CN114846365A - Black shading part - Google Patents
Black shading part Download PDFInfo
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- CN114846365A CN114846365A CN202080089852.6A CN202080089852A CN114846365A CN 114846365 A CN114846365 A CN 114846365A CN 202080089852 A CN202080089852 A CN 202080089852A CN 114846365 A CN114846365 A CN 114846365A
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- light
- layer
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- black
- shielding layer
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/003—Light absorbing elements
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B7/00—Mountings, adjusting means, or light-tight connections, for optical elements
- G02B7/02—Mountings, adjusting means, or light-tight connections, for optical elements for lenses
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
- G03B9/00—Exposure-making shutters; Diaphragms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Optical Elements Other Than Lenses (AREA)
- Laminated Bodies (AREA)
- Lens Barrels (AREA)
- Diaphragms For Cameras (AREA)
- Non-Portable Lighting Devices Or Systems Thereof (AREA)
- Liquid Crystal (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The invention provides a black light-shielding member having excellent anti-reflection effect based on low glossiness and high blackness. A black light-shielding member is produced which comprises a base film, a light-shielding layer made of a resin and having a concavo-convex shape formed on at least one surface of the base film, and a black layer formed on the light-shielding layer made of the resin. Blackness with an L value of 12 or less is achieved by adjusting the surface arithmetic average roughness Ra of the surface on which the light-shielding layer and the blackened layer are formed to be 0.25 [ mu ] m or more and the maximum thickness of the blackened layer to be smaller than Ra.
Description
Technical Field
The present invention relates to a black shading member, and more particularly, to a black shading member that can be suitably used for an optical apparatus such as a camera unit of a mobile phone or the like including a smartphone.
Background
In general, a light shielding member is used for a lens diaphragm, a shutter, and a lens spacer of a camera.
As such a light-shielding member, a black film having a predetermined uneven shape formed on a surface of a black polyester substrate or the like such as carbon black is known. Examples of the method for forming the irregularities include a method of covering the surface of the base material with a light-shielding layer containing a matting agent, and a method of roughening the surface of the base material by a method such as sandblasting.
Patent document 1 describes: by using the above method, etc., a film according to JIS B0601: 2001 of 0.5 μm or more and a difference (Rp-Rv) between a maximum peak height Rp and a maximum valley depth Rv of less than 3. The light-shielding member of patent document 1 exhibits excellent antireflection performance even when it is thin, and has excellent hardness and adhesion between the light-shielding layer and the film base material, so that the excellent antireflection performance can be maintained for a long period of time.
Documents of the prior art
Patent literature
Patent document 1: international publication No. WO2018/052044
Disclosure of Invention
Problems to be solved by the invention
In recent years, for the purpose of improving the design feeling, a member is required which makes the black color of a light shielding member used in an optical apparatus conspicuous. However, to date, no satisfactory results have been obtained.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a light shielding member having an excellent antireflection effect by low glossiness and a high blackening property.
Means for solving the problems
The present inventors have conducted extensive studies in view of the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by forming a black layer in addition to the above-mentioned uneven shape in a black light-shielding member having a base film and a light-shielding layer made of a resin having an uneven shape formed on at least one surface of the base film, and further controlling the uneven shape of the surface of the light-shielding member, and have arrived at the present invention. That is, the black light-shielding member of the present invention comprises a base film, a light-shielding layer made of a resin and having a concavo-convex shape formed on at least one surface of the base film, and a blackened layer formed on the light-shielding layer made of the resin, and is characterized in that the surface of the black light-shielding member on which the light-shielding layer and the blackened layer are formed has an arithmetic average roughness Ra of 0.25 μm or more and an L value of 12 or less, and the blackened layer has a maximum thickness smaller than Ra.
Here, the resin light shielding layer means that at least the uneven portion forming the surface of the blackening layer is made of resin. For example, as described later, a structure in which a light-shielding layer containing a matting agent and/or a light-shielding layer containing no matting agent is formed on the surface of a metal base film having a recessed and projected shape is also included in the light-shielding layer made of a resin of the present invention.
The arithmetic average roughness Ra described in the present invention is based on JIS B0601: 2001, and the L value is represented by L calculated based on JIS Z8781-4 * a * b * L of lightness in color space * The value is obtained.
Preferably, the light shielding layer made of a resin has a resin layer containing a matting agent and a resin component.
The resin light-shielding layer may include a roughened portion formed on the surface of the base film.
On the other hand, it is preferable that the blackening layer contains an inorganic material.
Preferably, the blackening layer includes at least one selected from the group consisting of magnesium fluoride, calcium fluoride, lithium fluoride, aluminum oxide, gallium oxide, and silicon oxide.
Preferably, the black layer is formed by any one method selected from the group consisting of a sputtering method, a vapor deposition method, an ion plating method, and a Chemical Vapor Deposition (CVD) method.
Further, it is preferable that the maximum thickness of the blackening layer is smaller than 1/2 which is a value of arithmetic average roughness Ra of the surface.
ADVANTAGEOUS EFFECTS OF INVENTION
The black light-shielding member of the present invention has not only an excellent anti-reflection effect due to low glossiness but also high blackness, distinct black color, and excellent design feeling. Therefore, the present invention is also suitable for use as a camera unit of a mobile phone such as a smartphone.
Drawings
Fig. 1 is a schematic sectional view showing the structure of a light shielding member in an embodiment of the present invention ((a) before formation of a blackened layer and (b) after formation of a blackened layer).
