JP2009222792A - Photosensitive resin composition, and method for forming light-shielding image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition with which a black matrix having excellent pattern precision and hardness is obtained by using nanoimprint lithography. <P>SOLUTION: The photosensitive resin composition is characterized in that it includes a coloring agent of at least 10 mass% or more and a polymerizable monomer, and has viscosity of 3 to 50 mPa.s in the state containing essentially no solvent after drying. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, a cured product, and a method for forming a light-shielding image. In particular, the present invention relates to a black matrix for liquid crystal display formed by a method for forming a light-shielding image.

 Currently, various efforts are being made to improve the display quality of liquid crystal display (hereinafter, sometimes referred to as “LCD”) and further reduce the cost. In particular, various methods for reducing the cost of color filters (hereinafter sometimes referred to as “CF”) that are expensive among the constituent members of the LCD panel are being studied. In particular, a black matrix (hereinafter sometimes referred to as “BM”) is being converted from a conventional Cr film to a resin BM from the viewpoint of environment and cost. The resin BM is usually formed by a photolithography process using a black photosensitive resin composition comprising a black pigment, an alkali-soluble binder, and a polymerizable monomer. The current problem of the resin BM is that there is a problem in pattern formation and profile because of its light shielding properties. In addition, due to market demand for higher contrast, it is necessary to further improve the light shielding property of BM, and the situation is further deteriorated from the viewpoint of patterning properties.

  On the other hand, we developed the embossing technology well-known for optical disc production, and pressed the resist on a die prototype (generally called mold, stamper, template) with a concave / convex pattern, and mechanically deformed it. Thus, a technique (nanoimprint method) for precisely transferring a fine pattern is being developed. The nanoimprint method is economical because it can be easily repetitively molded with fine structures such as nanostructures once a mold is fabricated, and it is a nanofabrication technology with less harmful waste and emissions. Application to the field is expected.

 Two types of nanoimprint methods are proposed: a thermal nanoimprint method using a thermoplastic resin as a material to be processed (Non-patent Document 1) and an optical nanoimprint method using a curable composition for optical nanoimprint lithography (Non-patent Document 2). Has been. In the case of the thermal nanoimprint method, a mold (mold) is pressed into a polymer resin heated to a temperature higher than the glass transition temperature, and the mold is released after cooling to transfer the fine structure to the resin on the substrate. Since it can be applied to various resin materials and glass materials, it is expected to be applied in various fields. For example, Patent Document 1 and Patent Document 2 disclose a nanoimprint method in which a nanopattern is formed at low cost using a thermoplastic resin.

On the other hand, in the optical nanoimprint method in which light is irradiated through a transparent mold and the curable composition for optical nanoimprint lithography is photocured, imprinting at room temperature becomes possible. Recently, new developments such as a nanocasting method combining the advantages of both and a reversal imprint method for producing a three-dimensional laminated structure have been reported. In such a nanoimprint method, the following applications are considered. The first is when the molded shape itself has a function and can be applied as various nanotechnology element parts or structural members. Various micro / nano optical elements, high-density recording media, optical films, flat panels Examples include structural members in displays. The second is to construct a laminated structure by simultaneous integral molding of the microstructure and nanostructure and simple interlayer alignment, and to apply it to the production of μ-TAS and biochips. The third is to apply high-precision alignment and high integration to the production of high-density semiconductor integrated circuits instead of conventional lithography, the production of transistors in liquid crystal displays, and the like. In recent years, there have been active efforts for practical application of nanoimprint methods related to these applications. For example, in Patent Documents 1 and 3, a nanoimprint that uses a silicone wafer as a stamper and forms a fine structure of 25 nanometers or less by transfer is used. Technology is disclosed. Patent Document 4 discloses a composite composition using nanoimprint applied in the field of semiconductor microlithography. On the other hand, studies to apply nanoimprint lithography to semiconductor integrated circuit fabrication such as micro mold fabrication technology, mold durability, mold fabrication cost, mold releasability from mold, imprint uniformity and alignment accuracy, inspection technology, etc. It started to become active. These are mainly developments in nano-scale patterning, and no efforts related to BM pattern formation have been disclosed so far.
As described above, regarding the composition used in optical nanoimprinting, there is a description of a request regarding viscosity, but there has been no report on a composition having a black pigment.

 The main technical problems as a black matrix include many problems such as thinning, pattern accuracy, adhesion, and solvent resistance. Especially for thinning, it is necessary to contain a black pigment such as carbon black at a high concentration. In the conventional black photosensitive resin composition for photolithography, in addition to the coloring pigment component such as carbon black, From the viewpoint of film properties, it is necessary to add a polymer component or a photosensitive component, and there has been a limit to thinning. Further, the formation of a black matrix by the conventional photolithography method has a limitation that it is not possible to limit the binder type and the amount of addition due to its development suitability. Furthermore, there is a problem in photocurability due to the optical density, and there is a tendency that underetching occurs at the time of development, and the problem that a pattern is not formed or a rectangular shape cannot be obtained becomes higher as the optical density becomes higher. In addition, in the black matrix, which is the partition wall of ink in the inkjet method, which is a color filter manufacturing method that has been recently studied, the pattern shape dominates the shape of the pixel, so a black matrix having a trapezoidal cross section is stably formed There was a need to do. Furthermore, Patent Document 5 discloses a method of forming fine irregularities on the surface of the black matrix by the imprint method to develop ink repellency, but does not disclose forming the black matrix itself.

US Pat. No. 5,772,905 US Pat. No. 5,956,216 US Pat. No. 5,259,926 JP 2005-527110 Gazette Japanese Unexamined Patent Publication No. 2007-183587

S. Chou et al .: Appl. Phys. Lett. Vol. 67, 3114 (1995) M. Colbun et al,: Proc.SPIE, Vol. 3676,379 (1999)

  The present invention has been accomplished in view of the above circumstances, and an object thereof is to provide a photosensitive resin composition suitable for a photosensitive resin composition, particularly a black matrix such as a flat panel display. In particular, it is possible to provide a cured film excellent in pattern accuracy, adhesion, pattern shape, etc. even in the case of increasing the optical density of a thin film and increasing the optical density of a thick film for ink jet, etc. It aims to provide a method.

（一般式（１）中、Ｒ¹は水素原子、または、ヒドロキシメチル基を表し、Ｘは有機基を表す。ｍは１〜３の整数を表し、ｎは１〜４の整数を表す。Ｙは、炭素−炭素不飽和結合を有する硬化性官能基、炭素−窒素不飽和結合を有する硬化性官能基、酸素原子を含む環状基を有する硬化性官能基または下記一般式（２）で表される基を表す。）

（Ｒ²はそれぞれアルキル基またはアリール基を表す。）
（４）一般式（１）中のＹの少なくとも１つが、ビニルエーテル基、アリルエーテル基、シクロヘキセニル基、シクロペンテニル基、ジシクロペニテニル基、スチリル基、メタクリロイルオキシ基、メタクリロイルアミド基、アクリルアミド基、ビニルシラン基、Ｎ−ビニル複素環基およびマレイミド基からなる群より選ばれる、（３）に記載の感光性樹脂組成物。
（５）一般式（１）中のＹの少なくとも１つが、イソシアネート基またはニトリル基である、（３）に記載の感光性樹脂組成物。
（６）一般式（１）中のＹの少なくとも１つが、オキセタン環、オキシラン環および炭酸エチレン基からなる群より選ばれる、（３）に記載の感光性樹脂組成物。
（７）前記感光性樹脂組成物の表面張力が１８〜３０ｍＮ／ｍの範囲にある、（１）〜（６）のいずれか１項に記載の感光性樹脂組成物。
（８）（１）〜（７）のいずれか１項に記載の感光性樹脂組成物を硬化させてなる硬化物。
（９）（１）〜（７）のいずれか１項に記載の感光性樹脂組成物を用い、かつ、下記の工程を含むことを特徴する遮光性画像の形成方法。
（１）基板上に前記感光性樹脂組成物を用いて感光性樹脂層を設ける工程
（２）必要に応じ、前記感光性樹脂層を５０〜１５０℃で熱処理し溶剤を除去する工程
（３）凹凸表面を有する型を、前記感光性樹脂層と前記凹凸表面とが接するように圧着させる工程
（４）少なくとも前記凹凸表面を有する型を通して光照射する工程
（５）前記凹凸表面を有する型を感光性樹脂層から剥離する工程
（６）必要に応じ、前記感光性樹脂層を１６０〜２５０℃で熱処理する工程
（１０）（９）に記載の遮光性画像の形成方法により形成した硬化物。
（１１）前記硬化物が、液晶表示用ブラックマトリックスである、（８）または（１０）の硬化物。 As a result of the inventor's earnest study under the above problems, when using a colorant, particularly a black colorant, and using a coating solution that does not substantially contain a solvent, the viscosity becomes remarkably high, It was found that image formation becomes difficult. That is, the present invention is characterized by finding and solving such problems. In particular, an object of the present invention is to provide a composition capable of forming an image by a conventionally known image forming method.
As a result of intensive studies, it has been found that the above problems can be solved by the following means.
(1) In the state which does not contain a solvent substantially after drying, it contains at least 10% by mass of a colorant and a polymerizable monomer, and has a viscosity of 3 to 50 mPa.s. A photosensitive resin composition characterized by being s.
(2) The photosensitive resin composition according to (1), wherein the colorant is a black colorant.
(3) The photosensitive resin composition according to (1) or (2), wherein at least one of the polymerizable monomers is represented by the following general formula (1).

(In General Formula (1), R ¹ represents a hydrogen atom or a hydroxymethyl group, X represents an organic group, m represents an integer of 1 to 3, and n represents an integer of 1 to 4. Y Is represented by a curable functional group having a carbon-carbon unsaturated bond, a curable functional group having a carbon-nitrogen unsaturated bond, a curable functional group having a cyclic group containing an oxygen atom, or the following general formula (2): Represents a group.

(R ² represents an alkyl group or an aryl group, respectively.)
(4) At least one of Y in the general formula (1) is a vinyl ether group, an allyl ether group, a cyclohexenyl group, a cyclopentenyl group, a dicyclopentenyl group, a styryl group, a methacryloyloxy group, a methacryloylamide group, or an acrylamide group. The photosensitive resin composition as described in (3) chosen from the group which consists of a vinylsilane group, N-vinyl heterocyclic group, and a maleimide group.
(5) The photosensitive resin composition as described in (3) whose at least 1 of Y in General formula (1) is an isocyanate group or a nitrile group.
(6) The photosensitive resin composition according to (3), wherein at least one of Y in the general formula (1) is selected from the group consisting of an oxetane ring, an oxirane ring, and an ethylene carbonate group.
(7) The photosensitive resin composition according to any one of (1) to (6), wherein the surface tension of the photosensitive resin composition is in a range of 18 to 30 mN / m.
(8) A cured product obtained by curing the photosensitive resin composition according to any one of (1) to (7).
(9) A method for forming a light-shielding image, comprising using the photosensitive resin composition according to any one of (1) to (7) and including the following steps.
(1) A step of providing a photosensitive resin layer using the photosensitive resin composition on a substrate (2) A step of removing the solvent by heat-treating the photosensitive resin layer at 50 to 150 ° C. as necessary (3) A step of pressure-bonding a mold having a concavo-convex surface so that the photosensitive resin layer and the concavo-convex surface are in contact with each other (4) a step of irradiating light through at least the mold having the concavo-convex surface; (6) A cured product formed by the method for forming a light-shielding image according to (10) and (9), wherein the photosensitive resin layer is heat-treated at 160 to 250 ° C. as necessary.
(11) The cured product according to (8) or (10), wherein the cured product is a black matrix for liquid crystal display.

  According to the present invention, a photosensitive resin composition containing a colorant, which can provide an excellent cured film, was obtained. In addition, the photosensitive resin composition of the present invention enables good image formation by an imprint method. In particular, in the conventional photosensitive resin composition, since the viscosity of the composition after removing the solvent exceeds 1000 mPa · s, sufficient image formation cannot be performed by the imprint method, but the viscosity is set to 3 to 50 mPa · s. Thus, a desired pattern can be formed by the imprint method.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the present specification, (meth) acrylate represents acrylate and methacrylate, (meth) acryl represents acryl and methacryl, and (meth) acryloyl represents acryloyl and methacryloyl. Furthermore, a monomer and a monomer in this specification are synonymous. The monomer in the present specification is a compound having a mass average molecular weight of 1,000 or less, distinguished from oligomers and polymers. In the present specification, the functional group refers to a group involved in polymerization.
Furthermore, the nanoimprint referred to in the present invention refers to pattern transfer having a size of about several tens of μm to several tens of nm, and is not necessarily limited to nano order.

