CN102666097A - Decoration film for insert molding, insert molded article, method for producing decoration film for insert molding - Google Patents
Decoration film for insert molding, insert molded article, method for producing decoration film for insert molding Download PDFInfo
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- CN102666097A CN102666097A CN2010800589317A CN201080058931A CN102666097A CN 102666097 A CN102666097 A CN 102666097A CN 2010800589317 A CN2010800589317 A CN 2010800589317A CN 201080058931 A CN201080058931 A CN 201080058931A CN 102666097 A CN102666097 A CN 102666097A
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- decorative layer
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Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000005034 decoration Methods 0.000 title abstract description 10
- 238000000465 moulding Methods 0.000 title abstract description 6
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 238000003780 insertion Methods 0.000 claims description 38
- 230000037431 insertion Effects 0.000 claims description 38
- 238000007493 shaping process Methods 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 238000013459 approach Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000007906 compression Methods 0.000 claims description 12
- 230000006835 compression Effects 0.000 claims description 11
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 238000010030 laminating Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 17
- 239000010955 niobium Substances 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 208000037656 Respiratory Sounds Diseases 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000008676 import Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 235000004418 Durio kutejensis Nutrition 0.000 description 1
- 240000002669 Durio kutejensis Species 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3464—Sputtering using more than one target
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/10—Glass or silica
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14688—Coating articles provided with a decoration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
- B29C45/14811—Multilayered articles
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Provided are an insert molded article having no crack or peeling generated on its exterior, and a decoration film for insert molding for such an article, as well as a method for producing the film so that the color and the brilliance of the film can be widely varied depending on the viewing angle. The decoration film for insert molding comprises a transparent resin film provided on one side thereof with a decoration layer, and is formed in a manner so that the decoration layer is located on the main body side of the resin molded article to be obtained by the insert molding, wherein the decoration layer is configured by laminating dielectric layers to have a thickness of 50 nm to 800 nm, and the decoration layer has a compressive stress of 250 MPa to 350 MPa.
Description
Technical field
The insertion that the present invention relates to be used for the external packing of coated with resin formed products is shaped with decorating film, inserts formed products and insert the manufacturing approach of shaping with decorating film.
Background technology
For the decoration of the outer surface of the resin forming product of mobile phone etc., carry out the setting of the film that color and taste etc. changes according to viewing angle.Have, the method (referenced patent document 1 and patent documentation 2) of in film, adding pearl pigment is arranged.
But in the method for the interpolation pearl pigment of institute's motion, the addition of pearl pigment is restricted in patent documentation 1 and patent documentation 2, and therefore, the scope of the color of reflectivity etc. is restricted, and therefore produces the decoration look such problem that can't become expectation.
In order to address this problem, in patent documentation 3 and patent documentation 4, to have through vapor deposition and will carry out the range upon range of method of adjusting optical characteristics by the film that dielectric material constitutes.
But the film reality that the method for institute's motion obtains in will be through patent documentation 3 or patent documentation 4 has film and peels off such problem inserting when using in being shaped.
The prior art document
Patent documentation
Patent documentation 1: the spy opens communique No. 3862814
Patent documentation 2: the spy opens the 2007-16056 communique
Patent documentation 3: the spy opens the 2002-350610 communique
Patent documentation 4: the spy opens the 2009-108220 communique
Summary of the invention
The problem that invention will solve
Therefore, the object of the present invention is to provide in external packing insertion formed products that does not crack, peels off and the insertion that is used for it to be shaped and use decorating film, provide simultaneously for this film can make color and taste, brightness according to viewing angle the variable manufacturing approach in wide region ground.
Be used to solve the means of problem
In order to solve above-mentioned problem, the inventor etc. concentrate on studies, and the result finds following solution.
Promptly; The insertion of the application's invention is shaped and uses decorating film; First aspect like the application is said, for the single face side at transparent resin film possesses decorative layer, is shaped with the insertion that said decorative layer side is formed in the mode of the resin forming product main body side that obtains through insert being shaped and uses decorating film, it is characterized in that; Above-mentioned decorative layer is so that all thickness reaches the mode layered dielectric layer of 50nm～800nm and constitutes, and the compression stress that makes above-mentioned decorative layer is 250MPa～350MPa.
The said invention of second aspect of the present invention is characterized in that, in the described insertion of first aspect of the present invention was shaped with decorating film, above-mentioned transparent resin film was made up of the resin of the polyethylene-based or polyolefin of thickness 50 μ m～200 μ m.
