JPH08286025A - Color filter and its production, and image forming method - Google Patents

Abstract

PURPOSE: To form a color filter free from uneven color with the small number of processes at high productivity by providing at least a radiation setting type adhesive layer and a photosensitive colored pattern in this order on a base material. CONSTITUTION: A mask 7 is mounted closely or with a certain space by press- fitting the photosensitive colored transfer layer 3 side of a transfer sheet 1 provided with the photosensitive colored transfer layer 3, which is to be weakened in adhesivity to a supporting body 2 by radiation, to the radiation setting type adhesive layer 5 on a color filter base material 4, on which a black matrix is previously formed. A latent image is formed by exposing image-wise. The transfer sheet 1 is separated from the base material 4, a part corresponding to the exposed part of the photosensitive colored transfer layer 3 is transferred and a transferred pattern 9a and a non-transferred pattern 9b are formed. The color filter patterns of red, green and blue are formed on a substrate 4 by repeating the process with the change of color of the colored transfer layer 3.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a transfer sheet provided with a photosensitive colored transfer layer whose adhesive strength with a support changes from the initial value upon exposure to radiation and the adhesive strength to a substrate upon exposure to radiation. A method of forming an image by peeling off the support of a transfer sheet after selective exposure using a substrate provided with a radiation curable adhesive layer that also changes, or a color filter by application of this image forming method And a color filter obtained by the method, which is used as a color reproducing color filter for a color liquid crystal display device mounted in a computer, a color television, a color monitor, or the like, or a color video camera or the like. It is used as a color filter for color separation used in a solid-state image sensor, and is particularly inexpensive and has less unevenness. There can provide a color filter, or it relates to a novel image forming method obtained a small color image unevenness at low cost.

[0002]

2. Description of the Related Art A number of techniques have been proposed so far for a method of manufacturing a color filter used in the above-mentioned color liquid crystal display device or solid-state image pickup device, and some of them have already been put into practical use. Has also been made.
And, as a typical one of the manufacturing methods, a dyeing method,
The pigment dispersion method, electrodeposition method and printing method are well known.

For example, an easily dyeable transparent photosensitive resin layer is provided on a transparent substrate to form a desired pattern according to a conventional method.
The pattern is dyed, for example, in red, and in the same manner as green,
A blue pattern is formed to manufacture a color filter,
There is a dyeing method. In addition to this, a dye dispersion method in which a photosensitive resin liquid in which pigments such as pigments or dyes are dispersed is applied onto a transparent substrate, and desired colored patterns of red, green, blue, etc. are sequentially formed according to a conventional method. Or a pigment dispersion method, an electrodeposition method of forming a colored pattern by forming a desired pattern consisting of a transparent conductor layer on a transparent substrate, and then electrodepositing while energizing only the pattern to be colored, and further offset printing, etc. Have proposed a printing method for manufacturing a color filter.

However, in the case of the above-mentioned manufacturing method which has already been put into practical use, those problems are becoming apparent with respect to the color filter manufacturing process and manufacturing quality.

First, the dyeing method or the pigment dispersion method will be described below. According to these manufacturing methods, the steps of coating a photosensitive colored resin solution, etc., soft baking, “exposure”, developing, dyeing (dyeing is performed in the case of dyeing method), and hard baking are usually carried out in sequence. By repeating one to four times, the desired color (eg RGB or red,
Green, blue, or even black. ),
A color filter in which each of these colors is arranged as a plurality of repeating patterns is manufactured.

However, according to these dyeing methods and pigment dispersion methods, it takes a relatively long time to apply the photosensitive colored resin liquid or the like, or to soft-bak or hard-bak it, and as a result, the color filter is manufactured. The time required for the process also becomes long. In addition, since it includes a wet development process using a developing solution or the like, it is inevitable that a treatment facility for waste liquid is required from the viewpoint of environmental protection, and as a whole, productivity improvement and cost reduction that exceed the current situation, and further, the color filter that is a product. It has become difficult to reduce the price.

Further, in order to increase the size of the color filter substrate that is expected in the future, for example, when applying a photosensitive coloring resin liquid, unlike the conventional situation of applying it on a small substrate, it is wide. In reality, it is never easy to evenly coat a substrate. In the following, infrared rays, visible rays, ultraviolet rays, X
Irradiating any one or a plurality of radiations such as rays or electron rays will be referred to as “exposure”.

Next, the electrodeposition method will be described. The electrodeposition method is
First, a transparent conductor is deposited on a transparent substrate to form a transparent conductor layer, and after fine processing is performed according to each color pattern, electricity is applied to the transparent conductor layer for each color and the coloring material is electrodeposited there. Let However, for this reason, in the transparent conductor layer, the pixels must be connected to each other in order to establish conduction in the terminal portion between the patterns of the same color, and the pixels must not be conducted in the patterns of different colors. Therefore, it is not possible to freely design the shape and arrangement of the pattern because the pixel shape and pixel arrangement are inevitably restricted, and the transparent conductor layer is patterned (especially with high precision fine patterning). ) Requires very advanced fine processing technology.

Incidentally, as the material of the transparent conductor layer,
For example, ITO (Indium-Tin-Oxide) is one of the most frequently used.

The printing method will be described below. The printing method has a great advantage that the manufacturing process is short because a photolithography technique such as application, exposure, and development of a photosensitive colored resin liquid is unnecessary. However, on the other hand, it is difficult for the printing method to maintain the pattern size, shape, and positional accuracy at high quality, and when the cross-sectional shape of each pixel of the formed pattern is focused, the cross section becomes mountain-shaped. Therefore, the thickness of each pixel is not constant as a whole, and as a result, there is a problem in terms of quality relating to display performance such as color unevenness.

