KR101741607B1 - Colored photosensitive resin composition, cured film, color filter, method for producing color filter, solid state imaging element, and image display device - Google Patents

Abstract

(C-1) a phosphoric acid-based dispersing agent represented by the following general formula (II), or (C-2) a polymer having a hydroxyl group at at least one terminal thereof, wherein the coloring photosensitive resin composition comprises (POH) or polymer having a primary amino group on at least one terminal (PNH ₂₎ and a tricarboxylic acid anhydride or a carboxylic acid formed by reacting a tetracarboxylic dianhydride-based dispersion agent, (D) a resin binder, (E) a photopolymerization initiator, And (F) a polymerizable compound.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, a cured film, a color filter, a method of manufacturing a color filter, a solid-state image pickup device, and an image display device. DEVICE}

The present invention relates to a colored photosensitive resin composition suitable for producing a color filter used for a liquid crystal display element (LCD) or a solid-state imaging element (CCD, CMOS, etc.), a color filter having a colored region produced by the composition, A solid-state image pickup device having a color filter, and a liquid crystal display device for an organic LED.

In recent years, with the development of personal computers, particularly large-screen liquid crystal televisions, there is a tendency that the demand of liquid crystal displays (LCDs), especially color liquid crystal displays, increases. And the spread of organic EL displays is also demanded from the demand for further high image quality. On the other hand, with the spread of digital cameras and mobile phones with cameras, solid-state image pickup devices such as CCD image sensors are also greatly in demand.

Color filters are used as key devices for these displays and optical elements, and there is an increasing demand for cost reduction with the demand for further high image quality. Such a color filter usually has coloring patterns of three primary colors of red (R), green (G), and blue (B). In a display device or an imaging device, .

Colorants used in color filters generally require the following characteristics.

That is, there should be no optical disturbance such as non-uniformity of optical density which causes favorable spectral characteristics on the color reproducibility, light scattering which is a cause of lowering contrast of liquid crystal display, color irregularity and roughness of solid state image pickup device, It is required to have good fastness under the conditions such as heat resistance, light resistance, moisture resistance and the like, a large molar extinction coefficient, and a thin film.

As a result, a pigment is generally used as the colorant.

In 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, a step of applying a colored photosensitive resin composition onto a substrate, And a step of carrying out development with an alkali developing solution are generally performed. At this time, there may be a delay of several days between the step of applying the colored photosensitive resin composition and the step of performing the exposure and development steps. Such post-coating delay is generally referred to as PCD (Post Coating Delay). This is because, in the course of manufacturing a color filter, it is sometimes possible to collect the substrate coated with the colored photosensitive resin composition and perform the subsequent exposure and development steps collectively as soon as the exposure / development device is emptied Because.

With the background as described above, it is required that the colored photosensitive resin composition does not cause a problem in formation of a colored pattern even after PCD. Specifically, Fig. 1 is a schematic view of a colored pattern 1 formed when a colored photosensitive resin composition is applied onto a substrate and immediately exposed and developed, from above the substrate. Here, the coloring pattern is formed in a rectangular shape. The colored photosensitive resin composition is required to maintain the formation of such a rectangular pattern even after PCD.

However, depending on the type of the colored photosensitive resin composition, as shown in Fig. 2, there was a case where the coloring pattern 1 after PCD was largely collapsed.

For example, Patent Document 1 and Patent Document 2 disclose a pigment composition containing a basic compound having a specific structure of a triazine ring-containing compound and a specific acrylic resin.

Also, Patent Document 3 discloses a pigment composition containing a triazine ring-containing basic compound having a specific structure and a carboxylic acid-based dispersant having a specific structure, and a color filter including the pigment composition. Patent Documents 4 and 5 disclose a pigment composition containing a basic phosphorus-containing basic compound having a specific structure and a phosphate-based dispersant having a specific structure.

Patent Document 1: JP-A-2006-291194 Patent Document 2: JP-A-2007-156395 Patent Document 3: JP-A-2007-131832 Patent Document 4: JP-A-2007-231106 Patent Document 5: JP-A-2007-231107

Patent Document 1 and Patent Document 2 disclose that a colored composition having excellent dispersion stability and the like can be obtained by using a specific triazine ring-containing basic compound having a specific structure and a specific acrylic resin in combination. However, There was room for further improvement in terms of stability over time (roughness) or roughness. This is because, in the colored photosensitive resin composition as described in Patent Document 1 or Patent Document 2, adsorption of the dispersion resin to pigment particles is unstable, and in the process of keeping the composition for a long period of time, It is considered that the dispersion resin is desorbed from the pigment particle surface. As a result, it is presumed that the pigment particles undergo secondary agglomeration during the process of keeping the composition for a long period of time, resulting in coarsening of the pigment particle size, resulting in deterioration of the roughness of the color filter after aging.

Patent Document 3 describes that a pigment composition having excellent viscosity stability can be obtained by using a basic pigment derivative having a specific structure and a carboxylic acid-based dispersant having a specific structure. However, when the pigment composition described in Patent Document 3 is used as it is in the colored photosensitive resin composition as it is, further improvement of color irregularity (roughness), stability with time of roughness and pattern formation after PCD There was room. This is because, when the pigment composition described in Patent Document 3 is used as the colored photosensitive resin composition, compatibility of each component constituting the colored photosensitive resin composition is poor, and a part of the components forming the coating film in the post-application delay (PCD) This phenomenon is considered to be caused by the fact that the color pattern obtained by the subsequent exposure and development is greatly collapsed.

Patent Document 4 and Patent Document 5 disclose that a pigment composition excellent in dispersion stability and the like can be obtained by using a basic compound having a specific structure of a triazine ring and a phosphoric acid-based dispersant having a specific structure. However, even when the pigment compositions described in Patent Document 4 and Patent Document 5 are used as they are in the colored photosensitive resin composition, the color unevenness (roughness) and stability with time of roughness when the color filter is used, There was room for further improvement in terms of sex. This is because, when the pigment composition described in Patent Document 4 and Patent Document 5 is used as a colored photosensitive resin composition, compatibility of each component constituting the colored photosensitive resin composition is poor, and in the PCD process after the application, It is considered that some components to be formed cause phase separation and the color pattern obtained by the subsequent exposure and development is largely collapsed.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a colored photosensitive resin composition which is excellent in stability of color unevenness (roughness), stability with time of roughness and pattern forming property after PCD, a cured film using a color photosensitive resin composition, A solid-state imaging device, and an image display device.

The present inventors have studied in detail and found that the above problems can be solved by using a basic pigment derivative and a predetermined dispersant.

Concretely, the above problem is solved by the following means <1>, preferably by <2> to <15>.

(C-1) a phosphoric acid-based dispersant represented by the following general formula (II), or (C-2) a polymer (POH) having at least one terminal hydroxyl group, or at least one polymer having a primary amino group at the terminal (PNH ₂₎ and a tricarboxylic acid anhydride or a carboxylic acid formed by reacting a tetracarboxylic dianhydride-based dispersion agent, (D) a resin binder, (E) a photopolymerization initiator, and (F ) A colored photosensitive resin composition containing a polymerizable compound;

[Chemical Formula 1]

In the formula (II), R ³ represents a polyester structure having a number average molecular weight of 400 to 30000, y represents an integer of 1 or 2; When y is 2, a plurality of R ³ may be the same or different.

<2> The colored photosensitive resin composition according to <1>, wherein (A) the pigment is at least one selected from the group consisting of red pigment, green pigment, and yellow pigment.

<3> The colored photosensitive resin composition according to <1> or <2>, wherein the number average molecular weight of the polyester structure represented by R ³ in the general formula (II) is 1900 to 10000.

<4> The colored photosensitive resin composition according to any one of <1> to <3>, wherein the polyester structure represented by R ³ in the general formula (II) is a polyester structure obtained by ring-opening polymerization of two or more different lactone monomers .

(5) A polymer (POH) having at least one terminal hydroxyl group or a polymer (PNH ₂ ) having at least one terminal primary amino group in a carboxylic acid-based dispersant is represented by the following general formula 1 &gt; to &lt; 4 &gt;, wherein R &lt; 1 &gt;

(2)

In formula (II '), Y ¹ represents a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms, and X ² represents -O-, -S-, Or -N (R ^b ) -, and R ^b represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms; G ¹ represents a repeating unit represented by -R ¹¹ O-, G ² represents a repeating unit represented by -C (═O) R ¹² O-, G ³ represents -C (═O) R ¹³ C (= O) -OR ¹⁴ O-, R ¹¹ represents a linear or branched alkylene group having 2 to 8 carbon atoms or a cycloalkylene group having 3 to 8 carbon atoms, R ¹² represents a linear or branched alkylene group having 3 to 8 carbon atoms, A linear or branched alkylene group having 2 to 6 carbon atoms or a cycloalkylene group having 4 to 8 carbon atoms; R ¹³ represents a linear or branched alkylene group having 2 to 6 carbon atoms; a linear or branched alkenyl group having 2 to 6 carbon atoms; group, having 3 to 20 carbon atoms in the cycloalkyl group, having from 6 to 20 carbon atoms or denotes an arylene group, R ^{14 is, -CH (R 15) -CH (} R 16) - represents a, R ¹⁵ and R ¹⁶ is either An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyloxymethylene group having 1 to 20 carbon atoms in the alkyl moiety, The carbon number of a portion of 2-20 alkenyl oxymethylene group, an aryloxy group which may methylene carbon atoms is substituted with 6-20 halogen atoms, and the aryl moiety of the aryl moiety can, or N- methylene-phthalimide represents an imide; Z ¹ is represents a -OH, or -NH _2, R ¹⁷ is a cycloalkyl group, a -C (= O) R ¹² in the alkylene group, 3 to 8 carbon atoms straight-chain or branched having 2 to 8, or ^{-C (= O) R 13 C} (= O) -OR 14 - shows a; m1 represents an integer of 0 to 100, m2 represents an integer of 0 to 60, and m3 represents an integer of 0 to 30; Provided that m1 + m2 + m3 is 1 or more and 100 or less; The arrangement of the repeating units G ¹ to G ^{3 in} the general formula (II ') is not limited to the order. In the polymer represented by the general formula (II'), the arrangement between the groups X ² and R ¹⁷ Indicates that the repeating units G ¹ to G ³ are included in an arbitrary order, and the repeating units G ¹ to G ³ may be either a random type or a block type.

<6> The carboxylic acid-based dispersant according to <6>, wherein the POH as a polymer having a hydroxyl group at at least one terminal or the PNH ₂ as a polymer having a primary amino group at at least one terminal thereof is represented by the following formula (III) The colored photosensitive resin composition according to any one of &lt; 1 &gt; to &lt; 4 &gt;

(3)

In the general formula (III), Y ¹ represents a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms and 0 to 3 nitrogen atoms, X ² represents -O-, -S-, or - N (R ^b ) -, R ^b represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms; Z ¹ represents -OH, or -NH ₂ ;

G ⁴ and G ⁵ each represent a repeating unit represented by -C (= O) R ¹² O-, R ¹² represents a linear or branched alkylene group having 1 to 8 carbon atoms or a cycloalkylene group having 4 to 8 carbon atoms Lt; / RTI &gt; However, G ⁴ and G ⁵ R ¹² R ¹² is of the of the different groups; R ²⁰ represents -C (= O) R ¹² -;

m4 represents an integer of 5 to 60, and m5 represents an integer of 5 to 60;

The repeating unit of the general formula (III) G ^4, the arrangement of G ⁵ is not limited to this order, in the polymer represented by the general formula (III), based repeated among the groups Z ¹ and X ² The units G ⁴ and G ⁵ are included in an arbitrary order, and the repeating units G ⁴ and G ⁵ may be either a random type or a block type.

<7> The resin composition according to any one of <1> to <6>, wherein the resin binder (D) is a resin obtained by copolymerizing a compound (x) represented by the following formula (IV) and a compound (y) having another ethylenically unsaturated double bond: A colored photosensitive resin composition according to any one of &lt; 1 &gt;

[Chemical Formula 4]

In the general formula (IV), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 2 or 3 carbon atoms, R ⁶ represents an alkyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring, N represents an integer of 1 to 15; When n is 2 or more, a plurality of R ⁵ may be the same or different.

<8> (G) The colored photosensitive resin composition according to any one of <1> to <7>, further comprising a resin having a polymerizable double bond in a side chain.

(9) The resin composition according to any one of the above (1) to (8), wherein the resin having a polymerizable double bond in the side chain is a copolymer of a polymerizable monomer (p) having 2 to 6 hydroxyl groups and a polymerizable monomer Is reacted with a compound (b) having a functional group capable of reacting with an ethylenically unsaturated double bond and an ethylenically unsaturated double bond.

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

<11> A cured film obtained by curing the colored photosensitive resin composition according to any one of <1> to <9>.

&Lt; 12 &gt; A process for producing a colored photosensitive layer, comprising the steps of: forming a colored photosensitive composition layer by applying a colored photosensitive resin composition according to any one of &lt; 1 & To form a colored pattern.

&Lt; 13 &gt; A process for producing a colored photosensitive resin composition, comprising the steps of applying a colored photosensitive resin composition according to any one of &lt; 1 &gt;

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 a step of dry-etching the colored layer using the resist pattern as an etching mask.

&Lt; 14 &gt; A color filter having a cured film according to &lt; 11 &gt;.

&Lt; 15 &gt; A color filter produced according to the method of manufacturing a color filter according to <12> or <13>.

&Lt; 16 &gt; A solid-state imaging device having a color filter according to &lt; 14 &gt; or &lt; 15 &gt;.

<17> An image display device having a color filter according to <14> or <15>.

According to the present invention, there is provided a colored photosensitive resin composition which is superior in color stability (roughness), stability with time of roughness and pattern formation property after PCD, a method of producing a cured film, a color filter and a color filter using the colored photosensitive resin composition, An image pickup device and an image display device can be provided.

1 is a schematic view of a colored pattern formed when a colored photosensitive resin composition is applied onto a substrate and immediately exposed and developed, from above the substrate.
2 is a schematic view of a colored pattern formed when a colored photosensitive resin composition is coated on a substrate and subjected to exposure and development after PCD, from above the substrate.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, "" is used to mean that the numerical values described before and after the lower limit and the upper limit are included. The organic EL element in the present invention refers to an organic electroluminescence element.

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

In the notation of the group (atomic group) in the present specification, the notations in which substitution and non-substitution are not described include those having no substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term "radiation " in the present specification means, for example, a line spectrum of a mercury lamp, far ultraviolet ray, extreme ultraviolet ray (EUV light) represented by an excimer laser, X-ray or electron ray. In the present invention, light means an actinic ray or radiation. The term "exposure" in this specification refers to not only exposure by deep ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, etc., but also imaging by particle beams such as electron beams and ion beams, .

In the present specification, "(meth) acrylate" represents both or both of acrylate and methacrylate, and "(meth) acrylate" represents both acrylate and methacrylate , And "(meth) acryloyl" represents both acryloyl and methacryloyl.

In the present specification, the terms "monomer" and "monomer" are synonyms. Monomers in the present specification are distinguished from oligomers and polymers and refer to compounds having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group involved in the polymerization reaction.

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

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

In the present specification, the term " process "is included in this term, not only in the independent process but also in the case where the desired action of the process is achieved even if it can not be clearly distinguished from other processes.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a colored composition excellent in color characteristics.

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene reduced values by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by TOSOH CORPORATION) and TSKgel Super AWM-H , 6.0 mm ID × 15.0 cm, and 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

&Lt; Colored photosensitive resin composition &

(A) a pigment, (B) a basic pigment derivative, (C-1) a coloring photosensitive resin composition represented by the following general formula ( (C-2) a polymer (POH) having at least one terminal hydroxyl group, or a polymer (PNH ₂ ) having at least one terminal primary amino group, and a tricarboxylic acid anhydride or tetra (D) a resin binder, (E) a photopolymerization initiator, and (F) a polymerizable (meth) acrylic resin, which is obtained by reacting a carboxylic acid dianhydride with a carboxylic acid dianhydride Or a compound thereof.

[Chemical Formula 5]

In the formula (II), R ³ represents a polyester structure having a number average molecular weight of 400 to 30000, y represents an integer of 1 or 2; When y is 2, a plurality of R ³ may be the same or different.

[Chemical Formula 6]

In the general formula (II), R ³ represents a polyester structure having a number average molecular weight of 400 to 30000, and y represents an integer of 1 or 2. When y is 2, a plurality of R ³ may be the same or different.

By using the composition of the present invention, color heterogeneity (roughness), stability with time of roughness, and pattern forming property after PCD are excellent. The reason why the effect of the present invention is obtained is not clear, but the following reason is presumed.

(C-1) or (C-2) can be obtained by using the basic pigment derivative (B) (especially the pigment derivative represented by the general formula (I) described later) ) Is presumed to have obtained the effect of strongly adsorbing the dispersant to the pigment particles and suppressing the deterioration of the roughness with time of the composition. It is also presumed that the basic pigment derivative (B) functions as one type of compatibilizer and that the components constituting the composition of the present invention are prevented from causing phase separation during the post-application delay (PCD) process. As a result, it is considered that the present invention is superior in color non-uniformity (roughness), stability with time of roughness, and pattern forming property after PCD.

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

<< (A) Pigment >>

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

Specific examples of the inorganic pigments include black pigments such as carbon black and titanium black; pigments such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium , Metal oxides such as zinc and antimony, and complex oxides of the above metals.

As the organic pigment, for example,

C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;

C. I. Pigment Orange 36, 38, 43, 71;

C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;

C. I. Pigment Violet 19, 23, 32, 39;

C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C. I. Pigment Green 7, 36, 37, 58;

C. I. Pigment Brown 25, 28;

C. I. Pigment Black 1; And the like.

Examples of pigments that can be preferably used in the present invention include the following pigments. However, the present invention is not limited thereto.

CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,

C. I. Pigment Orange 36, 71,

C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,

C. I. Pigment Violet 19, 23, 32,

C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,

C. I. Pigment Green 7, 36, 37, 58,

C. I. Pigment Black 1

These organic pigments can be used singly or in various combinations in order to enhance spectral control and color purity. Specific examples of the combination are shown below. As the red pigment, for example, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone, or at least one of them, a disazo yellow pigment, an isoindolin yellow pigment, a quinophthalone pigment A yellow pigment or a mixture of a perylene red pigment may be used. Examples of the anthraquinone pigments include CI Pigment Red 177, and the perylene pigments include CI Pigment Red 155 and CI Pigment Red 224. As the diketopyrrolopyrrole pigment, CI Pigment Red 254, and is preferably mixed with CI Pigment Yellow 139 in view of color resolution. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. When the ratio is 100: 4 or less, it is difficult to suppress the light transmittance of 400 nm to 500 nm. When the ratio is 100: 51 or more, the dominant wavelength approaches the short wavelength and the color resolution can not be increased. Particularly, the mass ratio is preferably in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the obtained spectroscopy.

As the green pigment, it is possible to use a halogenated phthalocyanine-based pigment alone or in combination with a disazo-based yellow pigment, a quinophthalone-based yellow pigment, an azomethan-based yellow pigment or an isoindolene-based yellow pigment Can be used. For example, CI Pigment Green 7, 36, 37 and 58 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or CI Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

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

As the black pigment, carbon, titanium black, iron oxide, titanium oxide alone or a mixture thereof is used. When these are mixed and used, a combination of carbon and titanium black is preferable, and a mass ratio of carbon to titanium black in this case is preferably in the range of 100: 0 to 100: 60.

As the pigment in the present invention, azo pigments represented by the following general formula (A2), tautomers thereof, salts thereof or hydrates thereof can also be used.

In general formula (A2)

(7)

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

A represents a heterocycle having at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom.

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

When n = 2, it represents a dimer containing R ¹ , R ² , A or G.

When n = 3, it represents a trimer containing R ¹ , R ² , A or G.

When n = 4, it represents a tetramer containing R ¹ , R ² , A or G.

The formula (A2) does not have an ionic hydrophilic group.

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

[Chemical Formula 8]

By having the specific structure represented by the general formula (A2), the azo pigment exhibits excellent characteristics in color characteristics such as tinting strength and color, and exhibits excellent properties in durability such as light resistance and ozone resistance. For example, the red pattern of the color filter formed using the coloring composition of the present invention containing an azo pigment represented by the general formula (A2) exhibits better spectral characteristics as red. Here, the "good spectral characteristic as red" means, for example, at least one of the following properties. The spectroscopic characteristics satisfying all of the following three properties are particularly excellent.

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

In the wavelength region of 540 nm or more, the transmittance curve increases sharply.

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

The substituent in the present invention may be any substitutable group and may be an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, An alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, a carbamoyl group, an aliphatic sulfonyl group, an arylsulfonyl group, a heterocyclic sulfonyl group, an aliphatic sulfonyloxy group, an arylsulfonyloxy group, a heterocyclic sulfonyloxy group, An aliphatic sulfonamido group, an arylsulfonamido group, a heterocyclic sulfonamido group, an amino group, an aliphatic amino group, an arylamino group, a heterocyclic amino group, an aliphatic oxycarbonylamino group, an aryloxycarbonylamino group, a heterocyclic oxycarbonylamino group, an aliphatic oxycarbonylamino group, A sulfinyl group, an arylsulfinyl group, an aliphatic thio group, an arylthio group, a hydroxyl group, a cyano group, a sulfo group, a carboxy group, an aliphatic oxyamino group , There may be mentioned an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, a halogen atom, a sulfamoyl carbamoyl group, a sulfamoyl group such as carbamoyl, di-aliphatic oxy group phosphine, diaryl phosphine oxy group. Hereinafter, the term "group described in the section of substituent (s) "

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

Preferred examples of the substituent which the aliphatic group represented by G may have include a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group and a carbamoylamino group.

The aliphatic group represented by G is preferably an aliphatic group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 6 carbon atoms in total, such as methyl, ethyl and cyclohexyl. have.

In the general formula (A2), the aryl group represented by G may be either a condensed or a substituted group, and the group which may be substituted is a group described in the above-mentioned substituent group, Preferred examples of the substituent include nitro group, halogen atom, aliphatic oxy group, carbamoyl group, aliphatic oxycarbonyl group, aliphatic thio group, amino group, aliphatic amino group, acylamino group and carbamoyl amino 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 total carbon atoms, such as phenyl, 4-nitrophenyl, 4-acetylamino Phenyl, 4-methanesulfonylphenyl, and the like.

In the formula (A2), the heterocyclic group represented by G may have a substituent, be saturated or unsaturated, and may be condensed. Examples of the substituent that may be substituted include any of the groups described in the above section of the substituent and may be any substitutable group, and preferable substituents include a halogen atom, a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, An amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The heterocyclic group represented by G is preferably a heterocyclic group bonded with a carbon atom number of 2 to 12 in total, more preferably a heterocyclic group having 5 to 6 carbon atoms in total having 2 to 10 carbon atoms bonded with a carbon atom, For example, 2-tetrahydrofuryl, 2-pyrimidyl and the like.

G is preferably a hydrogen atom. This is because it is easy to form an intramolecular hydrogen bond or an intramolecular cross hydrogen bond.

The amino group represented by R &lt; ¹ &gt; may have a substituent, and the group which may be substituted is a group described in the above section of the substituent. Any substitutable group may be used. As the substituent, an aliphatic group, And a heterocyclic group.

These substituents may further have a substituent. As the substituent, substituents having an aliphatic group, a hydroxyl group, an amide bond, an ether bond, an oxycarbonyl bond, a thioether bond and the like are preferable, and a hetero atom and a hydrogen atom Is more preferable from the viewpoint of facilitating intermolecular interaction such as intermolecular hydrogen bonding.

As the amino group represented by R ¹ , preferably an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms in total, a dialkylamino group having 2 to 10 carbon atoms in total (wherein a dialkyl group is bonded to each other to form a 5- to 6- An arylamino group having 6 to 12 carbon atoms in total, a saturated or unsaturated heterocyclic amino group having 2 to 12 carbon atoms in total, more preferably an unsubstituted amino group, a total carbon atom An alkylamino group having a number of 1 to 8, a dialkylamino group having a total of 2 to 8 carbon atoms, an arylamino group having a total of 6 to 10 carbon atoms, a saturated or unsaturated heterocyclic amino group having a total of 2 to 12 carbon atoms , For example, methylamino, N, N-dimethylamino, N-phenylamino, N- (2-pyrimidyl) amino and the like.

More preferably an arylamino group having 6 to 13 carbon atoms in total and a saturated or unsaturated heterocyclic amino group having 2 to 12 carbon atoms in total.

