JPH0728236A - Light shielding photosensitive resin composition and forming method of light shielding picture image - Google Patents

Abstract

PURPOSE:To provide a photosensitive resin compsn. having high optical density and light shielding property which can be cured with light to a deep part of the film even with low quantity of exposure light, to provide a transfer material using this resin compsn., and to provide a method to form a light shielding picture image of high optical density using this cmpsn. by self-alignment method. CONSTITUTION:This light shielding photosensitive resin compsn. contains at least (1) alkali-soluble binder, (2) photopolymn. initiator, (3) additional polymerizable monomer having a ethylene-type unsatd. double bond, and (4) at least two kinds of coloring agents. When this compsn. is used to form a light shielding photosensitive resin layer of 1-3mum thickness showing black or almost black color phase, the film has <=2 transmissivity for a visible ray region and the ratio of transmissivity for visible ray region to UV ray region is 1:1 to 20:1. This compsn. is formed on a temporary supporting body to constitute a transfer material. The compsn. above described or the transfer material is used fox the method to form a light shielding picture image.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-shielding photosensitive resin composition which is sufficiently photo-cured to the depth of a film, a light-shielding photosensitive transfer material, and a light-shielding image forming method using the same. In particular, the light-shielding photosensitive resin composition, the light-shielding photosensitive transfer material, and the image forming method using the same according to the present invention are suitably used for producing a color filter by a self-alignment exposure method.

[0002]

2. Description of the Related Art Conventionally, in the production of color filters, R (red), G (green), and B (blue) are provided with a black matrix R in the gap between pixels for the purpose of improving display contrast.
It is formed in the gap between the G and B pixels. Known methods include using a metal film of chromium or the like as a black matrix and using a photosensitive resin in which a light-shielding pigment or the like is dispersed. In any case, the black matrix and each of the R, G, and B pixels are formed so as to partially overlap each other for the purpose of preventing white spots and the like caused by misalignment. The black matrix using a metal film such as chromium is formed by forming a metal film on a substrate by a method such as vapor deposition, and then patterning the metal film by photolithography using a photoresist and an etching process. The method of using a photosensitive resin in which a light-shielding pigment or the like is dispersed is such that a photosensitive resin layer in which the light-shielding pigment or the like is dispersed is formed on a substrate by a method such as coating or printing, and a black matrix is used in the process of pattern exposure-development. Is formed.

On the other hand, as disclosed in, for example, Japanese Unexamined Patent Publication (Kokai) No. 62-9301, a method of forming a black matrix by a self-alignment method using a photosensitive resin in which a light-shielding pigment or the like is dispersed is cost and manufacturing. It is attracting attention from the aspect of the process. In this method, a photosensitive resin layer in which a black light-shielding pigment such as carbon black is dispersed is provided on a substrate on which each R, G, B pixel is formed, and each R, G, B pixel is a photomask. Exposure from the back side to form a black matrix in the pixel gap. In this case, there is an advantage that the alignment work which has been necessary in the past can be omitted and the white spot is not generated in principle.

In this self-alignment method, the light-shielding photosensitive resin layer is not sufficiently cured during exposure from the back surface, that is, the light-absorbing property of the black light-shielding pigment such as carbon in the light-sensing wavelength region of the light-shielding photosensitive resin layer. Since it is large, there is a problem that the exposure from the back surface does not reach the surface of the light-shielding film sufficiently to cause insufficient photo-curing, resulting in a low optical density of the obtained light-shielding film.

As a light-shielding photosensitive material which is photo-cured to the depth of the light-shielding film, Japanese Patent Laid-Open No. 3-274503 discloses a photoresist which is transparent to ultraviolet light and opaque to visible light. Also, a compound satisfying as a compound having a higher transmittance in the ultraviolet region and a black hue is very special, and some metal oxides are mentioned. However, these metal oxides have a problem in dispersibility in a photosensitive resin liquid or the like.

As a light-shielding material, Japanese Patent Application Laid-Open No. 4-13105 discloses a light-shielding film in which pigments of two colors complementary to each other are mixed. However, it is considered from the viewpoint of conductivity, and the hue is black. However, the transmittance in the ultraviolet region is not improved.