Fig. 2 is a schematic sectional view showing the structure of a light shielding member in another embodiment of the present invention ((a) before formation of a blackened layer and (b) after formation of a blackened layer).
Description of the reference symbols
1 light-shielding member (before formation of blackened layer)
10 light-shielding member (after formation of blackened layer)
2 base material film
3 light shielding layer
31 matting agent
32 matrix part
4 light-shielding layer (resin film)
5 blackened layer
Detailed Description
Embodiments of the present invention will be described in detail below.
In the present specification, "to" indicating a numerical range means to include numerical ranges in which an upper limit value and a lower limit value are described, respectively. In the numerical range, if only the upper limit value is described as a unit, it means that the lower limit value also has the same unit as the upper limit value.
In the numerical ranges recited in the present specification, the upper limit or the lower limit recited in a certain numerical range may be the upper limit or the lower limit of another numerical range recited in a stepwise manner.
In the numerical ranges described in the present specification, the upper limit or the lower limit described in a certain numerical range may be replaced with the values shown in the examples.
In the present specification, the content or content of each component in the composition refers to the total content or total content of a plurality of substances present in the composition when the plurality of substances corresponding to each component are present in the composition, unless otherwise specified.
Embodiments of the present invention will be described in detail below.
The black light-shielding member of the present invention comprises a base film, a light-shielding layer made of a resin and having a concavo-convex shape formed on at least one surface of the base film, and a blackened layer formed on the light-shielding layer made of the resin, wherein the surface of the black light-shielding member on which the light-shielding layer and the blackened layer are formed has an arithmetic average roughness Ra of 0.25 [ mu ] m or more, a blackness (L value) of 12 or less, and a maximum thickness of the blackened layer is smaller than the Ra.
First, the uneven shape of the light-shielding resin layer according to the present invention will be described with reference to the drawings.
Examples of the method for forming the uneven shape of the light-shielding resin layer include the following method (a), method (B), and method (C).
In the method (a), as shown in fig. 1(a), a light-shielding layer 3 is covered on the surface of a flat base film 2, and the light-shielding layer 3 contains a matting agent 31 and a base portion 32. On the surface of the light-shielding layer 3, irregularities are formed by the matting agent 31. Here, Ra on the surface of the light-shielding member 1 can be controlled by adjusting the particle diameter, particle size distribution, content, film thickness of the light-shielding layer 3, and the like of the matting agent 31. The coating liquid may be controlled by adjusting the type of solvent, the solid content concentration, and the amount of coating on the substrate film. Further, the coating liquid may be controlled by coating conditions such as a coating method of the coating liquid, drying temperature and time, and an air volume during drying.
In the method (B), as shown in fig. 2(a), irregularities are formed on the surface of the base material film 2. When the substrate film is a resin film, a sandblasting method, for example, can be applied to form irregularities. Here, Ra can be controlled by controlling the particle size, ejection pressure, and the like of the polishing agent used. Further, for example, a matting agent may be contained in the raw material of the base film to prepare a base film containing the matting agent. As the matting agent, the same kind of matting agent as that of the light-shielding layer described later can be preferably used. The Ra of the substrate film surface is controlled by controlling the particle size, particle size distribution, content of the matting agent and the thickness of the substrate film.
Further, the substrate film 2 having the irregularities may be coated with a coating liquid or the like, and a resin film 4 having a shape conforming to the irregularities of the surface of the substrate film 2 may be formed on the surface of the light-shielding member 1. Here, the resin film 4 on the light shielding member surface contains a resin component such as an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, a urea resin, a melamine resin, a fluorine resin, and an imide resin. The resin film 4 may be made to contain no matting agent, and Ra and the like on the surface of the light shielding member 1 may be controlled by controlling the uneven shape of the resin base film 2, the film thickness of the resin film 4, and the like.
The resin film 4 is different in material and film thickness from a blackened layer described later. That is, the resin film 4 is formed of a resin component and has a film thickness of about 1 to 50 μm, preferably about 2 to 10 μm. On the other hand, the blackening layer described later is formed of an inorganic material, submicron-sized resin particles, a binder resin component, or the like, and has a film thickness of about 10nm to 200 nm.
By the above difference, the black level of the black light-shielding member of the present invention having the black layer formed thereon is 12 or less.
In the method (C), the unevenness is formed on the surface of the base film as in the method (B), and the light-shielding member surface is covered with the light-shielding layer containing the matting agent as in the method (a). In this structure, Ra on the surface of the light-shielding member can be controlled by the shape of the irregularities on the surface of the base film 2, the film thickness of the light-shielding layer, the particle diameter, particle size distribution, content of the matting agent in the light-shielding layer, the production conditions such as the light-shielding layer, and the like.
Preferably, the black light-shielding member of the present invention has a structure in which a light-shielding layer is formed on at least one surface of a base film. In the following description, the light-shielding layer also includes a resin thin film formed by the method (B) and having a rough surface (roughened portion) formed on the surface of the base film and containing no matting agent covering the surface.
Next, a specific material composition of the black light-shielding member of the present invention will be described.
(1) Substrate film
The substrate film used in the present invention is not particularly limited, and may be a transparent or opaque substrate film. The base film of the present invention may be made of resin or metal.
Examples of the resin-made base film include polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymers, and copolymers of ethylene and an α -olefin having 4 or more carbon atoms, polyesters such as polyethylene terephthalate, polyamides such as nylon, ethylene-vinyl acetate copolymers, other general-purpose plastic films such as polyvinyl chloride and polyvinyl acetate, and engineering plastic films such as polycarbonate and polyimide.
