JPH0915582A - Color filter for liquid crystal, its production and liquid crystal panel - Google Patents

Abstract

PURPOSE: To provide a color filter having high reliability at a low cost by applying a pretreating liquid which can dissolve an ink-accepting layer in the part which is to be colored in the ink-accepting layer on a substrate and then applying the ink of a specified color. CONSTITUTION: Such a resin compsn. layer (ink-accepting layer) 3 that when the layer is irradiated with light or irradiated with light and heat treated, the absorptivity for ink in the irradiated part can be increased is formed by spin coating method or the like on a glass substrate 1 where a black matrix 2 is formed. The part of the layer 3 which is not shielded by the black matrix 2 is exposed for patterning to be changed to have affinity to ink. A pretreating liquid 27 which dissolves the part 26 having affinity with ink and having relatively high absorptivity for ink in the ink-accepting layer 3 is applied by dipping or the like. Then inks 28 of R, G, B colors are applied by ink-jet method to color the layer. Then the colored coating material is hardened by the irradiation of light and/or heat treatment. If necessary, a protective layer 29 is formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a color filter for a color liquid crystal display used in a color television, a personal computer, a pachinko game table, a car navigation system, a small television, etc., and particularly a liquid crystal utilizing an ink jet recording technology. The present invention relates to a method for manufacturing a color filter. The present invention also relates to a coating material for producing a color filter for liquid crystal using an inkjet recording technique and a method for producing a color filter for liquid crystal using the coating material. The present invention also relates to a liquid crystal color filter manufactured by using an inkjet method and a liquid crystal panel including the color filter.

[0002]

2. Description of the Related Art In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays, especially color liquid crystal displays, has been increasing. However, cost reduction is required for further popularization, and there is an increasing demand for cost reduction of a color filter, which has a large specific gravity in terms of cost.

Conventionally, various methods have been tried to satisfy the above requirements while satisfying the required characteristics of the color filter, but no method has yet been established which satisfies all the required characteristics. Hereinafter, each method will be described.

The first and most frequently used method is the dyeing method. The dyeing method involves first forming a layer of a water-soluble polymer material, which is a material for dyeing, on a glass substrate, patterning this into a desired shape by a photolithography process, and then dipping the obtained pattern in a dyeing bath. To obtain a colored pattern. By repeating this three times, R, G,
A color filter layer of B is formed.

[0005] The second method 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, this step is repeated three times to form R, G, and B color filter layers.

A third method is an electrodeposition method. In this method, first, a transparent electrode is patterned on a substrate, and a pigment,
The first color is electrodeposited by dipping in an electrodeposition coating solution containing a resin, an electrolytic solution or the like. This process is repeated 3 times to form R, G, B color filter layers. It is the one that is fired at the end.

As a fourth method, a pigment is dispersed in a thermosetting resin, and printing is repeated three times so that R, G,
After coating B separately, the colored layer is formed by thermosetting the resin. In any method, a protective layer is generally formed on the colored layer.

[0008]

However, what is common to these methods is that the same process needs to be repeated three times in order to color the three colors of R, G and B, resulting in high cost. That is. Also. There is a problem that the yield decreases as the number of processes increases. Further, in the electrodeposition method, since the pattern shape that can be formed is limited, it is difficult to apply the current technology for TFT. Further, the printing method is not suitable for forming a fine pitch pattern because of poor resolution.

As a method of manufacturing a color filter using an ink jet in order to make up for these drawbacks, Japanese Patent Laid-Open No. 59-59 has been proposed.
-75205, JP-A-63-235901, JP-A-1-
There is a proposal in 217320 etc., but it is still insufficient.

Therefore, an object of the present invention is to solve the problems of these conventional methods and to provide a highly reliable color filter satisfying the required properties such as heat resistance, solvent resistance and resolution at a low cost in a short process. Another object of the present invention is to provide a manufacturing method, a color filter and a liquid crystal panel with high reliability. In particular, it is an object of the present invention to provide a method for producing an excellent color filter for liquid crystal, which does not cause color mixture or color loss when a colored portion is formed with a dye ink by an inkjet method.

[0011]

The present invention provides a method of manufacturing a color filter for liquid crystal, which comprises a step of arranging colored portions of red (R), green (G) and blue (B) on a substrate. , (1) a step of forming an ink receiving layer on the substrate, (2) applying a liquid capable of dissolving the receiving layer (referred to as a pretreatment liquid) to a portion of the ink receiving layer to be the colored portion. Provided is a method for producing a color filter for liquid crystal, which comprises the step of (3) applying an ink of a predetermined color to a predetermined portion of the ink receiving layer.

In the above manufacturing method, it is preferable that the ink is applied by an ink jet method.

Further, it is preferable that the ink receiving layer is provided with an ink repellent portion having a relatively high ink absorbency and an ink repellent portion having a relatively low ink absorbency, and the ink receptive portion is colored.

Further, in the above-mentioned manufacturing method, (1) an ink receiving layer is formed by forming a resin composition layer on the substrate, the resin composition layer of which is capable of changing the ink absorbability of the light irradiated portion by light irradiation or light irradiation and heat treatment. Then, (2) a predetermined portion of the ink receiving layer formed on the substrate is pattern-exposed to change the ink absorbency of the exposed portion of the receiving layer to form an ink-philic portion and an ink repellent portion. In addition, it is preferable that the method further includes (3) curing the colored ink receiving layer by light irradiation and / or heat treatment.

In that case, in the pattern exposure, a portion of the ink-receiving layer to be colored is exposed so that the ink absorbency of the portion is relatively increased; or an uncolored portion of the ink-receiving layer is exposed. There may be a method of making the ink absorbency of the portion relatively low.