The described invention of the third aspect of the invention is characterized in that, of the present invention first or during the described insertion of second aspect is shaped with decorating film, is equipped with the hard conating of thickness 0.5 μ m～10 μ m at the mask opposite with above-mentioned decorative layer of above-mentioned transparent resin film.
The described invention of fourth aspect of the present invention; It is characterized in that; During each described insertion was shaped with decorating film in first～third aspect of the present invention, above-mentioned decorative layer was to carry out alternately laminated the silicon dioxide layer of thickness 5nm～200nm and niobium pentoxide layer layer.
In addition, insertion formed products of the present invention, of the 5th aspect of the present invention, it is characterized in that possessing in first～fourth aspect of the present invention each described insertion and be shaped and use decorating film.
In addition; Insertion of the present invention is shaped with the manufacturing approach of decorating film; Of the 6th aspect of the present invention; For the single face side at transparent resin film possess decorative layer, so that above-mentioned decorative layer side is shaped with the manufacturing approach of decorating film in the insertion that the mode of the main body side of the resin forming product that obtains through insert being shaped is formed; It is characterized in that, make into film pressure and be 0.5Pa～1.0Pa and come metallic atom is carried out sputter and after film forming is the metal atomic layer of thickness 5nm～200nm on the above-mentioned transparent resin film, carry out oxidation and form dielectric layer; The film forming that repeats above-mentioned dielectric layer forms above-mentioned decorative layer with range upon range of above-mentioned dielectric layer, and the compression stress that makes above-mentioned decorative layer is 250MPa～350MPa.
The described invention in the 7th aspect of the present invention; It is characterized in that; In the manufacturing approach of insertion shaping aspect the of the present invention the 6th with decorating film; Above-mentioned transparent resin film is made up of the resin of the polyethylene-based or polyolefin of thickness 50 μ m～200 μ m, is provided with the hard conating of thickness 0.5 μ m～10 μ m at the face opposite with above-mentioned decorative layer, and the thickness of above-mentioned decorative layer is 50nm～800nm.
The described invention of eight aspect of the present invention; It is characterized in that; Described insertion is shaped in the manufacturing approach with decorating film aspect the of the present invention the 6th or the 7th; To carry out alternately laminated and constitute above-mentioned decorative layer as the silicon dioxide layer of above-mentioned dielectric layer thickness 5nm～200nm and niobium pentoxide layer, the rate of film build that the temperature when making each dielectric layer sputter is below 80 ℃, make silicon dioxide layer be for
and to make the rate of film build of niobium pentoxide layer be 1.0～
The effect of invention
Be shaped based on insertion of the present invention and use decorating film, can prevent with the mobile phone be occur peeling off on the outer surface of resin forming product of representative, crackle.In addition, also can prevent to insert peeling off when being shaped, crackle.And then manufacturing method according to the invention can obtain can color and taste, brightness range being formed desired insertion shaping widely and use decorating film.
Description of drawings
Fig. 1 is the device profile that is used to explain manufacturing approach of the present invention.
Fig. 2 is that the insertion of embodiment 1 is shaped with the profile of film.
Fig. 3 (a) is the chart of dependence of angle of the film of expression embodiment 1, (b) is the chromatic diagram with embodiment.
Fig. 4 (a) is the chart of dependence of angle of the film of expression embodiment 2, (b) is the chromatic diagram with embodiment.
Fig. 5 is that the one-tenth film pressure-compression stress of the film of expression embodiment 1 reaches the chart that has carried out the evaluation of injection moulding with film.
The specific embodiment
Insertion of the present invention is shaped and use decorating film, in the insertion of known (for example disclosed in patent documentation 1 grade) is shaped, uses formation formed products when ester moulding and by integrated.
This insert to be shaped and to use decorating film, possesses the single face side different multilayer dielectric layer of (main body side opposite with the face side of formed products) laminated refractive index at transparent resin film and the decorative layer that constitutes.Each dielectric layer through the sputter of metallic atom and by sputter homoatomic oxidation form, all thickness of decorative layer becomes 50nm～800nm and compression stress becomes 250MPa～350MPa.Through all thickness of this decorative layer and the combination of compression stress, can prevent inserting when being shaped, crackle during the use of thereafter formed products in the decorative layer, peeling off.This is owing to finding: the not enough generation of closing force peeled off when thickness is lower than 50nm or compression stress and is lower than 250MPa, cracks because the stress of thickness when surpassing 800nm or compression stress above 350MPa, shaping becomes excessive.
