WO2011108496A1

WO2011108496A1 - Pigment dispersion, negative resist composition for color filter, color filter, liquid crystal display device, and organic light-emitting display device

Info

Publication number: WO2011108496A1
Application number: PCT/JP2011/054526
Authority: WO
Inventors: 教弘小倉; 武浩小澤; 裕章瀬川
Original assignee: 大日本印刷株式会社
Priority date: 2010-03-03
Filing date: 2011-02-28
Publication date: 2011-09-09
Also published as: CN102859400A; TWI428354B; JP5110223B2; JPWO2011108496A1; TW201139476A; CN102859400B

Abstract

Disclosed are: a pigment dispersion that is for a color filter and that has a large process margin in a production disperser while meeting the demand for high brightness and increased contrast; and a negative resist composition that is for a color filter and that has excellent alkaline developing characteristics, can form a color filter having high contrast and high brightness, and has excellent pigment dispersion characteristics. The pigment dispersion for a color filter contains: a pigment dispersing agent that is a particular block co-polymer of which at least a subset of the amino groups that a repeating unit has forms a salt with an organic phosphate compound; a pigment; a sulfonic acid derivative of C.I. pigment yellow 138, and a solvent. The negative resist composition contains: the aforementioned pigment dispersing agent; a pigment; a sulfonic acid derivative of C.I. pigment yellow 138; an alkali-soluble resin; a polyfunctional monomer; a photoinitiator; and a solvent.

Description

Pigment dispersion, negative resist composition for color filter, color filter, liquid crystal display device and organic light emitting display device

The present invention relates to a pigment dispersion, a negative resist composition for a color filter using the pigment dispersion, a color filter formed using the negative resist composition, a liquid crystal display device having the color filter, and an organic The present invention relates to a light emitting display device.

In recent years, with the development of personal computers, particularly portable personal computers, the demand for liquid crystal displays has increased. Recently, the penetration rate of home-use liquid crystal televisions is also increasing, and the market for liquid crystal displays is expanding. Furthermore, with regard to the performance of the liquid crystal display, further improvement in image quality such as improvement in contrast and color reproducibility and reduction in power consumption are strongly desired.
Under such circumstances, there is an increasing demand for higher brightness, higher contrast, and improved color reproducibility even for color filters having a function of color-displaying a liquid crystal display. Recently, particularly for television applications, there is a growing demand for higher brightness due to reduced power consumption of the backlight and the characteristics of the LED backlight.
The above-described problems are the same in organic EL displays that are expected to be widely used in the future, and higher luminance and improved color reproducibility are problems to be solved in the displays.

Here, as a general method for producing a color filter, a coating film made of a photocurable negative resist composition in which a pigment of each color is dispersed is formed on a substrate on which a light shielding portion is formed in a pattern, A method is used in which a colored layer of each color is formed into a pattern by exposure and alkali development through a photomask having a desired pattern shape.

The color filter is formed by forming a three-color pattern of red, green, and blue on a transparent substrate such as glass. In order to form a red or green coloring pattern, it is difficult to obtain a desired spectral spectrum only with a red or green pigment, and therefore, a spectral spectrum is adjusted by mixing a yellow pigment.

Generally, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, since light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state), display devices in the ON state and the OFF state There is a problem that the upper luminance ratio (contrast ratio) is low. Therefore, C.I. which has been conventionally suitable for increasing the contrast. I. Pigment Yellow 150 has been used as a yellow pigment for adjusting the red color and the green color. However, C.I. I. When CI Pigment Yellow 150 was used, there was a problem that the luminance was not sufficiently high.

In order to solve the problem that the transmittance is low when a pigment is used compared to a dye, Patent Document 1 discloses C.I. I. A green resin composition using Pigment Yellow 138 is disclosed. Conventionally, however, C.I. I. When Pigment Yellow 138 is used, the contrast becomes low, and there is a problem that it is difficult to use particularly in television applications.
For the purpose of a green pigment compound having high saturation, high color strength, and high transparency, Patent Document 2 discloses C.I. I. Pigment Green 36 and C.I. I. A green pigment formulation comprising Pigment Yellow 138 monosulfonic acid and copper phthalocyanine sulfonic acid is described. However, when a conventional pigment dispersant as disclosed in Patent Document 2 is used, there is a problem that brightness and contrast are not sufficiently increased.

On the other hand, in Patent Document 3, as a green pigment dispersion that can be used for forming a coating film having excellent long-term dispersion stability and excellent lightness, C.I. I. A pigment dispersion containing a halogenated phthalocyanine zinc complex corresponding to CI Pigment Green 58 and a sulfonated pigment derivative as a secondary pigment is disclosed. However, as shown in a comparative example described later, when a conventional pigment dispersant as disclosed in Patent Document 3 is used, C.I. I. There is a problem that the pigment green 58 is not sufficiently miniaturized and the contrast is not sufficiently high.

Japanese Patent Laid-Open No. 11-256053 Special table 2008-538792 Special table 2009-126994

While the present inventors have been studying to satisfy the demand for high brightness and high contrast of the color filter, the pigment dispersion stability obtained by the research disperser is the dispersion for circulation type production. I faced a problem that was not always possible. For example, as shown in the examples described later, C.I. I. Pigment Green 58 improves dispersibility by increasing the dispersion time in the initial stage of dispersion. However, in the production disperser, if the dispersion time is slightly longer than the point at which the dispersibility is maximized, the dispersibility is reversed. As a result, the contrast is remarkably lowered when a coating film is formed. If the process margin is small so that dispersibility deteriorates if it is slightly overdispersed, there is a possibility that defective products may be produced in large quantities just by slightly changing the process characteristics for some reason.

The present invention has been made under the above circumstances, and achieves a demand for high brightness and high contrast, while having a large process margin in a production disperser, a pigment dispersion for color filters, and pigment dispersion Color filter negative resist composition for color filters that is excellent in alkali resistance and excellent in alkali developability, and is capable of forming a color filter with excellent brightness, high brightness, and high contrast. It is an object of the present invention to provide a color filter formed using a negative resist composition, and a liquid crystal display device and an organic light emitting display device having the color filter.

As a result of intensive studies to achieve the above object, the inventors of the present invention formed a salt between the organic phosphate compound and at least a part of the amino group of the structural unit of the polymer as a pigment dispersant. A specific block copolymer; I. When used in combination with a sulfonic acid derivative of CI Pigment Yellow 138, the pigment dispersion for color filters and the pigment dispersibility have a large process margin in the production disperser while achieving the demand for high brightness and high contrast. It has been found that a negative color resist composition for color filters which is excellent, can form a color filter with high brightness and high contrast, and is excellent in alkali developability can be obtained.
The present invention has been completed based on such findings.

The present invention includes a pigment, C.I. I. Pigment Yellow 138, a sulfonic acid derivative, a pigment dispersant, and a solvent, wherein the pigment dispersant is represented by the following general formula (I) and the following general formula (II): For color filters, wherein the block unit is a block copolymer in which at least a part of the amino group of the repeating unit (1) and an organic phosphate compound form a salt. A pigment dispersion is provided.

[In Formula (I) and Formula (II), R ¹ is a hydrogen atom or a methyl group, R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon atom having 1 carbon atom. To 8 alkylene groups, — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — or — [(CH ₂ ) _y —O] _z — ( A divalent group represented by CH ₂ ) _y —, R ⁴ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁶ ) —CH A monovalent group represented by (R ⁷ ) —O] _x —R ⁸ or — [(CH ₂ ) _y —O] _z —R ⁸ . R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group, and R ⁸ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, A monovalent group represented by —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , wherein R ⁹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; The alkyl group, alkenyl group, aralkyl group, and aryl group each may have a substituent.
x represents an integer of 1 to 18, y represents an integer of 1 to 5, and z represents an integer of 1 to 18. m represents an integer of 3 to 200, and n represents an integer of 10 to 200. ]

The negative resist composition for color filters according to the present invention comprises a pigment, C.I. I. Pigment Yellow 138 sulfonic acid derivative, a pigment dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent,
The pigment dispersant has a repeating unit (1) represented by the general formula (I) and a repeating unit (2) represented by the general formula (II), and further the repeating unit (1). It is a block copolymer in which at least a part of an amino group possessed by and an organic phosphate compound form a salt.

In the pigment dispersion and negative resist composition according to the present invention, C.I. I. Pigment green 58, C.I. I. Pigment green 36, C.I. I. Pigment yellow 150, and C.I. I. The inclusion of at least one selected from the group consisting of CI Pigment Yellow 138 is preferred from the standpoint that it is easy to achieve the demand for high brightness and high contrast.

In the pigment dispersion and the negative resist composition according to the present invention, in the pigment dispersant, it is high brightness that the organic phosphate compound is at least one kind represented by the following general formula (III). In addition, it is easy to achieve the demand for high contrast, and among them, it is preferable from the viewpoint of excellent alkali resistance.

[In the formula (III), R ^a and R ^{a ′} each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or a monovalent group represented by — [(CH ₂ ) _t —O] _u —R ^e , and R ^a and R ^{a ′} Either contains carbon atoms.
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or a monovalent group represented by —CH ₂ COOR ^f , and R ^f is a hydrogen atom or carbon An alkyl group of 1 to 5;
In R ^a and R ^{a ′} , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s represents an integer of 1 to 18, t represents an integer of 1 to 5, and u represents an integer of 1 to 18. ]

In the pigment dispersion and negative resist composition according to the present invention, the C.I. I. Pigment Yellow 138 sulfonic acid derivative is contained in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the pigment to produce a liquid crystal display device and an organic light emitting display device with high brightness, high contrast and high quality. This is preferable because it is possible and the process margin in the production disperser becomes large.

The present invention provides a color filter comprising a colored layer formed by curing the negative resist composition for a color filter.
The present invention also provides a liquid crystal display device comprising the color filter, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Furthermore, the present invention provides an organic light emitting display device comprising the color filter and an organic light emitter.

According to the present invention, a pigment dispersion for a color filter having a large process margin in a production disperser, and excellent in pigment dispersibility, achieving high brightness and high contrast while achieving a demand for high brightness and high contrast. It is possible to provide a negative resist composition for a color filter that can form a contrast color filter and is excellent in alkali developability. By using the negative resist composition of the present invention, it is possible to provide a color filter with high brightness and high contrast and high productivity.
Furthermore, according to the present invention, by using the color filter, it is possible to provide a liquid crystal display device and an organic light emitting display device with high brightness and high contrast.

It is the schematic which shows an example of the color filter of this invention. It is the schematic which shows an example of the liquid crystal display device of this invention. It is the schematic which shows an example of the organic light emitting display apparatus of this invention.

Hereinafter, the pigment dispersion for color filter, the negative resist composition for color filter, the color filter, the liquid crystal display device and the organic light emitting display device of the present invention will be described in order.
In the present invention, the light includes electromagnetic waves having wavelengths in the visible and non-visible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it refers to an electromagnetic wave having a wavelength of 5 μm or less and an electron beam. In the present invention, (meth) acryl means either acryl or methacryl, and (meth) acrylate means either acrylate or methacrylate.