The present invention also provides a liquid crystal color filter manufactured by the above manufacturing method, and a liquid crystal panel having a color filter and a substrate facing the filter, and a liquid crystal compound enclosed between both substrates. It is a thing.

[0017]

The present invention will be described in detail below with reference to the drawings.

FIG. 1 is a process chart showing the procedure of one embodiment of the method for producing a color filter for liquid crystal of the present invention.

In the present invention, a glass substrate is generally used as the substrate, but it is not limited to the glass substrate as long as it has necessary properties such as transparency and mechanical strength as a liquid crystal color filter. FIG. 1 (a)
FIG. 3 is a diagram showing a glass substrate 1 on which a black matrix 2 is formed.

First, the coating material according to the present invention is applied onto a substrate on which a black matrix is formed, and if necessary, prebaking is performed to increase the ink absorption of the light-irradiated portion by light irradiation or light irradiation and heat treatment. A resin composition layer (ink receiving layer) 3 is formed (FIG. 1B).

The present invention is intended to prevent color mixing of ink and excessive diffusion of ink by utilizing the difference in ink absorbency between the exposed portion and the unexposed portion of the resin composition layer. As a material, a resin composition whose ink absorbency in the exposed area is increased by exposure or both exposure and heat treatment is used. At this time, as the material of the resin composition, a portion that is not ink-philic and a portion that is not ink-philic,
The solubility in the liquid that dissolves the ink receiving layer applied to the ink-philic portion in the step described below may be one that satisfies the relationship of the following formula (I). In the following, a portion of the ink receiving layer having a relatively high ink absorbability is referred to as an ink-philic portion, and a portion having a relatively low ink absorbability is referred to as an ink repellent portion.

[0022]

## EQU00002 ## (Solubility of the parent ink portion) / (Solubility of the ink repellent portion)> 5 ... (I) In this case, the solubility is measured in an atmosphere of a temperature of 23.degree. C. and a humidity of 55%. 10 ml in a large container
A liquid that dissolves the parent ink part of is injected, and a small amount of the resin composition (solid content 100%) is added. After that, the mixture is stirred for 6 hours with a mix rotor and visually confirmed to confirm that there is no residual dissolved substance. If not, add them little by little and check by visual observation in the same way for any residual dissolved substances.
When the input amount at the time when the residual dissolved substance is generated is A (mg), the solubility is A (mg) / 10 ml.

Further, in the embodiment shown in this figure, the ink absorbency is increased only by light irradiation, but there is no problem even if heat treatment is also used.

As a composition example of the coating material used in the present invention, in which the ink absorption of the light-irradiated portion is increased by light irradiation or combined use of light irradiation / heat treatment, specifically, a system utilizing a reaction by chemical amplification is preferable, As the base resin, a hydroxyl group of a cellulose derivative such as hydroxypropyl cellulose or hydroxyethyl cellulose, which has been modified with a synthetic ester or blocked with an acetyl group (eg, a cellulose acetate-based compound, etc.); a polymer such as polyvinyl alcohol Alcohols and their derivatives with hydroxyl groups modified or blocked with acetyl groups, etc. (eg, polyvinyl acetate compounds, etc.); Novolak resins such as cresol novolac, hydroxyl groups of polyparahydroxystyrene and their derivatives For example trime Although those blocked or the like is used in Rushiriru group, but is not limited thereto in the present invention of course.

As the photoinitiator, onium salts such as triphenylsulfonium hexafluoroantimonate,
A halogenated organic compound such as trichloromethyltriazine, or naphthoquinonediazide or a derivative thereof is preferably used, but not limited thereto.

Further, the resin layer is formed by spin coating,
A coating method such as mouth coating, bar coating, spray coating, or dip coating can be used and is not particularly limited.

Next, pattern exposure is performed in advance on the coating material of the portion that is not shielded by the black matrix to make the exposed portion ink-philic (FIG. 1C), and a latent image is formed (FIG. 1).
(D)). In FIG. 1D, 25 is an ink repellent portion,
Reference numeral 26 is a parent ink portion. At this time, even if the same material is used, the degree of lyophilic property differs depending on the exposure amount. If the exposure amount is too small, the lyophilic property does not proceed sufficiently, and the relationship of the formula (I) may be satisfied. It will be impossible.

Next, a liquid (hereinafter referred to as a "pretreatment liquid") that dissolves the ink-affinity treated portion, which is applied prior to the ink application, is applied to the ink-philic treatment portion (FIG. 1 (e)). ; In the figure, 27 is the applied pretreatment liquid). The method of applying the pretreatment liquid is not particularly limited,
A dipping method, a ring coating method, a spin method, a bar coating method or the like is used. Moreover, the inkjet method can also be used suitably. The pretreatment liquid is not particularly limited as long as it gives the above performance.
Specifically, ion-exchanged water, alkyl alcohols, glycols, amides, keto alcohols, alkylene glycols, alkyl ethers, polyalkylene glycols, N-methyl-2-pyrrolidone and the like can be mentioned. Further, a mixture of these can also be preferably used, and of course, is not limited to these. Further, a surfactant or the like may be added depending on the desired physical properties.

At this time, in the exposed portion, the amount of hydrophilic groups such as hydroxyl groups, alkoxy groups and amino groups increases with the progress of the reaction, and the ink absorbency is improved.

