Patent Application
20240336783
The present invention relates to an optical element suitably used in a variety of optical apparatuses.
Optical elements, such as a lens, used in a variety of optical apparatuses, such as a camera, binocular, microscope and semiconductor exposure apparatus, are sometimes formed with a black antireflection film on outside of its optical effective part in order to reduce a stray light (namely, a stray light incident from an inner side of the optical element) due to reflection inside the element (internal reflection). A stray light from an inner side of the optical element reached to outside of the optical effective part is absorbed by the antireflection film formed thereon, as a result, it contributes to a reduction of unnecessary lights, such as flare and ghost.
For example, the patent document 1 discloses a technique on an optical element, wherein a region outside of an effective diameter (an example of outside of an optical effective part) on an optical surface of a base substrate for an optical element is provided with an antireflection film having a multilayer configuration composed of an antireflection coat layer and an internal reflection prevention layer: wherein the antireflection coat layer has an outermost layer having a lower refractive index than that of the base substrate, and the internal reflection prevention layer is formed on a surface of the coat layer and has an outermost layer having a lower refractive index than that of the coat layer.
SUMMARY OF THE DISCLOSED SUBJECT MATTER
In recent years, since an optical element formed with an antireflection film is configured to be in various shapes, sometimes the antireflection film is provided to a position able to be seen by users. Consequently, the antireflection film is required to have a high appearance quality in some cases. Specifically, it is required to provide a membrane coated black to have higher designability (for example, a rough membrane).
The present invention was made in consideration with the circumstances above. The present invention has an object thereof to provide an optical element, which effectively reduces a stray light, has an antireflection film having high designability and is used suitably in a variety of optical apparatuses.
The present inventors conducted studies diligently and found that fulfilling the requirements below is effective to form an antireflection film, which is effective to reduce a stray light and has high designability.
Based on these newly acquired knowledge, the present inventors completed the invention as provided below and attained the object above.
Below, (A) indicates a resin component, (B) unevenness forming particles, (B1) inorganic small particles having a particle diameter (d1) of 0.05 μm or more and 0.4 μm or less, (B2) inorganic large particles having a particle diameter (d2) of 2 μm or more and 6 μm or less, and (C) a diluent solvent.
According to the present invention, there is provided an optical element used for optical apparatuses, wherein
According to the present invention, there is provided an antireflection film formed on outside of an optical effective part in an optical element comprising a base member having an optical effective part, and
The liquid composition above may include modes below.
According to the present invention, there is provided an optical apparatus comprising the optical element above. As an optical apparatus, for example, a camera, binocular, microscope and semiconductor exposure apparatus, etc. may be mentioned.
The optical apparatus above may include modes below.
According to the present invention, there is provided an optical element, which effectively reduces a stray light, has an antireflection film having high designability and is used suitably in a variety of optical apparatuses.
Below, the best modes for carrying out the invention will be explained. However, the present invention is not limited to the modes below and also includes those obtained by suitably modifying or improving the modes explained below based on ordinary knowledge of persons skilled in the art within the scope of the present invention.
As to a range of value in the present specification, an uppermost value or a lowermost value described in certain value ranges may be replaced by values indicated in the examples.
In the present specification, when there are a plurality of kinds of substances falling under each component in a composition, a content ratio or a content in each component in the composition indicates a content ratio or a content of a total of the plurality of kinds of substances being in the composition unless otherwise mentioned.
In the present specification, “outside of an optical effective part” indicates both of an outside the effective diameter on the optical surface and an outside of the optical surface (for example, an outer circumferential part of the optical element) unless particularly mentioned.
As shown in
The base member 2 has a shape of a spherical lens (a plano-concave lens having one surface plane in
An outer shape of the base member 2 is a circular shape having an optical axis ○ as the center. On one surface in the thickness direction along the optical axis ○ (hereinafter, abbreviated simply as “the X direction”) of the base member 2, a first lens surface 2a as an optical surface having a concave shape and a plane portion 2b formed by a plane surface extending from the outer circumference to the direction of perpendicularly crossing with the optical axis ○ are formed. On the other surface in the X direction of the base member 2, a second lens surface 2c as an optical surface formed by a plane perpendicularly crossing with the optical axis ○ is formed. On an outer circumference of the plane portion 2b formed on one surface and on an outer circumference of the second lens surface 2c formed on the other surface, a lens side surface (outer circumferential portion) 2d is formed, which is a cylindrical surface having a predetermined diameter having the optical axis ○ as the center.