Examples of the metal base film include a metal sheet using a metal such as gold, silver, copper, aluminum, titanium, zinc, beryllium, nickel, and tin, and an alloy sheet using an alloy such as phosphor bronze, copper nickel, copper beryllium, stainless steel, brass, and hard aluminum.
Among these materials, biaxially stretched polyethylene terephthalate is preferably used from the viewpoint of high strength, high economy, and high versatility, polyimide films are preferably used from the viewpoint of heat resistance, and metal sheets made of copper are preferably used from the viewpoint of high heat resistance. When the base film is a resin base film, a high light-shielding material having an optical density of 2 or more, preferably 4 or more can be obtained by kneading a black coloring agent such as carbon black or aniline black into these materials, and a more excellent light-shielding effect can be obtained.
The thickness of the base film is not particularly limited, and when a resin base film is used, the thickness is preferably 4 to 250 μm, more preferably 12 to 100 μm. By setting the thickness within the above range, the present invention can be applied to a small and thin optical component. In addition, in the case of using the optical device such as a camera unit of a mobile phone, etc., the thickness is preferably 4 to 20 μm.
When a metal base film is used, the thickness is preferably 6 to 40 μm, and particularly preferably 10 to 20 μm when the film is used in an optical device such as a camera unit of a mobile phone or the like.
In the case of using the above-described methods (B) and (C), the surface of the base film is matte to form irregularities (roughened portions). The matting method is not particularly limited, and a known method can be used. For example, when the base film is a base film made of a resin, a chemical etching method, a spray method, a calender method, a corona discharge method, a plasma discharge method, a chemical extinction method using a resin and a roughening agent, or the like can be used. Further, the base film may contain the matting agent as it is, and the surface of the resin base film may be provided with irregularities. Among the above-mentioned processing methods, the blasting method is preferably used, and particularly the blasting method is preferably used, from the viewpoints of easiness of shape control, economy, workability, and the like.
In the blasting method, Ra and the like of the surface can be controlled by controlling the particle diameter, the ejection pressure, and the like of the polishing agent used. In addition, in the calendering method, the Ra and the like of the surface can be controlled by adjusting the shape of the calender roll and the pressure.
On the other hand, when the base material film is a metal base material film, the surface may be formed with irregularities by blackening treatment, blasting treatment, etching treatment, or the like. In addition, when the base material film is a metal base material film, at least one of a light-shielding layer containing a matting agent described later and a light-shielding layer containing no matting agent needs to be formed on the irregularities (roughened portions) of the surface.
(2) Fixing layer
In order to improve the adhesion between the base film and the light-shielding layer, a fixing layer may be provided before the light-shielding layer is provided on at least one surface of the base film. As the anchor layer, a urea resin layer, a melamine resin layer, a urethane resin layer, a polyester resin, or the like can be applied. For example, the polyurethane resin layer can be obtained by applying a solution containing a polyisocyanate and an active hydrogen-containing compound such as a diamine or a diol on the surface of a substrate film and curing the solution. In the case where the anchor layer is a urea-formaldehyde resin or a melamine resin, the anchor layer can be obtained by applying a solution containing a water-soluble urea-formaldehyde resin or a water-soluble melamine resin to the surface of the base material and curing the applied solution. The polyester resin can be obtained by applying a solution dissolved or diluted with an organic solvent (methyl ethyl ketone, toluene, or the like) on the surface of a substrate and drying it.
(3) Light shielding layer
As described above, in the method (B), the light-shielding layer is covered on at least one surface of the base film, except for the light-shielding member in which only the uneven portion formed on the surface of the resin base film is used as the light-shielding layer. The light-shielding layer includes a light-shielding layer containing a matting agent used in the above-described methods (a) and (C) and a light-shielding layer (high-hardness layer, thin film) containing no matting agent used in the method (B).
Next, the structure of each light-shielding layer will be described.
i) Light shielding layer containing matting agent
The light-shielding layer contains a resin component, a matting agent, and a dyeing/conductive agent as constituent components.
The resin component acts as a binder for the matting agent and the dyeing/conducting agent. The material of the resin component is not particularly limited, and any of a thermoplastic resin and a thermosetting resin may be used. Specific examples of the thermosetting resin include acrylic resins, urethane resins, phenol resins, melamine resins, urea resins, allyl phthalate resins, unsaturated polyester resins, epoxy resins, and alkyd resins. Examples of the thermoplastic resin include a polyacrylate resin, a polyvinyl chloride resin, a butyral resin, and a styrene-butadiene copolymer resin. From the viewpoint of heat resistance, moisture resistance, solvent resistance and surface hardness, a thermosetting resin is preferably used. As the thermosetting resin, acrylic resin is particularly preferable in view of flexibility and toughness of the coating film.
By adding a curing agent as a constituent component of the light shielding layer, crosslinking of the resin component can be promoted. As the curing agent, a urea compound, a melamine compound, an isocyanate compound, an epoxy compound, an aziridine compound, an oxazoline compound, or the like having a functional group can be used. Among them, isocyanate compounds are particularly preferable. The compounding ratio of the curing agent is preferably 10 to 50% by weight with respect to 100% by weight of the resin component. By adding the curing agent in the above range, the light-shielding layer having more suitable hardness can be obtained, and even when sliding occurs with other members, Ra of the light-shielding layer can be maintained for a long period of time, and an excellent antireflection effect can be maintained.