When R &lt; ^{1 &gt;} is an arylamino group, the substituent on the aryl group preferably has a substituent on para to the position of bonding to the amino group, and most preferably has only a substituent on para. The substituent is a group described in the above-mentioned substituent group, and any substitutable group may be used, and preferably an aliphatic group having 1 to 7 carbon atoms in total, more preferably 1 to 4 carbon atoms in total (I) -propyl, (t) -butyl and the like), aliphatic oxy groups having 1 to 7 carbon atoms in total (for example, methoxy, ethoxy, , A halogen atom (e.g., fluorine, chlorine, bromine, etc.), a carbamoyl group having a total of 1 to 7 carbon atoms (e.g., carbamoyl, N-phenylcarbamoyl, N, N-dimethylurea, N, N-dimethylurea, etc.) having 1 to 7 carbon atoms in total, more preferably 1 to 4 carbon atoms in total Phenyl), a nitro group, an aryl group having 1 to 7 carbon atoms in total and a condensed heterocycle (for example, imidazolone), a hydroxyl group, a total carbon (I) -propylthio, allylthio, (t) -butylthiocyanate having 1 to 7, more preferably 1 to 4, total carbon atoms, such as methylthio, ethylthio, Etc.), an acylamino group having 2 to 7 total carbon atoms, more preferably 2 to 4 total carbon atoms (e.g., acetamino, propionylamino, pivaloylamino, benzoylamino, etc.) Aliphatic oxycarbonylamino group having a total number of carbon atoms of 2 to 4 (e.g., methoxycarbonylamino, propyloxycarbonylamino and the like) having a total number of carbon atoms of 2 to 7, more preferably a number of 2 to 7, An aliphatic oxycarbonyl group having 2 to 4 carbon atoms in total (e.g., methoxycarbonyl, ethoxycarbonyl and the like) having 2 to 4 carbon atoms in total, more preferably 2 to 4 carbon atoms in total An acyl group (which may be an aliphatic carbonyl group, an arylcarbonyl group, a heterocyclic carbonyl group, And the group which may be substituted is the group described in the above substituent group and may be any substitutable group. It is preferably an acyl group having 2 to 7 total carbon atoms, more preferably a total carbon atom An acyl group having a number of 2 to 4, and examples thereof include acetyl, propane oil, benzoyl, 3-pyridinecarbonyl and the like).

When the substituent on the aryl group of the arylamino group is substituted on the para-position from the bonding position with the amino group, since the substituent is at the terminal of the molecule, intermolecular interactions such as intermolecular hydrogen bonding are likely to occur and the color becomes sharp. When the substituent on the aryl group further has a substituent, a substituent having an aliphatic group, a hydroxyl group, an amide bond, an ether bond, an oxycarbonyl bond, a thioether bond or the like is preferable, and a bond between a hetero atom and a hydrogen atom Is more preferable in view of facilitating intermolecular interaction such as intermolecular hydrogen bonding.

When R ¹ is a heterocyclic amino group, the substituent is the group described in the above-mentioned substituent group, and any substitutable group may be used, and preferably the substituent is the same as that of the above-mentioned arylamino group, but a heterocyclic group A substituent having an aliphatic group, a hydroxyl group, an amide bond, an ether bond, an oxycarbonyl bond, a thioether bond or the like is preferable, and a substituent having a bond of a hetero atom and a hydrogen atom Is more preferable from the viewpoint of facilitating intermolecular interaction such as intermolecular hydrogen bonding.

More preferred substituents when R ¹ is an arylamino group or a heterocyclic amino group include aliphatic groups, aliphatic oxy groups, halogen atoms, carbamoyl groups, aryl groups and condensed heterocyclic rings, and aliphatic oxycarbonyl groups. The substituent is more preferably an aliphatic group having 1 to 4 carbon atoms in total, an aliphatic oxy group having 1 to 4 carbon atoms in total, a halogen atom, a nitro group, a carbamoyl group having 1 to 4 carbon atoms in total, An aliphatic oxycarbonyl group having 2 to 4 carbon atoms.

The aliphatic oxy group represented by R &lt; ¹ &gt; may have a substituent, and the substituent is the group described in the above-mentioned substituent group, and any substitutable group may be used, and preferable substituents include hydroxyl group, aliphatic oxy group, An aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino 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, such as methoxy, ethoxy, (t ) -Butoxy, methoxyethoxy, carbamoylmethoxy and the like.

The aliphatic group represented by R &lt; ¹ &gt; may have a substituent, and the substituent is the group described in the above-mentioned substituent group, and any substitutable group may be used, and preferable examples of the substituent include hydroxyl group, aliphatic oxy group, An aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group, and a carbamoylamino group. The aliphatic group represented by R ¹ is preferably an alkyl group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 4 carbon atoms in total.

The aryl group represented by R &lt; ¹ &gt; may have a substituent, and the substituent is the group described in the above-mentioned group of the substituents. Any substitutable group may be used, and preferable substituents include aliphatic groups, aliphatic oxy groups, , A carbamoyl group, an aryl group and a condensed heterocyclic ring, and an aliphatic oxycarbonyl group. The aryl group represented by R ¹ is preferably an aryl group having 6 to 12 total carbon atoms, more preferably an aryl group having 6 to 10 total carbon atoms, such as phenyl, 4-methylphenyl, 3-chloro- Phenyl and the like.

The heterocyclic group represented by R ¹ may be a saturated heterocyclic group, an unsaturated heterocyclic group, or may have a substituent. The substituent is the group described in the above-mentioned substituent group, Is an aliphatic group, an aliphatic oxy group, a carbamoyl group, a heterocyclic heterocyclic group with a hetero group, or an aliphatic oxycarbonyl group. The heterocyclic group of R ¹ is preferably a heterocyclic group having 2 to 10 total carbon atoms, more preferably a non-aromatic heterocyclic group having 5 to 6 member rings bonded with a nitrogen atom having 2 to 8 total carbon atoms, Include 1-piperidyl, 4-morpholinyl, 1-quinolyl, 2-pyrimidyl, 4-pyridyl and the like.

R ¹ is preferably a 5- to 6-membered non-aromatic heterocyclic group bonded through an amino group, an aliphatic oxy group or a nitrogen atom, more preferably an amino group, an aliphatic oxy group, and more preferably an amino group.

R ¹ is preferably an amino group.

The substituent represented by R &lt; ^{2 &gt;} is the group described in the above-mentioned substituent group, and any substitutable group may be used, and preferably an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carboxyl group, An acylamino group, a sulfonamido group, a carbamoylamino group, a sulfamoyl group, an aliphatic oxy group, an aliphatic thio group, a cyano group and a halogen atom, and more preferably an aliphatic oxycarbonyl group, a carbamoyl group, An aliphatic oxy group, a halogen atom, and particularly preferably an aliphatic oxy group.

When these substituents further have a substituent, a substituent having an aliphatic group, a hydroxyl group, an amide bond, an ether bond, an oxycarbonyl bond, a thioether bond or the like is preferable, and a substituent having a bond of a hetero atom and a hydrogen atom Is more preferable from the viewpoint of facilitating intermolecular interaction such as intermolecular hydrogen bonding.

m is preferably 0 to 3, more preferably 0 to 1, and even more preferably 0.

n is preferably 1 or 2.

The aliphatic group represented by R ² may have a substituent, may be saturated or unsaturated, and the group which may be substituted is a group described in the section of the above-mentioned substituent, and any substitutable group may be used. The aliphatic group of R ² is preferably an alkyl group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 6 carbon atoms in total, such as methyl, ethyl, i-propyl, cyclohexyl, butyl, and the like.

The aryl group represented by R ² may have a substituent, and the group which may be substituted is a group described in the above-mentioned substituent group, and any substitutable group may be used. The aryl group of R ² is preferably an aryl group having 6 to 12 total carbon atoms, more preferably an aryl group having 6 to 10 total carbon atoms, such as phenyl, 3-methoxyphenyl, 4 -Carbamoylphenyl and the like.

The heterocyclic group represented by R ² may have a substituent, may be saturated or unsaturated, may be condensed, and the group which may be substituted is a group described in the above-mentioned substituent, and any substitutable group may be used . The heterocyclic group of R ² is preferably a heterocyclic group having a total of 2 to 16 carbon atoms, more preferably a heterocyclic group having 5 to 6 member rings having a total of 2 to 12 carbon atoms, such as 1-pyrrole 4-morpholinyl, 2-pyridyl, 1-pyrroyl, 1-imidazolyl, 1-benzoimidazolyl and the like.

The aliphatic oxycarbonyl group represented by R ² may have a substituent, may be saturated or unsaturated, and the group which may be substituted is a group described in the section of the above-mentioned substituent, and any substitutable group may be used. The aliphatic oxycarbonyl group represented by R ² is preferably an alkoxycarbonyl group having 1 to 8 carbon atoms in total, more preferably an alkoxycarbonyl group having 1 to 6 carbon atoms in total, such as methoxycarbonyl, i-propyloxycarbonyl, carbamoylmethoxycarbonyl, and the like.

The carbamoyl group represented by R ² may have a substituent, and the group which may be substituted is a group described in the above-mentioned substituent group, and any substitutable group may be used, and preferably an aliphatic group, A heterocyclic group and the like. As the carbamoyl group of R ₂ , a carbamoyl group, an alkylcarbamoyl group having a total of 2 to 9 carbon atoms, a dialkylcarbamoyl group having a total of 3 to 10 carbon atoms, a carbonyl group having a total of 7 to 13 carbon atoms An arylcarbamoyl group and a heterocyclic carbamoyl group having a total of 3 to 12 carbon atoms, more preferably a carbamoyl group, an alkylcarbamoyl group having 2 to 7 carbon atoms in total, a dicarboxylic acid group having 3 to 6 carbon atoms An alkylcarbamoyl group, an arylcarbamoyl group having a total of 7 to 11 carbon atoms, a heterocyclic carbamoyl group having a total of 3 to 10 carbon atoms, for example, a carbamoyl group, a methylcarbamoyl group, a dimethylcarbamoyl group, 4-pyridinecarbamoyl, and the like.

The acylamino group represented by R ² may have a substituent, may be an aliphatic group, an aromatic group, or a heterocyclic group, and the group which may be substituted is a group described in the above-mentioned substituent group, do. The acylamino group of R ² is preferably an acylamino group having a total of 2 to 12 carbon atoms, more preferably an acylamino group having 1 to 8 total carbon atoms, more preferably an acylamino group having a total of 1 to 8 carbon atoms Alkylcarbonylamino group, and examples thereof include acetylamino, benzoylamino, 2-pyridinecarbonylamino, propanoylamino and the like.

The sulfonamide group represented by R ² may have a substituent, may be an aliphatic group, an aromatic group, or a heterocyclic group. The group which may be substituted is a group described in the above-mentioned substituent group, and any substitutable group may be used. The sulfonamide group of R ² is preferably a sulfonamido group having a total of 1 to 12 carbon atoms, more preferably a sulfonamido group having 1 to 8 total carbon atoms, more preferably a total of 1 To 8 carbon atoms, and examples thereof include methanesulfonamide, benzenesulfonamide and 2-pyridine sulfonamide.

The carbamoylamino group represented by R ² may have a substituent. The group which may be substituted is a group described in the above-mentioned substituent group, and any substitutable group may be used, and preferably an aliphatic group, an aryl group, Ventilation. As the carbamoylamino group of R ² , a carbamoylamino group, an alkylcarbamoylamino group having a total of 2 to 9 carbon atoms, a dialkylcarbamoylamino group having a total of 3 to 10 carbon atoms, a dialkylcarbamoylamino group having a total of 7 to 13 carbon atoms An arylcarbamoylamino group, and a heterocyclic carbamoylamino group having 3 to 12 carbon atoms in total, more preferably a carbamoylamino group, an alkylcarbamoylamino group having 2 to 7 carbon atoms in total, a dicycloalkylamino group having 3 to 6 carbon atoms in total An alkylcarbamoylamino group, an arylcarbamoylamino group having 7 to 11 carbon atoms in total, a heterocyclic carbamoylamino group having 3 to 10 carbon atoms in total, such as carbamoylamino, methylcarbamoylamino, N, N-di Methylcarbamoylamino, phenylcarbamoylamino, 4-pyridinecarbamoylamino, and the like.

The sulfamoyl group represented by R &lt; ² &gt; may have a substituent, and the group which may be substituted is a group described in the above-mentioned substituent group, and any substitutable group may be used, and preferably an aliphatic group, Ventilation. As the sulfamoyl group of R ² , a sulfamoyl group, an alkylsulfamoyl group having a total of 1 to 9 carbon atoms, a dialkylsulfamoyl group having a total of 2 to 10 carbon atoms, a sulfamoyl group having a total of 7 to 13 carbon atoms An arylsulfamoyl group, and a heterocyclic sulfamoyl group having a total of 2 to 12 carbon atoms, more preferably a sulfamoyl group, an alkylsulfamoyl group having 1 to 7 carbon atoms in total, a diester having 3 to 6 carbon atoms in total, An alkylsulfamoyl group, an arylsulfamoyl group having 6 to 11 carbon atoms in total, a heterocyclic sulfamoyl group having 2 to 10 carbon atoms in total, and examples thereof include sulfamoyl, methylsulfamoyl, N, Phenylsulfamoyl, 4-pyridine sulfamoyl, and the like.

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

The aliphatic sialide represented by R ² may have a substituent, may be saturated or unsaturated, and the group which may be substituted is a group described in the above section of the substituent, and any substitutable group may be used. As the aliphatic sioxy of R ² , preferably an alkylthio group having 1 to 8 carbon atoms in total, more preferably an alkylthio group having 1 to 6 carbon atoms in total, such as methylthio, Methylthio, t-butylthio, and the like.

The halogen atom represented by R ² is preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a chlorine atom. In view of the effects of the present invention, R ² is preferably an aliphatic oxycarbonyl group or a carbamoyl group. In view of the effects of the present invention, m is preferably 0 or 1, more preferably 0.

The general formulas (A-1) to (A-32) represented by A will be described. The moiety represented by formulas (A-1) to (A-32) preferably has 2 to 15 carbon atoms in total, more preferably 2 to 12 carbon atoms in total.

The substituent represented by R ⁵¹ to R ⁵⁴ is a group described in the above-mentioned substituent group, and any substitutable group may be used. ^Examples of the substituent of R ⁵¹ to R ⁵⁴ include an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carbamoyl group, an acylamino group, a sulfonamido group, an aliphatic oxy group, an aliphatic thio group, , More preferably an aliphatic group, an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic oxy group, a cyano group and the like.

From the viewpoint of the effect of the present invention, R ⁵¹ to R ^{54 each} represent a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carbamoyl group, an acylamino group, a sulfonamido group, an aliphatic oxy group, An amino group, an amino group, an amino group, an amino group, and an amino group, and more preferably a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic oxy group or a cyano group.

The substituent represented by R ⁵⁵ is a group described in the above-mentioned substituent group, and any substitutable group may be used. The substituent of R ⁵⁵ is preferably an aliphatic group, an aryl group, a heterocyclic group or the like, and more preferably an aromatic 5- to 6-membered heteroaromatic ring containing a nitrogen atom adjacent to a bonding site with an aliphatic group, It is ventilation.

In view of the effects of the present invention, R ⁵⁵ is preferably an aliphatic group, an aryl group, or a heterocyclic group, and is preferably an aromatic 5- to 6-membered ring containing a nitrogen atom adjacent to a bonding site with an aliphatic group, More preferably a heterocyclic group, and more preferably an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom adjacent to a bonding site with a nitrogen atom. R ⁵⁵ is an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom on the side adjacent to a bonding site with a nitrogen atom, so that intermolecular interaction as well as intramolecular interaction of the dye molecule can be firmly formed. This makes it easy to form a pigment having a stable molecular arrangement and is preferable in that it exhibits good color, high fastness (light fastness, gas, heat, water, etc.).

In view of the effects of the present invention, the aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom adjacent to the bonding site with a nitrogen atom, which is preferable as R ⁵⁵ , may have a substituent, Is a group described in the section of substituent, and any substitutable group may be used. Preferred examples of the substituent include a hydroxyl group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group and a carbamoylamino group, and may be a saturated heterocyclic ring or an unsaturated heterocyclic ring, Preferably an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom adjacent to a bonding site with a nitrogen atom having a total of 2 to 12 carbon atoms, more preferably a total of 2 to 10 Is an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom adjacent to a bonding site with a nitrogen atom of the nitrogen atom. For example, there may be mentioned 2-thiazolyl, 2-benzothiazolyl, 2-oxazolyl, 2-benzoxazolyl, 2- pyridyl, 2- pyrazinyl, 3- pyridazinyl, 4-pyrimidinyl, 2-imidazolyl, 2-benzimidazolyl, 2-triazinyl and the like, and these heterocyclic groups may have a tautomeric structure together with a substituent.

In terms of the effect of the present invention, the aryl group preferable as R ⁵⁵ may have a substituent, and the group which may be substituted is a group described in the above-mentioned substituent group, and any substitutable group may be used. , A hydroxyl group, a nitro group, an aliphatic group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group or a carbamoylamino group. The aryl group represented by R ₅₅ is preferably an aryl group having 6 to 12 total carbon atoms, more preferably an aryl group having 6 to 10 total carbon atoms, such as phenyl, 3-methoxyphenyl, 4 -Carbamoylphenyl, etc., and a phenyl group is preferable.

In terms of the effects of the present invention, the preferable aliphatic group as R &lt; ⁵⁵ &gt; may have a substituent, and the group which may be substituted is the group described in the above-mentioned substituent group, , A hydroxyl group, a nitro group, an aliphatic oxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aliphatic thio group, an amino group, an aliphatic amino group, an acylamino group or a carbamoylamino group. The aliphatic group represented by R ₅₅ is preferably an alkyl group having 1 to 6 carbon atoms in total, more preferably an aliphatic group having 1 to 4 carbon atoms in total, such as methyl, ethyl, methoxyethyl, carbamoyl Methyl, etc., and a methyl group is preferable.

In the general formula (A2), R ⁵⁵ is preferably any one of the following (Y-1) to (Y-13) (Y-1), (Y-3), (Y-4) and (Y-6) (Y-1) or (Y-4) shown below. * In the formulas (Y-1) to (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. (Y-13) G in ₁₁ denotes a five or six non-metal atom group that can be configured to membered heterocyclic ring, may be a heterocyclic ring unsubstituted represented by G ^11, which may have a substituent, and, heterocyclic ring may be a monocyclic It may be opened. The formulas (Y-1) to (Y-13) may be a tautomeric structure together with a substituent.

[Chemical Formula 9]

The substituent represented by Y ¹ to Y ¹¹ is the group described in the above-mentioned substituent group, and any substitutable group may be used. Examples of the substituent of Y ¹ to Y ¹¹ include an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carbamoyl group, an acylamino group, a sulfonamido group, an aliphatic oxy group, an aliphatic thio group, , More preferably an aliphatic group, an aliphatic oxy group, an aliphatic thio group, a cyano group and the like. Of Y ¹ to Y ¹¹ , two adjacent substituents may form a 5- to 6-membered ring.

Y ¹ to Y ¹¹ are preferably a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carbamoyl group, an acylamino group, a sulfonamido group, an aliphatic oxy group, An amino group, an amino group, an amino group, an amino group, and an amino group, and more preferably a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group, a carbamoyl group, an aliphatic oxy group or a cyano group.

In view of the effects of the present invention, A in the general formula (A2) is preferably a 5-membered ring heterocycle in terms of hue, more preferably a nitrogen-containing heterocycle or a 5-membered heteroaromatic ring, more preferably 2 or more Lt; RTI ID = 0.0 &gt; 5-membered &lt; / RTI &gt;

The substituent represented by R ⁵⁶ to R ⁵⁷ and R ⁵⁹ is a group described in the above-mentioned substituent group, and any substitutable group may be used. 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, a carbamoyl group, an acylamino group, a sulfonamido group, an aliphatic oxy group, Etc., more preferably an aliphatic group, an aliphatic oxy group, an aliphatic thio group, a cyano group and the like.

In view of the effects of the present invention, R ⁵⁶ to R ⁵⁷ and R ⁵⁹ may be the same or different and each represents an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carbamoyl group, an acylamino group, a sulfonamido group, an aliphatic oxy group, A cyano group, and the like, and more preferably an aliphatic group, an aliphatic oxy group, an aliphatic sioxy group, or a cyano group.

The substituent represented by R ⁵⁸ is the group described in the above-mentioned substituent group, and any substitutable group may be used. In view of the effects of the present invention, it is preferable that R ⁵⁸ is an electron-attracting group having a heterocyclic group, a Hammet's substituent constant? P value of 0.2 or more, and a? P value of 0.3 or more. The upper limit is 1.0 or less.

Specific examples of the electron-withdrawing group R ⁵⁸ having a? p value of 0.2 or more include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group, An alkylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, an acylsioxy group, a sulfamoyl group, a thiocyanate group, a thiocarbamoyl group, A halogenated alkyloxy group, a halogenated alkyloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with another electron-attracting group having a? P value of 0.20 or more, a heterocyclic group , A halogen atom, an azo group, or a selenocyanate group.

From the viewpoint of the effect of the present invention, it is also preferable that R ⁵⁸ is the above-mentioned (Y-1) to (Y-13) (Y-1), (Y-3), (Y-4) and (Y-6) , And the case of (Y-1) or (Y-4) is particularly preferable.

Among the heterocyclic rings of (A-1) to (A-32) as A in the general formula (A2), when the atoms adjacent to the carbon atom bonded to the azo group are heteroatoms, the toughness and heat fastness tend to increase , And it is preferable to use a pigment having such a structural feature in a color filter because a color filter exhibiting a high contrast can be obtained.

In view of the effects of the present invention, the azo pigment represented by the general formula (A2) is a saturated heterocyclic group in which G is a hydrogen atom, R ¹ is an amino group or a nitrogen atom, m is 0 or 1, m is 1 If, R ² is an aliphatic oxy carbonyl group, a carbamoyl group, or an aliphatic oxy group, a is, (a-1), ( a-10) ~ (a-17), (a-20) ~ (a -23), (A-27), (A-28), (A-30) to (A-32) and n is 1 or 2.

More preferably, when G is a hydrogen atom, R ¹ is a saturated heterocyclic group bonded with an amino group or a nitrogen atom, m is 0 or 1, and m is 1, R ₂ is an aliphatic oxycarbonyl group, , Or an aliphatic oxy group, and A is at least one selected from the group consisting of (A-1), (A-10), (A-11) (A-23), (A-27), (A-28), (A-30) to (A-32) and n is 1 or 2.

More preferably, G is a hydrogen atom, R ¹ is a saturated heterocyclic group bonded with an amino group or a nitrogen atom, m is 0, and A is (A-10), (A-11) (A-20), (A-22), (A-23) And n is 1 or 2.

Particularly preferably, G is a hydrogen atom, R ¹ is an amino group, m is 0, and A is (A-16) to (A-17), (A-20) (A-16), and n is 1 or 2. In the case where G is a hydrogen atom, R ¹ is an amino group, m is 0, A is (A-16) 2 &lt; / RTI &gt;

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

Azo pigments represented by the general formula (A3) is, Z, or R ⁵⁵ and the naphthalene ring hydroxy group, to form a hydrogen bonded cross to the azo group, increase the planarity of the pigment structure, the stronger the inside, intermolecular interaction molecules, and as a result, Light fastness, heat fastness, solvent resistance and the like are greatly improved.

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

In general formula (A3)

[Chemical formula 10]

R ²¹ , R ²² , R ⁵⁵ , R ⁵⁹ , m and n in the general formula (A3) each represent a group represented by R ¹ , R ² , R ⁵⁵ , R ⁵⁹ , m and n And agreement. And Z represents an electron-attracting group having a? P value of Hammett of 0.2 or more. In the case of n = 2 ^{is, R 21, R 22, R} 55, it represents a dimer through an R ⁵⁹ or Z. When n = 3, it represents a trimer containing R ²¹ , R ²² , R ⁵⁵ , R ⁵⁹ or Z. When n = 4, it represents a tetramer containing R ²¹ , R ²² , R ⁵⁵ , R ⁵⁹ or Z. The formula (A3) does not have an ionic hydrophilic group.

As the substituent having a? P value of Hammett represented by Z of not less than 0.2, there may be mentioned the groups described in the description of R ^{58 in} the general formula (A2).

The preferable substituents and ranges of R ²¹ , R ²² , R ⁵⁵ , R ⁵⁹ , m and n in the azo pigment represented by the general formula (A3) are as follows: R ¹ , R ² , R ⁵⁵ , R ⁵⁹ , m, and n.

In view of the effects of the present invention, Z is preferably an acyl group, a carbamoyl group, an alkyloxycarbonyl group, a cyano group, an alkylsulfonyl group or a sulfamoyl group, and a carbamoyl group, an alkyloxycarbonyl group, And more preferably a cyano group.