1. Color filter pigment dispersion The color filter pigment dispersion according to the present invention comprises a pigment, C.I. I. Pigment Yellow 138, a sulfonic acid derivative, a pigment dispersant, and a solvent,
The pigment dispersant has a repeating unit (1) represented by the following general formula (I) and a repeating unit (2) represented by the following general formula (II), and further the repeating unit (1) It is a block copolymer in which at least a part of an amino group possessed by and an organic phosphate compound form a salt.

According to the present invention, as the pigment dispersant, a specific block copolymer in which at least a part of the amino group of the structural unit of the polymer and an organic phosphate compound form a salt; I. By using a combination of Pigment Yellow 138 sulfonic acid derivatives, it is possible to obtain a pigment dispersion for a color filter having a high process margin in a production disperser while achieving high brightness and high contrast requirements. it can.

The use of the specific pigment dispersant as described above is not yet elucidated as an effect of exerting the above effects, but is presumed as follows.
According to the present invention, the pigment dispersant used has the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the general formula (II), And the said structural unit (1) which forms a salt formation site | part by being a salt-type block copolymer in which the amino group and organic phosphoric acid compound which the said structural unit (1) has formed a salt by salt formation. When the solubility in the solvent is lowered, the pigment has a high adsorptivity with respect to the pigment which is a component insoluble in the solvent, while the structural unit (2) is soluble in the solvent. And C.I. I. Pigment Yellow 138 sulfonic acid derivatives include C.I. I. The skeleton of Pigment Yellow 138 itself has an aromatic ring and has high affinity with the pigment, while the sulfo group interacts strongly with the amino group or ammonium salt portion of the pigment dispersant. Therefore, the salt type block copolymer and C.I. I. When combined with the sulfonic acid derivative of CI Pigment Yellow 138, the synergistic effect causes C.I. I. It is presumed that the sulfonic acid derivative of Pigment Yellow 138 and the salt-type block copolymer are immediately adsorbed, and the pigment can be stabilized in the solvent, and the pigment can be further refined. . As a result, a coating film with improved contrast can be obtained. In addition, C.I. I. When the sulfonic acid derivative of Pigment Yellow 138 acts on the surface of the refined pigment, the stability of the crystal state of the pigment is increased, and even when the pigment having a small process margin in the production disperser is overdispersed, It is presumed that the dispersibility does not deteriorate without any change in color or precipitation of aggregates.

Also, C.I. used in the present invention. I. Pigment Yellow 138, a sulfonic acid derivative, has been widely used as a yellow pigment in order to increase contrast. I. Brightness is higher than that of CI Pigment Yellow 150, and C.I. I. Compared to Pigment Yellow 138, the contrast is less likely to decrease due to light scattering. Therefore, it is estimated that the brightness is improved and the deterioration of contrast is suppressed.

The pigment dispersion for a color filter of the present invention contains at least a pigment, C.I. I. It contains a sulfonic acid derivative of Pigment Yellow 138, the specific salt-type pigment dispersant, and a solvent as essential components, and may contain other components as necessary.
Hereinafter, each component of the pigment dispersion of the present invention will be described in detail in order.

(Pigment)
The pigment used in the pigment dispersion for the color filter of the present invention is not particularly limited as long as it can produce a desired color when forming the color layer of the color filter, and various organic or inorganic colorants are used. These can be used alone or in admixture of two or more.

<Type of pigment>
As the organic colorant, for example, dyes, organic pigments, natural pigments, and the like can be used. Specific examples of the organic pigments include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists).
Examples of such compounds include C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, C.I. I. Yellow pigments such as C.I. Pigment Yellow 185; I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Red pigments such as C.I. Pigment Red 177; I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. C.I. Blue pigments such as CI Pigment Blue 15: 6; I. Pigment Violet 23 such as Pigment Violet 23; and Pigment Green 36, Pigment Green 7, C.I. I. And pigments having a color index (C.I.) number such as CI Pigment Green 58.

Further, as the inorganic colorant, for example, inorganic pigments, extender pigments and the like can be used. Specific examples include titanium oxide, silica, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, Bengala (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like can be mentioned.

Derivative pigments may also be used. For example, C.I. Pigment Yellow 150 derivative pigments are preferably used. C. I. Pigment Yellow 150 derivative pigments specifically include mono-, di-, tri- and tetraanions of azo compounds according to the following chemical formula or one of their tautomeric structures that act as hosts for at least one guest compound And metal complexes corresponding to Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, particularly preferably Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu, Mn and La Can be mentioned.

[Wherein R and R ′ are independently OH, NH ₂ , NH—CN, acylamino or arylamino, and R ^a and R ^a ′ are independently —OH or —NH ₂ Is]

These derivative pigments are disclosed in JP 2001-354869, JP 2005-325350, JP 2007-25687, JP 2007-23287, JP 2007-23288, and JP 2008. It can be obtained by referring to Japanese Patent No. -24927.

In the present invention, examples of the pigment include C.I. I. Pigment green 58, C.I. I. Pigment green 36, C.I. I. Pigment yellow 150, and C.I. I. The inclusion of at least one selected from the group consisting of CI Pigment Yellow 138 is preferred from the standpoint of easily achieving the demand for high brightness and high contrast. Among these, C.I. I. When the pigment green 58 is included, the advantage of the present application that a pigment dispersion for a color filter having a large process margin in a production disperser can be obtained can be enjoyed effectively.

In the present invention, in order to prepare a green pigment dispersion for forming a green colored layer, at least C.I. I. Pigment Green 58, and C.I. I. Pigment yellow 150 and / or C.I. I. It is preferable that Pigment Yellow 138 is included because it is easy to achieve the demand for high brightness and high contrast.

<Particle particle size>
The average primary particle size of the pigment used in the present invention is not particularly limited as long as it can produce a desired color when it is used as a colored layer of a color filter, and varies depending on the type of pigment used. It is preferably in the range of 10 to 100 nm, more preferably in the range of 10 to 50 nm. When the average primary particle size of the pigment is in the above range, a liquid crystal display device and an organic light emitting display device manufactured using the negative resist composition for a color filter of the present invention have high contrast and high quality. It can be. In addition, with conventional pigment dispersants, a large amount of pigment dispersant is required as the particle size of the pigment becomes finer, which may cause problems such as reduced alkali developability and increased residue. Since the pigment dispersant used for the color filter pigment dispersion and the negative resist composition is excellent in alkali developability, it is less likely to cause such a problem. Therefore, as the average primary particle size of the pigment is within the above range, the smaller the conventional primary particle size is, the more the characteristics of the negative resist composition for color filters of the present invention can be exhibited.
The average primary particle size of the pigment can be determined by a method of directly measuring the size of the primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of each primary particle were measured, and the average was taken as the particle diameter of the particle. Next, for 100 or more particles, the volume (weight) of each particle was obtained by approximating the obtained particle size to a rectangular parallelepiped, and the volume average particle size was obtained and used as the average particle size. The same result can be obtained regardless of whether the electron microscope is a transmission type (TEM) or a scanning type (SEM).

In the color filter pigment dispersion of the present invention, the pigment content is not particularly limited. Usually, the pigment content is preferably 5 to 40% by weight, more preferably 10 to 20% by weight, based on the total amount of the pigment dispersion for the color filter.

(C.I. Pigment Yellow 138 sulfonic acid derivative)
C. I. Pigment Yellow 138 has a sulfonic acid derivative in which at least one sulfo group has the above structure. I. It has a structure bonded to CI Pigment Yellow 138. The sulfo group may be C.I. via an alkyl group or an aryl group. I. Pigment Yellow 138 may be bonded to C.I. from the viewpoint that the reaction can be synthesized in one step. I. It is preferable that the structure is as follows in which a sulfo group is directly bonded to CI Pigment Yellow 138.

(In the formula, n represents the number of sulfo groups substituted and represents an integer of 1 to 5.)

The number of substitution of the sulfo group is preferably 1 to 2, more preferably 1.

C. I. Examples of the sulfonic acid derivative of CI Pigment Yellow 138 include C.I. I. Pigment Yellow 138 can be produced by adding it to concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, or a mixture thereof to carry out the sulfonation reaction. C. I. As the sulfonic acid derivative of Pigment Yellow 138, one kind can be used alone, or two or more kinds can be used in combination. For example, two or more sulfonic acid derivatives having different sulfo group substitution positions or substitution numbers may be used.

In the present invention, C.I. I. The sulfonic acid derivative of Pigment Yellow 138 is preferably contained in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the pigment. Among them, C.I. I. Pigment Yellow 138 sulfonic acid derivative is contained in an amount of 0.5 to 10 parts by weight, and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the pigment. This is preferable because an organic light emitting display device can be produced and a process margin in a production disperser becomes large.

(Pigment dispersant)
The pigment dispersant used in the present invention has the repeating unit (1) represented by the above general formula (I) and the repeating unit (2) represented by the above general formula (II), and further the above repeating It is a block copolymer in which at least a part of the amino group of the unit (1) and an organic phosphate compound form a salt.

<Block copolymer>
The block copolymer has a repeating unit (1) represented by the general formula (I) and a repeating unit (2) represented by the general formula (II).
In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Here, the alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl groups, various hexyl groups, and various octyl groups. Group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. Among these, a methyl group and an ethyl group are preferable.
In the present invention, R ² and R ³ may be the same as or different from each other.

A represents an alkylene group having 1 to 8 carbon atoms, * — [CH (R ⁶ ) —CH (R ⁷ ) —O] _x —CH (R ⁶ ) —CH (R ⁷ ) — **, or * — [(CH ₂ ) _y —O] _z — (CH ₂ ) _y — ** is a divalent group. Here, * represents a linking site on the ester bond side, and ** represents a linking site on the amino group side. In addition, the alkylene group having 1 to 8 carbon atoms may be linear or branched, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a propylene group, various butylene groups, various pentylene groups, and various types. Hexylene group and various octylene groups.
R ⁶ and R ⁷ are each independently a hydrogen atom or a methyl group.
x is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and y is an integer of 1 to 5, preferably an integer of 1 to 4, more preferably 2 or 3. is there. z is an integer of 1 to 18, preferably an integer of 1 to 4, more preferably an integer of 1 to 2. In the present invention, if x, y, and z are within the above ranges, the color filter pigment dispersion of the present invention has excellent pigment dispersibility.
A is preferably an alkylene group having 1 to 8 carbon atoms, more preferably a methylene group or an ethylene group. If the carbon number is in the range of 1 to 8, the dispersibility of the pigment can be kept good.

In the general formula (II), R ⁴ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ⁶ ) —CH (R ⁷ ) — O] _x -R ⁸ or-[(CH ₂ ) _y -O] _z -R ⁸ is shown.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group. , Sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, cyclopentyl groups, cyclohexyl groups, cyclohexane Examples include an octyl group, a cyclododecyl group, a bornyl group, an isobornyl group, a dicyclopentanyl group, an adamantyl group, and a lower alkyl group-substituted adamantyl group.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl, allyl, propenyl, various butenyl, various hexenyl, various octenyl, various decenyl, various dodecenyl, various tetradecenyl, various hexadecenyl, various octadecenyl, A cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, etc. can be mentioned. The position of the double bond of the alkenyl group is not limited, but from the viewpoint of the reactivity of the polymer obtained, it is preferable that a double bond is present at the terminal of the alkenyl group.

