KR101608292B1 - Colored curable composition, colored pattern, color filter and method of manufacturing the same, and liquid crystal display device - Google Patents

Abstract

The present invention provides a colored curable composition containing (A) a colorant, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a polyalkylene oxide and a dimethylpolysiloxane having a hydroxyl group. Further, the present invention provides a coloring pattern using the above-mentioned colored curable composition, a color filter having the coloring pattern, a method of manufacturing the color filter, and a liquid crystal display element provided with the color filter.

A coloring curable composition, a coloring pattern, a color filter, a liquid crystal display element

Description

TECHNICAL FIELD [0001] The present invention relates to a colored curable composition, a colored pattern, a color filter, a method of manufacturing a color filter, and a liquid crystal display

The present invention relates to a colored curable composition, a colored pattern, a color filter, a method for producing a color filter, and a liquid crystal display element.

A color filter constituting a liquid crystal display (LCD), a color image pickup tube device (Charge Coupled Device: CCD) and the like can be produced by mixing a binder resin and / or a monomer, a photopolymerization initiator, And a step of forming a photosensitive photosensitive composition containing the other components and applying the coating composition on a transparent substrate and drying the coating to form a coating film having a thickness of about 1 탆 to 3 탆 by a photolithographic method or the like .

The coating method of the colored photosensitive composition on a substrate includes a spin coating method and a die coating method, and is suitably used according to the characteristics thereof.

The spin coating method is a widely used method for forming a thin film on a substrate of a relatively small size. While the transparent substrate is rotated at a constant number of revolutions, the coating liquid is dropped to the center of the transparent substrate, the coating liquid is thinly extended by centrifugal force, A coating film having a desired film thickness is formed on the surface of the transparent substrate by controlling the number of revolutions or the rotation time of the transparent substrate in accordance with the coating liquid. However, there is a drawback that the thickness of the coated film of the center portion and the peripheral portion of the rotation of the transparent substrate becomes excessively thick as compared with the middle portion thereof due to the principle that the coating film is made thin by using the centrifugal force by rotation.

The die coating method is a suitable method for forming a thin film on a substrate of a large size, and is a coating method for forming a coating film having a desired film thickness on the surface of a transparent substrate while discharging the coating liquid from the slit and moving the slit. However, there is such a drawback that on the mechanism, unevenness on the line is likely to occur in the direction perpendicular to the advancing direction of the slit, and the outer peripheral portion of the coating rises and the film thickness becomes thicker than the center portion of the substrate.

In addition, if the dryness of the coating liquid and the surface tension are not appropriate regardless of the coating method, there arises a problem that pinholes (voids) are generated.

Various attempts have heretofore been made in order to solve the problem of unevenness of the coating film in the spin coating method or the die coating method. For example, Japanese Patent Application Laid-Open No. 2007-186683 discloses a technique for solving the problem by adjusting the surface tension of a composition, and a polysiloxane containing a polyalkylene oxide is preferably used. Japanese Patent Application Laid-Open No. 2006-259708 discloses a technique for solving the problem by optimizing the addition amount of the silicone surfactant and controlling the viscosity of the photosensitive composition.

SUMMARY OF THE INVENTION The present invention has been made in view of the background art described above, and an object thereof is to achieve the following objects.

An object of the present invention is to provide a colored curable composition capable of suppressing the surface deterioration caused by application and capable of forming a colored film having few defects.

Another object of the present invention is to provide a color filter having a good surface area formed by using the colored curable composition and having a less defective color pattern and the colored pattern, a method of producing the color filter, And a liquid crystal display element.

Means for solving the above problems are as follows.

That is, the colored curable composition of the present invention contains (A) a colorant, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a polyalkylene oxide and a dimethylpolysiloxane having a hydroxyl group.

Further, in the present invention, it is preferable that the hydroxyl group in the (D) polyalkylene oxide and the dimethylpolysiloxane having a hydroxyl group is an alcoholic hydroxyl group.

It is also a preferred embodiment that the (D) polyalkylene oxide and the dimethylpolysiloxane having a hydroxyl group are contained in an amount of 0.01% by mass to 0.20% by mass based on the total solid content in the composition.

The coloring pattern of the present invention is characterized by being formed by the colored curing composition of the present invention.

Further, the color filter of the present invention is characterized by having the coloring pattern of the present invention on a substrate. The method for producing a color filter according to the present invention includes a step of applying the colored curable composition of the present invention by a spin coating method, a slit-and-end spin method or a die coating method, and a coloring pattern is formed on a substrate do.

The liquid crystal display element of the present invention is characterized by using the color filter of the present invention.

(Effects of the Invention)

According to the present invention, it is possible to provide a colored curable composition capable of suppressing the surface deterioration caused by coating and forming a colored film having few defects.

Further, according to the present invention, it is possible to provide a color filter having a good surface area formed by using the above-mentioned colored curable composition and having less defects, and a color filter having the colored pattern, a method of manufacturing the color filter, And to provide a liquid crystal display element.

Hereinafter, the present invention will be described in detail.

In the present specification, " ~ " is used to mean that the numerical values described before and after that are included as the lower limit value and the upper limit value.

≪ Coloring curable composition >

The colored curable composition of the present invention is characterized by containing (A) a colorant, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a polyalkylene oxide and a dimethylpolysiloxane having a hydroxyl group.

Since the colored curable composition of the present invention contains the above components (A) to (D), the surface tension of the colored curable composition is lowered and the wettability to the surface to be coated such as a substrate is improved, thereby eliminating void defects. In addition, it is possible to homogenize the drying in the coating step owing to the extremely high surface film surface localization effect of the component (D), and the irregularity of the line shape caused by the drying irregularity can be greatly reduced.

Hereinafter, each of the components (A) to (D) will be described in detail.

[(D) a dimethylpolysiloxane having a polyalkylene oxide and a hydroxyl group]

The colored curable composition of the present invention (D) contains a polyalkylene oxide and a dimethylpolysiloxane having a hydroxyl group in the molecule.

Hereinafter, this compound will be appropriately referred to as " specific siloxane polymer ".

The specific siloxane polymer in the present invention has a structure containing a polyalkylene oxide, a hydroxyl group, and a dimethylpolysiloxane in the molecule.

Examples of the polyalkylene oxide in the molecule include polyethylene oxide and polypropylene oxide. The number of repeating units is preferably from 1 to 20, more preferably from 1 to 10.