When a curing agent is used, a reaction catalyst may be used together to promote the reaction. Examples of the reaction catalyst include ammonia and ammonium chloride. The mixing ratio of the reaction catalyst is preferably in the range of 0.1 to 10% by weight with respect to 100% by weight of the curing agent.
As the matting agent, resin-based particles or inorganic-based particles can be used. Examples of the resin-based particles include melamine resin, benzoguanamine/melamine/formalin polycondensate, acrylic resin, polyurethane resin, styrene resin, fluororesin, silicone resin, and the like. On the other hand, examples of the inorganic particles include silica, alumina, calcium carbonate, barium sulfate, titanium oxide, and the like. These may be used alone or in combination of two or more.
The average particle diameter, particle size distribution, and content of the matting agent vary depending on the film thickness of the light-shielding layer and the degree of the irregularities on the surface of the base film, and are adjusted to obtain Ra or the like necessary for the surface of the light-shielding member. In the case of the method (A), for example, when a light-shielding layer having a thickness of 2 to 35 μm is formed on a substrate film having a smooth surface, the average particle diameter of the matting agent is preferably 1 to 40 μm. When the thickness of the light-shielding layer is 4 to 25 μm, the average particle diameter of the matting agent is preferably 5 to 20 μm.
In the case of the method (C), for example, in the case of forming a light-shielding layer having a thickness of 1 to 35 μm on a substrate film having an uneven shape, the average particle diameter of the matting agent is preferably 2 to 15 μm. When the thickness of the light-shielding layer is 2 to 7 μm, the average particle diameter of the matting agent is preferably 2 to 10 μm.
The particle size distribution of the matting agent varies depending on the combination of the film thickness of the light-shielding layer and the size of the matting agent selected, and cannot be defined in a general way, but is preferably as sharp as possible. Further, Ra and the like can be adjusted by using a plurality of matting agents having different average particle diameters and particle size distributions.
The amount of the matting agent to be added varies depending on the average particle diameter and particle size distribution of the matting agent and the film thickness of the light-shielding layer, but in the case of the method (a), it is preferably 20 to 80 wt% with respect to 100 wt% of the entire light-shielding layer. In the case of the method (C), it is preferably from 1 to 40% by weight.
By controlling the surface shape of the resin base film, the average particle diameter, particle size distribution, and content of the matting agent, and further controlling the film thickness of the light shielding layer, Ra and the like on the surface of the light shielding layer can be adjusted, and excellent light shielding properties can be exhibited even when the film is thin.
The shape of the matting agent is not particularly limited, but a spherical matting agent is preferably used from the viewpoint of the flow property of the coating liquid, the coating property, the sliding property of the obtained light-shielding layer, and the like. Further, the matting agent may be colored black by an organic or inorganic coloring agent in order to suppress reflection of light. Specific examples of the coloring agent include carbon black, aniline black, and carbon nanotubes. By using a matting agent dyed with carbon black and further adding carbon black or the like as a dyeing/conductive agent to the light-shielding layer, more excellent light-shielding characteristics can be obtained.
As the dyeing/conductive agent, carbon black or the like is generally used. The light-shielding layer is dyed by adding a dyeing/conductive agent, and therefore, the antireflection effect can be improved and a good antistatic effect can be obtained.
The average particle diameter of the dyeing/conductive agent is preferably 1nm to 1000nm, more preferably 5nm to 500 nm. By setting the particle diameter of the dyeing/conductive agent to the above range, more excellent light-shielding properties can be obtained.
The content of the dyeing/conductive agent is preferably 9 to 38 wt% with respect to 100 wt% of the entire light-shielding layer. By setting the content of the dyeing/conductive agent to the above range, more excellent light-shielding properties can be obtained.
In the present invention, as a constituent component of the light-shielding layer, a leveling agent, a thickener, a pH adjuster, a lubricant, a dispersant, a defoaming agent, and the like may be further added as necessary.
As the lubricant, polyethylene wax, silicone particles, or the like can be used in addition to Polytetrafluoroethylene (PTFE) particles as a solid lubricant.
By adding the above-described constituent components to an organic solvent or water, and mixing and stirring, a uniform coating liquid is prepared. Examples of the organic solvent include methyl ethyl ketone, toluene, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, methanol, ethanol, isopropanol, and butanol.
The obtained coating liquid is directly applied to the surface of the base film or a fixing layer formed in advance, and dried to form the light-shielding layer. The coating method is not particularly limited, and a roll coating method, a doctor blade method, or the like can be used.
The thickness of the light-shielding layer in the present invention is preferably 1 μm to 35 μm. Particularly when the matting agent is contained, in the case of the method (A), the thickness of the light-shielding layer is preferably 2 to 30 μm, more preferably 4 to 25 μm. In the case of the method (C), the thickness of the light-shielding layer is preferably 1 to 10 μm, more preferably 2 to 7 μm.
By setting the thickness of the light-shielding layer to the above range, a desired antireflection effect and slidability can be obtained. The thickness of the light-shielding layer containing the matting agent is the height from the surface of the film base material to the base material portion of the light-shielding layer from which the matting agent does not protrude. The thickness of the light-shielding layer can be measured according to JIS K7130.
ii) a light-shielding layer containing no matting agent
Next, the light-shielding layer used in the method (B) which does not contain a matting agent will be described. As described above, in this structure, the light-shielding property of the light-shielding member can be controlled in accordance with the uneven shape of the base material film, and therefore, it is necessary to provide the light-shielding layer covering the surface of the base material film as a thin layer so as to maintain the uneven shape of the surface of the base material film. In such a structure, the light-shielding layer functions as a conductive layer and a sliding layer.
