IV), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 2 or 3 carbon atoms, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring, and n represents 1~. An integer of 15; when n is 2 or more, a plurality of R ^{5 's} may be the same or different. The colored photosensitive resin composition according to claim 1, wherein the (B) basic dye derivative is a compound having an amine group. The colored photosensitive resin composition according to claim 1, wherein The (A) pigment described in the above is selected from the group consisting of a red pigment, a green pigment, and a yellow pigment. The colored photosensitive resin composition according to claim 1, wherein in the general formula (II), the polyester structure represented by R ³ has a number average molecular weight of 1900 to 10,000. The colored photosensitive resin composition according to claim 1, wherein in the general formula (II), the polyester structure represented by the R ³ is a monomer of two or more different lactones. The polyester structure obtained by ring polymerization. The colored photosensitive resin composition according to any one of the items 1 to 5, further comprising (G) a resin having a polymerizable double bond in a side chain. The colored photosensitive resin composition according to claim 6, wherein the resin having a polymerizable double bond in the (G) side chain is a resin obtained by reacting the compound (b) with the copolymer (a). The compound (b) has a functional group reactive with a hydroxyl group and an ethylenically unsaturated double bond, and the copolymer (a) is a polymerizable monomer (p) having 2 to 6 hydroxyl groups and other polymerizable properties. a copolymer of monomer (q). The color-sensitive photosensitive resin composition according to any one of the items 1 to 5, wherein the (D) is a compound of the formula (IV) with respect to 100 parts by mass of the (A) pigment The content of the resin obtained by copolymerizing the compound (x) and the compound (y) having an ethylenically unsaturated double bond is 5 parts by mass to 80 parts by mass. The coloring photosensitive resin composition according to any one of the items 1 to 5, wherein the coloring photosensitive resin composition is such that the (A) pigment and the (B) are alkaline. a pigment derivative and the (C) represented by the formula (II) After dispersing the phosphate-based dispersant, the (D) resin obtained by copolymerizing the compound (x) represented by the formula (IV) and the compound (y) having an ethylenically unsaturated double bond is prepared. The colored photosensitive resin composition according to any one of the items 1 to 5, which is used for forming a colored region of a color filter. A cured film obtained by curing the colored photosensitive resin composition according to any one of the first to fifth aspects of the invention. A method of producing a color filter comprising: applying the colored photosensitive resin composition according to any one of claims 1 to 5 to a support to form a colored photosensitive composition layer; a step of exposing the colored photosensitive composition layer into a pattern; and a step of developing and removing the unexposed portion to form a colored pattern. A method of producing a color filter comprising: applying the colored photosensitive resin composition according to any one of the above-mentioned items of the first to fifth aspects to a support to form a colored photosensitive composition layer, And hardening to form a coloring layer; forming a photoresist layer on the colored layer; patterning the photoresist layer by performing exposure and development to obtain a resist pattern; and The resist pattern is used as an etch mask to dry etch the colored layer. A color filter having a hardness as described in claim 11 Film. A color filter manufactured by the method of producing a color filter according to claim 12 of the patent application. A color filter manufactured by the method of producing a color filter according to claim 13 of the patent application. A solid-state imaging device having the color filter according to any one of claims 14 to 16. An image display device having the color filter according to any one of claims 14 to 16.