JP3409925B2 - Light-shielding pixel and optical filter using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION A light-shielding pixel according to the present invention is provided.
The transparent substrate is the color filter block used for the display device.
Used for rack matrices, especially color liquid crystal displays
Suitable for black matrix of color filters
Used for [0002] 2. Description of the Related Art Conventionally, when a color filter is created,
Between each pixel of red (R), green (G), blue (B)
The gap is filled with black matte for the purpose of improving display contrast, etc.
Rix is forming. As a method, such as chrome
Method of using metal film as black matrix and light shielding
There is a known method of using a photosensitive resin in which a conductive pigment or the like is dispersed.
Have been. When a metal film such as chromium is used, (1)
(2) Environmental problems due to high light reflectance and poor display quality
(E.g., treatment with an etchant, etc.)
Black matrix on transistor (TFT) substrate side
If it is formed, it has high conductivity,
There is a problem, black matrices using photosensitive resin compositions
Is attracting attention. [0004] However, a black ink using a photosensitive resin composition is used.
In a black matrix, a brass
Black matrix with the same density as the black matrix
In order to obtain the thickness, it is necessary to increase the film thickness, and as a result,
(1) R, G or B after black matrix formation
At the time of applying a pigment dispersion liquid or transferring using a transfer sheet.
Including bubbles, (2) Color fill like MIM method
If a transparent electrode is created between the
Pixels exist between electrodes, making voltage control difficult
(3) Form a black matrix on the TFT substrate side
In this case, the alignment of the liquid crystal is disturbed by the steps of the matrix.
This has caused problems. [0005] The first object of the present invention
Is a thin film, high-concentration shielding
Provided are an optical pixel and an optical filter having the same.
It is in. A second object of the present invention is to provide a photosensitive transfer sheet.
Color filter creation method by transfer method using
To form a black matrix first and then
To provide a method for forming pixels of R, G, B, etc.
You. [0006] SUMMARY OF THE INVENTION A first object of the present invention is to:
For example, (1) It consists of a coloring material containing resin composition,
1.25 μm or more and an optical density of 2.8 or more
Forming a light-sensitive pixel on a transparent substrate, (2) light-shielding property
A step of heat-treating the pixel.
Comprising a resin composition containing 1.25 μm or less,
And a method for forming a light-shielding pixel having an optical density of 2.8 or more.
Achieved by more formed light-shielding pixels. Of the present invention
The second object is (1) to provide a colorant-containing resin composition on a transparent substrate.
Having a thickness of 1.25 μm or less and an optical density
Forming a light-shielding pixel having a degree of 2.8 or more, (2)
One wavelength of the three primary colors of light is transmitted through a part of the transparent part of the transparent substrate.
Pixels composed of excessively or absorbing colorant-containing resin composition
To, Color material that transmits or absorbs one wavelength of the three primary colors of light
Using a transfer sheet having a photosensitive resin composition layer containing
Photo(3) forming a part of a transparent portion of the transparent substrate;
Transmits one wavelength of the three primary colors of light different from (2) or
Pixels made of absorbing colorant-containing resin composition, Three fields of light
A photosensitive tree containing a colorant that transmits or absorbs one wavelength of color
Transfer using a transfer sheet having a fat composition layerWork to form
After the step (1), the steps (2) and (3)
An optical filter characterized by performing the step (3).
Was achieved by the method of forming. Hereinafter, the present invention will be described in detail.
I will tell. (1) Light-shielding image The light-shielding pixel according to the present invention can be formed by a conventional photolithography method or an electric device.
It can be formed by a wearing method and a printing method. Especially
Use a photosensitive light-shielding resin composition in terms of turn accuracy and process simplicity.
The photolithography method used is preferred. In that case, at least
Also, Step of providing a photosensitive light-shielding resin composition layer on a transparent substrate
(Spinner, Wheeler, Roller Coater, Carte
Coater, knife coater, wire bar coater,
Apply with an extruder, etc., dry and light-shield
A coating method in which a light-sensitive resin layer is provided on a substrate, or on a temporary support
At least a light-shielding feeling provided with a light-shielding photosensitive resin composition layer
Use layer transfer method to transfer onto substrate using optical transfer material
Can be. Particularly, a layer transfer method is preferable in terms of the process. Concrete
Japanese Patent Application No. 2-400047 and Japanese Patent Application No. Hei.
3-9292, Japanese Patent Application No. 3-120223, Japanese Patent Application No. 3-1
53227, the transfer material described in Japanese Patent Application No. 4-64870.