 The photosensitive resin composition of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) has high permeability before curing, excellent ability to form a fine concavo-convex pattern, and coating. It can be made excellent in aptitude and other process aptitudes. Moreover, after hardening, it is excellent in hardness, and also it can be set as the film property which was comprehensively excellent in other points. Therefore, the composition of the present invention can be widely used for optical nanoimprint lithography.

That is, the composition of the present invention can have the following characteristics when used in optical nanoimprint lithography.
(1) Since the solution fluidity at room temperature is excellent, the composition easily flows into the cavity of the mold recess, and the atmosphere is difficult to be taken in. Residues hardly remain after curing.
(2) The cured film after curing has excellent mechanical properties, excellent adhesion between the coating film and the substrate, and excellent peeling properties between the coating film and the mold. Since pulling does not cause surface roughness, a good pattern can be formed.
(3) Since it is excellent in coating uniformity, it is suitable for the field of coating / microfabrication on large substrates.
(4) Since mechanical properties such as residual film properties and scratch resistance and solvent resistance are high, it can be suitably used as a black matrix.

 For example, the composition of the present invention is suitably applied to semiconductor integrated circuits and liquid crystal display device members that have been difficult to develop until now (particularly for light-shielding films for liquid crystal displays and other fine processing applications for liquid crystal display device members). Other applications, for example, light shielding films for plasma display panels, flat screens, micro electro mechanical systems (MEMS), sensor elements, optical recording media such as high-density memory disks, optical components such as diffraction grating relief holograms, etc. , Nanodevices, optical devices, optical films and polarizing elements, organic transistors, color filters, overcoat layers, pillar materials, liquid crystal alignment rib materials, microlens arrays, immunoassay chips, DNA separation chips, microreactors, nanobiodevices, Optical waveguide, optical filter, photonic liquid Widely applicable to the production of crystals.

The viscosity of the composition of the present invention will be described. The viscosity in the present invention means a viscosity at 25 ° C. unless otherwise specified. The composition of the present invention has a viscosity at 25 ° C. of 3 to 50 mPa · s, preferably 3 to 20 mPa · s, and more preferably 3 to 15 mPa · s in a state substantially free of solvent after drying. s.
By setting the viscosity of the composition of the present invention to 3 mPa · s or more, there is a tendency that problems of substrate coating suitability and a decrease in mechanical strength of the film hardly occur. Specifically, by setting the viscosity to 3 mPa · s or more, it is preferable that unevenness on the surface is generated during the application of the composition or the composition can be prevented from flowing out of the substrate during the application. On the other hand, by setting the viscosity of the composition of the present invention to 50 mPa · s or less, even when a mold having a fine concavo-convex pattern is adhered to the composition, the composition flows into the cavity of the concave portion of the mold, and the atmosphere Is less likely to be taken in, so that it is difficult to cause bubble defects, and it is difficult for residues to remain after photocuring in the mold convex portion.
The composition of the present invention is preferably used so that the film thickness after drying is 5 μm or less. Particularly preferably, it is 3 μm or less. When the thickness exceeds 5 μm, a defect may be easily generated at the time of peeling from the mold.

Here, in the composition of the present invention, “in a state substantially free of solvent after drying” means, for example, a state in which the amount of residual solvent is 0.1% by weight or less, and does not contain any solvent Most preferably.
The composition of the present invention may contain a known organic solvent in advance. When the solvent is substantially contained in the state before drying, the amount of the solvent is selected so that the solid content concentration is 10 to 99% by mass. The organic solvent that can be preferably used in the composition of the present invention is a solvent that is generally used in a curable composition for optical nanoimprint lithography and a photoresist, and dissolves and uniformly disperses the compound used in the present invention. Any material can be used as long as it does not react with these components.

Examples of the organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol monoethyl ether; methyl cellosolve Ethylene glycol alkyl ether acetates such as acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; propylene glycol Propylene glycol alkyl ether acetates such as rumethyl ether acetate and propylene glycol ethyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2 Ketones such as pentanone and 2-heptanone; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2- Methyl hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, acetic acid Chill, methyl lactate, and the like esters such as lactic acid esters such as ethyl lactate.
Further, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. A high boiling point solvent can also be added.
These solvents may be used alone or in combination of two or more.
Among these solvents, methoxypropylene glycol acetate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, methyl isobutyl ketone, and 2-heptanone are particularly preferable.

  The composition of the present invention contains at least 10% by mass of a colorant and a polymerizable monomer. Here, the colorant and the polymerizable monomer may be only one type, or two or more types (hereinafter referred to as “monomer in the present invention” and “other polymerizable monomer”). Yes). The composition of the present invention may contain other polymerizable monomer, photopolymerization initiator, and the like in addition to the colorant as an essential component and the monomer in the present invention. Hereinafter, these contents will be described in detail.

（一般式（１）中、Ｒ¹は水素原子、または、ヒドロキシメチル基を表し、Ｘは有機基を表す。ｍは１〜３の整数を表し、ｎは１〜４の整数を表す。Ｙは、炭素−炭素不飽和結合を有する硬化性官能基、炭素−窒素不飽和結合を有する硬化性官能基、酸素原子を含む環状基を有する硬化性官能基または下記一般式（２）で表される基を表す。）

（Ｒ²はそれぞれアルキル基またはアリール基を表す。） Polymerizable monomer The composition of the present invention contains the polymerizable monomer in an amount of preferably 10 to 99% by mass, more preferably 20 to 80% by mass of the total solid content of the composition. The monomer in the present invention is preferably a monomer represented by the general formula (1).

(In General Formula (1), R ¹ represents a hydrogen atom or a hydroxymethyl group, X represents an organic group, m represents an integer of 1 to 3, and n represents an integer of 1 to 4. Y Is represented by a curable functional group having a carbon-carbon unsaturated bond, a curable functional group having a carbon-nitrogen unsaturated bond, a curable functional group having a cyclic group containing an oxygen atom, or the following general formula (2): Represents a group.

(R ² represents an alkyl group or an aryl group, respectively.)

The organic group represented by X preferably represents a 2-7 valent organic group, and may be aliphatic or aromatic, and the total number of carbon atoms is preferably 2-20. Further, the organic group may be blocked with an oxygen atom, a sulfur atom, an ester group, or a urethane group. Specific examples include a propanetriol skeleton, a pentaerythritol skeleton, and an aliphatic cyclic skeleton.
The curable functional group having a carbon-carbon unsaturated bond represented by Y may be either a double bond or a triple bond, and may have a substituent on the unsaturated bond, either a chain or a ring. It may be. The total carbon number is preferably 2-18. Specifically, vinyl ether group, allyl ether group, cyclohexenyl group, cyclopentenyl group, dicyclopentenyl group, styryl group, methacryloyloxy group, methacryloylamide group, acrylamide group, vinylsilane group, N-vinyl heterocyclic group and A maleimide group may be mentioned.
Examples of the curable functional group having a carbon-nitrogen unsaturated bond represented by Y include an isocyanate group and a nitrile group.
Examples of the curable functional group containing a cyclic group containing an oxygen atom represented by Y include an oxirane ring, an oxetane ring, and an ethylene carbonate group. More preferred are an oxirane ring and an oxetane ring.
The alkyl group represented by R ² is preferably an alkyl group having 1 to 8 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a benzyl group. As the aryl group, an aryl group having 6 to 12 carbon atoms is preferable. Examples of such an aryl group include a phenyl group, a p-tolyl group, and a p-chlorophenyl group.
m is preferably 1 or 2, and n is preferably 1 to 3. When m is 2 or more, the plurality of R ¹ may be the same or different from each other. When n is 2 or more, the plurality of Y may be the same or different.

Here, although the preferable example of the monomer in this invention is shown, it cannot be overemphasized that this invention is not what is limited to these.

Other polymerizable monomers The composition of the present invention may further contain other polymerizable monomers for the purpose of improving the composition viscosity, film hardness, flexibility and the like. The polymerizable monomer is preferably a polymerizable monomer having a bifunctional or higher polymerizable functional group. In particular, it is preferable that 50% by weight or more of the other polymerizable monomer contained in the composition of the present invention is a polymerizable monomer having a bifunctional or higher functional group. Hereinafter, other polymerizable monomers used in the present invention will be described in detail.
Another polymerizable monomer of the present invention includes a polymerizable unsaturated monomer having one ethylenically unsaturated bond-containing group (monofunctional polymerizable unsaturated monomer). Specifically, 2-acryloyloxyethyl phthalate, 2-acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol acrylate 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (Meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acrylic acid dimer, benzyl (meth) acrylate, butanediol mono (meth) acrylate Rate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, ethylene oxide modified (hereinafter referred to as “EO”) cresol (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) ) Acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclohentanyl (meth) acrylate, dicyclo Pentanyloxyethyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate Methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, Nonylphenoxy polypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, epichlorohydrin (hereinafter referred to as “ECH”) modified phenoxy acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol ( (Meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene Glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tert-butyl (meta ) Acrylate, tribromophenyl (meth) acrylate, EO-modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, p-isopropenylphenol, styrene, α-methylstyrene, acrylonitrile, and vinylcarbazole.

It is more preferable to use a polyfunctional polymerizable unsaturated monomer having two or more ethylenically unsaturated bond-containing groups as another polymerizable monomer.
Examples of the bifunctional polymerizable unsaturated monomer having two ethylenically unsaturated bond-containing groups that can be preferably used in the present invention include diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meta ) Acrylate, di (meth) acrylated isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, ECH modified 1,6-hexanediol di (meth) acrylate, allyloxy polyethylene glycol acrylate, 1,9-nonanediol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) Acrylate, modified screw Enol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, ECH modified hexahydrophthalic acid diacrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO modified Neopentyl glycol diacrylate, propylene oxide (hereinafter referred to as “PO”) modified neopentyl glycol diacrylate, caprolactone modified hydroxypivalate ester neopentyl glycol, stearic acid modified pentaerythritol di (meth) acrylate, ECH modified phthalic acid di ( (Meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) Di) (di) (meth) acrylate, polyester (di) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ECH modified propylene glycol di (meth) acrylate, silicone di (meth) acrylate, triethylene Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tricyclodecane dimethanol (di) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, tripropylene glycol di (meth) acrylate, EO modified Tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, divinylethyleneurine Examples thereof include silicon and divinylpropylene urea.

  Among these, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl hydroxypivalate Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and the like are preferably used in the present invention.

  Examples of the polyfunctional polymerizable unsaturated monomer having 3 or more ethylenically unsaturated bond-containing groups include ECH-modified glycerol tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meta) ) Acrylate, pentaerythritol triacrylate, EO modified phosphoric acid triacrylate, trimethylolpropane tri (meth) acrylate, caprolactone modified trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylol Propane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) Acrylate, dipentaerythritol hydroxypenta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) Examples include acrylate, pentaerythritol ethoxytetra (meth) acrylate, and pentaerythritol tetra (meth) acrylate.

  Among these, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like are preferably used in the present invention.

  In the composition of the present invention, for the purpose of further increasing the crosslinking density, a polyfunctional oligomer or polymer having a molecular weight higher than that of the other polyfunctional polymerizable monomer is blended within a range to achieve the object of the present invention. Can do. Examples of the polyfunctional oligomer having photo-radical polymerizability include various acrylate oligomers such as polyester acrylate, polyurethane acrylate, polyether acrylate, and polyepoxy acrylate.

 As another polymerizable monomer used in the present invention, a compound having an oxirane ring can also be employed. Examples of the compound having an oxirane ring include polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyl ethers of aromatic polyols, and aromatics. Mention may be made, for example, of hydrogenated compounds of polyglycidyl ethers of polyols, urethane polyepoxy compounds and epoxidized polybutadienes. These compounds can be used alone or in combination of two or more thereof.