Then, R, G, B are formed by an ink jet method.
Each color is colored (FIG. 1 (f); in the figure, 28 represents the applied ink), and the ink is dried if necessary. Since the exposed portion has improved ink absorption as described above, it is easy to absorb the pretreatment liquid. Therefore, it is possible to prevent color mixing between colors of ink applied later. In order to cause a substantial difference in the absorbability of the pretreatment liquid, generally, the conversion rate of the functional group capable of being converted into a hydrophilic group is 3 or less.
It is preferably 0% or more. If it is less than 30%, it is difficult to satisfy the relationship of the above formula (I) with the pretreatment liquid used. As a hydrophilic group quantification method in this case, spectral analysis such as IR and NMR is effective. Further, as the photomask 4 at the time of pattern exposure, one having an opening portion for exposing an opening portion which is not shielded by the black matrix 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, it is preferable to use a mask having an opening wider than the light shielding width of the black matrix. preferable. Further, as shown in FIGS. 2A and 2B, it is possible to form a latent image by using the black matrix as it is as a mask and exposing from the back surface.

As the ink used for coloring, it is possible to use both dye-based and pigment-based inks, but in the present invention, the alkaline type is more preferred. Further, as the ink jet method, a bubble jet type using an electrothermal converter as an energy generating element, a piezo jet type using a piezoelectric element, or the like can be used, and a coloring area and a coloring pattern can be arbitrarily set. . Further, in the example shown in FIG. 1, the black matrix is formed on the substrate, but there is no particular problem even if the black matrix is formed on the coating material after forming the coating material or after coloring. However, the form is not limited to the example of this figure. Further, as a method of forming the metal thin film, a method of forming a metal thin film on the substrate by sputtering or vapor deposition and patterning by a photolithography process is general, but not limited to this.

Next, the colored coating material is cured by performing light irradiation, heat treatment or a combination of light irradiation and heat treatment, and a protective layer 29 is formed if necessary (FIG. 1).
(G)). As the protective layer, a photocurable type, a thermosetting type or a photothermal combined type resin material, an inorganic film formed by vapor deposition, sputtering or the like can be used, and has transparency when used as a color filter, After that
Any material that can withstand the TO formation process, the alignment film formation process, etc. can be used.

Next, another embodiment of the method for producing a color filter for liquid crystal according to the present invention will be described with reference to FIGS.

A glass substrate is generally used as the substrate, but the substrate 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. 3A is a diagram showing a glass substrate 1 on which a black matrix 2 is formed.

First, the coating material according to the present invention is applied onto a substrate on which a black matrix is formed, and if necessary, prebaking is performed to increase the ink absorption of the light-irradiated portion by light irradiation or light irradiation and heat treatment. A resin layer (ink receiving layer) 3 is formed (FIG. 3B).

Next, the resin layer in the portion shielded by the black matrix 2 is preliminarily subjected to pattern exposure using the photomask 4 to cure a portion of the resin layer 8 so that it is difficult to absorb ink. An ink repellent portion: a non-colored portion is formed (FIG. 3C), and then a pretreatment liquid capable of dissolving the uncured portion of the resin layer is applied. The applying method is not particularly limited, and a dipping method, a mouth coating method, a spin method, a bar coating method, or the like is used. Also,
The inkjet method can also be used suitably. After that, the same layer is colored with the R, G, and B colors using the inkjet head 5 (FIG. 3D), and the ink is dried as necessary.

As the photomask 4 at the time of pattern exposure, one having an opening for curing the resin composition layer on the light shielding portion by the black matrix is used.
At this time, considering that it is necessary to eject a large amount of ink in order to prevent color loss at the boundary between the black matrix and the colored portion, a mask having an opening narrower than the width of the black matrix (light-shielding width) is used. It is preferable. As the ink used for coloring, it is possible to use both dye-based and pigment-based inks, and also liquid inks and solid inks.

As the curable resin composition used in the present invention, any curable resin composition can be used as long as it has ink receptivity and can be cured by at least one treatment of light irradiation or a combination of light irradiation and heating. Although possible, it is necessary that the above formula (I) is satisfied.

Examples of such a resin include a hydroxyl group,
Acrylic resins containing functional groups such as carboxyl groups, alkoxy groups, amide groups; epoxy resins; silicone resins; cellulose derivatives such as hydroxypropyl cellulose, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose or modified products thereof; novolak resins such as cresol novolac. And their derivatives;
Examples thereof include polyvinylpyrrolidone; polyvinyl alcohol; polyvinyl acetal, etc., but are not particularly limited as long as the above formula (I) is satisfied.

It is also possible to use a crosslinking agent or a photopolymerization initiator in order to promote a crosslinking reaction of these resins by light or light and heat. Melamine derivatives such as methylolated melamine can be used as the crosslinking agent, and dichromates, bisazide compounds, radical initiators, cationic initiators, anionic initiators, etc. can be used as the photopolymerization initiator. Further, a plurality of these photopolymerization initiators may be mixed or used in combination with other sensitizers. Note that heat treatment may be performed after light irradiation in order to accelerate the crosslinking reaction.

Further, depending on the amount of the photopolymerization initiator,
It is possible to adjust the solubility of the uncured portion and the cured portion of the resin layer in the ink used at that time, and generally 0.5 to 10 wt% with respect to the resin used.
%.

The resin layer containing these compositions is very excellent in heat resistance, water resistance and the like, and can sufficiently withstand a high temperature or a washing step in a subsequent step.

Further, with respect to the pretreatment liquid used at that time, the resin layer in the hardened portion and the uncured portion satisfies the above formula (I), so that a high-definition color filter without color mixture and unevenness can be produced. You can

At this time, the solubility in the pretreatment liquid also changes depending on the conditions of light irradiation and heat treatment. That is, the more severe the conditions of light irradiation and heat treatment, the smaller the solubility in the pretreatment liquid.

