JP2010186174A - Method for manufacturing color filter, color filter, and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To suppress void of a pixel by suppressing oozing of a liquid-repellent agent contained in a black matrix into a pixel, and to prevent color mixture of the pixels by securing sufficient liquid repellency on an upper surface of the black matrix. <P>SOLUTION: In the method for manufacturing the color filter, including the black matrix formed by using a coloring composition for a color filter containing (a) black pigments, (b) liquid-repellent agent having specified structure, and (c) binder resin and/or monomer, a forming step of the black matrix includes a post-exposure step after a developing step and before a baking step. There are provided the method for manufacturing the color filter, the obtained color filter and the use thereof. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a color filter. More specifically, the present invention relates to a method for producing a color filter particularly suitable for production by an inkjet method, a color filter obtained by the method, and use of the color filter.

A color filter usually forms a black matrix on the surface of a transparent substrate such as glass or plastic sheet, and then sequentially forms three or more different colored pixels such as red, green, and blue in a striped or mosaic shape. It is formed by a color pattern.
The pattern size varies depending on the use of the color filter and each color, but is usually about 5 to 700 μm. Further, the positional accuracy of superposition is several μm to several tens of μm, and it is manufactured by a fine processing technique with high dimensional accuracy.

In a color filter, the black matrix plays a role of improving contrast by suppressing color mixture between colors or preventing a malfunction of a thin film transistor (TFT) due to light leakage. For this reason, the black matrix is required to have high light shielding properties.
Conventionally, a method of forming a black matrix of a color filter with a metal thin film such as chromium has been generally used. In this method, since a chromium layer is etched on a transparent substrate, a high light-shielding property can be obtained with high accuracy with a thin film thickness. On the other hand, since the manufacturing process is long and the productivity is low, the cost is high, and there are problems such as environmental problems due to the waste liquid of the etching process.

For this reason, in recent years, a method of forming a low-cost, pollution-free resin black matrix with a photosensitive resin in which light-shielding pigments and dyes are dispersed has become mainstream.
A typical method for producing a color filter using a photosensitive resin is to apply a colored composition containing a color material on a transparent substrate, and form a color filter image by repeating exposure, development, and curing as necessary. There is a photolithography method. The color filter formed by this method is widely used because it has high accuracy such as pixel position and film thickness, is excellent in durability such as light resistance and heat resistance, and has few defects such as pinholes.

However, since the photolithography method performs coating, exposure, and development for each color (R, G, B), the number of processes increases, and most of the coating film is washed away in the development process. Has many problems.
In recent years, the increase in size and price of panels has been rapidly progressing, and thus it is essential to reduce the cost in the manufacturing process of color filters. An effective technique for these is the manufacture of color filters by the inkjet method.

In the inkjet method, a color filter is produced by a method in which a black matrix is used as a partition wall and a color ink (synonymous with a colored composition for forming a pixel for a color filter; the same applies hereinafter) is injected therein. This method does not require a mask, and further shortens the process by simultaneous printing of three colors and reduces the color ink to be used, leading to high productivity and low cost.

Since the black matrix in the inkjet system plays a role as a partition that separates color inks of multiple colors, it is thicker than the black matrix in a color filter formed by a conventional photolithography method (usually a film thickness of 1.5 μm or more) It is necessary to. A typical method for manufacturing an ink-jet color filter is as follows.

  First, a substantially rectangular partition wall (pixel bank) is formed of a black matrix on a light-transmitting substrate. Next, hydrophilization on the glass substrate and liquid repellency of the partition walls are performed by chemical treatment or physical treatment. After that, by simultaneously drawing three colors of red (R), green (G), and blue (B) with an inkjet device in the opening surrounded by the partition walls, drying and curing the colored layer completely, A predetermined color filter is obtained.

In the inkjet color filter manufacturing method, the black matrix is made liquid-repellent and glass is used to prevent color unevenness in the drawn ink, color mixing between adjacent pixels, and light leakage (white spots) at the periphery of the pixel bank. Control of lyophilization of the opening is very important.
Plasma treatment under atmospheric pressure is generally used as a method for making the liquid repellent and lyophilic.
The contact angle of the substrate surface is controlled by combining O ₂ plasma treatment for the purpose of lyophilicity by removing organic substances on the glass surface and CF ₄ plasma treatment for the purpose of making the black matrix lyophobic by chemical bonding of fluorine. Yes.

However, in the atmospheric pressure plasma treatment, there is a problem that the CF ₄ gas to be used is expensive and the quality defect due to the liquid repellent side of the black matrix (partition wall).
For plasma treatment, a resin or black resist liquid resist (non-polymerization type) is added in advance in the resin black resist, and then a pattern is formed to selectively impart liquid repellency only to the black matrix portion. A method has also been studied (see Patent Document 1). However, the non-polymerized liquid repellent is not fixed in the black matrix film, so it easily falls off during the development process, etc., and the resulting black matrix pattern lacks the liquid repellent property. There is a problem such that the surface of the substrate of the portion also becomes liquid repellent.

In order to solve the above situation, studies have been made to change the liquid repellent from a non-polymerized type to a polymerized type (see Patent Document 2). When the polymerized type is used, the liquid repellent and the matrix material are fixed by chemical bonding, so that the liquid repellency can be maintained for a long time as compared with the nonpolymerized type.
However, even in this method, when the thermosetting resin melt-flows in the post-development thermosetting step (about 140 ° C. to 250 ° C.), the liquid repellent oozes into the glass opening, and the ink drawn in the opening There is a problem that white spots are easily repelled.

  Therefore, in order to ultimately suppress the seepage in the thermosetting process, it is necessary to consider not only the advanced structural design of the liquid repellent but also matching with the matrix material. Not enough.

JP-A-11-281815 International Publication Pamphlet WO2004 / 042474A1

  The present invention has been made in order to solve the above-mentioned problems, and by suppressing the bleeding of the liquid repellent contained in the black matrix into the pixels, the white spots of the pixels can be suppressed and the black matrix can be suppressed. An object is to prevent color mixture of pixels by ensuring sufficient liquid repellency on the upper surface.

As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by combining a specific liquid repellent and a manufacturing process, and has reached the present invention. That is, the present invention is as follows.
[1] A liquid repellent comprising a polymer having (a) a black pigment, (b) a side chain having an ethylenically unsaturated group, and a side chain having a fluorinated alkyl group or a group containing an oxygen atom in a part thereof. (C) A method for producing a color filter comprising a black matrix formed using a coloring composition for a color filter containing a binder resin and / or a monomer, wherein the black matrix forming step comprises:
An application step of applying the coloring composition for a color filter on a transparent substrate;
A mask exposure step of exposing the coating film obtained by the coating step through a photomask;
In the cured film obtained through the exposure step, the development step of removing the unexposed portion, and the baking step of heating the exposed portion of the cured film obtained through the development step,
A method for producing a color filter, comprising a post-exposure step after the development step and before the baking step.
[2] The method for producing a color filter according to [1], wherein the post-exposure step is performed on at least one of the same surface or the opposite surface to the transparent substrate with respect to the mask exposure step.
[3] The method for producing a color filter according to [2], wherein the post-exposure step is performed on the transparent substrate on both the same surface and the opposite surface as in the mask exposure step.
[4] After the black matrix forming step, an ink jet coating step of supplying a pixel forming composition to a region sandwiched by the black matrix or a region surrounded by the black matrix by an ink jet method, and the pixel forming The method for producing a color filter according to any one of the above [1] to [3], further comprising a curing step of curing the composition for use.
[5] (b) The method for producing a color filter according to any one of [1] to [4], wherein the ethylenically unsaturated group in the liquid repellent is a part of a (meth) acryloyl group.
[6] (b) In the liquid repellent, the number of carbons substituted with a fluorine atom contained in the fluorinated alkyl group or a group containing an oxygen atom in a part thereof is 1 to 20 above. 5] The manufacturing method of the color filter as described in any one of.
[7] (b) The method for producing a color filter according to any one of [1] to [6], wherein the fluorinated alkyl group in the liquid repellent is a part of a fluoroalkoxy group or a fluoroalkylthio group.
[8] (b) The method for producing a color filter according to any one of [1] to [7], wherein the fluorine content in the liquid repellent is 10 to 60% by weight.
[9] The method for producing a color filter according to any one of [1] to [8], wherein (b) the liquid repellent has a double bond equivalent of 200 to 560 g / mol.
[10] The method for producing a color filter according to any one of [1] to [9], wherein (b) the main chain of the liquid repellent is a novolac resin.
[11] The method for producing a color filter according to any one of [1] to [10], wherein (b) the liquid repellent is a polymer having a repeating unit represented by the following general formula (1).

(In the above general formula (I), R ⁵¹ is

R ⁵² represents a (meth) acryloyloxy group, X ¹ represents an oxygen atom or a hydrogen atom, and R ⁵³ represents

R ⁵⁴ is

(However, u represents an integer of 1 to 3, and v = 4 to 12, and R ⁵⁵ represents a hydrogen atom or a fluorine atom.) In addition, s and t represent the number of each repeating unit, and are s / t = 0.1-10. )
[12] (b) The molecular weight of the liquid repellent agent is a weight average molecular weight measured by standard polystyrene conversion gel permeation chromatography, and is 7000 to 16000, as described in any one of the above [1] to [11]. Manufacturing method of color filter.
[13] The method for producing a color filter according to any one of [1] to [12], wherein the coloring composition for a color filter further contains (d) a dispersant.
[14] The method for producing a color filter according to any one of [1] to [13], wherein the colored composition for a color filter further contains (e) a photopolymerization initiator.
[15] A color filter obtained by the method according to any one of [1] to [14].
[16] A liquid crystal display device comprising the color filter according to [15].
[17] An organic EL display comprising the color filter according to [15].

As described above, in order to selectively repellate only the black matrix, simply putting a non-polymerized liquid repellant into the resin black resist will cause deterioration of the liquid repellency and openings in the actual industrial manufacturing process. In some cases, the liquid repellent bleeds into the surface.
According to the present invention, using (b) a liquid repellent which is a polymer having a side chain having an ethylenically unsaturated group and a side chain having a fluorinated alkyl group or a group containing an oxygen atom in a part thereof, Furthermore, by performing an exposure process (post-exposure process) after the development process and before the baking process, the exudation of the liquid repellent in the subsequent thermosetting process can be suppressed, and a highly accurate black matrix The liquid repellency and lyophilicity of the pattern can be controlled.

As a result, it is possible to easily control the liquid repellency and lyophilicity with high accuracy when industrially preparing a resin black matrix compatible with the ink jet method using the colored composition of the present invention. The effect of is remarkable.
In addition, by using the coloring composition of the present invention, a black matrix having a shape, optical density, and the like suitable for an ink jet color filter can be easily obtained, and a color filter and image superior in performance and cost. A display device can be provided.

It is a cross-sectional schematic diagram which shows an example of the organic EL element provided with the color filter of this invention.

Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of the embodiments of the present invention, and the present invention is not limited to the gist thereof. It is not limited to the contents of.
“(Meth) acryl” and the like mean “at least one of acryl and methacryl” and “(meth) acrylate” and the like mean “at least one of acrylate and methacrylate”. “Meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”. The same applies to “(meth) acryloyl”.

In addition, “total solid content” means all components other than the solvent components described later, which are contained in the pigment dispersion or the pixel forming composition.
In the present invention, unless otherwise specified, the weight average molecular weight refers to a weight average molecular weight (Mw) in terms of standard polystyrene by GPC (gel permeation chromatography). “C.I.” means a color index (c.I.).

Furthermore, in the present invention, “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the weight of the base amount per 1 g of the solid content of the dispersant and the equivalent weight of KOH. is there. The measuring method will be described later. On the other hand, the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.
The present invention relates to a polymer having at least (a) a black pigment, (b) a side chain having an ethylenically unsaturated group, and a side chain having a fluorinated alkyl group or a group containing an oxygen atom in a part thereof. A method for producing a color filter, comprising a black matrix formed using a coloring composition for a color filter comprising a liquid repellent, (c) a binder resin and / or a monomer, wherein the black matrix forming step comprises:
An application step of applying the coloring composition for a color filter on a transparent substrate;
A mask exposure step of exposing the coating film obtained by the coating step through a photomask;
In the cured film obtained through the exposure step, the development step of removing the unexposed portion, and the baking step of heating the exposed portion of the cured film obtained through the development step,
The present invention resides in a color filter manufacturing method comprising a post-exposure step after the development step and before the baking step.
[Coloring composition]
The constituent materials of the colored composition used in the present invention will be described below.
(A) Black pigment As the (a) black pigment used in the present invention, a single black pigment or a black pigment obtained by mixing red, green, blue, or the like can be used. These black pigments can be appropriately selected from inorganic or organic pigments and dyes, and can be used alone or in combination.

