JP6891553B2 - Colored resin composition, color filter, and image display device - Google Patents

Description

The present invention relates to a colored resin composition, a color filter, and an image display device. More specifically, a colored resin composition containing a specific zinc halide phthalocyanine pigment and a specific high boiling point solvent, a color filter having pixels created by using the colored resin composition, and an image display device having this color filter. Regarding.

Conventionally, a pigment dispersion method, a dyeing method, an electrodeposition method, and a printing method are known as methods for manufacturing a color filter used in a liquid crystal display device or the like. Among them, the pigment dispersion method having excellent characteristics on average is most widely adopted from the viewpoints of spectral characteristics, durability, pattern shape, accuracy and the like.

In recent years, color filters are required to have higher transmission, higher brightness, higher contrast, and higher color gamut. Pigments are generally used as the color material that determines the color of the color filter from the viewpoint of heat resistance, light resistance, etc., but among them, the unique transmission / absorption spectrum matches the phosphor spectrum of the backlight in the visible light wavelength region. Those are preferably used. For example, a combination of a halogenated copper phthalocyanine green pigment and various yellow pigments has long been used for forming green pixels.

Regarding the increase in brightness of green pixels, for example, a new halogenated zinc phthalocyanine green pigment having a specific hue as described in Patent Documents 1 to 3 has been proposed, and the brightness is increased as compared with the conventional halogenated copper phthalocyanine green pigment. Has been realized. Further, Patent Documents 1 to 3 describe an example in which a zinc halide phthalocyanine pigment is combined with a photopolymerization initiator such as biimidazole or α-aminoalkylphenone.
Further, in recent years, as described in Patent Document 4, as a halogenated zinc phthalocyanine green pigment, C.I. I. It has been found that in a coloring composition containing Pigment Green 58 and containing propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate and the like as a solvent, agglomerated foreign matter and surface roughness on the coated substrate can be improved. It has been issued.
Further, as described in Patent Document 5, by using a halogenated zinc phthalocyanine green pigment and a photopolymerization initiator composed of a specific oxime ester compound in combination, a colored resin composition is produced during production or during storage. It has been found that the generation of foreign matter can be suppressed, and the generation of precipitates when in contact with N-methylpyrrolidone can be suppressed. Further, Patent Documents 6 to 11 also describe an example in which a halogenated zinc phthalocyanine green pigment and a photopolymerization initiator composed of an oxime ester compound are combined.

Japanese Patent Application Laid-Open No. 2004-070342 Japanese Patent Application Laid-Open No. 2004-070343 Japanese Patent Application Laid-Open No. 2009-52010 Japanese Patent Application Laid-Open No. 2011-028219 Japanese Patent Application Laid-Open No. 2009-271502 Japanese Patent Application Laid-Open No. 2010-84119 Japanese Patent Application Laid-Open No. 2010-97172 Japanese Patent Application Laid-Open No. 2011-99974 Japanese Patent Application Laid-Open No. 2011-145668 Japanese Patent Application Laid-Open No. 2012-53278 Japanese Patent Application Laid-Open No. 2012-172003

C.I., a halogenated zinc phthalocyanine pigment described in Patent Documents 1 to 11 by the present inventor. I. When a colored resin composition containing Pigment Green 58 (hereinafter abbreviated as "G58") was examined, the coloring power was low, and the coating film thickness had to be increased in order to achieve a certain chromaticity. Was found.
Therefore, as a result of diligent studies to obtain a colored resin composition having high coloring power and capable of reducing the coating film thickness in order to achieve a certain chromaticity, a specific halogenated zinc phthalocyanine pigment is used. It was found to be achievable in. On the other hand, as a result of repeated studies on the colored resin composition containing the pigment, the dry film formed by using the composition has low solubility in a solvent, and therefore, when the composition is applied by the die coating method, it is dispensed. It has been found that there is a new problem that the foreign matter that dries and adheres to the tip of the nozzle adheres to the surface of the coating film as a foreign matter, which did not exist in the case of G58.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is a colored resin composition having high coloring power, high solubility of a dry film in a solvent, and capable of suppressing the generation of adhering foreign substances, this colored resin. It is an object of the present invention to provide a color filter having pixels formed by using the composition, an image display device having the color filter, and a pigment dispersion liquid used for the colored resin composition.

As a result of diligent studies to solve the above problems, the present inventor has found that the above problems can be solved by using a specific halogenated zinc phthalocyanine green pigment and a specific high boiling point solvent, and has completed the present invention. It was. That is, the gist of the present invention is as follows.

[1] A colored resin composition containing (A) a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator.
The pigment (A) contains a halogenated zinc phthalocyanine pigment, and the average number of hydrogen atoms contained in one molecule of the halogenated zinc phthalocyanine pigment is 3 or more, and
A colored resin composition in which the solvent (C) contains a high boiling point solvent having a boiling point of 150 ° C. or higher at 1013.25 hPa.
[2] The colored resin composition according to [1], wherein the solvent (C) further contains a low boiling point solvent having a boiling point of less than 150 ° C. at 1013.25 hPa.
[3] The colored resin composition according to [1] or [2], wherein the content ratio of the solvent (C) to the colored resin composition is 50% by mass or more.
[4] The colored resin composition according to any one of [1] to [3], wherein the content ratio of the high boiling point solvent to the solvent (C) is 0.5% by mass or more.
[5] The colored resin composition according to any one of [1] to [4], wherein the vapor pressure of the high boiling point solvent at 20 ° C. is 400 Pa or less.
[6] The colored resin composition according to any one of [1] to [5], wherein the dispersant (B) contains a block copolymer having a functional group containing a nitrogen atom.

[7] The colored resin composition according to any one of [1] to [6], wherein the (E) photopolymerization initiator contains an oxime ester compound.
[8] A color filter having pixels created by using the colored resin composition according to any one of [1] to [7].
[9] An image display device having the color filter according to [8].
[10] A pigment dispersion liquid containing (A) a pigment, (B) a dispersant, and (C) a solvent.
The pigment (A) contains a halogenated zinc phthalocyanine pigment, and the average number of hydrogen atoms contained in one molecule of the halogenated zinc phthalocyanine pigment is 3 or more, and
A pigment dispersion in which the solvent (C) contains a high boiling point solvent having a boiling point of 150 ° C. or higher at 1013.25 hPa.
[11] The pigment dispersion liquid according to [10], wherein the solvent (C) further contains a low boiling point solvent having a boiling point of less than 150 ° C. at 1013.25 hPa.
[12] The pigment dispersion liquid according to [10] or [11], wherein the content ratio of the solvent (C) to the pigment dispersion liquid is 50% by mass or more.
[13] The pigment dispersion liquid according to any one of claims [10] to [12], wherein the content ratio of the high boiling point solvent to the solvent (C) is 1% by mass or more.
[14] The pigment dispersion liquid according to any one of [10] to [13], wherein the vapor pressure of the high boiling point solvent at 20 ° C. is 400 Pa or less.
[15] The pigment dispersion liquid according to any one of [10] to [14], wherein the dispersant (B) contains a block copolymer having a functional group containing a nitrogen atom.

According to the present invention, a colored resin composition having high coloring power, high solubility of a dry film in a solvent, and capable of suppressing the generation of adhered foreign substances, and a color filter having pixels formed by using this colored resin composition. , An image display device having this color filter, and a pigment dispersion liquid used for the colored resin composition can be provided.

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL device having the color filter of the present invention. FIG. 2 is a mass spectrum of the green pigment A. FIG. 3 is a mass spectrum of the green pigment B. FIG. 4 is a measurement profile of the film surface evaluation of Example 8. FIG. 5 is a measurement profile of the film surface evaluation of Comparative Example 2. FIG. 6 is a measurement profile of the film surface evaluation of Comparative Example 4. FIG. 7 is a measurement profile of the film surface evaluation of Comparative Example 3.

Hereinafter, the constituent requirements and the like of the present invention will be described in detail, but these are examples of embodiments of the present invention and are not limited to these contents.
In addition, "(meth) acrylic", "(meth) acrylate" and the like shall mean "acrylic and / or methacrylic", "acrylate and / or methacrylate" and the like, for example, "(meth) acrylic acid" is "(meth) acrylic acid". It shall mean "acrylic acid and / or methacrylic acid". Further, the “total solid content” shall mean all the components other than the solvent component described later, which are contained in the pigment dispersion liquid or the colored resin composition.

In the present invention, the "weight average molecular weight" refers to the polystyrene-equivalent weight average molecular weight (Mw) obtained by GPC (gel permeation chromatography).
Further, in the present invention, the "amine value" represents an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the equivalent mass of KOH. ..
In addition, in this specification, all percentages and parts expressed by mass are the same as percentages and parts expressed by weight.

[1] Components of Colored Resin Composition and Pigment Dispersion Solution Each component of the coloring resin composition and pigment dispersion of the present invention will be described below. The colored resin composition according to the present invention contains (A) pigment, (B) dispersant, (C) solvent, (D) binder resin, and (E) photopolymerization initiator as essential components, and further, if necessary, Additives and the like other than the above components may be blended. Further, the pigment dispersion liquid according to the present invention contains (A) pigment, (B) dispersant, and (C) solvent as essential components, and further contains additives other than the above components, if necessary. You may.

In the colored resin composition according to the first aspect of the present invention, the pigment (A) contains a halogenated zinc phthalocyanine pigment, and the average number of hydrogen atoms contained in one molecule of the halogenated zinc phthalocyanine pigment is 3 or more. Yes, and the solvent (C) contains a high boiling point solvent having a boiling point of 150 ° C. or higher at 1013.25 hPa. Further, in the pigment dispersion liquid according to the second aspect, the pigment (A) contains a halogenated zinc phthalocyanine pigment, and the average number of hydrogen atoms contained in one molecule of the halogenated zinc phthalocyanine pigment is 3 or more. Moreover, the solvent (C) contains a high boiling point solvent having a boiling point of 150 ° C. or higher at 1013.25 hPa.

On the other hand, in the colored resin composition according to the third aspect of the present invention, the pigment (A) contains a halogenated zinc phthalocyanine pigment, and the average number of hydrogen atoms contained in one molecule of the halogenated zinc phthalocyanine pigment is 3. The above, and the (E) photopolymerization initiator contains an oxime ester-based compound.
Hereinafter, each component will be described. Hereinafter, unless otherwise specified, the first to third aspects will be described together.

[1-1] (A) Pigment The (A) pigment used in the colored resin composition and pigment dispersion of the present invention is a zinc halide phthalocyanine pigment (hereinafter, may be referred to as "green pigment a"). including. The average number of hydrogen atoms contained in one molecule of the halogenated zinc phthalocyanine pigment is 3 or more.
As described above, it is considered that the inclusion of the green pigment a as the (A) pigment makes it possible to achieve both high coloring and high brightness. The detailed mechanism is unknown, but the half-value width of the peak is narrow due to the change in the transmission spectrum due to the large amount of hydrogen atoms, and the transmitted light of red and blue is effectively blocked, resulting in high coloring and high brightness. Is presumed to have been realized.

Ordinary zinc phthalocyanine has 16 hydrogen atoms in one molecule, and a halogenated zinc phthalocyanine pigment used in the present invention is obtained by substituting a part of these hydrogen atoms with a halogen atom. In particular, from the viewpoint of high coloring and high brightness, a chlorinated brominated zinc phthalocyanine pigment is preferable.

The method for specifying the average number of hydrogen atoms in one molecule of the pigment is not particularly limited, but a method for calculating using the average number of halogen atoms measured by the fluorescent X-ray fundamental parameter method (FP method) or a laser desorption / ionization method (Laser). Measurement / Ionization, LDI) -Measurement by mass spectrometry (MS) and the like can be mentioned, but the FP method is preferable from the viewpoint of simplicity and accuracy.

In the method of calculation using the FP method, first, the average number of halogen atoms is measured by the FP method. Since the halogen atom and the hydrogen atom occupy 16 sites in the halogenated zinc phthalocyanine, the average number of hydrogen atoms can be obtained by calculating the remaining sites not occupied by the halogen atom. It is preferable to perform the measurement and calculate by adopting the apparatus and conditions used in the examples. Specifically, the average number of halogen atoms per zinc atom is obtained from the mass ratio of zinc atoms and halogen atoms measured by the FP method, and the average number of hydrogen atoms is obtained by subtracting the average number of halogen atoms from 16. ..

On the other hand, in the method of measuring by the LDI-MS method, the strength with respect to the molecular weight (m / z value) is measured by the LDI-MS method. Usually, the green pigment a is a mixture of molecules having different numbers of hydrogen atoms, chlorine atoms and bromine atoms, and the strength of each molecule obtained by measuring the mixture by the above method is used. Calculate the number of hydrogen atoms, chlorine atoms and bromine atoms contained in each molecule, and calculate the average value of the number of hydrogen atoms, chlorine atoms and bromine atoms contained in one molecule by averaging them. Can be done. It is preferable to perform the measurement and calculate by adopting the apparatus and conditions used in the examples.
In particular, the molecular weight of the major peaks of the mass spectrum, with the values of x and y in a chlorinated brominated zinc phthalocyanine molecule corresponding to each peak _{(H 16-x-y ZnC} 32 N 8 Br x Cl y) Next, the average number of atoms of each atom can be obtained by calculating the average value of a plurality of peaks (molecules) having a peak intensity of a certain value or more.

The green pigment a usually has an average number of hydrogen atoms contained in one molecule of 2 or more, preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and preferably 16 or less, more preferably 14. Below, it is more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. When it is set to the lower limit value or more, the coloring tends to be high. Further, the stability of the dispersion liquid tends to be improved by setting the value to the upper limit or less.

The average number of chlorine atoms contained in one molecule of the green pigment a is preferably 0.5 or more, more preferably 1 or more, further preferably 1.5 or more, and preferably 14 or less, more preferably. It is 13 or less, more preferably 12 or less. When it is set to the lower limit value or more, the coloring tends to be high. Further, when the value is not more than the upper limit value, the brightness tends to be high.

The average number of bromine atoms contained in one molecule of the green pigment a is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and preferably 14 or less, more preferably 13 or less, further. It is preferably 12 or less. When the value is equal to or higher than the lower limit, the brightness tends to be high. Further, when the value is not more than the upper limit value, the coloring tends to be high.

Further, in the green pigment a, the ratio of the average number of chlorine atoms contained in one molecule to the average number of bromine atoms contained in one molecule is preferably 0.1 or more, preferably 0.15 or more. Is more preferably 0.2 or more, more preferably 7 or less, more preferably 3 or less, further preferably 1 or less, and 0.5 or less. Is particularly preferable. When it is at least the lower limit value, it tends to be highly colored, and when it is at least the upper limit value, it tends to be high brightness.

On the other hand, the green pigment a has an average number of hydrogen atoms contained in one molecule of usually 2 or more, preferably 3 or more, more preferably 3.5 or more, still more preferably 4.0, calculated by the FP method. Above, more preferably 4.2 or more, particularly preferably 4.5 or more, still preferably 12 or less, more preferably 10 or less, still more preferably 8 or less, still more preferably 6 or less, particularly preferably 5. It is 5 or less. When it is set to the lower limit value or more, the coloring tends to be high. Further, the stability of the dispersion liquid tends to be improved by setting the value to the upper limit or less.

The average number of chlorine atoms contained in one molecule of the green pigment a, as measured by the FP method, is preferably 0.5 or more, more preferably 1 or more, still more preferably 1.5 or more, and preferably 1.5 or more. It is 14 or less, more preferably 12 or less, still more preferably 10 or less, still more preferably 8 or less, particularly preferably 6 or less, and most preferably 4 or less. When it is set to the lower limit value or more, the coloring tends to be high. Further, when the value is not more than the upper limit value, the brightness tends to be high.

The average number of bromine atoms contained in one molecule of the green pigment a measured by the FP method is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, still more preferably 6 or more, particularly. It is preferably 7 or more, most preferably 8 or more, and preferably 14 or less, more preferably 13 or less, still more preferably 12 or less, still more preferably 11 or less, and particularly preferably 10 or less. When the value is equal to or higher than the lower limit, the brightness tends to be high. Further, when the value is not more than the upper limit value, the coloring tends to be high.

Further, in the green pigment a, the ratio of the average number of chlorine atoms contained in one molecule to the average number of bromine atoms contained in one molecule, which is measured by the FP method, is preferably 0.1 or more, and is 0. .15 or more is more preferable, 0.2 or more is further preferable, 7 or less is preferable, 3 or less is more preferable, 1 or less is further preferable, and 0 It is particularly preferably 5.5 or less. When it is at least the lower limit value, it tends to be highly colored, and when it is at least the upper limit value, it tends to be high brightness.

The green pigment a preferably contains 3.5% by mass or more of chlorine atoms in the green pigment a, more preferably 4.0% by mass or more, and further preferably 4.3% by mass or more. It is particularly preferably 4.5% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 6% by mass or less. When it is at least the lower limit value, it tends to be highly colored, and when it is at least the upper limit value, it tends to be high brightness.
The content of chlorine atom and bromine atom contained in the green pigment a is determined by dissolving the pigment in ethyl benzoate and then burning it in a combustion device to absorb the combustion gas in a hydrogen peroxide absorbing solution and then in the absorbing solution. It can be measured by a combustion gas-ion chromatography method for measuring the ions of.

Further, the green pigment a preferably has a bromine atom content of 30% by mass or more, more preferably 40% by mass or more, and 45% by mass, as measured by the above analysis method. It is more preferably% or more, and particularly preferably 50% by mass or more. Further, the content of the bromine atom is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 55% by mass or less. preferable. When the value is equal to or higher than the lower limit, the brightness tends to be high. Further, when the value is not more than the upper limit value, the coloring tends to be high.

Such a chlorinated brominated zinc phthalocyanine pigment can be produced by a known production method disclosed in Japanese Patent Application Laid-Open No. 50-130816. For example, a method of synthesizing a pigment by appropriately using phthalic acid or phthalonitrile in which a part or all of hydrogen atoms of an aromatic ring is substituted with a halogen atom such as chlorine as a starting material can be mentioned. In this case, a catalyst such as ammonium molybdate may be used if necessary.

As another method, a method of brominating zinc phthalocyanine with bromine gas in a melt of about 110 to 170 ° C. consisting of a mixture of aluminum chloride, sodium chloride, sodium bromide and the like can be mentioned. In this method, the ratio of various brominated zinc phthalocyanines having different bromine contents is adjusted by adjusting the ratio of chloride and bromide in the molten salt and changing the amount of chlorine gas introduced and the reaction time. It can be controlled arbitrarily.
After completion of the reaction, when the obtained mixture is put into an acidic aqueous solution such as hydrochloric acid, the produced zinc brominated phthalocyanine is precipitated. Then, post-treatment such as filtration, washing, and drying is performed to obtain zinc brominated phthalocyanine.