In addition to this, some manufacturing methods generally called "transfer method" have been proposed. For example, as described in JP-A-5-341114, a colored layer is formed by applying a previously colored photosensitive resin liquid once on a temporary support, and then a colored layer of a certain color is formed. After being directly transferred onto a transparent substrate, it is selectively exposed in a predetermined pattern, and then the colored layer of a certain color is selectively removed by performing development to form a pattern of the colored layer, There is also one in which this is sequentially repeated for each color to form a desired pattern.

When the spin coating method, which is one of the most frequently used examples of applying a photosensitive colored resin liquid or the like onto the surface of a support, is supplied (pre-colored). Most of the photosensitive resin liquid is wasted, and only a small amount is actually used for image formation.

However, according to this transfer method, the situation is different from that in the case of the spin coating method, and the photosensitive resin liquid (pre-colored) supplied for coating is a waste liquid without being actually used. Since there is basically nothing to be thrown away, the waste of the photosensitive resin liquid is extremely small and the production cost can be reduced, which can contribute to the cost reduction of the color filter.

However, in the case where the color filter is manufactured by the transfer method, after the transfer of the colored layer, the steps of exposure, development, curing and the like are repeated as in the manufacturing method widely known as the pigment dispersion method. The fact that it is complicated and difficult to improve productivity remains the same, and the effect of price reduction is small.

Further, in the method described in Japanese Patent Laid-Open No. 5-257012, a photosensitive colored resin liquid is applied on a temporary support, and this is exposed and developed to form three monochromatic patterns separately. Are formed on the transparent substrate, and the transfer is sequentially repeated on the transparent substrate. Also with this method, since the waste of the photosensitive coloring resin liquid is small, the material cost can be expected to be reduced. However, when the temporary support is brought into close contact with the transparent substrate for transfer, Alignment becomes very difficult due to changes in the pitch of the formed pixels (due to deformation).

Furthermore, in the method described in JP-A-2-262108 or JP-A-4-75004, a "colored radiation curable resin layer" is provided between two transparent support sheets. After pattern-wise exposure, the support sheet is peeled off, and the resin layer in the exposed area is removed to perform development, and the remaining unexposed area in the patterned resin layer is separately prepared on a transparent substrate. Then, the color filter is manufactured by transferring the material by heating and pressurizing and repeating the transfer.

The advantage of this method is that since the colored resin liquid is less wasted and the production cost can be reduced, the price of the obtained color filter can be expected to be reduced, and further, the developing liquid or the like is used. Since it is a dry development that does not occur, it can be said that it is very advantageous in terms of equipment and productivity. However, when the support sheet provided with the pattern is adhered to the transparent substrate by pressure, the support sheet is deformed due to the stress generated by the pressure or the stress generated by heat, and as a result, the position of the pattern is changed. There is a serious problem that the alignment becomes very difficult because it is displaced from a desired position or the pattern pitch is changed.

As another example, Japanese Patent Laid-Open No. 4-317
In the method described in Japanese Patent Laid-Open No. 006, a "colored ionizing radiation curable resin" is filled in a groove for a pattern formed on a mother die, and a transparent substrate provided with an adhesive layer is brought into close contact with the ionizing radiation for irradiation. Then, the resin in a pattern form is transferred onto the transparent substrate along with peeling.

The advantage of this method is that it is less wasteful in terms of material because it is filled with the required amount of colored resin, and it is advantageous in terms of equipment and productivity because a developer or the like is not used to form a pattern. . However, it is technically very difficult to form an optically uniform pattern by filling the groove with the colored resin,
In addition, the existence of the already formed pattern causes a problem that it becomes difficult to adhere the mother dies for the second and subsequent colors to the transparent substrate.

After all, according to the above-mentioned several methods, which are generally called "transfer method", there is less waste in using the material as compared with the other manufacturing methods of the color filter. Although the common advantage is that the method for forming the pattern on the support is simple,
On the other hand, when trying to achieve good quality, high productivity, and low cost in closely transferring a pattern to a transparent substrate, there are technically very difficult points.

When this is examined in the order of steps, in the step of transferring the colored transfer layer from the temporary support to the transparent substrate by adhesion / peeling and the pattern forming step, for example, JP-A-5-341114 is used. It can be said that the technique disclosed in the publication does not have many problems in the order of the transfer process and then the pattern forming process. However, it can be said that the technique disclosed in the publication has a small degree of effect at the same time in terms of advantages of the technique and effects obtained by the method.

On the other hand, in the techniques disclosed in JP-A-5-257012, JP-A-2-262108, JP-A-4-75004, and JP-A-4-317006, on a temporary support. It can be said that there are not many problems in the order of the pattern forming step and the transfer step to the transparent substrate, and the advantages and effects can be expected to some extent. However, with the techniques disclosed in these publications, at the same time, it can be said that problems mainly occur in the transfer process.

[0023]

However, the transfer method has various problems as described below when a precise pattern is to be imparted to a transfer target or when a pattern is to be imparted to a minute transfer target. there were.

For example, a means such as printing is used to form a desired color pattern on the transfer layer of the transfer foil, but the precision with which a precise pattern can be formed by printing is at most 10.
It is said that the limit is about μm, and in fact, it is a problem that it is difficult to form a fine pattern having a precision higher than this accuracy.