Examples of the single black pigment include titanium black, carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, perylene black, and cyanine black. Among these, titanium black and carbon black are particularly preferable from the viewpoints of light shielding rate and image characteristics.
Examples of carbon black used in the present invention include those described in, for example, International Publication Pamphlet WO 2008 / 153000A1, and examples of titanium black include those described in, for example, Japanese Patent Application Laid-Open No. 2008-203841. Is mentioned.

In addition, organic pigments of three colors of red, green, and blue can be mixed and used as a black pigment, and barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, and the like can also be used.
Examples of the color material that can be mixed and used for preparing the black pigment include those described in International Publication Pamphlet WO2008 / 153000A1.

  Among these, carbon black is preferable from the viewpoint of obtaining a colored composition having a high optical density (OD). On the other hand, titanium black is preferable because it has a high UV transparency and thus a colored composition having high exposure sensitivity can be obtained, and a black matrix having a high surface resistance can be obtained. In addition, metal oxide black pigments are preferable from the viewpoint of high heat resistance, and black pigments prepared by using a plurality of organic pigments other than black are used from the viewpoint of low dielectric properties. preferable.

The content of the (a) black pigment in the colored composition of the present invention can be selected in the range of usually 1 to 70% by weight with respect to the total solid content of the colored composition. In this range, 10 to 70% by weight is more preferable, and 20 to 60% by weight is particularly preferable. (A) By setting the content of the black pigment to be equal to or higher than the above lower limit value, it becomes possible to realize a high color density with a thin film, and there is no possibility of adversely affecting the gap control when forming a liquid crystal cell, and thermosetting Generation of wrinkles at the time can be suppressed. In addition, by setting the content of the (a) black pigment to the above upper limit or less, a composition having good sensitivity and high image forming property can be obtained.
(B) Liquid repellent (b) The liquid repellent used in the present invention includes a side chain having an ethylenically unsaturated group and a side chain having a fluorinated alkyl group or a group containing an oxygen atom in a part thereof (hereinafter referred to as “containing”). A polymer having a fluorinated side chain).

  (B) The liquid repellent agent not only enhances functions such as water / oil repellency, antifouling property, and low refractive index of the color filter coloring composition, but also imparts leveling properties to the base material and improves coating properties. Also used for. In addition, by having an ethylenically unsaturated group in a part of the structure of the liquid repellent agent, (c) a binder resin and / or a monomer, which will be described later, contained in the coloring composition for a color filter, is immobilized. Therefore, even if the surface of the coating film is washed by development or the like, (b) the liquid repellent does not fall off, and as a result, the surface performance of the coating film can be maintained over a long period of time.

Here, “a group containing an oxygen atom in a part thereof (that is, a part of the fluorinated alkyl group)” means that “at least a part of fluorine is formed by inserting an ether group in the middle of the alkyl chain of the fluorinated alkyl group. An “alkoxyalkyl group substituted with an atom” is meant.
The number of carbon atoms in the “fluorinated alkyl group or a group containing an oxygen atom in a part thereof” is preferably a long chain from the viewpoint of surface function expression, but generally a long chain fluorinated alkyl group is In many cases, the compatibility with other components in the composition is reduced, or the synthesis method for producing the fluorosurfactant is restricted (a compound having a long-chain fluorinated alkyl group is generally crystalline). It ’s high.) Therefore, in order to effectively develop the coating property (leveling property) of the coloring composition for a color filter, carbon substituted with a fluorine atom in the “fluorinated alkyl group or a group containing an oxygen atom in a part thereof” is used. Is usually in the range of 1-20, preferably in the range of 4-12, particularly preferably in the range of 6-8.

Of the “fluorinated alkyl group or a group containing an oxygen atom in a part thereof”, a fluorinated alkyl group is preferable. The fluorinated alkyl group is preferably a part of a fluoroalkoxy group or a fluoroalkylthio group.
(B) The fluorine content in the liquid repellent is usually 10 to 60% by weight from the viewpoint of having a high level of surface active effects such as penetration / wetability and leveling properties and water / oil repellency of the coloring composition. Preferably 10 to 55% by weight, more preferably 15 to 40% by weight. If the fluorine content is too low, the intended liquid repellency effect may not be sufficiently obtained. Conversely, if the fluorine content is too high, it may be difficult to uniformly apply the composition onto the substrate.

Further, (b) one type of liquid repellent agent may be applied to the color filter coloring composition of the present invention, or two or more types may be used in combination. When using 2 or more types together, the fluorine content mentioned above is a weight fraction with respect to (b) liquid repellent whole quantity. The fluorine content is measured and calculated by the oxygen combustion tube absorption-IC method. Specifically, a sample is burned in an electric tubular furnace at 900 to 1000 ° C. in which oxygen gas is flowed, and the generated combustion gas is bubbled into an absorbing solution of alkaline water, so that it is captured as fluorine ions. Fluorine ions are quantified by graph analysis to determine the fluorine content in the liquid repellent (solid content).

In addition, when forming the black matrix, (c) in order to chemically bond and immobilize with a binder resin and / or monomer, which will be described later, to suppress dropping by surface cleaning and segregation to the air interface during thermosetting, (b) The double bond equivalent in the liquid repellent molecule is preferably in the range of 200 to 560, and particularly preferably in the range of 340 to 540. (B) When the double bond equivalent in the liquid repellent molecule is not less than the above lower limit, (c) the chemical bond with the binder resin and / or monomer is sufficiently generated, and the liquid repellent is prevented from falling off due to development or the like. Can do. Moreover, by setting it as the said upper limit or less, the grade of a chemical bond can be controlled moderately and the required and sufficient quantity of (b) liquid repellent can be segregated to an air interface. The double bond equivalent is determined by H-NMR method using an internal standard.

Specifically, a liquid repellent sample and an internal standard substance (dimethyl terephthalate) are weighed, mixed, deuterated chloroform is added and dissolved, and H-NMR measurement is performed with a 500 MHz NMR apparatus. Note that the measurement is performed with an accumulated repetition time of 10 seconds or more. The double bond equivalent is determined from the internal standard substance of the obtained H-NMR spectrum and the signal area of the ethylenically unsaturated group.
(B) The “side chain having an ethylenically unsaturated group” in the lyophobic agent is a compound having both an ethylenically unsaturated group and a group capable of binding to a polymer to be the main chain described later, and reacting with the main chain, It can be formed by adding.

As an ethylenically unsaturated group, the ethylenically unsaturated group which (meth) acryloyl group has is preferable, and as a compound which has such a group, isocyanate group containing (meth) acrylic acid ester, (meth) acrylic acid, for example are mentioned. And unsaturated monobasic acids.
As the liquid repellent (b) of the present invention, a polymer as a main chain having both the fluorine-containing side chain described above and a group having active hydrogen (hereinafter sometimes referred to as “active hydrogen group”) is used as an isocyanate. What is obtained by making group containing (meth) acrylic acid ester or (meth) acrylic acid react is preferable.

  The active hydrogen group of the main chain may be any group that can react with the isocyanate group in the aforementioned isocyanate group-containing (meth) acrylic monomer or the carboxyl group in (meth) acrylic acid, Although not limited in any way, it is a hydroxyl group from the viewpoint of easy introduction of active hydrogen groups into the main chain polymer and excellent reactivity with isocyanate groups or carboxyl groups. preferable.

(B) The main chain of the liquid repellent contributes to compatibility with the other components in the colored composition of the present invention. Examples of the main chain include (meth) acrylic resins and novolac resins, but novolac resins are preferred from the viewpoint of heat resistance.
(B) When the main chain is a (meth) acrylic resin, the liquid repellent is synthesized according to the method described in International Publication Pamphlet WO2004 / 042474A1. When the main chain is a novolac resin, a polymer that becomes the main chain is synthesized by a method in which a phenol compound is first polycondensed with aldehydes.

  Specific examples of the phenol compound include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, Catechol, resorcinol, hydroquinone, methylhydroquinone, pyrogallol, phloroglicinol and the like can be mentioned. As the aldehyde, formaldehyde is preferable.

Examples of such novolak resins include phenol / formaldehyde resins, cresol / formaldehyde resins, phenol / cresol / formaldehyde copolymer resins, and the like.
Examples of a method for introducing a side chain having an ethylenic double bond into the polymer that becomes the main chain described above include a method in which a monomer having an epoxy group is reacted with a part of a phenolic hydroxyl group. . Also, after reacting a part or all of the phenolic hydroxyl group with epichlorohydrin and introducing an epoxy group into the novolac resin, the epoxy group is reacted with a monomer having an ethylenically unsaturated group and a carboxyl group. The method of letting it be mentioned.

Furthermore, a hydroxyl group generated by this reaction may be reacted with an acid anhydride to introduce a carboxyl group into the molecule.
Commercially available novolak resins containing the above acidic group and ethylenic double bond include KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115, TCR-1025, TCR-1064, TCR-1286, ZFR-1122, ZFR-1124, ZFR-1185 (above, Nippon Kayaku Co., Ltd.) etc. are mentioned.

  Among (b) liquid repellents having a novolac resin in the main chain, a polymer having a repeating unit represented by the following general formula (1) is particularly preferable.

(In the above general formula (1), R ⁵¹ is

R ⁵² represents a (meth) acryloyloxy group, X ¹ represents an oxygen atom or a sulfur atom, and R ⁵³ represents

R ⁵⁴ is

(However, u represents an integer of 1 to 3, and v = 4 to 12, and R ⁵⁵ represents a hydrogen atom or a fluorine atom.) In addition, s and t represent the number of each repeating unit, and are s / t = 0.1-10. )
In the general formula (1), u is preferably 1 to 2, and v is preferably 6 to 8. Moreover, although it is s / t = 0.1-10 normally, from the point which can control the surface segregation of (b) lyophobic agent highly by the post-exposure process mentioned later, for example, it is a side chain which has an ethylenically unsaturated group ( That is, since a compound containing a large amount of —O—R ⁵¹ —R ⁵² ) in the general formula (1) is preferable, s / t = 3 to 4 is preferable.

  The polymer having the repeating unit represented by the general formula (1) is prepared by introducing an epoxy group by reacting an epichlorohydrin with the phenolic hydroxyl group of the cresol-formaldehyde resin, for example, according to a conventional method. An ethylenically unsaturated group is introduced into the part by reacting an isocyanate group-containing (meth) acrylic acid ester or acrylic acid (b3), and the other general formula (or the remainder) of the following general formula

(In the above general formula, X ¹ , R ⁵⁵ , u and v have the same meaning as in the general formula (1)), and can be obtained by reacting.
(B) The weight average molecular weight of the liquid repellent as measured by gel permeation chromatography in terms of standard polystyrene is usually 4,000 to 100,000, preferably 5,000 to 60,000, more preferably. Is 7000-16000. By making the weight average molecular weight not more than the above upper limit value, (b) the liquid repellent agent is sufficiently segregated on the surface, and by making it not less than the lower limit value, in the thermosetting step described later, The seepage into the pixel portion (opening surrounded by the black matrix) can be more completely suppressed.

  (B) As the liquid repellent, a commercially available product having the above-described structure may be used. For example, MIC Megafac RS-102, RS-101, RS-105, RS-107, RS- 401, RS-402, RS-501, RS-502, RS-585, RS-601, RS-701, RS-702, RS-713, RS-717, etc. Fluorine-containing organic compounds commercially available in (1) can be used.

(B) Content of liquid repellent is 0.1 to 10 weight% normally in the total solid in the coloring composition of this invention, Preferably it is 0.5 to 5 weight%, More preferably, it is 1-3 weight% It is. (B) By making content of a liquid repellent below the said upper limit, the fall of the surface tension of a coloring composition can be prevented too much, conversely, by making it more than the said lower limit, it is enough for the surface of a black matrix. Liquid repellency can be imparted.
(C) Binder resin and / or monomer (c-1) Binder resin
The (c-1) binder resin used in the colored composition of the present invention can be used without particular limitation as long as it is a resin used for the production of a resin black matrix in a color filter, and in particular, an epoxy having a carboxyl group. It is preferable to use an acrylate resin.

  The above-mentioned epoxy acrylate resin means that an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin (or epoxy compound), and further a polybasic It is synthesized by reacting an acid or its anhydride. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to “acrylate”, but epoxy resin (or epoxy compound) is a raw material, and “acrylate” is representative. Since it is an example, it is named in this way according to common usage.

  The raw material epoxy resin includes (o, m, p-) cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, or Examples thereof include epoxy resins (or epoxy compounds) represented by the general formulas (1-a) to (1-a ′ ″) described.

Particularly preferred as (c-1) binder resin in the present invention will be described below in (c-1-1) to (c-1-4).
(C-1-1)
One particularly preferable binder resin (c-1) in the present invention is an epoxy compound (a ″) represented by the following general formula (1-a ″) and an unsaturated group-containing carboxylic acid (b ″). An alkali-soluble resin (A ″) obtained by reacting the reaction product with a polybasic acid and / or its anhydride (c ″) can be mentioned.

