KR20140088862A - Method of manufacturing object with low reflection film - Google Patents

Method of manufacturing object with low reflection film Download PDF

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Publication number
KR20140088862A
KR20140088862A KR1020147008766A KR20147008766A KR20140088862A KR 20140088862 A KR20140088862 A KR 20140088862A KR 1020147008766 A KR1020147008766 A KR 1020147008766A KR 20147008766 A KR20147008766 A KR 20147008766A KR 20140088862 A KR20140088862 A KR 20140088862A
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coating
coating composition
roll
substrate
reflection film
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KR1020147008766A
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Korean (ko)
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요시미 오타니
사토시 모토타니
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아사히 가라스 가부시키가이샤
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Publication of KR20140088862A publication Critical patent/KR20140088862A/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/42—Gloss-reducing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2252/00—Sheets
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/73—Anti-reflective coatings with specific characteristics
    • C03C2217/732—Anti-reflective coatings with specific characteristics made of a single layer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Composite Materials (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Surface Treatment Of Glass (AREA)
  • Photovoltaic Devices (AREA)
  • Laminated Bodies (AREA)

Abstract

It is possible to cope with a wide substrate, to carry out the transporting speed of the substrate relatively fast, to have a comparatively small amount of the coating composition required and to have a relatively low drying or baking time or coating time, Reflective film having excellent film thickness controllability which is easy to form a low reflection film having an arbitrary film thickness which can be optically designed and which is easy to form. When the coating composition 20 is applied by the coating roll 14 of the reverse roll coater 10 to form a low reflection film on the base material 2 transported in a predetermined direction, (A), the fine particles (b) dispersed in the dispersion medium (a) and the binder (c) dissolved or dispersed in the dispersion medium (a) while the coating composition (20) ) And having a viscosity of 1 to 10 mPa · s is used.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing a low-

The present invention relates to a method for producing an article having a low reflection film on a substrate.

An article having an antireflection function for reducing external light reflection and improving light transmittance has been put to practical use. As a method of giving an antireflection function, there is known a method of forming a low reflection film on a substrate by a wet coating method (a spin coating method, a spray coating method, a roll coating method or the like).

The spin coating method is a method in which a coating composition for forming a low-reflection film is applied onto a substrate by centrifugal force by dropping a coating composition for forming a low-reflection film on a substrate and rotating the substrate.

In the spray coating method, a coating composition for forming a low-reflection film is applied on a substrate by spraying a coating composition for forming a low-reflection film from a spray head onto a substrate to be transported in a predetermined direction.

In the roll coating method, a coating composition for forming a low reflection film is applied on a substrate by transiting a coating composition for forming a low reflection film on the surface of a coating roll on a substrate to be transported in a predetermined direction.

However, the spin coating method has the following problems.

When the base material becomes large, it becomes difficult to rotate the base material.

The low reflective film tends to become thick at the peripheral edge of the substrate, and the uniformity of the film thickness of the low reflective film is inferior.

The extra low reflection film forming coating composition is blown off from the substrate by centrifugal force, so that the required amount of the low reflection film forming coating composition is increased.

The spray coat method has the following problems.

Since it is necessary to reciprocate the spray head in the width direction of the substrate, in order to uniformly form the low reflection film on the wide substrate, it is necessary to arrange a large number of spray heads along the transport direction of the substrate, You need to slow down.

There are many low-reflection film-forming coating compositions which do not adhere to the substrate but are scattered in the air, so that the required amount of the low-reflection film-forming coating composition is increased.

A roll coating method can be used as a wet coating method which can cope with a wide substrate, can speed up the transfer of a substrate relatively quickly, and requires a relatively small amount of the coating composition for low reflection film formation.

However, the roll coating method has the following problems.

The film thickness uniformity of the low reflection film is inferior because the gap adjustment between the substrate and the coating roll is difficult.

When the viscosity of the coating composition for forming a low reflection film is low, it is difficult to form a low reflection film having an arbitrary film thickness capable of optical design. That is, the film thickness controllability is inferior.

When the viscosity of the coating composition for forming a low reflection film is increased or the coating is applied in order to form a low reflection film having an arbitrary film thickness capable of optically designing, the drying or baking time or the application time becomes long.

As a roll coating method capable of forming a metal oxide film having a uniform film thickness, the following method has been proposed.

A method for forming a metal oxide film by applying a coating composition containing a metal compound and an organic solvent on a substrate conveyed in a predetermined direction by a coating roll of a reverse roll coater and firing the coating composition, Wherein the viscosity of the coating composition is 0.1 to 100 mPa s, the rotation speed of the coating roll is 2 to 55 m / min, the conveying speed of the substrate is 1 to 30 m / min , And the rotating speed of the coating roll is faster than the conveying speed of the substrate (see Patent Document 1).

However, in this method, when the viscosity of the coating composition is lowered, there is a problem that it is difficult to form a low reflection film having an arbitrary film thickness capable of optical design, that is, the film thickness controllability is inferior.

Japanese Laid-Open Patent Publication No. 07-068219

INDUSTRIAL APPLICABILITY The present invention can cope with a wide substrate, can relatively speed up the conveying speed of the substrate, requires a relatively small amount of the coating composition and has a relatively short drying or baking time or coating time, Reflective film having an excellent film thickness controllability and capable of forming a low-reflection film having an arbitrary film thickness capable of optically designing (that is, excellent in controllability of film thickness).

