JP2009083482A - Photosensitive resin laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin laminate excellent in transferability from a support layer to a substrate, having an adequate developing time, and excellent in sensitivity, shading properties and fine line formability; to provide a method for manufacturing a substrate with a black matrix; further to provide a color filter using the substrate with the black matrix. <P>SOLUTION: This photosensitive resin laminate is obtained by laminating at least the support layer, an oxygen-barrier layer and a photosensitive resin layer in order, where the support layer has 100-4,000 mN/25 mm peeling force of the surface opposite to the surface not laminated; the oxygen-barrier layer contains a water-soluble resin composition; the photosensitive resin layer contains a photosensitive resin composition, which contains 3-40 mass% of a specific alkali-soluble polymer, 3-50 mass% of a photo-polymerizable compound having an ethylenically unsaturated double bond, and 0.1-20 mass% of photo-polymerization initiator, to 100 mass% of the photosensitive resin composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a color filter, a black matrix, a photosensitive resist, and the like. The present invention also relates to a method for forming them and a photosensitive resin laminate for forming them.

  In many recent flat panel displays such as a liquid crystal display and an organic EL display, a member called a color filter is used as a coloring means. The color filter is composed of red, green, and blue color pixels and a black matrix that partitions them. Color pixels are necessary for colorization, but in the case of liquid crystal displays, the black matrix is a grid pattern between color pixels for the purpose of improving image quality, such as preventing TFT malfunction, and improving contrast and preventing color mixing. Arranged.

  In recent black matrix materials, the ratio of switching from chromium to resin is high in consideration of adverse effects on the environment. One of means for creating a black matrix made of a resin (hereinafter simply referred to as a black matrix) is photolithography using a photosensitive resin composition. Since the black matrix has a high light-shielding property, in order to make the photosensitive resin composition be more efficiently exposed, a device for increasing the sensitivity of the photosensitive resin composition is particularly required. Patent Document 1 discloses a photosensitive black matrix using a special resin.

  On the other hand, when a black matrix is prepared using a liquid photosensitive resin composition, the coating process is a wet process, and it is necessary to prepare exhaust drying equipment and a slit coater having a different coating width according to the substrate area. The slit coater needs to be designed precisely to ensure the flatness of the coating film and is very expensive. In the case of a liquid, the pot life is generally said to be short, and it is difficult to improve the sensitivity because it is exposed to oxygen during exposure. In contrast, in the method of preparing a photosensitive resin laminate in advance and laminating it on a base material, the lamination is completed in a dry process, and a plurality of photosensitive resin laminates are attached according to the size of the substrate. It is easy to cope with the size of the board. For example, in the case where a single photosensitive resin laminate is insufficient in the pasting width, it is possible to attach two to three or more photosensitive resin laminates to the entire substrate. Moreover, since exposure is carried out through a pot life or a support film, it is considered advantageous in terms of improving sensitivity (Patent Document 2).

  Therefore, if a photosensitive resin laminate is prepared using the photosensitive resin composition described in Patent Document 1 that is excellent in sensitivity and fine line formability, black matrix formation that is excellent in sensitivity and fine line formability and advantageous in productivity Although it is thought that material is obtained, even if the photosensitive resin composition of patent document 1 is apply | coated to a support layer as it is, and it becomes a photosensitive resin laminated body, the adhesiveness to the support layer of the photosensitive resin composition layer is strong. As a result, transfer failure occurred, and it was difficult to form a black matrix on the substrate (refer to Comparative Examples described later).

Furthermore, as a method for attaching the photosensitive resin laminate to the substrate, a method using a photosensitive transfer material in which a thermoplastic resin layer, an intermediate layer, and a colored photosensitive resin layer are laminated on a temporary support is also disclosed ( Patent Document 3). However, in such a transfer material, since a thermoplastic resin layer having a relatively low Tg is laminated, wrinkles are likely to occur during lamination. In addition, it is difficult to form fine lines because it is necessary to expose through a thermoplastic resin layer of several tens of μm. Further, it is necessary to develop a thermoplastic resin layer having a thickness of several tens of μm before or simultaneously with development of the photosensitive resin layer. When the thermoplastic resin layer has film thickness unevenness, the development time until the developer reaches the photosensitive resin layer varies, and it is difficult to ensure the uniformity of the line width. In general, the more coloring materials and light-shielding materials that do not contribute to photocrosslinking are included, the faster the development speed becomes, and the change in line width and adhesion with respect to the development time increases. It is difficult to achieve both a light shielding property and a fine line forming property at the same time with a configuration like the above transfer material. Moreover, even if the thermoplastic resin layer is omitted, the pattern cannot be easily formed as shown in the comparative examples described later in this specification.

JP 2004-69754 A JP-A-2005-208480 JP 08-44050 A

  An object of this invention is to provide the photosensitive resin laminated body which is excellent in the transferability from a support layer to a base material, has an appropriate development time, and is excellent in a sensitivity, light-shielding property, and a fine wire formation property. Furthermore, it aims at providing the manufacturing method of the board | substrate with a black matrix using the photosensitive resin laminated body of this invention with sufficient light-shielding property and thin film thickness. Furthermore, an object of the present invention is to provide a color filter using the substrate with the black matrix.

（上記式（Ｉ）中、Ｘは下記式（ＩＩ）で表される基、Ｙはジカルボン酸無水物の酸無水物基を除いた残基、Ｚはテトラカルボン酸二無水物の酸無水物基を除いた残基、ｎは１〜２０の整数である。下記式（ＩＩ）中のＲ_１及びＲ_２はそれぞれ独立に、Ｈ又はＣＨ_３を表す。）

（２） 前記水溶性樹脂組成物中の水溶性可塑剤がポリビニルピロリドンである（１）記載の感光性樹脂積層体。
（３） 前記支持層が、その積層しない面とは反対側の面の剥離力が１００〜１５００ｍＮ／２５ｍｍである（１）又は（２）記載の感光性樹脂積層体。
（４） 前記酸素遮断層の膜厚が２〜３μｍである（１）〜（３）のいずれか一項に記載の感光性樹脂積層体。
（５） 前記感光性樹脂組成物が、下記式（ＩＩＩ）で表されるエチレン性不飽和二重結合を有する光重合性化合物を含む（１）〜（４）のいずれか一項に記載の感光性樹脂積層体。

（上記式（ＩＩＩ）中、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ互いに独立なＨ又はＣＨ_３基を表す。Ｒ_６は２価の連結基で、炭素数２〜８のアルキレン基、炭素数３〜１０のシクロアルキレン基、及び炭素数６〜１０のフェニレン基からなる群から選ばれる一種の基を表す。）
（６） 前記感光性樹脂組成物が、該感光性樹脂組成物１００質量％に対して、（ｄ）着色顔料４０〜７０質量％を含む（１）〜（５）のいずれか一項に記載の感光性樹脂積層体。
（７） （１）〜（６）のいずれか一項に記載の感光性樹脂積層体を、基板にラミネートする工程、支持層を剥離する工程、露光する工程、及び現像する工程を順に行うブラックマトリックス付き基板の製造方法。
（８） （１）〜（６）のいずれか一項に記載の感光性樹脂積層体を、基板にラミネートする工程、露光する工程、支持層を剥離する工程、及び現像する工程を順に行うブラックマトリックス付き基板の製造方法。
（９） （７）又は（８）記載の方法で基板上にブラックマトリックスを形成する工程と、前記基板がガラス基板であり、該ガラス基板上のブラックマトリックスで覆われていない部分の少なくとも一部に感熱性又は感光性のカラーインクをインクジェット方式により印刷する印刷工程とを含むカラーフィルタの製造方法。
（１０） （９）記載の方法により製造されるカラーフィルタ。 In order to achieve the above object, the present invention is as follows.
(1) A photosensitive resin laminate in which at least a support layer, an oxygen blocking layer, and a photosensitive resin layer are sequentially laminated, and the support layer is peeled off from the surface opposite to the non-laminated surface. The force is 100 to 4000 mN / 25 mm, and the oxygen barrier layer contains a water-soluble resin composition, and the water-soluble resin composition has a water-soluble polymer having at least vinyl alcohol as a copolymer unit, and a weight average molecular weight of 5 2,000 to 2,000,000 water-soluble plasticizer, the photosensitive resin layer includes a photosensitive resin composition, and the photosensitive resin composition comprises 100% by mass of the photosensitive resin composition. In contrast, (a) 3-40% by mass of an alkali-soluble polymer represented by the following formula (I), (b) a photopolymerizable compound 3 having an ethylenically unsaturated double bond other than the following formula (I) To 50% by weight, and (c) photopolymerization initiator 0 The photosensitive resin laminated body characterized by including 1-20 mass%.

(In the above formula (I), X is a group represented by the following formula (II), Y is a residue excluding the acid anhydride group of dicarboxylic anhydride, Z is an acid anhydride of tetracarboxylic dianhydride. The residue excluding the group, n is an integer of 1 to 20. R ₁ and R ₂ in the following formula (II) each independently represent H or CH _3. )

(2) The photosensitive resin laminate according to (1), wherein the water-soluble plasticizer in the water-soluble resin composition is polyvinylpyrrolidone.
(3) The photosensitive resin laminate according to (1) or (2), wherein the support layer has a peeling force of 100 to 1500 mN / 25 mm on the surface opposite to the surface on which the support layer is not laminated.
(4) The photosensitive resin laminate according to any one of (1) to (3), wherein the oxygen blocking layer has a thickness of 2 to 3 μm.
(5) The said photosensitive resin composition as described in any one of (1)-(4) containing the photopolymerizable compound which has an ethylenically unsaturated double bond represented by following formula (III). Photosensitive resin laminate.

(In the formula _{(III), R 3, R} 4 and _{R 5} are .R ₆ represent each independently an H or CH ₃ group a divalent linking group, an alkylene group having 2 to 8 carbon atoms, carbon This represents a kind of group selected from the group consisting of a cycloalkylene group having 3 to 10 carbon atoms and a phenylene group having 6 to 10 carbon atoms.)
(6) The said photosensitive resin composition is as described in any one of (1)-(5) which contains 40-70 mass% of (d) coloring pigment with respect to 100 mass% of this photosensitive resin composition. Photosensitive resin laminate.
(7) Black which sequentially performs the step of laminating the photosensitive resin laminate according to any one of (1) to (6) on a substrate, the step of peeling the support layer, the step of exposing, and the step of developing. Manufacturing method of substrate with matrix.
(8) Black which sequentially performs the step of laminating the photosensitive resin laminate according to any one of (1) to (6) on a substrate, the step of exposing, the step of peeling the support layer, and the step of developing. Manufacturing method of substrate with matrix.
(9) The step of forming a black matrix on the substrate by the method according to (7) or (8), and the substrate is a glass substrate, and at least a part of the portion not covered with the black matrix on the glass substrate And a printing step of printing a heat-sensitive or photosensitive color ink by an ink jet method.
(10) A color filter produced by the method according to (9).