The specific siloxane polymer in the present invention may have both polyethylene oxide and polypropylene oxide in the molecule. Among them, a structure having only propylene oxide is particularly preferable from the viewpoint of wettability to a surface to be coated such as a substrate.

In the specific siloxane polymer, the bonding form of the polyalkylene oxide and the dimethylpolysiloxane may be a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethylpolysiloxane, a one-terminal modification in which the polyalkylene oxide unit is bonded to the terminal of the dimethylpolysiloxane, End-end modification, or a linear block copolymer type in which the polyalkylene oxide unit is alternately repeatedly bonded to the dimethylpolysiloxane. Of these, both end transformation are particularly preferable from the viewpoint of wettability to a surface to be coated such as a substrate.

The hydroxyl group in the specific siloxane polymer in the present invention may be bonded to the side chain of the polymer or may be bonded to one terminal or both terminals of the polymer molecular chain. However, the hydroxyl group may be bonded to one terminal or both terminals of the polymer molecular chain desirable.

This hydroxyl group may be introduced by any modification of carbinol denaturation, diol denaturation, phenol denaturation or silanol denaturation. Among them, carbinol transformation is particularly preferable. The hydroxyl group present in the molecule of the specific siloxane polymer is preferably an alcoholic hydroxyl group.

As the hydroxyl value in the specific siloxane polymer in the present invention,

It is preferably from 5 mgKOH / g to 150 mgKOH / g, more preferably from 5 mgKOH / g to 100 mgKOH / g, particularly preferably from 5 mgKOH / g to 80 mgKOH / g.

The viscosity of the specific siloxane polymer in the present invention at 25 캜 is preferably 10 mm 2 / s to 200 mm 2 / s, more preferably 10 mm 2 / s to 150 mm 2 / s, particularly preferably 10 mm 2 / Mm 2 / s to 120 mm 2 / s.

Specific examples (D-1 to D-5) of the specific siloxane polymer in the present invention are shown below together with the hydroxyl value and the viscosity at 25 DEG C, but the present invention is not limited thereto.

Here, the following specific examples D-1 to D-5 are available as commercial products, and corresponding commercial products are also described.

The colored curable composition of the present invention may contain at least one specific siloxane polymer, or may contain two or more kinds of specific siloxane polymers.

In the colored curable composition of the present invention, the amount of the specific siloxane polymer is preferably 0.01% by mass to 0.10% by mass, more preferably 0.01% by mass to 0.05% by mass, based on the solid content of the composition.

[(A) Colorant]

The colored curable composition of the present invention contains (A) a colorant, and as the colorant, a pigment and a dye can be used.

(Pigment)

As the pigment that can be used in the color-curable composition of the present invention, conventionally known various inorganic pigments or organic pigments can be used. In consideration of the fact that the pigment preferably has a high transmittance regardless of the inorganic pigment or the organic pigment, it is preferable to use a pigment having a small particle size and a minute particle size as much as possible. Considering that the handling property of the pigment is good, it is preferably a pigment having an average primary particle diameter of 0.01 to 0.3 mu m, more preferably 0.01 to 0.15 mu m. When the particle diameter is within the above range, a coloring film having a high transmittance and good color characteristics is obtained, which is also effective for forming a color filter with high contrast.

The average primary particle diameter was measured by observing pigment particles with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), measuring particle sizes of 100 particles at the areas where particles were not aggregated, And calculating the average value thereof.

As the inorganic pigment, metal compounds such as metal oxides and metal complex salts can be exemplified. Specifically, oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, and complex oxides of the above metals can be exemplified.

As the organic pigment, for example,

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: , 81: 2, 81: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 , 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,

CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12,13,14,15,16,17,18,20,24,31,32,34,35,35,136 , 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97 , 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139 , 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179 , 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214,

CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 ,

C. I. Pigment Green 7, 10, 36, 37,

CI Pigment Blue 79, the CI Pigment Blue 79, the CI Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, , CI Pigment Blue 80,

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,

C. I. Pigment Brown 25, 28,

C. I. Pigment Black 1, 7, etc. can be listed.

Among these pigments, the following pigments can be preferably used. However, the present invention is not limited to these.

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

C. I. Pigment Orange 36, 71,

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

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

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

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

C. I. Pigment Black 1, 7

- Minification of pigments -

In the present invention, if necessary, an organic pigment that is finely pulverized (having a reduced particle diameter) can be used. The fineness of a pigment is a step of mixing a pigment, a water-soluble organic solvent and a water-soluble inorganic salt to prepare a liquid composition having a high viscosity, and pulverizing the pigment using the liquid composition.

Examples of the water-soluble organic solvent to be used in the process of refining the pigment include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Ethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate, and the like. As long as it is adsorbed on the pigment and is not lost in the wastewater by using a small amount, it is possible to use benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, Propyl acetate, propyl acetate, butyl acetate, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, halogenated hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Dimethyl sulfoxide, N-methyl pyrrolidone and the like may be used. If necessary, two or more kinds of solvents may be mixed and used.

Examples of the water-soluble inorganic salt used in the step of refining the pigment in the present invention include sodium chloride, potassium chloride, calcium chloride, barium chloride and sodium sulfate.

The amount of the water-soluble inorganic salt to be used in the process of finishing the pigment is 1 to 50 times the mass of the pigment, and the majority of the water-soluble inorganic salt is 1 to 10 times mass from the viewpoint of productivity. The water content of the water-soluble organic solvent used in the micronization step is preferably 1% or less.

The amount of the water-soluble organic solvent to be used in the fineness of the pigment is in the range of 50 mass% to 300 mass%, preferably 100 mass% to 200 mass% with respect to the pigment.

After preparing the liquid composition using each of the above components, the pigment is finely pulverized by a wet pulverizer. Here, the operating conditions of the wet pulverizing apparatus are not particularly limited, but in order to effectively carry out the pulverization by the pulverizing medium, it is preferable that the number of revolutions of the blades in the apparatus is 10 to 200 rpm, In addition, it is preferable that the rotation ratio of the two axes is relatively large, because the effect of grinding is large. The operating time is preferably from 1 hour to 8 hours together with the dry milling time, and the internal temperature of the apparatus is preferably from 50 to 150 ° C. The water-soluble inorganic salt as a pulverizing medium has a particle size of 5 to 50 탆 and preferably has a sharp particle diameter distribution and a spherical shape.