  Examples of the epoxy compound that can be preferably used include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S. Diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin tri Glycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Glycidyl ethers; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; aliphatic long-chain dibasic acids Diglycidyl esters of aliphatic higher alcohols; monoglycidyl ethers of higher aliphatic alcohols; monoglycidyl ethers of polyether alcohols obtained by adding phenol, cresol, butylphenol or alkylene oxide to these; glycidyl esters of higher fatty acids, etc. can do.

  Among these components, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol Diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether are preferred.

  Commercially available products that can be suitably used as the glycidyl group-containing compound include UVR-6216 (manufactured by Union Carbide), glycidol, AOEX24, cyclomer A200, (manufactured by Daicel Chemical Industries, Ltd.), Epicoat 828, Epicoat 812, Epicoat 1031, Epicoat 872, Epicoat CT508 (above, manufactured by Yuka Shell Co., Ltd.), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 (above, Asahi Denka Kogyo ( Product)). These can be used alone or in combination of two or more.

  The production method of these compounds having an oxirane ring is not limited. For example, Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213, 1992, Ed. By Alfred Hasfner, The chemistry of cyclic compounds-Small Ring Heterocycles part3 Oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, Adhesion, Vol. 29, No. 12, 32, 1985, Yoshimura, Adhesion, Vol. 30, No. 5, 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, Japanese Patent Application Laid-Open No. 11-1000037, Japanese Patent No. 2906245, Japanese Patent No. 2926262 and the like can be synthesized.

As other polymerizable monomer used in the present invention, a vinyl ether compound may be used in combination.
The vinyl ether compound may be appropriately selected. For example, 2-ethylhexyl vinyl ether, butanediol-1,4-divinyl ether, diethylene glycol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2- Propanediol divinyl ether, 1,3-propanediol divinyl ether, 1,3-butanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, Trimethylolethane trivinyl ether, hexanediol divinyl ether, tetraethyleneglycol Rudivinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol diethylene vinyl ether, triethylene glycol Methylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether, pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether, 1,1,1-tris [4- (2 Vinyloxy ethoxy) phenyl] ethane, bisphenol A divinyloxyethyl carboxyethyl ether.

  These vinyl ether compounds can be obtained, for example, by the method described in Stephen C. Lapin, Polymers Paint Color Journal. 179 (4237), 321 (1988), that is, the reaction of a polyhydric alcohol or polyhydric phenol with acetylene, or They can be synthesized by the reaction of a polyhydric alcohol or polyhydric phenol and a halogenated alkyl vinyl ether, and these can be used singly or in combination of two or more.

 Moreover, a styrene derivative can also be employ | adopted as another polymerizable monomer used by this invention. Examples of the styrene derivative include p-methoxystyrene, p-methoxy-β-methylstyrene, p-hydroxystyrene, and the like.

 Other examples of styrene derivatives that can be used in combination with the monofunctional polymer of the present invention include styrene, p-methylstyrene, p-methoxystyrene, β-methylstyrene, p-methyl-β-methylstyrene, α-methylstyrene, Examples thereof include p-methoxy-β-methylstyrene, p-hydroxystyrene, etc. Examples of vinylnaphthalene derivatives include 1-vinylnaphthalene, α-methyl-1-vinylnaphthalene, β-methyl-1-vinyl. Naphthalene, 4-methyl-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene and the like can be mentioned.

 In addition, trifluoroethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, (perfluorobutyl) ethyl (meth) acrylate, perfluorobutyl-hydroxypropyl ( Use compounds with fluorine atoms such as (meth) acrylate, (perfluorohexyl) ethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, etc. Can do.

 As another polymerizable monomer used in the present invention, propenyl ether and butenyl ether can be blended. For example, 1-dodecyl-1-propenyl ether, 1-dodecyl-1-butenyl ether, 1-butenoxymethyl-2-norbornene, 1-4-di (1-butenoxy) butane, 1,10-di (1-butenoxy) ) Decane, 1,4-di (1-butenoxymethyl) cyclohexane, diethylene glycol di (1-butenyl) ether, 1,2,3-tri (1-butenoxy) propane, propenyl ether propylene carbonate, and the like can be suitably applied.

  The other polymerizable monomer is preferably contained in the composition of the present invention in the range of 10 to 90% by mass, and more preferably in the range of 20 to 80% by mass. In particular, as described above, the polymerizable monomer having a bifunctional or higher polymerizable functional group preferably accounts for 50% by weight or more of the other polymerizable monomer.

Next, a preferable blend form of the monomer and other polymerizable monomer in the present invention (hereinafter, these may be collectively referred to as “polymerizable unsaturated monomer”) will be described. The composition of the present invention has two or more kinds of curable functional groups having different reactivities in the same molecule, and at least one of the curable functional groups is an α, β-unsaturated ester group. It is preferable that the body is an essential component and contains other polymerizable monomers.
Monofunctional polymerizable monomers are usually used as reactive diluents and are effective in reducing the viscosity of the composition of the present invention. However, since it causes a decrease in the mechanical strength of the cured film, the amount used is adjusted in consideration of the balance between the composition viscosity and the mechanical strength of the cured film. The use ratio of the monofunctional polymerizable monomer is preferably 15% by mass or more of the total polymerizable unsaturated monomer in order to suppress the viscosity reduction of the composition. On the other hand, in order to further reduce the decrease in mechanical strength of the cured film, the content is preferably 30% by mass or less based on the total polymerizable unsaturated monomer.
In order to improve the mechanical strength of the cured film, it is preferable to use a bifunctional and trifunctional polymerizable monomer, and in particular, the mechanical strength can be improved by using a trifunctional polymerizable monomer. it can.
The monomer having two unsaturated bond-containing groups (bifunctional polymerizable unsaturated monomer) is preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 80% by mass or less of the total polymerizable unsaturated monomer. Preferably, it is added in a range of 70% by mass or less. The ratio of the monofunctional and bifunctional polymerizable unsaturated monomer is preferably 1 to 95% by mass, more preferably 3 to 95% by mass, and particularly preferably 5 to 90% by mass of the total polymerizable unsaturated monomer. % Is added. The ratio of the polyfunctional polymerizable unsaturated monomer having 3 or more unsaturated bond-containing groups is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably the total polymerizable unsaturated monomer. Is added in a range of 60% by mass or less. Since the viscosity of a composition can be lowered | hung by making the ratio of the polymerizable unsaturated monomer which has 3 or more of polymerizable unsaturated bond containing groups into 80 mass% or less, it is preferable.

Colorant The colorant contained in the composition of the present invention (hereinafter sometimes referred to as “colorant in the present invention”) will be described. The composition of the present invention contains at least a 10% by weight colorant of the solid content of the composition. The colorant is preferably a black colorant. The content of the colorant in the composition of the present invention is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and 40 to 70% by mass from the viewpoint of light shielding properties. Further preferred. When the amount is 20% by mass or more, the shielding property becomes more sufficient, and when the amount is 80% by mass or less, the pattern hardness tends to be improved.
As the colorant in the present invention, organic pigments, inorganic pigments, dyes and the like can be suitably used. The pigments and dyes described in paragraph Nos. 0038 to 0054 of JP-A No. 2005-17716 and JP-A No. 2004-361447 can be used. Preferable examples include the pigments described in paragraph Nos. 0068 to 0072 of JP-A No. 2005-105, and the colorants described in paragraph Nos. 0080 to 0088 of JP-A No. 2005-17521. In addition to light-shielding agents such as metal oxide powders such as carbon black, titanium oxide, and iron oxide, metal sulfide powders, and metal powders, a mixture of pigments such as red, blue, and green can be used. Examples of inorganic pigments are metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony And metal complex oxides. Organic pigments include CIPigment Yellow 11, 24, 31, 53, 83, 99, 108, 109, 110, 138, 139,151, 154, 167, CIPigment Orange 36, 38, 43, CIPigment Red 105, 122, 149, 150 , 155, 171, 175, 176, 177, 209, CIPigment Violet 19, 23, 32, 39, CIPigment Blue 1, 2, 15, 16, 22, 60, 66, CIPigment Green 7, 36, 37, CIPigment Brown 25 28, CIPigment Black 1, 7. Known colorants (dyes and pigments) can be used.
The pigment is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent or a vehicle. Here, the vehicle refers to a portion of the medium in which the pigment is dispersed when the paint is in a liquid state, and is a liquid portion that binds to the pigment and hardens the coating film (binder), which is dissolved and diluted. Component (organic solvent). The disperser used for dispersing the pigment is not particularly limited. For example, a kneader or a roll mill described in Kazuzo Asakura, “Encyclopedia of Pigments”, First Edition, Asakura Shoten, 2000, Item 438. And known dispersers such as an atrider, a super mill, a dissolver, a homomixer, and a sand mill. Further, the material may be finely pulverized using frictional force by mechanical grinding described in Item 310 of the document. In order to prepare a dispersion containing no organic solvent, a dispersion treatment is carried out in advance in a system containing a highly volatile (low boiling point) solvent, and then the solvent is volatilized or the monomer is gradually removed simultaneously with the solvent volatilization. It can be added to finally remove the solvent. Further, the monomer can be used as a diluent medium and dispersed.
In the present invention, a dispersion aid may be used in combination in preparing the dispersion.
From the viewpoint of dispersion stability, the colorant (pigment) used in the present invention preferably has a number average particle size of 0.001 to 1 μm, more preferably 0.01 to 0.5 μm, and 0.01 to 0. 0.1 μm is more preferable, and 0.02 to 0.08 is particularly preferable. On the other hand, when the pigment number average particle size exceeds 0.1 μm, the light shielding property is lowered, which is not preferable. The “particle size” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle size” refers to the above particle size for a number of particles, This means the average value of 100 pieces.

  In the present invention, when a black colorant is used, it is preferable to use at least one pigment. The pigments are generally roughly classified into organic pigments and inorganic pigments. Examples of pigments preferably used in the present invention include the color materials described in paragraph numbers 0038 to 0040 of JP-A-2005-17716, Examples thereof include pigments described in paragraph Nos. 0068 to 0072 of JP-A No. 2005-361447 and colorants described in paragraph Nos. 0080 to 0088 of JP-A No. 2005-17521.

Among the pigments, carbon black, titanium black or graphite is preferable. Among these, in the present invention, it is preferable that at least one colorant is carbon black from the viewpoint of light shielding properties and cost.
As an example of carbon black, Pigment Black 7 (carbon black CI No. 77266) is preferable. Examples of commercially available products include Mitsubishi Carbon Black MA100 (manufactured by Mitsubishi Chemical Corporation) and Mitsubishi Carbon Black # 5 (manufactured by Mitsubishi Chemical Corporation).
As an example of titanium black, TiO ₂ , TiO, TiN and a mixture thereof are preferable. Examples of commercially available products include (trade names) 12S and 13M manufactured by Mitsubishi Materials Corporation. The average particle size of titanium black is preferably 40 to 100 nm.
As an example of graphite, particles having a Stokes diameter of 3 μm or less are preferable. By using graphite of 3 μm or less, the contour shape of the light shielding pattern becomes uniform, and the sharpness is improved. Moreover, it is preferable that the abundance ratio of particles having a particle size of 0.1 μm or less is 70% or more.

Metal Particles or Metal-Containing Particles The composition of the present invention is metal particles or metal-containing particles (hereinafter sometimes referred to as “metal fine particles” in the present invention) as at least one black colorant. Is also preferred. Thereby, a light-shielding film for a display device that can obtain a high optical density with a thin film can be formed.
The metal in the metal particles and the metal-containing particles is not particularly limited, and any metal may be used. The metal particles may be a combination of two or more metals, or may be an alloy. Further, the metal-containing particles may be metal compound particles having at least one kind of metal, and may be composite particles of a metal and a metal compound.

Metal particles As the metal particles, it is particularly preferable that a metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the long periodic table (IUPAC 1991) is contained as a main component (60% by mass or more). . Moreover, it is preferable to contain the metal chosen from the group which consists of 2-14 groups, 2nd group, 8th group, 9th group, 10th group, 11th group, 12th group, 13th group and More preferably, a metal selected from the group consisting of Group 14 is included as a main component. Among these metals, the metal particles are metals of the fourth period, the fifth period, or the sixth period, and are of Group 2, Group 10, Group 11, Group 12, or Group 14. Metal particles are more preferred.