The light-shielding layer includes a resin component and a coloring/conductive agent as constituent components.
The resin component may use the same material as that of the light shielding layer containing the matting agent.
The same material as that used for the light-shielding layer containing a matting agent can be used for the dyeing/conductive agent.
In the light-shielding layer having such a structure, a leveling agent, a thickener, a pH adjuster, a dispersant, an antifoaming agent, and the like may be further added as necessary.
A uniform coating liquid is prepared by adding the above-described constituent components to water, alcohol, or an organic solvent, and mixing and stirring them.
The obtained coating liquid is directly applied to the surface of the substrate film having the uneven shape formed thereon by matting in advance, or is applied through a fixing layer formed in advance and dried to form a light-shielding layer. The coating method is not particularly limited, and a roll coating method, a doctor blade method, or the like can be used.
In the case where the matting agent is not contained as in this structure, the thickness of the light-shielding layer is preferably 1 μm to 15 μm, more preferably 2 μm to 10 μm. By setting the thickness of the light-shielding layer to the above range, conductivity, slidability, and the like can be provided without suppressing the uneven shape of the base film. The thickness of the light-shielding layer containing no matting agent is the thickness of the light-shielding layer itself in which the undulation of the surface of the film base material is eliminated.
(4) Blackening layer
The black light-shielding member of the present invention is characterized in that a blackened layer is formed on the irregularities of the resin light-shielding layer described in (3).
Fig. 1(b) and 2(b) show schematic cross-sectional views of the black light-shielding member 10 of the present invention formed with the blackening layer 5. The black light-shielding member 10 of the present invention is considered to have a structure in which the blackened layer 5 is thin and fine layers (fine particles) are unevenly present on the resin light-shielding layer 3. Further, it is presumed that the black light-shielding member of the present invention has an excellent anti-reflection effect by low glossiness and blackness by diffuse reflection of (black) light generated on the surface of the blackened layer of such a structure.
That is, the present invention has been completed based on the following findings: by forming a thin blackened layer on a light-shielding layer made of a resin having an uneven shape and adjusting the arithmetic average roughness Ra of the surface to 0.25 μm or more, an excellent antireflection effect by low glossiness and a blackness with an L value of 12 or less can be realized. The maximum thickness of the blackened layer is not particularly limited as long as it is less than Ra, and is preferably 10 to 200nm, more preferably 50 to 150nm, and further more preferably 70 to 110 nm.
The maximum thickness of the blackened layer can be calculated from a microscopic photograph or the like.
The blackened layer may be an inorganic material, an organic material, a mixed material of an organic material and an inorganic material, or a composite material, if the above conditions are satisfied. Examples of the inorganic material include metals such as gold, silver, copper, platinum, cobalt, tin, zinc, lead, palladium, ruthenium, neodymium, samarium, aluminum, magnesium, indium, gallium, bismuth, and alloys thereof; alumina, silica (silicon dioxide, etc.), titanium oxide (titanium monoxide, titanium pentoxide, titanium dioxide, etc.), Indium Tin Oxide (ITO), cerium oxide, zinc oxide, chromium oxide (Cr) 2 O 3 Etc.), gallium oxide, hafnium oxide, nickel oxide, magnesium oxide, niobium oxide (such as niobium pentoxide), tantalum oxide (such as tantalum pentoxide), yttrium oxide, zirconium oxide, and other metal oxides, and composites thereof; fluorides such as magnesium fluoride, aluminum fluoride, calcium fluoride, cerium fluoride, lanthanum fluoride, lithium fluoride, sodium fluoride, neodymium fluoride, samarium fluoride, ytterbium fluoride, and yttrium fluoride; nitrides such as titanium nitride, chromium nitride, titanium carbonitride, titanium aluminum nitride, boron nitride, aluminum nitride, carbon nitride, and boron carbonitride; carbides such as carbon (amorphous carbon, diamond-like carbon, graphite, etc.), titanium carbide, silicon carbide, boron carbide, and tungsten carbide.
Examples of the organic material include submicron particles such as acrylic resin, styrene resin, silicone resin, and fluororesin. Further, an organic-inorganic hybrid material (organic-inorganic nanocomposite material) in which the metal oxide and the organic molecule are combined may be used.
The method for forming the blackened layer is not particularly limited, and a dry method (dry method) such as a sputtering method, a vacuum deposition method, an ion plating method, or a Chemical Vapor Deposition (CVD) method, a wet method (wet method) such as a coating method using a sol-gel method, or a coating method of coating a dispersion liquid in which a material of the blackened layer is dispersed/mixed in a sol solution, a solvent, and a binder component can be used.
Among them, the dry method is preferable in terms of obtaining more excellent blackening effect. In the process of forming the blackened layer by the dry method, it is considered that the nano-scale particles adhere to the convex portions, concave portions, and inclined surfaces of the uneven shape of the light-shielding layer, and the uneven shape is formed more complexly. It is presumed that, in the light shielding member having such a surface shape, incident light is absorbed while being complexly reflected on the surface of the blackened layer, and therefore, more excellent antireflection effect and blackness by low glossiness are achieved.
The dry method is also preferable from the viewpoint that the surface roughness is not reduced by the coating liquid accumulated in the concave portion, unlike the wet method. Further, the dry method is also preferable from the viewpoint that a solvent is not used and thus an adverse effect on the environment is small and equipment is also small.
Among the dry methods, the sputtering method is preferable from the viewpoint of excellent adhesion to the light-shielding layer, scratch resistance, easy thickness adjustment, and the like.