Japanese Unexamined Patent Publication No. 63-309916 discloses a light-shielding photosensitive material in which pigments having a plurality of hues are combined. However, in this case, a plurality of pigments are simply combined to obtain a light-shielding property, and the light-shielding film cannot be cured to a deep portion.

Further, JP-A-4-40420 and JP-A-4-40420
190362 discloses a light-shielding material obtained by mixing a plurality of organic pigments and carbon or a mixture of a plurality of organic pigments and an organic black pigment. All of these were examined from the viewpoint of the conductivity of the light-shielding material, and by combining a light-shielding material such as carbon with a pseudo-black material obtained by mixing pigments having a complementary color relationship such as a combination of red and blue It forms a black matrix having a low light blocking property and a high light blocking property, and the light blocking image forming property by self-alignment is still insufficient.

[0009]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a high optical density light-shielding photosensitive resin composition which is photo-cured to a deep portion of a film even with a low exposure amount, and a transfer material using the same. is there. A second object of the present invention is to provide a method of forming a light-shielding image having high optical density by a self-alignment method.

[0010]

The object of the present invention is to provide at least (1) an alkali-soluble binder, (2) a photopolymerization initiator, (3) an addition-polymerizable monomer having an ethylenically unsaturated double bond, and (4) ) In a light-shielding photosensitive resin composition containing at least two kinds of colorants, it is visible when a light-shielding photosensitive resin layer having a hue equal to or close to black and a film thickness of 1 to 3 μm is formed. A light-shielding photosensitive resin composition, which has a transmittance in the light region of 2 or less, and a ratio of the transmittance in the visible light region to the transmittance in the ultraviolet light region is 1: 1 to 20: 1. This is achieved by a transfer material in which the composition is provided on a temporary support, and a light-shielding image forming method using the composition or the transfer material. Hereinafter, the present invention will be described in detail.

In the embodiment of claim 8, in order to transfer the light-shielding photosensitive resin composition, at least pressure is usually applied and heating is performed to bring the two film surfaces into close contact with each other. After this, the temporary support is peeled off, but this step may be carried out either before or after exposure through the transparent substrate, and it may be removed before the development processing.

The alkali-soluble binder used in the present invention is a polymer having a carboxylic acid group in its side chain,
For example, JP-A-59-44615 and JP-B-54-34.
No. 327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-2
5957, JP-A-59-53836, JP-A-59-
Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer as described in each specification of No. 71048. Examples thereof include cellulosics, which have a carboxylic acid group in the side chain. In addition, a polymer having a hydroxyl group and a cyclic acid anhydride added thereto is also useful. Particularly preferably, U.S. Pat. No. 413
Copolymer of benzyl (meth) acrylate and (meth) acrylic acid described in 9391 and benzyl (meth)
Mention may be made of multi-component copolymers of acrylate, (meth) acrylic acid and other monomers. The above are water-insoluble binders, but as a water-soluble polymer,
Examples thereof include polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol and the like. Besides the above,
In order to improve various properties, for example, the strength of the cured film, an alkali-insoluble polymer can be added within a range that does not adversely affect the developability and the like. Examples of these polymers include alcohol-soluble nylon and epoxy resin. The solid content of the binder in the light-shielding photosensitive resin composition solid content is 10 to 95% by weight, and more preferably 20 to 90% by weight. If it is less than 10% by weight, the tackiness of the photosensitive resin layer is too high, and if it exceeds 95% by weight, the strength and photosensitivity of the formed image are poor.

Examples of the photopolymerization initiator used in the present invention include vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,376,660 and US Pat. No. 244.
Acyloin ether compounds described in US Pat. No. 8,828, α described in US Pat. No. 2,722,512.
Hydrocarbon-substituted aromatic acyloin compounds, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, US Pat. No. 3,549.
No. 367, a combination of a triarylimidazole dimer and p-aminoketone, JP-B-51-4851.
Benzothiazole compound and trihalomethyl-s-triazine compound described in US Pat.
The trihalomethyl-s-triazine compound described in No. 0 specification, the trihalomethyl oxadiazole compound described in US Pat. No. 4,212,976 and the like can be mentioned. Particularly preferred are trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer. The solid content of the photopolymerization initiator in the photopolymerizable composition is 0.5 to 20% by weight.
And more preferably 1 to 15% by weight. If it is less than 0.5% by weight, the photosensitivity and image strength are low, and if it exceeds 20% by weight, no good effect on the performance is recognized.