Both of a first lens surface 2a and a second lens surface 2c are configured by a smooth surface with high accuracy subjected to mirror finish by polishing and have surface accuracy in accordance with necessary optical performance in an effective diameter range (inside the effective diameter) on each surface.
An effective diameter d1 of the first lens surface 2a is, as an example, set to be slightly smaller than an outer diameter d2 of the first lens surface 2a (d1<d2). An effective diameter d3 of the second lens surface 2c is, as an example, set to be larger than the outer diameter d2 of the first lens surface 2a (d1<d2<d3).
An antireflection film 4 is stacked on the plane portion 2b formed on one surface of the base member 2. The antireflection film 4 serves as below. Among lights entering from the second lens surface 2c side of the base member 2, a light going to the outside of the plane portion 2b (let's call it “incident light a”) becomes a transmission light to transmit the base member 2. On the other hand, among the incident lights to the base member 2, a light reached to the plane portion 2b (let's call it “incident light b”) hits the antireflection film 4 formed on the plane portion 2b. When the antireflection film 4 is not formed on the plane portion 2b, the light reached to the plane portion 2b reflects internally and goes out of the base substrate 2 as an internal reflection light, which has no direct relation with an image. The internal reflection light causes flare and ghost so as to deteriorate the image. On the other hand, as in one mode, when the antireflection film 4 is formed on the plane portion 2b, it is possible to reduce internal reflection of the incident light b entering obliquely from the second lens surface 2c of the base member 2. Consequently, internal reflection light, which adversely affects the image, is reduced and arise of flare and ghost can be prevented. Note that since the plane portion 2b is on one surface of the base member 2 and positions outside of the outer diameter d2 on the first lens surface 2a, it falls under “outside of the effective diameter on the optical surface”.
In addition to the position above, the antireflection film 4 may be formed on outside of the effective diameter d1 of the first lens surface 2a and on inside of the outer diameter d2 of the first lens surface 2a, alternately/furthermore, may be formed on outside of the effective diameter d3 of the second lens surface 2c formed on the other surface of the base member 2. Depending on cases, it may be formed only on the outside of the effective diameter 3d of the second lens surface 2c and not on the plane portion 2b.
The antireflection film 4 may be laminated at least on one of a part, which is outside of the effective diameter d1 of the first lens surface 2a and inside of the outer diameter d2 of the first lens surface 2a, and a part outside of the effective diameter d3 of the second lens surface 2c. Alternately, separately from them, as shown in
The antireflection film 4 according to one mode shown in
A liquid composition according to one mode (hereinafter, also simply referred to as “a composition”) is used for forming a membrane on a surface at a predetermined position on the base member 2 (the above-mentioned plane portion 2b and lens side surface 2d, etc. Hereinafter, “a predetermined position of the base member 2” will be also referred to simply as “an object to be coated”) and comprises (A) a resin component, (B) unevenness forming particles and (C) a diluent solvent. The (B) used for forming a composition comprises (B1) small particles having a particle diameter (d1) of 0.05 μm or more and 0.4 μm or less and (B2) large particles having a particle diameter (d2) of 2 μm or more and 6 μm or less, and it may also comprise components other than (B1) and (B2). Namely, a composition according to one mode is configured by comprising (A), (B1), (B2) and (C). A composition according to one mode may be used suitably in spray coating when applying to a surface of an object to be coated.
(A) to be used for forming a composition serves as a binder of (B). A material of (A) is not particularly limited and either of a thermoplastic resin and thermosetting resin may be used. As a thermosetting resin, for example, an acrylic-type resin, urethane-type resin, phenol-type resin, melamine-type resin, a urea-type resin, diallyl phthalate-type resin, unsaturated polyester-type resin, epoxy-type resin and alkyd-type resin, etc. may be mentioned. As a thermoplastic resin, a polyacrylic ester resin, polyvinyl chloride resin, butyral resin and styrene-butadiene copolymer resin, etc. may be mentioned. In terms of heat resistance, moisture resistance, solvent resistance and surface hardness of an uneven membrane to be formed, a thermosetting resin is preferably used as (A). As a thermosetting resin, when considering flexibility and strength of a membrane to be formed, an acrylic resin is particularly preferable. As (A), one kind may be used alone or two or more kinds may be combined for use.
A content (a total amount) of (A) is not particularly limited, however, when considering a blending balance with other components, it is preferably 5% by mass or more, more preferably 15% by mass or more, furthermore preferably 25% by mass or more and preferably 50% by mass or less, more preferably 45% by mass or less and furthermore preferably 40% by mass or less with respect to a total amount (100% by mass) of total solid content in the composition.
