JPH11302283A - Production of phthalocyanine compound, ink, color filter, liquid crystal panel, computer, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound which is useful as a dye suitable for forming a green pixel part of a color filter, especially satisfies propertied required for a green pixel of a color filter, and has excellent solubility to water which is favorable upon preparing an ink having an excellent ink-jet emission property. SOLUTION: This composition shown by the formula (Met is a metal ion having a valence of 2-4; two H atoms; one or the ligand(s) exist(s) when Met is a metal ion having a valance of 3 or 4, respectively; RPc is a 1-8 phenyl- introduced phthalocyanine residue; M is H, an alkali metal, or ammonium ion; (x) is 1-8; (y) is 0.7; (x)+(y)<8) is obtained by sulfoxylating a phthalocyanine compound shown by MetRPc such as octaphenyl Cu(II) phthalocyanine, preferably without any solvent, using fuming sulfuric acid or chlorosulfonic acid as a sulfoxylating agent and a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a green dye which can be suitably used for forming a color filter, an ink for ink-jet recording, a color filter of a color liquid crystal display used for a color television, a personal computer, etc. The present invention relates to a filter manufacturing method and a liquid crystal panel using such a color filter.

[0002]

2. Description of the Related Art A color filter is a valuable component of a color liquid crystal display. This filter has a large number of pixels consisting of three primary colors of red (R), green (G) and blue (B) repeatedly arranged on a transparent substrate. Has a structure. In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays, especially color liquid crystal displays, tends to increase. However, cost reduction is required for further widespread use, and in particular, there is an increasing demand for cost reduction of color filters having high specific gravity in terms of cost. Conventionally, various color filter manufacturing methods have been attempted to satisfy the above requirements while satisfying the required characteristics of the color filters. Hereinafter, a typical method for manufacturing a color filter will be described.

The first method most frequently used is a dyeing method. The dyeing method uses a photosensitive material added to a water-soluble polymer material that is a material for dyeing and sensitized.
After patterning this into a desired shape on a transparent support by a photolithography process, the obtained pattern is immersed in a dye bath to obtain a colored pattern. This is repeated three times to form R, G, B color filters.

[0004] The second method which is most frequently used is a pigment dispersion method, which has recently been replaced by a dyeing method. In this method, first, a photosensitive resin layer in which a pigment is dispersed is formed on a substrate, and a monochromatic pattern is obtained by patterning the photosensitive resin layer. Further, by repeating this process three times, color filters of three colors of R, G, and B are formed.

A third method is an electrodeposition method. In this method, a transparent electrode is first patterned on a substrate. Next, it is immersed in an electrodeposition coating solution containing a pigment, a resin, an electrolyte solution, etc.
Electrodeposit the color. This process is repeated three times, and R, G, B
The color filter layer is formed by forming the color filter layer and finally baking the color filter layer.

As a fourth method, there is a printing method. In this method, a coating material in which a pigment is dispersed in a thermosetting resin is applied in three colors R, G, and B by repeated printing, and then the resin as a coloring layer is cured by heating to form a coloring layer. Is formed.

[0007] The above-described various methods still have many problems to be solved. For example, in each of the above-described methods, a protective layer is generally formed on a colored layer. Common to these methods is that R,
The same process is required three times to form G and B, which inevitably increases the cost. There is also a problem that the yield increases as the number of steps increases.
Furthermore, in the third method, since the pattern that can be formed is limited, it is difficult to apply the present technology to a TFT color. Furthermore, the fourth method has a drawback that resolution and smoothness are poor, and it is difficult to form a fine pitch pattern.

In order to improve these drawbacks, a method of manufacturing a color filter using an ink jet system has been proposed (JP-A-59-75205 and JP-A-63-75205).
-235901, JP-A-1-217302, JP-A-4-123005). In this method, a coloring liquid (hereinafter, ink) containing a red (R), green (G), and blue (B) dye is ejected from a nozzle onto a filter substrate, and the ink adheres to the filter substrate.
The filter is formed by drying to form pixels. According to this method, each of the R, G, and B colored layers can be formed at a time, and the ink can be attached to the pixel forming portion. The cost can be improved, and the cost can be reduced.

Conventionally, phthalocyanine compounds have been frequently used as dyes for forming green and blue pixels. Phthalocyanine compounds have a strong structure,
It is excellent in various properties such as light resistance and heat resistance, is easy to synthesize, and is also excellent in optical properties such as extinction coefficient and transmittance.

[0010]

On the other hand, it is preferable that the ink used for producing a color filter by discharging the ink by an ink-jet method satisfy the following characteristics at a higher level, for example. a) High transparency of the color filter colored portion (pixel). b) Suppression of the change over time of the color filter colored portion (pixel) area (hereinafter referred to as “smearing”). c) High adhesion of the color filter colored portion (pixel). d) High light resistance of the color filter colored portion (pixel). e) High ejection stability when ejected by the inkjet recording method.

