JP2000075123A - Production of color filter by ink-jet method and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a color filter with high accuracy in which the uniformity of the color density is increased and sufficient heat resistance, sharpness, resolution and durability are obtd. by forming partitioning walls which separate pixels from one another on a substrate, treating the walls with a surface modifying agent and depositing inks corresponding to the respective pixels. SOLUTION: Partitioning walls to separate pixels from one another are formed on a substrate, and the walls are treated with a surface modifying agent which increases the contact angle on the interface between the partitioning walls and color ink, and dried. Then a desired amt. of ink is sprayed by ink-jet method to color the pixels, are cured by heat treatment or irradiation of light. The surface modifying agent is preferably a fluorine-based surfactant. The ink may be a dispersion of pigments, aq. soln. of dyes, dispersion of pigments in an org. solvent or ink using a dye, as far as the ink is suitable for the ink-jet method. Or, it is effective to polymerize and harden the color layer formed by ink jet method by supplying polymn. energy.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter used in a color liquid crystal display, a color video camera, an image scanner, a personal computer, and the like, and a method for producing a color filter using an ink jet system.

[0002]

2. Description of the Related Art With the rapid development of portable personal computers in recent years, the demand for liquid crystal displays, especially color liquid crystal displays, tends to increase. At the same time, the cost of the apparatus has been required to be reduced. In particular, the demand for the cost reduction of a color filter having a relatively high cost ratio has been increased.

[0003] However, there is no color filter which has the required characteristics of high quality. The conventional method will be described below.

The first method most frequently used is a dyeing method. In this method, a water-soluble polymer material, which is a material for dyeing, is formed on a glass substrate, patterned into a shape by a photolithography process, and the resulting pattern is immersed in a dyeing bath to obtain a colored pattern.

[0005] The second method is a pigment dispersion method. According to this method, a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and this is patterned to obtain a monochromatic pattern. Further, by repeating this step three times, red (hereinafter referred to as R), green (hereinafter referred to as G), and blue (hereinafter referred to as B) color filter layers are obtained.

As a third method, there is an electrodeposition method. In this method, a transparent substrate is first patterned on a substrate. Next, it is immersed in an electrodeposition coating solution containing a pigment, a resin, an electrolytic solution, and the like, and electrodeposited in a first color. By repeating this process three times,
R, G, and B colored layers are formed and finally baked.

As a fourth method, a pigment is dispersed in a thermosetting resin, R, G, and B are applied by repeating printing three times, and then a coloring layer is provided by thermosetting the resin. is there.

[0008] In any method, a protective layer is generally provided on the colored layer.

The common features of the conventional methods are R, G,
In order to color the three colors B, the same process needs to be repeated three times, which increases the cost.

Further, there is a disadvantage that the yield decreases as the number of steps increases.

Furthermore, in the electrodeposition method, since the pattern shape that can be formed is limited, the current technology uses TF
It is difficult to apply for T.

Further, since the printing method and the resolution are poor, it is not suitable for forming a fine pinch. Further, since irregularities are formed on the surface of the colored layer, it is difficult to apply the method to STN and FLC, which require more surface properties than TFTs, unless the irregularities are removed.

In order to solve these drawbacks, there have been proposed various color filter manufacturing methods using an ink jet system. Unlike the conventional method, this is a method in which each color of R, B, and G is jetted onto a substrate by a nozzle to form a colored layer. According to this method, the necessary ink can be attached to a desired position, and the colored layers of B, G, and R can be formed at one time, and the manufacturing process can be significantly shortened. In addition, the amount of useless ink can be greatly reduced, and a great effect of improving productivity and reducing costs can be obtained.

However, when a colored layer of various inks is formed in a partition for separating each pixel from each other by an ink jet method, physical properties such as surface tension and viscosity of the ink used and physical properties at a contact portion with the partition are determined. The unevenness of the film pressure in the colored layer due to the incompatibility causes the color density to become non-uniform and the light transmittance to be non-uniform. Further, there is a disadvantage in that the flatness of the colored layer is inferior to the height surface of the partition walls and the uniformity of the color density is insufficient.

[0015]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems and improves the uniformity of the color density of the ink coloring layer.
A high-precision color filter for a color liquid crystal display that satisfies heat resistance, sharpness, resolution, and durability, and a method of manufacturing a color filter by an inkjet method with improved productivity. Is to do.

[0016]

The above object of the present invention is attained by the following constitutions.