  Examples of preferable metals constituting the metal particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, calcium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, and tantel. And at least one selected from titanium, bismuth, antimony, lead, and alloys thereof. More preferable metals are copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, calcium, iridium, and alloys thereof, and more preferable metals are copper, silver, gold, platinum, palladium, tin, and calcium. And at least one selected from these alloys, and particularly preferred metals are at least one selected from copper, silver, gold, platinum, tin, and alloys thereof. In particular, silver or an alloy thereof is preferable (colloidal silver is preferable as silver), and particles having a silver-tin alloy part are most preferable. The particle | grains which have a silver tin alloy part are mentioned later.

Metal Compound Particle The “metal compound” is a compound of the metal and an element other than the metal. Examples of the compound of metal and other elements include metal oxides, sulfides, sulfates, carbonates, and the like, and these particles are preferable as the metal compound particles. Of these, sulfide particles are preferred because of their color tone and ease of fine particle formation.
Examples of the metal compound include copper oxide (II), iron sulfide, silver sulfide, copper sulfide (II), and titanium black. From the viewpoint of color tone, ease of fine particle formation and stability, silver sulfide is particularly preferable. preferable.

Composite Particles Composite particles are those in which a metal and a metal compound are combined into one particle. For example, the inside of the particle and the surface are different in composition, and the two kinds of particles are combined. Further, each of the metal compound and the metal may be one type or two or more types.

Specific examples of the composite fine particles of the metal compound and the metal preferably include composite fine particles of silver and silver sulfide, composite fine particles of silver and copper (II) oxide, and the like.
The metal fine particles in the present invention may be core-shell type composite particles (core-shell particles). Core-shell type composite particles (core-shell particles) are obtained by coating the surface of a core material with a shell material, and specific examples thereof include cores described in paragraphs 0024 to 0027 of JP-A-2006-18210. -Shell fine particles are mentioned.

Particles having a silver-tin alloy part It is also preferable to use particles having a silver-tin alloy part as at least one of the metal-based fine particles in the present invention. The particles having a silver-tin alloy part include those made of a silver-tin alloy part, those made of a silver-tin alloy part and another metal part, and those made of a silver-tin alloy part and another alloy part.

  In the particles having a silver-tin alloy part, at least a part of the particles is composed of a silver-tin alloy. For example, HD-2300 manufactured by Hitachi, Ltd. and EDS (energy dispersive X) manufactured by Noran. And a spectrum measurement of the center 15 nm □ area of each particle with an acceleration voltage of 200 kV.

  Particles having a silver-tin alloy part have a high black density, can exhibit excellent light-shielding performance in a small amount or in a thin film, and have high thermal stability, so that they do not impair the black density and are high temperature (for example, 200 ° C. or more) ), And a high degree of light shielding properties can be stably secured. For example, it is suitable for a light-shielding film (so-called black matrix) for a color filter that is required to have a high light-shielding property and is generally subjected to a baking process.

  The particles having a silver-tin alloy part are preferably obtained by combining (for example, alloying) Ag and tin (Sn) at a silver (Ag) ratio of 30 to 80 mol% with respect to tin (Sn). By setting the Ag ratio in the above-described range, it is possible to obtain a high black density with high thermal stability at a high temperature range and low light reflectance. In particular, particles having an Ag ratio of 75 mol%, that is, AgSn alloy particles are easy to produce, and the obtained particles are also stable and preferable.

  Particles having a silver-tin alloy part can be formed by alloying by a general method such as heating, melting and mixing in a crucible or the like, but the melting point of Ag is around 900 ° C. Since the melting point of Sn is around 200 ° C. and there is a large difference between the melting points of the two, an extra fine particle process after compounding (for example, alloying) is required. preferable. In other words, the Ag compound and the Sn compound are mixed and reduced, and the metal Ag and the metal Sn are precipitated at the positions close to each other at the same time, thereby achieving composite (for example, alloying) and micronization at the same time. Is the method. Since Ag tends to be reduced and tends to precipitate before Sn, it is preferable to control the precipitation timing by making Ag and / or Sn a complex salt.

Preferred examples of the Ag compound include silver nitrate (AgNO ₃ ), silver acetate (Ag (CH ₃ COO)), silver perchlorate (AgClO ₄ .H ₂ O), and the like. Of these, silver acetate is particularly preferred. Preferred examples of the Sn compound include stannous chloride (SnCl ₂ ), stannic chloride (SnCl ₄ ), stannous acetate (Sn (CH ₃ COO) ₂ ), and the like. Of these, stannous acetate is particularly preferable.

  As the reduction, a method using a reducing agent, a method of reducing by electrolysis, and the like can be mentioned as preferable reduction methods. Among these, the former method using a reducing agent is preferable in that fine particles can be obtained. Examples of the reducing agent include cetyltrimethylammonium bromide (CTAB), ascorbic acid, hydroquinone, catechol, paraaminophenol, paraphenylenediamine, and hydroxyacetone. Among these, hydroxyacetone is particularly preferable because it is easily volatilized and does not adversely affect the display device.

The metal-based fine particles in the present invention can be commercially available, and can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like.
For example, the rod-shaped silver fine particles are obtained by adding spherical silver fine particles as seed particles and then further adding a silver salt and using a reducing agent having a relatively low reducing power such as ascorbic acid in the presence of a surfactant such as CTAB. Silver bars and wires are obtained. This is described in Advanced Materials 2002, 14, 80-82. Similar descriptions are made in Materials Chemistry and Physics 2004, 84, 197-204, Advanced Functional Materials 2004, 14, 183-189.

Further, as a method using electrolysis, Materials Letters 2001, 49, 91-95 and a method of generating a silver bar by irradiating microwaves are described in Journal of Materials Research 2004, 19, 469-473. Journal of Physical Chemistry B 2003,107,3679-3683 can be cited as an example in which reverse micelles and ultrasonic waves are used in combination.
Similarly, gold is also described in Journal of Physical Chemistry B 1999,103, 3073-3077 and Langmuir 1999,15,701-709, Journal of American Chemical Society 2002,124,14316-14317.
The method for forming the rod-like particles can be prepared by improving the method described above (adjusting the addition amount and controlling the pH).

  The metal-based fine particles in the present invention can be obtained by combining various types of particles in order to bring them closer to an achromatic color. For example, a higher transmission density can be obtained by combining particles whose shape is changed from spherical or cubic to flat (hexagonal, triangular) or rod-like. By using such metal-based fine particles, a thin film can be achieved when the light shielding layer is formed.

As the particle size distribution of the metal-based fine particles, the particle distribution is preferably approximated by a normal distribution, and the particle size distribution width D ⁹⁰ / D ^{10 of the} number average particle size is preferably 1.2 or more and less than 50. Here, the particle size is the major axis length L as the particle diameter, D ⁹⁰ is the particle diameter at which 90% of the particles close to the average particle size are found, and D ¹⁰ is the particle diameter close to the average particle size. 10% is the particle diameter found. The particle size distribution width is preferably 2 to 30, more preferably 4 to 25 from the viewpoint of color tone. If the distribution width is less than 1.2, the color tone may be close to a single color, and if it is 50 or more, turbidity may occur due to scattering by coarse particles.

In addition, the measurement of the particle size distribution width D ⁹⁰ / D ¹⁰ is specifically performed by measuring 100 metal particles in the film randomly by a method of measuring a triaxial diameter to be described later, and determining the major axis length L. and particle diameter, the particle size distribution was a normal distribution approximation, the average particle diameter in the range of 90% by the number of close particle particle size and D ^90, a particle diameter in the range number of 10% from the average grain size with D ^10, it is possible to calculate the D ⁹⁰ / D ^10.

Triaxial diameter The metal-based fine particles in the present invention are captured as a rectangular parallelepiped by the following method, and each dimension is measured. That is, a rectangular parallelepiped box having a single metal-based fine particle that fits exactly (tightly) is considered, and the longest length of the box is defined as the long axis length L, and the thickness t, width b Is defined as the size of the metal-based fine particles. The dimensions have a relationship of L> b ≧ t, and the larger of b and t is defined as the width b unless otherwise the same. Specifically, first, metal-based fine particles are placed on a flat surface so that the center of gravity is the lowest and remains stable. Next, the metal-based fine particles are sandwiched between two parallel flat plates standing at right angles to the plane, and the flat plate interval at the position where the flat plate interval is the shortest is maintained. Next, metal-based fine particles are sandwiched between two parallel flat plates that are perpendicular to the two flat plates that determine the flat plate interval and are also perpendicular to the flat surface, and the distance between the two flat plates is maintained. Finally, the top plate is placed parallel to the plane so as to come into contact with the highest position of the metal-based fine particles. By this method, a rectangular parallelepiped defined by a plane, two pairs of flat plates and a top plate is formed.
In addition, a coil shape or a loop shape is defined as a value when the measurement is performed in a state where the shape is extended.

・ Long axis length L
In the case of rod-shaped metal-based fine particles, the major axis length L is preferably 10 nm to 1000 nm, more preferably 10 nm to 800 nm, and 20 nm to 400 nm (shorter than the wavelength of visible light). More preferably. When L is 10 nm or more, there is an advantage that preparation is easy in production and heat resistance and color are good, and when L is 1000 nm or less, there are advantages that there are few planar defects.

-Ratio between width b and thickness t The ratio between width b and thickness t, such as in the case of rod-shaped metal-based fine particles, is defined as the average value of values measured for 100 rod-shaped metal fine particles. The ratio (b / t) between the width b and the thickness t of the rod-like metal-based fine particles is preferably 2.0 or less, more preferably 1.5 or less, and particularly preferably 1.3 or less. preferable. If the b / t ratio exceeds 2.0, it may be nearly flat and heat resistance may be reduced.

-Relationship between the major axis length L and the width b and thickness t The major axis length L is preferably 1.2 to 100 times the width b, more preferably 1.3 to 50 times. It is particularly preferably 1.4 to 20 times. When the major axis length L is less than 1.2 times the width b, the characteristics of a flat plate may appear and the heat resistance may deteriorate. On the other hand, if the major axis length L exceeds 100 times the width b, the black density may become low, and the high density of the thin layer may not be achieved.

Measurement of length L, width b, and thickness t Measurement of length L, width b, and thickness t can be made with a surface observation diagram (× 500000) by an electron microscope and an atomic force microscope (AFM). The average value of the values measured for 100 rod-shaped metal fine particles. The atomic force microscope (AFM) has several operation modes, which are selectively used depending on the application.
Broadly divided into the following three.
(1) Contact method: A method in which the probe is brought into contact with the sample surface and the surface shape is measured from the displacement of the cantilever. (2) A tapping method: The probe is periodically brought into contact with the sample surface and the surface shape is determined from the change in the vibration amplitude of the cantilever. (3) Non-contact method: A method for measuring the surface shape from changes in the cantilever vibration frequency without contacting the probe with the sample surface.

On the other hand, the non-contact method needs to detect extremely weak attractive force with high sensitivity. For this reason, it is difficult to detect static force by directly measuring the displacement of the cantilever, and the mechanical resonance of the cantilever is applied.
The above three methods can be mentioned, and any method can be selected according to the sample.

  In the present invention, the electron microscope can be measured at an acceleration voltage of 200 kV using an electron microscope JEM2010 manufactured by JEOL. Moreover, the atomic force microscope (AFM) includes SPA-400 manufactured by Seiko Instruments Inc. In the measurement with an atomic force microscope (AFM), the measurement is facilitated by inserting polystyrene beads in the comparison.

  In the present invention, metal particles, particles containing an alloy, or metal compound particles are preferable as the metal particles or metal-containing particles, silver particles, particles containing a silver alloy or silver compound particles are more preferable, and have a silver-tin alloy part. Particles are most preferred.

  In the present invention, the number average particle size of metal particles or metal-containing particles is preferably 0.1 μm or less, more preferably 0.08 μm or less, and even more preferably 0.05 μm or less. When the number average particle size of the particles is 0.1 μm or less, the surface smoothness is good and the defects due to coarse particles are reduced.

  The composition of the present invention preferably has a surface tension in the range of 18 to 30 mN / m, and more preferably in the range of 20 to 28 mN / m. By setting it as such a range, surface smoothness can be improved.

