TW201641611A - Colored resin composition, color filter and image display device - Google Patents

Abstract

The present invention provides a colored resin composition that has a high coloring power and a high solubility in solvent of the dried film, and is capable of preventing an attached foreign object from generating, a color filter and an image display device using the colored resin composition, and a pigment dispersion liquid for use in the colored resin composition. The colored resin composition of the present invention comprises (A) a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin and (E) a photopolymerization initiator, wherein the pigment (A) includes a halogenated zinc phthalocyanine pigment having an average number of hydrogen atom per molecule of 3 or more, and the solvent (C) includes a high-boiling solvent having a boiling point of 150 DEG C or more at 1013.25 hpa.

Description

Colored resin composition, color filter, and image display device

The present invention relates to a colored resin composition, a color filter, and an image display device. More specifically, it relates to a colored resin composition containing a specific Halogenated zinc phthalocyanine pigment and a specific high boiling point solvent, a color filter having pixels produced using the colored resin composition, And an image display device having the color filter.

As a method of manufacturing a color filter used in a liquid crystal display device or the like, a pigment dispersion method, a dyeing method, an electrodeposition method, and a printing method are known. Among them, a pigment dispersion method having excellent balance characteristics is most widely used from the viewpoints of spectral characteristics, durability, pattern shape, and precision.

In recent years, color filters have required higher penetration, high brightness, high contrast, and high color gamut. As a coloring material for determining the color of the color filter, a pigment is generally used from the viewpoints of heat resistance, light resistance, etc., and it is preferable to use an inherent penetration absorption spectrum in a visible light wavelength region and a backlight. The fluorescence spectrum is consistent. For example, as a green pixel formation, a combination of a copper phthalocyanine green pigment and various yellow pigments has been used since.

For example, as disclosed in Patent Documents 1 to 3, a novel halogenated zinc phthalocyanine green pigment having a specific hue has been proposed, and high brightness of a conventional halogenated copper phthalocyanine green pigment has been achieved. Also, in Patent Documents 1 to 3 An example in which a halogenated zinc phthalocyanine pigment is combined with a photopolymerization initiator such as biimidazole or α-aminoalkylphenone is described. Further, in recent years, it has been found that CI Pigment Green 58 as a zinc halide phthalocyanine green pigment as described in Patent Document 4 contains propylene glycol monomethyl ether acetate, 3-ethoxypropionate ethyl acetate, and acetic acid 3- A coloring composition such as methoxybutyl ester as a solvent can improve agglomerated foreign matter or surface roughness on a coated substrate. Further, as described in Patent Document 5, it has been found that by using a combination of a halogenated zinc phthalocyanine green pigment and a photopolymerization initiator containing a specific oxime ester compound, it is possible to prevent the colored resin composition from generating foreign matter during production or storage; It can suppress the generation of precipitates when it comes into contact with N-methylpyrrolidone. Further, Patent Documents 6 to 11 also disclose an example in which a zinc halide phthalocyanine green pigment is combined with a photopolymerization initiator containing an oxime ester compound.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2004-70342

Patent Document 2: Japanese Patent Laid-Open Publication No. 2004-70343

Patent Document 3: Japanese Patent Laid-Open Publication No. 2009-52010

Patent Document 4: Japanese Patent Laid-Open No. 2011-028219

Patent Document 5: Japanese Patent Laid-Open Publication No. 2009-271502

Patent Document 6: Japanese Patent Laid-Open Publication No. 2010-84119

Patent Document 7: Japanese Patent Laid-Open Publication No. 2010-97172

Patent Document 8: Japanese Patent Laid-Open No. 2011-99974

Patent Document 9: Japanese Patent Laid-Open Publication No. 2011-145668

Patent Document 10: Japanese Patent Laid-Open Publication No. 2012-53278

Patent Document 11: Japanese Patent Laid-Open Publication No. 2012-172003

The inventors of the present invention studied the colored resin composition containing CI Pigment Green 58 (hereinafter abbreviated as "G58") as a zinc phthalocyanine pigment as described in Patent Documents 1 to 11, and found that the coloring power was low. In order to achieve a certain degree of chromaticity, it is necessary to make the coating film thicker. Therefore, the present inventors have conducted intensive studies in order to obtain a colored resin composition having a relatively small coloring power and a certain chromaticity, and found that by using a specific halogenated zinc phthalocyanine pigment. The above purpose can be achieved. On the other hand, the inventors of the present invention have repeatedly studied the coloring resin composition containing the pigment, and as a result, found that the dried film formed using the composition has low solubility in a solvent, and therefore exists in coating with a nozzle. When the composition is applied by the method, a foreign matter adhering to the tip end of the dispensing nozzle is adhered to the surface of the coating film in the form of a foreign material in the case of G58, which is not a new problem.

The present invention has been made in view of the above problems, and an object of the invention is to provide a colored resin composition which has a high coloring power, a high solubility of a dried film in a solvent, and can suppress the occurrence of adhesion of foreign matter, and has a colored resin composition. A color filter of the formed pixel, an image display device having the color filter, and a pigment dispersion liquid for the colored resin composition.

The present inventors have made an effort to solve the above problems, and as a result, have found that the above problems can be solved by using a specific halogenated zinc phthalocyanine green pigment and a specific high boiling point solvent, thereby completing the present invention. That is, the gist of the present invention is as follows.

[1] A colored resin composition comprising (A) a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator; wherein The pigment (A) contains a zinc phthalocyanide pigment, and the average number of hydrogen atoms contained in one of the molecules of the zinc phthalocyanine pigment is 3 or more, and the solvent (C) contains a boiling point of 150 ° C or higher at 1013.25 hPa. High boiling point solvent.

[2] The colored resin composition according to [1], wherein the (C) solvent 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 coloring resin composition according to any one of [1] to [3], wherein a content ratio of the high boiling point solvent to the (C) solvent is 0.5% by mass or more.

[5] The colored resin composition according to any one of [1] to [4] wherein the high boiling point solvent has a vapor pressure of not more than 400 Pa at 20 °C.

[6] The colored resin composition according to any one of [1] to [5] wherein the (B) dispersant comprises 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 comprises an oxime ester compound.

[8] A color filter having a pixel produced by using the colored resin composition according to any one of [1] to [7].

[9] An image display device comprising the color filter as described in [8].

[10] A pigment dispersion liquid comprising (A) a pigment, (B) a dispersant, and (C) a solvent; wherein the (A) pigment comprises a zinc phthalocyanide pigment, one of the molecules of the zinc phthalocyanine pigment The average number of hydrogen atoms contained in the solvent is 3 or more, and the solvent (C) contains a high boiling point of 150 ° C or higher at 1013.25 hPa. Solvent.

[11] The pigment dispersion liquid according to [10], wherein the (C) solvent 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 the above-mentioned (C), wherein the content ratio of the high-boiling solvent to the (C) solvent is 1% by mass or more.

[14] The pigment dispersion liquid according to any one of [10] to [13] wherein the high boiling point solvent has a vapor pressure of not more than 400 Pa at 20 °C.

[15] The pigment dispersion liquid according to any one of [10], wherein the (B) dispersant comprises a block copolymer having a functional group containing a nitrogen atom.

According to the present invention, it is possible to provide a colored resin composition which has a high coloring power, a high solubility of a dried film in a solvent, and which suppresses generation of foreign matter, and a color filter having a pixel formed using the colored resin composition. An image display device having the color filter and a pigment dispersion liquid for the colored resin composition.

10‧‧‧Transparent support substrate

20‧‧ ‧ pixels

30‧‧‧Organic protective layer

40‧‧‧Inorganic oxide film

50‧‧‧Transparent anode

51‧‧‧ hole injection layer

52‧‧‧ hole transport layer

53‧‧‧Lighting layer

54‧‧‧Electronic injection layer

55‧‧‧ cathode

100‧‧‧Organic EL components

500‧‧‧Organic emitters

Fig. 1 is a schematic cross-sectional view showing an example of an organic EL device having a color filter of the present invention.

Figure 2 is a mass spectrum of green pigment A.

Figure 3 is a mass spectrum of green pigment B.

Figure 4 is a measurement outline of the film surface evaluation of Example 8.

Fig. 5 is a measurement outline of the film surface evaluation of Comparative Example 2.

Fig. 6 is a measurement outline of the film surface evaluation of Comparative Example 4.

Fig. 7 is a measurement outline of the film surface evaluation of Comparative Example 3.

Hereinafter, the constituent elements and the like of the present invention will be described in detail, but these are examples of the embodiments of the present invention, and are not limited thereto. In addition, "(meth) propylene hydride", "(meth) acrylate", etc. mean "acryl hydrazine and / or methacryl oxime", " acrylate and / or methacrylate", etc., for example, (Meth)acrylic means "acrylic acid and/or methacrylic acid". In addition, the "total solid content" means all components other than the following solvent components contained in the pigment dispersion liquid or the colored resin composition.

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

[1] Composition of colored resin composition and pigment dispersion

Hereinafter, each constituent component of the colored resin composition and the pigment dispersion liquid of the present invention will be described. The colored resin composition of the present invention contains (A) a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator as an essential component, and may be blended as needed. Other additives other than the above components. Further, the pigment dispersion liquid of the present invention contains (A) a pigment, (B) a dispersant, and (C) a solvent as essential components, and may further contain other additives other than the above components, if necessary.

The colored resin composition of the first aspect of the present invention is as follows: (A) The pigment contains a zinc phthalocyanide pigment, and the average number of hydrogen atoms contained in one of the molecules of the zinc phthalocyanine pigment is 3 or more, and the solvent (C) contains a high boiling point solvent having a boiling point of 150 ° C or higher at 1013.25 hPa. Further, the pigment dispersion of the second aspect is as follows: (A) the pigment contains a zinc phthalocyanide pigment, and the average number of hydrogen atoms contained in one of the molecules of the zinc phthalocyanine pigment is 3 or more, and (C) The solvent contains a high boiling point solvent having a boiling point of 150 ° C or higher at 1013.25 hPa.

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

[1-1] (A) Pigment

The (A) pigment used in the colored resin composition and the pigment dispersion of the present invention contains a zinc phthalocyanide pigment (hereinafter sometimes referred to as "green pigment a"). The number of hydrogen atoms contained in one of the molecules of the zinc phthalocyanine pigment is 3 or more. As described above, it is considered that by including the green pigment a as the (A) pigment, high coloration and high luminance can be simultaneously achieved. The detailed mechanism is unknown, but it is speculated that by the change in the transmission spectrum due to the large amount of hydrogen atoms, the half value of the peak is narrow, and the red or blue light is effectively shielded, thereby achieving high coloration and high. Brightness.

The zinc phthalocyanine usually has 16 hydrogen atoms in one molecule, and one of the hydrogen atoms is partially substituted by a halogen atom, and the zinc phthalocyanine pigment used in the present invention is used. Particularly, from the viewpoint of high coloration and high brightness, a zinc bromide phthalocyanine pigment is preferred.

The method for measuring the average number of hydrogen atoms in the one-molecular pigment is not particularly limited, and examples thereof include a method of calculating the average number of halogen atoms measured by a fluorescent X-ray basic parameter method (FP method), or The method of measuring by Laser Desorption/Ionization (LDI)-mass spectrometry (MS) is preferably the FP method from the viewpoint of simplicity and precision.

In the method calculated by 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 positions in the halogenated zinc phthalocyanine, the remaining positions which are not occupied by the halogen atoms are calculated, whereby the average number of hydrogen atoms is obtained. It is preferred to carry out measurement and calculation using the apparatus and conditions used in the examples. Specifically, based on the mass ratio of the zinc atom to the halogen atom measured by the FP method, the average number of halogen atoms per zinc atom is determined, and the average number of halogen atoms is subtracted from 16, thereby obtaining the average number of hydrogen atoms. .

On the other hand, in the method of measurement by the LDI-MS method, the intensity with respect to the molecular weight (m/z value) was measured by the LDI-MS method. Usually, in the green pigment a, a mixture of molecules having different numbers of hydrogen atoms, chlorine atoms, and bromine atoms is calculated based on the intensity of each molecule obtained by measuring the mixture by the above method. The number of hydrogen atoms, chlorine atoms, and bromine atoms is averaged, and the average of the number of hydrogen atoms, chlorine atoms, and bromine atoms contained in one molecule can be calculated. It is preferred to carry out measurement and calculation using the apparatus and conditions used in the examples. Specifically, according to the molecular weight of the main peak of the mass spectrum, the values of x and y in the zinc bromide phthalocyanine molecule (H _16-xy ZnC ₃₂ N ₈ Br _x Cl _y ) corresponding to each peak are obtained, and secondly, The number of peaks (molecules) whose peak intensity is equal to or greater than a certain value is calculated as an average value of the peaks, and the average atomic number of each atom is obtained.

The average number of hydrogen atoms contained in a molecule of green pigment a is usually 2 or more, preferably 3 or more, more preferably 4 or more, still more preferably 5 or more; further preferably 16 or less, more preferably 14 or less, still more preferably 12 or less, still more preferably 10 or less, It is especially good for 8 or less. When it is set to the above lower limit value, it tends to be highly colored. Moreover, by setting it as the said upper limit or less, the stability of the dispersion liquid tends to it.

Further, the average number of chlorine atoms contained in the green pigment a in one molecule is preferably 0.5 or more, more preferably 1 or more, still more preferably 1.5 or more, and further preferably 14 or less, more preferably 13 or less. It is preferably 12 or less. When it is set to the above lower limit value, it tends to be highly colored. Moreover, when it is set to the said upper limit or less, it is set as the high brightness.

Further, the average number of bromine atoms contained in the green pigment a in one molecule is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and further preferably 14 or less, more preferably 13 or less, and further It is preferably 12 or less. When it is set to the above lower limit value, it tends to be high in brightness. Moreover, when it is set to the said upper limit or less, it is set as the high coloring.

Further, the ratio of the average number of chlorine atoms contained in one molecule of the green pigment a to the average number of bromine atoms contained in one molecule is preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.2 or more; It is preferably 7 or less, more preferably 3 or less, still more preferably 1 or less, and particularly preferably 0.5 or less. When it is set to the above lower limit value, it tends to be highly colored, and it is preferable to set it as the upper limit or less.

On the other hand, the average number of hydrogen atoms contained in one molecule of the green pigment a calculated by the FP method is usually 2 or more, preferably 3 or more, more preferably 3.5 or more, still more preferably 4.0 or more, and furthermore Better than 4.2, especially 4.5 Further, it is preferably 12 or less, more preferably 10 or less, still more preferably 8 or less, still more preferably 6 or less, and particularly preferably 5.5 or less. When it is set to the above lower limit value, it tends to be highly colored. Moreover, by setting it as the said upper limit or less, the stability of the dispersion liquid tends to it.

Further, the average number of chlorine atoms contained in one molecule of the green pigment a measured by the FP method is preferably 0.5 or more, more preferably 1 or more, still more preferably 1.5 or more, and further preferably 14 or less. It is more preferably 12 or less, further preferably 10 or less, further preferably 8 or less, particularly preferably 6 or less, and most preferably 4 or less. When it is set to the above lower limit value, it tends to be highly colored. Moreover, when it is set to the said upper limit or less, it is set as the high brightness.

Further, 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, and still more preferably 6 or more. Preferably, it is 7 or more, preferably 8 or more; further preferably 14 or less, more preferably 13 or less, further preferably 12 or less, further preferably 11 or less, and particularly preferably 10 or less. When it is set to the above lower limit value, it tends to be high in brightness. Moreover, when it is set to the said upper limit or less, it is set as the high coloring.

Further, the ratio of the average number of chlorine atoms contained in one molecule measured by the FP method to the average number of bromine atoms contained in one molecule is preferably 0.1 or more, and more preferably 0.15 or more. It is preferably 0.2 or more; more preferably, it is 7 or less, more preferably 3 or less, still more preferably 1 or less, and particularly preferably 0.5 or less. When it is set to the above lower limit value, it tends to be highly colored, and it is preferable to set it as the upper limit or less.

Further, the green pigment a is preferably contained in the green pigment a in an amount of 3.5% by mass or more, more preferably 4.0% by mass or more, and still more preferably 4.3% by mass. The amount is preferably 4.5% by mass or more, more preferably 30% by mass or less, still more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 6% by mass or less. When it is set to the above lower limit value, it tends to be highly colored, and it is preferable to set it as the upper limit or less. The content of the chlorine atom and the bromine atom contained in the green pigment a can be measured by the following combustion gas-ion chromatography: after the pigment is dissolved in ethyl benzoate, it is burned by a combustion device to cause combustion gas. It is absorbed into the hydrogen peroxide absorption liquid, and the ions in the absorption liquid are measured.

In addition, the content ratio of the bromine atom in the green pigment a measured by the above analysis method is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 45% by mass or more. More preferably, it is 50% by mass or more. Further, the content ratio 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. When it is set to the above lower limit value, it tends to be high in brightness. Moreover, when it is set to the said upper limit or less, it is set as the high coloring.

Such a zinc bromide phthalocyanine pigment can be produced by a known production method disclosed in Japanese Laid-Open Patent Publication No. SHO-50-130816. For example, a method of synthesizing a pigment by using, as a starting material, a part or all of a hydrogen atom of an aromatic ring, which is partially or wholly substituted with a halogen atom such as bromine or chlorine, as a starting material can be mentioned. In this case, a catalyst such as ammonium molybdate may also be used as needed.

As another method, a method of brominating zinc phthalocyanine with bromine gas in a melt containing a mixture of aluminum chloride, sodium chloride, sodium bromide or the like in a temperature of about 110 to 170 ° C is exemplified. In this method, the ratio of various brominated phthalocyanine zinc having different bromine contents can be arbitrarily controlled by adjusting the ratio of chloride to bromide in the molten salt, changing the introduction amount of chlorine gas or the reaction time. After the reaction is completed, if the obtained mixture is put into In an acidic aqueous solution such as hydrochloric acid, the resulting zinc bromide phthalocyanine precipitates. Thereafter, post-treatment such as filtration, washing, and drying is carried out to obtain zinc phthalocyanine bromide.

The zinc chlorobromide phthalocyanine pigment thus obtained is subjected to dry grinding in a pulverizer such as an attritor, a ball mill, a vibrating mill, a vibrating ball mill or the like as needed, followed by solvent salt milling or solvent boiling (Solvent) The boiling method or the like is pigmented, whereby a green brominated bromine phthalocyanine pigment exhibiting a high transmittance or contrast is obtained. The method of pigmentation is not particularly limited, and in terms of easily suppressing crystal growth and obtaining pigment particles having a large specific surface area, it is preferred to use a solvent salt milling treatment.

The term "solvent salt milling" means that the crude pigment, the inorganic salt and the organic solvent immediately after the synthesis are kneaded and ground. Specifically, a crude pigment, an inorganic salt, and an organic solvent in which it is not dissolved are added to a kneading machine, and kneading is carried out therein. As the kneading machine at this time, it is preferable to use, for example, a kneader, a kneader or a planetary mixer, or a circular rotating disc and a concentric rotating circle as described in Japanese Laid-Open Patent Publication No. 2006-77062. A continuous kneading machine for pulverizing space formed by the gap portion of the disk.

As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride or sodium sulfate is preferably used. Further, it is more preferred that the inorganic salt has an average particle diameter of 0.5 to 50 μm. Such an inorganic salt can be easily obtained by finely pulverizing a usual inorganic salt. Further, G59 manufactured by DIC Corporation can also be used as the green pigment a.

(A) The pigment may contain other green pigments in addition to the green pigment a. Examples of other green pigments include C.I. Pigment Green 7, C.I. Pigment Green 36, C.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, still more preferably 30% by mass or more. Furthermore, it is more preferably 50% by mass or more, particularly preferably 80% by mass or more, and usually 100% by mass or less. When it is more than the above lower limit value, there is a tendency to obtain more of the effect of the pigment.

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 particularly preferably 45% by mass or more; It is usually 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and particularly preferably 60% by mass or less. By setting it as the said lower limit or more, it is the tendency for the color gamut to become wide. Moreover, by setting it as the said upper limit or less, it is the tendency which improves the plate-formability.