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin laminated body which is excellent in the transferability from a support layer to a base material, has an appropriate image development time, and is excellent in a sensitivity, light-shielding property, and a fine wire formation property can be provided. Moreover, if the photosensitive resin laminate of the present invention is used, it is possible to produce a substrate with a black matrix having a high productivity and a sufficient light-shielding property, a thin film thickness, and a color filter using the same.

The photosensitive resin laminate of the present invention is formed by laminating at least a support layer, an oxygen blocking layer, and a photosensitive resin layer in this order.
Smooth paper or a synthetic resin film can be used for the support layer. A synthetic resin film is preferred from the viewpoint of dust resistance. Examples of synthetic resin films include polyethylene film, polypropylene film, polycarbonate film, polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, poly Examples include methyl acrylate copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, triacetyl cellulose film, and polypropylene film. These stretched ones can be used if necessary. A polyethylene terephthalate film is preferable from the viewpoint of heat resistance, flexibility, and strength. In the present invention, transparency is not particularly required for the support layer, but it is preferable to use a film for optical use in consideration of smoothness. When the oxygen barrier layer is arranged adjacent to the support layer, the smoothness may affect the uniform application property of the oxygen barrier layer, the defects (pinholes) of the photosensitive resin layer, the film thickness uniformity, etc. Is more preferable.

In general, the lower the haze, the higher the surface smoothness, which can be a useful index. The haze of the support layer is preferably 5.0 or less. More preferably, it is 2.0 or less, More preferably, it is 1.0 or less. The haze here is a value representing turbidity, and the haze value H = the total transmittance T that is irradiated by the lamp and transmitted through the sample and the transmittance D of the light diffused and scattered in the sample. It is calculated as D / T × 100. These are defined by JIS-K-7105 and can be easily measured by a commercially available turbidimeter.
The film thickness of the support layer is not particularly limited, but it is 10 μm from the viewpoint of wrinkles and deformation in processes such as subsequent release treatment, application of an oxygen blocking layer, application of a photosensitive resin layer, and lamination to a substrate. The above is preferable. More preferably, it is 15 μm or more. From the viewpoint of transferability of the photosensitive resin layer during lamination, the thickness is preferably 100 μm or less.

The support layer has a peel force of 100 to 4000 mN / 25 mm on the surface opposite to the non-laminated surface (that is, the surface to be laminated, the same applies hereinafter). The peeling force can be obtained by measuring the peeling force when the 31B tape manufactured by Nitto Denko is attached with a rubber roller.
The measurement conditions for the peel force are as follows. First, Nitto Denko 31B tape is repeatedly bonded to the measurement surface of the peeling force with a rubber roller with a load of 5 kgf (49 N) five times so as not to reciprocate in the length direction. This is stored for 24 hours in an environment of 23 ° C. and 50% RH, and a peeling test is performed at a peeling speed of 0.1 m / min and a peeling angle of 90 °. As the measuring device, Tensilon RTM-500 (load cell rating: 1 Kgf) manufactured by Orientec Co., Ltd. is used. The peel test distance is 60 mm, and the integral average weight when the load is plotted against the elongation is the peel force.
From the viewpoint of releasability, the peel force is 100 mN / 25 mm or more. More preferably, it is 200 mN / 25 mm or more. More preferably, it is 250 mN / 25 mm or more. From the viewpoint of applicability (repellency, uniform applicability) to the release treatment surface, it is 4000 mN / 25 mm or less. More preferably, it is 3000 mN / 25 mm or less, More preferably, it is 2000 mN / 25 mm or less, Most preferably, it is 1500 mN / 25 mm or less.

  A surface opposite to the surface on which the support layer is not laminated can be subjected to a release treatment in order to obtain a desired peeling force. The mold release treatment means, for example, that the surface is thinly coated with a release agent containing a silicone resin, a fluororesin, an alkyd resin (or alkyd resin), a long chain alkyl resin, an acrylic resin, or a polyolefin resin, and the release property It refers to chemical treatments that increase and physical treatments such as corona treatment.

As a release agent containing a silicone resin, a condensation reaction type silicone obtained by reacting both terminals silanol polydimethylsiloxane and polymethylhydrogensiloxane or polymethylmethoxysiloxane,
Addition reaction type silicone obtained by reacting dimethylsiloxane / methylvinylsiloxane copolymer or dimethylsiloxane / methylhexenylsiloxane copolymer with polymethylhydrogensiloxane,
UV curable type or electron beam curable silicone obtained by curing acrylic silicone or epoxy group-containing silicone with ultraviolet ray or electron beam,
Modification of epoxy modified silicone (silicone epoxy), polyester modified silicone (silicone polyester), acrylic modified silicone (silicone acrylic), phenol modified silicone (silicone phenol), alkyd modified silicone (silicone alkyd), melamine modified silicone (silicone melamine), etc. Silicone may be mentioned.

  The alkyd resin is also called an alkyd resin, which is a condensate of polybasic acid and polyhydric alcohol modified with fatty oil or fatty acid. It is preferable when the transfer of silicone on the release treatment surface is disliked. Moreover, it is preferable from a viewpoint of the balance of the applicability | paintability of an oxygen interruption | blocking layer and another layer, and peelability. Examples of polybasic acids include saturated polybasic acids such as phthalic anhydride, terephthalic acid, succinic acid, adipic acid, and sebacic acid, and unsaturated polybasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic anhydride. Other polybasic acids such as basic acid, cyclopentadiene-maleic anhydride adduct, terpene-maleic anhydride adduct, rosin-maleic anhydride adduct, and the like can be mentioned. Polyhydric alcohols include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol and tetramethylene glycol, trihydric alcohols such as glycerin and trimethylolpropane, diglycerin, triglycerin and pentaerythritol. , Tetravalent or higher alcohols such as dipentaerythritol, mannitol and sorbitol. Examples of denaturing agents include soybean oil, linseed oil, tung oil, castor oil, dehydrated castor oil, coconut oil, and fatty acids thereof, stearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid, dehydrated Examples thereof include fats and oils such as ricinoleic acid and fatty acids, natural resins such as rosin, kovar, amber, shellac, and synthetic resins such as ester gum, phenol resin, urea resin, and melamine resin. Further, a stearic acid-modified alkyd resin and / or a cured resin of a stearic acid-modified acrylic resin and an amino resin is also preferable from the viewpoint of the balance between coatability and peelability.

Examples of the polyolefin resin include olefin thermoplastic elastomers such as ethylene propylene copolymer and ethylene octene copolymer. You may mix and use a polyethylene resin etc.
When coating the release agent, it is preferable to coat as thin as possible as long as the release effect can be obtained. After coating, the release agent can be fixed to the support film by heat or UV treatment. When using a release agent especially for the release treatment applied to the support film, the component of the treatment agent, for example, the substituent of the organosilane should have a higher molecular weight (for example, change from a methyl group to a phenyl group, etc.) It is known that the peel strength increases. On the other hand, regarding the thickness of the release layer formed on the support film by the release treatment, the release force increases when forming a thin release layer, and the release force when forming the release layer sufficiently thick. Is also known to decline. These findings may be used to bring the peeling force of the support layer in the present invention into the target range. That is, in order to bring the peeling force of the support layer in the present invention into the target range, a release layer is formed on at least one side of the support film, and the components of the release layer on the support film and the thickness of the release layer are appropriately set. The peeling force can be adjusted by selecting.

  An oxygen blocking layer can be laminated on the surface of the support layer opposite to the non-laminated surface. In addition to the oxygen blocking layer, other layers can be provided depending on the purpose. For example, when laminating the photosensitive resin laminate, a cushion layer can be provided from the viewpoint of easily following the unevenness of the substrate. The cushion layer preferably contains a thermoplastic resin and has a lower viscosity than the photosensitive resin layer. Further, it is preferably water-soluble or alkali-soluble.

The oxygen-blocking layer is prepared by diluting the water-soluble resin composition with water or other solvent according to the coating film thickness and viscosity, and coating and drying on the surface opposite to the non-stacked surface of the support layer. Can be stacked. The coating can be performed by using an apparatus and a system that are appropriately selected according to the viscosity, coating film thickness, and film thickness accuracy of the water-soluble resin composition, such as a blade coater, bar coater, gravure coater, and die coater. Furthermore, the oxygen barrier layer can be laminated by forming an oxygen barrier layer on a temporary support in advance and laminating it on the surface of the support layer opposite to the non-laminated surface. Thus, when four layers of a support layer, an oxygen barrier layer, a photosensitive resin layer, and a temporary support are laminated, the peeling force between the temporary support and the photosensitive resin layer after the lamination is It is preferable that it is smaller than the peeling force between the oxygen barrier layer and the oxygen barrier layer.
The film thickness of the oxygen blocking layer is preferably 0.05 μm or more from the viewpoint of sensitivity and suppression of pinholes generated in the photosensitive resin layer transferred to the substrate. More preferably, it is 0.1 μm or more, more preferably 0.5 μm or more, further preferably 1 μm or more, and most preferably 2 μm or more. Moreover, 30 micrometers or less are preferable from the viewpoint of the transferability at the time of lamination, development time, fatigue of a developing solution, and cut chip property. More preferably, it is 10 μm or less, more preferably 6 μm or less, further preferably 4 μm or less, and most preferably 3 μm or less.

  As described above, the oxygen barrier layer is obtained by diluting the water-soluble resin composition with water or other solvent according to the coating film thickness and viscosity, and coating and drying, so that the surface on the side opposite to the non-laminated surface of the support layer is obtained. Can be laminated. Other solvents can be used as long as the components of the water-soluble resin composition do not precipitate. From the viewpoints of coating properties and drying properties, those having a boiling point lower than that of water are preferable, and it is more preferable to use a mixture of water and these other solvents. Specific examples include a mixed solvent of water and ethanol or methanol, and a mixed solvent of water and methanol is preferable. In addition, a water-soluble polymer having at least vinyl alcohol as a copolymer unit is often difficult to dissolve in cold water. Therefore, if it is dispersed in cold water in advance and then heated and dissolved, it is blended with a water-soluble plasticizer. Is often easy.