In view of the effect of the present invention, the azo pigment represented by the general formula (A3) is a compound wherein R ²¹ is an amino group which may have a substituent, m is 0 or 1, m is 1, R ²² is an aliphatic oxycarbo group, a carbamoyl group, or an aliphatic oxy group, R ⁵⁵ a, and an aromatic 5 ~ 6 membered heteroaryl ventilation containing a nitrogen atom on the adjacent bonding sites, and R ⁵⁹ is a hydrogen atom or an aliphatic group, Z is an acyl group, A carbamoyl group, an alkyloxycarbonyl group, a cyano group, an alkylsulfonyl group, or a sulfamoyl group, and n is preferably 1 or 2.

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

More preferably, R ²¹ is an amino group which may have a substituent, m is 0, R ⁵⁵ is any one of (Y-1) to (Y-6), R ⁵⁹ is a hydrogen atom or an aliphatic group , Z is a carbamoyl group, an alkyloxycarbonyl group or a cyano group, and n is 1 or 2.

Preferably, and R ²¹ is amino group which may have a substituent, m is 0, R, and ⁵⁵ is, (Y-1), ( Y-4), or (Y-6), R ⁵⁹ is a hydrogen atom , Z is a cyano group, and n is 1 or 2.

In view of the effects of the present invention, the azo pigment represented by the general formula (A2) or the general formula (A3) preferably has a "total carbon number / number of azo groups" of 40 or less, more preferably 30 or less. In view of the effects of the present invention, the azo pigment represented by the general formula (A2) or the general formula (A3) preferably has a "molecular weight / number of azo groups" of 700 or less. In view of the effects of the present invention, the azo pigment represented by formula (A2) or formula (A3) is preferably a compound in which an ionic substituent such as a sulfo group or a carboxyl group is not substituted.

The azo compound represented by the general formula (A2) is a compound represented by the general formula (A-1) to (A-9) (A-20) to (A-23), (A-27), (A- , More preferably from (A-17) to (A-20) to (A-23), from (A-27) (A-21), (A-20), (A-22) , More preferably (A-20), (A-28) and (A-32), particularly preferably (A-20). It is more preferable that R ^{56 in} (A-20) is R ⁵⁹ .

The present invention also includes tautomers of the azo pigment represented by the formula (A2) or the formula (A3). The general formula (A2) or the general formula (A3) is shown in the form of a strict structural formula among several kinds of tautomers which can be taken in terms of chemical structure. However, the tautomer may be a tautomer other than the structure described above, or a mixture containing a plurality of tautomers May be used.

For example, as the azo pigment represented by the general formula (A2), a tautomer of azo hydrazone represented by the following general formula (A1 ') can be considered.

The present invention also includes pigments represented by the following formula (A1 '), which is a tautomer of the azo pigment represented by the formula (A2).

In general formula (A1 '),

(11)

In the general formula (A1 '), G, R ¹ , R ² , m, n and A are synonymous with G, R ¹ , R ² , m and n in the general formula (A2).

Of the azo pigments represented by the formula (A2), particularly preferred examples of the azo pigments as described above include the azo pigments represented by the following formulas (A4-1) to (A4-4). The azo pigment represented by the general formula (A2) is preferably an azo pigment represented by the following general formulas (A4-1) to (A4-4).

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

[Chemical Formula 12]

General formula (A4-1) ~ (A4-4) of, R ^1, R ^2, m, and n, respectively, and R ^1, R ^2, m, and n and consent of the general formula (A2). X represents a carbon atom or a nitrogen atom, Ax forms an aromatic 5- to 6-membered heterocyclic group together with X and an adjacent carbon atom, and Bx forms an aromatic 5- to 6-membered heterocyclic group together with the adjacent carbon atom (A-1) to (A-32) defined by A in the general formula (A2). Yx together with the nitrogen atom and the adjacent carbon atom form a heterocyclic group and represent the corresponding heterocyclic group defined by R ⁵⁵ in formula (A2). R ²³ represents a substituent corresponding to the group in which the carbonyl group is removed from the corresponding substituent among the substituents R ⁵¹ , R ⁵⁴ , R ⁵⁷ and R ⁵⁸ defined by the general formula (A2). R ' ¹ represents a substituent corresponding to the group obtained by removing -NH- from the amino group of R ¹ defined by the general formula (A2).

In the azo pigments represented by the general formulas (A2), (A3), (A4-1) to (A4-4), a number of tautomers are conceivable.

In the present invention, it is preferable that the azo pigment represented by the general formula (A2) has a substituent which forms an intramolecular hydrogen bond or an intramolecular cross-linked hydrogen bond. More preferably at least one substituent which forms an intramolecular hydrogen bond, and particularly preferably at least one substituent which forms a cross-hydrogen bond in a molecule.

As a preferable factor of this structure, a nitrogen atom constituting a heterocyclic group contained in the azo pigment structure, a hydrogen atom of a hydroxyl group of a naphthalene substituent, and an oxygen atom constituting an azo pigment structure represented by the general formulas (A4-1) to (A4-4) And a nitrogen atom of a hydrazone group which is an azo group or a tautomer thereof, or a carbonyl group substituted by an azo component contained in an azo pigment structure, a hydrogen atom and an oxygen atom of a hydroxyl group of a naphthalene substituent, and an azo group or a tautomer thereof And the nitrogen atom of the hydrazone group is likely to easily form cross-hydrogen bonds in the molecule.

As a result, the planarity of the molecule is enhanced, the intramolecular-intermolecular interactions are improved, and the crystallinity of the azo pigment represented by formulas (A4-1) to (A4-4) Is more preferable because it can greatly improve light fastness, thermal stability, wet heat stability, water resistance, gas resistance and solvent resistance, which are required as pigments.

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

As specific examples of the azo pigments used in the present invention, reference can be made, for example, to the compounds described in paragraphs 0094 to 0116 of Japanese Laid-Open Patent Publication No. 2011-162760, the contents of which are incorporated herein by reference.

As the pigment in the present invention, a quinophthalone compound represented by the following general formula (1A), general formula (1B) and general formula (1C) (hereinafter occasionally referred to as "specific quinophthalone compound" ) May be used as the pigment. By using the quinophthalone compound, it is also possible to obtain a high contrast ratio, a high coloring power, and an excellent effect of lowering the viscosity of the coloring composition for a color filter.

In formula (1A)

[Chemical Formula 13]

In general formula (1B)

[Chemical Formula 14]

In general formula (1C)

[Chemical Formula 15]

In the general formula (1A) ~ (1C), R 14 ~ R 28, R 29 ~ R 43, R 44 ~ R 60 are, each independently, brought to Figure alkyl group, the substituent being a hydrogen atom, a halogen atom, the substituents can An optionally substituted alkoxyl group, an optionally substituted aryl group, -SO ₃ H; -COOH; And monovalent to trivalent metal salts of these acid groups; An alkylammonium salt, a phthalimide methyl group which may have a substituent, or a sulfamoyl group which may have a substituent.

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

Examples of the alkyl group which may have a substituent include alkyl groups such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n- , A 2-ethylhexyl group, and the like, as well as a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, Benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-methoxybenzyl group, 4-methoxybenzyl group, 4-methoxybenzyl group, An alkyl group having a substituent such as a nitrobenzyl group, a 2,4-dichlorobenzyl group and the like.

Examples of the alkoxyl group which may have a substituent include a methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutyloxy group, tert-butyloxy group, neopentyloxy group, In addition to the straight-chain or branched alkoxyl groups such as dimethyl-3-pentoxy, n-hexyloxy, n-octyloxy, stearyloxy and 2-ethylhexyloxy, trichloromethoxy, , 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group , 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

Examples of the aryl group which may have a substituent include an aryl group such as a phenyl group, a naphthyl group and an anthranil group, a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, 4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8- Naphthyl group, trichloro-2-naphthyl group, anthraquinone group, 2-aminoanthraquinonyl group and the like.

Examples of the acidic group include -SO ₃ H and -COOH. Examples of the monovalent to trivalent metal salt of the acid group include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts and aluminum salts. have. Examples of the alkylammonium salt of the acidic group include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, and ammonium salts such as palmityltrimethylammonium, diaryldimethylammonium and distearyldimethylammonium salts Alkylammonium salts.

As the "substituent" for the phthalimido methyl group (C ₆ H ₄ (CO) ₂ N-CH ₂ -) which may have a substituent and the sulfamoyl group (H ₂ NSO ₂ -) which may have a substituent, A halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and an aryl group which may have a substituent.

The quinophthalone compound is preferably a compound wherein R ¹⁴ to R ²⁸ , R ²⁹ to R ⁴³ and R ⁴⁴ to R ^{60 in} formulas (1A) to (1C) are a hydrogen atom or a halogen atom, From the viewpoint of drawing, it is more preferable.

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

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

As the pigment in the present invention, a phthalocyanine coloring matter represented by the following general formula (1) (hereinafter sometimes referred to as "specific phthalocyanine coloring matter") may be used.

In general formula (1)

[Chemical Formula 19]

In the general 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 each independently represent 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 , R ¹ and R ² are 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 that can be used in the present invention are shown below, but the present invention is not limited thereto.

[Chemical Formula 20]

[Chemical Formula 21]

As the pigment in the present invention, it is also possible to use a diketopyrrolopyrrole pigment represented by the following formula (2).

[Chemical Formula 22]

(2), A and B each independently represent 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 wherein R ¹ to R ¹¹ each independently represent 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, B does not simultaneously become a hydrogen atom.)

(2-1), (2-2), (2-3), (2-), and (2-4) among the specific heterodetallopyrrolopyrrole pigments represented by the formula (2) used in the pigment of the present invention. 4) is preferable in terms of brightness, contrast, and crystal precipitation inhibiting effect. R ⁶ to R ⁸ in the formulas (2-3) and (2-4) are preferably an alkyl group having 4 or more carbon atoms or a phenyl group which may have a substituent in terms of contrast and crystal precipitation inhibiting effect. The reason why they exhibit high contrast and suppression of crystal precipitation is that the aggregation of pigments is inhibited by the effect of steric hindrance by a bulky substituent such as a carbamoyl group having an alkyl group having 4 or more carbon atoms and a phenyl group or a t- . In addition, the specific heterodiketopyrrolopyrrole pigment having a carbamoyl group, a phenyl group and a t-butyl group has excellent color characteristics, so that the excellent brightness of the brominated diacetopyrrolopyrrole pigment is not hindered.

(23)

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

Specific examples of the specific diketopyrrolopyrrole pigment of formula (2) usable in the present invention are shown below, but the present invention is not limited thereto.

&Lt; EMI ID =

(25)

(26)

(27)

When the pigment is used for a color filter, the primary particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness or contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability. The primary particle size of the pigment is more preferably 5 to 75 nm, further preferably 5 to 55 nm, and particularly preferably 5 to 35 nm. The specific dispersion resin according to the present invention can exert particularly good effects in combination with a pigment having a primary particle size in the range of 5 to 35 nm.

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

The pigment is preferably a pigment selected from anthraquinone pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinophthalone pigments, isoindoline pigments, azomethine pigments, and dioxazine pigments. Particularly, CI Pigment Red 122, CI Pigment Red 177 (anthraquinone pigment), CI Pigment Red 254 (diketopyrrolopyrrole pigment), CI Pigment Green 7, 36, 58, CI Pigment Blue 15: CI Pigment Yellow 135 (quinophthalone pigment), CI Pigment Yellow 139, 185 (isoindoline pigment), CI Pigment Yellow 150 (azomethine pigment), CI Pigment Violet 23 (a dioxazine pigment) is most preferable.

The composition of the present invention may contain a known dye other than the pigment (A). For example, Japanese Patent Application Laid-Open Nos. 64-90403, 64-91102, 1-94301, 6-11614, 2592207, 4808501, US 5667920, US 505950, US 5667920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 And JP-A-6-194828 can be used. Examples of the chemical structure include a pyrazole group, a pyromethene group, an anilino group, a triphenylmethane group, an anthraquinone group, a benzylidene group, an oxolane group, a pyrazolotriazole group, a pyridazo group, And pyrrolopyrazole azo methane phosphoric acid, can be used.

As the dye, a dye multimer may be used. Examples of the pigment multimer include the compounds described in JP-A-2011-213925 and JP-A-2013-041097.

The content of the pigment in the composition of the present invention is preferably from 10% by mass to 70% by mass, more preferably from 20% by mass to 60% by mass, relative to the total components (solid content) excluding the solvent contained in the colored photosensitive resin composition By mass, and more preferably from 30% by mass to 60% by mass.

The pigment may be contained in only one kind or two or more kinds in the composition of the present invention. When two or more kinds are included, the total amount is preferably in the above range.

<< (B) Basic pigment derivative >>

The composition of the present invention has a basic pigment derivative. The basic dye derivative is preferably a compound having an amino group.

As one embodiment of the basic pigment derivative (B), there can be mentioned a pigment derivative represented by the general formula (P1).

(28)

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

[Chemical Formula 29]

(30)

In the general 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.

(31)

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

(32)

In the general formula (P2), Z represents a lower alkylene group. Z is represented by - (CH ₂ ) _b -, wherein b represents an integer of 1 to 5, preferably 2 or 3. In the general formula (P2), -NR ₂ represents a lower alkylamino group or a 5- to 6-membered saturated heterocycle containing a nitrogen atom. When -NR ₂ represents a lower alkylamino group, it is represented by -N (C _n H _{2n + 1} ) ₂ , and n represents an integer of 1 to 4, preferably 1 or 2. On the other hand, when -NR ₂ represents a 5- to 6-membered saturated heterocycle containing a nitrogen atom, a heterocycle represented by the following structural formula is preferable.

(33)

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

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

(34)

(35)

(36)

(37)

(38)

It is also preferable that the basic pigment derivative (B) is a pigment derivative represented by the general formula (I). Such a pigment derivative acts as a kind of compatibilizer. The reason for this is unclear, but the following mechanism is presumed. That is, the components (C-1) and (C-2) of the present invention are not easily aggregated and crystallized among the three-dimensional rebounder (polyester structure, etc.) (C-1) and (C-2) components are aggregated and crystallized in phase with the E-polymerization initiator and the (F) polymerizable compound. When the pigment derivative represented by the general formula (I) is added to the component (B), the quinophthalone residue moiety which may have a substituent represented by Dye in the general formula (I) or part represented by X ²⁾ is, into the steric repulsion group portion of the (C-1) component and the (C-2) ingredient to prevent agglomeration, crystallization between the steric repulsion group, resulting in (C-1) component and the ( C-2) component is inhibited from being phase-separated.

The compound of formula (I)

[Chemical Formula 39]

In the general formula (I), Dye represents a quinophthalone residue which may have a substituent, and X ¹ represents -NR'SO ₂ -, -SO ₂ NR'-, -CONR'-, -CH ₂ NR'COCH ₂ NR'-, or represent a -NR'CO-, X ^2, the carbon atoms are carbon atoms which may have a substituent which may have an aryl group, or a substituent of 6-20 1-20 which represents a heteroaromatic group, these groups, -NR'-, -O-, -SO ₂ - or may be coupled together in a or a divalent connecting group selected from -CO-. X ³ represents -NR'- or -O-. R 'represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms and may have a substituent. A and B each represent a group represented by the following general formula (1) or the following general formula (2), -O- (CH ₂ ) _n -R ⁸ , -OR ⁹ , -NR ¹⁰ R ¹¹ , -F ³ or -X ³ -X ² -X ¹ -Dye, R ⁸ represents a substituted or unsubstituted nitrogen-containing heterocyclic residue, R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom, An alkyl group of 1 to 20 carbon atoms which may have a substituent, an alkenyl group of 2 to 20 carbon atoms which may have a substituent or an aryl group of 6 to 20 carbon atoms which may have a substituent, and n is an integer of 0 to 20 . Wherein one of A and B is a group represented by the following general formula (1) or (2), -O- (CH ₂ ) n R ⁸ , -OR ⁹ or -NR ¹⁰ R ¹¹ , Represents an integer. When t is 2 or more, a plurality of X ¹ , X ² , X ³ , A, and B may be the same or different.

(40)

In the general formula (1), Y ¹ represents -NR'- or -O-, Y ² represents an alkylene group having 2 to 20 carbon atoms which may have a substituent, an alkylene group having 2 to 20 carbon atoms which may have a substituent Or an arylene group having 6 to 20 carbon atoms, which may have a substituent, and these groups are bonded to each other by a divalent linking group selected from -NR'-, -O-, -SO ₂ -, and -CO-, . R 'represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms and may have a substituent. R ¹ and R ² each represent an alkyl group having 1 to 20 carbon atoms which may have a substituent or an alkenyl group having 2 to 20 carbon atoms which may have a substituent (R ¹ and R ² are taken together to form a heterocyclic structure And the heterocyclic structure may further contain a nitrogen atom, an oxygen atom or a sulfur atom, and may have a substituent.

In the general formula (2), Z ¹ represents a single bond connecting a triazine ring and a nitrogen atom, -NR'-, -NR'-G-CO-, NR'-G-CONR " _{-SO 2 -, -NR'-G-} SO 2 NR "-, -OG-CO-, -OG-CONR'-, -OG-SO 2 - or -OG-SO ₂ represents NR'-, G is An alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent or an arylene group having 6 to 20 carbon atoms which may have a substituent, and R 'and R " Each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms and may have a substituent, R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, Having 6 to 20 carbon atoms R ⁷ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an alkenyl group having 2 to 20 carbon atoms and may have a substituent.

In the general formula (I), Dye represents a quinophthalone residue which may have a substituent. The quinophthalone residue is specifically represented by the following general formula (II).

In general formula (II)

(41)

In the general formula (II), D and E each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic ring or heterocyclic group which may be substituted with a benzene ring to which D and E are bonded, A carboxyl group or a salt thereof, an ester of 1 to 20 carbon atoms, an amide of 1 to 20 carbon atoms, a sulfone group or a salt thereof, a sulfamoyl group, -NR'R "-, a nitro group Wherein R 'and R "each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent or a substituent An aryl group having 6 to 20 carbon atoms which may be present. p represents an integer of 0 to 4, and q represents an integer calculated by 4-p. * Represents a bonding site with X ¹ in the general formula (I).

D and E each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic ring or heterocyclic group which may be substituted with a benzene ring to which D and E are bonded, a hydroxyl group, A carboxyl group or a salt thereof, an ester of 1 to 20 carbon atoms, an amide of 1 to 20 carbon atoms, a sulfone group or a salt thereof, a sulfamoyl group, a sulfamoyl group, or an alkoxyl group of 1 to 20 carbon atoms (e.g., methoxy group, ethoxy group, propoxy group) R 'and R "each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkyl group having 2 to 20 carbon atoms which may have a substituent, An alkenyl group having 6 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent.

The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl and n-octyl.

Examples of the aromatic ring or heterocyclic ring include a phenyl group, a naphthyl group, a thiophene ring group, a pyridine ring group and a pyrrole ring group.

The aromatic ring or heterocyclic group represented by D and E, the alkyl group having 1 to 20 carbon atoms represented by R 'and R ", the alkenyl group having 2 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms may have a substituent, , The groups described in the section of the above substituents.

Among them, D and E are preferably a hydrogen atom or a halogen atom.

p represents an integer of 0 to 4, more preferably an integer of 1 to 4, and more preferably 4. q represents an integer calculated by 4-p, specifically, an integer of 0 to 3 is preferable, an integer of 2 to 3 is more preferable, and a value of 4 is more preferable.

The bonding site with X ¹ in the general formula (I) is not particularly limited, but it is preferable that the 5th or 8th position of the quinolin skeleton in the quinophthalone residue is a bonding site, and the 8th position is a bonding site Do.

In the general formula (I), X ¹ represents -NR'SO ₂ -, -SO ₂ NR'-, -CONR'-, -CH ₂ NR'COCH ₂ NR'-, or -NR'CO-, -NR'SO ₂ - is preferred. When t is 2 or more, a plurality of X ¹ may be the same or different.

R 'in X ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an alkenyl group having 6 to 20 carbon atoms An aryl group, and a hydrogen atom are preferable.

The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl and n-octyl.

The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms. Specific examples thereof include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group.

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

These may have a substituent, and examples of the substituent include the groups described in the above section of the substituent.

In the general formula (I), X ² represents an arylene group having 6 to 20 carbon atoms which may have a substituent, or a heteroaromatic group having 4 to 20 carbon atoms which may have a substituent, , -O-, -SO ₂ - or -CO- (R 'is the same as R' in X ¹ above, and preferable range is also the same). When t is 2 or more, a plurality of X ² may be the same or different.

The arylene group having 6 to 20 carbon atoms is preferably an arylene group having 6 to 10 carbon atoms, and specific examples thereof include a phenylene group, a naphthylene group and an anthraceneylene group.

The complex aromatic ring having 4 to 20 carbon atoms is preferably a heterocyclic aromatic ring having 4 to 10 carbon atoms, and specific examples thereof include a thiophene ring group, a pyridine ring group and a pyrrole ring group.

These may have a substituent, and examples of the substituent include the groups described in the above section of the substituent.

X ³ represents -NR'- or -O-, and -NR'- is preferable. When t is 2 or more, a plurality of X ³ may be the same or different. R 'is synonymous with R' above, and the preferred range is also the same.

A and B each represent a group represented by the following general formula (1) or the following general formula (2), -O- (CH ₂ ) _n -R ⁸ , -OR ⁹ , -NR ¹⁰ R ¹¹ , -F ³ or -X ³ -X ² -X ¹ -Dye, and either A or B represents a group represented by the following general formula (1) or (2), -O- (CH ₂ ) n R ⁸ is -OR ^9, or -NR ¹⁰ R ^11. Among them, A and B are all groups represented by the following general formula (1) or the following general formula (2).

R ⁸ represents a nitrogen-containing heterocyclic residue which may be substituted, and specific examples thereof include a pyrrole ring residue and a pyridine ring residue.

R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, An aryl group having 6 to 20 carbon atoms. R ⁹ , R ¹⁰ and R ¹¹ are the same as the above R ', and preferable ranges are also the same.

In general formula (1)

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In the general formula (1), Y ¹ represents -NR'- or -O-, Y ² represents an alkylene group having 2 to 20 carbon atoms which may have a substituent, an alkylene group having 2 to 20 carbon atoms which may have a substituent Or an arylene group having 6 to 20 carbon atoms, which may have a substituent, and these groups are bonded to each other by a divalent linking group selected from -NR'-, -O-, -SO ₂ -, and -CO-, . R 'represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms and may have a substituent. R ¹ and R ² each represent an alkyl group having 1 to 20 carbon atoms which may have a substituent or an alkenyl group having 2 to 20 carbon atoms which may have a substituent (R ¹ and R ² are taken together to form a heterocyclic structure And the heterocyclic structure may further contain a nitrogen atom, an oxygen atom or a sulfur atom, and may have a substituent.

Y ¹ represents -NR'- or -O-, and -NR'- is preferable. R 'is synonymous with R' above, and the preferred range is also the same.

Y ² represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent, or an arylene group having 6 to 20 carbon atoms, which may have a substituent, _{groups, -NR'-, -O-, -SO 2 -} , or may be bonded to each other with a divalent connecting group selected from -CO- (R a 'is the R' and consent, are also the same preferable range.).

The alkylene group having 1 to 20 carbon atoms is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. Specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group. The alkylene group may have a substituent, and examples of the substituent include the groups described in the above section of the substituent.

The alkenylene group having 2 to 20 carbon atoms is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and still more preferably an alkenylene group having 2 to 3 carbon atoms. Specific examples include a vinylene group, a propyleneylene group, a butyleneylene group, a pentyleneylene group, and a hexyleneylene group. The alkenylene group may have a substituent. Examples of the substituent include the groups described in the above section of the substituent.

The arylene group having 6 to 20 carbon atoms is preferably an arylene group having 6 to 20 carbon atoms, and more preferably an arylene group having 6 to 10 carbon atoms. Specific examples thereof include a phenylene group, a naphthylene group, and an anthraceneylene group. The arylene group may have a substituent, and examples of the substituent include the groups described in the above section of the substituent.

R ¹ and R ² each represent an alkyl group having 1 to 20 carbon atoms which may have a substituent or an alkenyl group having 2 to 20 carbon atoms which may have a substituent (R ¹ and R ² are taken together to form a heterocyclic structure And the heterocyclic structure may further contain a nitrogen atom, an oxygen atom or a sulfur atom, and may have a substituent.

The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl and n-octyl.

The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms. Specific examples thereof include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group.

These groups may have a substituent, and examples of the substituent include the groups described in the above section of the substituent. It is preferable that R ¹ and R ² represent the same group.