That is, one of the major differences between the method for producing a color filter using the ink jet method and the conventional method for producing a color filter is that, as shown in FIG. That is, the ink is selectively adhered only to the portion, and thereafter, a solvent or a dispersion medium (water, an organic solvent, or the like) in the ink is evaporated to form a pixel.
However, according to the studies by the present inventors, depending on the ink used, in the process of drying the ink 24 adhered on the substrate on the substrate, when a dye is used as a coloring material in the ink, the dye becomes crystalline. A phenomenon was observed in which the transparency of the obtained pixel was reduced, and the bleeding occurred in the pixel due to the temporal migration of the dye forming the pixel due to the incomplete evaporation of the solvent. In some cases, the remaining solvent in the pixel may cause a decrease in adhesion due to some interaction with the substrate, and a decrease in light resistance due to the influence of active oxygen or the like due to thermal decomposition. Therefore, when viewed as an ink for forming a color filter, an ink that satisfies the above-described characteristics a) to d) at a higher level is preferable.

On the other hand, it is needless to say that the inkjet ink preferably has stable ejection performance and ejection accuracy. In order to achieve such inkjet discharge characteristics, it is preferable that the coloring material in the ink is water-soluble.

An object of the present invention is to prepare a dye suitable for forming a green pixel portion of a color filter, in particular, an ink which satisfies the specification of a green pixel of a color filter and has excellent ink jet discharge characteristics. An object of the present invention is to provide a phthalocyanine compound having preferable water solubility.
Another object of the present invention is to provide an ink which satisfies the above characteristics a) to e) at a higher level and is suitable for forming a color filter having excellent ejection stability and landing point accuracy. Another object of the present invention is to provide a color filter provided with a green filter portion having excellent transparency and light resistance.

It is another object of the present invention to provide a method of manufacturing a color filter having a green filter portion having high transparency, little bleeding, and excellent adhesion at low cost. Another object of the present invention is to provide a high quality liquid crystal panel. Another object of the present invention is to provide a computer having a high-quality image display unit.

[0015]

The phthalocyanine compound of the present invention as a green dye capable of achieving the above object is characterized by having a structure represented by the following formula (1).

[0016]

Embedded image [Wherein, Met represents a divalent to tetravalent metal ion or two hydrogen atoms, RPc represents a phthalocyanine residue having 1 to 8 phenyl groups introduced therein, and M represents a hydrogen atom, an alkali metal or Represents an ammonium ion, and x is 1 to
8, y is 0 to 7 (where x + y <8), and Met
Is a trivalent or tetravalent metal ion, there are one or two ligands, respectively. The ink for inkjet recording according to one embodiment of the present invention, which can achieve the above object, is characterized in that the ink containing a dye and a liquid medium contains the phthalocyanine compound as a dye.

According to another embodiment of the present invention, there is provided a color filter including a light-transmitting substrate and a green color pixel at a predetermined position on the substrate. The colored pixels include a dye comprising the phthalocyanine compound.

A liquid crystal panel according to one embodiment of the present invention capable of achieving the above object includes a light-transmitting substrate and a green colored pixel at a predetermined position on the substrate, and the colored pixel is A color filter containing a dye comprising a phthalocyanine compound, and a panel substrate opposed to the color filter, wherein a liquid crystal compound is sealed between the color filter and the panel substrate.

A computer according to one embodiment of the present invention, which can achieve the above object, includes a light-transmitting substrate,
And a color filter including a green color pixel at a predetermined position on the substrate, the color pixel including a color filter including a dye comprising the phthalocyanine compound, and a panel substrate disposed to face the color filter. A liquid crystal panel in which a liquid crystal compound is sealed between the liquid crystal panel and the panel substrate as an image display unit.

In one embodiment of a method of manufacturing a color filter which can achieve the above object, an ink containing a dye comprising the above phthalocyanine compound is ejected toward a light-transmitting substrate by an ink jet method. A step of forming a colored pixel by attaching the pixel to a predetermined position on the substrate.

Another embodiment of a method of manufacturing a color filter which can achieve the above object is to provide an ink containing a dye comprising a phthalocyanine compound and a curable resin on a light-transmitting substrate by an ink jet method. And a step of forming a colored pixel by curing the curable resin in the ink and discharging the ink to a predetermined position on the substrate surface.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Each embodiment of the present invention will be described below.

(Dye) The green dye used in the present invention is a phthalocyanine compound having a structure represented by the above formula (1).

The divalent to tetravalent metal ions which can be Met in the formula (1) include Cu, Zn, Fe, Co, Ni,
Mn, Cr, Mg, Al, Si, Sn, Ti, Ge, G
a, Pb and the like.

Examples of the alkali metal as M in the formula (1) include Li, Na, K, Rb, Cs, and Fr.

The phthalocyanine compound represented by the formula (1) can be obtained, for example, through a step of sulfoxylating a phthalocyanine compound represented by MetRPc. For this sulfoxylation, fuming sulfuric acid or chlorosulfonic acid can be suitably used. These may be used in a molar ratio of at least 8 times the phthalocyanine compound, and the reaction is preferably carried out in a large excess atmosphere. The solvent used in this reaction may be any solvent that is inert to the reaction, but without using a solvent, the solvent is also used with fuming sulfuric acid or chlorosulfonic acid,
A method for assisting the dissolution of a phthalocyanine compound having low solubility is preferred.

The optimum reaction temperature can be selected according to the type of the phthalocyanine compound used as a raw material, in particular, the type of metal. For example, the decomposition temperature of the phthalocyanine compound itself does not occur and a predetermined reaction can proceed. The reaction can be carried out at a temperature selected from the range of
It is preferably carried out at a temperature in the range from 5 to 50C. The reaction time varies depending on the starting materials used, the reaction temperature, the reaction concentration and the like, but can be usually selected from the range of 2 to 24 hours.

