JP4795086B2 - Photosensitive composition and photosensitive transfer material using the same, light shielding film for display device and method for producing the same, black matrix, substrate with light shielding film, and display device - Google Patents

Description

  The present invention relates to a photosensitive composition suitable for production of a color filter constituting a display device, a photosensitive transfer material using the same, a light shielding film for a display device and a method for producing the same, a black matrix, a substrate with a light shielding film, and a display. Relates to the device.

    In recent years, in order to improve the contrast of a display image, a black matrix has been required to have a high optical density of 4.0 or more. On the other hand, since the surface smoothness of the color filter is impaired when the black matrix is thick, it is required to be formed into a thin film.

  A metal thin film has been used for manufacturing a black matrix for a display device having high light shielding properties. This is after applying a photoresist on a metal thin film such as chromium formed by vapor deposition or sputtering, and then exposing and developing the photoresist using a photomask having a pattern for a light shielding film for a display device. This is due to a method in which the exposed metal thin film is etched and finally the photoresist remaining on the metal thin film is peeled and removed (see, for example, Non-Patent Document 1).

  Since this method uses a metal thin film, a high light-shielding effect can be obtained even if the film thickness is small, but there is a problem that a vacuum film forming process or an etching process such as a vapor deposition method or a sputtering method is required and the cost is increased. In addition, since it is a metal film, the reflectance is extremely high, and there is a problem that display contrast is lowered under strong external light. Corresponding to these, a method using a low-reflective chromium film (such as one composed of two layers of metal chromium and chromium oxide) has been proposed, but it cannot be denied that the cost is further increased. Furthermore, since the waste liquid containing metal ions is discharged in the etching process, there is a great disadvantage that the environmental load is large. In particular, chromium that is most frequently used is harmful and has a very large environmental impact.

  On the other hand, there is a technique using carbon black as one of techniques for obtaining a black matrix with a small environmental load (see, for example, Patent Document 1). In this method, a photosensitive resin composition containing carbon black is applied to a substrate, dried, and exposed and developed to form a black matrix.

  However, since carbon black has a low optical density per unit coating amount, it tends to have a large film thickness in order to ensure a high light-shielding property and optical density. For example, an optical density 4.0 equivalent to the above metal film is used. If it is going to ensure, film thickness will be 1.2-1.5 micrometers. Therefore, when red, blue, and green pixels are formed after the black matrix is formed, there is a drawback that the surface of the color filter becomes unsmooth due to the step of the pixel edge portion and the display quality is deteriorated.

  In addition to the above, as a method for obtaining a black matrix having a small environmental load and a high optical density, a method using metal fine particles instead of carbon black is known (see, for example, Patent Documents 2 to 3). According to this method, it is said that a black matrix having a small optical load and a high optical density can be obtained.

In addition, inventions relating to color filters using metal particles, oxime derivatives, and phosphine oxides are disclosed (see, for example, Patent Documents 4 to 7). Furthermore, an invention relating to a black matrix using 4-diethylaminoacetophenone as a hydrogen donor and a metal is disclosed (for example, see Patent Document 8 or 9).
JP-A-62-9301 JP 2004-240039 A JP 2005-17322 A JP 2006-18221 A JP 2006-18228 A JP 2006-18242 A JP 2006-23715 A JP 2004-219696 A JP 2005-189720 A “Color TFT LCD” p. 218-p. 220, issued by Kyoritsu Publishing Co., Ltd. (April 10, 1997)

However, although the metal fine particles are useful in that the black matrix is surely configured to be a thin film having a high optical density, the coating solution containing the metal fine particles has poor stability over time and has problems such as aggregation. There is also a problem that the sensitivity deteriorates with time.
The present invention has been made in view of the above problems, and a photosensitive composition having good sensitivity as a photosensitive material over a long period of time without causing aggregation of metal fine particles even when stored for a long time, and the use thereof. It is an object of the present invention to provide a photosensitive transfer material, a light-shielding film for a display device, a manufacturing method thereof, a black matrix, a substrate with a light-shielding film, and a display device.

That is, the present invention
<1> at least, (A) and particles containing a silver-tin alloy, and at least one photopolymerization initiator selected from the group consisting of (B) A sill phosphine oxide and oxime esters, (C) a resin and A photosensitive composition comprising at least one of the precursors.

  <2> The photosensitive composition according to <1>, further comprising (D) a photopolymerization initiation assistant.

<4> The photosensitive composition according to <1> or <2>, wherein the (A) metal particles or metal-containing particles have a number average particle diameter of 0.1 μm or less.

<5> A photosensitive transfer material having a photosensitive composition layer using the photosensitive composition according to any one of <1> , <2> and <4> on a temporary support.

<6> A method for forming a light-shielding film for a display device, comprising at least a step of applying the photosensitive composition according to any one of <1> , <2>, and <4> onto a substrate.

  <7> A method for forming a light-shielding film for a display device, comprising at least a step of transferring the photosensitive composition layer of the photosensitive transfer material according to <5> onto a substrate.

<8> A light-shielding film for a display device, which is formed using the photosensitive composition according to any one of <1> , <2>, and <4>.

  <9> A black matrix formed by the light shielding film for display device according to <8>.

  <10> A substrate with a light-shielding film, comprising: a substrate; and the light-shielding film for a display device according to <8> provided on the substrate.

  <11> The substrate with a light-shielding film according to <10>, which is used for producing a color filter.

  <12> A display device comprising the substrate with a light-shielding film according to <10> or <11>.

  According to the present invention, even when stored for a long time, the aggregation of metal fine particles does not occur, the photosensitive composition having good sensitivity as a photosensitive material over a long period of time, a photosensitive transfer material using the same, and a display device Provided are a light shielding film and a manufacturing method thereof, a black matrix, a substrate with a light shielding film, and a display device.

  Hereinafter, the photosensitive composition of the present invention, a photosensitive transfer material using the same, a light shielding film for a display device and a method for producing the same, a black matrix, a substrate with a light shielding film, and a display device will be described in detail.

<Photosensitive composition>
The photosensitive composition of the present invention has at least one photopolymerization initiation selected from the group consisting of (A) metal particles or metal-containing particles and (B) aminoacetophenone, acylphosphine oxide, and oxime ester. And (C) at least one of a resin and a precursor thereof. The photosensitive composition of the present invention may further contain (D) a photopolymerization initiation assistant.

  Conventional photosensitive compositions containing metals, particularly silver-tin alloy particles, have low storage stability as liquids (aggregation occurs) and low sensitivity as photosensitive materials. As a result of intensive studies, the present inventors have found that the problem of low storage stability and sensitivity can be solved by using a specific photopolymerization initiator.

The components (A) to (D) and (E) and other components that may be included in the photosensitive composition of the present invention are described below.
(A) Metal Particles or Metal-Containing Particles The photosensitive composition of the present invention contains metal particles or metal-containing particles (hereinafter sometimes referred to as “metal fine particles according to the present invention”).
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 used in combination of two or more metals, and may be used as an alloy. Moreover, the composite particle of a metal and a metal compound may be sufficient.