1. On the substrate surface, a partition for separating each pixel from each other is formed, and then the interface between the partition surface and the pixel surface is modified to perform a treatment using a surface modifying agent. A method for producing a color filter by an ink jet method, wherein the color filter is attached.

2. 2. The method for producing a color filter according to the above-mentioned item 1, wherein the surface modifier is a surfactant.

3. 2. The method for producing a color filter according to the above-mentioned item 1, wherein the method comprises a step of coloring.

4. 4. A color filter produced by the method for producing a color filter by an inkjet method according to any one of the above items 1 to 3.

That is, the object of the present invention can be achieved by the following method. The present invention, on the substrate surface, to form a partition to isolate each pixel from each other, and then treated with a surface modifier to increase the contact angle between the partition and the color ink interface,
This was achieved by a method for producing a color filter by an ink jet system in which ink is jetted and colored in a desired amount by an ink jet system after drying, and cured by heat treatment or light irradiation.

Hereinafter, the present invention will be described in more detail.

The surface modifier of the present invention may be a fluorine surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, a betaine surfactant or an alkyl ether surfactant. Any type of agents may be used, and low-molecular or high-molecular agents or different types may be used in combination.

In addition, a photographic surfactant can be used. Known activators include, for example, Research Disclosure No. 17643 (December 1978
No.) and the same No. No. 18716 (November 1979) and the same No. 308119 (December 1989).

Among these, a preferred surface modifier is a fluorine-based surfactant.

Specific examples are shown below, but the present invention is not limited to these.

Perfluoroalkylcarboxylic acid and salts thereof Perfluoroalkylphosphate ester Perfluoroalkyltrimethylammonium salt Perfluoroalkylbetaine Perfluoroalkylamine oxide Perfluoroalkylethylene oxide adduct Perfluoroalkyl-containing oligomer Anion preferably used in the present invention Examples of the fluorine-based surfactant include those represented by the following general formula (FA).

Formula (FA) (Cf)-(Y) _{n wherein} Cf is an n-valent group containing at least three fluorine atoms and at least two carbon atoms, and Y is —COO
_{M, -SO 3 M, -OSO 3} M or -P (= O) (OM)
Represents ₂ . M represents a cation such as a hydrogen atom, an alkali metal atom or a quaternary ammonium salt, and n is 1 or 2.

More preferably used anionic fluorine-based surfactants are those represented by the following general formula (FA ').

Formula (FA ') Rf- (D) _t- Y In the formula, Rf represents a fluorine atom-substituted alkyl group or an aryl group having 3 to 30 carbon atoms, and D represents -O-, -COO.
_{-, - CON (R 1)} - or -SO ₂ N (R ₁₎ - at least one bond selected from the comprising a divalent group having 1 to 12 carbon atoms.

R ₁ represents an alkyl group having 1 to 5 carbon atoms, t is 1 or 2, and Y is —COOM, —SO
₃ M, represents an -OSO ₃ M or -P (= O) (OM) 2,
M represents a cation such as a hydrogen atom, an alkali metal atom or a quaternary ammonium salt.

Next, specific examples of the compound represented by formula (FA) will be given, but the present invention is not limited thereto.

[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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It is particularly preferable to use an anionic fluorinated surfactant containing at least one --SO ₂ N (R ₁ )-bond.

The cationic fluorine-based surfactant preferably used in the present invention is a compound represented by the following formula (FK).

[0040] Formula (FK) Rf'-L-X + Z - wherein, Rf 'represents a hydrocarbon group having 1 to 20 carbon atoms, at least one hydrogen atom is substituted with a fluorine atom. L represents a chemical bond or a divalent group. X ⁺ is a cation, Z ^- represents a counter anion.

As an example of Rf ', -C _k F _{k + 1} (k = 1
20, particularly 3 to 12 is _{preferred), - C m F 2m,} -C m
F _2m-1 (m = 2 to 20, particularly preferably 3 to 12) and the like.

As an example of L, -SO ₂ N (R ¹ ) (CH
₂ ) _p- , -CON (R ¹ ) (CH ₂ ) _p- , -OASO ₂ N
(R ¹ ) (CH ₂ ) _p- , -OACON (R ¹ ) (CH ₂ ) _{p
-, - OAO (CH 2)} p -, - OA (CH 2) p -, - O
_{(CH 2 CH 2 O) q} (CH 2) p -, - O (CH 2) p -,
_{^{-N (R 1) (CH 2}} ) p -, - SO 2 N (R 1) (CH 2)
_{p O (CH 2) r -} , - CON (R 1) (CH 2) p O (CH
_{2) r -, - OASO 2} N (R 1) (CHR 1) p OA -, -
_{(CH 2) p (CHOH)} s (CH 2) r - , and the like.

