WO2016079933A1 - 積層塗膜及び塗装物 - Google Patents
積層塗膜及び塗装物 Download PDFInfo
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- WO2016079933A1 WO2016079933A1 PCT/JP2015/005448 JP2015005448W WO2016079933A1 WO 2016079933 A1 WO2016079933 A1 WO 2016079933A1 JP 2015005448 W JP2015005448 W JP 2015005448W WO 2016079933 A1 WO2016079933 A1 WO 2016079933A1
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- coating film
- layer coating
- refractive index
- laminated
- colorant
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- 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
- B05D5/065—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 having colour interferences or colour shifts or opalescent looking, flip-flop, two tones
- B05D5/066—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 having colour interferences or colour shifts or opalescent looking, flip-flop, two tones achieved by multilayers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
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- 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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/04—Electrophoretic coating characterised by the process with organic material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
Definitions
- the present invention relates to a laminated coating film and a coated product.
- an undercoating film is formed by an electrodeposition coating for rust prevention, an intermediate coating film having a base concealing property is formed thereon, and an overcoating film (base coating film is formed thereon.
- a coating film structure in which a clear coating film) is stacked is used.
- a base coating film having a base concealing property is formed on a cationic electrodeposition coating film, and a clear coating film is formed thereon.
- Patent Document 1 discloses that the clear coating film has a refractive index of 1.522, and the difference in refractive index between the base coating film and the clear coating film is 0.015 or more. Is changed depending on the viewing angle. Further, Patent Document 1 describes that an acrylic resin using 50% by mass or more of t-butyl methacrylate exhibits a low refractive index, and an acrylic resin using 40% by mass or more of styrene exhibits a high refractive index. Has been.
- Patent Document 2 describes that when ZnO 2 nanoparticles are dispersed in a resin, the refractive index of the resin can be increased, and that such a resin is used as a coating composition.
- Paint has a strong aspect of imparting design properties to the object to be coated, but in recent years, personal preferences have diversified. However, in terms of color preference, there are relatively many people who prefer bright colors. However, a technique for accurately controlling vivid color development cannot be derived from the above patent document.
- This invention is made
- the place made into the objective is to provide the laminated coating film and painted thing which a vivid color expresses.
- the laminated coating film of the present invention comprises a lower layer coating film containing a first colorant and a glittering material, and an upper layer coating film laminated on the lower layer coating film and containing a second coloring material,
- the color of the upper coating film is similar to the color of the lower coating film, and the first coloring of the lower coating film is higher than the refractive index of the coating film forming element excluding the second coloring material of the upper coating film. It has a configuration in which the refractive index of the coating film forming element excluding the material is larger.
- the “colorant” refers to a component that imparts color to the coating film, such as a pigment or a dye.
- the coating film forming element excluding the second colorant of the upper coating film contains a resin and nanoparticles having a refractive index lower than that of the resin. Thereby, the refractive index of an upper layer coating film can be easily adjusted small.
- the coating film forming element excluding the first colorant of the lower layer coating film includes a resin and nanoparticles having a higher refractive index than that of the resin.
- a protective coating film is provided on the upper coating film.
- an upper layer coating film can be protected reliably.
- the second colorant contains the same colorant as the first colorant.
- the coated article of the present invention has any of the above-mentioned laminated coating films on the article to be coated.
- the laminated coating film of the present invention since the colored light coming out through the two paths outside the laminated coating film is a similar color, a vivid color appears in the laminated coating film.
- the laminated coating film which concerns on Embodiment 1 has the two-layer structure of the upper layer coating film 20 and the lower layer coating film 30 in an order from the top.
- the upper layer coating film 20 is colored and transparent, for example, a synthetic resin containing a second colorant.
- the lower layer coating film 30 is colored and transparent and contains a bright material 32 that reflects light.
- a synthetic resin contains a first coloring material and a bright material 32.
- the second colorant contained in the upper layer coating film 20 contains a pigment
- the first colorant contained in the lower layer coating film 30 also contains a pigment.
- the colors of the upper layer coating film 20 and the lower layer coating film 30 are similar colors. In order to achieve the same color in this way, for example, at least one pigment included in the upper layer coating film 20 and at least one pigment included in the lower layer coating film 30 may be the same, but different pigments are included. However, it is possible to use similar colors.
- the color of the upper layer coating film 20 and the color of the lower layer coating film 30 are made similar to each other.
- the similar colors can be said to be colors belonging to the same hue in, for example, the Japan Color Research color scheme.
- acrylic resin used for automobile body painting has a refractive index of 1.5.
- the refractive index of the coating film component of the upper layer coating film 20 is 1.3 as shown in FIG. 1, and is smaller than an acrylic resin.
- the refractive index of the coating film component excluding the first colorant of the lower layer coating film 30 and the glittering material 32 may be larger than the refractive index of the coating film component of the upper layer coating film 20, and is 1.8 in this embodiment. is there.
- the refractive index of the coating film forming element of the upper layer coating film 20 is preferably 1.2 or more and less than 1.5, and more preferably 1.2 or more and 1.4 or less.
- the refractive index of the coating film forming element of the lower layer coating film 30 is preferably larger than 1.5, more preferably 1.6 or more.