The addition-polymerizable monomer having an ethylenically unsaturated double bond used in the present invention has at least one addition-polymerizable ethylenically unsaturated group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. Is a compound of. For example, monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate. Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate , Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxy) Ethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri Meth) acrylate, after the addition reaction of ethylene oxide by propylene oxide to a polyfunctional alcohol such as trimethylolpropane or glycerol (meth) those acrylated. Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50
Urethane acrylates described in JP-A-6034 and JP-A-51-37193. JP-A-48-6
No. 4183, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, described in each publication of No. 30490 can be mentioned. More preferable examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate. The solid content of the addition-polymerizable monomer having an ethylenically unsaturated double bond in the light-shielding photosensitive resin composition solid is 5 to 50% by weight, more preferably 10 to 40% by weight. If it is less than 5% by weight, photosensitivity and image strength are low, and if it exceeds 50% by weight, the tackiness of the photosensitive resin layer becomes excessive, which is not preferable.

As the at least two kinds of colorants used in the present invention, red, green, blue, yellow, purple, magenta, cyan and black pigments and dyes are used. The following are mentioned.

As red, monoazo type, disazo type,
Xanthene-based, anthraquinone-based, perylene-based, perinone-based, quinacridone-based and pyranthrone-based organic or inorganic pigments. Among these, anthraquinone pigments are preferable.

As green, triphenylmethane-based, phthalocyanine-based, nitroso-based, indamine-based, monoazo-based and anthraquinone-based organic or inorganic pigments. Of these, phthalocyanine pigments are preferable.

Blue is a triphenylmethane-based, phthalocyanine-based, anthraquinone-based, triarylmethane-based, disazo-based or indigoid-based organic or inorganic pigment. Of these, phthalocyanine pigments are preferable.

As yellow, monoazo type, disazo type,
Anthraquinone-based, isoindolinone-based, quinophthalone-based, benzimidazolone-based and dioxime-based organic or inorganic pigments are used. Of these, isoindolinone pigments are preferred.

Examples of purple include xanthene-based, triphenylmethane-based, anthraquinone-based, monoazo-based, dioxazine-based, quinacridone-based, indigoid-based and perylene-based organic or inorganic pigments. Of these, dioxazine-based pigments are preferable.

As the black color, a carbon type pigment is preferable.

Preferred specific examples of these include carmine 6B (CI. 12490), phthalocyanine green (CI. 74260), phthalocyanine blue (CI. 74160), Mitsubishi carbon black MA-
100, perylene black (BASF K0084, K
0086), cyanine black, # 1201 lionol yellow (CI 21090), lionol yellow GRO (CI 21090), shimura-first yellow 8GF (CI 21105), benzidine yellow 4T-564D ( CI 21095), Shimura-
Fast Red 4015 (C.I. 12355), Lionol Red 7B4401 (C.I. 15850),
Fast Gen Blue TGR-L (C.I. 7416
0), Rionol Blue SM (C.I. 26150),
Mitsubishi Carbon Black MA-100, Mitsubishi Carbon Black # 40, Victoria Pure Blue (C.I.425
95), auramine O (CI. 41000), carotene brilliant flavin (CI. Basic 13),
Rhodamine 6GCP (C.I.45160), Rhodamine B (C.I.45170), Safranine OK 70: 1
00 (C.I. 50240), Erioglaucine X
(C.I. 42080), Fast Black HB
(C.I. 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. I. Pigment Red 177, C.I. I.
Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 215, C.I.
I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Blue 15: 1,
C. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 2
2, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64, C.I. I. Pigment Yellow 13
9, C.I. I. Pigment Yellow 83, C.I. I. Pigment Violet 23 and the like. Other than these, metal powder, white pigment, fluorescent pigment, etc. are also used. Two or more kinds of these colorants are mixed and used so that the hue becomes black.