On the other hand, from the viewpoint of cost performance, the wet method is preferably used because it is excellent in economy, workability, yield, and the like. It is presumed that in the wet method, a sol solution or a dispersion is applied to the convex, concave, and inclined surfaces of the uneven shape of the light-shielding layer, and convection from the bottom to the top is generated when the solvent is evaporated during the drying process, so that the uneven shape is more complicated to form on the surface of the light-shielding layer having the concave and convex. It is presumed that, in the light shielding member having such a surface shape, incident light is absorbed while being complexly reflected on the surface of the blackened layer, and therefore, more excellent antireflection effect and blackness by low glossiness are achieved.
The material, formation method, layer thickness, and the like of the blackened layer can be appropriately set in consideration of the characteristics required for the light shielding member, cost, and the like.
[ examples ]
The present invention will be further described in detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, "%" and "parts" represent% by weight and parts by weight, unless otherwise specified.
Structure of black shading part
(1) Substrate film
(1-1) polyimide film: KAPTON 50MBC (thickness 12 μm), manufactured by Toledu Pont K.K
(1-2) copper foil film: NC-WS (thickness 12 μm), manufactured by Kogaku Kogyo K.K
(1-3) polyethylene terephthalate film: both surfaces of Lumiror X30 (thickness 50 μm, manufactured by Toray corporation) were subjected to sandblasting, and a rough film was formed on the surface.
(2) Light shielding layer
(a) Resin composition
(a1) Acrylic resin: acrydic A814, available from DIC corporation
(b) Curing agent
(b1) TDI polyisocyanate: coronate L, manufactured by Tosoh corporation
(c) Dyeing/conductive agent
(c1) Carbon black; NX-592 Black, manufactured by Dari chemical industries, Ltd
(d) Matting agent
(d1) Acrylic acid filler: MX-200 (average particle diameter: 2 μm), manufactured by Soken chemical Co., Ltd
(d2) Acrylic acid filler: MX-300 (average particle diameter: 3 μm), produced by Soken chemical Co., Ltd
(d3) Acrylic acid filler: MX-500 (average particle diameter: 5 μm), produced by Soken chemical Co., Ltd
(3) Blackening layer
(3-1) formation by sputtering
Magnesium fluoride (MgF) was added to the resultant mixture by using a sputtering apparatus (model: CFS-4ES) manufactured by Zhipu electromechanical Co., Ltd 2 ) As a target, a magnesium fluoride layer was formed by a sputtering method in argon gas. Here, the final pressure was 3X 10 -3 Pa, sputtering pressure of 7.6X 10 -3 Pa, Ar flow rate 11 sccm. Further, a magnesium fluoride layer was formed on a flat substrate under predetermined conditions (200W), and the relationship between the sputtering time and the thickness of the layer was determined. The sputtering deposition films of magnesium fluoride formed under the conditions that the layer thicknesses were 80nm, 100nm, and 120nm were respectively made to be thin films, intermediate films, and thick films.
(3-2) formation based on dispersion coating
(3-2-1) binder component: polyester resin
A coating liquid was prepared by mixing 1 part of a magnesium fluoride particle dispersion (9076MF, primary particle diameter 39nm, solid content 26%; manufactured by Tokuchi Co., Ltd.), 2 parts of a resin liquid dissolved in methyl ethyl ketone so that the concentration of a polyester resin (Bylon 200; manufactured by Toyo Boseki Co., Ltd.) became 10 wt%, and 87 parts of methyl ethyl ketone. The obtained coating liquid was applied by a bar coating method and dried by heating, thereby forming a blackened layer having a thickness of about 100 nm.
(3-2-2) binder component: silicon dioxide
A coating solution was prepared by mixing 1 part of the magnesium fluoride particle dispersion used in (3-2-1), 10 parts of a solution prepared by diluting a silica sol solution (Colcoat N-103X (2% in solid content), manufactured by Colcoat Co., Ltd.) to 20% with N-butanol, and 90 parts of dipropylene glycol monomethyl ether. The obtained coating liquid was applied by a bar coating method and dried by heating, thereby forming a blackened layer having a thickness of about 100 nm.
(3-3) formation based on Sol-gel Process
25 parts of a silica sol solution (Colcoat N-103X (2% in solid content), produced by Colcoat corporation), water: the weight ratio of the isopropanol is 1: 2, and 75 parts of a solvent were mixed to prepare a coating liquid. The obtained coating liquid was applied by a bar coating method and dried by heating, thereby forming a blackened layer having a thickness of about 100 nm.
Examples 1 to 12 and comparative examples 1 to 9
The components of the light-shielding layer (2) were added to a solvent at the mixing ratios (by weight) shown in tables 1 to 3, and stirred and mixed to obtain a coating liquid. Here, as the solvent, methyl ethyl ketone and toluene were used.
A light-shielding layer was formed by applying a coating liquid having the composition shown in tables 1 to 3 to one surface of a base film shown in tables 1 to 3, and then drying the coating liquid at 100 ℃ for 2 minutes.
On the obtained light-shielding layer, the blackening layer shown in tables 1 to 3 was formed by the method in (3) above. The measurement results of the average film thickness of the light-shielding layer, the average film thickness of the blackened layer, Ra of the light-shielding member, the glossiness of the incident light at an incident angle of 60 °, and the L value are shown in tables 1 to 3. Based on JIS B0601: 2001, the arithmetic average roughness Ra of the light shielding member was calculated, and the L value was calculated in accordance with JIS Z8781-4. Further, for the measurement of the glossiness of incident light with respect to the incident angle of 60 °, the specular glossiness with respect to the incident angle of 60 ° was measured in accordance with JIS Z8741.
