Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/201—Filters in the form of arrays
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
  • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors

Definitions

• the invention relates to a photosensitive composition preferable for producing a light shielding film provided within a display device such as a plasma display device, an EL display device and a CRT display device, a transfer material using the photosensitive composition, a light shielding film and production method thereof, a color filter for a display device, a substrate for a display device, and a display device.
• a light shielding film for a display device is provided as a black edge, a lattice pattern around a pixel, a striped black edge (a so-called black matrix), a dot pattern or a linear black pattern for light shielding of a thin film transistor (TFT), within a device such as a liquid crystal display device, a plasma display device, an EL display device and a CRT display device.
• a black matrix is an example of a light shielding film constituting the liquid crystal display and so on.
• the black matrix is usually provided so as to surround each colored pixel (red, green or blue pixel) of a color filter provided within the liquid crystal display device in- order to prevent contrast decreasing due to a light leakage through the space between the pixels.
• a light shielding film provided on a TFT for preventing image quality from being deteriorated due to current leakage from the TFT caused by light, in a liquid crystal device using an active matrix addressing method using the TFT.
• a light shielding performance with an optical density of 2 or more is usually required for the light shielding film, and the light shielding film is preferably black-colored from a viewpoint of the quality of displayed images of the display device.
• Using a metal for producing a light shielding film having a high light shielding performance has been proposed.
• a proposed method comprises the processes of producing a metal thin film by vacuum deposition or sputtering, forming a photo-resist film by coating a photo-resist on the metal thin film, exposing the photo-resist film to light using a pattern mask (photo-mask) for forming a light shielding film, developing the exposed photo-iresist film, etching the exposed thin film, and peeling the photo-resist film from the metal thin film (see, for example, Color TFT Liquid Oy stal Display, pp. 218-220, published on April 10, 1997 by Kyoritsu Shuppan Co., Ltd).
• a pattern mask photo-mask
• This light shielding film is a film obtained by applying a photosensitive resin composition containing carbon black onto the substrate, drying the composition, exposing the resultant film to light, and developing the film.
• the thickness of the light shielding film is inevitably increased to secure high light-shielding performance and optical density due to its low optical density per unit amount relative to metals. Accordingly, air bubbles are readily generated or uniform pixels are difficult to obtain when red, blue and green-colored pixels are formed after forming the light shielding film.
• a black matrix containing nickel fine particles has been formed by electroless deposition (for example, see JP-ANo. 7-218715). However, since only particles having an average particle diameter of 30 nm or less are obtained by this method, it is difficult to obtain a perfectly black color tone, or a thin film having a thickness of 0.5 ⁇ m.
• this method imposes a heavy burden on the environment since a plating liquid is used in the production process.
• a technique for forming a light shielding film using a composition containing metal particles or using a transfer material has been proposed (for example, see JP-ANo. 2004-240039). This technique can be solve the problems such as generating air bubbles, hardly forming uniform pixels, becoming poor black color tone, and imposing great burden on the environment as described above, and a thin light shielding film having high optical density and reflectivity can be obtained.
• the metal thin film having high reflectivity renders display contrast low under an external light.
• a technique exists of using a low reflection chromium film such as a two layer film comprising a layer of metallic chromium and a layer of chromium oxide
• chromium for such a film may also impose a heavy burden on the environment.
• the light shielding film obtained has the characteristics that reflectivity increases at higher temperatures. Since a high temperature treatment named a bake treatment is usually applied for producing a color filter, a light shielding film that causes no increase of reflectivity by baking is required in color filters that a high quality image is demanded in recent years.
• a first aspect of the invention is to provide a photosensitive composition comprising particles containing an alloy portion and a monomeiy wherein after the photosensitive composition is formed into a film, the film has an optical density of 2.0 or more per l ⁇ m of dry film thickness.
• a second aspect of the invention is to provide transfer material comprising a temporary support and a photosensitive layer provided on the temporary support, wherein the photosensitive layer comprises the photosensitive composition of the first aspect onto a temporary support.
• a third aspect of the invention to provide a light shielding film formed by applying the photosensitive composition of the first aspect onto a substrate.
• a fourth aspect of the invention to provide a light shielding film formed by transferring the photosensitive layer of the transfer material of the second aspect onto a substrate.
• a fifth aspect of the invention is to provide a substrate for a display device comprising the light shielding film of the third or fourth aspect.
• a sixth aspect of the invention is provide a color filter for a display device comprising the substrate for the display device of the fifth aspect.
• a seventh aspect of the invention is to provide display device comprising the color filter for a display device of the sixth aspect.
• a eighth aspect of the invention is to provide a method for producing a light shielding film, including forming a photosensitive layer by applying the photosensitive composition of the first aspect onto a substrate and then drying the applied photosensitive composition; forming a patterned image by exposing the photosensitive layer pattern-wise and then developing the exposed photosensitive layer; and conducting a heat treatment on the patterned image at a temperature of 150°C or higher for 5 minutes or more.
• a ninth aspect of the invention is provide a method for producing a light shielding film, including transferring a photosensitive layer of the transfer material of the second aspect 1 to a substrate; forming a patterned image by exposing the transferred photosensitive layer pattern-wise and then developing the exposed photosensitive layer; and conducting a heat treatment to the patterned image at a temperature of 150°C or higher for 5 minutes or more.
• a tenth aspect of the invention is to provide a light shielding film produced by the method of the eighth aspect.
• a eleventh aspect of the invention is to provide a light shielding film produced by the method of the ninth aspect.
• the invention provides a photosensitive composition that affords a thin film excellent in light shielding performance (with high optical density) and has small increment of reflectivity as a result of heating and a reduce burden on the environment, a transfer material, ⁇ light shielding film and a manufacturing method thereof, a substrate for a display device, a color filter for a display device capable of displaying bright images with high contrast, and a display device.
• the photosensitive composition of the invention will be described in detail hereinafter, while details of the transfer material, a light shielding film and a production method thereof, a color filter for a display device, a substrate for the display device and the display device are also presented in the description.
• the photosensitive composition of the invention comprises particles containing ah alloy portion and a monomer, wherein after the photosensitive composition is formed into a film, the film has an optical density of 2.0 or more per l ⁇ m of dry. film thickness.
• the photosensitive composition of the invention may be optionally contained other components such as a binder polymer, a photopolymerization initiator, a dispersing agent and a dispersion medium.
• the dry thickness of the film as used herein refers to a thickness of the film after drying the photosensitive composition of the invention applied onto a substrate, and is measured as follows.
• a photosensitive material having a photosensitive resin layer by applying the photosensitive composition onto a substrate (for example a PET or glass substrate), and drying the composition by blowing hot air at a temperature of IQO 0 C or less so that the amount of residual solvent is 2% by mass or less;
• a thickness of the photosensitive material is measured with a measuring apparatus such as a contact surface roughness meter (trade name: Pl, manufactured by TENKOR). Then, a thickness of the substrate after completely removing the photosensitive resin layer from the substrate is measured, and the difference between the two measurements is defined as the thickness of the dry film.
• the amount of the residual solvent is measured by gas chromatograph-mass spectroscopy.
• the photosensitive composition of the invention Since particles containing an alloy portion are used as a coloring agent in the photosensitive composition of the invention, a thin film with a high optical density is obtained.
• the hue (particularly black hue) of the film is excellent while the increment of reflectivity as a result of heat treatment is small.
• the photosensitive composition also has good compatibility with the environment with little burden on the environment.
• the photosensitive composition of the invention is able to secure a high optical density even when the film is thin since the film formed to have an optical density of 2.0 or more per l ⁇ m of dry film thickness.
• optical density per 1 ⁇ m of the thickness of the dry film While a higher optical density per 1 ⁇ m of the thickness of the dry film is desirable, an optical density of 3.0 or more is preferable, and an optical density of 4.0 or more is more preferable. The optical density in this range is effective for securing a good display quality with high contrast. Particles containing an alloy portion
• the photosensitive composition of the invention contains at least one kind of particles containing an alloy portion (hereinafter, may be referred to as "alloy portion containing particles.). Using metallic particles containing an alloy as a coloring agent, a image formation of thin film, and high density is possible.