Used. ), Pattern exposure, developing, As a result, a light-shielding pixel is formed. In addition, the light-shielding pixel
UV irradiation after development to prevent cracks and protrusions
May be performed. The photosensitive light-shielding resin composition used in the present invention
The product is at least (1) an alkali-soluble binder,
(2) photopolymerization initiator, (3) ethylenically unsaturated double bond
(4) at least one addition polymerizable monomer having
A light-shielding photosensitive resin composition having a coloring agent is preferred. The alkali-soluble vine used in the present invention
As a polymer, a polymer having a carboxylic acid group in a side chain,
For example, JP-A-59-44615, JP-B-54-34
No. 327, JP-B-58-12577, JP-B-54-2
No. 5957, JP-A-59-53836, JP-A-59-53836.
Methacrylic acid described in each of the publications of
Luic acid copolymer, acrylic acid copolymer, itaconic acid copolymer
Copolymer, crotonic acid copolymer, maleic acid copolymer,
There are stealized maleic acid copolymers, etc.
Cellulose derivatives having a boronic acid group are exemplified. this
Added cyclic acid anhydride to polymer with hydroxyl group
Things are also useful. Particularly preferably, US Pat.
Benzyl (meth) acrylate described in JP-A-391
And (meth) acrylic acid copolymers and benzyl (meth)
Of acrylate, (meth) acrylic acid and other monomers
And a base copolymer. The above are water-insoluble
Water-soluble polymer.
Livinylpyrrolidone, polyethylene oxide, polyvinyl
Alcohol and the like. [0010] In addition to the above, various performances, for example,
In order to improve strength, a range that does not adversely affect developability, etc.
In the box, an alkali-insoluble polymer can be added.
These polymers include alcohol-soluble nylon
Or an epoxy resin. Light shielding properties of binder
The solid content in the solid content of the photosensitive resin composition is 10 to 95.
%, More preferably 20-90% by weight. 1
If it is less than 0% by weight, the adhesiveness of the photosensitive resin layer is too high,
Exceeding the weight%, the intensity and light sensitivity of the image formed
Inferior. The photopolymerization initiator used in the present invention
Is disclosed in U.S. Pat. No. 2,367,660.
Vicinal polyketaldonyl compound, U.S. Pat. No. 2,448
No. 828, acyloin ether compound
, Α-carbonization described in U.S. Pat. No. 2,722,512.
Aromatic acyloin compounds substituted with hydrogen, U.S. Pat.
Nos. 3046127 and 2951758
Described polynuclear quinone compounds, US Pat. No. 3,549,367
Patent Application Publication Triarylimidazole dimer and p-a
Combination of minoketone, JP-B-51-48516
Described benzothiazole compound and trihalomethyl-s-
Triazine compounds disclosed in US Pat. No. 4,239,850.
Trihalomethyl-s-triazine compounds described
Which are described in U.S. Pat. No. 4,221,976.
Trihalomethyl oxadiazole compounds and the like.
You. Particularly preferably, trihalomethyl-s-triazine,
Trihalomethyloxadiazole, triarylimida
It is a sol dimer. Photopolymerizable composition of photopolymerization initiator
The solid content in the form is 0.5 to 20% by weight, more preferably.
Preferably it is 1 to 15% by weight. If it is less than 0.5% by weight
Light sensitivity and image intensity are low, and performance exceeds 20% by weight
No good effect is observed. The ethylenically unsaturated double used in the present invention
As an addition polymerizable monomer having a bond, a small amount
At least one addition-polymerizable ethylenically unsaturated group
A compound having a boiling point of 100 ° C. or higher at normal pressure. For example,
Polyethylene glycol mono (meth) acrylate, poly
Propylene glycol mono (meth) acrylate,
Monofunctional acrylic such as nonoxyethyl (meth) acrylate
Rate and monofunctional methacrylate. Polyethylene glycol
Luji (meth) acrylate, polypropylene glycol
Di (meth) acrylate, trimethylolethanetria
Acrylate, trimethylolpropane triacrylate
G, trimethylolpropane diacrylate, neopen
Tyl glycol di (meth) acrylate, pentaerythr
Litol tetra (meth) acrylate, pentaerythri
Tall tri (meth) acrylate, dipentaerythritol
Hexyl (meth) acrylate, dipentaerythritol
Penta (meth) acrylate, hexanediol di
(Meth) acrylate, trimethylolpropanetri
(Acryloyloxypropyl) ether, tri (ac
Liloyloxyethyl) isocyanurate, tri (ac
Liloyloxyethyl) cyanurate, glycerin tri
(Meth) acrylate, trimethylolpropane or grease
Polyfunctional alcohols such as serine are better than ethylene oxide
After addition reaction of pyrene oxide,
One that has been converted to JP-B-48-41708, JP-B-50
-6034 and JP-A-51-37193.