- Combination of pigments (color matching) -

The organic pigments as the coloring agents can be used alone, but they can be used in various combinations in order to increase color purity. Specific examples of combinations are shown below.

For example, as the red pigment, an anthraquinone pigment, a perylene pigment and a diketopyrrolopyrrole pigment may be used singly or in combination of two or more. However, at least one of them may be used in combination with a disazo yellow pigment, A yellow pigment, and a quinophthalone-based yellow pigment may be mixed and used. Examples of the anthraquinone pigments include CI Pigment Red 177, the perylene pigments include CI Pigment Red 155 and CI Pigment Red 224, and the diketopyrrolopyrrole pigments include CI Pigment Red 254. From the viewpoint of good color reproducibility, a mixture of a red pigment and C. I. Pigment Yellow 83, C. I. Pigment Yellow 139, or C. I. Pigment Red 177 is preferable.

The mass ratio of other pigments to the red pigment (other pigment / red pigment) is preferably in the range of 5/100 to 80/100. When it is less than 5/100, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and color purity can not be increased in some cases. If it exceeds 80/100, the coloring power may be lowered. Particularly, the mass ratio is preferably in the range of 10/100 to 65/100. When red pigments are combined with each other, the mass ratio can be adjusted in accordance with the chromaticity.

As the green pigment, a halogenated phthalocyanine-based pigment may be used singly, and it may be used in combination with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment It is also good. For example, in this example, a mixture of CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, Do.

The mass ratio of the yellow pigment to the green pigment (yellow pigment / green pigment) is preferably in the range of 5/100 to 200/100. When the mass ratio is less than 5/100, it is difficult to suppress the light transmittance in the range of 400 nm to 450 nm, so that the color purity can not be increased. On the other hand, when the ratio exceeds 200/100, the dominant wavelength becomes near the long wavelength and the deviation from the NTSC target color may become large. The mass ratio is particularly preferably in the range of 20/100 to 150/100.

As the blue pigment, a phthalocyanine-based pigment may be used singly, but it may be mixed with a dioxadine purple pigment. As a particularly preferable example, a mixture of C. I. Pigment Blue 15: 6 and C. I. Pigment Violet 23 can be listed.

The ratio of the purple pigment to the blue pigment (purple pigment / blue pigment) is preferably 0/100 to 100/100, more preferably 70/100 or less.

As a preferable pigment for black matrix use, carbon black, graphite, titanium black, iron oxide, and titanium oxide may be used singly or a mixture of two or more thereof may be used. Of these, a combination of carbon black and titanium black is preferable.

The mass ratio of titanium black to carbon black (titanium black / carbon black) is preferably in the range of 0/100 to 60/100. At 61/100 or higher, the dispersion stability may be lowered.

(dyes)

In the present invention, when a dye is used as the (A) coloring agent, a color-curable composition that is uniformly dissolved can be obtained.

The dye usable as the colorant is not particularly limited, and known dyes conventionally used for the color filter can be used. For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, U.S. Patent No. 4,808,501, U.S. Patent No. 5,667,920, U.S. Patent No. 5,059,500, JP-A-5-333207, JP-A-6-35183, and JP-A-6-51115 , Japanese Patent Application Laid-Open Nos. 6-194828, 8-211599, 4-249549, 10-123316, and 11-302283 , Japanese Patent Application Laid-Open Nos. 7-286107, 2001-4823, 8-15522, 8-29771, 8-146215, Japanese Patent Application Laid-Open No. 11-343437, 8-62416, 2002-14220, 2002-14221, 2002-14222, 2002-14223, and 08-302224, the disclosures of which are incorporated herein by reference. A pigment described in Japanese Patent Application Laid-Open Nos. 8-73758, 8-179120 and 8-151531, and the like are listed.

Examples of the chemical structure of the dye include pyrazole azo compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, anthrapyridone compounds, benzylidene compounds, oxolin compounds, pyrazolotriazole compounds, pyridazo compounds, cyanines, Dyes such as pyrrolopyrazole-zometine-based, xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes.

(Pigment dispersion)

In the present invention, when a pigment is used as the (A) coloring agent, it is preferable to prepare the colored curable composition of the present invention by using a pigment dispersion prepared in advance.

The content of the pigment in the pigment dispersion is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, based on the total solid content (mass) of the composition. When the content of the pigment is within the above range, a colored film having color characteristics sufficiently excellent in color density can be obtained.

- dispersant -

The pigment dispersion in the present invention preferably contains at least one dispersant. The dispersibility of the pigment can be improved by the inclusion of the dispersant.

As the dispersing agent, for example, a known pigment dispersing agent or a surfactant can be suitably selected and used.

Specifically, many kinds of compounds can be used. For example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid based (co) polymer polyphosphate No. 75, No. 90, No. 95 (a product of KYOEISHA CHEMICAL Co., LTD.) And W001 (a product of Yusho Co., Ltd.); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol distearate, polyethylene glycol distearate, sorbitan fatty acid Nonionic surfactants such as esters; Anionic surfactants such as W004, W005 and W017 (manufactured by Yusho Co., Ltd.); EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (all manufactured by Chiba Specialty Chemicals KK), Disperse AID 6, Disperse AID 8, Disperse A 15, EFKA-47, EFKA-47, EFKA-47EA, EFKA Polymer 100, , Disperse AID 9100 (all products of SAN NOPCO LIMITED); Various Solsperse dispersants (Lubrizol Japan Ltd.) such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000; ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.) ISONET S-20 (manufactured by SANYO KASEI Corporation), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 161, 162, 163, 164, 166, 167, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (BYK Japan KK). An oligomer or polymer having a polar group at the molecular end or side chain such as an acrylic copolymer.

The content of the dispersing agent in the pigment dispersion is preferably 1 to 100% by mass, more preferably 3 to 70% by mass with respect to the mass of the pigment.

- Pigment derivatives -

In the pigment dispersion of the present invention, a pigment derivative is added if necessary. A pigment derivative into which a moiety having affinity with a dispersant has been introduced or a pigment derivative into which a polar group has been introduced is adsorbed on the surface of the pigment and is used as an adsorption point of the dispersant to disperse the pigment as fine particles in the pigment dispersion or in the pigmented curable composition, It is possible to prevent re-aggregation. As a result, this colored curable composition can be preferably used when forming a color filter having high contrast and excellent transparency.