Examples of the aryl group that may have a substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, and a xylyl group. The aryl group preferably has 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms.
Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, and a biphenylmethyl group. The aralkyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 14 carbon atoms.
Examples of the substituent of the aromatic ring such as an aryl group and an aralkyl group include an alkenyl group, a nitro group, and a halogen atom in addition to a linear or branched alkyl group having 1 to 4 carbon atoms.
The preferred carbon number does not include the carbon number of the substituent.

R ⁶ and R ⁷ are the same as described above, and R ⁸ is a hydrogen atom or an optionally substituted alkyl group having 1 to 18 carbon atoms, alkenyl group having 2 to 18 carbon atoms, or aralkyl group. , An aryl group, —CHO, —CH ₂ CHO, or —CH ₂ COOR ⁹ , wherein R ⁹ is a hydrogen atom or a linear, branched, or cyclic group having 1 to 5 carbon atoms It is an alkyl group.
In the monovalent group represented by R ⁸ , examples of the substituent that may be included include linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms, and halogen atoms such as F, Cl, and Br. And so on.
The alkyl group, and alkenyl group having 2 to 18 carbon atoms having 1 to 18 carbon atoms of R ^8, an aralkyl group, an aryl group is as shown by the R ^4.
In the above R ⁴ , x, y and z are as described in the above A.
Moreover, R ⁴ in the repeating unit (2) represented by the general formula (II) may be the same or different.

In the present invention, as R ⁴ , it is preferable to use one having excellent solubility with a solvent described later, and specifically, it varies depending on the repeating unit constituting the block copolymer. When the solvent is an ether alcohol acetate solvent, an ether solvent, an ester solvent or the like generally used as a color filter solvent, a methyl group, an ethyl group, an n-butyl group, 2- An ethylhexyl group, a benzyl group and the like are preferable. Moreover, when the said solvent is a thing with lower polarity, such as pentane and hexane, it is preferable to use a pentyl group, a hexyl group, a heptyl group, etc.
Here, the reason for setting R ⁴ in this way is that the repeating unit (2) containing R ⁴ has good solubility in the solvent, and the amino group of the repeating unit (1) is described later. This is because the dispersibility and stability of the pigment can be made particularly excellent when the salt-forming site formed by the organophosphate compound has high adsorptivity to the pigment.

Further, R ⁴ is substituted with a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bond-forming group as long as it does not interfere with the dispersion performance of the block copolymer. Alternatively, after the synthesis of the block copolymer, the substituent may be added by reacting with the compound having the substituent. Moreover, after synthesizing a block copolymer having these substituents, a compound having a functional group that reacts with the substituent and a polymerizable group may be reacted to add a polymerizable group. For example, adding a polymerizable group by reacting a block copolymer having a carboxyl group with glycidyl (meth) acrylate, or reacting a block copolymer having an isocyanate group with hydroxyethyl (meth) acrylate. Can do.

The ratio m / n of the unit number m of the structural unit (1) and the unit number n of the structural unit (2) used in the present invention is preferably within the range of 0.01 to 1, preferably 0.05 to More preferably, it is in the range of 0.5. When the ratio m / n is within the above range, the ratio between the amino group of the structural unit (1) and the acid compound present on the pigment surface is appropriate, so that the adsorptivity to the pigment is good and the structural unit is The solubility with the solvent according to (2) does not decrease, and the dispersibility and stability of the pigment do not decrease.

Regarding the molecular size of the block copolymer used in the present invention, the number m of the repeating unit (1) is an integer of 3 to 200, preferably an integer of 3 to 50. The number n of the repeating units (2) is an integer of 10 to 200, preferably an integer of 20 to 100, more preferably an integer of 20 to 70. In the present invention, when m and n are within the above ranges, the solvent-soluble part and the solvent-insoluble part effectively act, and the pigment dispersion for the color filter of the invention is excellent in pigment dispersibility. Can be.
Further, the weight average molecular weight Mw of the block copolymer is preferably in the range of 500 to 20000, more preferably in the range of 1000 to 15000, and further preferably in the range of 3000 to 12000. preferable. By being within the above range, it becomes possible to achieve both wettability and dispersion stability with respect to a pigment in the initial stage of dispersion in which the pigment is uniformly dispersed.

The weight average molecular weight Mw is a value measured by GPC (gel permeation chromatography). For the measurement, HLC-8120GPC manufactured by Tosoh Corporation was used, the elution solvent was N-methylpyrrolidone to which 0.01 mol / liter of lithium bromide was added, and polystyrene standards for calibration curves were Mw377400, 210500, 96000, 50400. 206500, 10850, 5460, 2930, 1300, 580 (Easy PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Corporation), and TSK-GEL ALPHA-M × 2 (Tosoh Corporation) (Made by Co., Ltd.).

The bonding order of the block copolymer used in the present invention is not particularly limited as long as it has the repeating unit (1) and the repeating unit (2) and can stably disperse the pigment. However, it is preferable that the repeating unit (1) is bonded to only one end of the block copolymer. That is, the repeating unit (1) and the repeating unit (2) may be bonded in the order of the repeating unit (1) -the repeating unit (2), or the repeating unit (1) -the repeating unit. (2) -repeated unit (1) may be bonded in this order, or repeating unit (1) -repeating unit (2) may be bonded repeatedly, but in the present invention, However, those bonded in the order of the repeating unit (1) to the repeating unit (2) are preferred. The reason is that it is excellent in the adsorptivity with respect to a pigment, and also the aggregation of pigment dispersants using such a block copolymer can be effectively suppressed.

In the case where two or more types of the structural unit (1) and the structural unit (2) are included, a block copolymer in which the structural unit (1), the structural unit (2 ′), and the structural unit (2 ″) are combined in this order, A block copolymer bonded in the order of structural unit (1 ′) − structural unit (1 ″) − structural unit (2), structural unit (1 ′) − structural unit (1 ″) − structural unit (2 ′) -It may be a block copolymer bonded in the order of the structural unit (2 ").

<Organic phosphate compound>
An amino group contained in the structural unit (1) of the block copolymer having the structural unit (1) represented by the general formula (I) and the structural unit (2) represented by the general formula (II); Examples of the organic phosphate compound that forms a salt include an organic phosphate compound having a structure represented by the following general formula (III).

[In the formula (III), R ^a and R ^{a ′} each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or ^a monovalent group represented by —O—R ^{a ″} , R ^a and R ^{a ′} each contain a carbon atom. R ^{a ″} is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e ,-[(CH ₂ ) _t —O] _u —R ^e .
R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or a monovalent group represented by —CH ₂ COOR ^f , and R ^f is a hydrogen atom or carbon An alkyl group of 1 to 5;
In R ^a and R ^{a ′} , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s represents an integer of 1 to 18, t represents an integer of 1 to 5, and u represents an integer of 1 to 18. ]

In the present invention, by using the above organic phosphoric acid compound, the pigment dispersant can be made excellent in pigment dispersibility and stability. Furthermore, since an organic acid compound is used for the pigment dispersant, the salt-forming site has high solubility in an aqueous alkali solution at the time of alkali development, and therefore, the alkali developability can be improved.

In the general formula (III), R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [ CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , or —O—R ^{a ″} , R ^a and R ^a Any of ^' includes carbon atoms.

The alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the aryl group, and the aralkyl group are as described above for R ⁴ . The position of the double bond of the alkenyl group is not limited, but from the viewpoint of reactivity, it is preferable that the alkenyl group has a double bond at the terminal.
The alkyl group or alkenyl group may have a substituent, and examples of the substituent include halogen atoms such as F, Cl, and Br, nitro groups, and the like.
In addition, examples of the substituent of the aromatic ring such as the aryl group and the aralkyl group include alkenyl groups, nitro groups, and halogen atoms in addition to linear or branched alkyl groups having 1 to 4 carbon atoms. .

R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, or an aryl group. , —CHO, —CH ₂ CHO, —CO—CH═CH ₂ , —CO—C (CH ₃ ) ═CH ₂ or —CH ₂ COOR ^f , and R ^f is a hydrogen atom or A linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms.

In the monovalent group represented by R ^e, Examples of the substituent which may have, for example, C 1-4 straight, branched or cyclic alkyl group, F, Cl, halogen atom such as Br And so on.
The alkyl group having 1 to 18 carbon atoms in the above R ^e is as shown in the above R ⁴ , and the alkenyl group, aralkyl group and aryl group having 2 to 18 carbon atoms are represented by the above R ^a and R ^{a ′.} It is as shown in.

When R ^a and / or R ^{a ′} is —O—R ^{a ″} , it is an acidic phosphate ester. R ^a ″ represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e is a monovalent group represented by — [(CH ₂ ) _t —O] _u —R ^e .
The alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the aralkyl group, and the aryl group are as described above for R ^a and R ^{a ′} . When R ^{a ″} has an aromatic ring, it may have an appropriate substituent on the aromatic ring, for example, a linear or branched alkyl group having 1 to 4 carbon atoms.

In R ^a , R ^{a ′} and R ^{a ″} , s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. s is preferably an integer of 1 to 4, more preferably an integer of 1 to 2, and t is preferably an integer of 1 to 4, more preferably 2 or 3. u is preferably an integer of 1 to 4, more preferably an integer of 1 to 2.

As the organophosphate compound represented by the general formula (III), R ^a and R ^{a ′} in the general formula (III) are each independently a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, or a substituent. Aryl group or aralkyl group, vinyl group, allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O], which may have _u —R ^e or a monovalent group represented by —O—R ^{a ″} , one of R ^a and R ^{a ′} contains a carbon atom, and R ^{a ″} is a methyl group, An ethyl group, an aryl or aralkyl group which may have a substituent, a vinyl group, an allyl group, — [CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂₎ a _{_{^{^{t -O] u -R e, R}}}} c and ^{R d} are each independently a hydrogen atom or methyl , And the preferable from the viewpoint of can be made of those ^{R e} is -CO-CH = CH ₂ or _{-CO-C (CH} 3) a = CH ₂ is excellent in pigment dispersibility.

Among these, the organophosphate compound represented by the general formula (III) preferably has an aromatic ring as R ^a , R ^{a ′} and / or R ^{a ″} from the viewpoint of pigment dispersibility. At least one of R ^a , R ^{a ′} and R ^{a ″} may have an optionally substituted aryl group or aralkyl group, more specifically, a benzyl group, a phenyl group, a tolyl group, a naphthyl group, biphenyl A group is preferred from the viewpoint of pigment dispersibility. In the general formula (III), when one of R ^a and R ^{a ′} has an aromatic ring, the other of R ^a and R ^{a ′} is preferably a hydrogen atom or a hydroxyl group.