Examples of the basic substance used as a post-treatment after the reaction with fuming sulfuric acid and chlorosulfonic acid include alkaline metal compounds such as sodium hydroxide and potassium hydroxide, ammonia, triethylamine, N, N-dimethylaniline, pyridine and the like. , Piperidine, amines such as DBU, etc., which may be used alone or in combination of two or more. In the reaction system, these basic substances can be added as they are or dissolved in an appropriate solvent.

A conventional method of chemical modification of a starting material compound is generally a method of obtaining a target compound by a condensation cyclization reaction using a starting material into which a substituent has already been introduced.
Such a method has been studied for the introduction of a sulfoxyl group when studying the use of a phthalocyanine compound as a dye. However, a compound obtained by a condensation cyclization reaction using a raw material in which a sulfoxyl group has been introduced in advance, and a compound in which a sulfoxyl group has been introduced by post-treatment often have completely different solubility in water. In particular, the sulfoxylated phthalocyanine obtained by the former method often shows almost no solubility in water despite the introduction of a sulfoxyl group, and the latter method is exclusively adopted. become. The reason for this is that, in the former method, the number and position of sulfoxyl groups to be introduced are accurately determined, so that the obtained compound is regularly crystallized, and thus the solubility in water is reduced.
In the latter method, since the number of sulfoxyl groups to be introduced and the position of introduction thereof are random, it can be estimated that strong crystallization did not occur and the solubility in water could be maintained. Therefore, when an attempt was made to introduce a sulfoxyl group by post-treatment in an attempt to make the phthalocyanine compound having a phenyl group introduced water-soluble,
In the sulfoxylation at a temperature of about 130 ° C., which is performed with a normal phthalocyanine compound, a new problem occurs in that the phthalocyanine skeleton itself is decomposed.

On the other hand, the present inventors have found that the reaction must not proceed in a specific temperature range, that is, in general, when a phthalocyanine compound is sulfoxylated using a specific sulfoxylating agent such as fuming sulfuric acid or chlorosulfonic acid. By controlling the reaction in the low-temperature region, which has been considered, the phthalocyanine compound having a phenyl group introduced therein can be sulfoxylated without causing decomposition, and a phthalocyanine compound having sufficient water solubility as a dye can be obtained. And gained new knowledge. That is, the present invention is based on such findings, and provides a water-soluble phthalocyanine compound that could not be provided by the prior art.

The combinations of Met and M in the phthalocyanine compound of the formula (1) include those shown in Table 1.

[0032]

[Table 1] (Ink for Inkjet Recording) The ink for inkjet recording according to one embodiment of the present invention contains a phthalocyanine compound having the structure of the above formula (1) as a dye constituting a coloring material of the ink. This ink can be suitably used, for example, as an ink for forming a green pixel of a color filter.

The amount of the dye to be added to the ink is 0.1 to 15% by weight (weight), particularly 1% based on the total weight of the ink.
In the range of 10% by weight to 10% by weight, and more preferably, 2% to 8% by weight, the pixel can have satisfactory optical characteristics and the characteristics of the ink are changed so as to deviate from the range in which the ink can be ejected accurately by the ink jet recording method. It is preferable without doing. It should be noted that a dye having another color tone can be added as needed in order to adjust to a desired chromaticity.

The above-mentioned dye is held in a dissolved state, a dispersed state or a dissolved and dispersed state, and as a medium constituting the ink, for example, an aqueous medium containing water can be used. The proportion of water as a component of the aqueous medium is 10 to 90% by weight, especially 20% by weight based on the total weight of the ink.
It is preferable to set it to 80% by weight.

The aqueous medium may contain a water-soluble organic solvent. For example, by using a water-soluble organic solvent as described below, it is possible to improve the solubility of the ink constituents, adjust the viscosity, and the like. Particularly, a water-soluble organic solvent having a boiling point of about 150 to 250 ° C. The solvent ejects the ink using an ink jet recording method and, when attaching the ink to the substrate, reduces the possibility of clogging of the orifice and does not reduce the adhesion to the substrate. Therefore, it is suitably used. Further, the content of the water-soluble organic solvent is such that the boiling point is 150 to 2 with respect to the total amount of the ink.
The organic solvent at 50 ° C contains 5 to 50% by weight, more preferably 5 to 50% by weight of the organic solvent having a boiling point of 180 to 230 ° C. In addition, the organic solvent having a boiling point of 250 ° C. or more is more preferably 30% by weight or less, and the boiling point is 23% or less.
More preferably, the organic solvent at 0 ° C. or higher is 20% by weight or less. Representative examples of organic solvents that can be used are shown in Tables 1 and 2.

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5] Further, a nonionic, anionic, cationic, or other surfactant may be used in the ink.
Additives such as fungicides may be added as necessary.

By the way, such ink is ejected from a recording head by an ink jet system, for example, a bubble jet type using an electrothermal converter as an energy generating element, or a piezo jet type using a piezoelectric element, and the like, and a substrate of a color filter is formed. It is very suitably used to form green pixels when deposited on top. As a characteristic of this ink, at the time of ink preparation, the surface tension is 30 to 68 when the ink temperature is 25 ° C.
By setting the dyn / cm and the viscosity to 15 cP or less, particularly 10 cP or less, and more preferably 5 cP or less, the ink ejection characteristics become particularly excellent. And in this embodiment,
Specific ink compositions that can achieve such characteristics include, for example, the inks described in Examples described later.