A method for producing an article with a low reflection film of the present invention is a method for producing an article having a low reflection film on a substrate, comprising the steps of: applying a coating composition on a substrate conveyed in a predetermined direction by a coating roll of a reverse roll coater (A), fine particles (b) dispersed in the dispersion medium (a), and a binder (c) dissolved or dispersed in the dispersion medium (a) ) And a viscosity of 1.0 to 10.0 mPa · s is used, and in the above step, the rotation speed of the coating roll (that is, the peripheral speed of the coating roll at the time of application of the coating composition on the substrate) The " rotational speed " in the present specification means the main speed) is made lower than the conveying speed of the substrate.

It is preferable that the coating composition further contains a terpene derivative (d) dissolved or dispersed in the dispersion medium (a).

The amount of the terpene derivative (d) is preferably 0.01 to 2 parts by mass based on 1 part by mass of the solid content of the coating composition.

The solid content concentration of the coating composition is preferably 1 to 9% by mass.

The mass ratio (the fine particles (b) / the binder (c)) of the fine particles (b) and the binder (c) is preferably 10/90 to 95/5.

The transport speed of the substrate is preferably 3 to 20 m / min.

It is preferable that the rotation speed of the coating roll is 0.28 times or more and 0.98 times or less of the conveying speed of the substrate.

The surface hardness (JIS-A standard) of the coating roll is preferably 10 to 70. [

It is preferable that the base material is a template glass having rough unevenness on at least one surface thereof.

The " ~ " representing the above numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value, and unless otherwise specified, " ~ "

According to the production method of the article with a low reflection film of the present invention, it is possible to cope with a wide substrate, to relatively speed up the conveying speed of the substrate, to obtain a relatively small amount of the required coating composition, It is possible to form a low reflection film having a relatively short film thickness and a low reflection film having an arbitrary film thickness capable of being optically designed, that is, excellent in film thickness controllability.

1 is a cross-sectional view showing an example of an article with a low reflection film according to the present invention.
2 is a cross-sectional view showing another example of the article with a low reflection film according to the present invention.
3 is a schematic view showing an example of a reverse roll coater.

≪ Item having low reflective film &

1 is a cross-sectional view showing an example of an article with a low reflection film obtained by the manufacturing method of the present invention. The article 1 with a low reflection film has a base material 2 and a low reflection film 3 formed on the surface of the base material 2.

(materials)

Examples of the material of the base material 2 include glass, metal, resin, silicon, wood, paper and the like. Examples of the glass include soda lime glass, borosilicate glass, aluminosilicate glass, alkali-free glass, and mixed alkali glass. Examples of the resin include polyethylene terephthalate, polycarbonate, triacetyl cellulose, and polymethyl methacrylate.

There is no particular limitation on the shape of the base material 2, but generally, a plate, a film and the like can be given.

As the substrate 2 for the cover glass of the solar cell, a rough glass plate glass in which the surface is uneven is preferable. As the glass, there is a soda-lime glass (that is, a high-transmittance glass, collectively referred to as a white plate) having lower iron component ratio and higher transparency than soda lime glass (generally called glass sheet glass) Glass) is preferable. White board glass is in oxide-based, in mass percentage display, SiO 2: 65 ~ 75% , Al 2 O 3: 0 ~ 10%, CaO: 5 ~ 15%, MgO: 0 ~ 15%, Na 2 O: 10 ~ 0 to 3% of Li 2 O, 0 to 3% of Fe 2 O 3 , 0 to 5% of TiO 2 , 0 to 3% of CeO 2 , 0 to 3% of K 2 O, 0 to 3% of K 2 O, 0 to 5% ~ 5%, SrO: 0 ~ 5%, B 2 O 3: 0 ~ 15%, ZnO: 0 ~ 5%, ZrO 2: 0 ~ 5%, SnO 2: 0 ~ 3%, SO 3: 0 ~ 0.5 %. ≪ / RTI > In the case where the base material 2 is an alkali-free glass, it is preferable that 39 to 70% of SiO 2 , 3 to 25% of Al 2 O 3 , 1 to 30% of B 2 O 3 , It is preferable to have a composition of MgO: 0 to 10%, CaO: 0 to 17%, SrO: 0 to 20%, and BaO: 0 to 30%. In the case where the base material 2 is a mixed alkali glass, it is preferable that 50 to 75% of SiO 2 , 0 to 15% of Al 2 O 3 , MgO + CaO + SrO + BaO + ZnO : 6 to 24%, and Na 2 O + K 2 O: 6 to 24%.

As shown in Fig. 2, the base material 2 may have the functional layer 5 on the surface of the base material 4.

Examples of the functional layer 5 include an undercoat layer, an adhesion improving layer, and a protective layer.

The undercoat layer has a function as an alkali barrier layer or a wide band low refractive index layer. As the undercoat layer, a layer formed by applying a coating composition for undercoat containing a hydrolyzate of alkoxysilane (sol-gel silica, that is, a silica precursor by a sol-gel method) to a substrate is preferable. When a coating composition for a low reflection film described below is applied on the undercoat layer, the undercoat layer may be previously baked or wetted. When the coating composition for a low reflection film is applied on the undercoat layer, the coating temperature (that is, the substrate temperature at the time of coating) is preferably from room temperature to 80 ° C, and the baking temperature of the applied coating film is preferably from 30 to 700 ° C . The film thickness of the undercoat layer is preferably 10 to 500 nm.

