JP3342242B2 - Liquid crystal color filter, method of manufacturing the same, and liquid crystal panel - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a color filter for a color liquid crystal display used in a color television, a personal computer, a pachinko game console, an automobile navigation system, a small television, and the like, and more particularly, to a liquid crystal using an ink jet recording technique. The present invention relates to a method for producing a color filter for use. The present invention also relates to a coating material for producing a liquid crystal color filter using an ink jet recording technique, and a method for manufacturing a liquid crystal color filter using the coating material. In addition, the present invention relates to a color filter for liquid crystal manufactured by using an ink jet method and a liquid crystal panel having 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 in particular, there is an increasing demand for cost reduction of color filters having a large weight 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.

[0004] The first method most frequently used is a dyeing method. In the dyeing method, first, a layer of a water-soluble polymer material, which is a material for dyeing, is formed on a glass substrate, and this is patterned into a desired shape by a photolithography process, and the obtained pattern is immersed 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[0005] The second method is a pigment dispersion method, which has recently been replaced by a dyeing method.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. This process is further repeated three times to form R, G, 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 was repeated three times to form R, G, B color filter layers. Finally, it is fired.

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

[0008]

However, the common feature of these methods is that the same process must be repeated three times to color the three colors of R, G, and B, which increases the 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.

In order to make up for these drawbacks, Japanese Patent Application Laid-Open No.
-75205, JP-A-63-235901, JP-A-1-
Although there is a proposal in 217320 etc., it is still insufficient.

Therefore, an object of the present invention is to solve the problems of the conventional methods and to provide a highly reliable color filter which satisfies the required characteristics in heat resistance, solvent resistance, resolution and the like in a short process at low cost. And a highly reliable color filter and liquid crystal panel. In particular, it is an object of the present invention to provide a method of manufacturing an excellent color filter for liquid crystal, which does not cause color mixing and color omission when forming a colored portion with a dye ink by an inkjet method.

[0011]

According to the present invention, there is provided a method of manufacturing a color filter for liquid crystal, comprising the step of arranging red (R), green (G) and blue (B) colored portions on a substrate. (1) forming an ink receiving layer on the substrate; and (2) applying a liquid capable of dissolving the receiving layer (referred to as a pretreatment liquid) to a portion of the ink receiving layer that is to be the colored portion. And (3) a method for producing a color filter for liquid crystal, comprising: (3) applying a predetermined color ink 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.

Preferably, the ink receiving layer is provided with a parent ink portion having a relatively high ink absorbency and an ink repellent portion having a relatively low ink absorbency, and the parent ink portion is colored.

Further, in the above manufacturing method, (1) an ink receiving layer is formed by forming a resin composition layer on the substrate whose light absorbability can be changed by light irradiation or light irradiation and heat treatment. (2) pattern-exposing a predetermined portion of the ink receiving layer formed on the substrate to change the ink absorbency of the exposed portion of the receiving layer to form a parent ink portion and an ink-repellent portion; Preferably, the method further comprises (3) a step of curing the colored ink receiving layer by light irradiation and / or heat treatment.

In this case, the pattern exposure is performed by exposing a portion of the ink receiving layer to be colored to relatively increase the ink absorbency of the portion; or by exposing a non-colored portion of the ink receiving layer to light. There may be a method of relatively lowering the ink absorbency of the portion.

The present invention also provides a color filter for liquid crystal manufactured by the above manufacturing method, and a liquid crystal panel having the color filter and a substrate facing the filter, and having a liquid crystal compound sealed between the two substrates. Things.

[0017]

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

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

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

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

The present invention is intended to prevent color mixing of ink and unnecessary diffusion of ink by utilizing the difference in ink absorbency between exposed and unexposed areas of the resin composition layer. As the material, a resin composition that increases the ink absorbency of the exposed part by exposure or combined exposure / heat treatment is used. At this time, as the material of the resin composition, in the portion which is not made into the ink-philic portion,
It is only necessary that the solubility in a liquid for dissolving the ink receiving layer applied to the parent ink portion in the process described later satisfies the relationship of the following formula (I). In the following, a portion having a relatively high ink absorbency in the ink receiving layer is referred to as a parent ink portion, and a portion having a relatively low ink absorbency is referred to as an ink repellent portion.