In general formula (2)

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In the general formula (2), Z ¹ represents a single bond connecting a triazine ring and a nitrogen atom, -NR'-, -NR'-G-CO-, NR'-G-CONR " _{-SO 2 -, -NR'-G-} SO 2 NR "-, -OG-CO-, -OG-CONR'-, -OG-SO 2 - or -OG-SO represents a ₂ NR'-, G is An alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent or an arylene group having 6 to 20 carbon atoms which may have a substituent, and R 'and R " Each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms and may have a substituent, R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, Having 6 to 20 carbon atoms R ⁷ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an alkenyl group having 2 to 20 carbon atoms and may have a substituent.

Z ¹ represents a single bond connecting a triazine ring and a nitrogen atom, -NR'-, -NR'-GCO-, NR'-G-CONR "-, -NR'-G-SO ₂ - G-SO ₂ NR "-, -OG-CO-, -OG-CONR'-, -OG-SO ₂ - or -OG-SO ₂ NR'-, with single bonds being preferred.

R 'and R "each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an alkenyl group having 6 to 20 carbon atoms R 'and R "are the same as R' in the general formula (1), and preferred ranges are also the same.

G represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent, or an arylene group having 6 to 20 carbon atoms, which may have a substituent. G agrees with Y ² in the general formula (1), and the preferable range is also the same.

R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, Or an aryl group having 6 to 20 carbon atoms. R ³ , R ⁴ , R ⁵ , and R ⁶ are synonymous with R 'in formula (1), and the preferred ranges are also the same.

R ⁷ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent or an alkenyl group having 2 to 20 carbon atoms which may have a substituent. R ⁷ is synonymous with R ¹ in the general formula (1), and the preferred range is also the same.

In the general formula (I), t represents an integer of 1 to 3, preferably 1 or 2, and more preferably 1.

Specific examples of the dye derivative used in the present invention are shown below, but the present invention is not limited thereto.

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[Chemical Formula 45]

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(47)

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The content of the pigment derivative (B) in the present invention is preferably 0.5% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 15% by mass or less as solid content.

Further, it is preferably 0.5 part by mass or more and 50 parts by mass or less, and more preferably 1 part by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the pigment (A).

The pigment derivative may be contained in only one kind of the composition of the present invention, or may contain two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.

<< (C) Dispersant >>

The composition of the present invention is a composition comprising (C-1) a phosphoric acid-based dispersing agent represented by the general formula (II) or a polymer (POH) having at least one terminal hydroxyl group at a terminal (C- (PNH ₂ ) having an amino group and a carboxylic acid-based dispersant obtained by reacting a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride. By containing the above-mentioned dispersant, the dispersant is strongly adsorbed to the pigment particles, and it becomes possible to suppress the deterioration of the roughness of the composition over time. The dispersant used in the present invention tends to have poor compatibility with other components, has a large roughness with time, and has a very poor pattern formation property after PCD. In the present invention, however, the basic pigment derivative (B) I) in combination with a dye derivative represented by the formula (I).

- (C-1) a phosphoric acid-based dispersant represented by the general formula (II)

The composition of the present invention comprises (C-1) a phosphoric acid-based dispersant represented by the general formula (II). By containing the above-mentioned dispersant, the dispersant is strongly adsorbed to the pigment particles, and it becomes possible to suppress the deterioration of the roughness of the composition over time.

In general formula (II)

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In the general formula (II), R ³ represents a polyester structure having a number average molecular weight of 400 to 30000, and y represents 1 or 2. When y is 2, a plurality of R ³ may be the same or different.

R ³ represents a polyester structure having a number average molecular weight of 400 to 30000, and when y is 2, a plurality of R ³ may be the same or different. The number average molecular weight of the polyester structure is more preferably from 1900 to 10000, still more preferably from 400 to 3000, and still more preferably from 2000 to 3000. If it is less than 400, it can not be used because the pigment dispersing ability is insufficient.

Examples of the polyester structure include a polyester structure obtained by ring-opening polymerization of a lactone monomer, a polyester structure having a styrene group, an acryloyl group, a cyanoacryloyl group, a methacryloyl group, a vinyl ether group, Is preferably a polyester group obtained by ring-opening polymerization.

The phosphoric acid-based dispersant represented by the general formula (II) may be a phosphoric acid ester in which R ³ is a single species or a plurality of phosphoric acid esters composed of different R ³ may be used. Alternatively, the phosphoric acid-based dispersing agent of y = 1 may be used singly or a mixture of the phosphoric acid-based dispersing agent of y = 1 and the phosphoric acid-based dispersing agent of y = 2 may be used.

The phosphoric acid ester represented by the general formula (II) is preferably 100: 0 to 100: 30 in the case where the ratio of the phosphoric acid dispersant of y = 1 to the phosphoric acid dispersant of y = 2 is 100: 0 to 100: 30.

If the R ³ of the phosphoric acid-based dispersant represented by the general formula (II) has a polyester structure having a number average molecular weight of 400 to 10000, the pigment dispersibility is preferably good. More preferably, it is 400 to 3000.

Further, the effect of the present invention is excellent if R ³ of the phosphoric acid-based dispersant represented by the general formula (II) is a polyester structure obtained by ring-opening polymerization of two or more different lactone monomers.

The R ³ of the phosphoric acid-based dispersant represented by the general formula (II) is preferably represented by the following general formula (11).

In general formula (11)

^{R 12 -OR 13 - (OR 14} ) s ( wherein, R ¹² represents an alkylene group, R ¹³ is 3 represents a polyhydric alcohol structure above, R ¹⁴ is a group by group, a cyano acrylate as acryloyl, methacryloyl And s represents 2 or more).

R ¹² is preferably an alkylene group having 8 or less carbon atoms. From the viewpoint of pigment dispersibility, s is preferably 2 or more. In this case, different groups may be used for R ¹⁴ . s is more preferably 2 to 5, and 2 is particularly preferable.

Examples of the trivalent or higher polyvalent alcohol used in R ¹³ include glycerin, propyl alcohol, pentaerythritol, and dipentaerythritol. Particularly preferably 3 to 6 carbon atoms.

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

The production of the phosphoric acid-based dispersant can be carried out by a known method, and for example, reference can be made to the description of paragraphs 0037 to 0051 of Japanese Patent Application Laid-Open No. 2007-231107, the contents of which are incorporated herein by reference.

As the phosphate dispersant used in the present invention, it is preferable to use a phosphate dispersant obtained by ring-opening addition of? -Caprolactone and? -Valerolactone.

- (C-2) a polymer (POH) having at least one terminal hydroxyl group or a polymer (PNH ₂ ) having at least one terminal primary terminal amino group and a carboxylic acid anhydride or a tricarboxylic acid dianhydride Based dispersant -

(C-2) a polymer (POH) having at least one terminal hydroxyl group, or a polymer (PNH ₂ ) having at least one terminal primary terminal amino group, and a tricarboxylic acid anhydride or tetracarboxylic acid dianhydride And a carboxylic acid-based dispersant. By containing the above-mentioned dispersant, the dispersant is strongly adsorbed to the pigment particles, and it becomes possible to suppress the deterioration of the roughness of the composition over time.

The carboxylic acid-based dispersant can be obtained by reacting a polymer (POH) having a hydroxyl group at at least one terminal or a polymer (PNH ₂ ) having a primary amino group at at least one terminal with a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride .

(A polymer (POH) having at least one hydroxyl group at the terminal, and a polymer (PNH ₂ ) having a primary amino group at at least one terminal)

Preferred examples of the polymer (POH) having at least one hydroxyl group at the terminal or the polymer (PNH ₂ ) having the primary amino group at the terminal of at least one terminal are preferably represented by the general formula (II ').

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In formula (II '), Y ¹ represents a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms, and X ² represents -O-, -S-, Or -N (R ^b ) -, and R ^b represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms. G ¹ represents a repeating unit represented by -R ¹¹ O-, G ² represents a repeating unit represented by -C (═O) R ¹² O-, G ³ represents -C (═O) R ¹³ C (= O) -OR ¹⁴ O-, R ¹¹ represents a linear or branched alkylene group having 2 to 8 carbon atoms or a cycloalkylene group having 3 to 8 carbon atoms, R ¹² represents a linear or branched alkylene group having 3 to 8 carbon atoms, A linear or branched alkylene group having 2 to 6 carbon atoms or a cycloalkylene group having 4 to 8 carbon atoms; R ¹³ represents a linear or branched alkylene group having 2 to 6 carbon atoms; a linear or branched alkenyl group having 2 to 6 carbon atoms; group, having 3 to 20 carbon atoms in the cycloalkyl group, having from 6 to 20 carbon atoms or denotes an arylene group, R ^{14 is, -CH (R 15) -CH (} R 16) - represents a, R ¹⁵ and R ¹⁶ is either An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyloxymethylene group having 1 to 20 carbon atoms in the alkyl moiety, Of the carbon number of a portion 2-20 alkenyl oxymethylene group, an aryl moiety of 6 to 20 carbon atoms and which it may be optionally substituted halogen atoms whose aryl portion of aryloxy be a methylene group, or N- methylene-phthalimide represents an imide. Z ¹ is represents a -OH, or -NH _2, R ¹⁷ is a cycloalkyl group, a -C (= O) R ¹² in the alkylene group, 3 to 8 carbon atoms straight-chain or branched having 2 to 8, or ^{-C (= O) R 13 C} (= O) -OR 14 - shows a. m1 represents an integer of 0 to 100, m2 represents an integer of 0 to 60, and m3 represents an integer of 0 to 30. However, m1 + m2 + m3 is 1 or more and 100 or less. The arrangement of the repeating units G ¹ to G ^{3 in} the general formula (II ') is not limited to the order. In the polymer represented by the general formula (II'), the arrangement between the groups X ² and R ¹⁷ Indicates that the repeating units G ¹ to G ³ are contained in an arbitrary order, and their repeating units G ¹ to G ³ may be either random or block.

Y ¹ represents a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms, and represents a linear or branched alkyl group having 1 to 18 carbon atoms, From the viewpoint of low viscosity and storage stability of the pigment dispersion.

In still another embodiment, Y ¹ preferably has an ethylenically unsaturated double bond. In this case, the (C-2) dispersant can be imparted with active energy ray curability. Further, m2 = the case of 0, m3 = 0, Y ¹ preferably has a linear or branched, or an alkyl group on the, or ethylenically unsaturated double bond with a carbon number of 1-7.

In order to have an ethylenically unsaturated double bond, it is necessary to have a group having an ethylenically unsaturated double bond. These groups include, for example, a vinyl group or a (meth) acryloyl group, and a preferable example is a (meth) acryloyl group. These groups having a double bond may be of one kind or of a plurality of kinds.

X ² represents -O-, -S-, or -N (R ^b ) -, preferably -O- or -N (R ^b ) -.

R ^b represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms. As the linear or branched alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 6 carbon atoms is preferable. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl and cyclohexyl.

Z ¹ represents -OH or -NH ₂ , and -OH is preferable.

G ¹ represents a repeating unit represented by -R ¹¹ O-, and R ¹¹ represents a linear or branched alkylene group having 2 to 8 carbon atoms or a cycloalkylene group having 3 to 8 carbon atoms. Specific examples of the alkylene or cycloalkylene group represented by R ¹¹ include ethylene, propylene, butylene, pentylene, hexylene, cyclopentylene and cyclohexylene.

G ² represents a repeating unit represented by -C (= O) R ¹² O-, and R ¹² represents a linear or branched alkylene group having 1 to 8 carbon atoms or a cycloalkylene group having 4 to 8 carbon atoms. Specific examples of the alkylene or cycloalkylene group represented by R ¹² include methylene, ethylene, propylene, butylene, pentylene, hexylene, cyclopentylene and cyclohexylene.

G ³ represents a repeating unit represented by -C (= O) R ¹³ C (= O) -OR ¹⁴ O-, R ¹³ represents a linear or branched alkylene group having 2 to 6 carbon atoms, A linear or branched alkenylene group, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms. Specific examples of the alkylene or cycloalkylene group represented by R ¹³ include methylene, ethylene, propylene, butylene, pentylene, hexylene, cyclopentylene and cyclohexylene. Specific examples of the alkenylene group represented by R ¹³ include a vinylene group, a propylene group, a butyleneethylene group, a pentyleneylene group and a hexyleneylene group. Specific examples of the arylene group represented by R ¹³ include a phenylene group, a naphthylene group and an anthraceneylene group.

R ¹⁴ represents -CH (R ¹⁵ ) -CH (R ¹⁶ ) -. R ¹⁵ and R ¹⁶ each represent a hydrogen atom on one side and an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyloxy group having 1 to 20 carbon atoms in the alkyl moiety A methylene group, an alkenyloxymethylene group having 2 to 20 carbon atoms in the alkenyl moiety, an aryloxymethylene group in which the aryl moiety has 6 to 20 carbon atoms and the aryl moiety may be substituted with a halogen atom, Lt; / RTI &gt;

The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl and n-octyl.

The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms. Specific examples include an ethynyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group.

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

Group is an alkyl-oxy-methylene carbon atoms is from 1 to 20 in the alkyl moiety, an aspect that combines groups oxymethylene the alkyl group having 1 to 20 carbon atoms represented by R ^14, the alkyl group of the carbon number of 1 to 20, 1 to 20 carbon atoms represented by R ¹⁴ And the preferred range is also the same.

Wherein the alkenyl oxymethylene group is alkenyl having a carbon number of 2 to 20 parts, R and embodiment ¹⁴ is bonded represent groups a methylene-oxy in the alkenyl group of 2 to 20 carbon atoms, an alkenyl group of the 2 to 20 carbon atoms, R ¹⁴ represents And an alkenyl group having 2 to 20 carbon atoms, and the preferred range is also the same.

An aryloxy methylene carbon atoms is from 6 to 20 of the aryl moiety group, R is a mode ¹⁴ is shown which combines an aryl groups oxymethylene having from 6 to 20 carbon atoms, a group aryl in said group having from 6 to 20 carbon atoms, 6 to 20 carbon atoms represented by R ^14, And the preferred range is also the same.

R ¹⁷ represents a linear or branched alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, -C (= O) R ¹² -, or -C (= O) R ¹³ C -OR ¹⁴ -. Specific examples of the alkylene or cycloalkylene group represented by R ¹⁷ include ethylene, propylene, butylene, pentylene, hexylene, cyclopentylene and cyclohexylene. R ¹² and R ¹³ are synonymous with R ¹² and R ¹³ described above, and preferred ranges are also the same.

m1 represents an integer of 0 to 100, preferably an integer of 0 to 60, more preferably an integer of 0 to 40.

m2 represents an integer of 0 to 60, preferably an integer of 2 to 50, and more preferably an integer of 3 to 40. m2 is an integer of 3 to 15 from the viewpoint of low viscosity and storage stability of the pigment dispersion.

m3 represents an integer of 0 to 30, preferably an integer of 0 to 25, more preferably an integer of 0 to 20.

Further, m1 + m2 + m3 is preferably 1 or more and 100 or less, more preferably 2 to 60, and still more preferably 3 to 40.

The compound represented by the general formula (II ') can be synthesized by a known method. For example, reference can be made to paragraphs 0047 to 0082 of Japanese Patent Application Laid-Open No. 2007-131832, Quot;

As the carboxylic acid-based dispersant to be used in the present invention, it is preferable to use an ε-caprolactone-based compound and a carboxylic acid-based dispersant obtained by ring-opening addition of a δ-valerolactone-based compound.

The preferred form of the polymer (POH) having at least one hydroxyl group at the terminal thereof or the polymer (PNH ₂ ) having a primary amino group at the terminal of at least one terminal is more preferably represented by the general formula (III) .

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In the general formula (III), Y ¹ represents a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms and 0 to 3 nitrogen atoms, X ² represents -O-, -S-, or - N (R ^b ) -, and R ^b represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms. Z ¹ represents -OH, or -NH ₂ .

G ⁴ and G ⁵ each represent a repeating unit represented by C (= O) R ¹² O-, R ¹² represents a linear or branched alkylene group having 1 to 8 carbon atoms or a cycloalkylene group having 4 to 8 carbon atoms . However, G ⁴ and G ⁵ R ¹² R ¹² of the group of is different. R ²⁰ represents -C (= O) R ¹² . m4 represents an integer of 5 to 60, and m5 represents an integer of 5 to 60; The repeating unit of the general formula (III) G ^4, the arrangement of G ⁵ is not limited to this order, in the polymer represented by the general formula (III), based repeated among the groups Z ¹ and X ² Units G ⁴ and G ⁵ are contained in an arbitrary order, and their repeating units G ⁴ and G ⁵ may be either a random type or a block type.

In the general formula (III), Y is ^1, and Y ¹ and consent of the general formula (II '), are also the same preferable range. When m5 = 0, Y ¹ is preferably a linear or branched alkyl group having 1 to 7 carbon atoms or an ethylenically unsaturated double bond.

In the general formula (III), X ² is and X ² and the consent of the general formula (II '), are also the same preferable range.

In the general formula (III), Z ¹ is synonymous with Z ¹ in the general formula (II '), and the preferable range thereof is also the same.

G ⁴ and G ⁵ each represent a repeating unit represented by C (= O) R ¹² O-, R ¹² represents a linear or branched alkylene group having 1 to 8 carbon atoms or a cycloalkylene group having 4 to 8 carbon atoms . However, G ⁴ and G ⁵ R ¹² R ¹² of the group of is different. G ⁴ and G ⁵ are the same as G ² in the general formula (II '), and preferable ranges are also the same. R ¹² in the general formula (III) is, R ¹² is synonymous with the general formula (II '), it is also the same preferable range.

R ²⁰ represents -C (= O) R ¹² . Wherein R ¹² is R ¹² is synonymous with the general formula (II '), are also the same preferable range.

m4 represents an integer of 5 to 60, preferably an integer of 5 to 50, and more preferably an integer of 10 to 40.

m5 represents an integer of 5 to 60, preferably an integer of 5 to 50, more preferably an integer of 10 to 40. m5 is preferably an integer of 10 to 20 from the viewpoint of low viscosity of the pigment dispersion and storage stability.

As a method of synthesizing the compound represented by the general formula (III), it is possible to synthesize it by a known method. For example, reference can be made to paragraphs 0047 to 0082 of JP-A No. 2007-131832, .

As the carboxylic acid-based dispersant to be used in the present invention, it is preferable to use an ε-caprolactone-based compound and a carboxylic acid-based dispersant obtained by ring-opening addition of a δ-valerolactone-based compound.

In the present invention, a polymer represented by the following general formula (6) may also be used as the polymer (POH) having a hydroxyl group at one terminal or the polymer (PNH ₂ ) having a primary amino group at one terminal.

In general formula (6):

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In the general formula (6), Y ² represents a polymerization terminator of a vinyl polymer, Z ² represents -OH or -NH ₂ , R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group, R ²³ and R ²⁴ are each a hydrogen atom and the other is an aromatic group or -C (= O) -X ⁶ -R ²⁵ (wherein X ⁶ is -O- or -N (R ²⁶ ) , R ²⁵ and R ^{26 each} represent a hydrogen atom or a straight or branched chain having 1 to 18 carbon atoms and an alkyl group which may have an aromatic group as a substituent), X ⁴ represents -OR ²⁷ - or -SR ²⁷ - , R ²⁷ represents a linear or branched alkylene group having 1 to 18 carbon atoms, and n represents an integer of 2 to 50.

Y ² represents a polymerization terminator of a vinyl polymer, and is any known polymerization terminator introduced when the polymerization of an ordinary ethylenically unsaturated monomer is carried out by a conventional method. For example, a group derived from a polymerization initiator, a group derived from a chain transfer agent, a group derived from a solvent, or a group derived from an ethylenically unsaturated monomer. Even if Y ² has any of these chemical structures, the dispersant of the present invention can exert its effect without being affected by the polymerization terminator Y ² . Examples of the polymerization terminator include a carboxylic acid residue and an alcohol residue, and preferably a carboxylic acid residue.

Z ² represents -OH, or -NH ₂ .

R ²¹ and R ²² each represent a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

R ²³ and R ²⁴ are each a hydrogen atom and the other is an aromatic group or -C (= O) -X ⁶ -R ²⁵ wherein X ⁶ is -O- or -N (R ²⁶ ) -).

The aromatic group is preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having 6 to 14 carbon atoms, and more preferably an aromatic group having 6 to 10 carbon atoms. Specific examples thereof include a phenyl group, a naphthyl group, and an anthracene group.

X ⁶ represents -O- or -N (R ²⁶ ) -, R ²⁵ and R ²⁶ each represent a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms which may have an aromatic group as a substituent . As the linear or branched alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl and n-octyl. The aromatic group as a substituent of the alkyl group is preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having 6 to 14 carbon atoms, and more preferably an aromatic group having 6 to 10 carbon atoms. Specific examples thereof include a phenyl group, a naphthyl group, and an anthracene group.

X ⁴ represents a single bond, -OR ²⁷ - or SR ²⁷ -.

R ²⁷ represents a linear or branched alkylene group having 1 to 18 carbon atoms. The alkylene group having 1 to 18 carbon atoms is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms. Specific examples include methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene and hexylene.

n represents an integer of 2 to 50, preferably an integer of 2 to 40, more preferably an integer of 2 to 30.

(Tricarboxylic acid anhydride or tetracarboxylic acid dianhydride)

As the tricarboxylic acid anhydride, first, an aliphatic tricarboxylic acid anhydride or an aromatic tricarboxylic acid anhydride can be mentioned.

Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butane tricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid- , 2-anhydride, and 1,3,4-cyclopentane tricarboxylic acid anhydride.

Examples of the aromatic tricarboxylic acid anhydride include benzene tricarboxylic acid anhydride (1,2,3-benzene tricarboxylic acid anhydride, trimellitic anhydride (1,2,4-benzene tricarboxylic acid anhydride), etc.), naphthalene tricarboxylic acid anhydride , 2,4-naphthalene tricarboxylic acid anhydride, 1,4,5-naphthalene tricarboxylic acid anhydride, 2,3,6-naphthalene tricarboxylic anhydride, 1,2,8-naphthalene tricarboxylic anhydride, etc.), 3,4,4 Biphenyl tricarboxylic acid anhydride, 3, 2'-biphenyl tricarboxylic anhydride, 3, 4'-biphenyl tricarboxylic anhydride, 3, , 4,4'-biphenylmethane tricarboxylic acid anhydride, 3,4,4'-biphenylsulfonicarboxylic acid anhydride, and the like.

When a tricarboxylic acid anhydride is used, the heavy aromatic tricarboxylic acid anhydride is preferred.

Examples of the tetracarboxylic acid dianhydride include an aliphatic tetracarboxylic acid dianhydride, an aromatic tetracarboxylic dianhydride, and a polycyclic tetracarboxylic dianhydride.

Examples of the aliphatic tetracarboxylic acid dianhydride include 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl- 2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,3,5- Tetracarboxy cyclohexane dianhydride, 2,3,5,6-tetracarboxy norbornene dianhydride, 3,5,6-tricarboxy norbornene-2-acetic acid dianhydride, 2,3,4,6- 5-tetrahydrofuran tetracarboxylic acid dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, bicyclo [ ] -Octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride.

Examples of the aromatic tetracarboxylic acid dianhydride include pyromellitic dianhydride, ethylene glycol dianhydride trimellitic acid ester, propylene glycol dianhydride trimellitic acid ester, butyleneglycolic dianhydride trimellitic acid ester, 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfonetetracarboxylic acid 2 Naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,2 ', 3,3'-biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 3 ', 4,4'-biphenyletetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3 ', 4,4'-tetraphenyl (4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis 3,4 -Dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropyl (Triphenylphthalic acid) dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, Bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, (3,4-dicarboxyphenyl) fluorene dianhydride, and 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride.

Examples of polycyclic tetracarboxylic acid dianhydrides include 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, 3,4-dicarboxy- 4-tetrahydro-6-methyl-1-naphthalenesuccinic acid dianhydride and the like.

When a tetracarboxylic acid dianhydride is used, the heavy aromatic tetracarboxylic dianhydride is preferable.

The tricarboxylic acid anhydride or tetracarboxylic acid dianhydride used in the present invention is not limited to the above-exemplified compounds and may have any structure. These may be used alone or in combination. The aromatic tricarboxylic acid anhydride or the aromatic tetracarboxylic acid dianhydride is preferably used in the present invention in view of the low viscosity of the pigment dispersion or various inks. Further, it is also possible to use pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 6,7-naphthalenetetracarboxylic acid dianhydride, ethylene glycol dianhydride trimellitic acid ester, and trimellitic anhydride are preferable.