Further, when the specific design portion of the transfer layer of the transfer foil is to be transferred to a predetermined position of the transfer target,
It is required to accurately determine the positions of the transfer layer and the transfer target, but when the design of the transfer layer of the transfer foil becomes fine, it is very time-consuming to accurately position the transfer foil, which is a characteristic of the transfer method. That is, there is a problem that the efficiency of designing is impaired.

Then, as a method related to the present invention,
(1) First, a step of forming a latent image on a transfer sheet by imagewise exposing a transfer sheet provided with a photosensitive colored transfer layer whose adhesion to the support is weakened by irradiation with radiation. Then, a step of pressure-bonding the adhesive photosensitive layer of the transfer sheet on which the latent image is formed, to a color filter substrate provided with a radiation-curable pressure-sensitive adhesive layer whose adhesive force is increased by irradiating the substrate with radiation. (3) Thereafter, a step of separating the transfer sheet from the color filter base material and transferring the photosensitive colored transfer layer of the portion corresponding to the exposed portion onto the radiation-curable pressure-sensitive adhesive layer of the color filter base material, These (one) (two)
A technique for obtaining a color filter by a manufacturing method including the step (3) has also been proposed. However, when these processes are repeated a plurality of times, there is a problem in the transfer position accuracy, and in actual production, there remains a problem in terms of quality, productivity, and production cost of the obtained color filter.

The present invention was made by paying attention to the problems of the above-mentioned conventional techniques, and the purpose thereof is as follows.
(i) Color irregularity is small (that is, while maintaining high display quality), the number of steps is small, the time required for each step is short, the productivity is high, and the equipment for solution supply and waste liquid treatment is not required.
In addition, it is possible to reduce the price of the obtained color filter, to provide a color filter and a manufacturing method thereof that satisfy the above requirements, and (ii) to supply a solution with little color unevenness (that is, while maintaining high display quality). It is to provide a novel method for forming a color image, which does not require a facility for waste liquid treatment or waste liquid treatment.

[0028]

[Means for Solving the Problems] Means provided by the present invention for solving the above-mentioned problems are as follows. First, as described in claim 1, at least a radiation-curable pressure-sensitive adhesive is provided on a substrate. A color filter having a layer and a photosensitive coloring pattern in this order.

Preferably, the radiation-curable pressure-sensitive adhesive layer contains an acrylic polymer and a low molecular weight compound having a photopolymerizable carbon-carbon double bond in the molecule. The color filter according to claim 1, which is a composition obtained by:

Alternatively, as described in claim 3, (a) a pretreatment step of a transfer-receiving body in which a radiation-curable pressure-sensitive adhesive layer is provided on the substrate, and the substrate is exposed by radiation On the support, a pretreatment step using a radiation-curable pressure-sensitive adhesive layer for increasing the adhesive strength of (b), and (b) (A) a photosensitive colored transfer layer whose adhesion to a support is weakened by exposure to radiation. A step of superposing the transfer sheet provided so that the photosensitive colored transfer layer and the radiation-curable pressure-sensitive adhesive layer are in contact with each other, (B),
An exposure step of selectively exposing the photosensitive colored transfer layer in a region corresponding to a color pattern to be formed with radiation, (C) after which the exposed portion of the photosensitive colored transfer layer is transferred to A peeling step of peeling the transfer sheet off the body, a colored pattern forming step including these (A), (B) and (C), and the above steps (a) and (b). This is a method for manufacturing a color filter.

Preferably, as described in claim 4, an acrylic polymer and a low molecular weight compound having a photopolymerizable carbon-carbon double bond in the molecule are used as a radiation-curable pressure-sensitive adhesive layer. The method for producing a color filter according to claim 3, wherein a composition containing the same is used.

Alternatively, as described in claim 5,
A radiation-curable adhesive / adhesive layer whose adhesive strength with a substrate increases by exposure to radiation is provided on a transfer-receiving material provided on the substrate, and a photosensitive colored transfer layer whose adhesion to the support is weakened by exposure to radiation. The transfer sheet provided on the support is superposed so that the photosensitive colored transfer layer and the radiation-curable pressure-sensitive adhesive layer are in contact with each other, and then the photosensitive sheet in an area corresponding to an image pattern to be formed. Of the photosensitive colored transfer layer is selectively exposed to radiation, and then the exposed portion of the photosensitive colored transfer layer is left on the transfer target to peel off the transfer sheet, whereby the photosensitive colored transfer layer is removed. An image forming method is characterized in that an image pattern consisting of is formed on the transfer target.

Preferably, as described in claim 6, an acrylic polymer and a low molecular weight compound having a photopolymerizable carbon-carbon double bond in the molecule are used as the radiation curable pressure-sensitive adhesive layer. The image forming method according to claim 5, wherein a composition containing the composition is used.

The present invention will be described in more detail below with reference to the drawings. FIG. 1 shows the concept of pattern formation of a color filter according to the present invention. The radiation curable pressure-sensitive adhesive layer 5 is uniformly applied and dried on the transparent base material 6 to form the color filter base material 4.
The colored transfer layer side of the transfer sheet 1 in which the photosensitive colored transfer layer 3 is uniformly provided on the thin and transparent support 2 is brought into close contact with the radiation curable adhesive layer 5 of the color filter substrate 4, and the mask 7 is installed closely or with a gap.
This is exposed to radiation 8 (ultraviolet rays, electron beams, etc.).