Examples of X ⁺ include -N ⁺ (R ¹ ) ₃ , -N ⁺
_{(CH 2 CH 2 OCH 3)} 3, -N + C 4 H 8 O (R 1), - N
^{+ (R 1) (R 2} ) (CH 2 CH 2 OCH 3), - N + C
^{_{5 H 5, -N + (R}} 1) (R 2) (CH 2) p C 6 H 5, -N
⁺ (R ¹ ) (R ² ) (R ² ) and the like. Here, R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (which may have a substituent);
s is each 0-6, and q is 1-20. A represents an arylene group (eg, a phenylene group), an alkylene group (eg, a methylene group, an ethylene group), or an alkylene oxide group (eg, an ethylene oxide group (1 to 6 additions)).

[0044] Z ^- Examples ^{of, I -, Cl -, Br} -, C
H ₃ SO ₃ ⁻ , CH ₃ —C ₆ H ₄ —SO ₃ ^{— and the} like can be mentioned.

Specific examples of the cationic fluorine-based surfactant preferably used in the present invention are shown below, but are not limited thereto.

[0046]

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[0047]

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Anionic and cationic fluorine surfactants are described, for example, in US Pat.
No. 751, No. 2,567,011, No. 2,732, 3
No. 98, No. 2, 764, 602, No. 2, 806, 86
6, 2,809,998, 2,915,376
No. 2,915,528 and 2,918,501
No. 2,934,450 and 2,937,098
No. 2,957,031 and 3,472,894
No. 3,555,089, British Patent 1,143,9
No. 27, No. 1, 130, 822, Japanese Patent Publication No. 45-373
No. 04, JP-A-47-9613 and JP-A-49-13461.
No. 4, No. 50-117705, No. 50-117727
No. 50-121243, No. 52-41182,
No. 51-12392, the journal of the British Chemical Society (J. Che
m. Soc. P. 2789, p. 2789; 1957, p. 2
574 and 2640, American Chemical Society (J. Ame)
r. Chem. Soc. 79, 2549 (1957)
), Oil Chemistry (J. Japan Oil Chemis)
ts Soc. ) 12, 653, Journal of the Society of Organic Chemistry (J.
Org. Chem. 30) 3524 (1965)
And the like.

Certain of these fluorine-based surfactants are trade names of Megafac F from Dainippon Ink and Chemicals, Inc., and trade names of Surflon from Asahi Glass Co., Ltd., Minnesota Mining. -Under the trade name of Fluorad FC from the Company and the Manufacturing Company, under the trade name of Monflor from the Imperial Chemical Industry, and under the trade name of Zonils from the E.I.Dupont Nemelas and Company. Z
onyls) and Licovet VPF from Farbeberke Hoechst.

These surface modifiers are used as an aqueous solution or a solution of acetones, alcohols and esters alone or in a mixed solvent system thereof. The concentration of the interface modifier solution varies depending on the type of the partition wall, that is, the material of the black matrix or the substrate, but is preferably 10% by weight or less, more preferably 6% by weight or less.

As a method of applying these solutions to a substrate having a partition wall for separating each pixel from each other, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, and the like are used. Roll coating, blade coating, curtain coating, spray coating and the like are used. This dry film thickness is 30% of the height of the partition.
The following is preferred.

As the substrate of the present invention, a triacetate cellulose film, a glass plate, a polyethylene terephthalate film, a PEN (polyethylene naphthalate) film or the like can be used.

The ink used in the present invention may be a pigment dispersion, an aqueous solution of a dye or an ink in which a pigment is dispersed in an organic solvent, or an ink using a dye as long as it is suitable for jetting from an ink jet. Further, a method in which the colored layer formed by the ink jet method is polymerized and cured by supplying energy for polymerization is also effective.

As the energy for polymerization, any energy can be used as long as the transparent polymer substance can be appropriately polymerized, and examples thereof include radiation such as ultraviolet rays, visible rays, and electron beams, and heat. In particular, a photopolymerization method using ultraviolet light is preferable.

In order to polymerize the photopolymerizable composition, a light irradiation intensity and irradiation amount that are not less than a certain intensity are required, which are based on the reactivity of the photopolymerizable composition and the type and concentration of the photopolymerization initiator. The formation of the three-dimensional network structure and the size of the network can be made uniform by selecting an appropriate light intensity.