The chlorinated brominated zinc phthalocyanine pigment thus obtained is dry-ground in a crusher such as an attritor, a ball mill, a vibration mill, or a vibration ball mill, if necessary, and then the pigment is subjected to a solvent salt milling method or a solven boiling method. A chlorinated brominated zinc phthalocyanine pigment that develops a green color with high permeability and high contrast can be obtained. Although the pigmentation method is not particularly limited, it is preferable to adopt the solvent salt milling treatment because the crystal growth can be easily suppressed and the pigment particles having a large specific surface area can be obtained.

Solvent salt milling means kneading and grinding a crude pigment immediately after synthesis, an inorganic salt, and an organic solvent. Specifically, a crude pigment, an inorganic salt, and an organic solvent that does not dissolve the crude pigment are charged in a kneader, and kneading and grinding is performed in the kneader. As the kneading machine at this time, for example, a kneader, a mix maller, a planetary mixer, or a gap portion between an annular fixed disk and a concentric rotating disk as described in Japanese Patent Application Laid-Open No. 2006-77062 is formed. A continuous kneader or the like having a crushed space is preferably used.

As the inorganic salt, a water-soluble inorganic salt can be preferably used, and for example, an inorganic salt such as sodium chloride, potassium chloride, or sodium sulfate is preferably used. Further, the average particle size of these inorganic salts is more preferably 0.5 to 50 μm. Such an inorganic salt can be easily obtained by finely pulverizing an ordinary inorganic salt.
As the green pigment a, G59 manufactured by DIC Corporation can also be used.

The pigment (A) may contain other green pigments in addition to the green pigment a. Other green pigments include, for example, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58 and the like.

The content ratio of the green pigment a contained in the green pigment is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 30% by mass or more, and 50% by mass or more. It is more preferably 80% by mass or more, and usually 100% by mass or less. When it is equal to or more than the lower limit value, the effect of the pigment tends to be more obtained.

Further, the content ratio of the green pigment contained in the (A) pigment is preferably 30% by mass or more, more preferably 35% by mass or more, further preferably 40% by mass or more, and 45% by mass. % Or more is particularly preferable, and usually 100% by mass or less, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is further preferable. , 60% by mass or less is particularly preferable. There is a tendency that the color gamut can be widened by setting the value to the lower limit or higher. Further, the plate-making property tends to be improved by setting the value to the upper limit or less.

The content ratio of the pigment (A) in the colored resin composition of the present invention is usually 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass, based on the total solid content. Further, it is usually 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, and particularly preferably 45% by mass or less. When it is within the above range, the dispersion stability is good and the effect of the green pigment tends to be more obtained.

Further, the content ratio of the pigment (A) in the pigment dispersion liquid of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more, based on the total solid content. It is more preferably 50% by mass or more, more preferably 80% by mass or less, and even more preferably 70% by mass or less. When it is within the above range, the dispersion stability is good and the effect of the green pigment tends to be more obtained.

Further, the content ratio of the green pigment in the pigment dispersion liquid of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more with respect to the total solid content. Is more preferable, 50% by mass or more is particularly preferable, 80% by mass or less is preferable, and 70% by mass or less is more preferable. When it is within the above range, the dispersion stability is good and the effect of the green pigment tends to be more obtained.

The average primary particle size of the green pigment containing the green pigment a is usually 0.1 μm or less, preferably 0.04 μm or less, more preferably 0.03 μm or less, and usually 0.005 μm or more. By setting the average primary particle size within the above range, there is a tendency that deterioration of the extinction characteristic and decrease in transmittance can be suppressed.

The average primary particle size of the pigment can be determined by the following method. That is, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). In the case of organic pigments, the particle size of each pigment particle is converted to the diameter of a circle having the same area, and the particle size is calculated for each of a plurality of pigment particles, and then the following formula is used. As shown, calculate the average number and obtain the average particle size.

Particle size of individual pigment particles:
X ₁ , X ₂ , X ₃ , X ₄ , ..., X _i , ... X _m Average particle size = ΣX _i / m

Further, for adjusting the hue, the pigment (A) can include a yellow pigment. Examples of the yellow pigment include C.I. I. Pigment Yellow (P.Y.) 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127: 1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167,168,169,170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191: 1,192,193,194,195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, and 1: 1 complex of azobarbituric acid represented by the following formula (I) with nickel or its tautomer. Examples thereof include a compound in which another compound is inserted into the body (hereinafter, referred to as “nickel azo complex represented by the formula (I)”).

In addition, examples of the other compound include compounds represented by the following formula (II).

Among these, preferably C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and the nickel azo complex represented by the formula (I), more preferably C.I. I. Pigment Yellow 83, 138, 139, 180, and the nickel azo complex represented by the formula (I).

The average primary particle size of these yellow pigments is usually 0.2 μm or less, preferably 0.1 μm or less, and more preferably 0.04 μm or less. When atomizing the pigment, a method such as the solvent salt milling described above is preferably used.
The content ratio of the yellow pigment contained in the (A) pigment is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 80% by mass or less, and 70% by mass. The following is particularly preferable, 60% by mass or less is most preferable, usually 0% by mass or more, 10% by mass or more is preferable, 30% by mass or more is more preferable, 40% by mass or more is further preferable, and 50% by mass or more is particularly preferable. When it is not more than the upper limit value, the effect of the green pigment a tends to be more obtained.

Further, the colored resin composition and the pigment dispersion liquid of the present invention may contain a dye in addition to the pigment (A). In particular, from the viewpoint of brightness, it is preferable to contain a yellow dye.

[1-2] (B) Dispersant The colored resin composition and pigment dispersion liquid of the present invention contain (B) dispersant for the purpose of stably dispersing (A) pigment. Of these, the use of a polymer dispersant is preferable because it is excellent in dispersion stability over time.
Examples of the polymer dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyesters. A system dispersant can be mentioned. Specific examples of these dispersants include EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by Big Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei), and SOLSPERSE (registered trademark, manufactured by Kusumoto Kasei). Zol), KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.) and the like can be mentioned.

Among the polymer dispersants, a block copolymer having a functional group containing a nitrogen atom is preferable, and an acrylic block copolymer is more preferable, from the viewpoint of dispersibility and storage stability.
Block copolymers having a functional group containing a nitrogen atom include an A block having a quaternary ammonium base and / or an amino group in the side chain and a B block having no quaternary ammonium base and / or an amino group. The AB block copolymer and / or the BAB block copolymer is preferable.

Examples of the functional group containing a nitrogen atom include a 1st to 3rd amino group and a quaternary ammonium base, and it is preferable to have a 1st to 3rd amino group from the viewpoint of dispersibility and storage stability. It is more preferable to have a group.
The structure of the repeating unit having a tertiary amino group in the block copolymer is not particularly limited, but from the viewpoint of dispersibility and storage stability, the repeating unit represented by the following general formula (1) is preferable. ..

In the above formula (1), R ¹ and R ² each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is an aralkyl group which may be present, and R ¹ and R ² may be bonded to each other to form a cyclic structure. R ³ is a hydrogen atom or a methyl group. X is a divalent linking group.

The number of carbon atoms of the alkyl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 1 or more, preferably 10 or less, and more preferably 6 or less. It is preferably 4 or less, and more preferably 4 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like, and among these, a methyl group, an ethyl group, a propyl group and a butyl group. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The number of carbon atoms of the aryl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. It is preferably 8 or less, and more preferably 8 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthracenyl group and the like, and among these, a phenyl group, a methylphenyl group and an ethylphenyl group. , Dimethylphenyl group, or diethylphenyl group, more preferably a phenyl group, methylphenyl group, or ethylphenyl group.

The carbon number of the aralkyl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. It is preferably 9 or less, and more preferably 9 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, a phenylisopropylene group and the like, and among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or a phenylpropylene group. It is preferably a phenylbutylene group, more preferably a phenylmethylene group or a phenylethylene group.

Among these, from the viewpoints of dispersibility, storage stability, electrical reliability, and developability, R ¹ and R ² are preferably alkyl groups which may have independent substituents, and are preferably methyl groups or methyl groups. It is more preferably an ethyl group.

Examples of the substituent that the alkyl group, aralkyl group or aryl group in the above formula (1) may have include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group and the like, and there is no such group from the viewpoint of ease of synthesis. It is preferably a substitution.

Further, in the above formula (1), ^{the cyclic structure formed by bonding R 1} and R ² to each other is, for example, a nitrogen-containing heterocyclic monocycle having a 5- to 7-membered ring or a condensed ring formed by condensing two of them. Can be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, and more preferably a saturated ring. Specifically, for example, the following (IV) can be mentioned.

These cyclic structures may further have substituents.

In the above formula (1), divalent Examples of the linking group X, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, ^{-CONH-R 13} - group, -COOR ¹⁴ - group [ However, R ¹³ and R ¹⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms], and the like, preferably −COO-R ¹⁴ -Group.

Further, the content ratio of the repeating unit represented by the formula (1) in the total repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more. It is more preferably 10 mol% or more, further preferably 15 mol% or more, particularly preferably 20 mol% or more, most preferably 25 mol% or more, and 90 mol%. It is preferably less than or equal to, more preferably 70 mol% or less, further preferably 50 mol% or less, and particularly preferably 40 mol% or less. Within the above range, both dispersion stability and high brightness tend to be possible.

Further, the block copolymer preferably has a repeating unit represented by the following formula (2) from the viewpoint of increasing the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability.

In the above formula (2), R ¹⁰ is an ethylene group or a propylene group, R ¹¹ is an alkyl group which may have a substituent, and R ¹² is a hydrogen atom or a methyl group. n is an integer of 1 to 20.

^{The number of carbon atoms of the alkyl group which may have a substituent in R 11} of the above formula (2) is not particularly limited, but is usually 1 or more, preferably 2 or more, and 10 or less. It is preferably 6 or less, more preferably 4 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like, and among these, a methyl group, an ethyl group, a propyl group and a butyl group. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

Further, n in the above formula (2) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, from the viewpoint of compatibility and dispersibility with a binder component such as a solvent. More preferably, it is 5 or less.

Further, the content ratio of the repeating unit represented by the formula (2) in all the repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more. It is more preferably 4 mol% or more, more preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less. If it is within the above range, it tends to be possible to achieve both compatibility with a binder component such as a solvent and dispersion stability.

Further, the block copolymer preferably has a repeating unit represented by the following formula (3) from the viewpoint of increasing the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability.

In the above formula (3), R ⁸ is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. R ⁹ is a hydrogen atom or a methyl group.

^{The number of carbon atoms of the alkyl group which may have a substituent in R 8} of the above formula (3) is not particularly limited, but is usually 1 or more, preferably 2 or more, and 10 or less. It is preferable, and it is more preferable that it is 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like, and among these, a methyl group, an ethyl group, a propyl group and a butyl group. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

^{The number of carbon atoms of the aryl group which may have a substituent in R 8} of the above formula (3) is not particularly limited, but is usually 6 or more, preferably 16 or less, and preferably 12 or less. Is more preferable. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthracenyl group and the like, and among these, a phenyl group, a methylphenyl group and an ethylphenyl group. , Dimethylphenyl group, or diethylphenyl group, more preferably a phenyl group, methylphenyl group, or ethylphenyl group.

^{The number of carbon atoms of the aralkyl group which may have a substituent in R 8} of the above formula (3) is not particularly limited, but is usually 7 or more, preferably 16 or less, and preferably 12 or less. Is more preferable. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, a phenylisopropylene group and the like, and among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or a phenylpropylene group. It is preferably a phenylbutylene group, more preferably a phenylmethylene group or a phenylethylene group.

Among these, from the viewpoint of dispersion stability and solvent compatibility, it is preferred that R ⁸ is an alkyl group, or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethylene group.
Examples of the substituent that the alkyl group may have in R ^{8 include a halogen atom and an alkoxy group.} Examples of the substituent that the aryl group or the aralkyl group may have include a chain alkyl group, a halogen atom, an alkoxy group and the like. Further, the ^{chain-like alkyl group represented by R 8} includes both a linear chain and a branched chain.

The content of the repeating unit represented by the formula (3) in the total repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more. It is more preferably 50 mol% or more, more preferably 80 mol% or less, and even more preferably 70 mol% or less. Within the above range, both dispersion stability and high brightness tend to be possible.

The block copolymer contains a repeating unit other than the repeating unit represented by the general formula (1), the repeating unit represented by the general formula (2), and the repeating unit represented by the general formula (3). You may have. Examples of such repeating units are styrene-based monomers such as styrene and α-methylstyrene; (meth) acrylate-based monomers such as (meth) acrylate chloride; (meth) acrylamide, N- Examples thereof include (meth) acrylamide-based monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate ether; and repeating units derived from monomers such as N-methacryloylmorpholine.

From the viewpoint of further enhancing the dispersibility, it has an A block having a repeating unit represented by the general formula (1) and a B block having no repeating unit represented by the general formula (1). It is preferably a block copolymer. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. Further, it is more preferable that the B block has a repeating unit represented by the general formula (2) and a repeating unit represented by the general formula (3).

Further, a repeating unit other than the repeating unit represented by the general formula (1) may be contained in the A block, and examples of such a repeating unit include the above-mentioned (meth) acrylic acid ester type. Examples include repeating units derived from monomers. The content of the repeating unit other than the repeating unit represented by the general formula (1) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and the repeating unit is Most preferably, it is not contained in the A block.

A repeating unit other than the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (3) may be contained in the B block, and examples of such repeating units include , Styrene-based monomers such as styrene and α-methylstyrene; (meth) acrylate-based monomers such as (meth) acrylic acid chloride; (meth) acrylamide-based monomers such as (meth) acrylamide and N-methylol acrylamide. Monomers; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate ether; repeating units derived from monomers such as N-methacryloylmorpholine. The content of the repeating unit represented by the general formula (2) and the repeating unit other than the repeating unit represented by the general formula (3) in the B block is preferably 0 to 50 mol%, more preferably. Although it is 0 to 20 mol%, it is most preferable that such repeating units are not contained in the B block.

Further, the acid value of the block copolymer is preferably low, and particularly preferably 0 mgKOH / g, from the viewpoint of dispersibility. Here, the acid value represents the number of mg of KOH required to neutralize 1 g of the dispersant solid content.

Further, the amine value of the block copolymer is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 mgKOH / g or more from the viewpoint of dispersibility and developability. More preferably, it is more preferably 90 mgKOH / g or more, particularly preferably 100 mgKOH / g or more, most preferably 110 mgKOH / g or more, and preferably 150 mgKOH / g or less, 130 mgKOH or less. More preferably, it is / g or less. Here, the amine value represents an amine value in terms of effective solid content, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the equivalent mass of KOH.

The molecular weight of the block copolymer is preferably in the range of 1000 to 30,000 in terms of polystyrene-equivalent weight average molecular weight (hereinafter, may be referred to as “Mw”). When it is within the above range, the dispersion stability is good, and dry foreign matter tends to be less likely to be generated during coating by the slit nozzle method.

The block copolymer can be produced by a known method, and for example, it can be produced by living-polymerizing a monomer into which each of the above repeating units is introduced. Examples of the living polymerization method include Japanese Patent Application Laid-Open No. 9-62002, Japanese Patent Application Laid-Open No. 2002-31713, and P.M. Lutz, P. et al. Masson et al, Polym. Bull. 12, 79 (1984); B. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981); K. et al. Hatada, K. et al. Ute, et al, Polym. J. , 17, 977 (1985); K.K. Hatada, K. et al. Ute, et al, Polym. J. , 18,1037 (1986); Koichi Right Hand, Koichi Hatada, Polymer Processing, 36,366 (1987); Toshinobu Higashimura, Mitsuo Sawamoto, Proceedings of Polymers, 46,189 (1989); Kuroki, T.K. Aida, J. et al. Am. Chem. Soc, 109,4737 (1987); Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43,300 (1985); Y. Sogoh, W. et al. R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) and the like can be adopted.

In the colored resin composition and the pigment dispersion liquid of the present invention, the content ratio of the dispersant (B) is not particularly limited, but is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the (A) pigment. , More preferably 5 parts by mass or more, further preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more, and preferably 70 parts by mass or less, more preferably 50 parts by mass. Parts or less, more preferably 40 parts by mass or less. Within the above range, there is a tendency that a colorable resin composition having excellent dispersion stability and high brightness can be obtained.

[1-3] Dispersion Auxiliary Agent The colored resin composition and pigment dispersion liquid according to the present invention may contain a pigment derivative or the like as a dispersion aid in order to improve the dispersibility of the pigment and the dispersion stability. Good. Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrone, perylene, perinone, and diketopyrrolop. Derivatives such as pyrrolop-based and dioxazine-based pigments can be mentioned. As the substituent of the pigment derivative, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc. are directly on the pigment skeleton or an alkyl group, an aryl group, a complex group, etc. 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. Further, these substituents may be plurally substituted in one pigment skeleton, or may be a mixture of compounds having different numbers of substitutions. Specific examples of the pigment derivative include azo pigment sulfonic acid derivative, phthalocyanine pigment sulfonic acid derivative, quinophthalone pigment sulfonic acid derivative, isoindrin pigment sulfonic acid derivative, anthraquinone pigment sulfonic acid derivative, and quinacridone pigment sulfonic acid derivative. Examples thereof include a sulfonic acid derivative of a diketopyrrolopyrrole pigment and a sulfonic acid derivative of a dioxazine pigment.

Of these, a pigment derivative having less interference with the hue of the green pigment is preferable, and a sulfonic acid derivative of Pigment Yellow 138, a sulfonic acid derivative of Pigment Yellow 139, and a sulfonic acid derivative of Pigment Blue 15 are more preferable.
The amount of the pigment derivative used is usually 0.1 part by mass or more, usually 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably, with respect to 100 parts by mass of the pigment (A). Is 5 parts by mass or less.

[1-4] Dispersion Resin The pigment dispersion liquid according to the present invention may contain a part or all of a resin selected from the binder resins described later. Specifically, in the dispersion treatment step in the preparation of the pigment dispersion liquid described later, by containing a part or all of the binder resin together with the above-mentioned dispersant, the binder resin is dispersed and stabilized by a synergistic effect with the dispersant. It is preferable because it contributes to the property and as a result, the amount of the dispersant added may be reduced. As described above, the resin used in the dispersion treatment step may be referred to as a dispersion resin.

[1-5] (C) Solvent The (C) solvent has a function of dissolving or dispersing a pigment, a dispersant, and other components in the colored resin composition and the pigment dispersion liquid of the present invention to adjust the viscosity.
The solvent (C) may be any solvent that can dissolve or disperse each component.

In the colored resin composition according to the first aspect of the present invention and the pigment dispersion liquid according to the second aspect, the solvent (C) is a high boiling point solvent having a boiling point of 150 ° C. or higher at 1013.25 hPa (hereinafter, simply "high"). It is abbreviated as "boiling point solvent"). By including the high boiling point solvent in this way, the resolubility is improved, and the curing due to the resolubility of the colored resin composition occurs specifically when a specific chlorinated brominated zinc phthalocyanine green pigment is used. It is considered that the generation of foreign matter on the film surface can be suppressed.