(Reaction of a polymer (POH) having at least one terminal hydroxyl group or a polymer (PNH ₂ ) having a primary amino group at at least one terminal with a tricarboxylic acid anhydride or tetracarboxylic acid dianhydride)

The carboxylic acid-based dispersant in the present invention can be obtained by copolymerizing a hydroxyl group of a polymer (POH) having at least one terminal hydroxyl group or a hydroxyl group of a polymer (PNH ₂ ) having a primary amino group at at least one terminal thereof Or an anhydride group of a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride.

When the number of moles of the primary amino group of the polymer (POH) or the primary amino group of the polymer (PNH ₂ ) is <H> and the number of moles of the carboxylic acid anhydride group of the tricarboxylic acid anhydride or tetracarboxylic acid dianhydride is <N><H> / <N><1.2, more preferably 0.7 <H> / <N><1.1 and most preferably <H> / <N> = 1. <H> / <N><1, the remaining acid anhydride may be used by hydrolysis with a necessary amount of water.

A catalyst may be used for the reaction of the polymer (POH) or the polymer (PNH ₂ ) with the tricarboxylic acid anhydride or the tetracarboxylic acid dianhydride. As the catalyst, for example, a tertiary amine compound can be used, and examples thereof include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8- - [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene and the like.

The reaction of the polymer (POH) or the polymer (PNH ₂ ) with the tricarboxylic acid anhydride or the tetracarboxylic acid dianhydride may be carried out in the absence of a solvent, or a suitable dehydrated organic solvent may be used. The solvent used in the reaction may be removed by an operation such as distillation after completion of the reaction, or may be used as a part of the product of the dispersant.

The reaction temperature of the polymer (POH) or the polymer (PNH ₂ ) with the tricarboxylic acid anhydride or tetracarboxylic acid dianhydride is preferably 80 ° C or higher, when the "polymer (POH) having at least one hydroxyl group at the terminal" 180 deg. C, and more preferably 90 deg. C to 160 deg. When the reaction temperature is lower than 80 ° C, the reaction rate is slow. When the reaction temperature is higher than 180 ° C, the acid anhydride reacts to form a cyclic anhydride again to make the reaction difficult to complete. When the "polymer (PNH ₂ ) having a primary amino group at at least one end" is used, it is preferably carried out at a temperature in the range of 0 to 150 ° C, more preferably 10 ° C to 100 ° C. When the reaction temperature is lower than 0 ° C, the reaction may not proceed. When the reaction temperature exceeds 150 ° C, imidization may occur.

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

The content of the dispersing agent is preferably 5 to 60 parts by mass, more preferably 9 to 40 parts by mass, per 100 parts by mass of the pigment (A).

The dispersant may be contained in only one kind of the composition of the present invention, or may contain two or more kinds thereof. When two or more kinds are included, the total amount is preferably in the above range.

In addition to the above, other dispersing agents may be included, and the dispersing system described in Japanese Patent Application Laid-Open No. 2013-073104, 0338 to 0333 may be included.

<< (D) Resin binder >>

The composition of the present invention has (D) a resin binder. By adding the resin binder (D), it becomes possible to impart appropriate dispersion stability and alkali developability to the colored photosensitive resin composition of the present invention.

The kind of the resin binder (D) used in the composition of the present invention is not particularly limited. For example, the compound (x) represented by the following formula (IV) and the compound (y) having another ethylenically unsaturated double bond are copolymerized Is preferable.

In general formula (IV)

(53)

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

R ⁵ represents an alkylene group having 2 or 3 carbon atoms, and when n is 2 or more, a plurality of R ^{5 s} may be the same or different.

R ⁶ represents an alkyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or 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. When the number of carbon atoms of the alkyl group represented by R ⁶ is 1 to 10, the alkyl group is obstructed to restrict the approach of the resins to each other to promote the adsorption / orientation to the pigment. When the number of carbon atoms is more than 10, The adsorption / orientation of the ring to the pigment is also inhibited. This tendency becomes remarkable as the carbon chain phase of the alkyl group of R ⁶ becomes longer. When the number of carbon atoms exceeds 20, the adsorption / orientation of the benzene ring is extremely lowered.

Examples of the alkyl group represented by R ⁶ include 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 nonyl group and a decyl group.

Examples of the alkyl group containing a benzene ring represented by R ⁶ include 1-phenylethyl group, 1-phenylpropyl group, 1-phenylbutyl group, 1-phenylpentyl group, 1-phenylhexyl group, 1-phenylheptyl group, An octyl group, a 1-phenylnonyl group, a 1-phenyldecyl group, a benzyl group, and a 2-phenyl (isopropyl) group.

Among them, a benzyl group and a 2-phenyl (isopropyl) group are preferable.

Examples of the compound (x) include an ethylene oxide (EO) modified (meth) acrylate of phenol, an EO or a propylene oxide (PO) modified (meth) acrylate of paracylphenol, an EO modified (meth) acrylate of nonylphenol, And a PO-modified (meth) acrylate of phenol. Among these compounds, EO or PO-modified (meth) acrylate of para-cumylphenol has not only the effect of the π-electron of the benzene ring but also its stereoscopic effect, so that it is possible to form a better adsorption / It is more effective.

Examples of the compound (y) having an ethylenically unsaturated double bond include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) (Meth) acrylate, isophosphoryl (meth) acrylate, isobornyl (meth) acrylate, isobornyl (meth) acrylate, (Meth) acrylate, and acid phosphoxoxypolyethylene glycol mono (meth) acrylate.

The proportion of the compound (x) in the resin (D) in the present invention is 0.1 to 50 mass%, more preferably 10 to 35 mass%. If the proportion of the compound (x) is less than 10 mass%, the effect of dispersing the pigment is deteriorated. If the proportion is less than 0.1 mass%, a sufficient dispersion effect can not be obtained. On the other hand, if it is more than 35% by mass, the hydrophobicity increases, and the developability of the colored photosensitive resin composition may deteriorate or cause residues. On the other hand, if it exceeds 50% by mass, compatibility with other constituents in the colored photosensitive resin composition And the precipitation of the monomer or the photopolymerization initiator may occur.

The weight average molecular weight (Mw) of the resin (copolymer) (D) in the present invention is preferably 5000 to 100000, more preferably 10000 to 50000.

As the compound (y), there may be used an acid phosphoxyethyl (meth) acrylate, an acid phosphoxypropyl (meth) acrylate, a 3-chloro-2-acid phosphoxyethyl (meth) acrylate, an acid phosphoxypolyethylene In the case of using a (meth) acrylic acid ester containing a phosphoric acid group such as glycol mono (meth) acrylate, a higher pigment dispersing effect may be obtained in some cases.

The proportion of the (meth) acrylic ester containing a phosphoric acid group is 0.05 to 10% by mass, more preferably 0.1 to 5% by mass. If the proportion of the (meth) acrylic ester containing a phosphoric acid group is less than 0.05% by mass, a sufficient dispersing effect can not be obtained. On the other hand, if it exceeds 10% by mass, the polarity of the resin increases, the development speed remarkably increases, or the compatibility with other hydrophobic components deteriorates and the resin is precipitated.

In order to improve the sensitivity of the colored photosensitive resin composition, an ethylenic double bond can be introduced into the side chain of the resin (copolymer) (D) of the present invention by reacting monomers or resins with each other. Specifically, when the resin has a reactive functional group such as a hydroxyl group, a functional group reactive with the reactive functional group such as glycidyl (meth) acrylate and 2- (meth) acryloyloxyisocyanate, and an ethylenic An ethylenic double bond is introduced into the side chain by reacting a compound having an unsaturated group.

The production of the resin (D) can be carried out by a known method. For example, reference can be made to paragraphs 0041 to 0045 of Japanese Laid-Open Patent Publication No. 2004-101728, the contents of which are incorporated herein by reference.

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

The resin (D) may be contained in only one kind of the composition of the present invention, or may contain two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.

<(E) Photopolymerization initiator>

The composition of the present invention contains a photopolymerization initiator in view of further improvement in sensitivity.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound to be described later, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have photosensitivity to a visible ray from an ultraviolet ray region. It may also be an activator which generates an action with a photoexcited sensitizer and generates active radicals, or an initiator which initiates cationic polymerization depending on the kind of the monomer.

It is also preferable that the photopolymerization initiator contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, Oxime compounds such as imidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.

From the viewpoint of exposure sensitivity, it is also possible to use a trihalomethyltriazine compound, a benzyldimethylketal compound, an? -Hydroxyketone compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, Oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3 -Aryl-substituted coumarin compound is preferable.

As the trihalomethyltriazine compound, a commercially available product may also be used. For example, TAZ-107 (Midori Kagaku) may be used.

Particularly, when the composition of the present invention is used in the production of a color filter provided in a solid-state imaging device, it is important to form a fine pattern in a sharp shape, so that it is cured and developed with no residue on the unexposed portion . From this viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. Particularly, in the case of forming a fine pattern in a solid-state image pickup device, although stepper exposure is used for curing exposure, this exposure device may be damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator too low, Taking this into consideration, it is most preferable to use an oxime compound as the photopolymerization initiator (E) in order to form a fine pattern such as a solid-state image sensor.

As the halogenated hydrocarbon derivative having the triazine skeleton, the ketone compound, and the photopolymerization initiator other than the above, reference can be made to the compounds described in paragraphs 0074 to 0077 of JP-A No. 2013-077009, Quot;

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, the aminoacetophenone-based initiator disclosed in Japanese Patent Application Laid-Open No. 10-291969 or the acylphosphine oxide-based initiator disclosed in Japanese Patent Publication No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, commercially available IRGACURE-907, IRGACURE-369, IRGACURE-379 and IRGACURE-OXE379 (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source such as 365 nm or 405 nm can be used. As the acylphosphine-based initiator, commercially available IRGACURE-819 and DAROCUR-TPO (trade names, all manufactured by BASF) can be used.

The photopolymerization initiator is more preferably an oxime compound. As specific examples of the oxime compounds, compounds described in JP 2001-233842 A, compounds described in JP-A 2000-80068, and JP 2006-342166 A can be used. As oxime compounds, see J. C. S. Perkin II (1979) pp. 1653-1660), J. C. S. Perkin II (1979) pp. Pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-A 2004-534797, JP-A 2006-342166, etc. .

Also commercially available are IRGACURE-OXE01 from BASF, IRGACURE-OXE02 from BASF and TR-PBG-304 from Changzhou Tronly New Electronic Materials CO., LTD. .

As an oxime compound such as an oxime derivative suitably used as a photopolymerization initiator in the present invention, reference can be made to the compounds described in paragraphs 0080 to 0116 of Japanese Laid-Open Patent Publication No. 2013-077009, the contents of which are incorporated herein.

The oxime 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.

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

The molar extinction coefficient of the compound can be measured using a known method. Specifically, the molar extinction coefficient of the compound can be measured with an ultraviolet visible spectrophotometer (Carry-5 spactrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L By weight.

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

When the (E) photopolymerization initiator is contained in the composition of the present invention, the content of the photopolymerization initiator (E) is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.5% 30 mass% or less, and more preferably 1 mass% or more and 20 mass% or less. Within this range, more excellent sensitivity and pattern formability can be obtained.

<< (F) Polymerizable compound >>

The composition of the present invention contains (F) a polymerizable compound. In the present invention, known polymerizable compounds which can be crosslinked by radicals, acids and heat can be used. For example, polymerizable compounds containing ethylenic unsaturated bonds, cyclic ethers (epoxy, oxetane) . (F) The polymerizable compound is suitably selected from compounds having at least one, and preferably two or more, terminal ethylenic unsaturated bonds from the viewpoint of sensitivity. Of these, polyfunctional polymerizable compounds having four or more functionalities are preferable, and polyfunctional polymerizable compounds having five or more functionalities are more preferable.

Such a group of compounds is well known in the industrial field and can be used in the present invention without particular limitation. These may be, for example, monomers, prepolymers, i.e., chemical forms such as dimers, trimer and oligomers or mixtures thereof and oligomers thereof. The polymerizable compounds in 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 (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like), esters thereof, amides, And amides of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound, and oligomers thereof, preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxide, a monofunctional or polyfunctional A dehydration condensation reaction product with a carboxylic acid, and the like are suitably used. In addition, it is also possible to use an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, an addition reaction product of monofunctional or polyfunctional alcohols, amines, thiols, Unsaturated carboxylic acid esters or amides having a desilyl substituent group and mono- or polyfunctional alcohols, amines and thioes are also suitable. As another example, in place of the above unsaturated carboxylic acid, it is also possible to use a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like.

As such specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A No. 2009-288705 can be suitably used in the present invention.

The polymerizable compound is also preferably a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and a boiling point of at least 100 캜 at normal pressure. As an example thereof, reference can be made to the compound described in paragraph 0124 of Japanese Laid-Open Patent Publication No. 2013-077009, which disclosure is incorporated herein by reference.

As the compound having at least one addition-polymerizable ethylenic unsaturated group having a boiling point of 100 占 폚 or higher at normal pressure, the compounds described in paragraphs [0254] to [0257] of Japanese Laid-Open Patent Publication No. 2008-292970 are also suitable.

In addition to the above, there can be referred to radical polymerizable monomers represented by the general formulas (MO-1) to (MO-5) described in paragraphs 0126 to 0129 of Japanese Patent Laid-Open Publication No. 2013-077009, .

Further, in JP-A 10-62986, ethylene oxide or propylene oxide is added to the polyfunctional alcohol represented by the general formulas (1) and (2) together with the specific examples thereof and then (meth) acrylated The compound can also be used as the polymerizable compound.

Among them, dipentaerythritol triacrylate (KAYARAD D-330, manufactured by Nippon Kayaku Kabushiki Kaisha) and dipentaerythritol tetraacrylate (KAYARAD D-320, Nippon Kaya Co., (Trade name: KAYARAD D-310, manufactured by Nippon Kayaku K.K.), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA; A-DPH-12E manufactured by Nippon Kayaku Co., Ltd., Shin-Nakamura Kagaku Co., Ltd.), and a structure in which these (meth) acryloyl groups interpose ethylene glycol and propylene glycol residues. These oligomer types can also be used. Preferable examples of the polymerizable compound are shown below.

As the polymerizable compound, a polyfunctional monomer may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. If the ethylenic compound has an unreacted carboxyl group as described above, it can be used as it is. However, if necessary, the acid group may be introduced by reacting the hydroxyl group of the above-mentioned ethylenic compound with a nonaromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydrides to be used include anhydrous tetrahydrophthalic acid, alkylated anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, alkylated anhydrous hexahydrophthalic acid, succinic anhydride, and maleic anhydride.

In the present invention, examples of the monomer having an acid group include esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, which are obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride to give an acid group Lt; / RTI &gt;

Particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers made by Toagosei Co., Ltd.

These monomers may be used singly or in combination of two or more in view of difficulty in using a single compound in the production process. If necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as a monomer.

The preferable acid value of the polyfunctional monomer having an acid group is 0.1 mg KOH / g to 40 mg KOH / g, particularly preferably 5 mg KOH / g to 30 mg KOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are deteriorated. If the acid value is too high, the production and handling become difficult, and the photopolymerization performance deteriorates and the curability such as surface smoothness of the pixel becomes poor. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination or when polyfunctional monomers having no acid group are used in combination, it is preferable to adjust the acid groups as the entire polyfunctional monomer to fall within the above range.

It is also preferable that the polymerizable monomer contains a polyfunctional monomer having a caprolactone structure.

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 trimethylolethane, ditrimethylolethane, trimethylolpropane, (Meth) acrylic acid and? -Caprolactone obtained by esterifying polyhydric alcohols such as glycerin, diglycerol, trimethylolmelamine and the like with (meth) acrylic acid and? -Caprolactone, Modified polyfunctional (meth) acrylate. Among them, reference may be made to the compounds described in Japanese Laid-Open Patent Publication No. 2013-077009, paragraphs 0135 to 0153, the contents of which are incorporated herein by reference.

Examples of commercially available products of such polymerizable compounds include SR-494, a tetrafunctional acrylate having 4 ethylene oxycles, manufactured by Satomar Co., Ltd., 6 DPCA-60, which is a functional acrylate, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

The polymerizable compound is described in Japanese Patent Publication No. 48-41708, Japanese Laid-Open Patent Application No. 51-37193, Japanese Laid-Open Patent Application No. 2-32293, and Japanese Laid-Open Patent Publication No. 2-16765 Such as urethane acrylates as described in JP-A-58-49860, JP-A-56-17654, JP-A-62-39417, and JP-A-62-39418 Also suitable are urethane compounds having the ethylene oxide skeleton described therein. As the polymerizable compound described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, a polymer having an amino structure or a sulfide structure By using addition polymerizable compounds, a curable composition having an extremely high photosensitive speed can be obtained.

UA-7200 (manufactured by Shin-Nakamura Kagaku Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H (manufactured by Sanyo Chemical Industries, Ltd.) (Trade name: A-TMPT; manufactured by Shin-Nakamura Kagaku Co., Ltd.), and the like, and the like, .

JER-827, JER-834, JER-1001, JER-1002, JER-1003, and JER-823 as the bisphenol A type epoxy resin having an epoxy group, as the cyclic ether (epoxy, oxetane) EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), and the like, and bisphenol F type epoxy resins such as bisphenol F type epoxy resin (trade name: JER-1055, JER-1007, JER-1009, JER-1010 manufactured by Japan Epoxy Resin Co., (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (manufactured by DIC Co., Ltd.) as the resin, and JER-806, JER-4007, JER-4005, JER- , JER-152, JER-157, JER-157S70, JER-157S65 (as described above, Japan) as the phenol novolak type epoxy resin, EPICLON N-660, EPICLON N-770, EPICLON N-775 (manufactured by DIC Corporation), and the like as the cresol novolak type epoxy resin, EPICLON N-690, EPICLON N-670, EPICLON N-670, EPICLON N-670, EPICLON N-680, EPICLON N-690, (Manufactured by Nippon Kayaku Co., Ltd.), as the aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S and EP-4088S (manufactured by ADEKA Corporation), Celloxide 2021P, Celloxide 2081, 2083, Celloxide 2085, EHPE-3150 (1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) (Manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L and EX- NC-2000, NC-3000, NC-7300, XD-4011S, EP-4011S (manufactured by ADEKA Corporation), ADEKA RESIN EP-4000S, EP- 1000, EPPN-501, EPPN-502 (manufactured by ADEKA) and JER-1031S (manufactured by Japan Epoxy Resin Co., Ltd.). Such a polymerizable compound is suitable for forming a pattern by a dry etching method.

Details of the structure, the use of the polymerizable compound, whether it is used singly or in combination, and the like can be arbitrarily set in accordance with the final performance design of the colored photosensitive resin composition. For example, from the viewpoint of sensitivity, a structure having a large amount of unsaturated groups per molecule is preferable, and in many cases, a bifunctionality or more is preferable. Further, from the viewpoint of enhancing the strength of the cured film formed by the colored photosensitive resin composition, it is preferable to use trifunctional or more functional groups, and the number of functional groups differing from each other may be different (for example, acrylic acid ester, methacrylic acid ester, styrene- A compound) may be used in combination to control both the sensitivity and the strength. Further, it is preferable to use a different polymerizable compound having three or more functional groups on the side of the ethylene oxide chain from the viewpoint that the developability of the colored photosensitive resin composition can be controlled and an excellent pattern forming ability can be obtained.

The compatibility and dispersibility with other components (for example, a photopolymerization initiator, a dispersant, an alkali-soluble resin, etc.) contained in the colored photosensitive resin composition is also an important factor for selecting and using a polymerizable compound. The compatibility may be improved by the use of a low-purity compound or by a combination of two or more species. It is also possible to select a specific structure from the viewpoint of improving adhesion with a hard surface such as a support.

The content of the polymerizable compound (F) in the composition of the present invention is preferably from 0.1% by mass to 90% by mass, more preferably from 1.0% by mass to 50% by mass, more preferably from 2.0% by mass to 2.0% by mass relative to the total solid content in the colored photosensitive resin composition. And particularly preferably from 30% by mass to 30% by mass.

<< Other Ingredients >>

The composition of the present invention may further contain (G) other components such as a resin having a polymerizable double bond in its side chain, an organic solvent and a crosslinking agent, in addition to the above-mentioned respective components, do.

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

In the present invention, a resin having a polymerizable double bond in the side chain (hereinafter also referred to as "(G) resin") may be further contained if necessary. By further containing a resin having a polymerizable double bond in the side chain (G), it becomes possible to more effectively cure the composition of the present invention. The polymerizable double bond is preferably (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. However, the polymerizable monomer (p) having 2 to 6 hydroxyl groups and the other polymerizable monomer (q) Is reacted with a compound (b) having a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated double bond in the copolymer (a).

(G) The polymerizable monomer (p) having 2 to 6 hydroxyl groups constituting the resin having a polymerizable double bond in the side chain is a compound having 2 to 6 hydroxyl groups and an ethylenically unsaturated double bond, A monomer represented by the following general formula (1) can be used.

In general formula (1)

(54)

(Wherein R ¹ and R ⁴ each represent a hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms, R ² represents an alkylene group having 1 to 4 carbon atoms, R ³ represents an alkylene group having 1 to 4 carbon atoms, Or a single bond, and n represents an integer of 2 or more and 6 or less.

Examples of the monomer represented by the general formula (1) include a monoester of a polyhydric alcohol having an ethylenically unsaturated double bond, and glycerol mono (meth) acrylate is preferable.

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, methyl (meth) acrylate, ethyl (Meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert- Acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethylhexyl (Meth) acrylic acid esters such as tetrahydrofuran (meth) acrylate and tetrahydrofurfuryl (meth) acrylate; N-vinylpyrrolidone; Styrene and its derivatives, styrene such as? -Methylstyrene; Acrylamides such as (meth) acrylamide, methylol (meth) acrylamide, alkoxymethylol (meth) acrylamide and diacetone (meth) acrylamide; (Meth) acrylonitrile, other vinyl compounds such as ethylene, propylene, butylene, vinyl chloride and vinyl acetate, and macromonomers such as polymethyl methacrylate macromonomer and polystyrene macromonomer. These monomers may be used singly or in combination of two or more.

The copolymerization ratio of the polymerizable monomer (p) having 2 to 6 hydroxyl groups and the other polymerizable monomer (q) is preferably 5 to 95 mass%: 95 to 5 mass%, more preferably 30 to 70 mass% And more preferably 70 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 that can be introduced is small and the numerical value of the double bond equivalent (double bond equivalent defined by the following formula) becomes large, I can not get it. When the copolymerization ratio of the polymerizable monomer (p) is more than 95% by mass, it is possible to introduce a large number of ethylenically unsaturated double bonds. However, since the proportion of the polymerizable monomer (q) is low, dispersion stability, solubility, And the like.

The preparation of the copolymer (a) of the polymerizable monomer (p) having 2 to 6 hydroxyl groups and the other polymerizable monomer (q) can be carried out by a known method, for example, Japanese Patent Laid- 156930, the contents of which are incorporated herein by reference.

(G) A resin having a polymerizable double bond in a side chain is obtained by reacting the copolymer (a) with a compound (b) having a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated double bond. Examples of the functional group capable of reacting with the hydroxyl group of the compound (b) having a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated double bond include an isocyanate group and a carboxyl group. Among them, an isocyanate group Do.

Specific examples of the compound having an isocyanate group and an ethylenically unsaturated double bond include 2-acryloylethyl isocyanate and 2-methacryloyl ethyl isocyanate. 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) through the hydroxyl group is indicated by the "double bond equivalent" of the resulting resin. The double bond equivalent is a measure of the amount of double bonds contained in the molecule. If the photosensitive resin has the same molecular weight, the smaller the value of the double bond equivalent is, the larger the amount of double bonds introduced.

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

The double bond equivalent of the resin (G) in the present invention is preferably 200 to 2,000, more preferably 300 to 900. When the double bond equivalent of the (G) resin is less than 200, the proportion of the polymerizable monomer (p) introducing the ethylenically unsaturated double bond is increased, and the polymerizable monomer (q) in an amount sufficient to maintain the property is copolymerized I can not. When it exceeds 2,000, sufficient sensitivity can not be obtained because the number of ethylenically unsaturated double bonds is small.

The weight average molecular weight (Mw) of the (G) resin is preferably 2000 to 200000, and more preferably 5000 to 50000 from the viewpoint of good dispersibility of the composition of the present invention.

The reaction of the copolymer (a) with a compound (b) having a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated double bond can be carried out by a known method. For example, in Japanese Patent Application Laid-Open No. 2005-156930 , The contents of which are incorporated herein by reference.

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

(G) The resin having a polymerizable double bond in the side chain may be contained in only one kind of the composition of the present invention, or may contain two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.

