JP2003321633A - Ink, color filter and method for producing the same, liquid crystal panel, computer and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide ink excellent in ink jet characteristics and capable of producing a color filter excellent in heat resistance, washing resistance and adhesion to a substrate, an inexpensive color filter having high quality and to provide a method for producing the color filter and to provide a liquid crystal panel, a computer and an image display device. <P>SOLUTION: The ink comprises a water-soluble 1,2-naphthalocyanine dye represented by the formula. The method for producing the color filter has a picture element-forming step forming the colored picture element by attaching the ink drop to a prescribed position on a substrate having a light transmission property. The color filter is produced by the method. The liquid crystal panel has the color filter. The computer and the image display device are each equipped with the liquid crystal panel. Symbols in the formula are defined in the specification. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink which can be used for manufacturing a color filter of a color liquid crystal display used in a color television, a personal computer and the like, a color filter and a manufacturing method thereof, and a liquid crystal incorporating the color filter. Regarding the panel. The present invention also relates to a computer including an image display device incorporating a color filter and an image display device incorporating a color filter.

[0002]

2. Description of the Related Art A color filter is an important component of a color liquid crystal display. This filter has a large number of pixels of red (R), green (R), and blue (B) arranged repeatedly on a transparent substrate. It has a structure.

With the recent development of personal computers, especially portable personal computers, the demand for liquid crystal displays, especially color liquid crystal displays, has been increasing. However, for further popularization, it is necessary to satisfy the conflicting requirements that the manufacturing cost of the display main body must be reduced while providing a display with higher definition and higher image quality. In particular, the above-mentioned demand for a color filter, which has a high specific gravity in terms of cost, is rapidly increasing.

Various methods have hitherto been attempted in order to meet the above requirements while satisfying the required characteristics of color filters.

A typical method of manufacturing a color filter will be described below.

The first method is the most frequently used dyeing method. The dyeing method was obtained by adding a photosensitizer to a water-soluble polymer material that was easy to dye, and patterning this into a desired shape on a transparent support by a photolithography process. The pattern is dipped in a dye bath to obtain a colored pattern. By repeating this process three times, R, G, and B color filters are formed.

The second method is a pigment dispersion method which is used most frequently next time, and is recently replacing the dyeing method. In this method, first, a photosensitive resin layer in which a pigment is dispersed is formed on a substrate, and this is patterned to obtain a monochromatic pattern. By repeating this process three times, a three color filter of R, G and B is formed.

The third method is an electrodeposition method. In this method, first, a transparent electrode is patterned on the substrate. next,
The first color is electrodeposited by immersing it in an electrodeposition coating solution containing a pigment, a resin, an electrolytic solution and the like. This process is repeated three times to form R, G, and B color filter layers, and finally firing is performed to form a color filter. In any of these methods, a protective layer is generally formed on the colored layer.

The fourth method is a printing method. In the printing method, a pigment is dispersed in a thermosetting resin, printing is repeated three times to form R, G, and B color filter layers, and then the resin is thermoset to form a colored layer. .

However, by any of these methods, a color filter which does not sufficiently satisfy all the required characteristics required for the color filter has not been obtained yet. That is, the points common to these methods are
The same process is repeated three times for coloring the three colors of R, G and B, which inevitably increases the manufacturing cost. Further, there is a problem that the yield decreases as the number of processes increases. Furthermore, since the pattern shape that can be formed is limited in the electrodeposition method, the current technology cannot be applied to a TFT color. Further, the fourth printing method has a drawback that the resolution and smoothness are poor, and a fine pitch pattern cannot be formed. As mentioned above, there are some methods for manufacturing the color filter,
When the color property of the display is emphasized, a dyeing method using a dye as a coloring material is generally considered to be advantageous. However, as described above, in the dyeing method, the method of immersing the substrate in the dyeing solution when forming the pixel is used.
Dyes that are difficult to dye on the receiving layer used have the drawback that they cannot be used even if they have good color tone (spectral characteristics). In order to increase the types of dyes that can be used, attempts are generally made to improve the dyeing property of the dye by introducing a cation group such as quaternary ammonium into the receptor layer when the dye is an anionic type. However, there are problems such as a change in color tone of the dye (spectrum shift) and a decrease in heat resistance.

Furthermore, when a dyeing solution composed of a plurality of dyes is used for color matching, it is difficult to control the desired color tone because the dyeing properties of the dyes and the receiving layer are not the same. There are also problems. For this reason, in reality, it is difficult to finely control the color tone, and the types of dyes and receiving layer materials that can be used are greatly limited.

[0012]

In order to improve these drawbacks, a method of manufacturing a color filter using an ink jet method has been proposed (Japanese Patent Laid-Open No. 59-75205).
JP-A-63-235901, JP-A-1-
No. 217302, JP-A-4-123005, etc.). These are different from the above-mentioned methods, and a coloring liquid (hereinafter, ink) containing R, G, and B dyes is jetted from a nozzle to a filter substrate, and the attached ink is dried on the filter substrate to form pixels. It is a thing.

According to this method, since the formation of the colored portion does not go through the dyeing process between the dye and the receiving layer as in the above-mentioned dyeing method, a means for improving the dyeing property by introducing a cation group on the receiving layer side is used. You don't have to. Therefore, it is possible to avoid problems such as a change in color tone of the dye itself (spectrum shift) before and after dyeing and a decrease in heat resistance. Furthermore, in the case of using an ink containing a plurality of dyes for toning. However, the color tone does not differ greatly from what was expected. Also, R, G,
Since each colored layer B can be formed at once and the amount of ink used is not wasted, it is expected that the productivity can be greatly improved and the cost can be reduced.