<Metal particles>
As a metal particle, what is formed from a metal or a metal and a metal compound is preferable, and what is formed from a metal is especially preferable.
In particular, it is 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 included as a main component. 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 4th period, the 5th period, or the 6th period, and are of Group 2, Group 10, Group 11, Group 12, or Group 14. Metal particles are more preferred.

  Preferred examples of the metal particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, calcium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, The at least 1 sort (s) chosen from antimony, lead, and these alloys can be mentioned. 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 is preferable (as 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 particles>
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 particle>
Composite particles are particles 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 according to 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 paragraph numbers [0024] to [0027] of JP-A-2006-18210. And core / shell fine particles described in the above.

  At least one of the metal-based fine particles according to the present invention is preferably a particle having a silver-tin alloy part. 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 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 the black density is not impaired and high temperature (for example, 200 degrees or more) Heat treatment can be performed, and a high light-shielding property can be secured stably. For example, it is suitable for a color filter light-shielding film (so-called black matrix) that requires a high degree of light-shielding properties 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) with a silver (Ag) ratio of 30 to 80 mol%. 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, and an extra fine particle forming step after compounding (for example, alloying) is required, it is preferable to use the particle reduction method. . That is, the Ag compound and the Sn compound are mixed and reduced, and the metal Ag and the metal Sn are simultaneously precipitated at a position close to each other, thereby achieving composite (for example, alloying) and micronization at the same time. It is. 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 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 according to the present invention can be commercially available, or can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like.
For example, rod-shaped silver fine particles are reduced with relatively weak reducing power such as ascorbic acid in the presence of a surfactant such as CTAB (cetyltrimethylammonium bromide) after adding silver salt after using spherical silver fine particles as seed particles. By using the agent, a silver bar or a wire can be 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 is 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, 14316-143.
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 according to the present invention can be obtained by combining various types of particles in order to approximate an achromatic color. By changing the particles from a spherical shape or a cubic shape to a flat plate shape (hexagonal shape, triangular shape) or a rod shape, a higher transmission density can be obtained, and according to this, 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 diameter is preferably 1.2 or more and less than 50. Here, the particle diameter 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 diameter are found, and D ¹⁰ is the particle diameter close to the average particle diameter. 10% is the particle diameter found. From the viewpoint of color tone, the particle size distribution width is preferably 2 or more and 30 or less, more preferably 4 or more and 25 or less. 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, and normal distribution approximating the particle size distribution, the particle diameter by the number of close to the average particle diameter of the particles becomes 90% of the range as D ^90, the particle diameter in the range a few 10% from the average particle size with D ^10, it is possible to calculate the D ⁹⁰ / D ^10.

《Triaxial diameter》
The metal-based fine particles according to the present invention are regarded 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 fine particles, the long 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). Most preferred. 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 times to 100 times and more preferably 1.3 times to 50 times the width b. Is more preferably 1.4 times or more and 20 times or less. 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, the metal particles or metal-containing particles are preferably metal particles or metal-containing metal compound particles, more preferably silver particles or silver-containing silver compound particles, and particles having a silver-tin alloy part. Most preferred.

  In the present invention, the number average particle diameter of the metal particles or metal-containing particles is preferably 0.1 μm or less, more preferably 0.08 μm or less, and particularly preferably 0.05 μm or less. When the number average particle diameter of the particles is 0.1 μm or less, there is an advantage that the surface smoothness is good and the failure due to coarse particles is reduced.

--Dispersion of metallic fine particles according to the present invention--
The metal-based fine particles in the present invention are preferably present in a stable dispersed state, for example, more preferably in a colloidal state. In the colloidal state, for example, it is preferable that the metal fine particles are substantially dispersed in the fine particle state.

  Examples of the dispersant for dispersion and the additive that may be added to the composition of the present invention include the dispersants and additives described in paragraphs [0027] to [0031] of JP-A-2005-17322. However, it is mentioned as a suitable thing also in this invention.

  The content of the metal-based fine particles (and pigment if necessary) in the photosensitive composition of the present invention is such that the metal-based fine particles (and pigment if necessary) during post-baking, for example, during the production of a color filter. In consideration of preventing fusion, it is preferable to adjust so as to be about 10 to 90% by mass, preferably 10 to 80% by mass with respect to the mass of the formed light shielding layer. In addition, the content of the metal-based fine particles (and the pigment as necessary) is preferably determined in consideration of the optical density variation due to the average particle diameter.

(B) At least one photopolymerization initiator selected from the group consisting of aminoacetophenone, acylphosphine oxide, and oxime ester The photopolymerization initiator is selected from the group consisting of aminoacetophenone, acylphosphine oxide, and oxime ester. It is essential to use at least one photoinitiator selected.

Specific examples of the aminoacetophenone-based initiator include IRGACURE (Irg) 369, IRGACURE (Irg) 379, IRGACURE (Irg) 907 and the like (all manufactured by Ciba Specialty Chemicals Co., Ltd.).
Specific examples of the acylphosphine oxide-based initiator include DAROCUR TPO and Irgacure (Irg) 819 (all manufactured by Ciba Specialty Chemicals Co., Ltd.).
Specific examples of the oxime ester-based initiator include IRGACURE (Irg) OXE01, CGI242, etc. (all manufactured by Ciba Specialty Chemicals Co., Ltd.).
The structure of the above initiator is shown below.

  Two or more kinds of the above photopolymerization initiators may be mixed and used in addition to one kind alone. Moreover, 0.5-20 mass% is common and, as for content of the photoinitiator with respect to the total solid of a photosensitive composition, 1-15 mass% is preferable. When the content is within the above range, a decrease in photosensitivity and image intensity can be prevented, and the performance can be sufficiently improved.

(C) Resin and its precursor The photosensitive composition of this invention is comprised using at least 1 type of resin and its precursor. Here, the resin is a polymer component as a binder, and the precursor of the resin is a component that constitutes the resin when polymerized, and includes so-called monomers and oligomer components. The photosensitive composition includes those that can be developed with an alkaline aqueous solution and those that can be developed with an organic solvent. From the viewpoint of safety and the cost of the developer, those that can be developed with an aqueous alkaline solution are preferable, and from this point, it is preferable to use an alkali-soluble resin as the polymer that becomes the resin.

<Resin>
Examples of the resin include polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer described in JP-A-59-53836 and JP-A-59-71048 And partially esterified maleic acid copolymers. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group can also be preferably used. In particular, a copolymer of benzyl (meth) acrylate and (meth) acrylic acid or a multicomponent copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers described in US Pat. No. 4,139,391 is also available. Can be mentioned.