Urethane acrylates listed. JP-A-48-6
No. 4183, JP-B-49-43191, JP-B-52-
Polyester resin described in each publication of No. 30490
Of acrylates, epoxy resin and (meth) acrylic acid
Reaction products such as epoxy acrylates
Relate and methacrylate can be mentioned. Than
Preferably trimethylolpropane tri (meth) acryl
Rate, pentaerythritol tetra (meth) acryle
, Dipentaerythritol hexa (meth) acryle
, Dipentaerythritol penta (meth) acryle
Can be mentioned. Ethylenically unsaturated double bond
Light-shielding photosensitive resin composition of addition polymerizable monomer having
The solid content in the solid content is preferably 5 to 50% by weight.
Or 10 to 40% by weight. Less than 5% by weight
Degree and image intensity are low, and if it exceeds 50% by weight,
The adhesiveness of the fat layer becomes excessive, which is not preferable. At least one type of coloring used in the present invention
Red, green, blue, yellow, purple, magenta
Color, cyan, black pigments and / or dyes are used
However, preferred examples of these include carmine 6B
(CI. 12490), phthalocyanine green
(CI. 74260), phthalocyanine blue (C.I.
I. 74160), Mitsubishi Carbon Black MA-10
0, perylene black (BASF K0084, K00
86), cyanine black, # 1201 lionolye
Low (CI. 21090), Lionol Yellow GR
O (CI. 21090), Shimura-First Yellow
-8GF (CI. 21105), benzidine yellow
4T-564D (CI. 21095), Shimura-Fa
Ostred 4015 (CI. 12355), Riono
Red 7B4401 (CI. 15850),
-Stogen blue TGR-L (CI. 74160),
Lionol Blue SM (CI. 26150), Mitsubishi
Carbon Black MA-100, Mitsubishi Carbon Black #
40, Victoria Pure Blue (CI. 4259)
5), auramine O (CI.41000), carotene
Brilliant flavin (CI basic 13), b
-Damine 6GCP (CI. 45160), rhodamine
B (CI. 45170), Safranin OK 70:10
0 (C.I. 50240), Erioglaucine X (C.I.
I. 42080), First Black HB (CI.
26150), C.I. I. Pigment Red 97, C.I.
I. Pigment Red 122, C.I. I. Pigment
Red 149, C.I. I. Pigment Red 168,
C. I. Pigment Red 177, C.I. I. Pigmen
Tread 180, C.I. I. Pigment Red 19
2, C.I. I. Pigment Red 215, C.I. I. Pig
Men's Green 7, C.I. I. Pigment Green 3
6, C.I. I. Pigment Blue 15: 1, C.I. I. Pi
Pigment blue 15: 4, C.I. I. Pigment Bull
-15: 6, C.I. I. Pigment Blue 22, C.I.
I. Pigment Blue 60, C.I. I. Pigment B
Lou 64, C.I. I. Pigment Yellow 139, C.I.
I. Pigment yellow 83, C.I. I. Pigment Buy
Oret 23 and the like can be mentioned. In addition, metal powder,
White pigments, fluorescent pigments and the like are also used. These colorants
Or a mixture of two or more of
Used to Colorant light-shielding photosensitive resin composition solid
The solids content in the mixture is preferably 1 to 50% by weight.
New In addition to the above components, a thermal polymerization inhibitor is further added.
Is preferably added. Examples include hydroquino
, P-methoxyphenol, di-t-butyl-p-c
Resole, pyrogallol, t-butylcatechol, ben
Zoquinone, 4,4'-thiobis (3-methyl-6-t-
Butylphenol), 2,2'-methylenebis (4-meth
Tyl-6-t-butylphenol), 2-mercaptobe
Nsimidazole, phenothiazine and the like. Further, the composition used in the present invention is required.
Depending on the known additives, such as plasticizers, surfactants and the like
Can be added. The light-shielding photosensitive resin composition is formed from
The thickness of the light-shielding film is in the range of more than 1.25 μm and less than 8 μm.
Enclosure is preferable, and particularly preferably more than 1.25 μm and 4 μm
m or less. If it exceeds 8 μm, problems such as deterioration of developability may occur.
appear. Pixel thickness after development exceeds 1.25 μm
Therefore, heat treatment is performed after development, and the film thickness is 1.25 μm
The following steps are added. This heat treatment achieves the target film thickness
Although the conditions are more different, at least at a temperature of 280 ° C or higher
Heat treatment is required. If the heat treatment temperature is lower than 280 ℃
In this case, the effect of reducing the film thickness cannot be sufficiently obtained. The heat treatment process
Known people such as convection ovens and hot plates
Method, and heat treatment is performed in an inert gas atmosphere such as nitrogen gas.
You may go below. When the pixel thickness exceeds 1.25 μm
Is the R, G, B pigment content after the formation of the black matrix.
Bubbles are entrapped during liquid application and transfer of photosensitive transfer sheet
Problems such as white spots or color defects such as the MIM method
-When creating a transparent electrode between the filter and the substrate,
A light-shielding pixel exists between the electrodes,
A difficult problem arises. When the film thickness is 1.25 μm or less,
The light-shielding pixel having an optical density of 2.8 or more is
To be made by increasing the concentration of light-shielding pigments
Can be. However, prepared using a photosensitive light-shielding resin composition
In this case, the developability deteriorates and the development time becomes longer.