The boiling point of the high boiling point solvent at 1013.25 hPa (hereinafter, simply abbreviated as "boiling point" unless otherwise specified) is usually 150 ° C. or higher, preferably 170 ° C. or higher, more preferably 190 ° C. or higher, still more preferable. Is 210 ° C. or higher, preferably 340 ° C. or lower, more preferably 300 ° C. or lower, still more preferably 280 ° C. or lower. When it is at least the above lower limit value, the resolubility tends to be improved, and when it is at least the above upper limit value, the efficiency of VCD (vacuum drying) in the color filter manufacturing process tends to be improved.

The vapor pressure of the high boiling point solvent at 20 ° C. is not particularly limited, but is preferably 1 Pa or more, more preferably 10 Pa or more, still more preferably 100 Pa or more, and preferably 2000 Pa or less, more preferably 1000 Pa or less, still more preferable. Is 500 Pa or less, particularly preferably 400 Pa or less. When it is at least the above lower limit value, the efficiency of VCD (drying under reduced pressure) during the color filter manufacturing process tends to be improved, and when it is at least the above upper limit value, the resolubility tends to be improved.

Specific examples of the high boiling point solvent include ethylene glycol diacetate (boiling point: 191 ° C.), ethylene glycol mono-n-butyl ether (boiling point: 171 ° C.), propylene glycol mono-n-butyl ether (boiling point: 170 ° C.), and diethylene glycol. Glycol ethers such as diethyl ether (boiling point: 188 ° C.), diethylene glycol monoethyl ether (boiling point: 202 ° C.), ethylene glycol mono-n-butyl ether acetate (boiling point: 192 ° C.), diethylene glycol monoethyl ether acetate (boiling point: 217 ° C.) ), Diethylene glycol mono-n-butyl ether acetate (boiling point: 247 ° C), ethyl 3-ethoxypropionate (boiling point: 170 ° C), glycol ether acetates such as 3-methoxybutyl acetate (boiling point: 171 ° C), 1,3 Glycol diacetates such as −butylene glycol diacetate (boiling point: 232 ° C.) can be mentioned. From the viewpoint of solubility of the colored resin composition, acetates and glycol ethers are preferable, and glycol alkyl ether acetates are more preferable. ..

Further, in the colored resin composition according to the first aspect of the present invention and the pigment dispersion liquid according to the second aspect, the solvent (C) is a low boiling point solvent having a boiling point of less than 150 ° C. at 1013.25 hPa (hereinafter, simply referred to as simply. It is abbreviated as "low boiling point solvent"). By including the low boiling point solvent in this way, the efficiency of VCD (vacuum drying) during the color filter manufacturing process tends to be improved.

The boiling point of the low boiling point solvent at 1013.25 hPa (hereinafter, simply abbreviated as "boiling point" unless otherwise specified) is usually less than 150 ° C., preferably 140 ° C. or lower, more preferably 130 ° C. or lower, still more preferable. Is 120 ° C. or lower, preferably 80 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher. When it is set to the upper limit value or less, the efficiency of VCD (drying under reduced pressure) in the color filter manufacturing process tends to be improved, and when it is set to the lower limit value or more, the resolubility tends to be improved.

Specific examples of the low boiling solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, 2-peptanone, n-butyl acetate, i-butyl acetate, i-pentyl acetate, ethyl butyrate, n butyrate. -Propyl, i-propyl butyrate, ethyl pyruvate, methyl-3-methoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol diethyl ether, dibutyl ether, ethyl pyruvate, n-butyl acetate, isobutyl acetate , Amyl acetate, isoamyl acetate, butyl propionate, ethyl butyrate, propyl butyrate, methyl-3-methoxyisobutyrate, methyl glycolate, methyl lactate, methyl-2-hydroxyisobutyrate, 2-methoxyethyl acetate , Ethylene glycol methyl ether acetate, dibutyl ether, cyclopentanone, 2-hexanone, 3-hexanone, 5-methyl-2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 1-methoxy-2-propanol, etc. Can be mentioned.

The content ratio of the solvent (C) in the colored resin composition according to the first aspect of the present invention is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more. It is particularly preferably 75% by mass or more, most preferably 80% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less. When it is at least the lower limit value, the storage stability of the coloring composition tends to be improved, and when it is at least the upper limit value, the film thickness at the time of coating tends to be constant or less.

Further, in the colored resin composition according to the first aspect of the present invention, the content ratio of the high boiling point solvent to the (C) solvent is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass. Above, more preferably 2% by mass or more, further preferably 5% by mass or more, further preferably 8% by mass or more, particularly preferably 15% by mass or more, most preferably 30% by mass or more, and preferably 80% by mass. % Or less, more preferably 60% by mass or less, still more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less. When it is at least the above lower limit value, the solubility of the dry film in the solvent tends to be high, and when it is at least the above upper limit value, the drying time of the coating film after coating tends to be shortened.

Further, in the colored resin composition according to the first aspect of the present invention, the content ratio of the low boiling point solvent to the solvent (C) is not particularly limited, but is preferably 20% by mass or more, more preferably 40% by mass or more. More preferably 60% by mass or more, particularly preferably 80% by mass or more, preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, particularly preferably 95% by mass or less. Is. When it is at least the above lower limit value, the drying time of the coating film after cloth tends to be shortened, and when it is at least the above upper limit value, the solubility of the dried film in the solvent tends to be high.

The content ratio of the solvent (C) in the pigment dispersion according to the second aspect of the present invention is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more. Especially preferably 80% by mass or more, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less. When it is at least the above lower limit value, the storage stability of the pigment dispersion liquid tends to be improved, and when it is at least the above upper limit value, the solvent ratio of the amount brought into the coloring composition tends to be reduced.

Further, in the pigment dispersion liquid according to the second aspect of the present invention, the content ratio of the high boiling point solvent to the (C) solvent is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, and further. It is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 40% by mass or more, most preferably 60% by mass or more, and preferably 80% by mass or less. It is more preferably 60% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. When it is at least the above lower limit value, the solubility of the dry film in the solvent tends to be high, and when it is at least the above upper limit value, the drying time of the coating film after coating tends to be shortened.

Further, in the pigment dispersion liquid according to the second aspect of the present invention, the content ratio of the low boiling point solvent to the solvent (C) is not particularly limited, but is preferably 20% by mass or more, more preferably 40% by mass or more, and further. It is preferably 60% by mass or more, particularly preferably 70% by mass or more, preferably 99% by mass or less, more preferably 98% by mass or less, still more preferably 95% by mass or less, and particularly preferably 90% by mass or less. When it is at least the above lower limit value, the drying time of the coating film after coating tends to be shortened, and when it is at least the above upper limit value, the solubility of the dried film in the solvent tends to be high.

On the other hand, in the colored resin composition according to the third aspect of the present invention, the solvent can be used without particular limitation, and for example, those exemplified below can be used.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol Glycol monoalkyl ethers such as monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether;

Glycoldialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl Glycolalkyl ether acetates such as ether acetate, 3-methyl-3-methoxybutyl acetate;

Glycoldiacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamil ether, ethyl isobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methylnonyl ketone, methoxymethylpentanone. Ketones;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amilformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methylisobutyrate, ethylene glycol acetate, ethyl propionate, propylpropionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Chain or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride, amilk chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile.

Commercially available solvents corresponding to the above include Mineral Spirit, Barsol # 2, Apco # 18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2. Solvento # 150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like can be mentioned. These solvents may be used alone or in combination of two or more.

When forming the pixels of the color filter by the photolithography method, select a solvent having a boiling point in the range of 100 to 200 ° C. (under the condition of pressure 1013.25 [hPa]. Hereinafter, the boiling points are all the same). Is preferable. More preferably, it has a boiling point of 120 to 170 ° C.
Glycolalkyl ether acetates are preferable because they have a good balance of coatability and surface tension in the solvent and the solubility of the constituents in the composition is relatively high.

Further, the glycol alkyl ether acetates may be used alone or in combination with other solvents. Glycol monoalkyl ethers are particularly preferable as the solvent to be used in combination. Of these, propylene glycol monomethyl ether is particularly preferable because of the solubility of the constituent components in the composition. The glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate, and the storage stability of the colored resin composition obtained later tends to increase and the storage stability tends to decrease. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.

It is also preferable to use a solvent having a boiling point of 150 ° C. or higher in combination. By using such a solvent having a high boiling point in combination, the colored resin composition becomes difficult to dry, but there is an effect that it is difficult to break the mutual relationship of the pigment dispersion liquid due to rapid drying. The content of the high boiling point solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass with respect to the solvent. If the amount of the high boiling point solvent is too small, for example, the coloring material component may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects, and if it is too large, the drying temperature of the composition becomes slow, which will be described later. In the color filter manufacturing process, there is a concern that it may cause problems such as poor tact in the vacuum drying process and pin marks of pre-bake.
The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, it is not necessary to separately contain a solvent having a boiling point of 150 ° C. or higher.

When forming the pixels of the color filter by the inkjet method, a solvent having a boiling point of usually 130 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 280 ° C. or lower is suitable. If the boiling point is too low, the uniformity of the resulting coating film tends to be poor. On the other hand, if the boiling point is too high, as will be described later, the effect of suppressing the drying of the curable resin composition is high, but even after heat firing, a large amount of residual solvent is present in the coating film, which may cause quality problems. , The drying time in vacuum drying becomes long, and problems such as an increase in tact time may occur.
Further, from the viewpoint of the uniformity of the obtained coating film, the vapor pressure of the solvent is usually 10 mmHg or less, preferably 5 mmHg or less, and more preferably 1 mmHg or less.

In the color filter manufacturing by the inkjet method, the ink emitted from the nozzle is very fine, several to several tens of pL, so the solvent evaporates and the ink concentrates before landing around the nozzle opening or in the pixel bank.・ Tends to dry. In order to avoid this, it is preferable that the boiling point of the solvent is high, and specifically, it is preferable to contain a solvent having a boiling point of 180 ° C. or higher. More preferably, it contains a solvent having a boiling point of 200 ° C. or higher, particularly preferably 220 ° C. or higher. The high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total solvent contained in the pigment dispersion liquid and / or the colored resin composition described later. 90% by mass or more is most preferable. When the high boiling point solvent is less than 50% by mass, the effect of preventing evaporation of the solvent from the droplets may not be sufficiently exhibited.

As a preferable high boiling solvent, for example, among the various solvents described above, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanoldi Examples include acetate and triacetin.
Further, in order to adjust the viscosity of the pigment dispersion liquid and the colored resin composition described later and the solubility of the solid content, it is also effective to partially contain a solvent having a boiling point lower than 180 ° C. As such a solvent, a solvent having low viscosity, high solubility, and low surface tension is preferable, and ethers, esters, ketones, and the like are preferable. Of these, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate and the like are particularly preferable.

On the other hand, if the solvent contains alcohols, the ejection stability in the inkjet method may deteriorate. Therefore, the alcohol content is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less in the total solvent.

The content of the solvent in the entire colored resin composition according to the third aspect of the present invention is not particularly limited, but the upper limit thereof is usually 99% by mass or less, preferably 90% by mass or less, more preferably 85. It is less than mass%. If it exceeds the upper limit, the amount of pigment, dispersant, etc. may be too small to be suitable for forming a coating film. On the other hand, the lower limit of the solvent content is usually 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more in consideration of viscosity suitable for coating.

[1-6] (D) Binder Resin The colored resin composition of the present invention contains (D) a binder resin. By containing the binder resin (D), both film curability by photopolymerization and solubility by a developing solution can be achieved at the same time.
As the binder resin (D), the preferred resin tends to differ depending on the means by which the colored resin composition is cured. In the case of the photopolymerizable resin composition, examples of the binder resin include Japanese Patent Application Laid-Open No. 7-2072111, Japanese Patent Application Laid-Open No. 8-259876, Japanese Patent Application Laid-Open No. 10-300922, and Japanese Patent Application Laid-Open No. 11-2019. Uses known polymer compounds described in JP-A-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, etc. can do. Preferably,
[1-6-1]: With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, an unsaturated single base is added to at least a part of the epoxy group contained in the copolymer. An alkali-soluble resin [1-6-2] containing a carboxyl group in the main chain of a resin obtained by adding an acid or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction. Linear alkali-soluble resin [1-6-3] A resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the carboxyl group-containing resin [1-6-4] (meth) acrylic resin [1-6-4] 1-6-5] Epoxy (meth) acrylate resins having a carboxyl group, and the like can be mentioned.
Hereinafter, each of these resins will be described.

[1-6-1] With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, at least a part of the epoxy group of the copolymer is unsaturated monobasic acid. Or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction, as one of particularly preferable resins, "epoxy group-containing (meth) acrylate". An unsaturated monobasic acid is added to 10 to 100 mol% of the epoxy groups of the copolymer with respect to a copolymer of 5 to 90 mol% and another radically polymerizable monomer 10 to 95 mol%. Examples thereof include a resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of a hydroxyl group generated by the addition reaction, or an alkali-soluble resin obtained by adding a polybasic acid anhydride.

Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. ) Acrylate glycidyl ether and the like can be exemplified. Of these, glycidyl (meth) acrylate is preferable. One of these epoxy group-containing (meth) acrylates may be used alone, or two or more thereof may be used in combination.

As the other radically polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate, a mono (meth) acrylate having a structure represented by the following general formula (V) is preferable.

In formula (V), R ^{91 to} R ⁹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In addition, R ⁹⁶ and R ⁹⁸ , or R ⁹⁵ and R ⁹⁷ may be connected to each other to form a ring.
In formula (V), the ^{ring formed by connecting R 96} and R ⁹⁸ or R ⁹⁵ and R ⁹⁷ is preferably an aliphatic ring, which may be saturated or unsaturated, and carbon. The number is preferably 5-6.

Among them, as the structure represented by the general formula (V), the structure represented by the following formula (Va), (Vb), or (Vc) is preferable.
By introducing these structures into the binder resin, when the colored resin composition of the present invention is used for a color filter or a liquid crystal display element, the heat resistance of the colored resin composition can be improved or the colored resin composition can be used. It is possible to increase the intensity of the pixels formed by using.

As the mono (meth) acrylate having a structure represented by the general formula (V), one type may be used alone, or two or more types may be used in combination.

As the mono (meth) acrylate having the structure represented by the general formula (V), various known mono (meth) acrylates can be used as long as they have the structure, but those represented by the following general formula (VI) are particularly preferable. ..

In the formula (VI), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents the structure of the general formula (V).
In the copolymer of the epoxy group-containing (meth) acrylate and another radically polymerizable monomer, the repeating unit derived from the mono (meth) acrylate having the structure represented by the general formula (VI) is Among the repeating units derived from "other radically polymerizable monomers", those containing 5 to 90 mol% are preferable, those containing 10 to 70 mol% are more preferable, and those containing 15 to 50 mol% are particularly preferable. preferable.

The "other radically polymerizable monomer" other than the mono (meth) acrylate having the structure represented by the general formula (VI) is not particularly limited. Specifically, for example, vinyl aromatics such as styrene, α-, o-, m- of styrene, or p-alkyl, nitro, cyano, amide, ester derivatives; butadiene, 2,3-dimethylbutadiene, isoprene. , Chloroprene and the like; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, (meth) acrylate-iso-propyl, (meth) acrylate-n-butyl , (Meta) acrylate-sec-butyl, (meth) acrylate-tert-butyl, (meth) pentyl acrylate, (meth) neopentyl acrylate, (meth) isoamyl acrylate, (meth) hexyl acrylate, ( -2-ethylhexyl acrylate, (meth) lauryl acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, -2-methylcyclohexyl (meth) acrylate, (meth) ) Dicyclohexyl acrylate, isoboronyl (meth) acrylate, adamantyl (meth) acrylate, propagil (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracelyl (meth) acrylate, (meth) Anthraninonyl acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, frill (meth) acrylate, flufuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, ( Benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, -1,1,1-trifluoroethyl (meth) acrylate, perfluorethyl (meth) acrylate, (meth) acrylic Perfluoro-n-propyl acid, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, -3- (N, N-dimethyl) (meth) acrylate (Meta) acrylic acid esters such as amino) propyl, -2-hydroxyethyl (meth) acrylate, -2-hydroxypropyl (meth) acrylate; (meth) acrylate amide, (meth) acrylate N, N -Dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N-di-iso-propylamide, (meth) acrylic acid anthra (Meta) acrylic acid amides such as senylamide; T) Acrylic acid anilide, (meth) acryloylnitrile, achlorine, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate and other vinyl compounds; diethyl citraconate, maleic acid Unsaturated dicarboxylic acid diesters such as diethyl, diethyl fumarate, diethyl itacone; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide; N- (Meta) Acryloylphthalimide and the like can be mentioned.

Among these "other radically polymerizable monomers", at least one selected from styrene, benzyl (meth) acrylate, and monomaleimide in order to impart excellent heat resistance and strength to the colored resin composition. It is effective to use. In particular, among the repeating units derived from "other radically polymerizable monomers", the content ratio of the repeating units derived from at least one selected from these styrene, benzyl (meth) acrylate, and monomaleimide is 1 to 70 mol. It is preferably%, and more preferably 3 to 50 mol%.

A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer. The solvent used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate; and diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate and butyl carbitol acetate; Propropylene glycol monoalkyl ether acetates; Acetate esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methylcarbitol, ethylcarbitol, butylcarbitol; Triethylene glycol dialkyl Ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; benzene, toluene, xylene, octane, Hydrocarbons such as decane; Petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate; Be done. These solvents may be used alone or in combination of two or more.

The amount of these solvents used is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, based on 100 parts by mass of the obtained copolymer. If the amount of the solvent used is out of this range, it becomes difficult to control the molecular weight of the copolymer.
The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst should be used. Can be done. Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

Specific examples thereof include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, t-hexylperoxybenzoate, and t-butylperoxy-2-ethyl. Hexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (T-Butyl Peroxy) Hexyl-3,3-isopropylhydroperoxide, t-butylhydroperoxide, dicumyl peroxide, dicumylhydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) par Oxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane , 1,1-Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane and the like.

Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarboxylicamide.
From these, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature. The amount of the radical polymerization initiator used is 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the total amount of the monomers used in the copolymerization reaction.

The copolymerization reaction may be carried out by dissolving the monomer used in the copolymerization reaction and the radical polymerization initiator in a solvent and raising the temperature with stirring, or by adding the monomer to which the radical polymerization initiator is added. , The temperature may be raised, and the mixture may be added dropwise to the stirred solvent. Alternatively, the monomer may be dropped while the temperature is raised by adding a radical polymerization initiator to the solvent. The reaction conditions can be freely changed according to the target molecular weight.

In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer includes a repeating unit of 5 to 90 mol% derived from the epoxy group-containing (meth) acrylate, and the like. It is preferably composed of 10 to 95 mol% of the repeating unit derived from the radically polymerizable monomer of the above, more preferably 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and 30 to 30 to 20 mol% of the former. Those consisting of 70 mol% and the latter 70 to 30 mol% are particularly preferable.