However, in the conventional method for producing a color filter by the ink jet method, the dye used is not always suitable for the ink jet method, and the matching of the dye with the receiving layer material and the drawing condition by the ink jet method (receptive layer type). Also, there are many technically unclear points such as the amount of the dye injected there). For this reason, the following new technical problems have arisen, but none satisfy all of the following required characteristics, and therefore there has been a demand for an urgent solution to the problem. 1) Adhesion between the colored part and the color filter substrate is good. 2) Heat resistance of the colored part is good. 3) Can withstand washing with water after curing of the colored part. 4) Excellent ejection stability in the inkjet head.

An object of the present invention is to provide an ink which satisfies all the above technical problems and can be suitably used for forming a color filter having high quality colored pixels, particularly green pixels. Another object of the present invention is to provide a high-quality and inexpensive color filter and its manufacturing method, a high-quality and inexpensive liquid crystal panel, a computer and an image display device having the same.

[0016]

The inventors of the present invention have conducted extensive studies on inks that can be suitably used for forming green pixels of a color filter, and as a result, have found that 1,2-naphthalocyanine can be obtained by water-solubilizing it. The ink containing the dye as a coloring material satisfies the above conditions 1) to 4) at a high level, and the ink jet characteristics at a high level.
Further, the green pixel containing the color material has less color loss (dullness) in the color filter cleaning process in the actual color filter manufacturing process, good adhesion, and ejection stability (blurring) and The inventors have found that the heat resistance is good and have completed the present invention.

That is, the present invention is an ink containing a water-soluble 1,2-naphthalocyanine dye represented by the following general formula (I).

[0018]

[Chemical 4]

(In the formula (I), R is one or more independently of each other, a hydrogen atom, a sulfone group, a sulfamido group, a carboxyl group, a halogen atom, a hydroxyl group,
Cyano group, nitro group, amino group, phosphono group, trifluoromethyl group, linear or branched alkyl group having 1 to 6 carbon atoms, linear or branched alkoxy group having 1 to 6 carbon atoms, at least one substituent Represents an aryl group, a phenoxy group, a thiophenoxy group, a phenyl group, or a salt thereof, which may have, M is 2 hydrogen atoms, 2
Na atoms, 2 Li atoms, divalent metal, or 3
Represents a valent or tetravalent metal derivative, L represents a hydrogen atom, an alkali metal ion or an ammonium ion which may have a substituent, and n represents an integer of 2 to 8. ) The ink of the present invention contains a solvent having a boiling point of 150 to 240 ° C.
Preferably, the boiling point is 180 ° C.
It is more preferable to contain the solvent at 230 ° C. in an amount of 16 to 60.0 mass%.

The total dye concentration in the ink of the present invention is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass.

Further, the ink of the present invention preferably contains a curable component.

The curable component is represented by the following general formula (II)

[0023]

[Chemical 5]

(In the above formula (II), R ¹ is H or C
H ₃ and R ² represent H or a linear or branched alkyl group having 1 to 6 carbon atoms. It is preferable that it is a polymer which has a structure shown by these.

The ink of the present invention is suitable as an ink for ink jet recording.

The present invention is also a method for manufacturing a color filter, which comprises a pixel forming step of forming colored pixels by adhering the above-mentioned ink droplets of the present invention to a predetermined position on a light transmissive substrate.

In the pixel forming step, ink droplets are adhered to an ink receiving layer containing a polymer having an acrylic monomer unit provided on a light transmissive substrate, and then the ink receiving layer is cured. It is preferable to form colored pixels by doing so.

The acrylic monomer unit has the following general formula (II)

[0029]

[Chemical 6]

(In the formula (II), R ¹ is H or CH ₃ , R
² represents H or a linear or branched alkyl group having 1 to 6 carbon atoms. ) Is preferable.

It is also preferable that the ink receiving layer contains a photopolymerization initiator.

It is also preferable that the production method of the present invention has a step of curing the non-colored portion of the ink receiving layer by light irradiation or a combination of light irradiation and heat treatment prior to the attachment of ink droplets.

Further, according to the present invention, among the above inks, ink droplets containing a curable component are adhered to a predetermined position on a light transmissive substrate, and then the adhered ink is cured to form a colored pixel. And a method of manufacturing a color filter including a pixel forming step. In this method, it is preferable that the light transmissive substrate includes an ink color mixing prevention wall.

The present invention includes a color filter manufactured by the above manufacturing method.

Further, the present invention has the above-mentioned color filter of the present invention and a panel substrate arranged to face the color filter, and a liquid crystal composition is sealed between the color filter and the panel substrate. It also includes a liquid crystal panel characterized by that.

Further, the present invention also includes a computer and an image display device characterized by including the liquid crystal panel of the present invention as an image display section.

Further, the ink of the present invention is preferably used not only as an ink jet ink but also as an ordinary recording ink.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION (Regarding Dye) The dye that can be used in the present invention will be described below.