The resin is preferably selected to have an acid value in the range of 30 to 400 mg KOH / g and a weight average molecular weight in the range of 1,000 to 300,000.
In addition to the above, for the purpose of improving various performances, for example, the strength of the cured film, an alcohol-soluble polymer may be added within a range that does not adversely affect developability and the like. Examples of the alcohol-soluble polymer include alcohol-soluble nylon and epoxy resin.
As content of the said resin, 10-95 mass% is preferable normally with respect to the total solid of a photosensitive composition, and also 20-90 mass% is more preferable. In the range of 10 to 95% by mass, the adhesiveness of the photosensitive composition layer is not too high, and the strength and photosensitivity of the formed layer are not inferior.

The photosensitive composition may be a negative type in which a portion that receives radiation such as light and electron beam as described above is cured, or may be a positive type in which a radiation non-receiving portion is cured.
Examples of the positive photosensitive composition include those using a novolac resin. For example, an alkali-soluble novolak resin system described in JP-A-7-43899 can be used. Further, it contains a positive photosensitive resin layer described in JP-A-6-148888, that is, a mixture of an alkali-soluble resin described in the publication and a 1,2-naphthoquinonediazide sulfonate ester and a thermosetting agent as a photosensitive agent. A photosensitive resin layer can be used. Furthermore, the composition described in JP-A-5-262850 can also be used.

<Resin precursor>
Examples of the “resin precursor” include a monomer that becomes a resin by being cured.
Examples of the monomer include compounds having a boiling point of 100 ° C. or higher at normal pressure. For example, monofunctional (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tri Methylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, Ethylene oxide and propylene oxide to polyfunctional alcohols such as dimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane or glycerin And polyfunctional (meth) acrylates such as those obtained by addition reaction of (meth) acrylate.

  Further, urethane acrylates described in JP-B-48-41708, JP-A-50-6034 and JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, and 52- Polyfunctional acrylates and methacrylates such as polyester acrylates described in each publication of No. 30490, epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid can be mentioned. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.

The monomers may be used alone or in combination of two or more.
As for content with respect to the total solid of the photosensitive composition of a monomer, 5-50 mass% is common, and 10-40 mass% is preferable. When the content is within the above range, neither the photosensitivity nor the image strength is lowered, and the adhesiveness of the photosensitive composition layer is not excessive.

(D) Photopolymerization initiation assistant (D) The photopolymerization initiation assistant used in the photosensitive composition of the present invention is used in combination with the (B) photopolymerization initiator, and polymerization is initiated by the photopolymerization initiator. It is a compound used for promoting the polymerization of the photopolymerizable compound. The photopolymerization initiation assistant contains at least one amine compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4, Examples thereof include 4′-bis (ethylmethylamino) benzophenone, and among these, 4,4′-bis (diethylamino) benzophenone is preferable. Further, a plurality of amines and other photopolymerization initiation assistants may be used in combination. Examples of other photopolymerization initiation assistants include alkoxyanthracene compounds, thioxanthone compounds, and coumarin compounds.
Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
Moreover, a commercially available thing can also be used as a photoinitiation auxiliary agent, As a commercially available photoinitiation auxiliary agent, a brand name "EAB-F" (made by Hodogaya Chemical Co., Ltd.) etc. are mentioned, for example. .

  The amount of the (D) photopolymerization initiator auxiliary agent used in the photosensitive composition of the present invention is preferably 0.6 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more per 1 part by mass of the (C) photopolymerization initiator. The amount is preferably 8 parts by mass or less, particularly preferably 1.5 parts by mass or more and 5 parts by mass or less.

(E) Other components As the photosensitive composition, in addition to the above (A) to (D), if necessary, known additives such as pigments, plasticizers, surfactants, thermal polymerization inhibitors, Adhesion promoters, dispersants, sagging inhibitors, leveling agents, antifoaming agents, flame retardants, brighteners, solvents and the like can be added.

(Pigment)
In the present invention, other fine particles such as pigments can be used together with the above-mentioned metal-based fine particles. When a pigment is used, the hue can be made closer to black.
In general, the pigment is roughly classified into an organic pigment and an inorganic pigment. In the present invention, the organic pigment is preferable. Examples of pigments that can be suitably used include the color materials described in JP-A-2005-17716 [0038] to [0040] and the pigments described in JP-A-2005-361447 [0068] to [0072]. Alternatively, the colorants described in JP-A-2005-17521 [0080] to [0088] can be preferably used.

Among the pigments, carbon black, titanium black, or graphite is preferable.
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, a particle having a Stokes diameter of 3 μm or less is preferable. When graphite exceeding 3 μm is used, the contour shape of the light shielding pattern becomes non-uniform and sharpness may be deteriorated. Further, most of the particle diameter is desirably 0.1 μm or less.

It is desirable to use a pigment having a complementary color relationship with the hue of the metal-based fine particles. Further, the pigments may be used alone or in combination of two or more. Preferred pigment combinations include a combination of a red and blue pigment mixture complementary to each other and a yellow and purple pigment mixture complementary to each other, or a black pigment added to the above mixture. And combinations of blue, violet and black pigments.
The sphere equivalent diameter of the pigment is preferably 5 nm to 5 μm, particularly preferably 10 nm to 1 μm, and more preferably 20 nm to 0.5 μm for color filters.

(Thermal polymerization inhibitor)
As the photosensitive composition, it is preferable to add a thermal polymerization inhibitor in addition to the above components. Examples of thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, pt-butylcatechol, 2,6-di-t-butyl-p-cresol, β-naphthol, pyrogallol and other aromatic hydroxy compounds, benzoquinone Quinones such as p-toluquinone, amines such as naphthylamine, pyridine, p-toluidine, phenothiazine, aluminum salt or ammonium salt of N-nitrosophenylhydroxylamine, chloranil, nitrobenzene, 4,4′-thiobis (3-methyl) -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like.

(Adhesion promoter)
Examples of the adhesion promoter include alkylphenol / formaldehyde novolak resin, polyvinyl ethyl ether, polyvinyl isobutyl ether, polyvinyl butyral, polyisobutylene, styrene-butadiene copolymer rubber, butyl rubber, vinyl chloride-vinyl acetate copolymer, and chlorinated rubber. And acrylic resin-based pressure-sensitive adhesives, aromatic-based, aliphatic-based or alicyclic-based petroleum resins, silane coupling agents, and the like.

<Photosensitive transfer material>
The photosensitive transfer material of the present invention has a photosensitive composition layer using at least the photosensitive composition of the present invention on a temporary support, and if necessary, a thermoplastic resin layer, an intermediate layer, and A protective layer or the like can be provided.
The film thickness of the photosensitive composition layer is preferably about 0.2 to 2.0 μm, and more preferably 0.2 to 0.9 μm.
As a layer other than the photosensitive composition layer constituting the photosensitive transfer material of the present invention, the temporary support and the thermoplastic resin layer described in paragraphs [0023] to [0066] of JP-A-2005-3861 are used. An intermediate layer and a protective film are preferable.