Above-mentioned transparent resin film; For transparent and even translucent, as long as when inserting shaping, be difficult for because of the hot not restriction especially of just stretching, for example; Can by the polyester of polyvinyl chloride, amorphism or low-crystalline system or polypropylene-based, polybutylene terephthalate (PBT) system, stretch or the low ethylene-vinyl alcohol system that stretches etc. resin constitute; Wherein, consider, be preferably formed the resin of ethene system or polyolefin from the viewpoint of optical characteristics.In addition, for the also not special restriction of its thickness, to be preferably formed be 20 μ m～500 μ m about.This is because thickness operation property difficulty such as operation task when being lower than 20 μ m, and rigidity becomes too high, when being shaped, can not follow machining shape, therefore cracks etc. when surpassing 500 μ m.And then, in order to improve adaptation, even in above-mentioned scope, be preferably the scope of 50 μ m～200 μ m especially as the decorative layer that inserts formed products.
Need to prove, the hard conating of thickness 0.5 μ m～10 μ m preferably is set on the face opposite with decorative layer of transparent resin film.This is because can protect the surface of inserting formed products.In addition, because the protection on the thickness of hard conating surface of transparent resin film when being lower than 0.5 μ m becomes insufficient, the curing that can't fully obtain when surpassing 10 μ m being realized by heating or radioactive ray, becoming causes adhesion easily.In addition, the material of hard conating for example can use the material of silane-based, radiation-curable etc., but the material of preferred radiation-curable, wherein preferred ultra-violet solidified material.
Dielectric layer, can from as the metal oxide of the angle of reflection wanting to obtain expecting, colourity etc. select.For example under the situation of alternately laminated low-index layer and high refractive index layer, can use silicon compound such as the SiO of refractive index below 1.5
2Deng as low-index layer, use niobium oxide such as the Nb of refractive index more than 2.0
2O
5, titanium compound such as TiO
2Deng as high refractive index layer.In these metal oxides, preferably select SiO
2And Nb
2O
5This is because it is the material that the crystallization conversion temperature is high, optical Response is low.
For each dielectric layer thickness, as long as all thickness of dielectric layer becomes the just not special restriction of scope of the 50nm～800nm of above-mentioned explanation, but each dielectric layer thickness is preferably 5nm～200nm.Because the optics of each dielectric layer control difficulty when thickness is lower than 5nm, the commercial production cost uprises when surpassing 200nm.
Above-mentioned insertion is shaped and uses decorating film; When inserting shaping, be configured in the shaping dies, the shaping resin of in mould, injecting acrylic resin, acrylonitrile butadiene styrene resin, polystyrene resin, ethene oxidation vinyl acetate (エ チ レ Application acidifying PVC ニ Le) resin, polycarbonate resin, nylon resin etc. forms formed products and becomes one.Need to prove that inserting is shaped can be processed into three-dimensional in advance with decorating film self, also can in shaping dies, deform through injection pressure.
Then, describe with reference to Fig. 1 for the manufacturing approach of insertion shaping of the present invention with decorating film.
As far as in Fig. 1, showing the film formation device of section; Central configuration in cylindric vacuum chamber 1 is used for the cylindric rotary body 3 of supporting substrate 2, disposes the 1st sputter area 4, ion gun the 5, the 2nd sputter area 6 and the 3rd sputter area 7 along the interior Zhou Yici of chamber 1.In vacuum chamber 1, though diagram not is connected with vavuum pump, can be with carrying out exhaust in the chamber 1.
The the 1st～the 3rd sputter area 4,6,7 forms through sputtered film material on base material 2, in each zone 4,6,7, near base material 2, is provided with the gas introduction port (not shown) that is used to import sputter gas.In addition, in each zone 4,6,7, be provided with the negative electrode 11～13 that target 8～10 has been installed with mode respectively with cylindric rotary body 3 subtends.These negative electrodes 11～13 in order to drop into electric power to target 8～10, though do not illustrate, are connected in direct current or AC power.
In addition,, be respectively equipped with gate (シ ャ ッ タ ー) 14～16, optionally open gate 14～16 during film forming in each zone 4,6,7 in each zone base material 2 side of 4,6,7.