In some cases. Transmits at least one wavelength of the three primary colors of light
Or the three primary colors of light using a photosensitive coloring composition that absorbs
Pixels that transmit or absorb at least one wavelength
To achieve this, the conventional photolithography method, electrodeposition method, or
A printing method can be used. Especially for pattern accuracy,
Photographs using colorant-containing photosensitive resin compositions in terms of simplicity
Litho method is preferred. In that case, at least on the temporary support
Transfer material provided with a colorant-containing photosensitive resin composition layer
A layer transfer method of transferring the image onto a substrate by using is preferred. Transcription
Examples of the materials include JP-A-4-208940 and JP-A-5-208940.
-80503, JP-A-5-173320, JP-A-5-7
The transfer materials described in the examples of each of the publications 2724 and 2724 are cited.
You. Specifically, an alkali-soluble thermoplastic is placed on a temporary support.
Photosensitive with resin layer, intermediate layer and photosensitive resin layer in this order
The adhesion between the layers of the transfer material can be set arbitrarily. As the temporary support for the photosensitive transfer material, heat transfer
It has excellent releasability from the plastic resin layer, and has chemical and thermal properties.
Should be stable and flexible
Specifically, Teflon, polyethylene terephthalate
Sheet, polycarbonate, polyethylene, polypropylene
A thin sheet or a laminate thereof is preferred. Provisional
The thickness of the support is suitably from 5 μm to 300 μm.
More preferably, it is 20 μm to 150 μm. Depending on the transfer conditions of the photosensitive transfer material, the transfer
During copying, the thermoplastic resin protrudes into the surroundings and stains the permanent support.
May be dyed. To prevent this phenomenon,
Of these thermoplastic resins, those soluble in aqueous alkali solutions
Is preferred. If it can be dissolved in an alkaline aqueous solution,
Because it can be easily removed by later processing.
You. The resin constituting the thermoplastic resin layer is substantially
It is preferable that the softening point is 80 ° C. or less. Softening point
As an alkali-soluble thermoplastic resin of 80 ° C. or less,
Saponified ethylene and acrylate copolymers,
Saponification of Tylene and (meth) acrylate Copolymer
Product, vinyl toluene and (meth) acrylic acid ester
Saponified compound, poly (meth) acrylate,
Butyl (meth) acrylate and vinyl acetate
From saponified products such as acrylate copolymers
It is preferable that one is selected, but “Plastic
Performance Handbook ”(Japan Plastics Industry Federation, All Japan Plastic
Edited by the Stick Molding Industry Federation, published by the Industrial Research Council, 196
Softening point of about 80 ° C or less
Use organic polymers that are soluble in aqueous alkaline solutions
Can be Organic polymer having a softening point of 80 ° C or higher
Also in the substance, the organic polymer substance and the polymer substance
Adds various compatible plasticizers to increase the actual softening point
It is also possible to lower the temperature below 80 ° C. Also, these
To control the adhesive strength with temporary support in organic polymer
Various types of polyethers have a softening point not exceeding 80 ° C.
, Supercooled substances, adhesion improvers or surfactants,
It is possible to add a template, etc. Examples of preferred plasticizers include polypropylene
Len glycol, polyethylene glycol, dioctyl
Phthalate, diheptyl phthalate, dibutyl phthalate
G, tricresyl phosphate, cresyl diphenyl
Phosphate biphenyl diphenyl phosphate
Can be mentioned. The thickness of the thermoplastic resin layer is preferably 6 μm or more.
New This is because the thickness of the thermoplastic resin layer is 5 μm.
If it is less than 1 μm, the unevenness of the underlayer of 1 μm or more is completely absorbed
Because it is impossible. For the upper limit,
About 100 μm or less, preferably about 50
μm or less. As an intermediate layer, water or an aqueous alkali solution is used.
If it disperses or dissolves and shows low oxygen permeability
Well, known ones can be used. For example, JP-A-46-
No. 2121 and JP-B-56-40824.
Polyvinyl ether / maleic anhydride polymer
Water-soluble salt of boxyalkyl cellulose, water-soluble cellulose
Sugar ethers, water-soluble salts of carboxyalkyl starch,
Vinyl alcohol, polyvinylpyrrolidone, various
Liacrylamides, various water-soluble polyamides, polya
Water-soluble salt of crylic acid, gelatin, ethylene oxide
Water solubility of the group consisting of coalesced, various starches and their analogues
Salt, styrene / maleic acid copolymer, and maleine
And a combination of two or more of these.
It is. Particularly preferred is polyvinyl alcohol
And polyvinylpyrrolidone. Polyvinyl
It is preferable that the alcohol has a saponification rate of 80% or more.