(Low reflection film)

The low reflection film 3 is preferably a single layer film containing the binder (c) or its calcined product and the fine particles (b) formed by applying the coating liquid of the coating composition described later once. When the binder is a hydrolyzate of alkoxysilane, the low reflection film 3 is a film in which the fine particles (b) are dispersed in a matrix composed of a sintered product (SiO 2 ) of hydrolyzate of alkoxysilane. When the binder is a resin, the low reflection film 3 is a film in which the fine particles (b) are dispersed in a matrix made of a resin.

The film thickness of the low reflection film 3 is preferably 50 to 300 nm, more preferably 80 to 200 nm. If the film thickness of the low reflection film 3 is 50 nm or more, optical interference occurs and the antireflection performance is exhibited. If the film thickness of the low reflection film 3 is 300 nm or less, film formation can be performed without occurrence of cracks.

The film thickness of the low reflection film 3 is measured by a reflection spectroscopic film thickness meter.

The reflectance of the low reflection film 3 is the lowest value (so-called bottom reflection ratio) within a wavelength range of 300 to 1200 nm, preferably 2.6% or less, and more preferably 1.0%.

≪ Method for producing low reflective film article >

The method for producing a low reflection film-bearing article of the present invention is characterized in that a coating liquid of a coating composition described later is coated on a substrate 2 conveyed in a predetermined direction by a coating roll of a reverse roll coater, Or drying and curing the low reflection film 3 to form the low reflection film 3.

(Reverse roll coater)

3 is a schematic view showing an example of a reverse roll coater.

The reverse roll coater 10 includes a conveyor belt 12 for conveying the base material 2 in a predetermined direction; A coating roll (not shown) which rotates in a direction opposite to the traveling direction of the conveyor belt 12 and which is arranged with a predetermined gap above the conveyor belt 12 so that the direction of the rotation axis is perpendicular to the conveying direction of the conveyor belt 12 14); A doctor roll 16 (also referred to as a metering roll) disposed on the downstream side of the conveying belt 12 in the advancing direction of the coating roll 14 and contacting the coating roll 14 at a predetermined indentation thickness; A backup roll 18 disposed below the coating roll 14 via the transport belt 12 so as to contact the transport belt 12 and rotating in the same direction as the transport direction of the transport belt 12; The upper surface of the doctor roll 16 is brought into contact with the surface of the upper half of the doctor roll 16 so that a liquid reservoir for storing the coating composition 20 supplied to the surface of the doctor roll 16 is formed between the doctor roll 16 and the liquid roll 16. [ A first doctor blade (22) arranged; And a second doctor blade (24) disposed in contact with the surface of the coating roll (14) for scraping the coating composition (20) on the surface of the coating roll (14) not transferred to the substrate (2).

Instead of the transport belt 12, a plurality of transport rolls may be arranged in alignment in the transport direction of the substrate 2 so that the direction of the rotation axis is perpendicular to the traveling direction of the transport belt 12. [

(Application method)

In the reverse roll coater 10, the coating composition 20 is coated on the surface of the base material 2 as described below to form a coating film.

The paint composition 20 is supplied from above the doctor roll 16 to the surface of the doctor roll 16. A predetermined amount of the coating composition 20 is applied to the surface of the doctor roll 16 and between the doctor roll 16 and the first doctor blade 22 is applied to the surface of the coating roll 14 . At this time, since the movement of the coating composition 20 is regulated by the first doctor blade 22, the coating composition 20, which could not pass between the doctor roll 16 and the first doctor blade 22, Is stored between the doctor roll (16) and the first doctor blade (22), and a liquid reservoir is formed.

The coating composition 20 adhered to the surface of the doctor roll 16 and moved toward the coating roll 14 is transferred to the coating roll 14 while maintaining a predetermined amount between the coating roll 14 and the doctor roll 16. [ As shown in FIG. At this time, since the transfer of the coating composition 20 is regulated by the doctor roll 16, the coating composition 20, which could not pass between the coating roll 14 and the doctor roll 16, ) And the doctor roll 16, and a liquid reservoir is formed. The coating composition 20 transferred to the surface of the coating roll 14 moves to the conveyor belt 12 side as the coating roll 14 rotates.

The coating composition 20 attached to the surface of the coating roll 14 and moved toward the conveying belt 12 is moved in the predetermined direction in accordance with the gap between the conveying belt 12 and the coating roll 14 and the thickness of the base material 2. [ The amount is transferred to the surface of the substrate 2 to form a coating film. The coating composition 20 that has not been transferred to the surface of the substrate 2 at this time is adhered to the surface of the coating roll 14 and is conveyed toward the second doctor blade 24 And is scraped from the surface of the coating roll 14 by the second doctor blade 24.

Since the first doctor blade 22 and the second doctor blade 24 are formed on each of the doctor roll 16 and the coating roll 14 from the surface of the doctor roll 16 to the surface of the coating roll 14 Which is not shifted to the surface of the coating roll 14 but remains in a striped form on the surface of the doctor roll 16 and the stripes of the coating roll 14 which are not transferred from the surface of the coating roll 14 to the surface of the substrate 2. [ The stripes of the coating composition 20 remaining in the form of stripes on the surface can be removed by the first doctor blade 22 and the second doctor blade 24. As a result, The coating film thickness of the composition 20 can be made uniform.

(Coating roll)

As the coating roll 14, a rubber lining roll, which is typically lined with rubber, is used.

The surface hardness (JIS-A standard) of the coating roll 14 is preferably from 10 to 70, more preferably from 20 to 50. When the hardness is 10 or more, it is easy to control the film thickness of the coating composition 20 applied on the base material 2. If the hardness is 70 or less, the surface of the coating roll 14 can follow the unevenness of the surface of the template glass even if the template glass is used as the substrate 2, so that the coating film thickness of the coating composition 20 can be made uniform .