It is essential that the (B) to be used for forming a composition comprises a plurality of unevenness forming particles having different sizes in combination. Particularly, (B1) small particles and (B2) large particles are combined to be used as (B). For example, in the case of composing (B) only of two kinds of unevenness forming particles having different sizes (namely, (B1) and (B2)), a particle diameter (d2) of (B2) is preferably 10 times or more, more preferably 15 times or more a particle diameter (d1) of (B1) and preferably 40 times or less and more preferably 35 times or less. When using as (B) three or more kinds of unevenness forming particles having different sizes, a particle diameter (dmax) of unevenness forming particles with a maximum particle diameter and a particle diameter (dmin) of unevenness forming particles with a minimum particle diameter may be adjusted to have the relationship above (namely, (dmax) is preferably 10 times or more, more preferably 15 times or more the size of (dmin) and preferably 40 times or less and more preferably 35 times or less the size of (dmin)).
In one mode, (d1) is preferably 0.05 μm or more, more preferably 0.1 μm or more and preferably 0.4 μm or less and more preferably 0.3 μm or less, and (d2) is preferably 2 μm or more, more preferably 3 μm or more and preferably 6 μm or less, more preferably 5 μm or less and furthermore preferably 4 μm or less.
A particle diameter (d1) of (B1) and a particle diameter (d2) of (B2) are a median diameter based on volume measured by a laser diffraction/scattering particle size distribution measuring apparatus.
In one mode, a mass ratio of (B2) in (B) is, with respect to (B1):1, preferably exceeding 1.75, more preferably 1.8 or more and preferably less than 3.58 and more preferably 3.3 or less. The present inventors found that by using (B1) and (B2) having the specific ranges of particle diameters as explained above combined in a range of this mass ratio, one particle (B1) is easily buried between adjacent two particles (B2) in a membrane to be formed. As a result, low glossiness and low reflectivity on the membrane surface can be realized and a degree of blackness becomes high (an L value becomes low).
A total content (total amount) of (B1) and (B2) in (B) is preferably 90% by mass or more and more preferably 95% by mass or more. An upper limit thereof is not particularly limited and is 100% by mass. Namely, in one mode, (B1) and (B2) may be contained preferably 90% by mass or more in 100% by mass of (B).
A content (total amount) of (B) with respect to a total amount (100% by mass) of total solid content in the composition is preferably 20% by mass or more, more preferably 25% by mass or more, furthermore preferably 30% by mass or more and preferably 60% by mass or less, more preferably 50% by mass, furthermore preferably 45% by mass or less and particularly preferably 40% by mass or less. When a total amount of (B) is less than 20% by mass, disadvantages of an increase of glossiness and optical density shortage are caused, while when exceeding 60% by mass, (A) in a formed coating film is decreased relatively, which results in a disadvantage that a coating film falls off from an object to be coated.
As (B2), either of resin-type particles and inorganic-type particles may be used. As resin-type particles, for example, a melamine resin, bunzoguanamine resin, benzoguanamine/melamine/formalin condensate, acrylic resin, urethane resin, styrene resin, fluoric resin and silicon resin, etc. may be mentioned. As inorganic-type particles, silica, alumina, calcium carbonate, barium sulfate, titan oxide and carbon, etc. may be mentioned. They may be used alone or in combination of two or more kinds.
To obtain more excellent characteristics, it is preferable to use inorganic-type particles as (B2). By using inorganic-type particles as (B2), a lower glossy and high light-shielding membrane can be formed easily. As inorganic-type particles to be used as (B2), silica is preferable. A shape of (B2) is not particularly limited but it is preferable to use particles having a narrow particle distribution having a CV (Coefficient of Variation) value of, for example, 15 or less (a sharp product) to realize lower glossiness, lower reflectiveness and a lower L value on a membrane surface to be formed. The CV value is a numerically expressed degree of spread of a particle diameter distribution (variation of particle diameters) with respect to an average value of a particle diameter (calculated average particle diameter). When using a particle as above, a chance of contacting between (B2) and (B1) increases in a membrane to be formed so as to realize furthermore lower glossiness, lower reflectiveness and a lower L value on the membrane surface.
Also, in order to decrease glossiness on the membrane surface to be formed, a particle in indefinite form as (B2) is preferably used. It is particularly preferable to use a porous indefinite-shaped silica particle as (B2). When using particles as above as (B2), lights refract repeatedly inside and surface when formed into a membrane, consequently, a glossiness on the membrane surface can be furthermore reduced.