• the composition of the invention is particularly effective for forming a light shielding image (including a black matrix).
• the alloy portion containing particle includes the metal particles containing an alloy portion as well as a metallic compound particles containing an alloy portion. Particles comprising an alloy portion and a metal portion is preferable as the alloy portion containing particles.
• the alloy is described in "Alloy", p.447 of Iwanami Scientific Dictionary, fifth edition, published by Iwanami Shoten, 1998, and includes a solid solution, a eutectic crystal, a compound and an intermetallic compound composed of a plurality of metals.
• the metal in the metal particles also refers to that described in "Metal”, p.352 of Iwanami Scientific Dictionary, fifth edition, published by Iwanami Shoten, 1998.
• the "metallic compound” refers to a compound of a metal with elements other than metals, and the metal as used herein is a synonym of the metal in the metal particles.
• the fact that at least a portion of the alloy portion containing particle according to the invention is composed of an alloy can be confirmed by a spectroscopic measurement in an area of 15 nm square of each particle using, for example, an energy dispersive X-ray analyzer (trade name: HD-2300, manufactured by Hitachi. Ltd.; EDS: trade name, manufactured by Noran) at an acceleration voltage of 200 kV.
• an energy dispersive X-ray analyzer trade name: HD-2300, manufactured by Hitachi. Ltd.; EDS: trade name, manufactured by Noran
• metals in groups III to IVX in the long period periodic table are preferable, and gold, silver, copper, palladium, tungsten, titanium and tin are preferable. Silver and tin are particularly preferably among them from the viewpoint of safety and cost.
• the alloy portion of the alloy portion containing particle is preferably including plural metals selected from these metals.
• Examples of the compound of a metal with an element other than the metal include oxides, sulfides, sulfates and carbonates of metals. Sulfides are particularly preferable among them from the viewpoint of the coloer and readiness for forming the particles.
• the metallic compound examples include copper (II) oxide, iron sulfide, silver sulfide, copper (II) sulfide and titanium black. Silver sulfide is particularly preferable among them from the viewpoint of the color and readiness for forming the particles.
• the metallic compound particles include the following particles: (1) particles of the metallic compound;
• the particles of a composite of two or more kinds of metallic particle include composite particles of copper sulfide and silver sulfide, composite particles of iron sulfide and silver sulfide, and composite particles of copper (II) oxide and iron sulfide.
• the particles of the metal particles and metallic compound particles include composite particles of silver and silver sulfide, composite particles of silver and copper (II) oxide, and composite particles of palladium and palladium sulfide.
• the shape of the composite particles is not particularly limited, and examples thereof include those having different compositions between the inside and surface of the particle, and those comprising two kinds of particles combined together.
• the particle diameter of the alloy portion containing particles according to the invention is not particularly limited, but the number average diameter of the particle is preferably 60 to 3000 nm, more preferably 70 to 2000 nm, and particularly preferably 80 to 200 nm.
• a superior color (particularly a black hue) and dispersibility may be obtained when the number average particle diameter is within the above described range.
• particles of the metallic compound (which are not composite particles) with a number average particle diameter of 60 nm or more is preferable with respect to the color.
• the particle diameter distribution is not particularly limited.
• the number average particle diameter is measured as follows using a photograph taken by a transmission electron microscope (trade name: JEM-2010, manufactured by JEOL Ltd.). One hundred particles are selected at first, the diameter of a circle having the same area as respective particle images is defined as the particle diameter, and an average of the diameters, of 100 particles is defined as a number average particle diameter. The photograph was taken at a magnification of 1 x 10 5 under an acceleration voltage of 200 kV.
• the alloy portion containing particles of the invention should be colored in order to attain the necessary optical density.
• “Colored” particles are those having optical absorption of wavelength in a range of from 400 to 700 nm.
• the colored metallic compound include silver sulfide, copper sulfide, iron sulfide, palladium sulfide, silver oxide and titanium black.
• the shape of the alloy portion containing particles of the invention is not particularly limited. Particles having a spherical, amorphous, plate-like, cubic, regular octahedral and columnar shapes can be used.
• the alloy portion containing particles according to the invention may be used by mixing plural kinds of particles, if necessary, other than using one of them alone.
• the production method of the alloy portion containing particles of the invention is not particularly limited, and examples of the method include known methods such as gas phase methods including an evaporation condensation method and a gas phase reduction method, and liquid phase methods including s liquid phase reduction method. These methods are described, for example, in Newest Trends in Technologies and Applications of Particles II (in Japanese; published in 2002 by Sumibe Techno Research Co.).
• Preferable examples of the reduction method include a method using a reducing agent and an electrolytic reduction method.
• the method using the reducing agent is preferable in view of obtaining fine particles.
• the reducing agent include hydroquinone, catechol, para-aminophenol, para-phenylenediamine and hydroxyacetone. Hydroxyacetone is preferable among them since it is readily evaporated and gives no adverse effect to. the display device. .
• the content of the particles containing particles according to the invention in the photosensitive composition is preferably in the range of from 5 to 70%, more preferably in the range of from 10 to 50%.
• volume fraction is in the above range, an excellent dispersion stability of the particles in the. photosensitive composition is exhibited, and a thin film with a high optical density can be obtained.
• the photosensitive composition of the invention is effectively applied for forming a film with a thickness of 1 ⁇ m or less having a sufficient optical density.
• volume fraction refers to the ratio of the total volume of the particles to the total volume of the photosensitive composition or to the total volume of the formed thin film.
• the photosensitive composition contains at least one kind of monomer.
• the monomer is a component constituting a polymerized resin (a polymer compound) when a polymerization is carried out.
• An oligomer component may be used in addition to the monomer component.
• the photosensitive composition of the invention is constituted so that the alloy portion containing particles according to the invention are dispersed in the polymer formed by polymerization of the monomer for forming the film.
• the monomer contains ethylenic unsaturated double bonds, and can be polymerized by addition polymerization with light.
• the preferable monomer include . polyfunctional acrylicmonomers such as ethyleneglycol (meth)acrylate, triethyleneglycol di(meth)acrylate, 1,3-butanedioi di(meth)acrylate, tetramethyleneglycol di(meth)acrylate, propyl eneglycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-hexanediol di(meth)acrylate, pentaerythritol hexa(meth)acrylate and dipentaerythritol hexa(meth)acrylate. Oligomers formed by partly polymerizing these monomers may also be used.
• the photosensitive composition of the invention is preferably formed into a photosensitive polymerizable composition, which is favorably a photosensitive resin composition comprising a monomer (and an oligomer, if necessary) as well as a photopolymerization initiator and a binder (a polymer). Other components may also be contained.
• the photosensitive resin compositions include those developable with an aqueous alkali solution and those developable with an organic solvent.
• a resin composition capable of developing with the aqueous alkali solution is preferable from the viewpoint of safety and cost.
• the photopolymerization initiator is not particularly limited so long as it is able to polymerize the monomer, and examples thereof include the compounds described in paragraph No. [0024] in JP-ANo. 2004-347831 and polymerization initiator C described in JP-ANo. 11-133600.
• halomethyl-S-triazine compounds such as bis[4-[N-[4-(4,6-bistrichloromethyl-S-triazin-2-yl)phenyl]carbamoyl]phenyl]cebacate are preferable.
• the photosensitive composition of the invention can be preferably applied to a photopolymerization system.
• the content of the photopolymerization initiator in the photosensitive composition is usually in the range from 0.5 to 20% by mass, preferably from 1 to 15% by mass, relative to the total solid content of the composition.
• binder examples include polyvinyl alcohol, gelatin, cellulose polymers such as methyl cellulose, and acrylic or styrene acrylic polymers prepared by polymerizing methyl methacrylate, ethyl methacrylate, benzyl acrylate, acrylic acid, methacrylic acid and styrene.
• the polymers prepared by polymerizing acrylic acid and methacrylic acid are preferable, and alkali-soluble acrylic polymers containing acrylic acid and/or methacrylic acid, or styrene-acrylic polymers are preferable since patterning is preferable since they can be patterned by alkali development.