The ink used in the present invention preferably further contains a curable resin. As this curable resin,
A resin that can be cured by light or heat can be used,
For example, a copolymer using an acrylic monomer can be suitably used. Acrylic monomers that can constitute this copolymer include N, N-dimethylolacrylamide, N, N-dimethoxymethylacrylamide,
Examples thereof include N-diethoxymethylacrylamide, N, N-dimethylol methacrylamide, N, N-dimethoxymethyl methacrylamide, and N, N-diethoxymethyl methacrylamide. These monomers can be used alone or in combination of two or more.

Other monomers to be copolymerized with the acrylic monomer include vinyl monomers, styrene, α-methylstyrene, acrylamide methacrylamide, acrylonitrile, allylamine, vinylamine, vinyl acetate, vinyl propionate and the like. Or a combination of two or more thereof. Examples of the vinyl monomer include acrylic acid,
Acrylic esters such as methacrylic acid, methyl acrylate and ethyl acrylate; containing hydroxyl groups such as methacrylic esters such as methyl methacrylate and ethyl methacrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxymethyl acrylate and hydroxyethyl acrylate A vinyl monomer can be mentioned.

Furthermore, other photocurable resins, photopolymerization initiators, and the like can be added to the ink within a range that does not impair the effects of the present invention. Further, an acrylic resin, an epoxy resin, or the like may be used in combination. The amount of the curable resin in the ink can be selected according to the desired ink composition, and can be, for example, 0.1 to 50% by weight, and preferably 1 to 20% by weight.

(Method for Manufacturing Color Filter Using Ink) Next, a method for manufacturing a color filter using the above-described ink will be described. FIG. 1 is an explanatory diagram of a method for manufacturing a color filter for liquid crystal according to one embodiment of the present invention.
FIG. 1A shows a light-transmitting substrate 1 (for example, a glass substrate or the like) on which a light-shielding portion (hereinafter referred to as a “black matrix”) 2 is formed in a pattern. When the black matrix 2 is formed directly on a substrate, for example, a method of forming a thin film of a metal (for example, chromium, chromium oxide, or the like) by sputtering or vapor deposition and patterning the thin film by a photolithography process may be used. When it is provided on an object, a patterning method by a general photolithography process may be used.

First, a layer (ink receiving layer) 3 containing a curable resin composition is formed on the substrate 1 on which the black matrix 2 is formed (FIG. 1B).

The substrate 1 can be made of a material which can satisfy characteristics required for a color filter such as light transmittance (transparency) and mechanical strength. For example, a glass plate,
Acrylic resin, polyethylene resin, vinyl chloride resin, vinylidene chloride resin, polycarbonate resin, ethylene resin, polyolefin copolymer resin, vinyl chloride copolymer resin,
A film or plate made of a resin such as a vinylidene chloride copolymer resin can be used. Further, when a pixel portion is directly provided in various products, for example, a substrate on which a black matrix for a liquid crystal display is formed, or a substrate on which a liquid crystal display semiconductor element such as a TFT or STN is formed is used as the substrate 1.

As the material for forming the ink receiving layer 3, known materials can be used. For example, in consideration of heat resistance and the like, acrylic resins, epoxy resins, and imide resins are preferable. Considering the properties, those containing a cellulose-based water-soluble polymer such as hydroxypropylcellulose, hydroxyethylcellulose, methylcellulose and carboxymethylcellulose are preferable. Other examples include natural resins such as polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetal, polyurethane, carboxymethyl cellulose, polyester and the like, and albumin, gelatin, casein, starch, cationized starch, gum arabic, sodium alginate and the like. In particular, in consideration of the transparency of the colored portion, bleeding, light resistance of the dye, and the like in addition to the heat resistance and the ink absorbency, a mixture of hydroxypropylcellulose and methylolated melamine, or a compound represented by the following formula (x): It is preferable to use at least a single monomer that supplies the structural unit to be used and / or a copolymer with another vinyl monomer.

[0048]

Embedded image In the formula (x), R ₁₉ is H or CH ₃ and the like, R ₂₀
Represents H or an alkyl group which may be unsubstituted or substituted with a linear or branched alkyl group having 1 to 5 carbon atoms. Examples of the monomer for supplying the structural unit represented by the formula (x) include N-methylolacrylamide, N-methoxymethylacrylamide, and N-methylacrylamide.
Examples include ethoxymethyl acrylamide, N-isopropoxymethyl acrylamide, N-methylol methacrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl methacrylamide and the like. Further, as other vinyl monomers, acrylic acid, methacrylic acid, acrylate (methyl acrylate, ethyl acrylate, etc.), methacrylate (methyl methacrylate,
Vinyl monomers containing hydroxy groups (hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxymethyl acrylate, etc.)
Hydroxyethyl acrylate), styrene, α-methylsterene, acrylamide, methacrylamide, acrylonitrile, allylamine, vinylamine, vinyl acetate, vinyl propionate, and the like. The copolymerization ratio between the monomer corresponding to the structural unit of the above formula (x) and another vinyl monomer is desirably in the range of 95: 5 to 5:95 in molar ratio.

The receiving layer 3 may contain various additives as necessary. Specific examples of additives include various surfactants, dye fixatives (waterproofing agents), defoamers, antioxidants, fluorescent brighteners, ultraviolet absorbers, dispersants, viscosity adjusters, and pH adjusters. , A fungicide and a plasticizer. These additives may be arbitrarily selected from conventionally known compounds according to the purpose.