(Rotation speed of the coating roll)

The rotational speed (i.e., the main speed) of the coating roll 14 is made slower than the conveying speed of the substrate 2 when the coating composition is applied onto the substrate. By making the rotation speed of the coating roll 14 slower than the conveying speed of the substrate 2, it is easy to form a low reflection film having an arbitrary film thickness capable of optical design (that is, excellent in film thickness controllability). The rotation speed of the coating roll 14 is preferably 0.28 times or more of the transport speed of the substrate 2 and 0.98 times or less of the transport speed of the substrate 2 in view of better film thickness controllability, More preferably 0.35 times or more of the transporting speed and 0.90 times or less of the substrate 2 transporting speed.

Further, in Patent Document 1, the rotation speed of the coating roll 14 is made higher than the conveying speed of the substrate 2 in order to make the film thickness uniform, but in the present invention, by using the specific coating composition 20 described later, The coating film thickness of the coating composition 20 applied on the base material 2 can be made uniform even if the rotation speed of the roll 14 is made slower than the conveying speed of the base material 2. [

(Doctor Roll)

As the doctor roll 16, a metal roll whose surface is metal or a rubber lining roll lined with rubber is used.

It is preferable that the doctor roll 16 be formed with a plurality of grooves on the surface of the doctor roll 16 in view of easiness of holding the coating composition 20 on the surface of the doctor roll 16, It is more preferable that a groove on the lattice is formed on the surface in order to make the film thickness of the film 20 uniform.

(Indentation thickness)

The pressing thickness of the doctor roll 16 relative to the coating roll 14 is such that when the coating roll 14 and the doctor roll 16 are placed the coating roll 14 is brought into contact with the doctor roll 16 Is the amount of indentation in a state in which the doctor roll is pressed by the rubber lining on the surface of the coating roll with respect to the tangent line in the state where the indentation is not pressed by the doctor roller) is more preferably 0.1 to 1.0 mm and more preferably 0.3 to 0.9 mm. If the indentation thickness is within this range, the coating film thickness of the coating composition 20 applied on the base material 2 can be made uniform, and the coating film thickness of the coating composition 20 applied on the base material 2 .

(gap)

The gap between the conveyor belt 12 and the coating roll 14 is appropriately adjusted in accordance with the thickness of the substrate 2, the thickness of the coating composition 20 applied on the substrate 2, and the like.

(Conveying speed of substrate)

The conveying speed of the substrate 2 is preferably 3 to 20 m / min, more preferably 5 to 15 m / min. When the conveying speed of the base material 2 is 3 m / min or more, the productivity is improved. When the conveying speed of the base material 2 is 20 m / min or less, it is easy to control the thickness of the coating film of the coating composition 20 applied on the base material 2.

(Temperature)

The application temperature (the application temperature means the temperature of the base material when applied to the substrate surface) is preferably from room temperature to 80 ° C, more preferably from room temperature to 60 ° C.

The drying or firing temperature of the coating film of the coating composition is preferably 30 DEG C or higher and may be suitably determined according to the material of the substrate 2, the fine particles (b) or the binder (c). For example, when all of the materials of the base material 2, the fine particles (b), and the binder (c) are resins, the drying or baking temperature is not lower than 30 占 폚 and not higher than the heat resistance temperature of the resin, Is obtained. When the substrate 2 is glass, the firing temperature is preferably 30 占 폚 or higher and 750 占 폚 or lower. When the substrate 2 is glass, the firing step of the low reflection film 3 and the glass physical strengthening step may be combined. In the physical strengthening process, the glass is heated to around the softening temperature. In this case, the firing temperature is set in a range of about 600 ° C to about 700 ° C. The firing temperature is preferably set to be not higher than the heat distortion temperature of the base material 2. The lower limit of the firing temperature is determined according to the blend of the coating composition (20). Since the polymerization proceeds to some extent even in the natural drying, it is theoretically possible to set the drying or calcination temperature to a temperature near the room temperature as long as there is no restriction in time.

(Coating composition)

The coating composition 20 contains a dispersion medium (a), fine particles (b) dispersed in the dispersion medium (a) and a binder (c) dissolved or dispersed in the dispersion medium (a) (D) dissolved or dispersed in an organic solvent and, if necessary, may further contain other additives. The coating composition 20 is prepared by mixing, for example, a dispersion of the fine particles (b), a solution of the binder (c) and, if necessary, an additional dispersion medium (a), a terpene derivative (d) and other additives.

The viscosity of the coating composition 20 as a coating liquid is preferably 1.0 to 10.0 mPa · s and preferably 2.0 to 5.0 mPa · s. When the viscosity of the coating composition 20 is 1.0 mPa s or more, it is easy to control the coating film thickness of the coating composition 20 applied on the base material 2. When the viscosity of the coating composition 20 is 10.0 mPa s or less, the drying or baking time or the application time is shortened.

The viscosity of the coating composition (20) is measured by a B-type viscometer.

The solid content concentration of the coating composition (20) is preferably from 1 to 9% by mass, more preferably from 2 to 6% by mass. If the solid content concentration is 1% by mass or more, the coating film thickness of the coating composition 20 can be made thin and the film thickness of the low reflection film 3 finally obtained can be made uniform. When the solid content concentration is 9 mass% or less, it is easy to make the coating film thickness of the coating composition 20 applied on the base material 2 uniform.