FIG. 2 is a diagram showing a process of forming a color filter pattern according to the present invention.
The respective states of exposure (b) and peeling (c) are shown. By the way, in FIG. 2 (a), the color of the transfer sheet 1 provided with the photosensitive colored transfer layer 3 whose adhesion to the support 2 is weakened by the radiation is indicated by the black matrix 10 formed in advance. The radiation curing type tacky-adhesive layer 5 of the filter substrate 4 is pressure-bonded, and the mask 7 is closely attached or is placed with a gap.

FIG. 2B shows a latent image formed by imagewise exposure. In FIG. 2C, the transfer sheet 1 is separated from the color filter substrate 6 on which the black matrix 10 is formed, and the portion of the photosensitive colored transfer layer 3 corresponding to the exposed portion is transferred to the color filter substrate 6. The transferred pattern 9a and the non-transfer pattern 9b are being formed.

FIG. 3 is a diagram showing a method of manufacturing a color filter according to the present invention along the manufacturing process. As shown in FIGS. 2A to 2C, the color of the colored transfer layer is changed and repeated a plurality of times, so that the red color filter pattern 11a, the green color filter pattern 11b, Blue color filter pattern 1
1c can be formed.

Since the adhesive / adhesive layer functions as a cushion for the second and subsequent colors, the transfer sheet may be formed even if the radiation-curable adhesive / adhesive layer 5 has a pixel pattern of another color and is not a flat surface. Adhesion during lamination is maintained. In addition, by slightly enlarging the pixel pattern, the black matrix 10 and the edge overlap each other to prevent the defective pattern. Although the black matrix 10 is formed on the base material 6 in advance in the figure, it may be formed after forming all the color filter patterns.

After forming all the color filter patterns and the black matrix, post-baking is performed to completely cure the resin and adhesive layer forming the patterns,
Thereafter, as shown in FIG. 3D, the protective layer 12 is applied evenly and cured, and the electrode 13 is further applied as shown in FIG.
Is prepared. Alternatively, the electrode 13 is directly formed on the photosensitive colored transfer layer without applying the protective layer.

As the photosensitive color transfer layer, an epoxy acrylate resin, an epoxy resin, a photopolymerizable monomer,
A composition containing a photopolymerization initiator and a pigment as main components.

Examples of the epoxy acrylate resin include a bisphenol fluorene type epoxy acrylate resin obtained by addition reaction of an acid anhydride. As a specific example, the epoxy acrylate compound is 9,
9-bis (4-hydroxyphenyl) fluorene, 9,
9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-)
3-Bromophenyl) fluorene, 9,9-bis (4-
Hydroxy-3-fluorophenyl) fluorene, 9,
9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) Fluorene, 9,
9-bis (4-hydroxy-3,5-dibromophenyl) fluorene and the like, and examples of acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and methyltetrahydroanhydride. Phthalic acid, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, etc. .

Further, instead of fluorene in the above-mentioned bisphenol fluorene type epoxy acrylate resin,
Epoxy acrylate resin containing methane, propane, ether, ketone, sulfone, hexafluoropropane or dimethylsilane may also be used. Using one or more of these monomers, the molecular weight of 5,000-
It is preferable to use a resin synthesized to about 1,000,000.

As the epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin,
Examples thereof include phenyl glycidyl ether, P-butylphenol glycidyl ether, diglycidyl isocyanurate, triglycidyl isocyanurate, allyl glycidyl ether and glycidyl methacrylate.

The photopolymerizable monomer includes bifunctional, trifunctional and polyfunctional monomers, and as the bifunctional monomer,
1,6-hexadiol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, etc., and trifunctional monomers such as trimethylolpropaton triacrylate, pentaerythritol triacrylate, and tris ( 2-hydroxyethyl) isocyanate, etc., and polyfunctional monomers such as ditrimethylolpropane tetraacrylate, dipentaerythritol penta and hexaacrylate. These monomers are available from Showa High Polymer Co., Ltd., Toa Gosei Co., Ltd.,
There are commercial products such as Nippon Kayaku Co., Ltd.

The addition amount of the photopolymerizable monomer is not particularly limited, but it is 20 to 150% in the acrylic resin for dispersion.
It is preferably part by weight.

As a photopolymerization initiator, a triazine compound, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s- Triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-
Triazine, 2- (4'-methoxy-1'-naphthyl)
-4,6-bis (trichloromethyl) -s-triazine and the like, and the imidazole compounds include 2-
(2,3-Dichlorophenyl) -4,5-diphenyl-
Imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-bis (3-methoxyphenyl) -imidazole dimer, 2- (2,3-dichlorophenyl)-
4,5-bis (4-methoxyphenyl) -imidazole dimer, 2- (2,3-dichlorophenyl) -4,5-
Bis (4-chlorophenyl) -imidazole dimer, 2
-(2,3-Dichlorophenyl) -4,5-di (2-furyl) -imidazole, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1-
2'-biimidazole, HB22 (Hodogaya Chemical Co., Ltd.)
Manufactured) etc. In addition, as the photopolymerization initiator other than the above, Irgacure 907, 651 (benzyl dimethyl ketal), 184 (manufactured by Ciba Geigy), dieterthioxanthone (manufactured by Nippon Kayaku Co., Ltd.), benzophenone, etc. It is possible to mix and use these.

The addition amount of the photopolymerization initiator is not particularly limited, but preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight of the total amount of the resin is added by 1 type or 2 types. Used.

A photopolymerization initiation aid may be used to accelerate the photoreaction. Generally, amines are used,
For example, tertiary amines such as triethanolamine,
Examples include 4,4-dimethylaminobenzophenone and ethyl 4-dimethylaminobenzoate.

