JP4401112B2 - Coloring composition and photosensitive transfer material for producing black matrix, black matrix, and color filter - Google Patents

Description

【０１０１】
《感光材料の作製》
ガラス基板と得られた感光性転写材料とを、感光性遮光層がガラス基板に接触するように重ね合わせ、ラミネーター（商品名：ＶＰ−ＩＩ、大阪ラミネーター（株）製）を用いて両者を貼り合わせた。ラミネーション条件は、圧力０．８ｋｇ／ｃｍ²、温度１３０℃であった。その後、感光性転写材料から支持体（ポリエチレンテレフタレート）を剥離し、感光材料を作製した。
【０１０２】
《ブラックマトリックスの作製》
超高圧水銀灯を用いて塗布面側から７０ｍＪ／ｃｍ²の露光を行った。次いで以下の３工程の現像処理をおこない、ブラックマトリックスを得た。
〔現像処理〕
第１工程：現像処理液（商品名：ＴＰＤ、富士写真フイルム（株）製、アルカリ現像液）を用い、温度３０℃・４０秒の条件で現像処理を行った。
第２工程：現像処理液（商品名：ＴＣＤ、富士写真フイルム（株）製、アルカリ現像液）を用い、温度３３℃・２０秒の条件で現像処理を行った。
第３工程：現像処理液（商品名：ＴＳＤ、富士写真フイルム（株）製、アルカリ現像液）を用い、温度３３℃・２０秒の条件で現像処理を行った。
【０１０３】
《評価》
実施例１と同様の評価を行った。結果を下記表１に示す。
【０１０４】
［実施例２０〜２７］
実施例１９の感光性転写材料の作製において用いた実施例１の感光性遮光層用塗布液を、それぞれ実施例２〜９の感光性遮光層用塗布液に変更した以外は実施例９と同様にして、ブラックマトリックスを作製し、同様の評価を行った。結果を下記表１に示す。
【０１０５】
［比較例１］
実施例１の銀微粒子分散液の調製の際、平均アスペクト比２．２の銀微粒子に代えて、平均アスペクト比１．４の銀微粒子を使用した以外は実施例１と同様に感光材料を作製し、同様の評価を行った。結果を下記表１に示す。
【０１０６】
［比較例２］
実施例１の銀微粒子分散液に代えて、カーボンブラック分散液（商品名：ＣＦＰ−９４９Ｋ、富士フイルムアーチ（株）製）２１９部を使用した以外は実施例１と同様に感光材料を作製し、同様の評価を行った。結果を下記表１に示す。
【０１０７】
【表１】

【０１０８】
表１から、実施例のブラックマトリックスは、いずれもＯＤが３．６以上であり、高品位であることがわかった。これに対し、比較例１のブラックマトリクスはＯＤが３．６未満であり、ブラックマトリックスの品位も低下した。さらに、比較例２のブラックマトリクスは、ＯＤが０．７とブラックマトリックスとして満足のいく性能を発揮できなかった。
【０１０９】
【発明の効果】
以上のように本発明により、薄膜で遮光性能が高いブラックマトリックスを低コストで作製することができ、環境性に優れるブラックマトリックス作製用着色組成物および感光性転写材料を提供することができる。
また、本発明によれば薄膜で遮光性能が高いブラックマトリックス、および、表示コントラストが高くまた平坦性に優れたカラーフィルターを提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a coloring composition for producing a black matrix, a photosensitive transfer material, a black matrix, and a color filter.
[0002]
[Prior art]
A color filter used for a color liquid crystal display or the like has a colored pixel layer (R, G, B) formed on a transparent substrate. A black matrix is formed in the gaps between the colored pixels of R, G, and B (red, green, and blue) for the purpose of improving display contrast. In particular, in an active matrix driving type liquid crystal display element using a thin film transistor (TFT), the black matrix is required to have a high light-shielding property in order to prevent deterioration in image quality due to current leakage due to light from the thin film transistor.
[0003]
As a method for forming a black matrix using a metal film such as chromium as a light shielding layer, for example, a metal thin film is produced by vapor deposition or sputtering, a photoresist is applied on the metal thin film, and then a black matrix pattern is formed. There is a method of forming a black matrix by exposing and developing a photoresist layer using a photomask having the same, etching the exposed metal thin film, and finally peeling off the resist layer on the metal thin film (for example, non-patent literature) 1).
[0004]
Since this method uses a metal thin film, there is an advantage that a high light shielding effect can be obtained even if the film thickness is small. However, there is a problem that a vacuum film forming process or an etching process such as a vapor deposition method or a sputtering method is required, which increases the cost and cannot be ignored. In addition, since it is a metal film, there is a problem that the reflectance is high and the display contrast is low under strong external light. On the other hand, as the metal thin film, there is a means of using a low-reflective chromium film (such as one made of two layers of metal chromium and chromium oxide), but it cannot be denied that the cost is further increased.
[0005]
As another black matrix forming method, a method using a light-sensitive pigment, for example, a photosensitive resin composition containing carbon black is also known. As the method, for example, after forming R, G, B pixels on a transparent substrate, a carbon black-containing photosensitive resin composition is applied onto the pixels, and the R, G, B pixel non-formation surface of the transparent substrate is applied. There is known a self-alignment black matrix forming method in which the entire surface is exposed from the side (see, for example, Patent Document 1).
Although the manufacturing cost is lower than the method by etching the metal film, the method has a problem that the film thickness is increased in order to obtain sufficient light shielding properties. As a result, there is an overlap (step) between the black matrix and the R, G, B pixels, the flatness of the color filter is deteriorated, and the cell gap unevenness of the liquid crystal display element occurs, leading to display defects such as color unevenness. become.
[0006]
On the other hand, a photosensitive resist layer containing a hydrophilic resin is formed on a transparent substrate, and exposed and developed through a photomask having a black matrix pattern to form a relief on the transparent substrate. By bringing the metal compound into contact with an aqueous solution of a metal compound serving as a catalyst for electroplating, drying the metal compound in the relief, applying heat treatment, and then bringing the relief on the transparent substrate into contact with the electroless plating solution, A method of producing a black matrix in which metal particles for light shielding having a diameter of 0.01 to 0.05 μm are uniformly dispersed therein has been proposed (for example, see Patent Document 2). Nickel, cobalt, iron, copper and chromium are described as the metal particles, and nickel is shown as a specific example.
However, this method has many troublesome processing steps for handling water, such as relief formation including exposure and development steps, application of an electroless plating catalyst, heat treatment, and electroless plating. Therefore, it cannot be expected to produce a black matrix at a low cost.
[0007]
[Patent Document 1]
JP-A-62-9301
[Patent Document 2]
Japanese Patent No. 3318353
[Non-Patent Document 1]
Published by Kyoritsu Shuppan Co., Ltd. “Color TFT LCD”, pp. 218-220 (April 10, 1997)
[0008]
[Problems to be solved by the invention]
The present invention has been made in view of the problems as described above, and its purpose is to produce a black matrix having a high light-shielding performance with a thin film at a low cost, and a colored composition for producing a black matrix having excellent environmental properties. And providing a photosensitive transfer material. Another object of the present invention is to provide a black matrix that is a thin film and has high light shielding performance, and a color filter that has high display contrast and excellent flatness.
[0009]
[Means for Solving the Problems]
The above problem is solved by means.
<1> The aspect ratio is 2 or more The particle diameter is 0.05 to 5.0 μm At least one metal fine particle An alkali-soluble binder polymer, a photopolymerization initiator, and a photopolymerizable monomer. It is a coloring composition for black matrix preparation characterized by including.