Specifically, the pigment derivative is a compound in which an organic pigment is used as a parent skeleton and an acidic group, a basic group or an aromatic group is introduced into the side chain as a substituent. Specific examples of the organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindolin pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, Pigments, and the like. In general, pale yellow aromatic polycyclic compounds such as naphthalene-based, anthraquinone-based, triazine-based, and quinoline-based compounds not referred to as pigments are also included.

Examples of the pigment derivative include those described in JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810 Those described in JP-A-11-199796, JP-A-2005-234478, JP-A-2003-240938, and JP-A-2001-356210 can be used.

The content of the pigment derivative in the pigment dispersion is preferably from 1 to 30% by mass, more preferably from 3 to 20% by mass, based on the mass of the pigment. When the content is within the above range, dispersion of the pigment can be favorably performed while suppressing the viscosity of the pigment dispersion to be low, dispersion stability of the pigment after dispersion can be improved, A colored film is obtained, and when a color filter is manufactured using the colored curable composition, a high contrast structure having good color characteristics can be obtained.

- Dispersion method -

As a dispersing method of the pigment, for example, a pigment and a dispersing agent are mixed and dispersed in advance by a homogenizer or the like is finely dispersed using a bead dispersing machine using zirconia beads or the like (for example, a dispenser of GETZMANN) Method is used.

The dispersion time is preferably about 3 to 6 hours.

[(B) Photopolymerizable compound]

The colored curable composition of the present invention contains (B) a photopolymerizable compound.

The photopolymerizable compound is preferably a compound having at least one addition-polymerizable ethylenic unsaturated group and having a boiling point of 100 DEG C or higher at normal pressure, and among these, an acrylate compound having four or more functionalities is more preferable.

Examples of the compound having at least one addition polymerizable ethylenic unsaturated group and having a boiling point of 100 ° C or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl ) Acrylate; a monofunctional acrylate or methacrylate such as acrylate; (Meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate such as pentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylol propane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohol, poly (meth) acrylate of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. 48-41708, Japanese Patent JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-A- Polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resin with (meth) acrylic acid, epoxy acrylates and the like, as disclosed in JP-B-49-43191 and JP-A-52-30490 Can be listed.

Also, 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers.

Further, in Japanese Patent Application Laid-Open No. 10-62986, it is also possible to add ethylene oxide or propylene oxide to the above polyfunctional alcohol represented by general formulas (1) and (2) together with specific examples thereof and then to (meth) Compounds can also be used.

Among them, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) acrylate, and structures in which the acryloyl group is interposed between ethylene glycol and propylene glycol moieties (a structure in which dipentaerythritol and acryloyl Is bonded to ethylene glycol, propylene glycol residue). These oligomer types can also be used.

Also, urethane acrylates such as those described in Japanese Patent Publication Nos. 48-41708, 51-37193, 2-32293 and 2-16765, JP-B-58-49860, JP-A-56-17654, JP-B-62-39417, and JP-A-62-39418 are also preferable as urethane compounds having an ethylene oxide skeleton. Further, by using addition polymerizable compounds having an amino structure or sulfide structure in the molecule described in Japanese Patent Application Laid-Open Nos. 63-277653, 63-260909, and 1-105238, A photopolymerizable composition having a very high speed can be obtained. UA-7200 "(product of Shin-nakamura Chemical Co. Ltd., DPHA-40H (product of NIPPON KAYAKU CO., LTD.) ), UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (products of KYOEISHA CHEMICAL CO., LTD.

Ethylenic unsaturated compounds having an acid group are also preferable, and commercially available products include, for example, TOAGOSEI CO., LTD. TO-756 which is a carboxyl functional group-containing trifunctional acrylate, and TO-1382 which is a carboxyl functional group-containing pentafunctional acrylate.

The photopolymerizable compound may be used singly or in combination of two or more kinds.

The content of the photopolymerizable compound in the colored curable composition is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, and still more preferably 10 to 35% by mass in the total solid content.

[(C) Photopolymerization initiator]

The colored curable composition of the present invention contains (C) a photopolymerization initiator.

Examples of the photopolymerization initiator include halomethyloxadiazole described in Japanese Patent Application Laid-Open No. 57-6096, halomethyl-s-aminophenol disclosed in Japanese Patent Publication No. 59-1281, Japanese Patent Application Laid-open No. 53-133428, Aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in each specification of U.S. Patent No. 4318791 and European Patent Application Publication No. 88050, benzoin compounds described in U.S. Patent No. 4,199,420, (Thio) xanthones or acridine compounds described in the specification of French Patent No. 2456741, compounds such as coumarins or ropin dyes described in JP-A No. 10-62986, And sulfonium organic boron complexes such as those disclosed in JP-A-8-015521.

The photopolymerization initiator may be at least one selected from the group consisting of acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, triazine, halomethyloxadiazole, acridine, coumarin, , Oxime ester type and the like are preferable.

Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl- Acetophenone, 4'-isopropyl-2-hydroxy-2-methyl-propiophenone, and the like can be preferably exemplified.

As the ketal-based photopolymerization initiator, for example, benzyldimethyl ketal, benzyl- beta -methoxyethyl acetal and the like can be preferably exemplified.

Examples of the benzophenone-based photopolymerization initiator include benzophenone, 4,4'- (bisdimethylamino) benzophenone, 4,4 '- (bisdiethylamino) benzophenone, 4,4'-dichlorobenzophenone, Cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, and the like can be preferably exemplified.

Examples of the benzoin or benzoyl photopolymerization initiator include benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl benzoate, and the like.

Examples of the xanton-based photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

Examples of the triazine photopolymerization initiator include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (Trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (Trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl (Trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxystilyl- Di (trichloromethyl) -s-triazine, 4- benzoxorane-2,6-di (trichloromethyl) -s-triazine, 4- (o- (Chloromethyl) - phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) s-triazine, and the like.

Examples of the halomethyloxadiazole photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (cyanostyryl) (2-trichloromethyl-5- (naphtho-1-yl) -1,3,4-oxadiazole, 2-trichloromethyl-5- 1,3,4-oxadiazole, and the like can be preferably exemplified.

Examples of the acridine photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

Examples of the coumarinite photopolymerization initiator include 3-methyl-5-amino- ((s-triazin-2-yl) amino) 3-phenylcoumarin, 3-butyl-5-dimethylamino- ((s-triazin-2-yl) amino) -3-phenyl coumarin and the like have.