- Alkali soluble resin -

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

As the alkali-soluble resin, a linear organic polymer can be appropriately selected from an alkali-soluble resin having at least one group capable of promoting alkali solubility in a molecule (preferably an acrylic copolymer, a styrene-based copolymer as a main chain) . From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin and an acryl / acrylamide copolymer resin are preferable. From the viewpoint of development control, an acrylic resin, an acrylamide resin , An acrylic / acrylamide copolymer resin is preferable.

As the alkali-soluble resin, for example, reference can be made to the alkali-soluble resin described in paragraphs 0179 to 0208 of JP-A-2013-077009, the content of which is incorporated herein by reference.

As the alkali-soluble resin, reference can be made to the following description in Japanese Laid-Open Patent Publication No. 2012-208494, paragraphs 0558 to 0571 (corresponding to United States Patent Application Publication No. 2012/0235099 [0685] to [0700]), Are incorporated herein by reference.

The copolymer (B) described in paragraphs [0029] to [0063] of JP-A No. 2012-32767 and the alkali-soluble resin used in the examples, the binder resin described in paragraphs 0088 to 0098 of JP-A No. 2012-208474 And the binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of Japanese Laid-Open Patent Publication No. 2012-137531 and the binder resin used in the examples, and Japanese Patent Application Laid-Open No. 2013-024934, paragraphs 0132 to 0143 And binder resins used in the examples, paragraphs 0092 to 0098 of Japanese Laid-Open Patent Publication No. 2011-242752 and binder resins used in the examples, paragraphs 0030 to 0072 of JP-A No. 2012-032770 Is preferably used as the binder resin. The contents of which are incorporated herein by reference.

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

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and most preferably 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 1% by mass to 15% by mass, more preferably 2% by mass, To 12% by mass, and 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 of alkali-soluble resins. When two or more kinds are included, the total amount is preferably in the above range.

- Organic solvents -

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

The organic solvent is not particularly limited so long as it satisfies the solubility of each component and the coatability of the colored photosensitive resin composition, but is selected in consideration of the solubility, coatability, and safety of an ultraviolet absorber, an alkali- desirable. In order to prepare the composition of the present invention, it is preferable to include at least two kinds of organic solvents.

Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, butyl lactate, Ethyl lactate, alkyloxyacetate (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ), 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate, ethyl 3-oxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, etc.)), 2-oxypropionic acid alkyl esters (such as methyl 2-oxypropionate, ethyl 2-oxypropionate, Methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-oxy-2 (2-methoxypropionate, Methyl propionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate and the like), methyl pyruvate, ethyl pyruvate, Propyl acetate, methyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate and ethyl 2-oxobutanoate, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Lycol monobutyl ether, pro Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and ketones such as methyl ethyl ketone, methyl ethyl ketone, Cyclohexanone, 2-heptanone, 3-heptanone, and the like, and aromatic hydrocarbon, for example, toluene, xylene, cyclopentanone, and the like.

From the viewpoints of solubility of the ultraviolet absorber and the alkali-soluble resin, and improvement of the shape of the coated surface, these organic solvents are also preferably mixed with two or more kinds. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3- A mixed solution composed of two or more kinds selected from methyl propionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate to be.

The content of the organic solvent in the composition is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 60% by mass, and more preferably 5% by mass to 10% by mass, And particularly preferably from 50% by mass to 50% by mass.

- Cross-linking agent -

By using a crosslinking agent as a complement to the composition of the present invention, the hardness of the cured film obtained by curing the composition can be further increased.

The crosslinking agent is not particularly limited as long as it can perform film curing by a crosslinking reaction. Examples of the crosslinking agent include (a) an epoxy resin, (b) at least one substituent selected from a methylol group, an alkoxymethyl group and an acyloxymethyl group A phenol compound, a naphthol compound or a hydrolyzate substituted with at least one substituent selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group; (c) And a hydroxyanthracene compound. Among them, a polyfunctional epoxy resin is preferable.

Details of specific examples of crosslinking agents and the like can be found in paragraphs 0134 to 0147 of Japanese Laid-Open Patent Publication No. 2004-295116.

When the crosslinking agent is contained in the composition of the present invention, the blending amount of the crosslinking agent is not particularly limited, but is preferably from 2 to 30 mass%, more preferably from 3 to 20 mass%, of the total solid content of the composition.

The composition of the present invention may contain only one kind of crosslinking agent or two or more kinds of crosslinking agents. When two or more kinds are included, the total amount is preferably in the above range.

- Polymerization inhibitor -

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

Examples of the polymerization inhibitor usable in the present invention include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'- (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N- have.

When the polymerization inhibitor is contained in the composition of the present invention, the addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the whole composition.

The composition of the present invention may contain only one kind of polymerization inhibitor or two or more kinds thereof. When two or more kinds are included, the total amount is preferably in the above range.

-Surfactants-

Various surfactants may be added to the composition of the present invention from the viewpoint of further improving the applicability.

As the surfactant, various surfactants such as a fluorine surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

Particularly, since the composition of the present invention contains a fluorine-containing surfactant, the liquid properties (particularly, fluidity) when the coating liquid is prepared can be further improved, and the uniformity of coating thickness and the liquid- Can be further improved.

That is, in the case of forming a film by using a coating liquid to which a composition containing a fluorine-containing surfactant is applied, wettability to the surface to be coated is improved by lowering the interfacial tension between the surface to be coated and the coating liquid, . Thus, even when a thin film of about several micrometers is formed in a small amount of liquid, it is effective in that it is possible to more appropriately form a film having a uniform thickness with a small thickness deviation.

The fluorine content in the fluorine surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. The fluorine-containing surfactant having a fluorine content within this range is effective from the viewpoint of the uniformity of the thickness of the coating film and the lyophobic property, and the solubility in the composition is also good.

Examples of the fluorine-based surfactant include Megapak F171, Dong F172, Dong F173, Dong F176, Dong F177, Dong F141, Dong F142, Dong F143, Dong F144, Dong R30, Dong F437, Dong F475, Dong F479, Dong F482 (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, and SC-101 (manufactured by Sumitomo 3M Limited), F554, F780, and F781 (manufactured by DIC Corporation), Fluorad FC430, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393 and KH-40 (manufactured by Asahi Glass Co., Ltd.) have.

Specific examples of the nonionic surfactant include glycerol, trimethylol propane, trimethylol ethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate and the like), polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diallylate, polyethylene glycol Diisostearate and consumptive fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904 and 150R1 from BASF) Ltd.) and the like.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) Acrylic acid-based (co) polymer Polflor No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusoh Co., Ltd.).

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

Examples of silicon based surfactants include fluororesins such as "TORAY Silicon DC3PA", "TORAY Silicone SH7PA", "TORAY Silicon DC11PA", "TORAY Silicone SH21PA", "TORAY Silicone SH28PA", "DORAY Silicone SH29PA "TSF-4440", "TSF-4445", "TSF-4460", "TSF-4440", "TSF- KP341 ", " KF6001 ", "KF6002 ", manufactured by Shin-Etsu Silicone Co., Ltd., BYK307, BYK323 and BYK330 manufactured by Big Chemie.

Only one surfactant may be used, or two or more surfactants may be combined.

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

The composition of the present invention may contain only one kind of surfactant or two or more kinds of surfactants. When two or more kinds are included, the total amount is preferably in the above range.

- Other additives -

In the composition of the present invention, various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, antiflocculants and the like may be added as necessary. Examples of the additives include those described in paragraphs 0155 to 0156 of Japanese Patent Application Laid-Open No. 2004-295116. The composition of the present invention may contain a sensitizer or light stabilizer described in paragraph 0078 of Japanese Patent Application Laid-Open No. 2004-295116, or a thermal polymerization inhibitor described in paragraph 0081 of the same publication. As the ultraviolet absorber, specifically, the following compounds are preferably used.

(55)

- an organic carboxylic acid, an organic carboxylic acid anhydride-

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

Specific examples of the organic carboxylic acid compound include an aliphatic carboxylic acid and 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, pivalic acid, caproic acid, glycolic acid, acrylic acid and methacrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid , Dicarboxylic acids such as adipic acid, fumaric acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, tricarbalic acid and tricarboxylic acids such as aconitic acid, . Examples of the aromatic carboxylic acid include a carboxylic acid in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid or phthalic acid, and a carboxylic acid in which a carboxyl group is bonded through a carbon bond from a phenyl group. Among these, particularly preferred are those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically, 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, anhydrous trichloroacetic acid, trifluoroacetic anhydride, anhydrous tetrahydrophthalic acid, N-octadecyl succinic anhydride, anhydrous 5-norbornene-2,3-dicarboxylic acid, and the like can also be used in the presence of an acid anhydride such as maleic anhydride, citraconic anhydride, itaconic anhydride, anhydroglutaric acid, And an aliphatic carboxylic acid anhydride. Examples of the aromatic carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and anhydrous naphthalic acid. Among these, particularly preferred are those having a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, such as maleic anhydride, succinic anhydride, citraconic anhydride and itaconic anhydride.

When the composition of the present invention contains an organic carboxylic acid or an organic carboxylic acid anhydride, the addition amount of these organic carboxylic acid and / or organic carboxylic acid anhydride is usually 0.01 to 10% by mass, preferably 0.03 to 5% by mass, And preferably 0.05 to 3% by mass.

By adding these organic carboxylic acids and / or organic carboxylic anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the remnant of the undissolved product of the composition while maintaining high pattern adhesion.

&Lt; Preparation method of colored photosensitive resin composition &gt;

The composition of the present invention is prepared by mixing the above-mentioned components.

Further, at the time of preparation of the composition, each component constituting the composition may be blended at one time, or each component may be blended in succession after being dissolved and dispersed in a solvent. In addition, the order of application and the working conditions at the time of compounding are not particularly limited. For example, the composition may be prepared by dissolving and dispersing the entire components in a solvent at the same time. If necessary, the components may be appropriately prepared as two or more solutions and dispersions, and they may be mixed at the time of use .

The composition prepared as described above is preferably filtered and separated by using a filter having a pore diameter of 0.01 to 3.0 m, more preferably a pore diameter of about 0.05 to 0.5 m, .

The composition of the present invention is suitably used for forming a coloring pattern (coloring layer) of a color filter because a cured film having excellent heat resistance and color characteristics can be formed. The composition of the present invention can be suitably used for forming a coloring pattern of a solid-state imaging element (for example, a CCD, a CMOS or the like) or a color filter used for an image display apparatus such as a liquid crystal display have. In addition, it can be suitably used for producing printing ink, inkjet ink, and paint. Among them, it can be suitably used for the production of color filters for solid-state image pickup devices such as CCD and CMOS.

&Lt; Cured Film, Pattern Forming Method, Color Filter, and Manufacturing Method of Color Filter &gt;

Next, the colored cured film, the pattern forming method and the color filter according to the present invention will be described in detail with reference to their production methods.

The pattern forming method of the present invention comprises a step of forming a colored photosensitive composition layer by providing a colored photosensitive resin composition (hereinafter also referred to as "colored composition layer") by applying the colored photosensitive resin composition of the present invention onto a support, An exposure step of exposing the layer in a pattern shape, and a pattern forming step of forming a colored pattern by removing the unexposed portion.

The pattern forming method of the present invention can be suitably applied to the formation of a colored pattern (pixel) of a color filter.

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 in addition to a plate-like member such as a substrate.

Hereinafter, each step in the pattern forming method of the present invention will be described in detail with reference to a method of manufacturing a color filter for a solid-state imaging device, but the present invention is not limited to this method.

The method of producing a color filter of the present invention is to apply the pattern forming method of the present invention and includes a step of forming a coloring pattern on a support using a pattern forming method.

That is, the method of manufacturing a color filter of the present invention is a method of applying the pattern forming method of the present invention, and includes the steps of forming a colored photosensitive composition layer by applying the colored photosensitive composition of the present invention onto a support, And a step of forming a colored pattern by removing the unexposed portion by development.

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

The color filter of the present invention can be suitably obtained by the above production method.

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

Each step in the pattern forming method of the present invention will be described in detail below with reference to a method for producing a color filter of the present invention.

&Lt; Step of forming colored photosensitive resin 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.

Examples of the support that can be used in the present step include a solid-state imaging device (solid-state imaging device) provided with an imaging element (light-receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) A substrate for a device can be used.

The coloring pattern in the present invention may be formed on the imaging element formation surface side (surface) of the substrate for the solid-state imaging element, or on the imaging element formation surface side (back surface).

The color pattern of the solid-state imaging element or the back surface of the substrate for a solid-state imaging element may be provided with a light-shielding film.

If necessary, an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing diffusion of substances, or planarizing the surface of the substrate.

As the application method of the composition of the present invention on the support, various coating methods such as slit coating, inkjet coating, spin coating, flex coating, roll coating, screen printing and the like can be applied.

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

<< Step of exposing the colored photosensitive resin composition layer to a pattern (when pattern is formed by photolithography method) >>

- Exposure process -

In the exposure step, the colored photosensitive composition layer formed in the step of forming the colored photosensitive composition layer is subjected to pattern exposure through a mask having a predetermined mask pattern by using an exposure apparatus such as a stepper. Thus, a cured film is obtained.

As the radiation (light) usable at the time of exposure, ultraviolet rays such as g-line and i-line are preferably used (particularly preferably i-line). Irradiation dose (exposure dose) is most preferably ^{30mJ / cm 2 ~ 1500mJ / cm} 2 is preferably 50mJ / cm ² ~ 1000mJ / cm ^2, and more ^{preferably, 80mJ / cm 2 ~ 500mJ /} cm 2 (a)

The thickness of the cured film is preferably 1.0 占 퐉 or less, more preferably 0.1 占 퐉 to 0.9 占 퐉, and further preferably 0.2 占 퐉 to 0.8 占 퐉.

By setting the film thickness to 1.0 m or less, high resolution and high adhesion can be obtained, which is preferable.

In this step, a cured film having a thin film thickness of 0.7 m or less can be suitably formed, and the cured film thus obtained is subjected to development processing in a pattern forming step described later, whereby the cured film can be formed into a thin film, , And a colored pattern excellent in the pattern shape can be obtained.

<<< Step of forming a colored pattern >>>

Next, by carrying out the alkali developing treatment, the colored photosensitive resin composition layer in the irradiated portion in the exposure step is eluted into the aqueous alkaline solution, leaving only the photo-cured portion.

As the developing solution, an organic alkali developing solution which does not cause damage to the imaging element, circuit, etc. on the ground (base) is preferable. The developing temperature is usually 20 to 30 DEG C, and the developing time is conventionally 20 to 90 seconds. In order to remove the residues, it is sometimes carried out 120 to 180 seconds in recent years. Furthermore, in order to further improve the removability of the residue, the step of removing the developing solution every 60 seconds and newly supplying the developing solution may be repeated a number of times.

Examples of the alkali agent used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , Benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo- [5,4,0] -7-undecene, and these alkaline agents An alkaline aqueous solution diluted with pure water to a concentration of 0.001 mass% to 10 mass%, preferably 0.01 mass% to 1 mass% is preferably used as the developer.

As the developing solution, an inorganic alkali may be used. As the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate and the like are preferable.

When a developer comprising such an alkaline aqueous solution is used, it is generally cleaned (rinsed) with purified water after development.

Next, it is preferable to carry out a heat treatment (post-baking) after drying. If a multicolor colored pattern is formed, the above-mentioned steps may be repeated for each color in order to produce a cured film. As a result, a color filter is obtained.

The post-baking is a post-development heat treatment for making the curing to be complete, and is generally subjected to a heat curing treatment at 100 캜 to 240 캜, preferably at 200 캜 to 240 캜.

The post-baking treatment can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot-air circulation type drier), a high-frequency heater or the like so as to achieve the above-

<< Process for forming a photoresist layer, process for obtaining a resist pattern, and process for dry etching (when a pattern is formed by a dry etching method) >>

The dry etching can be performed using an etching gas using the patterned photoresist layer as a mask. Specifically, a positive or negative radiation sensitive composition is coated on the colored layer obtained by curing the colored photosensitive resin composition layer, and this is dried to form a photoresist layer. In forming the photoresist layer, it is preferable to further perform prebaking treatment. Particularly, as the photoresist layer forming process, it is preferable to perform the post-exposure baking (PEB) and the post-baking baking (post-baking).

As the photoresist, for example, a positive radiation-sensitive composition is used. Examples of the positive radiation sensitive composition include those suitable for positive photoresists sensitive to radiation such as deep ultraviolet rays including ultraviolet rays (g line, h line, i line), excimer laser, electron beam, ion beam and X ray A positive resist composition can be used. Among the radiation, g line, h line and i line are preferable, and among them, i line is preferable.

Specifically, as the positive radiation sensitive composition, a composition containing a quinone diazide compound and an alkali-soluble resin is preferable. A positive radiation-sensitive composition containing a quinone diazide compound and an alkali-soluble resin is decomposed by irradiation with light having a wavelength of 500 nm or less to generate a carboxyl group and consequently to be alkali-soluble . This positive type photoresist has remarkably excellent resolving power and is used in the production of integrated circuits such as IC and LSI. As the quinone diazide compound, a naphthoquinone diazide compound can be mentioned. Examples of commercially available products include FHi622BC (manufactured by Fuji Film Electronics Materials Co., Ltd.) and the like.

The thickness of the photoresist layer is preferably 0.1 to 3 占 퐉, more preferably 0.2 to 2.5 占 퐉, and still more preferably 0.3 to 2 占 퐉. The formation of the photoresist layer by coating can be suitably performed by using the coating method in the above-described colored layer.

Next, the photoresist layer is exposed and developed to form a resist pattern (patterned photoresist layer) provided with a resist through-air group. The formation of the resist pattern can be performed by suitably optimizing the conventionally known technique of the photolithography without particular limitation. A resist through-air group is provided in the photoresist layer by exposure and development, whereby a resist pattern as an etching mask used in the next etching is provided on the colored layer.

The exposure of the photoresist layer can be performed by exposing the positive or negative radiation sensitive composition to a g-line, h-line or i-line, preferably i-line, through a predetermined mask pattern. After the exposure, the photoresist is removed in accordance with the region where the coloring pattern is to be formed by developing with a developer.

The developing solution may be any solution as far as it dissolves the exposed portion of the positive resist and the uncured portion of the negative resist without affecting the colored layer containing the colorant. For example, a combination of various organic solvents or an alkaline aqueous solution may be used . As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving the alkaline compound in an amount of 0.001 to 10 mass%, preferably 0.01 to 5 mass%, is suitable. The alkaline compound may be, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide , Choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, and the like. When an alkaline aqueous solution is used as a developing solution, cleaning treatment is generally performed with water after development.

Next, using the resist pattern as an etching mask, patterning is performed by dry etching so that a through-air group is formed in the colored layer. Thus, a colored pattern is formed. The penetrating air group is provided on the colored layer in the form of a checkerboard. Therefore, the first coloring pattern formed by providing the through-air group in the colored layer has a plurality of rectangular colored first colored pixels in the form of a checkerboard.

The dry etching is preferably performed in the following manner, from the viewpoint of forming the cross-section of the pattern closer to a rectangle or further reducing the damage to the support.

(N ₂ ) and oxygen (N ₂ ) after the first-stage etching and a first-step etching in which a mixed gas of a fluorine-based gas and an oxygen gas (O ₂ ) It is preferable to use a mixed gas of gas (O ₂ ) and a mode including a second-step etching for performing etching to a region (depth) where the support is exposed, and an over-etching to be performed after the support is exposed. Hereinafter, a specific method of dry etching, first-stage etching, second-stage etching, and over-etching will be described.

Dry etching is performed by obtaining etching conditions in advance by the following method.

(1) The etching rate (nm / min) in the first-stage etching and the etching rate (nm / min) in the second-stage etching are respectively calculated. (2) The time for etching the desired thickness by the first-stage etching and the time for etching the desired thickness by the second-stage etching are respectively calculated. (3) The first-stage etching is performed according to the etching time calculated in (2) above. (4) The second-stage etching is performed in accordance with the etching time calculated in (2) above. Alternatively, the etching time may be determined by end point detection, and the second-step etching may be performed according to the determined etching time. (5) Overetching time is calculated for the total time of (3) and (4), and overetching is performed.

As the mixed gas used in the first step etching step, it is preferable to include a fluorine-based gas and oxygen gas (O ₂ ) from the viewpoint of processing the organic material as the etching film into a rectangular shape. In addition, the first-stage etching step may be performed so as to etch to a region where the support is not exposed, so that damage to the support can be avoided. The second etching step and the overetching step may be performed after the first etching step has been performed to a region where the support is not exposed by the mixed gas of the fluorine gas and the oxygen gas, , A mixed gas of nitrogen gas and oxygen gas is preferably used for the etching treatment.

It is important that the ratio of the etching amount in the first step etching step to the etching amount in the second step etching step is determined so as not to inhibit the rectangularity by the etching treatment in the first step etching step. The latter ratio in the total etching amount (the sum of the etching amount in the first-stage etching step and the etching amount in the second-step etching step) is preferably in the range of more than 0% and not more than 50% 20% is more preferable. The etching amount refers to an amount calculated from the difference between the film thickness where the etched film remains and the film thickness before etching.

It is preferable that the etching includes an overetching treatment. The overetching treatment is preferably performed by setting an overetching ratio. The overetching ratio is preferably calculated from the first etching treatment time. The overetching ratio can be arbitrarily set, but from the viewpoint of the etching resistance of the photoresist and the maintaining of the rectangularity of the etched pattern, it is preferably 30% or less of the etching treatment time in the etching step, more preferably 5 to 25% , And particularly preferably 10 to 15%.

Next, the resist pattern (i.e., etching mask) remaining after etching is removed. The removal of the resist pattern preferably includes a step of applying a removing liquid or a solvent to the resist pattern to bring the resist pattern into a removable state and a step of removing the resist pattern by using washing water.

Examples of the step of applying a releasing liquid or a solvent to the resist pattern to remove the resist pattern include a step of applying at least a peeling liquid or a solvent on the resist pattern to paddle the resist pattern for a predetermined time, . The time for stagnating the peeling liquid or the solvent is not particularly limited, but is preferably several tens seconds to several minutes.

Examples of the step of removing the resist pattern using the washing water include a step of spraying washing water onto the resist pattern from a spraying nozzle or a shower type spraying nozzle to remove the resist pattern. As the washing water, pure water can be preferably used. As the injection nozzle, there can be mentioned a spray nozzle including the entire support within its spray range, and a spray nozzle having a movable range of its movable range including the entire support. When the spray nozzle is of the movable type, the resist pattern can be more effectively removed by moving the cleaning fluid from the center of the support to the end of the support more than twice during the process of removing the resist pattern.

The peeling liquid generally contains an organic solvent, but may further contain an inorganic solvent. Examples of the organic solvent include organic solvents such as 1) hydrocarbon-based compounds, 2) halogenated hydrocarbon-based compounds, 3) alcohol compounds, 4) ether or acetal compounds, 5) ketones or aldehyde compounds, A polyol compound, 7) a polyhydric alcohol compound, 8) a carboxylic acid or an acid anhydride compound, 9) a phenol compound, 10) a nitrogen compound, 11) a sulfur compound, 12) a fluorine compound. The release liquid preferably contains a nitrogen-containing compound, and more preferably includes an uncyclosed nitrogen compound and a cyclic nitrogen compound.

The non-cyclic nitrogen compound is preferably a non-cyclic nitrogen compound having a hydroxyl group. Specific examples thereof include mono isopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, Triethanolamine, and the like. Monoethanolamine, diethanolamine and triethanolamine are preferable, and monoethanolamine (H ₂ NCH ₂ CH ₂ OH) is more preferable. Examples of cyclic nitrogen compounds include isoquinoline, imidazole, N-ethylmorpholine, epsilon -caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, , pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, pyrrolidine, Pyridine, 2,4-lutidine, 2,6-lutidine and the like, preferably N-methyl-2-pyrrolidone and N-ethylmorpholine, 2-pyrrolidone (NMP).

It is preferable that the exfoliating liquid contains a non-cyclic nitrogen compound and a cyclic nitrogen compound. Among them, as the non-cyclic nitrogen compound, at least one selected from monoethanolamine, diethanolamine, and triethanolamine, , And as the cyclic nitrogen compound, at least one selected from N-methyl-2-pyrrolidone and N-ethylmorpholine is more preferable, and monoethanolamine and N-methyl- It is more preferable to include them.

In the case of removing with the exfoliation liquid, it is sufficient that the resist pattern formed on the first colored pattern is removed, and even when the deposit (deposit) as an etching product adheres to the side wall of the first colored pattern, do. The sediment means that the etching product adheres to the side wall of the colored layer and is deposited.