The water-soluble resin composition includes a water-soluble polymer having at least vinyl alcohol as a copolymer unit and a water-soluble plasticizer having a weight average molecular weight of 5,000 to 2,000,000.
Examples of the water-soluble polymer having at least vinyl alcohol as a copolymer unit include polyvinyl alcohol and its derivatives, and polyvinyl alcohol obtained by copolymerizing 1 to 20 mol% of olefin.

Polyvinyl alcohol is generally produced by alkali saponification of polyvinyl acetate. The weight average molecular weight of polyvinyl alcohol is preferably 1,000 to 100,000. From the viewpoint of oxygen barrier properties and developability, it is more preferably 5,000 to 50,000. The saponification degree is preferably 50 mol% or more from the viewpoint of developability, preferably 70 mol% or more, more preferably 80 mol% or more. Examples of such polyvinyl alcohol include PVA-103, PVA-105, PVA-110, PVA-117, PVA-124, PVA-203, PVA-205, PVA-217, and PVA-220 manufactured by Kuraray Co., Ltd. , PVA-224, PVA-226, PVA-235, PVA-403, PVA-405, and PVA-420.
Examples of the polyvinyl alcohol derivative include carboxylated polyvinyl alcohol described in JP-A-63-197942.

  Polyvinyl alcohol obtained by copolymerizing 1 to 20 mol% of olefin is generally produced by copolymerizing olefin and vinyl acetate and saponifying the copolymer. Examples of the olefin include ethylene, propylene, 1-hexene and the like. Ethylene is preferable from the viewpoint of copolymerization and alkali solubility. From the viewpoint of alkali solubility, the olefin copolymerization ratio is 20 mol% or less. Examples of such polyvinyl alcohol obtained by copolymerizing 1 to 20 mol% of olefin include Eval (trade name) manufactured by Kuraray Co., Ltd.

The water-soluble polymer having at least vinyl alcohol as a copolymer unit is preferably blended in the water-soluble resin composition from 50% by mass to 95% by mass from the viewpoint of developability and cost. More preferably, it is 60 mass% or more and 90 mass% or less.
The water-soluble resin composition contains a water-soluble plasticizer having a weight average molecular weight of 5,000 or more and 2,000,000 or less. From the viewpoint of fine line formation of the photosensitive resin layer, the weight average molecular weight is 5,000 or more. From the viewpoint of developability and solubility of the water-soluble resin composition in water or other solvents, 2,000,000 or less is preferable. More preferably, it is 500,000 or less, More preferably, it is 200,000 or less.

  Examples of the water-soluble plasticizer include polyvinyl pyrrolidone and derivatives thereof, water-soluble cellulose derivatives such as hydroxyethyl cellulose, polyethylene oxide, polyethylene oxide ester compounds, polyethylene oxide ether derivatives such as polyethylene oxide ether compounds, and vinyl ether-anhydrous maleic acid. Examples include acid copolymers and water-soluble salts thereof, carboxyalkyl starch water-soluble salts, polyacrylamide, polyamide, water-soluble polyacrylic acid salts, gelatin, and polypropylene glycol. When the oxygen barrier layer is laminated directly on the support layer, polyvinylpyrrolidone and derivatives thereof are preferable from the viewpoints of coatability to the support layer and releasability from the support layer. Even when the oxygen barrier layer is not directly laminated on the support layer, polyvinylpyrrolidone is preferable from the viewpoints of sensitivity and fine wire formability. Specific examples include K-15 manufactured by Nippon Shokubai Co., Ltd. (weight average molecular weight 40,000), K-30 (weight average molecular weight 100,000), K-85 (weight average molecular weight 900,000), K-90 (weight average molecular weight). 1 million).

  The weight average molecular weight of a water-soluble polymer having at least vinyl alcohol as a copolymer unit and a water-soluble plasticizer having a weight average molecular weight of 5,000 to 2,000,000 is gel permeation chromatography (GPC) (pump: Gulliver) manufactured by JASCO Corporation. , PU-1580 type, column: Shodex (trademark) (HFIP-805, HFIP-803) manufactured by Showa Denko KK in series, moving bed solvent: hexafluoroisopropanol, polystyrene standard sample (produced by Showa Denko KK) Calculated as a weight average molecular weight (polystyrene conversion) by using a calibration curve according to Shodex STANDARD SM-105).

The photosensitive resin layer contains a photosensitive resin composition, and the photosensitive resin composition comprises (a) an alkali-soluble polymer 3 represented by the following formula (I) with respect to 100% by mass of the photosensitive resin composition. -40 mass%, (b) 3-50 mass% of photopolymerizable compounds which have an ethylenically unsaturated double bond, and (c) 0.1-20 mass% of photoinitiators.
The content of the alkali-soluble polymer represented by the following formula (I) is 3% by mass or more from the viewpoint of sensitivity, adhesion, and fine wire formability, and 40% by mass or less from the viewpoint of developability and fine wire formability. is there. When the amount of the alkali-soluble polymer represented by the following formula (I) is extremely large, the development time is slowed, the apparent line width is increased, and it is difficult to form a thin line. The content is preferably 5 to 30% by mass, more preferably 8 to 25% by mass, and still more preferably 8 to 25% by mass.

（上記式（Ｉ）中、Ｘは下記式（ＩＩ）で表される基、Ｙはジカルボン酸無水物の酸無水物基を除いた残基、Ｚはテトラカルボン酸二無水物の酸無水物基を除いた残基、ｎは１〜２０の整数である。下記式（ＩＩ）中のＲ_１及びＲ_２はそれぞれ互いに独立なＨ又はＣＨ_３基を表す。）

(In the above formula (I), X is a group represented by the following formula (II), Y is a residue excluding the acid anhydride group of dicarboxylic anhydride, Z is an acid anhydride of tetracarboxylic dianhydride. The residue excluding the group, n is an integer of 1 to 20. R ₁ and R ₂ in the following formula (II) each independently represent H or CH ₃ group.)

Here, the “acid anhydride group” refers to a “—CO—O—CO— group”.
Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyl Examples include tetrahydrophthalic anhydride and glutaric anhydride.
Examples of tetracarboxylic dianhydrides include aromatic polycarboxylic anhydrides such as pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride. Things.

  The compound represented by the above formula (I) used in the present invention can be obtained, for example, by the method described in JP-A No. 2001-354735. The compound represented by the above formula (I) has substantially no dicarboxylic anhydride residue in the polymer chain, but has at its end. Therefore, unlike a compound having a dicarboxylic acid anhydride residue in the polymer chain, it is easy to control the solution viscosity even at the same solid content concentration, improving workability during coating, improving coating properties, and making the film thickness uniform. Can be achieved.

  The alkali-soluble polymer represented by the above formula (I) used in the present invention has at least two ethylenically unsaturated double bonds capable of addition polymerization in the compound. The photosensitive resin composition containing the polymer is cured by addition polymerization by the action of the photopolymerization initiator, even when the optical density is high, when irradiated with light of a predetermined wavelength that activates the photopolymerization initiator. can do. For this reason, a color filter having a high display contrast and a beautiful color of R, G, B can be manufactured. In particular, this effect is remarkable in the relationship between the light shielding property and the sensitivity when the alkali-soluble polymer represented by the above formula (I) is used for forming the black matrix. Increasing the amount of black pigment to increase the light shielding property usually increases the light shielding property and decreases the sensitivity. However, when the alkali-soluble polymer represented by the above formula (I) is used, the sensitivity decreases. It can be suppressed.

  In general, carbon black widely used as a black pigment has a large surface area, and when used in a pigment-dispersed photosensitive resin composition, it tends to be a liquid with poor thirotropic properties and poor fluidity. In order to improve the light-shielding properties, it is necessary to add a lot of such black pigments, but it is difficult to ensure coating uniformity with the manufacturing method that applies directly to the substrate (Akitoshi Taniguchi, “Latest Color Filter Technology Trends—Component Materials “Manufacturing / Evaluation / Overseas Trends”, First Printing, Information Organization Co., Ltd., May 31, 2005, p81-101). On the other hand, in the present invention, a large amount of the alkali-soluble polymer represented by the above formula (I), which is excellent in patterning characteristics, is blended and transferred as a uniform film state in advance, so that the photosensitive resin layer can be easily formed on the substrate. Can be laminated. Then, by simply applying a photosensitive resin composition containing a large amount of the alkali-soluble polymer represented by the above formula (I) in advance to the support layer, it can be uniformly transferred to the substrate as in the comparative example of the present application. Can not. The peeling force of the surface of the support layer on the side opposite to the non-laminated surface is 100 to 4000 mN / 25 mm, and the oxygen blocking layer containing a specific water-soluble resin composition and the photosensitive property containing a specific photosensitive resin composition It is possible to produce a uniform photosensitive resin laminate only after laminating a resin layer, and further using it to form a black matrix with excellent sensitivity, light-shielding property, and fine line-formability on a substrate. it can.

In addition to the alkali-soluble polymer represented by the above formula (I), the photosensitive resin composition includes sensitivity, light-shielding property, fine wire formability, heat resistance, chemical resistance, cross-sectional shape, transferability, storage stability, etc. In consideration of the above, other alkali-soluble polymers can be appropriately blended. The blending amount is preferably 1 to 10% by mass of the entire photosensitive resin composition (100% by mass). More preferably, it is 1-5 mass%.
Other alkali-soluble polymers preferably have an acid equivalent of 200 to 2,000. An acid equivalent shows the mass of the linear polymer which has a 1 equivalent carboxyl group. The acid equivalent is preferably 2,000 or less from the viewpoint of developability, and the acid equivalent is preferably 200 or more from the viewpoint of suppressing the black pigment from adhering to the substrate after development. The acid equivalent is more preferably 400 to 900, and even more preferably 500 to 800. In addition, the measurement of an acid equivalent uses Hiranuma Sangyo Co., Ltd. Hiranuma automatic titration apparatus (COM-555), and is measured by a potentiometric titration method using 0.1 mol / L sodium hydroxide.