[0022]

(Solubility of the parent ink portion) / (solubility of the ink repellent portion)> 5 (I) In this case, the solubility may be measured in an atmosphere at a temperature of 23 ° C. and a humidity of 55%. 10ml in a container of size
Is injected, and a small amount of the resin composition (solid content: 100%) is introduced. Thereafter, the mixture is stirred for 6 hours with a mix rotor, and visually observed to confirm that there is no residual dissolved substance. If not, charge them little by little, and confirm the presence of residual dissolved matter by visual observation in the same manner.
Assuming that the input amount at the time when the residual dissolved matter is generated is A (mg), the solubility is A (mg) / 10 ml.

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

As a composition example of the coating material used in the present invention, which increases the ink absorbency of the light-irradiated portion by light irradiation or combined light irradiation / heat treatment, specifically, a system utilizing a reaction by chemical amplification is preferable. Examples of the base resin include those in which hydroxyl groups of cellulose derivatives such as hydroxypropylcellulose and hydroxyethylcellulose are esterified or blocked with acetyl groups (eg, cellulose acetate-based compounds); polymers such as polyvinyl alcohol Hydroxyl groups of alcohols and their derivatives in which the hydroxyl groups have been modified or blocked with acetyl groups (eg, polyvinyl acetate compounds); novolak resins such as cresol novolak, and hydroxyl groups of polyparahydroxystyrene and their derivatives The trimming for example Although those blocked or the like is used in Rushiriru group, but is not limited thereto in the present invention of course.

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

The resin layer is formed by spin coating,
Coating methods such as mouth coating, bar coating, spray coating, and dip coating can be used, and are not particularly limited.

Next, by subjecting the coating material in a portion not shaded by the black matrix to pattern exposure in advance, the exposed portion is made to be ink-philic (FIG. 1C), and a latent image is formed (FIG. 1C).
(D)). In FIG. 1D, 25 is an ink-repellent portion,
Reference numeral 26 denotes a parent ink portion. In this case, depending on the exposure amount, the degree of ink-affinity is different even for the same material. If the exposure amount is too small, the ink-inphilicity does not proceed sufficiently, and the relationship of the above formula (I) may be satisfied. Becomes impossible.

Next, a liquid (hereinafter, referred to as a "pretreatment liquid") for dissolving the ink-affected portion, which is applied prior to the ink application, is applied to the ink-affected 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 mouth coating method, a spin method, a bar coating method and the like are used. In addition, an inkjet method can also be suitably used. The pretreatment liquid is not particularly limited as long as it gives the above-mentioned performance.
Specific examples include ion-exchanged water, alkyl alcohols, glycols, amides, keto alcohols, alkylene glycols, alkyl ethers, polyalkylene glycols, and N-methyl-2-pyrrolidone. Also, a mixture of these can be suitably used, and, of course, is not limited thereto. Further, a surfactant or the like may be added depending on desired physical properties.

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

Subsequently, R, G, B are formed by the ink jet method.
(FIG. 1 (f); in the figure) 28 represents the applied ink), and ink drying is performed as necessary. Since the exposed portion has improved ink absorbency as described above, the exposed portion easily absorbs the pretreatment liquid. Therefore, it is possible to prevent color mixture between colors of ink applied later. In order to cause a substantial difference in the absorbency of the pretreatment liquid, generally, the conversion of a functional group that can be converted to a hydrophilic group is 3%.
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 respect to the pretreatment liquid used. As a method for quantifying the hydrophilic group in this case, spectrum analysis such as IR and NMR is effective. Further, as the photomask 4 at the time of pattern exposure, a photomask having an opening for exposing an opening that is not shaded by the black matrix is used.
At this time, in order to prevent color loss at a portion in contact with the black matrix, it is necessary to use a mask having an opening wider than the light shielding width of the black matrix, considering that it is necessary to discharge a large amount of ink. preferable. Further, as shown in FIGS. 2A and 2B, it is also 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, both a dye-based ink and a pigment-based ink can be used, but in the case of the present invention, an alkali-type ink is more preferable. 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. . In the example shown in FIG. 1, a black matrix is formed on the substrate. However, even if the black matrix is formed on the coating material after forming the coating material or after coloring, there is no particular problem. However, the form is not limited to the example shown in FIG. In addition, as a forming method, a method of forming a metal thin film on a substrate by sputtering or vapor deposition and patterning by a photolithography process is generally used, but is not limited thereto.