If the amount of the epoxy group-containing (meth) acrylate is too small, the amount of the polymerizable component and the alkali-soluble component described later may be insufficient, while the amount of the epoxy group-containing (meth) acrylate is too large to add other radicals. If the amount of the polymerizable monomer is too small, the heat resistance and strength may be insufficient.
Subsequently, an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali) are added to the epoxy group portion of the copolymer of the epoxy resin-containing (meth) acrylate and another radically polymerizable monomer. React with soluble component).

As the "unsaturated monobasic acid" to be added to the epoxy group, known ones can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.
Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, or p-vinylbenzoic acid, in which the α-position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group, or the like. Examples thereof include monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferable. One of these may be used alone, or two or more thereof may be used in combination.

By adding such a component, the binder resin used in the present invention can be imparted with polymerizable properties.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy groups of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. If the addition ratio of the unsaturated monobasic acid is too small, there is a concern that the residual epoxy group may adversely affect the stability of the colored resin composition over time. As a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be adopted.

Further, as the "polybasic acid anhydride" to be added to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer, known ones can be used.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone. Examples thereof include anhydrides of acids having three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferred. One of these polybasic acid anhydrides may be used alone, or two or more thereof may be used in combination.

By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl groups generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30-80 mol%. If this addition ratio is too large, the residual film ratio during development may decrease, and if it is too small, the solubility may be insufficient. As a method for adding the polybasic acid anhydride to the hydroxyl group, a known method can be adopted.

Further, in order to improve the photosensitivity, after the above-mentioned polybasic acid anhydride is added, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl groups. You may.
Further, in order to improve the developability, a glycidyl ether compound having no polymerizable unsaturated group may be added to a part of the generated carboxyl groups.

Moreover, you may add both of these.
Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group and an alkyl group. As commercial products, for example, the product names "Denacol (registered trademark, the same applies hereinafter) EX-111", "Denacol EX-121", "Denacol EX-141", "Denacol EX-145", "Denacol EX-145" manufactured by Nagase Kasei Kogyo Co., Ltd. There are "Denacol EX-146", "Denacol EX-171", "Denacol EX-192" and the like.

The structure of such a resin is described in, for example, Japanese Patent Application Laid-Open No. 8-297366 and Japanese Patent Application Laid-Open No. 2001-89533, and is already known.
The polystyrene-equivalent weight average molecular weight (Mw) of the above-mentioned binder resin measured by GPC is preferably 3000 to 100,000, and particularly preferably 5000 to 50000. If the molecular weight is less than 3000, the heat resistance and film strength may be inferior, and if it exceeds 100,000, the solubility in a developing solution tends to be insufficient. As a guideline for the molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

[1-6-2] Linear alkali-soluble resin containing a carboxyl group in the main chain The linear alkali-soluble resin containing a carboxyl group in the main chain is not particularly limited as long as it has a carboxyl group. , Usually obtained by polymerizing a polymerizable monomer containing a carboxyl group.

Examples of the carboxyl group-containing polymerizable monomer include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, phthalic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl. Adipic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxypropyl succinic acid, 2 -(Meta) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyl Oxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutyl maleic acid, 2- (meth) acryloyloxybutyl hydrophthalic acid, 2- (meth) acryloyloxybutyl phthalic acid, etc. Vinyl-based monomer; a monomer obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to acrylic acid; Examples thereof include succinic acid, maleic acid, phthalic acid, and monomers to which an acid such as an anhydride thereof or an anhydride is added. A plurality of these may be used.

Of these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is even more preferable.
Further, in the linear alkali-soluble resin containing a carboxyl group in the main chain, the above-mentioned carboxyl group-containing polymerizable monomer may be copolymerized with another polymerizable monomer having no carboxyl group. ..

The other polymerizable monomer is not particularly limited, but is limited to methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. , Benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxy (Meta) acrylic acid esters such as ethyl (meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobonyl (meth) acrylate, and adamantyl (meth) acrylate. Vinyl aromatics such as styrene and derivatives thereof; Vinyl compounds such as N-vinylpyrrolidone; N-substituted maleimides such as N-cyclohexyl maleimide, N-phenylmaleimide, N-benzylmaleimide; polymethyl (meth) acrylate macro Examples thereof include macromonomers such as monomers, polystyrene macromonomers, poly2-hydroxyethyl (meth) acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, and polycaprolactone macromonomers. These may be used in combination of two or more.

Particularly preferred are styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Butyl (meth) acrylate, isobutyl (meth) acrylate, tricyclodecanyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, and N-phenylmaleimide.

The linear alkali-soluble resin containing a carboxyl group in the main chain may further have a hydroxyl group. Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, and glycerol mono (meth) acrylate. Can be mentioned. By copolymerizing these with the above-mentioned various monomers, a resin having a carboxyl group and a hydroxyl group can be obtained.

Specific examples of the linear alkali-soluble resin containing a carboxyl group in the main chain include (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (. Polymeric monomers containing no hydroxyl groups such as meta) acrylates, cyclohexyl (meth) acrylates and cyclohexyl maleimides, 2-hydroxyethyl (meth) acrylates, hydroxypropyl (meth) acrylates, 4-hydroxybutyl (meth) acrylates and the like. Copolymer with hydroxyl group-containing monomer; (meth) acrylic acid and methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate, etc. Copolymer with (meth) acrylic acid ester; copolymer of (meth) acrylic acid and styrene; copolymer of (meth) acrylic acid, styrene and α-methylstyrene; (meth) acrylic acid and cyclohexyl Examples thereof include a copolymer with maleimide.

From the viewpoint of excellent pigment dispersibility, a copolymer resin containing benzyl (meth) acrylate is particularly preferable.
The acid value of the linear alkali-soluble resin containing a carboxyl group in the main chain in the present invention is usually 30 to 500 KOH mg / g, preferably 40 to 350 KOH mg / g, and more preferably 50 to 300 KOH mg / g.

The polystyrene-equivalent weight average molecular weight measured by GPC is usually 2000 to 80,000, preferably 3000 to 50000, and more preferably 4000 to 30000. If the weight average molecular weight is too small, the stability of the colored resin composition tends to be inferior, and if it is too large, the solubility in a developing solution tends to be deteriorated when used in a color filter or a liquid crystal display device described later. ..

[1-6-3] A resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the resin according to [1-6-2]. The linear alkali-soluble resin having a carboxyl group in the main chain. A resin in which an epoxy group-containing unsaturated compound is added to a carboxyl group portion of the resin is also particularly preferable.

The epoxy group-containing unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.
For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, glycidyl ether (iso) crotonate, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4- Acyclic epoxy group-containing unsaturated compounds such as hydroxybutyl (meth) acrylate glycidyl ether can also be mentioned, but from the viewpoint of heat resistance and dispersibility of pigments described later, alicyclic epoxy group-containing unsaturated compounds are used. preferable.

Here, as the alicyclic epoxy group-containing unsaturated compound, as the alicyclic epoxy group, for example, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5]. 2.1.0] deci-2-yl] group and the like. The ethylenically unsaturated group is preferably derived from a (meth) acryloyl group, and suitable alicyclic epoxy group-containing unsaturated compounds are shown in the following general formulas (5a) to (5m). Examples of the compound to be used.

In formulas (5a) to (5m), R ²¹ represents a hydrogen atom or a methyl group, R ²² represents an alkylene group, R ²³ represents a divalent hydrocarbon group, and m is an integer of 1 to 10. The two R ²¹ and R ²² in the equation may be the same or different.
^{The alkylene group of R 22} in the general formulas (5a) to (5m) preferably has 1 to 10 carbon atoms. Specifically, a methylene group, an ethylene group, a propylene group, a butylene group and the like can be exemplified, but a methylene group, an ethylene group and a propylene group are preferable. The hydrocarbon group of R ²³ is preferably one having 1 to 10 carbon atoms, and examples thereof include an alkylene group and a phenylene group.

These alicyclic epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.
Of these, the compound represented by the general formula (5c) is preferable, and 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.
A known method can be used to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the resin according to [1-6-2]. For example, a carboxyl group-containing resin and an epoxy group-containing unsaturated compound are mixed with a tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride. Quaternary ammonium salts such as; in the presence of a catalyst such as pyridine or triphenylphosphine, by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours, the carboxyl group of the resin does not contain an epoxy group. Saturated compounds can be introduced.

The acid value of the carboxyl group-containing resin into which the epoxy group-containing unsaturated compound is introduced is usually 10 to 200 KOH mg / g, preferably 20 to 150 KOH mg / g, and more preferably 30 to 150 KOH mg / g.
The polystyrene-equivalent weight average molecular weight measured by GPC is usually 2000 to 100,000, preferably 4000 to 50000, and more preferably 5000 to 30000.

[1-6-4] (Meta) Acrylic Resin The (meth) acrylic resin is a polymer obtained by polymerizing (meth) acrylic acid and / or (meth) acrylic acid ester as a monomer component. To say. Preferred (meth) acrylic resins include, for example, a polymer obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate, and the following general formulas (6) and / or (7). Examples thereof include a polymer obtained by polymerizing a monomer component that requires the represented compound.

In formula (6), R ^1a and R ^2a each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.

In the formula (7), R ^1b represents an alkyl group which may have a hydrogen atom or a substituent, L ³ represents a divalent linking group or a direct bond, and X is represented by the following formula (8). Group or optionally substituted adamantyl group. L ^{3 may be combined with R 3b} or R ^4b in the following formula (8) to form a ring.

In formula (8), R ^2b , R ^3b , and R ^4b independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an amino group, or an organic group, and L ¹ and L ² represent divalent linking groups. , * Represent a bond, and L ¹ , L ^{2 and 2 or more of L 3} in the above formula (7) may be bonded to each other to form a ring.

[1-6-4a] Polymer obtained by polymerizing a monomer component containing (meth) acrylic acid and benzyl (meth) acrylate A monomer component containing (meth) acrylic acid and benzyl (meth) acrylate is polymerized. The polymer is preferably used because it has a high affinity with the pigment.

The ratio of the (meth) acrylic acid and the benzyl (meth) acrylate in the monomer component is not particularly limited, but the (meth) acrylic acid in the total monomer component is usually 10 to 90% by mass, preferably 15. -80% by mass, more preferably 20-70% by mass. The benzyl (meth) acrylate is usually 5 to 90% by mass, preferably 15 to 80% by mass, and more preferably 20 to 70% by mass in all the monomer components. If the amount of (meth) acrylic acid is too large, the surface of the coating film tends to be rough during development, and if it is too small, development may not be possible. Also, if the amount of benzyl (meth) acrylate is too large or too small, it tends to be difficult to disperse.

[1-6-4b] Polymer obtained by polymerizing a monomer component that requires a compound represented by the general formula (6) and / or (7) First, the compound of the general formula (6) will be described.
In the ether dimer represented by the general formula (6), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by ^{R 1a} and R ^{2a is not particularly limited, but for example.} , Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl and other linear or branched alkyl groups; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl Alkyl groups that have been added; alkyl groups substituted with aryl groups such as benzyl; and the like can be mentioned. Among these, a substituent of a primary or secondary carbon such as methyl, ethyl, cyclohexyl, benzyl, etc., which is difficult to be eliminated by acid or heat, is particularly preferable in terms of heat resistance. In addition, R ^1a and R ^2a may be the same type of substituents or different substituents.

Specific examples of the ether dimer include, for example, dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, and di. (N-propyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2'-[Oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2'-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (stearyl) -2,2'-[ Oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2'-[oxybis (methylene) ] Bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] Bis-2-propenoate, di (1-ethoxyethyl) -2,2'-[oxybis (methylene)] ] Bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[Oxybis (methylene)] bis-2-propenoate, di (t-butylcyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2, 2'-[oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'- [Oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2'-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (Methylene)] Bis-2-propenoate and the like can be mentioned.

Among these, dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate are preferable. These ether dimers may be used alone or in combination of two or more.

The proportion of the ether dimer in the monomer component when obtaining the acrylic resin is not particularly limited, but is usually 2 to 60% by mass, preferably 5 to 55% by mass, and further, in the total monomer component. It is preferably 5 to 50% by mass. If the amount of ether dimer is too large, it may be difficult to obtain a low molecular weight one or gelation may occur easily during polymerization, while if it is too small, transparency, heat resistance, etc. may be deteriorated. The coating film performance may be insufficient.

Subsequently, the compound of the general formula (7) will be described.
In the general formula (7), R ^1b preferably represents a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom and a methyl group.
Further, in the general formula (8), ^{the organic groups of R 2b} , R ^3b , and R ^4b are independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, and an acyl group. Examples thereof include a group, a carboxyl group, an acyloxy group and the like, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a cyclo having 3 to 18 carbon atoms. An alkenyl group, an alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom number, or an acyloxy group having 1 to 15 carbon atoms. Preferably, it is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms.

Among R ^2b , R ^3b , and R ^4b , preferred substituents are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
L ¹ and L ² are not particularly limited as long as they are divalent linking groups and L ³ is a divalent linking group or a direct bond, but at least ^{either L 1} or L ² is a linking group having 1 or more carbon atoms. Is preferable. In addition, L ¹ , L ² , and L ³ are independently bonded directly, alkylene with 1 to 15 carbon atoms, -O-, -S-, -C (= O)-, and alkenylene having 1 to 15 carbon atoms. , Phenylene, or a combination thereof.

As a preferred combination of ^{L 1} , L ² and L ^{3 , L 3} is a ring formed by direct bonding, an alkylene having 1 to 5 carbon atoms, or a ring formed by bonding with ^{R 3b} or R ^{4b , where L 1} and L ² are. It is an alkylene having 1 to 5 carbon atoms.
Moreover, as a preferable thing of the general formula (8), the compound represented by the following general formula (9) can be mentioned.

In formula (9), R ^2b , R ^3b , R ^4b , L ¹ , L ² , and * are synonymous with those in formula (8), and R ^5b and R ^6b are independently hydrogen atoms and hydroxyl groups, respectively. , Halogen atom, amino group, or organic group.
In the general formula (9), ^{the organic groups of R 5b} and R ^6b are independently, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, an acyl group, a carboxyl group, and the like. Alternatively, an acyloxy group or the like can be mentioned, preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, or a cycloalkenyl group having 3 to 18 carbon atoms. It is an alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms, an acyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon atom number, or an acyloxy group having 1 to 15 carbon atoms, more preferably carbon atoms. It is an alkyl group of 1 to 10 or a cycloalkyl group having 3 to 15 carbon atoms.

Among R ^5b and R ^6b , preferred substituents are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms.
Further, the alkyl group of ^{R 1b} , the organic groups of ^{R 2b} , R ^3b , and R ^{4b , the divalent linking groups of L 1} , L ² , and L ³ , and the adamantyl group of X each independently have a substituent. It may have, and specific examples thereof include the following substituents.

Halogen atom; hydroxyl group; nitro group; cyano group; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, t-amyl group, n-hexyl group , N-Heptyl group, n-octyl group, t-octyl group, etc., linear or branched alkyl group having 1 to 18 carbon atoms; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, etc. Cycloalkyl group of 3 to 18; linear or branched alkenyl group having 2 to 18 carbon atoms such as vinyl group, propenyl group and hexenyl group; cycloalkenyl group having 3 to 18 carbon atoms such as cyclopentenyl group and cyclohexenyl group Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, s-butoxy group, t-butoxy group, amyloxy group, t-amyloxy group, n-hexyloxy group, n-heptyloxy group , N-octyloxy group, t-octyloxy group and other linear or branched alkoxy groups having 1 to 18 carbon atoms; methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, s- A linear or branched alkylthio group having 1 to 18 carbon atoms such as a butylthio group, a t-butylthio group, an amylthio group, a t-amylthio group, an n-hexylthio group, an n-heptylthio group, an n-octylthio group and a t-octylthio group. An aryl group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xsilyl group and a mesityl group; an aralkyl group having 7 to 18 carbon atoms such as a benzyl group and a phenethyl group; a vinyloxy group, a propenyloxy group, a hexenyloxy group and the like. linear or branched alkenyloxy group having 2 to 18 carbon atoms; represented by -COR ^17; vinylthio group, propenylthio group, alkenylthio group linear or branched 2 to 18 carbon atoms such as hexenyl thio group Acyl group; carboxyl group; acyloxy group represented by ^{-OCOR 18} ; amino group represented by ^{-NR 19} R ²⁰ ; acylamino group represented by ^{-NHCOR 21} ; carbamate group represented by ^{-NHCOOR 22; -CONR 23} Carbamoyl group represented by R ²⁴ ; Carboxyl ester group represented by ^{-COOR 25} ; Sulfamoyl group represented by _{-SO 3} NR ²⁶ R ²⁷ ; Sulphonic acid ester group represented by _{-SO 3} R ^28; 2-thienyl group, 2-pyridyl group, frill group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group , Saturated or unsaturated heterocyclic groups such as morpholino group, pyrrolidinyl group, tetrahydrothiophene dioxide group; trialkylsilyl group such as trimethylsilyl group and the like.

In addition, R ^{17 to} R ²⁸ are a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or Indicates an aralkyl group which may have a substituent.
Further, the positional relationship of the above-mentioned substituents is not particularly limited, and when having a plurality of substituents, they may be of the same type or different.

Specific examples of the compound represented by the general formula (7) include the following.

The proportion of the general formula (7) in the monomer components constituting the polymer of [1-6-4b] according to the present invention is not particularly limited, but is usually 0.5 to 60 mass by mass in all the monomer components. %, preferably 1 to 55% by mass, more preferably 5 to 50% by mass. If it is too large, the dispersion stability of the dispersion liquid may decrease when it is used as a dispersant, while if it is too small, the suitability for soil contamination may decrease.

The (meth) acrylic resin of [1-6-4] in the present invention preferably has an acid group, including the polymers described in [1-6-4a] and [1-6-4b]. .. A colored resin composition obtained by having an acid group can be cured by a cross-linking reaction (hereinafter abbreviated as acid-epoxy curing) in which an acid group reacts with an epoxy group to form an ester bond. The material or the uncured portion can be a composition that can be visualized with an alkaline developing solution. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic acid anhydride group. These acid groups may be only one kind or two or more kinds.

To introduce an acid group into a (meth) acrylic resin, for example, a monomer having an acid group and / or a "monomer capable of imparting an acid group after polymerization" (hereinafter, "monomer for introducing an acid group"). (Sometimes referred to as) may be used as a monomer component. When a "monomer capable of imparting an acid group after polymerization" is used as a monomer component, a treatment for imparting an acid group as described later is required after the polymerization.

Examples of the monomer having an acid group include a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; maleic anhydride, itaconic anhydride and the like. Monomers having a carboxylic acid anhydride group and the like can be mentioned, and among these, (meth) acrylic acid is particularly preferable.
Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; a monomer having an epoxy group such as glycidyl (meth) acrylate; and 2-isocyanate ethyl (meth). ) Monomers having an isocyanate group such as acrylate can be mentioned.