Examples of the phosphineimide-based photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5- Dimerolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, and the like can be preferably exemplified.

As the imidazole-based photopolymerization initiator, for example, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide and the like can be preferably exemplified.

In addition to the above, there may be mentioned 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4'- (benzmercapto) benzoyl- -Trimethylphenylcarbonyl-diphenylphosphonyloxide, hexafluorophosphorothio-trialkylphenylphosphonium salt, and the like.

The present invention is not limited to the photopolymerization initiator described above, and other known ones can be used. For example, bisphenol polyketol aldonyl compounds described in U.S. Patent No. 2,367,660, α-carbonyl compounds described in U.S. Patent Nos. 2,367,661 and 2,367,670, acyloin ethers described in U.S. Patent No. 2,448,828 , Aromatic acyloin compounds substituted with [alpha] -hydrocarbon described in U.S. Patent No. 2,722,512, polynuclear quinone compounds described in U.S. Patent Nos. 3,046,127 and 2,951,758, triarylimine described in U.S. Patent No. 3,549,367 Benzothiazole compounds / trihalomethyl-s-triazine compounds described in Japanese Patent Publication No. 51-48516, JCS Perkin II (1979) 1653-1660, JCS Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and JP-A 2000-66385.

A plurality of these photopolymerization initiators may be used in combination.

The content of the photopolymerization initiator in the tinting curable composition is preferably from 0.1 to 10.0% by mass, more preferably from 0.5 to 5.0% by mass, based on the total solid content of the composition. When the content of the photopolymerization initiator is within the above range, it is possible to form a film with good strength by progressing the polymerization reaction well.

[Optional Ingredients]

Hereinafter, the colored curable composition of the present invention may contain components that can be optionally added, such as a binder polymer (alkali-soluble resin), a solvent, etc., in addition to the components (A) to (D)

Hereinafter, optional components that can be added to the color-curable composition of the present invention will be described.

(Binder polymer)

The colored curable composition of the present invention may contain an alkali-soluble resin as a binder polymer.

The alkali-soluble resin is preferably a linear organic polymer and is a group which promotes the solubility of at least one alkali in a molecule (preferably an acrylic copolymer, a molecule having a styrenic copolymer as a main chain) (for example, a carboxyl group, a phosphoric acid group, And the like). Of these, more preferred is an alkali-soluble resin which is soluble in an organic solvent and can be developed by a weakly alkaline aqueous solution.

The alkali-soluble resin can be produced, for example, by a known radical polymerization method. Polymerization conditions such as the temperature, pressure, kind and amount of the radical initiator and the kind of the solvent when the alkali-soluble resin is produced by the radical polymerization method can be easily set by those skilled in the art and can be determined experimentally.

As the above-mentioned linear organic polymer, a polymer having a carboxylic acid in its side chain is preferable. For example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Application Laid-open No. 59-53836, Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like as described in each publication of JP-A No. 59-71048, Acidic cellulose derivatives having a carboxylic acid, acid anhydride added to a polymer having a hydroxyl group, and the like, and a polymer having a (meth) acryloyl group in the side chain are also preferable.

Among these, a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid copolymer or benzyl (meth) acrylate / (meth) acrylic acid / other monomer is preferable.

In addition to these, copolymers of 2-hydroxyethyl methacrylate and the like are also listed as useful. The polymers may be used in any amount and mixed.

In addition to the above, there may be mentioned 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxy Propyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydro Hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, and the like.

As specific constituent units of the alkali-soluble resin, copolymers of (meth) acrylic acid and other monomers copolymerizable therewith are preferable. Here, (meth) acrylic acid is a generic name of acrylic acid and methacrylic acid, and (meth) acrylate is also collectively referred to as acrylate and methacrylate.

Examples of the other monomer copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.

Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, Acrylate, cyclohexyl (meth) acrylate, and the like.

Examples of the vinyl compound include styrene,? -Methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate _{^{macromonomer, CH 2 = CR 31 R 32}} , CH 2 = C (R 31) (COOR 33) [ here, R ³¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R ³³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms].

These copolymerizable other monomers may be used singly or in combination of two or more. Preferred other copolymerizable monomers are at least one member selected from CH ₂ ═CR ³¹ R ³² , CH ₂ ═C (R ³¹ ) (COOR ³³ ), phenyl (meth) acrylate, benzyl (meth) acrylate, Particularly preferably, CH ₂ = CR ³¹ R ³² and / or CH ₂ = C (R ³¹ ) (COOR ³³ ).

The content of the alkali-soluble resin in the colored curable composition is preferably from 1 to 15% by mass, more preferably from 2 to 12% by mass, and particularly preferably from 3 to 10% by mass, based on the total solid content of the composition.

(solvent)

The colored curable composition of the present invention may contain a solvent as required.

Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, alkyl esters, Methyl methoxyacetate, methyl methoxyacetate, methyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 3- 3-oxypropionic acid alkyl esters such as ethyl oxypropionate; Methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy- , Methyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, 2- Ethyl butanoate; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons such as toluene and xylene.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate and the like are preferable.

The solvent may be used alone or in combination of two or more.

These solvents may be used when preparing the pigment dispersion described above.

(Other components)

The colored curable composition of the present invention may optionally contain a heat polymerization initiator, a thermopolymerization component, a thermal polymerization inhibitor, other fillers, a polymer compound other than the above alkali-soluble resin, an adhesion promoter, an antioxidant, an ultraviolet absorber, And may contain various additives.

- Thermal polymerization initiator -

It is also effective to incorporate a thermal polymerization initiator into the colored curable composition of the present invention.

Examples of the thermal polymerization initiator include various azo-based compounds and peroxide-based compounds, and azo-based compounds may include azobis-based compounds. Examples of the peroxide-based compounds include ketone peroxide, peroxyketal, Peroxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

- thermal polymerization component -

It is also effective to incorporate a thermally polymerizable component in the colored curable composition of the present invention in order to improve the strength of the cured film formed from the colored curable composition.

As the thermally polymerizable component, an epoxy compound is used. The epoxy compound includes compounds having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolak type, biphenyl type, and alicyclic epoxy compound.