<2> The colored composition for producing a black matrix according to <1>, wherein the metal fine particles have an aspect ratio of 5 or more.
[0010]
< 3 <1>, wherein the metal fine particles are silver particles Or <2> This is a coloring composition for preparing a black matrix.
[0011]
< 4 <1> The optical density when the light shielding layer having a film thickness of 1 μm is formed is 1 or more. ~ < 3 The coloring composition for producing a black matrix.
[0013]
< 5 > A photosensitive transfer material for producing a black matrix in which at least a photosensitive light-shielding layer is provided on a support, wherein the photosensitive light-shielding layer is the above-mentioned Any of <1> to <4> It is formed from the coloring composition for black matrix preparation of this, The photosensitive transfer material for black matrix preparation characterized by the above-mentioned.
[0014]
< 6 ><1> to < 4 It is formed using the coloring composition for black matrix preparation of>.
[0015]
< 7 > Above < 5 It is formed using the photosensitive transfer material for black matrix preparation of>.
[0016]
< 8 A color filter having two or more pixel groups exhibiting different colors on a light-transmitting substrate, wherein each pixel constituting the pixel group is separated from each other by a black matrix, < 6 > Or < 7 It is a color filter characterized by being a black matrix.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
<< Coloring composition for black matrix preparation >>
The coloring composition for producing a black matrix of the present invention contains at least one metal fine particle having an aspect ratio of 2 or more, and if necessary, pigment fine particles, a polymer serving as a binder, a photopolymerizable monomer, a photopolymerization initiator, You may contain a solvent etc.
[0018]
<Metal fine particles>
The metal fine particles used in the present invention are not particularly limited as long as the metal fine particles have an aspect ratio of 2 or more, and any fine particles may be used. The metal fine particles in the present invention preferably include, as a main component, a metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the periodic table of elements, for example, the group 8 and group 9 It is preferable that a metal selected from the group consisting of Group 10, Group 10, Group 11 and Group 12 is included as a main component. Among these metals, the metal fine particles in the present invention are metals of the fourth period, the fifth period, or the sixth period, and metals of Group 10, Group 11, or Group 12 are more preferable, and gold Silver, copper, platinum, or palladium is particularly preferred. Among these, gold, silver, and copper are preferable, and silver is particularly preferable. As the silver, triangular or hexagonal flat plate hydrosol (citric acid reduction) or silver having the same shape is preferable. Further, the fine metal particles in the present invention are preferably triangular or hexagonal flat plate hydrosols (citric acid reduction) or those having the same shape, and the silver is most preferably colloidal silver. In the production of metal fine particles, two or more of the above metals may be used in combination, or may be used as an alloy.
[0019]
As the metal fine particles, commercially available ones can be used, and they can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like.
In particular, silver fine particles can be adjusted by adjusting pH, concentration of gelatin solution, coexisting ionic species and the amount thereof at the time of silver reduction based on Examples, JP-A-5-134358, US Pat. No. 2,688,601, Silver halides such as silver bromide, silver iodobromide, silver iodochlorobromide and silver chlorobromide whose shape can be easily controlled may be prepared using a mild reducing agent.
[0020]
For example, tabular silver halide fine grains are described in “Theory and Practice of Photography” by Cleeve (Cleve, Photography Theory and Practice (1930)), page 131; “Photographic Science and Engineering by Gutoff, Photographic Science and Engineering”. 14], 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520 and the United Kingdom. It can be prepared by improving the method described in Japanese Patent No. 2,112,157.
[0021]
-Shape-
The shape of the metal fine particles that can be used in the present invention is not particularly limited, but those having an elliptical shape, a plate shape (triangle, hexagonal shape, circular shape), and the like are preferable. Most preferred is a plate shape (triangle, hexagon, circle).
[0022]
-Aspect ratio-
In the present invention, the “aspect ratio” means an average aspect ratio of tabular grains, and specifically, an average value of values (aspect ratio) obtained by dividing the longest diameter of grains by the minimum diameter. About the tabular grain which has a grain diameter, it is the average value of the value (aspect ratio) which divided the grain diameter by thickness, respectively. The particle thickness can be easily measured by using a reference latex, measuring the shadow length on an electron micrograph, and referring to the latex shadow length.
[0023]
The “particle diameter” in the present invention is a diameter of a circle having an area equal to the projected area of the parallel outer surface of the particle. The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification. The diameter in the case of tabular grains is preferably 0.05 to 5.0 μm. The thickness of the tabular grains is preferably 0.02 to 0.5 μm.
[0024]
The metal fine particles in the present invention can control the absorption spectrum by increasing the aspect ratio, and can also bring the hue closer to an achromatic color. In the present invention, the metal fine particles have an aspect ratio of 2 or more, preferably 5 or more, and more preferably 20 or more from the above viewpoint. In addition, the upper limit of the average aspect ratio of the metal fine particles in the present invention is not particularly limited, but is usually preferably 500 or less.
Further, by adsorbing the dye on the tabular grains, the hue can be adjusted more easily than the grains having a low aspect ratio.
[0025]
Moreover, when a light shielding layer is formed using the coloring composition of this invention, it is preferable that the optical density per 1 micrometer of film thickness of a light shielding layer will be 1 or more. In consideration of preventing the metal fine particles from fusing during the heating process during the color filter production, the content of the metal fine particles in the colored composition is the content of the metal fine particles contained in the formed light shielding layer. Is preferably adjusted to be about 10 to 90% by mass, preferably about 10 to 80% by mass. The content is preferably determined in consideration of optical density variation due to the average particle size of the metal fine particles.
The same applies to the content of metal fine particles in the photosensitive coloring composition described below.
[0026]
From the viewpoint of the optical density (OD) of the light shielding layer, the average particle size of the metal fine particles used in the colored composition of the present invention is preferably 1 to 500 nm, more preferably 60 to 250 nm, and 70 to 200 nm. It is particularly preferred that
[0027]
In the present invention, it is desirable that the metal fine particles are dispersed. The presence state of the metal fine particles at the time of dispersion is not particularly limited, but the metal fine particles are preferably present in a stable dispersion state, for example, more preferably in a colloidal state. In the colloid state, for example, it is preferable that the metal fine particles are dispersed in a substantially spherical fine particle state.
Here, as the dispersant, a thiol group-containing compound, an amino acid or a derivative thereof, a peptide compound, a polysaccharide, a natural polymer derived from a polysaccharide, a synthetic polymer, a gel derived from these, or the like can be used.
The kind of the thiol group-containing compound used here is not particularly limited, and any compound having one or two or more thiol groups may be used. Examples of the thiol group-containing compound include alkyl thiols (eg, methyl mercaptan, ethyl mercaptan, etc.), aryl thiols (eg, thiophenol, thionaphthol, benzyl mercaptan, etc.), amino acids or derivatives thereof (eg, cysteine, glutathione). Etc.), peptide compounds (eg, dipeptide compounds containing cysteine residues, tripeptide compounds, tetrapeptide compounds, oligopeptide compounds containing 5 or more amino acid residues), or proteins (eg, metallothionein or cysteine residues on the surface) And the like, but are not limited thereto.
[0028]
Polymers used for the dispersant include polymers having protective colloidal properties, such as gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, polyalkyleneamine, and partial alkyl esters of polyacrylic acid. The polymer that can be used as the dispersant is described in, for example, “Encyclopedia of Pigments” (edited by Seijiro Ito, published by Asakura Shoin Co., Ltd., 2000).