More preferably, the method of irradiating light uniformly in time and in a plane is such that the photopolymerizable composition interposed between the substrates is instantaneously irradiated with strong light to promote polymerization, This is effective in making the mesh size uniform. That is, by irradiating ultraviolet light in a pulsed manner with appropriate intensity, a transparent polymer substance having a uniform three-dimensional network structure can be formed in the ink.

In the photopolymerizable composition used in the present invention,
In addition to the polymerizable compound having a fluorene ring, (1) a polymer-forming monomer such as a monofunctional (meth) acrylate derivative; (2) a polyfunctional type such as a polyfunctional acrylic monomer or a polyfunctional acrylic oligomer ( A meth) acrylate derivative may be contained.

In the liquid crystal device used in the present invention, by using a monofunctional (meth) acrylate derivative in combination, it is possible to realize particularly low voltage driving. The proportion of the monofunctional (meth) acrylate derivative in the polymerizable composition is preferably in the range of 5 to 95% by weight, and 20 to 80% by weight.
A range of weight% is particularly preferred.

The polymerizable compound having a fluorene ring used in the present invention is preferably a (meth) acrylate derivative having a fluorene ring. Such a derivative may be prepared by a known method using (meth) acrylic acid or (meth) acrylic acid. It is obtained by (meth) acryl esterification of an alcohol having fluorenic acid or a fluorene ring-substituted -OH group using an acid chloride.

Further, an alcohol having a fluorene ring or a compound having a fluorene ring-substituted —OH group is reacted with a reactive compound or a cyclic ester compound having an epoxy group, a carboxylic acid compound having a hydroxyl group, and the like. It can also be obtained by (meth) acrylic esterification.

The alcohol having a fluorene ring or the compound having a fluorene ring-substituted --OH group used herein includes, for example, 9-fluorenemethanol, 9,9-bis (4-hydroxyethyloxyphenyl) fluorene,
9,9-bis (3-methyl-4-hydroxyethyloxyphenyl) fluorene, 9,9-bis (3-ethyl-
4-hydroxyethyloxyphenyl) fluorene,
9,9-bis (3,3'-dimethyl-4-hydroxyethyloxyphenyl) fluorene, 9,9-bis (4-
(Hydroxyphenyl) fluorene, 9,9-bis (3-
Methyl-4-hydroxyphenyl) fluorene, 9,9
-Bis (3-ethyl-4-hydroxyphenyl) fluorene and the like.

The reactive compound having an epoxy group includes, for example, ethylene oxide, propylene oxide,
Styrene oxide, epoxide compounds such as cyclohexene oxide and methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, 2-ethylhexyl,
Glycidyl ether or glycidyl ester compounds having groups such as lauryl, stearyl, phenyl, 2-methylphenyl, and furfuryl can be given.

As the cyclic ester compound, for example, γ
-Lactone, δ-lactone and the like.

Commercially available (meth) acrylate derivatives having a fluorene ring used in the present invention include, for example, bisphenol full orange hydroxyacrylate and bisphenol full orange methacrylate manufactured by Nippon Steel Chemical Co., Ltd.

The polymerizable compound that can be used in addition to the polymerizable compound having a fluorene ring used in the present invention includes, for example, styrene, chlorostyrene, α-methylstyrene, divinylbenzene; , Propyl, butyl, amyl, 2-ethylhexyl, octyl, nonyl, dodecyl, hexadecyl,
Acrylate, methacrylate or fumarate having a group such as butoxyethyl, phenoxyethyl, aryl, methallyl, glycidyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-chloro-2-hydroxyethyl, dimethylaminoethyl or diethylaminoethyl; ethylene glycol Mono (meth) acrylate or poly (meth) acrylate such as polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, trimethylolpropane, glycerin and pentaerythritol ; Vinyl acetate, vinyl butyrate or vinyl benzoate, acrylonitrile, cetyl vinyl ether, limonene, cyclohexene Diallyl phthalate, 2-, 3-
Or 4-vinylpyridine, acrylic acid, methacrylic acid,
Acrylamide, methacrylamide, N-hydroxymethylacrylamide or N-hydroxyethyl methacrylamide and their alkyl ether compounds; di (meth) of diol obtained by adding 2 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol ) Acrylate; trimethylolpropane 1
Diol or tri (meth) acrylate of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to mol of diol; di (di) of diol obtained by adding 2 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A (Meth) acrylate; reaction product of 1 mol of 2-hydroxyethyl (meth) acrylate and 1 mol of phenyl isocyanate or n-butyl isocyanate; poly (meth) of dipentaerythritol
Acrylate; pivalic acid ester neopentyl glycol diacrylate; caprolactone-modified hydroxypivalic acid ester neopentyl glycol diacrylate; linear aliphatic diacrylate; polyolefin-modified neopentyl glycol diacrylate; epoxy (meth) acrylate, polyester (meth) acrylate, Examples thereof include polyurethane (meth) acrylate and polyether (meth) acrylate.