Specific examples of the bisphenol A type include Eftop YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF- GL-61, GL-62, G101, EX-1102, and EX-1103 manufactured by Tohto Kasei Co., Ltd., Denacol EX- G102 (manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.), Bisphenol F type and bisphenol S type similar to these can also be listed. Epoxy acrylates such as Ebecryl 3700, 3701, 600 (manufactured by Daicel-UCB Co., Ltd.) can also be used.

Examples of the cresol novolak type include Eftop YDPN-638, YDPN-701, YDPN-702, YDPN-703 and YDPN-704 (available from Tohto Kasei Co., Ltd.), Denacol EM- LTD.),

Examples of the biphenyl type include 3,5,3 ', 5'-tetramethyl-4,4'-diglycidylbiphenyl,

Examples of the alicyclic epoxy compound include Seroxide 2021, 2081, 2083, 2085, Epolite GT-301, GT-302, GT-401, GT-403, EHPE- 3150 (available from DAICEL CHEMICAL INDUSTRIES, LTD. ST-4000, ST-5080, and ST-5100 (manufactured by Tohto Kasei Co., Ltd.).

Also, there may be mentioned 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyl tris (hydroxyethyl) isocyanurate, o - diglycidyl phthalate ester, diglycidyl terephthalate ester, other amine type epoxy resins such as Eftop YH-434 and YH-434L, and glycidyl esters modified by introducing dimer acid into the skeleton of bisphenol A type epoxy resin Can be used.

- Thermal polymerization inhibitor -

A heat polymerization inhibitor may be added to the colored curable composition of the present invention.

Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t- butylcatechol, benzoquinone, 4,4'- Methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzoimidazole and the like are useful.

[Preparation of colored curable composition]

The colored curable composition of the present invention may further contain optional components in addition to the colorant, (B) the photopolymerizable compound, (C) the photopolymerization initiator, and (D) the specific siloxane polymer (preferably together with the solvent) , Followed by mixing and dispersing the mixture using various mixers and dispersers. Particularly, when the (A) coloring agent is a pigment, it is preferable to prepare a pigment dispersion in advance and use it.

The mixing and dispersing step is preferably composed of a kneading dispersion followed by a non-dispersion treatment followed by kneading dispersion, but it is also possible to omit kneading dispersion.

An example of a method of preparing the colored curable composition of the present invention is shown below.

A mixture of a pigment, a water-soluble organic solvent and a water-soluble inorganic salt is kneaded using a kneader such as a 2 roll, a 3 roll, a ball mill, a tron mill, a disperser, a kneader, a coneerator, a homogenizer, a blender, The pigment is crushed while imparting a strong shearing force, the mixture is put into water, and the slurry is formed into a slurry by a stirrer or the like. Subsequently, the slurry is filtered, washed with water, and then the water-soluble organic solvent and the water-soluble inorganic salt are removed and dried to obtain a finely divided pigment. It is also possible to omit the process of making the pigment finer.

The beads are dispersed with the pigment, the dispersant and / or the pigment derivative and the solvent. A pigment dispersion is obtained mainly by using a sand grinder of a vertical or horizontal type, a pin mill, a steel mill, an ultrasonic dispersing machine or the like and finely dispersing with beads made of glass or zirconia having a particle diameter of 0.01 mm to 1 mm.

Further, details concerning kneading and dispersing are described in T. C. Patton, "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons Ltd., 1964).

After adding the photopolymerizable compound (B), the photopolymerization initiator (C), the photopolymerization initiator (D), the specific siloxane polymer, and an optional component to the pigment dispersion obtained as described above, The colored curable composition of the present invention can be obtained.

≪ Coloring pattern, color filter, and manufacturing method thereof &

The coloring pattern of the present invention is characterized by being formed by the above-mentioned colored curable composition of the present invention.

In the obtained coloring pattern, the surface deterioration due to coating is suppressed, and the coloring pattern can form a colored film having few defects. As a result, the coloring pattern of the present invention can be applied to a pixel portion of a color filter or the like.

The color filter of the present invention is characterized by having a coloring pattern formed on the substrate by the above-mentioned colored curable composition of the present invention.

The method for manufacturing a color filter of the present invention includes a step of applying the above-mentioned colored curable composition of the present invention by a spin coating method, a slit-and-spin method, or a die coating method, and a step of forming a coloring pattern on a substrate .

Hereinafter, the color filter of the present invention will be described in detail through a manufacturing method thereof (a manufacturing method of a color filter of the present invention).

As a method of producing the color filter of the present invention, first, the step of applying the colored curable composition of the present invention directly or through another layer on a substrate by a spin coating method, a slit-and-spin method, or a die coating method is performed. After the photocurable coating film is formed on the substrate by this process, the coating film is exposed through a predetermined mask pattern. After exposure, the uncured portions are developed and removed with a developing solution to form a colored pattern. By repeating such a process, a pixel portion (color pattern) of each color (three colors or four colors) is formed on a substrate to obtain a color filter.

With the above method, the color filter used in the liquid crystal display element or the solid-state image pickup element can be manufactured with less difficulty in process, and with high quality and low cost.

Hereinafter, each step of coating, exposure, and development will be described.

[Application step]

In the coating step, the colored curable composition of the present invention is coated on a substrate by a spin coating method, a slit-and-spin method, or a die coating method.

In the case of the slit-and-spin or die coating method, conditions are different depending on the size of the application substrate. For example, when a glass substrate (1100 mm x 1250 mm) of the fifth generation is applied by the die coating method, The spraying rate of the curable composition is usually from 500 to 2000 / / sec, preferably from 800 to 1500 / / sec, and the coating speed is from 50 to 300 mm / sec, preferably 100 mm / ~ 200mm / sec. The solid content of the colored curable composition is usually 10 to 20%, preferably 13 to 18%.

When the 3.5th generation glass substrate of 720 mm x 600 mm is coated by the spin coat method, the discharge amount of the colored curable composition from the nozzle is usually 40 mL to 50 mL, and the application rotation speed is 500 rpm to 1000 rpm. The solid content of the colored curable composition is usually 15 to 25%, preferably 18 to 22%.

When a coating film of the color curable composition of the present invention is formed on a substrate, the thickness of the coating film (after the prebaking treatment) is generally 0.3 to 5.0 mu m, preferably 0.5 to 4.0 mu m, 0.8 mu m to 3.0 mu m.

Next, the substrate to which the colored curable composition of the present invention is applied will be described.