In one mode, in order to suppress reflection of lights on a surface of a membrane to be formed, (B2) may be colored black by using an organic-type or inorganic-type colorant. As a material therefor, composite silica, conductive silica and black silica, etc. may be mentioned.
As composite silica, for example, what obtained by synthesizing carbon black (hereinafter, also simply referred to as “CB”) and silica at a nano level and composing may be mentioned. As conductive silica, for example, what obtained by coating silica particles with conductive particles, such as CB, may be mentioned. As black silica, for example, natural ore containing graphite in silica may be mentioned.
As well as (B2), material of (B1) is not particularly limited and either of resin-type particles and inorganic-type particles may be used. As resin-type particles, for example, a melamine resin, bunzoguanamine resin, benzoguanamine/melamine/formalin condensate, acrylic resin, urethane resin, styrene resin, fluoric resin and silicon resin, etc. may be mentioned. As inorganic-type particles, silica, alumina, calcium carbonate, barium sulfate, titan oxide and CB, etc. may be mentioned. They may be used alone or in combination of two or more kinds.
As (B1), for example, CB added as a colorant/conductive agent may be also used. When using CB as (B1), a membrane to be formed is colored, so that an effect of reflection prevention is increased furthermore and a preferable antistatic effect can be obtained.
The (C) used for forming a composition is contained for the purpose of dissolving (A) and adjusting viscosity of the whole composition. When using (C), (A) and other component to be added as needed can be mixed more easily and uniformity of the composition is improved. Also, viscosity of the composition can be adjusted properly, so that, when forming a membrane on a surface of an object to be coated, operability of the composition and uniformity of a thickness when applying can be improved. As a result, it can contribute largely to enhance designability of a finally obtained product.
As (C), it is not particularly limited as long as it is a solvent capable of dissolving (A), and an organic solvent or water may be mentioned. As an organic solvent, for example, methylethylketone, toluene, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, methanol, ethanol, isopropyl alcohol and butanol, etc. may be used. They may be used alone or in combination of two or more kinds.
A content (total amount) of (C) in a composition is, with respect to 100 parts by mass of (A), preferably 1 part by mass or more, more preferably 3 parts by mass or more and preferably 20 parts by mass or less in order to obtain the effects of containing (C) as explained above.
Other than the components ((A), (B) and (C)) above, the composition may contain (D) to an extent of not hindering the effects of the present invention. As (D), for example, a leveling agent, thickener, pH adjusting agent, lubricant, dispersant, defoaming agent, curing agent and reaction catalyst, etc. may be mentioned.
Particularly when using a thermosetting resin as (A), crosslinking of (A) can be accelerated by blending a curing agent. As a curing agent, a urea compound having a functional group, melamine compound, isocyanate compound, epoxy compound, aziridine compound and oxazoline compound, etc. may be mentioned. As a curing agent, isocyanate compound is preferable among them. The curing agent may be used alone or in combination of two or more kinds.
A ratio of blending a curing agent in a composition is, with respect to 100 parts by mass of (A), preferably 10 parts by mass or more and 80 parts by mass or less. When adding a curing agent in this range, hardness of a membrane to be formed is enhanced, consequently, characteristics of the membrane surface can be maintained for a long term even when the membrane is exposed to an environment of rubbing against other member, and low glossiness, a high light-shielding characteristic, low reflectiveness and high degree of blackness can be maintained easily.
When a curing agent is contained in a composition, a reaction catalyst may be used together so as to accelerate reaction of the curing agent with (A). As a reaction catalyst, for example, ammonia and aluminum chloride, etc. may be mentioned. A ratio of a reaction catalyst to be contained in the composition is, with respect to 100 parts by mass of a curing agent, preferably 0.1 part by mass or more and 10 parts by mass or less.
A composition according to one mode has viscosity at 25° C. of preferably 1 mPa·s or more, preferably 30 mPa·s or less and more preferably 20 mPa·s or less for the reason of coating by using a spray (spray coating) while maintaining smoothness of the composition on a surface of an object to be coated. When viscosity of the composition is too low, there is a possibility of not being able to form a membrane having a thickness sufficient to realize better designability. When viscosity of the composition is too high, it becomes difficult to spray the composition uniformly on a surface of an object to be coated, so that there is a possibility that a membrane having a uniform thickness with better designability cannot be obtained.
The viscosity differs depending on components contained in the composition, that is, kinds and molecular weights, etc. of (A) and (B) to be used. Also, when blending (D) in addition to the (A) and (B) above, it differs depending on a kind and molecular weight, etc. of (D). However, it can be adjusted easily by adjusting an amount of (C) in the composition in the range stated above.