Photopolymerization initiator The composition of the present invention preferably contains a photopolymerization initiator. The photoinitiator used for this invention contains 0.1-15 mass% in all the compositions, for example, Preferably it is 0.2-12 mass%, More preferably, it is 0.3-10 mass %. When using 2 or more types of photoinitiators, it is preferable that the total amount becomes the said range.
It is preferable that the ratio of the photopolymerization initiator is 0.1% by mass or more because sensitivity (fast curability), resolution, line edge roughness, and coating film strength tend to be improved. On the other hand, when the ratio of the photopolymerization initiator is 15% by mass or less, the light transmittance, the colorability, the handleability and the like tend to be improved, which is preferable.

  As the photopolymerization initiator used in the present invention, one that has activity with respect to the wavelength of the light source to be used is blended, and one that generates appropriate active species is used.

  As the radical photopolymerization initiator used in the present invention, for example, a commercially available initiator can be used. Examples of these include Irgacure® 2959 (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, Irgacure (available from Ciba). (Registered trademark) 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure (registered trademark) 500 (1-hydroxycyclohexyl phenyl ketone, benzophenone), Irgacure (registered trademark) 651 (2,2-dimethoxy-1,2-diphenylethane- 1-one), Irgacure® 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1), Irgacure® 907 (2-methyl-1 [4- Methylthiophenyl] -2-morpholinop Lopan-1-one, Irgacure® 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethyl-pentylphosphine oxide, 1-hydroxy-cyclohexyl-phenyl-ketone), Irgacure® 1800 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide) , 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Irgacure® OXE01 (1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- ( O-benzoyloxime), Darocur (registered) Standard) 1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one), Darocur (R) 1116, 1398, 1174 and 1020, CGI242 (ethanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide), Lucirin TPO available from BASF -L (2,4,6-trimethylbenzoylethoxyphenylphosphine oxide), ESACURE 1001M (1- [4-benzoylphenylsulfanyl] phenyl] -2-methyl-2- (4-methyl), available from ESACUR Nippon Siber Hegner Phenyls Honyl) propan-1-one, N-1414 Adeka optomer (registered trademark) N-1414 (carbazole phenone system), Adeka optomer (registered trademark) N-1717 (acridine system) available from Asahi Denka Co., Ltd. Adekaoptomer (registered trademark) N-1606 (triazine type), TFE-triazine (2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -1 manufactured by Sanwa Chemical Co., Ltd.) , 3,5-triazine), TME-triazine (2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -1,3,5, manufactured by Sanwa Chemical Co., Ltd.) -Triazine), MP-triazine (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine) manufactured by Sanwa Chemical, Midori Chemical TAZ-113 (2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine), TAZ-108 (2- (3 , 4-dimethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine), benzophenone, 4,4'-bisdiethylaminobenzophenone, methyl-2-benzophenone, 4-benzoyl-4'- Methyl diphenyl sulfide, 4-phenylbenzophenone, ethyl Michler's ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, thioxa Nton ammonium salt, benzoin, 4,4'-dimethoxybenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, 1,1,1-trichloroacetophenone, diethoxyacetophenone and dibenzosuberone , Methyl o-benzoylbenzoate, 2-benzoylnaphthalene, 4-benzoyl biphenyl, 4-benzoyl diphenyl ether, 1,4-benzoylbenzene, benzyl, 10-butyl-2-chloroacridone, [4- (methylphenylthio) Phenyl] phenylmethane), 2-ethylanthraquinone, 2,2-bis (2-chlorophenyl) 4,5,4 ′, 5′-tetrakis (3,4,5-trimethoxyphenyl) 1,2′-biimidazole, 2,2-bis (o-chlorophenyl) 4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, tris (4-dimethylaminophenyl) methane, ethyl Examples include -4- (dimethylamino) benzoate, 2- (dimethylamino) ethyl benzoate, butoxyethyl-4- (dimethylamino) benzoate.

  Furthermore, in addition to the photopolymerization initiator, a photosensitizer can be added to the composition of the present invention to adjust the wavelength in the UV region. Typical sensitizers that can be used in the present invention include those disclosed in Krivello [JVCrivello, Adv. In Polymer Sci, 62, 1 (1984)], specifically, pyrene. Perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like.

Surfactant A surfactant may be added to the composition of the present invention, and the surfactant used in the present invention contains, for example, 0.001 to 5% by mass in the total composition, preferably It is 0.002-4 mass%, More preferably, it is 0.005-3 mass%. When using 2 or more types of surfactant, the total amount becomes the said range. If the surfactant is less than 0.001 in the composition, the effect of coating uniformity may be insufficient. On the other hand, if it exceeds 5% by mass, mold transfer characteristics may be deteriorated.
The surfactant preferably contains at least one of a fluorine-based surfactant, a silicone-based surfactant, and a fluorine / silicone-based surfactant. Both the fluorine-based surfactant and the silicone-based surfactant or fluorine -More preferably, a silicone-based surfactant is included, and most preferably, a fluorine-silicone-based surfactant is included.
Here, the fluorine / silicone surfactant refers to one having both requirements of a fluorine surfactant and a silicone surfactant.
By using such a surfactant, the composition of the present invention can be applied to a silicon wafer for manufacturing a semiconductor device, a glass square substrate for manufacturing a liquid crystal device, a chromium film, a molybdenum film, a molybdenum alloy film, a tantalum film, and tantalum. Striations and scale-like patterns (such as alloy films, silicon nitride films, amorphous silicone films, tin oxide-doped indium oxide (ITO) films, tin oxide films, etc.) The purpose is to solve the problem of poor coating such as uneven drying of the resist film), and the fluidity of the composition into the cavity of the mold recess is improved, the peelability between the mold and the resist is improved, and between the resist and the substrate It becomes possible to improve the adhesion and to lower the viscosity of the composition. In particular, in the composition of the present invention, the coating uniformity can be greatly improved by adding the above-mentioned surfactant, and in coating using a spin coater or slit scan coater, good coating suitability can be obtained regardless of the substrate size. can get. Furthermore, when applied to an inkjet black matrix, the pattern surface is ink repellent and convenient.

Examples of the nonionic fluorosurfactant used in the present invention include trade names Florard FC-430 and FC-431 (Sumitomo 3M), trade names Surflon “S-382” (Asahi Glass Co., Ltd.), EFTOP “ EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 "(manufactured by Tochem Products), trade names PF-636, PF-6320, PF-656, PF-6520 ( All are OMNOVA), brand names FT250, FT251, DFX18 (all manufactured by Neos Co., Ltd.), brand names Unidyne DS-401, DS-403, DS-451 (all manufactured by Daikin Industries, Ltd.) ), Trade name Megafuk 171, 172, 173, 178K, 178A (all manufactured by Dainippon Ink & Chemicals, Inc.) Examples of nonionic silicon-based surfactants include the trade name SI-10 series (manufactured by Takemoto Yushi Co., Ltd.), MegaFuck Paintad 31 (manufactured by Dainippon Ink and Chemicals), KP-341 (Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd.).
Examples of fluorine / silicone surfactants used in the present invention include trade names X-70-090, X-70-091, X-70-092, X-70-093 (all Shin-Etsu Chemical Co., Ltd.). Manufactured), and trade names Megafuk R-08 and XRB-4 (all manufactured by Dainippon Ink & Chemicals, Inc.).

Antioxidant Furthermore, the composition of the present invention may contain a known antioxidant. By including the antioxidant, the film thickness reduction can be further reduced. The antioxidant used for this invention contains 0.01-10 mass% in all the compositions, for example, Preferably it is 0.2-5 mass%. When using 2 or more types of antioxidant, the total amount becomes the said range.
Antioxidants have the advantage of being able to reduce film thickness reduction due to decomposition. Examples of such antioxidants include hydrazides, hindered amine antioxidants, nitrogen-containing heterocyclic mercapto compounds, thioether antioxidants, hindered phenol antioxidants, ascorbic acids, zinc sulfate, thiocyanates, Examples include thiourea derivatives, sugars, nitrites, sulfites, thiosulfates, hydroxylamine derivatives, and the like. Among these, hindered phenol antioxidants and thioether antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness.

  As commercially available products of antioxidants, Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Geigy Co., Ltd.), Antigene P, 3C, FR, Sumilyzer S, Sumilyzer GA80 (manufactured by Sumitomo Chemical), Adekastab AO70, AO80, AO503 (made by ADEKA Co., Ltd.) etc. are mentioned, These may be used independently and may be used in mixture.

Binder The composition of the present invention may contain a binder. Various known polymers can be used as the binder. According to the present invention, in conventional photolitho, the binder used from the viewpoint of developability needs to be alkali-soluble such as an acid group, but the binder used in the present invention is not limited thereto. Specifically, organic polymer materials described in JP-A-5-72724 are preferable, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, and ethylene and acrylic. Acid ester or saponified product thereof, polyvinyl chloride, vinyl chloride copolymer such as vinyl chloride and vinyl acetate and saponified product thereof, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene and (meth) acrylic acid ester or Styrene copolymer such as saponified product, polyvinyltoluene, vinyltoluene and (meth) acrylic ester or vinyltoluene copolymer such as saponified product, poly (meth) acrylate, butyl (meth) acrylate And (meth) acrylic acid esters such as vinyl acetate Polymers, vinyl copolymers nylon acetate, copolymer nylon, N- alkoxymethyl nylon, organic polymeric polyamide resins such as N- dimethylamino nylon and the like. The weight average molecular weight of the binder to be used is 1,000 to 100,000, and if it is 1000 or less, the effect as a binder cannot be obtained, and if it exceeds 100,000, the viscosity of the composition of the present invention becomes too high. The amount of the binder added is preferably 10% by weight or less, more preferably 5% by weight or less, based on the total solid content. When the amount is more than 10% by weight, the pigment addition amount and the monomer addition amount tend to be relatively reduced, and the strength of the cured product and the optical density may be lowered. In particular, the composition of the present invention can be made free of a binder, and is extremely significant in that it enables realization of an unprecedented high pigment concentration.

Other components In addition to the above-described components, the composition of the present invention may include a release agent, a silane coupling agent, a polymerization inhibitor, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, and an adhesion promoter. , Thermal polymerization initiators, colorants, elastomer particles, photoacid proliferators, photobase generators, basic compounds, flow regulators, antifoaming agents, dispersants and the like may be added.

  For the purpose of further improving the peelability, a release agent can be arbitrarily blended in the composition of the present invention. Specifically, it is added for the purpose of allowing the mold pressed against the photosensitive resin layer comprising the composition of the present invention to be peeled cleanly without causing surface roughness or plate removal of the photosensitive resin layer. Examples of the release agent include conventionally known release agents such as silicone-based release agents, polyethylene wax, amide wax, solid wax such as Teflon powder (Teflon is a registered trademark), fluorine-based compounds, phosphate ester-based compounds, etc. Can also be used. Moreover, these mold release agents can be adhered to the mold.

  Silicone release agents have particularly good releasability from the mold when combined with the above-mentioned photocurable resin used in the present invention, and the phenomenon of taking a plate is difficult to occur. The silicone release agent is a release agent having an organopolysiloxane structure as a basic structure, for example, unmodified or modified silicone oil, polysiloxane containing trimethylsiloxysilicate, silicone acrylic resin, and the like. It is also possible to apply a silicone leveling agent generally used in hard coat compositions.

The modified silicone oil is obtained by modifying the side chain and / or terminal of polysiloxane, and is classified into a reactive silicone oil and a non-reactive silicone oil. Examples of the reactive silicone oil include amino modification, epoxy modification, carboxyl modification, carbinol modification, methacryl modification, mercapto modification, phenol modification, one-end reactivity, and different functional group modification. Examples of the non-reactive silicone oil include polyether modification, methylstyryl modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, higher alkoxy modification, higher fatty acid modification, and fluorine modification.
Two or more of the above-described modification methods can be performed on one polysiloxane molecule.

  The modified silicone oil is preferably compatible with the composition components. In particular, when using a reactive silicone oil that is reactive with other coating film forming components blended as necessary in the composition, it is chemically bonded in the cured film obtained by curing the composition of the present invention. Therefore, since it is fixed, problems such as adhesion inhibition, contamination, and deterioration of the cured film are unlikely to occur. In particular, it is effective for improving the adhesion with the vapor deposition layer in the vapor deposition step. Moreover, in the case of silicone modified with a photocurable functional group such as (meth) acryloyl-modified silicone, vinyl-modified silicone, etc., since it crosslinks with the composition of the present invention, it has excellent properties after curing.