• the proportion of acrylic acid and methacrylic acid in the acrylic polymers or the styrene-acrylic polymers is preferably 10 to 60% by mass, more preferably from 20 to 50% by mass, as a total amount of acrylic acid and methacrylic acid.
• the content of the binder in the photosensitive composition is preferably in the range from 20 to 50% by mass, more preferably from 25 to 45% by mass, relative to the total solid content (a mass standard) of the composition.
• the photosensitive composition of the invention maybe favorably prepared using other components such as known dispersing agents, dispersion media, pigments, surfactants as described bellow.
• Dispersing agent dispersing agent
• a dispersing agent may be added for preparing the photosensitive composition of the invention in order to improve dispersion stability of the particles.
• dispersing agent examples include polyvinyl alcohol, acrylamide/acrylic acid copolymers, styrene/maleic anhydride copolymers, sodium polyacrylate, and sodium alginate.
• the dispersing agent is described in Pigment Dispersion Technology (in Japanese, published by Kazuhiro Takasu, Technical Information Institute Co., Ltd. 1999). Hydrophobic dispersing agents are particularly preferable among them.
• Dispersion stabilizer A dispersion stabilizer may be used for the photosensitive composition of the invention. Appropriate dispersion stabilizers described in Pigment Dispersion Technology (in Japanese, published by Technical Information Institute Co., Ltd. 1999) may be used.
• Dispersion medium examples include polyvinyl alcohol, acrylamide/acrylic acid copolymers, styrene/maleic anhydride copolymers, sodium polyacrylate, and sodium alginate.
• the dispersing agent is described in Pigment Dispersion Technology (in Japanese, published by Kazuhiro Takasu
• a dispersion medium may be used for preparing the photosensitive composition of the invention.
• the dispersion medium is not particularly limited, and either water or an organic solvent may be used.
• the organic solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol; 1-propyl alcohol, methylethyl ketone, acetone, toluene, xylene, dimethylaminoethanol and dibutylaminoethanol.
• a black pigment such as carbon black may be used as the pigment.
• the amount of addition of the pigment is preferably 50% by mass or less, particularly preferably 30% by mass or less, relative to the above described particles containing an alloy portion .
• the thickness of the light shielding film necessary for obtaining required optical density increases, and the quality of red, blue and green pixels formed on the light shielding film may be deteriorated when the amount of addition of the pigment exceeds 50% by mass.
• a blue pigment and other pigments except the black pigment may be added for adjusting perceptual color tones.
• the amount of addition of the pigment other than the black pigment is preferably 40% by mass or less, more preferably 20% by mass or less, relative to the particles containing an alloy portion .
• the perceptual color tone of the film may be deteriorated after forming the film when the amount of addition of the pigment exceeds 40% by mass.
• a surfactant may be added to the photosensitive composition of the invention for improving applicability and dispersion stability of the particles.
• the surfactant available is not particularly limited including nonionic, anionic and cationic surfactants.
• the anionic surfactant is preferable from the viewpoint of stability of the solution.
• Fluorinated surfactants are preferable surfactants.
• surfactant examples include C 8 F 17 SO 2 N(C 2 H 5 )(C 2 H 4 O) 14 H, C 8 F n SO 3 Li, C 7 F 15 COONH 4 and C 8 F 17 SO 2 N(C 2 H 5 )C 2 H 4 OPO(OH) 2 .
• the commercially available surfactant include FIlO, F113, F120, F150, F176PF, F177 and F780 (trade names, manufactured by Dainippon Ink & Chemicals, Inc., oligomer type fluorinated surfactants).
• the photosensitive composition of the invention can be prepared by mixing particles containing an alloy portion , a monomer, a binder capable of adding when necessary, a photopolymerization initiator and other additives (preferably by adding a dispersion medium), and by dispersing the mixture.
• a photopolymerization initiator and other components added when necessary are added after preparing a dispersion solution of the particles dispersed in the dispersion medium containing the alloy portion containing particles, monomer and binder.
• the photosensitive composition of the invention can be prepared by subjecting a mixed solution of the particles containing an alloy portion and the monomer (and preferably the binder and dispersion medium) to dispersion treatment using a known dispersion machine such as an ultrasonic disperser, paint shaker, ball mill and Eiger mill.
• a known dispersion machine such as an ultrasonic disperser, paint shaker, ball mill and Eiger mill.
• the ultrasonic disperser is preferable among the dispersion machines.
• the photosensitive composition of the invention containing the dispersed particles containing an alloy portion is suitable for uses such as colored film-forming inks (preferably a black film) and light shielding film (including a black image of color filters such as black matrix).
• colored film-forming inks preferably a black film
• light shielding film including a black image of color filters such as black matrix.
• the light shielding film of the invention is produced using the light shielding material of the invention, or a transfer material of the invention described below.
• the light shielding film formed by using the photosensitive composition of the invention has high optical density even in a thin film with a excellent hue (particularly a excellent hue of the black color) while the film exhibits little increment of reflectivity when the film is heat-treated.
• the film is also excellent in compatibility with the environment with little burden on the environment.
• the thin film is able to secure high optical density since an optical density of 2.0 or more is obtained per 1 ⁇ m of the thickness of the dry film.
• the light shielding film of the invention is produced by the processes comprising: applying the photosensitive composition of the invention onto a desired substrate, and drying the applied film (coating method); or applying the above described photosensitive composition onto a temporary support, preparing a transfer material having a photosensitive layer provided by drying the applied photosensitive composition (hereinafter, may also be referred to as a light shielding layer), and transferring the photosensitive layer to a desired substrate (transfer method).
• the patterned light shielding film is formed by patterning the photosensitive light shielding layer provided by the above described coating method or transfer method.
• Patterning methods include an exposure and development method; a method for abrading unnecessary portions with laser heat (abrasion method); and a method for applying a photosensitive resist film on the photosensitive layer formed on the substrate, patterning the resist film by exposure and development, and removing the photosensitive resist film. While any of these methods may be used in the invention, the following methods (1) to (3) are preferable from the view point of their simple production processes and the resolution of the patterning. .
• (1) a method that includes applying the photosensitive composition onto the substrate, drying the applied composition to form a light shielding layer, applying a photo-resist onto the light shielding layer, patterning the photo-resist layer formed by coating by exposure and development, and then dissolving and removing the photo-resist layer and the underlying light shielding layer together.
• (2) a method that includes applying the photosensitive composition on the substrate, drying the applied composition to form the photosensitive light shielding layer, and patterning the photosensitive light shielding layer by exposure and development (removal of non-hardened portions).
• a method that includes forming a laminate (a photosensitive transfer material) by forming the photosensitive light shielding layer in advance by applying the photosensitive composition onto a temporary support and drying the applied composition, laminating the laminate onto a desired substrate, transferring the photosensitive light shielding layer onto the substrate by removing the temporary support, and then patterning the photosensitive light shielding layer transferred on the substrate by exposure and development (removal of non-hardened portions).
• a laminate a photosensitive transfer material
• the light shielding film of the invention may be most preferably produced by the production methods of the invention shown in (I) and (II) below.
• (II) a method including transferring a photosensitive layer of the transfer material of the invention to a substrate (layer-forming process); forming a patterned image by exposing the transferred photosensitive layer in pattern-wise and then developing the exposed photosensitive layer(patterning process); arid conducting a heat treatment to the patterned image at a temperature of 150°C or higher for 5 minutes or more (heating process).
• a photosensitive composition coating and the like
• a coating method is preferable as the method for applying the photosensitive composition onto the substrate or temporary supports.
• the coating method is not particularly limited, and a slit coat method described in JP-A Nos. 2004-89851 and 2004-17043, a spin coat method described in JP-ANo. 5-224011 and a die coat method described in JP-ANo. 9-323472 may be used.