As for the exfoliation liquid, it is preferable that the content of the non-cyclic nitrogen compound is 9 parts by mass or more and 11 parts by mass or less with respect to 100 parts by mass of the exfoliation liquid, and the content of the cyclic nitrogen compound is 65 parts by mass or more to 70 parts by mass By mass or less. It is preferable that the exfoliating liquid is a mixture of the non-cyclic nitrogen compound and the cyclic nitrogen compound diluted with pure water.

Further, the manufacturing method of the present invention may have a known process as a manufacturing method of a color filter for a solid-state image pickup device, as necessary, as the other processes described above. For example, the curing step may include a curing step of curing the coloring pattern formed by heating and / or exposure, if necessary, after the step of forming a colored photosensitive composition layer, the step of exposing, and the step of forming a pattern.

In addition, when the composition of the present invention is used, for example, clogging of nozzles and piping of the dispenser discharge portion, contamination due to deposition, sedimentation and drying of the coloring composition or pigment into the dispenser may occur. Therefore, in order to efficiently clean the contamination caused by the composition of the present invention, it is preferable to use the above-mentioned solvent relating to the present composition as a cleaning liquid. Also, Japanese Patent Application Laid-Open Nos. 7-128867, 7-146562, 8-278637, 2000-273370, 2006-85140, The cleaning liquids described in JP-A-2006-291191, JP-A-2007-2101, JP-A-2007-2102 and JP-A-2007-281523 are also suitable as cleaning liquids for the composition of the present invention Can be used.

Among these, alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoalkyl ethers are preferred.

These solvents may be used alone or in combination of two or more. When mixing two or more species, it is preferable 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. It is particularly preferable that the mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) has a ratio of 60/40. Further, in order to improve the permeability of the cleaning liquid to the contaminants, the above-described surfactant relating to the present composition may be added to the cleaning liquid.

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 colored pattern (colored pixel) formed is excellent in pattern shape, And the color characteristic is excellent in that the residue in the developing portion is suppressed.

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

The thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 占 퐉 or less, more preferably 1.0 占 퐉 or less, and even more preferably 0.7 占 퐉 or less.

The size (pattern width) of the coloring pattern (coloring pixel) is preferably 2.5 占 퐉 or less, more preferably 2.0 占 퐉 or less, and particularly preferably 1.7 占 퐉 or less.

[Solid-state image pickup device]

The solid-state image pickup device of the present invention includes the above-described color filter of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it has the color filter according to the present invention and functions as a solid-state imaging device.

A plurality of photodiodes constituting a light receiving area of a solid-state image sensor (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode composed of polysilicon or the like are formed on a support, and on the photodiode and the transfer electrode, And a device shielding film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion. The device protective film is provided with the color filter for solid- Filter.

Further, the device protective layer may be provided with a condensing means (for example, a microlens or the like hereinafter) on the lower side of the color filter (near the support) or a condensing means on the color filter .

[Image display device]

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

The definition of the display device and the details of each display device are described in detail, for example, in "Electronic Display Device (Sasaki Akio Kogyo Co., Ltd., Sakai, 1990 issued)", "Display Device (Ibukisumi Akira, Note) published in the first half of the year). The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Uchida Tatsuo, published by Sakai High School Co., Ltd. in 1994) ". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention can be applied to various types of liquid crystal display devices described in the "next generation liquid crystal display technology ".

The color filter of the present invention may be used in a color TFT type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, "Color TFT liquid crystal display (published by Kyoritsu Publishing Co., Ltd.) ". The present invention can also be applied to a liquid crystal display device such as a transverse electric field driving system such as an IPS or a pixel division system such as an MVA or an STN, TN, VA, OCS, FFS and R-OCB .

In addition, the color filter in the present invention can be used for a color-filter on array (COA) method which is bright and high definition. In the COA type liquid crystal display device, the required characteristics for the color filter layer may require the characteristics required for the interlayer insulating film, that is, the low dielectric constant and the peel liquid resistance, in addition to the above-mentioned usual required characteristics. The color filter of the present invention uses a dye multimer having excellent color, and is excellent in color purity, light transmittance and the like and excellent in the color tone of a colored pattern (pixel). Therefore, the COA type liquid crystal display Device can be provided. 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 in, for example, page 43 of "EL, PDP, and LCD display technology and the latest trend in the market" (published by Toray Research Center Research Division, 2001).

The liquid crystal display device provided with the color filter in the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle compensation film in addition to the color filter in the present invention. The color filter of the present invention can be applied to a liquid crystal display device constituted by these known members. As for these members, for example, "Market of liquid crystal display peripheral materials, Chemicals (market issued by Shimada Kentaro Co., Ltd. in 1994)", "2003 Present condition and future prospect of liquid crystal related market (Issued by Fuji Chimera Soken Co., Ltd., 2003).

The backlight is described in SID meeting Digest 1380 (2005) (A. Konnoet. Al.), Monthly Display December 2005, pages 18-24 (Yoshihiro Shimaya), 25-30 pages (Yagi Takaaki) have.

When the color filter according to the present invention is used in a liquid crystal display device, high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, and LED light sources (RGB-LEDs) of red, As the light, it is possible to provide a liquid crystal display device having high luminance, high color purity, and good color reproducibility.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts to be used, the ratios, the contents of the treatments, the processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. Unless otherwise stated, "%" and "part" are based on mass.

&Lt; Synthesis of Phosphoric Acid Dispersant (C-1) &gt;

Synthesis Example 1

To the reaction vessel equipped with a cooling tube, a nitrogen gas introducing tube and a stirrer was charged 18.6 g of lauryl alcohol (manufactured by Nacalai Tesque KK), 57.1 g of? -Caprolactone monomer (manufactured by Wako Pure Chemical Industries, Ltd.) And 0.06 g of tetrabutyltitanate (manufactured by TOKYO KASEI KABUSHIKI KAISHA) were introduced, the inside of the reaction vessel was replaced with nitrogen gas, and the mixture was heated and stirred at 120 DEG C for 3 hours. The disappearance of the lactone monomer was confirmed by ¹ H-NMR. After the reaction solution was cooled to room temperature, it was mixed with 8.45 g of 116% polyphosphoric acid in terms of orthophosphoric acid content, gradually heated and stirred under heating at 80 캜 for 6 hours to obtain a number average molecular weight of R ³ of 760 , a phosphate dispersant (C-1) having an abundance ratio of y = 1 and 2 of 100: 12 was obtained. The acid value of the obtained phosphoric acid dispersant was 166.

Synthesis Examples 2 to 4

(C-2) to (C-2) were prepared in the same manner as in Synthesis Example 1, except that the type and amount of the monoalcohol to be used and the type and amount of the lactone monomer used were changed as shown in Table 1, 4).

[Table 1]

&Lt; Synthesis of Resin Binder 1 &gt;

Synthesis Example 5

Propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube and a stirring device in a separable four-necked flask, and heated to 100 DEG C while nitrogen gas was introduced 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 effect polymerization reaction.

After cooling the obtained resin solution to room temperature, about 3 g of the resin solution was sampled and heated and dried at 180 DEG C for 20 minutes to measure the nonvolatile content. Propylene glycol acetate was added to the resin solution so that the nonvolatile content became 40 mass% To obtain a solution of the resin binder 1.

&Lt; (D) Synthesis of resin binder &gt;

Synthesis Example 6

Propylene glycol monomethyl ether acetate was placed in a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube and a stirrer, and heated to 80 DEG C while nitrogen gas was introduced into the reaction vessel , 123.3 g of benzyl methacrylate, 17.2 g of methacrylic acid, 31.0 g of para-cumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), 0.10 g of azobisisobutyric acid Nitrile was added dropwise over 2 hours to carry out a polymerization reaction.

After cooling the obtained resin solution to room temperature, about 3 g of the resin solution was sampled and heated and dried at 180 DEG C for 20 minutes to measure the nonvolatile content. Propylene glycol acetate was added to the resin solution so as to have a nonvolatile content of 40 mass% To obtain a solution of the resin binder (D-1).

&Lt; (Synthesis of resin having polymerizable double bond in side chain)

Synthesis Example 7

Propylene glycol monomethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube and a stirrer, and heated to 80 DEG C while nitrogen gas was introduced 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 at the same temperature for 2 hours to obtain a polymerization reaction I did.

To the obtained resin solution, a mixture of 23.3 g of 2-methacryloylethyl isocyanate ("Car lens MOI" manufactured by Showa Denko KK), 0.3 g of dibutyltin laurate, and 90 g of cyclohexanone was added Followed by dropwise addition at 70 占 폚 for 3 hours.

After cooling the obtained resin solution to room temperature, about 3 g of the resin solution was sampled and heated and dried at 180 DEG C for 20 minutes to measure the nonvolatile content. Propylene glycol acetate was added to the resin solution so that the nonvolatile content became 40 mass% To thereby obtain a solution of the resin binder (G-1).

&Lt; Preparation of red pigment dispersion composition &gt;

A mixture having the following composition was uniformly mixed and stirred and then mixed and dispersed for 3 hours by a bead mill to prepare a red pigment dispersion composition (R-a).

Diketopyrrolopyrrole-based red pigment (CI Pigment Red 254) 8.3 parts by mass

Isoprene yellow pigment (C. I. Pigment Yellow 139) 3.7 parts by mass

1.5 parts by mass of a coloring matter derivative represented by the following formula (B-1)

1.2 parts by mass of the phosphoric acid-based dispersant (C-1)

Resin binder 1 5.3 parts by mass (nonvolatile matter)

Propylene glycol monomethyl ether acetate (PGMEA) 80.0 parts by mass

(56)

Red pigment dispersion compositions (R-b) to (R-q) were prepared in the same manner as in the preparation of the red pigment dispersion composition (R-a) except that the composition was changed to the composition shown in Table 2 below.

[Table 2]

In Table 2, each symbol means the following compound.

PR254 ... A diketopyrrolopyrrole-based red pigment (CI Pigment Red 254)

P139 ... Isoprene-based yellow pigment (C. I. Pigment Yellow 139)

PR177 ... Anthraquinone-based red pigment (C. I. Pigment Red 177)

PR122 ... A quinacridone red pigment (CI Pigment Red 122)

PO71 ... Diketopyrrolopyrrole-based orange pigment (C. I. Pigment Orange 71)

Red-a ... Azo-based red pigment of the following structural formula

(57)

Dye derivative (B-2) ... A compound of the following structural formula

(58)

Dye derivative (B-3) ... A compound of the following structural formula

[Chemical Formula 59]

Dye derivative (B-4) ... A compound of the following structural formula

(60)

&Lt; Preparation of green pigment dispersion composition &gt;

A mixture having the following composition was uniformly stirred and mixed and dispersed for 3 hours by a bead mill to prepare a green pigment dispersion composition (G-a).

A halogenated copper phthalocyanine green pigment (C. I. Pigment Green 36)

1.4 parts by mass

Isophorone-based yellow pigment (C.I. Pigment Yellow 139) 3.4 parts by mass

2.0 parts by mass of the dye derivative represented by the above formula (B-1)

Phosphoric acid dispersant (C-1) 1.6 parts by mass

Resin binder 1 6.9 parts by mass (nonvolatile content)

50.7 parts by mass of propylene glycol monomethyl ether acetate (PGMEA)

Cyclohexanone 24.0 parts by mass

Green pigment dispersion compositions (G-b) to (G-p) were prepared in the same manner as in the preparation of the green pigment dispersion composition (G-a) except that the composition was changed to the composition shown in Table 3 below.

[Table 3]

In Table 3, each symbol means the following compound.

PG7 ... Chlorinated phthalocyanine green pigment (CI Pigment Green 7)

PG36 ... A halogenated copper phthalocyanine green pigment (C. I. Pigment Green 36)

PG58 ... Zinc phthalocyanine based green pigments (C. I. Pigment Green 58)

P139 ... Isoprene-based yellow pigment (C. I. Pigment Yellow 139)

PY150 ... Nickel azo yellow pigment (CI Pigment Yellow 150)

PY185 ... Isoprene-based yellow pigment (C. I. Pigment Yellow 185)

The dye derivative (B-2)

(61)

Dye derivative (B-4) ... A compound of the following structural formula

(62)

&Lt; Preparation of Yellow Pigment Dispersion Composition &gt;

A mixture having the following composition was uniformly mixed and stirred and then mixed and dispersed for 3 hours by a bead mill to prepare a yellow pigment dispersion composition (Y-a).

Isoprene yellow pigment (C. I. Pigment Yellow 139) 14.2 parts by mass

1.6 parts by mass of the dye derivative represented by the above formula (B-1)

3.5 parts by mass of the phosphoric acid-based dispersant (C-1)

Resin binder (D-1) 5.7 parts by mass (non-volatile matter)

Propylene glycol monomethyl ether acetate (PGMEA) 58.0 parts by mass

Cyclohexanone 17.0 parts by mass

&Lt; Preparation of Red Photosensitive Resin Composition &gt;

(RR-a) was prepared by uniformly stirring the mixture of the following composition.

Red pigment dispersion composition (R-a) 50.0 parts by mass

Resin binder 1 2.6 parts by mass (as a 40% by mass resin solution)

Photopolymerization initiator (E-1) 1- [4- (phenylthio) -2- (O-benzoyloxime)] (IRGACURE OXE01, manufactured by BASF)

0.3 parts by mass

Ethylenically unsaturated compound (F-1) Ethylene oxide modified product of dipentaerythritol hexaacrylate (NK Ester A-DPH-12E, manufactured by Shin Nakamura Kagaku Kogyo K.K.)

0.7 parts by mass

(Megapac F-781F, manufactured by Dainippon Ink and Chemicals, Incorporated)

4.2 parts by mass (as a propylene glycol monomethyl ether acetate solution having a nonvolatile content of 1% by mass)

p-methoxyphenol 0.0003 parts by mass

42.2 parts by mass of propylene glycol monomethyl ether acetate (PGMEA)

Red photosensitive resin compositions (RR-b) to (RR-w) were prepared in the same manner as the preparation of the red photosensitive resin composition (RR-a) except that the composition was changed to the composition according to the following table.

<Evaluation>

(Evaluation of Pattern Formability 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.

Propylene glycol monomethyl ether acetate 5.20 parts

· Cyclohexanone 52.60 parts

· Binder 30.50 parts

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

Dipentaerythritol hexaacrylate 10.20 parts

Polymerization inhibitor (p-methoxyphenol) 0.006 part

Fluorine-based surfactant (DIC, F-475) 0.80 parts

Photopolymerization initiator: 4-benzoxazole-2,6-bis (trichloromethyl) -s-triazine (Midazolagaku, TAZ-107)

0.58 part

(2) Fabrication of glass substrate with undercoat layer

The glass substrate (Corning 1737) was ultrasonically cleaned with 0.5% NaOH water, followed by washing with water and dehydration baking (200 ° C / 20 minutes). Next, the transparent resist solution A obtained in the above (1) was applied to a cleaned glass substrate using a spin coater so that the film thickness after drying became 2 탆, and dried by heating at 220 캜 for one hour to form an undercoat layer , A glass substrate with an undercoat layer was prepared.

(3) Exposure and development of a colored photosensitive resin composition (formation of a colored pattern)

The red photosensitive resin compositions (RR-a) to (RR-w) obtained by the above procedure were applied on the undercoat layer of the glass substrate with the undercoat layer obtained in the above (2) using a spin coater And two substrates prebaked at 100 占 폚 for 120 seconds were prepared.

One side of the substrate was immediately passed through a mask having a line width of 1.1 m and a wavelength of 365 nm onto the coated film using an i-line stepper exposure apparatus FPA-i5 + (manufactured by Canon Inc.) immediately after application of the red photosensitive resin composition And a checker board pattern having a side length of 1.1 m was formed. After exposure, development was carried out at 25 占 폚 for 40 seconds using Developer CD-2000 (manufactured by Fuji Film Electronics Materials Co., Ltd.). Thereafter, after rinsing with running water for 30 seconds, spray drying was performed to obtain a colored pattern.

Next, the other side of the substrate was coated with the red photosensitive resin composition, allowed to stand in a clean room at room temperature for 72 hours (PCD), and then a coloring pattern was obtained in the same manner as described above.

The two types of colored patterns thus obtained were observed with an SEM, and the shapes of the coloring patterns obtained by performing exposure and development immediately after the application (no PCD) and the coloring patterns obtained by performing exposure and development after the PCD were compared, .

A: The shape of the colored pattern after the PCD is not changed at all compared with the shape of the colored pattern without the PCD

B: The shape of the colored pattern after PCD shows a slight change but no problem

C: There is a problem because the shape of the color pattern after PCD is collapsed

D: The shape of the colored pattern after PCD is largely collapsed

The results of this PCD evaluation are summarized in the following table.

(4) Evaluation of roughness (color unevenness)

The red photosensitive resin compositions (RR-a) to (RR-w) obtained by the above procedure were applied on a glass substrate using a spin coater so as to have a film thickness of 0.6 mu m after drying and prebaked at 100 DEG C for 120 seconds To obtain a colored coating film 1.

Further, the red photosensitive resin compositions (RR-a) to (RR-w) obtained in the above-mentioned manner were aged at room temperature for 6 months and then applied on a glass substrate using a spin coater so that the film thickness after drying was 0.6 탆 And prebaked at 100 캜 for 120 seconds to obtain a colored coating film 2.

Each obtained colored coating film was placed between an observation lens of an optical microscope and a light source, the light was irradiated toward the observation lens, and the state of the transmitted light was observed using an optical microscope equipped with a digital camera having a magnification of 1000 times. The digital camera installed in the optical microscope was equipped with a CCD of 128 megapixels, and the surface of the colored coating film in the transmitted light state was photographed with the digital camera. The photographed image was stored as digital-converted data (digital image) in an 8-bit bitmap format.

In addition, the photographing of the surface of the colored coating film was performed on arbitrarily selected 20 regions. The digitally converted data was obtained by digitizing the photographed image as the density distribution of 256 gradations ranging from 0 to 255 for each of the three primary colors of RGB.

Next, with respect to the stored digital image, the lattice size was divided into lattice shapes so that one lattice size corresponded to 0.5 mu m square on the actual plate, and the luminance in one compartment was averaged. In this embodiment, since an optical image of 1000 times magnification was photographed with a digital camera of 1.28 million pixels, 0.5 mu m on the actual plate was 0.5 mm on the photographed image, and the image size on the display was 452 mm x 352 mm , The total number of compartments in one area was 636416.

The average luminance of one arbitrary section and all adjacent sections adjacent thereto was measured for the whole section of each area. A section having a difference of 5 or more from the average luminance of the adjacent section was regarded as a significant difference section and the average total number of the significant difference sections of the whole section was calculated. The smaller the numerical value, the smaller the difference in density from the adjacent compartments, the smaller the roughness, and the better the characteristic as a color filter.

The average total number of roughness of the colored coating film 1 was taken as the value of roughness immediately after preparation and the average value of the roughness of the colored coating film 2 was taken as the value of the roughness after 6 months at room temperature, The increase rate of roughness after aging is shown in Table 4 below.

[Table 4]

In Table 4, each symbol means the following compound.

Photopolymerization initiator (E-2) ... (1-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (0-acetyloxime) (IRGACURE OXE02,

Photopolymerization initiator (E-3) ... (IRGACURE 379, manufactured by BASF) was added to a solution of 2- (dimethylamino) -2 - [(4-methylphenyl) methyl]

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

Ethylenically unsaturated compounds (F-3) ... Trimethylol propyl acrylate (A-TMPT, manufactured by Shin Nakamura Kagaku Kogyo K.K.)

UV absorber ... A compound of the following structural formula

(63)

From the results shown in Table 4, the red photosensitive resin compositions (RR-s) and (RR-u) of Comparative Examples 1 and 3 contain (C-1) phosphoric acid dispersant, which is an essential component in the composition of the present invention However, since the pigment derivative of the specific structure (B), which is an essential component of the composition of the present invention, is not contained, the pattern formability after PCD is greatly inferior and the increase in roughness with time is also slightly large. The red photosensitive resin compositions (RR-t) and (RR-v) of Comparative Examples 2 and 4 contain a coloring matter derivative of the specific structure (B) which is an essential component in the composition of the present invention, (C-1) phosphoric acid-based dispersant, which is an essential component in the present invention, the increase in the roughness over time is very large, and there is room for improvement in the pattern formation property after the PCD.

For example, the red photosensitive resin composition (RR-a) of the present invention shown in Example 1 is obtained by mixing the coloring matter derivative of the specific structure (B), which is a component essential to the composition of the present invention, It is understood that the increase in the roughness with time is suppressed, and the pattern formability after the PCD is greatly improved.

It was also found that in Examples 5 to 19 using the resin (G-1) having a polymerizable double bond in the side chain as the (G) resin, the increase rate of the roughness was further suppressed.

Examples 11 and 18 using the phosphoric acid type dispersant (C-3) were found to be superior in the pattern formability after PCD to the examples using other phosphoric acid type dispersants.

&Lt; Preparation of green photosensitive resin composition &gt;

A mixture having the following composition was uniformly stirred to prepare a green photosensitive resin composition (GR-a).

Green pigment dispersion composition (G-a) 50.7 parts by mass

Resin binder 1 4.7 parts by mass (as a 40% by mass resin solution)

Photopolymerization initiator (E-1) (IRGACURE OXE01, manufactured by BASF), 0.5 part by mass of 1,2-octanedione, 1- [4- (phenylthio) -2-

Ethylenically unsaturated compound (F-1) Ethylene oxide modified product of dipentaerythritol hexaacrylate (NK Ester A-DPH-12E, manufactured by Shin Nakamura Kagaku Kogyo K.K.)

4.9 parts by mass

(Megapac F-781F, manufactured by Dainippon Ink and Chemicals, Incorporated)

4.2 parts by mass (as a propylene glycol monomethyl ether acetate solution having a nonvolatile content of 1% by mass)

0.3 parts by mass of an ultraviolet absorber (the above compound)

p-methoxyphenol 0.0003 parts by mass

34.7 parts by mass of propylene glycol monomethyl ether acetate (PGMEA)

Green photosensitive resin compositions (GR-b) to (GR-v) were prepared in the same manner as in the preparation of the green photosensitive resin composition (GR-a) except that the composition was changed to the composition shown in the following table.

The obtained green photosensitive resin compositions (GR-a) to (GR-v) were evaluated for the roughness value immediately after preparation and after 6 months at room temperature and the pattern formability after PCD by the same method as in Example 1. The results are summarized in Table 5 below.

[Table 5]

From the results shown in Table 5, the green photosensitive resin compositions (GR-s) and (GR-u) of Comparative Examples 5 and 7 contained the (C-1) phosphoric acid dispersant which is an essential component in the composition of the present invention However, since the pigment derivative of the specific structure (B), which is an essential component of the composition of the present invention, is not contained, the pattern formability after PCD is greatly inferior and the increase in roughness with time is also slightly large. The green photosensitive resin compositions (GR-t) and (GR-v) of Comparative Examples 6 and 8 contain the pigment derivative of the specific structure (B), which is an essential component of the composition of the present invention, (C-1) phosphoric acid-based dispersant, which is an essential component in the present invention, the increase in the roughness over time is very large, and there is room for improvement in the pattern formation property after the PCD.

For example, the green photosensitive resin composition (GR-a) of the present invention shown in Example 20 is a green photosensitive resin composition (GR-a), which is a component essential to the composition of the present invention, It is understood that the increase of the roughness after the lapse of 6 months at room temperature is suppressed and the pattern formability after the PCD is greatly improved.

It was also found that in Examples 24 to 37 using the resin (G-1) having a polymerizable double bond in the side chain as the (G) resin, the increase rate of the roughness was further suppressed.

Examples 30 and 37 using the phosphoric acid type dispersant (C-3) were found to be superior in pattern formation properties after PCD than the examples using other phosphoric acid type dispersants.

&Lt; (C-2) Synthesis of carboxylic acid dispersant &gt;

Synthesis Example 8

6.26 g of 1-dodecanol, 28.74 g of epsilon -caprolactone and 0.01 g of monobutyltin (IV) oxide as a catalyst were placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube and a stirrer in a four- The inside of the reaction vessel was purged with nitrogen, and the mixture was heated and stirred at 120 ° C for 4 hours. After disappearance of the caprolactone monomer was confirmed by ¹ H-NMR measurement, 3.66 g of pyromellitic anhydride was added thereto, and the reaction was carried out at 120 ° C for 2 hours. By measuring the acid value, it was confirmed that at least 98% of the acid anhydride was half-esterified, and the reaction was terminated to obtain a dispersant (C-11). The acid value of the obtained dispersant (C-11) was 49 mgKOH / g.