A composition according to one mode of the present invention may be prepared (produced) by adding (A), (B) and, when needed, (D) to (C), and mixing and agitating. An order of mixing the respective components is not particularly limited as long as the components are mixed uniformly.
A composition according to one mode of the present invention may be one-liquid type or two-liquid type. When containing a curing agent as (D) in the composition, the composition according to one mode may be two-liquid type with, for example, a first liquid comprising components other than a curing agent and a second liquid comprising a curing agent.
A method of forming a membrane is not particularly limited. A membrane may be formed on an object to be coated by any method or by an apparatus, for example, spray coating (for example, air spray, airless spray and electrostatic spray, etc.), paint brush, curtain flow coating, roller brush coating, bar coating, kiss roll, metaling bar, gravure roll, reverse roll, dip coating and die coating may be used.
Particularly, a composition according to one mode preferably forms a membrane by using spray coating, which requires spray of droplet from a small spray hole. In other words, a membrane formed from the liquid composition according to one mode is a spray coated membrane.
According to spray coating using a composition according to one mode, droplets of the composition adhere successively to a surface of an object to be coated and, at the same time, volatilization of (C) in the droplets adhered to the object to be coated proceeds. As a result, a solid content (particles) obtained by removing (C) from droplets laminates successively on the surface of the object to be coated so as to form a solid particle laminate. According to one mode, this solid particle laminate configures a membrane.
In the case of using a composition comprising a thermosetting resin as (A) and furthermore comprising a curable agent as (D), it is preferable that a solid particle laminate is applied to a surface of an object to be coated and, after that, the laminate is heated to be cured. Here, even if a trace of (C) remains in the preheated laminate, it volatilizes almost completely by the heating.
Heating condition may be adjusted properly depending on a thickness of the laminate before heating, heat resistant characteristic of an object to be coated and kinds of (C) to be used, etc. The heating condition is, for example, one minute or more and 10 minutes or less at 70° C. or more and 150° C. or less, and preferably 2 minutes or more and 5 minutes or less at 100° C. or more and 130°° C. or less.
A thickness of the antireflection film 4 is not particularly limited as long as adhesion strength with the base member 2 becomes preferable and internal reflection on the plane portion 2b is suppressed so as to be able to suppress flare and ghost due to internal reflection light. An example of a preferable film thickness is preferably 2 μm or more, more preferably 5 μm or more and preferably 40 μm or less and more preferably 25 μm or less. Note that a film thickness of the antireflection film 4 is a height from a surface of an object to be coated including protruding portions due to (B2) and (B1) on the membrane. The film thickness can be measured by the method based on JIS K7130.
Characteristics of a membrane formed from a composition according to one mode are as below.
(Glossiness, Reflectance, L value, Optical Density and Adhesiveness)
A surface of a membrane formed from a composition according to one mode preferably has glossiness at 60° of less than 1%, glossiness at 85° of less than 5%, reflectance of 4% or less, an L value of 22 or less and an optical density of 1.0 or more.
Here, when it is configured that a membrane formed from a composition according to one mode is exposed as an outermost surface, 60°-glossiness, 85°-glossiness, reflectance, an L value and optical density on a surface of the membrane are preferably in the ranges as above. When another membrane is coated on a membrane formed from a composition according to one mode, 60°-glossiness, 85°-glossiness, reflectance, an L value and optical density on a surface of this another membrane (that is, an outermost surface of the optical element) are preferably in the ranges as above. Hereinafter, these surfaces will be referred to as “an outermost surface of a membrane”.
An outermost surface of a membrane formed from a composition according to one mode preferably has 60°-glossiness of less than 1%, 85°-glossiness of less than 5%, reflectance of 4% or less, an L value of 22 or less, and optical density of 1.0 or more. When 60°-glossiness, 85°-glossiness, reflectance, an L value and optical density on an outermost surface of a membrane are in the ranges as above, it is possible to attain low glossiness, low reflectance (excellent antireflection property: which will be the same below), a high blackness degree and a high light-shielding characteristic on the outermost surface of the membrane.
The uppermost value of 60°-glossiness is more preferably less than 0.8% and furthermore preferably less than 0.5%. When 60°-glossiness is adjusted to be in the range above, a flare ghost phenomenon due to irregular reflection of lights can be prevented effectively. A lower limit value of 60°-glossiness is not particularly limited, and the lower the better.
The uppermost value of 85°-glossiness is more preferably less than 3.5% and furthermore preferably less than 2.5%. When 85°-glossiness is adjusted to be in the range above, a flare ghost phenomenon is prevented, dependency on an angle is eliminated, and an advantage of improving designability can be obtained easily. A lower limit value of 85°-glossiness is not particularly limited, and the lower the better.