As other alkali-soluble polymers, for example, an acrylic alkali-soluble polymer such as carboxymethylcellulose, carboxyethylcellulose, carboxypropylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose are reacted with a polybasic acid anhydride. Cellulose resin and novolac resin can be used. In addition to the above performance, an acrylic alkali-soluble polymer is preferred from the viewpoint of compatibility with the alkali-soluble polymer represented by the formula (I) and the color pigment.
Examples of the acrylic alkali-soluble polymer include alkali-soluble polymers obtained by copolymerizing a monomer having a carboxyl group or a carboxylic anhydride group in the side chain with another monomer.

  Monomers having a carboxyl group or carboxylic anhydride group in the side chain include, for example, (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic acid Examples include half esters. From the viewpoint that it is easy to synthesize an alkali-soluble polymer, (meth) acrylic acid is preferred. The proportion of copolymerization of the monomer having a carboxyl group in the side chain is preferably 5% by mass or more from the viewpoint of developability, from the viewpoint of suppressing the black pigment dispersibility and the black pigment from adhering to the substrate after development. 30 mass% or less is preferable. More preferably, it is copolymerized in an amount of 5 to 20% by mass.

  Examples of other monomers include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and sec-butyl (meth) acrylate. , Tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, aromatic (meth) acrylate such as benzyl (meth) acrylate, phenyl (meth) acrylate, triphenylmethyl (meth) acrylate, hydroxyl group (Meth) acrylates having, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, (meth) acrylates having cycloalkyl groups, examples For example, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, adamantyl (meth) acrylate, and others such as (meth) acrylamide, (meth ) Acrylonitrile, glycidyl methacrylate, styrene. In particular, one or more selected from the group consisting of benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate is preferred.

  Other monomers may be appropriately selected from one or more in consideration of the effects of the present invention and developability and compatibility. Among these, benzyl (meth) acrylate and / or 2-hydroxyethyl (meth) acrylate are preferable. The copolymerization ratio of benzyl (meth) acrylate is preferably 50 to 95% by mass from the viewpoints of the alkali-soluble polymer represented by the above formula (I), the compatibility with the coloring pigment, the development residue, and the laminating property. More preferably, it is 70-90 mass%. The copolymerization ratio of 2-hydroxyethyl (meth) acrylate is preferably 5% by mass or more from the viewpoint of dispersibility and laminating properties of the black pigment, and preferably 30% by mass or less from the viewpoints of heat resistance and chemical resistance. 5-15 mass% is more preferable.

The weight average molecular weight of the acrylic alkali-soluble polymer is preferably 3,000 to 100,000. The molecular weight is preferably 100,000 or less from the viewpoint of developability, and preferably 3,000 or more from the viewpoint of adhesion. The weight average molecular weight is more preferably 10,000 to 40,000.
The molecular weight was measured by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M). , KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK) weight average molecular weight (polystyrene conversion) As required.

  An acrylic alkali-soluble polymer is a radical polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile in a solution obtained by diluting a mixture of the above various monomers with a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to synthesize by adding an appropriate amount of and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, and emulsion polymerization may be used in addition to solution polymerization.

The photosensitive resin composition contains (b) a photopolymerizable compound having an ethylenically unsaturated double bond. Content is 3-50 mass% with respect to 100 mass% of this photosensitive resin composition. From the viewpoint of developability, it is 3% by mass or more, and from the viewpoint of adhesion, it is 50% by mass or less. By setting the content to 50% by mass or less, an appropriate development time can be secured and sufficiently stable adhesion can be secured. The content is more preferably 5 to 20% by mass, and further preferably 5 to 15% by mass.
(B) The photopolymerizable compound having an ethylenically unsaturated double bond preferably contains a compound represented by the following formula (III). The blending amount is preferably 2% by mass or more of the photosensitive resin composition from the viewpoint of adhesion, and preferably 20% by mass or less from the viewpoint of transferability.

（上記式（ＩＩＩ）中、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ互いに独立なＨ又はＣＨ_３基を表す。Ｒ_６は２価の連結基で、炭素数２〜８のアルキレン基、炭素数３〜１０のシクロアルキレン基、及び炭素数６〜１０のフェニレン基からなる群から選ばれる一種の基を表す。）

(In the formula _{(III), R 3, R} 4 and _{R 5} are .R ₆ represent each independently an H or CH ₃ group a divalent linking group, an alkylene group having 2 to 8 carbon atoms, carbon This represents a kind of group selected from the group consisting of a cycloalkylene group having 3 to 10 carbon atoms and a phenylene group having 6 to 10 carbon atoms.)

  Examples of the compound represented by the formula (III) include succinic acid-modified pentaerythritol tri (meth) acrylate, phthalic acid-modified pentaerythritol tri (meth) acrylate, isophthalic acid-modified pentaerythritol tri (meth) acrylate, and terephthalic acid-modified pentaerythritol. Examples include tri (meth) acrylate. From the viewpoint of adhesion, succinic acid-modified pentaerythritol triacrylate is preferable.

  As a photopolymerizable compound having an ethylenically unsaturated double bond other than the compound represented by the above formula (III), for example, an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide were added to both ends of bisphenol A, respectively. Polyalkylene glycol dimethacrylate, polyethylene glycol dimethacrylate (NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) with an average of 5 moles of ethylene oxide added to both ends of bisphenol A, 1,6-hexanediol di- (Meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propanedi (meth) acrylate Rate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, and β-hydroxypropyl-β ′-(acryloyloxy) propyl phthalate, phenoxypolyethylene glycol (meth) ) Acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyalkylene Call (meth) acrylate, polypropylene glycol mono (meth) acrylate. From the viewpoint of adhesion, pentaerythritol tetra (meth) acrylate is preferable, and it is more preferable to use in combination with the compound of the above formula (III).

  Further, for example, a compound obtained by adding 1 to 3 mol of ethylene oxide to 2-hydroxyethyl (meth) acrylate and a half ester compound of hexahydrophthalic acid, and 1 to 3 mol of ethyleneoside was added to 2-hydroxyethyl (meth) acrylate. A half ester compound of a compound and succinic acid, a compound obtained by adding 1 to 3 moles of ethylene oxide to 2-hydroxyethyl (meth) acrylate and a half ester compound of isophthalic acid, and 1 to 2 of ethylene oxide in 2-hydroxyethyl (meth) acrylate A half ester compound of a compound added with 3 mol and terephthalic acid can be mentioned.

  Further, for example, a diisocyanate compound such as hexamethylene diisocyanate, tolylene diisocyanate, or 2,2,4-trimethylhexamethylene diisocyanate, and a compound having a hydroxyl group and a (meth) acryl group in one molecule, such as 2- Examples thereof include urethane compounds obtained by reacting hydroxypropyl acrylate and oligopropylene glycol monomethacrylate. Specifically, the compound part obtained by making hexamethylene diisocyanate and oligo propylene glycol monomethacrylate (Nippon Yushi Co., Ltd. product, Bremma-PP1000) react can be mentioned.

In the photosensitive resin composition, 0.1-20 mass% of (c) photoinitiators are contained with respect to 100 mass% of this photosensitive resin composition. It is 0.1% by mass or more from the viewpoint of sensitivity and adhesion, and 20% by mass or less from the viewpoint of line width reproducibility. The content is more preferably 1 to 10% by mass, and further preferably 1 to 5% by mass.
The photopolymerization initiator is preferably an oxime ester compound. Specifically, oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime Alternatively, compounds described in JP-T-2004-534797 can be raised. Among these, a compound represented by the following formula (IV) is preferable.

上記式（ＩＶ）で表される化合物の具体例は、１−［９−エチル−６−（２−メチルベンゾイル）−９．Ｈ．−カルバゾール−３−イル］−エタン−１−オンオキシム−Ｏ−アセテート（チバ・スペシャリティ・ケミカルズ製 ＩＲＧＡＣＵＲＥ ＯＸＥ−０２）である。

Specific examples of the compound represented by the formula (IV) include 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate (IRGACURE OXE-02 manufactured by Ciba Specialty Chemicals).

The photosensitive resin laminated body of this invention can contain photoinitiators other than said Formula (IV) in the photosensitive resin composition. For example, the following are mentioned. Thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2-chlorothioxanthone, 2,4,5-triarylimidazole dimers, such as 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer 2- (o-chlorophenyl) -4,5-bis- (m-methoxyphenyl) imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer. Also, p-aminophenyl ketones such as p-aminobenzophenone, p-butylaminophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p′-bis (ethylamino) benzophenone, p, p ′ -Bis (dimethylamino) benzophenone [Michler's ketone], p, p'-bis (diethylamino) benzophenone, p, p'-bis (dibutylamino) benzophenone. Moreover, quinones, for example, 2-ethylanthraquinone, 2-tert-butylanthraquinone, aromatic ketones, for example, benzoin ethers such as benzophenone, benzoin, benzoin methyl ether, and benzoin ethyl ether. Acridine compounds such as 9-phenylacridine. Triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2 , 4-Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-) 1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′- Methoxystyryl) -6-triazine. Others, benzyl dimethyl ketal, benzyl diethyl ketal, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl Examples include various known compounds such as 2-morpholino-1- (4- (methylthiophenyl) -propan-1-one.

  Further, the photosensitive resin composition can contain a sensitizer and a chain transfer agent. For example, N-arylglycine, mercaptotriazole derivative, mercaptotetrazole derivative, mercaptothiadiazole derivative, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol Bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, penta Erythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4- Known various compounds such as polyfunctional thiols such as methyl mercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine It is done.

(D) It is preferable to contain 40-70 mass% of color pigments with respect to 100 mass% of the photosensitive resin composition. It is 40% by mass or more from the viewpoint of light shielding properties, and is 70% by mass or less from the viewpoints of transferability, black matrix adhesion, line width stability, and shape. The content is preferably 45 to 65% by mass, and more preferably 50 to 65% by mass.
Examples of the color pigment include organic pigments such as azo, phthalocyanine, indigo, anthraquinone, perylene, quinacridone, methine / azomethine, and isoindolinone, carbon blacks, titanium black, and titanium oxynitride. There are inorganic pigments such as black low-order titanium oxide, graphite powder, iron black, and copper oxide, which may contain a plurality of pigments. These pigments may be subjected to a surface treatment for enhancing the dispersibility in the photosensitive resin composition or for increasing the electric resistance value.

Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C .. I.) Numbers can be mentioned. Listed below.
C. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 105, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 176, 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 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Pigment Red 264, C.I. I. Pigment Red 265.

  Furthermore, C.I. I. Pigment orange 13, C.I. I. Pigment orange 31, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 42, 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 64, C.I. I. Pigment orange 65, C.I. I. Pigment orange 71, C.I. I. Pigment Orange 73.

  Furthermore, C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 53, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, 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 128, C.I. I. Pigment yellow 137, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment Yellow 173.

  Furthermore, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38, C.I. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment black 1, C.I. I. Pigment Black 7.

  The photosensitive resin laminated body of this invention can also contain dye as needed in the photosensitive resin composition. Examples of the dye include fuchsin, phthalocyanine green, auramin base, chalcoxide green S, paramadienta, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green (Eizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.). ), Basic Blue 20, Diamond Green (Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.), and the like.

The photosensitive resin laminate of the present invention is useful as a black matrix forming material when the color pigment is a black pigment. Examples of the black pigment include those that are black among the colored substances listed above. That is, as an organic pigment, C.I. I. Pigment black 1, C.I. I. Examples of inorganic pigments such as CI Pigment Black 7 include carbon blacks, titanium black, titanium oxynitride, black low-order titanium oxide, graphite powder, iron black, and copper oxide. In addition, Cu, Fe, Mn, Cr, Co, Ni, V, Zn, S
e, Mg, Ca, Sr, Ba, Pd, Ag, Cd, In, Sn, Sb, Hg, Pb, Bi, Si, Al, and other various metal oxides, composite oxides, metal sulfides, lead metal sulfate, or Inorganic pigments such as metal carbonates can also be used. Carbon black is preferred from the viewpoints of light shielding properties and sensitivity to black matrix, resolution, and adhesion. Titanium black is preferred from the viewpoint of black matrix insulation.

As a preferable carbon black, at least one of the carbon blacks exemplified below can be used.
For example, as carbon black manufactured by Mitsubishi Chemical Corporation, carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40 , # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black N33 Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LP be able to.

Examples of carbon blacks manufactured by Cancarb include Thermox N990, N991, N907, and N908.
Asahi Carbon Corporation carbon blacks include Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55 Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15.

  The Degussa AG of carbon black, mention may be made of ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2V, ColorBlackFw1, ColorBlack Fw18, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printex140U, the Printex140V.

Carbon blacks manufactured by Cabot Corporation include Regal (registered trademark), Black Pearls (registered trademark), Elftex (registered trademark), Monarch (registered trademark), and Mogul (registered trademark). Mogul® and carbon black sold under the Vulcan® trademark name {eg Black Pearls® 2000, Black Pearls® 1400, Black Pearls® 1300, Black Pearls (registered trademark) 1100, Black Pearls (registered trademark) 1000, Black Pearls (registered trademark) 900, Black Pearls (registered trademark) 880, Black Pearls (registered trademark) 8 0, Black Pearls (registered trademark) 700, Black Pearls (registered trademark) L, Elftex (registered trademark) 8, Monarch (registered trademark) 1400, Monarch (registered trademark) 1300, Monarch (registered trademark) 1100, Monarch (registered) Trademark) 1000, Monarch (registered trademark) 900, Monarch (registered trademark) 880, Monarch (registered trademark) 800, Monarch (registered trademark) 700, Mogul (registered trademark) L, Legal (registered trademark) 330, Legal (registered trademark) ) 400, Vulcan (registered trademark) P}.
Examples of carbon black manufactured by Columbia Chemical Corporation include Raven 780, Raven 890, Raven 1020, Raven 1040, Raven 1255, Raven 1500, Raven 5000, and Raven 5250.

A dispersing agent can be contained in the photosensitive resin composition. As will be described later, the photosensitive resin laminate can be produced by coating the photosensitive resin composition on the support layer, but the black pigment is previously dispersed in a solvent with a dispersant and added to the photosensitive resin. It can also be set as a composition and it can apply to a support layer and can also be set as the photosensitive resin layer.
Examples of the dispersant include polyurethane, polycarboxylic acid ester such as polyurethane, unsaturated polyamide, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polysiloxane, hydroxyl group-containing polycarboxylic acid. Examples thereof include acid esters, modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) and polyester having a free carboxylic acid group, and salts thereof. Moreover, the polymeric dispersing agent which has a basic functional group as described in Unexamined-Japanese-Patent No. 2005-25169 can be utilized.
Specifically, Disperbyk 160, Disperbyk 161, Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166, SOLPERSE 2000SE, SOLSPERSE 24000, SOLSPERSE24000, SOLSPERSE24000, SOLSPERSE24000, SOLSPERSE24000, SOLSPERSE24000, SERSPERSE24000 As for content in the case of containing a dispersing agent, 0.1-15 mass% is preferable. From the viewpoint of dispersion stability of the pigment, 0.1% or more is preferable, and from the viewpoint of adhesion, 15% by mass or less is preferable. More preferably, it is 1-10 mass%.

In addition, anionic activators such as polycarboxylic acid type polymer activators and polysulfonic acid type polymer activators, and nonionic activators such as polyoxyethylene and polyoxylene block polymers are dispersed together with the aforementioned dispersants. It can be used as an auxiliary agent.
In addition, black pigments, particularly carbon black, can be coated with a resin or modified with a resin or a low-molecular compound in consideration of dispersibility, insulation, and the like. Examples of the resin used for the surface modification include polymers having a functional group capable of reacting with a carboxyl group on the surface of carbon black, such as polycarbodiimide and epoxy resin. Similarly, examples of the low molecular weight compound include substituted benzenediazonium compounds and substituted allyldiazonium compounds. Moreover, as a method of coating and modifying with a resin, JP-A No. 2004-219978, JP-A No. 2004-217785, JP-A No. 2004-360723, JP-A No. 2003-201381, JP-A No. 2004-292672 are disclosed. JP-A-2004-29745, JP-A-2005-93965, JP-A-2004-4762, US Pat. No. 5,554,739, US Pat. No. 5,922,118 Etc. can be used.

The photosensitive resin composition may contain a coloring dye that develops color when irradiated with light. Examples of the coloring dye used include a combination of a leuco dye or a fluorane dye and a halogen compound. The coloring dye can be blended in an appropriate amount depending on the desired optical density and color purity of the color pixel.
Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane (also known as leuco crystal violet).
Examples of the fluorane dye include 2-N, N-dibenzylamino-6-diethylaminofluorane and 3-dibutylamino-6-methyl-7-anilinofluorane.

Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, 2,4,6-tris (Trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.

  In the photosensitive resin composition, in order to improve thermal stability and storage stability, a radical polymerization inhibitor can be contained. Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2 '-Methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), triethylene glycol-bis- [3- (3-tertiary Ributyl-5-methyl-4-hydroxyphenyl) propionate] (IRGANOX245 manufactured by Ciba Specialty Chemicals), diphenylnitrosamine and the like. IRGANOX 245 is preferable because both the decrease in sensitivity is low and the storage stability is good.

  In the photosensitive resin composition, a plasticizer can also be contained as needed. Examples of such plasticizers include phthalates such as diethyl phthalate, p-toluenesulfonamide, polypropylene glycol, polyethylene glycol monoalkyl ether, polyalkylene oxide-modified bisphenol A derivatives, such as ethylene oxide adducts of bisphenol A. And propylene oxide adducts. A preferable amount in the case of containing a plasticizer is 0.1 to 5% by mass with respect to the photosensitive resin composition. The amount is preferably 0.1% by mass or more from the viewpoint of suppressing the flexibility of the photosensitive resin layer and chip jumping and cracking at the time of cutting after lamination, and 5% by mass or less is preferable from the viewpoint of adhesion.

  A silane coupling agent can be contained in the photosensitive resin composition. Silane coupling agents include vinyl groups, epoxy groups, styryl groups, methacryloxy groups, acryloxy groups, amino groups, ureido groups, chloropropyl groups, mercapto groups, sulfide groups, isocyanate groups, imidazolyl groups, and alkoxy groups. Examples thereof include compounds having a silyl group in the molecule. Specifically, Shin-Etsu Silicone Co., Ltd., KBM-1003, KBE-1003, KBM-403, KBE-403, KBM-502, KBE-502, KBM-503, KBE-503, KBM-603, KBE- Examples thereof include 603, KBM-903, KBE-903, KBE-585, KBM-802, KBE-846, KBE-9007, and the like, and imidazole silane compounds described in JP-A-2004-280057. The blending amount can be appropriately selected in consideration of the effect of adhesion and the adhesion of the residue to the substrate after development, and is in the range of 0.01 to 1% by mass with respect to the photosensitive resin composition. preferable. In addition, after diluting these silane coupling agents with an organic solvent such as water or alcohol, they are uniformly coated on a glass substrate using a coating method such as a spin coating method, and heat treatment or the like is performed as necessary. It is also possible to improve the adhesion between the substrate and the photosensitive resin layer.

  In the present invention, a leveling agent may be added as necessary when forming the photosensitive resin layer. By adding a leveling agent, a smoother coated surface can be obtained when the photosensitive resin composition is applied to a substrate. Examples of the leveling agent include a silicon leveling agent, an acrylic leveling agent, and a fluorine leveling agent. Particularly, a fluorine leveling agent is particularly preferable since an effective effect appears when a small amount is added. Specific examples of the fluorine-based leveling agent include F-474, F-479 (above, Dainippon Ink Industries, Ltd.), FC-4430, FC-4432 (above, made by Sumitomo 3M), KP323, KP341 (above, Shin-Etsu). Chemical Industries), PAINTAD32, PAINTAD54, DK8-8011 (above, manufactured by Toray Dow Corning), Surflon S-111N, Surflon S-113, Surflon S-121, Surflon S-131, Surflon S-132, Surflon S -141, Surflon S-381, Surflon S-383 (above, manufactured by AGC Sey Chemical Co., Ltd.).

  The amount of the surfactant that can be added in the present invention is preferably 0 to 15%, more preferably 0 to 10% by weight, particularly preferably 0 to 5% by weight based on 100% by weight of the photosensitive resin composition. %. By making the addition amount of the surfactant 15% by weight or less, the adhesion of the photosensitive resin composition to the substrate can be kept high.