The water-soluble 1,2-naphthalocyanine dye represented by the above formula (I) used in the present invention has excellent heat resistance and is exposed to a high heat of 180 ° C. or higher which is required in the production of color filters. Even if it occurs, the degree of discoloration and fading is small, which is preferable. Further, the water-soluble 1,2-naphthalocyanine dye is excellent in water solubility, and even if the concentration of the coloring material in the ink is higher than that of the conventional phthalocyanine dye, it is difficult to increase the viscosity of the ink. Therefore, this water-soluble 1,2-naphthalocyanine dye is particularly suitably used for manufacturing a color filter for a monitor which requires a color filter having a high color density.

In formula (I), R is one or more independently a hydrogen atom; a sulfone group; a sulfamido group;
Carboxyl group; halogen atom; hydroxyl group; cyano group; nitro group; amino group; phosphono group; trifluoromethyl group; linear or branched alkyl group having 1 to 6 carbon atoms; An alkoxy group of
It represents an aryl group, a phenoxy group, a thiophenoxy group or a phenyl group which may have at least one substituent; or a salt thereof. Alkali metal (L
(i, Na, K, etc.) salts and ammonium salts.

The substituent which the aryl group, phenoxy group, thiophenoxy group or phenyl group may have is, for example, a sulfone group, a sulfamido group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, a nitro group, At least one selected from the group consisting of an amino group, a phosphono group and a trifluoromethyl group can be mentioned.

In the formula (I), M is 2 hydrogen atoms, 2 Na atoms, 2 Li atoms, a divalent metal such as iron,
Magnesium, nickel, cobalt, copper, palladium,
Oxides or halides of trivalent or tetravalent metals such as zinc, such as aluminum chloride, indium chloride, germanium chloride, tin chloride, silicon chloride, titanyl,
Examples thereof include vanadyl, but are not limited thereto.

In the formula (I), L represents a hydrogen atom, an alkali metal ion or an ammonium ion which may have a substituent. Examples of the alkali metal ion as L of the counter ion include Li ⁺ , Na ⁺ , K ^{+ and the} like.
L may also be an ammonium ion.

(Production of Water-Soluble 1,2-Naphthalocyanine Dye) As a method for producing water-soluble 1,2-naphthalocyanine, a 1,2-dicyanonaphthalene derivative is reacted with a metal salt by a conventional method for cyclization. After obtaining 1,2,2-naphthalocyanine metal salt, it can be easily obtained by sulfonation with fuming sulfuric acid.

At this time, four types of positional isomers are generated during the cyclization of 1,2-naphthalocyanine, and the isomers due to the uncertainty of the number and position of the sulfone groups substituted by the sulfonation are further increased. It occurs and is obtained as a mixture of 1,2-dicyanonaphthalene sulfonates.

(Example of Water-Soluble 1,2-Naphthalocyanine Dye) Specific examples of the water-soluble 1,2-naphthalocyanine sulfonate represented by the above formula (I) include, for example, the following formulas (Ia) to (Ic). Examples include:

[0047]

[Chemical 7]

[0048]

[Chemical 8]

[0049]

[Chemical 9]

[0050]

[Chemical 10]

(Composition of Ink) The amount of the dye represented by the formula (I) contained in the ink is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass. . Further, the dye may include other dyes if necessary.

Examples of the liquid medium for dissolving, dispersing or dissolving and dispersing the dye represented by the formula (I) and another dye optionally added include, for example, an aqueous medium containing water, that is, water and an organic solvent. A mixture of The organic solvent has the effect of continuously and stably ejecting the ink (staining liquid) used in the inkjet method from a minute nozzle, and the effect of preventing clogging due to the deposition of dye at the nozzle tip. Therefore, it is preferable to include it in the ink. Regarding this organic solvent, the solvent having a boiling point of 150 ° C. to 240 ° C. is preferably 10 to 60% by mass in the ink, and more preferably the solvent having a boiling point of 180 ° C. to 230 ° C. is 16 to 60.0% by mass in the ink. .

Further, preferably, the content of the solvent having a boiling point of 250 ° C. or higher in the ink is set to 30.0% by mass or less (it may not be contained), and more preferably, the content of the solvent having a boiling point of 245 ° C. or higher in the ink To 19.0 mass% or less (not necessarily contained).

A high boiling point solvent is preferably added to the ink used for ink jet for the purpose of avoiding a clogging phenomenon due to the deposition of dye at the tip of the head, and the solvent contained in the ink. As the seed, those satisfying the above-mentioned physical properties are preferable because the adhesiveness of the colored portion, which may be exhibited when an ink containing a large amount of a high boiling solvent is applied to a color filter, does not occur.

If the amount of solvent is within the above range, deposition of dye at the tip of the ink jet head, which may occur when the amount of solvent in the ink is too small, and inclusion of bubbles in the ink jet head, etc. It is possible to avoid deterioration of the continuous ejection property of the ink due to the phenomenon.

Specific examples of preferred solvents that can be used in the ink according to the present invention are shown in Tables 1 and 2 below.

[0057]

[Table 1]

[0058]

[Table 2]

Further, a nonionic, anionic or cationic surface active agent may be used in the ink, and other additives such as a pH adjusting agent and a fungicide may be added if necessary. May be.

Therefore, as a preferable composition of the ink (mass% in the ink), the entire dye is 0.5 to 20 mass% and the boiling point is 150 to 240 ° C. (more preferably 180 to 2).
The solvent at 30 ° C. is 10 to 60 mass% (more preferably 1
6 to 60.0% by mass), and the balance of water may be appropriately added to a surfactant or an additive. Here, the phthalocyanine derivative of the present invention as a dye is 0.5 to 20% by mass (more preferably 1%). 15 mass%). Further, the curable component described below may be contained in an amount of 0.1 to 20% by mass.