An uppermost value of reflectance is more preferably 3% or less and furthermore preferably 2.5% or less. A lower limit value of reflectance is not particularly limited. The lower the reflectance is, the better. When reflectance is adjusted to be in the range above, a flare ghost phenomenon due to irregular reflection (internal reflection) of lights can be prevented furthermore effectively.
An uppermost value of an L value (blackness degree) is more preferably 20 or less and furthermore preferably 18 or less. A lower limit value of an L value is not particularly limited. However, in terms of demands for real blackness on appearance, the lower, the better. When an L value is adjusted to be in the range above, the blackness is enhanced and blackness outstands so as to attain excellent designability, therefore, a higher appearance quality can be maintained even provided at a position seen by users.
The L value above is a lightness L*value on an outermost surface of a membrane, which is in CIE 1976 L*a*b* (CIELAB) color space system based on a SCE method. The SCE method is a specularly reflected light removal method, which means a method of measuring color by removing specularly reflected lights. Definition of the SCE method is defined in JIS Z8722 (2009). Since specularly reflected lights are removed in the SCE method, the color is close to the color actually viewed by human.
CIE is abbreviation of Commission Internationale de l'Eclairage, which means international committee on illumination. The CIELAB color space was adopted in 1976 in order to measure color difference between perception and devices and is a uniform color space defined in JIS Z 8781 (2013). Three coordinates in CIELAB are indicated by L*value, a*value and b*value. The L*value indicates lightness and expressed from 0 to 100. When L*value is 0, it indicates black, while it indicates white diffusion color when L*value is 100. The a*value indicates colors between red and green. When a*value is in minus, it indicates colors close to green, while when in plus, it indicates colors close to red. The b*value indicates colors between yellow and blue. When b*value is in minus, it indicates colors close to blue, while it indicates colors close to yellow when in plus.
A lower limit value of optical density is more preferably 1.5 or more and furthermore preferably 2.0 or more. When optical density is adjusted to be in the range above, a light-shielding characteristic can be enhanced furthermore. An upper limit value of optical density is not particularly limited, and the higher the better.
The glossiness, reflectance, an L value and optical density explained above can be measured by methods explained later on.
In addition to the characteristics (glossiness, reflectance, an L value and optical density) above, a membrane formed from a composition preferably has good adhesiveness to a surface of an object to be coated. Adhesiveness of a membrane formed from a composition to a surface of an object to be coated preferably satisfies that 75% or more of the coating remain as explained in adhesiveness evaluation in later-explained examples.
In a membrane formed from a composition according to one mode, it is preferable that a maximum height Rz is 7 μm or more, an average length Rsm of contour curve element is 80 μm or more, skewness Rsk of contour curve is 0.3 or less and Kurtosis Rku of a contour curve is 3 or more. When Rz, Rsm, Rsk and Rku are in the ranges above on the uppermost surface, glossiness, optical density, reflectance, an L value and optical density on the outermost surface of a membrane can become in the ranges above (60°-glossiness less than 1%, 85°-glossiness less than 5%, reflectance 4% or less, an L value 22 or less and optical density 1.0 or more), consequently, low glossiness, low reflectance, a high blackness degree and a high light-shielding characteristic on the outermost surface of a membrane can be attained.
The lower limit value of Rz is more preferably 10 μm or more. When the lower limit value of Rz is as above, low glossiness, low reflectance and high light-shielding characteristic can be furthermore adjusted easily.
An upper limit value of Rz is not particularly limited but is preferably 50 μm or less and more preferably 30 μm or less. When an upper limit value of Rz is as above, furthermore lower glossiness, a higher light-shielding characteristic, lower reflectance and higher blackness degree on the outermost surface of a membrane can be attained easily.
The Rsm indicates an average length of contour curve elements within a standard length. A lower limit value of Rsm is more preferably 100 μm or more and furthermore preferably 120 μm or more. When a lower limit value of Rsm is as above, an advantage of low glossiness can be attained furthermore easily. An upper limit value of Rsm is not particularly limited, but preferably 160 μm or less. In this range, furthermore excellent adhesiveness between an object to be coated and a membrane to be formed thereon can be obtained.