• the transfer material When the photosensitive composition is applied onto the temporary support, the transfer material may be composed of a temporary support, a light shielding layer formed the photosensitive composition, and an optionally provided thermoplastic resin layer and an intermediate layer. Patterning
• a patterned image is formed by pattern-wise exposing of the photosensitive layer formed in the layer forming process, and then developing the exposed photosensitive layer.
• a known light source may be used in the exposing for forming a desired pattern.
• the light source may be selected depending on photosensitivity of the light shielding layer of the photo-resist layer or photosensitive light shielding layer.
• Examples of the known light source include an extra-high pressure mercury vapor lamp, a xenon lamp,, a carbon arc lamp and an argon laser, as well as a high pressure mercury vapor lamp and metal halide lamp.
• An optical filter having a light transmittance of 2% or less at a wavelength of .400 nm or more as described in JPrA No. 6-59119 may be used together.
• the entire surface to be exposed may be collectively exposed by one process exposure, or may be exposed several times by partitioning the surface.
• a scanning exposure method of the surface using a laser may be employed.
• a development after exposing can be carried out by using a developer.
• a dilute aqueous alkaline solution is favorable as the developer, and an organic solvent miscible with water may be used together.
• suitable alkaline substance include alkali metal hydroxides (such as sodium hydroxide, potassium hydroxide), alkali metal carbonates (such as sodium carbonate, potassium carbonate), alkali metal bicarbonates (such as sodium hydrogen carbonate, potassium hydrogen carbonate), alkali metal silicate (such as sodium silicate, potassium silicate), alkali metal metasilicates (such as sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (such as tetramethylammonium hydroxide) and trisodium phosphate.
• alkali metal hydroxides such as sodium hydroxide, potassium hydroxide
• alkali metal carbonates such as sodium carbonate, potassium carbonate
• alkali metal bicarbonates
• the concentration of the alkaline substance is preferably in the range from 0.01 to 30% by mass, and pH is preferably in the range from 8 to 14.
• the pH may be changed, for example, depending on the properties of the photosensitive light shielding layer such as an oxidative property in order to permit the layer to be peeled as a film by development.
• the organic solvent miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethyleneglycol monomethyl ether, ethyleneglycol monoethyl ether, ethyleneglycol mono-n-butyl ether, benzyl alcohol, acetone, methylethyl ketone, cyclohexanone, ⁇ -caprolactone, ⁇ -butylolactone, dimethylformamide, dimethylacetamide, hexamethyl sulfonamide, ethyl lactate, methyl lactate, ⁇ -caprolactam and N-methyl pyrrolidone.
• concentration of the organic solvent miscible with water is usually in the range from 0.1 to 30% by mass.
• a known surfactant may be added to the developer.
• the concentration of the surfactant is preferably in the range from 0.01 to 10% by mass.
• the developer may be used in a bath or may be used as a spray liquid.
• Non-hardened portions of the photosensitive light shielding layer may be removed as a solid (preferably as a film), wherein the surface of the layer may be scraped with a rotating brush or a sponge, or by a spray pressure when the developer is sprayed may be preferably used.
• the temperature of the developer is usually in the range from room temperature to 4O 0 C.
• a roller conveyer may be provided in a developer tank filled with the developer in order to allow the substrate to horizontally move.
• the photosensitive resin is preferably formed on the upper surface of the substrate for preventing the resin surface from being damaged with the roller conveyer. Since there may arise a problem that developability is different between the center and peripheral portions of the substrate due to residence of the developer at near the center of the substrate by horizontally conveying the substrate when the length of the substrate exceeds 1 m, the substrate is preferably inclined for avoiding irregular development. The angle of inclination is preferably in the range from 5° to 30°. Dampening the photosensitive resin layer by spraying pure water just before development is desirable for obtaining a uniform development result.
• a rinsing process may be provided after development.
• a more uniform development result is obtained by rinsing the substrate by showering after gently browning air onto the substrate for roughly removing an excess liquid after development.
• a high quality image without any residues may be obtained by removing the residues by jetting ultra-pure water at a pressure in the range from 3 to 10 MPa through an ultra-high pressure nozzle. Since the process may be contaminated or specs may be left behind on the substrate when the substrate is conveyed to post processes while water drops remain adhered on the substrate, residual water is dripped with, an air knife to remove excess water or water drops. Heating and other processes
• the light shielding film of the invention is preferably heat-treated, and is heat-treated after the patterning process when the light shielding film is produced by the production method of the light shielding film according to the invention.
• the patterned image formed in the patterning process is heated at a temperature of 150°C or higher for 5 minutes or more in the heating process.
• Hardening of the photosensitive light shielding layer by exposure is accelerated by the heat treatment, and solvent resistance and alkali resistance of the hardened image may be enhanced.
• the substrate after developing may be heated in an electric furnace, a drying machine, or the like, or heated by an infrared lamp
• the heating treatment is preferably conducted at a temperature in the range from 150 to 250°C for 5 to 300 minutes, more preferably from 170 to 240°C for 10 to 200 minutes.
• the substrate may be further exposed after development and before heating in order to accelerate hardening.
• the exposure method in this case is the same. as the above described exposure method.
• a protective layer may be formed on the light shielding layer after forming the light shielding layer and before pattern-wise exposure.
• the protective layer functions as an oxygen barrier layer for enhancing sensitivity to exposure of the photosensitive light shielding layer by blocking oxygen during pattern- wise exposure. Since this protective layer is no necessary after forming the light shielding layer
• the thickness of the light shielding layer is preferably in the range from 0.2 to 1.5 ⁇ m, more preferably from 0.3 to 1.0 ⁇ m. Good display contrast is obtained by securing required optical density when the thickness is within the above described range, while there is no trouble for forming RBG pixels on the light shielding layer due to a too large roughness
• the transmission density (optical density) of the light shielding film of the invention is preferably in the range from 2.0 or more to 14.0 or less, more preferably from 3.5 or more to 13.0 or less, and particularly from 6.0 or more and 12.0 or less. A good display quality may be secured with high contrast when the optical density is within the above described range.
• optical density refers to an optical density (transmission density) in the wavelength region from 300 to 650 nm.
• the substrate used in the invention is preferably a glass substrate which is ordinarily used in display devices.
• the glass substrate may be a glass substrate made of a known glass such as sodium glass, low-alkali glass or nonalkali glass. Examples of the glass substrate are described in, for example, "Guide to Liquid Crystal Display Engineering (written by Hanae
• the substrate include a silicon wafer and a transparent plastic substrate such as a transparent plastic substrate made of a polyolefin.
• a TFT substrate can also be used.
• the thickness of the substrate is preferably from 0.5 to 3 mm, more preferably from 0.6 to 2 mm.
• the light shielding film of the invention is preferably black colored from the viewpoint of contrast of the displayed image and visibility. A better black color can be evaluated as a color difference from a desired chromaticity of ideal. black color, when the chromaticity of .the light shielding film is represented by a (x, y) value in a xyz color table. This means that the color approaches ideal black color as the color difference is smaller, while the color is out of the range of the black color when the difference is larger.
• the transfer material of the invention is a material used for forming the light shielding film, preferably for forming the light shielding film for the display device of the invention.
• the transfer material of the invention includes at least one layer of the photosensitive layer including the photosensitive composition of the invention, and is further composed of a thermoplastic resin, an intermediate layer and a protective layer covering the outermost surface of the layer when necessary.
• the photosensitive layer in the transfer material of the invention contains at least particles containing an alloy portion and a monomer and, preferably, further contains a photopolymerization initiator and binder.
• the photosensitive layer is formed to be photosensitive so that the optical density per 1 ⁇ m of the thickness, of the film after drying is 2.0 or more. Other components may be added to the photosensitive layer when necessary.
• the transfer material of the invention preferably comprises a photosensitive transfer material suitable for method (3) exemplified as one of the suitable method for forming the above described light shielding film.
• the photosensitive transfer material may comprise a temporary support, and a dried photosensitive layer formed by applying the photosensitive composition of the invention on the temporary support directly or indirectly with interposition of another layer.