Next, the colored coating material is cured by light irradiation, heat treatment, or a combination of light irradiation and heat treatment, and a protective layer 29 is formed as necessary (FIG. 1).
(G)). As the protective layer, a photo-curable type, a thermo-curable type or a combination of light and heat 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, Then I
Any material that can withstand the TO forming process, the alignment film forming process, or the like can be used.

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

Although a glass substrate is generally used as the substrate, it is not limited to a glass substrate as long as it has necessary characteristics such as transparency and mechanical strength as a color filter for liquid crystal. FIG. 3A is a diagram illustrating a glass substrate 1 on which a black matrix 2 is formed.

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

Next, a portion of the resin layer, which is shielded from light by the black matrix 2, is subjected to pattern exposure in advance using the photomask 4 to cure a portion of the resin layer and hardly 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 method of applying 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,
An inkjet method can also be suitably used. Thereafter, the same layer is colored with each of R, G, and B using the inkjet head 5 (FIG. 3D), and the ink is dried if necessary.

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

As the curable resin composition used in the present invention, any resin composition which has an ink receiving property and can be cured by at least one of light irradiation or a combination of light irradiation and heating can be used. It is possible, but it is necessary that the above formula (I) is satisfied.

Examples of such a resin include a hydroxyl group,
Acrylic resin containing a functional group such as a carboxyl group, an alkoxy group, or an amide group; an epoxy resin; a silicone resin; a cellulose derivative or a modified product thereof such as hydroxypropylcellulose, hydroxyethylcellulose, methylcellulose, and carboxymethylcellulose; a novolak resin such as cresol novolak And their derivatives;
Examples thereof include polyvinyl pyrrolidone; polyvinyl alcohol; polyvinyl acetal, and the like, 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 to cause these resins to undergo a crosslinking reaction by light or light and heat. Melamine derivatives such as methylolated melamine can be used as a crosslinking agent, and dichromates, bisazide compounds, radical initiators, cationic initiators, anionic initiators, and the like can be used as photopolymerization initiators. These photopolymerization initiators can be used as a mixture of a plurality of them or in combination with other sensitizers. Note that heat treatment may be performed after light irradiation in order to promote a crosslinking reaction.

Also, 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.
%.

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

Further, a high-definition color filter free from color mixing and unevenness can be produced by satisfying the above-mentioned formula (I) in the resin layer of the cured portion and the uncured portion with respect to the pretreatment liquid used at that time. Can be.

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 lower the solubility in the pretreatment liquid.

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

Dyes and pigments can be suitably used as coloring materials for ink-jet inks used as coloring agents. Further, a preferable medium of the ink for ink jet is a mixed solvent of water and a water-soluble organic solvent. In the case of 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 are water-soluble organic solvents 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 and dioxane Ethers; polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Alkylene groups such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, and diethylene glycol;
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 tert-yl) ether, triethylene glycol monomethyl (or tert-yl) ether; N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3- Dimethyl-2-imidazolidinone and the like. 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-mentioned components, a surfactant, an antifoaming agent, a preservative, and the like can be added to the ink liquid for inkjet, if necessary, in order to obtain a liquid having desired physical properties. .

Next, the curable resin composition is cured by performing light irradiation or a combination of light irradiation and heat treatment (FIG. 3).
(E)), if necessary, forming a protective layer 6 (FIG. 3 (f))
I do. The protective layer 6 can be formed by using a second resin composition of a photo-curing type, a thermo-setting type, or a combination of light and heat, or can be formed by vapor deposition or sputtering using an inorganic material. With transparency in the case of doing, the subsequent ITO formation process,
Any material that can sufficiently withstand the alignment film forming process or the like can be used.

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

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

On the glass substrate 1 shown in FIG. 4A, a composition that reduces the ink absorbability of the light-irradiated portion by light irradiation or a combination of light irradiation and heat treatment is applied, and prebaking is performed as necessary. To form a resin composition layer 3 (FIG. 4).
(B)).