In addition, from the viewpoint of heat resistance, chemical resistance, particularly alkali resistance of the colored layer to be formed, as an organic phosphate compound represented by the general formula (III), a carbon atom is directly bonded to phosphorus (P). R ^a and R ^{a ′} are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [ CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , — [(CH ₂ ) _t —O] _u —R ^e , a monovalent group represented by R ^a and R ^{a ′} Any of them contains a carbon atom, and R ^c and R ^d are each independently a hydrogen atom or a methyl group, and R ^e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. Alkenyl group, aralkyl group, aryl group, —CHO, —C _{_{2 CHO, -CO-CH = CH}} 2, a monovalent group represented by _{-CO-C (CH 3) =}

CH

2 or _-CH 2 COOR ^{^f, R} ^f is a hydrogen atom or a C 1-5 An alkyl group is preferred. By using an organic phosphoric acid compound in which a carbon atom is directly bonded to phosphorus (P), the alkali resistance of a colored layer formed using a negative resist composition for a color filter can be improved. In general, organophosphate compounds have high adhesion to inorganic materials such as glass, and the structure in which carbon atoms are directly bonded to phosphorus is excellent in heat resistance and hydrolysis resistance. Therefore, it is presumed that the hydrolysis reaction in the presence of alkali hardly occurs.
When the alkali resistance of the colored layer is high, the colored layer is not peeled off in the step of treating the color filter substrate with a strong alkaline agent.

The organophosphate compound represented by the general formula (III) has a polymerizable group as R ^a , R ^{a ′} and / or R ^{a ″} , that is, a vinyl group, an allyl group, or — [ CH (R ^c ) —CH (R ^d ) —O] _s —R ^e , or — [(CH ₂ ) _t —O] _u —R ^e , and R ^e is —CO—CH═CH ₂ or Those in which —CO—C (CH ₃ ) ═CH ₂ are preferred, and in particular, R ^a , R ^{a ′} and / or R ^{a ″} are vinyl, allyl, 2-methacryloyloxyethyl, 2-acryloyl. Those that are oxyethyl groups are preferred.
In such a case, the above-mentioned polymerizable groups and / or the above-mentioned polymerizable groups and the color filter of the present invention are exposed during exposure when forming a colored layer using the negative resist composition for color filters of the present invention. Can be easily polymerized with an alkali-soluble resin and a polyfunctional monomer contained in the negative resist composition for use, and the pigment dispersant can be stably present in the colored layer of the color filter. To do. When a liquid crystal display device is manufactured using such a color filter, the pigment dispersant can be prevented from bleeding out to the liquid crystal layer or the like.

In addition, since the organic phosphate compound contains a polymerizable group, the polymerizable group of the organic phosphate compound can be polymerized before being used for forming the colored layer, and as a result, the pigment dispersant is high. Since the molecular weight is increased, the negative resist composition for a color filter at an unexposed portion can be made particularly excellent in alkali developability during development for forming a colored layer.

In addition, the organic phosphoric acid compound represented by the general formula (III) can be used alone or in combination of two or more.
The content of the organic phosphoric acid compound used in the present invention is not particularly limited as long as good dispersion stability is exhibited, and is generally a tertiary amino group represented by the general formula (I). On the other hand, it is about 0.05 to 5.0 molar equivalents, more preferably 0.2 to 2.0 molar equivalents. In such a case, the pigment dispersibility and the pigment dispersion stability are excellent. In addition, when using 2 or more types of the said organic phosphoric acid compounds together, content which added these should just be in the said range.

<Manufacture of pigment dispersant>
In the present invention, as a method for producing a block copolymer used as a pigment dispersant, the repeating unit (1) and the repeating unit (2) are included, and the repeating unit (1) has an amino group. Any method can be used as long as it can produce a salt in which the above organic phosphate compound forms a salt. In the present invention, for example, the repeating unit (1) and the repeating unit (2) are polymerized using a known polymerization means, and then dissolved or dispersed in a solvent described later, and then the organic phosphorus is dissolved in the solvent. A pigment dispersant can be produced by adding an acid compound and stirring.

The polymerization means is not particularly limited as long as it is a means capable of polymerizing the above repeating unit (1) and repeating unit (2) in a desired number to obtain a desired molecular weight, and has a vinyl group. A method generally used for polymerization of a compound can be employed, and for example, anionic polymerization, living radical polymerization, or the like can be used. In the present invention, among them, a method in which polymerization proceeds in a living manner, such as group transfer polymerization (GTP) disclosed in “J. Am. Chem. Soc.” 105, 5706 (1983), is used. preferable. According to this method, the molecular weight, the molecular weight distribution, etc. can be easily set in a desired range, so that the dispersibility of the pigment dispersant can be made uniform.

In the pigment dispersion for a color filter of the present invention, as the pigment dispersant, one type of the block copolymer may be used, or two or more types may be used in combination. The content thereof is not particularly limited as long as the pigment can be uniformly dispersed. For example, 10 to 150 parts by weight can be used with respect to 100 parts by weight of the pigment. Further, it is preferably blended at a ratio of 15 to 45 parts by weight with respect to 100 parts by weight of the pigment, particularly preferably at a ratio of 15 to 40 parts by weight. If the content of the salt type block copolymer is within the above range, the pigment can be uniformly dispersed. In the present invention, the pigment used when the content other than the pigment derivative is defined includes a pigment derivative in addition to the pigment. I. Also included is the sulfonic acid derivative of CI Pigment Yellow 138.

(solvent)
The pigment dispersion for a color filter according to the present invention contains a solvent for dispersing the pigment. The solvent used in the pigment dispersion is not particularly limited as long as it is an organic solvent that does not react with each component in the pigment dispersion and can dissolve or disperse them.
Examples of the solvent used in the pigment dispersion of the present invention include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; methoxyethoxyethanol, Carbitol solvents such as ethoxyethoxyethanol; ester solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone and cyclohexanone; methoxyethyl acetate , Propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, methoxybutyl acetate, ethoxy Cellosolve acetate solvents such as til acetate and ethyl cellosolve acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, and butyl carbitol acetate (BCA); Diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol Ether solvents such as monomethyl ether and tetrahydrofuran; aprotic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; benzene, toluene and xylene , Unsaturated hydrocarbon solvents such as naphthalene; saturated hydrocarbons such as N-heptane, N-hexane and N-octane Organic solvents such as system solvents can be mentioned. Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 3-methoxybutyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate; Carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate, butyl carbitol acetate (BCA); ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether; methyl methoxypropionate, ethoxypropionic acid Ester solvents such as ethyl and ethyl lactate; ketone solvents such as cyclohexanone are preferred Used. Among them, as the solvent used in the present invention, propylene glycol monomethyl ether acetate (CH ₃ OCH ₂ CH (CH ₃ ) OCOCH ₃ ), propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl- One or more selected from the group consisting of 1-butyl acetate, 3-methoxybutyl acetate and cyclohexanone is preferable from the viewpoint of solubility of other components and coating suitability.

These solvents may be used alone or in combination of two or more.
The pigment dispersion of the present invention is prepared using the solvent as described above usually in a proportion of 50 to 85% by weight with respect to the total amount of the pigment dispersion containing the solvent. Further, it is preferably prepared by using 60 to 85% by weight. When the amount of the solvent is too small, the viscosity increases and the pigment dispersibility tends to decrease. Moreover, when there are too many solvents, a pigment density | concentration will fall and it may be difficult to achieve the chromaticity coordinate which makes a resist composition the target after preparation.

(Other ingredients)
If necessary, the pigment dispersion liquid of the present invention may further contain a pigment dispersion auxiliary resin and other components.
Examples of the pigment dispersion auxiliary resin include alkali-soluble resins exemplified by a resist composition described later. In some cases, the steric hindrance of the alkali-soluble resin makes it difficult for the pigment particles to come into contact with each other.
Moreover, as long as the effect of this invention is not impaired, the other pigment dispersant and pigment derivative may be included.
Other components include, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, antifoaming agents, repellency inhibitors, antioxidants, anti-aggregation agents, and UV absorbers. Etc.

<Method for producing pigment dispersion>
The pigment dispersion of the present invention is prepared by mixing and stirring the specific salt type pigment dispersant in a solvent to prepare a pigment dispersant solution, and then adding the pigment and the pigment derivative to the pigment dispersant solution. A pigment dispersion can be prepared by dispersing using a machine. The pigment dispersion of the present invention may be prepared by mixing a pigment, a pigment derivative, and a pigment dispersant in a solvent and dispersing the mixture using a known disperser. Further, the pigment dispersion of the present invention comprises the above-mentioned specific salt type pigment dispersant and the C.I. I. Pigment Yellow 138 sulfonic acid derivative is mixed in a solvent and stirred, and a part of the amino group of the pigment dispersant and C.I. I. Pigment Yellow 138 sulfonic acid derivative and a salt are formed to prepare a pigment dispersant solution, and then a pigment is added to the pigment dispersant solution and dispersed using a disperser to prepare a pigment dispersion. May be.

Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibration ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 2.00 mm, more preferably 0.10 to 1.0 mm.
According to the present invention, the process margin of the dispersion condition is increased, and even if dispersed for a long time, the dispersibility can be suppressed immediately. In addition, a pigment dispersion having excellent dispersion stability can be prepared.

Specifically, preliminary dispersion is performed with 1.0 to 2.0 mm zirconia beads having a relatively large bead diameter, and the main dispersion is further performed with 0.03 to 0.1 mm zirconia beads having a relatively small bead diameter. Can be mentioned. Further, after dispersion, it is preferably filtered through a membrane filter of 0.5 to 0.1 μm.

In the present invention, the dispersion time for dispersion using a known disperser is appropriately adjusted and is not particularly limited, but is preferable from the viewpoint of realizing high contrast by refining the pigment.
In this manner, a pigment dispersion having excellent pigment particle dispersibility is obtained. The pigment dispersion is used as a preliminary preparation for preparing a negative resist composition for color filters having excellent pigment dispersibility.

2. Negative resist composition for color filter The negative resist composition for color filter according to the present invention comprises a pigment, C.I. I. Pigment Yellow 138 sulfonic acid derivative, a pigment dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent,
The pigment dispersant has a repeating unit (1) represented by the following general formula (I) and a repeating unit (2) represented by the following general formula (II), and further the repeating unit (1) It is a block copolymer in which at least a part of an amino group possessed by and an organic phosphate compound form a salt.

The negative resist composition for a color filter according to the present invention is a specific block copolymer in which at least a part of an amino group of a constituent unit of a polymer and an organic phosphate compound form a salt as a pigment dispersant. And C.I. I. By using the sulfonic acid derivative of Pigment Yellow 138 in combination, it is excellent in pigment dispersibility, can form a color filter with high brightness and high contrast, and is excellent in alkali developability.

The negative resist composition for color filters according to the present invention is excellent in pigment dispersibility, and can form a color filter with high brightness and high contrast, as described in the pigment dispersion according to the present invention. It is estimated that it is the same effect.
In addition, in conventional pigment dispersants, increasing the amount added reduces alkali developability, lengthens the time required for alkali development, and unexposed photocurable resist composition on the substrate. There has been a problem of remaining, resulting in a decrease in productivity and quality. On the other hand, the pigment dispersant used in the present invention has a salt-forming site formed by at least a part of the amino group of the structural unit of the polymer and the organic phosphate compound, with respect to the alkaline aqueous solution at the time of alkali development. Since it has high solubility, it can be excellent in alkali developability. Therefore, when a color filter is produced using the negative resist composition for a color filter of the present invention, the alkali development time can be shortened and the productivity can be improved. Moreover, by being excellent in alkali developability, it is possible to obtain a high-quality color filter with little residue of the negative resist composition for color filter in an unexposed area.