The combination and mixing ratio of these colorants when mixed are such that the light-shielding photosensitive resin composition is equal to or close to black in hue, and the light-shielding photosensitive resin composition is When the thickness of the material layer is 1 to 3 μm, the transmittance in the visible light region is 2 or less, and the ratio of the transmittance in the visible light region to the transmittance in the ultraviolet light region is 1: 1 to 20: 1. To be selected.

Hue equal to or close to black means that the achromatic color point defined by the CIE colorimetric method in a light source (F10 light source, etc.) used in a display device such as a liquid crystal display panel is black. Is defined and its achromatic point x, y
It is defined that the values of Δx and Δy, which are the differences from the values, are in the range of Δx ≦ 0.1 and Δy ≦ 0.1. If the hue is other than the above, the display contrast of the liquid crystal display panel will be insufficient.

The transparency of the light-shielding photosensitive resin composition in the visible light region is defined by the Y value which is one of the three stimulus values represented by the CIE colorimetric method, and 0.01≤Y≤2. It is preferably in the range of. When the Y value exceeds 2, the light transmittance is too high and the performance as a light shielding film is insufficient. The transparency in the ultraviolet light region is 350 nm or more of the light source used during exposure.
It is defined as the transmittance (%) at an emission peak wavelength of 0 nm or less. 365n when an ultra-high pressure mercury lamp is used as a light source
The transmittance is m. When using an ultra-high pressure mercury lamp as a light source, in order to photo-cure to the deep part of the high optical density light-shielding film, the ratio of the visible light region transmittance to the ultraviolet light region transmittance,
That is, the ratio between the Y value and the 365 nm transmittance is 1: 1 to 20:
It is essential that it is 1. If the ratio exceeds 20: 1, the light-shielding film is not sufficiently hardened to the deep portion of the light-shielding film, and a light-shielding film having a sufficient film thickness cannot be obtained. Further, if this ratio is less than 1: 1, only a film having an insufficient light-shielding property can be produced in a practical film thickness range.

As a preferable combination of colorants, a combination of a pigment mixture having a red color and a blue color having a complementary color relationship with each other and a pigment mixture having a yellow color and a purple color having a complementary color relationship with each other, or a black color in addition to the above mixture is used. It is a combination with a pigment added. It is possible to obtain a light-shielding film having a Y value of 2 or less by combining the complementary colors of red and blue, but this combination has a large absorption in the ultraviolet region, and the ratio of the Y value and the 365 nm transmittance exceeds 20: 1. It is difficult to photo-cure to the deep part of the light shielding film. Further, in the case of the combination of the complementary colors of yellow and purple, the ratio of the Y value and the 365 nm transmittance is 20: 1.
Although it can be suppressed below, a light-shielding film having a Y value of 2 or less cannot be obtained unless the thickness of the light-shielding film exceeds 3 μm.

Further, by adding a blue pigment to the combination of the complementary colors of yellow and violet, a light-shielding film having a Y value of 2 or less and a ratio of the Y value and the 365 nm transmittance of 20: 1 or less. Can be obtained. Also in this case, it is possible to reduce the Y value by adding the black pigment in the range where the ratio of the above Y value and the 365 nm transmittance does not exceed 20: 1.

Thus, for the first time by combining the pigments as described above, the Y value is 2 or less within the range of the light-shielding film thickness of 1 to 3 μm, and the ratio of the Y value to the 365 nm transmittance is 20: 1.
The following light shielding film can be obtained. Further, in order to reduce the Y value (improve the light shielding property) without significantly changing the light shielding film thickness, a black pigment such as carbon is added within the range where the ratio of the above Y value and the 365 nm transmittance does not exceed 20: 1. It is possible by The solid content of the colorant in the light-shielding photosensitive resin composition solid is preferably 1 to 50% by weight.

In addition to the above components, it is preferable to add a thermal polymerization inhibitor. Examples thereof include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-).
Butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.

Further, known additives such as a plasticizer, a surfactant and a solvent can be added to the composition of the present invention as required.