(Method of Manufacturing Color Filter: First Mode) FIG. 1 shows a method of manufacturing a color filter for liquid crystal according to the present invention. An example of the structure of the color filter for liquid crystal according to the present invention is shown. Has been done. Generally, a glass substrate can be used as the light transmissive substrate 1, but it is not limited to the glass substrate as long as it has necessary properties such as transparency and mechanical strength as a color filter for liquid crystal.

FIG. 1A shows the glass substrate 1 on which the black matrix 2 is formed, and 7 is a light transmitting portion. As a method for forming the black matrix, when directly provided on the substrate, a method of forming a metal thin film by sputtering or vapor deposition and patterning by a photolithography process is used, and when provided on the resin composition, a general photolithography process is used. A patterning method may be used, but the patterning method is not limited thereto.

In the procedure of FIG. 1, first, a layer containing a resin composition curable by light and / or heat is formed on the substrate 1 on which the black matrix 2 is formed, and the layer is dried to form a layer on the substrate 1. Then, the ink receiving layer 3 is formed (FIG. 1 (b)).

As the material for forming the ink receiving layer 3, known materials can be used. For example, considering heat resistance and the like,
Acrylic resins, epoxy resins, and imide resins are preferable, and in consideration of water-based ink absorbability, hydroxypropyl cellulose, hydroxyethyl cellulose,
Those containing a cellulosic water-soluble polymer such as methyl cellulose and carboxymethyl cellulose are preferable. Other examples include polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetal, polyurethane, carboxymethyl cellulose, polyester, and the like, and natural resins such as albumin, gelatin, casein, starch, cationized starch, gum arabic, and sodium alginate. .

In particular, considering not only the above heat resistance and ink absorbability but also the above-mentioned transparency of the colored portion, bleeding, light resistance of the dye, etc., a water-soluble aqueous solution comprising a structural unit represented by the formula (II) A compound containing at least a homophilic acrylamide monomer and / or a copolymer with another vinyl-based monomer is preferable. The molecular weight of the above polymer is preferably in the range of 10 ² to 10 ⁷ .

[0066]

[Chemical 11]

(In the formula (II), R ¹ is H or CH ₃ , R
² represents H or a linear or branched alkyl group having 1 to 6 carbon atoms. ) Specific examples of the acrylamide monomer corresponding to the structural unit represented by the above formula (II) include N-methylolacrylamide, N-methoxymethylacrylamide, N-
Examples thereof include ethoxymethyl acrylamide, N-isopropoxymethyl acrylamide, N-methylol methacrylamide, N-methoxymethyl methacrylamide, and N-ethoxymethyl methacrylamide, but are not limited thereto. As the other vinyl-based monomer, acrylic acid; methacrylic acid; methyl acrylate,
Acrylic acid esters such as ethyl acrylate; Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate; Hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxymethyl acrylate, vinyl-based mono-monomers containing hydroxyl groups such as hydroxyethyl acrylate Styrene; α-methylstyrene; acrylamide; methacrylamide; acrylonitrile; allylamine; vinylamine; vinyl acetate; vinyl propionate and the like, but not limited thereto.

If desired, the receiving layer 3 may contain various additives. Specific examples of additives include various surfactants, dye fixing agents (waterproofing agents), antifoaming agents, antioxidants, optical brighteners, ultraviolet absorbers, dispersants, viscosity adjusting agents, pH adjusting agents. Agents, fungicides, plasticizers and the like. These additives may be arbitrarily selected from conventionally known compounds according to the purpose.

As a method of forming the above-mentioned ink receiving layer, methods such as spin coating, roll coating, bar coating, spray coating and dip coating can be used. Further, after pre-baking if necessary, inks of R, G, and B colors are attached to predetermined positions by an inkjet method to color the ink receiving layer (FIG. 1).
(C)).

In FIG. 1, 4 is an ink jet head. As the ink jet system, a type using an electrothermal converter as an energy generating element, a type using a piezoelectric element, or the like can be used, and the coloring area and the coloring pattern can be set arbitrarily.

After the step of FIG. 1C, the ink receiving layer having the above-mentioned curable composition is cured (FIG. 1D). For curing, light irradiation and / or heat treatment may be performed. Through the above steps, R, G, and B colored pixels are formed.

Further, a protective layer 6 is formed if necessary (FIG. 1 (e)). As the protective layer 6, a resin material curable by light irradiation or heat treatment, an inorganic film formed by vapor deposition or sputtering, or the like can be used, and it has transparency as a color filter, and the subsequent ITO forming process Any material can be used as long as it can withstand the alignment film forming process. As a result, the color filter of the present invention is completed.

In addition, the above-mentioned ink receiving layer material further contains a photopolymerization initiator, and the non-colored portion corresponding to the black matrix is previously irradiated with light or irradiated with light and cured to be cured, and the ink in that portion Absorption can also be reduced. As a result, it is possible to prevent troubles due to color mixture, color unevenness, etc. between the pixels which are likely to occur when forming the R, G and B pixels by the inkjet method, and to manufacture a color filter of low cost and high image quality. Is possible. Such a manufacturing procedure is shown in FIG.