  An epoxy resin can be added to the photosensitive resin layer of the present invention. Conventionally, epoxy resins have been cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc. This resin has been used in a wide range of fields such as plates, molding materials and casting materials. By adding an epoxy resin to the photosensitive resin layer, the above-described characteristics can be imparted to the photosensitive resin.

  Examples of the epoxy resin that can be used in the present invention include an epoxy resin obtained by reacting a polyhydric alcohol, a polyhydric phenol, or the like with an excess of epichlorohydrin or alkylene oxide. Examples of polyhydric alcohols include ethylene glycol, polyethylene glycol, propylene glycol, neopentyl glycol, butylene glycol, hexanediol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, diglycerol, sorbitol, etc. Examples of phenol include 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), halogenated bisphenol A, 4,4-dihydroxyphenylmethane (also known as bisphenol F), and tris (4-hydroxyphenyl). ) Propane, resorcin, tetrahydroxyphenyl ethane, novolac polyhydric phenol, cresol polyhydric phenol, and the like.

  Specific examples of these epoxy resins include DER431, DER438, DER439, and the like (manufactured by Dow Chemical Co., Ltd.) jER-1001, jER-1004, jER-1007H, jER-404P, jER-1256, jER-154, jER- (Above, manufactured by Japan Epoxy Resin Co., Ltd.), AER-6003, AER-6071, AER-6072, AER-6097, AER-ECN1273, etc. (above, manufactured by Asahi Kasei Chemicals), EPICLON-N-740-80M, EPICLON -FQ-065-P (Dainippon Ink & Chemicals, Inc.).

  In the present invention, the amount of the epoxy resin that can be added is preferably 0.1 to 20% by weight with respect to 100% by weight of the photosensitive resin composition. More preferably, it is 0.1-10 weight%, Most preferably, it is 0.1-5 weight%. By setting the addition amount to 20% by weight or less, there is no decrease in developability of the photosensitive resin composition with respect to an alkaline developer, and a pattern free from development residues and burrs can be obtained. Moreover, sufficient hardening characteristic can be provided to hardened | cured material by adding 0.1 weight% or more.

  In the case of using an epoxy resin in the present invention, a curing agent may be further added. Examples of the curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and the like. Specific examples include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride. Acid, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexene tetracarboxylic anhydride, phenol novolac, polyhydric phenols and their modified products, imidazole, BF3-amine complex, etc. However, it is not limited to these. These may be used alone or in combination of two or more.

  In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. A cured product having good cured properties can be obtained by adding the amount of the curing agent in the range of 0.5 equivalent to 1.5 equivalent with respect to 1 equivalent of the epoxy group.

  Moreover, when using the said hardening | curing agent, you may use a hardening accelerator together as needed. Specific examples of the curing accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 1-benzyl-2-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5 , 4, 0) tertiary amines such as undecene-7, phosphines such as triphenylphosphine, metal compounds such as tin octylate, and the like. The curing accelerator is preferably 0.1 to 5.0% by weight with respect to 100% by weight of the epoxy resin.

  The photosensitive resin layer can be obtained by appropriately diluting the photosensitive resin composition with a solvent, and applying and drying on the oxygen blocking layer. Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol. Monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether Ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2 -Ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxyb Acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate , 4-methyl-4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, benzene, toluene, xylene, cyclohexanone, methanol, ethanol , Propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin. Methyl ethyl ketone and methyl isobutyl ketone are preferred from the viewpoints of toxicity and drying properties when applied to the support layer. The dispersion stability of colored pigments, particularly black pigments, and the alkali solubility high represented by the above formula (I) used in the present invention are preferred. From the viewpoint of molecular solubility, propylene glycol monomethyl ether acetate (PGMEA) is preferred. In order to achieve the above-mentioned performance, methyl ethyl ketone, methyl isobutyl ketone, etc. and PGMEA may be mixed and used at an appropriate ratio. For example, PGMEA in which a black pigment is dispersed in advance, PGMEA in which the alkali-soluble polymer of the above formula (I) is previously dissolved, an alkali-soluble polymer, a photopolymerizable compound having an ethylenically unsaturated double bond, and photopolymerization initiation An agent and various other additives can be mixed and appropriately diluted with a solvent such as methyl ethyl ketone or PGMEA, and can be prepared as a photosensitive resin composition solution having good coatability and dryability to the oxygen barrier layer.

  As for the photosensitive resin laminated body of this invention, a protective layer can also be laminated | stacked on the surface on the opposite side to the side by which the support layer of the photosensitive resin layer is laminated | stacked as needed. It is preferable that the adhesive force between the protective layer and the photosensitive resin layer is sufficiently small compared to the adhesive force of each layer and can be easily peeled off. Examples of such a protective layer include a polyethylene film, a polyethylene terephthalate film, a polypropylene film, a stretched polypropylene film (for example, E-200C, E-200A, etc. manufactured by Oji Paper Co., Ltd.), and a release-treated polyethylene terephthalate film. Etc. The preferred thickness of the protective layer is 15 to 50 μm. 15 μm or more is preferable from the viewpoint of smooth surface production, and 50 μm or less is preferable from the viewpoint of stackability with the photosensitive resin layer and winding property.

The photosensitive resin laminate of the present invention can be produced by the following method.
First, a water-soluble resin composition diluted with a solvent is applied and dried on the surface of the release layer that is opposite to the surface on which the support layer is not stacked, and an oxygen blocking layer is stacked on the support layer. When providing another layer between the support layer and the oxygen barrier layer, first, the resin composition constituting the other layer is applied and dried on the surface opposite to the surface on which the support layer is not laminated, A water-soluble resin composition diluted with a solvent is applied to the layer and dried, and an oxygen barrier layer is laminated on the support layer.
The water-soluble resin composition can be prepared by, for example, dispersing polyvinyl alcohol in water, dissolving by heating and allowing to cool, adding a water-soluble plasticizer, dissolving by stirring, and adding methanol as appropriate. The water-soluble resin composition is preferably filtered with a filter of 10 μm or less before coating.

As a coating device, a blade coater, a bar coater, and a gravure coater can be mentioned as those useful for a small area. Examples of the sealed die method include a capillary coater, a lasing and rising coater, a slot die coater, and a lip coater, and examples of an open type include a comma coater and a gravure coater. The drying temperature can be appropriately selected according to the solvent. It is preferably at or above the temperature at which the solvent is sufficiently dried, and is preferably dried at or below the temperature at which the dimensional stability of the support layer can be ensured. 60-120 degreeC is preferable. The drying time is preferably longer than the solvent can be sufficiently dried, and is preferably dried at such a rate that the solvent can be uniformly evaporated from the coated surface. It is preferable that the dimensional stability of the support layer is not more than the extent that the dimensional stability cannot be ensured and the workability is not significantly impaired. If the drying means is a small area, a casting method or a hot air circulation type drying furnace can be used. In order to dry through a drying chamber of several meters or more, it can be dried by spraying hot air on the coating surface or the support layer, or by passing the upper support layer of a heated roll. The hot air nozzle includes a jet type, a positive pressure air floating type, a negative pressure air floating type, a negative pressure nozzle + roll type, a punching hole type, and a parallel flow type.
The support layer on which the oxygen blocking layer is laminated may be wound after coating and appropriately wound with a protective film, or may be coated with the photosensitive resin layer as it is after drying.

  Next, as the photosensitive resin composition, for example, an alkali-soluble polymer represented by the above formula (I), a photopolymerizable compound having an ethylenically unsaturated double bond, a photopolymerization initiator, a color pigment, Is mixed with an appropriate amount of solvent so as to be 1 to several tens cps to prepare a photosensitive resin composition solution. A photosensitive resin composition solution is applied on the oxygen barrier layer laminated on the release layer, and dried to form a photosensitive resin layer. Application is performed using an apparatus according to the application area, application speed, and the like. As a coating device, the thing similar to what was used for the coating of the said water-soluble resin composition can be mentioned. From the light shielding property of the black matrix and the film thickness accuracy at the time of application, the thickness of the photosensitive resin layer after drying is preferably 0.3 μm or more. Moreover, it is preferable that it is 4.5 micrometers or less from flatness when it uses for a color filter.

  When creating a color filter using a resin black matrix, if the height of the black matrix is high, irregularities on the surface of the color filter will disturb the orientation of the liquid crystal, so a flattening film called an overcoat layer may be provided, It may be polished to make it flat. Since the influence on the orientation of the liquid crystal can be reduced, the overcoat layer can be made thin, and the thickness of the entire color filter can be made thin, the height of the black matrix is preferably 4.5 μm or less. From the viewpoint of light shielding properties, 0.3 μm or more is preferable. More preferably, it is 0.3-2 micrometers, More preferably, it is 0.3-0.9 micrometers.

  The black matrix described in the present invention can be formed by the following method using the above photosensitive resin laminate. First, after removing the protective layer, the photosensitive resin laminate is laminated (thermocompression bonding) to the glass substrate. For example, lamination is performed at a lamination temperature of 120 ° C., a cylinder pressure of 0.4 MPa, and 2 m / min (VA-400III manufactured by Taisei Laminator). At this time, the glass substrate is preferably preheated. The preheating temperature of the glass substrate is preferably 100 ° C. or higher from the viewpoint of laminating properties and air entrained during lamination to ensure sufficient adhesion, and preferably 150 ° C. or lower from the viewpoint of heat resistance of the support layer. More preferably, it is 110 degreeC or more and 140 degrees C or less.

Next, the support layer is peeled off and image exposure is performed with active light through a mask film. You may peel a support film after exposure as needed.
Subsequently, the photosensitive resin layer in the unexposed area is developed and removed using an alkaline aqueous solution. As the alkaline aqueous solution, a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, a potassium hydroxide aqueous solution, a mixed aqueous solution of sodium hydrogen carbonate and sodium carbonate, an organic amine aqueous solution such as tetramethylammonium hydroxide, or the like is used. These alkaline aqueous solutions are selected according to the characteristics of the photosensitive resin layer. Generally, a 0.1 to 3% by mass aqueous sodium carbonate solution and a 0.03 to 0.1% by mass potassium hydroxide aqueous solution are used. In order to remove the photopolymerizable resin layer remaining undeveloped as required, further development may be performed in another developer.
Another developer may be an alkaline aqueous solution having a different alkalinity from the developer used for developing the photosensitive resin layer first, an acidic developer, or a developer containing an organic solvent. The composition of the photosensitive resin layer can be appropriately selected according to the developer. Further, the photosensitive resin layer in the unexposed area remaining undeveloped, the color pigment, and the black pigment can be physically removed by a method such as high-pressure water washing. A water washing pressure of 0.2 MPa or more is effective.