If the conditions of light irradiation and heat treatment become too mild, the solubility ratio of the resin layer in the cured portion and the uncured portion will deviate from the range of the formula (I), and it will be impossible to obtain sufficient contrast. Become. The liquid that can be used as the pretreatment liquid is as described above.

Dyes and pigments can be preferably used as the colorant of the ink jet ink used as the colorant. Further, a suitable medium for the inkjet ink is a mixed solvent of water and a water-soluble organic solvent, and as the water, ion exchanged water (deionized water) is used instead of general water containing various ions. Is preferred.

Other solvent components that can be used in combination include water-soluble organic solvents that are used by mixing with water, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and n-butyl alcohol. , Sec-butyl alcohol, tert-butyl alcohol, and other alkyl alcohols having 1 to 4 carbon atoms; amides, such as dimethylformamide and dimethylacetamide; ketones and keto alcohols, such as acetone and diacetone alcohol; tetrahydrofuran, dioxane, and the like. Ethers; Polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
The alkylene groups such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol and diethylene glycol have 2 to 2 alkylene groups.
Alkylene glycols containing 6 carbon atoms; glycerin; ethylene glycol monomethyl (or ethyl)
Lower alkyl ethers of polyhydric alcohols such as ether, diethylene glycol methyl (or industrial chill) ether and triethylene glycol monomethyl (or industrial chill) ether; N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3- Examples include dimethyl-2-imidazolidinone. Among these water-soluble organic solvents, polyhydric alcohols such as diethylene glycol, lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether, and N-methyl-2-pyrrolidone are preferable.

In addition to the above components, a surfactant, an antifoaming agent, an antiseptic agent, etc. may be added to the ink liquid for ink jet in order to obtain a liquid having desired physical properties. .

Then, the curable resin composition is cured by performing light irradiation or a combination of light irradiation and heat treatment (see FIG. 3).
(E)), forming the protective layer 6 if necessary (FIG. 3 (f))
I do. The protective layer 6 can be formed by using a second resin composition of a photo-curing type, a thermosetting type, or a photo-thermal combination type, or can be formed by vapor deposition or sputtering using an inorganic material, and can be formed as a color filter. If it is transparent, the subsequent ITO formation process,
Any material can be used as long as it can withstand the alignment film forming process and the like.

FIG. 4 shows a method of manufacturing a color filter used in a liquid crystal panel in which a black matrix is provided on the opposing substrate.

In this case, the method of providing the black matrix not on the color filter side but on the opposing substrate is effective as a method of improving the aperture ratio.

On the glass substrate 1 shown in FIG. 4 (a), a composition whose ink absorptivity in the light-irradiated portion is lowered by light irradiation or a combination of light irradiation and heat treatment is applied, and prebaked if necessary. To form the resin composition layer 3 (see FIG. 4).
(B)).

Then, pattern exposure is performed using the photomask 4 to reduce the ink absorbency of the exposed portion of the composition layer 3 (FIG. 4C), and then a pretreatment liquid is applied. The applying method is as described above.

After that, the unexposed portion is colored with each color of R, G and B by using the ink jet head 5 (FIG. 4 (d)).
Dry if necessary. In this case, in order to prevent color loss, it is important that the width of the non-colored portion 8 is narrower than the width of the black matrix (not shown) provided on the opposing substrate.

Next, the colored resin composition layer is cured by light irradiation or light irradiation and heat treatment (FIG. 4).
(E)), the protective layer 6 is formed if necessary (FIG. 4 (f)).
Then, a color filter is obtained. As the protective layer, a photocurable type, a thermosetting type or a photothermal combined type resin material, an inorganic film formed by vapor deposition, sputtering, or the like can be used, and has transparency when used as a color filter. Any material that can withstand the ITO forming process, the alignment film forming process, etc. can be used.

In this way, the resin layer is provided on the substrate,
A color filter having a plurality of colored portions and non-colored portions whose resin layers are colored with different colors is manufactured.

FIG. 5 shows a TF incorporating a color filter (having a black matrix) according to the present invention.
The sectional view of an example of the T color liquid crystal panel is shown. The mode is not limited to this example. In FIG.
1 is a glass substrate, 2 is a black matrix, 3 is a resin layer, 6 is a protective film layer, 8 is a non-colored portion, 9 is a color filter, 10 is a common electrode, 11 is an alignment film, 12 is a liquid crystal compound, and 13 is a pixel. Electrodes, 14 are glass substrates, 15 are polarizing plates, and 16 is backlight light.

A color liquid crystal panel is generally formed by combining a color filter substrate and a counter substrate and enclosing a liquid crystal compound. TFTs (not shown) and transparent pixel electrodes are formed in a matrix on the inner side of the other substrate of the liquid crystal panel. Also, inside the other board,
A color filter is installed at a position facing the pixel electrode so that RGB color materials are arranged, and a transparent counter electrode is formed on one surface of the color filter. Further, an alignment film is formed in the plane of both substrates, and rubbing the alignment film allows liquid crystal molecules to be aligned in a certain direction. Also,
A polarizing plate is adhered to the outside of each glass substrate, and the liquid crystal compound has a gap (2 to 5) between these glass substrates.
(about μm). As a backlight, a combination of a fluorescent lamp (not shown) and a scattering plate (not shown) is generally used, and a liquid crystal compound is displayed by functioning as an optical shutter for changing the transmittance of the backlight. I do.

Further, as described above, it is possible to manufacture a liquid crystal panel in which a color filter not provided with a black matrix and a substrate provided with a black matrix opposite thereto are arranged so as to face each other. An example of such a liquid crystal panel is shown in FIG.