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

Thereafter, the unexposed portion is colored with each of R, G, and B using the ink jet head 5 (FIG. 4D).
Dry if necessary. In this case, in order to prevent color omission, it is important that the width of the non-colored portion 8 is smaller than the width of a 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)), if necessary, forming a protective layer 6 (FIG. 4 (f))
Then, a color filter is obtained. As the protective layer, a photocurable type, a thermosetting type or a photocurable 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 can be used as long as it can withstand the ITO forming process, the alignment film forming process, and the like.

Thus, the resin layer is provided on the substrate,
A color filter having a plurality of colored portions and non-colored portions in which the resin layer is colored with different colors is manufactured.

FIG. 5 shows a TF incorporating a color filter (having a black matrix) according to the present invention.
1 shows a cross-sectional view of one example of a T-color liquid crystal panel. 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. The electrode, 14 is a glass substrate, 15 is a polarizing plate, and 16 is backlight.

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 inside of the negative substrate of the liquid crystal panel. Also, inside the other board,
A color filter is provided so that RGB color materials are arranged at positions facing the pixel electrodes, and a transparent counter electrode is formed on one surface thereof. 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 is placed between the glass substrates (2 to 5).
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 also possible to manufacture a liquid crystal panel formed by arranging a color filter having no black matrix and a substrate having a black matrix facing the color filter. FIG. 6 shows an example of such a liquid crystal panel.

[0060]

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

Preparation Example 1 100 parts by weight of polyparahydroxystyrene protected with a hydroxyl group by a trimethylsilyl group and 3 parts by weight of triphenylsulfonium hexafluoroantimonate were dissolved in 1000 parts by weight of tylcellosolve acetate to give light irradiation or light irradiation. And a heat treatment were used to prepare a resin composition in which the ink absorbability of the light-irradiated portion was increased. Example 1 The resin composition obtained in Preparation Example 1 was spin-coated on a silicon substrate so as to have a thickness of 1 μm.
Prebaking was performed at 00 ° C. for 15 minutes. Then 15
After performing overall exposure with an exposure amount of J / cm ² , FT-IR
(Nihon Bunko Kogyo: Micro FTIR-100) was used to measure the infrared absorption spectrum in the reflection mode,
When the amount of hydroxyl groups was compared by comparing with the spectrum before exposure, it was confirmed that the amount was increased to 700% before exposure.

The ratio of (solubility of ink-affinized portion) / (solubility of non-ink-affected portion) of the resin layer to a 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 on which a black matrix was formed so as to have a thickness of 2 μm, and prebaked at 100 ° C. for 15 minutes.

Then, 1.5 J / cm 2 was applied through a photomask having an opening wider than the width of the black matrix.
^With the exposure amount of ² , the resin layer under the opening portion of the photomask was subjected to pattern exposure, and an ink-philic treatment was performed. Further, a pretreatment liquid is applied to the above-mentioned ink by an ink-jet method, and R, G, and B matrix pattern coloring with a dye ink is performed on an exposed portion using an ink-jet printer. 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-part thermosetting resin SS-7625 (manufactured by JSR) as a protective layer was formed on the resin layer to a thickness of 1 μm.
Then, heat treatment was performed at 230 ° C. for 1 hour to cure the composition.

Observation of the thus prepared liquid crystal color filter with an optical microscope showed no problems such as color mixing, color unevenness, and color omission.

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

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

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

Then, 1.5 J / c is applied through a photomask having an opening wider than the width of the black matrix.
The resin layer under the opening of the photomask at an exposure amount of m ² to pattern exposure, further on a hot plate 0.99 ° C., 1
For a minute, PEB was performed, and an ink-philic conversion process was performed.

Further, the pretreatment liquid described in Example 1 was applied using an ink jet printer, and R, G, B matrix pattern coloring was performed on the exposed portion with a dye ink using an ink jet printer. 9
The ink was dried at 0 ° C. for 5 minutes. Continue 200
The resin layer was cured by performing heat treatment at a temperature of 1 ° C. for 1 hour.