- the coating component of the lower coating film 30 is a synthetic resin such as an acrylic resin, a urethane resin, or an epoxy resin, and the refractive index is controlled (increased).
- the refractive index is controlled (increased).
- inorganic nanoparticles In order to add inorganic nanoparticles.
- another kind of inorganic nanoparticles are added to the synthetic resin such as acrylic resin, urethane resin, epoxy resin, etc. .
- examples of inorganic nanoparticles that increase the refractive index include ZrO 2 , TiO 2 , and ZnO.
- As the inorganic nanoparticles to decrease the refractive index can be mentioned SiO 2, CaF 2, MgF and the like.
- the magnitude of the refractive index of the coating film constituent element can be controlled by the kind and amount of the nanoparticles to be added.
- the particle diameter of the nanoparticles is not particularly limited as long as it can be said to be at the nano level, but is usually 20 nm or less. If it exceeds 20 nm, the transparency may be lowered, for example, when dispersed in a resin. More preferably, they are 1 nm or more and 19 nm or less, More preferably, they are 2 nm or more and 18 nm or less.
- a general method can be used. For example, the particles are enlarged and observed with a transmission electron microscope (TEM), a field emission transmission electron microscope (FE-TEM), a field emission scanning electron microscope (FE-SEM), and 100 particles are selected at random. The length in the major axis direction is measured, and the average value is taken as the particle diameter.
- the particle shape may be spherical, elliptical, cubic, rectangular, pyramidal, needle, columnar, rod, cylindrical, flake shaped, plate shaped, flake shaped, etc. Shall measure the length in the major axis direction.
- the content ratio of the colorant to the synthetic resin is preferably larger in the lower coating film 30 than in the upper coating film 20. If the content of the upper layer coating film 20 is greater than or equal to the lower layer coating film 30, the light absorption rate of the upper layer coating film 20 increases, so that the laminated coating film itself becomes a dark color and loses vividness. If the total amount of the coloring material is reduced in order to avoid it, there is a possibility that a desired dark color cannot be obtained.
- a base layer may be provided between the object to be coated and the lower coating film 30.
- the undercoat layer is, for example, an undercoat film made of an epoxy-based cationic electrodeposition paint formed on the surface of a steel object (eg, an automobile body plate), and light resistance and chipping resistance formed thereon.
- a coating film composed of two layers of an intermediate coating film having a base concealing property for enhancing color developability may be used.
- the reflected light 70 is white light.
- the remainder of the incident light 60 enters the upper layer coating film 20, and light having a wavelength other than a part of the wavelength region is absorbed by the coloring material to become light of a specific color (for example, red).
- a part of the light of a specific color is reflected at the interface between the upper layer coating film 20 and the lower layer coating film 30 and goes out of the laminated coating film as reflected light 82.
- the emitted light 84 is darker than the reflected light 82.
- the laminated coating film of the present embodiment When the laminated coating film of the present embodiment is observed from the outside, two lights of specific colors of the reflected light 82 and the emitted light 84 appear to overlap each other, so that it looks bright.
- the refractive index of the lower coating film 30 is larger than the refractive index of the upper coating film 20, the amount of light reflected at the interface between the upper coating film 20 and the lower coating film 30 increases.
- size of the refractive index of each coating film is adjusted by mixing inorganic nanoparticles, it can be easily set as a desired refractive index.
- the laminated coating film according to the example has the structure shown in FIG. 1, and the coating film of each layer was produced as shown in Table 1.
- acrylic resin is an acrylic resin manufactured by Nippon Paint Co., Ltd. (acid value: 20 mgKOH / g, hydroxyl value: 75 mgKOH / g, number average molecular weight: 5000, solid content: 60 mass%).
- a ZrO 2 nanoparticle dispersion (ZrO 2 solid content 20 mass%) manufactured by Sumitomo Osaka Cement Co., Ltd. was employed as the nanoparticles contained in the lower layer coating film 30.
- SiO 2 nanoparticles Naano Tek Slurry (SiO 2 solid content 20% by mass) manufactured by C-I Kasei Co., Ltd.) were employed.
- pigments contained in the lower coating film 30 and the upper coating film 20 include quinacrine magenta (Chromofine manufactured by Dainichi Seika Kogyo Co., Ltd.), perylene (Paliogen Maroon L3920 manufactured by BASF), iron oxide (Toda Kogyo Co., Ltd.) IPJ-218H manufactured by Co., Ltd.) and carbon black (carbon black # 2650 manufactured by Mitsubishi Chemical Corporation) were employed.
- Aluminum flakes (76 series manufactured by Toyo Aluminum Co., Ltd.) were used as the glitter material contained in the lower layer coating film 30.
- the refractive index of the upper layer coating film 20 was 1.3 and the lower layer coating film 30 was 1.8.
- the laminated coating film according to the comparative example has the structure shown in FIG. 2, and the coating film structure of each layer was produced as shown in Table 2.
- the laminated coating film which concerns on a comparative example is the point which the colorant is not contained in the upper layer coating film 21, is colorless and transparent, and the refractive index of the lower layer coating film 31 is 1. 5 is different from the embodiment.