[0060]

The present invention will be described below in detail with reference to examples.

Preparation Example 1 100 parts by weight of polyparahydroxystyrene having a hydroxyl group protected by a trimethylsilyl group and 3 parts by weight of triphenylsulfonium hexafluoroantimonate were dissolved in 1000 parts by weight of chlorocellosolve acetate and irradiated with light or light. A resin composition in which the ink absorbency of the light-irradiated portion is increased by the combined use of the above and heat treatment was prepared. Example 1 The resin composition obtained in Preparation Example 1 was spin-coated on a silicon substrate to a film thickness of 1 μm, and 1
Prebaking was performed at 00 ° C. for 15 minutes. Then 15
FT-IR after full-surface exposure with an exposure amount of J / cm ²
(Nippon Bunko Kogyo: Micro FTIR-100) is used to measure an infrared absorption spectrum in a reflection mode,
When the amount of hydroxyl groups was compared by comparing with the spectrum before exposure, it was confirmed that the amount increased to 700% before exposure.

In addition, the (solubility of the ink-philic portion) / (solubility of the non-ink-philic portion) of the resin layer in the pretreatment liquid having a composition of ion-exchanged water: ethylene glycol = 50: 50 on a weight basis. The ratio was 12.

Subsequently, the resin composition obtained in Preparation Example 1 was spin-coated on a glass substrate having a black matrix formed thereon so as to have a film thickness of 2 μm, and prebaked at 100 ° C. for 15 minutes.

Then, through a photomask having an opening wider than the width of the black matrix, 1.5 J / cm.
^The resin layer under the opening of the photomask was pattern-exposed with an exposure amount of ² to perform an ink-philic treatment. Further, a pretreatment liquid was applied to the above ink by an inkjet method, and the exposed portion was subjected to R, G, B matrix pattern coloring with a dye ink using an inkjet printer, and then at 90 ° C. The ink was dried for 5 minutes. Subsequently, heat treatment was performed at 200 ° C. for 60 minutes to cure the resin layer.

Further, a two-component thermosetting resin SS-7625 (manufactured by JSR) is formed as a protective layer on the resin layer to a film thickness of 1 μm.
Was spin-coated so as to obtain a heat treatment at 230 ° C. for 1 hour to be cured.

When the color filter for liquid crystal thus produced was observed with an optical microscope, no troubles such as color mixture, color unevenness and color loss were observed.

Example 2 The resin composition obtained in Preparation Example 1 was spin-coated on a silicon substrate to a film thickness of 1 μm, and prebaked at 100 ° C. for 15 minutes.
Then, after performing whole surface exposure with an exposure amount of 15 J / cm ² , heat treatment was performed on a hot plate at 150 ° C. for 1 minute, and the amount of hydroxyl groups before and after exposure and heating was compared in the same manner as in Example 1. However, it was confirmed that after the exposure, it increased to 800% before the exposure.

The ratio of (solubility of ink-philic portion) / (solubility of non-ink-philic portion) of the resin layer to the pretreatment liquid described in Example 1 was 18.

Next, the resin composition obtained in Preparation Example 1 was spin-coated on a glass substrate on which a black matrix had been formed so as to have a film thickness of 2 μm, and prebaked at 100 ° C. for 15 minutes to form a resin composition layer. Was formed.

Next, through a photomask having an opening wider than the width of the black matrix, 1.5 J / c
The resin layer under the opening of the photomask is pattern-exposed with an exposure amount of m ² , and further on a hot plate at 150 ° C. for 1
PEB for 1 minute was performed to perform ink-philic treatment.

Further, the pretreatment liquid described in Example 1 was applied using an ink jet printer, and the exposed areas were subjected to R, G and B matrix pattern coloring with dye ink using an ink jet printer. 9
The ink was dried at 0 ° C. for 5 minutes. 200 continuously
The resin layer was cured by heat treatment at 1 ° C. for 1 hour.

Further, a two-component thermosetting resin SS-7625 (manufactured by JSR) is formed as a protective layer on the resin layer to a film thickness of 1 μm.
Was spin-coated so as to obtain a heat treatment at 230 ° C. for 1 hour to be cured.

When the color filter for liquid crystal thus produced was observed with an optical microscope, no troubles such as color mixture, color unevenness and color loss were observed.

(Embodiment 3) The black matrix is used as it is as a photomask without using a photomask.
A color filter was produced in the same manner as in Example 2 except that the back surface of the substrate, that is, the side where the resin composition layer does not exist was exposed.

When the color filter for liquid crystal thus produced was observed with an optical microscope, no troubles such as color mixing, color unevenness and color loss were observed.

Preparation Example 2 100 parts by weight of cellulose triacetate, 1-naphthyl-bis-
1.5 parts by weight of trichloromethyl-S-triazine was dissolved in 1200 parts by weight of chloroform to prepare a resin composition in which the ink absorbability of the light-irradiated portion was increased by light irradiation or light irradiation and heat treatment.

(Example 4) Using the resin composition obtained in Preparation Example 2, the entire surface was exposed in the same manner as in Example 1, the infrared absorption spectrum was measured, and the infrared absorption spectrum was compared with that before exposure. When comparing the amount of hydroxyl groups,
It was confirmed that the amount increased to 500% before exposure.

The ratio of (solubility of ink-philic portion) / (solubility of non-ink-philic portion) of the resin layer to the pretreatment liquid having the following composition was 8.