• the thickness of the photosensitive layer is preferably in the range from 0.2 to 1.5 ⁇ m, more preferably from 0.3 to 1.0 ⁇ m. Excellent display contrast is obtained by securing required optical density when the thickness is within the above described range, while there is no trouble for forming RBG pixels on the light shielding layer due to a too large roughness (the step height between the portion where the light shielding film is provided and the portion where no light shielding film is provided).
• the photosensitive transfer material preferably includes a thermoplastic resin layer between the temporary support and photosensitive layer, more preferably includes an alkali soluble intermediate layer between the thermoplastic resin layer and photosensitive layer. A protective layer may be provided on the exposed surface of the photosensitive layer.
• the temporary support is chemically and thermally stable, and preferably comprises a flexible substance.
• the preferable substance include thin a sheet or a laminate of the sheet made of Teflon®, polyethylene terephthalate, polyethylene naphthalate, polyacrylate, polycarbonate, polyethylene and polypropylene.
• the temporary support preferably has good peelability from the thermoplastic resin layer when such layer is formed.
• a suitable thickness of the temporary support is in the range from 5 to 300 ⁇ m, and a thickness in the range from 20 to 150 ⁇ m is particularly preferable.
• Thermoplastic resin layer is particularly preferable.
• the thermoplastic resin layer includes at least a resin having thermoplasticity, and is generally formed using a thermoplastic resin-containing liquid prepared using a solvent.
• thermoplastic resin examples include an acrylic resin, a polystyrene resin, a polyester resin, a polyurethane resin, a rubber-base resin, a vinyl acetate-base resin, a polyolefin-base resin and copolymers thereof.
• the resin constituting the thermoplastic resin is desirably alkali-soluble.
• the resin containing the thermoplastic resin include at least one selected from a saponification product of an ethylene/acrylate ester copolymer, a saponification product of a styrene/(meth)acrylate ester copolymer, a three component copolymer of styrene/(meth)acrylic acid/(meth)acrylate ester copolymer, a saponification product of vinyl toluene/(meth)acrylate ester copolymer, poly(meth)acrylate ester, and a saponification product of a (meth)acrylate ester copolymer such as a copolymer between butyl (meth)acrylate and vinyl acetate; and resins soluble in an aqueous alkali solution of the organic polymers described in Handbook of Performance of Plastics (ed.
• One of the resins is preferably (A) a resin having a weight average molecular weight in the range from 50,000 to 500,0000 and a glass transition temperature (Tg) in the range from 0 to 14O 0 C (referred to resin (A) hereinafter), more preferably a resin having a weight average molecular weight in the range from 60,000 to 200,000 and a glass transition temperature (Tg) in the range from 30 to 110°C. . ' .' " '
• resin examples include those soluble in an aqueous alkali solution as described in Japanese Patent Application Publication (JP-B) Nos. 54-343227, 55-38961 , 58-12577, 54-25957 and 59-44614; JP-ANos.
• Resin (B) is preferably used together with above described various resins (A).
• Another resin (B) preferably has a weight average molecular weight in the range from 3000 to 30,000 and glass transition temperature (Tg) in the range from 30 to 17O 0 C, more preferably a weight average molecular weight in the range from 4000 to 20,000 and glass transition temperature (Tg) in the range from 60 to 140°C. While preferable examples may be selected from those described in the above patent publications, styrene/(meth)acrylic copolymers described in JP-B No. 55-38961 and JP-ANo. 5-241340 are preferable.
• thermoplastic resin When resin (A) has a weight average molecular weight of less than 50,000 and glass transition temperature (Tg) of lower than O 0 C, reticulation may occur or the thermoplastic resin may contaminate a permanent support by creeping into the periphery during transfer. When resin (A) has a weight average molecular weight exceeding 500,000 and a glass transition temperature (Tg) of exceeding 140 0 C, on the other hand, bubbles may appear during transfer or removability of the thermoplastic resin with the aqueous alkali solution may be deteriorated.
• Tg glass transition temperature
• the thickness of the thermoplastic resin layer is preferably 1 ⁇ m or more. Roughness of a transfer object (underlayer) with a magnitude of 1 ⁇ m or more can be completely relaxed when the thickness of the thermoplastic resin layer is within the above described range.
• the upper limit of the thickness is preferably about 100 ⁇ m, more preferably about 50 ⁇ m from the viewpoint of removability with the aqueous alkali solution and compatibility to production.
• thermoplastic resin-containing solution for forming the thermoplastic resin layer is not particularly limited so long as the resin constituting the layer is soluble in the solution, and the solvent may be selected from methylethyl ketone, n-propanol and i-propanol.
• thermoplastic resin layer When the thermoplastic resin layer is provided, an intermediate layer is preferably provided between the thermoplastic resin layer and photosensitive layer for preventing both layers from being mixed during application of the solutions of both layers, and for blocking oxygen.
• the intermediate layer is formed using at least a resin, and is usually formed using a resin-containing solution prepared by using an aqueous solvent system that has little compatibility to the solvent used for forming the thermoplastic resin layer and photosensitive layer.
• the resin containing in the intermediate layer is preferably alkali soluble, and examples of the resin include polyvinyl alcohol resins, polyvinyl pyrrolidone resins, cellulose resins, acrylamide resins, polyethylene oxide resins, gelatin, vinylether resins, polyamide resins and copolymers thereof.
• Resins prepared by making a resin usually insoluble in alkali to be soluble in an alkali by copolymerizing with a monomer having a carboxylic group or sulfonyl group may also be used.
• Polyvinyl alcohol is preferable among them.
• Polyvinyl alcohol preferably has a degree of saponification of 80% or more, more preferably in the range from 83 to 98%.
• a mixture of a plurality of resins is preferably used as the resin constituting the intermediate layer.
• a mixture of polyvinyl alcohol and polyvinyl pyrrolidone is more preferably used.
• the mixing ratio between them is preferably in the range from 1/99 to 75/25, more preferably from 10/90 to 50/50, in the mass ratio of polyvinyl alcohol to polyvinyl pyrrolidone.
• Decrease of sensitivity as a result of the oxygen blocking function may be suppressed when the mass ratio of mixing is within the above described range, while an intermediate layer having a good surface condition can be formed to permit adhesivity with the photosensitive resin layer applied on the intermediate layer to be favorable.
• the thickness of the intermediate layer is preferably in the range form 0.1 to 5 ⁇ m, more preferably from 0.5 to 3 ⁇ m.
• the thickness of the intermediate layer in the above range permits oxygen blocking performance to be excellent while the intermediate layer can be removed in a short period of time during development.
• the photosensitive layer in including in the photosensitive transfer material is formed by applying a solution prepared by mixing the particles containing an alloy portion and a monomer (preferably using a solvent), a high optical density is obtained even as a thin film while the hue is good (particularly good black hue).
• increment of reflectivity by the heat is small after applying a heat treatment and the production process of the layer has good compatibility with the environment with little burden on the environment.
• the method for forming the photosensitive layer on the substrate by transfer using the photosensitive transfer material will be mainly described below.
• the photosensitive layer is laminated on. the substrate by allowing the surface of the photosensitive layer as an uppermost surface to tightly contact the surface of the substrate, and is preferably transferred onto the substrate by peeling the temporary support.
• a known laminators or a vacuum laminator may be used for lamination.
• An auto-cutter laminator may also be used for increasing friction.
• the heating temperature of the substrate for lamination is preferably in the range from about 60 to 150°C, and the temperature of a rubber roller is preferably in the range from about 80 to 14O 0 C.
• the pressurizing pressure (linear pressure) is preferably in the range from about 50 to 200 N/cm.
• the photosensitive layer is preferably laminated on the substrate at a line convey speed in the range from about 1 to 5 m/minute. The transfer material may be winkled when the temperature of the rubber roller exceeds 140 0 C, while adhesivity between the photosensitive resin layer and substrate may be weakened when the temperature is lower than 80°C.
• the temporary support is peeled after lamination between the photosensitive transfer material and substrate, the photosensitive layer is exposed followed by development, and is heat treated after exposure and development.
• the above described methods may be used as the exposure, development and heat-treatment conditions.