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, and still more preferably 35% based on the total amount of the solid content. In addition, it is usually 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 45% by mass or less. In the case of the above range, there is a tendency that the dispersion stability is good and the effect which can be obtained by using a green pigment is more obtained.

In addition, 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 still more preferably 40% by mass or more, more preferably 40% by mass or more. It is 50% by mass or more; more preferably, it is 80% by mass or less, and more preferably 70% by mass or less. In the case of the above range, there is a tendency that the dispersion stability is good and the effect which can be obtained by using a green pigment is 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, still more preferably 40% by mass or more, and particularly preferably 50% based on the total amount of the solid content. Above mass%; again, preferably 80 The amount is less than or equal to, more preferably 70% by mass or less. In the case of the above range, there is a tendency that the dispersion stability is good and the effect which can be obtained by using a green pigment is more obtained.

The average primary particle diameter 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 is usually 0.005 μm or more. When the average primary particle diameter is within the above range, the deterioration of the depolarization characteristics and the decrease in the transmittance are suppressed.

Further, the average primary particle diameter of the pigment can be obtained by the following method. Namely, the pigment was ultrasonically dispersed in chloroform, dropped onto a sieve to which a sponge film was attached, dried, and observed by a transmission electron microscope (TEM) to obtain a primary particle image of the pigment. In the case of an organic pigment, the particle diameter of each pigment particle is defined as the area circle equivalent diameter of the diameter of the circle of the same area, and after determining the particle diameter of each of the plurality of pigment particles, the calculation formula is calculated according to the following formula. The average particle diameter was determined from the number average.

The particle size of each pigment _{particles: X 1, X 2, X} 3, X 4, ..., X i, ...... X m average particle diameter = ΣX _i / m

Further, in order to adjust the hue, the (A) pigment may contain a yellow pigment. Examples of the yellow pigment include CI Pigment Yellow (PY) 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 other compounds inserted into the 1:1 complex of azo barbituric acid and nickel or a tautomer thereof represented by the following formula (I) The compound (hereinafter referred to as "nickel azo complex represented by the formula (I)") or the like.

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

Among them, preferred are CI Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, and the nickel azo complex represented by the formula (I), and further preferably CI Pigment Yellow 83, 138, 139, 180, and a nickel azo complex represented by the formula (I).

The average primary particle diameter of the yellow pigments is usually 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.04 μm or less. In the case of microparticulation of the pigment, a method such as the above-described solvent salt milling can be preferably used. The content ratio of the yellow pigment contained in the pigment (A) is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less, still more preferably 70% by mass or less, and most preferably 60% by mass or less. Below mass%, In general, it is 0% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and particularly preferably 50% by mass or more. When it is below the above upper limit value, there is a tendency that the effect of the green pigment a can be more obtained.

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

[1-2] (B) Dispersant

The colored resin composition and the pigment dispersion of the present invention contain (B) a dispersant in order to stably disperse the (A) pigment. Among them, when a polymer dispersant is used, it is preferred because it has excellent dispersion stability over time. Examples of the polymer dispersant include an urethane dispersant, a polyethylenimine dispersant, a polyoxyethylene alkyl ether dispersant, and a polyoxyethylene glycol diester dispersant. A sorbitan fatty ester dispersant or an aliphatic modified polyester dispersant. Specific examples of such a dispersing agent include EFKA (registered trademark, manufactured by BASF Corporation), DisperBYK (registered trademark, manufactured by BYK-Chemie Co., Ltd.), Disparlon (registered trademark, manufactured by Nanben Chemical Co., Ltd.), and SOLSPERS ( Registered trademark, manufactured by Lubrizol, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), etc.

In the polymer dispersant, from the viewpoint of dispersibility or storage stability, a block copolymer having a functional group containing a nitrogen atom is preferred, and an acrylic block copolymer is more preferred. As the block copolymer having a functional group containing a nitrogen atom, it is preferred to include an A block having a quaternary ammonium salt group and/or an amine group in a side chain and having no quaternary ammonium salt group and/or an amine group. AB block copolymers and/or BAB block copolymers of B blocks.

The functional group of the nitrogen-containing atom may, for example, be a mono- or tertiary-order amine group, or a quaternary ammonium salt group, and preferably has a mono- to tertiary amine group from the viewpoint of dispersibility or storage stability, and more preferably It has a tertiary amino group. The structure of the repeating unit having a tertiary amino group in the above-mentioned block copolymer is not particularly limited, and from the viewpoint of dispersibility or storage stability, a repeating unit represented by the following formula (1) is preferred.

In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom, 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, and R ¹ and R ^{2 are} also They can be bonded to each other to form a ring 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, more preferably 10 or less, still more preferably 6 or less, still 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. Among them, a methyl group, an ethyl group and a propyl group are preferred. A butyl group, a pentyl group or a hexyl group is more preferably a methyl group, an ethyl group, a propyl group or a butyl group. Further, it may be either linear or branched. Further, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be contained.

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, more preferably 16 or less, still more preferably 12 or less, still more preferably 8 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, and a a phenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, a fluorenyl group, etc., among which phenyl, methylphenyl, ethylphenyl, dimethylphenyl, Or diethylphenyl, more preferably phenyl, methylphenyl or ethylphenyl.

The number of carbon atoms of the aralkyl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 7 or more, more preferably 16 or less, still more preferably 12 or less, still more preferably 9 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethyl group, a phenyl propyl group, a phenyl butyl group, a phenyl isopropyl group, and the like. Among them, a phenyl group is preferred. Methyl, phenylethyl, phenyl propyl or phenyl butyl, more preferably phenylmethylene or phenylethyl.

In the above, R ¹ and R ² are each independently preferably an alkyl group which may have a substituent, more preferably a methyl group or an ethyl group, from the viewpoints of dispersibility, storage stability, electrical reliability, and developability. .

Examples of the substituent which the alkyl group, the aralkyl group or the aryl group in the above formula (1) may have include a halogen atom, an alkoxy group, a benzamidine group, a hydroxyl group, etc., from the viewpoint of easiness of synthesis. Preferably, it is unsubstituted.

Further, in the above formula (1), examples of the cyclic structure in which R ¹ and R ² are bonded to each other include a nitrogen-containing heterocyclic monocyclic ring of 5 to 7 member rings or two of these condensation products. Condensation ring. The nitrogen-containing hetero ring is preferably one which does not have aromaticity, more preferably a saturated ring. Specifically, for example, the following (IV) can be mentioned.

These cyclic structures may further have a substituent.

In the above formula (1), examples of the divalent linking group X include an alkylene group having 1 to 10 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, a -CONH-R ¹³ - group, and -COOR ^{14 .} a group [wherein, R ¹³ and R ¹⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkoxyalkyl group)], etc., preferably -COO-R ¹⁴ -based.

Further, the content ratio of the repeating unit represented by the above formula (1) in the above-mentioned block copolymer to all repeating units is preferably 1 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more, and more preferably 15 mol% or more, more preferably 20 mol% or more, most preferably 25 mol% or more; further, preferably 90 mol% or less, more preferably 70 mol The ear% or less is further preferably 50% by mole or less, and more preferably 40% by mole or less. In the case of the above range, there is a tendency to achieve dispersion stability and high brightness at the same time.

Moreover, it is preferable that the block copolymer has a repeating unit represented by the following formula (2) from the viewpoint of improving compatibility with a binder component such as a solvent of a dispersing agent and improving dispersion stability.

In the above formula (2), R ¹⁰ is an exoethyl group or a propyl 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 from 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 more preferably 10 or less, more preferably 6 or less. More preferably, it is 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. Among them, a methyl group, an ethyl group and a propyl group are preferred. A butyl group, a pentyl group or a hexyl group is more preferably a methyl group, an ethyl group, a propyl group or a butyl group. Further, it may be either linear or branched. Further, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be contained.

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

Further, the content ratio of the repeating unit represented by the above formula (2) represented by the above formula (2) to all repeating units is preferably 1 mol% or more, more preferably 2 mol% or more, and still more preferably 4 mol% or more; further preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less. In the case of the above range, the compatibility with the binder component such as a solvent and the dispersion stability tend to be achieved at the same time.

Moreover, it is preferable that the block copolymer has a repeating unit represented by the following formula (3) from the viewpoint of improving compatibility with a binder component such as a solvent of a dispersing agent and improving 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 more preferably 10 or less, and still more preferably 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. Among them, a methyl group, an ethyl group and a propyl group are preferred. A butyl group, a pentyl group or a hexyl group is more preferably a methyl group, an ethyl group, a propyl group or a butyl group. Further, it may be either linear or branched. Further, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be contained.

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, and more preferably 16 or less, and still more preferably 12 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. Among these, it is preferably Phenyl, methylphenyl, ethylphenyl, dimethylphenyl or diethylphenyl, more preferably phenyl, methylphenyl or ethylphenyl.

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, and is preferably 16 or less, more preferably 12 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethyl group, a phenyl propyl group, a phenyl butyl group, a phenyl isopropyl group, and the like. Among them, a phenyl group is preferred. Methyl, phenylethyl, phenyl propyl or phenyl butyl, more preferably phenylmethylene or phenylethyl.

Among these, R ^{8 is} preferably an alkyl group or an aralkyl group from the viewpoint of solvent compatibility and dispersion stability, and more preferably a methyl group, an ethyl group or a phenylmethylene group. As the alkyl group in R ⁸ may have the substituent include: a halogen atom, an alkoxy group and the like. Further, examples of the substituent which 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 alkyl group represented by R ⁸ includes either a linear chain or a branched chain.

Further, the content ratio of the repeating unit represented by the above formula (3) represented by the above formula (3) to all repeating units is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more; further preferably 80 mol% or less, more preferably 70 mol% or less. In the case of the above range, there is a tendency to achieve dispersion stability and high brightness at the same time.

The block copolymer may have a repeating unit other than the repeating unit represented by the above formula (1), the repeating unit represented by the above formula (2), and the repeating unit represented by the above formula (3). Examples of such a repeating unit include a repeating unit derived from a styrene monomer such as styrene or α-methylstyrene or a (meth)acrylic acid salt such as (meth)acrylonium chloride. Monomer; (meth) acrylamide, N-methylol acrylamide, etc. (meth) acrylamide monomer; vinyl acetate; acrylonitrile; allyl epoxide propyl ether, crotonic acid Epoxy propyl ether; N-methyl propylene fluorenyl Monomer such as phenyl.

From the viewpoint of further improving the dispersibility, it is preferred to include an A block having a repeating unit represented by the above formula (1) and a B block having no repeating unit represented by the above formula (1). Segmental copolymer. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. Further, it is more preferred that the B block has a repeating unit represented by the above formula (2) and a repeating unit represented by the above formula (3).

In addition, the repeating unit other than the repeating unit represented by the above formula (1) may be contained in the A block, and examples of such a repeating unit include those derived from the above (meth)acrylate monomer. Repeat units and so on. The content of the repeating unit other than the repeating unit represented by the above formula (1) is preferably from 0 to 50 mol%, more preferably from 0 to 20 mol%, most preferably in the A block. The repeat unit is not included in the segment.

The repeating unit other than the repeating unit represented by the above formula (2) and the repeating unit represented by the above formula (3) may be contained in the B block, and examples of such a repeating unit may be exemplified as follows The repeating unit of the monomer: a styrene monomer such as styrene or α-methylstyrene; a (meth)acrylic acid monomer such as (meth)acrylonium chloride; (meth)acrylamide, N- (Meth) acrylamide amine monomer such as methylol acrylamide; vinyl acetate; acrylonitrile; allyl epoxidized propyl ether, butyric acid epoxidized propyl ether; N-methyl propylene fluorenyl Monomer such as phenyl. The content of the repeating unit other than the repeating unit represented by the above formula (2) and the repeating unit represented by the above formula (3) is preferably 0 to 50 mol%, more preferably 0. ~20% by mole, most preferably no such repeating unit is present in the B block.

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

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

Moreover, the molecular weight of the above-mentioned block copolymer is preferably in the range of 1,000 to 30,000 in terms of polystyrene-equivalent weight average molecular weight (hereinafter sometimes referred to as "Mw"). In the case of the above range, the dispersion stability is good, and the tendency to dry foreign matter is less likely to occur when coating by the slit nozzle method.

The block copolymer can be produced by a known method, and can be produced, for example, by living polymerization by introducing a monomer of each of the above repeating units. As the living polymerization method, Japanese Patent Laid-Open Publication No. Hei 9-62002, Japanese Patent Laid-Open Publication No. 2002-31713, or P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984); BC Anderson, GD Andrews et al, Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute, et al, Polym. J., 17, 977 (1985); K. Hatada, K. Ute , et al, Polym. J., 18, 1037 (1986); Right Hand Hao Yi, Putian Gengyi, Polymer Processing, 36, 366 (1987); Dong Cun Min Yan, Ze Benguang, Proceedings of Polymers, 46, 189 (1989); Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987); Xiangtian Zhuo San, Inoue Xiangping, Organic Synthetic Chemistry, 43, 300 (1985); DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 ( A well-known method described in 1987).

In the colored resin composition and the pigment dispersion liquid of the present invention, the content ratio of the (B) dispersant is not particularly limited, and is preferably 0.5 parts by mass or more, and more preferably 5 parts by mass based on 100 parts by mass of the (A) pigment. The amount is more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, and further preferably 70 parts by mass or less, more preferably 50 parts by mass or less, and further preferably It is 40 parts by mass or less. When it is in the above range, there is a tendency that a color-developing resin composition having excellent dispersion stability and high luminance can be obtained.

[1-3] Dispersing aid

In the colored resin composition and the pigment dispersion liquid of the present invention, a pigment derivative or the like may be contained as a dispersing aid in order to improve the dispersibility of the pigment and improve the dispersion stability. Examples of the pigment derivative include an azo type, a phthalocyanine type, a quinophthalone type, a benzimidazolone type, a quinophthalone type, an isoindolinone type, an isoporphyrin type, and the like. Department, lanthanide, indanthrene, lanthanide, purple ketone, diketopyrrolopyrrole, two It is a derivative such as a pigment. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonylamino group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, a decylamino group, and the like. The sulfonamide group and its quaternary salt, sulfonic acid group, and more preferably a sulfonic acid group, are preferably exemplified by bonding to the pigment skeleton directly or via an alkyl group, an aryl group or a heterocyclic group. Further, the substituents may be substituted with a plurality of pigment skeletons or a mixture of compounds having different substitution numbers. Specific examples of the pigment derivative include a sulfonic acid derivative of an azo pigment, a sulfonic acid derivative of a phthalocyanine pigment, a sulfonic acid derivative of a quinophthalone pigment, and a sulfonic acid derivative of an isoindoline pigment. a sulfonic acid derivative of an anthraquinone pigment, a sulfonic acid derivative of a quinacridone pigment, a sulfonic acid derivative of a diketopyrrolopyrrole pigment, A sulfonic acid derivative of a pigment or the like.

Among them, a derivative of a pigment which is less interfered with the hue of the green pigment is preferable, and a sulfonic acid derivative of the pigment yellow 138, a sulfonic acid derivative of the pigment yellow 139, and a sulfonic acid derivative of the pigment blue 15 are more preferable. The amount of the pigment derivative to be used is usually 0.1 parts by mass or more based on 100 parts by mass of the pigment (A), and is usually 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably. It is 5 parts by mass or less.

[1-4] Dispersion resin

In the pigment dispersion of the present invention, part or all of the resin selected from the following binder resins may be contained. Specifically, in the dispersion treatment step in the preparation of the pigment dispersion described below, the binder resin is assisted by a synergistic effect with the dispersant by including a part or all of the binder resin together with the dispersant. As a result of the dispersion stability, there is a possibility that the amount of the dispersant added can be reduced, which is preferable. As such, the resin used in the dispersion treatment step is sometimes referred to as a dispersion resin.

[1-5] (C) Solvent

(C) The solvent has a function of dissolving or dispersing a pigment, a dispersant, and other components in the colored resin composition or pigment dispersion of the present invention to adjust the viscosity. The solvent (C) may be any one which can dissolve or disperse each component.

In the colored resin composition of the first aspect of the present invention or the pigment dispersion liquid of the second aspect, the solvent (C) contains a high boiling point solvent having a boiling point of 150 ° C or more at 1013.25 hPa (hereinafter simply referred to as "high". Boiling point solvent"). Thus, by containing a solvent having a high boiling point, it is considered that the resolubility is improved, and it can be suppressed from being caused by the resolubility of the colored resin composition when it is specifically used in the case of using a specific zinc bromide phthalocyanine green pigment. Foreign matter is generated on the surface of the cured film.

The boiling point of the above-mentioned high-boiling point solvent at 1013.25 hPa (hereinafter simply referred to as "boiling point" unless otherwise specified) is usually 150 ° C or higher, preferably 170 ° C or higher, more preferably 190 ° C or higher, and further preferably 210 ° C or more; further preferably 340 ° C or less, more preferably 300 ° C or less, further preferably 280 ° C or less. When the value is at least the above lower limit value, the resolubility tends to be improved, and the efficiency of VCD (decompression drying) in the color filter manufacturing step is improved by setting it as the upper limit or less. .

Further, 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 further preferably 2,000 Pa or less, more preferably 1000 Pa or less. Further, it is preferably 500 Pa or less, and particularly preferably 400 Pa or less. When the value is equal to or higher than the lower limit value, the efficiency of VCD (decompression drying) in the color filter manufacturing step tends to increase, and the re-solubility tends to be improved by setting it as the upper limit or lower. .

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), and propylene glycol mono-positive Diol ether (boiling point: 170 ° C), diethylene glycol diethyl ether (boiling point: 188 ° C), diethylene glycol monoethyl ether (boiling point: 202 ° C) and other glycol ethers, 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 (Bleak: 170 ° C), diol ether acetate such as 3-methoxybutyl acetate (boiling point: 171 ° C), diol diol such as 1,3-butanediol diacetate (boiling point: 232 ° C) The acetate is preferably an acetate or a glycol ether, and more preferably a glycol alkyl ether acetate, from the viewpoint of solubility of the colored resin composition.

Further, in the colored resin composition of the first aspect of the invention or the pigment dispersion of the second aspect, the solvent (C) preferably contains a low boiling point solvent having a boiling point of less than 150 ° C at 1013.25 hPa (hereinafter) It is simply referred to as "low boiling solvent". As described above, the efficiency of VCD (depressurization drying) in the color filter manufacturing step tends to increase by containing a low boiling point solvent.

The boiling point of the low boiling point solvent at 1013.25 hPa (hereinafter simply referred to as "boiling point" unless otherwise specified) is usually less than 150 ° C, preferably 140 ° C or less, more preferably 130 ° C or less, and further preferably 120 ° C or less; more preferably 80 ° C or more, more preferably 90 ° C or more, further preferably 100 ° C or more. When the value is equal to or less than the above-described upper limit, the efficiency of the VCD (decompression drying) in the color filter manufacturing step tends to increase, and the resolubility tends to be improved by the above lower limit value. .

Specific examples of the low boiling point solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, n-butyl acetate, isobutyl acetate, isoamyl acetate, butyric acid. Ethyl ester, n-propyl butyrate, isopropyl butyrate, ethyl pyruvate, methyl 3-methoxypropionate, ethylene glycol methyl ether, ethylene glycol 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, acetic acid 2-methoxyethyl ester, 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, and the like.

The content ratio of the solvent (C) in the colored resin composition of the first aspect of the invention is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more. It is preferably 75 mass% or more, more preferably 80 mass% or more, further preferably 95 mass% or less, more preferably 90 mass% or less, still more preferably 8 mass% or less. When it is set to the above lower limit value, the storage stability of the coloring composition tends to be improved, and the film thickness at the time of coating tends to be equal to or lower than a predetermined value. .

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

Furthermore, in the colored resin composition of the first aspect of the 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, and more preferably 40% by mass or more. Further, it is preferably 60% by mass or more, and particularly preferably 80% by mass or more; more preferably, it is 99.5% by mass or less, and more preferably 99% by mass. The amount is not more than 5% by mass, more preferably 98% by mass or less, and particularly preferably 95% by mass or less. When it is set to the above lower limit value, the drying time of the coating film after application tends to be shortened, and when it is at most the above upper limit value, the solubility of the dried film in the solvent tends to be improved.