Further, the average film thickness of the light-shielding layer was measured based on JIS K7130. The thickness of the light-shielding layer containing the matting agent is set to a height from the surface of the film base material to the base material portion of the light-shielding layer where the matting agent does not protrude. On the other hand, the thickness of the light-shielding layer containing no matting agent is set to the thickness of the light-shielding layer itself in which the undulation of the surface of the film base material is eliminated.
The average film thickness of the magnesium fluoride black layer by the sputtering method described in the table is not an actual measurement value, but an average film thickness when the magnesium fluoride layer is formed on the flat substrate by the sputtering method under the same conditions as when formed on the light-shielding layer. The average film thicknesses of the blackened layers by the dispersion coating method and the sol-gel method described in table 3 are not actually measured in the same manner as in the formation of the blackened layer by the sputtering method, but are average film thicknesses when the blackened layers are formed on the flat substrate by the dispersion coating method and the sol-gel method under the same conditions as in the formation of the light shielding layer.
As shown in table 1, in reference example 1, which is a flat polyimide film, Ra was low and 0.2 μm, the gloss at an incident angle of 60 ° was 35.4%, the L value was 28.3, and both the antireflection effect and the blackness were low due to the low gloss. On the other hand, in comparative example 1 in which the light-shielding layer containing a matting agent was provided, Ra increased to 0.48 μm, the surface was roughened, and the antireflection effect and the blackness due to the low glossiness were both improved, but the blackness was insufficient.
On the other hand, it was confirmed that in examples 1 to 3 in which a blackened layer as a sputtering film of magnesium fluoride was further provided on the light-shielding layer, both the glossiness and the L value at an incident angle of 60 ° were greatly reduced, and the light antireflection effect and the blackness were excellent due to the low glossiness. In particular, the Ra of the black light-shielding members of examples 1 and 2, in which the black layer of the intermediate film and the thin film was formed, was greatly increased from 0.48 μm to 1.28 μm and 1.32 μm, respectively, as compared with the black light-shielding member of comparative example 1, in which the black layer was not provided. In example 3 in which the thick black layer was formed, the black light-shielding member had an Ra of 0.49 μm, and the rate of increase in Ra was lower than in examples 1 and 2. From this, it is found that by setting the film thickness of the black layer to an appropriate range without excessively increasing the film thickness, the unevenness on the surface of the black light-shielding member can be further effectively formed into a more complicated shape, and a light-shielding member having an excellent anti-reflection effect by low glossiness and a higher black color can be obtained.
In addition, it is found that both the glossiness and the L value at the incident angle of 60 ° hardly change in reference example 2 in which the black layer of the middle film was formed on the flat polyimide film, as compared with reference example 1. This confirmed the effect of the present invention in which the black layer was formed on the surface of the light-shielding layer having the uneven shape.
[ Table 1]
Table 2 shows the results of comparison of Ra, glossiness at an incident angle of 60 °, and L values of the light-shielding member surface when an intermediate-film blackening layer was formed on the surface of the light-shielding layer with the surface roughness changed using matting agents of different particle diameters. As shown in comparative examples 1, 4 and 5, it is understood that the Ra of the surface changes by changing the particle diameter of the matting agent added to the light-shielding layer, but the L value exceeds 20 in all of the comparative examples, and sufficient blackness cannot be obtained. On the other hand, it was confirmed that in examples 1, 4 and 5 in which the intermediate-film black layer of magnesium fluoride was formed by the sputtering method, the glossiness and the L value were both greatly reduced at the incident angle of 60 °, and the antireflection effect by the low glossiness and the high black color were excellent.
[ Table 2]
The evaluation results of the samples in which the light shielding layer and the black layer were formed in the same manner as in example 1, except that the copper foil film was used as the base film, are shown in example 6 of table 3. In example 6, Ra increased, and the gloss at an incident angle of 60 ° and the L value were both significantly reduced, compared to comparative example 6 in which no black layer was formed. This confirmed that the effects of the present invention can be obtained even when a metal base film is used as the base film.
[ Table 3]
The same evaluation was made for example 7 in which a polyethylene terephthalate film was used as a base film and a black layer was formed directly on the surface subjected to the spray treatment, example 8 in which a light-shielding layer containing a matting agent was formed on the surface subjected to the spray treatment and then a black layer was formed, and example 9 in which a light-shielding layer containing no matting agent was formed on the surface subjected to the spray treatment and then a black layer was formed. In comparison with comparative examples 7, 8 and 9 in which no black layer was formed, Ra of the light-shielding member in each of these examples was increased, and the gloss at an incident angle of 60 ° and the L value were significantly reduced. As described above, the effect of the present invention can be obtained regardless of the method of forming the irregularities of the light-shielding layer.
In example 10, a black light-shielding member was prepared and evaluated in the same manner as in example 1, except that the blackened layer was replaced with a sputtered layer and set such that a magnesium fluoride/polyester resin layer was formed by a dispersion coating method. The Ra of example 10 was also increased, the gloss at an incident angle of 60 ° was decreased, and the L value was greatly decreased, as compared with comparative example 1. This confirmed that the effect of the present invention can be obtained also in the black layer formed by the wet process.