In addition, it is also effective to add a small amount of an antioxidant or a heat stabilizer in order to improve the heat resistance of the resin. For example, 2,6-di-t-butyl-p-cresol, n-octadecyl-3- (4'-hydroxy-
3 ', 5'-di-tert-butylphenol) propionate, tetrakis [methylene-3- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionate] methane, thiobis (β-naphthol), tetramethylthiuram disulfide, distearyl thiodipropionate, triphenylphosphite, tri (nonylphenyl) phosphite, trilauryltrithiophos Examples include fights.

As the pigment, C.I.
I. Pig. 9, 97, 122, 123, 149, 16
8, 177, 180, 192, 215, etc., and as green, C.I. I. Pig. 7, 36, and C. for blue. I. Pig. 15:
3, 15: 6, 22, 60, 64, and yellow (Yel
low) is C.I. I. Pig. 12, 20, 83,
86, 138, 139, 154 and then purple (Vio
Let) is C.I. I. Pig. 23 is commonly used.

As the dispersant, a wide variety of dispersants such as surfactants, intermediates of pigments, intermediates of dyes and sol-spars are used. The composition ratio at the time of dispersion is not particularly limited, but the addition amount of the pigment to the resin is 50 to 15
The dispersant is preferably about 1 to 10 parts by weight of the pigment. In addition, for spectral adjustment of the color filter, arbitrary pigments are mixed and adjusted at 2-3 points.

An example of the composition of the photosensitive colored layer is an epoxy acrylate resin 100 obtained by addition reaction of an acid anhydride.
5 to 50 parts by weight of the epoxy resin, 50 parts by weight or less of the photopolymerizable monomer, and 0.1 parts by weight of the photopolymerization initiator with respect to parts by weight.
-30 parts by weight, 10-200 parts by weight of pigment, and a small amount of other components. Then, the composition is used by dissolving and dispersing it in an appropriate amount of solvent according to the material coating method for forming the photosensitive colored layer.

As the photosensitive colored layer composition and the color filter ink, the photosensitive resin and the photosensitive resin composition disclosed in JP-A-5-70528 or JP-A-6-1938 are disclosed. Ink for a photosensitive color filter, etc. disclosed in 1) is effective.

As the solvent, toluene, xylene, ethylcellosolve, ethylcellosolve acetate, diclime, cyclohexanone, etc. are used. However, since it depends on the monomer composition of the resin, the photopolymerizable monomer, the photopolymerization initiator, etc., a single solvent is used. Alternatively, a solvent having a plurality of solvent compositions is appropriately selected. The photo-curable resin liquid in which the pigment is dispersed, which constitutes the photosensitive colored layer, is applied to the support by gravure coater, gravure offset coater gravure reverse coater, bar coater, lip coater, knife coater, spinner, silk screen. Alternatively, a roll coater may be used.

The non-volatile component contained in the solution at the time of coating and the amount thereof may be appropriately selected depending on the intended layer thickness and the type of coater, and are not particularly limited.
From the viewpoint of resolution, the layer thickness after drying is usually 0.5 to 3 μm.
m is good, and more preferably 1 to 1.5 μm.

The support is preferably made of a material which is stable to heat, chemicals, light and the like and at the same time transmits actinic rays. For example, polyethylene terephthalate, polypropylene, triacetate, cellulose acetate, polystyrene,
It is a film or sheet of polyvinyl chloride, polycarbonate, polyimide or the like. Especially polyester film and polypropylene film (biaxially stretched)
Is preferable because it has excellent transparency, heat stability, strength and dimensional stability, and has an appropriate adhesive force with the photosensitive colored layer.

These sheets may be used as they are, but may be subjected to appropriate primer treatment, corona discharge treatment or peeling treatment to control the adhesive strength. The thickness of the support is not particularly limited, but a thickness of about 5 to 100 μm is usually preferably used from the viewpoint of easy handling.

The substrate is transparent and has good dimensional stability,
It is not particularly limited as long as it can withstand heat during image formation, but from the viewpoint of easy availability, handleability, processability or cost, for example, polyethylene terephthalate, polyethylene naphthalate, polyamide A heat-resistant plastic film or glass substrate such as polyimide, polycarbonate, polysulfone, polyvinyl alcohol cellophane, or polystyrene can be used.

As the method for forming the light-shielding layer pattern (black matrix etc.) on the above-mentioned base material, a method of forming it beforehand on the transferred material to be the color filter substrate and a method of forming it after forming the colored layer pattern are formed. There is a way to do it. As the former (formation method in advance), a method of forming a Cr thin film on the entire surface by vapor deposition or sputtering on a substrate to form a pattern by a photolithography method and a photocurable resin used in the photosensitive colored layer of the present invention There is a method of forming a pattern by mixing a black pigment such as carbon black to prepare a black photosensitive resin, coating it on a substrate, and exposing and developing it by a photolithography method.

As the latter (method to be formed later), a black transfer sheet having a photosensitive black colored layer and an adhesive photosensitive layer provided on a support is prepared in the same manner as the transfer sheet of the present invention. There is also a method of forming a black matrix depending on the method. With either method, the black matrix can be formed on the substrate.

Next, the radiation-curable pressure-sensitive adhesive layer will be described. The radiation-curable tacky-adhesive layer may be made of any kind of material as long as it exhibits tackiness in the unirradiated state and is cured by irradiation to increase the adhesive strength. Examples of such a material include a composition containing an acrylic polymer and a low molecular weight compound (radiation-curable compound) having a photopolymerizable carbon-carbon double bond in the molecule.