[In the above general formula (1-a ″), X represents a linking group represented by the following general formula (2a), (2b) or (3), provided that one or more adamantane structures are present in the molecular structure. 1 represents an integer of 2 or 3.

(In the above general formulas (2a) and (2b), R ^{1 to} R ⁴ and R ^{13 to} R ¹⁵ each independently have an adamantyl group, a hydrogen atom, and a substituent which may have a substituent. An optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted phenyl group is shown.
In the general formula (3), R ^{5 to} R ¹² may each independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms that may have a substituent, or a substituent. Represents a phenyl group; Y represents a divalent linking group containing an adamantane structure, which may have a substituent.

In the general formulas (2a), (2b), and (3), * represents a binding site with the glycidyloxy group in the general formula (1-a ″).
(1) Epoxy compound (a ″) represented by general formula (1-a ″)
First, the group X in the epoxy compound (a ″) represented by the general formula (1-a ″) (hereinafter sometimes referred to as “(a ″) component”) will be described.

When the group X has the structure represented by the general formula (2a) or (2b), it is preferable that the general formulas (2a) and (2b) both have an adamantane structure of 2 or more and 4 or less. When the adamantane structure is 1, the developer resistance tends to decrease and the resolution tends to be inferior.
When the group X is a structure represented by the general formula (3), Y in the general formula (3) is “a divalent linking group including an adamantyl structure which may have a substituent”. If it is, there is no restriction | limiting in particular other than that, For example, it is preferable that it is a coupling group represented by the following general formula (4) or (5).

[All of the above general formulas (4) and (5) may have a substituent. * Represents a binding site with the benzene ring in the general formula (3). ]
In particular, the epoxy compound (a ″) represented by the general formula (1-a ″) is preferably represented by the following general formula (6) or (7).

[The adamantyl group represented by the general formulas (6) and (7) may have a substituent.
In General Formula (6), R ^{16 to} R ²³ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group. Indicates a group.
In General Formula (7), R ²⁴ and R ²⁵ are each independently an adamantyl group that may have a substituent, a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms that may have a substituent. Or a phenyl group which may have a substituent. ]
The general formula (2a), (2b), (3), as the ^R 1 to R ² 5 alkyl group having 1 to 12 carbon atoms in the (6) and (7), preferably an alkyl having 1 to 10 carbon atoms Groups.

Examples of the substituent that these alkyl groups may have include a halogen atom, a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, A phosphino group, an amino group, a nitro group, etc. are mentioned.
In addition, examples of the substituent that the phenyl group of R ^{1 to} R ^{25 in} the general formulas (2a), (2b), (3), (6), and (7) may have include a halogen atom, a hydroxyl group, Examples thereof include an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group, and a nitro group.

Also, adamantane ring contained in Y of the general formula (2a) and adamantyl groups ^R 1 ^{~ R4} and ^R 13 ^{to R 15} in (2b), the general formula (3), adamantane ring in the general formula (6), the general The substituent that the adamantyl group in formula (7), the adamantyl group of R ²⁴ and R ²⁵ in general formula (7), and the adamantane ring in general formulas (4) and (5) may have a halogen atom , A hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group, and a nitro group.

In the general formula (6), R ^{16 to} R ²³ are particularly preferably an alkyl group, a halogen atom, an alkoxyl group, an alkenyl group, or a phenyl group.
In the general formula (7), R ²⁴ and R ²⁵ are particularly preferably an alkyl group, a halogen atom, an alkoxyl group, an alkenyl group, or a phenyl group.
The molecular weight of X represented by the general formula (1-a ″) is preferably 200 or more and 1000 or less. By setting the molecular weight of X to 200 or more, sufficient chemical resistance can be secured, and 1000 By making it below, good sensitivity can be ensured.

  The epoxy equivalent of the epoxy compound (a ″) represented by the general formula (1-a ″) is preferably 210 or more, and more preferably 230 or more. The epoxy equivalent is preferably 450 or less, and more preferably 400 or less. When the epoxy equivalent of the epoxy compound (a ″) is 210 or more, sufficient alkali resistance can be ensured, and when it is 450 or less, good sensitivity of the organic binder produced can be ensured.

As the epoxy compound (a ″), one type may be used alone, or two or more types may be used in combination.
As the epoxy compound (a ″), a commercially available product may be used, or it may be synthesized from a phenol compound as described below by a known method.

[R ^{1 to} R ¹⁵ in the general formulas (9a), (9b), and (10) have the same meanings as in the general formulas (2a), (2b), and (3), respectively. ]
For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added in advance to a dissolved mixture of the compound represented by the general formula (9a) or (9b) and an excess of epihalohydrin such as epichlorohydrin or epibromhydrin. The connecting group in which X in the general formula (1-a ″) is represented by the general formula (2a) or (2b) by adding or reacting at a temperature of 20 to 120 ° C. for 1 to 10 hours while adding. An epoxy compound (a ″) can be obtained.

  In addition, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added in advance or added to a dissolved mixture of the compound represented by the general formula (10) and an epihalohydrin such as excess epichlorohydrin or epibromohydrin. The epoxy compound (a ″) in which X in the general formula (1-a ″) is represented by the general formula (3) can be obtained by reacting at a temperature of 20 to 120 ° C. for 1 to 10 hours. .

  In the reaction for obtaining the epoxy compound (a ″), an aqueous solution thereof may be used as the alkali metal hydroxide. In that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system. Alternatively, water and epihalohydrin may be continuously distilled off under reduced pressure or normal pressure, followed by liquid separation, removal of water, and epihalohydrin being continuously returned to the reaction system.

  Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like is catalyzed to a dissolved mixture of the compound represented by the general formula (9a), (9b) or (10) and epihalohydrin. To the halohydrin etherified product of the compound represented by the general formula (9a), (9b), or (10) obtained by reacting at 50 to 150 ° C. for 1 to 5 hours. The epoxy compound (a) represented by the general formula (1-a ″) can also be obtained by adding a solid or aqueous solution of the product and reacting again at a temperature of 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure). )) Can be manufactured.

  The amount of epihalohydrin used in such a reaction is usually 1 to 20 mol, preferably 2 to 10 mol, relative to 1 equivalent of the hydroxyl group of the compound represented by general formula (9a), (9b), or (10). It is. Moreover, the usage-amount of an alkali metal hydroxide is 0.8-15 mol normally with respect to 1 equivalent of hydroxyl groups of the compound represented by general formula (9a), (9b), or (10), Preferably 0.9- 11 moles.

In the above-mentioned reaction, in addition to alcohols such as methanol and ethanol, an aprotic polar solvent such as dimethyl sulfone and dimethyl sulfoxide may be added to perform the reaction smoothly. When alcohols are used, the amount used is 2 to 20% by weight, preferably 4 to 15% by weight, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, the usage-amount is 5 to 100 weight% with respect to the quantity of an epihalohydrin, Preferably it is 10 to 90 weight%.
(2) Unsaturated carboxylic acid (b ″)
Examples of the unsaturated group-containing carboxylic acid (b ″) (hereinafter sometimes referred to as “(b ″) component”) include unsaturated carboxylic acids having an ethylenically unsaturated group, and specific examples include ( (Meth) acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, cinnamic acid, α-position substituted with haloalkyl group, alkoxyl group, halogen atom, nitro group, or cyano group Monocarboxylic acids such as (meth) acrylic acid; 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2 -(Meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, -(Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (Meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutyl hydrophthalic acid, 2- (meth) acryloyloxybutyl phthalic acid, 2- ( (Meth) acryloyloxybutylmaleic acid and the like (meth) acryloyloxyalkyl esters of dibasic acids; (meth) acrylic acid such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, etc. Monomers to which lactones are added; (meth) acrylic acid dimers, etc. That.

  Also, anhydrous hydroxyl-containing unsaturated compounds such as pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane diacrylate, glycidyl methacrylate acrylic acid adduct, and glycidyl methacrylate methacrylic acid adduct. The compound which added acid anhydrides, such as succinic acid, maleic anhydride, tetrahydrophthalic anhydride, and phthalic anhydride, is also mentioned.

Particularly preferred is (meth) acrylic acid.
These may be used alone or in combination of two or more.
As a method of reacting the epoxy group in the component (a ″) with the component (b ″), a known method can be used. For example, the component (a ″) and the component (b ″) are combined with tertiary amines such as triethylamine and benzylmethylamine, quaternary compounds such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, and benzyltriethylammonium chloride. Carboxylic acid can be added to the epoxy compound by reacting ammonium salt, pyridine, triphenylphosphine or the like in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours.

The amount of the catalyst used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5% by weight, based on the reaction raw material mixture (the sum of the components (a ″) and (b ″)). is there. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, phenothiazine, etc.). Preferably it is 0.01 to 10 weight% with respect to the reaction raw material mixture, Most preferably, it is 0.03 to 5 weight%.

The ratio of adding the (b ″) component to the epoxy group of the (a ″) component is usually 90 to 100 mol%. Since the remaining epoxy group tends to adversely affect storage stability, the component (b ″) is usually 0.8 to 1.5 equivalents, particularly 0, relative to 1 equivalent of the epoxy group of the component (a ″). It is preferable to carry out the reaction at a ratio of .9 to 1.1 equivalents.
(3) Polybasic acid and / or its anhydride (c ″)
As the polybasic acid and / or anhydride (c ″) (hereinafter, sometimes referred to as “(c ″) component” or “polybasic acid (anhydride)”), the dibasic acid and / or anhydride thereof Product (hereinafter referred to as “dibasic acid (anhydride)”, 3 basic acid and / or anhydride thereof (hereinafter referred to as “3 basic acid (anhydride)”), 4 basic acid and / or anhydride thereof (Hereinafter referred to as “4-basic acid (anhydride)”) and the like.

  As the 4-basic acid (anhydride) (tetracarboxylic acid and / or dianhydride thereof), known ones can be used, such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, etc. Tetracarboxylic acid, or these dianhydrides are mentioned. These may be used alone or in combination of two or more.

As the 4-basic acid (anhydride), among the above exemplified compounds, biphenyltetracarboxylic acid or an anhydride thereof is particularly preferable.
By reacting a reaction product of the component (a ″) and the component (b ″) with a tetrabasic acid (anhydride) as the component (c ″), the molecular weight increases due to a crosslinking reaction. It is preferable because of the effects such as improvement of adhesion, adjustment of solubility, improvement of sensitivity and alkali resistance.

  Examples of the dibasic acid (anhydride) (dicarboxylic acid and / or anhydride thereof) include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, and chlorende. An acid, methyltetrahydrophthalic acid, or these anhydrides are mentioned. Among these, tetrahydrophthalic acid, succinic acid, or anhydrides thereof are preferable. These may be used alone or in combination of two or more.

By reacting the reaction product of the component (a ″) and the component (b ″) with a dibasic acid (anhydride) as the component (c ″), it is possible to easily adjust the solubility and to adhere to the substrate. Is preferable.
Examples of the tribasic acid (anhydride) (tricarboxylic acid and / or anhydride thereof) include trimellitic acid, hexahydrotrimellitic acid, and anhydrides thereof. Particularly preferred are trimellitic anhydride and hexahydrotrimellitic anhydride. These may be used alone or in combination of two or more.

By using a tribasic acid (anhydride) as the component (c ″), the molecular weight of the alkali-soluble resin (A ″) can be increased, branching can be introduced into the molecule, and the molecular weight and viscosity must be balanced. Can do. Moreover, the amount of acid groups introduced into the molecule can be increased, and a resin having a good balance of sensitivity, adhesion, and the like can be obtained.
As the component (c ″), it is particularly preferable to use a 4-basic acid (anhydride). In this case, the addition rate of the 4-basic acid (anhydride) is the addition of the component (b ″) to the component (a ″). It is usually 10 to 100 mol%, preferably 20 to 100 mol%, more preferably 30 to 100 mol%, based on the hydroxyl group produced when the tetrabasic acid (anhydride) as component (c ″). ) Is set to the above lower limit value or more, sufficient solubility of the alkali-soluble resin (A ″) and good adhesion to the substrate can be ensured.

In addition, it is preferable to replace a part of the 4-basic acid (anhydride) described above with a dibasic acid (anhydride) from the viewpoint of adjusting the viscosity and solubility of the colored composition.
When (c ″) a 4-basic acid (anhydride) and a 2-basic acid (anhydride) are used in combination, the molar ratio is 2 basic acid (anhydride): 4 basic acid (anhydride) = 99: 1 It is preferably ~ 20: 80, more preferably 80: 20 ~ 30: 70 By making the ratio of 4-basic acid (anhydride) more than the above lower limit value, a film having a high coating film obtained It becomes possible to obtain physical properties, and by setting the dibasic acid (anhydride) to the above lower limit or more, an increase in the viscosity of the obtained resin solution can be suppressed, and handling properties can be improved.