As a method for forming the ink receiving layer 3, methods such as spin coating, roll coating, bar coating, spray coating, and dip coating can be used. Prebaking may be performed as needed.

Next, the ink according to the present invention described above is applied to the pixel forming portion of the ink receiving layer 3 by an ink jet method, and a predetermined portion of the ink receiving layer 3 is colored (FIG. 1C). As the ink jet method, a bubble jet type using an electrothermal converter or a piezo jet type using a piezoelectric element can be used as the energy generating element, and the coloring area and the coloring pattern can be set arbitrarily. Here, a preferred method for forming pixels by ejecting ink by an ink-jet method will be described with reference to FIG. 2. FIG. 2 is a block diagram showing a configuration of an apparatus for drawing a colored portion of a color filter by an ink-jet method. is there. In FIG. 2, the CPU 21
Is connected to the inkjet recording head 4 via a head drive circuit 22. Further, the CPU 21 is configured so that control program information in the program memory 23 is input. Then, the CPU 21 moves the ink jet recording head 23 to a predetermined position on the substrate 1 (not shown), brings a desired pixel position on the substrate 1 below the ink jet head, and places a desired color ink 24 on the position.
Is discharged for coloring. By performing this for a desired pixel position on the substrate 1, a color filter can be manufactured.

If the color filter to be created has R, G, and B pixels, G and R
As the ink used for forming the pixel of the present invention, a known ink is used as appropriate, and simultaneously with the ink B of the present invention, or
A predetermined portion of the ink receiving layer 3 may be dyed for each color to form R, G, and B pixels.

Next, the ink receiving layer 3 is cured (FIG. 1)
(D)). As a curing method, a method suitable for the curable resin used for the ink receiving layer may be used. For example, heating, light irradiation, or heating and light irradiation are performed to cure to form colored pixels of each color. Here, the light to be applied to the ink absorbing layer is not particularly limited.
UV light is preferable, and light irradiation conditions are 1 to 300.
About 0 mJ / cm ² is preferable. Examples of the heat treatment include a method using an oven, a hot plate, or the like. The heat treatment may be performed at a temperature of 50 ° C. to 180 ° C. for 10 seconds to 20 minutes.

Thereafter, a protective layer is formed on the cured ink receiving layer 3 as required (FIG. 1 (e)). The protective layer 6 can be provided by applying a resin material curable by, for example, light irradiation or heat treatment, and subsequently curing the resin material, or by forming an inorganic film by vapor deposition or sputtering. As a material that can be used for the protective layer, a material that does not impair the transparency required for the color filter when the protective layer is formed and that can withstand the ITO forming process or the alignment film forming process that is performed as necessary thereafter is preferable. Specifically, for example, an organic material includes an acrylic resin such as epoxy acrylate and urethane acrylate, and an inorganic material includes SiO ₂ . Thus, the color filter 9 according to the present embodiment can be obtained.

Next, a method of manufacturing a color filter without providing the ink receiving layer 3 will be described with reference to FIG.

First, a substrate having a black matrix 2 formed on the surface in the same manner as described above is prepared (FIG. 3).
(A)). In addition, an appropriate thickness (for example, 0.
It is preferable to make a wall of about 8 μm or more). Such a wall can be formed by, for example, patterning a black resin resist so that the black matrix 2 has a desired thickness when forming the black matrix 2.

Next, as shown in FIG. 3B, the above-described green (G) ink 52 and various known red (R) inks 5 according to the present invention are utilized by using an ink jet method.
1 and blue (B) ink 53 are applied so as to fill the light transmitting portions 55 between the black matrices 2. At this time, it is preferable that each color ink is applied so as not to overlap on the black matrix 2. As the G ink used here, an ink containing the phthalocyanine derivative represented by the formula (1) described above is used, and an ink containing a curable resin is more preferable. It is preferable to use the G ink and the R ink containing the resin.

Next, as shown in FIG.
Heating or both light irradiation and heating are performed to partially cure the ink applied to the openings 55 on the substrate 1 and then to 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 the ink of each color, and the colored portion 54 is completely cured by light irradiation and / or heat treatment. Thus, the colored pixel 17 is completed, and the curable resin composition is cured to form the protective layer 6, thereby obtaining a color filter. The protective layer 6 may be formed by curing a resin material that can be cured by light irradiation or heat treatment, or both, or may be formed by depositing or sputtering an inorganic film to form the protective film 6. Materials that can be used for forming the protective film 6 include:
It has the transparency of a color filter,
What can withstand a TO formation process, a light distribution film formation process, etc. can be used suitably.