The monomer for introducing these acid groups may be only one type or two or more types.
When the monomer component for obtaining the (meth) acrylic resin also contains the monomer for introducing the acid group, the content ratio thereof is not particularly limited, but usually 5 out of all the monomer components. ~ 70% by mass, preferably 10-60% by mass.

Further, the [1-6-4] (meth) acrylic resin may have a radically polymerizable double bond.
In order to introduce a radically polymerizable double bond into the (meth) acrylic resin, for example, "a monomer capable of imparting a radically polymerizable double bond after polymerization" (hereinafter, "for introducing a radically polymerizable double bond"). (Sometimes referred to as “monomer”) may be polymerized as a monomer component, and then a treatment for imparting a radically polymerizable double bond as described later may be performed.

Examples of the monomer capable of imparting a radically polymerizable double bond after polymerization include a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; and having a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride. Monomers; Monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether and the like can be mentioned. The monomer for introducing these radically polymerizable double bonds may be only one kind or two or more kinds.

When the monomer component for obtaining the (meth) acrylic resin of [1-6-4] also contains a monomer for introducing the radically polymerizable double bond, the content ratio thereof is particularly limited. However, it is usually 5 to 70% by mass, preferably 10 to 60% by mass, based on all the monomer components.
When the (meth) acrylic resin of the present invention is a polymer containing the compound of the general formula (6) as an essential monomer component described in the section [1-6-4a], it has an epoxy group. Is preferable.

In order to introduce an epoxy group, for example, a monomer having an epoxy group (hereinafter, also referred to as "monomer for introducing an epoxy group") may be polymerized as a monomer component.
Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether and the like. The monomer for introducing these epoxy groups may be only one kind or two or more kinds.

When the monomer component for obtaining the (meth) acrylic resin of [1-6-4] also contains the monomer for introducing the epoxy group, the content ratio is not particularly limited, but is usually used. Is preferably 5 to 70% by mass, preferably 10 to 60% by mass, based on all the monomer components.
The monomer component for obtaining the (meth) acrylic resin of [1-6-4] contains, if necessary, other copolymerizable monomer in addition to the above-mentioned essential monomer component. You may.

Other copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (Meta) acrylic acid esters such as; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadiene such as butadiene and isoprene or Substituted butadiene compounds; ethylene such as ethylene, propylene, vinyl chloride and acrylic nitrile, or substituted ethylene compounds; vinyl esters such as vinyl acetate and the like can be mentioned.

Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable because they have good transparency and do not easily impair heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.
Further, particularly when a part or all of the (meth) acrylic resin is used as a dispersant as described later, it is preferable to use benzyl (meth) acrylate, and the content thereof is usually all monomer components. It is preferably 1 to 70% by mass, preferably 5 to 60% by mass.

When the monomer component for obtaining the (meth) acrylic resin also contains the other copolymerizable monomer, the content ratio is not particularly limited, but is preferably 95% by mass or less, preferably 85% by mass or less. Is more preferable.
Next, the method (polymerization method) for producing the (meth) acrylic resin of [1-6-4] will be described.

The polymerization method of the monomer component is not particularly limited, and various conventionally known methods can be adopted, but the solution polymerization method is particularly preferable. The polymerization temperature and the polymerization concentration (polymerization concentration = [total mass of monomer components / (total mass of monomer components + solvent mass)] × 100) are the types and ratios of the monomer components used. It depends on the molecular weight of the target polymer. The polymerization temperature is preferably 40 to 150 ° C, more preferably 60 to 130 ° C. The polymerization concentration is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.

When a solvent is used at the time of polymerization, the solvent used in a normal radical polymerization reaction may be used. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform; dimethyl sulfoxide and the like Can be mentioned. These solvents may be used alone or in combination of two or more.

When polymerizing the monomer component, a polymerization initiator may be used, if necessary. The polymerization initiator is not particularly limited, but for example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-amyl. Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexane) Carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) and other azo compounds can be mentioned. These polymerization initiators may be used alone or in combination of two or more.

The amount of the initiator used may be appropriately set according to the combination of the monomers used, the reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but the weight average molecular weight can be adjusted without gelation. It is usually 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, based on all the monomer components, in that thousands to tens of thousands of polymers can be obtained.
Further, a chain transfer agent may be added for adjusting the molecular weight. Examples of the chain transfer agent include mercaptan-based chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid, and methyl mercaptoacetate, α-methylstyrene dimer, and the like, but preferably, the chain transfer effect is high and the residual monomer is used. N-dodecyl mercaptan and mercaptoacetic acid, which can be reduced and easily obtained, are preferable. When a chain transfer agent is used, the amount used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but does not gel. It is usually 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, based on all the monomer components, in that a polymer having a weight average molecular weight of several thousand to several tens of thousands can be obtained.

When the compound of the general formula (6) is used as an essential monomer component, it is considered that the cyclization reaction of the ether dimer proceeds at the same time in the polymerization reaction, but the ring of the ether dimer at this time. The conversion rate does not necessarily have to be 100 mol%.
When an acid group is introduced by using the above-mentioned monomer capable of imparting an acid group as a monomer component when obtaining the acrylic resin, it is necessary to perform a treatment for imparting the acid group after the polymerization. .. The treatment varies depending on the type of monomer used, but when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used, for example, succinic anhydride, tetrahydrophthalic anhydride, and maleic anhydride are used. An acid anhydride such as a substance may be added. When a monomer having an epoxy group such as glycidyl (meth) acrylate is used, a compound having an amino group and an acid group such as N-methylaminobenzoic acid and N-methylaminophenol is added, or first ( An acid such as meta) acrylic acid may be added, and an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, or maleic anhydride may be added to the resulting hydroxyl group. When a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate is used, for example, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

When the (meth) acrylic resin of [1-6-4] is obtained, a radically polymerizable double bond is formed by using a monomer capable of imparting the above-mentioned radically polymerizable double bond as a monomer component. When introducing, it is necessary to carry out a treatment for imparting a radically polymerizable double bond after the polymerization.
The treatment varies depending on the type of monomer used, but for example, when a monomer having a carboxyl group such as (meth) acrylic acid or itaconic acid is used, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl ( A compound having an epoxy group and a radically polymerizable double bond, such as a meta) acrylate or an o- (or m- or p-) vinylbenzyl glycidyl ether, may be added. When a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radically polymerizable double bond such as 2-hydroxyethyl (meth) acrylate is added. Just do it. When a monomer having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether is used, (meth). ) A compound having an acid group such as acrylic acid and a radically polymerizable double bond may be added.

The weight average molecular weight of the (meth) acrylic resin of [1-6-4] is not particularly limited, but the polystyrene-equivalent weight average molecular weight measured by GPC is preferably 2000 to 200,000, more preferably 4000 to 100,000. Is. If the weight average molecular weight exceeds 200,000, the viscosity may become too high and it may be difficult to form a coating film, while if it is less than 2000, it tends to be difficult to develop sufficient heat resistance.

When the (meth) acrylic resin has an acid group, the preferable acid value is 30 to 500 mgKOH / g, more preferably 50 to 400 mgKOH / g. If the acid value is less than 30 mgKOH / g, it may be difficult to apply it to alkaline development, and if it exceeds 500 mgKOH / g, the viscosity tends to be too high and it tends to be difficult to form a coating film.
Among the (meth) acrylic resin components, the polymer containing the compound represented by the general formula (6) as an essential monomer component is a compound known per se, for example, Japanese Patent Application Laid-Open No. 2004. Examples of the compounds described in JP-A-300203 and JP-A-2004-300204 can be mentioned.

[1-6-5] Epoxy (meth) acrylate resin having a carboxyl group The epoxy (meth) acrylate resin is an α, β-unsaturated monocarboxylic acid in the epoxy resin or α, β-non having a carboxyl group in the ester moiety. It is synthesized by adding a saturated monocarboxylic acid ester and further reacting with a polybasic acid anhydride. Such a reaction product has substantially no epoxy group in terms of chemical structure and is not limited to "(meth) acrylate", but an epoxy resin is a raw material and "(meth) acrylate" is used. Since it is a typical example, it is named in this way according to convention.

As the raw material epoxy resin, for example, bisphenol A type epoxy resin (for example, "Epicoat (registered trademark, the same applies hereinafter) 828", "Epicoat 1001", "Epicoat 1002", "Epicoat 1004", etc. manufactured by Mitsubishi Chemical Corporation) , An epoxy resin obtained by the reaction of an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (for example, "NER-1302" (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), a bisphenol F type resin ( For example, "Epicoat 807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Mitsubishi Chemical Corporation), an epoxy resin obtained by the reaction of an alcoholic hydroxyl group of a bisphenol F type epoxy resin with epichlorohydrin. (For example, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), Phenol novolac type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Co., Ltd.), ( o, m, p-) Cresol novolac type epoxy resin (for example, "EOCN (registered trademark, the same shall apply hereinafter) -102S", "EOCN-1020", "EOCN-104S") manufactured by Nippon Kayakusha Co., Ltd., triglycidyl Isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Corporation), trisphenol methane type epoxy resin (for example, "EPPN (registered trademark) -501", "EPN-502" manufactured by Nippon Kayaku Co., Ltd., "EPPN-503"), fluorene epoxy resin (for example, cardo epoxy resin "ESF-300" manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin ("Selokiside (registered trademark, same below) manufactured by Daicel Chemical Industry Co., Ltd." 2021P ”,“ Celoxide EHPE ”), Dicyclopentadiene type epoxy resin obtained by glycidylating a phenol resin produced by the reaction of dicyclopentadiene and phenol (for example,“ XD-1000 ”manufactured by Nippon Kayaku Co., Ltd. "EXA-7200" manufactured by Nippon Kayakusha, "NC-3000", "NC-7300" manufactured by Nippon Kayakusha), and epoxy resin represented by the following structural formula (see Japanese Patent Application Laid-Open No. 4-355450), etc. Can be preferably used.

These may be used alone or in combination of two or more.
Another example of the epoxy resin is a copolymerized epoxy resin. Examples of the copolymerized epoxy resin include glycidyl (meth) acrylate, (meth) acryloylmethylcyclohexene oxide, vinylcyclohexene oxide and the like (hereinafter referred to as “the first component of the copolymerized epoxy resin”) and 1 other than these. Functional ethylenically unsaturated group-containing compounds (hereinafter referred to as "second component of copolymerized epoxy resin"), for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxy Ethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methylstyrene, glycerin mono (meth) acrylate, the following general formula (10) ) Is one or more selected from the compounds represented by), and a copolymer obtained by reacting with one or more thereof can be mentioned.

In formula (10), R ⁶¹ represents a hydrogen atom or an ethyl group, R ⁶² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and r is an integer of 2 to 10. Examples of the compound of the general formula (10) include polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and tetraethylene glycol mono (meth) acrylate; Examples thereof include alkoxypolyethylene glycol (meth) acrylate such as meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, and methoxytetraethylene glycol mono (meth) acrylate.

The molecular weight of the copolymerized epoxy resin is preferably about 1000 to 200,000. The amount of the first component of the copolymerized epoxy resin used is preferably 10% by mass or more, particularly preferably 20% by mass or more, preferably 70% by mass or more, based on the second component of the copolymerized epoxy resin. It is 0% by mass or less, particularly preferably 50% by mass or less.
Specific examples of such a copolymerized epoxy resin include "CP-15", "CP-30", "CP-50", "CP-20SA", and "CP-510SA" manufactured by NOF CORPORATION. Examples thereof include "CP-50S", "CP-50M", and "CP-20MA".

The molecular weight of the raw material epoxy resin is usually in the range of 200,000 to 200,000, preferably 300 to 100,000 as the polystyrene-equivalent weight average molecular weight measured by GPC. If the weight average molecular weight is less than the above range, a problem in film forming property often occurs, and conversely, if the resin exceeds the above range, gelation is likely to occur during the addition reaction of α, β-unsaturated monocarboxylic acid. May be difficult.

Examples of the α, β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, and methacrylic acid, preferably acrylic acid and methacrylic acid, and acrylic acid is particularly reactive. Therefore, it is preferable.
Examples of the α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion include -2-succinoyloxyethyl acrylate, -2-maleinoyloxyethyl acrylate, and -2-phthaloyloxyethyl acrylate. -2-Hexahydrophthaloyloxyethyl acrylate, -2-succinoyloxyethyl methacrylate, -2-maleinoyloxyethyl methacrylate, -2-phthaloyloxyethyl methacrylate, -2-hexahydrophthalomethacrylate Examples thereof include yloxyethyl, -2-succinoyloxyethyl crotonate, and the like, preferably -2-maleinoyloxyethyl acrylate and -2-phthaloyloxyethyl acrylate, and particularly -2-malei acrylate. Noyloxyethyl is preferred. These may be used alone or in combination of two or more.

The addition reaction of α, β-unsaturated monocarboxylic acid or its ester with an epoxy resin can be carried out by using a known method, for example, by reacting at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. can do. As the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine; and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride and dodecyltrimethylammonium chloride can be used.

The amount of α, β-unsaturated monocarboxylic acid or its ester used is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1.1, with respect to 1 equivalent of the epoxy group of the raw material epoxy resin. It is in the range of equivalents. If the amount of α, β-unsaturated monocarboxylic acid or its ester used is small, the amount of unsaturated group introduced is insufficient, and the subsequent reaction with the polybasic acid anhydride is also insufficient. It is also not advantageous that a large amount of epoxy groups remain. On the other hand, when the amount used is large, α, β-unsaturated monocarboxylic acid or an ester thereof remains as an unreacted product. In either case, the curing characteristics tend to deteriorate.

Examples of the polybasic acid anhydride to be further added to the epoxy resin to which α, β-unsaturated carboxylic acid or an ester thereof is added include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. Hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, methyl hexahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, chlorendic anhydride, methyl tetrahydrophthalic anhydride, biphenyl tetra Examples thereof include carboxylic acid dianhydride, preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and the like. Biphenyltetracarboxylic dianhydride, particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. These may be used alone or in combination of two or more.

A known method can also be used for the addition reaction of polybasic acid anhydride, and it can be carried out by continuing the reaction under the same conditions as the addition reaction of α, β-unsaturated carboxylic acid or an ester thereof.
The amount of the polybasic acid anhydride added is preferably such that the acid value of the produced epoxy acrylate resin is in the range of 10 to 150 mgKOH / g, and more preferably in the range of 20 to 140 mgKOH / g. If the acid value of the resin is too small, the alkali developability is poor, and if the acid value of the resin is too large, the curing performance tends to be inferior.

Other epoxy acrylate resins having a carboxyl group include, for example, naphthalene-containing resins described in Japanese Patent Application Laid-Open No. 6-49174; Japanese Patent Application Laid-Open No. 2003-89716, Japanese Patent Application Laid-Open No. 2003-165830, Japan. Fluorene-containing resins described in Japanese Patent Application Laid-Open No. 2005-325331 and Japanese Patent Application Laid-Open No. 2001-354735; Japanese Patent Application Laid-Open No. 2005-126674, Japanese Patent Application Laid-Open No. 2005-55514, Japanese Patent Application Laid-Open No. 2004- Examples of the resin described in Japanese Patent Application Laid-Open No. 295084 can be mentioned.

Further, a commercially available epoxy acrylate resin having a carboxyl group can also be used, and examples of the commercially available product include "ACA-200M" manufactured by Daicel Corporation.
As the binder resin, for example, an acrylic binder described in Japanese Patent Application Laid-Open No. 2005-154708 can also be used.
Among the various binder resins described above, particularly preferable is the copolymer of the "epoxy group-containing (meth) acrylate of [1-6-1] and another radically polymerizable monomer, which has the same weight. A resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group of the coalescence, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups generated by the addition reaction. " Is.

As the binder resin in the present invention, one of the above-mentioned various binder resins may be used alone, or two or more of them may be used in combination.
The various binder resins described above contribute to dispersion stability due to the synergistic effect of the combined use with the above-mentioned dispersant and the like, and as a result, the amount of the dispersant added can be reduced, so that the developability is improved. Specifically, for example, it is preferable because it has an effect that undissolved matter does not remain in the non-image portion on the substrate and has excellent adhesion to the substrate and can form high-density color pixels.

Specifically, a part of the binder resin is used in the dispersion treatment step described later together with the above-mentioned dispersant and dispersion aid. At this time, the binder resin is preferably used in an amount of about 5 to 200% by mass, more preferably about 10 to 100% by mass, based on the total amount of the pigment in the pigment dispersion liquid.
As described above, as the binder resin used in the dispersion treatment step, the above-mentioned various resins can be used, but the (meth) acrylic resin of [1-6-4] is particularly preferable, and among them, the above-mentioned general formula is used. A polymer obtained by polymerizing a monomer component that requires the compound represented by (6) is most preferable.

When used in a dispersion treatment step together with a dispersant, the acid value of the binder resin is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, most preferably 50 mgKOH / g or more, and preferably 500 mgKOH / g or less, preferably 300 mgKOH or less. It is more preferably / g or less, and most preferably 200 mgKOH / g or less. If the acid value is too high, the viscosity tends to be high and synthesis tends to be difficult, and if it is too low, it may be difficult to apply it to alkaline development.

When used in a dispersion treatment step together with a dispersant, the polystyrene-equivalent weight average molecular weight of the binder resin measured by GPC is preferably 1000 or more, more preferably 1500 or more, most preferably 2000 or more, and 200,000 or less. Is preferable, 50,000 or less is more preferable, and 30,000 or less is most preferable. If the molecular weight is too large, it tends to be difficult to apply to alkaline development, and if the molecular weight is too small, the dispersion stability may decrease.

In the colored resin composition of the present invention, the content ratio of the binder resin is usually 0.1% by mass or more, preferably 1% by mass or more, and usually 80% by mass or less, preferably 60% by mass, based on the total solid content. % Or less. By setting the value to the lower limit or more, a strong film can be obtained, and the adhesion to the substrate tends to be excellent. Further, when the value is not more than the upper limit value, the permeability of the developing solution to the exposed portion is low, and there is a tendency that deterioration of the surface smoothness and sensitivity of the pixel can be suppressed.