In addition to the effects of improving adhesion to the substrate, easy adjustment of solubility, improvement of sensitivity and alkali resistance, etc., in order to achieve various balances such as molecular weight, viscosity, sensitivity, and adhesion, 4-basic acid is used. (Anhydride) and / or dibasic acid (anhydride) and tribasic acid (anhydride) are preferably used in combination.
In the case where a 4-basic acid (anhydride) and / or a 2-basic acid (anhydride) and a 3-basic acid (anhydride) are used in combination as the component (c ″), the amount of the 3-basic acid (anhydride) used is small. If the amount is too high, the effect is diminished and the alkali resistance may be lowered. Therefore, the amount of tribasic acid (anhydride) used is the amount of hydroxyl group produced when component (b ″) is added to component (a ″). On the other hand, it is usually about 5 to 70 mol%, preferably about 10 to 40 mol%.

The total addition rate of component (c ″) is usually 10 to 100 mol%, preferably 20 to 100 mol%, based on the hydroxyl group produced when component (b ″) is added to component (a ″). More preferably, it is 30 to 100 mol%. By setting the addition rate of the component (c ″) to the above lower limit or more, the solubility of the alkali-soluble resin (A ″) and the adhesion to the substrate are better. Become.
In addition, the component (c ″) is added with the component (b ″) to the component (a ″) in addition to reacting with the hydroxyl group generated when the component (b ″) is added to the component (a ″). When a polyhydric alcohol (d ″), which will be described later, is mixed therewith, it may be reacted with any hydroxyl group present in the mixture.

As a method of adding the component (c ″) after adding the component (b ″) to the component (a ″) or mixing a polyhydric alcohol (d ″) described later thereto, a known method is known. Can be used.
The reaction temperature is usually 80 to 130 ° C, preferably 90 to 125 ° C. When the reaction temperature exceeds 130 ° C., some of the unsaturated groups in the component (b ″) are polymerized, which may lead to a rapid increase in molecular weight. , (C ″) may remain.
(4) Polyhydric alcohol (d ″)
In the colored composition of the present invention, the other binder resin (F) used in combination with the alkali-soluble resin (A) is further added to the reaction product obtained by adding the component (b ″) to the component (a ″) described above. A monohydric alcohol (d ″) (hereinafter sometimes referred to as “(d ″) component”) is mixed, and the above-described (c ″) component is added to any hydroxyl group present in the mixture. An alkali-soluble resin (A1 ″) obtained by the above method may be used.

Examples of the component (d ″) include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. An alcohol is preferred.
By using the component (d ″), the molecular weight of the alkali-soluble resin (A1 ″) can be increased, branching can be introduced into the molecule, and a balance between the molecular weight and the viscosity can be achieved. Moreover, the rate of introduction of acid groups into the molecule can be increased, and an organic binder having a good balance of sensitivity and adhesion can be obtained.

When the amount of the component (d ″) used is too small, the effect is thin, and when it is too large, there is a possibility of thickening or gelation. Therefore, the amount of the component (a ″) and the component (b ″) is reduced with respect to the reaction product. In general, it is about 0.01 to 0.5 times by weight, preferably about 0.02 to 0.2 times by weight.
(5) Acid value and molecular weight of alkali-soluble resins (A ″) and (A1 ″)
The acid value of the alkali-soluble resins (A ″) and (A1 ″) thus obtained is usually 10 mgKOH / g or more, preferably 50 mgKOH / g or more. In order to ensure good developability, the acid value is preferably not less than the above lower limit value, and sufficient alkali resistance of the colored composition is ensured (that is, the pattern surface is roughened by an alkaline developer or The acid value is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.

The weight average molecular weight (Mw) in terms of standard polystyrene as measured by gel permeation chromatography (GPC) of the alkali-soluble resins (A ″) and (A1 ″) is preferably 1,500 or more, preferably 2,000 or more. More preferably. Moreover, it is preferable that it is 20,000 or less, and it is more preferable that it is 10,000 or less. By setting the weight average molecular weight to the above lower limit value or more, sensitivity, coating film strength, alkali resistance and the like are improved. Moreover, favorable developability and re-dissolution property can be obtained by setting it as the said upper limit or less.
(C-1-2)
As another example of the (c-1) binder resin particularly preferable in the present invention, an epoxy resin (a) represented by the following general formula (1-a) and an unsaturated group-containing carboxylic acid (b) Alkali-soluble resin (A) obtained by making a reaction material react with a polybasic acid and / or its anhydride (c) is mentioned.

[In the said general formula (1-a), n shows an average value and shows the number of 0-10. R ⁴¹ represents any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, and a biphenyl group. A plurality of R ⁴¹ present in one molecule may be the same or different. G represents a glycidyl group. ]
(1) Epoxy resin (a) represented by general formula (1-a)
R ⁴¹ in the general formula (1-a) represents any of a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. As represented, from the viewpoint of sensitivity and solubility, R ⁴¹ is particularly preferably a hydrogen atom or a methyl group. A plurality of R ⁴¹ present in one molecule may be the same or different.

  The epoxy resin (a) represented by the general formula (1-a) includes, for example, a compound represented by the following general formula (1-a-1) and an epihalohydrin in the presence of an alkali metal hydroxide. It can be obtained by reacting.

(In the formula, n and R ⁴¹ represent the same meaning as in the general formula (1-a).)
The compound represented by the general formula (1-a-1) is obtained by, for example, subjecting a compound represented by the following general formula (1-a-2) and a phenol compound to a condensation reaction in the presence of an acid catalyst. Obtainable.

(In the formula, Z represents a halogen atom, a hydroxyl group, or a lower alkoxy group. R ⁴¹ represents the same meaning as in the general formula (1-a).)
In Z of the general formula (1-a-2), a halogen atom is preferably a chlorine atom, a bromine atom or the like, and a lower alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group. As a group.

On the other hand, the phenolic compound is an aromatic compound having one phenolic hydroxyl group in one molecule, and specific examples thereof include phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butylphenol, Various o-, m-, and p-isomers of alkylphenols such as octylphenol, xylenol, methylbutylphenol, di-t-butylphenol and the like, or cycloalkylphenols such as cyclopentylphenol, cyclohexylphenol, cyclohexylresole and the like, or phenyl phenol, substituted phenol compounds substituted by groups exemplified as R ⁴¹ can be mentioned in the general formula (1-a). These phenolic compounds can be used alone or in combination of two or more.
(2) Unsaturated group-containing carboxylic acid (b)
As unsaturated group containing carboxylic acid (b), the unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned, As a specific example, (meth) acrylic acid, crotonic acid, o-, m-, p -Monocarboxylic acid such as vinyl benzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substitution, 2- (meth) acryloyloxyethyl succinic acid, 2-acryloyloxyethyl adipic acid 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (Meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) Acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid (meth), acrylic acid with ε-caprolactone, β-propiolactone, γ- Monomers to which lactones such as butyrolactone and δ-valerolactone are added, or hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate, (anhydrous) succinic acid, (anhydrous) phthalic acid, ( Monomer) to which acid (anhydride) such as maleic acid is added, (meth) acrylic acid dye Chromatography and the like.

Of these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity. These may be used alone or in combination of two or more.
(3) Polybasic acid and / or its anhydride (c)
As the polybasic acid and / or anhydride (c) added to the hydroxyl group of the reaction product of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b), known ones can be used. Acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene-2 Dibasic carboxylic acids such as 1,3-dicarboxylic acid or anhydrides thereof; polybasic carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, or anhydrides thereof. Among these, tetrahydrophthalic anhydride or succinic anhydride is preferable. These may be used alone or in combination of two or more.

  The addition rate of the polybasic acid and / or its anhydride (c) is usually 10 to 100 mol% of the hydroxyl group produced when the unsaturated group-containing carboxylic acid (b) is added to the epoxy resin (a). , Preferably 20 to 100 mol%, more preferably 30 to 100 mol%. By making this addition rate not more than the above upper limit value, it is possible to prevent a decrease in the remaining film ratio during development, and by making it not less than the above lower limit value, it has good solubility and adhesion to the substrate. Can do.

As a method of adding the polybasic acid and / or anhydride (c) thereof after adding the unsaturated group-containing carboxylic acid (b) to the epoxy resin (a), a known method can be used. .
Moreover, in this invention, after adding a polybasic acid and / or its anhydride (c) in this way, you may add an epoxy-group containing compound (d) to a part of produced | generated carboxyl group. In this case, as an epoxy group-containing compound (d), in order to improve photosensitivity, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, glycidyl ether compound having a polymerizable unsaturated group, etc. In order to add an epoxy group-containing unsaturated compound or to improve developability, a glycidyl ether compound having no polymerizable unsaturated group can be added, or both of them may be used in combination. Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group (manufactured by Nagase Chemical Industries, Ltd., trade names: Denacol EX-111, Denacol EX-121, Denacol) EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192) and the like.

The alkali-soluble resin (A) according to the present invention is obtained by reacting the reaction product of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b) with a polybasic acid and / or its anhydride (c). The resin obtained by adding such an epoxy group-containing compound (d) to a part of the carboxyl group of the resin obtained by the above process may be used.
(4) Physical properties of alkali-soluble resin (A)
The weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A) used in the present invention is usually 3,300 or more, preferably 3,500 or more. 50,000 or less, preferably 30,000
00 or less, more preferably 10,000 or less. When the weight average molecular weight is 3300 or more, the exposure sensitivity of the resulting colored composition is remarkably improved, and when it is 50000 or less, high solubility in a developer can be obtained.

The exposure sensitivity of the coloring composition is significantly improved. The details of the mechanism for improving the sensitivity are unknown, but (1) the efficiency of photopolymerization is usually increased by preliminarily increasing the molecular weight of the portion that has been increased by photopolymerization (before photopolymerization). And (2)
Since the basic skeleton has a higher molecular weight, it is estimated that the resistance to the developer is increased.

Moreover, the acid value (mgKOH / g) of the alkali-soluble resin (A) used in the present invention is usually 10 or more, preferably 50 or more, and usually 200 or less, preferably 150 or less. If the acid value of the alkali-soluble resin (A) is too low, sufficient solubility may not be obtained. If the acid value is too high, curability is insufficient and the surface properties of the coating film tend to deteriorate.
In addition, a condensation reaction of the compound represented by the general formula (1-a-2) and a phenol compound, a compound represented by the general formula (1-a-1) obtained by the condensation reaction, and an epihalohydrin The synthesis reaction of the alkali-soluble resin (A) such as reaction, addition reaction of unsaturated group-containing carboxylic acid (b) and polybasic acid and / or anhydride (c) thereof can be performed by known methods, for example, It can be performed by the method described in JP-A-2005-55814.
(C-1-3)
In addition, as another example of the (c-1) binder resin particularly preferable in the present invention, an epoxy compound (a ′) represented by the following general formula (1-a ′) and an unsaturated group-containing carboxylic acid (b ′) ) And an alkali-soluble resin (A ′) obtained by reacting the reaction product with a polybasic acid and / or its anhydride (c ′).

[In the general formula (1-a ′), p and q each independently represent an integer of 0 to 4, and R ³¹ and R ³² each independently represent an alkyl group or a halogen atom. R ³³ and R ³⁴ each independently represents an alkylene group. x and y each independently represents an integer of 0 or more. ]
(1) Epoxy compound (a ′) represented by general formula (1-a ′)
First, the epoxy compound (a ′) represented by the general formula (1-a ′) (hereinafter sometimes referred to as “(a ′) component”) will be described.

In the general formula (1-a ′), the alkyl group of R ³¹ and R ³² is preferably an alkyl group having 1 to 10 carbon atoms, and the halogen atom includes Cl, Br, F, and the like. R ³¹ and R ³² are each particularly preferably an alkyl group having 1 to 5 carbon atoms.
Although details of the mechanism of action of the alkyl groups and halogen atoms of R ³¹ and R ³² are not clear, it is assumed that they affect the three-dimensional structure of the molecule and control the solubility in the developer. Is done.

Therefore, from the above viewpoint, p and q in the general formula (1-a ′) each independently represent an integer of 0 to 4, preferably 1 or 2.
The bonding position of R ³ 1 and R ^{32 to} the benzene ring is not particularly limited,

Or

The o-position is preferred.
R ³¹ and R ³² may be the same group or different groups, but are preferably the same group from the viewpoint of production cost.
Examples of the alkylene group of R ³³ and R ³⁴ include an alkylene group having 1 to 10 carbon atoms, and it is particularly preferable that they are each independently an ethylene group or a propylene group.

x and y each independently represents an integer of 0 or more, but is usually about 0 to 6, preferably about 0 to 3. In general, the larger x and y, the higher the solubility, but if it is too large, the sensitivity may decrease.
R ³³ and R ³⁴ may be the same group or different groups, but are preferably the same group from the viewpoint of production cost.