Hereinafter, components used in such a negative resist composition for a color filter of the present invention will be described.
The above-mentioned specific salt-type pigment dispersant, pigment, C.I. which is an essential component of the color filter pigment dispersion according to the present invention. I. As the sulfonic acid derivative and the solvent of Pigment Yellow 138, the same ones as those described in the above-mentioned pigment dispersion can be used, and thus description thereof is omitted here.

(Alkali-soluble resin)
As the alkali-soluble resin used in the negative resist composition for a color filter of the present invention, those generally used for negative resists can be used as long as they are soluble in an alkaline aqueous solution. As described above, the alkali-soluble resin can also be used as a pigment dispersion auxiliary resin. In some cases, the steric hindrance of the alkali-soluble resin makes it difficult for the pigment particles to come into contact with each other, and may have the effect of stabilizing the dispersion and reducing the pigment dispersant due to the dispersion stabilization effect.
The alkali-soluble resin is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (Meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate , N-decyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicycle Pentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, allyl (meth) acrylate, 2,2′-oxybis (methylene) bis-2-propenoate, styrene, γ-methylstyrene, glycidyl (meth) acrylate, 2- Selected from hydroxylethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, N-vinyl-2-pyrrolidone, N-methylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, etc. One or more, (meth) acrylic acid, dimer of acrylic acid (for example, M-5600 manufactured by Toagosei Co., Ltd.), itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and anhydrous Copolymer comprising at least one selected from among products It can be exemplified. In addition, for example, a polymer having an ethylenically unsaturated bond introduced by adding an ethylenically unsaturated compound having a reactive functional group such as a glycidyl group or a hydroxyl group to the above copolymer can be exemplified, but the present invention is not limited thereto. Is not to be done.
Among these, a polymer having an ethylenically unsaturated bond introduced, for example, by adding an ethylenically unsaturated compound having a glycidyl group or a hydroxyl group to the copolymer is polymerized with a polyfunctional monomer described later at the time of exposure. This is particularly suitable in that the colored layer becomes more stable.

The alkali-soluble resin used in the negative resist composition for color filters of the present invention may be used singly or in combination of two or more, and the content thereof is a negative resist for color filters. The amount is usually in the range of 10 to 1000 parts by weight, preferably in the range of 20 to 500 parts by weight with respect to 100 parts by weight of the pigment contained in the composition. If the content of the alkali-soluble resin is too small, sufficient alkali developability and a function as a dispersion auxiliary resin may not be obtained. If the content of the alkali-soluble resin is too large, the ratio of the pigment is relatively high. In some cases, a sufficient color density cannot be obtained.

(Multifunctional monomer)
The polyfunctional monomer used in the negative resist composition for color filters of the present invention is not particularly limited as long as it can be polymerized by a photoinitiator described later, and usually contains an ethylenically unsaturated double bond. A compound having two or more compounds is used, and a polyfunctional (meth) acrylate having two or more acryloyl groups or methacryloyl groups is particularly preferable.

Examples of such polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, long chain aliphatic di (meth) acrylate, and neopentyl glycol di (Meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerol di (meth) acrylate, triethylene glycol di (meth) Acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, dicyclopentani Di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, allylated cyclohexyl di (meth) acrylate , Methoxylated cyclohexyl di (meth) acrylate, acrylated isocyanurate, bis (acryloxyneopentyl glycol) adipate, bisphenol A di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, bisphenol S di (meth) acrylate , Butanediol di (meth) acrylate, phthalic acid di (meth) acrylate, phosphoric acid di (meth) acrylate, zinc di (meth) acrylate, etc. Meth) acrylate.

Examples of trifunctional or higher polyfunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, succinic anhydride-modified pentaerythritol tetra (meth) acrylate, phosphoric acid tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacrylic) Roxyethyl) isocyanurate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, alkyl-modified dipentaerythritol Tora (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, succinic anhydride-modified dipentaerythritol penta (meth) acrylate, urethane tri (Meth) acrylate, ester tri (meth) acrylate, urethane hexa (meth) acrylate, ester hexa (meth) acrylate and the like.

These polyfunctional (meth) acrylates may be used individually by 1 type, and may be used in combination of 2 or more type. In addition, when the negative resist composition for color filter of the present invention requires excellent photocurability (high sensitivity), the polyfunctional monomer has three polymerizable double bonds (trifunctional). Those having the above are preferable, and for example, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are suitably used.
The content of the polyfunctional monomer used in the negative resist composition for color filters of the present invention is not particularly limited, but is usually about 5 to 500 parts by weight, preferably 100 parts by weight of the alkali-soluble resin. Is in the range of 20 to 300 parts by weight. If the content of the polyfunctional monomer is less than the above range, the photocuring may not sufficiently proceed and the exposed part may be eluted, and if the content of the polyfunctional monomer is more than the above range, the alkali developability is lowered. There is a risk.

(Photoinitiator)
There is no restriction | limiting in particular as a photoinitiator used in the negative resist composition for color filters of this invention, It can select and use suitably from conventionally well-known various photoinitiators. For example, aromatic ketones such as benzophenone, Michler ketone, 4,4′-bisdiethylaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrene, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, etc. Benzoin ethers, benzoin such as methylbenzoin, ethylbenzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) Imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-tria Reel imidazole dimer 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-trichloromethyl- 5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) ) 1,3,4-oxadiazole and other halomethyloxadiazole compounds, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl Ru-S-triazine, 2- (naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloro Halomethyl-S-triazine compounds such as methyl-S-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldipheny Sulfide, benzylmethyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, Isopropylthioxanthone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy -Cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4- Morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2 -(4-morpholinyl) -1-propanone and the like. These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the photoinitiator used in the negative resist composition for a color filter of the present invention is usually about 0.01 to 100 parts by weight, preferably 5 to 60 parts by weight with respect to 100 parts by weight of the polyfunctional monomer. Part. If this content is less than the above range, the polymerization reaction cannot be sufficiently caused, so that the hardness of the colored layer may not be sufficient. In some cases, the content of the pigment or the like in the solid content of the resist composition becomes relatively small, and a sufficient coloring density cannot be obtained.

(Other pigment dispersants)
The negative resist composition may contain other pigment dispersants as long as the effects of the present invention are not impaired.
Other pigment dispersants are not particularly limited, and for example, cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants can be used. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable. A pigment derivative that dissolves in a small amount in a solvent may be used as a pigment dispersant.

The pigment dispersant is appropriately selected and used in order to favorably disperse the pigment used. Specific examples include amide compounds such as nonanamide, decanamide, dodecanamide, N-dodecylhexadecanamide, N-octadecylpropioamide, N, N-dimethyldodecanamide and N, N-dihexylacetamide, diethylamine, diheptylamine, Amine compounds such as dibutylhexadecylamine, N, N, N ′, N′-tetramethylmethanamine, triethylamine, tributylamine and trioctylamine, monoethanolamine, diethanolamine, triethanolamine, N, N, N ′, N ′-(tetrahydroxyethyl) -1,2-diaminoethane, N, N, N′-tri (hydroxyethyl) -1,2-diaminoethane, N, N, N ′, N′-tetra (hydroxyethyl) Polyoxyethylene) -1,2-diaminoethane, 1 , 4-bis (2-hydroxyethyl) piperazine, 1- (2-hydroxyethyl) piperazine, and other amines having a hydroxy group, and other compounds such as nipecotamide, isonipecotamide, and nicotinamide. be able to.

Further, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts, (partial) ammonium salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid ( Partially) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphorus Acid salts; amides obtained by the reaction of poly (lower alkyleneimine) and free carboxyl group-containing polyester, salts thereof, and the like can be mentioned.

(Other pigment derivatives)
Unless the effect of the present invention is impaired, C.I. I. Another pigment derivative different from the sulfonic acid derivative of CI Pigment Yellow 138 may be included. Other pigment derivatives suitably used in the pigment dispersion of the present invention include, for example, C.I. I. And CI Pigment Yellow 138 phthalimide derivatives, naphthalimide derivatives, sulfonamide derivatives, metal salts of sulfonic acid derivatives, amine salts of sulfonic acid derivatives, and the like. The sulfonamide group, which is an amine salt of sulfonic acid, is preferably represented by —SO ₂ NHR (where R is a monovalent organic group). Examples of R include dimethylaminopropyl group, diethylamino group, and the like. Examples thereof include a propyl group, a dibutylaminopropyl group, a benzyl group, and a phenyl group.

(Optional additive)
The negative resist composition for a color filter of the present invention may contain various additives as necessary within a range that does not impair the object of the present invention. Examples of the additive include a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter.
Among these, surfactants that can be used include, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene Examples include glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, fatty acid-modified polyesters, and tertiary amine-modified polyurethanes. In addition, a fluorosurfactant can also be used.
Furthermore, examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl. Examples of the antifoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic compounds.

<Combination ratio of each component in negative resist composition>
The total pigment content is preferably 10 to 50% by weight, more preferably 20 to 40% by weight, based on the total solid content of the negative resist composition. If the amount of the pigment is too small, the transmission density when the negative resist composition is applied to a predetermined film thickness (usually 1.0 to 4.0 μm) may be insufficient. If the amount of the pigment is too large, There is a risk that the properties as a coating film such as adhesion to the substrate when the resist composition is applied and cured on the substrate, surface roughness of the cured film, coating film hardness, etc. may be insufficient, and its negative type Since the ratio of the amount of the dispersant used for dispersing the pigment in the resist composition increases, characteristics such as developability and heat resistance may be insufficient. In addition, in this invention, solid content is all things other than the solvent mentioned above, and the polyfunctional monomer etc. which are melt | dissolving in the solvent are also included.
Further, the total content of the pigment dispersant is preferably in the range of 1 to 40% by weight, particularly in the range of 5 to 30% by weight, based on the total solid content of the negative resist composition. Preferably there is. If the content is less than 1% by weight relative to the total solid content of the negative resist composition, it may be difficult to uniformly disperse the pigment, and if it exceeds 40% by weight , There is a risk of lowering curability and developability.
The total amount of the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator is blended in a proportion of 15 to 89% by weight, preferably 25 to 80% by weight, based on the total solid content of the negative resist composition. Is preferred.
Further, the content of the solvent is not particularly limited as long as the colored layer can be formed with high accuracy. Usually, it is preferably in the range of 65 to 95% by weight, more preferably in the range of 75 to 88% by weight, based on the total amount of the negative resist composition containing the solvent. When the content of the solvent is within the above range, the coating property can be excellent.