The thickness of the light-shielding film formed of the light-shielding photosensitive resin composition of the present invention is preferably 1 μm or more and 3 μm or less. If it is less than 1 μm, the pigment concentration in the light-shielding film becomes high and the developability deteriorates. If it exceeds 3 μm, the developability deteriorates,
Problems such as deterioration of image forming reproducibility occur. The thickness of the light shielding film can be set arbitrarily within the above range. Especially when making color filters, it is desirable that the finished color filters have good flatness. Therefore, in this case, set the same thickness as the other colored layers (red, blue, green, etc.). Is desirable.

The light-shielding photosensitive resin composition of the present invention can be provided on the substrate by a known method. Specifically, it is applied using a spinner, a whiler, a roller coater, a curtain coater, a knife coater, a wire bar coater, an extruder or the like, and dried to provide a light-shielding photosensitive resin layer on the substrate. In particular, a method of transferring onto a substrate using a light-shielding photosensitive transfer material having at least the light-shielding photosensitive resin composition layer of the present invention provided on a temporary support is preferable. Specific transfer materials include JP-A-4-208940, JP-A-5-72724, JP-A-5-80503, and JP-A-5-250403.
The transfer material described in 173320 is used.

Upon exposure through the transparent substrate (rear surface exposure), the light source is selected according to the photosensitivity of the light-shielding photosensitive resin layer, and a known material such as an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, an argon laser, etc. Can be used. Japanese Patent Application 4-
As described in 150691, an optical filter having a light transmittance of 2% or less at a wavelength of 400 nm or more may be used together. Also, the red, green, and
As described in Japanese Patent Application No. 4-150691, the blue pixel preferably has a light transmittance of 2% or less for each pixel in the photosensitive wavelength region of the light-shielding photosensitive resin layer. Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

[0034]

【Example】

Examples 1 to 8 A coating solution having the following formulation H1 was applied onto a polyethylene terephthalate film temporary support having a thickness of 100 μm,
It was dried to provide a thermoplastic resin layer having a dry film thickness of 20 μm.

Thermoplastic resin layer formulation H1: Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 28.8 / 11.7 / 4.5, Weight average molecular weight = 80,000) 15.0 parts by weight BPE-500 (Shin-Nakamura Chemical Co., Ltd. multifunctional acrylate) 7.0 parts by weight F177P (Dainippon Ink and Chemicals, Inc. fluorine-containing surfactant) 0.3 parts by weight Methanol 30. 0 parts by weight Methyl ethyl ketone 19.0 parts by weight 1-methoxy-2-propanol 10.0 parts by weight

Next, the following formulation B1 was formed on the thermoplastic resin layer.
Applying a coating solution consisting of
An m-thick intermediate layer was provided. Separation layer formulation B1: Polyvinyl alcohol (PVA205 manufactured by Kuraray Co., Ltd., saponification rate = 80%) 130 parts by weight Polyvinylpyrrolidone (PVP, K-30 manufactured by GAF Corporation) 60 parts by weight Distilled water 2110 parts by weight Methanol 1750 parts by weight

On the temporary support having the thermoplastic resin layer and the intermediate layer, a coating solution having the formulation shown in Table 1 below was applied,
After drying, a light-shielding photosensitive resin layer having a dry film thickness of 2 μm was formed, and a polypropylene (12 μm-thick) coating sheet was pressure-bonded onto the light-shielding photosensitive resin layer to prepare a light-shielding photosensitive resin layer of Examples 1 to 8. A light-shielding photosensitive transfer material was prepared.

[0038]

[Table 1]

The Y value is a value when an F10 light source is used.

On a glass substrate (thickness 1.1 mm), a solution having the formulation shown in Table 2 below was applied by a method known to those skilled in the art,
Mask exposure and development were performed to prepare a color filter having R, G, and B pixels with a film thickness of 2 μm.