[0029]
In addition, a hydrophilic polymer, a surfactant, a preservative, a stabilizer, or the like may be appropriately added to the dispersion. As the hydrophilic polymer, any polymer may be used as long as it can be dissolved in water and can substantially maintain a solution state in a diluted state. For example, proteins and protein-derived substances such as gelatin, collagen, casein, fibronectin, laminin, elastin; derived from polysaccharides and polysaccharides such as cellulose, starch, agarose, carrageenan, dextran, dextrin, chitin, chitosan, pectin, mannan Natural polymers such as substances; synthetic polymers such as poval, polyacrylamide, poly (vinyl pyrrolidone acrylate), polyethylene glycol, polystyrene sulfonic acid, polyallylamine; or gels derived therefrom can be used. When gelatin is used, the type of gelatin is not particularly limited. For example, beef bone alkali-treated gelatin, pig skin alkali-treated gelatin, beef bone acid-treated gelatin, cow bone phthalated gelatin, pig skin acid-treated gelatin, etc. Can be used.
[0030]
As the surfactant, any of anionic, cationic, nonionic, and betaine surfactants can be used, and anionic and nonionic surfactants are particularly preferable. The HLB value of the surfactant cannot be generally specified depending on whether the solvent of the coating solution is aqueous or organic solvent, but is preferably about 8 to 18 when the solvent is aqueous, and about 3 to 6 when the solvent is organic. Are preferred.
[0031]
The HLB value is described in, for example, “Surfactant Handbook” (Tokiyuki Yoshida, Shinichi Shindo, Yoshiyoshi Yamanaka, published by Engineering Book Co., Ltd. 1987). Specific examples of the surfactant include propylene glycol monostearate, propylene glycol monolaurate, diethylene glycol monostearate, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, and the like. Examples of the surfactant are also described in the aforementioned “Surfactant Handbook”.
[0032]
<Pigment fine particles>
By incorporating pigment fine particles into the black matrix of the present invention, achromatic black can be obtained.
In general, the pigment is roughly classified into an organic pigment and an inorganic pigment. In the present invention, the organic pigment is preferable. Examples of pigments that can be suitably used include azo pigments, phthalocyanine pigments, anthraquinone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and nitro pigments. The hue of the organic pigment is preferably, for example, a yellow pigment, an orange pigment, a red pigment, a violet pigment, a blue pigment, a green pigment, a brown pigment, or a black pigment. The pigments used in the photosensitive resin layer are listed below according to hue, but are not limited thereto.
[0033]
1) Red pigment
C. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 123, 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 red 216, C.I. I. Pigment red 217, C.I. I. Pigment red 220, C.I. I. Pigment red 223, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 227, C.I. I. Pigment red 228, C.I. I. Pigment red 240, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 209, C.I. I. Pigment red 146, C.I. I. Pigment red 11, C.I. I. Pigment red 81, C.I. I. Pigment red 123, C.I. I. Pigment red 213, C.I. I. Pigment red 272, C.I. I. Pigment red 270, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 254, C.I. I. No. 12085, C.I. I. No. 12120, C.I. I. No. 12140, C.I. I. No. Organic pigments such as 12315
2) Green pigment
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. No. 42053, C.I. I. No. 42085, C.I. I. No. Organic pigments such as 42095
3) Blue pigment
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64, C.I. I. No. 42052, C.I. I. No. Organic pigments such as 42090
[0034]
4) Yellow pigment
Pigment Yellow (Pigment Yellow) 12 (C.I.No. 21090)
Example) Permanent Yellow (permanent yellow) DHG (manufactured by Clariant Japan Co., Ltd.), Lionol Yellow (Rionol Yellow) 1212B (manufactured by Toyo Ink Co., Ltd.), Irgalite Yellow (Irgarite Yellow) LCT (Ciba Specialty Tea) Chemicals Co., Ltd.), Symbol Fast Yellow (Shimla First Yellow) GTF 219 (Dainippon Ink Chemical Co., Ltd.)
Pigment Yellow (Pigment Yellow) 13 (C.I.No. 21100)
Example) Permanent Yellow (permanent yellow) GR (manufactured by Clariant Japan), Lionol Yellow (Rionol Yellow) 1313 (manufactured by Toyo Ink Manufacturing Co., Ltd.)
Pigment Yellow (Pigment Yellow) 14 (C.I.No. 21095)
Example) Permanent Yellow (permanent yellow) G (manufactured by Clariant Japan Co., Ltd.), Lionol Yellow (Lionol Yellow) 1401-G (manufactured by Toyo Ink Co., Ltd.), Seika Fast Yellow (Seika First Yellow) 2270 (Daisensei) Chemical Industry Co., Ltd.), Symfaster Yellow (Shimla First Yellow) 4400 (Dainippon Ink Chemical Co., Ltd.)
Pigment Yellow (Pigment Yellow) 17 (C.I.No. 21105)
Example) Permanent Yellow (permanent yellow) GG02 (manufactured by Clariant Japan Co., Ltd.), Symbol Fast Yellow (Shimler First Yellow) 8GF (manufactured by Dainippon Ink & Chemicals, Inc.)
Pigment Yellow (Pigment Yellow) 155
Example) Graphtol Yellow (Graphtor Yellow) 3GP (manufactured by Clariant Japan Co., Ltd.)
Pigment Yellow (Pigment Yellow) 180 (C.I.No. 21290)
Example) Novoperperm Yellow (Novo Palm Yellow) P-HG (Clariant Japan Co., Ltd.), PV Fast Yellow (First Yellow) HG (Clariant Japan Co., Ltd.)
Pigment Yellow (Pigment Yellow) 139 (C.I.No. 56298)
Example) Novoperm Yellow (Novo Palm Yellow) M2R 70 (manufactured by Clariant Japan Co., Ltd.)
[0035]
C. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 125, C.I. I. Pigment yellow 137, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment Yellow 185
[0036]
5) Magenta pigment
Pigment Red 57: 1 (C.I.No. 15850: 1)
Example) Graphtol Rubine (Graphtor Rubin) L6B (manufactured by Clariant Japan Co., Ltd.), Lionol Red (Rionol Red) 6B-4290G (manufactured by Toyo Ink Co., Ltd.), Irgalite Rubine (Irgarite Rubin) 4BL (Ciba Specialty Chemicals Co., Ltd.), Symbler Brilliant Carmine 6B-229 (Dainippon Ink Chemical Co., Ltd.)
Pigment Red 122 (C.I.No. 73915)
Example) Hosterperm Pink (Hoster Palm Pink) E (manufactured by Clariant Japan Co., Ltd.), Lionogen Magenta (Rionogen Genagenta) 5790 (manufactured by Toyo Ink Co., Ltd.), Fastogen Super Magenta (Fastgen Super Magenta) RH (Large) (Made by Nippon Ink Chemical Co., Ltd.)
Pigment Red 53: 1 (C.I.No. 15585: 1)
Example) Permanent Lake Red (Permanentley Red) LCY (manufactured by Clariant Japan Co., Ltd.), Symbole Lake Red (Shimla Lake Red) C conc (manufactured by Dainippon Ink & Chemicals, Inc.)
Pigment Red 48: 1 (C.I.No. 15865: 1)
Example) Lionol Red (Rionol Red) 2B 3300 (manufactured by Toyo Ink Manufacturing Co., Ltd.), Simulator Red (Shimla Red) NRY (manufactured by Dainippon Ink & Chemicals, Inc.)