[1-7] (E) Photopolymerization Initiator The colored resin composition of the present invention contains (E) a photopolymerization initiator. By containing (E) a photopolymerization initiator, film curability by photopolymerization can be obtained.
(E) The photopolymerization initiator is usually used as a mixture (photopolymerization initiator) with an accelerator and an additive such as a sensitizing dye added as needed. The photopolymerization initiation system is a component having a function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

Examples of the photopolymerization initiator that can be used in the colored resin composition according to the first aspect of the present invention are described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Laid-Open No. 61-151197. Metallocene compounds containing titanosen compounds, hexaarylbiimidazole derivatives described in JP-A-10-39503, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N- Radical activators such as aryl-α-amino acid salts and N-aryl-α-amino acid esters, α-aminoalkylphenone-based compounds, oxime ester-based initiators described in Japanese Patent Application Laid-Open No. 2000-80068, etc. Can be mentioned.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4) Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;

2-Trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5-[β- (2'-benzofuryl) vinyl] -1,3,4-oxa Diazole, 2-trichloromethyl-5-[β- (2'-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 monofuryl-1,3 Halomethylated oxadiazole derivatives such as 4-oxadiazole;
2- (2'-Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2-( 2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5- Imidazole derivatives such as diphenylimidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butyl anthraquinone, 1-chloroanthraquinone;

Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p) -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 1,1,1 -Acetophenone derivatives such as trichloromethyl- (p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;

Ethyl benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as Benz anthrone;
Dicyclopentadienyl-Ti-dichloride, dicyclopentagenyl-Ti-bis-phenyl, dicyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, Dicyclopentagenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentagenyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, Dicyclopentagenyl-Ti-2,6-dipuroolofeni-1-yl, dicyclopentagenyl-Ti-2,4-difluoropheni-1-yl, dimethylcyclopentagenyl-Ti-bis-2,3 , 4,5,6-pentafluoropheni-1-yl, dimethylcyclopentagenyl-Ti-bis-2,6-difluoropheni-1-yl, dicyclopentagenyl-Ti-2,6-difluoro- Titanocene derivatives such as 3- (pill-1-yl) -pheni-1-yl;

2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) butane-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Etc. α-aminoalkylphenyl compounds;
1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) esterone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-3 Oxime ester compounds such as -1- (O-acetyloxime).

Among these, an oxime ester-based compound is preferable from the viewpoint of sensitivity.

Examples of the accelerator constituting the photopolymerization initiation system component include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, and 2-mercaptobenzoxazole. A mercapto compound having a heterocycle such as 2-mercaptobenzimidazole or an aliphatic polyfunctional mercapto compound is used.

As these photopolymerization initiators and accelerators, one type may be used alone, or two or more types may be mixed and used.
Specific examples of the photopolymerization initiation system component include the dialkylacetophenone system described on pages 16 to 26 of "Fine Chemical" (March 1, 1991, vol.20, No. 4). In addition to benzoin, thioxanthone derivative, etc., hexaarylbiimidazole type, S-trihalomethyltriazine type, Japan, which are described in Japanese Patent Application Laid-Open No. 58-403023, Japanese Patent Publication No. 45-373777, etc. A combination of titanosen and an addition-polymerizable ethylenic saturated double bond-containing compound having a xanthene dye, an amino group or a urethane group, which is described in JP-A-4-221958, JP-A-4-219756, etc. The system, etc. can be mentioned.

The blending ratio of the photopolymerization initiator is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1% by mass or more, based on the total solid content of the colored resin composition of the present invention. Is 1.5% by mass or more, 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less. When it is set to the lower limit value or more, the sensitivity to the exposed light tends to be sufficiently secured, and when it is set to the upper limit value or less, the deterioration of the solubility of the unexposed portion in the developing solution is suppressed and the development failure is prevented. Tend to be able to.

On the other hand, the colored resin composition according to the third aspect of the present invention is characterized in that the (E) photopolymerization initiator contains an oxime ester compound.
When the known zinc halide phthalocyanine pigments described in Patent Documents 1 to 11 are used, the photopolymerization initiator can be appropriately selected and used depending on the use of the colored resin composition and the like, and biimidazole and the like. It can also be sufficiently photocured by using α-aminoalkylphenone or the like.
However, when a halogenated zinc phthalocyanine pigment having an average number of hydrogen atoms contained in one molecule of 3 or more is used, the pigmentation becomes highly colored due to the change in the transmission spectrum due to the large amount of hydrogen atoms, but the wavelength of the coating film is low. As the absorption of the region becomes stronger, the exposure amount is attenuated. Therefore, when biimidazole, α-aminoalkylphenone, or the like is used, photocuring cannot be sufficiently performed, and it becomes difficult to form a fine pattern. Tend. On the other hand, by using an oxime ester-based compound having a larger absorption in the low wavelength region as the photopolymerization initiator, it is considered that a fine pattern can be formed because sufficient photocuring can be performed.

Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in their structure, so they are highly sensitive to small amounts and stable to thermal reactions. Therefore, it is possible to design a highly sensitive photosensitive resin composition with a small amount. In particular, an oxime ester-based compound having a carbazole ring, which may have a substituent, is preferable from the viewpoint of light absorption of the exposure light source for i-ray (365 nm).

Examples of the oxime ester compound include compounds represented by the following general formula (I-1).

In the above formula (I-1), R ^21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ^21b represents any substituent, including aromatic or heteroaromatic rings.
R ^22a represents an alkanoyl group which may have a substituent or an allyloyl group which may have a substituent.

The ^{number of carbon atoms of the alkyl group in R 21a} is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity to exposure, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably. It is 10 or less, more preferably 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, a propyl group and the like.
Substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl. Examples thereof include a group or an N-acetyl-N-acetoxyamino group, which is preferably unsubstituted from the viewpoint of easiness of synthesis.

Examples of the aromatic ring group in R ^21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, further preferably 12 or less, and particularly preferably 8 or less.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a frill group and the like. Among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable, from the viewpoint of developability.
The substituents that the aromatic ring group may have include a hydroxyl group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a carboxyl group, a halogen atom, and an amino group. , Amid group, alkyl group and the like. From the viewpoint of developability, a hydroxyl group and a carboxyl group are preferable, and a carboxyl group is more preferable. Further, examples of the substituent in the alkyl group which may have a substituent and the alkoxy group which may have a substituent include a hydroxyl group, an alkoxy group and a halogen atom.
Among these, from the viewpoint of developability, R ^21a is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and further preferably a methyl group. ..

Further, R ^21b is an arbitrary substituent containing an aromatic ring or a heteroaromatic ring, but has a carbazolyl group or a substituent which may have a substituent from the viewpoint of solubility in a solvent and sensitivity to exposure. Preferred are diphenylsulfide groups which may have a thioxanthonyl group or a substituent which may have a substituent. Among these, a carbazolyl group which may have a substituent is preferable from the viewpoint of light absorption of the exposure light source for i-line (365 nm).

The carbon number of the alkanoyl group in R ^22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably. It is 10 or less, more preferably 5 or less. Specific examples of the alkanoyl group include an acetyl group, an ethyloyl group, a propanoyl group, a butanoyl group and the like.
Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and the like, and from the viewpoint of easiness of synthesis, the substituent should be unsubstituted. Is preferable.

The ^{number of carbon atoms of the allylloyl group in R 22a} is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably. It is 10 or less. Specific examples of the allylloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the allylloyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group and the like, and from the viewpoint of easiness of synthesis, it is preferably unsubstituted. ..

Among the compounds represented by the general formula (I-1), the compounds represented by the following general formula (I-2) can be mentioned from the viewpoint of light absorption of the exposure light source for i-line (365 nm).

In the above formula (I-2), R ^21a and R ^22a are synonymous with the above general formula (I-1).
R ^23a represents an alkyl group which may have a substituent.
R ^24a represents an alkyl group which may have a substituent, an aryloyl group which may have a substituent, a heteroarylloyl group which may have a substituent, or a nitro group.
The benzene ring constituting the carbazole ring may be further condensed by an aromatic ring to form a polycyclic aromatic ring.

The ^{number of carbon atoms of the alkyl group in R 23a} is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further. It is preferably 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group and the like.
Examples of the substituent that the alkyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group and the like, and from the viewpoint of easiness of synthesis, there is no substitution. Is preferable.

The carbon number of the allylloyl group in R ^23a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less. It is preferably 10 or less, more preferably 9 or less. Specific examples of the allylloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the allylloyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group and the like, and from the viewpoint of easiness of synthesis, an ethyl group is used. Is preferable.

The ^{number of carbon atoms of the heteroallyloyl group in R 23a} is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less. , More preferably 10 or less, still more preferably 9 or less. Specific examples of the heteroaryl group include a fluorobenzoyl group, a chlorobenzoyl group, a bromobenzoyl group, a fluoronaphthyl group, a chloronaphthyl group, a bromonaphthyl group and the like.
Examples of the substituent that the heteroarylloyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group and the like, and there is no substituent from the viewpoint of easiness of synthesis. It is preferably a substitution.
Among these, R ^23a is preferably an alkyl group, more preferably an ethyl group, from the viewpoint of solubility in a solvent and easiness of synthesis.

The benzene ring constituting the carbazole ring may be further condensed by an aromatic ring to form a polycyclic aromatic ring.

Commercially available products of such oxime ester compounds include OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304, TR-PBG-314 manufactured by Changzhou Power Electronics Co., Ltd., and NCI-831 manufactured by ADEKA Corporation. is there.

Specific examples of the oxime ester-based compound include, but are not limited to, the compounds exemplified below.

The colored resin composition according to the third aspect of the present invention contains an oxime ester-based compound as the (E) photopolymerization initiator, but may contain a photopolymerization initiator other than the oxime ester-based compound. For example, a metallocene compound containing a titanosen compound described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Laid-Open No. 61-151197, or a hexaarylbiimidazole derivative described in Japanese Patent Application Laid-Open No. 10-39503. , Halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, radical activators such as N-aryl-α-amino acid esters, α-amino Examples thereof include alkylphenone compounds.

Examples of the accelerator constituting the photopolymerization initiation system component include N, N-dialkylaminobenzoic acid alkyl ester such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, and 2-mercaptobenzo. A mercapto compound having a heterocycle such as oxazole or 2-mercaptobenzimidazole, an aliphatic polyfunctional mercapto compound or the like is used.

As these photopolymerization initiators and accelerators, one type may be used alone, or two or more types may be mixed and used.

In the colored resin composition according to the third aspect of the present invention, the blending ratio of the photopolymerization initiator is usually 0.1% by mass or more, preferably 0.% by mass, based on the total solid content of the colored resin composition of the present invention. 5% by mass or more, more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, particularly preferably 2.0% by mass or more, usually 40% by mass or less, preferably 30% by mass or less. , More preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less. When it is set to the lower limit value or more, the sensitivity to the exposed light tends to be sufficiently secured, and when it is set to the upper limit value or less, the deterioration of the solubility of the unexposed portion in the developing solution is suppressed and the development failure is prevented. Tend to be able to.

On the other hand, the photopolymerization initiation system component may be blended with a sensitizing dye according to the wavelength of the image exposure light source, if necessary, for the purpose of increasing the sensitivity. Examples of these sensitizing dyes include xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958, Japanese Patent Application Laid-Open No. 4-219756, Japanese Patent Application Laid-Open No. 3-239703, and Japanese Patent Application Laid-Open No. 5-289335. A coumarin dye having a heterocycle described in Japanese Patent Application Laid-Open No. 3-239703, a 3-ketocoumarin compound described in Japanese Patent Application Laid-Open No. 5-289335, and a Japanese Patent Application Laid-Open No. 6-19240. Pyromethene dyes, etc., Japanese Patent Application Laid-Open No. 47-2528, Japanese Patent Application Laid-Open No. 54-155292, Japanese Patent Application Laid-Open No. 45-373777, Japanese Patent Application Laid-Open No. 48-84183, Japan Japanese Patent Application Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88805, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69 The dialkylaminobenzene skeletons described in Japanese Patent Application Laid-Open No. 57-168808, Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, and Japanese Patent Application Laid-Open No. 4-288818. Examples include pigments and the like.

Of these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone. , 3,4-Diaminobenzophenone and other benzophenone compounds; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1, 3,4-Thiazazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, ( It is a p-dialkylaminophenyl group-containing compound such as p-diethylaminophenyl) pyrimidine. The most preferred of these is 4,4'-dialkylaminobenzophenone.

The sensitizing dye may also be used alone or in combination of two or more.
The blending ratio of the sensitizing dye in the colored resin composition according to the present invention is usually 0% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% by mass or more, based on the total solid content of the colored resin composition. It is in the range of mass% or more, usually 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less.

[1-8] Other solids
The colored resin composition of the present invention may further contain a solid content other than the above components, if necessary. Such components include photopolymerizable monomers, organic carboxylic acids, organic carboxylic acid anhydrides, surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protectants, adhesion improvers, development improvers, etc. Examples include dyes.

[1-8-1] Photopolymerizable Monomer The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular weight compound, but is an addition-polymerizable compound having at least one ethylenic double bond (hereinafter, (Refered to be "ethyleney compound") is preferable. The ethylenic compound is a compound having an ethylenic double bond such that when the colored resin composition of the present invention is irradiated with active light, it is addition-polymerized and cured by the action of the photopolymerization initiation system described later. .. The monomer in the present invention means a concept opposite to a so-called polymer substance, and means a concept containing a dimer, a trimer, and an oligomer in addition to a monomer in a narrow sense.

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

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethanetriacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. , Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate and other acrylic acid esters. Further, the acrylic acid moiety of these acrylates is replaced with a methacrylic acid ester instead of a methacrylic acid moiety, an itaconic acid ester substituted with an itaconic acid moiety, a crotonic acid ester substituted with a crotonic acid moiety, or a maleic acid substituted with a maleic acid moiety. Esters and the like can be mentioned.

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

Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate and isophorone diisocyanate. Alicyclic diisocyanate; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3- Examples thereof include a reaction product with a (meth) acryloyl group-containing hydroxy compound such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane.

In addition, as the ethylenic compound used in the present invention, for example, acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinylphthalate are also useful.
Further, the ethylenic compound may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is formed by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The provided polyfunctional monomer is preferable, and the aliphatic polyhydroxy compound in this ester is pentaerythritol and / or dipentaerythritol.

One of these monomers may be used alone, but since it is difficult to use a single compound in production, two or more of these monomers may be mixed and used. Further, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as the monomer.
The acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the developing and dissolving characteristics deteriorate, and if it is too high, the production and handling become difficult, the photopolymerization performance deteriorates, and the curability such as the surface smoothness of the pixel tends to be poor. Therefore, when two or more kinds of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid group as the whole polyfunctional monomer should be adjusted so as to fall within the above range. Is preferable.

In the present invention, the polyfunctional monomer having a more preferable acid group is mainly a succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, or dipentaerythritol pentaacrylate, which is commercially available as TO1382 manufactured by Toa Synthetic Co., Ltd. It is a mixture as an ingredient. Other polyfunctional monomers of this polyfunctional monomer can also be used in combination. Further, those described in paragraphs [0056] and [0057] of Japanese Patent Application Laid-Open No. 2013-140346 can also be used.

Further, in the present invention, from the viewpoint of improving the chemical resistance of the pixel and the linearity of the edge of the pixel, it is preferable to use the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2013-195971. From the viewpoint of achieving both the sensitivity of the coating film and the shortening of the developing time, it is preferable to use the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2013-195974.

The content ratio of these photopolymerizable monomers is usually 0% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass, based on the total solid content of the colored resin composition of the present invention. % Or more, usually 80% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, still more preferably 30% by mass or less, particularly preferably 20% by mass or less. Is. The ratio of (A) pigment to 100 parts by mass is usually 0 parts by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, particularly preferably 20 parts by mass or more, and usually 200 parts by mass or less. It is preferably 100 parts by mass or less, more preferably 80 parts by mass or less.

[1-8-2] Organic Carboxylic Acid, Organic Carboxylic Acid Anhydrous The colored resin composition of the present invention may contain an organic carboxylic acid and / or an organic carboxylic acid anhydride having a molecular weight of 1000 or less.
Specific examples of the organic carboxylic acid compound include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid and methacrylic acid, oxalic acid, malonic acid, succinic acid and glutaric acid. , Adipic acid, Pimeric acid, Cyclohexanedicarboxylic acid, Cyclohexendicarboxylic acid, Itaconic acid, Citraconic acid, Maleic acid, Dicarboxylic acid such as fumaric acid, Tricarboxylic acid such as tricarbaryl acid and Aconitic acid. Examples of aromatic carboxylic acids include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and carboxylic acids in which a carboxyl group is bonded from a phenyl group via a carbon bond. Among these, those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, specifically, maleic acid, malonic acid, succinic acid, and itaconic acid are preferable.

Examples of the organic carboxylic acid anhydride include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides, and specific examples thereof include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, and succinic anhydride. Alipid carboxylic acids such as maleic anhydride, citraconic anhydride, itaconic anhydride, glutacon anhydride, 1,2-cyclohexenedicarboxylic acid anhydride, n-octadecylsuccinic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride Things can be mentioned. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride and the like. Among these, those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, specifically maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferable.

The amount of these organic carboxylic acids and / or organic carboxylic acid anhydrides added is usually 0.01% by mass or more, preferably 0.03% by mass or more, and more preferably 0.05% by mass or more in the total solid content. Yes, it is in the range of 10% by mass or less, preferably 5% by mass or less, and more preferably 3% by mass or less.
By adding these organic carboxylic acids and / or organic carboxylic acid anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the residual undissolved material of the colored resin composition while maintaining high pattern adhesion. ..

[1-8-3] Surfactants Various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used, but they may adversely affect various properties. It is preferable to use a nonionic surfactant because of its low value. The concentration range of the surfactant is usually 0.001% by mass or more, preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and most preferably 0.03% by mass with respect to the total solid content. As described above, the range of usually 10% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, and most preferably 0.3% by mass or less is used.

[1-8-4] Thermal Polymerization Inhibitor As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used. .. The blending amount of the thermal polymerization inhibitor is preferably in the range of 3% by mass or less with respect to the total solid content of the composition.

[1-8-5] Plasticizer Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. Is used. The blending amount of these plasticizers is usually preferably in the range of 10% by mass or less with respect to the total solid content of the composition.

[2] Preparation of Colored Resin Composition Next, a method for preparing a colored resin composition (hereinafter, may be referred to as a resist) according to the present invention will be described.

First, the pigment, the solvent and the dispersant are weighed in predetermined amounts, and in the dispersion treatment step, the pigment containing the chlorinated brominated zinc phthalocyanine pigment is dispersed to prepare a pigment dispersion liquid. In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer and the like can be used. By performing this dispersion treatment, the coloring material is made into fine particles, so that the coating characteristics of the colored resin composition are improved, and the transmittance of pixels in the color filter substrate of the product is improved.

When the pigment is dispersed, it is preferable to appropriately use a dispersion aid, a dispersion resin, or the like as described above.
Further, although it is essential that the pigment contains a pigment containing the above-mentioned chlorinated brominated zinc phthalocyanine pigment, it may be mixed with another pigment for color matching and dispersed.
When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads having a diameter of 0.1 to several mm or zirconia beads. The temperature at the time of the dispersion treatment is usually set in the range of 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time varies depending on the composition of the pigment dispersion liquid, the size of the sand grinder device, and the like, and therefore needs to be adjusted as appropriate.

A solvent, a binder resin, a photopolymerization initiator, a predetermined amount of a photopolymerizable monomer, a component other than the above, and the like are mixed with the pigment dispersion liquid obtained by the above dispersion treatment to obtain a uniform dispersion solution. .. Since fine dust may be mixed in each of the dispersion treatment step and the mixing step, it is preferable to filter the obtained pigment dispersion liquid with a filter or the like.