However, the content ratio of the solvent (C) in the pigment dispersion liquid 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, and still more preferably 70% by mass or more. In particular, it is preferably 80% by mass or more, more preferably 95% by mass or less, still more preferably 90% by mass or less, still more preferably 85% by mass or less. When the value is at least the above lower limit, the storage stability of the pigment dispersion liquid tends to be improved. Further, by setting it as the upper limit or less, it is possible to reduce the solvent ratio of the coloring composition to be introduced. .

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, and more preferably 2% by mass or more. Further, it is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 15% by mass or more, particularly preferably 40% by mass or more, most preferably 60% by mass or more; and more preferably 80% by mass. % or less is more preferably 60% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less. When the value is at least the above lower limit, the solubility of the dried film in the solvent tends to be improved. Further, by setting it as the upper limit or less, the drying time of the coating film after application 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 (C) solvent is not particularly limited, but is preferably 20% by mass or more, and more preferably 40% by mass or more. Further, it is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 99% by mass or less, more preferably 98% by mass or less. Further, it is preferably 95% by mass or less, and particularly preferably 90% by mass or less. When it is set to the above lower limit value, the drying time of the coating film after application tends to be shortened, and the solubility of the dried film in the solvent can be improved by setting it as the upper limit or less. .

On the other hand, in the colored resin composition of the third aspect of the invention, the solvent can be used without particular limitation, and for example, the following examples 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 tert-butyl ether, diethyl 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- a diol monoalkyl ether such as 3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether or tripropylene glycol methyl ether; 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 glycol dialkyl ethers; Alcohol 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 ether acetate, acetic acid 3- Glycol alkyl ether acetates such as methyl-3-methoxybutyl ester; ethylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanol diethyl a diol diacetate such as an acid ester; Alkyl acetates such as cyclohexanol acetate; pentyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl Ethers such as ethers, dihexyl ethers; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl Ketones such as ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl decyl ketone, methoxy methyl pentanone; ethanol , propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, benzyl alcohol Monohydric or polyhydric alcohols; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; cyclohexane, Alicyclic hydrocarbons such as cyclohexane, methylcyclohexene, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; amyl formate, ethyl formate, Ethyl acetate, butyl acetate, acetic acid Ester, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, Butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate a chain or cyclic ester such as propyl 3-methoxypropionate, butyl 3-methoxypropionate or γ-butyrolactone; 3-methoxypropionic acid, 3-ethoxyl Alkoxycarboxylic acids such as propionic acid; halogenated hydrocarbons such as chlorobutane and chloropentane; ether ketones such as methoxymethylpentanone; A nitrile such as acetonitrile or benzonitrile.

As a solvent which is commercially available as described above, examples thereof include mineral spirits, Varsol #2, Apco #18 Solvent, Apco thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TS28 Solvent, carbitol, Ethyl carbitol, butyl carbitol, methyl stilbene, ethyl celecoxib, ethyl stilbene acetate, methyl sarbuta acetate, diethylene glycol dimethyl ether ( Diglyme) (all product names) and so on. These solvents may be used alone or in combination of two or more.

In the case of forming a pixel of a color filter by photolithography, it is preferred to use a solvent having a boiling point of 100 to 200 ° C (at a pressure of 1013.25 [hPa]. The following are all the same boiling points). Range. More preferably, it has a boiling point of 120 to 170 °C. Among the above solvents, a glycol alkyl ether acetate is preferred in terms of a good balance between coatability and surface tension, and a relatively high solubility of constituent components in the composition.

Further, the glycol alkyl ether acetates may be used singly or in combination with other solvents. As the solvent to be used in combination, a diol monoalkyl ether is particularly preferable. Among them, in particular, the solubility of the constituent components in the composition is preferably propylene glycol monomethyl ether. Further, the diol monoalkyl ether has a high polarity, and when the amount is too large, the pigment tends to aggregate, and the storage stability of the colored resin composition obtained afterwards tends to decrease, and the storage stability is lowered. The ratio of the monoalkyl ethers is preferably from 5% by mass to 30% by mass, more preferably from 5% by mass to 20% by mass.

Further, it is also preferred to use a solvent having a boiling point of 150 ° C or more in combination. By using such a high boiling point solvent in combination, the colored resin composition is less likely to dry out, and it is difficult to cause an effect of destroying the mutual relationship of the pigment dispersion liquid caused by rapid drying. The content of the high boiling point solvent is preferably from 3% by mass to 50% by mass, more preferably 5% by mass based on the solvent. %~40% by mass, particularly preferably 5% by mass to 30% by mass. When the amount of the high-boiling solvent is too small, for example, the color component of the slit nozzle tip is precipitated and solidified to cause foreign matter defects. If too large, the drying temperature of the composition becomes slow, and the fear is caused. The problem of poor production distance (Tact) or pre-baked stitching in the vacuum drying process in the color filter manufacturing step is described. Further, the solvent having a boiling point of 150 ° C or higher may be a glycol alkyl ether acetate or a glycol alkyl ether. In this case, a solvent having a boiling point of 150 ° C or higher may not be additionally contained.

In the case where a pixel of a color filter is formed by an inkjet method, the boiling point of the solvent is usually 130 ° C or more and 300 ° C or less, preferably 150 ° C or more and 280 ° C or less. If the boiling point is too low, the uniformity of the obtained coating film tends to be poor. On the other hand, when the boiling point is too high, the effect of suppressing the drying of the curable resin composition is high as described below, and even after the thermal baking, a large amount of residual solvent is present in the coating film, which may cause deterioration in quality, or There are cases where the drying time due to vacuum drying or the like is prolonged, and the production time is increased. Further, the vapor pressure of the solvent is usually 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less, from the viewpoint of uniformity of the obtained coating film.

Further, when the color filter is manufactured by the inkjet method, the ink ejected from the nozzle is several to several tens of pL and is very fine. Therefore, the solvent is evaporated and the ink is concentrated before being sprayed into the periphery of the nozzle opening or in the pixel array. The tendency to dry. In order to avoid this, it is preferred that the solvent has a high boiling point; specifically, it preferably contains 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, and more preferably a boiling point of 220 ° C or higher. Further, the high-boiling solvent having a boiling point of 180 ° C or higher is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 70% by mass or more, based on the total amount of the solvent contained in the pigment dispersion liquid and/or the colored resin composition described below. 90% by mass or more. High boiling point solvent When it is less than 50% by mass, the effect of preventing evaporation of the solvent from the droplets may not be sufficiently exerted.

Preferred examples of the high-boiling solvent include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, and 1,3. - Butanediol diacetate, 1,6-hexanol diacetate, triacetin, and the like. Further, in order to adjust the viscosity of the pigment dispersion or the colored resin composition described below or to adjust the solubility of the solid portion, it is also effective to contain a solvent having a part of boiling point lower than 180 °C. As such a solvent, a solvent having a low viscosity, a high solubility, and a low surface tension is preferred, and an ether, an ester or a ketone is preferable. Among them, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate, and the like are particularly preferable.

On the other hand, when the solvent contains an alcohol, the discharge stability in the inkjet method may be deteriorated. Therefore, the alcohol is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, based on the total amount of the solvent.

Further, the content of the solvent in the entire coloring resin composition of the third aspect of the present invention is not particularly limited, and the upper limit thereof is usually 99% by mass or less, preferably 90% by mass or less, more preferably 85% by mass. the following. When it exceeds the above upper limit value, there are cases where the pigment, the dispersant, and the like become 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 view of viscosity or the like suitable for coating.

[1-6] (D) Adhesive resin

The colored resin composition of the present invention contains (D) a binder resin. By containing the (D) binder resin, the film hardenability by photopolymerization and the solubility of the developer can be simultaneously achieved. As the (D) binder resin, it is colored according to what means it is hardened. The resin composition tends to have a better resin. In the case of the photopolymerizable resin composition, as the binder resin, for example, Japanese Patent Laid-Open No. Hei 7-207211, Japanese Patent Laid-Open No. Hei 8-259876, Japanese Patent Laid-Open No. Hei 10-300922, and Japan A well-known polymer described in each of the publications of Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Compound. Preferably,

[1-6-1]: for a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, at least a part of the epoxy group of the copolymer has an unsaturated one unit An acid-soluble resin or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxyl group produced by the addition reaction

[1-6-2] Linear alkali-soluble resin having a carboxyl group in its main chain

[1-6-3] A resin obtained by adding an epoxy group-containing unsaturated compound to a carboxyl group of the above carboxyl group-containing resin

[1-6-4] (meth)acrylic resin

[1-6-5] An epoxy (meth) acrylate resin having a carboxyl group or the like. Hereinafter, each of these resins will be described.

[1-6-1] For a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, at least a part of the epoxy group of the copolymer is added with an unsaturated monobasic acid An alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxyl group produced by the addition reaction

One of the resins which are particularly preferred is "copolymerization of 5 to 90 mol % of an epoxy group-containing (meth) acrylate and 10 to 95 mol % of other radical polymerizable monomers. a resin obtained by adding 10 to 100 mol% of the epoxy group of the copolymer to an unsaturated monobasic acid, or 10 to 100 mol% of a hydroxyl group produced by the addition reaction An alkali-soluble resin obtained by forming a polybasic acid anhydride".

Examples of the (meth) acrylate containing the epoxy group include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and (meth)acrylic acid (3, 4-epoxycyclohexyl)methyl ester, 4-hydroxybutyl (meth)acrylate, glycidyl ether, and the like. Among them, preferred is glycidyl (meth)acrylate. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is preferably a mono (meth) acrylate having a structure represented by the following formula (V).

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

In particular, the structure represented by the general formula (V) is preferably a structure represented by the following formula (Va), (Vb), or (Vc). Applying the colored resin composition of the present invention to a color filter or a liquid crystal display element by introducing the structures into the binder resin In the case of a member, the heat resistance of the colored resin composition can be increased, or the strength of a pixel formed using the colored resin composition can be increased.

Further, the mono(meth)acrylate having a structure represented by the formula (V) may be used alone or in combination of two or more.

As the mono(meth)acrylate having the structure represented by the above formula (V), any of various known ones can be used as long as it has such a structure, and it is particularly preferably those represented by the following formula (VI).

In the formula (VI), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure of the above formula (V). In the copolymer of the above epoxy group-containing (meth) acrylate and another radical polymerizable monomer, a repeating unit derived from a mono(meth) acrylate having a structure represented by the above formula (VI) In the repeating unit derived from "other radical polymerizable monomer", it is preferably contained in an amount of 5 to 90 mol%, more preferably 10 to 70 mol%, and particularly preferably 15 to 50 mol%. %.

In addition, the "other radical polymerizable monomer" other than the mono (meth) acrylate having the structure represented by the above formula (VI) is not particularly limited. Specific examples include, for example, styrene, styrene α-, ortho, meta- or para-alkyl, nitro, cyano, decylamine, ester derivatives, and the like; butadiene, 2 , a diene such as 3-dimethylbutadiene, isoprene or chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, Isopropyl methacrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, (meth) acrylate Neopentyl ester, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecane (meth)acrylate Base ester, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, (meth)acrylic acid different Base ester, adamantyl (meth) acrylate, propynyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, decyl (meth) acrylate, (methyl) Acetyl o-benzyl acrylate, sunflower (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, decyl (meth) acrylate, (meth) acrylate Tetrahydrofuran ester, pyryl (meth)acrylate, benzyl (meth)acrylate, phenylethyl (meth)acrylate, toluene (meth)acrylate, 1,1,1-tri(meth)acrylate Fluoroethyl ester, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, triphenylmethyl (meth)acrylate, (methyl) )acrylic acid Base ester, 3-(N,N-dimethylamino)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. Acrylates; (meth) acrylamide, N,N-dimethyl decyl (meth) acrylate, N,N-diethyl decyl (meth) acrylate, (meth) acrylate N , (N-dipropyl decylamine, N,N-diisopropyl decylamine (meth) acrylate, (meth) acrylamide, etc.; (meth) acrylamide) , (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, etc.; Unsaturated dicarboxylic acid diesters such as diethyl benzoate, diethyl maleate, diethyl fumarate, diethyl itaconate; N-phenylbutylene A mono-n-butenylene diamine such as an amine, N-cyclohexylmethyleneimine, N-lauryl maleimide, N-(4-hydroxyphenyl) maleimide Amines; N-(methyl) propylene decyl phthalimide and the like.

In the "other radical polymerizable monomer", in order to impart excellent heat resistance and strength to the colored resin composition, it is effective to use styrene, benzyl (meth) acrylate, and monobutylene. At least one of quinone imines. In particular, in a repeating unit derived from "other radical polymerizable monomer", a repetition derived from at least one selected from the group consisting of styrene, benzyl (meth) acrylate, and mono-n-butylene diimide The content ratio of the unit is preferably from 1 to 70 mol%, and more preferably from 3 to 50 mol%.

Further, a copolymerization method using a known epoxy group-containing (meth) acrylate and the above other radical polymerizable monomer is a known solution polymerization method. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and an organic solvent which is usually used can be used. Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, 赛苏苏 acetate, and butyl racelus acetate; Diethylene glycol monoalkyl ether acetates such as ether acetate, carbitol acetate, butyl carbitol acetate; propylene glycol monoalkyl ether acetate; dipropylene glycol monoalkyl ether acetate Acetate such as ethylene glycol dialkyl ether; diethylene glycol dialkyl ether such as methyl carbitol, ethyl carbitol, butyl carbitol; triethylene glycol dialkyl Ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; 1,4-two Ethers such as alkane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, octane, and decane; petroleum ether and stone brain Petroleum solvent such as oil, hydrogenated naphtha, solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate; dimethylformamide, N-methylpyrrolidone, and the like. These solvents may be used singly or in combination of two or more.

The amount of use of the solvent is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, per 100 parts by mass of the copolymer obtained. If the amount of the solvent used is outside this range, it is difficult to control the molecular weight of the copolymer. In addition, the radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can start radical polymerization, and an organic peroxide catalyst or an azo compound catalyst which is usually used can be used. The organic peroxide catalyst is generally classified into ketone peroxide, peroxyketal, hydrogen peroxide, diallyl peroxide, dinonyl peroxide, peroxyester, and peroxydicarbonate. Ester.

As specific examples thereof, benzammonium peroxide and peroxide II are mentioned. Base, diisopropyl peroxide, dibutyl butyl peroxide, tert-butyl peroxybenzoate, third hexyl peroxybenzoate, tert-butyl peroxy 2-ethylhexanoate, peroxidation Tert-hexyl 2-ethylhexanoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5 - bis(t-butylperoxy)hexyl-3,3-isopropylhydroperoxide, tert-butyl hydroperoxide, peroxide II Base, two Hydrogen peroxide, acetonitrile peroxide, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, peroxy 3,3,5- Trimethylhexyl hydrazine, lauryl peroxide, 1,1-bis(t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis(trihexylperoxy) 3,3,5-trimethylcyclohexane and the like.

Further, examples of the azo compound catalyst include azobisisobutyronitrile and azodimethylamine. One or two or more types are used from the above depending on the polymerization temperature. A half-life free radical polymerization initiator. The amount of use of the radical polymerization initiator is from 0.5 to 20 parts by mass, preferably from 1 to 10 parts by mass, per 100 parts by mass of the total of the monomers used in the copolymerization reaction.

In the copolymerization reaction, the monomer used in the copolymerization reaction and the radical polymerization initiator are dissolved in a solvent, and the mixture is heated while stirring, and the monomer to which the radical polymerization initiator is added may be added dropwise to the monomer. It is carried out by heating and stirring the solvent. Further, a radical polymerization initiator may be added to the solvent and the monomer may be added dropwise at elevated temperature. The reaction conditions can be freely changed depending on the target molecular weight.

In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer preferably contains a repeat derived from an epoxy group-containing (meth) acrylate. The unit is 5 to 90 mol% and the repeating unit derived from other radical polymerizable monomers is 10 to 95 mol%, and further preferably comprises 20 to 80 mol% of the former and 80 to 20 mol% of the latter. It is especially good for the former 30-70% of the former and 70~30% of the latter.

When the (meth) acrylate containing an epoxy group is too small, the amount of addition of the following polymerizable component and the alkali-soluble component may be insufficient. On the other hand, if the epoxy group-containing (meth) acrylate is contained, If it is too much, and other radical polymerizable monomers are too small, there is a possibility that heat resistance or strength is insufficient. Then, an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali soluble component) are reacted with an epoxy group of a copolymer of a (meth)acrylate containing an epoxy resin and another radical polymerizable monomer.

As the "unsaturated monobasic acid" to which an epoxy group is added, a known one can be used, and examples thereof include an unsaturated carboxylic acid having an ethylenically unsaturated double bond. Specific examples thereof include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, α-position haloalkyl group, alkoxy group, halogen atom, nitro group, or cyano group. Substituted (methyl) A monocarboxylic acid such as acrylic acid. Among them, (meth)acrylic acid is preferred. These may be used alone or in combination of two or more.

By adding such a component, the binder resin used in the present invention can be imparted with polymerizability. The unsaturated monobasic acid is usually added in an amount of 10 to 100 mol%, preferably 30 to 100 mol%, more preferably 50 to 100 mol%, based on the epoxy group of the above copolymer. . When the addition ratio of the unsaturated monobasic acid is too small, there is concern about the adverse effect of the residual epoxy group on the temporal stability of the colored resin composition and the like. Further, as a method of adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be employed.

Further, as a "polybasic acid anhydride" for adding a hydroxyl group generated when an unsaturated monobasic acid is added to the epoxy group of the copolymer, a known one can be used. For example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorinated anhydride, etc.; A trivalent or higher anhydride such as tricarboxylic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride or biphenyltetracarboxylic anhydride. Among them, tetrahydrophthalic anhydride and/or succinic anhydride are preferred. These polybasic acid anhydrides may be used alone or in combination of two or more.

By adding such a component, the binder resin used in the present invention can be made alkali-soluble. The polybasic acid anhydrides are usually added to a hydroxyl group of 10 to 100 mol%, preferably 20 to 90 mol%, by addition of an unsaturated monobasic acid to the epoxy group of the above copolymer. More preferably 30 to 80 mole% bonus. If the addition ratio is too large, the residual film ratio at the time of development may be lowered, and if it is too small, the solubility may be insufficient. Further, as a method of adding a polybasic acid anhydride to the hydroxyl group, a known method can be employed.

Further, in order to increase the light sensitivity, after the addition of the polybasic acid anhydride described above, A part of the generated carboxyl group is added with a glycidyl (meth)acrylate or a glycidyl ether compound having a polymerizable unsaturated group. 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 group.

Also, the two can be added. Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group. As a commercial item, for example, the product name "DENACOL (registered trademark, the same below) EX-111", "DENACOL EX-121", "DENACOL EX-141", "DENACOL EX-145" manufactured by Nagase Chemical Industry Co., Ltd. "DENACOL EX-146", "DENACOL EX-171", "DENACOL EX-192", etc.

In addition, the structure of such a resin is known, for example, from Japanese Laid-Open Patent Publication No. Hei 8-297366, or JP-A No. 2001-89533. The weight average molecular weight (Mw) of the above-mentioned binder resin measured by GPC is preferably from 3,000 to 100,000, particularly preferably from 5,000 to 50,000. If the molecular weight is less than 3,000, the heat resistance or the film strength may be inferior, and if it exceeds 100,000, the solubility in the developer tends to be insufficient. Further, as a standard of the molecular weight distribution, the weight average molecular weight (Mw) / the number average molecular weight (Mn) is preferably from 2.0 to 5.0.

[1-6-2] Linear alkali-soluble resin having a carboxyl group in its main chain

The linear alkali-soluble resin having a carboxyl group in the main chain is not particularly limited as long as it has a carboxyl group, and is usually obtained by polymerizing a carboxyl group-containing polymerizable monomer.