Pigment Red 48: 2 (C.I.No. 15865: 2)
Example) Permanent Red (Permanent Red) W2T (manufactured by Clariant Japan Co., Ltd.), Lionol Red (Lionol Red) LX235 (manufactured by Toyo Ink Manufacturing Co., Ltd.), Simulator Red (Shimler Red)
3012 (Dainippon Ink Chemical Co., Ltd.)
Pigment Red 48: 3 (C.I.No. 15865: 3)
Example) Permanent Red (Permanent Red) 3RL (manufactured by Clariant Japan Co., Ltd.), Symuler Red (Shimla Red) 2BS (manufactured by Dainippon Ink & Chemicals, Inc.)
Pigment Red (Pigment Red) 177 (C.I.No. 65300)
Example) Chromophthal Red (chromophthaled red) A2B (Ciba Specialty Chemicals Co., Ltd.)
[0037]
6) Cyan pigment
Pigment Blue (Pigment Blue) 15 (C.I.No. 74160)
Example) Lionol Blue (Lionol Blue) 7027 (Toyo Ink Manufacturing Co., Ltd.), Fastogen Blue (Fastgen Blue) BB (Dainippon Ink Chemical Co., Ltd.)
Pigment Blue (Pigment Blue) 15: 1 (C.I.No. 74160)
Example) Hosterperm Blue (Hoster Palm Blue) A2R (manufactured by Clariant Japan), Fastogen Blue (Fastgen Blue) 5050 (manufactured by Dainippon Ink & Chemicals, Inc.)
Pigment Blue (Pigment Blue) 15: 2 (C.I.No. 74160)
Example) Hosterperm Blue (Hoster Palm Blue) AFL (Clariant Japan Co., Ltd.), Irgalite Blue (Irgarite Blue) BSP (Ciba Specialty Chemicals Co., Ltd.), Fastogen Blue (Fastgen Blue) GP (Large) (Made by Nippon Ink Chemical Co., Ltd.)
Pigment Blue (Pigment Blue) 15: 3 (C.I.No. 74160)
Example) Hosterperm Blue (Hoster Palm Blue) B2G (manufactured by Clariant Japan Co., Ltd.), Lionol Blue (Rionol Blue) FG7330 (manufactured by Toyo Ink Co., Ltd.), Chromophthal Blue (chromophthal blue) 4GNP (Ciba Specialty)・ Chemicals Co., Ltd.), Fastogen Blue (Fastgen Blue) FGF (Dainippon Ink Chemical Co., Ltd.)
Pigment Blue (Pigment Blue) 15: 4 (C.I.No. 74160)
Example) Hosterperm Blue (Hoster Palm Blue) BFL (manufactured by Clariant Japan), Cyanine Blue (cyanine blue) 700-10FG (manufactured by Toyo Ink Manufacturing Co., Ltd.), Irgalite Blue (Irgarite Blue) GLNF (Ciba Special) Tea Chemicals Co., Ltd.), Fastogen Blue (Fastgen Blue) FGS (Dainippon Ink Chemical Co., Ltd.)
Pigment Blue (Pigment Blue) 15: 6 (C.I.No. 74160)
Example) Lionol Blue (Lionol Blue) ES (Toyo Ink Manufacturing Co., Ltd.)
Pigment Blue (Pigment Blue) 60 (C.I.No. 69800)
Example) Hosterperm Blue (Hoster Palm Blue) RL01 (manufactured by Clariant Japan), Lionogen Blue (Rionogen Blue) 6501 (manufactured by Toyo Ink Manufacturing Co., Ltd.)
[0038]
7) Brown, black pigment
C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment Brown 26, Pigment Black (Pigment Black) 7 (Carbon Black CI No. 77266)
Example) Mitsubishi Carbon Black MA100 (manufactured by Mitsubishi Chemical Corporation), Mitsubishi Carbon Black # 5 (manufactured by Mitsubishi Chemical Corporation), Black Pearls (Black Pearls) 430 (manufactured by Cabot Co. (Cabot Corporation))
8) Orange pigment
C. I. Pigment orange 36, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51, C.I. I. Pigment orange 55, C.I. I. Pigment orange 59, C.I. I. Pigment orange 61, C.I. I. Pigment orange
[0039]
9) Violet pigment
C. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 30, C.I. I. Pigment violet 37, C.I. I. Pigment violet 40, C.I. I. Pigment Violet 50
Examples of pigments that can be used in the present invention include “Pigment Handbook, edited by Japan Pigment Technical Association, Seibundo Shinkosha, 1989”, “COLOUR INDEX, THE SOCIETY OF DYES & COLORIST, THIRD EDITION, 1987” and the like. A product can be selected as appropriate by referring to it.
[0040]
In the present invention, among the above pigments, phthalocyanine pigments are preferable. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 185, C.I. I. Pigments having an acidic group such as CI Pigment Yellow 83 are preferred. Particularly preferred are C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 83, C.I. I. Pigment red 254, C.I. I. Pigment green 36, C.I. I. Pigment blue 15, carbon black and the like.
[0041]
It is desirable to use a pigment having a complementary color relationship with the hue of the silver fine particles. Further, the pigments may be used alone or in combination of two or more. Preferred pigment combinations include a combination of a red and blue pigment mixture complementary to each other and a yellow and purple pigment mixture complementary to each other, or a black pigment added to the above mixture. And combinations of blue, violet and black pigments. The content of the pigment in the light shielding layer is preferably in the range of 1 to 70% by mass, preferably in the range of 1 to 40% by mass, and more preferably in the range of 1 to 20% by mass.
[0042]
The pigment is preferably uniformly dispersed in the coloring composition for producing the black matrix. The average particle size of the pigment is preferably 5 μm or less, particularly preferably 1 μm or less, and more preferably 0.5 μm or less for color filters.
[0043]
The average particle size of the metal fine particles and pigment fine particles in the present invention is obtained by measuring 50 particle sizes by observation with a transmission electron microscope (TEM) and calculating the average value.
[0044]
<Photosensitivity>
The colored composition for producing a black matrix of the present invention preferably has photosensitivity. Photosensitivity can be imparted to the colored composition of the present invention by adding a photosensitive resin composition. The photosensitive resin composition is a monomer that undergoes addition polymerization upon irradiation with light having an alkali-soluble binder polymer, a photopolymerization initiator, and an ethylenically unsaturated double bond (hereinafter sometimes referred to as “photopolymerizable monomer”). Etc.
[0045]
The photosensitive resin composition includes those that can be developed with an aqueous alkali solution and those that can be developed with an organic solvent. From the viewpoint of safety and the cost of the developer, those capable of developing with an aqueous alkali solution are preferred.
The photosensitive resin composition may be a negative type in which a part that receives radiation such as light or electron beam is cured, or a positive type in which a radiation non-receptive part is cured.
[0046]
Examples of the positive photosensitive resin composition include those using a novolac resin. For example, an alkali-soluble novolak resin system described in JP-A-7-43899 can be used. Further, a positive photosensitive resin layer described in JP-A-6-148888, that is, an alkali-soluble resin described in the publication and a 1,2-naphthoquinonediazide sulfonic acid ester as a photosensitive agent and a thermosetting agent described in the publication. A photosensitive resin layer containing a mixture can be used. Furthermore, the composition described in JP-A-5-262850 can also be used.