[3] Manufacture of Color Filter Substrate Next, the color filter according to the present invention will be described.
The color filter according to the present invention has pixels formed by using the above-mentioned colored resin composition.
[3-1] Transparent substrate (support)
The material of the transparent substrate of the color filter is not particularly limited as long as it is transparent and has appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethylmethacrylate, and polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylics. Examples thereof include a thermosetting resin sheet such as a based resin, and various types of glass. Among these, glass or heat-resistant resin is preferable from the viewpoint of heat resistance.

For the transparent substrate and the black matrix-forming substrate, in order to improve the surface physical properties such as adhesiveness, if necessary, corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc. May be done. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. When thin film formation treatment of various resins is performed, the film thickness is usually in the range of 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably 5 μm or less.

[3-2] Black Matrix The color filter according to the present invention can be manufactured by providing a black matrix on the above-mentioned transparent substrate and further forming a pixel image of usually red, green, and blue. The colored resin composition is used as a coating liquid for forming green pixels (resist pattern) among red, green, and blue pixels. Coating, heat drying, image exposure, coating, heat drying, image exposure, on the resin black matrix forming surface formed on the transparent substrate using the green resist, or on the metal black matrix forming surface formed by using a chromium compound or other light-shielding metal material. Each process of development and thermosetting is performed to form a pixel image.

The black matrix is formed on a transparent substrate by using a light-shielding metal thin film or a colored resin composition for a black matrix. As the light-shielding metal material, a chromium compound such as metallic chromium, chromium oxide, or chromium nitride, a nickel-tungsten alloy, or the like is used, and these may be laminated in a plurality of layers.
These metal light-shielding films are generally formed by an etching method, and after forming a desired pattern in a film shape by a positive photoresist, dicerium ammonium nitrate and perchloric acid and / or nitric acid are added to chromium. A black matrix is formed by using an etching solution mixed with the above, and for other materials, etching with an etching solution suitable for the material, and finally peeling the positive photoresist with a special release agent. be able to.

In this case, first, a thin film of these metals or metal / metal oxides is formed on the transparent substrate by a vapor deposition or sputtering method. Next, after forming a coating film of the colored resin composition on this thin film, the coating film is exposed and developed using a photomask having a repeating pattern such as stripes, mosaics, and triangles to form a resist image. After that, the coating film can be etched to form a black matrix.

When a photosensitive colored resin composition for a black matrix is used, a colored resin composition containing a black coloring material is used to form a black matrix. For example, black color materials such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, etc., or red, green, blue, etc. appropriately selected from inorganic or organic pigments and dyes. A black matrix can be formed by using a colored resin composition containing a black color material by mixing in the same manner as the method for forming red, green, and blue pixel images described below.

[3-3] Pixel formation The method for forming pixels differs depending on the type of colored resin composition used, but here, a case where a photopolymerizable composition is used as the colored resin composition will be described as an example.
A colored resin composition of one of red, green, and blue is applied onto a transparent substrate provided with a black matrix, dried, and then a photomask is placed on the coating film, and an image is exposed through this photomask. A pixel image is formed by development and, if necessary, thermosetting or photocuring to create a colored layer. A color filter image can be formed by performing this operation on each of the three colored resin compositions of red, green, and blue.

The colored resin composition for a color filter 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. Above all, according to the die coating method, the amount of coating liquid used is significantly reduced, there is no influence of mist adhering when the spin coating method is used, and the generation of foreign substances is suppressed. It is preferable from the above viewpoint.

If the thickness of the coating film is too large, pattern development becomes difficult and it may be difficult to adjust the gap in the liquid crystal cell formation process, while if it is too small, it becomes difficult to increase the pigment concentration, which is desired. Color development may be impossible. The thickness of the coating film after drying is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm. The range is as follows.

[3-4] Drying of Coating Film The coating film after coating the colored resin composition on the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after pre-drying, it is heated again to dry. The conditions for pre-drying can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying temperature and drying time are selected according to the type of solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 ° C. or higher. The temperature is in the range of ° C. or lower, preferably 70 ° C. or lower, and the drying time is usually in the range of 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, preferably 3 minutes or shorter.

The temperature condition for reheating and drying is preferably higher than the pre-drying temperature, specifically, usually 50 ° C. or higher, preferably 70 ° C. or higher, and usually 200 ° C. or lower, preferably 160 ° C. or lower, particularly preferably 130. It is in the range of ℃ or less. The drying time is usually 10 seconds or more, particularly preferably 15 seconds or more, and usually 10 minutes or less, particularly preferably 5 minutes, although it depends on the heating temperature. The higher the drying temperature, the better the adhesiveness to the transparent substrate. However, if the drying temperature is too high, the binder resin may be decomposed to induce thermal polymerization, resulting in poor development. As the drying step of the coating film, a vacuum drying method in which the coating film is dried in the vacuum chamber without raising the temperature may be used.

[3-5] Exposure Step Image exposure is performed by superimposing a negative matrix pattern on a coating film of a colored resin composition and irradiating a light source of ultraviolet rays or visible light through this mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. The light source used for the above image exposure is not particularly limited. Examples of the light source include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, etc. Examples thereof include laser light sources such as an excimer laser, a nitrogen laser, a helium cadmium laser, and a semiconductor laser. An optical filter can also be used when irradiating light of a specific wavelength for use.

[3-6] Development Step In the color filter according to the present invention, an organic solvent or a surfactant is used after image exposure is performed on a coating film using the colored resin composition according to the present invention with the above-mentioned light source. An image can be formed on a substrate and produced by developing with an aqueous solution containing the above and an alkaline compound. The aqueous solution can further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

As alkaline compounds, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate , Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di or triethanolamine, mono-di or trimethylamine , Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), organic alkaline such as choline. Examples include compounds. These alkaline compounds may be a mixture of two or more kinds.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples thereof include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates and sulfosuccinic acid ester salts, and amphoteric surfactants such as alkyl betaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.
The conditions of the development process are not particularly limited, but the development temperature is usually in the range of 10 ° C. or higher, particularly 15 ° C. or higher, further 20 ° C. or higher, and usually 50 ° C. or lower, particularly 45 ° C. or lower, further 40 ° C. or lower. Is preferable. The developing method can be any one of a dipping developing method, a spray developing method, a brush developing method, an ultrasonic developing method and the like.

[3-7] Thermosetting treatment The color filter after development is subjected to a thermosetting treatment. The thermosetting treatment conditions at this time are usually selected in a temperature range of 100 ° C. or higher, preferably 150 ° C. or higher, and usually 280 ° C. or lower, preferably 250 ° C. or lower, and the time is 5 minutes or longer and 60 minutes or shorter. Selected by range. Through these series of steps, the formation of a one-color patterning image is completed. This process is repeated in sequence to pattern black, red, green, and blue to form a color filter. The order of patterning the four colors is not limited to the above-mentioned order.

The color filter according to the present invention is a curable colored resin composition containing (1) a solvent, a chlorinated brominated zinc phthalocyanine pigment as a coloring material, and a polyimide resin as a binder resin in addition to the above-mentioned production method. Can also be produced by a method of applying the above to a substrate and forming a pixel image by an etching method. Further, (2) a method of forming a pixel image directly on a transparent substrate by a printing machine using a colored resin composition containing a chlorinated brominated zinc phthalocyanine pigment as a coloring ink, and (3) chlorinated brominated zinc phthalocyanine. Examples thereof include a method in which a colored resin composition containing a pigment is used as an electrodeposition solution, a substrate is immersed in the electrodeposition solution, and a colored film is deposited on an ITO electrode having a predetermined pattern. Further, (4) a method in which a film coated with a colored resin composition containing a chlorinated brominated zinc phthalocyanine pigment is attached to a transparent substrate and peeled off, and image exposure and development are performed to form a pixel image, and (5) chlorine. Examples thereof include a method of forming a pixel image by an inkjet printer using a colored resin composition containing a brominated zinc phthalocyanine pigment as a coloring ink. As the method for producing the color filter, a method suitable for the composition of the colored resin composition is adopted.

[3-8] Formation of Transparent Electrode The color filter according to the present invention is used as a part of parts such as a color display and a liquid crystal display device by forming a transparent electrode such as ITO on an image as it is. However, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image if necessary. Further, in some applications such as a plane orientation type drive system (IPS mode), a transparent electrode may not be formed.

[4] Image display device (panel)
Next, the image display device of the present invention will be described. The image display device of the present invention has the above-mentioned color filter. Hereinafter, as the image display device, a liquid crystal display device and an organic EL (Electroluminescence) display device will be described in detail.

[4-1] Liquid Crystal Display Device A method for manufacturing a liquid crystal display device according to the present invention will be described. In the liquid crystal display device according to the present invention, an alignment film is usually formed on the color filter according to the present invention, a spacer is sprayed on the alignment film, and then the liquid crystal cell is formed by bonding with an opposing substrate. The liquid crystal is injected into the liquid crystal cell and connected to the counter electrode to complete the process. The alignment film is preferably a resin film such as polyimide. A gravure printing method and / or a flexographic printing method is usually adopted for forming the alignment film, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by heat firing, it is surface-treated by irradiation with ultraviolet rays or treatment with a rubbing cloth to obtain a surface state in which the inclination of the liquid crystal can be adjusted.

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

The gap for bonding with the facing substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After bonding to the facing substrate, the parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by 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 depressurized in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. .. The degree of decompression in the liquid crystal cell is usually in the range of 1 × ^10-2 Pa or more, preferably 1 × 10 ^-3 Pa or more, and usually 1 × 10 ^-7 Pa or less, preferably 1 × 10 ^-6 Pa or less. is there. Further, it is preferable to heat the liquid crystal cell at the time of depressurization, and the heating temperature is usually in the range of 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower.

The warming retention at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. In the liquid crystal cell into which the liquid crystal is injected, the liquid crystal display device (panel) is completed by sealing the liquid crystal injection port by curing the UV curable resin.
The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic type, an aliphatic type, or a polycyclic compound, and may be any of a liotropic liquid crystal, a thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, a nematic liquid crystal, a smestic liquid crystal, a cholesteric liquid crystal and the like are known, but any of them may be used.

[4-2] Organic EL Display Device When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, the pixels 20 are formed on the transparent support substrate 10 by the colored resin composition of the present invention. A multicolored organic EL element is produced by laminating an organic illuminant 500 via an organic protective layer 30 and an inorganic oxide film 40 on a blue color filter on which the above is formed.

As a method of laminating the organic illuminant 500, a method of sequentially forming 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 on the upper surface of the color filter, or , A method of laminating the organic light emitter 500 formed on another substrate on the inorganic oxide film 40 and the like can be mentioned. The organic EL element 100 produced in this manner can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. In the following embodiment, "part" represents "part by mass".

<Green pigment>
In Examples and Comparative Examples, the green pigments A and B shown in Table 1 were used.
The average number of chlorine atoms and the average number of bromine atoms in Table 1 are values measured by the fluorescent X-ray fundamental parameter method (FP method), and the number of chlorine atoms in one 16 substitution sites of zinc phthalocyanine molecule. , The average value of the number of bromine atoms. Further, since chlorinated brominated zinc phthalocyanine is obtained by substituting all or part of 16 hydrogen atoms in one molecule of zinc phthalocyanine with chlorine atoms or bromine atoms, the average number of chlorine atoms and the average bromine atom are 16 to 16. The average number of hydrogen atoms was calculated by subtracting the sum with the number. The average number of chlorine atoms and the average number of bromine atoms were calculated as relative values per zinc atom from the mass ratios of zinc atoms, chlorine atoms and bromine atoms measured by the FP method. The fluorescent X-ray evaluation device used was RIX-3000 manufactured by Rigaku Denki Kogyo Co., Ltd., and the X-ray tube was used at Rh50 kV / 50 mA, and the measurement was performed in a vacuum atmosphere with a measurement diameter of 30 mmφ. The amount of the measurement sample was 2 g, and pressure molding (30 mmφ, 200 kN) was used. The average number of chlorine atoms and the average number of bromine atoms in one molecule were taken as the average values of the entire measurement sample. Table 2 shows other detailed conditions set on the screen of RIX-3000. The green pigment B is C.I. I. Pigment Green 58.

Further, Table 3 shows the chlorine atom content ratio and the bromine atom content ratio measured by combustion ion chromatography for the same green pigments A and B as in Table 1. Specifically, after dissolving each pigment in ethyl benzoate, it was burned in a combustion device, the combustion gas was absorbed by a hydrogen peroxide absorbing solution, and the ions in the absorbing solution were measured by ion chromatography.
The average number of hydrogen atoms contained in one molecule of the green pigments A and B shown in Table 3 is the Laser Desorption / Ionization (LDI) -Mass Spectrometry (MS). It is a value measured in. For the measurement, 1 to 3 mg of the pigment is dissolved in 100 mg of THF (tetrahydrofuran) or NMP (N-methylpyrrolidone), ultrasonically applied, the solution is mounted on a several μL plate, and Bruker's autoflex speed is used. The measurement was performed in the reflection mode and the solution mode under the conditions of laser power: about 40% to 60%, 500 shots × 3, m / z = 300 to 3000. The mass spectrum of the green pigment A is shown in FIG. 2, and the mass spectrum of the green pigment B is shown in FIG. The average number of hydrogen atoms contained in one molecule was measured by the following procedure.
First, the maximum peak intensity in the mass spectrum was used as a reference, and the 40% intensity thereof was used as a threshold value. Next, the peaks above the threshold value were set as the peaks to be calculated, the number of hydrogen atoms was calculated from the molecular weight at the peak top for each peak, and the average number of hydrogen atoms was calculated to calculate the average number of hydrogen atoms.

<Dispersed resin A>
The dispersion resin A was synthesized by the following procedure.
First, a separable flask equipped with a cooling tube was prepared as a reaction vessel, 400 parts by mass of propylene glycol monomethyl ether acetate was charged, and after nitrogen substitution, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. The temperature was raised.

On the other hand, in the monomer tank, 30 parts by mass of dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, and t-butylperoxy-2-ethyl. 5.2 parts by mass of hexanoate and 40 parts by mass of propylene glycol monomethyl ether acetate were charged, and 5.2 parts by mass of n-dodecyl mercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were charged in the chain transfer agent tank, and the temperature of the reaction tank was charged. Was stabilized at 90 ° C., and then dropping was started from the monomer tank and the chain transfer agent tank to start the polymerization. The dropping was carried out over 135 minutes while maintaining the temperature at 90 ° C., and 60 minutes after the dropping was completed, the temperature was raised to 110 ° C.

After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 parts by mass of triethylamine were charged in the reaction vessel, and the temperature was 110 ° C. Was reacted for 9 hours.
The mixture was cooled to room temperature to obtain a polymer solution having a weight average molecular weight of 8000 and an acid value of 101 mgKOH / g as the dispersed resin A.

<Dispersant A: Dispersant "BYK-LPN6919" manufactured by Big Chemie>
A methacrylic acid-based AB block copolymer composed of an A block having a nitrogen atom-containing functional group and a B block having a prosolvent property. It has the repeating units of the following formulas (2b) and (3b), and does not have the repeating units of the following formula (1b). The amine value is 120 mgKOH / g and the acid value is 1 mgKOH / g or less.

The content ratio of the following formula (2b) in all the repeating units of the A block is 100 mol%, and the content ratio of (3b) in all the repeating units of the B block is 11 mol%, respectively.

<Binder resin A>
Binder resin A was synthesized by the following procedure.
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while substituting with nitrogen, and the temperature was raised to 120 ° C. To this, 20 parts by mass of styrene, 57 parts by mass of glycidyl methacrylate and 82 parts by mass of monoacrylate (FA-513M manufactured by Hitachi Kasei Co., Ltd.) having a tricyclodecane skeleton were added dropwise, and stirring was continued at 120 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 27 parts by mass of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Then, 52 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the mixture was reacted at 120 ° C. for 3.5 hours. The polystyrene-equivalent weight average molecular weight Mw of the binder resin A thus obtained measured by GPC was about 15,000.

<Photopolymerization initiator 1>
In Examples and Comparative Examples, [9-ethyl-6- (1-acetoxyimimino-4-methyloxycarbonylbutyl) carbazole-3-yl] (2-methylphenyl) having the following structure as a photopolymerization initiator Ketone was used.

"Me" in the above structural formula represents a methyl group.

<Surfactant A>
Mega Fvck F-559 (manufactured by DIC, fluorine-based surfactant)

(Examples 1 to 5, Comparative Examples 1 to 3)
Using the green pigment and the solvent in the types and amounts shown in Table 4, the dispersant A was used as a dispersant in an amount of 4.0 parts by mass in terms of solid content, and the dispersion resin was used in an amount of 4.0 parts by mass in terms of solid content. Using 225 parts by mass of zirconia beads having a diameter of 0.5 mm, they were filled in a stainless steel container and dispersed for 6 hours with a paint shaker to prepare green pigment dispersions of Examples 1 to 5 and Comparative Examples 1 to 3. .. The boiling point in Table 4 is a value at 1013.25 hPa, and the vapor pressure is a value at 20 ° C. The blending amount of the solvent 1 in Table 4 is the total amount contained in the green pigment dispersion liquid.

DEGEA: Diethylene glycol monoethyl ether acetate DEGBEA: Diethylene glycol monobutyl ether acetate 1,3-BGDA: 1,3-butylene glycol diacetate EEP: 3-ethoxypropionate ethyl MBA: 3-methoxybutyl acetate BA: Butyl acetate (butyl acetate)
PGMEA: Propylene glycol monomethyl ether acetate

<Preparation of colored resin composition>
Other components shown in Table 5 were mixed with each of the above pigment dispersions to prepare a colored resin composition. The blending amount of the binder resin and the photopolymerizable monomer in Table 5 is a solid content conversion value, and the blending amount of the solvent is a value including the amount of the solvent contained in the binder resin and the photopolymerizable monomer.

<Evaluation of deposits>
The evaluation was carried out according to the [Appropriate coating evaluation method (I)] described in Examples of Japanese Patent Application Laid-Open No. 2007-270147.
In evaluating the colored resin composition obtained by the above procedure through the steps (1) to (4) described below, a test piece is attached to the arm of the actuator to form a colored resin composition filled in a bottle. A control device was used that automatically moves the tip in and out repeatedly.
(1) At an atmospheric temperature of 23 ° C., a 20 mm vertical tip portion of a glass test piece having a length of 100 mm, a width of 5 mm and a thickness of 0.6 mm is immersed in a colored resin composition at a speed of 12.5 mm / sec. Then it was maintained for 4 seconds.
(2) The glass test piece is taken out from the colored resin composition at a speed of 12.5 mm / sec, held vertically with the tip of the glass test piece facing down, and then has an atmospheric temperature of 23 ° C., a humidity of 55%, and a wind speed. It was dried for 56 seconds under the condition of 0.5 ± 0.2 m / sec.
(3) Steps (1) and (2) were repeated 120 times in total to form deposits derived from the colored resin composition on the glass test piece.
(4) The deposits on the glass pieces were observed with a microscope. The results are shown in Table 6. The evaluation criteria for deposits are as follows. The numerical values in parentheses in Table 6 indicate the ratio (%) of the area covered with the deposit to the total immersion area of the glass piece.