(Liquid Crystal Panel) The color filter 9 which can be formed by the above-described method is, for example, as shown in FIG. 4, a color filter 9 and a substrate 14 are arranged to face each other, and a liquid crystal composition 12 is sealed therebetween. Thus, a liquid crystal panel can be formed. FIG. 4 shows a sectional view of an example of a TFT color liquid crystal panel incorporating the color filter of the present invention.
That is, the color liquid crystal panel is formed by aligning the substrate 14 facing the color filter 9 and sealing the liquid crystal composition 12 therebetween. TFTs (not shown) and transparent pixel electrodes 13 are formed in a matrix on the inside of one substrate of the liquid crystal panel. On the surface of the protective layer 5 of the color filter 9, a transparent opposing (common) electrode 10 is formed on one surface. Further, an alignment film 11 is formed on an inner surface of the counter substrate 14 so as to cover the pixel electrode 13, and an alignment film 11 is formed on an inner surface of the counter electrode 10. By subjecting these alignment films to a rubbing treatment, liquid crystal molecules can be arranged in a certain direction.
In the liquid crystal panel thus manufactured, a polarizing plate 15 is adhered to the outside of the color filter substrate 1 and the counter substrate 14, and the liquid crystal compound is generally backed using a backlight in which a fluorescent lamp and a scattering plate are combined. Display can be performed by functioning as an optical shutter that changes the transmittance of the light 16 of the light. The black matrix and the colored portion are usually formed on the color filter substrate side as shown in FIG. 6, but their positions are changed depending on the structure of the liquid crystal panel. For example, in a black matrix (BM) on-array type liquid crystal panel, the BM is formed on the opposite TFT substrate side as shown in FIG. 7, and in a color filter (CF) on-array type, the CF section is shown in FIG.
It is formed on the TFT substrate side as shown in FIG. The liquid crystal panel thus created is used as a pixel display device 92 such as a computer 91 as shown in FIG.

[0060]

Next, each embodiment of the present invention will be described more specifically with reference to examples.

Example 1 2.0 g of octaphenylcopper (II) phthalocyanine was charged into a 4-necked corbane equipped with a reflux condenser and a thermometer, and 80 g of 25% by weight fuming sulfuric acid was added thereto.
Stirred for hours. Immediately after the reaction, the system became a dark green homogeneous solution, and the progress of sulfoxylation was confirmed. Further, 20 g of fuming sulfuric acid of 25% by weight was added, and the temperature was raised to 85 ° C. over 6 hours to complete the reaction. The obtained reaction solution was poured into ice water, neutralized with 28% by weight of aqueous ammonia and sodium hydroxide, and precipitated from acetone to obtain 1.71 g of a target phthalocyanine compound. The infrared absorption spectrum of the obtained target compound was compared with the raw material, that is, a large absorption was confirmed at around 1180 cm ^−1, and it was confirmed that the sulfoxyl group had been introduced. From the measurement with a spectrophotometer, 654 nm was obtained.
And a spectrum having a large absorption at 691 nm. Also, x in equation (1) is measured by titration,
Further, when the sulfonamide was hydrolyzed and titrated in the same manner to measure y in the formula (1), x =
5.4, y = 1.5.

Example 2 0.5 g of octaphenylzinc (II) phthalocyanine was charged into a 4-necked corvene equipped with a reflux condenser and a thermometer.
To this was added 30 g of chlorosulfonic acid, and the mixture was stirred for 8 hours while maintaining the temperature at 15 ° C. Thereafter, the temperature was raised to 35 ° C., and the mixture was stirred for 1 hour. Then, the same treatment as in Example 1 was performed to obtain 0.35 g of a target phthalocyanine compound. Similarly, it was confirmed that the sulfoxyl group was introduced by comparing the infrared absorption spectrum of the obtained target compound with the raw material, and spectra having absorptions at 660 nm and 698 nm were obtained from the measurement with a spectrophotometer. Further, x in the formula (1) was measured by titration, and y was measured in the formula (1) by further performing titration after hydrolyzing the sulfonamide. As a result, x = 6.1, y = 1.1.

Example 3 The procedure of Example 1 was repeated, except that octaphenylcopper (II) phthalocyanine was replaced by tetraphenylcopper (II) phthalocyanine, to obtain 1.88 g of the desired phthalocyanine compound. Similarly, the presence of the sulfoxyl group was confirmed from the infrared absorption spectrum, and the spectra having absorption at 635 nm and 670 nm were obtained from the spectrophotometer measurement. In addition, x was 3.0 and y was 0.6.

Example 4 5.7% by weight of a dye, 39.0% by weight of ethylene glycol monobutyl ether (boiling point: 170 ° C.), 6.0% by weight of ethyl alcohol (boiling point: 78 ° C.), and 49.3% by weight of water were prepared in the usual manner. To prepare R, G and B inks, respectively. The following dyes were used. R ink: C.I. I. Acid Red 158 B ink: C.I. I. Acid Blue 83 G ink: Octaphenyl copper (I) obtained in Example 1
I) Phthalocyanine Derivative (At the time of ink preparation, chromaticity calculation is performed by computer simulation based on the spectrum data, and the yellow dye CI Direct is obtained as necessary to obtain the desired chromaticity.
Toned with Yellow 86. On a glass substrate provided with a black matrix of chromium having openings of 60 to 150 μm, a copolymer of N-methylolacrylamide and hydroxyethyl methacrylate (1: 1, molar ratio) was used as an ink receiving layer. The resulting curable resin composition was spin-coated so as to have a film thickness of 1.2 μm, and prebaked at 120 ° C. for 20 minutes. Next, R, G, and B inks previously prepared using an inkjet printer were applied to predetermined portions to color the R, G, and B matrix patterns. Next, baking is performed at 230 ° C. for 50 minutes to accelerate the curing reaction, and after drying, a two-component acrylic thermosetting resin material (trade name: SS-7625,
(Nippon Synthetic Rubber Co., Ltd.) was spin-coated so as to have a thickness of 1 μm after curing, and heat-treated at 240 ° C. for 20 minutes to be cured to form a protective layer. A color filter having a similar structure was obtained. The obtained color filters were evaluated for the following items. Table 6 shows the results.