[0047]
Examples of the negative photosensitive resin composition include a photosensitive resin composed of a negative diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition composed of an azide compound and a binder, and a cinnamic acid type photosensitive resin composition. Is mentioned. Among them, particularly preferred is a photopolymerizable composition containing a photopolymerization initiator, a photopolymerizable monomer and a binder as basic constituent elements. As the photopolymerizable composition, “polymerizable compound B”, “polymerization initiator C”, “surfactant”, “adhesion aid” described in JP-A No. 11-133600, and other compositions can be used.
For example, a photosensitive resin composition that is a negative photosensitive resin composition and can be developed in an aqueous alkali solution has a binder containing a carboxylic acid group as a main component (an alkali-soluble binder such as the alkali-soluble thermoplastic resin described above) and light. It contains a polymerization initiator and an ethylenically unsaturated double bond-containing monomer (hereinafter sometimes referred to as “photopolymerizable monomer”) that can undergo addition polymerization by irradiation with light.
[0048]
Examples of the alkali-soluble binder include polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer as described in JP-A-59-53836 and JP-A-59-71048 , Maleic acid copolymer, partially esterified maleic acid copolymer, and the like. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned. In addition, a polymer having a hydroxyl group added to a cyclic acid anhydride can also be preferably used. In particular, a copolymer of benzyl (meth) acrylate and (meth) acrylic acid or a multicomponent copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers described in US Pat. No. 4,139,391 is also available. Can be mentioned.
[0049]
The alkali-soluble binder polymer is preferably selected from those having an acid value in the range of 30 to 400 mg KOH / g and a weight average molecular weight in the range of 1000 to 300,000. In addition to the above, an alkali-insoluble polymer may be added within a range that does not adversely affect developability and the like in order to improve various performances, for example, the strength of the cured film. Examples of these alkali-soluble binder polymers include alcohol-soluble nylon and epoxy resin.
[0050]
The alkali-soluble binder polymer is usually 10 to 95% by mass, more preferably 20 to 90% by mass, based on the total solid content of the photosensitive resin composition. In the range of 10 to 95% by mass, the adhesiveness of the photosensitive resin layer is not too high, and the strength and photosensitivity of the formed layer are not inferior.
[0051]
Examples of the photopolymerization initiator include vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660, acyloin ether compounds described in US Pat. No. 2,448,828, and US Pat. No. 2,722,512. Aromatic acyloin compounds substituted with α-hydrocarbons described in the specification, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, tria described in US Pat. No. 3,549,367 A combination of a reel imidazole dimer and a p-aminoketone, a benzothiazole compound and a trihalomethyl-s-triazine compound described in JP-B-51-48516, and a trihalomethyl-s described in US Pat. No. 4,239,850 -Triazine compounds, U.S. Pat. No. 4,221,976 Trihalomethyl oxadiazole compounds described in the book, and the like. Particularly preferred are trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer.
[0052]
The said photoinitiator is 0.5-20 mass% generally with respect to the total solid of the photosensitive resin composition, and 1-15 mass% is preferable. When the content is in the above range, the photosensitivity and image strength can be prevented from being lowered, and the performance can be sufficiently improved.
[0053]
Examples of the photopolymerizable monomer include compounds having a boiling point of 100 ° C. or higher at normal pressure. For example, monofunctional (meth) acrylates 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, tri Methylolethane 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 Ethylene oxide and propylene oxide to polyfunctional alcohols such as trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane or glycerin And polyfunctional (meth) acrylates such as those obtained by addition reaction of (meth) acrylate.
[0054]
Further, urethane acrylates disclosed in JP-B-48-41708, JP-A-50-6034 and JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, are disclosed in each publication of No. 52-30490. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable. The photopolymerizable monomers may be used alone or in combination of two or more. As for content with respect to the total solid of the photosensitive resin composition of the said photopolymerizable monomer, 5-50 mass% is common, and 10-40 mass% is preferable. When the content is within the above range, neither the photosensitivity nor the image strength is lowered, and the adhesiveness of the photosensitive light-shielding layer is not excessive.
[0055]
The photosensitive resin composition preferably further contains a thermal polymerization inhibitor in addition to the above components. Examples of the thermal polymerization inhibitor include aromatic hydroxy such as hydroquinone, p-methoxyphenol, pt-butylcatechol, 2,6-di-t-butyl-p-cresol, β-naphthol, pyrogallol and the like. Compounds, quinones such as benzoquinone and p-toluquinone, amines such as naphthylamine, pyridine, p-toluidine and phenothiazine, aluminum salt or ammonium salt of N-nitrosophenylhydroxylamine, chloranil, nitrobenzene, 4,4′-thiobis ( 3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like.
[0056]
The photosensitive resin composition further contains known additives as necessary, for example, plasticizers, surfactants, adhesion promoters, dispersants, plasticizers, anti-sagging agents, leveling agents, antifoaming agents, flame retardants. Agents, brighteners, solvents and the like can be added.
[0057]
Examples of the adhesion promoter include alkylphenol / formaldehyde novolak resin, polyvinylethyl ether, polyvinyl isobutyl ether, polyvinyl butyral, polyisobutylene, styrene-butadiene copolymer rubber, butyl rubber, vinyl chloride-vinyl acetate copolymer, and chlorinated rubber. And acrylic resin-based pressure-sensitive adhesives, aromatic-based, aliphatic-based or alicyclic-based petroleum resins, silane coupling agents, and the like.
[0058]
Further, when the metal fine particles in the present invention are used as an aqueous dispersion like silver colloid, it is necessary to use an aqueous one as the photosensitive resin composition. Examples of such a photosensitive resin composition include those described in paragraphs [0015] to [0023] of JP-A-8-271727, and commercially available products such as “SPP-” manufactured by Toyo Gosei Kogyo Co., Ltd. M20 "and the like.
[0059]
By forming the black matrix using the coloring composition for preparing a black matrix (including a photosensitive material) of the present invention, a black matrix having a thin film and a high optical density can be produced.
[0060]
<< Photosensitive transfer material for black matrix preparation >>
In the present invention, a photosensitive transfer material is prepared using the above-described coloring composition for preparing a black matrix having photosensitivity, and this can be used to prepare a black matrix.
The photosensitive transfer material is provided with a photosensitive light-shielding layer formed using a coloring composition for producing a black matrix having at least the above-described photosensitivity on a support, and a thermoplastic resin layer, if necessary. An intermediate layer, a protective layer, or the like can be provided.
The film thickness of the photosensitive light-shielding layer is preferably in the range of 0.2 to 2 μm, particularly preferably in the range of 0.2 to 0.9 μm.
[0061]
<Support>
As the support in the present invention, a known support such as polyester or polystyrene can be used. Among these, biaxially stretched polyethylene terephthalate is preferable from the viewpoints of cost, heat resistance, and dimensional stability. The thickness of the support is preferably about 15 to 200 μm, more preferably about 30 to 150 μm. When the thickness of the support is within the above range, it is possible to effectively suppress the occurrence of the wrinkle of the tin plate due to heat during the lamination process, which is advantageous in terms of cost.
Moreover, you may provide the electroconductive layer described in Unexamined-Japanese-Patent No. 11-149008 in the said support body as needed.
[0062]
(Thermoplastic resin layer)
Moreover, it is preferable to provide an alkali-soluble thermoplastic resin layer between the support and the photosensitive light-shielding layer, or between the support and the intermediate layer.
Since the thermoplastic resin layer plays a role as a cushioning material so as to be able to absorb unevenness on the base surface (including unevenness due to an already formed image, etc.), depending on the unevenness It preferably has a property that can be deformed.