That is, an ink receiving layer containing a photopolymerization initiator was formed on the substrate 1 (FIG. 2 (a) and FIG. 2).
(B) After that, pattern exposure is performed on the non-colored portion 81 corresponding to the black matrix through the photomask 84 (FIG. 2C), and the ink absorbency of the non-colored portion is reduced. As a photomask for pattern exposure, a photomask having an opening 90 for reducing the ink absorbency of the non-colored portion 81 corresponding to the black matrix 2 is used. At this time, considering that it is necessary to eject a large amount of ink in order to prevent color loss in the portion in contact with the black matrix 2, a mask having an opening width Y narrower than the width X of the black matrix 2 is taken into consideration. Is preferably used. Non-colored portion 8 formed by this
The width of 1 is narrower than the width of the black matrix 2. Subsequent steps (FIGS. 2D to 2F) are performed in the same manner as in FIG. 1 (FIGS. 1C to 1E) to manufacture a color filter.

The light irradiation means for forming the layer (non-colored portion) 81 in which the ink absorbability of the light irradiation portion is lowered is not particularly limited, but in the present invention, it is particularly deep ultraviolet (Deep-UV). ) Light is preferable, and light irradiation conditions 1 to 3
It is preferably about 000 mJ / cm ² . The heat treatment may be performed by means of an oven, a hot plate, or the like, and may be performed, for example, at a temperature condition of 50 ° C to 180 ° C for 10 seconds to 20 minutes.

The photopolymerization initiator for imparting the performance of lowering the ink absorbability will be described below. The photopolymerization initiator is not particularly limited, but onium salts and halogenated triazine compounds are preferably used. Specifically, onium salts include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium trifluoromethyl sulfonate and their derivatives, and further diphenyliodonium hexafluoro. Examples thereof include antimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethyl sulfonate and derivatives thereof. Among them, a halogenated triazine compound is preferably used. However, it is not limited thereto. Further, derivatives of these compounds and the like can be mentioned,
As a matter of course, the present invention is not limited to these derivatives and the like. The content of the photopolymerization initiator is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass based on the acrylamide homopolymer / copolymer which is the ink receiving layer material. is there. Further, additives can be appropriately added as required, and for example, compounds such as perylene and anthracene may be added as sensitizers.

Next, an example of a method for ejecting the ink of the present invention by the ink jet method to form pixels will be described with reference to FIGS. 3 and 4.

FIG. 3 is a block diagram showing the arrangement of an apparatus for drawing a colored portion of a color filter by the ink jet method. In FIG. 3, an inkjet head 23 is connected to the CPU 21 via a head drive circuit 22. Further, the control program information in the program memory 24 is input to the CPU 21. The CPU 21 moves the inkjet head 23 to a predetermined position (not shown), arranges the inkjet head above a predetermined pixel position on the glass substrate 25, and ejects an ink droplet 26 of a predetermined color at that position. To color. This is performed for all pixel positions on the substrate 25 to form pixels.

FIG. 4 shows a process of forming a colored portion (pixel) by the ink jet method. The major difference from the dyeing method is that the ink is selectively adhered only to the pixel forming portion on the surface of the color filter substrate, and then the water and the organic solvent in the ink are evaporated to form the pixel. The property particularly required here is the adhesion between the colored portion and the color filter substrate.

(Method of Manufacturing Color Filter: Second Mode) Next, the color according to the second embodiment of the present invention, which has one feature in manufacturing a color filter without providing the ink receiving layer 3. The filter will be described along with its manufacturing process with reference to FIG.

First, the substrate 1 having the black matrix 2 formed on the surface thereof by the same method as that described in the first embodiment.
Are prepared (FIG. 5A). In this aspect, in order to prevent color mixture of ink, it is preferable to form an ink color mixture prevention wall that is a wall having a predetermined thickness (for example, 0.5 μm or more) between pixels, and for that reason, a black color is used. It is preferable to form the black matrix 2 by patterning the above resin resist.

Next, as shown in FIG. 5B, the G ink 52 according to the present invention described above and various known R inks 51 and B inks 5 are used by utilizing an ink jet system.
3 is applied so as to fill the light transmission part 55 between the black matrixes 2. Black matrix 2 at this time
It is preferable to apply the respective color inks so that they do not overlap each other.

(Ink Composition) As the ink for giving a green pixel used in this embodiment, an ink containing the water-soluble 1,2-naphthalocyanine dye represented by the general formula (I) can be used. The ink containing a curable component, that is, a resin curable by application of light, heat or energy such as light and heat can be particularly preferably used.

(Explanation / content of curable resin component in ink) As the above resin, various commercially available resins and curing agents can be used, but those which do not cause problems such as sticking in the ink preferable. Examples of such materials include acrylic resin, epoxy resin, melamine resin,
Those containing a cellulosic water-soluble polymer such as hydroxypropyl cellulose, hydroxyethyl cellulose, methyl cellulose and carboxymethyl cellulose are preferable. Other examples include polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetal, polyurethane, carboxymethyl cellulose, polyester, and natural resins such as albumin, gelatin, casein, starch, cationized starch, gum arabic, and sodium alginate. The amount of the photo-curable component, the heat-curable component or the component curable by both light and heat contained in the ink is, for example, about 0.1 to 20 mass% based on the total mass of the ink. Is preferred.