Examples of the carboxyl group-containing polymerizable monomer include (meth)acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, and 2-(methyl)acryloxyloxy group B. Butyric acid, 2-(methyl) propylene methoxyethyl adipate, 2-(methyl) propylene Ethoxyethyl maleic acid, 2-(methyl)propenyloxyethylhexahydrophthalic acid, 2-(methyl)acryloxyethyl phthalate, 2-( Methyl) propylene methoxy succinic acid, 2-(methyl) propylene methoxy propyl adipic acid, 2-(methyl) propylene methoxy propyl maleic acid, 2- ( Methyl) propylene methoxy propyl hydrogen phthalate, 2-(methyl) propylene methoxy propyl phthalate, 2-(methyl) propylene oxy butyl succinic acid, 2- (Meth) propylene methoxy butyl adipate, 2-(methyl) propylene oxy butyl maleate, 2- (meth) propylene oxy butyl hydrogen phthalate, 2- a vinyl monomer such as (meth)acryloxybutyl phthalate; and addition of ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to acrylic acid a monomer derived from an ester; a single acid or anhydride obtained by adding a hydroxyalkyl (meth) acrylate to an acid such as succinic acid, maleic acid, phthalic acid, or the like; Body and so on. These can also be used in several ways.

Among them, (meth)acrylic acid and 2-(meth)acryloxyethyl succinic acid are preferred, and (meth)acrylic acid is further preferred. Further, the linear alkali-soluble resin having a carboxyl group in the main chain may be copolymerized with another polymerizable monomer having no carboxyl group and the carboxyl group-containing polymerizable monomer.

The other polymerizable monomer is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. ) butyl acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, Phenyloxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid Ester, 2-hydroxyethyl (meth)acrylate, mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tricyclodecyl (meth) acrylate, (meth) acrylate (meth)acrylates such as esters, adamantyl (meth)acrylates, vinyl aromatics such as styrene and its derivatives; vinyl compounds such as N-vinylpyrrolidone; N-cyclohexyl N-substituted maleimide, such as maleimide, N-phenyl maleimide, N-benzyl maleimide, poly(meth)acrylic acid Methyl ester macromonomer, polystyrene macromonomer, poly(meth)acrylic acid 2-hydroxyethyl macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer, etc. Giant monomer and so on. These can also be used in combination.

Particularly preferred are styrene, methyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyl (meth)acrylate Ethyl ester, hydroxypropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tricyclodecyl (meth) acrylate, N-cyclohexyl maleimide , N-benzyl maleimide, N-phenyl maleimide.

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

Specific examples of the linear alkali-soluble resin having a carboxyl group in the main chain include (meth)acrylic acid, methyl (meth)acrylate, benzyl (meth)acrylate, and (meth)acrylate. a polymerizable monomer having no hydroxyl group such as ester, isobutyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexylmethyleneimine, and 2-hydroxyethyl (meth)acrylate a copolymer of a hydroxyl group-containing monomer such as hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate; (meth)acrylic acid with methyl (meth)acrylate or benzyl (meth)acrylate a copolymer of (meth) acrylate such as ester, butyl (meth)acrylate, isobutyl (meth)acrylate or 2-hydroxyethyl methacrylate; a copolymer of (meth)acrylic acid and styrene; (meth)acrylic acid with styrene and α-methylstyrene a copolymer; a copolymer of (meth)acrylic acid and cyclohexylmethyleneimine, and the like.

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

Further, the weight average molecular weight in terms of polystyrene measured by GPC is usually from 2,000 to 80,000, preferably from 3,000 to 50,000, and more preferably from 4,000 to 30,000. When the weight average molecular weight is too small, the stability of the colored resin composition tends to be poor, and if it is too large, when it is used in the following color filter or liquid crystal display device, the solubility to the developer is deteriorated. tendency.

[1-6-3] A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group of the resin described in [1-6-2]

It is also preferable to add a resin containing an epoxy group-containing unsaturated compound to the carboxyl group of the linear alkali-soluble resin having a carboxyl group in the main chain.

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, (meth)acrylic acid propyl acrylate, allyl epoxidized propyl ether, α-ethyl methacrylate propyl acrylate, butenyl epoxidized propyl ether, (iso) crotonic acid Epoxypropyl ether, N-(3,5-dimethyl-4-epoxypropyl)benzylacrylamide, 4-hydroxybutyl (meth)acrylate, epoxypropyl ether, etc. The epoxy group-unsaturated compound is preferably an alicyclic epoxy group-containing unsaturated compound from the viewpoint of heat resistance or dispersibility of the following pigment.

Here, as the alicyclic epoxy group-containing unsaturated compound, examples of the alicyclic epoxy group include 2,3-epoxycyclopentyl group and 3,4-epoxycyclohexyl group. 7,8-epoxy[tricyclo[5.2.1.0]non-2-yl]yl and the like. In addition, as the ethylenically unsaturated group, those derived from a (meth) acrylonitrile group are preferable, and as the unsaturated compound containing an alicyclic epoxy group, the following general formula (5a) to (5m) are mentioned. ) the compound represented.

Formula (5a) ~ (5m) in, R ²¹ represents a hydrogen atom or a methyl group, R ²² represents a alkylene group, R ²³ represents a divalent hydrocarbon group, m is an integer of from 1 to 10. Furthermore, the two R ²¹ and R ^{22 of the} formula may be the same or different. The alkylene group of R ^{22 in} the formula (5a) to (5m) is preferably a carbon number of 1 to 10. Specifically, a methylene group, an ethylidene group, a propyl group, a butyl group, and the like can be illustrated, and a methylene group, an ethyl group, and a propyl group are preferable. Further, the hydrocarbon group of R ²³ is preferably a carbon number of 1 to 10, and examples thereof include an alkyl group and a phenyl group.

These alicyclic epoxy group-containing unsaturated compounds may be used alone or in combination of two or more. Among them, a compound represented by the formula (5c) is preferred, and a 3,4-epoxycyclohexylmethyl (meth)acrylate is preferred. When the above-mentioned epoxy group-containing unsaturated compound is added to the carboxyl group of the resin described in the above [1-6-2], a known method can be used. For example, it may be a tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, a quaternary ammonium salt such as benzyltriethylammonium chloride; a catalyst containing a carboxyl group and an unsaturated compound containing an epoxy group in an organic solvent in the presence of a catalyst such as pyridine or triphenylphosphine at a reaction temperature of 50~ The reaction is carried out at 150 ° C for several hours to several tens of hours, whereby an epoxy group-containing unsaturated compound is introduced into the carboxyl group of the resin.

The acid value of the carboxyl group-containing resin to which the epoxy group-containing unsaturated compound is introduced is usually 10 to 200 KOHmg/g, preferably 20 to 150 KOHmg/g, more preferably 30 to 150 KOHmg/g. Further, the weight average molecular weight in terms of polystyrene measured by GPC is usually from 2,000 to 100,000, preferably from 4,000 to 50,000, and more preferably from 5,000 to 30,000.

[1-6-4] (meth)acrylic resin

The (meth)acrylic resin refers to a polymer obtained by polymerizing (meth)acrylic acid and/or (meth)acrylic acid ester as a monomer component. As a better (A Examples of the acrylic resin include a polymer obtained by polymerizing a monomer component containing (meth)acrylic acid and benzyl (meth)acrylate, and a compound of the following formula (6) and/or ( 7) A polymer obtained by polymerizing a compound represented as a constituent monomer component.

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

In the formula (7), R ^1b represents a hydrogen atom or an alkyl group which may have a substituent, L ³ represents a divalent linking group or a direct bond, and X represents a group represented by the following formula (8) or a substituted adamantane. base. L ³ may also be bonded to R ^3b or R ^4b in the following formula (8) to form a ring.

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

[1-6-4a] A polymer obtained by polymerizing a monomer component containing (meth)acrylic acid and benzyl (meth)acrylate

A polymer obtained by polymerizing a monomer component containing (meth)acrylic acid and benzyl (meth)acrylate can be preferably used in terms of high affinity with a pigment.

The ratio of the above (meth)acrylic acid and benzyl (meth)acrylate in the monomer component is not particularly limited, and among all the monomer components, (meth)acrylic acid is usually 10 to 90% by mass, preferably 15 ~80% by mass, and more preferably 20 to 70% by mass. Further, among all the monomer components, benzyl (meth)acrylate is usually 5 to 90% by mass, preferably 15 to 80% by mass, and more preferably 20 to 70% by mass. When the amount of (meth)acrylic acid is too large, the surface of the coating film is likely to be rough at the time of development, and if it is too small, development may not be possible. Further, the amount of benzyl (meth)acrylate tends to be difficult to disperse regardless of too much or too little.

[1-6-4b] A polymer obtained by polymerizing a compound represented by the general formula (6) and/or (7) as a monomer component of an essential composition

First, the compound of the formula (6) will be described. In the ether dimer represented by the 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, and examples thereof include a methyl group and an ethyl group. a straight or branched alkyl group such as n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-pentyl, stearyl, lauryl or 2-ethylhexyl Aryl such as phenyl; cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, iso An alicyclic group such as an adamantyl group or a 2-methyl-2-adamantyl group; an alkyl group substituted with an alkoxy group such as a 1-methoxyethyl group or a 1-ethoxyethyl group; a benzyl group, etc. An alkyl group substituted with an aryl group or the like. Among these, in terms of heat resistance, a substituent such as a methyl group, an ethyl group, a cyclohexyl group, a benzyl group or the like which is not easily desorbed from a primary or secondary carbon by acid or heat is preferable. Further, R ^1a and R ^2a may be the same substituent or different substituents.

Specific examples of the ether dimer include 2,2'-[oxybis(methylene)]bis(2-acrylic acid) dimethyl ester and 2,2'-[oxybis (Asian). Methyl)]bis(2-acrylic acid) diethyl ester, 2,2'-[oxybis(methylene)]bis(2-acrylic acid) di(n-propyl) ester, 2,2'-[oxygen Bis(methylene)]bis(2-acrylic acid) di(isopropyl) ester, 2,2'-[oxybis(methylene)]bis(2-acrylic acid) di(n-butyl) ester , 2,2'-[oxybis(methylene)]bis(2-acrylic acid) di(isobutyl) ester, 2,2'-[oxybis(methylene)]bis(2-acrylic acid Bis(tert-butyl)ester, 2,2'-[oxybis(methylene)]bis(2-acrylic acid) bis(tripentyl)ester, 2,2'-[oxybis( Methylene)]bis(2-acrylic acid) bis(stearyl)ester, 2,2'-[oxybis(methylene)]bis(2-acrylic acid) bis(lauryl)ester, 2,2 '-[oxybis(methylene)]bis(2-acrylic acid) bis(2-ethylhexyl)ester, 2,2'-[oxybis(methylene)]bis(2-acrylic acid) (1-methoxyethyl)ester, 2,2'-[oxybis(methylene)]bis(2-acrylic acid) bis(1-ethoxyethyl)ester, 2,2'-[ Oxyxybis(methylene)]bis(2-acrylic acid) dibenzyl ester, 2,2'-[oxybis(methylene)]bis(2-acrylic acid) diphenyl ester, 2,2 '-[oxybis(methylene)]bis(2-acrylic acid)dicyclohexyl ester, 2,2'-[oxybis(methylene)]bis(2-acrylic acid) bis(t-butyl group) Cyclohexyl)ester, 2,2'-[oxybis(methylene)]bis(2-acrylic acid) bis(dicyclopentadienyl)ester, 2,2'-[oxybis(methylene) )] bis(2-acrylic acid) bis(tricyclodecyl)ester, 2,2'-[oxybis(methylene)]bis(2-acrylic acid) di(iso) Ester, 2,2'-[oxybis(methylene)]bis(2-acrylic acid) diadamantyl, 2,2'-[oxybis(methylene)]bis(2- Acrylic acid bis(2-methyl-2-adamantyl) ester and the like.

In these, it is especially preferred that 2,2'-[oxybis(methylene)]bis(2-acrylic acid) Dimethyl, 2,2'-[oxybis(methylene)]bis(2-acrylic acid) diethyl ester, 2,2'-[oxybis(methylene)]bis(2-acrylic acid) Dicyclohexyl ester, 2,2'-[oxybis(methylene)]bis(2-acrylic acid) dibenzyl ester. These ether dimers may be used alone or in combination of two or more.

When the acrylic resin is obtained, the ratio of the ether dimer in the monomer component is not particularly limited, but is usually 2 to 60% by mass, preferably 5 to 55% by mass, based on the total monomer component, and further Good is 5~50% by mass. When the amount of the ether dimer is too large, it may be difficult to obtain a low molecular weight at the time of polymerization, or it may be easily gelled. On the other hand, if the amount is too small, the coating performance such as transparency or heat resistance may be insufficient. .

Next, the compound of the formula (7) will be described. In the formula (7), R ^{1b is} preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group. Further, in the general formula (8), examples of the organic group of R ^2b , R ^3b and R ^4b include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group and an anthracene, respectively. a base, a carboxyl group, a decyloxy group or 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 cycloalkenyl group having 3 to 18 carbon atoms. And an alkoxy group having 1 to 15 carbon atoms, an alkylthio group having 1 to 15 carbon atoms, a fluorenyl group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon number, or a decyloxy group having 1 to 15 carbon atoms, and further 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 , a preferred substituent is a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 10 carbon atoms. L ^1, L ² is a divalent linking group as long as, L ³ groups as long as the link is a direct bond or a divalent is not particularly limited, preferably at least any one of L ¹ or L ² of one or more carbon atoms of a connecting base. Further, L ¹ , L ² and L ³ are each independently and preferably a direct bond, an alkyl group having 1 to 15 carbon atoms, -O-, -S-, -C(=O)-, and a carbon number of 1 to 15. A combination of an alkenyl group, a phenyl group, or the like.

As a preferred combination of L ¹ , L ² and L ³ , L ³ is a direct bond, an alkylene group having 1 to 5 carbon atoms, or a ring formed by bonding with R ^3b or R ^4b , and L ¹ and L ² are An alkyl group having 1 to 5 carbon atoms. Further, preferred examples of the formula (8) include compounds represented by the following formula (9).

In the formula (9), R ^2b , R ^3b , R ^4b , L ¹ , L ² and * have the same meanings as in the formula (8), and R ^5b and R ^6b each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, Amine group, or organic group. In the general formula (9), examples of the organic group of R ^5b and R ^6b each independently include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, a decyl group, a carboxyl group, or The decyloxy group or the like is 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, and a carbon number of 1 to 15 alkoxy group, carbon number 1 to 15 alkylthio group, carbon number 1 to 15 fluorenyl group, carbon number 1 carboxyl group, or carbon number 1 to 15 decyloxy group, and more preferably carbon number 1~ An alkyl group of 10 or a cycloalkyl group having 3 to 15 carbon atoms.

Preferred examples of R ^5b and R ^6b include a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 10 carbon atoms. Further, each of the alkyl group of R ^1b , each of the organic groups of R ^2b , R ^3b and R ^4b , the divalent linking group of L ¹ , L ² and L ³ and the adamantyl group of X may each independently have a substituent, specifically In other words, the following substituents can be mentioned.

Halogen atom; hydroxyl group; nitro group; cyano group; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, third pentyl group, n-hexyl group, positive a linear or branched alkyl group having 1 to 18 carbon atoms such as heptyl, n-octyl or trioctyl; carbon 3 to 18 such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or adamantyl a cycloalkyl group; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group or a hexenyl group; a cycloalkenyl group having 3 to 18 carbon atoms such as a cyclopentenyl group or a cyclohexenyl group; Oxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy, tert-butoxy, pentyloxy, third pentyloxy, n-hexyloxy, n-glycol a linear or branched alkoxy group having 1 to 18 carbon atoms such as an oxy group, a n-octyloxy group or a third octyloxy group; a methylthio group, an ethylthio group, a n-propylthio group, an isopropylthio group and a n-butylene sulfide Carbon number 1 to 18 such as a base, a second butylthio group, a third butylthio group, a pentylthio group, a third pentylthio group, a n-hexylthio group, an n-heptylthio group, a n-octylthio group, a third octylthio group, and the like Linear or branched alkylthio; phenyl, tolyl, xylyl, An aryl group having 6 to 18 carbon atoms; a aralkyl group having 7 to 18 carbon atoms such as a benzyl group or a phenethyl group; a linear chain having 2 to 18 carbon atoms such as a vinyloxy group, a propyleneoxy group or a hexenyloxy group; branched alkenyloxy group; vinyl group, propenyl group, hexenyl group and the like having a carbon number of 2 to 18 straight-chain or branched alkenyl group; -COR ¹⁷ represented by the acyl; carboxyl; represented by -OCOR ¹⁸ the acyl groups; -NR ¹⁹ R ²⁰ represented by the group; the acyl group represented by -NHCOR ^21; represented by the urethane group -NHCOOR ^22; -CONR ²³ R ²⁴ represented by the group A Sulfhydryl group; carboxylate group represented by -COOR ²⁵ ; sulfonamide group represented by -SO ₃ NR ²⁶ R ²⁷ ; sulfonate group represented by -SO ₃ R ²⁸ ; 2-thienyl group, 2-pyridine Base, furanyl, Azolyl, benzo Azyl, thiazolyl, benzothiazolyl, a saturated or unsaturated heterocyclic group such as a phenyl group, a pyrrolidinyl group or a tetrahydrothiophenyl group; a trialkylalkylene group such as a trimethyldecyl group.

Further, R ¹⁷ to R ²⁸ each independently represent 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 an aralkyl group which may have a substituent. Further, the positional relationship of the above substituents is not particularly limited, and when it has a plurality of substituents, it may be the same or different.

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

[Chemistry 16]

In the monomer component constituting the polymer of [1-6-4b] of the present invention, the ratio of the formula (7) is not particularly limited, and is usually from 0.5 to 60% by mass based on the total of the monomer components, preferably 1 to 55% by mass, and more preferably 5 to 50% by mass. If it is too much, the dispersion stability of the dispersion may be lowered when it is used as a dispersant. On the other hand, if it is too small, the scum suitability may be lowered.

The (meth)acrylic resin of [1-6-4] in the present invention preferably contains the polymers described in [1-6-4a] and [1-6-4b], and each has an acid group. . By having an acid group, the obtained colored resin composition can be made into a coloring resin which can be hardened by a crosslinking reaction (hereinafter referred to as acid-epoxy hardening) by reacting an acid group with an epoxy group to form an ester bond. The composition or the composition which can develop the uncured portion 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 used alone or in combination of two or more.

When an acid group is introduced 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 may be used (hereinafter sometimes referred to as "to introduce an acid" The monomer "" can be used as a monomer component. In the case where "a monomer capable of imparting an acid group after polymerization" is used as a monomer component, it is necessary to carry out a treatment for imparting an acid group as described below after the polymerization.

Examples of the monomer having an acid group include a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid, and a monomer having a phenolic hydroxyl group such as N-hydroxyphenyl maleimide. A monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride, and the like, and particularly preferably (meth)acrylic acid. Examples of the monomer which can provide an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or a monomer having an epoxy group such as glycidyl (meth)acrylate. A monomer having an isocyanate group such as 2-isocyanate ethyl (meth)acrylate or the like.

These monomers for introducing an acid group may be used alone or in combination of two or more. When the monomer component in the case where the (meth)acrylic resin is obtained also includes the above-mentioned monomer for introducing an acid group, the content ratio thereof is not particularly limited, and is usually 5 to 70% by mass based on the entire monomer component. Preferably, it is 10 to 60% by mass.

Further, the [1-6-4] (meth)acrylic resin may be a radical polymerizable double bond. When a radically polymerizable double bond is introduced into the above-mentioned (meth)acrylic resin, for example, "a monomer which can impart a radical polymerizable double bond after polymerization" (hereinafter sometimes referred to as "introduction of freedom" After the monomer of the polymerizable double bond is polymerized as a monomer component, the following treatment for imparting a radical polymerizable double bond is carried out. Just fine.

Examples of the monomer which can impart a radically polymerizable double bond after the polymerization include a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid, and a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride. Monomer; (meth)acrylic acid propyl acrylate, (meth)acrylic acid 3,4-epoxycyclohexyl methyl ester, o- (or m, or p-) vinyl benzyl epoxy propyl ether, etc. A monomer such as an oxy group. These monomers for introducing a radically polymerizable double bond may be used alone or in combination of two or more.