Synthesis Examples 9 to 13

(C-12) to (C-12) were obtained in the same manner as in Synthesis Example 8, except that the kinds and amounts of monoalcohols, alkylene oxide, lactone monomers and carboxylic anhydrides used were changed as shown in Table 6, 16).

[Table 6]

In Table 6, each symbol means the following compound.

Blemmer PP-500 ... Polypropylene glycol monomethacrylate (Blemmer PP-500, manufactured by Nippon Oil Co., Ltd., hydroxyl value: 95.1 mgKOH / g)

PMA ... Pyromellitic dianhydride

BPAF ... 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride

NPDA ... 2,3,6,7-naphthalenetetracarboxylic acid dianhydride

TMEG ... Ethylene glycol di-anhydride trimellitic acid ester (trade name: Rikacid TMEG-100, manufactured by Shin-Nippon Rikagaku Co., Ltd.)

TMA ... Trimellitic anhydride

DMBA ... Dimethylbenzylamine

Synthesis Example 14

35.0 g of Zephamine XTJ-506 (manufactured by Mitsui Chemicals, Inc., one-end methoxylated polyoxyethylene polyoxypropyleneamine, number average molecular weight 1000, amine value 56 mgKOH / g) was added to the same reaction vessel as in Synthesis Example 5, And 7.18 g of ethylene glycol dianhydride trimellitic acid ester (trade name: Rikacid TMEG-100, manufactured by Shin-Nippon Rikagaku Co., Ltd.) were added and reacted at 50 ° C for 3 hours. By measuring the acid value, it was confirmed that at least 97% of the acid anhydride was converted to a half amide, and the reaction was terminated to obtain a carboxylic acid dispersant (C-17).

Synthesis Example 15

6.26 g of 1-dodecanol, 28.74 g of epsilon -caprolactone and 0.1 part of monobutyltin (IV) oxide as a catalyst were introduced into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a gas introducing tube, After purging with nitrogen gas, the mixture was heated and stirred at 120 占 폚 for 4 hours. After disappearance of the caprolactone monomer was confirmed by ¹ H-NMR measurement, 3.36 g of succinic anhydride, 6.25 g of 2-ethylhexyl glycidyl ether and 0.2 g of N, N-dimethylbenzylamine were added thereto , And reacted at 80 DEG C for 8 hours.

2.88 g of pyromellitic dianhydride was added to the resulting reaction solution, and the reaction was carried out at 100 ° C for 5 hours. By measuring the acid value, it was confirmed that at least 97% of the acid anhydride was converted to a half amide, and the reaction was terminated to obtain a carboxylic acid-based dispersant (C-18).

Synthesis Example 16

10.0 g of n-butyl methacrylate, 10.0 g of benzyl methacrylate, and 1.0 g of 2-mercaptoethanol were introduced into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a gas introducing tube, and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 캜 and reacted for 12 hours. The disappearance of the monomer component was confirmed by ¹ H-NMR measurement.

1.4 g of pyromellitic dianhydride, 9.59 g of cyclohexanone and 0.04 g of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added to the resulting reaction solution, Lt; / RTI &gt; By measuring the acid value, it was confirmed that at least 98% of the acid anhydride was half-esterified. To the reaction solution, 12.8 g of cyclohexanone was added and the reaction was terminated to obtain a carboxylic acid dispersant (C-19).

&Lt; Preparation of red pigment dispersion composition &gt;

A mixture of the following composition was uniformly mixed and stirred and then mixed and dispersed for 3 hours by a bead mill to prepare a red pigment dispersion composition (R-1a).

Diketopyrrolopyrrole-based red pigment (CI Pigment Red 254) 8.3 parts by mass

Isoprene yellow pigment (C. I. Pigment Yellow 139) 3.7 parts by mass

1.5 parts by mass of a coloring matter derivative represented by the following formula (B-1)

1.2 parts by mass of a carboxylic acid-based dispersant (C-11)

Resin binder 1 5.3 parts by mass (nonvolatile matter)

Propylene glycol monomethyl ether acetate (PGMEA) 80.0 parts by mass

&Lt; EMI ID =

Red pigment dispersion compositions (R-1B) to (R-1v) were prepared in the same manner as in the preparation of the red pigment dispersion composition (R-1a) except that the composition was changed to the composition according to the following table.

[Table 7]

In Table 7, each symbol means the following compound.

PR254 ... A diketopyrrolopyrrole-based red pigment (CI Pigment Red 254)

P139 ... Isoprene-based yellow pigment (C. I. Pigment Yellow 139)

PR177 ... Anthraquinone-based red pigment (C. I. Pigment Red 177)

PR122 ... A quinacridone red pigment (CI Pigment Red 122)

PO71 ... Diketopyrrolopyrrole-based orange pigment (C. I. Pigment Orange 71)

Red-a ... Azo-based red pigment of the following structural formula

(65)

Dye derivative (B-2) ... A compound of the following structural formula

(66)

Dye derivative (B-3) ... A compound of the following structural formula

(67)

Dye derivative (B-4) ... A compound of the following structural formula

(68)

&Lt; Preparation of green pigment dispersion composition &gt;

A mixture having the following composition was uniformly stirred and mixed and dispersed for 3 hours by a bead mill to prepare a green pigment dispersion composition (G-1a).

A halogenated copper phthalocyanine green pigment (C. I. Pigment Green 36)

11.4 parts by mass

Isophorone-based yellow pigment (C.I. Pigment Yellow 139) 3.4 parts by mass

2.0 parts by mass of the dye derivative represented by the above formula (B-1)

1.6 parts by mass of a carboxylic acid-based dispersant (C-11)

Resin binder 1 6.9 parts by mass (nonvolatile content)

50.7 parts by mass of propylene glycol monomethyl ether acetate (PGMEA)

Cyclohexanone 24.0 parts by mass

Green pigment dispersion compositions (G-1b) to (G-1u) were prepared in the same manner as in the preparation of the above green pigment dispersion composition (G-1a) except that the composition was changed to the composition shown in Table 8 below.

[Table 8]

In Table 8, each symbol means the following compound.

PG7 ... Chlorinated phthalocyanine green pigment (CI Pigment Green 7)

PG36 ... A halogenated copper phthalocyanine green pigment (C. I. Pigment Green 36)

PG58 ... Zinc phthalocyanine based green pigments (C. I. Pigment Green 58)

P139 ... Isoprene-based yellow pigment (C. I. Pigment Yellow 139)

PY150 ... Nickel azo yellow pigment (CI Pigment Yellow 150)

PY185 ... Isoprene-based yellow pigment (C. I. Pigment Yellow 185)

Dye derivative (B-2) ... A compound of the following structural formula

(69)

Dye derivative (B-4) ... A compound of the following structural formula

(70)

&Lt; Preparation of Yellow Pigment Dispersion Composition &gt;

A mixture having the following composition was uniformly mixed and stirred and then mixed and dispersed for 3 hours by a bead mill to prepare a yellow pigment dispersion composition (Y-a).

Isoprene yellow pigment (C. I. Pigment Yellow 139) 14.2 parts by mass

1.6 parts by mass of the dye derivative represented by the above formula (B-1)

3.5 parts by mass of the phosphoric acid-based dispersant (C-1)

Resin binder (D-1) 5.7 parts by mass (non-volatile matter)

Propylene glycol monomethyl ether acetate (PGMEA) 58.0 parts by mass

Cyclohexanone 17.0 parts by mass

&Lt; Preparation of Red Photosensitive Resin Composition &gt;

A mixture of the following compositions was uniformly stirred to prepare a red photosensitive resin composition (RR-1a).

Red pigment dispersion composition (R-1a) 50.0 parts by mass

Resin binder 1 2.6 parts by mass (as a 40% by mass resin solution)

Photopolymerization initiator (E-1) 1- [4- (phenylthio) -2- (O-benzoyloxime)] (IRGACURE OXE01, manufactured by BASF)

0.3 parts by mass

Ethylenically unsaturated compound (F-1) Ethylene oxide modified product of dipentaerythritol hexaacrylate (NK Ester A-DPH-12E, manufactured by Shin Nakamura Kagaku Kogyo K.K.)

0.7 parts by mass

(Megapac F-781F, manufactured by Dainippon Ink and Chemicals, Incorporated)

4.2 parts by mass (as a propylene glycol monomethyl ether acetate solution having a nonvolatile content of 1% by mass)

p-methoxyphenol 0.0003 parts by mass

42.2 parts by mass of propylene glycol monomethyl ether acetate (PGMEA)

(RR-1b) to (RR-1z), (RR-1aa), and (RR-1b) were obtained in the same manner as in the preparation of the red photosensitive resin composition (RR-1a) except that the composition was changed to the composition shown in the following table. ) To (RR-1ab).

The obtained red photosensitive resin compositions (RR-1a) to (RR-1ab) were evaluated for roughness immediately after preparation and after 6 months at room temperature and patterning properties after PCD by the same method as in Example 1. [ The results are summarized in Table 9 below.

[Table 9]

In Table 9, each symbol means the following compound.

Photopolymerization initiator (E-2) ... (1-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (0-acetyloxime) (IRGACURE OXE02,

Photopolymerization initiator (E-3) ... (IRGACURE 379, manufactured by BASF) was added to a solution of 2- (dimethylamino) -2 - [(4-methylphenyl) methyl]

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

Ethylenically unsaturated compounds (F-3) ... Trimethylol propyl acrylate (A-TMPT, manufactured by Shin Nakamura Kagaku Kogyo K.K.)

UV absorber ... A compound of the following structural formula

(71)

From the results shown in the above table, the red photosensitive resin compositions (RR-1x) and (RR-1z) of Comparative Examples 101 and 103 include the (C-2) carboxylic acid dispersant which is an essential component in the composition of the present invention , Since the pigment derivative of the specific structure (B), which is an essential component of the composition of the present invention, is not contained, the pattern formability after PCD is greatly inferior and the increase in roughness over time is also slightly large. The red photosensitive resin compositions (RR-1y) and (RR-1aa) of Comparative Examples 102 and 104 contain a coloring matter derivative (B) having a specific structure as a component essential to the composition of the present invention, (C-2) carboxylic acid-based dispersing agent, which is an essential component in the present invention, the increase in the roughness with time is very large, and there is room for improvement in the pattern formability after PCD.

For example, the red photosensitive resin composition (RR-1a) of the present invention shown in Example 101 is obtained by mixing the coloring matter derivative of the specific structure (B) and the (C-2) It is understood that the increase in the roughness with time is suppressed, and the pattern formability after the PCD is greatly improved.

It was also found that in Examples 104 to 124 using the resin (G-1) having a polymerizable double bond in the side chain as the (G) resin, the increase rate of the roughness was further suppressed.

It was found that Examples 105, 108 and 123 using the carboxylic acid dispersants (C-12) and (C-15) were superior in pattern formation properties after PCD than the Examples using other carboxylic acid dispersants.

&Lt; Preparation of green photosensitive resin composition &gt;

A mixture having the following composition was uniformly stirred to prepare a green photosensitive resin composition (GR-1a).

Green pigment dispersion composition (G-1a) 50.7 parts by mass

Resin binder 1 4.7 parts by mass (as a 40% by mass resin solution)

Photopolymerization initiator (E-1) 1- [4- (phenylthio) -2- (O-benzoyloxime)] (IRGACURE OXE01, manufactured by BASF)

0.5 parts by mass

Ethylenically unsaturated compound (F-1) Ethylene oxide modified product of dipentaerythritol hexaacrylate (NK Ester A-DPH-12E, manufactured by Shin Nakamura Kagaku Kogyo K.K.)

4.9 parts by mass

(Megapac F-781F, manufactured by Dainippon Ink and Chemicals, Incorporated)

4.2 parts by mass (as a propylene glycol monomethyl ether acetate solution having a nonvolatile content of 1% by mass)

0.3 parts by mass of an ultraviolet absorber (the above compound)

p-methoxyphenol 0.0003 parts by mass

34.7 parts by mass of propylene glycol monomethyl ether acetate (PGMEA)

Green photosensitive resin compositions (GR-1b) to (GR-1z), and (GR-1z) were obtained in the same manner as in the preparation of the green photosensitive resin composition (GR-1a) except that the composition was changed to the composition shown in Table 10 below. -1aa) was prepared.

The obtained green photosensitive resin compositions (GR-1a) to (GR-1aa) were evaluated for the roughness values immediately after preparation and after 6 months at room temperature and the patterning properties after PCD by the same method as in Example 1. The results are summarized in the following table.

[Table 10]

From the results shown in Table 10, the green photosensitive resin compositions (GR-1x) and (GR-1z) of Comparative Examples 105 and 107 contained the (C-2) carboxylic acid dispersant, which is an essential component in the composition of the present invention However, since the pigment derivative of the specific structure (B), which is an essential component of the composition of the present invention, is not contained, the pattern formability after PCD is greatly inferior and the increase in roughness with time is also slightly large. The green photosensitive resin compositions (GR-1y) and (GR-1aa) of Comparative Examples 106 and 108 contained the pigment derivative of the specific structure (B), which is an essential component in the composition of the present invention, (C-2) carboxylic acid-based dispersing agent, which is an essential component in the present invention, the increase in the roughness with time is very large, and there is room for improvement in the pattern formability after PCD.

For example, the green photosensitive resin composition (GR-1a) of the present invention shown in Example 125 can be produced by mixing a coloring matter derivative (B) having a specific structure and a (C-2) It is understood that the increase in the roughness with time is suppressed, and the pattern formability after the PCD is greatly improved.

It is also seen that in Examples 128 to 147 using the resin (G-1) having a polymerizable double bond in the side chain as the (G) resin, the increase rate of the roughness is further suppressed.

It was found that Examples 129, 132 and 147 using the carboxylic acid dispersants (C-12) and (C-15) were superior in pattern formability after PCD than the Examples using other carboxylic acid dispersants.

In each of the above Examples, a photosensitive resin composition was prepared in the same manner as (B) except that the basic dye derivative was changed to an equivalent amount of the following compound. The pattern-forming properties of the obtained photosensitive resin composition were evaluated, and it was confirmed that a good pattern could be formed.

(72)

Claims (18)

(C-1) a phosphoric acid-based dispersant represented by the following general formula (II), or (C-2) a polymer (POH) having at least one terminal hydroxyl group, or at least one polymer to the terminal having a primary amino group (PNH ₂₎ and a tri by reacting a carboxylic acid anhydride or tetracarboxylic acid dianhydride consisting of carboxylic acid-based dispersing agent, (D) a resin binder, (E) a photopolymerization initiator, and (F) a polymerizable &Lt; / RTI &gt;
The (B) basic dye derivative is a dye derivative represented by the following general formula (I): a colored photosensitive resin composition;

In the formula (II), R ³ represents a polyester structure having a number average molecular weight of 400 to 30000, y represents an integer of 1 or 2;
when y is 2, plural R ³ may be the same or different;

In the general formula (I), Dye represents a quinophthalone residue represented by the following general formula (II-1), X ¹ represents -NR'SO ₂ -, -SO ₂ NR'-, -CONR'-, ₂ represents a -CH ₂ NR'COCH NR'-, or -NR'CO-, X ^2, the carbon atoms are carbon atoms which may have a substituent which may have an aryl group, or a 6- to 20 1 to 20 And these groups may be bonded to each other through a divalent linking group selected from -NR'-, -O-, -SO ₂ - or -CO-. X ³ represents -NR'- or -O-. R 'represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms and may have a substituent;
In the general formula (I), A and B each represent a group represented by the following general formula (1) or the following general formula (2), -O- (CH ₂ ) _n -R ⁸ , -OR ⁹ , -NR ¹⁰ R ^11, represents a group selected from -Cl, -F, or ^{-X 3 -X 2 -X 1 -Dye,} R 8 denotes a nitrogen-containing heterocyclic ring residue which may be ^{substituted, R 9, R 10, R} 11 Each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms and may have a substituent, and n Represents an integer of 0 to 20. Either A or B is a group represented by the following general formula (1) or (2), -O- (CH ₂ ) nR ⁸ , -OR ⁹ , or -NR ¹⁰ R ¹¹ . and t represents an integer of 1 to 3. When t is 2 or more, a plurality of X ¹ , X ² , X ³ , A, and B may be the same or different;

(II-1)
In the general formula (II-1), D and E are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a benzene ring formed by bonding D and E to form an aromatic ring or heterocyclic ring , A hydroxyl group, an alkoxyl group having 1 to 3 carbon atoms, a carboxyl group or a salt thereof, an ester having 1 to 20 carbon atoms or an amide having 1 to 20 carbon atoms, a sulfone group or a salt thereof, a sulfamoyl group, -NR'R " R 'and R "each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent or a substituent group An aryl group having 6 to 20 carbon atoms which may be present;
In the general formula (II-1), p represents an integer of 0 to 4, and q represents an integer calculated by 4-p. * Represents a bonding site with X ¹ in the general formula (I);

In the general formula (1), Y ¹ represents -NR'- or -O-, Y ² represents an alkylene group having 2 to 20 carbon atoms which may have a substituent, an alkylene group having 2 to 20 carbon atoms which may have a substituent Or a divalent linking group selected from -NR'-, -O-, -SO ₂ -, or -CO-, and these groups may be bonded to each other through a divalent linking group selected from -NR'-, -O-, . R 'represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms and may have a substituent;
In formula (1), R ¹ and R ² each represent an alkyl group having 1 to 20 carbon atoms, which may have a substituent, or an alkenyl group having 2 to 20 carbon atoms, which may have a substituent, and R ¹ and R ² May be combined to form a heterocyclic structure, and the heterocyclic structure may further contain a nitrogen atom, an oxygen atom or a sulfur atom, and may have a substituent;
In the general formula (2), Z ¹ represents a single bond connecting a triazine ring and a nitrogen atom, -NR'-, -NR'-G-CO-, NR'-G-CONR " _{-SO 2 -, -NR'-G-} SO 2 NR "-, -OG-CO-, -OG-CONR'-, -OG-SO 2 - or -OG-SO ₂ represents NR'-, G is An alkylene group having 1 to 20 carbon atoms which may have a substituent, an alkenylene group having 2 to 20 carbon atoms which may have a substituent or an arylene group having 6 to 20 carbon atoms which may have a substituent, and R 'and R " Each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms and may have a substituent;
In the general formula (2), R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkene having 2 to 20 carbon atoms, carbon atoms which may have a group, or the substituent represents a 6-20 aryl, R ⁷ is the number of carbon atoms which may have a substituent of 1 to 20 alkyl group, or a represents an alkenyl group having the carbon number of 2 to 20 which may have a substituent . The method according to claim 1,
Wherein the pigment (A) is at least one selected from the group consisting of red pigment, green pigment, and yellow pigment. The method according to claim 1,
The number average molecular weight of the polyester structure represented by R ³ in the general formula (II) is 1900 to 10000. The method according to claim 1,
Wherein the polyester structure represented by R ³ in the general formula (II) is a polyester structure obtained by ring-opening polymerization of two or more different lactone monomers. The method according to claim 1,
The polymer (POH) having at least one terminal hydroxyl group or the polymer (PNH ₂ ) having at least one terminal primary terminal amino group in the (C-2) carboxylic acid dispersant is represented by the following general formula (II) &Quot;),&lt; / RTI &gt;

In formula (II '), Y ¹ represents a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms, and X ² represents -O-, -S-, Or -N (R ^b ) -, R ^b represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms or a branched alkyl group having 3 to 8 carbon atoms;
G ¹ represents a repeating unit represented by -R ¹¹ O-, G ² represents a repeating unit represented by -C (═O) R ¹² O-, G ³ represents -C (═O) R ¹³ C (= O) -OR ¹⁴ O-, R ¹¹ represents a linear or branched alkylene group having 2 to 8 carbon atoms or a cycloalkylene group having 3 to 8 carbon atoms, R ¹² represents a linear or branched alkylene group having 3 to 8 carbon atoms, R ⁸ is a linear or branched alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 2 to 8 carbon atoms or a cycloalkylene group having 4 to 8 carbon atoms; R ¹³ is a linear or branched alkylene group having 2 to 6 carbon atoms; Or a branching alkenylene group, a cycloalkylene group having 3 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, R ¹⁴ represents -CH (R ¹⁵ ) -CH (R ¹⁶ ) -, R ¹⁵ and R ¹⁶ is either a hydrogen atom, the other is an alkyl group having 1 to 20 carbon atoms, an alkyloxy of 1 to 20 carbon atoms of the aryl group, the alkyl moiety having 2 to 20 carbon atoms an alkenyl group, having 6 to 20 of A methylene group, an alkenyloxymethylene group having 2 to 20 carbon atoms in the alkenyl moiety, an aryloxymethylene group in which the aryl moiety has 6 to 20 carbon atoms and the aryl moiety may be substituted with a halogen atom, Lt; / RTI &gt;
Z ¹ is represents a -OH, or -NH _2, R ¹⁷ is a cycloalkyl group, a -C (= O) R ¹² in the alkylene group, 3 to 8 carbon atoms straight-chain or branched having 2 to 8, or ^{-C (= O) R 13 C} (= O) -OR 14 - shows a;
m1 represents an integer of 0 to 100, m2 represents an integer of 0 to 60, and m3 represents an integer of 0 to 30;
Provided that m1 + m2 + m3 is 1 or more and 100 or less;
The arrangement of the repeating units G ¹ to G ^{3 in} the general formula (II ') is not limited to the order. In the polymer represented by the general formula (II'), the arrangement between the groups X ² and R ¹⁷ Indicates that repeating units G ¹ to G ³ are contained in an arbitrary order, and these repeating units G ¹ to G ³ may be either a random type or a block type. The method according to claim 1,
In the above-mentioned (C-2) carboxylic acid-based dispersant, POH as a polymer having a hydroxyl group at the at least one terminal or PNH ₂ as a polymer having a primary amino group at at least one terminal thereof is represented by the following formula A colored photosensitive resin composition;

In the general formula (III), Y ¹ represents a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms and 0 to 3 nitrogen atoms, X ² represents -O-, -S-, or - N (R ^b ) -, R ^b represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms or a branched chain having 3 to 18 carbon atoms;
Z ¹ represents -OH, or -NH ₂ ;
G ⁴ and G ⁵ each represent a repeating unit represented by -C (= O) R ¹² O-, R ¹² represents a straight-chain or branched alkylene group having 1 to 8 carbon atoms or a branched alkylene group having 2 to 8 carbon atoms, 8 cycloalkylene group; However, G ⁴ and G ⁵ R ¹² R ¹² is of the of the different groups;
R ²⁰ represents -C (= O) R ¹² -;
m4 represents an integer of 5 to 60, and m5 represents an integer of 5 to 60;
The repeating unit of the general formula (III) G ^4, the arrangement of G ⁵ is not limited to this order, in the polymer represented by the general formula (III), based repeated among the groups Z ¹ and X ² The units G ⁴ and G ⁵ are included in an arbitrary order, and the repeating units G ⁴ and G ⁵ may be either a random type or a block type. The method according to claim 1,
Wherein the resin binder (D) is a resin obtained by copolymerizing a compound (x) represented by the following formula (IV) and a compound (y) having another ethylenically unsaturated double bond:

In the general formula (IV), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 2 or 3 carbon atoms, R ⁶ represents an alkyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring, N represents an integer of 1 to 15;
When n is 2 or more, a plurality of R ⁵ may be the same or different. The method according to any one of claims 1 to 7,
(G) a resin having a polymerizable double bond in a side chain thereof. The method of claim 8,
Wherein the resin having a polymerizable double bond in the side chain (G) is a copolymer of a polymerizable monomer (p) having a hydroxyl group having 2 or more and 6 or less and a different polymerizable monomer (q) (B) having a functional group and an ethylenically unsaturated double bond. The method according to any one of claims 1 to 7,
A colored photosensitive resin composition used for forming a coloring region of a color filter. A cured film obtained by curing the colored photosensitive resin composition of claim 1. A step of forming a colored photosensitive resin composition layer by applying the colored photosensitive resin composition according to claim 1 on a support, a step of exposing the colored photosensitive resin composition layer in a pattern shape, a step of forming a colored pattern by developing the unexposed portion, &Lt; / RTI &gt; A step of applying the colored photosensitive resin composition according to claim 1 on a support to form a colored photosensitive resin composition layer and curing the colored photosensitive resin composition layer to form a colored 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 a step of dry-etching the colored layer using the resist pattern as an etching mask. A color filter having the cured film according to claim 11. A color filter produced by the method of manufacturing a color filter according to claim 12. A color filter produced by the method of manufacturing a color filter according to claim 13. A solid-state imaging element having the color filter according to any one of claims 14 to 16. An image display apparatus having the color filter according to any one of claims 14 to 16.

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