Diethylene glycol 30 parts by weight N-methyl-2-pyrrolidone 30 parts by weight Isopropyl alcohol 10 parts by weight Ion-exchanged water 30 parts by weight Subsequently, on a glass substrate on which a black matrix was formed, the resin obtained in Preparation Example 2 was obtained. The composition has a film thickness of 2 μm
Roll coating was performed so that the pre-baking was performed at 90 ° C. for 20 minutes.

Then, through a photomask having an opening wider than the width of the black matrix, the resin layer under the opening of the photomask is pattern-exposed with an exposure amount of 1 J / cm ² , and an ink-philic treatment is performed. Was done. further,
A pretreatment liquid is applied to the above ink by an inkjet method, and the exposed portion is subjected to R, G, B matrix pattern coloring with a dye ink using an inkjet printer, and then at 90 ° C. for 5 minutes. The ink was dried. Subsequently, heat treatment was performed at 200 ° C. for 60 minutes to cure the resin layer.

Further, a two-component thermosetting resin SS-7625 (manufactured by JSR) is formed on the resin layer as a protective layer to a film thickness of 1 μm.
Was spin-coated so as to obtain a heat treatment at 230 ° C. for 1 hour to be cured.

When the color filter for liquid crystal thus produced was observed with an optical microscope, no problems such as color mixing, color unevenness, and color loss were observed.

(Example 5) Using the resin composition obtained in Preparation Example 2, the entire surface was exposed in the same manner as in Example 2 and the infrared absorption spectrum was measured to compare the amount of hydroxyl groups before and after exposure and heating. After exposure, 600
It has been confirmed that the percentage has increased to%.

The ratio of (solubility of ink-philic portion) / (solubility of non-ink-philic portion) of the resin layer to the pretreatment liquid was 9.

Then, the resin composition obtained in Preparation Example 2 was roll-coated on a glass substrate on which a black matrix had been formed so as to have a film thickness of 2 μm, and the resin composition was dried at 90 ° C. for 2 hours.
Pre-baking was performed for 0 minutes to form a resin composition layer.

Next, through a photomask having an opening wider than the width of the black matrix, the resin layer under the opening of the photomask was pattern-exposed with an exposure dose of 1 J / cm ² , and further on a hot plate. At 150 ° C,
PEB was carried out for 1 minute to carry out an ink-philic treatment. Further, a pretreatment liquid is applied to the above ink by an inkjet method, and R, G, B by the above pigment ink is further applied to an exposed portion by using an inkjet printer.
After performing the matrix pattern coloring of, the ink was dried at 90 ° C. for 5 minutes. After performing the whole surface exposure,
A heat treatment was performed at 200 ° C. for 1 hour to cure the resin layer.

Further, a two-component thermosetting resin SS-7625 (manufactured by JSR) is formed as a protective layer on the resin layer to a film thickness of 1 μm.
Was spin-coated so as to obtain a heat treatment at 230 ° C. for 1 hour to be cured.

When the color filter for liquid crystal thus produced was observed with an optical microscope, no troubles such as color mixing, color unevenness and color loss were observed.

Example 6 The black matrix was used as it was as a photomask without using a photomask.
A color filter was produced in the same manner as in Example 5 except that the back surface of the substrate, that is, the side where the resin composition layer does not exist was exposed.

When the color filter for liquid crystal thus produced was observed with an optical microscope, no troubles such as color mixing, color unevenness and color loss were observed.

Comparative Example 1 A liquid crystal filter was prepared in the same manner as in Example 1 except that the exposure amount was 10 mJ / cm ² . The infrared absorption spectrum was measured in the same manner as in Example 1 and the amount of hydroxyl groups before and after exposure / heating was compared. As a result, it was confirmed that the amount after exposure increased to 200% before exposure.

The ratio of (solubility of ink-philic portion) / (non-ink-philic portion) of the resin layer to the pretreatment liquid was 3.

When the color filter for liquid crystal thus produced was observed with an optical microscope, the contrast between the exposed area and the unexposed area was not sufficient, and defects such as color mixing and color unevenness were recognized.

Example 7 As shown in FIG. 3, (1) was formed on the glass substrate 1 on which the black matrix 2 was formed.
100 parts by weight of a terpolymer of N-methylol acrylamide, methyl methacrylate and hydroxyethyl methacrylate (charge ratio 20:45:35) and (2) triphenylsulfonium triflate (Midori Kagaku: T
PS-105) containing 2 parts by weight of a composition having a film thickness of 15 μm
Then, spin coating was performed so as to have a thickness of m and bribaking was performed at 70 ° C. for 15 minutes to form a photocurable resin layer 3.

Next, a part of the resin layer on the black matrix is deep-cut to 100 mJ / cm ² through a photomask having an opening narrower than the width of the black matrix.
The pattern was exposed to UV light and cured.

Next, an ink-jet head is used to apply the pretreatment liquid to the uncured portion, and the ink-jet head 5 is used to color the R, G, and B matrix patterns with the dye ink, and then at 90 ° C. for 5 minutes. The ink was dried. Then, subsequently, heat treatment was performed at 230 ° C. for 30 minutes to cure the resin layer 3.