Further, a two-part thermosetting resin SS-7625 (manufactured by JSR) as a protective layer on the resin layer is 1 μm thick.
Then, heat treatment was performed at 230 ° C. for 1 hour to cure the composition.

Observation of the thus prepared color filter for liquid crystal with an optical microscope showed no problems such as color mixing, color unevenness, and color omission.

(Embodiment 3) A black matrix is used as a photomask without using a photomask.
A color filter was prepared in the same manner as in Example 2, except that exposure was performed from the back surface of the substrate, that is, from the side where no resin composition layer was present.

Observation of the thus prepared color filter for liquid crystal with an optical microscope showed no problems such as color mixing, color unevenness, and color omission.

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, and the infrared absorption spectrum was measured and compared with the spectrum before exposure. When comparing the amount of hydroxyl groups,
It was confirmed that it increased to 500% before exposure.

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

30 parts by weight of diethylene glycol 30 parts by weight of N-methyl-2-pyrrolidone 30 parts by weight of isopropyl alcohol 30 parts by weight of ion-exchanged water Subsequently, the resin obtained in Preparation Example 2 was placed on a glass substrate on which a black matrix was formed. The composition was applied to a thickness of 2 μm.
Then, roll coating was performed and prebaking was performed at 90 ° C. for 20 minutes.

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

Further, a two-part type thermosetting resin SS-7625 (manufactured by JSR) as a protective layer was formed on the resin layer to a thickness of 1 μm.
Then, heat treatment was performed at 230 ° C. for 1 hour to cure the composition.

Observation of the thus prepared liquid crystal color filter with an optical microscope revealed no obstacles such as color mixing, color unevenness and color omission.

(Example 5) Using the resin composition obtained in Preparation Example 2, exposure was performed over the entire surface in the same manner as in Example 2, infrared absorption spectra were measured, and a comparison of the amount of hydroxyl groups before and after exposure and heating was performed. After the exposure, 600
%.

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

Subsequently, the resin composition obtained in Preparation Example 2 was roll-coated on a glass substrate on which a black matrix was formed so as to have a thickness of 2 μm.
Prebaking was performed for 0 minutes to form a resin composition layer.

Next, the resin layer under the opening of the photomask is pattern-exposed at a dose of 1 J / cm ² through a photomask having an opening wider than the width of the black matrix. At 150 ° C,
PEB was performed for 1 minute, and an ink-philic conversion process was performed. Further, a pretreatment liquid is applied to the above ink by an ink jet method, and R, G, B by the above pigment ink is applied to an exposed portion using an ink jet printer.
After the matrix pattern was colored, the ink was dried at 90 ° C. for 5 minutes. After continuous exposure,
Heat treatment was performed at 200 ° C. for 1 hour to cure the resin layer.

Further, a two-part type thermosetting resin SS-7625 (manufactured by JSR) as a protective layer having a film thickness of 1 μm was formed on the resin layer.
Then, heat treatment was performed at 230 ° C. for 1 hour to cure the composition.

Observation of the thus prepared liquid crystal color filter with an optical microscope showed no problems such as color mixing, color unevenness, and color omission.

(Embodiment 6) Using a black matrix as a photomask without using a photomask,
A color filter was prepared in the same manner as in Example 5, except that exposure was performed from the back surface of the substrate, that is, from the side where no resin composition layer was present.

Observation of the thus prepared color filter for liquid crystal with an optical microscope revealed no obstacles such as color mixture, color unevenness and color omission.

Comparative Example 1 A liquid crystal power filter was prepared in the same manner as in Example 1 except that the exposure amount was changed to 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 and heating was compared. As a result, it was confirmed that the amount after exposure increased to 200% of that before exposure.

The ratio of the solubility of the resin layer in the pretreatment liquid, ie, the solubility of (the portion of the ink-affinized portion) / (the non-ink-affected portion) was 3.

When the thus prepared liquid crystal color filter was observed with an optical microscope, the contrast between the exposed portion and the unexposed portion was insufficient, and obstacles such as color mixing and color unevenness were observed.