The content of polyvinylpyrrolidone is 1% of the solid content of the intermediate layer.
% By weight to 75% by weight, more preferably 1% by weight.
% To 60% by weight, more preferably 10% to 50% by weight
%. If the content is less than 1% by weight, sufficient
If the adhesion cannot be obtained and the amount exceeds 75% by weight,
descend. The thickness of the intermediate layer is very thin, about 0.1 to 5
μm, especially 0.5 to 2 μm. Less than about 0.1μm
If the oxygen permeability is too high and exceeds 5 μm,
Or it takes too much time to remove the intermediate layer. The temperature of the photosensitive resin layer is at least 150 ° C.
Preferably softened or tacky, thermoplastic
Preferably, there is. Layer using known photopolymerizable composition
Most of these layers have this property, but some of the known layers
Addition of a plastic binder or a compatible plasticizer
Can be further modified. In the present invention, the material of the photosensitive resin layer is
For example, Japanese Patent Laid-Open No. 3-282404, No. 2
Photosensitivity described on page 0, line 7 to page 32, line 10
All resins can be used. Specifically, a negative-type diazo tree
Photosensitive resin layer composed of fat and binder, photopolymerizable composition,
Photosensitive resin composition consisting of azide compound and binder
And a cinnamic acid-type photosensitive resin composition. Among them
However, particularly preferred is a photopolymerizable resin. Its photopolymerization
Resins are photopolymerization initiators, photopolymerizable monomers and binders.
And a basic component. As the photosensitive resin composition, an aqueous alkali solution is used.
Developable with liquid and Developable with organic solvent
Are known, but pollution prevention and occupational safety
From the viewpoint, those which can be developed with an aqueous alkali solution are preferable. The photosensitive resin composition layer further contains a dye and a pigment.
Can be added. All pigments are photosensitive resin layer
Particles that are uniformly dispersed in
Diameter, particularly preferably not more than 1 μm
Must. When creating a color filter,
Those having a particle size of 0.5 μm or less are preferred. Examples of preferred dyes or pigments are as follows:
is there. Victoria Pure Blue BO (CI.42
595), auramine (CI.41000),
To Black HB (CI. 26150), Monolight
-Yellow GT (CI Pigment Yellow 12), par
Monant Yellow GR (CI Pigment Yellow 1
7), permanent yellow HR (CI pigment)
-Yellow 83), permanent carmine FBB (C.
I. Pigment Red 146), Hoster Bamurette
ESB (CI Pigment Violet 19),
Permanent Ruby FBH (C.I.
11) Fastel Pink B Supra (CI Pig)
Mento Red 81) Monastral First Bull
-(CI Pigment Blue 15), Monolight
First Black B (CI Pigment Black
1) and carbon. Further form color filters
Pigments suitable for use include C.I. I. Pigment Red
De 97, C.I. I. Pigment Red 122, C.I. I.
Pigment Red 149, C.I. I. Pigment Red
C. 168, C.I. I. Pigment Red 177, C.I.
I. Pigment Red 180, C.I. I. Pigment
Red 192, C.I. I. Pigment Red 215,
C. I. Pigment Green 7, C.I. I. Pigment
・ Green 36, C.I. I. Pigment Blue 15:
1, C.I. I. Pigment Blue 15: 4, C.I. I. Pi
Pigment blue 15: 6, C.I. I. Pigment Bull
-22, C.I. I. Pigment Blue 60, C.I. I. Pi
Gment Blue 64. [0033] On the photosensitive resin composition layer,
Provide a thin covering sheet to protect from contamination and damage
Is preferred. The covering sheet is the same as the temporary support or
It may be made of a similar material, but the photosensitive resin composition layer
Must be easily separated. As covering sheet material
For example, silicone paper, polyolefin or polyethylene
Trafluoroethylene sheets are suitable. Cover sheet
Is preferably about 5 to 100 μm. Especially good
Preferably 10 to 30 μm thick polyethylene or polyp
It is a propylene film. The photosensitive transfer material used in the present invention is a temporary support.
Apply the thermoplastic resin layer solution on the support and dry it.
A thermoplastic resin layer, and then apply heat on the thermoplastic resin layer.
Dissolution of interlayer material consisting of solvent that does not dissolve the plastic resin layer
Apply the solution, dry it, and then dissolve the photosensitive resin layer into the intermediate layer.
Apply and dry with a solvent that does not dissolve. Or another coating
Provide a photosensitive resin layer on the sheet, and on the temporary support
The sheet of both the thermoplastic resin layer and the sheet with the intermediate layer
Paste each other so that the intermediate layer and the photosensitive resin layer are in contact with each other.
Or as a separate covering sheet
A temporary support having a resin layer is prepared, and the thermoplastic resin layer is prepared.
With the photosensitive resin layer and the intermediate layer on the cover sheet.