Polysiloxane containing trimethylsiloxysilicic acid is easy to bleed out on the surface and has excellent releasability, excellent adhesion even when bleeded out to the surface, and excellent adhesion to metal deposition and overcoat layer This is preferable.
The said mold release agent can be added only in 1 type or in combination of 2 or more types.

When a release agent is added to the composition of the present invention, it is preferably added in a proportion of 0.001 to 10% by mass in the total amount of the composition, more preferably in a range of 0.01 to 5% by mass. preferable. If the ratio of a mold release agent is less than the said range, the peelable improvement effect of the photosensitive resin layer which consists of a mold and the composition of this invention tends to become inadequate. On the other hand, if the ratio of the release agent exceeds the above range, the surface of the coating film may be rough due to repelling during coating of the composition, or the substrate itself and the adjacent layer in the product, for example, the adhesion of the vapor deposition layer It is not preferable from the viewpoint of inhibiting the properties and causing film breakage or the like during transfer (film strength becomes too weak).
When the ratio of the release agent is 0.01% by mass or more, the effect of improving the peelability between the mold and the curable composition layer for photo nanoimprint lithography is sufficient. On the other hand, if the ratio of the release agent is within the above range of 10% by mass, the problem of surface roughness of the coating film due to repelling during coating of the composition is unlikely to occur, and the substrate itself and adjacent layers in the product, for example, It is preferable in that it hardly inhibits the adhesion of the deposited layer and hardly causes film breakage or the like (film strength becomes too weak) during transfer.

  In the composition of the present invention, an organic metal coupling agent may be blended in order to improve the heat resistance, strength, or adhesion to the metal vapor deposition layer of the surface structure having a fine concavo-convex pattern. In addition, the organometallic coupling agent is effective because it has an effect of promoting the thermosetting reaction. As the organometallic coupling agent, for example, various coupling agents such as a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a tin coupling agent can be used.

  Examples of the silane coupling agent used in the composition of the present invention include vinyl silanes such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane; γ-methacryloxypropyltrimethoxysilane An epoxy silane such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane; N-β- (aminoethyl)- aminosilanes such as γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; and Other sila Examples of the coupling agent include γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, and γ-chloropropylmethyldiethoxysilane.

  Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) Titanate, tetra (2,2-diallyloxymethyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl Titanate, isopropyl isostearoyl diacryl titanate, isop Pirutori (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- aminoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate.

  Examples of the zirconium coupling agent include tetra-n-propoxyzirconium, tetra-butoxyzirconium, zirconium tetraacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethyl acetoacetate, zirconium butoxyacetylacetonate bis. (Ethyl acetoacetate) and the like.

  Examples of the aluminum coupling agent include aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, ethylacetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), alkylacetate Acetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethyl acetoacetate), aluminum tris (acetylacetoacetate) and the like can be mentioned.

  The said organometallic coupling agent can be arbitrarily mix | blended in the ratio of 0.001-10 mass% in solid content whole quantity of the composition of this invention. By setting the ratio of the organometallic coupling agent to 0.001% by mass or more, there is a tendency to be more effective in improving heat resistance, strength, and adhesion with the vapor deposition layer. On the other hand, when the ratio of the organometallic coupling agent is 10% by mass or less, the stability and film forming property of the composition of the present invention tend to be suppressed, which is preferable.

  The composition of the present invention may contain a polymerization inhibitor in order to improve storage stability and the like. Examples of the polymerization inhibitor include phenols such as hydroquinone, tert-butylhydroquinone, catechol, and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; coppers and the like. The polymerization inhibitor is preferably blended arbitrarily in a proportion of 0.001 to 10% by mass with respect to the total amount of the composition of the present invention.

  Commercially available UV absorbers include Tinuvin P, 234, 320, 326, 327, 328, 213 (above, manufactured by Ciba Geigy Co., Ltd.), Sumisorb 110, 130, 140, 220, 250, 300, 320, 340, 350. 400 (above, manufactured by Sumitomo Chemical Co., Ltd.). It is preferable to mix | blend an ultraviolet absorber arbitrarily in the ratio of 0.01-10 mass% with respect to the whole quantity of the curable composition for optical nanoimprint lithography.

  Commercially available light stabilizers include Tinuvin 292, 144, 622LD (above, manufactured by Ciba Geigy Co., Ltd.), Sanol LS-770, 765, 292, 2626, 1114, 744 (above, manufactured by Sankyo Kasei Kogyo Co., Ltd.) Etc. The light stabilizer is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the composition.

  Examples of commercially available anti-aging agents include Antigene W, S, P, 3C, 6C, RD-G, FR, and AW (manufactured by Sumitomo Chemical Co., Ltd.). The anti-aging agent is preferably blended at a ratio of 0.01 to 10% by mass with respect to the total amount of the composition.

  A plasticizer can be added to the composition of the present invention in order to adjust adhesion to the substrate, flexibility of the film, hardness, and the like. Specific examples of preferred plasticizers include, for example, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin, dimethyl adipate, diethyl adipate , Di (n-butyl) adipate, dimethyl suberate, diethyl suberate, di (n-butyl) suberate and the like, and a plasticizer can be optionally added at 30% by mass or less in the composition. Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less. In order to obtain the effect of adding a plasticizer, 0.1% by mass or more is preferable.

  An adhesion promoter may be added to the composition of the present invention in order to adjust adhesion to the substrate. Adhesion promoters include benzimidazoles and polybenzimidazoles, lower hydroxyalkyl-substituted pyridine derivatives, nitrogen-containing heterocyclic compounds, urea or thiourea, organophosphorus compounds, 8-oxyquinoline, 4-hydroxypteridine, 1,10-phenanthroline 2,2'-bipyridine derivatives, benzotriazoles, organophosphorus compounds and phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-ethylethanol Amines and derivatives, benzothiazole derivatives, and the like can be used. The adhesion promoter in the composition is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. The addition of the adhesion promoter is preferably 0.1% by mass or more in order to obtain the effect.

  When hardening the composition of this invention, a thermal-polymerization initiator can also be added as needed. Preferable examples of the thermal polymerization initiator include peroxides and azo compounds. Specific examples include benzoyl peroxide, tert-butyl-peroxybenzoate, azobisisobutyronitrile, and the like.

  The composition of the present invention may contain a photobase generator as necessary for the purpose of adjusting the pattern shape, sensitivity, and the like. For example, 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, bis [[(2-nitrobenzyl) Oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, N- (2-nitro Benzyloxycarbonyl) pyrrolidine, hexaamminecobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6-dimethyl-3,5- Diacetyl-4 Preferred examples include (2′-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2 ′, 4′-dinitrophenyl) -1,4-dihydropyridine, and the like. It is done.

In the composition of the present invention, elastomer particles may be added as optional components for the purpose of improving mechanical strength, flexibility and the like.
The elastomer particles that can be added as an optional component to the composition of the present invention preferably have an average particle size of 10 nm to 700 nm, more preferably 30 to 300 nm. For example, polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, ethylene / propylene copolymer, ethylene / α-olefin copolymer, ethylene / α-olefin / Polyene copolymer, acrylic rubber, butadiene / (meth) acrylic acid ester copolymer, styrene / butadiene block copolymer, styrene / isoprene block copolymer and other elastomer particles. Further, core / shell type particles in which these elastomer particles are coated with a methyl methacrylate polymer, a methyl methacrylate / glycidyl methacrylate copolymer or the like can be used. The elastomer particles may have a crosslinked structure.

  Examples of commercially available elastomer particles include Resin Bond RKB (manufactured by Resinas Kasei Co., Ltd.), Techno MBS-61, MBS-69 (manufactured by Techno Polymer Co., Ltd.), and the like.

  These elastomer particles can be used alone or in combination of two or more. The content of the elastomer component in the composition of the present invention is preferably 1 to 35% by mass, more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass.

  A basic compound may be optionally added to the composition of the present invention for the purpose of suppressing curing shrinkage and improving thermal stability. Examples of the basic compound include amines, nitrogen-containing heterocyclic compounds such as quinoline and quinolidine, basic alkali metal compounds, basic alkaline earth metal compounds, and the like. Among these, amine is preferable from the viewpoint of compatibility with the photopolymerization monomer, for example, octylamine, naphthylamine, xylenediamine, dibenzylamine, diphenylamine, dibutylamine, dioctylamine, dimethylaniline, quinuclidine, tributylamine, Examples include octylamine, tetramethylethylenediamine, tetramethyl-1,6-hexamethylenediamine, hexamethylenetetramine, and triethanolamine.

 A chain transfer agent may be added to the composition of the present invention in order to improve photocurability. Specifically, 4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine-2,4,6 (1H, 3H , 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate).

 The composition of the present invention can be prepared as a solution by mixing each of the above components and then filtering with a filter having a pore size of 0.05 μm to 5.0 μm, for example. Mixing and dissolution of the composition of the present invention is usually performed in the range of 0 ° C to 100 ° C. Filtration may be performed in multiple stages or repeated many times. Moreover, the filtered liquid can be refiltered. Materials used for filtration can be polyethylene resin, polypropylene resin, fluorine resin, nylon resin, etc., but are not particularly limited.

 When the composition of the present invention is used for a permanent film (resist for a structural member) used in a liquid crystal display (LCD) or the like, an ionic impurity of a metal or an organic substance in the resist is used so as not to hinder the operation of the display. It is preferable to avoid mixing as much as possible. In the composition of the present invention, the content of Na and K elements is particularly preferably 1000 ppm or less, and more preferably 100 ppm or less.

Next, the formation method of the pattern (especially fine concavo-convex pattern) using the composition of this invention is demonstrated. In the present invention, it is preferable to provide a light-shielding image (pattern) by the following steps.
(1) A step of providing a photosensitive resin layer using the photosensitive resin composition on a substrate (2) A step of removing the solvent by heat-treating the photosensitive resin layer at 50 to 150 ° C. as necessary (3) A step of pressure-bonding a mold having a concavo-convex surface so that the photosensitive resin layer and the concavo-convex surface are in contact with each other (4) a step of irradiating light through at least the mold having the concavo-convex surface; Step (6) for peeling from the photosensitive resin layer Step for heat-treating the photosensitive resin layer at 160 to 250 ° C. as necessary Hereinafter, these steps will be described in detail.

(1) Step of providing a photosensitive resin layer using a photosensitive resin composition on a substrate In providing a photosensitive resin layer using the composition of the present invention, the coating of the composition is a generally well-known coating method. For example, it can be formed by coating by a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scanning method, or the like. The composition of the present invention may be applied in multiple layers.
The thickness of the layer made of the composition of the present invention varies depending on the application to be used, but is usually 0.05 μm to 30 μm, and 0.3 to 3.0 μm in a black matrix used for an LCD or the like. Is preferred.

 In the light-shielding image forming method using the composition of the present invention, it is necessary to select a light-transmitting material as a mold material (mold material) having an uneven surface. Substrates for applying the composition of the present invention are quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflection film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG, polyester film Polymer substrates such as polycarbonate films and polyimide films, TFT array substrates, plasma display (PDP) electrode plates, glass and transparent plastic substrates, conductive substrates such as ITO and metals, insulating substrates, silicone, silicone nitride, There are no particular restrictions on semiconductor fabrication substrates such as polysilicone, silicone oxide, and amorphous silicone. The shape of the substrate may be a plate shape or a roll shape.

(2) The process of removing the solvent by heat-treating the photosensitive resin layer at 50 to 150 ° C. as necessary In the present invention, when the photosensitive resin composition to be used contains a solvent, the solvent is removed by a drying process. To do. The drying step can be performed at a temperature of 50 to 150 ° C. by a known method, a convection oven, a hot plate, an infrared heater, or the like. Moreover, you may perform drying at 500-10 < ^-6 > Torr under pressure reduction as needed.

(3) Step of pressure-bonding a mold having a concavo-convex surface so that the photosensitive resin layer and the concavo-convex surface are in contact In the present invention, a mold having a concavo-convex surface (mold) is converted into a photosensitive resin layer and a concavo-convex surface (mold pattern). Crimp so that is in contact.
In general, the pressure of the mold is preferably 10 kN or less. It is preferable that the mold pressure be 10 kN or less because the mold and the substrate are less likely to be deformed and the pattern accuracy tends to be improved, and because the pressure is low, the apparatus can be reduced. The mold pressure is preferably selected in a range where the mold transfer uniformity can be ensured within a range in which the residual film of the composition on the mold convex portion is reduced.