(Embodiment 7) As shown in FIG. 3, on a glass substrate 1 on which a black matrix 2 is formed, (1)
100 parts by weight of a terpolymer of N-methylolacrylamide, methyl methacrylate and hydroxyethyl methacrylate (charge ratio 20:45:35) and (2) triphenylsulfonium triflate (manufactured by Midori Kagaku: T
PS-105) A composition consisting of 2 parts by weight was coated with a film having a thickness of 15 μm.
m and spin-baked at 70 ° C. for 15 minutes to form a photocurable resin layer 3.

Next, a part of the resin layer on the black matrix was removed by a 100 mJ / cm ² Deep through a photomask having an opening smaller than the width of the black matrix.
The pattern was exposed to UV light and cured.

Next, a pretreatment liquid is applied to the uncured portion using an ink-jet head, and the R, G, B matrix pattern is colored with a dye ink using the ink-jet head 5 and then at 90 ° C. for 5 minutes. The ink was dried. Subsequently, a 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 exchange water 50 parts by weight Ethylene glycol 50 parts by weight R ink dye: CI Acid Red 118 5 parts by weight N-methyl-2-pyrrolidone 10 parts by weight Tylene glycol 20 parts by weight Ion exchange water 65 parts by weight G ink dye = CIAcid Green 25 5 parts by weight N-methyl-2-pyrrolidone 10 parts by weight Tylene glycol 20 parts by weight Ion exchange water 65 parts by weight B ink dye: CIAcid Blue 113 5 parts by weight N-methyl-2-pyrrolidone 10 parts by weight Tylene Glycol 20 parts by weight Ion-exchanged water 65 parts by weight The solubility of the resin layer in the uncured portion 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 portion cured by the deep UV light was 0.02 g / ml at room temperature. That is, the ratio of (solubility of the uncured portion of the resin layer) / (solubility of the cured portion of the resin layer) is 10.

On the resin layer 3 thus colored,
A photocurable resin composition comprising a modified epoxy acrylate and a photopolymerization initiator was spin-coated so as to have a thickness of 1 μm, and prebaked at 90 ° C. for 30 minutes to form a protective layer 6. Next, the entire surface was exposed to cure the protective layer 6, thereby producing a color filter for liquid crystal.

Observation of the thus prepared liquid crystal color filter with an optical microscope showed no problems such as color mixing, color unevenness and color omission.

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

Example 8 On the resin layer 3 obtained in Example 7, a two-component type epoxy acrylate-based thermosetting resin composition was mouth-coated so as to have a film thickness of 1 μm.
Pre-baking was performed at 30 ° C. for 30 minutes to form a protective layer 6. Next, a heat treatment was performed at 230 ° C. for 30 minutes to cure the protective layer 6, thereby producing a color filter for liquid crystal. Observation of the thus prepared liquid crystal color filter with an optical microscope revealed no obstacles such as color mixing, color unevenness, and color omission.

Using this color filter, a liquid crystal panel as shown in FIG. 5 was manufactured and driven, and a 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. Coating was performed and prebaking was performed at 90 ° C. for 30 minutes to form a protective layer 6. Next, after performing overall exposure, a heat treatment was performed at 230 ° C. for 30 minutes to completely cure the protective layer 6, thereby producing a color filter for liquid crystal.

Observation of the thus prepared liquid crystal color filter with an optical microscope showed no problems such as color mixing, color unevenness, and color omission.

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

(Embodiment 10) A Si ₂ film (protective layer 6) is formed on the colored resin layer 3 by the embodiment 7 by sputtering.
Was formed to a film thickness of 0.5 μm to produce a color filter for liquid crystal.

Observation of the thus prepared liquid crystal color filter with an optical microscope showed no obstacles such as color mixing, color unevenness and color omission.

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

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

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

Observation of the thus prepared color filter for liquid crystal by an optical microscope showed no obstacles such as color mixing, color unevenness and color omission.

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

(Example 12) A color filter for liquid crystal was prepared in the same manner as in Example 7, except that the composition of the pretreatment liquid was changed as follows. Composition of pretreatment liquid 30 parts by weight of diethylene glycol 30 parts by weight of N-methyl-2-pyrrolidone 10 parts by weight of isopropyl alcohol 30 parts by weight of ion-exchanged water The solubility of the uncured resin layer 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 part cured by ep UV light was 0.1 g / ml at room temperature. That is, the ratio of (solubility of the uncured portion of the resin layer) / (solubility of the cured portion of the resin layer) is 8.