The Rsk is an average of the cubes of a height Z (x) in a dimentionless reference length obtained by a root mean square height (Zq) cubed, which is an index indicating deviation from an average line of uneven shape, that is, a degree of strain, on an outermost surface of a membrane. There is a tendency that when Rsk value is in plus (Rsk>0), the uneven shape is deviated to the concave side, so that protruding shape becomes sharp. On the other hand, when in minus (Rsk<0), the uneven shape is deviated to the convex side, so that protruding shape becomes dull. When the protruding shape of contour curve is dull, haze becomes low comparing with the case with a sharp shape.
An upper limit value of Rsk is more preferably 0.2 or less. When an upper limit value of Rsk is as above, an advantage of low glossiness can be obtained furthermore easily. A lower limit value of Rsk is not particularly limited but is preferably 0 or more. When a lower limit value of Rsk is as above, an advantage of low glossiness can be obtained easily.
The Rku indicates an average of the fourth-power of a height Z (x) in a dimentionless reference length obtained by the four-power of a root-mean-square height (Zq), and is an index indicating a degree of sharpness at tips of unevenness on an outermost surface of a membrane. When Rku is larger, there are more sharp tips on unevenness, so that an inclined angle close to tips of unevenness becomes larger while inclined angles of other parts become smaller, so that reflection of background tends to arise.
A lower limit value of Rku is more preferably 3.3 or more. When a lower limit value of Rku is as above, an advantage of low glossiness can be obtained more easily. An upper limit value of Rku is not particularly limited, but is preferably 5 or less. When an upper limit value of Rku is as above, an advantage of low glossiness can be obtained more easily.
In a membrane formed from a composition according to one mode, an arithmetic average roughness (Ra) on an outermost surface is preferably 0.5 μm or more, more preferably 1.0 μm or more and furthermore preferably 1.5 μm or more.
Those Rz, Rsm, Rsk, Rku and Ra on an outermost surface of a membrane as explained above can be measured or calculated based on JIS B0601:2001.
Below, the present invention will be explained specifically based on examples (including modes and comparative examples), however, the present invention is not limited to the examples. Below, “part” indicates “part by mass” and “%” indicates “% by mass”.
As A (a resin component), a substance below was prepared.
As B1 (small particles) falling under B (unevenness forming particles), substances below were prepared.
As B2 (large particles) falling under B, substances below were prepared.
Note that BECSIA ID used as B2a (complex silica) is complex particles of CB and silica, wherein CB/silica=about 25/75 (mass ratio). The MHI black #273 used as B1a (CB) is a CB dispersant and, in a solid content total amount 18% of the dispersant, 9.5% is CB and remaining 8.5% is other compounds. In the 8.5% of remaining compounds, 3% is a copper compound and 5.5% is an acrylic resin.
As D (optional component), a substance below was prepared.
As an object to be coated, substrates as samples for evaluation were prepared. As the substrates as samples for evaluation, a glass material (S-LAH53 produced by OHARA Inc.) was used and glass plates (30 mm in diameter and 5 mm in thickness), wherein both surfaces of each plate in the thickness direction (X direction) were finished to be smooth surface, were used.
Respective components for each example with each solid content ratio shown in Table 1 were prepared, so that a total solid content becomes approximately 25% by mass, and added to a necessary amount of (C) a diluent solvent, which is a mixed solvent (methylethyl ketone:butyl acetate=50:50), and agitated to mix, and a liquid composition (hereinafter, also simply referred to as “a liquid”) was prepared.
Each liquid obtained for each of the examples was sprayed toward an outer surface of an object to be coated (a glass plate) by spray coating in the same method as explained in (3-1) Coating Performance below. Then, the resultant was heated at 120° C. for 3 minutes to dry, a solid particle laminate was formed by spray coating and heated to be a coating (hereinafter, also simply referred to as “a coating”) having an average membrane thickness of 20 μm on a surface of the object to be coated, so that samples for evaluation were obtained.
On each liquid obtained in each of the examples, a variety of characteristics (coating performance) were evaluated (liquid evaluation) in the methods explained below. Also, on each coating formed on each sample for evaluation obtained in each of the examples, a variety of characteristics (characteristics and surface properties) were evaluated in the methods explained below (evaluation on samples). The results are shown in Table 1.
Coating performance of a liquid was evaluated by observing coating uniformity after coating by spray coating. Each liquid was poured in an air spray configured by attaching an air brush (Spray-Work HG Single Airbrush produced by TAMIYA, Inc.) to an air can (Spray-Work Air Can 420D produced by TAMIYA, Inc.), sprayed toward an outer surface of an object to be coated for 10 seconds from a 10 cm distance from a tip of the air brush, and a formed solid particle laminate was evaluated its coating uniformity visually. Evaluation reference is as below.