The solid content of the coating composition 20 means the sum of the fine particles (b) and the binder (c) (in the case where the binder (c) is a hydrolyzate of alkoxysilane, the solid content in terms of SiO 2 ).

The amount of the terpene derivative (d) is preferably 0.01 to 2 parts by mass, more preferably 0.03 to 1 part by mass, relative to 1 part by mass of the solid content of the coating composition (20). When the amount of the terpene derivative (d) is 0.01 parts by mass or more, the antireflection effect becomes sufficiently high as compared with the case where the terpene derivative (d) is not added. When the content of the terpene derivative (d) is 2 parts by mass or less, the strength of the low reflection film (3) is improved.

The mass ratio (fine particle (b) / binder (c)) of the fine particles (b) and the binder (c) is preferably 10/90 to 95/5 and more preferably 70/30 to 90/10. When the fine particle (b) / binder (c) is 95/5 or less, the adhesion between the low reflection film 3 and the base material 2 is sufficiently high. When the fine particle (b) / binder (c) is 10/90 or more, the antireflection effect becomes sufficiently high.

(Dispersion medium (a))

Examples of the dispersion medium (a) (excluding the terpene derivative (d) described later) include water, alcohols (methanol, ethanol, isopropanol, butanol, diacetone alcohol, etc.), ketones (acetone, methyl ethyl ketone, (Methyl acetate, ethyl acetate, etc.), glycol ethers (e.g., methyl ethyl ketone, methyl ethyl ketone, and the like), ethers (tetrahydrofuran, (N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and the like) and a sulfur compound (dimethylsulfoxide and the like) .

The dispersion medium (a) in the case where the binder (c) is a hydrolyzate of an alkoxysilane needs to contain water because water is required for hydrolysis of the alkoxysilane.

It is preferable that the dispersion medium (a) is appropriately selected in accordance with the base material (2) or the binder (c).

As the dispersion medium (a) in the case where the substrate (2) is polycarbonate, an alcohol-based dispersion medium containing a solvent capable of dissolving polycarbonate (for example, nitrogen-containing compound) is preferable.

As the dispersion medium (a) in the case where the substrate (2) is polyethylene terephthalate, an alcohol-based dispersion medium containing a solvent capable of dissolving polyethylene terephthalate (e.g., dichloromethane) is preferable.

When the base material 2 is triacetylcellulose, polyester, acrylic resin, silicone resin or the like is used as the binder (c), and ethyl acetate is preferably used as the dispersion medium (a) when the binder (c) is polyester.

(Fine particles (b))

As the fine particles (b), at least one kind selected from the group consisting of metal oxide fine particles, metal fine particles, pigment fine particles and resin fine particles can be mentioned as a preferable material.

As the material of the metal oxide fine particles, Al 2 O 3 , SiO 2 , SnO 2 , TiO 2 , ZrO 2 , ZnO, CeO 2 , SnO x (ATO) containing Sb, In 2 O 3 (ITO) 2 may be mentioned as a preferable material. Of these, SiO 2 is particularly suitable as a material for the low reflection film 3 in view of low refractive index.

Examples of the material of the metal fine particles include metals such as Ag and Ru, and alloys such as AgPd and RuAu.

Examples of the pigment-based fine particles include inorganic pigments such as titanium black and carbon black, and organic pigments.

Examples of the material of the resin fine particles include polystyrene, melanin resin and the like.

Examples of the shape of the fine particles (b) include a spherical shape, an oval shape, a needle shape, a plate shape, a rod shape, a circular shape, a columnar shape, a cube shape, an oblong shape, a diamond shape, a star shape or an irregular shape. The fine particles (b) may be in the form of hollow, pore-like, or fused-in-air. Each of the fine particles (b) may exist in an independent state, each fine particle may be connected in a chain, and each fine particle may be aggregated. As the fine particles (b), those having the above-described shape may be mixed.

The fine particles (b) may be used alone or in combination of two or more.

The average particle size of the fine particles (b) is preferably from 1 to 1,000 nm, more preferably from 3 to 500 nm, still more preferably from 5 to 300 nm. When the mean particle size of the fine particles (b) is 1 nm or more, the antireflection effect becomes sufficiently high. When the average aggregate particle diameter of the fine particles (b) is 1000 nm or less, the haze of the low reflection film (3) is suppressed to be low.

The average agglomerated particle diameter of the fine particles (b) is measured by a dynamic light scattering method as an average agglomerated particle diameter of the fine particles (b) in the dispersion medium (a). In the case of monodisperse fine particles (b) in which agglomeration is not observed, the average aggregate particle size is equivalent to the average primary particle size.

Since the low reflection film 3 in the present invention exhibits an antireflection effect by a void selectively formed around the fine particles (b), the material having a low refractive index (for example, SiO 2 ) need not be used. Therefore, the low reflection film 3 having the various characteristics of the fine particles (b) and the antireflection effect can be formed. For example, when the material of the fine particles (b) is SiO 2 , the refractive index of the low reflection film 3 can be further lowered, so that the low reflection film 3 having a sufficiently low reflectance can be formed. When the material of the fine particles (b) is ATO, the low reflection film 3 having conductivity and / or infrared blocking ability and antireflection effect can be formed. When the material of the fine particles (b) is CeO 2 or ZnO, a low reflection film 3 having both ultraviolet ray absorbing property and antireflection effect can be formed. Further, when the material of the fine particles (b) and the TiO 2 having a refractive index even, in the prior art, it is possible to form a low reflection film 3 to the first layer coating it could not be considered, because of this reflection as hydrophilic, antimicrobial having a TiO 2 anti It is possible to form the low reflection film 3 having the effect. When the material of the fine particles (b) is an organic pigment or an inorganic pigment, a colored low reflection film (3) can be formed and a color filter having an antireflection function can be produced.