The molecular weight of these components (a ′) is usually in the range of 200 to 200,000, preferably 300 to 100,000, as a weight average molecular weight (Mw) in terms of standard polystyrene as measured by gel permeation chromatography (GPC). . By setting the molecular weight to be equal to or higher than the lower limit value, the film forming property is improved, and by setting the molecular weight to be equal to or lower than the upper limit value, gelation during the addition reaction of the unsaturated group-containing carboxylic acid (b ′) described later is suppressed.
(2) Unsaturated group-containing carboxylic acid (b ')
The unsaturated group-containing carboxylic acid (b ′) (hereinafter, sometimes referred to as “(b ′) component”) is the same as that in the alkali-soluble resin (A ″) in the section (c-1-2). The same compounds as those mentioned as the saturated group-containing carboxylic acid (b ″) can be used. Of these, (meth) acrylic acid is preferable among α, β-unsaturated carboxylic acids, and acrylic acid is particularly preferable because of its high reactivity. Among α, β-unsaturated carboxylic acid esters having a carboxyl group in the ester moiety, 2- (meth) acryloyloxyethyl phthalic acid and 2- (meth) acryloyloxyethyl maleic acid are preferred.

The amount of component (b ′) used is preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents, relative to 1 equivalent of the epoxy group of component (a ′). .
By setting the amount of component (b ′) used to be at least the lower limit, a sufficient amount of unsaturated groups can be introduced, and the subsequent reaction with polybasic acid and / or its anhydride (c ′) is also possible. It will be enough. Moreover, the point that a large amount of epoxy groups does not remain is also preferable. By making the usage-amount of (b ') component or less into an upper limit, it is preferable at the point which does not remain as an unreacted substance. By satisfying the above range, high photocuring characteristics can be obtained.
(3) Polybasic acid and / or its anhydride (c ′)
As the polybasic acid and / or its anhydride (c ′), as the polybasic acid and / or its anhydride (c ″) in the alkali-soluble resin (A ″) in the section (c-1-2) The compounds similar to those mentioned can be mentioned, among which tetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof are preferable.

The addition rate of the polybasic acid and / or anhydride (c ′) is preferably such that the acid value of the finally obtained alkali-soluble resin (A ′) is 10 to 150 mgKOH / g.
mgKOH / g is more preferred. By setting the acid value to be equal to or higher than the above lower limit, alkali developability is improved, and by setting the acid value to be equal to or lower than the upper limit, sufficient photocurability is obtained.
In addition, it is good also as what introduce | transduced polyfunctional alcohol (d '), such as a trimethylol propane, a pentaerythritol, a dipentaerythritol, and introduce | transduced the multibranched structure at the time of this addition reaction of (c') component. Examples of the polyhydric alcohol (d ′) include the same compounds as those described above as the polyhydric alcohol (d ″) in the alkali-soluble resin (A ″), and preferred compounds and preferred use amounts are also the same.

  All synthetic reactions of alkali-soluble resins (A ′) such as addition reaction of unsaturated group-containing carboxylic acid (b ′) and polybasic acid and / or its anhydride (c) to epoxy compound (a ′) are known. For example, it can be performed with reference to the methods described in JP-A-2005-126665, JP-A-2005-325331, JP-A-2006-241224, and the like.

The weight average molecular weight (Mw) in terms of standard polystyrene as measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A ′) is usually 1,000 or more, preferably 1,500 or more, and usually 30,000 or less. , Preferably 20,000 or less, more preferably 10,000 or less, particularly preferably 8,000 or less. When the weight average molecular weight is not more than the above upper limit value, the developability is good, and when it is not less than the lower limit value, the alkali resistance is good.
(C-1-4)
As another example of the (c-1) binder resin particularly preferable in the present invention, an epoxy resin (a ′ ″) represented by the following general formula (1-a ′ ″) and an unsaturated group-containing carboxylic acid ( Examples thereof include alkali-soluble resins (A ′ ″) obtained by reacting a reaction product with b ′ ″) with a polybasic acid and / or an anhydride thereof (c ′ ″).

[In the general formula (1-a ′ ″), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² represents a divalent polycyclic hydrocarbon group having 5 to 16 carbon atoms. R ³ and R ⁴ each independently represents a hydrogen atom or a glycidyl group. n represents 1 or 2. m and x represent the ratio of each repeating unit, and m ≧ x ≧ 0.5 m. ]
In the general formula (1-a ′ ″), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and among them, a hydrogen atom or a methyl group is preferable from the viewpoint of photocurability. N represents 1 or 2, but is preferably 1.

R ² represents a divalent polycyclic hydrocarbon group having 5 to 16 carbon atoms. Such a group refers to an unsaturated polycyclic hydrocarbon ring compound having the same skeleton and at least two carbon-carbon double bonds (hereinafter sometimes simply referred to as “unsaturated polycyclic hydrocarbon compound”). It can be formed by using the raw material and carrying out the reaction described below.
Examples of the unsaturated polycyclic hydrocarbon ring compound used as a raw material include the following compounds, but are not limited thereto.

Among these, a bridged carbocycle is more preferable, and dicyclopentadiene is particularly preferable.
The epoxy resin (a ′ ″) represented by the general formula (1-a ′ ″) is a polyaddition of the unsaturated polycyclic hydrocarbon compound described above and a phenol compound represented by the following general formula. It can be obtained by glycidylation of the hydroxyl group of the reaction product.

(In the above general formula, R ¹ and n are as defined in the general formula (1-a ′ ″).)
As the epoxy resin (a ′ ″) in the (c-1-4) resin of the present invention, the following general formula (1-a) obtained by glycidylation of a polyaddition reaction product of dicyclopentadiene and the above phenol compound is used. The compound represented by '''-1) is particularly preferable.

(In the above general formula (1-a ′ ″-1), R ³ , R ⁴ , m and x have the same meaning as in the general formula (1-a ′ ″).
The introduction ratio of the glycidyl group in the general formula (1-a ′ ″) and the general formula (1-a ′ ″-1) is 50 to 100 mol% of the phenolic hydroxyl group in the phenol resin before glycidylation. That is, m and x in the general formula (1-a ′ ″) and the general formula (1-a ′ ″-1) must have a relationship of m ≧ x ≧ 0.5 m, preferably 70 It is preferable that ˜100 mol% is substituted with a glycidyl group.

The alkali-soluble resin (A ′ ″) is a reaction product of the epoxy resin (a ′ ″) represented by the general formula (1-a ′ ″) and the unsaturated group-containing carboxylic acid (b ′ ″). Is a resin obtained by reacting with a polybasic acid and / or its anhydride (c ′ ″).
Examples of the unsaturated group-containing carboxylic acid (b ′ ″) include those listed as the unsaturated group-containing carboxylic acid (b ″) in the alkali-soluble resin (A ″) in the section (c-1-2). Similar compounds can be used, and preferred compounds and the reasons thereof are the same as described above.

The proportion of the unsaturated group-containing carboxylic acid (b ′ ″) added to the epoxy group of the epoxy resin (a ′ ″) is usually 90 to 100 mol%. Since the remaining epoxy group adversely affects storage stability, the unsaturated group-containing carboxylic acid (b ′ ″) is usually 0.8 to 1 with respect to 1 equivalent of the epoxy group of the epoxy resin (a ″ ′). It is preferable to carry out the reaction at a ratio of 0.5 equivalent, particularly 0.9 to 1.1 equivalent.

As the polybasic acid and / or anhydride (c ′ ″), the polybasic acid and / or anhydride (c ″) in the alkali-soluble resin (A ″) in the section (c-1-2) is used. The same compounds as those mentioned above are mentioned, and preferred compounds and the reasons thereof are also the same as described above.
The addition rate of the polybasic acid and / or its anhydride (c ′ ″) is generated when the unsaturated group-containing carboxylic acid (b ′ ″) is added to the epoxy resin (a ′ ″). Of the hydroxyl group, usually 15-100
It is preferable that the acid value of the alkali-soluble resin (A ′ ″) finally obtained is 45 to 160 mgKOH / g. By making this addition rate not more than the above upper limit value, it is possible to prevent a decrease in the remaining film rate during development, and by making it not less than the above lower limit value, good solubility and adhesion to the substrate can be obtained. Can do.

Reaction of unsaturated polycyclic hydrocarbon compound and phenolic compound, glycidylation reaction of hydroxyl group in phenol resin obtained by the reaction, unsaturated group-containing carboxylic acid (b ′ ″), polybasic acid and / or Alternatively, the synthesis reaction of the alkali-soluble resin (A ′ ″), such as an addition reaction of the anhydride (c ′ ″) thereof, can be carried out by a known method, for example, as described in JP-A-5-214048 This can be done with reference to the method.

The weight average molecular weight of the alkali-soluble resin (A ′ ″) is usually 1300 to 4000, preferably 1500 to 3000, and more preferably 1600 to 2500. By controlling the weight average molecular weight within this range, it is possible to have more appropriate development solubility suitable for the color filter manufacturing process described later.
As the binder resin (c-1) in the colored composition of the present invention, among the alkali-soluble resins (A) to (A ′ ″), a melt flow occurs during the balance between the sensitivity, the adhesion and the image forming property and the heat curing. Alkali-soluble resin (A ″) is preferable from the viewpoint of difficulty.

(C-1) The content of the binder resin is usually 5% by weight or more, preferably 10% by weight or more, and usually 80% by weight or less, preferably 70% with respect to the total solid content of the colored composition of the present invention. % By weight or less. (C-1) By making content of binder resin more than the said lower limit, sufficient exposure sensitivity and the solubility with respect to the developing solution of an unexposed part are securable. Moreover, generation | occurrence | production of the wrinkle by the excessive shrinkage | contraction at the time of thermosetting can be suppressed by setting it as q or less than the said upper limit.
(C-2) Monomer
The monomer used in the colored composition of the present invention is not particularly limited as long as it contains a photopolymerizable and polymerizable low molecular compound, and is preferably a polyfunctional monomer having a functional group, A compound capable of addition polymerization (hereinafter referred to as “ethylenic compound”) having at least one ethylenic double bond is more preferred. Moreover, the monomer may have an acid group.

  The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiator described later when the colored composition of the present invention is irradiated with actinic rays. The term “monomer” in the present invention means a concept relative to a so-called polymer substance, and in addition to “monomer” in a narrow sense, “dimer”, “trimer”, “oligomer”. Means a concept that also includes

  Examples of the ethylenic compound having an acid group include an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid and a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an aromatic polyhydroxy compound and an unsaturated compound. Esters obtained by esterification with unsaturated carboxylic acid, unsaturated carboxylic acid and polyvalent carboxylic acid, and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, and polyisocyanate compounds Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting a (meth) acryloyl-containing hydroxy compound.

Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, ilotonic acid, maleic acid and the like.
Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, penta Acrylic esters such as erythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate and the like can be mentioned. In addition, the acrylic acid part of these acrylates is a methacrylic acid ester replaced with a methacrylic acid part, an itaconic acid ester replaced with an itaconic acid part, a crotonic acid ester replaced with a crotonic acid part, or a maleic acid replaced with a maleic acid part Examples include esters.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol and glycerin. And the like.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanate; aromatic diisocyanate such as toluene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3-hydroxy (1 , 1,1-Trimethacryloyloxymethyl) propane and other (meth) acryloyl group-containing hydroxy compounds And the like.

In addition, as examples of the ethylenic compound used in the present invention, acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are also useful.
In the present invention, the monomer is a polyfunctional monomer and may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Therefore, if the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is. The acid group may be introduced by reacting the group with a non-aromatic carboxylic acid anhydride. In this case, specific examples of the non-aromatic carboxylic acid anhydride used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydrous Maleic acid is mentioned.

  In the present invention, the monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group is preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

Of the epoxy acrylate resins described in the epoxy acrylate, those having no carboxyl group can also be used as monomers.
These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.

  A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. By making the acid value of the polyfunctional monomer more than the above lower limit value, it is possible to obtain better solubility in the developer, and by making the acid value not more than the above upper limit value, the production and handling properties are improved and sufficient. Photopolymerizability can be ensured, and the resulting coating film has good curability such as surface smoothness. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

  In the present invention, more preferred polyfunctional monomers having an acid group are mainly dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate which are commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is a mixture as a component. This polyfunctional monomer can also be used in combination with other polyfunctional monomers.