[0063]
Examples of the resin contained in the alkali-soluble thermoplastic resin layer include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meth). Saponified product such as saponified product with acrylic ester copolymer, poly (meth) acrylic acid ester, and saponified product such as (meth) acrylic acid ester copolymer of butyl (meth) acrylate and vinyl acetate, etc. It is preferable that there is at least one. In addition, use organic polymers soluble in alkaline aqueous solution among the organic polymers according to "Plastic Performance Handbook" (edited by the Japan Plastic Industry Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, issued on October 25, 1968). You can also. Of these thermoplastic resins, those having a softening point of 80 ° C. or less are preferable. In the present specification, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid, and the same applies to derivatives thereof.
[0064]
Among the resins contained in the alkali-soluble thermoplastic resin layer, the weight average molecular weight is in the range of 50,000 to 500,000 (Tg = 0 to 140 ° C.), more preferably the weight average molecular weight is 60,000 to 200,000 (Tg = 30 to 110 ° C.). Specific examples of these resins include JP-B-54-34327, JP-B-55-38961, JP-B-58-12777, JP-B-54-25957, JP-A-61-134756, JP-B-59-1444615. JP, 54-92723, JP 54-99418, JP 54-137085, JP 57-20732, JP 58-93046, JP 59-97135, JP 60-159743, JP 60-247638, JP 60-208748, JP 60-214354, JP 60-230135, JP 60-258539, JP JP 61-1669829, JP 61-213213, JP 63-147159, JP 63-213837, JP 63-266448, JP 64- No. 5551, JP-A-64-15555, JP-A-2-191955, JP-A-2-199403, JP-A-2-199404, JP-A-2-208602, and Japanese Patent Application No. 4-139653. Resins that are soluble in the alkaline aqueous solution described in the book. Particularly preferred is a methacrylic acid / 2 monoethylhexyl acrylate / benzyl methacrylate / methyl methacrylate copolymer described in JP-A-63-147159.
[0065]
Of the various resins described above, the weight average molecular weight is preferably in the range of 3,000 to 30,000 (Tg = 30 to 170 ° C.), and more preferably the weight average molecular weight is 4,000 to 20,000 (Tg = 60 to 140). In the range of ° C.). These preferred specific examples can be selected from those described in the above patent specifications, and particularly preferably, styrene described in JP-B-55-38961 and JP-A-5-241340. / (Meth) acrylic acid copolymer.
[0066]
The thermoplastic resin layer has various plasticizers, various polymers, supercooling substances, adhesion improvers, surfactants, or mold release agents in order to adjust the adhesive force between the thermoplastic resin layer and the support. Etc. can be added. Specific examples of preferred plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate, biphenyl diphenyl phosphate, polyethylene glycol mono (meth) acrylate, Polyethylene glycol di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, addition reaction product of epoxy resin and polyethylene glycol mono (meth) acrylate, organic diisocyanate and polyethylene glycol mono ( Addition reaction product with (meth) acrylate, organic diisocyanate and polypropylene glycol mono (meth) acrylate Addition reaction products of rate, may be mentioned condensation products and the like of bisphenol A and polyethylene glycol mono (meth) acrylate. As for the quantity of the plasticizer in the said thermoplastic resin layer, 200 mass% or less is common with respect to this thermoplastic resin, Preferably it is 20-100 mass%. Further, the thickness of the alkali-soluble thermoplastic resin layer is preferably 6 μm or more. If the thickness of the thermoplastic resin is 6 μm or more, irregularities on the base surface can be completely absorbed. Further, the upper limit is generally about 100 μm or less, preferably about 50 μm or less, from the viewpoint of developability and production suitability.
[0067]
In the present invention, the solvent of the coating solution used when forming the thermoplastic resin layer can be used without particular limitation as long as it dissolves the resin constituting this layer. Examples of the solvent include methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, i-propanol and the like.
[0068]
(Middle layer)
In the photosensitive transfer material of the present invention, an intermediate layer may be provided between the temporary support and the photosensitive light-shielding layer.
The resin constituting the intermediate layer is not particularly limited as long as it is alkali-soluble. Examples of the resin include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and copolymers thereof. . Further, a resin obtained by copolymerizing a monomer having a carboxyl group or a sulfonic acid group with a resin that is not usually alkali-soluble, such as polyester, can also be used.
Of these, polyvinyl alcohol is preferred. The polyvinyl alcohol preferably has a saponification degree of 80% or more, more preferably 83 to 98%.
[0069]
It is preferable to use a mixture of two or more resins constituting the intermediate layer, and it is particularly preferable to use a mixture of polyvinyl alcohol and polyvinyl pyrrolidone. The mass ratio between the two is preferably polyvinylpyrrolidone / polyvinyl alcohol = 1/99 to 75/25, more preferably 10/90 to 50/50. If the mass ratio is within the above range, the surface shape of the intermediate layer is good, the adhesiveness with the photosensitive light-shielding layer coated thereon is good, and further, the oxygen barrier property is lowered and the sensitivity is lowered. Can be prevented.
[0070]
You may add additives, such as surfactant, to the said intermediate | middle layer as needed.
The intermediate layer has a thickness of preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When the thickness of the intermediate layer is within the above range, it is possible to prevent an increase in the intermediate layer removal time during development without reducing the oxygen barrier property.
The coating solvent for the intermediate layer is not particularly limited as long as the above resin dissolves, but water is preferable. A mixed solvent obtained by mixing the aforementioned water-miscible organic solvent with water is also preferable. Preferred examples include the following. Water, water / methanol = 90/10, water / methanol = 70/30, water / methanol = 55/45, water / ethanol = 70/30, water / 1-propanol = 70/30, water / acetone = 90 / 10. Water / methyl ethyl ketone = 95/5 (where the ratio represents a mass ratio).
[0071]
<Production of photosensitive transfer material>
In order to prepare the photosensitive transfer material of the present invention, a support is prepared by adding a solution of the coloring composition for preparing a black matrix having photosensitivity of the present invention to, for example, a spinner, a wheeler, a roller coater, a curtain coater, a knife coater, It can form by apply | coating and drying using coating machines, such as a wire bar coater and an extruder. In the case of providing an alkali-soluble thermoplastic resin layer, it can be formed in the same manner.
[0072]
Since the photosensitive transfer material of the present invention is provided with a photosensitive light-shielding layer using the photosensitive coloring composition for black matrix preparation of the present invention as described above, a thin black matrix having a high optical density is prepared. be able to.
[0073]
《Black Matrix》
The black matrix of this invention can be comprised from the light shielding layer formed using the said coloring composition or photosensitive transfer material. The film thickness of the black matrix is about 0.2 to 2.0 μm, preferably 0.9 μm or less. Since the black matrix of the present invention is a dispersion of fine metal particles and fine pigment particles, even a thin film as described above can exhibit a sufficient optical density (3.5 or more).
[0074]
Moreover, the method for producing (patterning) the black matrix using the coloring composition for producing the black matrix of the present invention is not particularly limited. The following is an example of a black matrix pattern forming method.
[0075]
In the first method, first, a photosensitive blackout layer containing metal fine particles is formed by applying a photosensitive black matrix-containing coloring composition of the present invention containing metal fine particles to a substrate. Thereafter, the pattern formation is performed by removing the light shielding layer other than the pattern by exposure and development. In addition, a layer having the same composition as the above-described intermediate layer can be formed on the photosensitive light-shielding layer to form a protective layer. In this case, it is preferable to apply the coating solution by a spin coating method.