• the substrate for the display device of the invention comprises the light shielding film formed on the substrate. Since the light shielding film is formed using the above described photosensitive material of the invention or the above described transfer material of the invention, the optical density is high even when the light shielding film is thin with good hues (particularly good black hue), and increment of reflectivity by the heat of heat treatment is small to render the contrast of the image and shielding performance of wiring lines excellent.
• the production process of the substrate has good compatibility with the environment with little burden on the environment.
• Color filter for display device Each component constituting the photosensitive composition and transfer material is as described previously, and preferable embodiments are also the same.
• the thickness and transmission density are the same as in the above described light shielding film.
• the color filter for the display device of the invention is composed of the substrate for the display device of the invention, or the light shielding film of the invention. Since the light shielding film is formed using the above described photosensitive composition of the invention or the above described transfer material, the optical density is high even when the light shielding film is thin with excellent hues (particularly excellent black hue), and increment of reflectivity by the heat of heat treatment is small to render the contrast of the image and shielding performance of wiring lines excellent.
• the production process of the substrate has good compatibility with the environment with little burden on the environment.
• the color filter of the invention comprises, on a light permeable substrate, a group of pixels containing plural pixels exhibiting different colors to one another, and the above described light shielding film of the invention as a light shielding image (so-called black matrix) for partitioning each pixel constituting the pixel group.
• a light permeable substrate a group of pixels containing plural pixels exhibiting different colors to one another
• the above described light shielding film of the invention as a light shielding image (so-called black matrix) for partitioning each pixel constituting the pixel group.
• the above described substrate, an addressing substrate comprising TFT elements (TFT element substrate) may be used as the light permeable substrate.
• Light permeability refers to a property for permitting a light to permeate the substrate, and preferably 90% or more of the light from a light source is permeated.
• the light shielding film for the display device is provided on the TFT element substrate for partitioning the pixel group and each pixel constituting the, pixel group.
• the color filter of the invention other than that described above may comprise only the light shielding film (black matrix) for the display device on the TFT element substrate without providing the pixel group.
• the pixel group is formed on a light permeable substrate independently from the TFT element substrate in this case, and the substrate on which the. pixel group is formed is used so as to face the TFT element substrate. This permits the aperture ratio of the TFT array to be excellent. . .
• the pixel group comprises a plurality of pixels having different hues to one another, and may be formed by a conventional method using a plurality of colored photosensitive resin composition and photosensitive transfer material for forming the pixels. A heat treatment is preferably applied after forming the pixel group.
• the display device of the invention comprises the color filter of the invention. Since the display device comprises the color filter of the invention, or specifically the photosensitive composition or transfer material of the invention, the optical density is high even when the light shielding film is thin with good hues (particularly good black hue), and increment of reflectivity by the heat of heat treatment is small to render the contrast of the image and shielding performance of wiring lines excellent.
• the production process of the substrate has good compatibility with the environment with little burden on the environment.
• the display device is not particularly limited so long as it comprises the color filter of the invention.
• the display device may further comprise constituting elements of known display devices.
• the display device may comprise a color filter substrate and a transparent substrate disposed to face the color filter substrate, a liquid crystal layer provided between these substrates, and a liquid crystal addressing means (including a passive matrix addressing means or an active matrix addressing means) for addressing the liquid crystal in the liquid crystal layer, and the above described color filter of the invention may be used as the color filter substrate.
• the display method of the liquid crystal is not particularly limited, and may be appropriately selected depending on objects.
• Examples of the display method available include ECB (electrically controlled birefringence), TN (twisted nematic), OCB (optically compensatory bend), VA (vertically aligned), HAN (hybrid aligned nematic), STN (super twisted nematic), IPS (in-plane switching), GH (guest host), FLC (ferroelectric liquid crystal), AFLC (anti-ferroelectric liquid crystal) and PDLC (polymer dispersion liquid crystal) methods.
• particle dispersion solution comprising silver/palladium alloy and silver
• Solution 1 obtained above was vigorously stirred while the temperature was kept at 25 0 C, and solution 2 was added to this solution over 10 minutes followed by gently stirring for an additional 6 hours. Then, the mixed solution turned into a black solution, and metal particles (referred to as particles 1 hereinafter) containing an alloy part of silver/palladium were obtained. Subsequently, particles 1 were precipitated by centrifugation of this mixed solution. For centrifugation, the mixed solution was divided into 150 ml aliquots of solution, and each aliquot was centrifuged at a rotation speed of 2,000 rpm for 30 minutes using a desk-top centrifuge H-103N (trade name, manufactured by KOKUSAN Co., Ltd.).
• the solution was centrifuged thereafter in order to precipitate particles 1,. folio wed by centrifugation under the same above described conditions. The supernatant was discarded as described above after centrifugation, and the total volume of the solution was adjusted to 150 ml. Pure water (850 ml) and acetone (500 ml) were added to the solution, and particles 1 were allowed to disperse again by stirring for 15 minutes. The dispersion solution was centrifuged again as described above and, after precipitating particles 1, the supernatant was discarded and the volume was adjusted to 150 ml. Pure water (150 ml) and acetone (1200 ml) were added followed by stirring for an additional 15 minutes to disperse particles 1 again.
• Particles 1 were separated by centrifugation.
• the conditions of centrifugation were the same as described above, except that the centrifugation time was lengthened to 90 minutes. After discarding the supernatant, the total volume was adjusted to 70 ml. Acetone (30 ml) was added to the solution, and the resulting, solution was dispersed using an Eiger mill (trade name: Eiger mill M-50 (media: 130 g of zirconia beads with a diameter of 0.65 mm), manufactured by Eiger Japan) to obtain a dispersion solution (dispersion solution Al) of particles 1.
• Eiger mill trade name: Eiger mill M-50 (media: 130 g of zirconia beads with a diameter of 0.65 mm), manufactured by Eiger Japan
• compositions were added to dispersion solution Al to prepare the coating solution for photosensitive light shielding layer: [Composition]
• composition of surfactant 1 is as follows:
• a non-alkali .glass substrate was cleaned with a cleaning liquid using a brush after washing with a UV washing apparatus, followed by ultrasonic cleaning with ultra-pure water.
• the substrate after cleaning was heated at 120°C for 3 minutes to stabilize the surface condition.
• the temperature was controlled to 23°C, and the coating solution for the photosensitive light shielding layer obtained as described above was applied on the substrate using a glass substrate coater provided with a slit nozzle (manufactured by Hirata Corporation) so that the optical density is 4.0, and the photosensitive light shielding layer was formed.
• the coating film was eliminated by drying a part of the solvent for 30 seconds using a vacuum drying apparatus (trade name: VCD, manufactured by Tokyo Ohka Kogyo Co., Ltd.), and the coating film was pre-baked at 12O 0 C for 3 minutes to obtain a photosensitive light shielding layer with an optical density of 4.0 and a thickness of 0.87 ⁇ m.
• the coating liquid for the protective layer was applied on the photosensitive light shielding layer by the same method as forming the photosensitive light shielding layer so that thickness after drying is 1.5 ⁇ m, and the applied liquid layer was dried at 100°C for 5 minutes.
• the photosensitive light shielding layer was exposed with a luminous energy of 70 mJ/cm from the coating face side of the substrate under an extra-high pressure mercury vapor lamp. Subsequently, the exposed layer was developed (33 0 C, 20 seconds; development process) using a developer (trade name: TCD, manufactured by Fuji Photo Film Co.; Ltd.; an alkaline developer) diluted five times (pH of use; 10.2), and the layer was further heat-treated at 220 0 C for 30 minutes to produce the light shielding film.
• a developer trade name: TCD, manufactured by Fuji Photo Film Co.; Ltd.; an alkaline developer
• The, particle dispersion solution (dispersion solution A2) was prepared by the same method as in Example 1, except that the amounts of palladium (II) acetate and silver (I) acetate in Example 1 were replaced by 70.0 g and 26.0 g, respectively.
• Example 3 The light shielding film was produced by the same method as in Example 1 , except that dispersion solution (Al) was replaced by the following particle dispersion solution (dispersion solution A3).