(Manufacture of negative resist compositions for color filters)
As a method for producing a negative resist composition for a color filter of the present invention, it is preferable to prepare the pigment dispersion according to the present invention in advance and prepare it using the pigment dispersion. As a method for producing the negative resist composition of the present invention, the pigment dispersion according to the present invention includes an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and, if necessary, a pigment dispersion of another color. Examples thereof include a method of adding and mixing a liquid, a solvent, and various additive components used.
The negative resist composition for a color filter of the present invention is preferably used by previously producing and using a pigment dispersion because it can effectively prevent aggregation of the pigment and disperse it uniformly.

Next, the color filter of the present invention will be described.
[Color filter]
The color filter of the present invention is characterized by having a colored layer formed by curing the above-described negative resist composition for color filters of the present invention.
Such a color filter of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a transparent substrate 1, a light shielding part 2, and a colored layer 3.

(Colored layer)
The colored layer used in the color filter of the present invention is not particularly limited as long as it is formed by curing the negative resist composition for a color filter of the present invention described above. Depending on the type of pigment formed in the opening of the light-shielding part and contained in the negative resist composition for color filter, it is composed of a coloring pattern of three or more colors.
Further, the arrangement of the colored layers is not particularly limited, and for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type can be used. Moreover, the width | variety, area, etc. of a colored layer can be set arbitrarily.
The thickness of the colored layer is appropriately controlled by adjusting the coating method, solid content concentration, viscosity, etc. of the color filter negative resist composition, but is usually preferably in the range of 1 to 5 μm.

The colored layer can be formed, for example, by the following method.
First, the above-described negative resist composition for a color filter of the present invention is applied onto a transparent substrate to be described later using an application means such as a spray coating method, a dip coating method, a bar coating method, a coal coating method, or a spin coating method. Then, a wet coating film is formed.
Next, after drying the wet coating film using a hot plate or oven, it is exposed to light through a mask having a predetermined pattern, and an alkali-soluble resin and a polyfunctional monomer are photopolymerized. And a coating film of a negative resist composition for color filters. Examples of the light source used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp, and an electron beam. The exposure amount is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to promote a polymerization reaction after exposure, you may heat-process. The heating conditions are appropriately selected depending on the blending ratio of each component in the color filter negative resist composition to be used, the thickness of the coating film, and the like.

Next, it develops using a developing solution, a coating film is formed with a desired pattern by melt | dissolving and removing an unexposed part. As the developer, a solution in which an alkali is dissolved in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to the alkaline solution. Further, a general method can be adopted as the developing method.
After the development treatment, the developer is usually washed and the cured coating film of the negative resist composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after image development processing. The heating conditions are not particularly limited and are appropriately selected depending on the application of the coating film.

(Shading part)
The light shielding part in the color filter of the present invention is formed in a pattern on a transparent substrate described later, and can be the same as that used as a light shielding part in a general color filter.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape. Examples of the light-shielding portion include those obtained by dispersing or dissolving a black pigment in a binder resin, and metal thin films such as chromium and chromium oxide. The metal thin film may be a CrO _x film (x is an arbitrary number) and a laminate of two Cr films, and a CrO _x film (x is an arbitrary number) with a reduced reflectance. , CrN _y films (y is an arbitrary number) and three layers of Cr films may be laminated.
When the light-shielding part is a material in which a black colorant is dispersed or dissolved in a binder resin, the light-shielding part can be formed by any method that can pattern the light-shielding part, and is not particularly limited. For example, a photolithography method, a printing method, an ink jet method and the like using a negative resist composition for a light shielding part can be exemplified.

In the above case, when a printing method or an inkjet method is used as a method for forming the light shielding portion, examples of the binder resin include polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, hydroxy Examples thereof include ethyl cellulose resin, carboxymethyl cellulose resin, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin, polyamide resin and the like.

In the above case, when a photolithography method is used as a method for forming the light shielding portion, the binder resin may be, for example, an acrylate-based, methacrylate-based, polyvinyl cinnamate-based, or cyclized rubber-based reactive material. A photosensitive resin having a vinyl group is used. In this case, a photopolymerization initiator may be added to the negative resist composition for a light shielding part containing a black colorant and a photosensitive resin, and further a sensitizer, a coating property improver, if necessary. A development improver, a crosslinking agent, a polymerization inhibitor, a plasticizer, a flame retardant, and the like may be added. In the present invention, the negative resist composition for color filters having a black pigment such as carbon black or titanium black as a pigment may be used as the negative resist composition for the light shielding part.

On the other hand, when the light shielding part is a metal thin film, the method for forming the light shielding part is not particularly limited as long as the light shielding part can be patterned, and for example, photolithography, vapor deposition using a mask. Law, printing method and the like.

The thickness of the light shielding part is set to about 0.2 to 0.4 μm in the case of a metal thin film, and about 0.5 to 2 μm in the case where a black colorant is dispersed or dissolved in a binder resin. Is set.

(Transparent substrate)
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is a base material transparent to visible light, and a transparent substrate used for a general color filter can be used. Specific examples include inflexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials having flexibility such as transparent resin films and optical resin plates. It is done.
The thickness of the transparent substrate is not particularly limited, but for example, a thickness of about 100 μm to 1 mm can be used according to the use of the color filter of the present invention.
The color filter of the present invention may be one in which, for example, an overcoat layer, a transparent electrode layer, an alignment film, a columnar spacer, or the like is formed in addition to the transparent substrate, the light shielding portion, and the colored layer. .

Next, the liquid crystal display device of the present invention will be described.
[Liquid Crystal Display]
The liquid crystal display device of the present invention includes the color filter of the present invention described above, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
Note that the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, but can be a configuration generally known as a liquid crystal display device using a color filter.

The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be employed. Examples of such a driving method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be preferably used.
Further, the counter substrate can be appropriately selected and used depending on the driving method of the liquid crystal display device of the present invention.
Furthermore, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.
In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and a counter substrate, and the liquid crystal is heated to obtain an isotropic liquid, and the liquid crystal is applied to the liquid crystal cell using the capillary effect. The liquid crystal layer can be formed by injecting in this state and sealing with an adhesive. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.
In the liquid crystal dropping method, for example, a sealant is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, and the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like. Then, the color filter and the counter substrate are overlapped with each other under a reduced pressure, and bonded through a sealant, whereby a liquid crystal layer can be formed. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

Next, the organic light emitting display device of the present invention will be described.
[Organic light emitting display]
The organic light emitting display device of the present invention includes the above-described color filter of the present invention and an organic light emitter.
Such an organic light emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic view showing an example of the organic light emitting display device of the present invention. As illustrated in FIG. 3, the organic light emitting display device 100 of the present invention includes a color filter 10 and an organic light emitter 80.
An organic protective layer 50 or an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80.

As a method for laminating the organic light emitter 80, for example, the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, and the cathode 76 are sequentially formed on the upper surface of the color filter. Examples thereof include a method and a method in which an organic light emitter 80 formed on another substrate is bonded to the inorganic oxide film 60. As the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other configurations in the organic light emitter 80, known configurations can be appropriately used. The organic light emitting display device 100 manufactured as described above can be applied to, for example, a passive drive type organic EL display or an active drive type organic EL display.
Note that the organic light emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may be a known configuration as an organic light emitting display device that generally uses a color filter.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
(Production Example 1 Synthesis of Pigment Derivative A (PY138 Monosulfonic Acid Derivative))
Stirring 374.76 parts by weight of 11 wt% fuming sulfuric acid while cooling to 10 ° C, C.I. I. 74.96 parts by weight of Pigment Yellow 138 was added. Subsequently, it stirred at 90 degreeC for 6 hours.
The reaction solution was added to 1600 parts by weight of ice water and stirred for 15 minutes, and then the precipitate was filtered. The obtained wet cake was washed with 800 ml of water three times. The wet cake was vacuum dried at 80 ° C. to obtain 81.55 parts by weight of a yellow product.
The result of gravimetric analysis of this yellow product by TOF-MS was consistent with the molecular weight (Mw = 774) of the PY138 monosulfonic acid derivative having the following structure.

(Production Example 2 Synthesis of Binder Resin A)
A polymerization tank was charged with 130 parts by weight of diethylene glycol ethyl methyl ether (EMDG) as a solvent, heated to 110 ° C. in a nitrogen atmosphere, then 32 parts by weight of methyl methacrylate (MMA), 22 parts by weight of cyclohexyl methacrylate (CHMA). , A mixture containing 24 parts by weight of methacrylic acid (MAA), 2 parts by weight of azoisobutyronitrile (AIBN) as an initiator and 4.5 parts by weight of n-dodecyl mercaptan as a chain transfer agent over 1.5 hours. It was dripped continuously.
Thereafter, the reaction was continued while maintaining the synthesis temperature, and 0.05 parts by weight of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the completion of the dropwise addition.
Next, 22 parts by weight of glycidyl methacrylate (GMA) was added while blowing air, the temperature was raised to 110 ° C., 0.2 part by weight of triethylamine was added, and an addition reaction was carried out at 110 ° C. for 15 hours, and the binder Resin A (44 wt% solid content) was obtained.
The obtained binder resin A had a weight average molecular weight of 8,500 and an acid value of 85 mgKOH / g. The weight average molecular weight was calculated by gel permeation chromatography (GPC) using polystyrene as a standard substance and THF as an eluent, and the acid value was measured according to JIS-K0070.

(Production Example 3 Preparation of Dispersant / Binder Resin Solution A)
In a 225 mL mayonnaise bottle, 68.51 parts by weight of propylene glycol monomethyl ether acetate (PGMEA), a block copolymer containing a tertiary amino group (the repeating unit (1) represented by the above general formula (I) and the above general formula) Block copolymer having repeating unit (2) represented by (II)) (trade name: BYK-LPN6919, manufactured by Big Chemie) (amine value 135 mgKOH / g, solid content 60% by weight) 4.85 parts by weight Each of 13.30 parts by weight of the binder resin A of Production Example 2 was dissolved. Add 0.34 parts by weight of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) to the mixed solution (0.3 molar equivalent with respect to the tertiary amino group of the block copolymer), and stir at room temperature for 30 minutes. Thus, a dispersant / binder resin solution A was prepared.
At this time, the amino group of the block copolymer (BYK-LPN6919) is salt-formed by an acid / base reaction with the phosphonic acid group of PPA.

(Production Example 4 Preparation of Dispersant / Binder Resin Solution B)
In a 225 mL mayonnaise bottle, 68.49 parts by weight of propylene glycol monomethyl ether acetate (PGMEA), a block copolymer containing a tertiary amino group (trade name: BYK-LPN6919, manufactured by Big Chemie) 4.90 parts by weight, production example 2 binder resin A13.30 weight part was melt | dissolved, respectively. To the mixed solution was added 0.31 part by weight of phenylphosphinic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.3 molar equivalent with respect to the tertiary amino group of the block copolymer), and the mixture was stirred at room temperature for 30 minutes. A binder resin solution B was prepared.
At this time, the amino group of the block copolymer (BYK-LPN6919) is salt-formed by an acid / base reaction with the phosphinic acid group of phenylphosphinic acid.