The content ratio of these (c-2) monomers is usually 1 to 80% by weight, preferably 5 to 70% by weight, based on the total solid content of the colored composition of the present invention. 5 to 200% by weight, preferably 10 to 100% by weight, more preferably 15 to 80% by weight. (C-2) The content ratio of the monomer is appropriately adjusted according to the type of the (a) black pigment in the coloring composition and the acid value of the monomer used. (C-2) By making the content rate of a monomer more than the said lower limit, since sufficient exposure sensitivity is ensured, favorable resolution can be obtained. Moreover, by setting it as the upper limit value or less, it is possible to have more appropriate exposure sensitivity, and it is possible to prevent occurrence of chipping and deterioration of patterning characteristics.
(D) Dispersant
The coloring composition of the present invention preferably contains a dispersing agent because it is important for quality stability to finely disperse the (a) black pigment and stabilize the dispersion state.

  Examples of the dispersant include surfactants such as nonions, cations, and anions, and polymer dispersants. Among these, polymer dispersants are preferable, and primary, secondary, or tertiary amino groups, and pyridine are particularly preferable. , Polymer dispersants having basic functional groups such as nitrogen-containing heterocycles such as pyrimidine and pyrazine (in the present invention, polymer dispersants having such basic functional groups are referred to as “basic polymer dispersants”) Is advantageously used.

  Examples of the basic polymer dispersant include urethane-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, acrylic dispersants, and the like, but urethane-based dispersants are preferable, for example, polyisocyanate compounds, Examples thereof include a polymer dispersant obtained by reacting a compound having one or two hydroxyl groups in the same molecule with a compound having active hydrogen and a tertiary amino group in the same molecule.

  As an example of said polyisocyanate compound, each compound as described in international publication pamphlet WO2008 / 153000A1 is mentioned, for example. Among them, a trimer of organic diisocyanate is preferable, and a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate are most preferable. These polyisocyanate compounds may be used alone or in combination of two or more.

  The polyisocyanate trimer can be produced by using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. Examples include a method of obtaining a desired isocyanurate group-containing polyisocyanate by performing partial trimerization, stopping the trimerization by adding a catalyst poison, and then removing unreacted polyisocyanate by solvent extraction and thin-film distillation. .

Examples of compounds having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms. And mixtures of two or more of these. Specific examples thereof include the compounds described in International Publication Pamphlet WO2008 / 153000A1, for example. Among these, the most preferable polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms. Most preferred is polycaprolactone glycol or polycaprolactone initiated with an alcohol having 1 to 25 carbon atoms.

The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.
In a compound having an active hydrogen and a tertiary amino group in the same molecule, the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom may be a functional group such as a hydroxyl group, an amino group or a thiol group. The hydrogen atom in group is mentioned, Among these, the hydrogen atom of an amino group, especially a primary amino group is preferable. The tertiary amino group is not particularly limited. Moreover, as a tertiary amino group, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, More specifically, an imidazole ring or a triazole ring is mentioned.

  Examples of the compound having an active hydrogen and a tertiary amino group in the same molecule include the compounds described in International Publication Pamphlet WO2008 / 153000A1, and among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole and the like can be mentioned.

  A preferable content ratio of the urethane-based dispersant raw material is 10 to 200 parts by weight of a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. 20 to 190 parts by weight, more preferably 30 to 180 parts by weight, and the compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight.

The synthesis reaction of the urethane-based dispersant is performed according to a known method for producing a polyurethane resin, and can be performed, for example, according to the method described in International Publication Pamphlet WO2008 / 153000A1.
In addition, it is preferable to control the introduction amount of the compound having an active hydrogen and a tertiary amino group in the same molecule in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. The amine value is more preferably in the range of 5 to 95 mgKOH / g. Here, the amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is less than the above range, the dispersing ability tends to be lowered, and when it exceeds the above range, developability tends to be lowered.

In the case where an isocyanate group remains in the polymer dispersant produced by the above reaction, it is preferable to modify the remaining isocyanate group with an alcohol or an amino compound because the stability with time of the product becomes high.
The weight average molecular weight of such a polymer dispersant is usually 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. By making the weight average molecular weight more than the above lower limit, the pigment dispersibility and dispersion stability become better, and by making the weight average molecular weight or less the above upper limit, better solubility and dispersibility can be secured, Also, the reaction can be easily controlled.

  As the above-described polymer dispersant, commercially available ones can be used. For example, by trade name, Disperbyk-161, 162, 163, 164, 166, 182 and EFKA manufactured by Big Chemie 4046, Solsperse 38500, 20000, 24000, 27000, 28000, etc. manufactured by Lubrizol.

These dispersing agents may be used individually by 1 type, and may mix and use 2 or more types.
The ratio of these dispersants (d) to the total solid content in the colored composition of the present invention is usually 0.5% by weight or more, preferably 1% by weight or more, more preferably 5% by weight or more, and usually 50%. % By weight or less, preferably 30% by weight or less, more preferably 25% by weight or less. (D) By making the content rate of a dispersing agent more than the said lower limit, dispersion stability becomes more favorable and re-aggregation, thickening, etc. can be suppressed. Moreover, by setting it as the above upper limit or less, the composition can contain a sufficient amount of pigment, and high coloring power and sensitivity can be obtained.
(E) Photopolymerization initiator
(E) The photopolymerization initiator is usually used as a mixture (photopolymerization initiator system) with an accelerator, and a sensitizing dye added as necessary is used in combination.

The photopolymerization initiator system is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.
As the (e) photopolymerization initiator constituting the photopolymerization initiator system component, for example, various compounds described in International Publication Pamphlet WO2008 / 153000A1 and the like can be used.

  The (e) photopolymerization initiator used in the colored composition of the present invention is particularly preferably an oxime ester compound from the viewpoint of good generation efficiency of polymerization active radicals. Among them, the compounds exemplified below are preferably used. be able to.

Examples of the accelerator and the sensitizing dye constituting the photopolymerization initiator component include, for example, various compounds described in International Publication Pamphlet WO2008 / 153000A1, etc., and preferred compounds are the same as the compounds described in the pamphlet. is there.
The content ratio of the photopolymerization initiator system component ((e) the mixture of the photopolymerization initiator and the accelerator) is usually 0.1 to 40% by weight, preferably 0 in the total solid content in the colored composition of the present invention. 0.5 to 30% by weight. If this content is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if it is extremely high, the solubility of the unexposed portion in the developer may be reduced, leading to poor development.

The content of the sensitizing dye in the colored composition of the present invention is usually 0 to 20% by weight, preferably 0 to 15% by weight, more preferably 0 to 10% by weight, based on the total solid content in the colored composition. is there.
(F) Surfactant The colored composition of the present invention includes a surfactant having no side chain having an ethylenically unsaturated group (hereinafter referred to as “(f) surfactant”) as necessary. You may contain.

(F) As the surfactant, one or more of various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used, but they are less likely to adversely affect various properties. Therefore, it is preferable to use a nonionic surfactant.
(F) The addition amount of the surfactant is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, more preferably 0.01 to the total solid content in the colored composition of the present invention. -0.5 wt%, most preferably 0.03-0.3 wt%. (F) When the addition amount of the surfactant is less than the above range, the smoothness and uniformity of the coating film cannot be expressed, and when it is large, the smoothness and uniformity of the coating film cannot be expressed and other characteristics deteriorate. There is a case.
(G) Solvent
The colored composition of the present invention is generally prepared by dissolving or dispersing the above-described solid content in (g) a solvent.

(G) The solvent has a function of adjusting viscosity by dissolving or dispersing (a) a black pigment, (b) a liquid repellent, (c) a binder resin and / or a monomer in the colored composition of the present invention.
(G) It is preferable to select a solvent having a boiling point in the range of 100 to 300 ° C. More preferably, it is a solvent having a boiling point of 120 to 280 ° C.

Examples of such solvents include various solvents described in International Publication Pamphlet WO2008 / 153000A1.
These solvents may be used alone or in combination of two or more.
When the black matrix is formed by photolithography, the solvent (g) having a boiling point in the range of 100 to 200 ° C. (under a pressure of 101.25 [hPa]. Hereinafter, all the boiling points are the same) is selected. More preferably. Particularly preferred are those having a boiling point of 120-170 ° C.

Of the solvents described in the above-mentioned international publication pamphlets, glycol alkyl ether acetates are preferred from the viewpoints of good balance in applicability, surface tension and the like, and relatively high solubility of constituent components in the composition.
In addition, glycol alkyl ether acetates may be used alone or in combination with other solvents. As the solvent used in combination, glycol monoalkyl ethers are particularly preferable. Among these, propylene glycol monomethyl ether is particularly preferable because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment is likely to aggregate, and the storage stability tends to decrease such as the viscosity of the colored composition obtained later increases. The proportion of glycol monoalkyl ethers in them is preferably 5% by weight to 30% by weight, and more preferably 5% by weight to 20% by weight.

  It is also preferable to use a solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”). By using such a high boiling point solvent in combination, the colored composition is difficult to dry, but has an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation or solidification of a color material or the like at the tip of the slit nozzle. Of these various effects, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable among the various solvents described in the above-mentioned international publication pamphlet.

(G) The content of the high boiling point solvent in the solvent is preferably 3% by weight to 50% by weight, more preferably 5% by weight to 40% by weight, and particularly preferably 5% by weight to 30% by weight. By setting the amount of the high boiling point solvent to the above lower limit value or more, for example, (a) it is possible to prevent the occurrence of foreign matter defects due to precipitation and solidification of black pigment etc. at the tip of the slit nozzle, and by setting the amount to the upper limit value or less. In the color filter manufacturing process to be described later, it becomes possible to keep the drying speed of the composition moderate so as not to cause problems such as tact defects in the vacuum drying process and pre-baked pin marks.
The high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is not separately contained. It doesn't matter.

Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.
The content of the solvent (g) in the entire colored composition of the present invention is not particularly limited, but is usually 99% by weight or less, usually 50% by weight or more, preferably 55% by weight or more, more preferably 60% by weight. That's it. (G) By making the ratio of a solvent below the said upper limit, solid content, such as (a) black pigment, (b) lyophobic agent, (c) binder resin and / or a monomer, is necessary and sufficient in a coloring composition. It can be contained in an amount. Moreover, by setting it as more than the said lower limit, thickening can be suppressed and favorable applicability | paintability and the film thickness uniformity of a coating film can be obtained.

In consideration of the above circumstances, the colored composition of the present invention is prepared using (g) a solvent so that the solid content concentration is usually 5 to 50% by weight, preferably 10 to 30% by weight. Is done.
(H) Dispersion aid (a) In order to improve the dispersibility and dispersion stability of the black pigment, (h) a pigment derivative or the like may be added as a dispersion aid. Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolo Derivatives such as pyrrole and dioxazine pigments may be mentioned.

  Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, preferably a sulfonamide group and a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group.

In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions. Specific examples of pigment derivatives include azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, isoindoline pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, Examples thereof include sulfonic acid derivatives of diketopyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments.

(H) The amount of the dispersion aid added is usually 0.1% by weight or more, and usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, based on (a) the black pigment. More preferably, it is 5 weight% or less. By setting the addition amount to be equal to or higher than the above lower limit value, the effect can be effectively exerted, and by setting the addition amount to be equal to or lower than the upper limit value, better pigment dispersibility and dispersion stability can be ensured.
(I) Organic carboxylic acid and / or organic carboxylic acid anhydride
The colored composition of the present invention may further contain (i) an organic carboxylic acid and / or an organic carboxylic acid anhydride in addition to the above components.

Specific examples thereof include, for example, each compound described in JP-A-2008-203841.
Of the organic carboxylic acids, monocarboxylic acids and dicarboxylic acids are preferred, with malonic acid, glutaric acid, and glycolic acid being more preferred, and malonic acid being particularly preferred.
The molecular weight of the organic carboxylic acid is usually 1000 or less, and usually 50 or more. By setting the molecular weight of the organic carboxylic acid to 1000 or less, it is possible to achieve a higher effect of improving soil stains. Moreover, by setting it as 50 or more, the reduction of the addition amount by a sublimation, volatilization, etc. and process contamination can be prevented.

Among the organic carboxylic acid anhydrides, maleic anhydride, succinic anhydride, itaconic anhydride, and citraconic anhydride are preferable, and maleic anhydride is more preferable.
The molecular weight of the organic carboxylic acid anhydride is usually 800 or less, preferably 600 or less, more preferably 500 or less, and usually 50 or more. By setting the molecular weight of the organic carboxylic acid anhydride to 800 or less, it is possible to achieve a higher effect of improving background stains. Further, by setting it to 50 or more, it is possible to prevent a decrease in the amount of addition or process contamination due to sublimation, volatilization, or the like.