According to above-mentioned formation; Through the 1st sputter area 4 thickness of the 1st metal about with monoatomic layer carried out film forming on the base material 2, rotational circle tubular rotary body 3 carries out oxidation through ion gun 5 and forms the 1st metal oxide film (the 1st dielectric layer); Be further rotated cylindric rotary body 3; Through the 2nd sputter area 6 thickness of the 2nd metal about with monoatomic layer carried out film forming, rotational circle tubular rotary body 3 carries out oxidation through ion gun 5 and forms the 2nd metal oxide film (the 2nd dielectric layer); Alternately repeat above operation, the decorating film of the dielectric layer that on base material 2, forms multilayer range upon range of.Need making of explanation, under the situation of 3 kinds of metallic atoms of sputter, can likewise utilize the sputter of the 3 one-tenth diaphragm areas 7 with the 1 one-tenth diaphragm area 4, the 2 one-tenth diaphragm areas 6 and utilize the oxidation of ion gun 5.Need to prove, be meant about so-called monoatomic layer to be the scope of thickness 5nm～200nm on the film thickness.
According to said method, can give color and taste, the brightness of expectation to decorating film.
In addition, in said method, during the sputter of metal material and the one-tenth film pressure during oxidation be 0.5Pa～1.0Pa.Because the compression stress of decorative layer surpasses 350MPa, when inserting shaping, cracks, peels off when becoming film pressure to be lower than 0.5Pa; The compression stress of decorative layer becomes less than 250MPa when becoming film pressure to surpass 1.0Pa, and closing force is not enough, and generation is peeled off.
In said method, using under silicon atom and the situation of niobium atom as metallic atom, the temperature when preferably making these sputters be below 80 ℃ (need to prove, be limited to down after oxidation in the temperature of generation plasma.)。Because film forming is the film of the thickness about uniformly monatomic at high speed.Need to prove that the rate of film build under this situation can at random be adjusted, for example, if Nb
2O
5, then do
At SiO
2Situation under, then do
Deng.
Embodiment
Then, the insertion shaping for embodiments of the invention describes with decorating film.
Need to prove in following examples, mainly do not have declaration condition especially, then under following condition, carry out film forming.
(1) base material
Use is provided with the base material of the hard conating of thickness 1 μ m on the single face of the transparent resin film of the polyethylene system of thickness 100 μ m, width 500mm, length 1000mm.
(2) membrance casting condition of dielectric layer
In the present embodiment, as dielectric layer, film forming is SiO
2And Nb
2O
5
A) SiO
2Membrance casting condition
Target: Si
Power supply: DC power supply
Oxidation source: ion gun
Film-forming temperature: room temperature
Negative electrode drops into electric power: 6w/cm
2
Ar flow: 500sccm
O
2Flow: 100sccm
b)Nb
2O
5
Target: Si
Power supply: DC power supply
Oxidation source: ion gun
Film-forming temperature: room temperature
Negative electrode drops into electric power: 5w/cm
2
Ar flow: 500sccm
O
2Flow: 300sccm
(embodiment 1)
Using the device of explaining in the above-mentioned embodiment, will be 8.0 * 10 with decompression in the vacuum chamber 1 of device
-4Pa, general formula are importing Ar to first sputter area 4; At this state, drop into electric power to negative electrode 11, as shown in Figure 2; Repetition is the operation of Nb film through spatter film forming and makes cylindric rotary body 3 rotations pass through the operation of ion gun 5 with the oxidation of Nb film at the single face of base material 2, forms the Nb of thickness 87.0nm
2O
5Film (dielectric layer) 17.Then, with being adjusted into 8.0 * 10 in the vacuum chamber 1
-4Pa, general formula import Ar to sputter area 6, drop into electric power to negative electrode 12, are the Si film of thickness 100.0nm through spatter film forming.Then, cylindric rotary body 3 is selected, with the oxidation of Nb film, formed SiO through ion gun 5
2Film (dielectric layer) 18.And, above that with Nb
2O
5The film forming of film 17 likewise film forming is the Nb of thickness 87.0nm
2O
5Film (dielectric layer) 19.
Then, at Nb
2O
5Being coated with carbamate through serigraphy with thickness 3 μ m on the film 19 is the printing ink (セ イ コ ー ア De バ Application ス corporate system WO7 (RX002)) of 2 solution curing types, forms the insertion shaping as decorating film 20 and uses film.