The compositions of the pretreatment liquid and the ink used are as follows. Pretreatment liquid Ion-exchanged water 50 parts by weight Ethylene glycol 50 parts by weight R ink dye: CIAcid Red 118 5 parts by weight N-methyl-2-pyrrolidone 10 parts by weight Engineering ethylene glycol 20 parts by weight Ion-exchanged water 65 parts by weight G ink dye = CIAcid Green 25 5 parts by weight N-methyl-2-pyrrolidone 10 parts by weight Engineering ethylene glycol 20 parts by weight Ion-exchanged water 65 parts by weight B Ink dye: CIAcid Blue 113 5 parts by weight N-methyl-2-pyrrolidone 10 parts by weight Engineering ethylene Glycol 20 parts by weight Ion-exchanged water 65 parts by weight The solubility of the resin layer in the uncured part in the pretreatment liquid having the above composition is 0.20 g / ml at room temperature and D of 100 mJ / cm ²
The solubility of the resin layer in the cured part cured by eep UV light was 0.02 g / ml at room temperature. That is, the ratio of (solubility of uncured portion of resin layer) / (solubility of cured portion of resin layer) is 10.

On the resin layer 3 colored in this way,
A photocurable resin composition comprising a modified epoxy acrylate and a photopolymerization initiator was spin-coated to a film thickness of 1 μm, and prebaked at 90 ° C. for 30 minutes to form a protective layer 6. Next, by exposing the entire surface to cure the protective layer 6, a color filter for liquid crystal was produced.

When the color filter for liquid crystal thus produced was observed with an optical microscope, no troubles such as color mixing, color unevenness and color loss were observed.

When a liquid crystal panel as shown in FIG. 5 was produced using this color filter and driven, high-definition color display was possible.

Example 8 On the resin layer 3 obtained in Example 7, a two-pack type epoxy acrylate-based thermosetting resin composition was applied by a mouth coating so as to have a film thickness of 1 μm, and 90
Pre-baking was performed at 30 ° C. for 30 minutes to form the protective layer 6. Then, heat treatment was performed at 230 ° C. for 30 minutes to cure the protective layer 6, thereby producing a color filter for liquid crystal. When the color filter for liquid crystal thus produced was observed with an optical microscope, no problems such as color mixture, color unevenness, and color loss were observed.

When a liquid crystal panel as shown in FIG. 5 was produced using this color filter and driven, high-definition color display was possible.

Example 9 On the resin layer 3 obtained in Example 7, a photocurable resin composition comprising a bisphenol A type epoxy resin and a cationic photopolymerization initiator was spun to a film thickness of 1 μm. The coated layer was prebaked at 90 ° C. for 30 minutes to form the protective layer 6. Next, after exposing the entire surface, a heat treatment was carried out at 230 ° C. for 30 minutes to completely cure the protective layer 6, thereby producing a color filter for liquid crystal.

When the color filter for liquid crystal thus produced was observed with an optical microscope, no troubles such as color mixing, color unevenness and color loss were observed.

When a liquid crystal panel as shown in FIG. 5 was produced using this color filter and driven, high-definition color display was possible.

(Embodiment 10) On the resin layer 3 colored according to Embodiment 7, a Si ₂ film (protective layer 6) is formed by sputtering.
Was formed to have a film thickness of 0.5 μm, and a color filter for liquid crystal was produced.

When the color filter for liquid crystal thus produced was observed with an optical microscope, no troubles such as color mixing, color unevenness and color loss were observed.

When a liquid crystal panel as shown in FIG. 5 was produced using this color filter and was driven, high-definition color display was possible.

(Example 11) Resin layer 3 was prepared by using (1) 100 parts by weight of hydroxypropyl cellulose, (2) 150 parts by weight of trimethylolmelamine, and (3) triphenylsulfonium triflate (manufactured by Midori Kagaku: TPS).
-105) A liquid crystal color filter was produced in the same manner as in Example 7 except that the composition was 2 parts by weight.

At this time, the solubility of the uncured resin layer in the pretreatment liquid was 0.6 g / ml and 100 mJ / c at room temperature.
The solubility of the resin layer in the cured part cured with Deep UV light of m ² was 0.05 g / ml at room temperature. That is,
The ratio of (solubility of uncured portion of resin layer) / (solubility of cured portion of resin layer) is 12.

When the color filter for liquid crystal thus produced was observed with an optical microscope, no troubles such as color mixing, color unevenness and color loss were observed.

When a liquid crystal panel as shown in FIG. 5 was produced using this color filter and was driven, high-definition color display was possible.

Example 12 A liquid crystal color filter was produced in the same manner as in Example 7 except that the composition of the pretreatment liquid was changed as follows. Composition of pretreatment liquid Diethylene glycol 30 parts by weight N-methyl-2-pyrrolidone 30 parts by weight Isopropyl alcohol 10 parts by weight Ion-exchanged water 30 parts by weight Solubility of the resin layer in the uncured part in the pretreatment liquid having the above composition is 0 at room temperature. 0.8 g / ml, 100 mJ / cm ² De
The solubility of the resin layer in the cured portion cured with ep UV light was 0.1 g / ml at room temperature. That is, the ratio of (solubility of uncured portion of resin layer) / (solubility of cured portion of resin layer) is 8.

When the color filter for liquid crystal thus produced was observed with an optical microscope, no troubles such as color mixture, color unevenness and color loss were observed.

When a liquid crystal panel as shown in FIG. 5 was produced using this color filter and driven, high-definition color display was possible.

Example 13 The composition of Example 7 was applied onto a glass substrate 1 to form a resin composition layer 3 as shown in FIG. Next, pattern exposure was performed from the resin layer 3 side using the photomask 4 to reduce the resin ink absorbency of the exposed portion. Furthermore, after the R, G, and B matrix patterns were colored in the unexposed portions with the same dye ink as in Example 7 using the inkjet head 5, heat treatment was performed under the same conditions as in Example 7.

Further, the protective layer 6 was formed in the same manner as in Example 8 to prepare a color filter for liquid crystal.

When the color filter for liquid crystal thus produced was observed with an optical microscope, no troubles such as color mixing, color unevenness and color loss were observed.