◯: The ratio of the area covered with deposits to the total immersion area of the glass piece is 0%.
Δ: The ratio of the area covered with the deposit to the total immersion area of the glass piece exceeds 0% and is less than 10% ×: The ratio of the area covered with the deposit to the total immersion area of the glass piece 10% or more

From Table 6, in Example 1 using the green pigment A and using DEGEA having a boiling point of 217 ° C., and Example 2 using DEGEA having a boiling point of 247 ° C., almost all deposits were observed on the glass pieces. Very good without being able to. Further, Example 3 using 1,3-BGDA having a boiling point of 232 ° C, Example 4 using EP having a boiling point of 170 ° C, and Example 5 using MBA having a boiling point of 171 ° C are also glass. Good with only a few deposits on one piece. In this way, by using a high boiling point solvent having a boiling point of 150 ° C. or higher, it becomes more difficult to dry during the 56 seconds of drying during the step (2) of the deposit evaluation, and it becomes easier to maintain a wet state. 1) It is considered that the colored resin composition facilitated the dissolution again during the immersion for 4 seconds during the step, and the amount of deposits remaining on the glass piece was reduced.
On the other hand, in Comparative Example 1 using BA having a boiling point of 126 ° C. and Comparative Example 2 using only PGMEA having a boiling point of 146 ° C., a large amount of deposits were observed on the glass pieces.
Further, in Comparative Example 3 using the green pigment B, it was confirmed that almost no deposits were observed on the glass piece even though it did not contain a high boiling point solvent having a boiling point of 150 ° C. or higher. Although the detailed reason is unknown, the green pigment B has a very small average number of hydrogen atoms contained in one molecule, has good wettability and adsorptivity of the pigment, and removes the dispersant and the dispersed resin from the pigment. It is considered that this is because the pigment surface is sufficiently coated with little separation and therefore has good solubility in a solvent.

Summarizing the results in Table 6, when the green pigment A was used, the colored resin compositions of Examples 1 to 5 using a solvent having a relatively high boiling point were compared with Comparative Example 1 using a solvent having a relatively low boiling point. Compared with the colored resin compositions of No. 2 and No. 2, the amount of deposits on the glass pieces tends to be small, and it can be said that the coating characteristics are very high.

(Examples 6 to 11)
The green pigment dispersions of Examples 6 to 11 were prepared in the same manner as in Example 1 except that the green pigment and the solvent were used in the types and amounts shown in Table 7. The boiling point in Table 7 is a value at 1013.25 hPa, and the vapor pressure is a value at 20 ° C. The blending amount of the solvent 1 in Table 7 is the total amount contained in the green pigment dispersion liquid.

<Preparation of colored resin composition>
Other components shown in Table 8 were mixed with each pigment dispersion liquid in Table 7 to prepare a colored resin composition. The blending amount of the binder resin and the photopolymerizable monomer in Table 8 is a solid content conversion value, and the blending amount of the solvent is a value including the amount of the solvent contained in the binder resin and the photopolymerizable monomer.

Next, the deposits were evaluated by the above-mentioned method in the same manner as in Example 1. The results are shown in Table 9 together with the results of Example 3 and Example 5.

From Table 9, from the comparison of Examples 3, 6 and 7, and the comparison of Examples 5, 8 and 9, the area ratio covered with the deposit tends to decrease by increasing the content ratio of the high boiling point solvent. Was seen. Further, from the comparison of Examples 6, 10 and 11, it was confirmed that there is no difference in the area ratio covered with the deposits between the case where one kind of high boiling point solvent is used and the case where two kinds or more kinds are used. ..

<Evaluation of film wrinkles after high temperature treatment>
Next, using the colored resin compositions of Example 8 and Comparative Examples 2, 3 and 4, the film wrinkles after the high temperature treatment were evaluated. Comparative Example 4 was obtained in the same manner as in Example 8 except that the green pigment type was changed to green pigment B.
First, the colored resin composition was applied on a glass substrate (manufactured by Asahi Glass Co., Ltd., AN100) having a size of 50 mm square and a thickness of 0.6 mm with a spin coater, and then dried at 80 ° C. for 3 minutes. The coating film thickness was set so that the chromaticity (sx, sy) after post-baking was (0.250, 0.580) with the C light source. Next, the entire surface was exposed with a 2 kW high-pressure mercury lamp at ^{an exposure amount of 40 mJ / cm 2.} Then, post-baking was performed in an oven at 230 ° C. for 30 minutes.

Sq (squared average square root deviation roughness, nm), Sa (arithmetic mean roughness, nm), Sz (maximum roughness height, nm) are micromapped on the film surface of the high-temperature treated substrate thus obtained. It was measured by a three-dimensional non-contact surface shape measurement system manufactured by Ryoka System Co., Ltd.). The measurement was performed using a 50x optical lens in a Focus mode in a field of view of 12800 nm × 6400 nm. Sq, Sa and Sz were calculated in accordance with ISO 25178. The results are shown in Table 10.
Further, the profiles obtained by the measurement are shown in FIG. 4 (Example 8), FIG. 5 (Comparative Example 2), FIG. 6 (Comparative Example 4) and FIG. 7 (Comparative Example 3). In the profiles of FIGS. 4 to 7, the width is 12800 nm and the depth is 6400 nm. Dozens of irregularities seen in each figure correspond to film wrinkles.

From Table 10, it was confirmed that in Example 8 in which the green pigment A was used and the high boiling point solvent was used, the values of Sq, Sa and St were all small, and the film wrinkles were effectively suppressed. .. In particular, since the difference between Sq and Sa is small and the St value is small, it was confirmed that there is little surface unevenness due to wrinkles and that there is no wrinkle variation in the measurement field of view. With the recent widening of the color gamut, the pigment concentration in the color filter increases, and the film wrinkles tend to occur accordingly. When the film wrinkles occur, color unevenness occurs accordingly, and problems such as disconnection failure during panel formation also occur. Therefore, by using the colored resin composition or pigment dispersion liquid of the present invention, it is possible to suppress the occurrence of film wrinkles even when the color gamut is widened, and further, it is effective to prevent color unevenness and disconnection defects during panel formation. It was suggested that it could be suppressed.

On the other hand, in Comparative Example 2 in which the green pigment A was used and no high boiling point solvent was used, the values of Sq, Sa and St were all large, and it was confirmed that film wrinkles were generated. In particular, since the difference between Sq and Sa is small and the St value is large, it was confirmed that wrinkles were generated on the entire measurement field of view.

On the other hand, in Comparative Examples 4 and 3 using the green pigment B, the values of Sq, Sa and St were all very large, and it was confirmed that film wrinkles were generated. In particular, although the Sq and Sa values are improved by the use of the high boiling point solvent, the St value is large regardless of the presence or absence of the high boiling point solvent. Although the wrinkles were improved, it was confirmed that some large film wrinkles remained.

The difference between these results is that, as will be described later, since the green pigment A has a higher coloring power than the green pigment B, the film thickness required to obtain a film having the same chromaticity can be made thinner with the green pigment A. It is considered that this is because the amount of the solvent which is a volatile component can be relatively reduced, and the amount of the component such as the binder resin which is a component contributing to thermal deformation can also be relatively reduced. Further, when the green pigment A is used as compared with the green pigment B, the St value is greatly improved by the use of the high boiling point solvent, but the detailed reason is unknown, but with respect to the green pigment B. Since the average number of hydrogen atoms of the green pigment A is equal to or higher than a predetermined value, the affinity with the solvent is increased, the high boiling point solvent is likely to be uniformly present in the entire film, and the volatile components are vaporized on the entire surface of the film. It is considered that the film could be suppressed, and as a result, the occurrence of film wrinkles could be suppressed on the entire surface of the film.

<Coloring power evaluation>
The above, except that the green pigment dispersion of Comparative Example 2 or 3 shown in Table 4 and the yellow pigment dispersion described below were used and the amount of the pigment dispersion used was changed to the amount shown in Table 11. A colored resin composition was prepared in the same manner as in <Preparation of colored resin composition>. The amount of the pigment dispersion liquid used was adjusted so that the chromaticity of the C light source when a coating film having a film thickness of 2.00 μm was prepared was sx = 0.280 and sy = 0.600. .. The pigment concentration shown in Table 11 is the content ratio of the total pigment to the total solid content of the colored resin composition.

<Preparation of yellow pigment dispersion>
Yellow pigment C as a yellow pigment is 12.0 parts by mass in terms of solid content, dispersant A is 4.0 parts by mass in terms of solid content as a dispersant, and dispersion resin A is 4.0 parts by mass in terms of solid content as a dispersion resin. Using 80.0 parts by mass of propylene glycol monomethyl acetate and 225 parts by mass of zirconia beads having a diameter of 0.5 mm as a solvent, they were filled in a stainless steel container and dispersed for 6 hours with a paint shaker to prepare a yellow pigment dispersion liquid. did.

<Yellow pigment C>
As the yellow pigment C, a nickel azo complex formed by inserting a compound represented by the following formula (II) into a 1: 1 complex of azobarbituric acid represented by the following formula (I) with nickel or a compatible isomer thereof. (E4GN-GT, manufactured by LANXESS) was used.

From Table 11, it can be seen that in Reference Example 1 using the green pigment A, the pigment concentration is low and the coloring power is high, as opposed to Reference Example 2 in which the green pigment B is used. When the pigment concentration is small, more binder resin, photopolymerizable monomer, photopolymerization initiator and the like can be used in terms of solid content, which is advantageous for many properties such as developability and reliability. Although the detailed reason is unknown, when comparing the transmission spectra at the same pigment concentration, the peak width of green pigment A is half that of green pigment B due to the influence of the average number of hydrogen atoms contained in one molecule. It is thought that this is because it is narrow and effectively blocks the transmitted light of red and blue.

(Experimental Examples 1 to 6, Comparative Experimental Examples 1 to 5)
The green pigment, yellow pigment C, dispersant A, dispersion resin A, solvent (propylene glycol monomethyl ether acetate) shown in Table 12 and 225 parts by mass of zirconia beads having a diameter of 0.5 mm are filled in a stainless steel container and used as a paint shaker. The mixture was dispersed for 6 hours to prepare green pigment dispersions A and B. The blending amount of the components other than the "solvent" in the table is a solid content conversion value.

<Preparation of colored resin composition>
Other components shown in Table 13 were mixed with each of the above pigment dispersions to prepare a colored resin composition. The combinations of the green pigment type and the photopolymerization initiator type are as shown in Table 14.
The blending amount of the binder resin and the photopolymerizable monomer in Table 13 is a solid content conversion value, and the blending amount of the solvent is a value including the amount of the solvent contained in the binder resin and the photopolymerizable monomer.

The photopolymerization initiators A to I in Table 14 are as follows.

<Photopolymerization Initiator A> An oxime ester compound having the following chemical structure

<Photopolymerization Initiator B> Irgacure OXE02 (manufactured by BASF)

<Photopolymerization Initiator C> Irgacure OXE03 (manufactured by BASF)

<Photopolymerization Initiator D> An oxime ester compound having the following chemical structure

<Photopolymerization Initiator E> TR-PBG-304 (manufactured by Changzhou Power Electronics Co., Ltd.)

<Photopolymerization Initiator F> TR-PBG-314 (manufactured by Changzhou Strong Electronics Co., Ltd.)

<Photopolymerization Initiator G> 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole (BCIM)

<Photopolymerization Initiator H> Irgacure 907 (manufactured by BASF)

<Photopolymerization Initiator I> Irgacure 369 (manufactured by BASF)

<Minimum adhesion evaluation>
Each colored resin composition was spin-coated on a glass substrate on which chromium was vapor-deposited, and prebaked on a hot plate at 80 ° C. for 3 minutes. At the time of coating, after post-baking, the rotation speed was adjusted so that the film thickness of the coating film was 2.0 μm.

Next, a mask pattern having a width of 1 to 50 μm (1 to 10 μm: every 1 μm, 15 to 50 μm: every 5 μm) with a linear opening was installed with a 150 μm gap, through which a sample was sampled by a high-pressure mercury lamp at 40 mJ / cm ² After exposure with, a 0.04 mass% potassium hydroxide aqueous solution was used for spray development at a developer temperature of 23 ° C. and a pressure of 0.25 MPa. The developing time was twice the dissolution time of the colored resin composition measured in advance. The substrate was developed, rinsed with sufficient water, and dried with clean air. Then, post-baking was performed in an oven at 230 ° C. for 30 minutes.
The linear pattern obtained by the above procedure is observed with an optical microscope, and among the linear mask patterns having different widths, the pattern remaining on the substrate has the smallest opening width of the corresponding mask. Was specified, and the width of the opening was set to the minimum close contact. The results are shown in Table 14.

From Table 14, when the green pigment B is used as in Comparative Experimental Examples 1 and 2, the case where the oxime ester compound is used as the photopolymerization initiator and the case where the initiator other than the oxime ester compound is used. The minimum adhesion was good in both cases.
On the other hand, when the green pigment A is used as in Comparative Experimental Examples 3 to 5, it can be said that when an initiator other than the oxime ester compound is used as the photopolymerization initiator, the minimum adhesion value is large and the adhesion is poor. .. On the other hand, when the green pigment A was used as in Experimental Examples 1 to 6, the minimum adhesion value was small and the adhesion was good by using the oxime ester compound as the photopolymerization initiator.
Compared to the green pigment B, the green pigment A has a higher average number of hydrogen atoms, and due to the accompanying difference in light absorption characteristics, it tends to be difficult to sufficiently photocure the inside of the coating film, but the photopolymerization initiator Therefore, it is considered that by using an oxime ester-based compound having a larger absorption band in the low wavelength region, the inside of the coating film could be sufficiently photocured and a fine pattern could be formed with good adhesion.

<Evaluation of film thickness and coloring power>
The colored resin composition was applied on a glass substrate (manufactured by Asahi Glass Co., Ltd., AN100) having a size of 50 mm square and a thickness of 0.6 mm with a spin coater, and then dried at 80 ° C. for 3 minutes. Next, the entire surface was exposed with a 2 kW high-pressure mercury lamp at ^{an exposure amount of 40 mJ / cm 2.}
Then, post-baking was performed in an oven at 230 ° C. for 30 minutes.

The transmission spectrum of the coated substrate thus obtained was measured with a spectrophotometer U-3310 manufactured by Hitachi, Ltd. From the obtained transmission spectrum, the film thickness required to set the chromaticity at the C light source to (sx = 0.240, sy = 0.580) is calculated, and further, to set the film thickness to 2.00 μm. The required pigment concentration (mass% of total pigment with respect to total solid content) was calculated and evaluated as coloring power. The results are shown in Table 14.

From Table 14, it can be seen that the required pigment concentration is low and the coloring power is high in Experimental Examples 1 to 6 using the green pigment A, as opposed to Comparative Experimental Examples 1 and 2 using the green pigment B. When the required pigment concentration is small, more binder resin, photopolymerizable monomer, photopolymerization initiator, etc. can be blended in terms of solid content, which is advantageous for many properties such as developability and reliability. Is.
The detailed reason for the difference in coloring power is unknown, but when the transmission spectra are compared at the same pigment concentration, the peak half-value width of green pigment A is narrower than that of green pigment B, so that it is red or blue. It is considered that this is because the transmitted light of the above is effectively blocked.

From the above, by sharing the halogenated zinc phthalocyanine pigment having an average number of hydrogen atoms contained in one molecule or more and the oxime ester-based compound, it is possible to achieve both coloring power and adhesion.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is a Japanese patent application filed on March 27, 2015 (Japanese Patent Application No. 2015-067187), a Japanese patent application filed on October 20, 2015 (Japanese Patent Application No. 2015-206474), and an application filed on October 21, 2015. It is based on a Japanese patent application (Japanese Patent Application No. 2015-207298) and a Japanese patent application filed on March 11, 2016 (Japanese Patent Application No. 2016-048419), the contents of which are incorporated herein by reference.

100 Organic EL element 10 Transparent support substrate 20 pixels 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode

Claims (16)

A colored resin composition containing (A) a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator.
The pigment (A) contains a halogenated zinc phthalocyanine pigment in which a part of 16 hydrogen atoms in one molecule of zinc phthalocyanine is replaced with a halogen atom.
The average number of hydrogen atoms contained in one molecule of the halogenated zinc phthalocyanine pigment calculated using the average number of halogen atoms measured by the fluorescent X-ray fundamental parameter method (FP method) is 3 or more and 8 or less .
The average number of chlorine atoms contained in one molecule of the halogenated zinc phthalocyanine pigment calculated using the average number of halogen atoms measured by the fluorescent X-ray fundamental parameter method (FP method) is 1 or more and 12 or less.
The average number of bromine atoms contained in one molecule of the halogenated zinc phthalocyanine pigment calculated using the average number of halogen atoms measured by the fluorescent X-ray fundamental parameter method (FP method) is 1 or more and 12 or less, and
A colored resin composition in which the solvent (C) contains a high boiling point solvent having a boiling point of 150 ° C. or higher at 1013.25 hPa. The colored resin composition according to claim 1, wherein the content ratio of the solvent (C) to the colored resin composition is 50% by mass or more. The colored resin composition according to claim 1 or 2, wherein the content ratio of the high boiling point solvent to the solvent (C) is 0.5% by mass or more. The colored resin composition according to any one of claims 1 to 3, wherein the solvent (C) further contains a low boiling point solvent having a boiling point of less than 150 ° C. at 1013.25 hPa. The colored resin composition according to claim 4, wherein the content ratio of the low boiling point solvent to the solvent (C) is 20% by mass or more. The colored resin composition according to claim 5, wherein the content ratio of the low boiling point solvent to the solvent (C) is 40% by mass or more. The colored resin composition according to any one of claims 1 to 6, wherein the vapor pressure of the high boiling point solvent at 20 ° C. is 400 Pa or less. The colored resin composition according to any one of claims 1 to 7, wherein the high boiling point solvent has a boiling point of 170 ° C. or higher at 1013.25 hPa. The colored resin composition according to any one of claims 1 to 8, wherein the high boiling point solvent has a boiling point of 190 ° C. or higher at 1013.25 hPa. The colored resin composition according to any one of claims 1 to 9, wherein the high boiling point solvent has a boiling point of 210 ° C. or higher at 1013.25 hPa. The colored resin composition according to any one of claims 1 to 10, wherein the high boiling point solvent is glycol ethers. The colored resin composition according to any one of claims 1 to 10, wherein the high boiling point solvent is glycol diacetate. The colored resin composition according to any one of claims 1 to 12, wherein the dispersant (B) contains a block copolymer having a functional group containing a nitrogen atom. The colored resin composition according to any one of claims 1 to 13, wherein the (E) photopolymerization initiator contains an oxime ester-based compound. A color filter having pixels created by using the colored resin composition according to any one of claims 1 to 14. An image display device having the color filter according to claim 15.

Images