In addition to the above-mentioned radiation-curable pressure-sensitive adhesive, there is a polymer in which a radiation-polymerizable group having one carbon-carbon double bond or an epoxy group is bonded to the side chain or main chain of the polymer. The main chain polymer is an acrylic polymer having an acrylic ester as a main constituent monomer unit, a copolymer selected from homopolymers and copolymers, copolymers with other functional monomers, and copolymers thereof. A mixture of coalesces is used. For example, acrylic acid ester, methacrylic acid ester, vinyl acetate ester, acrylonitrile, vinyl ethyl ether and the like of alkyl alcohol having 1 to 10 carbon atoms can be preferably used.

The above acrylic polymers may be used alone or in combination of two or more.

Specific examples of the compound introduced into the side chain or main chain of the above acrylic polymer to derive a radiation-polymerizable group having one carbon-carbon double bond or an epoxy group include pentaerythritol. Compounds having a carbon-carbon double bond such as monoacrylate, pentaerythritol monomethacrylate, dipentaerythritol monoacrylate, dipentaerythritol monomethacrylate, trimethylolpropane monoacrylate, and trimethylolpropane monomethacrylate, or glycidyl acrylate, glycidyl methacrylate, etc. The compound having an epoxy group can be mentioned.

The above compounds may be used alone or in combination of two or more.

To produce a radiation-curable pressure-sensitive adhesive using a compound having an epoxy group, for example, active sites (eg, --COOH, --NC) are added to the main chain of the polymer as described above.
It is obtained by introducing O, an epoxy group, —OH, —NH ₂ ) and then reacting the active site with a compound that induces the radiation-polymerizable group.

In order to introduce the above-mentioned active sites into the polymer, it is different from "cleavage of double bond" such as carboxyl group, isocyanate, hydroxyl group, amino group, epoxy group, etc. when producing an acrylic polymer. A monomer or oligomer having both a functional group capable of reacting by a mechanism and a carbon-carbon double bond may coexist in the reaction system. The following compounds are used as specific examples.

Acrylic acid and methacrylic acid are used to introduce a --COOH group. Methacryloyloxyisocyanate, acryloyloxyisocyanate, and the like are used to introduce the —NCO group. Further, to introduce an epoxy group, glycidyl acrylate, glycidyl methacrylate, etc. are used.

To introduce a --OH group, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,6-hexanediol monoacrylate, 1,6-hexanediol monomethacrylate,
1,6-hexanediol dimethacrylate or the like is used. Alternatively, N-methylacrylamide, N-methylmethacrylamide, or the like is used to introduce the —NH ₂ group.

The radiation-curable pressure-sensitive adhesive polymer as described above has a molecular weight of about 1 × 10 ⁴ to 1 × 10 ⁶ , more preferably about 1 × 10 ⁵ to 8 × 10 ⁵ .

Suitable materials for the above-mentioned binder are thermoplastic resins or mixtures thereof, examples of which are acrylic monomers, methacrylic acid, acrylic acid esters, methacrylic acid esters, etc. Polymer or copolymer, methyl cellulose, ethyl cellulose,
Cellulosic polymers such as cellulose acetate,
Vinyl-based polymers such as polystyrene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinylpyrrolidone, polyvinyl butyral, polyvinyl alcohol and the like, and their copolymers, condensation polymers such as polyester and polyamide, chlorinated rubber Rubber-based polymers such as butadiene-styrene copolymer, and polyolefin-based polymers such as chlorinated polyethylene and chlorinated polypropylene. Among these, copolymers of various acrylic monomers are preferable because it is easy to control the thermal properties such as the softening point in a wide range and the compatibility with the photopolymerizable monomer is good.

These polymers have a content of 10,000 to 20.
Those having an average molecular weight of 10,000 are preferred. Here, the mixing ratio of the photopolymerizable monomer and the organic polymer binder, the suitability ratio varies depending on the combination of the photopolymerizable monomer and the binder used, but generally, the photopolymerizable monomer: binder The ratio is 0.1: 1.0 to 2.0:
It is preferably 1.0 (weight ratio).

As the above-mentioned photopolymerization initiator, benzophenone, Michler-ketone [4,4'-bis- (dimethylamino) benzophenone], 4,4'-bis- (methylamino) benzophenone, 4-methoxy is used. -4'-Dimethylaminobenzophenone, 2-ethylanthraquinone, phenonetraquinone, and other aromatic ketones, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin ethers such as benzoin phenyl ether, methylbenzoin, ethylbenzoin And other benzoins, and 2- (O-
Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (O-fluorophenyl) -4,5-diphenylimidazole, 2- (O-methoxyphenyl)-
4,5-Diphenylimidazole dimer, 2- (P-methoxyphenyl) -4,5-diphenylimidazo-dimer, 2,4-di (P-methoxyphenyl) -4,5-diphenylimidazo-2 A monomer, a 2,4,5-triacrylimidazole dimer, and the like are used.

The amount of the photopolymerization initiator added is preferably 0.01 to 30% by weight based on the photopolymerizable monomer.

A thermal polymerization inhibitor can be added to the radiation-curable pressure-sensitive adhesive layer. Examples of this include P-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, tertiary butyl catechol,
Examples include, but are not limited to, pyrogallol, naphthylamine, β-naphthol, phenothiazine, pyridine, nitrobenzene, φ-tortinone, and aryl phosphite.

Other components that can be added to the radiation-curable pressure-sensitive adhesive layer include plasticizers, residual solvents, surfactants, inert fillers and the like.