After forming the black matrix, the color filter of the present invention comprises the photosensitive resin laminate of the present invention and the heat-sensitive or photosensitive color on at least a part of the glass substrate with the black matrix not covered with the black matrix. It can be produced by forming red, blue and green color pixels with ink.
The shape of the black matrix is generally a lattice shape surrounding the color pixels. Further, the pattern width of each side of the lattice is generally 5 to 50 μm, and the lattice point interval is generally 30 to 500 μm.

  Red, blue, and green color pixels can be produced by photolithography using a color resist such as the photosensitive resin laminate of the present invention or a liquid resist, or by an inkjet method or a printing method using a color ink. Various methods can be used. The ink jet method is a method of injecting color ink by an ink jet method using a black matrix formed on a glass substrate as a weir. The inkjet method does not require an exposure process that requires an expensive mask, does not require a development process, can form a pixel pattern regardless of unevenness, and improves yield, and is simple and low-cost. It is preferable because a pixel pattern can be formed. Since it can be cured without depending on photolithography, it may be heat sensitive, or it may be cured by exposure to the entire surface and may be photosensitive. Known heat-sensitive or photosensitive color inks can also be used. Further, in the present invention, the composition includes a pigment and a dye exemplified as a coloring substance, a photopolymerizable compound having an ethylenically unsaturated double bond, a heat or a photopolymerizable initiator, and the viscosity is appropriately adjusted with a solvent. Can be used. For example, the colored ink described in Example 1 of JP-A-2004-213033 can be used. The black matrix is preferably color repellent ink. Due to this property, due to the problem of ink landing accuracy, the color ink on the black matrix can also slide down the weir to fill the space for the color pixels.

In the method for producing a black matrix of the present invention, a photosensitive resin laminate is used. The manufacturing method is a method of applying a photosensitive resin composition directly to a glass substrate, drying it, and then exposing and developing it through a photomask, and does not use a drying process. This is a preferable method from the standpoint that unevenness does not occur and the transparent support layer prevents contact between the photopolymerizable resin composition and the photomask, so that the photomask is not easily soiled.
Furthermore, by exposing through the oxygen blocking layer, the photosensitive resin layer is prevented from coming into direct contact with oxygen, so that a very high sensitivity can be obtained. This shows that it is useful in terms of sensitivity as compared with a method in which a photosensitive resin composition is directly applied and dried on a glass substrate as disclosed in Patent Document 1 and the like. Since the sensitivity is high, the amount of initiator can be kept low, and the storage stability is improved.

The present invention will be described based on examples.
<Preparation of support layer>
For the support layer, the film shown in Table 1 (however, other than A-3 has a release treatment) was used.
<Preparation of resin composition solution for oxygen barrier layer>
Resin composition solutions for the oxygen barrier layer were prepared so that the solid contents were in the proportions shown in Table 2, respectively. The solvent was adjusted so that water / methanol was 8/2 by mass and the total solid content was 20% by mass. At this time, resin B-1 was mixed in advance with an appropriate amount of water, dissolved by heating, and other components were added. In Table 2, the components represented by abbreviations (B-1) to (C-3) are as follows.
B-1: Polyvinyl alcohol, PVA-205 manufactured by Kuraray Co., Ltd., polymerization degree 500, saponification value 87-89
B-2: Polyvinyl alcohol, Kuraray PVA-220, polymerization degree 2000, saponification value 87-89
C-1: polyvinylpyrrolidone having a weight average molecular weight of 100,000 (K-30, manufactured by Nippon Shokubai Co., Ltd.)
C-2: Polyvinylpyrrolidone having a weight average molecular weight of 40,000 (K-15 manufactured by Nippon Shokubai Co., Ltd.)
C-3: Polyethylene glycol monomethyl ether having a number average molecular weight of 550 (Niox M-550, manufactured by NOF Corporation)

<Preparation of oxygen barrier layer>
The resin composition solution for the oxygen barrier layer was uniformly coated on the support layer using a bar coater so that the film thickness after drying was 4 μm. When the release treatment was applied to the support layer, it was applied on the release treatment surface.
<Synthesis of Compound of Formula (I)>
First, Compound 1 represented by the above formula (I) was synthesized according to the method described in JP-A No. 2001-354735.
That is, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol and 72.0 g of acrylic acid were added. Prepared. This was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. Here, although the solution gradually became transparent and viscous, stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target. And it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by the following formula (V) which is a colorless and transparent solid.

  Next, 600 g of propylene glycol monomethyl ether acetate (PGMEA) was added to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained and dissolved. Thereafter, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed, gradually heated to react at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain Compound 1 corresponding to the above formula (I). It was. The disappearance of the acid anhydride group was confirmed by IR spectrum.

Here, the compound 1 is a compound represented by the above formula (I), wherein X is a group represented by the above formula (II), and Y is an acid anhydride group from 1,2,3,6-tetrahydrophthalic anhydride. Residue excluding (—CO—O—CO—), Z is a residue obtained by removing acid anhydride from 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and Y / Z The molar ratio corresponds to a compound of 50.0 / 50.0.
This compound 1 was made into an alkali-soluble polymer, adjusted so that the solid content concentration in PGMEA would be 40% by mass, and used to prepare the following photosensitive resin composition solution.

<Preparation of photosensitive resin composition solution>
Each component of the photosensitive resin composition is mixed in the proportions shown in Table 3 (the numerical values shown in the table are parts by mass in terms of solid content), and the photosensitive resin composition solution having a solid content of 10% by mass using methyl ethyl ketone as a solvent. Got. In Table 3, components constituting the photosensitive resin compositions represented by abbreviations (D-1) to (H-1) are as follows.
D-1: PGMEA solution of compound 1 synthesized above (solid content concentration 40% by mass)
D-2: Methyl ethyl ketone solution of benzyl methacrylate / methacrylic acid copolymer (mass ratio 85/15, weight average molecular weight 30,000, solid content concentration 40 mass%)
E-1: Pentaerythritol tetraacrylate E-2: Succinic acid-modified pentaerythritol triacrylate (Aronix TO-756 manufactured by Toa Gosei Co., Ltd.)
F-1: 1- [9-Ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate (IRGACURE OXE-02 manufactured by Ciba Specialty Chemicals)
G-1: PGMEA solution of carbon black dispersion in which carbon black and dispersant are dispersed at a ratio of 18: 3 (solid content concentration: 22% by mass)
H-1: Hindered phenol type inhibitor (IRGANOX 245 manufactured by Ciba Specialty Chemicals)

(Examples 1-7)
<Preparation of photosensitive resin laminate>
As shown in Table 4, the photosensitive resin composition solution was applied onto the oxygen barrier layer formed on the support layer prepared above so that the optical density value after drying was 4.2. Was applied uniformly. Next, a 20 μm-thick stretched polypropylene protective layer (Alphan E-200A manufactured by Oji Paper Co., Ltd.) was laminated to the photosensitive resin layer to obtain a photosensitive resin laminate. The results are shown in Table 4.

<Formation of black matrix>
The protective layer of the photosensitive resin laminate was peeled off and laminated on a glass substrate. As a laminator, VA-400III manufactured by Taisei Laminator Co., Ltd. was used. The glass substrate was preheated at 120 ° C., the laminating roll was heated to 120 ° C., the laminating speed was 2 m / min, and the cylinder pressure was 0.4 MPa. It took about 5 seconds to laminate the photosensitive resin laminate on a 10 cm square substrate. Thereafter, the support layer is peeled off and passed through a glass mask having a matrix pattern with a line width: space width of 1: 9, and an ultrahigh pressure mercury lamp (EXM-1066-H, an automatic exposure apparatus for high-precision substrates manufactured by Oak Manufacturing Co., Ltd. was exposed at 40mJ / cm ² by -01). At this time, the distance between the surface of the laminated base material after peeling the support layer and the glass mask was set to 100 μm. After peeling off the support layer, a 0.2% by mass aqueous sodium carbonate solution was sprayed at 26 ° C. to dissolve and remove the unexposed photopolymerizable resin layer and developed. The spraying time at this time was 2.5 times the time (minimum development time) when the unexposed portion of the photopolymerizable resin layer was just removed from the glass substrate. After development, the substrate was spray-washed with a water washing pressure of 0.3 MPa and air-dried. Then, it was post-baked at 240 ° C. for 5 minutes with a conveyor type far-infrared drying furnace (manufactured by Furness Co., Ltd., furnace infrastein heater 0.9 kW × 4 pieces × 3 sets, furnace length 1500 mm) to form a black matrix.

<Evaluation>
1) Applicability of oxygen barrier layer When the oxygen barrier layer was applied on the support layer, the applicability was evaluated as follows.
○ (good): The oxygen barrier layer is uniformly applied.
X (impossible): repelling occurs and it is not uniformly applied.
2) Coating property of photosensitive resin layer When coating the photosensitive resin layer on the support layer, coating property was evaluated as follows.
○ (good): The photosensitive resin layer is uniformly applied.
X (impossible): repelling occurs and it is not uniformly applied.

3) Transferability from support layer to substrate When the support layer was peeled off after the laminate, whether or not the oxygen blocking layer and the photosensitive resin layer were both transferred to the glass substrate was evaluated as follows.
○ (good): The oxygen blocking layer and the photosensitive resin layer are integrally peeled off from the support layer and transferred to the glass substrate.
X (impossible): The photosensitive resin layer is transferred to the glass substrate, but part or all of the oxygen blocking layer does not peel from the support layer and is separated from the photosensitive resin layer, and is not transferred to the glass substrate. Alternatively, a part or all of the photosensitive resin layer and the oxygen blocking layer are not peeled off from the support layer and are not transferred to the glass substrate. Or when there is no oxygen interruption | blocking layer, one part or all part of the photosensitive resin layer does not peel from a support layer, but does not transfer to a glass substrate.