[0076]
In the second method, first, a light shielding layer containing metal fine particles is formed by applying a non-photosensitive coloring composition for producing a black matrix of the present invention to a substrate. Thereafter, a photosensitive resist solution is applied on the light shielding layer to form a resist layer. Next, the resist layer is exposed and developed by exposure to form a pattern in the resist layer, and then the non-patterned portion of the light shielding layer is dissolved according to this pattern to form a pattern in the light shielding layer. Finally, the resist layer is removed to produce a black matrix.
[0077]
In the third method, a coating layer is formed in advance on a portion other than the pattern on the substrate, and the non-photosensitive coloring composition for producing a black matrix of the present invention containing metal fine particles thereon is applied. A light shielding layer containing the fine particle-containing layer is formed. Subsequently, the coating layer formed first is removed together with the upper light shielding layer to produce a black matrix.
[0078]
As a method for producing a black matrix using the photosensitive transfer material, the photosensitive transfer material is arranged and laminated on a light-transmitting substrate so that the photosensitive light-shielding layer of the photosensitive transfer material is in contact. Next, the support is peeled off from the laminate of the photosensitive transfer material and the light-transmitting substrate, and then the layer is exposed through a black matrix photomask and then developed to form a black matrix. .
This black matrix manufacturing method does not require a cumbersome process and is low in cost.
[0079]
"Color filter"
The color filter of the present invention comprises a colored layer on a light-transmitting substrate and has two or more pixel groups exhibiting different colors, and each pixel constituting the pixel group is separated from each other by a black matrix. The black matrix is produced using the above-mentioned coloring composition for producing a black matrix or a photosensitive transfer material of the present invention. The number of pixel groups may be two, three, or four or more. For example, in the case of three, three hues of red (R), green (G), and blue (B) are used. When three types of pixel groups of red, green, and blue are arranged, a mosaic type, a triangle type, and the like are preferable, and any arrangement may be used when four or more types of pixel groups are arranged.
[0080]
As the light transmissive substrate, a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass plate, a non-alkali glass plate, a quartz glass plate, or a plastic film is used.
In order to produce a color filter, after forming two or more pixel groups on a light-transmitting substrate by a conventional method, a black matrix may be formed as described above, or a black matrix is first formed. Thereafter, two or more pixel groups may be formed.
Since the color filter of the present invention includes the black matrix as described above, it has a high display contrast and excellent flatness.
[0081]
<Liquid crystal display element>
The coloring composition for producing a black matrix of the present invention can also be suitably used for a liquid crystal display device. At least one of the liquid crystal display elements includes at least a color filter, a liquid crystal layer, and liquid crystal driving means (including a simple matrix driving method and an active matrix driving method) between a pair of light-transmitting substrates. Things. As the color filter, a color filter having a plurality of pixel groups as described above and each pixel constituting the pixel group being separated from each other by the black matrix according to the present invention can be used. Since the color filter has high flatness, a liquid crystal display element including the color filter does not cause cell gap unevenness between the color filter and the substrate, and display defects such as color unevenness do not occur.
[0082]
Further, as another aspect of the liquid crystal display element, at least one includes at least a color filter, a liquid crystal layer, and liquid crystal driving means between a pair of light transmissive substrates, and the liquid crystal driving means is an active element (for example, TFT), and a black matrix produced using the colored composition for producing a black matrix or a photosensitive transfer material of the present invention is formed between the active elements.
[0083]
Examples of the liquid crystal that can be used for the liquid crystal display element include nematic liquid crystal, cholesteric liquid crystal, smectic liquid crystal, and ferroelectric liquid crystal.
[0084]
《Black matrix substrate》
The coloring composition for producing a black matrix of the present invention can also be suitably used for a black matrix substrate. The black matrix substrate has a light-shielding layer provided on a light-transmitting substrate, and the light-shielding layer is formed using the colored composition for producing a black matrix of the present invention.
[0085]
The black matrix substrate can be used for producing a color filter.
The thickness of the light shielding layer in this black matrix substrate is preferably 0.2 to 2.0 μm, particularly preferably 0.2 to 0.9 μm. Since the light shielding layer in the black matrix substrate is obtained by dispersing metal fine particles having an average aspect ratio of 2 or more, even a thin film as described above has a sufficient optical density.
[0086]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following, “part” means “part by mass” unless otherwise specified.
[0087]
[Example 1]
<< Production of photosensitive material >>
<Preparation of silver fine particle dispersion>
73.5 g of silver fine particles having an average aspect ratio of 2.2, 1.05 g of the dispersant Solsperse 20000 (trade name: Solsperse 20000, manufactured by Avicia Co., Ltd.), and 16.4 g of methyl ethyl ketone were mixed. This was dispersed using an ultrasonic disperser (trade name: Ultrasonic generator model US-6000 ccvp, manufactured by nissei) to obtain a silver fine particle dispersion having an equivalent circle diameter of 100 nm.
[0088]
<Preparation of coating solution for photosensitive light shielding layer>
The following composition was mixed and the coating liquid for photosensitive light shielding layers was prepared.
〔composition〕
Silver fine particle dispersion (aspect ratio 2.2) 40.00 parts
Propylene glycol monomethyl ether acetate 28.6 parts
・ Methyl ethyl ketone 37.6 parts
・ 0.2 parts of fluorosurfactant (20%)
(Product name: F176PF, manufactured by Dainippon Ink & Chemicals, Inc.
Hydroquinone monomethyl ether 0.001 part
-Benzyl methacrylate / methacrylic acid copolymer 2.1 parts
(Molar ratio = 73/27, molecular weight 30000)
・ Dipentaerythritol hexaacrylate
Added so that the sum of volume fractions of metal particles and pigment particles is 0.13
-Bis [4- [N- [4- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate 0.1 part
[0089]
<Preparation of coating solution for protective layer>
The following composition was mixed to prepare an intermediate layer (protective layer) coating solution.
・ Polyvinyl alcohol 3.0 parts
(Product name: PVA205, manufactured by Kuraray Co., Ltd.)
・ Polyvinylpyrrolidone 1.3 parts
(Product name: PVP-K30, manufactured by GAF Corporation)
・ Distilled water 50.7 parts
・ Methyl alcohol 45.0 parts
[0090]
<Production of photosensitive material>
The photosensitive light-shielding layer coating solution was applied onto a glass substrate using a spin coater so that the film thickness was 0.65 μm, and dried at 100 ° C. for 5 minutes to form a photosensitive light-shielding layer. Next, the above protective layer coating solution is applied onto this with a spin coater so that the dry film thickness is 1.5 μm, and dried at 100 ° C. for 5 minutes to form a protective layer. The material was made.
[0091]
<Production of black matrix>
The photosensitive material of the present invention obtained using an ultrahigh pressure mercury lamp is 70 mJ / cm from the coated surface side. ² The exposure was performed. Next, development processing (33 ° C., 20 seconds) was performed using a development processing solution TCD (manufactured by Fuji Photo Film Co., Ltd.) to obtain a black matrix.
[0092]
<Evaluation>
The obtained black matrix was evaluated as follows. The results are shown in Table 1 below.
[0093]
-Optical density measurement-
The optical density of the film was measured by the following method.
First, 500 mJ / cm from the coated surface side using a super high pressure mercury lamp to the photosensitive light-shielding layer coated on the glass substrate before black matrix preparation. ² The exposure was performed. Next, the optical density (OD) was measured using a Macbeth densitometer (trade name: TD-904, manufactured by Macbeth). Separately, the optical density (OD) of the glass substrate ₀ ) Was measured by the same method, and O. D. To OD ₀ The value obtained by subtracting was used as the optical density of the film.