(embodiment 2)
From the base material side successively with the likewise alternately laminated 7 layers of Nb of embodiment 1
2O
5Film and SiO
2Film is at last through being decorating film with embodiment 1 identical printing ink film forming.
Each thickness forms Nb successively from the base material side
2O
5Film (17.00nm), SiO
2Film (164.00nm), Nb
2O
5Film (40.00nm), SiO
2Film (76.50nm), Nb
2O
5Film (100.00nm), SiO
2Film (53.50nm), Nb
2O
5Film (49.00nm).
Be shaped for the insertion that obtains in embodiment 1 and 2 and use film, will be shown in Fig. 3 and Fig. 4 respectively with respect to the reflection characteristic and the chromatic diagram of the incidence angle of the light that incides film.Can know by these:, can form decorating film arbitrarily through adjusting range upon range of number and thickness for color and taste, brightness according to viewing angle.
Then, the one-tenth film pressure of each dielectric film of embodiment 1 is changed, shown in the transverse axis of Fig. 5, the compression stress of making decorating film is that the insertion of 11 of the totals of 0.4Pa～2.0Pa scope is shaped and uses film.
Use device with injection moulding, mold temperature is set at 50 degree and drying condition 80 degree, the insertion that obtains is shaped makes injection-molded article with PMMA resin (the レ イ ヨ of the Mitsubishi Application corporate system ACRYPETVRL40-001 of society) with film.
Its result, as shown in Figure 5, be during the insertion of the scope of 0.5Pa～1.0Pa is shaped with film, does not have crackle, peel off becoming film pressure,, confirm to crackle, peel off beyond the scope at this.
The explanation of symbol
1 cylindric vacuum chamber
2 base materials
3 cylindric rotary bodies
4,6,7 the 1st～the 3rd sputter area
5 ion guns
8～10 targets
11～13 negative electrodes
14～16 gates
17～19 dielectric layers
20 ink laies
21 hard conatings
Claims (8)
1. an insertion is shaped and uses decorating film; It is for the single face side at transparent resin film possesses decorative layer, decorating film is used in the insertion shaping that is formed with the main body side ground that said decorative layer side is positioned at the resin forming product that obtains through insert being shaped; It is characterized in that; Said decorative layer makes the compression stress of said decorative layer be made as 250MPa～350MPa so that all thickness is 50nm～800nm laminated dielectric layer constitutes.
2. insertion according to claim 1 is shaped and uses decorating film, it is characterized in that said transparent resin film is made up of the resin of the polyethylene-based or polyolefin of thickness 50 μ m～200 μ m.
3. insertion according to claim 1 and 2 is shaped and uses decorating film, it is characterized in that, is equipped with the hard conating of thickness 0.5 μ m～10 μ m at the mask opposite with said decorative layer of said transparent resin film.
4. described insertion is shaped and use decorating film according to each of claim 1～3, it is characterized in that, said decorative layer is to have carried out alternately laminated the silicon dioxide layer of thickness 5nm～200nm and niobium pentoxide layer layer.
5. one kind is inserted formed products, it is characterized in that, each the described insertion that possesses claim 1～4 is shaped and uses decorating film.
6. one kind is inserted the manufacturing approach that is shaped with decorating film; It is for the single face side at transparent resin film possesses decorative layer, the insertion shaping that is formed with the main body side ground that said decorative layer side is positioned at the resin forming product that obtains through insert being shaped is with the manufacturing approach of decorating film; It is characterized in that; Making into film pressure and be 0.5Pa～1.0Pa comes metallic atom is carried out sputter and after film forming is the metal atomic layer of thickness 5nm～200nm on the said transparent resin film; Carry out oxidation and form dielectric layer, the film forming that repeats said dielectric layer forms said decorative layer with range upon range of said dielectric layer, and the compression stress that makes said decorative layer is 250MPa～350MPa.
7. insertion according to claim 6 is shaped with the manufacturing approach of decorating film; It is characterized in that; Said transparent resin film is made up of the resin of the polyethylene-based or polyolefin of thickness 50 μ m～200 μ m; On the face opposite with said decorative layer, be provided with the hard conating of thickness 0.5 μ m～10 μ m, the thickness of said decorative layer is 50nm～800nm.