4) Minimum development time After laminating, the support layer was peeled off and developed without exposure. The time from the development of the photosensitive resin layer to the beginning of the appearance of the glass substrate was defined as the minimum development time and evaluated as follows.
○ (good): minimum development time 30 seconds or less △ (possible): minimum development time exceeds 30 seconds, 60 seconds or less × (impossible): minimum development time exceeds 60 seconds

5) Sensitivity Based on the formation of the black matrix, exposure is performed at 50 mJ / cm ² through a matrix pattern mask of line width: space width = 1: 9, and development is performed for 2.5 times the minimum development time to form a matrix pattern. did. The line width of the black matrix corresponding to the pattern having a mask width of 10 μm was measured with an optical microscope and evaluated as follows based on the line width.
○ (good): line width 10 μm or more Δ (possible): line width 8 μm or more and less than 10 μm × (impossible): line width less than 8 μm

6) Light-shielding property First, a pattern was prepared based on the formation of the black matrix. The height of the pattern formed on the glass substrate was measured using an alpha step (AS200) manufactured by Tencor Instruments, and this was defined as the film thickness (μm). At the same time, a solid pattern was created by the same method, and the optical density was measured using an optical densitometer D200-II manufactured by Gretag Macbeth. The optical density is expressed by a relationship of optical density = log10 (I0 / I), where the incident light intensity is I0 and the transmitted light intensity is I with respect to light from a certain light source. A value obtained by dividing the optical density by the film thickness was obtained, and this was defined as a light shielding property. The light shielding property was evaluated according to the following rank.
○ (good): 4.5 or more △ (possible): 3.0 or more and less than 4.5 × (impossible): less than 3.0

7) Fine line formability Based on the formation of the black matrix, the matrix pattern was exposed at 50 mJ / cm ² through a matrix pattern mask of line width: space width = 1: 9 and developed for 2.5 times the minimum development time. Formed. Whether the matrix pattern was formed was visually observed with an optical microscope, and the line width of the smallest matrix pattern that could be formed was measured. Based on the measurement results, the fine line formability was evaluated as follows.
○ (good): less than 8 μm Δ (possible): 8 μm or more and less than 12 μm × (impossible): 12 μm or more (Examples 8 to 12)
<Preparation of photosensitive resin laminate>
The film prepared in Example 1 was used and evaluated as shown in 8) and 9) below, and this was designated as Example 8. Furthermore, a film was prepared and evaluated in the same manner as in Example 8 except that the film thickness of the oxygen barrier layer was changed as shown in Table 5. Further, a film was prepared in the same manner as in Example 6 except that the film thickness of the oxygen blocking layer was changed as shown in Table 5, and the evaluation was performed as shown in 8) and 9) below. It was set to 11. Furthermore, a film was prepared in the same manner as in Example 7 except that the film thickness of the oxygen barrier layer was changed as shown in Table 5, and evaluated as shown in 8) and 9) below. It was set to 12.
8) Pinhole Observation In the examples shown in Table 5, the film was observed as follows and the number of pinholes was calculated. First, a dark room was created by completely shielding the surroundings. In the dark room, a projector capable of projecting with six 40 W UV-cut fluorescent lamps (National FLR40S-YF / M colored pure yellow) was installed from the lower surface through a transparent glass plate. The film of the Example shown in Table 5 was installed without a gap on the glass plate of the projector, and the film was visually observed. The number of pinholes was counted in a range of 40 cm × 50 cm and ranked as follows.
◎ (excellent): less than 300 pieces ○ (good): 300 pieces or more and less than 500 pieces △ (possible): 500 pieces or more 9) Cut chip evaluation In the examples shown in Table 5, cut chip properties were evaluated as follows. did. The protective layer was peeled off from the photosensitive resin laminate, and a film was placed on the cutting mat so that the photosensitive resin layer was on the upper surface. The angle was fixed so that the cutter blade was 45 ° with respect to the cutting mat, and the film was cut at a time by a length of 5 cm. The cut portion was observed with a microscope. The states where the oxygen blocking layer and the photosensitive resin layer were peeled off from the support at the cut portions were ranked as follows.
◎ (excellent): hardly peeled ○ (good): peeling occurred from the cut portion with a substantially uniform width along the cutting direction.
Δ (possible): Large peeling or cracking occurs from the cut portion in a direction perpendicular to the cutting direction.

(Comparative Examples 1-8)
<Preparation of photosensitive resin laminate>
The photosensitive resin laminated body of Comparative Examples 1-8 was produced by the method similar to an Example with the structure shown in Table 4. Using these photosensitive resin laminates of Comparative Examples 1 to 8, a black matrix was formed on a glass substrate in the same manner as in the Examples. Regarding the evaluation, the same items as in the examples were evaluated, and the results are shown in Table 4. Hereinafter, the meaning of each comparative example will be described.

Comparative Example 1 is an example in which a support layer having a peeling force of less than 100 mN / 25 mm is used. When the oxygen barrier layer was applied, cissing occurred on the coated surface, and coating could not be performed uniformly. Since uniform coating could not be performed, other evaluations could not be performed.
Comparative Example 2 is an example using a support layer in which the peeling force of the support layer exceeds 4000 mN / 25 mm. Production of the photosensitive resin laminate was possible, but when the support layer was peeled after lamination, the photosensitive resin layer was only transferred to the glass substrate, and the oxygen blocking layer was not peeled from the support layer. Therefore, no sensitivity was obtained and a pattern could not be formed.

Comparative Example 3 is an example in which the weight average molecular weight of the plasticizer in the oxygen barrier layer is less than 5000. An image could not be formed because a pattern flowed during development.
Comparative Example 4 is an example in which no plasticizer is contained in the oxygen barrier layer. When the support layer was peeled after lamination, a part of the oxygen barrier layer was transferred to the glass substrate together with the photosensitive resin layer, but a part of the oxygen barrier layer was not peeled off from the support layer and separated from the photosensitive resin layer. In the portion where the oxygen blocking layer was not transferred together with the photosensitive resin layer, the sensitivity could not be obtained and the pattern could not be formed.

Comparative Example 5 is an example of a photosensitive resin laminate that does not include an oxygen blocking layer. An attempt was made to apply the photosensitive resin composition to the release-treated surface of the support layer, but the repellency occurred and could not be applied uniformly.
Comparative Example 6 is an example of a photosensitive resin laminate that has no mold release treatment and does not include an oxygen blocking layer. When the support layer is peeled off after lamination, a part of the photosensitive resin adheres to the support layer side, while the photosensitive resin layer transferred to the glass substrate generates a peeling line when the support layer is peeled off. Could not be transcribed. Furthermore, when the support layer is peeled off after exposure and before development, the support layer, the photosensitive resin layer, and the glass substrate are bonded and integrated at the exposed portion, and when the support layer is peeled off, the support layer is supported from the exposed portion. The layer was torn and could not be peeled off.

Comparative Example 7 is an example in which the blending amount of the alkali-soluble polymer represented by formula (I) in the photosensitive resin composition is less than 3% by mass. Sensitivity and fine line formation were not sufficient.
Comparative Example 8 is an example in which the blending amount of the alkali-soluble polymer represented by the formula (I) in the photosensitive resin composition exceeds 40% by mass. Development time was significantly delayed.

Claims (10)

A photosensitive resin laminate obtained by sequentially laminating at least a support layer, an oxygen blocking layer, and a photosensitive resin layer, wherein the support layer has a peel force of 100 on the surface opposite to the non-laminated surface. ˜4000 mN / 25 mm, and the oxygen barrier layer contains a water-soluble resin composition, and the water-soluble resin composition has a water-soluble polymer having at least vinyl alcohol as a copolymer unit, and a weight average molecular weight of 5,000 or more. 2,000,000 or less water-soluble plasticizer, and the photosensitive resin layer contains a photosensitive resin composition, and the photosensitive resin composition is based on 100% by mass of the photosensitive resin composition. (A) 3-40% by mass of an alkali-soluble polymer represented by the following formula (I), (b) 3-50% by mass of a photopolymerizable compound having an ethylenically unsaturated double bond other than the following formula (I) %, And (c) a photopolymerization initiator 0.1 The photosensitive resin laminate which comprises 0 wt%.

(In the above formula (I), X is a group represented by the following formula (II), Y is a residue excluding the acid anhydride group of dicarboxylic anhydride, Z is an acid anhydride of tetracarboxylic dianhydride. The residue excluding the group, n is an integer of 1 to 20. R1 and R2 in the following formula (II) each independently represent H or CH3.)

  The photosensitive resin laminate according to claim 1, wherein the water-soluble plasticizer in the water-soluble resin composition is polyvinylpyrrolidone.   3. The photosensitive resin laminate according to claim 1, wherein the support layer has a peeling force of 100 to 1500 mN / 25 mm on the surface opposite to the surface on which the support layer is not laminated.   The photosensitive resin laminate according to claim 1, wherein the oxygen blocking layer has a thickness of 2 to 3 μm. The photosensitive resin laminated body as described in any one of Claims 1-4 in which the said photosensitive resin composition contains the photopolymerizable compound which has an ethylenically unsaturated double bond represented by following formula (III). .

(In the above formula (III), R 3, R 4 and R 5 each independently represent H or CH 3 group. R 6 is a divalent linking group having 2 to 8 carbon atoms, 3 to 10 carbon atoms. This represents a kind of group selected from the group consisting of a cycloalkylene group and a phenylene group having 6 to 10 carbon atoms.)   The photosensitive resin laminate according to any one of claims 1 to 5, wherein the photosensitive resin composition contains (d) 40 to 70 mass% of a coloring pigment with respect to 100 mass% of the photosensitive resin composition. body.   Manufacturing of the board | substrate with a black matrix which performs the process of laminating the photosensitive resin laminated body as described in any one of Claims 1-6 on a board | substrate, the process of peeling a support layer, the process of exposing, and the process of developing in order. Method.   Manufacturing of the board | substrate with a black matrix which performs the process of laminating the photosensitive resin laminated body as described in any one of Claims 1-6 to a board | substrate, the process of exposing, the process of peeling a support layer, and the process of developing in order. Method.   A step of forming a black matrix on a substrate by the method according to claim 7 or 8, and the substrate is a glass substrate, and at least a part of the portion not covered with the black matrix on the glass substrate is thermally sensitive or photosensitive. A color filter manufacturing method comprising: a printing step of printing a color ink having a color characteristic by an inkjet method.   A color filter produced by the method according to claim 9.