<Production of photosensitive transfer material>
The photosensitive transfer material is prepared by applying a solution of the above-described photosensitive composition on a temporary support, for example, a spinner, a wheeler, a roller coater, a curtain coater, a knife coater, a wire bar coater, an extruder, or the like. It can be performed by applying and drying using a machine. The same process can be performed when a thermoplastic resin layer and an intermediate layer are provided.

<Light shielding film for display device>
The light-shielding film for a display device of the present invention is formed using the photosensitive composition of the present invention.
When a light shielding film for a display device is produced using the photosensitive composition of the present invention, a light shielding film for a display device having a high optical density (for example, an optical density of 1 or more) can be produced.
The “light shielding film for display device” referred to in the present invention is used to include a black matrix. “Black matrix” means a black edge provided around the periphery of a display device such as a liquid crystal display device, a plasma display device, an EL display device, a CRT display device, or a grid between red, blue, and green pixels. And stripe-like black portions, and further, dot-like and linear black patterns for TFT light shielding, etc. The definition of this black matrix is, for example, “Liquid Crystal Display Manufacturing Device Dictionary” (2nd edition, Tadasu Kanno, p. 64, Nikkan Kogyo Shimbun, 1996). Examples of the black matrix include an organic EL display (for example, Japanese Patent Application Laid-Open No. 2004-103507), a PDP front panel (for example, Japanese Patent Application Laid-Open No. 2003-51261), and for PALC, light shielding of a backlight.

<Black matrix>
The black matrix of the present invention is formed by the light shielding film for a display device of the present invention.
The black matrix improves the display contrast, and in the case of an active matrix driving type liquid crystal display device using a thin film transistor (TFT), in order to prevent deterioration in image quality due to light current leakage, The optical density OD is 3 or more).

<Method for Forming Light-shielding Film for Display Device>
The 1st formation method of the light shielding film for display apparatuses of this invention has at least the process of apply | coating the photosensitive composition of this invention on a board | substrate. The second method for forming a light-shielding film for a display device of the present invention comprises at least a step of transferring the photosensitive composition layer of the photosensitive transfer material of the present invention onto a substrate. By the method for forming a light-shielding film for a display device of the present invention, a photosensitive composition layer (hereinafter sometimes referred to as “photosensitive light-shielding layer”) made of a photosensitive composition is formed on a substrate.

  In the method for forming a light-shielding film for a display device according to the present invention, after the photosensitive light-shielding layer is formed as described above, the photosensitive light-shielding layer is exposed on the entire surface or in a pattern, and developed if exposed in a pattern. A step of forming a light-shielding film for a display device, and other steps may be provided as necessary.

<Board>
Although the board | substrate used for this invention is not specifically limited, The board | substrate with a frame formed by the transparent board | substrate (for example, glass substrate and plastics board | substrate) which comprises a display apparatus, a board | substrate with wiring, a light shielding film, etc., transparent electroconductivity Examples include a substrate with a film (for example, an ITO film), a substrate with a color filter, and a driving substrate with a driving element (for example, a thin film transistor [TFT]).
Although the size of the board | substrate used for this invention is not specifically limited, 300-6000 mm is preferable in a longitudinal direction and a transversal direction, 800-4000 mm is further more preferable, 1500-3500 mm is especially preferable.

The film thickness of the layer made of the photosensitive composition of the present invention (photosensitive composition layer) is preferably about 0.2 to 2.0 μm, more preferably 0.2 to 0.9 μm. Since the layer is formed by dispersing metal particles or metal-containing particles, a high optical density (2.5 or more) can be obtained with a thin film as described above.
In particular, it is effective to use particles having a silver-tin alloy part as metal particles or particles having a metal.
The optical density of the light shielding film for display device is preferably 2.5 or more and 10.0 or less, more preferably 3.0 or more and 6.0 or less. When the optical density is within the above range, light shielding properties can be imparted.

Hereinafter, a method for forming a light-shielding film for a display device according to the present invention will be specifically described by taking a method for forming a black matrix pattern as an example.
As a first specific example, first, the photosensitive composition of the present invention is applied to a substrate to form a photosensitive light-shielding layer containing metal particles or metal-containing particles. Then, pattern formation is performed by removing the light shielding layer other than the pattern by pattern exposure and development to obtain a black matrix (light shielding film for display device).
In addition, a layer having the same composition as the intermediate layer described above can be formed on the photosensitive light-shielding layer to form a protective layer. In this case, the coating liquid can be applied by using the coating machine listed in the section <Preparation of photosensitive transfer material> described above. Of these, the spin coating method is preferred.

  As a second specific example, a photosensitive transfer material is disposed and laminated on a light-transmitting substrate so that the photosensitive composition layer is in contact, and then the photosensitive transfer material and the light-transmitting substrate are stacked. In this method, the temporary support is peeled off from the body, the photosensitive composition layer is exposed and developed to obtain a black matrix (light-shielding film for display device). This method does not require a cumbersome process and can be performed at low cost.

Next, exposure and development will be described.
A predetermined mask is arranged above the photosensitive light-shielding layer formed on the substrate, the photosensitive light-shielding layer is exposed through the mask from above the mask, and then developed with a developer to form a pattern image, and subsequently A black matrix can be produced by performing a washing process as necessary. In addition to the method of performing exposure by arranging a mask as described above, it is also possible to obtain a pattern image by directly scanning light based on image data directly without using a mask.

As the light source used for the exposure, any light source capable of irradiating light in a wavelength region capable of curing the photosensitive light-shielding layer (for example, 365 nm, 405 nm, etc.) can be appropriately selected and used. Specific examples include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, an LD, an ultrahigh pressure mercury lamp, a YAG-SHG solid laser, a KrF laser, and a solid laser.
As an exposure amount, it is about 5-300 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.
Although the exposure machine used in this case is not particularly limited, a scattered light exposure machine, a parallel light exposure machine, a stepper, a laser exposure machine, etc. are used in addition to a proximity exposure machine that exposes through a mask. be able to.

  There is no restriction | limiting in particular as a developing solution used for image development, Well-known developing solutions, such as what is described in Unexamined-Japanese-Patent No. 5-72724, can be used, Especially the dilute aqueous solution of an alkaline substance is used preferably. Specifically, the developer preferably has a development type developing behavior of the photosensitive composition layer. A small amount of an organic solvent miscible with water may be added.

Moreover, it is preferable to spray the pure water with a shower nozzle or the like before the development so that the surface of the photosensitive light-shielding layer is uniformly moistened.
In the formation method by applying a black matrix and the formation method using a photosensitive transfer material, the alkaline substance used for development includes alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates ( For example, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate, potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, , Sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide), trisodium phosphate, etc. It is. The concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14.
Examples of the “organic solvent miscible with water” include, for example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n- Preferable examples include butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, and N-methylpyrrolidone. It is done. The concentration of the organic solvent miscible with water is preferably 0.1 to 30% by mass.