In particular, considering not only the above heat resistance and ink absorbability but also the above-mentioned transparency of the colored portion, bleeding, light resistance of the dye, and the like, the water-soluble water-soluble polymer comprising the structural unit represented by the formula (II) is used. A compound containing at least a homophilic acrylamide monomer and / or a copolymer with another vinyl-based monomer is preferable. The molecular weight of the above polymer is preferably in the range of 10 ² to 10 ⁷ .

[0086]

[Chemical 12]

In the above formula (II), R ¹ is H or CH ₃ ,
R ² represents H or a linear or branched alkyl group having 1 to 6 carbon atoms.

Specific examples of the monomer corresponding to the structural unit represented by the above formula (II) include N-methylolacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-isopropoxymethylacrylamide, N-methylol methacrylamide, N
-Methoxymethyl methacrylamide, N-ethoxymethyl methacrylamide, etc. are mentioned, but not limited to these. As the other vinyl-based monomer above,
Acrylic acid; Methacrylic acid; Acrylic acid esters such as methyl acrylate, ethyl acrylate; Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate; Hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxymethyl acrylate, hydroxyethyl acrylate Vinyl monomers containing hydroxyl groups such as styrene; α-methylstyrene; acrylamide;
Methacrylamido; acrylonitrile; allylamine;
Examples thereof include, but are not limited to, vinylamine; vinyl acetate; vinyl propionate and the like.

Then, as shown in FIG. 5C, light irradiation,
The ink applied to the opening 55 on the substrate 1 is partially cured by heating or both irradiation with light and heating, and then, as shown in FIG.
As shown in (d), the curable resin composition is applied so as to cover the colored portion 54 formed by the black matrix 2 and each color ink, and the colored portion 54 is completely cured by light irradiation and / or heat treatment. To complete the colored pixels 56 and cure the curable resin composition to form the protective layer 6 to obtain a color filter. The protective layer 6 may be formed by curing a resin material curable by light irradiation, heat treatment, or both, or by forming an inorganic film by vapor deposition or sputtering to form the protective film 6. Further, as a material that can be used for forming the protective film 6,
A material having transparency when used as a color filter and capable of withstanding the subsequent ITO forming process, light distribution film forming process and the like can be suitably used.

(Liquid Crystal Panel / Image Display Device) FIG. 6 shows a sectional view of a TFT color liquid crystal panel incorporating a color filter according to the present invention. The color LCD panel is
It is a display portion of a liquid crystal display used in a generally well-known personal computer, and is formed by fitting a TFT element substrate 14 facing a color filter 9 and enclosing a liquid crystal composition 12 between them. Known liquid crystal compositions can be used without particular limitation.

TF is provided inside one substrate 14 of the liquid crystal panel.
T (not shown) and transparent pixel electrodes 13 are formed in a matrix. The color filter 9 is installed inside the other substrate 16 at a position facing the pixel electrode.
A transparent counter (common) electrode 10 is formed on the entire surface thereof. Further, an alignment film 11 is formed inside both substrates, and by rubbing the alignment film 11, liquid crystal molecules can be aligned in a certain direction. A polarizing plate 15 is adhered to the outside of each glass substrate, and the liquid crystal compound is filled in the gap (about 2 to 5 μm) between these glass substrates. Further, as the light source of the backlight light 17,
A combination of a fluorescent lamp and a scattering plate (neither of which is shown) is used, and a liquid crystal compound functions as an optical shutter that changes the transmittance of backlight light to perform display.

Although the black matrix and the colored portion are usually formed on the color filter substrate side as shown in FIG. 6, in the black matrix on array type liquid crystal panel, as shown in FIG. If the black matrix is formed on the opposing TFT substrate side, or in the case of the color filter on array type,
As shown in FIG. 8, the entire color filter in FIG.
It is formed on the FT substrate side.

The liquid crystal panel thus created is
It can be used as the image display unit 92 of the computer 91 as shown in FIG. Also, it can be used for a liquid crystal monitor or the like.

[0094]

EXAMPLES Example 1 On a glass substrate provided with a black matrix in which a large number of openings of 60 × 150 μm are arranged, a film of a copolymer having the formulation shown in Table 5 as an ink receiving layer is formed. It was spin-coated to a thickness of 1.5 μm, and prebaked at 70 ° C. for 20 minutes.

A part of the ink receiving layer on the black matrix is removed through a photomask having an opening (width 30 μm) narrower than the width (40 μm) of the black matrix.
Patterning exposure was performed with pUV light at an energy amount of 100 mJ / cm ² , and the ink absorbency of the portion was reduced.

Then, using an inkjet printer,
An R, G, B matrix pattern was prepared using an ink prepared based on Ink Formulation 1 using the dye set shown in Table 3. The phthalocyanine derivative was used as the dye in the G ink, and a dye (mixture) based on the dye blending ratio (Table 4) was used. The formulas Ia, Ib, and
The compound represented by Ic was prepared by synthesizing a corresponding naphthalocyanine derivative having no sulfone group or sulfonate, sulfonated by a known method, neutralized with sodium hydroxide, and then desalted and purified. Therefore, each dye is a mixture of naphthalocyanine derivatives having 2 to 6 sulfone groups or sodium sulfonate introduced.