(Binder (c))

Examples of the binder (c) include a hydrolyzate of alkoxysilane (sol-gel silica, that is, a silica precursor by the sol-gel method) and a resin (e.g., thermoplastic resin, thermosetting resin or ultraviolet ray curable resin).

The binder (c) is preferably selected appropriately according to the base material (2).

As the binder (c) in the case where the base material 2 is glass, a hydrolyzate of alkoxysilane is preferable.

Examples of the alkoxysilane include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like), alkoxysilane having a perfluoropolyether group (perfluoropolyether triethoxysilane Alkoxysilane having a vinyl group (vinyltrimethoxysilane, vinyltriethoxysilane, etc.), alkoxysilane having an epoxy group (such as vinyltriethoxysilane having an epoxy group) (2), alkoxysilane having a perfluoroalkyl group - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.) , Alkoxysilane having an acryloyloxy group (such as 3-acryloyloxypropyltrimethoxysilane), and the like.

The hydrolysis of the alkoxysilane is carried out in the case of a tetraalkoxysilane using at least four times the molar amount of the alkoxysilane as a water and as an acid or an alkali as a catalyst. Examples of the acid include inorganic acids (HNO 3 , H 2 SO 4 , HCl and the like), and organic acids (formic acid, oxalic acid, monochloracetic acid, dichloroacetic acid and trichloracetic acid). Examples of the alkali include ammonia, sodium hydroxide, potassium hydroxide and the like. As the catalyst, an acid is preferable from the viewpoint of long-term preservability, and it is preferable that the catalyst does not disturb the dispersion of the fine particles (b).

(Terpene derivative (d))

Terpene means a hydrocarbon having a composition of (C 5 H 8 ) n (wherein n is an integer of 1 or more) having isoprene (C 5 H 8 ) as a constitutional unit. A terpene derivative means a terpene having a functional group derived from terpene. The terpene derivative (d) includes those having different degrees of unsaturation.

As the terpene derivative (d), a terpene derivative having a hydroxyl group and / or a carbonyl group in the molecule is preferable from the viewpoint of the antireflection effect of the low reflection film (3), and a hydroxyl group, an aldehyde group (-CHO) More preferably a terpene derivative having at least one functional group selected from the group consisting of a carboxyl group (═O) -, an ester bond (-C (═O) O-) and a carboxyl group (-COOH) A terpene derivative having at least one functional group selected from the group consisting of an aldehyde group and a keto group is more preferable.

Examples of the terpene derivative (d) include terpene alcohols (e.g., alpha -terpineol, terpinene 4-ol, L-menthol, (+) citronellol, mirtenol, nerol, borneol, Etc.), terpene aldehydes (e.g., citral,? -Cyclosity, and perilla aldehyde), terpene ketones (e.g., (±) camphor, (E.g., citronellic acid, abietic acid, etc.), terpene esters (e.g., terpinyl acetate and menthyl acetate), and the like. Terpene alcohols are particularly preferred.

The terpene derivative (d) may be used alone or in combination of two or more.

(Other additives)

Examples of other additives include a surfactant for improving leveling property and a metal compound for improving the durability of the low reflection film 3.

Examples of the surfactant include silicone oil, acrylic, and the like.

As the metal compound, a zirconium chelate compound, a titanium chelate compound, an aluminum chelate compound and the like are preferable. Examples of the zirconium chelate compound include zirconium tetraacetylacetonate and zirconium tributoxystearate.

(Action effect)

In the method of manufacturing the article with a low reflection film of the present invention described above, since the coating composition is applied by the coating roll of the reverse roll coater as described above, it is possible to cope with a wide substrate, The amount of the coating composition required is relatively small.

In the method for producing a low reflection film-containing article of the present invention described above, since the viscosity of the coating composition is 10 mPa s or less and relatively low viscosity, the drying or baking time or application time is relatively short.

Further, in the above-described method for producing a low reflection film-containing article of the present invention, since the specific coating composition is used and the rotation speed of the coating roll of the reverse roll coater is made slower than the conveying speed of the substrate, Reflection film having a uniform film thickness can be formed even if the film thickness is relatively low, and a low reflection film having an arbitrary film thickness capable of optical design can be easily formed. That is, the film thickness controllability is excellent.

Since the coating composition described above contains the dispersion medium (a), the fine particles (b) and the binder (c) as described above, the low-reflection film having an antireflection effect can be obtained at low cost, It can also be formed at a relatively low temperature.

That is, when a low reflection film is formed by the reverse roll coating method unique to the present invention using the above-described coating composition, a void is selectively formed around the fine particles (b) in the low reflection film, .

For example, if the film thickness is thick and uneven, the terpenes do not uniformly volatilize at the time of firing, and voids are not made as intended. On the other hand, if the film thickness is thin and uniform, the terpene is efficiently and smoothly volatilized at the time of firing, the point where the terpene is present remains as a gap, and the volume of the void portion is increased.

In addition, the article having a low reflection film described above has a high antireflection effect because it has a high antireflection effect, can be manufactured at low cost, and has a coating film which can be formed even at a relatively low temperature. In addition, the substrate that can be used in the production of the article is not so limited and can be manufactured at a relatively low cost.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples.