Furthermore, a known surfactant can be added, and the concentration of the surfactant is preferably 0.01 to 10% by mass.
The developer may be used as a bath solution or as a spray solution. When removing the uncured portion of the light shielding layer, methods such as rubbing with a rotating brush or a wet sponge in the developer can be combined. The liquid temperature of the developer is usually preferably from about room temperature to 40 ° C. The development time depends on the composition of the light-shielding layer, the alkalinity and temperature of the developing solution, and the type and concentration when an organic solvent is added, but is usually about 10 seconds to 2 minutes. If it is too short, the development of the non-exposed area may be insufficient, and the absorbance of ultraviolet rays may be insufficient, and if it is too long, the exposed area may be etched. In either case, it is difficult to make the black matrix shape suitable. In this development process, the black matrix becomes obvious.

<Substrate with light shielding film>
The substrate with a light-shielding film of the present invention comprises a substrate and the light-shielding film for a display device of the present invention provided on the substrate. The details of the substrate and the light shielding film for display device used in the substrate with the light shielding film of the present invention are as described above. The substrate with a light-shielding film of the present invention can be suitably used for producing a color filter.

<Color filter and manufacturing method thereof>
The color filter manufacturing method of the present invention is to produce a color filter having a pixel group composed of a plurality of colored pixels of two or more colors and a black matrix separating the colored pixels of the pixel group. Specifically, the photosensitive light-shielding layer of the present invention is exposed in a pattern and developed to form a black matrix, and a plurality of colored pixels of two or more colors are formed in the recesses between the formed black matrices. (Hereinafter, also referred to as “pixel formation process”), and can be configured by providing other processes as necessary.

  Examples of the pixel forming step include a step using a known method. For example, in the pixel forming method described in Japanese Patent Laid-Open No. 5-39450, Japanese Patent Laid-Open No. 2003-330184, or Japanese Patent Laid-Open No. 10-195358. There is a pixel forming method by the inkjet method described.

The color filter of the present invention is a black filter that separates a pixel group composed of two or more colored pixels that are formed of a colored layer and have different colors on a light-transmitting substrate, and each pixel constituting the pixel group. A matrix is provided, and is produced by the above-described method for producing a color filter of the present invention.
The pixel group may be a pixel group composed of two colored pixels or three color pixels that exhibit different colors, or a pixel group composed of four or more colored pixels that represent different colors. There may be. For example, in the case of three colors, three hues of red (R), green (G), and blue (B) are preferably used. When three types of pixel groups of red, green, and blue are arranged, a mosaic type, a triangle type, and the like are preferable, and any arrangement may be used when four or more types of pixel groups are arranged.

As the light transmissive substrate, a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass plate, a non-alkali glass plate, a quartz glass plate, or a plastic film is used.
As described above, the color filter of the present invention is a thin film prepared using the photosensitive composition of the present invention and has a high-concentration black matrix. Therefore, for example, when a liquid crystal display device is configured, the color filter displays over time. Unevenness can occur and display contrast fluctuation can be suppressed, and an image with high contrast can be displayed stably.

<Display device>
A display device according to the present invention includes the substrate with a light-shielding film according to the present invention.
The display device of the present invention refers to a display device such as a liquid crystal display device, a plasma display display device, an EL display device, or a CRT display device. For the definition of display devices and explanation of each display device, refer to “Electronic Display Devices (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Devices (Junaki Ibuki, Industrial Books Co., Ltd.) Issue)).
Among the display devices of the present invention, a liquid crystal display device is particularly preferable. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. Among these, the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, IPS, OCS, FFS, and R-OCB. Applicable. These methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(issued in 2001 by Toray Research Center Research Division)".

  In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The black matrix of the present invention can be applied to a liquid crystal display device composed of these known members. For example, “'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Kentaro Shima, CMC Co., Ltd., 1994)”, “2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)” (Table Yoshiyoshi) Fuji Chimera Research Institute, published in 2003) ”.

    EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

( Reference Example 1): Coating method <Preparation of dispersion of particles having silver-tin alloy part (dispersion A1)>
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 obtained above was vigorously stirred while maintaining at 25 ° C., the above solution 2 was added thereto over 2 minutes, and the stirring was continued gently for 6 hours. Then, the liquid mixture 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 liquid was centrifuged to precipitate silver-tin alloy part-containing particles. Centrifugation is subdivided into a volume of 150 ml, and a rotational speed of 2,000 r.m. using a desktop centrifuge H-103n (manufactured by Kokusan Co., Ltd.). p. m. For 30 minutes. Then, the supernatant was discarded and the total liquid volume was made 150 ml. To this, 1350 ml of pure water was added and stirred for 15 minutes to re-disperse the silver-tin alloy part-containing particles. This operation was repeated twice to remove soluble substances in the aqueous phase.

Thereafter, the liquid was further centrifuged to precipitate silver tin alloy part-containing particles again. Centrifugation was performed under the same conditions as described above. After centrifuging, the supernatant was discarded as described above, the total liquid volume was made 150 ml, 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 described above to precipitate silver-tin alloy part-containing particles, and then the supernatant was discarded as described above to a liquid volume of 150 ml, and 150 ml of pure water and 1200 ml of normal propyl alcohol were added thereto for another 15 minutes. Agitation was performed and the silver tin alloy part-containing particles were dispersed 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, the total liquid volume was made 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: diameter 0.65 mm zirconia beads 130 g, manufactured by Eiger Japan Co., Ltd.)), and silver-tin alloy part-containing particles (silver-tin particle concentration 25% by mass) The aqueous dispersion (dispersion A1) of PVP-K30 remaining amount 1.0% by mass was prepared.

It was confirmed by X-ray scattering that the silver-tin alloy part-containing particles were a composite composed of an AgSn alloy (2θ = 39.5 °) and a Sn metal (2θ = 30.5 °). Here, the numbers in parentheses are the scattering angles of the respective (III) planes. As a result of observing this fine particle dispersion with a transmission electron microscope, the dispersion average particle diameter was about 40 nm in terms of number average particle diameter.
The number average particle size was measured using a photograph obtained with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.) as follows.
100 particles were selected, the diameter of a circle having the same area as each particle image was defined as the particle diameter, and the average of the particle diameters of 100 particles was defined as the number average particle diameter. At this time, a photograph taken at a magnification of 100,000 times and an acceleration voltage of 200 kV was used.

<Preparation of photosensitive coating liquid A1 for black matrix (BM)>
The composition shown in Table 1 below was mixed to prepare a photosensitive coating solution A1 for BM.

The prescriptions of the starting systems A to H in Table 1 are as shown in Table 2.

  Here, Irgacure 379 is an aminoacetophenone photopolymerization initiator, Irgacure 369 is an aminoacetophenone photopolymerization initiator, CGI242 is an oxime ester photopolymerization initiator, and Irgacure 819 is an acylphosphine oxide photopolymerization initiator. Irgacure (Irg) 651 is a benzyldimethyl ketal photopolymerization initiator. The structure of Irg651 is as follows.