One of these organic carboxylic acids and / or organic carboxylic acid anhydrides may be used alone, or two or more thereof may be mixed and used.
The amount of these organic carboxylic acids and / or organic carboxylic anhydrides added is generally 0.01% by weight or more, preferably 0.03% by weight or more, more preferably in the total solid content of the colored composition of the present invention. It is 0.05% by weight or more, usually 10% by weight or less, preferably 5% by weight or less, and more preferably 3% by weight or less. By making this addition amount more than the above lower limit value, a sufficient addition effect can be obtained more reliably, and by making it the above upper limit value or less, better surface smoothness and sensitivity can be secured, Generation | occurrence | production of an undissolved peeling piece can be prevented.
(J) Other solid content
The colored composition of the present invention may further contain a solid content other than the above components as necessary. Examples of such components include thermal polymerization inhibitors, plasticizers, dyes, storage stabilizers, surface protective agents, adhesion improvers, development improvers and the like. Specific examples thereof include, for example, each compound described in JP-A-2008-203841.

The content of these components is preferably 20% by weight or less in total with respect to the total solid content of the colored composition of the present invention.
[Method for Preparing Colored Composition]
The coloring composition for a color filter in the present invention is prepared according to a conventional method. Hereinafter, the present invention will be specifically described with reference to examples, but the method for preparing the color filter coloring composition in the present invention is not limited to this method.

Note that (b) the liquid repellent may be included in any stage in the process of preparing the colored composition, for example, it may be included in a black pigment dispersion described later, or when other components are mixed in the dispersion. You may mix together. Moreover, when not preparing black pigment dispersion liquid but mix | blending and mixing all the components at once or in multiple times, it should just mix | blend in one of the steps.
From the viewpoint of ensuring the dispersion stability of the black pigment dispersion, the colored composition of the present invention is preferably prepared in advance by preparing a black pigment dispersion in advance and mixing other components thereto, as described below. In the case (b), the liquid repellent is preferably mixed with the black pigment dispersion together with other components for the purpose of ensuring the dispersion stability of the black pigment dispersion.
[1] Method for producing black pigment dispersion
(A) A black pigment, usually (g) a solvent, and (d) a dispersant, if necessary, are weighed in predetermined amounts, and in the dispersion treatment step, (a) a black pigment is dispersed to disperse a liquid black pigment. Use liquid. In this dispersion treatment step, a paint conditioner (paint shaker), a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. Since the black pigment is finely divided by this dispersion treatment, the colored composition using the black pigment dispersion prepared in this way has improved coating properties and improved light shielding ability of the product color filter substrate. To do.

  When the dispersion treatment is performed using a sand grinder or a paint shaker, it is preferable to use 0.1 to 8 mm diameter glass beads or zirconia beads. The temperature for the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. The dispersion time varies depending on the composition of the black pigment dispersion (black pigment, solvent, dispersant, etc.), the size of the apparatus, and the like, and therefore needs to be adjusted as appropriate.

  In this case, the standard of dispersion is to control the gloss of the black pigment dispersion so that the 20-degree specular gloss in JIS Z8741 is in the range of 100 to 200. When the gloss of the black pigment dispersion is low, the dispersion treatment is not sufficient and rough black pigment particles often remain, which may be insufficient in terms of developability, adhesion, resolution, and the like. Further, when the dispersion treatment is performed until the gloss value exceeds the above range, a large number of ultrafine particles are generated, and the dispersion stability tends to be impaired.

(A) When the black pigment is subjected to a dispersion treatment, the (c-1) binder resin or (h) a dispersion aid may be appropriately used in combination. (C-1) By containing a binder resin, the dispersion stability at the time of manufacturing a black pigment dispersion liquid can be improved.
In this case, the amount of (c-1) binder resin added is usually 5 to 100% by weight, preferably 10 to 50% by weight, based on (a) black pigment in the black pigment dispersion. By making the addition amount of the binder resin more than the above lower limit value, it can have higher dispersion stability, and by making it the upper limit value or less, a sufficiently high (a) black pigment concentration can be secured and higher. Since light-shielding property is obtained, it is preferable.

The solid content concentration of the black pigment dispersion is usually about 10 to 40% by weight.
Here, “total solid content” refers to all components of the black pigment dispersion other than the solvent.
[2] Method for producing colored composition
The colored composition of the present invention is prepared by adding the other components contained in the colored composition to the black pigment dispersion obtained by the above steps and mixing them to obtain a uniform solution. In addition, the dispersion process with the liquid which mixed all the components mix | blended as a coloring composition simultaneously has a possibility that a highly reactive component may modify | denature because of the heat_generation | fever which arises at the time of dispersion | distribution. In addition, since fine dust is often mixed in the liquid in the manufacturing process, it is desirable to filter the obtained colored composition with a filter or the like.
[3] Production of Color Filter Next, a specific example of the production method of the color filter of the present invention will be described.

The color filter in the present invention is usually produced by sequentially forming pixels of each color of red, green, and blue after providing a black matrix on the transparent substrate using the above-described coloring composition of the present invention. .
The coloring composition of the present invention is particularly used as a coating liquid for forming a black matrix for an ink jet color filter.

[3-1] Transparent substrate (support)
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, and poly (meth). Examples thereof include thermosetting resin sheets such as acrylic resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.

For transparent substrates and black matrix forming substrates, to improve surface properties such as adhesion, corona discharge treatment, UV ozone treatment, silane coupling agents, and thin film formation treatment of various resins such as urethane resins, as necessary Etc. may be performed.
The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

[3-2] Formation of black matrix
As described above, the black matrix included in the color filter of the present invention includes at least (a) a black pigment, (b) a side chain having an ethylenically unsaturated group, and a fluorinated alkyl group or a part thereof having an oxygen atom. Formed by using a color repellent composed of a polymer having a side chain having a group containing, (c) a binder resin and / or a colored composition for a color filter containing a monomer.
An application step of applying the coloring composition for a color filter on a transparent substrate;
A mask exposure step of exposing the coating film obtained by the coating step through a photomask;
In the cured film obtained through the exposure step, the development step of removing the unexposed portion, and the baking step of heating the exposed portion of the cured film obtained through the development step,
It has a post-exposure step after the development step and before the baking step.

Hereinafter, each process will be described in detail.
[3-2-1] Formation of coating film
The coloring composition can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Among them, the die coating method is currently mainstream because it not only greatly reduces the amount of coating solution used but also has excellent film thickness uniformity over a large transparent substrate.

[3-2-2] Drying of coating film
The coating film formed by applying the colored composition to the transparent substrate is first made into a non-flowable coating film by volatilizing the solvent by a vacuum drying method in which drying is performed in a vacuum chamber, and then hot plate, IR oven, convection A general method is to improve the adhesion of the coating film to the transparent substrate by a heat drying method using an oven. The conditions for the heat drying can be appropriately selected according to the kind of the solvent component in the colored composition, the performance of the dryer to be used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 150 ° C., preferably 30 to 60 to 120 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of seconds to 3 minutes. The higher the drying temperature is, the better the adhesion of the coating film to the transparent substrate is. However, if the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure.

[3-2-3] Exposure process
The exposure is performed by overlaying a negative pattern quartz mask on the dried coating film of the colored composition and irradiating an ultraviolet or visible light source through the mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the coating film in order to prevent a decrease in sensitivity of the coating film due to oxygen.

  The light source used for the exposure is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, etc. And a laser light source such as an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium cadmium laser, and a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

[3-2-4] Development process
Development can be performed after the exposure using a solvent or an aqueous solution containing a surfactant and an alkaline compound. This aqueous solution may further contain a solvent, a buffering agent, a complexing agent, a dye or a black pigment.
Examples of each component contained in these developers include the compounds described in International Publication Pamphlet WO2008 / 153000A1.

There are no particular limitations on the conditions for the development treatment, and usually the development temperature is in the range of 10 to 50 ° C., especially 15 to 45 ° C., particularly preferably 20 to 40 ° C. The development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.
[3-2-5] Post-exposure step The color filter manufacturing method of the present invention is characterized by having a post-exposure step between the development step and the thermosetting (post-bake) step. By having this post-exposure step, it is possible to prevent the black matrix from fluidizing during post-baking and causing the liquid repellent to segregate not only on the upper surface but also on the side surface to give liquid repellency.

  The light source used for the post-exposure is not particularly limited, but a metal halide lamp is preferable from the viewpoint of high luminance, power saving, and long life. In the post-exposure process, exposure is performed from at least one of the image forming surface (that is, the same surface as the mask exposure step) or the opposite surface, but more precise black matrix pattern lyophobic and lyophilic control is possible. It is more preferable to perform exposure on both surfaces in view of the possibility.

Exposure energy in the post exposure step is usually 50 to 5000 mJ / cm ² or so, preferably 100~1000mJ / cm ^2, more preferably about 300~800mJ / cm ² approximately.
In addition, the exposure energy of the post-exposure process in this invention can be measured using "Industrial UV Checker UV-350N" made from GS-YUASA as a measuring apparatus, for example.

[3-2-6] Thermosetting treatment (post bake)
The post-exposure color filter substrate is subjected to a thermosetting process (post-bake).
The post-baking is performed using an oven or the like, and the temperature is selected in the range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes.
[3-2-7] Film thickness of black matrix
The black matrix formed in the present invention is suitable for a color filter formed by an ink jet method. When applied to an ink jet color filter, the thickness of the black matrix is preferably 1.4 μm or more, more preferably 1.6 μm or more, and particularly preferably 1.8 μm or more. When the film thickness is less than 1.4 μm, the film thickness obtained when sprayed into a colored resin composition (ink) pixel bank (substantially rectangular recess surrounded by a black matrix) for pixel formation and dried. May cause a problem of non-uniformity. From the viewpoint of obtaining a uniform film thickness, the film thickness is usually 3 μm or less.

In order to obtain such a film thickness, the solid content concentration in the composition and the above-described post so that the film thickness after drying becomes the target film thickness of the black matrix by the various coating methods described above. The film thickness at the time of application may be set in consideration of the heat shrinkage rate in the baking process.
[3-3] Method of forming pixel
Next, a method for producing a pixel for a color filter by an inkjet method using a resin composition (ink) containing each color pigment such as red, blue, and green will be described.

In the ink jet method, first, ink for forming pixels is directly applied to a black matrix (partition) provided on a substrate by an ink jet apparatus to produce a color filter. Since ink droplets can be drawn at a desired position, high productivity and low cost of the color filter can be achieved.
The black matrix of the color filter by the ink jet method not only functions as a light blocking function that is conventionally required, but also functions as a partition to prevent the RGB ink driven into the pixel bank from being mixed, so the conventional photolithography method Compared with the case of the color filter according to the above, there is a feature that the film thickness is thick as described above. Moreover, since it is calculated | required to prevent color mixing of RGB ink, the black matrix formed as mentioned above using the coloring composition of this invention is preferable.

  Heat drying such as a hot plate, IR oven, or convection oven can be used to dry the pixel forming ink coating film. Preferred drying conditions are 40 to 150 ° C., and drying time is in the range of 10 seconds to 60 minutes. is there. Further, reduced pressure (vacuum) drying can be used, and preferable drying conditions are 0.1 to 1 Torr, and drying time is in the range of 10 seconds to 60 minutes. Furthermore, both can be used together and can also be performed sequentially or simultaneously.

  When the pixel forming ink is cured by photocuring, the light source used for exposure is, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, etc. Examples of the light source include a lamp light source, an argon ion laser, a YAG laser, an excimer laser, and a nitrogen laser. In the case where only the wavelength of specific irradiation light is used, an optical filter can also be used.

[3-4] Formation of transparent electrode
The color filter according to the present invention is used as a part of components such as a color display and a liquid crystal display device by forming a transparent electrode such as ITO on the pixel and the black matrix as it is. In order to enhance durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary.

Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.
When the top coat layer is provided, there is a possibility that the coatability of the top coat is lowered due to the liquid repellency of the black matrix surface. In that case, the liquid surface repellency of the black matrix surface is lost by washing the image with UV ozone or atmospheric pressure O ₂ plasma as needed immediately before the top coat layer coating step, and the top coat layer. The coating property can be improved.

Cleaning methods include light cleaning such as UV ozone, dry cleaning such as ashing of atmospheric pressure O ₂ plasma, and wet cleaning with pure water or an alkaline detergent, but a drying step is not required. Therefore, dry cleaning is desirable.
[4] Liquid crystal display device (panel)
Next, a specific example of the manufacturing method of the liquid crystal display device (panel) of the present invention will be described.

The liquid crystal display device of the present invention comprises the color filter of the present invention obtained by the manufacturing method described above. Usually, after forming an alignment film on the color filter of the present invention, a spacer is dispersed on the alignment film, and then a liquid crystal cell is formed by bonding to a counter substrate, and a liquid crystal is injected into the formed liquid crystal cell. It is made by connecting to electrodes.
As the alignment film, a resin film such as polyimide is suitable. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is usually several tens of nm. The alignment film is cured by thermal baking, and then surface-treated by irradiation with ultraviolet rays or a rubbing cloth to process the surface state so that the tilt of the liquid crystal can be adjusted.

A spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography, and this can be used instead of the spacer.
As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by ultraviolet (UV) irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of reduced pressure in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The warming hold during decompression is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected is completed by sealing and sealing the liquid crystal injection port with a UV curable resin.

The type of liquid crystal is not particularly limited, and conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds are used, and any of lyotropic liquid crystals, thermotropic liquid crystals, and the like may be used. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.
[Organic EL display]
The organic EL display of the present invention comprises the color filter of the present invention obtained by the manufacturing method described above.

When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. 1, first, a pattern (that is, the pixel 20 and adjacent) formed on the transparent support substrate 10 by the colored resin composition. A color filter in which a resin black matrix (not shown) provided between the pixels 20 is formed is manufactured, and the organic light-emitting body 500 is formed on the color filter via the organic protective layer 30 and the inorganic oxide film 40. By laminating, the organic EL element 100 can be manufactured. The resin black matrix is prepared using the colored composition of the present invention. As a method for laminating the organic light-emitting body 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. A method described in, for example, “Organic EL display” (Ohm, published on August 20, 2004, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 thus manufactured, etc. Thus, an organic EL display can be produced.

  The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to a following example, unless the summary is exceeded.
[Synthesis example]
<Synthesis Example 1: Preparation of ink (pigment dispersion)>
Carbon black for color (“MA-8” manufactured by Mitsubishi Chemical Co., Ltd., average particle size 24 μm, DBP oil absorption 58 ml / 100 g), propylene glycol monomethyl ether acetate (PGMEA) and urethane polymer dispersant Disperbyk-182 "(manufactured by Big Chemie) was added so that the dispersant was in a proportion of 10 parts by weight as a solid content and the solid content concentration was 30% by weight. Their total weight was 181 g.

This was thoroughly stirred with a stirrer and premixed. Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As the beads, zirconia beads having a diameter of 0.5 mm were used, and the same weight as the dispersion was added. After completion of dispersion (20-degree specular gloss in JIS Z8741 was 170), the ink was prepared by separating the beads and the dispersion with a filter.
<Synthesis Example 2: Synthesis of alkali-soluble resin>

50 parts by weight of an epoxy compound having the above structure (epoxy equivalent 264), 13.65 parts by weight of acrylic acid, 60.5 parts by weight of methoxybutyl acetate, 0.936 parts by weight of triphenylphosphine, and 0.032 parts by weight of paramethoxyphenol The mixture was placed in a flask equipped with a thermometer, a stirrer, and a condenser, and reacted at 90 ° C. with stirring until the acid value reached 5 mgKOH / g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.

25 parts by weight of the above epoxy acrylate solution, 0.76 parts by weight of trimethylolpropane (TMP), 3.3 parts by weight of biphenyltetracarboxylic dianhydride (BPDA), 3.5 parts by weight of tetrahydrophthalic anhydride (THPA) Was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution becomes transparent, it is diluted with methoxybutyl acetate, prepared to have a solid content of 50% by weight, an acid value of 131 mg KOH / g, and an alkali-soluble resin having a polystyrene equivalent weight average molecular weight (Mw) of 2600 measured by GPC Got.
<Synthesis Example 3: Synthesis of Photopolymerization Initiator>
According to Synthesis Example 7 described in JP-A-2008-179611, a photopolymerization initiator represented by the following structural formula was synthesized and used.

[Examples 1 to 6 and Comparative Examples 1 to 4]
(1) Preparation of BM resist (photosensitive coloring composition)
Using the ink prepared in Synthesis Example 1, each component was added so as to have the following blending ratio (however, components other than the solvent were converted to solid content), and stirred and dissolved with a stirrer to prepare a BM resist ( A colored composition for a color filter according to the present invention for forming a black matrix was prepared.
<Combination ratio>
The blending amounts of the colored composition coating liquids used in Examples 1 to 6 and Comparative Examples 1 to 4 are as shown in Table 1 below.

In Table 1 above, details regarding “Megafuck RS-101”, “Megafuck RS-102”, and “Megafuck F-475” are as follows. The weight average molecular weight is a standard polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography), and the fluorine content and double bond equivalent were measured by the methods described below.
“Megafac RS-101”: a polymer having the following repeating units, weight average molecular weight: 14000, fluorine content: 19% by weight, double bond equivalent: 520 g / mol, s / t = 3-4 .

“Megafac RS-102”: a polymer having the following repeating units, weight average molecular weight: 8830, fluorine content: 23 wt%, double bond equivalent: 350 g / mol, s / t = 3-4 .

“Megafac F-475”: a fluorosurfactant having no ethylenically unsaturated groups.
<Fluorine content>
Measured and calculated by oxygen combustion tube absorption-IC method. Specifically, the oxygen gas first flowed 900
The sample ((b) lyophobic agent) is burned in an electric tubular furnace at ˜1000 ° C., and the generated combustion gas is bubbled into the absorbent of alkaline water to capture it as fluorine ions. Ions were quantified to determine the fluorine content in the liquid repellent (solid content). <Double bond equivalent>
It calculated | required by the H-NMR method using the internal standard. Specifically, a sample ((b) liquid repellent) and an internal standard substance (dimethyl terephthalate) were weighed and mixed, deuterated chloroform was added and dissolved, and H-NMR measurement was performed with a 500 MHz NMR apparatus. Note that the measurement was performed at an accumulated repetition time of 10 seconds or more. The double bond equivalent was determined from the internal standard substance of the obtained H-NMR spectrum and the signal area of the ethylenically unsaturated group.
(2) Adjustment of Inkjet Green (G) Ink for CF According to [Example 1] of JP 2008-199717 A, an inkjet green (G) ink was adjusted.
(3) Evaluation of resist
The BM resist prepared in (1) was applied to a glass substrate (“AN100” manufactured by AGC) using a spin coater, and dried on a hot plate at 80 ° C. for 3 minutes. It was 2.4 micrometers when the film thickness of the resist after drying was measured with the stylus type film thickness meter ("α-step" by Tencor). Next, this sample was image-exposed with a high-pressure mercury lamp through a photomask. Then, a resist pattern was obtained by spray development using a potassium hydroxide aqueous solution having a concentration of 0.025 wt% at a temperature of 23 ° C. and a pressure of 0.1 MPa. Thereafter, post-exposure was performed with a metal halide lamp from both sides of the sample (glass substrate on which a resist pattern was formed) as necessary. The obtained resist pattern was dried in an oven at a high temperature (230 ° C., 30 minutes) to form a black matrix having a thickness of 2.2 μm. In addition, the measurement of the exposure energy in a post-exposure process was implemented using "Industrial UV Checker UV-350N" made from GS-YUSAS as a measuring apparatus.

The formed black matrix was measured and evaluated for contact angle, white spot and breakage according to the following criteria, and the results are shown in Table-2 and Table-3.
1. Contact angle The contact angle of diethylene glycol monobutyl ether acetate (DEGBEA) on a black matrix was measured with a contact angle meter ("DropMaster DM500" manufactured by Kyowa Interface Science Co., Ltd.). Higher values indicate higher liquid repellency on the black matrix.
2. White color Green (G) ink adjusted in (2) for 225 pixels (opening size: 150 μm × 420 μm, partition wall width: 30 μm, vertical × horizontal = 15 pixels × 15 pixels) of the formed black matrix In the inkjet printing apparatus equipped with a 10 pL, 100 dpi head, 60 picoliter droplets were printed in each pixel by 60 droplets, and the pixels after printing were observed at 5 times using an optical microscope.

All pixels are buried, and the printed ink has good flatness after drying: ◎
All pixels are buried: ○
White spots are seen in several (1 to 10) pixels:
White spots are seen in 10 to 30 pixels: Δ
White spots are seen in 30 to 225 (all) pixels: ×
3. Breakdown An inkjet printer equipped with a 10pL, 100 dpi head using the green (G) ink adjusted in (2) for 225 pixels (vertical x horizontal = 15 pixels x 15 pixels) of the black matrix formed A droplet of 10 picoliter was printed in each pixel by 180 drops, and the pixel after printing was observed at 5 times using an optical microscope.

No ink color mixing between adjacent pixels is seen: ◎
Ink color mixing is observed in several (1-5) places:
Ink color mixture is seen in some (5 to 50) locations:
Ink mixing is seen in almost (50 ~) places: ×

本発明によると、特定の重合型撥液剤を含むカラーフィルター用着色組成物を用い、かつ後露光工程を組み合わせることにより、白抜け、決壊の特性を高精度にコントロールし、高い撥液性を有するブラックマトリックスを容易に形成可能となることが分かる。

According to the present invention, by using a coloring composition for a color filter containing a specific polymerization type liquid repellent and combining a post-exposure process, the characteristics of white spots and breakage are controlled with high accuracy and high liquid repellency is achieved. It can be seen that the black matrix can be easily formed.

10 Transparent support substrate
20 pixels
30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode
51 Hole injection layer 52 Hole transport layer 53 Light emitting layer
54 Electron injection layer 55 Cathode
100 Organic EL device
500 Organic light emitter

Claims (17)

(A) a black pigment, (b) a liquid repellent comprising a polymer having a side chain having an ethylenically unsaturated group and a side chain having a fluorinated alkyl group or a group containing an oxygen atom in part thereof, (c ) A method for producing a color filter comprising a black matrix formed using a coloring composition for a color filter containing a binder resin and / or a monomer, wherein the black matrix forming step comprises:
An application step of applying the coloring composition for a color filter on a transparent substrate;
A mask exposure step of exposing the coating film obtained by the coating step through a photomask;
In the cured film obtained through the exposure step, the development step of removing the unexposed portion, and the baking step of heating the exposed portion of the cured film obtained through the development step,
A method for producing a color filter, comprising a post-exposure step after the development step and before the baking step.   The method for producing a color filter according to claim 1, wherein the post-exposure step is performed on at least one of the same surface as the mask exposure step or the opposite surface with respect to the transparent substrate.   The manufacturing method of the color filter of Claim 2 with which the said post-exposure process is performed with respect to both surfaces of the same surface as the time of a mask exposure process, and a reverse surface with respect to a transparent substrate.   After the black matrix forming step, an ink jet coating step of supplying a pixel forming composition by an ink jet method to a region sandwiched by the black matrix or a region surrounded by the black matrix, and the pixel forming composition The manufacturing method of the color filter as described in any one of Claim 1 thru | or 3 which further has the hardening process which hardens | cures.   (B) The manufacturing method of the color filter as described in any one of Claim 1 thru | or 4 whose ethylenically unsaturated group in a liquid repellent is a part of (meth) acryloyl group.   (B) In the lyophobic agent, the number of carbons substituted with fluorine atoms contained in a fluorinated alkyl group or a group containing an oxygen atom in a part thereof is 1-20. The manufacturing method of the color filter as described in a term.   (B) The method for producing a color filter according to any one of claims 1 to 6, wherein the fluorinated alkyl group in the liquid repellent is a part of a fluoroalkoxy group or a fluoroalkylthio group.   (B) The manufacturing method of the color filter as described in any one of Claim 1 thru | or 7 whose fluorine content rate in a liquid repellent is 10 to 60 weight%.   (B) The manufacturing method of the color filter as described in any one of Claim 1 thru | or 8 whose double bond equivalent of a liquid repellent is 200-560 g / mol.   (B) The manufacturing method of the color filter as described in any one of Claim 1 thru | or 9 whose main chain of a liquid repellent is a novolak-type resin. (B) The manufacturing method of the color filter as described in any one of Claim 1 thru | or 10 whose liquid repellent is a polymer which has a repeating unit represented by following General formula (1).

(In the above general formula (I), R ⁵¹ is

R ⁵² represents a (meth) acryloyloxy group, X ¹ represents an oxygen atom or a hydrogen atom, and R ⁵³ represents

R ⁵⁴ is

(However, u represents an integer of 1 to 3, and v = 4 to 12, and R ⁵⁵ represents a hydrogen atom or a fluorine atom.) In addition, s and t represent the number of each repeating unit, and are s / t = 0.1-10. )   (B) Manufacture of the color filter as described in any one of Claims 1 thru | or 11 whose molecular weight of a liquid repellent is 7000-16000 in the weight average molecular weight measured by the gel permeation chromatography of standard polystyrene conversion. Method.   The method for producing a color filter according to any one of claims 1 to 12, wherein the coloring composition for a color filter further contains (d) a dispersant. The method for producing a color filter according to any one of claims 1 to 13, wherein the colored composition for a color filter further contains (e) a photopolymerization initiator.   The color filter obtained by the method as described in any one of Claims 1 thru | or 14.   A liquid crystal display device comprising the color filter according to claim 15.   An organic EL display comprising the color filter according to claim 15.

Images