Examples of the plasticizer include diphenyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, dihydroabietyl phthalate, dimethyl isophthalate, sucrose benzoate, ethylene glycol dibenzoate, trimethylol ethane tribenzoate, tribenzoic acid. Examples thereof include glyced, pentaerythritol tetrabenzoate, sucrose octaacetate, tricyclohexyl citrate, and N-cyclohexyl-p-toluenesulfonamide.

The radiation-curable adhesive / adhesive layer contains the above-mentioned components according to a coating film forming method known per se, which is the same as the method for forming the photosensitive colored layer. It can be formed by applying the coating liquid for formation on the base material and drying. Further, the radiation curable pressure-sensitive adhesive layer can be laminated on the substrate by a dry laminating method.

The film thickness of the radiation curable pressure-sensitive adhesive layer is about 0.1.
μm to 100 μm, and more preferably about 1 μm to 5
It is preferably in the range of 0 μm. The reason for this is 0.
If it is less than 1 μm, it is difficult to apply it uniformly.
If it exceeds 00 μm, it may be a hindrance in fulfilling a good function as a color filter, and 1 μm.
If it is less than 0.1%, the adhesiveness may decrease (however,
Even if μm ≦ thickness t <1 μm, there is adhesiveness. ), The cushioning property is lost, the adhesion with the photosensitive colored transfer layer is deteriorated, and when it exceeds 50 μm, the degree of curing by exposure is difficult to spread over the entire film thickness of the radiation curable pressure-sensitive adhesive layer (however, Even if 50 μm <thickness t ≦ 100 μm, it can be cured to some extent.)

The radiation-curable pressure-sensitive adhesive layer cures when irradiated with energy rays such as radiation (ultraviolet rays, electron beams, etc.) and changes from tackiness to adhesion, resulting in extremely high adhesion and holding power. .

When the trace amount of active points remaining in the radiation-curable adhesive / adhesive is —COOH group, —OH group, or —NH ₂ , the radiation-curable adhesive / adhesive will be contained in the radiation-curable adhesive / adhesive. The initial adhesive strength can be set to an arbitrary value by mixing the isocyanate curing agent. As such a curing agent, a polyvalent isocyanate compound can be cited as a good example, and more specifically, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4- Xylene diisocyanate, diphenylmethane-4,4'-
Diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclomexylmethane-4,
4'-diisocyanate, dicyclohexylmethane-
2,4'-diisocyanate, lysine isocyanate, etc. are used.

Similarly, when the active site is an -NCO group, a curing agent such as glycol, cresol,
Diols such as hexamethylene diol and trimethylol propane are preferred examples.

Similarly, when the active point is an epoxy group, an amine such as hexamethylenediamine or ethylenetetraamine is used as a curing agent. Further, in the case of UV irradiation, a UV initiator is mixed into the above-mentioned radiation-curable adhesive / adhesive so that UV
The polymerization and curing time by irradiation and the UV irradiation amount can be reduced.

[0084]

EXAMPLE First, 2-ethylhexyl acrylate 67 was used as a radiation-curable adhesive layer of a color filter substrate.
Parts by weight, 10 parts by weight of vinyl acetate, 3 parts by weight of hydroxyethyl methacrylate, and 2 of glycidyl acrylate
0 parts by weight are reacted in ethyl acetate at 60 ° C. for 10 hours. To 100 parts by weight of the polymer obtained by this reaction, 0.5 part by weight of a cross-linking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate L) is added to prepare a radiation curable adhesive. This was applied onto a transparent glass substrate with a spinner and then dried at 40 ° C. to prepare a color filter substrate (transfer target). The thickness of the radiation-curable pressure-sensitive adhesive layer was 20 μm.

Next, a photosensitive pigment-dispersed resist for a red filter (trade name: V-25, manufactured by Nippon Steel Chemical Co., Ltd.) was used as a photosensitive coloring layer on a polyester film having a thickness of 30 μm.
9-R) was applied with a wire bar coater and dried at 70 ° C., and the thickness after drying was set to 1.2 μm. Similarly, a photosensitive pigment-dispersed resist for green filters (manufactured by Nippon Steel Chemical Co., Ltd., product name: V-259-G), a photosensitive pigment-dispersed resist for blue filters (manufactured by Nippon Steel Chemical Co., Ltd., products) Name: V-259-B) was used to produce a green filter transfer sheet and a blue filter transfer sheet, respectively.

Next, the photosensitive colored transfer layer of the transfer sheet for the red filter was brought into close contact with the transparent glass substrate having the radiation-curable pressure-sensitive adhesive layer formed thereon, and the pressure-sensitive roll was used to press-bond the photosensitive colored transfer layer to the glass substrate. It was Further, from the support side of the transfer sheet, a chrome mask having a color filter pattern formed thereon was superposed on the glass substrate. Then, from the support side of the transfer sheet, an ultraviolet exposure machine (Oak Seisakusho, trade name:
UV-330AP1) is used to perform exposure of 300 mJ to weaken the adhesive force between the photosensitive colored transfer layer in the mask opening (exposed portion) and the support, and increase the adhesive force of the radiation curable pressure-sensitive adhesive layer. Also planned.

Then, the support of the transfer sheet was peeled off and developed to form a red pattern of the color filter. Subsequently, the color filter base material (transfer target) on which the red pattern is formed is similarly brought into close contact with the photosensitive colored transfer layer of the transfer sheet for the green filter, and the chromium mask of the green filter pattern is provided on the support side of the transfer sheet. Were exposed to ultraviolet light in the same manner as described above, and then the transfer sheet was peeled off and developed to form a green pattern.