The binder A in Table 1 is a random copolymer of methacrylic acid / ethyl methacrylate / cyclohexyl methacrylate / benzyl methacrylate (= 13.8 / 30.5 / 12 / 43.7 [molar ratio]) (Mn 13,000, Mw 3 Million).
The outline of the DPHA solution in Table 1 and the surfactant 1 in Table 2 will be described later.
Further, Solsperse 20000 in Table 1 is a dispersant manufactured by Avicia Co., Ltd.

<Preparation of coating solution for protective layer>
The following compositions were mixed to prepare a protective layer coating solution.
・ Polyvinyl alcohol: 3.0 parts (PVA-105, manufactured by Kuraray Co., Ltd.)
・ Carboxymethylcellulose 0.15 part (TC-5E, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ Surfactant 2
(Surflon S-131, Seimi Chemical Co., Ltd .... 0.01 part, distilled water ... 50.7 parts, methyl alcohol ... 45.0 parts

<Formation of black matrix (BM) by coating>
(1) The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. Thereafter, this substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
Subsequently, after cooling the substrate and adjusting the temperature to 23 ° C., the film thickness is 1 on the substrate using a glass substrate coater MH-1600 (manufactured by FS Asia Co., Ltd.) equipped with a slit-like nozzle. The photosensitive coating solution A1 for BM obtained above was applied so as to have a thickness of 0.0 μm, and dried at 100 ° C. for 5 minutes to form a photosensitive composition layer (application step). Next, using the slit-shaped nozzle on this photosensitive composition layer, the protective layer coating solution obtained above was applied to a dry film thickness of 1.5 μm, and dried at 100 ° C. for 5 minutes for protection. A layer was formed to prepare a photosensitive material for BM.

(2) Subsequently, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp, the mask (quartz exposure mask having an image pattern) and the above-mentioned photosensitive material for BM were set up vertically. In this state, the entire surface was exposed at an exposure amount of 30 mJ / cm ² with the distance between the mask surface and the surface of the photosensitive composition layer in contact with the protective layer being 200 μm (exposure process). Next, the exposed BM photosensitive material is developed using a developing solution T-CD1 (Fuji Photo Film Co., Ltd .; alkaline developer) diluted 5 times (pH in use is 10.2). (33 ° C., 20 seconds; development step) to form a black matrix (BM) on the glass substrate.
Next, the glass substrate on which the BM is formed is heated at 220 ° C. for 60 minutes by a substrate preheating device, and then further heated at 240 ° C. for 50 minutes and baked (baking process), and the opening in the pixel formation region is 86 μm. A black matrix having a line width of 24 μm, a film thickness of 0.8 μm, and an optical density of 4.0 was formed so as to be × 304 μm. Hereinafter, the glass substrate on which the black matrix is formed is referred to as a “black matrix substrate”.

The optical density was measured using the material in which the black matrix was formed, and a thin film layer having an OD of 3.0 or less was formed on a transparent substrate, and each example was not exposed in a pattern . A sample for measurement (film-like) was obtained through the same steps as the reference example and the comparative example. This transmission optical density was measured at 555 nm using a spectrophotometer (manufactured by Shimadzu Corporation, UV-2100) (OD). Separately, the transmission optical density of the glass substrate was measured by the same method (OD ₀ ).
The value obtained by subtracting OD ₀ from OD was taken as the transmission optical density of the black matrix. Using a contact surface roughness meter P-10 (manufactured by KLA-Tencor Corporation), the film thickness of the measurement sample was measured, and was prepared in the example from the relationship between the transmission optical density and the film thickness of the measurement result. The optical density of the black matrix of the film thickness was calculated.

<Production of color filter and liquid crystal display device>
-Preparation of colored photosensitive resin composition-
Colored photosensitive resin compositions R1, G1, and B1 having the compositions shown in Table 3 below were prepared.

-Formation of red (R) pixels-
Using the colored photosensitive resin composition R1 obtained above on the BM formation surface side of the glass substrate on which the black matrix (BM) is formed, the same process as the formation of the black matrix described above is performed, and heat treatment is performed. A finished R pixel was formed.

-Formation of green (G) pixels-
Using the colored photosensitive resin composition G1 obtained above on the surface of the glass substrate on which the black matrix and R pixels are formed, the same process as the formation of the black matrix described above is performed, and heat treatment is performed. A finished G pixel was formed.

-Formation of blue (B) pixels-
Using the colored photosensitive resin composition B1 obtained above on the surface of the glass substrate on which the black matrix, R pixel, and G pixel are formed, the same process as the formation of the black matrix described above is performed. Thus, a heat-treated B pixel was formed.
A color filter (hereinafter referred to as a color filter substrate) was produced as described above.

In addition, the detail of each composition in composition R1 of the said Table 3 is as follows.
* Composition of R pigment dispersion 1-C.I. I. Pigment Red 254 (trade name: Irgaphor Red B-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 8.0 parts-Compound 1 (dispersant) below: 0.8 parts-Polymer (benzyl methacrylate / methacrylic acid) (= 72/28 [molar ratio]) random copolymer, molecular weight: 30,000) 8 parts propylene glycol monomethyl ether acetate 83 parts

* Composition of R pigment dispersion 2-C.I. I. Pigment Red 177 (trade name: Chromophthal Red A2B, manufactured by Ciba Specialty Chemicals Co., Ltd.) 18 parts ・ Random copolymer (weight) of polymer [benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio])) Average molecular weight 37,000)] ... 12 parts Propylene glycol monomethyl ether acetate 70 parts

* Composition of binder 2-Random copolymer of polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate (= 38/25/37 [molar ratio]), molecular weight: 40,000) ... 27 parts-Propylene glycol monomethyl ether acetate 73 Part

* Composition of DPHA solution-Dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ, trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) ... 76 parts-Propylene glycol monomethyl ether acetate ... 24 parts

* Composition of surfactant 1-Structure 1 below: 30 parts-Methyl ethyl ketone: 70 parts

In addition, the detail of each composition in the composition G1 of the said Table 3 is as follows.
* G pigment dispersion 1
Product name: GT-2 (Fuji Film Electronics Materials Co., Ltd.)
* Y pigment dispersion 1
Product name: CF Yellow EX3393 (manufactured by Gokoku Color Co., Ltd.)
* Composition of binder 1-Random copolymer of polymer (benzyl methacrylate / methacrylic acid (= 78/22 [molar ratio]) (weight average molecular weight 38,000) ... 27 parts-Propylene glycol monomethyl ether acetate ... 73 parts

In addition, the detail of each composition in composition B1 of the said Table 3 is as follows.
* B Pigment dispersion 1
Product name: CF Blue EX3357 (Mikuni Dye Co., Ltd.)
* B Pigment dispersion 2
Product name: CF Blue EX3383 (manufactured by Gokoku Color Co., Ltd.)
* Composition of binder 3-Random copolymer of polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate (= 36/22/42 [molar ratio]) (weight average molecular weight 38,000) ... 27 parts-Propylene glycol monomethyl ether acetate ... 73 copies

-Production of liquid crystal display device-
A transparent electrode made of ITO (Indium Tin Oxide) was further formed on the R pixel, G pixel, B pixel and black matrix of the color filter substrate obtained above by sputtering. 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 liquid crystal for PVA mode 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. A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, FR1112H (chip type LED manufactured by Stanley Co., Ltd.) as a red (R) LED, DG1112H (chip type LED manufactured by Stanley Co., Ltd.) as a green (G) LED, and DB1112H (Stanley (as a blue (B) LED) A side-light type backlight was constructed using a chip type LED manufactured by Co., Ltd., and was placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.