Further, in example 11, a black light-shielding member was prepared in the same manner as in example 1, except that the blackened layer was replaced with the sputtered layer and was formed as the magnesium fluoride/silicon oxide layer, and that the sputtered layer was formed as the silicon oxide layer in example 12. Both of examples 11 and 12 increased in Ra, and the gloss at an incident angle of 60 ° was reduced, and the L value was greatly reduced, as compared with comparative example 1. It was thus confirmed that the effect of the present invention can be obtained by a structure in which a thin and uneven blackening layer is formed on a resin light-shielding layer, regardless of the method and material for forming the blackening layer.
Claims (7)
1. A black light-shielding member, comprising: a base film, a light-shielding layer made of a resin and having a concavo-convex shape formed on at least one surface of the base film, and a blackened layer formed on the light-shielding layer made of the resin,
in the black light-shielding member, the surface of the light-shielding layer and the black layer has an arithmetic average roughness Ra of 0.25 [ mu ] m or more and an L value of 12 or less, and the maximum thickness of the black layer is smaller than Ra.
2. The black light shielding member according to claim 1,
the light shielding layer made of resin has a resin layer containing a matting agent and a resin component.
3. The black light-shielding member according to claim 1 or 2,
the light shielding layer made of resin includes a roughened portion formed on the surface of the base film.
4. The black light shielding member according to any one of claims 1 to 3,
the blackening layer contains an inorganic material.
5. The black light shielding member according to claim 4,
the blackening layer contains at least one selected from magnesium fluoride, calcium fluoride, lithium fluoride, aluminum oxide, gallium oxide and silicon oxide.
6. The black light-shielding member according to claim 4 or 5,
the blackened layer is formed by any one method selected from a sputtering method, an evaporation method, an ion plating method, and a Chemical Vapor Deposition (CVD) method.
7. The black light-shielding member according to any one of claims 1 to 6,
the maximum thickness of the blackening layer is less than 1/2 of the value of the arithmetic mean roughness Ra of the surface.
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| JP2019-239871 | 2019-12-27 | ||
| JP2019239871A JP7157042B2 (en) | 2019-12-27 | 2019-12-27 | black light shielding material |
| PCT/JP2020/048790 WO2021132585A1 (en) | 2019-12-27 | 2020-12-25 | Black light shielding member |
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| KR (1) | KR102570913B1 (en) |
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| JP2023016199A (en) * | 2021-07-21 | 2023-02-02 | ソマール株式会社 | optical element |
| KR102567450B1 (en) * | 2021-10-18 | 2023-08-16 | 티에스엠카본 주식회사 | Composition for light-shielding film and light-shielding film using the same |
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| JP2001350003A (en) | 2000-06-09 | 2001-12-21 | Nikon Corp | Black antireflection film and optical device using the same |
| JP4237148B2 (en) | 2005-02-17 | 2009-03-11 | 住友大阪セメント株式会社 | Black fine particle dispersion, black light shielding film using the same, and substrate with black light shielding film |
| US7848021B2 (en) * | 2006-02-17 | 2010-12-07 | Fujifilm Corporation | Optical film, antireflection film, polarizing plate and image display device |
| JP5114995B2 (en) * | 2006-11-30 | 2013-01-09 | 住友金属鉱山株式会社 | Heat-resistant light-shielding film, method for producing the same, and diaphragm or light amount adjusting device using the same |
| WO2010026853A1 (en) * | 2008-09-05 | 2010-03-11 | 住友金属鉱山株式会社 | Black coating film, process for producing same, black light-shielding plate, and diaphragm plate, diaphragm for light quantity control, shutter, and heat-resistant light-shielding tape each comprising the black light-shielding plate |
| JP5428105B2 (en) | 2008-09-30 | 2014-02-26 | 日本金属株式会社 | Black chemical conversion treatment liquid, chemical conversion treatment method and chemical conversion treatment member for magnesium alloy |
| JP5831229B2 (en) | 2010-05-20 | 2015-12-09 | 東洋紡株式会社 | Shading film |
| JP2012203310A (en) | 2011-03-28 | 2012-10-22 | Sumitomo Metal Mining Co Ltd | Heat-resistant light-shielding multilayer film, production method of the same, and application |
| JP2012247518A (en) | 2011-05-26 | 2012-12-13 | Sumitomo Metal Mining Co Ltd | Black heat-resistant light-shielding film, diaphragm using the same, shutter blade, diaphragm blade for light quantity adjustment module, and light-shielding tape |
| JP6112891B2 (en) | 2013-02-08 | 2017-04-12 | デクセリアルズ株式会社 | RESIN COMPOSITION FOR ADHESIVE TAPE, ADHESIVE TAPE AND METHOD FOR PRODUCING ADHESIVE TAPE |
| KR20160145589A (en) | 2014-04-15 | 2016-12-20 | 미쓰비시 가가꾸 가부시키가이샤 | Substrate with light-blocking material, color filter, liquid crystal display device and coloring resin composition for forming said light-blocking material |
| KR102195942B1 (en) * | 2016-09-16 | 2020-12-29 | 소마 가부시기가이샤 | Light blocking member for optical devices |
| JP6721783B2 (en) * | 2017-03-27 | 2020-07-15 | 富士フイルム株式会社 | Antireflection laminate, polarizing plate having the same, and image display device |
| CN110446974B (en) * | 2017-03-29 | 2023-09-12 | 东丽株式会社 | Photosensitive composition, cured film, and organic EL display device |
| JP6504299B1 (en) | 2017-12-07 | 2019-04-24 | 東洋インキＳｃホールディングス株式会社 | Black low reflection film, and method of manufacturing laminate |
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| TW202138847A (en) | 2021-10-16 |
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