Glossiness against a measurement light having an incident angle of 60° (specular glossiness at) 60° and glossiness against a measurement light having an incident angle of 85° (specular glossiness at) 85° on a surface of a coating formed on each sample for evaluation was measured on 9 spots by using a glossmeter (VG 7000 produced by NIPPON DENSHOKU Industries Co., Ltd.) by the method based on JIS Z8741, and an average value thereof was adopted as a glossiness degree. Evaluation reference is as below.
Reflectance against a light having a wavelength from 400 nm to 700 nm on a surface of coating formed on each sample for evaluation was measured at 9 spots at 1 nm intervals by using a spectral colorimeter (CM-5 produced by Konica Minolta Inc.) by the method based on JIS Z8722, and an average value thereof was adopted as reflectance. Evaluation reference is as below.
A degree of blackness on a surface of a coating formed on each sample for evaluation was evaluated by measuring lightness L*value in CIE 1976 L*a*b* (CIELAB) color space system on the surface by the SCE method. The lightness L*value was measured by using a spectral colorimeter (CM-5 produced by Konica Minolta Inc.) by the method based on JIS Z8781-4:2013. Evaluation reference is as below.
When measuring, a CIE standard light source D65 was used as a light source and L* value in the CIELAB color space system was obtained at a viewing angle of 10° by the SCE method. The CIE standard light source D65 is defined in JIS Z8720 (2000) “Standard Illuminants and Sources for Colorimetry”, and ISO 10526 (2007) also shows the same definition. The CIE standard light source D65 is used in the case of displaying colors of an object illuminated by daylight. A viewing angle of 10° is defined in JIS Z8723 (2009) “Methods of Visual Comparison for Surface Colours”, and ISO/DIS 3668 also shows the same definition.
A light-shielding characteristic of a coating formed on each sample for evaluation was evaluated by calculating optical density of the coating. Optical density of a coating formed on each sample for evaluation was obtained by using an optical density meter (X-rite 361T (ortho filter) produced by Nihon Heihan Kizai Kabushiki Kaisha), irradiating a vertical transmission light flux to the coated film side of a sample, and calculating by expressing a ratio with respect to a state without a coating film in log (logarithms). Optical density of 6.0 or more is an upper limit value of detection in the measurement. Evaluation reference is as below.
Adhesiveness of a coating film formed on each sample for evaluation to a surface of an object to be coated was evaluated by cutting the coating film in a grid pattern with a market-available cutter, putting thereon a cellophane tape (Cellulose tape produced by NICHIBAN Co., Ltd.), then taking off the tape, and visually observing a remaining state of the coating film. Evaluation reference is as below.
Glossiness, reflectance, blackness degree, light-shielding characteristic and adhesiveness as above were evaluated comprehensively. Evaluation reference is as below.
Properties (Rz value, Rsm value, Rsk value, Rku value and Ra value) of a surface of a coating film formed on each sample for evaluation was measured by using a surface roughness measuring device (SURFCOM 480B produced by TOKYO SEIMITSU Co., Ltd.) based on JIS B0601:2001. Evaluation reference is as below.
As shown in Table 1, when a liquid for forming membrane did not comprise as (B) one or more of (B1) and (B2) (Examples 6, 7, 9, 11 and 12), at least one of the membrane characteristics of glossiness, reflectance, L value, light-shielding characteristic and adhesiveness was not satisfied. On the other hand, even both of (B1) and (B2) were contained as (B) in the liquid (Examples 1 to 5, 8 and 10), when mass ratio of (B2) with respect to (B1):1 was 1.75 or less (Example 1) or 3.58 or more (Example 5), at least one of an L value and adhesiveness as membrane characteristics was not satisfied. Even if both of (B1) and (B2) are contained and a mass ratio of (B2) with respect to (B1):1 was in a proper range (exceeding 1.75 and less than 3.58) (Examples 2 to 4 and 13 to 17), when a content (total amount) of (B) in 100% by mass of a total solid content was less than 20% by mass (Example 13) or exceeding 60% by mass (Example 17), one or more of membrane characteristics of glossiness, reflectance, an L value, light-shielding characteristic and adhesiveness was not satisfied.
On the other hand, when a mass ratio of (B2) with respect to (B1):1 was exceeding 1.75 and less than 3.58 and a total content of (B) with respect to a total solid amount of 100% by mass in a composition was 20% by mass or more and 60% by mass or less (Examples 2 to 4, 8, 10 and 14 to 16), coating performance of the liquid, membrane characteristics, and membrane properties were all satisfied.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2021-120360 | Jul 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2022/027839 | 7/15/2022 | WO |