[0094]
-Black matrix quality-
The glass substrate on which the black matrix was formed was visually observed to evaluate its quality (color) according to the following criteria. A to C are substantially within the allowable range among the following criteria.
[Standard]
A: It was almost completely considered as pure black.
B: There was a slight shift in hue.
C: There was a slight hue shift.
D: There was a hue shift to the extent that it would be an obstacle in practical use.
E: There was a complete hue shift.
[0095]
[Examples 2 to 5]
When preparing the silver fine particle dispersion of Example 1, instead of silver fine particles having an average aspect ratio of 2.2, the average aspect ratios were “6.5”, “19”, “58”, and “148”, respectively. A light-sensitive material was prepared in the same manner as in Example 1 except that silver fine particles were used, and the same evaluation was performed. The results are shown in Table 1 below.
[0096]
[Example 6]
In Example 4, the amount of silver fine particles having an average aspect ratio of 2.2 was changed to 38 parts during the preparation of the coating solution for the photosensitive light-shielding layer, and carbon black (trade name: trade name: CFP- A photosensitive material was prepared in the same manner as in Example 4 except that 21.9 parts of FF-949K (Fuji Film Arch Co., Ltd.) were added, and the same evaluation was performed. The results are shown in Table 1 below.
In comparison with Example 4, the black matrix of Example 6 is O.D. D. Was slightly lower than that of Example 4, but was closer to achromatic black.
[0097]
[Examples 7 to 9]
When preparing the silver fine particle dispersion of Example 1, instead of silver fine particles having an average aspect ratio of 2.2, titanium fine particles, nickel fine particles, and palladium fine particles having an average aspect ratio of 2.2 were used. Produced a photosensitive material in the same manner as in Example 1 and evaluated it in the same manner. The results are shown in Table 1 below.
[0098]
[Examples 10 to 18]
In Examples 1 to 9, the protective layer was not provided, and the exposure amount when producing the black matrix was “70 mJ / cm. ² To "500mJ / cm ² A photosensitive material was prepared in the same manner as in Examples 1 to 9 except that the value was changed to "", and the same evaluation was performed. The results are shown in Table 1 below.
[0099]
[Example 19]
<< Production of photosensitive transfer material >>
A biaxially stretched 75 μm thick polyethylene terephthalate support surface was coated with a coating solution for a thermoplastic resin layer prepared as follows using a slide coater to a thickness of 15 μm and dried at 100 ° C. for 5 minutes. A thermoplastic resin layer was formed. Next, an intermediate layer coating solution having the same composition as that of the protective layer coating solution in Example 1 was applied thereon so that the dry film thickness was 1.5 μm, and dried at 100 ° C. for 5 minutes. Formed. Further on this, the photosensitive light-shielding layer coating solution in Example 1 was applied to a dry film thickness of 0.6 μm and dried at 100 ° C. for 5 minutes to form a photosensitive light-shielding layer to produce a photosensitive transfer material. did.
[0100]

[0101]
<< Production of photosensitive material >>
The glass substrate and the resulting photosensitive transfer material are overlaid so that the photosensitive light-shielding layer is in contact with the glass substrate, and both are attached using a laminator (trade name: VP-II, manufactured by Osaka Laminator Co., Ltd.). Combined. Lamination conditions are pressure 0.8kg / cm ² The temperature was 130 ° C. Thereafter, the support (polyethylene terephthalate) was peeled from the photosensitive transfer material to produce a photosensitive material.
[0102]
<Production of black matrix>
70mJ / cm from the coated surface side using an ultra-high pressure mercury lamp ² The exposure was performed. Next, development processing in the following three steps was performed to obtain a black matrix.
[Development processing]
First step: Development processing was performed using a developing solution (trade name: TPD, manufactured by Fuji Photo Film Co., Ltd., alkaline developer) at a temperature of 30 ° C. for 40 seconds.
Second step: Development processing was performed using a developing solution (trade name: TCD, manufactured by Fuji Photo Film Co., Ltd., alkaline developer) at a temperature of 33 ° C. for 20 seconds.
Third step: Development processing was performed using a developing solution (trade name: TSD, manufactured by Fuji Photo Film Co., Ltd., alkaline developer) at a temperature of 33 ° C. for 20 seconds.
[0103]
<Evaluation>
Evaluation similar to Example 1 was performed. The results are shown in Table 1 below.
[0104]
[Examples 20 to 27]
Similar to Example 9, except that the photosensitive light-shielding layer coating solution of Example 1 used in the production of the photosensitive transfer material of Example 19 was changed to the photosensitive light-shielding layer coating solution of Examples 2 to 9, respectively. Thus, a black matrix was produced and evaluated in the same manner. The results are shown in Table 1 below.
[0105]
[Comparative Example 1]
In preparing the silver fine particle dispersion of Example 1, a photosensitive material was prepared in the same manner as in Example 1 except that silver fine particles having an average aspect ratio of 1.4 were used instead of silver fine particles having an average aspect ratio of 2.2. The same evaluation was performed. The results are shown in Table 1 below.
[0106]
[Comparative Example 2]
A photosensitive material was prepared in the same manner as in Example 1 except that 219 parts of carbon black dispersion (trade name: CFP-949K, manufactured by Fuji Film Arch Co., Ltd.) was used in place of the silver fine particle dispersion of Example 1. The same evaluation was performed. The results are shown in Table 1 below.
[0107]
[Table 1]

[0108]
From Table 1, it was found that all of the black matrices of the examples had high OD with an OD of 3.6 or more. On the other hand, the black matrix of Comparative Example 1 had an OD of less than 3.6, and the quality of the black matrix was also lowered. Further, the black matrix of Comparative Example 2 could not exhibit satisfactory performance as a black matrix with an OD of 0.7.
[0109]
【The invention's effect】
As described above, according to the present invention, a black matrix having a high light-shielding performance can be produced at a low cost, and a colored composition for producing a black matrix and a photosensitive transfer material that are excellent in environmental performance can be provided.
Further, according to the present invention, it is possible to provide a black matrix that is a thin film and has a high light-shielding performance, and a color filter that has a high display contrast and excellent flatness.

Claims (8)

Aspect ratio Ri der 2 or more, comprising at least one particle diameter 0.05~5.0μm der Ru metal particles, an alkali-soluble binder polymer, a photopolymerization initiator, a photopolymerizable monomer, a A coloring composition for producing a black matrix.   The colored composition for producing a black matrix according to claim 1, wherein the metal fine particles have an aspect ratio of 5 or more.   The colored composition for producing a black matrix according to claim 1 or 2, wherein the metal fine particles are silver particles.   The colored composition for producing a black matrix according to any one of claims 1 to 3, wherein an optical density when a light-shielding layer having a thickness of 1 µm is formed is 1 or more. A photosensitive transfer material for producing a black matrix having at least a photosensitive light-shielding layer provided on a support, wherein the photosensitive light-shielding layer is formed from the colored composition for producing a black matrix according to any one of claims 1 to 4. A photosensitive transfer material for producing a black matrix. It forms using the coloring composition for black matrix preparation in any one of Claims 1-4 , The black matrix characterized by the above-mentioned. A black matrix formed using the photosensitive transfer material for producing a black matrix according to claim 5 . A color filter having two or more pixel groups exhibiting different colors on a light transmissive substrate, wherein each pixel constituting the pixel group is separated from each other by a black matrix, a color filter which is a black matrix according to claim 6 or 7.