  As the mold that can be used in the present invention, a mold having a pattern to be transferred can be widely used. The mold can be formed in a pattern according to the desired processing accuracy by, for example, photolithography or electron beam drawing method, or a replica can be taken from the finished product to be aimed at. Not limited.

 The light-transmitting molding material used in the present invention is not particularly limited as long as it has predetermined strength and durability. Specifically, a light transparent resin such as glass, quartz, PMMA, and polycarbonate resin, a transparent metal vapor-deposited film, a flexible film such as polydimethylsiloxane, a photocured film, and a metal film are exemplified.

  The mold used in the present invention may be a mold that has been subjected to a release treatment in order to improve the releasability between the composition of the present invention and the mold. Those having been treated with a silane coupling agent such as silicone or fluorine, for example, commercially available mold release agents such as those manufactured by Daikin Industries, Optool DSX, Sumitomo 3M, Novec EGC-1720, etc., can also be suitably used.

(4) Step of irradiating light through at least a mold having an uneven surface In the present invention, light irradiation is performed through a mold having at least an uneven surface to cure the composition of the present invention. The light irradiation may be performed in a state where the mold is attached, or may be performed after the mold is peeled off, but in the present invention, it is preferably performed in a state where the mold is adhered. Furthermore, it is preferable for light-shielding image formation that exposure is performed simultaneously or sequentially from both the substrate side and the mold side.
The light for curing the composition of the present invention is not particularly limited, and examples thereof include high energy ionizing radiation, light or radiation having a wavelength in the region of near ultraviolet, far ultraviolet, visible, infrared or the like. As the high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron is industrially most conveniently and economically used. However, radiation such as γ rays, X rays, α rays, neutron rays, proton rays emitted from radioisotopes or nuclear reactors can also be used. Examples of the ultraviolet ray source include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a solar lamp. Examples of radiation include microwaves and EUV. Also, laser light used in semiconductor microfabrication such as LED, semiconductor laser light, or 248 nm KrF excimer laser light or 193 nm ArF excimer laser can be suitably used in the present invention. These lights may be monochromatic light, or may be light having a plurality of different wavelengths (mixed light).

In the present invention, the light irradiation may be sufficiently larger than the irradiation amount necessary for curing. The amount of irradiation necessary for curing is determined by examining the consumption of unsaturated bonds of the curable composition for optical nanoimprint lithography and the tackiness of the cured film.
During exposure is preferably in the range of exposure intensity of ^{1mW / cm 2 ~50mW / cm 2} . By making the exposure time 1 mW / cm ² or more, the exposure time can be shortened so that productivity is improved, and by making the exposure time 50 mW / cm ² or less, deterioration of the properties of the permanent film due to side reactions can be suppressed. It tends to be preferable. The exposure amount is preferably in the range of 5 mJ / cm ^{2 to} 1000 mJ / cm ² . If it is less than 5 mJ / cm ² , the exposure margin becomes narrow, photocuring becomes insufficient, and problems such as adhesion of unreacted substances to the mold tend to occur. On the other hand, if it exceeds 1000 mJ / cm ² , the permanent film may be deteriorated due to decomposition of the composition.
Further, during exposure, in order to prevent radical polymerization from being inhibited by oxygen, an inert gas such as nitrogen or argon may be flowed to control the oxygen concentration to less than 100 mg / L.

In the photoimprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually room temperature, but light irradiation may be performed while heating in order to increase the reactivity. As a pre-stage of light irradiation, if it is in a vacuum state, it is effective in preventing bubble mixing, suppressing reactivity decrease due to oxygen mixing, and improving the adhesion between the mold and the curable composition for optical nanoimprint lithography. Light irradiation may be performed. In the present invention, the preferred degree of vacuum is in the range of 10 ⁻¹ Pa to normal pressure.

(5) Process of peeling the type | mold which has an uneven | corrugated surface from the photosensitive resin layer In this invention, the type | mold which has an uneven | corrugated surface is peeled from the photosensitive resin layer. Peeling is performed after light irradiation.

(6) The process of heat-processing the said photosensitive resin layer at 160-250 degreeC as needed The composition of this invention may be heat-processed at 160-250 degreeC as needed. By adopting such means, curing can be further promoted. The heat treatment may be performed before the peeling or after the peeling.
As heat for hardening, 160-250 degreeC is preferable and 200-250 degreeC is more preferable. Moreover, as time to provide heat, 5 to 60 minutes are preferable and 15 to 45 minutes are more preferable. As a heat treatment method, a known method, a method using a convection oven, a hot plate, an infrared heater or the like is used. Moreover, you may carry out under reduced pressure as needed, for example, 500-10 < ^-6 > Torr.

 Permanent films (resist for structural members) used for liquid crystal displays (LCDs) are bottled in containers such as gallon bottles and coated bottles after manufacture, and are transported and stored. In this case, the purpose is to prevent deterioration. The inside of the container may be replaced with inert nitrogen, argon, or the like. Further, at the time of transportation and storage, the room temperature may be used, but the temperature may be controlled in the range of −20 ° C. to 0 ° C. in order to prevent the permanent film from being altered. Of course, it is necessary to shield from light so that the reaction does not proceed.

 The composition of the present invention can also be applied as an etching resist for semiconductor integrated circuits, recording materials, flat panel displays and the like.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

 Compositions of Examples and Comparative Examples were prepared by blending a black pigment dispersion, a photopolymerization initiator, a surfactant, a polymerization inhibitor, and a solvent as necessary so as to have the compositions shown in Tables 1 to 4. .

<Preparation of black pigment dispersion>
In Tables 1 to 4, the pigment dispersion containing no solvent was previously dispersed in propylene glycol monomethyl ether acetate by adding a pigment or a pigment dispersion and a dispersion aid of the following compound 1. Dispersion was performed using an Eiger mill (Eiger mill M-50 type, media: diameter 0.65 mm, zirconia beads 130 g, manufactured by Eiger Japan Co., Ltd.) for 6 hours). Thereafter, various polymerizable unsaturated monomers were added, and propylene glycol monomethyl ether acetate was removed at 60 ° C. under reduced pressure. When a solvent was included, it was used without being subjected to a heat-reduced pressure treatment after dispersion.

<Preparation of dispersion A1>
Dispersion A1 (a dispersion of particles having a prepared silver-tin alloy part) was prepared by the following method.
In 1000 ml of pure water, 23.1 g of silver (I) acetate, 65.1 g of tin (II) acetate, 54 g of gluconic acid, 45 g of sodium pyrophosphate, 2 g of polyethylene glycol (molecular weight 3,000), and PVP-K30 (ISP A solution 1 was obtained by dissolving 5 g of a polyvinyl pyrrolidone polymer manufactured by Japan Co., Ltd.
Separately, 46.1 g of hydroxyacetone was dissolved in 500 ml of pure water to obtain a solution 2.
While the solution 1 was vigorously stirred while being kept at 25 ° C., the solution 2 was added thereto over 2 minutes, and the stirring was gently continued for 6 hours. The mixed liquid turned black, and metal particles having a silver-tin alloy part (hereinafter, sometimes referred to as “silver-tin alloy part-containing particles”) were obtained. Next, this mixed solution was centrifuged to precipitate silver-tin alloy part-containing particles. Centrifugation was carried out for 30 minutes at a rotational speed of 2,000 rpm using a desktop centrifuge H-103n (manufactured by Kokusan Co., Ltd.) in a small volume of 150 ml. The supernatant was discarded and the total liquid volume was 150 ml. To this was added 1350 ml of pure water, and the mixture was stirred for 15 minutes to disperse the silver-tin alloy part-containing particles again. This re-dispersed liquid was centrifuged in the same manner as described above to precipitate silver-tin alloy part-containing particles. This operation (pure water addition and centrifugation) was repeated twice to wash the silver-tin alloy part-containing particles.

The silver-tin alloy part-containing particles obtained above were again used as a dispersion, and the dispersion was further centrifuged to precipitate the silver-tin alloy part-containing particles again. Centrifugation was performed under the same conditions as described above. After centrifugation, the supernatant was discarded as described above to make the total liquid volume 150 ml, and 850 ml of pure water and 500 ml of normal propyl alcohol were added thereto, and the mixture was further stirred for 15 minutes to disperse the silver-tin alloy part-containing particles again. .
Centrifugation was performed again in the same manner as above to precipitate the silver-tin alloy part-containing particles, and then the supernatant was discarded to make the liquid volume 150 ml, and 150 ml of pure water and 1200 ml of normal propyl alcohol were added thereto. The mixture was further stirred for 15 minutes to disperse the silver-tin alloy part-containing particles again. Again, centrifugation was performed. The centrifugation conditions at this time are the same as described above except that the time is extended to 90 minutes. Thereafter, the supernatant was discarded to make the total liquid volume 70 ml, and 30 ml of normal propyl alcohol was added thereto. This was dispersed for 6 hours using an Eiger mill (Eiger mill M-50 type, media: 130 g of zirconia beads having a diameter of 0.65 mm, manufactured by Eiger Japan Co., Ltd.), and silver-tin alloy part-containing particles (silver-tin particle concentration 25% by mass) A dispersion (dispersion A1) of PVP-K30 remaining amount 1.0% by mass was prepared.

The silver-tin alloy part-containing particles obtained above were analyzed using HD-2300 manufactured by Hitachi, Ltd. and EDS (energy dispersive X-ray analyzer) manufactured by Noran. It was confirmed by X-ray scattering that the composite was composed of (2θ = 39.5 °) and Sn metal (2θ = 30.5 °). Here, the numbers in parentheses are the scattering angles of the respective (III) planes. The number average particle size of the silver-tin alloy part-containing particles in this dispersion A1 was about 40 nm.
The number average particle size was measured as follows using a photograph obtained with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd., magnification: 100,000 times, acceleration voltage: 200 kV).
100 particles were selected, the diameter of a circle having the same area as each particle image was defined as the particle size, and the average value of the particle sizes of 100 particles was defined as the number average particle size.

<Preparation of dispersion B1>
Dispersion B1 (silver fine particle dispersion) was prepared by the following procedure.
3.0 g of the following compound T-4 was added to 2.5 L of an aqueous solution adjusted to pH 12.0 using a 1 mol / L sodium hydroxide aqueous solution, and stirred at 45 ° C. for 30 minutes until it was completely dissolved. .

The temperature of this solution was controlled at 45 ° C., 700 mL of an aqueous solution containing 8.5 g of ascorbic acid, 700 mL of an aqueous solution containing 5 g of hydroquinone and 1.5 g of sodium sulfite, and 500 mL of an aqueous solution containing 30 g of silver nitrate were added simultaneously. A silver nanoparticle-containing solution was prepared.
The obtained silver nanoparticles were connected particles in which spherical particles having an arithmetic average particle size: 16.1 nm and an average aspect ratio of 2.2 were randomly connected. Centrifugation treatment (12,000 rpm, 30 min) was performed on the prepared silver nanoparticle-containing liquid, and the supernatant was discarded, followed by washing with water to which distilled water was added three times. Acetone was added to the obtained silver nanoparticle-containing solution, and the mixture was stirred with a stirrer and then centrifuged (12000 rpm, 30 min). Thereafter, the supernatant was removed, cyclohexanone and propylene glycol monomethyl ether acetate were added, and 20 kHz ultrasonic waves were irradiated for 5 minutes using a “Sonifer II type” ultrasonic homogenizer manufactured by Branson. Thereafter, ultrasonic waves at 40 kHz were irradiated for 10 minutes with a model (Model) 200bdc-h 40, 0.8 type ultrasonic homogenizer manufactured by Branson. The silver nanoparticle dispersion thus obtained had the same shape and color as after the formation of the particles (silver particle concentration 25% by mass). Moreover, the density | concentration in the solvent dispersion of the high molecular compound T-4 obtained from loss on drying using TG-DTA (Seiko Co., Ltd.) was 1.1 mass%. This silver nanoparticle dispersion was designated as metal-containing dispersion B1.