[0097]

[Table 3]

[0098]

[Table 4]

[Ink Formulation 1] • Dye (or a mixture described in the dye set) 8% by mass • Ethylene glycol 39% by mass (boiling point 197.9 ° C) • Ethyl alcohol (boiling point 78 ° C) 6% by mass • Water 47% by mass %, Then, a curing reaction was allowed to proceed by baking at 200 ° C. for 50 minutes to produce a color filter for liquid crystal.

<Evaluation Method> (Evaluation 1: Adhesion) The above color filter was output 10
5 in a water bath using a 0 W (35 kHz) ultrasonic cleaner
Washed for minutes. Next, the adhesion of the washed part was evaluated according to the following three grades. A: Adhesiveness is good (no peeling occurs in 100 pixels in the central portion) B: Adhesion is slightly poor (Peeling is 5 pixels or less in 100 pixels in the central portion) C: Adhesiveness is poor (100 pixels in the central portion) 6 peeling inside
Pixels or more).

(Evaluation 2: Dullness of colored portion) A specific cell of the above color filter was spectroscopically measured, immersed in warm pure water at 60 ° C. for 10 minutes, and then placed on a 120 ° C. hot plate.
Dry for minutes. The same cell was subjected to spectroscopic measurement, and the rate of decrease in absorbance from the absorbance at the initial maximum absorption wavelength was evaluated as follows. A: A decrease in the absorbance of the colored portion is less than 1% B: A decrease in the absorbance of the colored portion is 1% or more and less than 3% C: A decrease in the absorbance of the colored portion is 3% or more. Table 6 shows the above evaluation results.

(Evaluation 3: Heat resistance) The above color filter was left in an oven at 250 ° C. for 1 hour, the magnitude of discoloration was calculated as ΔE defined by CIE, and evaluated according to the following criteria. The evaluation results are shown in Table 6.

[0103] A: ΔE is 3 or less B: ΔE exceeds 3 and 10 or less C: ΔE is greater than 10.

(Evaluation 4: Discharge Stability) The G inks of Examples 9 to 16 prepared above were loaded into an ink jet printer (manufactured by Canon Inc., trade name BJ-10V), and A4 was used.
300 character patterns were printed on the paper. 300
The fourth printed A4 sheet was visually observed and evaluated according to the following criteria. The evaluation results are shown in Table 5.

[0105] A: No problem at all B: Some fading occurred C: Almost no ejection.

In each of the evaluations, it is judged that a product having a rating of B or higher can withstand use, and a product having a rating of A is judged to be particularly suitably used.

(Examples 2 to 3) Color filters of Examples 2 and 3 were prepared under the same conditions as in Example 1 except that the dye set used was changed as shown in Table 3, and the same as in Example 1. Was evaluated. The evaluation results are shown in Table 6.

(Comparative Examples 1 and 2) Color filters of Comparative Examples 1 and 2 were prepared under the same conditions as in Example 1 except that the dye set used was changed as shown in Table 3, and the same as in Example 1. An evaluation was made. The evaluation results are shown in Table 6.

[0109]

[Table 5]

[0110]

[Table 6]

(Example 4) First, a black pigment resist CK-S171B manufactured by Fuji Hunt Co., Ltd. was applied on a glass substrate by a spin coating method, and then exposed, developed and heat-treated to give a thickness of 1 on the substrate. A black matrix of 0.0 μm was formed.

Next, a curable ink was prepared based on Ink Formulation Example 2 using the dye set shown in Table 3. As the dye in the G ink, a dye (mixture) based on the dye compounding ratio (Table 4) was used. The inks of R, G, and B were discharged to the openings by an inkjet printer, and the inks were formed into a film by heat treatment at 230 ° C. for 30 minutes to form color filters for liquid crystal elements.

[Ink Formulation 2] Dye Dye (or dye mixture based on Table 4) 6.0% by mass Acrylic copolymer having the following mass composition 10.0% by mass N-methylolacrylamide 20 parts N, N-dimethylaminoethyl methacrylate 10 parts Methyl methacrylate 25 parts 2-Hydroxyethyl methacrylate 40 parts Acrylic acid 5 parts-Ethylene glycol 36.0 mass% (boiling point 197.9 ° C) -Ethyl alcohol (boiling point 78 ° C) 6.0 Mass% -Water 42.0 mass% The same evaluation as in Example 1 was performed. The evaluation results are shown in Table 7.

(Examples 5 to 6) Color filters of Examples 5 and 6 were prepared under the same conditions as in Example 4 except that the dye set used was changed as shown in Table 3, and the same as in Example 1. Was evaluated. The evaluation results are shown in Table 7.

(Comparative Examples 3 and 4) Color filters of Comparative Examples 3 and 4 were prepared under the same conditions as in Example 4 except that the dye set used was changed as shown in Table 3, and the same as in Example 1. An evaluation was made. The evaluation results are shown in Table 7.

[0116]

[Table 7]

[0117]

As described above, according to the present invention, a color filter having excellent heat resistance, cleaning resistance and adhesion to a substrate is produced, and an excellent liquid crystal panel is produced using the color filter. be able to.

According to the present invention, the water-soluble 1,2-naphthalocyanine dye has excellent water-solubility, and as a result, a high concentration of the coloring material in the ink is achieved without sacrificing the ink jet suitability of the ink. Therefore, the cost of the high quality color filter can be reduced.

Furthermore, a computer and an image display device having a high-quality and low-cost display section can be manufactured.

[Brief description of drawings]

FIG. 1 is a process drawing showing an example of a manufacturing procedure of a color filter of the present invention.