When the monomer component in the case of obtaining the (meth)acrylic resin of [1-6-4] also contains the monomer for introducing a radical polymerizable double bond, the content ratio thereof is not particularly limited, and usually It is 5 to 70% by mass, preferably 10 to 60% by mass based on all the monomer components. In the case where the (meth)acrylic resin of the present invention is a polymer having the compound of the above formula (6) as an essential monomer component described in the section [1-6-4a], it is preferred to have Epoxy group.

When an epoxy group is introduced, for example, a monomer having an epoxy group (hereinafter sometimes referred to as "a 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, ortho (or m- or p-)vinyl group. Benzylepoxypropyl ether and the like. These monomers for introducing an epoxy group may be used alone or in combination of two or more.

When the monomer component in the case of obtaining the (meth)acrylic resin of [1-6-4] also includes the above-mentioned monomer for introducing an epoxy group, the content ratio thereof is not particularly limited, and is usually in all singles. The body composition is preferably from 5 to 70% by mass, preferably from 10 to 60% by mass. The monomer component in the case of obtaining the (1-6)] (meth)acrylic resin may contain other copolymerizable monomers as needed in addition to the above-mentioned essential monomer components.

Examples of other copolymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (methyl). ) n-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, methyl 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, (a) (meth) acrylate such as benzyl acrylate or 2-hydroxyethyl (meth) acrylate; aromatic vinyl compound such as styrene, vinyl toluene or α-methyl styrene; N-phenyl cis N-substituted maleimide such as butylene diimide, N-cyclohexyl maleimide, butadiene or substituted butadiene compound such as butadiene or isoprene; Ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride and acrylonitrile; vinyl esters such as vinyl acetate.

Among these, methyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. These other monomers which can be copolymerized may be used alone or in combination of two or more. Further, in the case where a part or all of the (meth)acrylic resin is used as a dispersing agent as described below, it is preferred to use benzyl (meth)acrylate, and the content thereof is usually preferably in all the monomer components. It is 1 to 70% by mass, preferably 5 to 60% by mass.

When the monomer component in the case where the above (meth)acrylic resin is obtained also includes the other monomer which can be copolymerized, the content ratio thereof is not particularly limited, but is preferably 95% by mass or less, more preferably 85 mass%. %the following. Next, a method (polymerization method) for producing a (meth)acrylic resin of [1-6-4] will be described.

The polymerization method of the above monomer component is not particularly limited, and various conventionally known methods can be employed, and it is particularly preferred to use a solution polymerization method. Further, the polymerization temperature or the polymerization concentration (the polymerization concentration = [total mass of the monomer component / (total mass of the monomer component + solvent mass)] × 100) is based on the kind or ratio of the monomer component to be used, Target polymer The molecular weight varies. The polymerization temperature is preferably 40 to 150 ° C, and more preferably the polymerization temperature is 60 to 130 ° C. Further, the polymerization concentration is preferably from 5 to 50% by mass, and more preferably from 10 to 40% by mass.

Further, when a solvent is used in the polymerization, a solvent used in a usual radical polymerization reaction may be used. Specifically, for example, tetrahydrofuran, two Ethers such as alkane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, An ester such as propylene glycol monomethyl ether acetate or 3-methoxybutyl acetate; an alcohol such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether or propylene glycol monomethyl ether; toluene, two An aromatic hydrocarbon such as toluene or ethylbenzene; chloroform; dimethyl hydrazine or the like. These solvents may be used alone or in combination of two or more.

When the above monomer component is polymerized, a polymerization initiator may also be used as needed. The polymerization initiator is not particularly limited, and examples thereof include cumene hydroperoxide, diisopropylbenzene hydroperoxide, dibutyl butyl peroxide, laurel peroxide, benzammonium peroxide, and peroxidation. Organic peroxides such as tert-butyl isopropyl carbonate, third amyl peroxide 2-ethylhexanoate, and tert-butyl 2-ethylhexanoate; 2,2'-azobis(iso Butyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-A An azo compound such as dimethylpropionate). These polymerization initiators may be used alone or in combination of two or more.

In addition, the amount of the initiator to be used is not particularly limited as long as it is appropriately determined depending on the combination of the monomers to be used, the reaction conditions, the molecular weight of the target polymer, and the like; In terms of obtaining a polymer having a weight average molecular weight of several thousands to several tens of thousands, it is usually 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass based on the total of the monomer components. Also, in order to adjust the molecular weight, it is also possible to add Chain transfer agent. Examples of the chain transfer agent include a mercaptan chain transfer agent such as n-dodecyl mercaptan, mercaptoacetic acid or methyl thioglycolate, and an α-methylstyrene dimer, and the chain transfer effect is preferred. It is high in n-dodecyl mercaptan and thioglycolic acid, which can reduce residual monomers and is easy to obtain. In the case of using a chain transfer agent, the amount thereof to be used may be appropriately set depending on the combination of the monomers to be used, the reaction conditions, the molecular weight of the target polymer, and the like, and is not particularly limited, so that gelation does not occur. In the case of obtaining a polymer having a weight average molecular weight of several thousands to several tens of thousands, it is usually 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass based on the total of the monomer components.

Further, when the compound of the formula (6) is used as the essential monomer component, it is considered that the cyclization reaction of the ether dimer is carried out simultaneously in the above polymerization reaction, and the cyclization ratio of the ether dimer at this time may not necessarily be Must be 100% by mole. When the acrylic resin is obtained, when the acid group is introduced by using the monomer capable of imparting an acid group as a monomer component, it is necessary to carry out a treatment for imparting an acid group after the polymerization. The treatment differs depending on the kind of the monomer to be used, for example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate is used, as long as succinic anhydride or tetrahydroortylene is added. An acid anhydride such as formic anhydride or maleic anhydride may be used. When a monomer having an epoxy group such as glycidyl (meth)acrylate is used, an N-methylaminobenzoic acid or N-methylaminophenol may be added to have an amine group and an acid group. The compound may be added with an acid such as (meth)acrylic acid, and the resulting hydroxyl group may be added with an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride or maleic anhydride. When a monomer having an isocyanate group such as 2-isocyanate ethyl (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 the above [1-6-4] is obtained, it is introduced as a monomer component by using the monomer capable of imparting a radical polymerizable double bond as described above. In the case of a radically polymerizable double bond, it is necessary to carry out a treatment for imparting a radical polymerizable double bond after the polymerization. This treatment differs depending on the kind of the monomer to be used. For example, when a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid is used, it is only necessary to add glycidyl (meth)acrylate, A compound having an epoxy group and a radical polymerizable double bond such as 3,4-epoxycyclohexylmethyl (meth)acrylate or o- (or m- or p-)vinylbenzylepoxypropyl ether may be used. 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 radical polymerizable double bond such as 2-hydroxyethyl (meth)acrylate may be added. . Use epoxy methacrylate (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, o- or (or, or) p-vinylbenzyl epoxy propyl ether, etc. In the case of a monomer, a compound having an acid group and a radical polymerizable double bond such as (meth)acrylic acid may be added.

The weight average molecular weight of the (meth)acrylic resin of the above [1-6-4] is not particularly limited, and it is preferably a polystyrene-converted weight average molecular weight measured by GPC of from 2,000 to 200,000, more preferably It is 4000~100000. When the weight average molecular weight exceeds 200,000, the viscosity may become too high to form a coating film. On the other hand, if it is less than 2,000, the heat resistance tends to be insufficient.

When the (meth)acrylic resin has an acid group, the acid value is preferably from 30 to 500 mgKOH/g, more preferably from 50 to 400 mgKOH/g. When the acid value is less than 30 mgKOH/g, it is difficult to apply it to alkaline development. When it exceeds 500 mgKOH/g, the viscosity tends to be too high and the coating film tends to be formed. In the above-mentioned (meth)acrylic resin component, the polymer represented by the formula (6) as a monomer component is a known compound, and, for example, Japanese Patent Laid-Open No. 2004-300203 The compound described in the publication of Japanese Laid-Open Patent Publication No. 2004-300204.

[1-6-5] Epoxy (meth) acrylate resin having a carboxyl group

An epoxy (meth) acrylate resin is obtained by adding an α,β-unsaturated monocarboxylic acid to an epoxy resin, or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group at an ester moiety, and further with a polybasic acid anhydride. Synthesis by reaction. The reaction product does not substantially have an epoxy group in chemical structure, and is not limited to "(meth) acrylate". Since epoxy resin is a raw material and "(meth) acrylate" is a representative example, Named as usual.

As the epoxy resin to be used as a raw material, for example, a bisphenol A type epoxy resin (for example, "Epikote (registered trademark, the same below) 828", "Epikote 1001", "Epikote 1002" manufactured by Mitsubishi Chemical Corporation, "Epikote 1004", etc.) 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" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323) , softening point 76 ° C)), bisphenol F resin (such as "Epikote 807", "EP-4001", "EP-4002", "EP-4004", etc.) by Mitsubishi Chemical Corporation, by bisphenol F An epoxy resin obtained by reacting an alcoholic hydroxyl group of an epoxy resin with epichlorohydrin (for example, "NER-7406" (epoxy equivalent 350, softening point 66 ° C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S type Epoxy resin, biphenyl epoxypropyl ether (such as "YX-4000" manufactured by Mitsubishi Chemical Corporation), and phenol novolac epoxy resin (such as "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., manufactured by Mitsubishi Chemical Corporation "EP-152", "EP-154", "DEN-438" manufactured by Dow Chemical Co., Ltd., (neighbor, inter, and pair) A cresol novolak type epoxy resin (for example, "EOCN (registered trademark, the same below) -102S", "EOCN-1020", "EOCN-104S") manufactured by Nippon Kayaku Co., Ltd., triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.) and trisphenol methane-based epoxy resin (for example, "EPPN (registered trademark)-501" and "EPN-502" manufactured by Nippon Kayaku Co., Ltd. "EPPN-503"), epoxy resin (such as phenolic epoxy resin "ESF-300" manufactured by Nippon Steel Chemical Co., Ltd.), and alicyclic epoxy resin (Celloxide (registered trademark) manufactured by Daicel Chemical Industry Co., Ltd. , the same as the above) 2021P", "Celloxide EHPE"), a dicyclopentadiene type epoxy resin obtained by epoxy-propylating a phenol resin obtained by the reaction of dicyclopentadiene with phenol (for example) "XD-1000" manufactured by Nippon Kayaku Co., Ltd., "EXA-7200" manufactured by Dainippon Ink Co., Ltd., "NC-3000" manufactured by Nippon Kayaku Co., Ltd., "NC-7300"), and the following structural formula Epoxy resin (refer to Japanese Laid-Open Patent Publication No. Hei-4-355450) and the like.

These may be used alone or in combination of two or more. As another example of the epoxy resin, a copolymerization type epoxy resin can be mentioned. Examples of the copolymerizable 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 is obtained by reacting a compound containing a monofunctional ethylenically unsaturated group other than the above (hereinafter referred to as "the second component of the copolymerized epoxy resin"). The copolymer, the compound containing a monofunctional ethylenically unsaturated group is, for example, selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, (meth)acrylic acid, styrene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methyl styrene, glycerol mono (methyl An acrylate or one or two of the compounds represented by the following formula (10) on.

In the formula (10), R ⁶¹ represents a hydrogen atom or an ethyl group, and 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 formula (10) include polydiethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, and tetraethylene glycol mono(meth)acrylate. Ethylene glycol mono (meth) acrylate; methoxy diethylene glycol mono (meth) acrylate, methoxy triethylene glycol mono (meth) acrylate, methoxy tetraethylene glycol single ( An alkoxy polyethylene glycol (meth) acrylate such as methyl acrylate.

The molecular weight of the above copolymerized epoxy resin is preferably from about 1,000 to 200,000. In addition, the amount of the first component of the copolymerized epoxy resin is preferably 10% by mass or more, and particularly preferably 20% by mass or more, based on the second component of the copolymerized epoxy resin. The content is preferably 70% by mass or less, and more 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 Nippon Oil Co., Ltd. , "CP-50S", "CP-50M", "CP-20MA", etc.

The molecular weight of the raw material epoxy resin is usually in the range of 200 to 200,000, preferably 300 to 100,000, based on the weight average molecular weight in terms of polystyrene measured by GPC. When the weight average molecular weight is less than the above range, there are many problems in the film formability; on the other hand, when the resin exceeds the above range, there is an addition reaction of the α,β-unsaturated monocarboxylic acid. It is easy to gel and it is difficult to manufacture.

Examples of the α,β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid, etc., preferably acrylic acid and methacrylic acid, especially acrylic acid, which is more reactive. good. Examples of the α,β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety include 2-butanedimethoxyethyl acrylate, 2-butyleneoxyethyl acrylate, and acrylic acid-2. - o-phthalic acid ethyl ester, 2-hexahydrophthalic acid ethyl acrylate, 2-butyl dimethoxy methacrylate, 2-butylene methacrylate Dimethoxyethyl ester, 2-phthalic acid ethyl methacrylate, 2-hexahydrophthalic acid ethyl methacrylate, 2-butane dibutanoic acid Ethyl oxyethyl ester, etc., preferably 2-butyleneoxyethyl acrylate and 2-phthalic acid ethyl acrylate, particularly preferably 2-butylene oxide Base ethyl ester. These may be used alone or in combination of two or more.

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

The amount of the α,β-unsaturated monocarboxylic acid or its ester to be used is preferably from 0.5 to 1.2 equivalents, more preferably from 0.7 to 1.1 equivalents, per equivalent of the epoxy group of the starting epoxy resin. . When the amount of the α,β-unsaturated monocarboxylic acid or its ester used is small, the amount of introduction of the unsaturated group is insufficient, and the reaction with the polybasic acid anhydride is also insufficient. Further, it is also disadvantageous that a large amount of epoxy groups remain. On the other hand, when the amount used is large, the α,β-unsaturated monocarboxylic acid or an ester thereof remains as an unreacted product. In either case, the tendency of the hardening characteristics to deteriorate is observed.

As an epoxy resin added to an α,β-unsaturated carboxylic acid or its ester The polybasic acid anhydride to be added may, for example, be maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or pyromellitic acid. Anhydride, trimellitic anhydride, benzophenone tetracarboxylic dianhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chloric anhydride, methyltetrahydroortylene Formic anhydride, biphenyltetracarboxylic dianhydride, etc., preferably maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride And pyromellitic anhydride, trimellitic anhydride, biphenyltetracarboxylic dianhydride, and particularly preferred compounds are tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. These may be used alone or in combination of two or more.

The addition reaction of the polybasic acid anhydride can also be carried out by a known method, and the reaction can be carried out by continuing the reaction under the same conditions as the addition reaction of the α,β-unsaturated carboxylic acid or its ester. The addition amount of the polybasic acid anhydride is preferably such that the acid value of the epoxy acrylate resin to be produced 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 lacking; and if the acid value of the resin is too large, the curing property tends to be inferior.

In addition, as the epoxy acrylate resin having a carboxyl group, for example, a naphthalene-containing resin described in Japanese Laid-Open Patent Publication No. Hei 6-49174, Japanese Patent Laid-Open Publication No. Hei No. 2003-89716, and Japanese Patent Laid-Open No. 2003-165830 The ruthenium-containing resin described in Japanese Laid-Open Patent Publication No. Hei. No. 2005-355735, and the Japanese Patent Laid-Open Publication No. Hei. No. Hei. A resin described in JP-A-2004-295084 or the like.

In addition, a commercially available epoxy acrylate resin having a carboxyl group can be used as a commercial product, and examples thereof include "ACA-200M" manufactured by Daicel Co., Ltd., and the like. Make For the binder resin, for example, an acrylic adhesive described in JP-A-2005-154708 or the like can be used. Among the above various binder resins, it is particularly preferable that the copolymer of the epoxy group-containing (meth) acrylate and another radical polymerizable monomer is [1-6-1], and the copolymer has A resin obtained by adding at least a part of an epoxy group to an unsaturated monobasic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxyl group produced by the addition reaction.

As the binder resin in the present invention, one of the above 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 the dispersion stability by utilizing a synergistic effect obtained by the combination with the above dispersant or the like, and as a result, the amount of the dispersant added can be reduced, and thus the developability is improved, specifically For example, it is preferable that the undissolved matter remains on the non-image portion of the substrate and the adhesion to the substrate is excellent, and a color pixel having a high concentration can be formed.

Specifically, a part of the binder resin is used together with the above dispersing agent or dispersing aid or the like in the following dispersion treatment step. In this case, the total amount of the binder resin in the pigment dispersion liquid is preferably from about 5 to 200% by mass, more preferably from about 10 to 100% by mass. Thus, as the binder resin used in the dispersion treatment step, various kinds of the above resins may be used, and a (meth)acrylic resin of [1-6-4] is preferable, and among them, it is preferable to use the above formula ( 6) A polymer obtained by polymerizing a compound represented by the composition as a monomer component necessary for the composition.

When used together with the dispersing agent for the dispersion treatment step, the acid value of the binder resin is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, and most preferably 50 mgKOH/g or more; more preferably, It is 500 mgKOH/g or less, more preferably 300 mgKOH/g or less, and most preferably 200 mgKOH/g or less. If the acid value is too high, there is a tendency to become highly viscous and difficult to synthesize; and if it is too low, it is difficult to apply. The case of alkaline development.

Further, in the case where the dispersant is used in the dispersion treatment step together, the weight average molecular weight of the binder resin measured by GPC is preferably 1,000 or more, more preferably 1,500 or more, and most preferably It is 2,000 or more; more preferably, it is 200,000 or less, more preferably 50,000 or less, and most preferably 30,000 or less. If the molecular weight is too large, it tends to be difficult to apply to alkaline development. Further, if the molecular weight is too small, the dispersion stability may be lowered.

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, based on the total solid content, and is usually 80% by mass or less, preferably 60% by mass. %the following. When it is set to the above lower limit value, a strong film can be obtained, and the adhesion to the substrate tends to be excellent. In addition, when the upper limit is equal to or less than the above upper limit, the permeability of the developing solution to the exposed portion is low, and the surface smoothness of the pixel is deteriorated or the sensitivity tends to be deteriorated.

[1-7] (E) Photopolymerization initiator

The colored resin composition of the present invention contains (E) a photopolymerization initiator. The film hardenability by photopolymerization can be obtained by containing (E) a photopolymerization initiator. (E) The photopolymerization initiator is usually used in the form of a mixture (photopolymerization initiator) with an accelerator and an additive such as a sensitizing dye added as needed. The photopolymerization initiator has a function of directly absorbing light or undergoing a photo-sensitization to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

The photopolymerization initiator which can be used in the coloring resin composition of the first aspect of the present invention, for example, is disclosed in Japanese Laid-Open Patent Publication No. Sho 59-152396, and Japanese Patent Laid-Open No. 61-151197. The metallocene compound containing a titanocene compound, or the hexaarylbiimidazole derivative described in Japanese Laid-Open Patent Publication No. Hei 10-39503, and the halomethyl group are all three. Free radicals such as N-aryl-α-amino acids such as derivatives and N-phenylglycine, N-aryl-α-amino acid salts, and N-aryl-α-amino acid esters An active agent, an α-aminoalkylphenone compound, an oxime ester-based initiator described in JP-A-2000-80068, and the like.

Specific examples of the photopolymerization initiator which can be used in the present invention are listed below.