Table 2: Formulation of photosensitive layer R layer G layer B layer ─────────────────────────────────── Benzyle methacrylate / 60.0 60.0 60.0 Methacrylic acid copolymer (molar ratio = 73/27 viscosity = 0.12) Pentaerythritol 43.2 43.2 43.2 Tetraacrylate Michler's ketone 2.4 2.4 2.4 2- (o-chlorophenyl 2.5 2.5 2.5 Diphenylimidazole dimer Irgacine red BPT (red) 5.4 --- --- Sudan blue (blue) --- 5.2 --- Copper phthalocyanine (green) --- --- 5.6 Carbon black (black) --- --- --- Methyl Cellosolve acetate 560 560 560 Methyl ethyl ketone 280 280 280

The covering sheet of the light-shielding photosensitive transfer material of Examples 1 to 8 was peeled off, and the light-shielding photosensitive resin layer surface was laminated on each color filter surface of the R, G and B color filters (Taisei Laminator). VP-I manufactured by
I) using pressure (0.8 kg / cm ² ) and heating (13
(0 ° C.) and then pasted together, followed by peeling at the interface between the temporary support and the thermoplastic resin layer to remove the temporary support.

Next, in Examples 1 to 8, back exposure was performed from the side opposite to the color filter surface using an ultrahigh pressure mercury lamp. At this time, a Toshiba glass filter (UVD36c) was provided between the light source and the sample to cut off light having a wavelength of 400 nm or more. The exposure amount was 100 mj / cm ² .
After that, development was performed with a 1% sodium carbonate aqueous solution to remove unnecessary portions, and a light-shielding film was formed in the R, G, and B pixel gaps. The finished color filter did not overlap the light-shielding film and the RGB layer, and each had the light-shielding film with high optical density of Y value shown in Table 1. In addition, flatness is ±
It was as good as 0.1 μm.

Comparative Example 1 The procedure of Example 1 was repeated except that a coating solution having the following formulation C1 was applied and dried to form a light-shielding photosensitive resin layer having a dry film thickness of 2 μm. Formulation C1: benzyl methacrylate / methacrylic acid copolymer (molar ratio = 70/30, intrinsic viscosity = 0.12) 11.00 parts by weight dipentaerythritol hexaacrylate 10.60 parts by weight 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbomethyl) -3-bromophenyl] -s-triazine 0.52 parts by weight carbon black 1.70 parts by weight Hydroquinone monomethyl ether 0.01 parts by weight F177P (Dainippon Nihon) Ink surfactant) 0.07 parts by weight methyl cellosolve acetate 40.00 parts by weight methyl ethyl ketone 125.00 parts by weight

The Y value of the obtained light-shielding photosensitive resin layer was 0.7 when the light source was the F10 light source. 365n
The transmittance of m was 0.02%, and the ratio of the Y value and the transmittance of 365 nm was 35: 1. Also, x from the achromatic point,
The absolute values of the difference in y value were 0.03 and 0.04, respectively. Further, in the finally obtained color filter, although the light-shielding film and the RGB layer do not overlap with each other, the Y value of the obtained light-shielding film is 5 because the light-curing film does not harden to the deep portion.
The optical density was insufficient.

Comparative Example 2 The procedure of Example 1 was repeated except that a coating solution having the following formulation C2 was applied and dried to form a light-shielding photosensitive resin layer having a dry film thickness of 2 μm. Formulation C2: benzyl methacrylate / methacrylic acid copolymer (molar ratio = 70/30, intrinsic viscosity = 0.12) 11.00 parts by weight dipentaerythritol hexaacrylate 10.60 parts by weight 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbomethyl) -3-bromophenyl] -s-triazine 0.52 parts by weight Pigment Red 177 4.00 parts by weight Pigment Blue 15: 6 2.86 parts by weight Hydroquinone Monomethyl ether 0.01 parts by weight F177P (Surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.07 parts by weight Methyl cellosolve acetate 40.00 parts by weight Methyl ethyl ketone 125.00 parts by weight

The Y value of the obtained light-shielding photosensitive resin layer was 0.7 when the light source was the F10 light source. 365n
The transmittance of m was 0.02%, and the ratio of the Y value and the transmittance of 365 nm was 35: 1. Also, x from the achromatic point,
The absolute values of the difference in y value were 0.04 and 0.03, respectively. Further, in the finally obtained color filter, although the light-shielding film and the RGB layer do not overlap with each other, the Y value of the obtained light-shielding film is 5 because the light-curing film does not harden to the deep portion.
The optical density was insufficient.