Examples 1 to 4 are Examples, and Examples 5 and 6 are Comparative Examples.

(Average primary particle diameter of fine particles)

The average primary particle diameter of the fine particles was calculated from the specific surface area measured by the BET method and the volume of the spherical particles on the assumption that the spherical particles were uniformly dispersed in the carrier.

(Average aggregate particle size of fine particles)

The mean aggregate particle size of the fine particles was measured using a dynamic light scattering method particle size analyzer (Microtrack UPA, manufactured by Nikkiso Co., Ltd.).

(Viscosity)

The viscosity of the coating composition was measured using a B-type viscometer (MODEL BL, manufactured by TOKI INDUSTRIAL CO., LTD.) After adjusting the liquid temperature at 25 캜 in a thermostat bath.

(Film thickness)

The film thickness of the low reflection film was measured by measuring the spectral reflectance using a reflection spectrometer (FE3000, manufactured by Otsuka Electronics Co., Ltd.) and fitting the curve obtained in the dispersion formula of nk Cauchy and the measured reflection curve by the minimum yield method Respectively. Further, the film thickness of the low reflection film was measured at four points, and the difference (difference) between the average value and the maximum value and the minimum value was obtained.

(Transmittance)

The transmittance of the article with a low reflection film was determined by measuring the transmittance of light at a wavelength of 400 nm to 1100 nm using a spectrophotometer (V670, manufactured by Nippon Broadcasting Co.).

The difference in transmittance was determined based on the following formula (1).

Transmittance difference = Transmittance of article with low reflection film - Transmittance of substrate only (1).

(reflectivity)

A black vinyl tape was attached to the surface of the substrate opposite to the low reflectance film so as not to include bubbles and the reflectance of the low reflectance film of 100 mm x 100 mm at the center of the substrate was measured. In addition, the reflectance is the bottom reflectance (that is, the lowest value within a wavelength range of 300 to 1200 nm) in the wavelength range of 300 to 1200 nm. When the wavelength representing the bottom reflectance is 380 nm or less or 780 nm or more, a spectrophotometer (V670, manufactured by Nippon Bunko K.K.) is used. When the wavelength representing the bottom reflectance is 380 to 780 nm, a spectrophotometer (MCPD-3000, instantaneous multi-photometric system, manufactured by Otsuka Electronics Co., Ltd.) is used.

(Abrasion resistance)

A felt (puff AM-1, manufactured by Niitaka Yuka Kogyo Co., Ltd.) was mounted on a rubbing tester (manufactured by Ohira Chemical Co., Ltd.), and the felt was horizontally reciprocated on the surface of the low reflection film at a load of 1 kg, The transmittance of the low reflectance film-provided article was measured in the same manner as the measurement of the transmittance.

The change in transmittance was determined based on the following formula (2).

Transmittance change = transmittance of low reflection coated article before abrasion resistance test - Transmittance of article after low resistance coated article after abrasion resistance test (2).

(Exterior)

The outer appearance of the low reflection film of the article with the low reflection film was visually observed and evaluated according to the following criteria.

?: There are no deviations and coarseness in the film and are uniform.

?: Slight unevenness, roughness can be confirmed.

X: Non-uniformity, multiple sets can be confirmed.

(Preparation of binder solution (c-1)) [

And 77.6 g of denatured ethanol (manufactured by Nippon Alcohol Distributor, Sorumix AP-11, a solvent mixed with ethanol as a main agent, hereinafter the same) was added with stirring to 11.9 g of ion-exchanged water and 61 mass% And the mixture was stirred for 5 minutes. 10.4 g of tetraethoxysilane (solid content in terms of SiO 2 : 29% by mass) was added and stirred at room temperature for 30 minutes to obtain a binder solution (c-1) having a solid content in terms of SiO 2 of 3.0% by mass Lt; / RTI >

Further, SiO 2 in terms of solid content concentration, the solid content concentration when all Si of tetraethoxysilane was phone to SiO 2.

(Preparation of binder solution (c-2)) [

(11.9 g of ion-exchanged water and 0.1 g of 61 mass% nitric acid solution) of 80.4 g of denatured ethanol (manufactured by Nippon Alcohol Distributor, Sorumix AP-11, mixed solvent based on ethanol, the same applies hereinafter) And the mixture was stirred for 5 minutes. 7.6 g of tetraethoxysilane (solid content in terms of SiO 2 : 29 mass%) was added and stirred at room temperature for 30 minutes to obtain a binder solution (c-2) having a solid content concentration of 2.2 mass% in terms of SiO 2 Lt; / RTI >

(Chain-like SiO 2 fine particle dispersion (b-1))

"Snowtex OUP", solid content in terms of SiO 2 : 15.5 mass%, average primary particle diameter: 10 to 20 nm, average agglomerated particle diameter: 40 to 100 nm, manufactured by Nissan Chemical Industries, Ltd.

(Preparation of coating composition (A)) [

24.0 g of isobutyl alcohol, 20.0 g of the binder solution (c-1) and 15.5 g of the dispersion of the fine SiO 2 particles (b-1) were added to 24.5 g of the denatured ethanol while stirring, 15.0 g of an alcohol (hereinafter referred to as DAA) and 1.0 g of? -Terpineol as a terpene derivative (d) were added to prepare a coating composition (A) having a solid content concentration of 3.0% by mass. Composition and viscosity are shown in Table 1.