As the substrate in the present invention, for example, a substrate made of alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and a transparent conductive film attached thereto, A conversion element substrate such as a silicon substrate, and a plastic substrate are enumerated. On these substrates, a black matrix for isolating each pixel is usually formed, or a transparent resin layer may be provided for facilitating adhesion.

The plastic substrate preferably has a gas barrier layer and / or a solvent-resistant layer on its surface.

Other than this, on the substrate for driving (hereinafter referred to as " TFT type liquid crystal driving substrate ") on which the thin film transistor (TFT) of the thin film transistor A colored pattern can be formed by the curable composition, and a color filter can be produced. Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, and the like. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum deposition or the like, as desired. For example, a substrate on which a passivation (passivation) film such as a silicon nitride film is formed on the surface of a TFT type liquid crystal driving substrate or on the surface of the driving substrate may be used.

In addition, when a colored pattern is formed by the colored curable composition of the present invention on a TFT type liquid crystal driving substrate, a photomask used for exposure may have a through hole or a rectangle It is preferable that a pattern for forming a rectangular-shaped depression is also formed.

After the photocurable coating film is formed as described above, a prebaking treatment is usually carried out. Further, if necessary, a vacuum process can be performed before pre-baking. Vacuum drying conditions are usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.

The pre-baking treatment can be performed at a temperature of 50 to 140 占 폚 (preferably 70 to 110 占 폚) for 10 seconds to 300 seconds using a hot plate, an oven or the like. Here, high-frequency processing may be used in combination with the pre-bake processing. In addition, the high frequency processing can be used alone.

[Exposure step]

In the exposure step, a photocurable coating film is formed on the substrate, and then the coating film is exposed through a predetermined mask pattern.

In this case, as the radiation to be used, ultraviolet rays such as g line, h line, i line and j line are particularly preferable. When manufacturing a color filter for a liquid crystal display device, it is preferable that exposure is performed mainly using h-line and i-line with a proximity photolithography machine and a mirror projection exposure machine.

[Development process]

In the developing step, the uncured portions of the coated film after exposure are dissolved in the developer to leave only the cured portions.

The developing temperature is usually 20 to 30 占 폚, and the developing time is 20 to 90 seconds.

Any developer may be used as long as it dissolves the coating film of the photo-curable color-curable composition in the un-cured portion and does not dissolve the cured portion. Concretely, a combination of various organic solvents or an alkaline aqueous solution can be used.

As the organic solvent, the above-mentioned solvents which can be used when preparing the pigment dispersion or colored curable composition in the present invention are listed.

The alkaline aqueous solution includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetra Alkaline compounds such as ethyl ammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo- [5,4,0] -7-undecene in an amount of 0.001 to 10% by mass, To 0.01% by mass to 1% by mass of the aqueous solution. To the alkaline aqueous solution, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added.

The development method may be a dip method, a shower method, a spray method, or the like, and a swing method, a spin method, an ultrasonic method, or the like may be combined with the method. It is also possible to wet the surface to be developed with water or the like before coming into contact with the developing solution to prevent uneven development.

Further, the substrate may be inclined and developed.

After the development process, the rinse process is carried out to rinse and remove the surplus developer, and after the drying process, the heat treatment (post-baking) is performed to complete the curing.

The rinse process is usually performed with pure water, but in order to save the liquid, pure water is used in the final rinse, and the used pure water may be used for cleaning, or the substrate may be rinsed or ultrasonically irradiated.

After the rinsing step, dehydration and drying are carried out, the heat treatment is usually carried out at a temperature of about 200 ° C to 250 ° C. This heating treatment (post-baking) can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation type drier), a high frequency heater or the like so that the coated film after development is in the above-

By repeating the above operations sequentially for each color in accordance with the desired number of colors, a color filter in which a plurality of colored patterns (pixels) are formed can be manufactured.

The use of the colored curable composition of the present invention has been mainly described for use in a color filter. However, it can also be applied to the formation of a black matrix for isolating each colored pixel constituting a color filter.

The black matrix is formed by exposing and developing the pigment dispersion according to the present invention using a black pigment such as carbon black or titanium black as a pigment, and then post-baking further if necessary to promote curing of the film.

<Liquid crystal display element>

The liquid crystal display element of the present invention comprises the color filter of the present invention.

More specifically, an orientation film is formed on the inner surface side of the color filter of the present invention, and the space is opposed to the electrode substrate and filled with liquid crystal and sealed to obtain a liquid crystal display element of the present invention.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, reagents, amounts of substances, ratios, operations, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the purpose of the present invention. Accordingly, the scope of the present invention is not limited to the following specific examples. In the following, parts and percentages are all on a mass basis unless otherwise specified.

(Example 1)

200 Parts of Green Pigment CI Pigment Green 36, 1600 parts of sodium chloride, and 360 parts of diethylene glycol were put into a stainless steel first gallon kneader (manufactured by INOUE MANUFACTURING CO., LTD.) And kneaded at 50 ° C for 8 hours. Subsequently, this kneaded product was charged into 10 liters of warm water and stirred for 2 hours while being heated to 80 DEG C to form a slurry, which was then filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, followed by drying at 60 DEG C for one day , 190 parts of a green pigment were obtained.

Subsequently, 200 parts of yellow pigment CI Pigment Yellow 138, 2000 parts of sodium chloride and 360 parts of diethylene glycol were added to a stainless steel first gallon kneader (manufactured by INOUE MANUFACTURING CO., LTD.) And kneaded at 50 ° C for 8 hours. Subsequently, this kneaded product was charged into 10 liters of warm water and stirred for 2 hours while being heated to 80 DEG C to form a slurry, which was then filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, followed by drying at 60 DEG C for one day , 190 parts of yellow pigment were obtained.

Using the homogenizer, the mixture was stirred at the number of revolutions of 3,000 rpm for 3 hours to prepare a mixed solution.

[Furtherance]

· Pigment Green 36 (average primary particle diameter 25 nm) ... 66 parts

Pigment Yellow 138 (average primary particle diameter 25 nm) 68

· Dispersant (Solsperse 5000 Lubrizol Japan Ltd.) ... 10 copies

Benzyl methacrylate / methyl methacrylate (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 30,000) 32

· Dispersant (Disperbyk-161, manufactured by BYK JAPAN K. K.) ... 10 copies

· Propylene glycol monomethyl ether acetate ... 720 part

Subsequently, the mixed solution obtained above was covariance-treated for 6 hours with a bead disperser ULTRA APEX MILL (KOTOBUKI INDUSTRIES CO., LTD.) Using 0.1 mm phi zirconia beads.