8. be shaped with the manufacturing approach of decorating film according to claim 6 or 7 described insertions; It is characterized in that; Will be alternately laminated and constitute said decorative layer as the silicon dioxide layer of said dielectric layer thickness 5nm～200nm and niobium pentoxide layer, the rate of film build that the temperature when making each dielectric layer sputter is below 80 ℃, make silicon dioxide layer for
and make the niobium pentoxide layer rate of film build is
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009-295924 | 2009-12-25 | ||
| JP2009295924 | 2009-12-25 | ||
| PCT/JP2010/007475 WO2011077738A1 (en) | 2009-12-25 | 2010-12-24 | Decoration film for insert molding, insert molded article, method for producing decoration film for insert molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102666097A true CN102666097A (en) | 2012-09-12 |
| CN102666097B CN102666097B (en) | 2015-03-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080058931.7A Active CN102666097B (en) | 2009-12-25 | 2010-12-24 | Decorative film for insert molding, insert molded product, and method for producing decorative film for insert molding |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5497790B2 (en) |
| CN (1) | CN102666097B (en) |
| TW (1) | TWI454361B (en) |
| WO (1) | WO2011077738A1 (en) |
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|---|---|---|---|---|
| WO2017090498A1 (en) * | 2015-11-24 | 2017-06-01 | コニカミノルタ株式会社 | Method for producing gas barrier film |
| CN111850491A (en) * | 2019-04-30 | 2020-10-30 | 中光科技（福建）有限公司 | Colorful coating film of mobile phone rear cover |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0995571A1 (en) * | 1998-02-27 | 2000-04-26 | Nissha Printing Co., Ltd. | Sheet for in-mold decorating and in-mold decorated article |
| CN101236263A (en) * | 2007-02-01 | 2008-08-06 | 甘国工 | High light transmittance ratio glass display protection panel and LCD device using same |
| WO2009008278A1 (en) * | 2007-07-11 | 2009-01-15 | Kimoto Co., Ltd. | Resin molded article using film for insert molding |
| JP2009075324A (en) * | 2007-09-20 | 2009-04-09 | Toppan Printing Co Ltd | Optical thin film laminate |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3663304B2 (en) * | 1998-09-16 | 2005-06-22 | 日本写真印刷株式会社 | Manufacturing method of sheet with simultaneous molding and molded product with simultaneous molding |
| JP2005298833A (en) * | 2002-10-22 | 2005-10-27 | Asahi Glass Co Ltd | Multilayer substrate and method for manufacturing the same |
| TWI295233B (en) * | 2003-07-18 | 2008-04-01 | Mitsui Chemicals Inc | Laminate and uses thereof |
| JP4969919B2 (en) * | 2006-05-30 | 2012-07-04 | 株式会社アルバック | Film forming apparatus and film forming method |
| JP2006342055A (en) * | 2006-07-04 | 2006-12-21 | Nakajima Glass Co Inc | Method of manufacturing titanium oxide thin film applied glass plate, glass plate manufactured by the method and use for the same |
| JP2008056967A (en) * | 2006-08-30 | 2008-03-13 | Konica Minolta Holdings Inc | Gas barrier property resin base material, and organic electroluminescence device |
-
2010
- 2010-12-24 JP JP2011547316A patent/JP5497790B2/en active Active
- 2010-12-24 TW TW099145803A patent/TWI454361B/en active
- 2010-12-24 WO PCT/JP2010/007475 patent/WO2011077738A1/en not_active Ceased
- 2010-12-24 CN CN201080058931.7A patent/CN102666097B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0995571A1 (en) * | 1998-02-27 | 2000-04-26 | Nissha Printing Co., Ltd. | Sheet for in-mold decorating and in-mold decorated article |
| CN101236263A (en) * | 2007-02-01 | 2008-08-06 | 甘国工 | High light transmittance ratio glass display protection panel and LCD device using same |
| WO2009008278A1 (en) * | 2007-07-11 | 2009-01-15 | Kimoto Co., Ltd. | Resin molded article using film for insert molding |
| JP2009075324A (en) * | 2007-09-20 | 2009-04-09 | Toppan Printing Co Ltd | Optical thin film laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2011077738A1 (en) | 2013-05-02 |
| CN102666097B (en) | 2015-03-04 |
| TWI454361B (en) | 2014-10-01 |
| WO2011077738A1 (en) | 2011-06-30 |
| JP5497790B2 (en) | 2014-05-21 |
| TW201139107A (en) | 2011-11-16 |
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