2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-all three , 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-all three , 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-all three , 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-all three Isohalogen methylation Derivative; 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4- Diazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4- Diazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuranyl)vinyl)]-1,3,4- Diazole, 2-trichloromethyl-5-furanyl-1,3,4- Halogenation of oxadiazole Diazole derivatives; 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxy Phenylphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-methoxyphenyl)-4,5-di Imidazole derivatives such as phenylimidazole dimer, (4'-methoxyphenyl)-4,5-diphenylimidazole dimer; benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl Benzoin alkyl ethers such as ether; anthracene derivatives such as 2-methylindole, 2-ethylindole, 2-tert-butylindole, 1-chloroindole; benzophenone, Michelin Ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxydiphenyl a benzophenone derivative such as ketone; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α- Hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)one, 1-hydroxy-1-(p-dodecylphenyl)one, 2- Methyl-1-[4-(methylthio)phenyl]-2- Acetophenone derivative such as phenylpropan-1-one or 1,1,1-trichloromethyl-(p-butylphenyl) ketone; 9-oxosulfur 2-ethyl 9-oxosulfur 2-isopropyl 9-oxosulfur 2-chloro 9-oxosulfur 2,4-dimethyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-diisopropyl 9-oxosulfur 9-oxosulfur a derivative; a benzoate derivative such as p-dimethylaminobenzoic acid ethyl ester or p-diethylaminobenzoic acid ethyl ester; 9-phenyl acridine, 9-(p-methoxyphenyl) acridine, etc. Acridine derivative; 9,10-dimethylbenzophenone Ethyl a derivative; an anthrone derivative such as benzofluorenone; dicyclopentadienyl titanium dichloride, dicyclopentadienyl bisphenyl titanium, dicyclopentadienyl bis (2, 3, 4, 5) ,6-pentafluorophenyl-1-yl)titanium, dicyclopentadienylbis(2,3,5,6-tetrafluorophenyl-1-yl)titanium, dicyclopentadienyl bis (2 ,4,6-trifluorophenyl-1-yl)titanium, dicyclopentadienyl-2,6-difluorophenyl-1-yltitanium, dicyclopentadienyl-2,4-difluoro Phenyl-1-yl titanium, dimethylcyclopentadienyl bis(2,3,4,5,6-pentafluorophenyl-1-yl)titanium, dimethylcyclopentadienyl bis (2) , 6-difluorophenyl-1-yl)titanium, dicyclopentadienyl-2,6-difluoro-3-(pyrrol-1-yl)-phenyl-1-yltitanium, etc. 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)butan-1-one, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylamine Phenylpropiophenone, 2-ethylhexyl 1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzimidyl)-α-aminoalkylphenone-based compound such as coumarin, 4-(diethylamino)chalcone; 1,2-octanedione-1-[ 4-(phenylthio)phenyl]-2-(O-benzylidenehydrazide)ethanone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole An oxime ester compound such as -3-yl]-1-(O-acetamidine).

Among these, from the viewpoint of sensitivity, an oxime ester compound is preferred.

As the accelerator constituting the photopolymerization initiator component, for example, an alkyl N,N-dialkylaminobenzoate such as N,N-dimethylaminobenzoate or 2-mercaptobenzothiazole can be used. 2-mercaptobenzophenone A mercapto compound having a heterocyclic ring such as azole or 2-mercaptobenzimidazole or an aliphatic polyfunctional mercapto compound.

These photopolymerization initiators and accelerators may be used alone or in combination of two or more. Specific examples of the photopolymerization initiator component include a dialkyl group described on pages 16 to 26 of "Precision Chemicals" (March 1, 1991, vol. 20, No. 4). Acetophenone, benzoin, 9-oxosulfur The hexaarylbiimidazole type and the S-trihalomethyl group described in the above-mentioned Japanese Patent Publication No. SHO-58-403023, and the like. Titanium and titanium alloys described in Japanese Patent Laid-Open No. Hei 4-221958 A dye, an addition-polymerizable compound having an ethylenic or urethane group, and a compound containing an ethylenic saturated double bond are combined.

The blending ratio of the photopolymerization initiator is usually 0.1% by mass or more, preferably 0.5%, based on the total solid content of the colored resin composition of the present invention. The amount is at least 1% by mass, more preferably 1% by mass or more, further preferably 1.5% by mass or more, and 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass. % or less, particularly preferably 5% by mass or less. When it is set to the above lower limit value, the sensitivity to the exposure light can be sufficiently ensured, and by setting it as the upper limit or less, the solubility of the unexposed portion in the developer can be suppressed from being lowered. And the tendency to prevent development failure.

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

Since the oxime ester compound has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals, the sensitivity is high only with a small amount, and the heat reaction is stable, and only a small amount can be used for high sensitivity. The design of the photosensitive resin composition. In particular, from the viewpoint of light absorbability of the i-ray (365 nm) of the exposure light source, an oxime ester compound having a carbazole ring which may have a substituent is preferable.

Examples of the oxime ester-based compound include the following formula (I-1). Compound.

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 an arbitrary substituent containing an aromatic ring or a heteroaromatic ring. R ^22a represents an alkane group which may have a substituent, or an aryl group which may have a substituent.

The number of carbon atoms of the alkyl group in R ^21a is not particularly limited, and is usually 1 or more, preferably 2 or more, from the viewpoint of solubility in a solvent or sensitivity to exposure, and is usually 20 or less. It is preferably 15 or less, more preferably 10 or less, still more preferably 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group. Examples of the substituent which the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amine group, a decylamino group, and a 4-(2-methoxy-1-methyl)ethoxy group-2. -Methylphenyl or N-ethinyl-N-acetoxyamino group or the like is preferably unsubstituted from the viewpoint of easiness of synthesis.

R ^21a as in the aromatic ring group include an aromatic hydrocarbon ring group and aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, and 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, and a furyl group. Among these, from the viewpoint of developability, a phenyl group or a naphthyl group is preferred, and more preferably Phenyl. Examples of the substituent which the aromatic ring group may have include a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a carboxyl group, a halogen atom, an amine group, a decylamino group, an alkyl group, and the like. From the viewpoint of developability, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred. Further, examples of the substituent in the alkoxy group which may have a substituent or the alkoxy group which may have a substituent include a hydroxyl group, an alkoxy group, and a halogen atom. In the above, 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 any substituent containing an aromatic ring or a heteroaromatic ring, and from the viewpoints of solubility in a solvent or sensitivity to exposure, a carbazolyl group which may have a substituent may be preferably used. 9-oxo sulfur with substituent a base or a diphenyl sulfide group which may have a substituent. Among these, from the viewpoint of light absorbability of i-rays (365 nm) of the exposure light source, a carbazolyl group which may have a substituent is preferable.

Further, the number of carbon atoms of the alkyl fluorenyl group in R ^22a is not particularly limited, and is usually 2 or more, preferably 3 or more, from the viewpoint of solubility or sensitivity in a solvent, and is usually 20 or less. It is preferably 15 or less, more preferably 10 or less, still more preferably 5 or less. Specific examples of the alkane group include an acetyl group, an ethyloyl group, a propyl group, and a butyl group. Examples of the substituent which the alkano group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amine group, and a guanamine group. From the viewpoint of easiness of synthesis, it is preferably unsubstituted.

Further, the number of carbon atoms of the aryl group in R ^22a is not particularly limited, and is usually 7 or more, preferably 8 or more, and usually 20 or less, from the viewpoint of solubility or sensitivity in a solvent. Preferably, it is 15 or less, more preferably 10 or less. Specific examples of the aryl group include a benzamidine group, a naphthylmethyl group, and the like. Examples of the substituent which the aryl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amine group, a decylamino group, and an alkyl group. From the viewpoint of easiness of synthesis, it is preferably unsubstituted.

In the compound represented by the above formula (I-1), the compound represented by the following formula (I-2) is exemplified as a light absorbing property of the i-ray (365 nm) of the exposure light source.

In the above formula (I-2), R ^21a and R ^22a have the same meanings as in the above 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 aryl group which may have a substituent, a heteroaryl group which may have a substituent, or a nitro group. The benzene ring constituting the carbazole ring can 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, and is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of solubility in a solvent. More preferably, it is 10 or less, More preferably, it is 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a cyclohexyl group. Examples of the substituent which the alkyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, or a nitro group. From the viewpoint of easiness of synthesis, it is preferably unsubstituted.

The carbon number of the aryl group in R ^23a is not particularly limited, and is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less from the viewpoint of solubility in a solvent. It is preferably 15 or less, more preferably 10 or less, still more preferably 9 or less. Specific examples of the aryl group include a benzamidine group, a naphthylmethyl group, and the like. Examples of the substituent which the aryl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, or a nitro group. From the viewpoint of easiness of synthesis, an ethyl group is preferred.

The number of carbon atoms of the heteroaryl group in R ^23a is not particularly limited, and is usually 7 or more, preferably 8 or more, more preferably 9 or more, from the viewpoint of solubility in a solvent; Hereinafter, it is preferably 15 or less, more preferably 10 or less, still more preferably 9 or less. Specific examples of the heteroaryl group include a fluorobenzamide group, a chlorobenzylidene group, a bromobenzylidene group, a fluoronaphthylmethyl group, a chloronaphthylmethyl group, and a bromonaphthalene group. Examples of the substituent which the heteroaryl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, or a nitro group. From the viewpoint of easiness of synthesis, it is preferably unsubstituted. Among these, R ^23a is preferably an alkyl group, more preferably an ethyl group, from the viewpoint of solubility in a solvent and ease of synthesis.

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

As a commercial product of such an oxime ester compound, there are OXE-02, OXE-03 manufactured by BASF Corporation, TR-PBG-304 manufactured by Changzhou Strong Electronics Co., Ltd., TR-PBG-314 or NCI-831 manufactured by ADEKA Corporation. Wait.

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

[Chem. 21]

[化22]

[化23]

The colored resin composition of the third aspect of the present invention contains an oxime ester compound as the (E) photopolymerization initiator, but may also contain a photopolymerization initiator other than the oxime ester compound. For example, a metallocene compound containing a titanocene compound described in each of Japanese Laid-Open Patent Publication No. Hei 59-152396, or Japanese Patent Laid-Open No. Hei 61-151197, or Japanese Patent Laid-Open No. Hei 10-39503 The hexaarylbiimidazole derivative and the halomethyl group are all described. Free radicals such as N-aryl-α-amino acids such as derivatives and N-phenylglycine, N-aryl-α-amino acid salts, and N-aryl-α-amino acid esters An active agent, an α-aminoalkylphenone compound, or the like.

Further, as the accelerator constituting the photopolymerization initiator component, for example, N,N-dialkylaminobenzoic acid alkyl ester such as N,N-dimethylaminobenzoic acid ethyl ester or 2-mercaptobenzoic acid can be used. Thiazole, 2-mercaptobenzophenone A mercapto compound having a heterocyclic ring such as azole or 2-mercaptobenzimidazole or an aliphatic polyfunctional mercapto compound.

These photopolymerization initiators and accelerators may be used alone or in combination of two or more.

In the coloring resin composition of the third aspect of the invention, the blending ratio of the photopolymerization initiator is usually 0.1% by mass or more, preferably 0.1% by mass or more based on the total solid content of the colored resin composition of the present invention. 0.5% 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, and usually 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or more The mass% or less is more preferably 10% by mass or less, and particularly preferably 5% by mass or less. When it is set to the above lower limit value, the sensitivity to the exposure light can be sufficiently ensured, and by setting it as the upper limit or less, the solubility of the unexposed portion in the developer can be suppressed from being lowered. And the tendency to prevent development failure.

On the other hand, in the photopolymerization initiator component, it is necessary to adjust the sensitizing dye corresponding to the wavelength of the image exposure light source in order to improve the sensitivity. Examples of the sensitizing dyes include those described in JP-A-4-221958 and JP-A-4-219756. The coumarin dye having a heterocyclic ring described in Japanese Laid-Open Patent Publication No. Hei No. Hei. The 3-keto coumarin compound described in Japanese Patent Publication No. 289335, and the pyrrole methine pigment described in JP-A-6-19240, Japanese Patent Laid-Open No. Sho 47-2528, and Japanese Patent Laid-Open No. 54 Japanese Patent Publication No. Sho 45-37377, Japanese Patent Laid-Open No. SHO-48-84183, Japanese Patent Laid-Open No. Sho 52-112681, Japanese Patent Laid-Open Publication No. SHO-58-15503, Japanese Patent JP-A-60-88005, JP-A-59-56403, Japanese Patent Laid-Open No. Hei 2-69, Japanese Patent Laid-Open No. Hei 57-168088, and Japanese Patent Laid-Open No. Hei 5-170761 A dye having a dialkylamino benzene skeleton described in Japanese Laid-Open Patent Publication No. Hei. No. Hei.

Among these sensitizing dyes, an amine group-containing sensitizing dye is preferred, and a compound having an amine group and a phenyl group in the same molecule is more preferred. More preferably, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, a benzophenone compound such as 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone or 3,4-diaminobenzophenone; 2-(pair two Methylaminophenyl)benzo Oxazole, 2-(p-diethylaminophenyl) benzo Oxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzo Oxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzo Azole, 2,5-bis(p-diethylaminophenyl) 1,3,4- Azole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-( p-Diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl) 1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (pair two Ethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminobenzene) A compound containing a p-dialkylaminophenyl group such as pyrimidine or the like. Among them, the most preferred is 4,4'-dialkylaminobenzophenone.

Further, the sensitizing dye may be used singly or in combination of two or more. The blending ratio of the sensitizing dye in the colored resin composition of the present invention is usually 0% by mass or more, preferably 0.2% by mass or more, and more preferably 0.5 in the total solid content of the colored resin composition. Further, it is usually 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less.

[1-8] Other solid parts

In the colored resin composition of the present invention, a solid content other than the above components may be further blended as needed. Examples of such a component include a photopolymerizable monomer, an organic carboxylic acid, an organic carboxylic acid anhydride, a surfactant, a thermal polymerization inhibitor, a plasticizer, a storage stabilizer, a surface protective agent, a adhesion improving agent, a development improving agent, and the like. Dyes, etc.

[1-8-1] photopolymerizable monomer

The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, and is preferably an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as "ethylene compound"). In the case where the colored resin composition of the present invention is irradiated with active light, the compound having an ethylenic double bond which is hardened by addition polymerization by the action of the photopolymerization initiator described below. Furthermore, the monomer in the present invention means a concept of a dimer, a trimer or an oligomer in addition to a narrowly defined monomer with respect to the concept of a so-called high molecular substance.

Examples of the ethylenic compound include an unsaturated carboxylic acid, an ester of an unsaturated carboxylic acid and a monohydroxy compound, an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. An ester obtained by esterification of an ester, an aromatic polyhydroxy compound and an unsaturated carboxylic acid, and an esterification reaction of a polyvalent hydroxy compound such as an unsaturated carboxylic acid and a polyvalent carboxylic acid, and the above aliphatic polyhydroxy compound or aromatic polyhydroxy compound An ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a hydroxy compound containing a (meth) acrylonitrile group.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. Acrylates such as ester, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerin acrylate, and the like. Further, examples thereof include a methacrylate obtained by replacing the acrylic acid moiety of the acrylate with a methacrylic acid moiety, an itaconate obtained by replacing the itaconic acid moiety, and a butyl acid obtained by replacing the butyric acid moiety. An enoate or a maleic acid ester obtained by substituting a maleic acid moiety.

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

An ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a hydroxy compound containing a (meth) acrylonitrile group, for example Examples thereof include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; toluene diisocyanate and diphenyl group; An aromatic diisocyanate such as methane diisocyanate or the like with 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-tripropenyloxymethyl)propane, 3-hydroxy ( A reactant of a (meth) acrylonitrile-containing hydroxy compound such as 1,1,1-trimethylpropenyloxymethyl)propane.

In addition, as the ethylenic compound used in the present invention, for example, acrylamide such as ethyl bis acrylamide; allyl ester such as diallyl phthalate; and divinyl phthalate Vinyl compounds and the like are also useful. Further, the ethylenic compound may also be a monomer having an acid value. As the monomer having an acid value, it is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, preferably a polyfunctional acid anhydride which reacts with an unreacted hydroxyl group of an aliphatic polyhydroxy compound to have an acid group. The monomer is particularly preferably one in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol.

These monomers may be used singly, but it is difficult to use a single compound in the production. Therefore, two or more kinds may be used in combination. Further, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as a monomer. The acid value of the polyfunctional monomer having an acid group is preferably from 0.1 to 40 mgKOH/g, particularly preferably from 5 to 30 mgKOH/g. When the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are lowered. When the acid value is too high, it is difficult to manufacture or handle, the photopolymerization performance is lowered, and the surface smoothness of the pixel or the like tends to be poor. Therefore, when a polyfunctional monomer having two or more different acid groups is used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is preferred to adjust the acid group of the polyfunctional monomer as a whole. Within the above range.

In the present invention, a more preferable polyfunctional monomer having an acid group is commercially available dipentaerythritol hexaacrylate as TO1382 manufactured by East Asia Synthetic Co., Ltd. A mixture of dipentaerythritol pentaacrylate and dipentaerythritol pentaacrylate succinate as a main component. A polyfunctional monomer other than the polyfunctional monomer may also be used in combination. Further, those described in paragraph [0056] or [0057] of JP-A-2013-140346 may be used.

Further, in the present invention, it is preferable to use the polymerizable single sheet described in JP-A-2013-195971 from the viewpoint of improving the chemical resistance of the pixel or the linearity of the edge of the pixel. body. The polymerizable monomer described in JP-A-2013-195974 is preferably used from the viewpoint of achieving the sensitivity of the coating film and shortening the development time.

The content ratio of the photopolymerizable monomer is usually 0% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass or more, based on the total solid content of the colored resin composition of the present invention. It is preferably 15% by mass or more, and is usually 80% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, and still more preferably 30% by mass or less. More preferably, it is 20% by mass or less. Further, the ratio of 100 parts by mass of the (A) pigment is usually 0 parts by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, and usually 200 parts by mass. The amount is preferably 100 parts by mass or less, more preferably 80 parts by mass or less.

[1-8-2]Organic carboxylic acid, organic carboxylic anhydride

The colored resin composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1,000 or less and/or an organic carboxylic anhydride. Specific examples of the organic carboxylic acid compound include an aliphatic carboxylic acid or an aromatic carboxylic acid. Examples of the aliphatic carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid, and the like. Monocarboxylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, cis-butane a dicarboxylic acid such as enedic acid or fumaric acid, a tricarboxylic acid such as 1,2,3-propanetricarboxylic acid or aconitic acid, or the like. In addition, examples of the aromatic carboxylic acid include a carboxylic acid in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid or phthalic acid, and a carboxylic acid in which a carboxyl group is bonded to a phenyl group via a carbon bond. Among these, it is especially preferably a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically, maleic acid, malonic acid, succinic acid, and itaconic acid.

Examples of the organic carboxylic acid anhydride include an aliphatic carboxylic acid anhydride and an aromatic carboxylic acid anhydride. Specific examples thereof include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, and cis. Butic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, 5-nor An aliphatic carboxylic anhydride such as an alkene-2,3-dicarboxylic anhydride. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, it is particularly preferably a molecular weight of 600 or less, particularly a molecular weight of 50 to 500, specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride.

The amount of the organic carboxylic acid and/or the organic carboxylic acid anhydride added is usually 0.01% by mass or more, preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and 10% by mass based on the total solid content. Hereinafter, it is preferably 5% by mass or less, more preferably 3% by mass or less. By adding these organic carboxylic acids and/or organic carboxylic anhydrides having a molecular weight of 1,000 or less, high pattern adhesion can be maintained, and the residual of the undissolved matter of the colored resin composition can be further reduced.

[1-8-3] surfactant

As the surfactant, an anionic system, a cationic system, a nonionic system, and two It is preferable to use a nonionic surfactant in various aspects, such as a surfactant, if it is less likely to adversely affect various characteristics. 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 or more, based on the total solid content; 10% by mass or less, preferably 1% by mass or less, further preferably 0.5% by mass or less, and most preferably 0.3% by mass or less.

[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, or the like can be used. The blending amount of the thermal polymerization inhibitor is preferably in the range of 3% by mass or less based on the total solid content of the composition.

[1-8-5] plasticizer

As the plasticizer, for example, dioctyl phthalate, di(dodecyl) phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, phosphoric acid can be used. Tricresol ester, dioctyl adipate, dibutyl sebacate, triethylene glycol glycerin, and the like. The blending amount of the plasticizer is usually preferably in the range of 10% by mass or less based on the total solid content of the composition.

[2] Preparation of colored resin composition

Next, a method of preparing the colored resin composition of the present invention (hereinafter sometimes referred to as a resist) will be described.