( Reference Examples 2 to 4, Examples 5 and 6, and Comparative Examples 1 and 2): Coating Method In the above Reference Example 1, except that the photosensitive coating liquid A1 for BM was changed to A2 to A8 described in Table 1. A black matrix, a color filter, and a liquid crystal display device were produced in the same manner as in Reference Example 1.

Reference Example 7: Transfer Method A color filter and a liquid crystal display device were prepared in the same manner as in Reference Example 1 except that the black matrix preparation method was changed to the following transfer method.
<Formation of black matrix (BM)>
-Production of photosensitive transfer material-
Using a slit-like nozzle on a 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), a thermoplastic resin layer coating solution having the following formulation H1 is applied and dried to form a thermoplastic resin layer. Formed. Next, an intermediate layer coating solution having the following formulation P1 was further applied onto the thermoplastic resin layer and dried to laminate the intermediate layer. Subsequently, the photosensitive coating solution A1 for BM prepared in Reference Example 1 was applied on the intermediate layer and dried to further laminate a black photosensitive composition layer.

  As described above, the thermoplastic resin layer having a dry layer thickness of 14.6 μm, the intermediate layer having a dry layer thickness of 1.6 μm, and the photosensitive composition layer having a dry layer thickness of 1.2 μm are formed on the PET temporary support. A photosensitive film having a laminated structure of a temporary support / thermoplastic resin layer / intermediate layer / photosensitive composition layer is provided by pressure-bonding a protective film (polypropylene film having a thickness of 12 μm) to the surface of the photosensitive composition layer. A transferable material was prepared. Hereinafter, this is referred to as BM photosensitive transfer material K1.

<Prescription H1 of coating solution for thermoplastic resin layer>
-Methanol ... 11.1 parts-Propylene glycol monomethyl ether acetate ... 6.36 parts-Methyl ethyl ketone ... 52.4 parts-Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer ... 5.83 parts (copolymerization (Molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 90,000, Tg≈70 ° C.)
Styrene / acrylic acid copolymer: 13.6 parts (copolymerization ratio [molar ratio] = 63/37, weight average molecular weight = 10,000, Tg≈100 ° C.)
2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd .; a compound obtained by dehydrating condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate) 9.1 parts Surfactant 1 0.54 parts

<Prescription P1 of coating solution for intermediate layer>
・ Polyvinyl alcohol: 3.0 parts (PVA-105, manufactured by Kuraray Co., Ltd.)
・ Carboxymethylcellulose 0.15 part (TC-5E, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ Surfactant 2
(Surflon S-131, Seimi Chemical Co., Ltd. 0.01 parts) Distilled water 524 parts Methanol 429 parts

-Formation of black matrix (BM)-
A non-alkali glass substrate (hereinafter referred to as a unit “glass substrate”) was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds with a shower, and after pure water shower washing, Silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% by mass aqueous solution; trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) is sprayed for 20 seconds with a shower and washed with pure water. did. Then, this board | substrate was heated for 2 minutes at 100 degreeC with the board | substrate preheating apparatus, and it sent to the laminator.
The protective film is peeled off from the BM photosensitive transfer material K1 obtained above from the glass substrate after the silane coupling treatment, and the surface of the photosensitive composition layer exposed after the removal is in contact with the surface of the glass substrate. And laminator Lamic II type (manufactured by Hitachi Industries, Ltd.) was laminated under the conditions of a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveying speed of 2.2 m / min.
Subsequently, the PET temporary support was peeled off at the interface with the thermoplastic resin layer, and the temporary support was removed. After peeling off the temporary support, use a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp to vertically stand the substrate and mask (quartz exposure mask with image pattern) In this state, the distance between the mask surface and the photosensitive composition layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 30 mJ / cm ² .

Next, a triethanolamine developer (containing 30% by mass of triethanolamine, 0.1% by mass in total of polypropylene glycol, glycerol monostearate, polyoxyethylene sorbitan monostearate and stearyl ether, trade name: T -PD2, manufactured by Fuji Photo Film Co., Ltd.) with pure water diluted 12 times (1 part by mass of T-PD2 and 11 parts by mass of pure water) (30 ° C.) for 50 seconds. Then, shower development was performed with a flat nozzle at a pressure of 0.04 MPa, and the thermoplastic resin layer and the intermediate layer were removed. Subsequently, air was blown onto the substrate to drain the liquid, and then pure water was sprayed for 10 seconds by a shower to perform pure water shower cleaning, and air was blown to reduce the liquid pool on the substrate.
Subsequently, a sodium carbonate-based developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% by weight sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and Stabilizer-containing; trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd.) diluted 5 times with pure water (29 ° C.) for 30 seconds, shower with cone type nozzle at pressure of 0.15 MPa Development was performed to develop and remove the photosensitive composition layer to obtain a pattern image.
Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, and stabilizer; trade name: T-SD1, manufactured by Fuji Photo Film Co., Ltd.) was diluted 10 times with pure water. The liquid (33 ° C.) was used as a shower with a cone type nozzle at a pressure of 0.02 MPa for 20 seconds, and the residue was removed by rubbing the pattern image with a rotating brush having nylon bristles to obtain a black matrix. . Thereafter, the substrate on which the black matrix was formed was post-exposed with an ultrahigh pressure mercury lamp from both sides at an exposure amount of 500 mJ / cm ² and then heat-treated (baked) at 220 ° C. for 15 minutes (black matrix substrate).

( Reference Example 8): Coating method
Reference Example 1, instead of the silver particle dispersion B1 was prepared as follows dispersion A1 of silver-tin alloy-containing particles, except that the addition using a BM for light-sensitive coating liquid B1, in the same manner as in Reference Example 1 Thus, a black matrix substrate was manufactured and a liquid crystal display device was manufactured.