Comparative Example 3 The procedure of Example 1 was repeated except that a coating solution having the following formulation C3 was applied and dried to form a light-shielding photosensitive resin layer having a dry film thickness of 2 μm. Formulation C3: benzyl methacrylate / methacrylic acid copolymer (molar ratio = 70/30, intrinsic viscosity = 0.12) 11.00 parts by weight dipentaerythritol hexaacrylate 10.60 parts by weight 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbomethyl) -3-bromophenyl] -s-triazine 0.52 parts by weight Pigment Yellow 139 2.27 parts by weight Pigment Violet 23 0.39 parts by weight Carbon Black 1 70 parts by weight Hydroquinone monomethyl ether 0.01 parts by weight F177P (Surfactant manufactured by Dainippon Ink and Chemicals Inc.) 0.07 parts by weight Methyl cellosolve acetate 40.00 parts by weight Methyl ethyl ketone 125.00 parts by weight

The Y value of the obtained light-shielding photosensitive resin layer was 5.0 when the light source was the F10 light source. 365n
The transmittance of m was 1.0%, and the ratio of the Y value and the transmittance of 365 nm was 5: 1. The absolute values of the difference between the x and y values from the achromatic color point were 0.04 and 0.03, respectively.
Further, in the finally obtained color filter, the light-shielding film and the RGB layer did not overlap each other, and the surface of the light-shielding film was photo-cured, but the Y-value of the obtained light-shielding film was 5, and the optical density was insufficient. It was

[0050]

EFFECT OF THE INVENTION When the light-shielding photosensitive resin composition of the present invention containing two or more colorants is used, the light-shielding performance is high,
A light-shielding image having no defects such as white spots can be obtained by a simple method of exposure from the back surface (self-alignment).

Claims (9)

[Claims] 1. At least (1) an alkali-soluble binder, (2) a photopolymerization initiator, (3) an addition polymerizable monomer having an ethylenically unsaturated double bond, and (4) at least two kinds of colorants. In the light-shielding photosensitive resin composition, which has a hue equal to or close to black and has a transmittance of 2 or less in the visible light region when a light-shielding photosensitive resin layer having a film thickness of 1 to 3 μm is formed, Moreover, the ratio of the transmittance in the visible light region to the transmittance in the ultraviolet light region is 1: 1 to 20: 1.
And a light-shielding photosensitive resin composition. 2. The light-shielding photosensitive resin composition according to claim 1, wherein each of the at least two kinds of colorants is a color pigment. 3. The light-shielding photosensitive material according to claim 2, wherein a mixture of red and blue pigments having a complementary color relationship with each other and a mixture of yellow and purple pigments having a complementary color relationship with each other are mixed. Resin composition. 4. The light-shielding photosensitive resin composition according to claim 3, further comprising a black pigment. 5. A light-shielding photosensitive resin composition according to claim 2, wherein a mixture of pigments having a complementary color relationship of yellow and purple and a pigment of blue color are mixed. 6. The light-shielding photosensitive resin composition according to claim 5, further comprising a black pigment. 7. The method according to claim 1, wherein (1) a step of forming an image composed of red, blue, and green pixels on a transparent substrate, and (2) the surface on which the image is formed according to (1). Or a step of providing a layer using the light-shielding photosensitive resin composition according to item 1,
(3) exposing through the transparent substrate, (4) developing, and forming a light-shielding image on the substrate of the non-pixel portion of the image formed in (1) at least Method of forming light-shielding image. 8. (1) a step of forming an image composed of red, blue and green pixels on a transparent substrate, (2) provided on a temporary support on the surface on which the image is formed by (1) A step of transferring a layer using the light-shielding photosensitive resin composition according to any one of claims 1 to 6, (3) a step of exposing through the transparent substrate, and (4) a temporary if necessary. After removing the support, a development process is performed to form a light-shielding image on the substrate of at least the non-pixel portion of the image formed in (1),
A method of forming a light-shielding image, comprising: 9. A light-shielding photosensitive transfer material comprising a temporary support provided with a layer using the light-shielding photosensitive resin composition according to any one of claims 1 to 6.