When a liquid crystal panel as shown in FIG. 6 was produced using this color filter and driven, high-definition color display was possible.

(Comparative Example 2) The negative part of the resin layer on the black matrix was 5 mJ / cm ² deep through a photomask having an opening narrower than the width of the black matrix.
A color filter for liquid crystals was produced in the same manner as in Example 7 except that the pattern exposure was performed with UV light and the curing was performed.

At this time, the solubility of the uncured resin layer in the pretreatment liquid was 0.20 g / ml and 5 mJ / cm at room temperature.
The solubility of the resin layer in the cured part cured with Deep UV light of No. ² was 0.1 g / ml at room temperature. That is, the ratio of (solubility of uncured portion of resin layer) / (solubility of cured portion of resin layer) is 2.

When the color filter for liquid crystal thus produced was observed with an optical microscope, problems such as color mixing and color unevenness were recognized.

[0123]

As described above, according to the present invention, a highly reliable color filter having no trouble such as color mixture, color unevenness, and color loss can be manufactured in a short process at low cost, and a highly reliable liquid crystal panel. Can be obtained.

[Brief description of the drawings]

FIG. 1 is a method 1 for manufacturing a color filter for liquid crystal according to the present invention.
It is a process drawing showing an embodiment.

FIG. 2 is a diagram showing an alternative method of steps (c) and (d) of the manufacturing method of the present invention shown in FIG.

FIG. 3 is a process drawing showing another embodiment of the method for manufacturing a color filter for liquid crystal of the present invention.

FIG. 4 is a process drawing showing still another embodiment of the method for manufacturing a color filter for liquid crystal of the present invention.

FIG. 5 is a schematic cross-sectional view of an example of a liquid crystal panel manufactured using the color filter of the present invention.

FIG. 6 is a schematic cross-sectional view of another example of a liquid crystal panel manufactured using the color filter of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Black matrix 3 Resin composition layer 4 Photomask 5 Inkjet head 6 Protective layer 7 Light transmitting part 8 Non-colored part 9 Color filter 10 Common electrode 11 Alignment film 12 Liquid crystal compound 13 Pixel electrode 14 Glass substrate 15 Polarizing plate 16 Back Light light 25 Ink-repellent portion 26 Ink-philic portion 27 Pre-treatment liquid applied 28 Ink applied 29 Protective film

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akinori Shiota 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (16)

[Claims] 1. A method for manufacturing a color filter for liquid crystal, which comprises a step of arranging colored portions of red (R), green (G) and blue (B) on a substrate, (1) Forming an ink receiving layer, (2) applying a liquid capable of dissolving the receiving layer (referred to as a pretreatment liquid) to a portion of the ink receiving layer to be the colored portion, and (3) the ink A method for producing a color filter for liquid crystal, comprising a step of applying an ink of a predetermined color to a predetermined portion of a receiving layer. 2. The manufacturing method according to claim 1, wherein the ink application is performed by an inkjet method. 3. The ink receptive layer is provided with an ink repellent portion having a relatively high ink absorbency and an ink repellent portion having a relatively low ink absorbency, and the ink receptive portion is colored. Manufacturing method. 4. The manufacturing method according to claim 3, wherein the solubility of the ink receiving layer in the pretreatment liquid is related to the following formula (I). ## EQU1 ## (Solubility of ink-philic portion) / (Solubility of ink-repellent portion)> 5 ... (I) 5. (1) An ink receiving layer is formed by forming a resin composition layer on a substrate, the resin composition layer of which is capable of changing the ink absorbability of the light-irradiated portion by light irradiation or light irradiation and heat treatment.
(2) A predetermined portion of the ink receiving layer formed on a substrate is pattern-exposed to change the ink absorbency of the exposed portion of the receiving layer to form a lyophilic portion and an ink repellent portion. Item 5. The method for producing a color filter for liquid crystal according to any one of Items 2 to 4, which comprises a step of curing the colored ink receiving layer by light irradiation and / or heat treatment. 6. A black matrix is provided on the substrate before the ink receiving layer is formed, and the ink receiving layer portion on the black matrix is made an ink repellent portion by pattern exposure after forming the resin composition layer. The manufacturing method according to claim 5. 7. The manufacturing method according to claim 6, wherein the width of the ink repellent portion formed on the ink receiving layer on the black matrix is smaller than the width of the black matrix. 8. The manufacturing method according to claim 5, wherein the pattern exposure exposes a portion of the ink receiving layer to be colored so that the ink absorbency of the portion is relatively high. 9. The manufacturing method according to claim 5, wherein the pattern exposure exposes a non-colored portion of the ink receiving layer to make ink absorption of the portion relatively low. 10. The method according to claim 5, wherein the inorganic film layer is formed on the cured ink receiving layer by any one of vapor deposition and sputtering. 11. The method according to claim 5, wherein a curable second resin composition layer is formed on the cured ink receiving layer, and the second resin composition layer is cured. Method. 12. The method according to claim 11, wherein the curable second resin composition layer is a resin composition layer curable by light irradiation and is cured by light irradiation. 13. The method according to claim 11, wherein the curable second resin composition layer is a resin composition layer curable by heat treatment, and is cured by heat treatment. 14. The curable second resin composition layer is a resin composition layer curable by combined use of light irradiation and heat treatment, and is cured by combined use of light irradiation and heat treatment. Production method. 15. A color filter for liquid crystal manufactured by the method according to claim 1. 16. A liquid crystal panel comprising a color filter according to claim 15 and a substrate facing the filter, wherein a liquid crystal compound is sealed between both substrates.