First, the pigment, the solvent and the dispersing agent are weighed separately, and the pigment containing the zinc phthalocyanine bromide pigment is dispersed in the dispersion treatment step to prepare the pigment. Dispersions. In the dispersion treatment step, a paint conditioner, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By performing the dispersion treatment to pulverize the color material, the coating property of the colored resin composition is improved, and the transmittance of the pixel on the color filter substrate of the product is improved.

When dispersing the pigment, as described above, it is preferred to use a dispersing aid or a dispersion resin as appropriate. Further, the pigment must contain a pigment containing the above-described zinc phthalocyanine phthalocyanine pigment, but it may be mixed with other pigments for dispersion to be used for coloring. In the case of performing a dispersion treatment using a sand mill, it is preferred 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 to 0 ° C or higher, preferably room temperature or higher; and usually, it is usually 100 ° C or lower, preferably 80 ° C or lower. Further, since the dispersion time varies depending on the composition of the pigment dispersion liquid, the size of the sand mill device, and the like, it is necessary to appropriately adjust the dispersion time.

In the pigment dispersion liquid obtained by the above dispersion treatment, a solvent mixture, a binder resin, a photopolymerization initiator, and, if appropriate, a photopolymerizable monomer, and components other than the above, are uniformly dispersed. Solution. Further, in the steps of the dispersion treatment step and the mixing, there is a case where fine dirt is mixed, and therefore it is preferred to filter the obtained pigment dispersion liquid by a filter or the like.

[3] Manufacturing of color filter substrate

Next, the color filter of the present invention will be described. The color filter of the present invention has a pixel formed using the above colored resin composition.

[3-1] Transparent substrate (support)

The transparent substrate as the color filter is not particularly limited as long as it is transparent and has moderate strength. As a material, for example, polyethylene terephthalate can be cited. Polyester resin such as ester, polyolefin resin such as polypropylene or polyethylene, polycarbonate, polymethyl methacrylate, polystyrene thermoplastic resin sheet, epoxy resin, unsaturated polyester resin, poly A thermosetting resin sheet such as a (meth)acrylic resin or various glasses. Among them, from the viewpoint of heat resistance, glass or a heat resistant resin is preferred.

In order to improve surface physical properties such as adhesion, a transparent substrate and a black matrix forming substrate may be subjected to a film forming treatment of various resins such as a corona discharge treatment, an ozone treatment, a decane coupling agent, or a urethane resin. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and is usually 10 mm or less, preferably 7 mm or less. Further, in the case of performing film formation treatment of various resins, the film thickness is usually 0.01 μm or more, preferably 0.05 μm or more, and is usually 10 μm or less, preferably 5 μm or less.

[3-2] Black matrix

A black matrix is disposed on the transparent substrate, and a pixel image of red, green, and blue is generally formed, whereby the color filter of the present invention can be manufactured. The colored resin composition is used as a coating liquid for forming a green pixel (resist pattern) among pixels of red, green, and blue. Coating, heat drying, image exposure, and development on a resin black matrix forming surface formed on a transparent substrate or a metal black matrix forming surface formed using a chromium compound and other light shielding metal material using the green resist And each process of thermal hardening to form a pixel image.

The black matrix is formed on a transparent substrate by using a light-shielding metal film or a colored resin composition for a black matrix. As the light-shielding metal material, a chromium compound such as metal chromium, chromium oxide or chromium nitride, nickel or a tungsten alloy, or the like may be used, or a laminate of these layers may be used. The metal light-shielding films are generally formed by sputtering, and the positive-type photoresist is used. After forming a desired pattern in the form of a film, an etching solution in which cerium ammonium nitrate is mixed with perchloric acid and/or nitric acid is used for chrome plating; for other materials, etching is performed using an etching solution corresponding to the material, and finally, A special stripper strips the positive photoresist, thereby forming a black matrix.

In this case, first, a film of the metal or metal-metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Then, after forming a coating film of a colored resin composition on the film, a coating film having a repeating pattern such as a stripe, a mosaic, or a triangle is used to expose and develop the coating film to form a resist image. Thereafter, the coating film may be subjected to an etching treatment to form a black matrix.

In the case of using a photosensitive colored resin composition for a black matrix, a black matrix is formed using a colored resin composition containing a black colorant. For example, one or several kinds of black coloring materials containing carbon black, graphite, iron black, aniline black, cyanine black, titanium black, or the like, or red or green, which are appropriately selected from inorganic or organic pigments and dyes, may be used. The colored resin composition of the black color material obtained by mixing blue or the like forms a black matrix in the same manner as the method of forming a pixel image of red, green, and blue as described below.

[3-3] Formation of pixels

The method of forming the pixel differs depending on the type of the colored resin composition to be used. Here, a case where a photopolymerizable composition is used as the colored resin composition will be described as an example. Applying a colored resin composition of one of red, green, and blue to a transparent substrate provided with a black matrix, and drying the composition, superimposing a photomask on the coating film, and exposing the image through the photomask Development, thermal hardening or photohardening as needed to form a pixel image, thereby producing a colored layer. This operation is performed on the colored resin compositions of the three colors of red, green, and blue, thereby forming a color filter shadow. image.

The application of the colored resin composition for a color filter can be carried out by a spin coating method, a wire bar coating method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. In addition, when the die coating method is used, the amount of the coating liquid to be used is drastically reduced, and the influence of the mist or the like adhered by the spin coating method is eliminated, and the generation of foreign matter is suppressed. It is preferred from the viewpoint.

If the thickness of the coating film is too large, it is difficult to perform pattern development, and it is difficult to adjust the gap in the liquid crystal unitization step. On the other hand, if it is too small, it is difficult to increase the pigment concentration, and it is impossible to express the desired pigment. situation. The thickness of the coating film 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 or less, in terms of film thickness after drying. The scope.

[3-4] Drying of coated film

The drying of the coating film after applying the colored resin composition to the substrate is preferably a drying method using a hot plate, an IR oven, or a convection oven. It is usually dried again after pre-drying to dry it. The pre-drying conditions can be appropriately selected depending on the kind of the solvent component described above, the performance of the dryer to be used, and the like. The drying temperature and the drying time are selected depending on the type of the solvent component, the performance of the dryer to be used, and the like, and specifically, the drying temperature is usually 40 ° C or higher, preferably 50 ° C or higher; and usually, 80 ° C or lower. It is preferably in the range of 70 ° C or lower, and the drying time is usually 15 seconds or longer, preferably 30 seconds or longer; and usually, it is usually 5 minutes or shorter, preferably 3 minutes or shorter.

The temperature condition for reheating and drying is preferably a temperature higher than the pre-drying temperature, specifically, usually 50 ° C or higher, preferably 70 ° C or higher; It is 200 ° C or less, preferably 160 ° C or less, and particularly preferably 130 ° C or less. Further, although the drying time depends on the heating temperature, it is usually 10 seconds or longer, preferably 15 seconds or longer; and usually, it is preferably 10 minutes or shorter, and preferably 5 minutes or less. The higher the drying temperature, the higher the adhesion to the transparent substrate. However, if the drying temperature is too high, the binder resin is decomposed to cause thermal polymerization to cause development failure. Further, as the drying step of the coating film, a vacuum drying method in which drying is performed in a decompression chamber without increasing the temperature may be used.

[3-5]Exposure step

The image exposure is performed by superposing a negative matrix pattern on a coating film of a colored resin composition, and irradiating a light source of ultraviolet rays or visible rays through the mask pattern. In this case, in order to prevent the sensitivity of the photopolymerizable layer due to oxygen from being lowered, it is also possible to form an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer, followed by exposure. The light source used in the above image exposure is not particularly limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, or the like, or an argon ion mine. Laser, YAG laser, excimer laser, nitrogen laser, helium-cadmium laser, semiconductor laser and other laser sources. An optical filter can also be used when it is used to illuminate light of a specific wavelength.

[3-6] Development step

The color filter of the present invention can image-develop the coating film using the colored resin composition of the present invention by using the above-mentioned light source, and then develop the organic solvent or an aqueous solution containing a surfactant and a basic compound. Forming an image on the substrate Made of. The aqueous solution may further contain an organic solvent, a buffer, a binder, a dye or a pigment.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium citrate, potassium citrate, sodium metasilicate, and sodium phosphate. An inorganic basic compound such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate or ammonium hydroxide, or monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or Trimethylamine, monoethylamine, diethylamine or triethylamine, monoisopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine or tri An organic basic compound such as isopropanolamine, ethyl iminoamine, ethyldiimide, tetramethylammonium hydroxide (TMAH), or choline. These basic compounds may also be a mixture of two or more kinds.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. Anionic interfacial activity such as nonionic surfactants, alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, sulfosuccinates Amphoteric surfactants such as alkyl, betaine and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl sirolius, butyl siroli, phenyl racessu, propylene glycol, and diacetone alcohol. The organic solvent may be used singly or in combination with an aqueous solution. The conditions of the development treatment are not particularly limited, and the development temperature is usually 10 ° C or higher, preferably 15 ° C or higher, more preferably 20 ° C or higher; and usually 50 ° C or lower, preferably 45 ° C or lower, and further It is preferably in the range of 40 ° C or less. The developing method may be any one of a dipping development method, a jet development method, a brush development method, an ultrasonic development method, and the like.

[3-7] Thermal hardening treatment

The developed color filter is subjected to a heat hardening treatment. The temperature hardening treatment conditions at this time may be usually 100 ° C or higher, preferably 150 ° C or higher, and usually 280 ° C or lower, preferably 250 ° C or lower, and the time may be 5 minutes or longer. Choose within the range of 60 minutes or less. After a series of steps, a patterned image of one color is completed. This step is repeated in sequence, and black, red, green, and blue are patterned to form a color filter. Furthermore, the order of patterning of the four colors is not limited to the above order.

Further, the color filter of the present invention may be produced by the following method in addition to the above production method: (1) a zinc chloride bromine phthalocyanine pigment containing a solvent as a coloring material, as a binder resin The curable colored resin composition of the polyimine-based resin is applied onto a substrate, and a pixel image is formed by an etching method. Further, examples thereof include (2) using a colored resin composition containing a zinc phthalocyanine bromide pigment as a colored ink, and directly forming a pixel image on a transparent substrate by a printing machine; or (3) using a chlorinated product The colored resin composition of the zinc phthalocyanine bromide pigment is used as an electrodeposition liquid, and the substrate is immersed in the electrodeposition liquid to deposit a colored film on the ITO electrode having a predetermined pattern. Further, a method of: (4) attaching a film coated with a colored resin composition containing a zinc phthalocyanine phthalocyanine pigment onto a transparent substrate, peeling off, and performing image exposure and development to form a pixel image; Or (5) using a colored resin composition containing a zinc phthalocyanine bromide pigment as a coloring ink, and forming a pixel image using an ink jet printer. The method of producing the color filter is a method suitable for the composition of the colored resin composition.

[3-8] Formation of transparent electrode

The color filter of the present invention forms ITO and the like on the image in such a state. The bright electrode is used as a part of a color display or a liquid crystal display device. However, in order to improve the surface smoothness or durability, it is also possible to provide a top coat such as polyimide or polyimide on the image. Further, some of the applications such as the planar alignment type driving method (IPS mode) do not form a transparent electrode.

[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 color filter. Hereinafter, a liquid crystal display device and an organic electroluminescence (EL) display device will be described in detail as an image display device.

[4-1] Liquid crystal display device

A method of manufacturing the liquid crystal display device of the present invention will be described. In the liquid crystal display device of the present invention, an alignment film is usually formed on the color filter of the present invention, and a spacer is dispersed on the alignment film, and then bonded to the counter substrate to form a liquid crystal cell, and the liquid crystal cell is formed. Liquid crystal is injected into the liquid crystal cell and completed by wiring the counter electrode. The alignment film is preferably a resin film such as polyimide. The formation of the alignment film is usually performed by a gravure printing method and/or a flexographic printing method, and the thickness of the alignment film is set to several tens of nm. After the hardening treatment of the alignment film by thermal baking, the surface treatment is performed by ultraviolet irradiation or treatment with a rubbing cloth, and processed into a surface state in which the inclination of the liquid crystal can be adjusted.

The spacer may use a size corresponding to a gap of the opposite substrate, and is usually preferably 2 to 8 μm. Instead of the spacer, a photosensitive spacer (PS) of a transparent resin film may be formed on the color filter substrate by photolithography. As the opposite substrate, an array substrate is generally used, and particularly a thin film transistor (TFT, Thin Film) Transistor) substrate.

The gap to be bonded to the counter substrate differs depending on the use of the liquid crystal display device, and is usually selected from the range of 2 μm or more and 8 μm or less. After bonding to the counter substrate, a portion other than the liquid crystal injection port is sealed with a sealing material such as an epoxy resin. The sealing material is hardened by UV irradiation and/or heating to seal the periphery of the liquid crystal cell. After the peripherally sealed liquid crystal cell is cut into panel units, the liquid crystal injection port is evacuated in the vacuum chamber, and the liquid crystal injection port is immersed in the liquid crystal, and then leaked into the chamber to inject the liquid crystal into the liquid crystal cell. The degree of pressure reduction in the liquid crystal cell is usually 1 × 10 ^-2 Pa or more, preferably 1 × 10 ^-3 Pa or more, and is usually 1 × 10 ^-7 Pa or less, preferably 1 × 10 ^-6 Pa or less. The scope. Further, it is preferred to heat the liquid crystal cell at a reduced pressure, and the heating temperature is usually 30 ° C or higher, preferably 50 ° C or higher, and usually 100 ° C or lower, preferably 90 ° C or lower.

The heating at the time of pressure reduction is usually set to a range of 10 minutes or more and 60 minutes or less, and thereafter immersed in a liquid crystal. The liquid crystal cell to which the liquid crystal is injected is cured, and the liquid crystal injection port is sealed by curing the UV curable resin, thereby completing the liquid crystal display device (panel). The type of the liquid crystal is not particularly limited, and may be a previously known liquid crystal such as an aromatic system, an aliphatic system or a polycyclic compound, and may be any of a liquid crystal liquid or a thermal liquid crystal. Regarding the thermal liquid crystal, a nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, or the like is known, and any of them may be used.

[4-2] Organic EL display device

In the case of fabricating an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, a blue color filter having pixels 20 formed on the transparent support substrate 10 by the colored resin composition of the present invention is formed. Light film, on which the organic guarantee The cover layer 30 and the inorganic oxide film 40 are laminated to form the organic light-emitting body 500, thereby producing a multi-color organic EL element.

As a method of laminating the organic light-emitting body 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. A method of bonding an organic light-emitting body 500 formed on another substrate to the inorganic oxide film 40 or the like. The organic EL element 100 thus produced can be applied to an organic EL display device of a passive driving method, and can also be applied to an organic EL display device of an active driving method.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded. Further, in the following examples, "parts" means "parts by mass".

<green pigment>

In the examples and comparative examples, the green pigments A and B described in Table 1 were used. In addition, the average number of chlorine atoms and the average number of bromine atoms in Table 1 are measured by the fluorescent X-ray basic parameter method (FP method), and occupy 16 substitution positions of one molecule of zinc phthalocyanine. The average of the number of chlorine atoms and the number of bromine atoms. In addition, since zinc chlorobromide phthalocyanine is obtained by substituting all or a part of 16 hydrogen atoms in one molecule of zinc phthalocyanine with a chlorine atom or a bromine atom, the average chlorine is subtracted from 16. The sum of the number of atoms and the average number of bromine atoms is used to calculate the average number of hydrogen atoms. Further, the average number of chlorine atoms and the average number of bromine atoms are calculated as the relative values of the zinc atoms, the chlorine atoms, and the bromine atoms measured by the FP method as the relative values of each of the zinc atoms. Furthermore, the fluorescent X-ray evaluation apparatus uses RIX-3000 manufactured by Rigaku Electric Co., Ltd., and the X-ray tube system is used at Rh50kV/50 mA for measuring 30 mm in diameter. The measurement was carried out under vacuum. The measurement sample amount was set to 2 g, and pressure molding was performed (30 mm). , 200kN) and use. Further, the average number of chlorine atoms and the average number of bromine atoms in one molecule are the average values of the entire measurement sample. Other detailed conditions that will be set on the RIX-3000 screen are shown in Table 2. Further, the green pigment B is CI Pigment Green 58.

Further, in Table 3, the chlorine atom content ratio and the bromine atom content ratio obtained by measuring the green pigments A and B similar to those in Table 1 by combustion ion chromatography are described. Specifically, after dissolving each pigment in ethyl benzoate, it is burned by a combustion apparatus, and the combustion gas is absorbed into the hydrogen peroxide absorption liquid, and the ions in the absorption liquid are measured by ion chromatography. Further, the average number of hydrogen atoms contained in one of the green pigments A and B described in Table 3 is by Laser Desorption/Ionization (LDI)-mass spectrometry (Mass Spectrometry, MS) The measured value. The measurement is carried out by dissolving 1 to 3 mg of the pigment in 100 mg of THF (tetrahydrofuran) or NMP (N-methylpyrrolidone) and applying ultrasonic waves, and then several μL of the solution. Mounted on the board, using the autoflex speed manufactured by BRUKER in the reflective mode and the positive mode, the laser power is about 40%~60%, 500 shots×3, and m/z=300~3000. Further, 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. 3. The average number of hydrogen atoms contained in one molecule was measured in the following order. First, the maximum peak intensity in the mass spectrum is used as a reference, and the 40% intensity is set as a threshold. Then, the peak above the threshold value is used as a peak to be calculated, and the number of hydrogen atoms is calculated from the molecular weight of the peak top for each peak, and the average number of hydrogen atoms is calculated by averaging the hydrogen atoms.

<Disperse Resin A>

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

On the other hand, 30 parts by mass of 2,2'-[oxybis(methylene)]bis(2-acrylic acid) dimethyl ester, 60 parts by mass of methacrylic acid, and methacrylic acid cyclohexane are added to the monomer tank. 110 parts by mass of ester, 5.2 parts by mass of dibutyl acrylate 2-ethylhexanoate, and 40 parts by mass of propylene glycol monomethyl ether acetate, and 5.2 parts by mass of n-dodecyl mercaptan was added to the chain transfer agent tank. 27 parts by mass of propylene glycol monomethyl ether acetate, stable at the temperature of the reaction tank After 90 ° C, the dropwise addition from the monomer tank and the chain transfer agent tank was started to start the polymerization. While maintaining the temperature at 90 ° C, the dropwise addition was carried out for 135 minutes each time, and after 60 minutes from the end of the dropwise addition, the temperature was raised to set the reaction vessel to 110 ° C.

After maintaining at 110 ° C for 3 hours, the gas introduction tube was attached to a separable flask, and a mixed gas of oxygen/nitrogen = 5/95 (v/v) was started. Then, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and triethylamine 0.8 were added to the reaction vessel. The mass fraction was reacted at 110 ° C for 9 hours in this state. After cooling to room temperature, a polymer solution having a weight average molecular weight of 8,000 and an acid value of 101 mgKOH/g was obtained as the dispersion resin A.

<Dispersant A: Dispersant "BYK-LPN6919" manufactured by BYK-Chemie Co., Ltd.>

A methacrylic AB block copolymer comprising an A block having a nitrogen atom-containing functional group and a solvophilic B block. It has a repeating unit of the following formulas (2b) and (3b) and does not have a repeating unit of the following formula (1b). The amine value was 120 mgKOH/g, and the acid value was 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>

The binder resin A was synthesized in the following order. While substituting nitrogen gas, 145 parts by mass of propylene glycol monomethyl ether acetate was stirred and heated to 120 °C. 20 parts by mass of styrene, 57 parts by mass of glycidyl methacrylate, and 82 parts by mass of a monoacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, and further, 120 Stirring was continued for 2 hours at °C. Then, the inside of the reaction vessel was changed to air displacement, and 0.7 parts by mass of tris-dimethylaminomethylphenol 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. Thereafter, 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 weight average molecular weight Mw of the binder resin A thus obtained, which was measured by GPC, was about 15,000.

<Photopolymerization initiator 1>

In the examples and comparative examples, [9-ethyl-6-(1-ethoxyindolimido-4-methyloxycarbonylbutyl)oxazol-3-yl] having the following structure was used. (2-Methylphenyl) ketone is used as a photopolymerization initiator.