Advantageously manufactured by laminating the intermediate layer of
It is. Here, a photosensitive transfer material is placed on a permanent support.
Attempt to peel temporary support after laminating photosensitive resin layer
Then, the film and the human body become charged, causing an unpleasant electric shock
May be received, and because of this charging,
In the subsequent exposure process, unexposed areas occur,
May cause holes. To prevent electrification
To provide a conductive layer on at least one surface of the temporary support.
The surface electric resistance is set to 1013Ω or less, or
The support itself is given conductivity and its surface electric resistance is reduced to 10
It is preferable to use one having a resistance of 13Ω or less. Hereinafter, the present invention will be described in more detail with reference to Examples.
Although described, the present invention is limited to these examples.
There is no. [0037] 【Example】 Example 1 100 μm thick polyethylene terephthalate film
A coating solution having the following formulation H1 is applied on the temporary support,
After drying, provide a thermoplastic resin layer with a dry film thickness of 20 μm.
Was. Thermoplastic resin layer formulation H1: ・ Methyl methacrylate / 2-ethylhexyl acrylate / benzyl       Methacrylate / methacrylic acid copolymer (copolymer composition ratio (molar ratio)       = 55 / 28.8 / 11.7 / 4.5, weight average molecular weight = 90000)                                                             15 parts by weight ・ Polypropylene glycol diacrylate (average molecular weight = 822)                                                           6.5 parts by weight ・ 1.5 parts by weight of tetraethylene glycol dimethacrylate ・ 0.5 parts by weight of p-toluenesulfonamide ・ Benzophenone 1.0 parts by weight ・ 30 parts by weight of methyl ethyl ketone Next, the following formulation B1 was placed on the thermoplastic resin layer.
And dried to a dry film thickness of 1.6 μm.
An intermediate layer having a thickness of m was provided. Intermediate layer formulation B1: ・ Polyvinyl alcohol (PVA205 manufactured by Kuraray Co., Ltd., saponification rate = 80%)                                                           130 parts by weight ・ Polyvinylpyrrolidone (PVP, K-90, manufactured by GAF Corporation)                                                             60 parts by weight ・ 10 parts by weight of fluorine-based surfactant (Surflon S-131 manufactured by Asahi Glass Co., Ltd.) ・ Distilled water 3350 parts by weight 4 having the thermoplastic resin layer and the intermediate layer
On a temporary support, each having the formulation of Table 1
For optical layer, red (for R layer), green (for G layer) and blue (for B layer)
4 layers of the photosensitive solution), dried and dried.
Is a colored photosensitive resin having a light-shielding layer of 2 μm and R, G, and B layers of 1 μm.
A layer was formed. [0040]                         Table 1: Composition of coating solution for colored photosensitive layer                                         Red green blue black                                       (G) (g) (g) (g) ──────────────────────────────────── Benzyl methacrylate /   Methacrylic acid copolymer 25.7 33.5 39.9 40.6   (Molar ratio = 72/28, molecular weight = 30,000) ──────────────────────────────────── Dipentaerythritol hexaacry 27.0 25.2 31.9 30.5   Rate (DPHA made by Nippon Kayaku) ──────────────────────────────────── F177P (Dainippon Ink Fluorine 0.17 0.19 0.19 0.30   Surfactant) ──────────────────────────────────── 2,4-bis (trichloromethyl)-   6- [4- (N, N-diethoxycal 1.31 0 1.52 1.47   Bonylmethyl) -3-bromophenyl]   -S-triazine (photopolymerization initiator) ──────────────────────────────────── 2-trichloromethyl-5- (P-styrene   Rylstyryl) -1,3,4-oxa 0 1.20 0 0   Diazole (photopolymerization initiator) ──────────────────────────────────── Phenothiazine 0.022 0.020 0.026 0.015 ──────────────────────────────────── Chromophthal Red A2B 27.0 0 0 0 ──────────────────────────────────── Paliotor Yellow LY-1820 9.3 7.98 0 0 ──────────────────────────────────── Monastral Green 6Y 0 31.92 0 0 ──────────────────────────────────── Heliogen Blue L6700F 0 0 25.6 0 ──────────────────────────────────── Lionogen Violet VRL 0 0 0.8 0 ──────────────────────────────────── Carbon black 0 0 0 27.1 ──────────────────────────────────── Methoxy propylene glycol 310 310 310 310 ──────────────────────────────────── Methyl ethyl ketone 460 460 460 460 ──────────────────────────────────── Further, a polypropylene is formed on the photosensitive resin layer.