To the resulting pigment dispersion was further added the components of the following composition and mixed with stirring to prepare the colored curable composition (color resist solution) of the present invention.

[Furtherance]

· Dipentaerythritol pentahexaacrylate ... 72

Photopolymerization initiator A: 1,2-octanedione 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) 4.5 parts

Photopolymerization initiator B: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Part 15

· Photopolymerization initiator C: Diethyl thioxanthone ... 4.5 parts

Benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 30,000) 172 parts

· Propylene glycol monomethyl ether acetate ... 106 copies

· Epoxy resin: (product name EHPE 3150 DAICEL CHEMICAL INDUSTRIES, LTD.) ... Part 11

The specific siloxane polymer D-1 (KF-6001 from Shin-Etsu Chemical Co., Ltd.) 0.10 part

· 3-ethoxyethyl propionate ... 814 part

Here, dipentaerythritol pentahexaacrylate represents KAYARAD DPHA (NIPPON KAYAKU CO., LTD.).

(Examples 2 to 7 and Comparative Examples 1 to 3)

The specific siloxane polymer D-1 in Example 1 was changed to various compounds (commercially available products of Shin-Etsu Chemical Co., Ltd. or comparative compounds described later) as shown in Table 1 below, (Color resist liquid) of Examples and Comparative Examples were prepared in the same manner as in Example 1, except that the coloring composition was changed as shown in Table 1 below.

(Preparation and Evaluation of Sample for Evaluation)

-One. Line unevenness, and evaluation of pinholes (voids)

Each of the colored curable compositions (color resist solution) prepared in each of the Examples and Comparative Examples was spin-coated on a 550 mm x 650 mm glass substrate (product of Corning Incorporated, 1737) at a rotation number of 740 rpm to 850 rpm, And then dried (pre-baked) for 60 seconds to obtain a coating film having a film thickness of 1.3 mu m.

The surface of the coated film was observed with the naked eye and an optical microscope, and the unevenness on the line and pinholes (voids) were evaluated. The evaluation index is as follows.

(Unevenness on the line)

A: Unevenness on line was not observed

B: Some line-like unevenness was observed at the end portion

C: Some unevenness on the line is observed at the end, exceeding the allowable range

D: Unevenness in line was observed at the end and the center portion.

(Pinhole (void))

A: Pinholes are not observed at all

B: A little pinhole is observed but within acceptable limits

C: Pinhole is observed and exceeded the allowable range

-2. Fabrication and Evaluation of Colored Filter Substrate -

The color curable composition (color resist solution) prepared in each of the Examples and Comparative Examples was spin-coated on a glass substrate (1737, manufactured by Corning Incorporated) having a size of 550 mm x 650 mm at a rotation number of 740 rpm to 850 rpm, Dried (prebaked). Thereafter, the entire surface of the coated film was exposed at 200 mJ / cm 2 (roughness 20 mW / cm 2), and the coated film after the exposure was covered with a 1% aqueous solution of alkali developer CDK-1 (FUJIFILM ELECTRONIC MATERIALS product) and stopped for 60 seconds. After stopping, pure water was dispersed in a shower, and the developer was flowed and cleaned. Then, the coated film on which the exposure and development processes were performed as described above was heat-treated (post-baked) in an oven at 220 ° C for 1 hour to form a colored resin film for forming a color filter on the glass substrate, Color filter).

The surface of the obtained color filter was observed with a sodium lamp and an optical microscope, and evaluated for image defects (non-uniform luminance on the surface, pinhole). The evaluation index is as follows.

(Image defect)

A: Image defect is not observed

B: Some image defects are observed but within acceptable limits

C: Image defect is observed and exceeded the allowable range

The evaluation results of the unevenness on the lines and the pinholes (voids) of the coating film obtained as described above and the evaluation results of the image defects of the color filters are shown in Table 1 below.

Comparative compounds Dc-1 to Dc-3 used in Comparative Examples 1 to 3 shown in Table 1 are shown below.

Comparative compound Dc-1: TORAY Dow Corning Corporation FZ-2110

Comparative compound Dc-2: TORAY Dow Corning Corporation FZ-2207

Comparative compound Dc-3: TORAY Dow Corning Corporation FZ-2203

As shown in Table 1, the colored curable composition using the specific siloxane polymer (D) in the present invention has a good surface without any unevenness on the line during coating and forms a good coating film free from pinholes (voids) Can be seen. It was also found that image defects of the coloring pattern after post-baking were also suppressed, and it was found that excellent color filters could be produced from the colored curable composition of the present invention.

Claims (9)

(A) a colorant, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a dimethylpolysiloxane having a polyalkylene oxide and a hydroxyl group, The (D) polyalkylene oxide and the dimethylpolysiloxane having a hydroxyl group may be produced by reacting a linking group selected from polyethylene oxide having a repeating number of 1 to 20 and a polypropylene oxide having a number of repeating number of 1 to 20 and an alcoholic hydroxyl group connected to the linking group, And a dimethylpolysiloxane at one end or at both ends of the polymer, Wherein the photopolymerization initiator (C) comprises an oxime ester-based photopolymerization initiator. delete The method according to claim 1, Wherein the (D) polyalkylene oxide and the dimethylpolysiloxane having a hydroxyl group are contained in an amount of 0.01% by mass to 0.20% by mass based on the total solid content in the composition. A colored pattern formed by the colored curable composition according to claim 1. A color filter having the coloring pattern according to claim 4 on a substrate. A process for producing a color filter, comprising the step of applying the colored curable composition according to claim 1 by a spin coating method, a slit-and-spine method, or a die coating method, wherein a colored pattern is formed on a substrate. A liquid crystal display element using the color filter according to claim 5. The method according to claim 1, Wherein the (D) polyalkylene oxide and the dimethylpolysiloxane having a hydroxyl group are compounds represented by the following general formula (I).

Wherein R ^a represents C ₃ H ₆ OC ₂ H ₄ OH. n is an integer of 1 or more.] The method according to claim 1, Wherein the (D) polyalkylene oxide and the dimethylpolysiloxane having a hydroxyl group are compounds represented by the following general formula (II).

Wherein R ^b represents C ₃ H ₆ OC ₂ H ₄ OH. R represents a methyl group. n is an integer of 1 or more.]