• particle dispersion solution comprising silver/gold alloy and silver Solution 3 was obtained by dissolving tetrachloro auric acid tetrahydrate (49.8 g), glucuronic acid (20 g), sodium pyrophosphate (24 g), polyethyleneglycol (1.5 g; molecular weight 3,000) and E735 (2.5 g; trade name of vinyl pyrrolidone/vinyl acetate copolymer, manufactured by International Specialty Products) in pure water (500 ml). hi a separate.
• solution 4 was obtained by dissolving silver (I) acetate (40.4 g), glucuronic acid (35 g), sodium pyrophosphate (24 g), polyethyleneglycol (1.5 g; molecular weight 3,000) and E735 (2.5 g; trade name of vinyl pyrrolidone/vinyl acetate copolymer, manufactured by International Specialty Products) in pure water (500 ml).
• Solution 5 was obtained by dissolving hydroxyacetone (28.0 g) in pure water (500 ml). Solution 5 obtained above was vigorously stirred while the temperature is kept at
• the solution was centrifuged thereafter in order to precipitate particles 3 again. After centrifugation, the supernatant was discarded as described above, and total volume of the solution was adjusted to 150 ml. Pure water (850 ml) and acetone (500 ml) were added to the solution, and particles 3 were allowed to disperse again by stirring for 15 minutes.
• the dispersion solution was centrifuged again as described above and, after precipitating particles 3, the supernatant was discarded.
• the volume was adjusted to 150 ml by adding pure water, and pure water (150 ml) and acetone (1200 ml) were added followed by stirring for additional 15 minutes to disperse particles 3 again. Particles 3 were separated by centrifugation.
• the conditions of centrifugation were the same as described above, except that the centrifugation time was elongated to 90 minutes. After discarding the supernatant, the total volume was adjusted to 70 ml.
• Example 4 Acetone (30 ml) was added to the solution, and the resulting solution was dispersed using an Eiger mill (trade name: Eiger mill M-50 (media: 130 g of zirconia beads with a diameter, of 0.65 mm), manufactured by Eiger Japan) to obtain a dispersion solution (dispersion solution A3) of particles 3.
• Eiger mill trade name: Eiger mill M-50 (media: 130 g of zirconia beads with a diameter, of 0.65 mm), manufactured by Eiger Japan
• the light shielding film was produced by the same method as in Example 1, except that dispersion solution Al in Example 1 was replaced by the following particle dispersion solution (dispersion solution A4).
• particle dispersion solution comprising silver/tin alloy and tin
• Solution 6 was obtained by dissolving silver (I) acetate (23.1 g), tin (II) acetate (65.1 g), glucuronic acid (54 g), sodium pyrophosphate (45 g), polyethyleneglycol (2 g; molecular weight 3,000) and E735 (5 g; trade name of vinyl pyrrolidone/vinyl acetate copolymer, manufactured by International Specialty Products) in pure water (500 ml).
• solution 7 was obtained by dissolving hydroxyacetone (36.1 g) in pure water (500 ml).
• Solution 6 obtained above was vigorously stirred while the temperature is kept at 25 0 C, and solutions 7 was added to this solution in 2 minutes followed by gently stirring for additional 6 hours. Then, the mixed solution turned into a black solution, and metal particles (referred to particles 4 hereinafter) containing an alloy part of silver/tin was obtained. Subsequently, particles 4 were precipitated by centrifugation of this mixed solution.
• the mixed solution was divided into 150 ml aliquot of solutions, and each fraction was centrifuged at a rotation speed of 2,000 rpm for 30 minutes using a desk-top centrifuge H-103n (trade name, manufactured by KOKUSAN Co., Ltd The supernatant was discarded, and the total volume was adjusted to 150 ml. Pure water (1350 ml) was added to this supernatant and the mixed solution was stirred for 15 minutes to disperse particles 4 again. This procedure was repeated twice to remove soluble substances in the aqueous phase.
• the solution was centrifuged thereafter in order to precipitate particles 4 again.
• the solution was centrifuged under the above described condition. After centrifugation, the supernatant was discarded as described above, and total volume of the solution was adjusted to 150 ml. Pure water (850 ml) and acetone (500 ml) were added to the solution, and particles 4 were allowed to disperse again by stirring for 15 minutes.
• the dispersion solution was centrifuged again as described above and, after precipitating particles 4, the supernatant was discarded.
• the volume was adjusted to 150 ml by adding pure water, and pure water (150 ml) and acetone (1200 ml) were added followed by stirring for additional 15 minutes to disperse particles 4 again. Particles 4 were separated by centrifugation.
• the conditions of centrifugation were the same as described above, except that the centrifugation time was elongated to 90 minutes. After discarding the supernatant, the total volume was adjusted to 70 ml.
• thermoplastic resin layer prepared by prescription Hl was applied on the surface of a polyethylene terephthalate temporary support (PET temporary support) with a thickness of 75 ⁇ m so that the dry thickness of the layer is 14.6 ⁇ m using a slit nozzle.
• PET temporary support polyethylene terephthalate temporary support
• the coating solution was dried at 100°C for 3 minutes to form the thermoplastic resin layer.
• the coating solution for the intermediate layer prepared by above described prescription Pl was applied on the thermoplastic resin layer so that the dry thickness of the layer is 1.6 ⁇ m using a slit coater.
• the coating layers were dried at 100°C for 3 minutes to laminate an intermediate layer (oxygen blocking layer).
• the coating liquid for the photosensitive light shielding layer (containing dispersion solution Al) prepared in Example 1 was applied on this intermediate layer with a slit coater so that the optical density is 4.0, and the photosensitive light shielding layer was formed by drying the coated layer at 100 0 C for 3 minutes.
• thermoplastic layer a film comprising the thermoplastic layer, intermediate layer and photosensitive light shielding layer sequentially laminated on the PET temporary support was thus produced, and the photosensitive transfer material was produced by press-bonding a polypropylene film with a thickness of 12 ⁇ m on the light shielding layer as a protective film.
• a non-alkali glass substrate was washed with a rotating brush having nylon yarns while a glass cleaning liquid warmed at 25°C is blowing for 20 seconds by showering.
• a silane coupling solution (3% aqueous solution of N- ⁇ -aminoethyl)- ⁇ -aminopropyl trimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd) was blown for 20 seconds by showering, followed by showering pure water.
• the substrate was heated at 100°C for 2 minutes using a pre-heating apparatus.
• the transfer material was placed on the glass substrate so that the exposed photosensitive light shielding layer contacts the surface of the glass substrate after heating, and bonded to the surface of the glass substrate using a laminator (trade name: Lamic II, manufactured by Hitachi Industries) under the conditions of rubber roller temperature of 130°C, linear pressure of 100 N/cm and a convey speed of 2.2 m/minute (laminate process). Then, the PET temporary support was peeled (Transfer process).
• the substrate was exposed pattern- wise at a luminous energy of 70 mJ/cm 2 from the side of the substrate on which the photosensitive light shielding layer was transferred using a proximity aligner (manufactured by Hitachi Electronic Engineering) equipped with a extra-high pressure mercury vapor lamp (exposure process).
• a proximity aligner manufactured by Hitachi Electronic Engineering
• the substrate was developed by shower development by jetting triethanolamine developer (trade name: T-PDl, contains 2.5% of triethanolamine, nonionic surfactant and polypropylene anti-foaming agent, manufactured by Fiji Photo Film Co.) solution 12X diluted (that is mixed at, a ratio of 1 part by mass of T-PDl to 11 parts by mass pure water) from above the thermoplastic resin layer for 50 seconds through a flat nozzle at 30°C at a nozzle pressure of 0.04 MPa, and the thermoplastic resin layer and intermediate layer was removed by development.
• triethanolamine developer trade name: T-PDl, contains 2.5% of triethanolamine, nonionic surfactant and polypropylene anti-foaming agent, manufactured by Fiji Photo Film Co.