Crimping a ren (12 μm thick) coated sheet, red and blue
A color, green and light-shielding photosensitive transfer material was prepared. Using this photosensitive transfer material, the following method
Created a color filter. Light-shielding photosensitive transfer material
The cover sheet is peeled off, and the photosensitive resin layer surface is
Laminator (Taisei Laminator)
Pressure (0.8 kg / cm) using VP-II
^Two), Heating (130 ° C) and bonding, then temporary support
At the interface between the body and the thermoplastic resin layer, removing the temporary support
did. Next, it is exposed through a predetermined photomask,
Develop with an aqueous solution of sodium acid to remove unnecessary parts,
A light-shielding image with a film thickness of 2.0 μm and an optical density of 3.0 on the substrate
An elementary pattern was formed. After that, 1000mj / c from both sides
m^TwoExposure to UV light was performed. In addition, 350
1 hour heat treatment in a convection oven at ℃
As a result, a light-shielding property with a film thickness of 1.0 μm and an optical density of 3.0 was obtained.
Image obtained. Next, a light-shielding pixel pattern was formed.
On a glass substrate, apply a red photosensitive transfer material
, Peeling, exposing, and developing.
Formed a turn. After that, the red pixel pattern
In a convection oven at 220 ° C to cure
Heat treatment was performed for 20 minutes. Similar process with green and blue feeling
Repeat with optical transfer material and color
A filter was formed. In these steps, red light
Bubbles during transfer in the process after the transfer of conductive transfer material
No good transferability was exhibited. MIM liquid crystal
When a display device is created, color filters including light-shielding pixels
Since the filter layer is 1 μm or less, voltage control is easy.
Was. Embodiment 2 In Example 1, the thickness of the R, G, and B layers was changed to 2 μm.
The other steps were the same as in Example 1. Color filter obtained
気 indicates a vacuum during transfer in a process after transfer of the red photosensitive transfer material.
No transfer of bubbles, good transferability, whitening defects
A color filter having no color was obtained. Embodiment 3 The photosensitive solution for a light-shielding layer of Example 1 was directly applied to a transparent glass substrate.
It is applied so that the film thickness after drying becomes 2 μm,
Exposure through a mask and 1% aqueous solution of sodium carbonate
Developing to remove unnecessary parts, 2.0 μm thick on glass substrate
m to form a light-shielding pixel pattern having an optical density of 3.0
Was. After that, 1000mj / cm from both sides^TwoEnergy of purple
External light exposure was performed. In addition, convection at 350 ° C
A heat treatment was performed in an oven for 1 hour.
At 0 μm, a light-shielding image having an optical density of 3.0 was obtained. That
Thereafter, R, G, and B pixels are formed in the same manner as in the first embodiment, and the transparent pixel is formed.
A color filter was formed on a lath substrate. These engineering
In the process after the transfer of the red photosensitive transfer material.
No bubbles in the transfer of color photosensitive transfer material, good
Good transcription properties were shown. In addition, MIM type liquid crystal display device
If created, color filter layer including light-shielding pixels
Was 1 μm or less, so that voltage control was easy. Embodiment 4 Photopolymerization initiator was removed from the photosensitive solution for a light-shielding layer in Example 1.
Using the liquid with the prescribed formulation, dry directly on a transparent glass substrate by printing.
Print the pattern so that the film thickness after drying becomes 2 μm.
2.0 μm thick and optical density of 3.0 on a substrate
A pixel pattern was formed. Thereafter, at 350 ° C.
Perform heat treatment for one hour in a convection oven.
As a result, a light-shielding image having a film thickness of 1.0 μm and an optical density of 3.0 was obtained.
I got Then, the R, G, and B pixels are formed as in the first embodiment.
To form a color filter on a transparent glass substrate.
Was. In these steps, the transfer of the red photosensitive transfer material
Bubble during transfer of colored photosensitive transfer material in subsequent steps
It showed good transferability without any bleeding. In addition, the MIM method
When a liquid crystal display device is created, color
-Voltage control is easy because the filter layer is 1 μm or less.
Was. Examples 5 to 7 On the substrate after forming the light-shielding image of Examples 1, 3 and 4,
Forming a light-shielding image directly with the photosensitive solution for the R layer of Example 1
Coated so that the film thickness after drying becomes 1 μm on the dried substrate
Exposure and development to form a red pixel pattern.
Was. Then, to fully cure the red pixel pattern
In a convection oven at 220 ° C for 20 minutes.
Was done. Then, the photosensitive solution for the G and B layers of Example 1
In the same manner, the coating-exposure-development-
A color filter was formed on a glass substrate. these
In the process, in the process after the transfer of the red photosensitive transfer material,
Good without air bubbles when applying colored photosensitive solution
It showed excellent applicability. In addition, a MIM type liquid crystal display device was created.