Evaluation 1: Transparency of colored part A liquid crystal panel was prepared using a color filter, and G (green) was used.
The transparency of the pattern portion was visually evaluated by being divided into three groups. A: Good transparency B: Slightly poor transparency C: More dull than those of A and B Evaluation 4: Impact position accuracy Nozzle density 360 dpi (nozzle pitch 70.4μ)
m) An ink jet printer equipped with a recording head having 64 nozzles is filled with G ink, all the nozzles are simultaneously driven, and a line of 64 dots is drawn once every 0.5 seconds 200 times. The accuracy was evaluated according to the following criteria. A: The number of dots that deviate from the straight line by at least one dot is 0.1.
%: B: The number of dots that deviate from the straight line by one dot or more is 0.1
% To less than 0.5% C: The number of dots deviating from the straight line by one dot or more is 0.5
% Or more Evaluation 3: Light fastness A color filter was irradiated with xenon light for 50 hours using an Atlas Fademeter Ci35, and the magnitude of discoloration and fading of the B pattern portion was calculated as ΔE determined by CIE, and the following criteria were used. Was evaluated. A: ΔE is 10 or less B: ΔE is more than 10 and 20 or less C: ΔE is more than 20 Evaluation 2: Bleeding of colored part The above color filter is left at 60 ° C for 48 hours, and the colored part of the R pattern is formed. The degree of bleeding (increase in the colored area) was evaluated. A: less than 5% B: 5% or more and less than 10% C: 10% or more For the color filter produced as described above,
A series of operations such as TO (electrode formation), alignment film formation, and liquid crystal material encapsulation were performed by a conventional method to produce a color liquid crystal element having the structure shown in FIG. 2, and an element having good characteristics was obtained. .

Example 5 A color filter was prepared in the same manner as in Example 4 except that the octaphenylzinc (II) phthalocyanine derivative obtained in Example 2 was used instead of the octaphenylcopper (II) phthalocyanine derivative. The evaluation was performed. Table 6 shows the evaluation results.

Example 6 A color filter was prepared in the same manner as in Example 4, except that the tetraphenyl copper (II) phthalocyanine derivative obtained in Example 3 was used instead of the octaphenyl copper (II) phthalocyanine derivative. The evaluation was performed. Table 6 shows the evaluation results.

Comparative Examples 1 and 2 Instead of the octaphenylcopper (II) phthalocyanine derivative, C.I. I. AcidBlue 185 (Comparative Example 1) or C.I. I. Acid Blue 254 (Comparative Example 2)
A color filter was prepared and evaluated in the same manner as in Example 4 except for using. Table 6 shows the evaluation results.

[0069]

[Table 6]

[0070]

As described above, according to the present invention, it is possible to provide a high quality color filter, particularly a color filter having excellent characteristics in a green pixel portion. Further, according to the present invention, it is possible to provide a dye suitable for forming the green pixel portion of the color filter and an ink jet ink using the dye. Further, according to the present invention, it is possible to obtain an ink that satisfies the ink ejection characteristics when the ink jet recording method is used for forming the color filter. Further, according to the present invention, a liquid crystal panel having excellent characteristics and a computer using the same can be obtained.

[Brief description of the drawings]

FIG. 1 is a process chart of an example of a method for manufacturing a color filter using an inkjet method according to the present invention.

FIG. 2 is a schematic explanatory view of a method of forming a pixel of a color filter using an inkjet method.

FIG. 3 is a process chart of an example of a method for manufacturing a color filter using the inkjet method of the present invention.

FIG. 4 is a schematic sectional view of a liquid crystal panel.

FIG. 5 is an explanatory diagram of a transient phenomenon when pixels of a color filter are formed using an inkjet method.

FIG. 6 is a schematic sectional view of a liquid crystal panel.

FIG. 7 is a schematic sectional view of a liquid crystal panel.

FIG. 8 is a schematic sectional view of a liquid crystal panel.

FIG. 9 is a schematic perspective view of a computer.

[Explanation of symbols]

 Reference Signs List 1 light-transmitting substrate 2 black matrix 3 ink receiving layer 4 inkjet recording head 5, 6 protective layer 9 color filter 10 common electrode 11 alignment film 12 liquid crystal compound 13 pixel electrode 14 glass substrate 15 polarizing plate 16 backlight light 17 colored pixel portion Reference Signs List 21 CPU 22 Head drive circuit 23 Program memory 24 Ink 51 Red (R) ink 52 Green (G) ink 53 Blue (B) ink 54 Colored portion 61 Counter substrate 62 Liquid crystal composition 63 Pixel electrode 64 Common electrode 65, 66 Alignment film 67 Deflection plate 68 Backlight 91 Computer 92 Image display

[Procedure amendment]

[Submission date] May 29, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction contents]

The amount of the dye added to the ink is 0.1 to 15% by weight , particularly 1 to 10% by weight , and more preferably 2 to 8% by weight based on the total weight of the ink. It is preferable that the obtained optical characteristics can be carried and the characteristics of the ink do not change so as to deviate from the range where the ink can be ejected accurately by the ink jet recording method. Note that it is necessary to adjust to the desired chromaticity.
Flip and those that can be added other color dyes.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction contents]