Observation of the thus prepared liquid crystal color filter with an optical microscope showed no problems such as color mixing, color unevenness, and color omission.

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

Example 13 As shown in FIG. 4, the composition of Example 7 was applied on a glass substrate 1 to form a resin composition layer 3. 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. Further, 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, a protective layer 6 was formed in the same manner as in Example 8, and a color filter for liquid crystal was manufactured.

Observation of the thus prepared liquid crystal color filter with an optical microscope showed no problems such as color mixing, color unevenness and color omission.

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

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

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

Observation of the thus prepared liquid crystal color filter with an optical microscope revealed that there were obstacles such as color mixing and color unevenness.

[0123]

As described above, according to the present invention, a highly reliable color filter free from obstacles such as color mixing, color unevenness and color omission can be manufactured in a short process at a low cost. Can be obtained.

[Brief description of the drawings]

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

FIG. 2 is a view 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 chart showing another embodiment of the method for producing a color filter for liquid crystal of the present invention.

FIG. 4 is a process chart showing still another embodiment of the method for producing 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 transmission 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 Polarizer 16 Back Light light 25 Ink-repellent part 26 Ink-philic part 27 Pretreatment liquid applied 28 Ink applied 29 Protective film

Continuation of the front page (72) Inventor Akinori Shiota 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-7-120611 (JP, A) JP-A-7-72325 (JP, a) JP flat 7-77607 (JP, a) JP flat 1-217302 (JP, a) JP flat 5-142417 (JP, a) (58 ) investigated the field (Int.Cl. ⁷ , DB name) G02F 1/1335 505 G02B 5/20 101

Claims (16)

(57) [Claims] 1. A method for manufacturing a liquid crystal color filter, comprising the steps of arranging red (R), green (G), and blue (B) colored portions on a substrate. A step of forming an ink receiving layer, (2) a step of 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) a step of forming the ink receiving layer. A method for producing a liquid crystal color filter, comprising a step of applying a predetermined color ink to a predetermined portion of a receiving layer. 2. The method according to claim 1, wherein the ink is applied by an ink-jet method. 3. The ink receiving layer according to claim 1, wherein the ink receiving layer is provided with a parent ink portion having a relatively high ink absorbency and an ink repellent portion having a relatively low ink absorbency, and the parent ink portion is colored. Manufacturing method. 4. The method according to claim 3, wherein the solubility of the ink receiving layer in the pretreatment liquid has a relationship represented by the following formula (I). ## EQU1 ## (Solubility of parent ink portion) / (Solubility of ink repellent portion)> 5 (I) 5. An ink receiving layer is formed by forming, on a substrate, a resin composition layer whose light absorbability can be changed by light irradiation or light irradiation and heat treatment.
(2) pattern-exposing a predetermined portion of the ink receiving layer formed on the substrate to change the ink absorbency of the exposed portion of the receiving layer to form a parent ink portion and an ink repellent portion; Item 5. The method according to any one of Items 2 to 4, wherein the method further comprises a step of curing the colored ink receiving layer by light irradiation and / or heat treatment. 6. A black matrix is provided on a substrate before an ink receiving layer is formed, and an ink receiving layer portion on the black matrix is used as an ink-repellent portion by pattern exposure after forming the resin composition layer. The method according to claim 5. 7. The 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 method according to claim 5, wherein the pattern exposure exposes a portion of the ink receiving layer to be colored, thereby increasing the ink absorbency of the portion. 9. The production method according to claim 5, wherein the non-colored portion of the ink receiving layer is exposed by the pattern exposure to relatively lower the ink absorbency of the portion. 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 method according to claim 11, wherein the curable second resin composition layer is a resin composition layer curable by a combination of light irradiation and heat treatment, and is cured by a combination of light irradiation and heat treatment. Production method. 15. A liquid crystal color filter produced by the method according to claim 1. Description: 16. A liquid crystal panel comprising the color filter according to claim 15 and a substrate facing the filter, wherein a liquid crystal compound is sealed between the two substrates.