<Production of cured product>
Each composition was applied on a glass substrate by spin coating so that the coating film thickness shown in Table 5 was obtained after curing. In Examples 12 to 14, in order to remove the solvent, the coating was dried at 100 ° C. for 2 minutes. The spin-coated coated base film was set in a nanoimprint apparatus using an ORC high pressure mercury lamp (lamp power: 2000 mW / cm ² ) as a light source, the mold pressure was 0.8 kN, the degree of vacuum during exposure was 10 Torr, and the recess diameter was 20 μm. And a polydimethylsiloxane (Toray Industries, Inc.) having a pattern in which cylindrical recesses having a recess depth of 3.5 μm are two-dimensionally arranged at a pitch of 900 μm, a line width of 20 μm, a pitch of 300 μm, a depth of 1 μm, and a cross-sectionally ridged pattern. Exposed under the condition of 240 mJ / cm ² from the surface of the mold made from Dow Corning, made of SILPOT184 cured at 80 ° C. for 60 minutes, and after exposure, the mold was released to obtain a resist pattern. The obtained resist pattern was completely cured by heating in an oven at 230 ° C. for 30 minutes.
The following evaluation was performed. The results are shown in Table 5.

<Viscosity measurement>
The viscosity of the composition before curing in a substantially solvent-free state was measured at 25 ± 0.2 ° C. using a RE-80L rotational viscometer manufactured by Toki Sangyo Co., Ltd.
The rotational speed during the measurement is 100 rpm for 0.5 mPa · s to less than 5 mPa · s, 50 rpm for 5 mPa · s to less than 10 mPa · s, 20 rpm for less than 30 mPa · s for 10 mPa · s, and 60 mPa · s for 30 mPa · s to 60 mPa · s Less than 10 rpm, 60 mPa · s or more and less than 120 mPa · s was 5 rpm, and 120 mPa · s or more was 1 rpm or 0.5 rpm, respectively.

<Film thickness measurement>
The film thickness of the film was measured using a contact type surface roughness meter P-10 (manufactured by KLA Tencor).

<Evaluation of optical density>
The chromaticity of the image obtained from the above was measured at a pinhole diameter of 5 μm using a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100), calculated as a result of the F10 light source field of view of 2 degrees, and the logarithm of the Y value (-Log (Y / 100)) was calculated.

<Observation of pattern accuracy>
The pattern shape after the transfer was observed with a scanning electron microscope or an optical microscope, and the pattern shape was evaluated as follows.
A: Almost the same as the pattern of the original plate that is the basis of the pattern shape of the mold. B: There is a portion that is partially different from the pattern shape of the original plate that is the basis of the pattern shape of the mold (the range of the original pattern is less than 10%). C: There is a part (a range of 10% or more and less than 20% of the pattern of the original plate) that is partly different from the original pattern shape of the mold pattern shape. D: Clearly different from the original pattern of the mold pattern shape. Or the film thickness of the pattern differs from the original pattern by 20% or more.

<Evaluation of peelability>
Using the same sample used for pattern accuracy observation, observe whether the composition component is attached to the mold used for pattern formation with a scanning electron microscope or optical microscope, and evaluate the peelability as follows: did.
A: Adhesion of the curable composition to the mold was not recognized at all.
B: Slight adhesion of the curable composition was observed on the mold.
C: Adhesion of the curable composition of the mold was clearly recognized.

<Evaluation of hardness>
Each composition was spin-coated on a glass substrate so that the film thickness was in the range of 3 to 10 μm, the mold was not pressure-bonded, and was exposed at an exposure amount of 240 mJ / cm ² in a nitrogen atmosphere. The film cured by heating for 30 minutes was measured for dynamic hardness using a micro hardness tester manufactured by Shimadzu Corporation. The measurement conditions were a triangular pyramid indenter, a load of 1 mN, and a holding time of 1 second.
Dynamic hardness A: 32 or more B: 28 or more, less than 32 C: 25 or more, less than 28 D: less than 25

<Evaluation of chip defects>
The base plate with the black matrix obtained in the above examples and comparative examples was observed on the entire surface with an optical microscope (differential interference mode, 200 times), and generation of a chip (a portion where a portion lacking 20% or more of the fine line width was present) was generated. The number was observed. The number of chippings was evaluated according to the following criteria.
◎ ... less than 20 pieces / m ² ○ ... 20 pieces / m ² or more and less than 40 pieces / m ² ,
Δ: 40 / m ² or more and less than 80 / m ² ,
× ... 80 / m ² or more and less than 120 / m ² ×× ... 120 / m ² or more

<Solvent resistance test>
Each composition was spin-coated on a glass substrate so as to have a film thickness of 3.0 μm, the mold was not pressure-bonded, and was exposed at an exposure amount of 240 mJ / cm ² in a nitrogen atmosphere, and then heated in an oven at 230 ° C. for 30 minutes. The cured film was immersed in an N-methylpyrrolidone solvent at 25 ° C. for 30 minutes, and changes in the cured film before and after immersion were evaluated as follows.
A: Film thickness change 2% or less B: Film thickness change 2% to 10% or less C: Surface roughness occurs

<Production of liquid crystal display device>
Using the materials of Examples and Comparative Examples, ITO (Indium Tin Oxide) transparent electrodes were further formed by sputtering on R pixels, G pixels, B pixels, and a black matrix of a color filter substrate prepared in advance. Next, according to the method described in <Preparation of Cured Product>, spacers and rib bodies were formed so that a columnar pattern was formed on BM and a bowl-shaped pattern was formed on each RGB pixel.
Separately, a glass substrate was prepared as a counter substrate, patterned on the transparent electrode of the color filter substrate and the counter substrate for the PVA mode, and an alignment film made of polyimide was further provided thereon.
After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided around the pixel group of the color filter, and a PVA mode liquid crystal is dropped and attached to the counter substrate. After bonding, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealant. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained. Next, FR1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a red (R) LED, DG1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a green (G) LED, and DB1112H (as a blue (B) LED. A side-light type backlight was constructed using a chip-type LED manufactured by Stanley Electric Co., Ltd. and placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.

<Display unevenness>
For each liquid crystal display device, the gray display when a gray test signal was input was visually observed, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.
<Evaluation criteria 1>
A: No unevenness at all (very good)
B: Slight unevenness is observed on the edge of the glass substrate, but there is no problem in the display (good)
C: Slight unevenness on the display, but practical level (normal)
D: Display is uneven (somewhat bad)
E: Strong unevenness in display (very bad)

<Monomer having two or more kinds of curable functional groups having different reactivity in the same molecule, wherein at least one of the curable functional groups is an α, β-unsaturated ester group>
Q-1: Compound (M-12) Dicyclopentenyl acrylate (FA-511AS: manufactured by Hitachi Chemical Co., Ltd.)
Q-2: Compound (M-13) Dicyclopentenyloxyethyl acrylate (FA-512AS: manufactured by Hitachi Chemical Co., Ltd.)
Q-3: Compound (M-32) 3-Cyclohexenylmethyl acrylate Q-4: Compound (M-22) Acryloyloxyethyl isocyanate (Karenz AOI: Showa Denko)
Q-5: Compound (M-24) (3-Ethyl-3-oxetanyl) methyl acrylate (Biscoat OXE10: manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Q-6: Compound (M-29) 3-trimethoxysilylpropyl acrylate (KBM-5103: manufactured by Shin-Etsu Chemical Co., Ltd.)
Q-7: Compound (M-30) Allyl acrylate (Aldrich Reagent)

<Other monofunctional monomers>
R-1: benzyl acrylate (Biscoat # 160: manufactured by Osaka Organic Chemical Co., Ltd.)

<Other bifunctional monomers>
S-01: Neopentyl glycol diacrylate <other trifunctional or higher monomer>
S-10: Trimethylolpropane triacrylate (Aronix M-309: manufactured by Toagosei Co., Ltd.)

<Photopolymerization initiator>
P-1: 2,4,6-trimethylbenzoyl-ethoxyphenyl-phosphine oxide (Lucirin TPO-L: manufactured by BASF)

<Surfactant>
W-1: Fluorosurfactant (manufactured by Tochem Products: Fluorosurfactant)
W-2: Silicone-based surfactant (Dainippon Ink & Chemicals, Inc .: Megafuck Paintad 31)

表２中、ＭＦＧＡＣは、プロピレングリコールモノメチルエーテルアセテートを表す。

In Table 2, MFGAC represents propylene glycol monomethyl ether acetate.

表２中、ＭＦＧＡＣは、プロピレングリコールモノメチルエーテルアセテートを表す。

In Table 2, MFGAC represents propylene glycol monomethyl ether acetate.

In Table 5, the film thickness indicates the film thickness after drying (unit: μm).
The composition of the present invention was excellent in all of pattern accuracy, peelability, hardness, defects, solvent resistance, and display unevenness in a liquid crystal display device.

When the composition of the present invention is used as a black matrix in an imprint system, it has become possible to provide a black matrix that is comprehensively excellent in mechanical strength, peelability, pattern shape, coatability, and solvent resistance. . Moreover, when used as a black matrix, it is possible to provide a composition having excellent residual film properties, mechanical properties such as scratch resistance, and solvent resistance.
Furthermore, according to the present invention, it is possible to reduce the addition amount of the binder to the photosensitive resin composition for patterning, and to make addition unnecessary. As a result, an unprecedented high pigment concentration can be realized. Further, since the state before curing is in a liquid state, the substrate is well wetted and higher adhesion can be ensured. In particular, in the conventional photosensitive resin composition, since the viscosity of the composition after removing the solvent exceeds 1000 mPa · s, sufficient image formation could not be performed by the imprint method. However, the viscosity of 3 to 50 mPa · s of the present invention was not achieved. Thus, a desired pattern can be formed by the imprint method.
Furthermore, even in a high optical density, it is difficult to make the pattern shape rectangular due to the optical density in the conventional photolithography process, but there is an advantage that it can be designed freely with the shape of the mold to be used.

Claims (11)

In the state which does not contain a solvent substantially after drying, it contains at least 10% by mass of a colorant and a polymerizable monomer, and has a viscosity of 3 to 50 mPa.s. A photosensitive resin composition characterized by being s. The photosensitive resin composition according to claim 1, wherein the colorant is a black colorant. The photosensitive resin composition according to claim 1, wherein at least one of the polymerizable monomers is represented by the following general formula (1).

(In General Formula (1), R ¹ represents a hydrogen atom or a hydroxymethyl group, X represents an organic group, m represents an integer of 1 to 3, and n represents an integer of 1 to 4. Y Is represented by a curable functional group having a carbon-carbon unsaturated bond, a curable functional group having a carbon-nitrogen unsaturated bond, a curable functional group having a cyclic group containing an oxygen atom, or the following general formula (2): Represents a group.

(R ² represents an alkyl group or an aryl group, respectively.) At least one of Y in the general formula (1) is a vinyl ether group, an allyl ether group, a cyclohexenyl group, a cyclopentenyl group, a dicyclopentenyl group, a styryl group, a methacryloyloxy group, a methacryloylamide group, an acrylamide group, or a vinylsilane group. The photosensitive resin composition according to claim 3, which is selected from the group consisting of N-vinyl heterocyclic group and maleimide group. The photosensitive resin composition of Claim 3 whose at least 1 of Y in General formula (1) is an isocyanate group or a nitrile group. The photosensitive resin composition according to claim 3, wherein at least one of Y in the general formula (1) is selected from the group consisting of an oxetane ring, an oxirane ring, and an ethylene carbonate group. The photosensitive resin composition of any one of Claims 1-6 which exists in the range whose surface tension of the said photosensitive resin composition is 18-30 mN / m. Hardened | cured material formed by hardening the photosensitive resin composition of any one of Claims 1-7. A method for forming a light-shielding image, comprising using the photosensitive resin composition according to claim 1, and including the following steps.
(1) A step of providing a photosensitive resin layer using the photosensitive resin composition on a substrate (2) A step of removing the solvent by heat-treating the photosensitive resin layer at 50 to 150 ° C. as necessary (3) A step of pressure-bonding a mold having a concavo-convex surface so that the photosensitive resin layer and the concavo-convex surface are in contact with each other (4) a step of irradiating light through at least the mold having the concavo-convex surface; Step (6) for peeling from the photosensitive resin layer: Step for heat-treating the photosensitive resin layer at 160 to 250 ° C. as necessary A cured product formed by the method for forming a light-shielding image according to claim 9. The cured product according to claim 8 or 10, wherein the cured product is a black matrix for liquid crystal display.