• a sodium carbonate developer trade name: T-CD-I, containing 0.38 mole/liter of sodium hydrogen carbonate and 0.47 moles/liter of sodium carbonate, 5% by mass sodium dibutylnaphthalene sulfonic acid, anionic surfactant, anti-foaming agent and a stabilizer, manufactured by Fuji Photo Film Co., Ltd., five-times dil
• a cleaning agent (trade name: T-SDl, containing a phosphate salt, nonionic surfactant and stabilizer; manufactured by Fuji Photo Film Co., Ltd.) 1OX diluted with pure water from a cone nozzle at a temperature of 33°C and a pressure of 0.2 MPa using a rotating brush having nylon yarns to obtain the light shielding film.
• the film was post-exposed with a light form an extra-high pressure mercury vapor lamp at a luminous energy of 500 mJ/cm 2 from the side of the glass substrate on which the image is formed, and was heat-treated at 200°C for 15 minutes.
• Examples 6 to 8
• the light shielding film was produced by the same method as in Example 5, except that dispersion solution Al used for preparing the coating solution for the photosensitive light shielding layer in Example 5 was replaced by dispersion solution A2 (Example 6), dispersion solution A3 (Example 7) and dispersion solution A4 (Example 8).
• the light shielding film was produced by the same method as in Example 1, except that dispersion solution Al used for preparing the coating solution for the photosensitive light shielding layer in Example 1 was replaced by the following carbon black dispersion solution
• Carbon black (3.8 g; trade name Legal 400, manufactured by Legal Co.), Solsperse 2000 (0.38 g; trade name, manufactured by Abisia Co;) and methylethyl ketone (50 ml) were mixed. Glass beads (40 g; particle diameter 3 mm) were added to this mixed solution, and were dispersed for 6 hours with a paint shaker. Carbon black dispersion solution Bl was prepared by removing glass beads.
• Comparative Example 2 The light shielding film was produced by the same method as in Example 1, except that dispersion solution Al used for preparing the coating solution for the photosensitive light shielding layer in Example 1 was replaced by silver particle dispersion solution B2 described below.
• Distilled water (3,488 g) was added to gelatin (112 g), and the mixture obtained was heated at 47 0 C to dissolve gelatin.
• Distilled water was further added, and the final weight of the solution was adjusted to 5.0 kg. Then, after cooling the product to near gelling temperature, the solution was allowed to pass through small hales into cooled water to form fine noodles.
• the noodle was supplied as an amplification catalyst for forming blue silver.
• Solution A sodium sulfite (anhydrous) : 19.5 g sodium hydrogen sulfite (anhydrous) :0.98 g distilled water : 122.0 g
• Solution B silver nitrate: 9.75 g distilled water: 122.0 g Solutions A and B were mixed and continued to stir to form white precipitates that are to be extinguished. Immediately thereafter, the mixture was added to the slurry of noodle in a short period (within 5 minutes) with vigorous stirring. The temperature was kept at 10°C, and an amplification reaction was allowed to proceed for about 80 minutes until entire soluble silver salt is reduced on nuclei to obtain blue slurry particles.
• blue silver comprises platelets of particles with an edge length in the range from about 20 to 30 nm and a thickness of about 7 nm. Production of silver particles
• a dispersing agent (6 g; trade name: pyrazole B90, manufactured by Nippon Oil & Fats Co.) and 5% aqueous solution (2000 g) of papain were added to the slurry of dispersed silver (4,000 g), and was the mixture was kept at 37°C for 24 hours.
• the solution after preservation was centrifuged at 2,000 rpm for 5 minutes to allow silver particles to precipitate.
• gelatin decomposed by enzyme is removed by washing with distilled water to' obtain a precipitate of silver particles. Then, the precipitate of silver particles was washed with methyl alcohol and dried to obtain about 60 g of aggregates of the silver particles.
• the optical density of each light shielding film was measured as follows: Using the photosensitive light shielding liquids that formed the black matrixes of each of the Examples and the Comparative Examples a thin film layer on a transparent substrate was formed so that the transmission optical density was 3.0 or less, and then processing was carried out in the same way as in each of the Examples and the Comparative Examples except that light exposure for patterning was not carried out, to obtain samples for measuring the transmission optical density of a thin film formed on a transparent substrate.
• the optical density (OD) of the light shielding film provided on the samples as described above were measured using a Macbeth densitometer (trade name: TD-904, manufactured by Macbeth Co.) together with a glass substrate.
• the optical density (OD 0 ) of the glass substrate used was separately measured by the same method. A value obtained by subtracting OD 0 from OD (OD - OD 0 ) is defined to be the optical density of the thin film formed on the sample base.
• Reflectivity (%) of each light shielding film was measured from the non-coated surface side of the glass substrate Using a measuring apparatus as a combination of a spectrophotometer (trade named: U-560, manufactured by JASCO Co.) and a reflectivity measuring unit (trade name: ARV-474, manufactured by JASCO Co.). The incident angle and reflection angle were 5°, and the measuring wavelength was 500 nm. Subsequently, each light shielding film after the measurement was placed in a substrate heating apparatus together with the glass substrate, and was baked at 22O 0 C for 30 minutes with respect to the samples in Examples 1 to 4 and Comparative Examples 1 and 2, and at 22O 0 C for 15 minutes with respect to the samples in Examples 5 to 8. The reflectivity (%) of each light shielding film after baking and cooling was measured by the same above described method.
• Example 1 in which carbon black was used as a coloring agent, while increment of reflectivity by heating could not be suppressed in Comparative Example 2 in which the film comprises silver particles, although high optical density could be obtained in the thin film.
• Comparative Example 2 in which the film comprises silver particles, although high optical density could be obtained in the thin film.
• Examples 9 to 12 The laminate process, transfer process and exposure process were applied to non-alkali glass substrates after cleaning and heating by the same method in Example 5 using the photosensitive transfer materials obtained in Examples 5 to 8.
• the temporary support was peeled at the interface between the support and thermoplastic resin layer, and the photosensitive transfer material was exposed pattern-wise with a luminous energy of 70 mJ/cm 2 , wherein the substrate and a mask (a quartz exposure mask having an image pattern) were stood upright, the distance between the mask surface and the surface of the thermoplastic resin layer was adjusted to 200 ⁇ m, and the photosensitive transfer material was irradiated with a proximity aligner (manufactured by Hitachi Electronic Engineering Co.). Subsequently, the photosensitive transfer material was subjected to a development process as follows:
• development 1 developed with a 10-times dilution developer (trade name: T-PD2, alkali developer manufactured by Fuji Photo Film Co., Ltd.) at pH 11 (33°C, 20 seconds; development process);
• development 2 developed with a 5-times dilution developer (trade name: T-CDl, alkali developer manufactured by Fuji Photo Film Co., Ltd.) at pH 10.2 (33 0 C, 20 seconds; development process);
• each light shielding film has a lattice pattern with a line with of 15 ⁇ m in the longitudinal and lateral directions; and the window portion was rectangular with a length of 270 ⁇ m and a width of 80 ⁇ m.
• a color filter was produced by providing red (R), green (G) and blue (B) pixels by the following method.
• the surface of the photosensitive resin layer of a red transfer material is piled on the surface of the substrate at the side having the light shielding film so that the former surface is in close contact with the latter surface. Both surfaces were laminated using a laminator (trade name: Lamic II, manufactured by Hitachi Industries Co.) under conditions of a rubber roller temperature of 13O 0 C, a linear pressure of 100 N/cm and a convey speed of 2.2 m/minute (lamination process). Then, the PET temporary support was peeled (transfer process).
• a laminator trade name: Lamic II, manufactured by Hitachi Industries Co.
• the substrate was exposed from the side on which the photosensitive resin layer of the substrate having the light shielding film is transferred at a luminous energy of 200 mJ/cm 2 via a mask using a high pressure mercury vapor lamp.
• the substrate was developed by the same procedure as in the development processes (development 1, development 2, rinsing and drying) in the production of the substrate having the light shielding film.
• Red colored pixels R pixels
• blue and green colored pixels B and G pixels, respectively
• a color filter comprising three pixels of R, B and G colored pixels and light shielding films partitioning respective colored pixels was thus produced.

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