- the red light from the pigment is only the outgoing light 85 from the lower layer coating film 31.
- the reflection on the surface of the upper layer coating film 21 in the comparative example since the refractive index of the upper layer coating film 21 is 1.5, the vertical reflectance is 4.0%, and the reflected light 71 corresponding thereto is obtained.
- the reflection on the surface of the upper layer coating film 20 in the example has a vertical reflectance of 1.7% because the refractive index of the coating layer component of the upper layer coating film 20 is 1.3. Is about 40% of the reflected light 71 of the comparative example. Therefore, the amount of light entering the laminated coating film is larger in the embodiment, and therefore the amount of light emitted from the embodiment is larger.
- the laminated coating film according to the example looks brighter red than the laminated coating film according to the comparative example.
- a transparent protective coating film may be formed on the upper coating film.
- the protective coating film is preferably made of a resin, and preferably has the same refractive index as that of the upper coating film.
- a resin other than an acrylic resin may be used, and other colors and types of pigments may be used.
- the refractive index of each layer is not limited to the above values.
- a copper flake may be used as the glitter material.
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- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
Description
図1に示すように、実施形態1に係る積層塗膜は上から順に、上層塗膜20及び下層塗膜30の二層構造を有している。上層塗膜20は有色透明であり、例えば合成樹脂に第2の着色材を含有させてなっている。下層塗膜30は有色透明であるとともに光を反射する光輝材32を含有しており、例えば合成樹脂に第1の着色材と光輝材32とを含有させてなっている。
実施例に係る積層塗膜として、図1に示す構造を有しており、各層の塗膜の構成は表1に示す通りの積層塗膜を作製した。
上述の実施形態は本願発明の例示であって、本願発明はこれらの例に限定されず、これらの例に周知技術や慣用技術、公知技術を組み合わせたり、一部置き換えたりしてもよい。また当業者であれば容易に思いつく改変発明も本願発明に含まれる。
30 下層塗膜
32 光輝材
Claims (6)
- 第1の着色材及び光輝材を含有する下層塗膜と、該下層塗膜上に積層されており第2の着色材を含有する上層塗膜とを備えてなる積層塗膜において、
前記上層塗膜の色は、前記下層塗膜の色と同系色であり、
前記上層塗膜の第2の着色材を除く塗膜形成要素の屈折率よりも、前記下層塗膜の第1の着色材を除く塗膜形成要素の屈折率の方が大きい、積層塗膜。 - 前記上層塗膜の第2の着色材を除く塗膜形成要素は、樹脂と、該樹脂よりも低屈折率のナノ粒子とを含む、請求項1に記載されている積層塗膜。
- 前記下層塗膜の第1の着色材を除く塗膜形成要素は、樹脂と、該樹脂よりも高屈折率のナノ粒子とを含む、請求項1又は2に記載されている積層塗膜。
- 前記上層塗膜の上に保護塗膜が設けられている、請求項1から3のいずれか一つに記載されている積層塗膜。
- 前記第2の着色材には、前記第1の着色材と同じ着色材が含まれている、請求項1から4のいずれか一つに記載されている積層塗膜。
- 被塗物に請求項1乃至5のいずれか一つに記載の積層塗膜を備える、塗装物。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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DE112015003694.6T DE112015003694T5 (de) | 2014-11-21 | 2015-10-29 | Geschichteter Beschichtungsfilm und beschichtetes Erzeugnis |
US15/324,109 US10370772B2 (en) | 2014-11-21 | 2015-10-29 | Layered coating film, and coated article |
CN201580037864.3A CN107073879A (zh) | 2014-11-21 | 2015-10-29 | 叠层涂膜和涂装物 |
RU2017104792A RU2664067C1 (ru) | 2014-11-21 | 2015-10-29 | Многослойная покровная пленка и покрытое изделие |
MX2017002283A MX2017002283A (es) | 2014-11-21 | 2015-10-29 | Pelicula de revestimiento estratificada y articulo revestido. |
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JP2014236687A JP2016097594A (ja) | 2014-11-21 | 2014-11-21 | 積層塗膜及び塗装物 |
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JP (1) | JP2016097594A (ja) |
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DE (1) | DE112015003694T5 (ja) |
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- 2015-10-29 US US15/324,109 patent/US10370772B2/en not_active Expired - Fee Related
- 2015-10-29 WO PCT/JP2015/005448 patent/WO2016079933A1/ja active Application Filing
- 2015-10-29 CN CN201580037864.3A patent/CN107073879A/zh active Pending
- 2015-10-29 DE DE112015003694.6T patent/DE112015003694T5/de not_active Ceased
- 2015-10-29 MX MX2017002283A patent/MX2017002283A/es unknown
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Also Published As
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JP2016097594A (ja) | 2016-05-30 |
DE112015003694T5 (de) | 2017-05-04 |
US10370772B2 (en) | 2019-08-06 |
US20170211201A1 (en) | 2017-07-27 |
CN107073879A (zh) | 2017-08-18 |
RU2664067C1 (ru) | 2018-08-14 |
MX2017002283A (es) | 2017-05-01 |
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