<Preparation of silver fine particle dispersion B1>
73.5 g of silver fine particles having an average aspect ratio of 2.2, 1.05 g of a dispersant (trade name: Solsperse 20000, manufactured by Avicia Co., Ltd.), and 16.4 g of methyl ethyl ketone were mixed. This was dispersed using an ultrasonic disperser (trade name: Ultrasonic generator model US-6000 ccvp, manufactured by nissei) to obtain a dispersion of silver fine particles having an equivalent circle diameter of 100 nm. Subsequently, the obtained silver fine particle dispersion was centrifuged (10,000 rpm, 20 minutes), and the supernatant was discarded, followed by concentration as appropriate. This operation was repeated 3 times to remove the soluble substance in the aqueous phase to obtain a silver fine particle dispersion B1. (Silver particle concentration 25% by mass)

<Preparation of photosensitive coating solution B1 for BM>
A BM photosensitive coating solution B1 was prepared in the same manner except that the dispersion A1 used in Reference Example 1 was changed to the silver fine particle dispersion B1.

<Evaluation>
(Evaluation of sensitivity)
The photosensitive coating solution for BM obtained in Reference Examples 1 to 4, Examples 5 and 6 , Reference Example 8, and Comparative Examples 1 and 2 was applied to the substrate used for black matrix preparation with a thickness of 1 μm. An evaluation photosensitive layer was prepared. The BM photosensitive coating solution was used immediately after preparation. Next, the exposure apparatus used in the examples was exposed (30 mJ / cm ² ) using a 15-step step wedge pattern (Δlog E = 0.15) and developed. The development conditions were the same as in Reference Example 1. Then, the number of solid stages after development (the number of stages whose thickness did not change due to development) was evaluated according to the following evaluation criteria.
◎: When 11 or more stages ○: When 8 to 10 stages △: When 6 to 8 stages ×: When 5 or less stages

The sensitivity of the BM photosensitive transfer material of Reference Example 7 was evaluated as follows. The evaluation criteria are as described above.
The photosensitive transfer material for BM produced in the same manner as in Reference Example 7 was transferred onto the substrate used for producing the black matrix, and the exposure apparatus used in the example used a 15-step step wedge pattern (ΔlogE = 0. 15) for exposure (30 mJ / cm ² ) and development. The development conditions were the same as in Reference Example 7. The photosensitive transfer material for BM was used immediately after production. The number of solid stages after development (the number of stages whose thickness did not change due to development) was evaluated according to the above evaluation criteria.

(Evaluation of sensitivity after storage)
Regarding the photosensitive coating solution for BM after storing the photosensitive coating solution for BM obtained in Reference Examples 1 to 4, Examples 5 and 6 , Reference Example 8 and Comparative Examples 1 and 2 at room temperature for 3 days, A photosensitive layer for evaluation was prepared in the same manner as in “Evaluation of sensitivity”, and the sensitivity was evaluated. The evaluation method is the same as described above.
◎: When 11 or more stages ○: When 8 to 10 stages △: When 6 to 8 stages ×: When 5 or less stages

Further, the sensitivity after storage of the photosensitive transfer material for BM of Reference Example 7 was evaluated as follows. The evaluation criteria are as described above.
The photosensitive transfer material for BM produced in the same manner as in Reference Example 7 was transferred onto the substrate used for producing the black matrix, and the exposure apparatus used in the example used a 15-step step wedge pattern (ΔlogE = 0. 15) for exposure (30 mJ / cm ² ) and development. The development conditions were the same as in Reference Example 7. As the photosensitive transfer material for BM, one stored at room temperature for 1 month after production was used. The number of solid stages after development (the number of stages whose thickness did not change due to development) was evaluated according to the above evaluation criteria.

(Evaluation of aggregation after storage)
Using the photosensitive coating solution for BM obtained in Reference Examples 1 to 4, Examples 5 and 6 , Reference Example 8 and Comparative Examples 1 and 2, a 0.5 μm thin film layer was formed on a transparent substrate, A sample (film-like) A for measurement was obtained.
Next, using the photosensitive coating solution for BM obtained in Reference Examples 1 to 4, Examples 5, 6 and Reference Examples 8 and Comparative Examples 1 and 2 after storage for 3 days, the same method as described above was used. A sample (film-like) B for measurement was obtained.
The sample A and the spectrophotometer a transmission optical density of B (Shimadzu, UV-2100) was measured at 555nm using a (OD _A, OD _B). Separately, the transmission optical density of the glass substrate was measured by the same method (OD ₀ ).
The value obtained by subtracting OD ₀ from OD _A and OD _B is the transmission optical density of samples A and B, and the transmission optical density residual ratio (OD residual ratio) of sample B when the transmission optical density of sample B is 100%. Calculated.
It was considered that the remaining rate was lower as aggregation occurred, and the remaining rate of 90% or more was evaluated as ○, and the less than 90% was evaluated as ×.
The evaluation results are shown in Table 4.

From the results in Table 4, the photosensitive coating solution for BM of the present invention using at least one photopolymerization initiator selected from the group consisting of aminoacetophenone, acylphosphine oxide, and oxime ester has no sensitivity to aggregation. It was good and the sensitivity of storage was also good. The formulations containing the photopolymerization initiation assistants of Reference Examples 2 and 4 showed higher sensitivity. In addition, the liquid crystal display devices using the black matrix produced in Reference Examples 1 to 4, Examples 5 and 6, and Reference Examples 7 and 8 have low reflectivity, so that the TFT does not malfunction and the image quality is good. It was.
On the other hand, in Comparative Example 1 using a conventional photopolymerization initiator, aggregation occurs, and in Comparative Example 2, the sensitivity is inferior. Therefore, the liquid crystal display device using the black matrix according to the comparative example has poor productivity and contrast. Inferior image quality with uneven color.

Claims (11)

At least, (A) and particles containing a silver-tin alloy, and at least one photopolymerization initiator selected from the group consisting of (B) A sill phosphine oxide and oxime esters, (C) a resin and its precursor A photosensitive composition comprising: at least one of the above.   The photosensitive composition according to claim 1, further comprising (D) a photopolymerization initiation assistant. 3. The photosensitive composition according to claim 1, wherein the (A) metal particles or metal-containing particles have a number average particle diameter of 0.1 μm or less. The photosensitive transfer material which has a photosensitive composition layer which uses the photosensitive composition of any one of Claims 1 thru | or 3 on a temporary support body. Forming method of a display device for a light-shielding film of the photosensitive composition having at least a step of applying onto a substrate according to any one of claims 1 to 3. A method for forming a light-shielding film for a display device, comprising at least a step of transferring the photosensitive composition layer of the photosensitive transfer material according to claim 4 onto a substrate. Display device for a light-shielding film, which is formed using the photosensitive composition according to any one of claims 1 to 3. A black matrix formed by the light shielding film for a display device according to claim 7 . A substrate with a light-shielding film, comprising: a substrate; and the light-shielding film for a display device according to claim 7 provided on the substrate. The substrate with a light-shielding film according to claim 9 , which is used for producing a color filter. Display apparatus comprising the light-shielding film with a substrate according to claim 9 or 10.