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

<Surfactant A>

MEGAFAC F-559 (manufactured by DIC, fluorine-based surfactant)

(Examples 1 to 5, Comparative Examples 1 to 3)

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

DEGEA: Diethylene glycol monoethyl ether acetate

DEGBEA: Diethylene glycol monobutyl ether acetate

1,3-BGDA: 1,3-butanediol diacetate

EEP: 3-ethoxypropionate ethyl ester

MBA: 3-methoxybutyl acetate

BA: butyl acetate (butyl acetate)

PGMEA: propylene glycol monomethyl ether acetate

<Preparation of Colored Resin Composition>

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

<Appendage evaluation>

The evaluation was carried out in accordance with the [coating suitability evaluation method (I)] described in the examples of JP-A-2007-270147. When the colored resin composition obtained by the above procedure is evaluated by the steps (1) to (4) described below, the test piece is attached to the arm of the actuator, and the tip is used in the bottle automatically. A control device that is filled with the operation of repeatedly entering and exiting the colored resin composition.

(1) The front end portion of the glass test piece having a length of 100 mm, a width of 5 mm, and a thickness of 0.6 mm was immersed in a colored resin composition at a rate of 12.5 mm/sec at an ambient temperature of 23 ° C, and thereafter maintained at 4 hours. second.

(2) The glass test piece was taken out from the colored resin composition at a rate of 12.5 mm/sec, and the front end of the glass test piece was kept vertical, at an ambient temperature of 23 ° C, a humidity of 55%, and a wind speed of 0.5. Dry for 56 seconds at ±0.2 m/sec.

(3) Steps (1) and (2) were repeated 120 times in total, and an adherent derived from the colored resin composition was formed on the glass test piece.

(4) The attachment of the glass piece was observed with a microscope. The results are shown in Table 6. Furthermore, the evaluation criteria of the attached matter are as follows. Further, the numerical values in ( ) in Table 6 indicate the area ratio (%) of the coated object with respect to the total impregnation area of the glass piece.

○: The ratio of the area covered by the attached matter is 0% with respect to the total impregnation area of the glass piece

△: The area ratio of the coated object exceeds 0% and is less than 10% with respect to the total impregnation area of the glass piece.

×: The area ratio of the coated object is 10% or more with respect to the total impregnation area of the glass piece

According to Table 6, in Example 1 in which green pigment A was used and DEGEA having a boiling point of 217 ° C or DEGBEA having a boiling point of 247 ° C was used, almost no deposit was found on the glass sheet and it was very good. Further, in Example 3 using 1,3-BGDA having a boiling point of 232 ° C, Example 4 using EEP having a boiling point of 170 ° C, or Example 5 using an MBA having a boiling point of 171 ° C, it was found only on the glass sheet. A small amount of attachment is good. Thus, it is considered that by using a high boiling point solvent having a boiling point of 150 ° C or higher, it is less likely to be dried during drying at the 56 seconds in the step (2) of the evaluation of the adhering matter, and it is easy to maintain a wet state, and in the next step (1). When immersed for 4 seconds, it is easily dissolved again by the colored resin composition, thereby reducing the amount of the adhering matter remaining on the glass sheet. On the other hand, in Comparative Example 1 using BA having a boiling point of 126 ° C or Comparative Example 2 using only PGMEA having a boiling point of 146 ° C, a very large amount of deposit was found on the glass piece. Further, in Comparative Example 3 using green pigment B, it was confirmed that although no high-boiling solvent having a boiling point of 150 ° C or higher was contained, almost no deposit was observed on the glass piece. The reason for the details is unknown, but the reason is considered to be that the green pigment B contains a very small average number of hydrogen atoms in one molecule, the wettability or adsorption of the pigment is good, and the dispersant or dispersion resin is less detached from the pigment. The surface of the pigment is sufficiently coated, so that the solubility in the solvent is good.

When the results of Table 6 were combined, Comparative Examples 1 and 2 of the colored resin compositions of Examples 1 to 5 and the solvent having a relatively low boiling point were used in the case of using the green pigment A, using a solvent having a relatively high boiling point. Compared with the colored resin composition, there is a tendency that the adhesion of the glass piece is small, and the coating property is extremely high.

(Examples 6 to 11)

Use the type and amount of Table 7 as a green pigment and solvent, in addition to The green pigment dispersions of Examples 6 to 11 were prepared in the same manner as in Example 1. Further, the boiling point in Table 7 is a value at 1013.25 hPa, and the vapor pressure is a value at 20 °C. Further, the amount of the solvent 1 in Table 7 is the total amount contained in the green pigment dispersion.

<Preparation of Colored Resin Composition>

The other components shown in Table 8 were mixed in each of the pigment dispersions of Table 7, and a colored resin composition was prepared. In addition, the blending amount of the binder resin and the photopolymerizable monomer in Table 8 is a solid content conversion value, and the solvent amount is a value including the amount of the solvent contained in the binder resin and the photopolymerizable monomer.

Next, in the same manner as in Example 1, the evaluation of the attached matter was carried out by the above method. The results are shown in Table 9 together with the results of Example 3 and Example 5.

According to Table 9, from the comparison of Examples 3, 6 and 7, and the comparison of Examples 5, 8 and 9, it was found that the area ratio of the coating of the deposits tends to be small by increasing the content ratio of the high-boiling solvent. Further, according to the comparison between Examples 6, 10, and 11, it was confirmed that when one type of high-boiling solvent was used and when two or more types of high-boiling solvents were used, the area ratio of the coating was not different.

<Evaluation of film wrinkles after high temperature treatment>

Next, film wrinkle evaluation after high temperature treatment was carried out using the colored resin compositions of Example 8 and Comparative Examples 2, 3 and 4. Further, Comparative Example 4 was obtained in the same manner as in Example 8 except that the green pigment type was replaced with the green pigment B. First, a colored resin composition was applied onto a glass substrate (manufactured by Asahi Glass Co., Ltd., AN100) of 50 mm square and 0.6 mm thick by a spin coater, and then dried at 80 ° C for 3 minutes. Further, the coating film thickness was set such that the chromaticity (sx, sy) after baking was set to (0.250, 0.580) under the C light source. Then, a full exposure treatment was performed with a 2 kW high pressure mercury lamp at an exposure amount of 40 mJ/cm ² . Thereafter, it was baked in an oven at 230 ° C for 30 minutes.

For the film surface of the thus obtained high temperature treated substrate, by MicroMap (manufactured by Ryoka Systems, Inc., 3D non-contact surface shape measurement system) measures Sq (root mean square deviation thickness, nm), Sa (arithmetic mean thickness, nm), Sz (maximum height of thickness, nm ). The measurement was carried out using a 50-fold optical lens in the Focus mode at a field of view of 12800 nm x 6400 nm. Furthermore, Sq, Sa and Sz are calculated according to ISO 25178. The results are shown in Table 10. Further, the outline obtained by the measurement is shown in Fig. 4 (Example 8), Fig. 5 (Comparative Example 2), Fig. 6 (Comparative Example 4), and Fig. 7 (Comparative Example 3). In the outlines of Figures 4-7, the lateral width is 12800 nm and the depth is 6400 nm. Furthermore, the tens of embossings visible in each of the figures correspond to film wrinkles.

According to Table 8, in Example 8 in which green pigment A was used and a high boiling point solvent was used, it was confirmed that any of Sq, Sa, and St was small, and film wrinkles were effectively suppressed. In particular, it was confirmed that since the difference between Sq and Sa is small, the value of St is small, so that the surface unevenness due to wrinkles is small; and the unevenness of wrinkles in the measurement field is not measured. With the wide color gamification in recent years, the concentration of the pigment in the color filter becomes high, and there is a tendency for film wrinkles to occur. When film wrinkles occur, color unevenness occurs, and problems such as poor disconnection when forming a panel occur. Therefore, it is suggested that by using the colored resin composition or the pigment dispersion of the present invention, film wrinkles can be suppressed even in the case of wide color gamification, and further, color unevenness or panel formation can be effectively suppressed. Poor disconnection Wait.

On the other hand, in Comparative Example 2 in which the green pigment A was used and the high boiling point solvent was not used, it was confirmed that any of Sq, Sa, and St was large, and film wrinkles were generated. In particular, it was confirmed that since the difference between Sq and Sa is small and the value of St is large, wrinkles are generated in a comprehensive manner in the measurement field of view.

On the other hand, in Comparative Examples 4 and 3 in which green pigment B was used, it was confirmed that any of Sq, Sa, and St was extremely large, and film wrinkles were generated. In particular, it has been confirmed that although the values of Sq and Sa are improved by using a high boiling point solvent, the value of St is large regardless of the presence or absence of a high boiling point solvent, and thus the film wrinkles are partially improved by using a high boiling point solvent. , but partially residual large film wrinkles.

The reason why the results are considered to be different is that since the green pigment A has a higher coloring power than the green pigment B as described below, the green pigment A can make the film thickness required for obtaining the film of the same chromaticity thin. The amount of the solvent as the volatile component is relatively reduced, and the amount of the component such as the binder resin which is a component contributing to thermal deformation can be relatively reduced. Further, compared with the green pigment B, in the case of using the green pigment A, the value of St is greatly improved by using a high boiling point solvent, and the reason for the details is unknown, but it is considered that the green pigment A is relative to the green pigment B. Since the average number of hydrogen atoms is equal to or greater than a predetermined value, the affinity with a solvent is increased, and a high-boiling solvent is easily present uniformly in the entire film, thereby suppressing evaporation of a volatile component over the entire surface of the film, and as a result, it is possible to suppress the entire surface of the film. The production of film wrinkles.

<Coloring strength evaluation>

The amount of the pigment dispersion liquid used was changed to the table using the green pigment dispersion liquid of Comparative Example 2 or Comparative Example 3 described in Table 4 and the yellow pigment dispersion liquid described below. In addition to the above, the colored resin composition was prepared by the same method as the above <Preparation of the colored resin composition>. Further, the amount of the pigment dispersion liquid used was adjusted such that the chromaticity under the C light source when the coating film having a film thickness of 2.00 μm was formed was sx=0.280 and sy=0.600. Further, the pigment concentration described in Table 11 is the content ratio of all the pigments to the total solid content of the colored resin composition.

<Preparation of yellow pigment dispersion>

The yellow pigment C which is 12.0 parts by mass in terms of solid content as a yellow pigment, the dispersant A which is 4.0 parts by mass in terms of solid content as a dispersing agent, and the dispersing resin which is 4.0 parts by mass in terms of solid content as a dispersing resin are used. A, 80.0 parts by mass of propylene glycol monomethyl acetate as a solvent, 225 parts by mass of zirconia beads having a diameter of 0.5 mm, which were filled into a stainless steel container and dispersed by a paint shaker for 6 hours to prepare yellow Pigment dispersion.

<Yellow pigment C>

a nickel azo obtained by inserting a compound represented by the following formula (II) into a 1:1 complex of azo barbituric acid and nickel represented by the following formula (I) or a tautomer thereof; The complex (E4GN-GT, manufactured by Lanxess Co., Ltd.) was used as the yellow pigment C.

[化27]

According to Table 11, in Reference Example 1 using green pigment A with respect to Reference Example 2 using green pigment B, the pigment concentration was low and the coloring power was high. When the pigment concentration is small, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, or the like can be used in a larger amount in terms of solid content, which is advantageous for various properties such as developability and reliability. The reason for the details is unknown, but it is considered that the reason is that when comparing the breakthrough spectra at the same pigment concentration, the green pigment A is compared with the green pigment B due to the influence of the average number of hydrogen atoms contained in one molecule. The half value of the peak is narrower, and effectively blocks the red or blue penetrating light.

(Experimental Examples 1 to 6 and Comparative Experimental Examples 1 to 5)

225 parts by mass of the green pigment, yellow pigment C, dispersant A, dispersion resin A, solvent (propylene glycol monomethyl ether acetate), and zirconia beads having a diameter of 0.5 mm described in Table 12 were filled in a stainless steel container. The green pigment dispersions A and B were prepared by dispersing for 6 hours using a paint shaker. Further, the blending amount of the components other than the "solvent" in the table is a solid content conversion value.

<Preparation of Colored Resin Composition>

The other components shown in Table 13 were mixed in each of the above pigment dispersions to prepare a colored resin composition. Further, the combination of the green pigment type and the photopolymerization initiator type is as shown in Table 14. In addition, the blending amount of the binder resin and the photopolymerizable monomer in Table 13 is a solid content conversion value, and the solvent amount 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 shown below.

<Photopolymerization initiator A> an oxime ester compound having the following chemical structure

[化28]

<Photopolymerization initiator B> Irgacure OXE02 (manufactured by BASF Corporation)

<Photopolymerization initiator C> Irgacure OXE03 (manufactured by BASF Corporation)

<Photopolymerization initiator D> an oxime ester compound having the following chemical structure

[化31]

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

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

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

[化34]

<Photopolymerization initiator H> Irgacure 907 (manufactured by BASF Corporation)

<Photopolymerization initiator I> Irgacure 369 (manufactured by BASF Corporation)

<Minimum connection evaluation>

Each of the colored resin compositions was applied by spin coating on a glass substrate on which chromium was deposited, and prebaked for 3 minutes using a hot plate at 80 °C. The number of revolutions was adjusted so that the film thickness of the coating film became 2.0 μm after baking at the time of coating.

Next, a mask pattern having a linear opening having a width of 1 to 50 μm (1 to 10 μm: every 1 μm, 15 to 50 μm: every 5 μm) was provided with a gap of 150 μm, and the mask pattern was used with a high-pressure mercury lamp at 40 mJ. The sample was exposed to /cm ² , and thereafter, spray development was carried out using a 0.04% by mass aqueous potassium hydroxide solution at a developer temperature of 23 ° C and a pressure of 0.25 MPa. The development time was set to twice the dissolution time of the previously measured colored resin composition. For the substrate, it is rinsed with sufficient water after development, and then dried with clean air. Thereafter, it was baked in an oven at 230 ° C for 30 minutes. Obtaining the linear pattern obtained in the above-described order by an optical microscope, and in the linear mask pattern having different widths, the width of the opening portion corresponding to the mask remaining on the substrate is specified to be the smallest The width of the opening is set to be the minimum adhesion. The results are shown in Table 14.

According to Table 14, in the case where the green pigment B is used as in Comparative Example 1 or 2, the case where an oxime ester compound is used as a photopolymerization initiator and the case where an initiator other than the oxime ester compound is used In both cases, the minimum adhesion is good. On the other hand, when green pigment A is used as in Comparative Experimental Examples 3 to 5, when an initiator other than an oxime ester-based compound is used as a photopolymerization initiator, the value of the minimum adhesion is large, and it can be said that the adhesion is small. Poor sex. On the other hand, when green pigment A was used as in Experimental Examples 1 to 6, by using an oxime ester-based compound as a photopolymerization initiator, the value of the minimum adhesion was small and the adhesion was good. It is considered that the green pigment A has a higher average number of hydrogen atoms than the green pigment B, and because of the difference in light absorption characteristics, photohardening tends not to sufficiently proceed to the inside of the coating film, but is used by The oxime ester compound having a larger absorption band in the low-wavelength region serves as a photopolymerization initiator, and the photocuring can be sufficiently carried out to the inside of the coating film, and a fine pattern can be formed with good adhesion.

<film thickness, coloring strength evaluation>

The colored resin composition was applied onto a glass substrate (manufactured by Asahi Glass Co., Ltd., AN100) of 50 mm square and 0.6 mm thick by a spin coater, and then dried at 80 ° C for 3 minutes. Then, a full exposure treatment was performed with a 2 kW high pressure mercury lamp at an exposure amount of 40 mJ/cm ² . Thereafter, it was baked in an oven at 230 ° C for 30 minutes.

With respect to the coated substrate thus obtained, the breakthrough spectrum was measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd. Based on the obtained breakthrough spectrum, the film thickness required to set the chromaticity under the C light source to (sx=0.240, sy=0.580) was calculated, and the pigment concentration required to set the film thickness to 2.00 μm (all the pigments) was calculated. The mass % relative to the total solid content was evaluated as the coloring power. The results are shown in Table 14.

According to Table 14, it was found that in Comparative Examples 1 and 2 using Green Pigment B, in Experimental Examples 1 to 6 in which green pigment A was used, the required pigment concentration was low and the coloring power was high. When the concentration of the pigment is small, it is possible to blend more binder resin, photopolymerizable monomer, photopolymerization initiator, etc., in accordance with the solid content, and it is advantageous for various properties such as developability and reliability. The reason for the difference in the coloring power is unknown, but it is considered to be because the green pigment A and the green pigment B have a narrower half-value width than the green pigment B when the transmittance spectrum is compared at the same pigment concentration, so that it is effective. The ground obscures the red or blue penetrating light.

According to the above, by using a zinc phthalocyanine pigment and an oxime ester compound having an average number of hydrogen atoms contained in one molecule in a single molecule, the coloring power and the adhesion can be achieved.

The present invention has been described in detail with reference to the preferred embodiments thereof. This application is based on a Japanese patent application filed on March 27, 2015 (Japanese Patent Application No. 2015-067187), and a Japanese patent application filed on October 20, 2015 (Japanese Patent Application No. 2015-206474), The Japanese Patent Application (Japanese Patent Application No. 2015-207298) filed on Jan. 21, and the Japanese patent application filed on March 11 .

10‧‧‧Transparent support substrate

20‧‧ ‧ pixels

30‧‧‧Organic protective layer

40‧‧‧Inorganic oxide film

50‧‧‧Transparent anode

51‧‧‧ hole injection layer

52‧‧‧ hole transport layer

53‧‧‧Lighting layer

54‧‧‧Electronic injection layer

55‧‧‧ cathode

100‧‧‧Organic EL components

500‧‧‧Organic emitters

Claims (15)

A colored resin composition comprising (A) a pigment, (B) a dispersant, (C) a solvent, (D) a binder resin, and (E) a photopolymerization initiator; wherein the (A) pigment comprises a halogenation a zinc phthalocyanine pigment, the average number of hydrogen atoms contained in one of the molecules of the zinc phthalocyanine pigment is 3 or more, and the solvent of the above (C) is contained at 1013.25 hPa and has a boiling point of 150 ° C or higher. Boiling point solvent. The colored resin composition of claim 1, wherein the (C) solvent further comprises a low boiling point solvent having a boiling point of less than 150 ° C at 1013.25 hPa. The colored resin composition of Claim 1 or 2, wherein the content ratio of the (C) solvent to the colored resin composition is 50% by mass or more. The colored resin composition of any one of the above-mentioned (C) solvents, wherein the content ratio of the high-boiling solvent to the (C) solvent is 0.5% by mass or more. The colored resin composition according to any one of claims 1 to 4, wherein the high boiling point solvent has a vapor pressure of not more than 400 Pa at 20 °C. The colored resin composition according to any one of claims 1 to 5, wherein the (B) dispersant comprises a block copolymer having a functional group containing a nitrogen atom. The colored resin composition according to any one of claims 1 to 6, wherein the (E) photopolymerization initiator comprises an oxime ester compound. A color filter having a pixel produced using the colored resin composition of any one of claims 1 to 7. An image display device having the color filter of claim 8. A pigment dispersion containing (A) a pigment, (B) a dispersant, and (C) a solvent Wherein the (A) pigment comprises a zinc phthalocyanide pigment, the average number of hydrogen atoms contained in one of the molecules of the zinc phthalocyanine pigment is 3 or more, and the boiling point of the solvent (C) contained in 1013.25 hPa is High boiling point solvent above 150 °C. The pigment dispersion according to claim 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. The pigment dispersion liquid according to claim 10 or 11, wherein the content ratio of the solvent (C) to the pigment dispersion liquid is 50% by mass or more. The pigment dispersion liquid according to any one of claims 10 to 12, wherein a content ratio of the high boiling point solvent to the (C) solvent is 1% by mass or more. The pigment dispersion according to any one of claims 10 to 13, wherein the high boiling point solvent has a vapor pressure of 400 Pa or less at 20 °C. The pigment dispersion according to any one of claims 10 to 14, wherein the (B) dispersant comprises a block copolymer having a functional group containing a nitrogen atom.