(Production Example 5 Preparation of dispersant / binder resin solution C)
In a 225 mL mayonnaise bottle, 68.28 parts by weight of PGMEA, a block copolymer containing a tertiary amino group (trade name: BYK-LPN6919, manufactured by BYK Chemie) 5.42 parts by weight, 13.3% by weight of binder resin A of Production Example 2 Dispersant / binder resin solution C was prepared by dissolving each part.

(Production Example 6 Preparation of Dispersant / Binder Resin Solution D)
In a 225 mL mayonnaise bottle, 66.16 parts by weight of PGMEA, 4.79 parts by weight of “Disperbyk 162” (manufactured by Big Chemie, solid concentration 38% by weight) and “Disperbyk 110” (manufactured by BYK Chemy, solid concentration 52) Dispersant / binder resin solution D was prepared by dissolving 2.75 parts by weight) and 13.30 parts by weight of binder resin A of Production Example 2.

(Production Example 7 Preparation of dispersant / binder resin solution E)
In a 225 mL mayonnaise bottle, 70.45 parts by weight of PGMEA, 3.25 parts by weight of Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd., solid concentration 100% by weight) as a commercially available dispersant, binder resin A13.30 of Production Example 2 Dispersant / binder resin solution E was prepared by dissolving each part by weight.

Example 1
(1) Preparation of Green Pigment Dispersion A for Color Filters CI Pigment Green 58 (PG58: average primary particle size 10 to 50 nm) as a coloring material component in 87 parts by weight of the dispersant / binder resin solution A prepared in Production Example 3 8.71 parts by weight, CI Pigment Yellow 150 (PY150: average primary particle size 10 to 50 nm) 3.64 parts by weight, Pigment derivative A (PY138 monosulfonic acid derivative) of Production Example 1 0.65 parts by weight Were mixed in a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 1 hour with 2 mm zirconia beads and further for 4 hours with 0.1 mm zirconia beads to obtain a green pigment dispersion A.

(2) Preparation of Green Negative Resist Composition A for Color Filter 47.5 parts by weight of the green pigment dispersion A obtained in (1) above, 43.4 parts by weight of the following binder composition A, and 9.1 parts by weight of PGMEA After mixing and pressure filtration, a green negative resist composition A for color filters was obtained.
<Binder composition A>
Alkali-soluble resin (Binder resin A of Production Example 3, solid content 44 wt%): 4.28 parts by weight Trifunctional to tetrafunctional acrylate monomer (trade name: Aronix M305, manufactured by Toagosei Co., Ltd.): 4.39 Part by weight / photopolymerization initiator: 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) : 0.47 parts by weight. Photopolymerization initiator: 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (trade name: biimidazole) (Manufactured by Kurokin Kasei Co., Ltd.)): 0.94 parts by weight. Photopolymerization initiator: 2-mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.15 parts by weight. Photosensitizer: 2.4. Diethylthioxanthone (trade name: Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.): 1.57 parts by weight. Solvent: propylene glycol monomethyl ether acetate (PGMEA): 41.5 parts by weight

(Example 2)
(1) Preparation of Green Pigment Dispersion B for Color Filter Example 1 except that the dispersant / binder resin solution A was changed to the dispersant / binder resin solution B prepared in Production Example 4 in Example 1 (1). Green pigment dispersion B was prepared in the same manner as (1).

(2) Preparation of green negative resist composition B for color filter In Example 1 (2), green pigment dispersion B obtained in (1) above was used instead of green pigment dispersion A. In the same manner as in Example 1 (2), a green negative resist composition B for color filters was obtained.

(Comparative Example 1)
(1) Preparation of Green Pigment Dispersion C for Color Filter Example 1 except that the dispersant / binder resin solution A in Example 1 (1) was changed to the dispersant / binder resin solution C prepared in Production Example 5. Green pigment dispersion C was prepared in the same manner as (1).

(2) Preparation of green negative resist composition C for color filter In Example 1 (2), instead of the green pigment dispersion A, the green pigment dispersion C obtained in (1) above was used. Then, a green negative resist composition C for color filters was obtained in the same manner as in Example 1 (2).

(Comparative Example 2)
(1) Preparation of Green Pigment Dispersion D for Color Filter In Example 1 (1), CI Pigment Green 58 (PG58: average primary particle size 10 to 50 nm) 8.71 parts by weight as a colorant component, C Pigment Yellow 150 (PY150: average primary particle size 10 to 50 nm) 3.64 parts by weight, CI Pigment Yellow 138 (PY138: average primary particle size 10 to 50 nm) 0.65 parts by weight A green pigment dispersion D was prepared in the same manner as in Example 1 (1).

(2) Preparation of green negative resist composition D for color filter In Example 1 (2), instead of the green pigment dispersion A, the green pigment dispersion D obtained in (1) above was used. In the same manner as in Example 1 (2), a green negative resist composition D for color filters was obtained.

(Comparative Example 3)
(1) Preparation of Green Pigment Dispersion Liquid E for Color Filter In Example 1 (1), CI Pigment Green 58 (PG58: average primary particle size 10 to 50 nm) 8.84 parts by weight as a color material component, C Pigment Yellow 150 (PY150: average primary particle size 10 to 50 nm) was prepared in the same manner as in Example 1 (1) except that the amount was changed to 4.16 parts by weight.

(2) Preparation of green negative resist composition E for color filter In Example 1 (2), instead of the green pigment dispersion A, the green pigment dispersion E obtained in (1) above was used. In the same manner as in Example 1 (2), a green negative resist composition E for color filters was obtained.

(Comparative Example 4)
(1) Preparation of Green Pigment Dispersion Solution F for Color Filter Example 1 except that the dispersant / binder resin solution A was changed to the dispersant / binder resin solution D prepared in Production Example 6 in Example 1 (1). A green pigment dispersion F was prepared in the same manner as (1).

(2) Preparation of green negative resist composition F for color filter In Example 1 (2), instead of the green pigment dispersion A, the green pigment dispersion F obtained in (1) above was used. A green negative resist composition F for color filters was obtained in the same manner as in Example 1 (2).

(Comparative Example 5)
(1) Preparation of Green Pigment Dispersion Liquid G for Color Filter Example 1 except that the dispersant / binder resin solution A in Example 1 (1) was changed to the dispersant / binder resin solution E prepared in Production Example 6. A green pigment dispersion G was prepared in the same manner as (1).

(2) Preparation of green negative resist composition G for color filter In Example 1 (2), instead of the green pigment dispersion A, the green pigment dispersion G obtained in (1) above was used. Then, a green negative resist composition G for color filters was obtained in the same manner as in Example 1 (2).

(Evaluation)
<Evaluation of pigment dispersion stability>
As an evaluation of pigment dispersion stability, the pigment dispersion liquid for color filters obtained in each of the examples and comparative examples was allowed to stand at 40 ° C. for 1 week, and the average particle size of the pigment particles in the pigment dispersion liquid before and after standing. The diameter and shear viscosity were measured. The average particle size was measured using a Nikkiso Co., Ltd. “Microtrac particle size distribution meter”, and the viscosity was measured using a Japan Siber Hegner Co., Ltd. “MCR301” shear when the shear rate was 60 rpm. The viscosity was measured.
The results are shown in Table 1.

<Optical performance (chromaticity, brightness, contrast)>
The green negative resist composition for a color filter obtained in each example and comparative example was applied on a 0.7 mm thick glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater. did. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. A cured film (green colored layer) was obtained by irradiating 30 mJ / cm ² of ultraviolet rays using an ultrahigh pressure mercury lamp. The film thickness after drying and curing was adjusted so that the target chromaticity y = 0.492. The glass plate on which the green colored layer was formed was post-baked in a clean oven at 240 ° C., and the contrast, chromaticity (x, y) and luminance (Y) of the obtained green colored substrate were measured. Contrast was measured using “Contrast measuring device CT-1B” manufactured by Aisaka Electric Co., Ltd., and chromaticity and luminance were measured using “Microspectrophotometric measuring device OSP-SP200” manufactured by Olympus Corporation.
The results are shown in Table 1.

<Alkali developability>
The green negative resist composition for color filter obtained in each Example and Comparative Example was applied on a 0.7 mm thick glass substrate using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. This colored layer was irradiated with ultraviolet rays of 30 mJ / cm ² through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the glass plate on which the colored layer has been formed is shower-developed using an aqueous 0.05 wt% potassium hydroxide solution as an alkaline developer, and the time until the glass surface where the colored layer is formed is developed. Measured as time.
The results are shown in Table 1.

<Alkali resistance evaluation>
The negative resist composition for color filter obtained in each Example and Comparative Example was applied on a 0.7 mm thick glass substrate using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. This colored layer was irradiated with ultraviolet rays of 30 mJ / cm ² through a photomask on which a stripe pattern having a line and space of 80 μm was drawn using an ultra-low pressure mercury lamp. Thereafter, the glass plate on which the colored layer was formed was subjected to shower development for 60 minutes using an aqueous 0.05 wt% potassium hydroxide solution as an alkaline developer, and further washed with ultrapure water for 60 seconds. Post-baked in a clean oven.
The obtained glass substrate on which the colored pattern was formed was immersed in a 5.0 wt% sodium hydroxide aqueous solution maintained at 40 degrees, and the time until the colored pattern peeled off from the glass substrate was measured.
The results are shown in Table 1.

From the results in Table 1, Examples 1 to 2 of the present invention are C.I. I. By using a combination of the sulfonic acid derivative of Pigment Yellow 138 and the pigment dispersant made of the specific salt-type block copolymer, the alkali developability is achieved while achieving the demand for high brightness and high contrast. It was clarified that it was excellent in alkali resistance.
On the other hand, Comparative Example 1 using a block copolymer having an amino group that is not salt-formed as a pigment dispersant is inferior in contrast to the Examples, inferior in alkali developability, and further inferior in alkali resistance. It was made. In addition, C.I. I. Pigment Yellow 138 without using a sulfonic acid derivative. I. In Comparative Example 2 using Pigment Yellow 138 pigment, it was revealed that the contrast deteriorated. Moreover, it was clarified that the luminance was inferior in Comparative Example 3 using only PY150.
Furthermore, in Comparative Example 4 corresponding to Patent Document 3 (Japanese Patent Publication No. 2009-126994), it was revealed that dispersibility and dispersion stability were remarkably deteriorated, contrast was greatly deteriorated, and alkali resistance was also deteriorated. It was also clarified that Comparative Example 5 using a commercially available dispersant was inferior in dispersibility and dispersion stability, poor in contrast and poor in alkali resistance as compared with the present application.

(Production Example 8 Preparation of dispersant / binder resin solution F)
In a 1 L reaction vessel, 413.9 parts by weight of propylene glycol monomethyl ether acetate (PGMEA), a block copolymer containing a tertiary amino group (trade name: BYK-LPN6919, manufactured by BYK Chemie) (amine value 135 mgKOH / g, solid 36.3 parts by weight) and 99.7 parts by weight of binder resin A of Production Example 2 were dissolved. 2.6 parts by weight of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) (0.3 molar equivalent to the tertiary amino group of the block copolymer) is added to the mixed solution, and the mixture is stirred at room temperature for 30 minutes. Thus, a dispersant / binder resin solution A was prepared.
At this time, the amino group of the block copolymer (BYK-LPN6919) is salt-modified by an acid / base reaction with the phosphonic acid group of PPA.