Example 4 5.7% by weight of a dye, 39.0% by weight of ethylene glycol monobutyl ether (boiling point: 170 ° C.), 6.0% by weight of ethyl alcohol (boiling point: 78 ° C.), and 49.3% by weight of water were prepared in the usual manner. To prepare R, G and B inks, respectively. The following dyes were used. R ink: C.I. I. Acid Red 158 B ink: C.I. I. Acid Blue 83 G ink: Octaphenyl copper (I) obtained in Example 1
I) Phthalocyanine derivative (At the time of ink production, computer based on spectral data
The chromaticity is calculated by simulation , and if necessary, the yellow dye C.I. I. Direct
Toned with Yellow 86. On a glass substrate provided with a black matrix of chromium having openings of 60 to 150 μm, a copolymer of N-methylolacrylamide and hydroxyethyl methacrylate (1: 1, molar ratio) was used as an ink receiving layer. The resulting curable resin composition was spin-coated so as to have a film thickness of 1.2 μm, and prebaked at 120 ° C. for 20 minutes. Next, R, G, and B inks previously prepared using an inkjet printer were applied to predetermined portions to color the R, G, and B matrix patterns. Next, baking is performed at 230 ° C. for 50 minutes to accelerate the curing reaction, and after drying, a two-component acrylic thermosetting resin material (trade name: SS-7625,
(Nippon Synthetic Rubber Co., Ltd.) was spin-coated so as to have a thickness of 1 μm after curing, and heat-treated at 240 ° C. for 20 minutes to be cured to form a protective layer. A color filter having a similar structure was obtained. The obtained color filters were evaluated for the following items. Table 6 shows the results.

[Procedure amendment 3]

[Document name to be amended] Drawing

[Correction target item name] Fig. 6

[Correction method] Change

[Correction contents]

FIG. 6

[Procedure amendment 4]

[Document name to be amended] Drawing

[Correction target item name] Fig. 7

[Correction method] Change

[Correction contents]

FIG. 7

Continuing on the front page (72) Katsuhiro Shirota, Canon, Inc. 3- 30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Koichiro Nakazawa 3-30-2, Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Mayumi Yokoyama 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc.

Claims (21)

[Claims] 1. The following formula (1): [Wherein, Met represents a divalent to tetravalent metal ion or two hydrogen atoms, RPc represents a phthalocyanine residue having 1 to 8 phenyl groups introduced therein, and M represents a hydrogen atom, an alkali metal or Represents an ammonium ion, and x is 1 to
8, y is 0 to 7 (where x + y <8), and Met
Is a trivalent or tetravalent metal ion, there are one or two ligands, respectively. ] The phthalocyanine compound characterized by having the structure represented by the formula: 2. An ink-jet ink containing a dye and a liquid medium, wherein the dye contains the phthalocyanine compound according to claim 1. 3. The ink according to claim 2, wherein the dye concentration is 0.1 to 15% by weight based on the total weight of the ink. 4. A solvent having a boiling point of 150 to 250 ° C.
4. The ink according to claim 2, wherein the content of the ink is by weight. 5. The ink according to claim 2, further comprising a curable resin. 6. The ink according to claim 5, wherein the curable resin is a resin that is cured by application of at least one of light and heat. 7. A light-transmitting substrate and a color filter having a green colored pixel at a predetermined position on the substrate, wherein the colored pixel contains the dye comprising the phthalocyanine compound according to claim 1. A color filter characterized by the following. 8. The color filter according to claim 7, wherein the substrate has a resin layer on a surface, and a part of the resin layer constitutes the colored pixel. 9. The color filter according to claim 7, further comprising a plurality of the colored pixels, wherein each of the colored pixels is separated from each other, and a light shielding layer is provided between each of the colored pixels. 10. The color filter according to claim 13, wherein the surface of the light-shielding layer is non-colored. 11. A color filter according to claim 7, further comprising: a panel substrate facing the color filter, wherein a liquid crystal compound is sealed between the color filter and the panel substrate. A liquid crystal panel characterized by the following. 12. The liquid crystal panel according to claim 11, wherein an electrode for controlling the alignment of the liquid crystal compound is provided on a surface of the light transmitting substrate of the color filter opposite to a side having the colored pixels. 13. A computer comprising the liquid crystal panel according to claim 11 as an image display unit. 14. A colored pixel is formed by ejecting the ink according to any one of claims 2 to 6 toward a light-transmissive substrate using an inkjet method and attaching the ink to a predetermined position on the substrate. A method for manufacturing a color filter, comprising the steps of: 15. The method for manufacturing a color filter according to claim 14, wherein the light-transmitting substrate has a resin layer on a surface. 16. The method according to claim 15, wherein the material forming the resin layer is a polymer containing at least a water-soluble acrylic monomer unit. 17. The method for producing a color filter according to claim 15, wherein the material forming the resin layer contains at least a cellulose-based water-soluble polymer. 18. The ink according to claim 5 or 6, which is ejected toward the surface of the light-transmitting substrate using an ink-jet method, adheres to a predetermined position on the surface of the substrate, and then cures in the ink. A process for curing a color filter to form a colored pixel. 19. The method for manufacturing a color filter according to claim 18, wherein a substrate having a light-shielding layer that separates a plurality of pixels formed on the surface from each other is used as the light-transmitting substrate. 20. The method for producing a color filter according to claim 19, further comprising a step of forming a curable resin layer so as to cover the colored pixels, and curing the curable resin layer. 21. The method for manufacturing a color filter according to claim 20, wherein the curable resin layer is cured by applying at least one of light energy and heat energy.