Furthermore, the photosensitive colored transfer layer of the transfer sheet for the blue filter is similarly adhered to the color filter substrate (transferred material) on which the red and green patterns are formed, and the blue filter is provided on the support side of the transfer sheet. A pattern chrome mask was overlaid, ultraviolet rays were irradiated and peeling development was performed in the same manner as described above to form a blue pattern. As described above,
A color filter having a pattern of three colors of red, green and blue (so-called RGB) was produced.

[0089]

According to the method of manufacturing a color filter of the present invention, the transfer sheet in the exposed area has a weak adhesive force between the support and the photosensitive colored transfer layer, and the color filter substrate is a radiation-curable adhesive. The adhesive strength of the adhesive layer increases, the adhesive strength between the support and the photosensitive colored transfer layer remains strong in the unexposed area, and the radiation-curable adhesive layer remains weakly tacky. Due to the synergistic effect of the two, it was possible to accurately transfer onto the color filter substrate and prevent transfer unevenness.

Further, according to the method of manufacturing a color filter of the present invention, the color filter can be easily manufactured with high productivity as compared with the conventional transfer method, printing method, electrodeposition method and dyeing method. The part could be formed with high accuracy.

Further, before the formation of these red, green, and blue color filter portions, before the formation of these red, green, and blue color filter portions, at the boundary portion of the red, green, and blue color filter portions, the concealing property is made to overlap. By forming the black filter pattern by a method other than transfer, the concealing property of the black filter part was improved, and a constant color filter part could be formed even when the transfer position of the color filter part was slightly displaced. .

In summary, according to the present invention, (i) there is little color unevenness (that is, while maintaining high display quality), the number of steps is small, the time required for each step is short, the productivity is high, and the solution supply and waste liquid treatment are performed. , The cost of the obtained color filter can be reduced, the color filter and the manufacturing method thereof satisfying the above requirements, and
(ii) It is possible to provide both of a new method of forming a color image, in which there is little color unevenness (that is, while maintaining high display quality), there is no need for equipment for solution supply and waste liquid treatment, and a new method for forming a color image.

[Brief description of drawings]

FIG. 1 is a conceptual diagram schematically showing a pattern forming method according to the present invention.

FIG. 2 is an explanatory diagram showing each step of pattern formation in an example of the method for manufacturing a color filter according to the present invention.

FIG. 3 is an explanatory diagram showing each step in one embodiment of the method for manufacturing a color filter according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Transfer sheet 2 ... Support body 3 ... Photosensitive coloring transfer layer 4 ... Color filter base material 5 ... Radiation-curable pressure-sensitive adhesive layer 6 ... Base material 7 ... Mask 8 ... Radiation (ultraviolet rays, electron beams, etc.) 9a ... Transferred pattern (exposed area) 9b ... Non-transferred pattern (unexposed area) 10 ... Black matrix 11a ... Red color filter Pattern 11b ... Green color filter pattern 11c ... Blue color filter pattern 12 ... Protective layer 13 ... Electrode

Claims (6)

[Claims] 1. A color filter comprising at least a radiation-curable pressure-sensitive adhesive layer and a photosensitive coloring pattern on a substrate in this order. 2. A radiation-curable pressure-sensitive adhesive layer is a composition comprising an acrylic polymer and a low molecular weight compound having a photopolymerizable carbon-carbon double bond in the molecule. The color filter according to claim 1. 3. (a) A radiation-curable pressure-sensitive adhesive layer in which a radiation-curable pressure-sensitive adhesive layer is provided on a substrate in a pretreatment step of a transfer-receiving body, the adhesive force with the substrate being increased by radiation exposure. A pretreatment step using an adhesive layer, and (b) (A) a transfer sheet having a photosensitive coloring transfer layer on the support, the adhesion of which is weakened by exposure to radiation is weakened. A step of superposing so that the transfer layer and the radiation-curable pressure-sensitive adhesive layer are in contact with each other, (B)
An exposure step of selectively exposing the photosensitive colored transfer layer in a region corresponding to a color pattern to be formed with radiation, (C) after which the exposed portion of the photosensitive colored transfer layer is transferred to A peeling step of peeling off the transfer sheet while leaving it on the body; a colored pattern forming step comprising these (A), (B) and (C); and the steps (a) and (b) above. Method for manufacturing color filter. 4. A composition comprising an acrylic polymer and a low molecular weight compound having a photopolymerizable carbon-carbon double bond in the molecule is used as the radiation-curable pressure-sensitive adhesive layer. The method for manufacturing a color filter according to claim 3. 5. A photosensitizer whose adhesion to a support is weakened by radiation exposure on a transfer-receiving material provided with a radiation-curable adhesive / adhesive layer whose adhesion to the substrate is increased by radiation exposure. A transfer sheet having a color-sensitive transfer layer provided on the support so that the photosensitive color-transfer layer and the radiation-curable pressure-sensitive adhesive layer are in contact with each other, and then a transfer sheet corresponding to the image pattern to be formed is formed. The photosensitive colored transfer layer in the region is selectively exposed to radiation, and then the transfer sheet is peeled off by leaving the exposed portion of the photosensitive colored transfer layer on the transfer target. An image forming method comprising forming an image pattern comprising a photosensitive colored transfer layer on the transfer target. 6. A composition comprising an acrylic polymer and a low molecular weight compound having a photopolymerizable carbon-carbon double bond in the molecule is used as the radiation curable pressure-sensitive adhesive layer. The image forming method according to claim 5.