When formed, the color filter layer including the light-shielding pixels
Since it was 1 μm or less, voltage control was easy. Examples 8 to 10 On the substrate after forming the light-shielding image of Examples 1, 3 and 4,
Removal of photopolymerization initiator from photosensitive solution for R layer in Example 1
After drying on the substrate on which the light-shielding pixels are formed,
The pattern is printed so that the film thickness of
A pattern was formed. After that, the red pixel pattern
Convection oven at 220 ° C to cure
For 20 minutes. Then, G of Example 1
The solution obtained by removing the photopolymerization initiator from the photosensitive solution for layer B is
Perform the pattern printing-heat treatment process in the same way
A color filter was formed on the substrate. In these steps
In the process after the transfer of the red photosensitive transfer material,
Shows good printability with no bubbles during liquid printing
did. When a MIM type liquid crystal display device is created,
The color filter layer including the light-shielding pixel is 1 μm or less.
Therefore, voltage control was easy. Embodiment 11 The photosensitive solution for the light-shielding layer in Example 1 was changed as shown in Table 2 below.
A light-shielding photosensitive composition having the same layer structure as that of Example 1
A transfer material was prepared. Light-shielding photosensitive resin layer in this case
Had a dry film thickness of 1.0 μm. [0050]                         Table 2: Composition of coating solution for colored photosensitive layer ・ Benzyl methacrylate / methacrylic acid copolymer 30.6 g     (Molar ratio = 72/28, molecular weight = 30,000) ・ Dipentaerythritol hexaacrylate 20.5g     (DPHA manufactured by Nippon Kayaku) ・ F177P (fluorinated surfactant manufactured by Dainippon Ink) 0.30 g -2,4-bis (trichloromethyl) -6- [4-1.47 g     (N, N-diethoxycarbonylmethyl) -3-     Bromophenyl] -s-triazine (photopolymerization initiator) ・ Phenothiazine 0.015g ・ Carbon black 47.1g ・ 310 g of methoxypropylene glycol ・ 460 g of methyl ethyl ketone In the same manner as in Example 1, the exposure-development process
A light-shielding image was formed. In this case, the current
Although the image time is as long as 150 seconds, the obtained light-shielding image
Had a film thickness of 1.0 μm and an optical density of 3.1.
Therefore, the heat treatment at 350 ° C. performed in Example 1 needs to be performed.
There was no. After that, the color filter is used in the same manner as in the first embodiment.
After creating a color filter, the obtained color filter was implemented
The same result as in Example 1 was obtained. Embodiment 12 Uses a substrate on which a thin film transistor circuit (TFT) is formed
And the light-shielding photosensitive transfer material of Example 1 was used.
A light-shielding image was formed on the TFT substrate in the same process as in step 1.
Since the thickness of the obtained light-shielding image is as thin as 1.0 μm,
In the case of a crystal display panel, no alignment disorder occurred. Comparative Examples 1 to 9 The heat treatment of the light-shielding pixel patterns of Examples 1 and 3 to 10
Same as Examples 1, 3 and 4 except that the temperature was 20 ° C. for 1 hour
I went to. As a result, the optical density was 3.0 in the heat treatment.
Despite this, the thickness is as thick as 1.5 μm, followed by R, G, B
In the pixel formation process, white defects occur due to the inclusion of bubbles.
Was. When a MIM type liquid crystal display device is created,
The color filter layer including the light-shielding pixel is 1 μm or more.
Therefore, voltage control was difficult. Comparative Example 10 In Example 12, the heat treatment of the light-shielding image was performed at 220 ° C.
The procedure was performed in the same manner as in Example 12 except that the procedure was performed for 1 hour. The result
As a result, the thickness of the obtained light-shielding image was as thick as 1.5 μm,
When a crystal display panel is used, the step caused by the light-shielding image
It was large and disordered alignment occurred. [0055] According to the present invention, a substrate having light-shielding pixels according to the present invention is used.
Color filters have no defects due to air bubbles.
In addition, when a MIM type liquid crystal display device is created,
The color filter layer including the light-shielding pixel is 1 μm or less.
Therefore, voltage control is easy.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-8-5829 (JP, A) JP-A-2-239204 (JP, A) JP-A-5-264985 (JP, A) JP-A-7- 34031 (JP, A) JP-A-58-49941 (JP, A) JP-A-58-137830 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7 / 42 G02B 5/20 101

Claims (1)

(1) Claims: (1) On a transparent substrate, a colorant-containing resin composition having a film thickness of 1.25 μm or less and an optical density of 2.8 or more. (2) forming a pixel made of a colorant-containing resin composition that transmits or absorbs one wavelength of the three primary colors on a part of the transparent portion of the transparent substrate ; Color material that transmits or absorbs one wavelength
Using a transfer sheet having a photosensitive resin composition layer containing
To copy forming step, (3) a part of the transparent portion of the transparent substrate a pixel composed of a coloring material-containing resin composition which transmits or absorbs one wavelength of the three primary colors of different light and (2), light 3 fields
A photosensitive tree containing a colorant that transmits or absorbs one wavelength of color
A method of forming a transfer using a transfer sheet having a fat composition layer , wherein the steps (2) and (3) are performed after the step (1). .