FIG. 2 is a process drawing showing another example of the manufacturing procedure of the color filter of the present invention.

FIG. 3 is a block diagram showing a configuration example of an inkjet device used for manufacturing a color filter of the present invention.

FIG. 4 is an explanatory diagram showing a process of forming pixels by an inkjet method.

FIG. 5 is a process drawing of a method of manufacturing a color filter according to another embodiment of the present invention.

FIG. 6 is a schematic sectional view showing an example of a liquid crystal panel incorporating the color filter of the present invention.

FIG. 7 is a schematic explanatory diagram of a liquid crystal panel showing another embodiment of the present invention.

FIG. 8 is a schematic sectional view of a liquid crystal panel according to still another embodiment of the present invention.

FIG. 9 is a schematic perspective view of a computer according to the present invention.

[Explanation of symbols]

1 substrate 2 Black matrix 3 Ink receiving layer 4 inkjet head 6 protective layer 7 Light transmission part 9 color filters 10 Common electrode 11 Alignment film 12 Liquid crystal composition 13 pixel electrodes 14 board 15 Polarizer 16 substrates 17 Backlight light 21 CPU 22 Head drive circuit 23 Inkjet head 24 program memory 25 substrates 26 ink droplets 51 red ink 52 green ink 53 blue ink 54 Colored parts 55 Light transmission part 56 colored pixels 81 Non-coloring part 84 Photomask 90 openings 91 Computer 92 Image display section X black matrix width Y mask opening

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 5/20 101 G02F 1/1335 505 G02F 1/1335 505 C09B 47/00 // C09B 47/00 B41J 3/04 101Y (72) Inventor Ryuta Kato 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F-term (reference) 2C056 EA13 FC02 2H048 BA02 BA57 BA64 BB02 BB42 2H086 BA01 BA02 BA15 BA36 BA53 BA57 BA62 2H091 FA02Y FB02 FC01 LA12 LA15 LA16 4J039 AD12 BC60 BC72 BC74 BC75 BC76 BC77 BC78 BC79 BE02 FA02 FA04 GA24

Claims (19)

[Claims] 1. A water-soluble compound represented by the following general formula (I):
An ink comprising a 2-naphthalocyanine dye. [Chemical 1] (In the formula (I), R is one or more independently of each other, hydrogen atom, sulfone group, sulfamide group, carboxyl group, halogen atom, hydroxyl group, cyano group, nitro group, amino group, phosphono group, trifluoro group. Methyl group,
A straight-chain or branched alkyl group having 1 to 6 carbon atoms, a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, an aryl group which may have at least one substituent, a phenoxy group, a thiophenoxy group or phenyl. Represents a group or a salt thereof, M is 2 hydrogen atoms, 2 Na atoms,
It represents two Li atoms, a divalent metal, or a trivalent or tetravalent metal derivative, L represents a hydrogen atom, an alkali metal ion or an ammonium ion which may have a substituent, and n is 2 to 8 Represents the integer. ) 2. A solvent having a boiling point of 150 to 240.degree.
The ink according to claim 1, comprising 60% by mass. 3. A solvent having a boiling point of 180 ° C. to 230 ° C.
The ink according to claim 2, wherein the ink content is ˜60.0 mass%. 4. The ink according to claim 1, wherein the total dye concentration is 0.5 to 20 mass%. 5. The ink according to claim 4, wherein the total dye concentration is 1 to 15% by mass. 6. The ink according to claim 1, which contains a curable component. 7. The curable component is represented by the following general formula (II): (In the above formula (II), R ¹ is H or CH ₃ , and R ² is H or a linear or branched alkyl group having 1 to 6 carbon atoms.) Item 7. The ink according to Item 6. 8. The ink according to claim 1, which is for inkjet. 9. A pixel forming step of forming colored pixels by adhering the ink droplets according to claim 1 to a predetermined position on a light transmissive substrate. Color filter manufacturing method. 10. In the pixel forming step, ink drops are adhered to an ink receiving layer containing a polymer having an acrylic monomer unit provided on a light transmissive substrate, and then the ink receiving layer is formed. The method of claim 9, wherein the is cured to form colored pixels. 11. The acrylic monomer unit has the following general formula (II): 11. The method according to claim 10, wherein R ¹ is H or CH ₃ , and R ² is H or a linear or branched alkyl group having 1 to 6 carbon atoms in the formula (II). 12. The method according to claim 10, wherein the ink receiving layer contains a photopolymerization initiator. 13. The method according to claim 12, further comprising the step of curing the non-colored portion of the ink receiving layer by irradiation with light or a combination of irradiation with light and heat treatment prior to the deposition of ink drops. 14. A pixel forming step of depositing ink droplets according to claim 6 or 7 at a predetermined position on a light transmissive substrate and then curing the deposited ink to form colored pixels. A method for manufacturing a color filter, comprising: 15. The method of claim 14, wherein the light transmissive substrate comprises an ink color mixing prevention wall. 16. A color filter manufactured by the method according to any one of claims 9 to 15. 17. The color filter according to claim 16 and a panel substrate arranged to face the color filter, wherein a liquid crystal composition is sealed between the color filter and the panel substrate. Characteristic liquid crystal panel. 18. A computer comprising the liquid crystal panel according to claim 17 as an image display unit. 19. An image display device, comprising the liquid crystal panel according to claim 17 as an image display unit.