Examples of the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (“Darocur 1173” manufactured by Merck) and 1-hydroxycyclohexylphenyl ketone (manufactured by Ciba Geigy). "Irgacure 184"), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-
ON (“Darocure 1116” manufactured by Merck), benzyldimethyl ketal (“Irgacure 651” manufactured by Ciba-Geigy), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (Ciba -"Irgacure 907" manufactured by Geigy Corporation), 2,4-diethylthioxanthone ("Kayacure DET" manufactured by Nippon Kayaku Co., Ltd.)
X ") and ethyl p-dimethylaminobenzoate (" Kayacure-EPA "manufactured by Nippon Kayaku Co., Ltd.), isopropylthioxanthone (" Kantacure ITX "manufactured by Ward Prekinsopp) and ethyl p-dimethylaminobenzoate And the like.

The proportion of the photopolymerization initiator used is preferably in the range of 0.1 to 10.0% by weight based on the polymerizable composition.

[0068]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

The following use solution 1 containing the following interface modifier
The glass substrate on which the black matrix is formed is immersed in the substrate for 2 minutes. Then, the excess solution on the surface was removed with an air knife and dried at 70 ° C. for 20 minutes to prepare Samples 1 to 6. Using the following use solutions 7 to 11 containing the following interface modifier, a black matrix was formed. Spray coating is performed on a glass substrate, and then dried at 70 ° C. for 20 minutes.
To 11 were produced. The treatment of Comparative Example 1 used distilled water. Comparative 2 is untreated.

Working solution 1: S-381 (trade name: Surflon S-381, manufactured by Asahi Glass) 1.0% ethyl acetate solution 2: S-381 0.1% ethyl acetate solution 3: S-145 (trade name: Surflon S-145, manufactured by Asahi Glass) 0.05% ethyl acetate: water (1: 6) solution 4: D-1 (di-2-ethylhexyl-sulfosuccinate sodium) 0.5% aqueous solution 5: S-1 01% aqueous solution 6: S-2 0.02% aqueous solution 7: S-2 0.005% aqueous solution 8: Triton-100 (manufactured by Kao Corporation) 0.001 aqueous solution 9: FC-430 (manufactured by Sumitomo 3M) 0.2% ethyl acetate solution 10: FC-430 (manufactured by Sumitomo 3M) 0.03% ethyl acetate solution 11: S-381 0.1% ethanol solution Comparative 1 Distilled water Comparative 2 Untreated Next, an inkjet method was used. Septum B within, G, R
Were prepared according to a desired pattern.

The ink used was a pigment-dispersed ink, and the ink jet printer used was Canon BJ.

After printing, the sample was dried at 95 ° C. for 40 minutes, or dried at 90 ° C. for 60 minutes after UV irradiation to prepare a sample.

The prepared sample was micr manufactured by Olympus Corporation.
The uniformity within the pixel was evaluated by measuring the distribution of the film thickness of each pixel and the standard deviation of the transmission density measured value using oscop STM-MJS.

Further, in order to measure the adhesiveness between the substrate and the ink, the sample was immersed in an ultrasonic cleaner with water,
After 100 minutes, 100 pixels were observed, and the number of missing pixels was measured.

[0075]

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[0076]

[Table 1]

As is clear from Table 1, in one printing,
It can be seen that the sample of the present invention is superior to the comparative sample.

[0078]

The method for producing a color filter according to the present invention and a color filter using an ink-jet method can improve the uniformity of the color density of the ink colored layer, and improve the heat resistance, sharpness, and the like.
The resolution and durability are satisfied, and the productivity is improved to have an excellent effect.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2C056 FB01 FB08 HA41 2H048 BA64 BB42 BB46 2H086 BA01 BA17

Claims (4)

[Claims] Claims: 1. A partition wall for separating pixels from each other is formed on a substrate surface, and then the interface between the partition wall surface and the pixel surface is modified to perform a treatment using a surface modifying agent. A method for producing a color filter by an ink-jet method, wherein a corresponding ink is attached. 2. The method according to claim 1, wherein the surface modifier is a surfactant. 3. The method according to claim 1, further comprising a step of coloring. 4. A color filter produced by the method for producing a color filter by an ink-jet method according to claim 1.