(Example 3)
92.6 parts by weight of CI Pigment Green 58 (PG58: average primary particle size 10 to 50 nm) as a colorant component was added to 552.5 parts by weight of the dispersant / binder resin solution F prepared in Production Example 8. Production Example 1 4.9 parts by weight of Pigment Derivative A (PY138 monosulfonic acid derivative) was mixed, and a bead mill disperser (Ultra Apex Mill “UAM-01” manufactured by Kotobuki Industries Co., Ltd.) was used as a circulating disperser. Pre-dispersion was performed by filling 2 mm zirconia beads at a filling rate of 65% and circulating at a peripheral speed of 7.7 m / sec and a dispersion discharge flow rate of 150 ml / min for 30 minutes. Subsequently, zirconia beads having a diameter of 0.1 mm as the main dispersion were filled at a filling rate of 65%, and the peripheral speed was 7.7 m / sec and the dispersion discharge flow rate was 150 ml / min for 30, 45, 60, and 75 minutes. 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, and 165 minutes were used for the main dispersion to obtain green pigment dispersions (1) to (10).

(Comparative Example 6)
95.5 parts by weight of CI Pigment Green 58 (PG58: average primary particle size 10 to 50 nm) as a color material component was mixed with 552.5 parts by weight of the dispersant / binder resin solution F prepared in Production Example 8 and circulated. The zirconia beads having a diameter of 2 mm were filled at a filling rate of 65% using a bead mill dispersing machine of the type (Sumi Kogyo Co., Ltd. Ultra Apex Mill “UAM-01”). Pre-dispersion was performed by circulating operation for 30 minutes at a discharge flow rate of 150 ml / min. Subsequently, zirconia beads having a diameter of 0.1 mm as the main dispersion were filled at a filling rate of 65%, and the peripheral speed was 7.7 m / sec and the dispersion discharge flow rate was 150 ml / min for 30, 45, 60, and 75 minutes. , 90 minutes, 105 minutes, 120 minutes, 135 minutes, 150 minutes, and 165 minutes for circulation, this dispersion was carried out to obtain green comparative pigment dispersions (1) to (10).

Example 4 Preparation of Green Pigment Dispersion (Paint Shaker Dispersion) In 87 parts by weight of the dispersant / binder resin solution A prepared in Production Example 3, CI Pigment Green 58 (PG58: average primary) was used as a color material component. 12.35 parts by weight (particle size 10 to 50 nm) and 0.65 parts by weight of pigment derivative A (PY138 monosulfonic acid derivative) of Production Example 1 were mixed, and 1 with 2 mm zirconia beads using a paint shaker (manufactured by Asada Tekko Co., Ltd.). The resulting mixture was further dispersed for 4 hours with 0.1 mm zirconia beads to obtain a green pigment dispersion (r) (paint shaker dispersion).

(Comparative Example 7) Preparation of Green Comparison Pigment Dispersion (Paint Shaker Dispersion) CI Pigment Green 58 (PG58: average primary) as a coloring material component in 87 parts by weight of the dispersant / binder resin solution A prepared in Production Example 3 13.00 parts by weight (particle size: 10 to 50 nm) were mixed, and dispersed with a paint shaker (manufactured by Asada Tekko) for 1 hour with 2 mm zirconia beads, and further with 0.1 mm zirconia beads for 4 hours. r) (dispersed paint shaker) was obtained.

(Process margin evaluation with circulating dispersers)
In Example 1 (2), instead of the green pigment dispersion A, the green pigment dispersions (1) to (10) and (r) obtained above and the green comparison pigment dispersions (1) to (10) were obtained. A green negative for color filter in the same manner as in Example 1 (2) except that 37.77 parts by weight of (r), 49.11 parts by weight of the binder composition and 13.12 parts by weight of PGMEA were used. Mold resist compositions (1) to (10) and (r) and comparative green negative resist compositions (1) to (10) and (r) for color filters were obtained.

The negative resist composition obtained in each Example and Comparative Example was applied onto a glass substrate having a thickness of 0.7 mm (“NA35” manufactured by NH Techno Glass Co., Ltd.) using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. A cured film (green colored layer) was obtained by irradiating 30 mJ / cm ² of ultraviolet rays using an ultrahigh pressure mercury lamp. The film thickness after drying and curing was adjusted so that the target chromaticity y = 0.500. The glass plate on which the green colored layer was formed was post-baked in a clean oven at 240 ° C., and the contrast of the obtained green colored substrate was measured. Contrast was measured using “Contrast measuring device CT-1B” manufactured by Aisaka Electric Co., Ltd., and chromaticity and luminance were measured using “Microspectrophotometric measuring device OSP-SP200” manufactured by Olympus Corporation.

Table 2 shows the results of the process margin evaluation with the obtained circulating disperser.
From Table 2, C.I. I. In the pigment dispersion obtained in Example 3 in which the sulfonic acid derivative of Pigment Yellow 138 and the pigment dispersant composed of the specific salt-type block copolymer are combined, the product is used for a long time using a circulating disperser. It has been clarified that the contrast can be maintained well without dispersion of the pigment aggregate even when the dispersion is performed. On the other hand, in the pigment dispersion obtained in Comparative Example 6 using only the pigment dispersant composed of the specific salt type block copolymer, the time during which the contrast is kept high is short, and this dispersion time is slightly extended. It was clarified that the contrast deteriorated and the process margin was small just by mere grabbing. In the pigment dispersion obtained in Comparative Example 6, precipitation of the pigment aggregate was observed after dispersion for a certain period of time.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Opposite substrate 30 Liquid crystal layer 40 Liquid crystal display device

Claims

Pigments, C.I. I. Pigment Yellow 138, a sulfonic acid derivative, a pigment dispersant, and a solvent,
The pigment dispersant has a repeating unit (1) represented by the following general formula (I) and a repeating unit (2) represented by the following general formula (II), and further the repeating unit (1) A pigment dispersion for a color filter, which is a block copolymer in which at least a part of the amino group of the compound and an organic phosphate compound form a salt.

[In Formula (I) and Formula (II), R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon atom having 1 carbon atom. To 8 alkylene groups, — [CH (R 6 ) —CH (R 7 ) —O] x —CH (R 6 ) —CH (R 7 ) — or — [(CH 2 ) y —O] z — ( A divalent group represented by CH 2 ) y —, R 4 is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R 6 ) —CH A monovalent group represented by (R 7 ) —O] x —R 8 or — [(CH 2 ) y —O] z —R 8 . R 6 and R 7 are each independently a hydrogen atom or a methyl group, and R 8 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, A monovalent group represented by —CHO, —CH 2 CHO, or —CH 2 COOR 9 , wherein R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; The alkyl group, alkenyl group, aralkyl group, and aryl group each may have a substituent.
x represents an integer of 1 to 18, y represents an integer of 1 to 5, and z represents an integer of 1 to 18. m represents an integer of 3 to 200, and n represents an integer of 10 to 200. ]
As the pigment, C.I. I. Pigment green 58, C.I. I. Pigment green 36, C.I. I. Pigment yellow 150, and C.I. I. The pigment dispersion for a color filter according to claim 1, comprising at least one selected from the group consisting of CI Pigment Yellow 138.
The pigment dispersion for a color filter according to claim 1 or 2, wherein in the pigment dispersant, the organophosphate compound is at least one kind represented by the following general formula (III).

[In the formula (III), R a and R a ′ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R c ) —CH (R d ) —O] s —R e , or a monovalent group represented by — [(CH 2 ) t —O] u —R e , and R a and R a ′ Either contains carbon atoms.
R c and R d are each independently a hydrogen atom or a methyl group, and R e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH 2 CHO, —CO—CH═CH 2 , —CO—C (CH 3 ) ═CH 2 or a monovalent group represented by —CH 2 COOR f , and R f is a hydrogen atom or carbon An alkyl group of 1 to 5;
In R a and R a ′ , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s represents an integer of 1 to 18, t represents an integer of 1 to 5, and u represents an integer of 1 to 18. ]
C. I. The pigment dispersion for color filter according to any one of claims 1 to 3, wherein the sulfonic acid derivative of Pigment Yellow 138 is contained in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the pigment. .
Pigments, C.I. I. Pigment Yellow 138 sulfonic acid derivative, a pigment dispersant, an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a solvent,
The pigment dispersant has a repeating unit (1) represented by the following general formula (I) and a repeating unit (2) represented by the following general formula (II), and further the repeating unit (1) A negative resist composition for a color filter, characterized in that it is a block copolymer in which at least a part of the amino group possessed by the organic phosphate compound forms a salt.

[In Formula (I) and Formula (II), R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and A is a carbon atom having 1 carbon atom. To 8 alkylene groups, — [CH (R 6 ) —CH (R 7 ) —O] x —CH (R 6 ) —CH (R 7 ) — or — [(CH 2 ) y —O] z — ( A divalent group represented by CH 2 ) y —, R 4 is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R 6 ) —CH A monovalent group represented by (R 7 ) —O] x —R 8 or — [(CH 2 ) y —O] z —R 8 . R 6 and R 7 are each independently a hydrogen atom or a methyl group, and R 8 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, A monovalent group represented by —CHO, —CH 2 CHO, or —CH 2 COOR 9 , wherein R 9 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; The alkyl group, alkenyl group, aralkyl group, and aryl group each may have a substituent.
x represents an integer of 1 to 18, y represents an integer of 1 to 5, and z represents an integer of 1 to 18. m represents an integer of 3 to 200, and n represents an integer of 10 to 200. ]
As the pigment, C.I. I. Pigment green 58, C.I. I. Pigment green 36, C.I. I. Pigment yellow 150, and C.I. I. The negative resist composition for a color filter according to claim 5, comprising at least one selected from the group consisting of CI Pigment Yellow 138.
The negative resist composition for a color filter according to claim 5 or 6, wherein in the pigment dispersant, the organic phosphate compound is at least one kind represented by the following general formula (III). .

[In the formula (III), R a and R a ′ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R c ) —CH (R d ) —O] s —R e , or a monovalent group represented by — [(CH 2 ) t —O] u —R e , and R a and R a ′ Either contains carbon atoms.
R c and R d are each independently a hydrogen atom or a methyl group, and R e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, —CHO, —CH 2 CHO, —CO—CH═CH 2 , —CO—C (CH 3 ) ═CH 2 or a monovalent group represented by —CH 2 COOR f , and R f is a hydrogen atom or carbon An alkyl group of 1 to 5;
In R a and R a ′ , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s represents an integer of 1 to 18, t represents an integer of 1 to 5, and u represents an integer of 1 to 18. ]
C. I. The negative type for color filter according to any one of claims 5 to 7, wherein the sulfonic acid derivative of Pigment Yellow 138 is contained in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the pigment. Resist composition.
A color filter comprising a colored layer formed by curing the negative resist composition for a color filter according to any one of claims 5 to 8.
A liquid crystal display device comprising: the color filter according to claim 9; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.
An organic light-emitting display device comprising the color filter according to claim 9 and an organic light emitter.