(Preparation of coating compositions (B) and (C)) [

The coating compositions (B) and (C) were prepared in the same manner as the coating composition (A) except that the formulation shown in Table 1 was used. Composition and viscosity are shown in Table 1.

Figure pct00001

[Example 1]

(Size: 100 mm x 100 mm) having a surface roughness of unevenness as a soda-lime glass (white plate glass) having a high transmittance of low iron, Mm, thickness: 3.2 mm) was prepared, and the rough surface of the template glass was polished and washed with a cerium oxide aqueous dispersion. The cerium oxide was rinsed with water, rinsed with ion-exchanged water and dried.

The above-mentioned template glass was preheated in a preheating furnace (VTR-115, manufactured by ISUZU Co., Ltd.), and the glass surface temperature of the template glass was kept at 30 占 폚. The coating composition (A) was applied by a coating roll of a roll mill (manufactured by Mitsubishi Electric Corporation). The application conditions were as follows.

Transfer speed of substrate: 13.8 m / min,

Rotation speed of coating roll: 9.0 m / min,

Rotation speed of the doctor roll: 9.0 m / min,

Gap between coating roll and transport belt: 2.9 mm,

Pressing thickness of coating roll and doctor roll: 0.6 mm.

As the coating roll, a rubber lining roll having a surface hardness (JIS-A standard) rubber (ethylene propylene diene rubber) lined with 30 was used. Dr. Rollo used a metal roll with a lattice-shaped groove formed on its surface.

Thereafter, the film was baked at 500 캜 for 30 minutes in the air to obtain an article having a low reflective film. The article was evaluated. The results are shown in Table 2.

[Examples 2 to 5]

An article in which a low reflection film was formed was obtained in the same manner as in Example 1 except that the coating composition and coating conditions were changed to coating compositions and coating conditions shown in Table 2. The article was evaluated. The results are shown in Table 2.

[Example 6]

A template glass kept at 30 占 폚 in a preheating furnace was set in a stand in a booth where a spray coating robot (JE005F, manufactured by Kawasaki Robotics Co., Ltd.) was installed, and the coating composition X) was applied. Thereafter, the film was baked at 500 ° C for 30 minutes in the air to obtain an article having a low reflective film. The article was evaluated. The results are shown in Table 2.

Figure pct00002

In Example 1, it is found that a low reflection film having a target film thickness is formed, and the film thickness deviation of the low reflection film is small and the uniformity is good. In Example 2 and Example 3, the conveying speed was changed and the rotational speed with respect to the conveying speed was changed, but a uniform film was obtained in the same manner. In Example 4, a film in which the ratio of the fine particles and the binder was changed was obtained in the same manner.

In Example 5, since the rotation speed of the coating roll was faster than the conveying speed of the substrate, a low reflection film having a target film thickness was not obtained.

In Example 6, since the low reflection film was formed by the spray coating method, the film thickness deviation of the low reflection film was large.

Industrial availability

The article with a low reflection film obtained by the production method of the present invention is useful as an article having an antireflection function for the purpose of reducing external light reflection and improving light transmittance, for example, a cover glass of a solar cell, a display (LCD, PDP, Organic EL, CRT, SED, etc.), window plates for vehicles (cars, trains, airplanes, etc.), window glass for houses, and cover glass for touch panels.

The contents of the specification, claims, drawings and summary of Japanese Patent Application No. 2011-219241 filed on October 3, 2011 are hereby incorporated herein by reference as the disclosure of the present invention.

1: article having low reflective film
2: substrate
3: Low reflection film
4:
5: functional layer
10: Reverse roll coater
12: conveyor belt
14: Coating roll
16: Doctor roll
18: Backup Roll
20: paint composition
22: First Doctor Blade
24: 2nd doctor blade

Claims (9)

A method of producing an article having a low reflection film on a substrate,
The method includes a step of forming a low reflection film by applying a coating composition on a substrate conveyed in a predetermined direction by a coating roll of a reverse roll coater,
Wherein the coating composition comprises a dispersion medium (a), fine particles (b) dispersed in the dispersion medium (a), and a binder (c) dissolved or dispersed in the dispersion medium (a) and having a viscosity of 1.0 to 10.0 m Pa · s,
Wherein the rotating speed of the coating roll at the time of applying the coating composition onto the substrate in the step is made slower than the conveying speed of the substrate. The method according to claim 1,
Wherein the coating composition further comprises a terpene derivative (d) dissolved or dispersed in the dispersion medium (a). 3. The method of claim 2,
Wherein the amount of the terpene derivative (d) is 0.01 to 2 parts by mass based on 1 part by mass of the solid content of the coating composition. 4. The method according to any one of claims 1 to 3,
Wherein the solid content concentration of the coating composition is 1 to 9% by mass. 5. The method according to any one of claims 1 to 4,
Wherein the mass ratio of the fine particles (b) and the binder (c) is 10/90 to 95/5. 6. The method according to any one of claims 1 to 5,
Wherein the substrate has a conveying speed of 3 to 20 m / min. 7. The method according to any one of claims 1 to 6,
Wherein the rotation speed of the coating roll is 0.28 times or more and 0.98 times or less of the conveying speed of the base material. 8. The method according to any one of claims 1 to 7,
Wherein the surface hardness (JIS-A standard) of the coating roll is 10 to 70. The low- 9. The method according to any one of claims 1 to 8,
Wherein the base material is a template glass having a rough shape on at least one surface thereof.
KR1020147008766A 2011-10-03 2012-10-03 Method of manufacturing object with low reflection film KR20140088862A (en)

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