WO2016080445A1 - 保護フィルム付き機能性シート - Google Patents
保護フィルム付き機能性シート Download PDFInfo
- Publication number
- WO2016080445A1 WO2016080445A1 PCT/JP2015/082420 JP2015082420W WO2016080445A1 WO 2016080445 A1 WO2016080445 A1 WO 2016080445A1 JP 2015082420 W JP2015082420 W JP 2015082420W WO 2016080445 A1 WO2016080445 A1 WO 2016080445A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- protective film
- aromatic polycarbonate
- melting point
- film
- Prior art date
Links
- 230000001681 protective effect Effects 0.000 title claims abstract description 115
- 239000010410 layer Substances 0.000 claims abstract description 140
- 238000002844 melting Methods 0.000 claims abstract description 75
- 230000008018 melting Effects 0.000 claims abstract description 75
- 125000003118 aryl group Chemical group 0.000 claims abstract description 73
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 64
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- 239000012790 adhesive layer Substances 0.000 claims abstract description 49
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- 229920000098 polyolefin Polymers 0.000 claims abstract description 29
- -1 polypropylene Polymers 0.000 claims abstract description 19
- 239000004743 Polypropylene Substances 0.000 claims abstract description 18
- 229920001155 polypropylene Polymers 0.000 claims abstract description 18
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 17
- 239000002346 layers by function Substances 0.000 claims abstract description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 11
- 238000010030 laminating Methods 0.000 claims abstract description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 11
- 229920006124 polyolefin elastomer Polymers 0.000 claims abstract description 10
- 239000011342 resin composition Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 53
- 238000005452 bending Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 25
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- 239000000047 product Substances 0.000 description 30
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- 239000000155 melt Substances 0.000 description 14
- 230000008859 change Effects 0.000 description 8
- 230000037303 wrinkles Effects 0.000 description 7
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- 238000012545 processing Methods 0.000 description 6
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
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- QIYHCQVVYSSDTI-UHFFFAOYSA-N 2-(phenyliminomethyl)phenol Chemical compound OC1=CC=CC=C1C=NC1=CC=CC=C1 QIYHCQVVYSSDTI-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 150000001336 alkenes Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
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- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001988 diarylethenes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
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- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- G—PHYSICS
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- 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
- G02B1/12—Optical coatings produced by application to, or surface treatment of, optical elements by surface treatment, e.g. by irradiation
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- G02B5/23—Photochromic filters
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
- B29K2995/0034—Polarising
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- B32B2307/402—Coloured
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
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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
- B32B2551/00—Optical elements
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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
- B32B2571/00—Protective equipment
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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
- B32B2571/00—Protective equipment
- B32B2571/02—Protective equipment defensive, e.g. armour plates or anti-ballistic clothing
Definitions
- the present invention relates to a functional sheet using an aromatic polycarbonate sheet or film as a protective layer for a functional layer such as a polarizing film layer or a photochromic layer, and is temporarily bonded to the surface to protect the surface in distribution, processing steps, etc. It relates to a functional sheet with a protective film.
- a lens for sunglasses made of aromatic polycarbonate is usually obtained by punching a functional sheet made of an aromatic polycarbonate sheet or film into a desired shape as a protective layer for a functional layer such as a polarizing film layer or a photochromic layer. It is manufactured by subjecting a partial spherical surface to heat bending, injection-molding an aromatic polycarbonate for a lens on the concave surface side, and surface treatment as appropriate.
- This protective sheet is attached with a protective film for protecting the surface from scratches, dirt and foreign matter during handling such as distribution and processing.
- a polyolefin-based protective film has been proposed as one that can withstand thermal bending in a high-temperature environment near the glass transition temperature of an aromatic polycarbonate (Patent Documents 1 and 2).
- Patent Document 1 discloses a two-layer structure in which a polyolefin film layer having a substantial melting point of 150 ° C. or more is used as a surface layer, and a polyolefin film having a substantial melting point of 125 to 145 ° C. is used as an adhesive or adhesive film layer.
- a protective film is disclosed.
- Patent Document 2 has a melting peak (A) of 105 to 130 ° C. and a melting peak (B) of 160 to 175 ° C. as a protective film, and the area ratio of melting peaks [(A) / (B)].
- a co-extruded polyolefin-based film is disclosed having a 35/65 to 80/20.
- Patent Documents 1 and 2 describe the evaluation (effect) after performing thermal bending, but there is no description regarding an injection molded lens formed by mounting a heat bent product on an injection mold, as an injection molded lens. There is no evaluation.
- This invention makes the subject the functional sheet
- the punched piece of the functional sheet with a protective film produced above is subjected to hot bending.
- the protective sheet of the functional layer is easily heated, that is, heated to 135 to 145 ° C., which is lower than the glass transition temperature of the aromatic polycarbonate resin which is the protective sheet, as a maximum temperature at which bending can be performed with a small stress.
- the protective film is also at this temperature, and as a result, the resin having a melting point lower than this temperature is melted.
- a material whose adhesion with the aromatic polycarbonate resin surface is greatly increased by melting becomes an improper adhesive or adhesive layer resin.
- the resin of the extended portion, the small piece, or the cracked portion of the cut end also melts and flows, and in some cases, solidifies and adheres or adheres at the flow destination.
- this developed product has a narrow range of suitable adhesive strength.
- the adhesive strength is smaller, peeling flaws occur from around the protective film during hot bending, and the additive of the adhesive layer of the protective film precipitates in the voids and remains on the surface as fine crystals.
- cloudiness There was a problem of causing cloudiness. For these reasons, there has been a demand for a material that does not cause peeling wrinkles even with a smaller adhesive strength, or that has a smaller increase in adhesive strength due to heat bending.
- unevenness corrugation may be observed on the surface of a heat bending product, and also a melamel may be observed as another defect. From the more detailed surface observation of the unevenness, a dent may be observed on the surface of the protective film, and coincidence between this dent and the dent on the surface of the heat bent product was recognized. It is more likely to occur when the level of cleaning (dust-free) of the work environment is low. However, even in the working environment where unevenness is generated and observed in the developed product with no white stripes, the unevenness was not substantially observed in the conventional protective film having two white stripes. In addition, in some prototypes in the process of developing a protective film in which no white streaks are generated, there was a case where this unevenness was hardly observed.
- the cleanliness of the manufacturing environment may be strictly controlled, but the problem remains that the manufacturing cost increases and the process becomes complicated.
- the melamela is observed as an irregular turbulent image.
- the surface of the protective layer of the same heat-bent product was observed with transmitted light, it was confirmed that the shape of the protective layer surface was changed in a undulating manner according to the disordered image.
- the unevenness described above has no difference in the height of the shape change part, and in such a way that the boundary of the change part is not clear, so that it cannot be captured by a microscope that spreads unevenly on the surface of the hot-bent product. It is a minute shape change on the surface.
- This melamella occurs in the case of a development product that does not generate white streaks, and the degree is weak in the conventional two-layer protective film in which white streaks occur, or does not occur as much as observed as the above-mentioned melamella. . Also in this respect, the biggest difference between the two is whether or not a resin layer that melts and flows at the time of thermal bending is provided. Specifically, when heat-bending processing, the developed product protection film that does not have a resin layer that melts and flows does not follow the shape change of the heat-bending product. Distorted to become the melamel.
- the adhesive layer that melts and flows at the time of thermal bending easily follows the shape change of the surface of the thermal bent product, so that it is presumed that the melamel is not induced.
- the inventors of the present invention manufactured a prototype protective film having a resin layer that melts under hot bending conditions in the intermediate layer under conditions where white stripes are frequently generated, and manufactured and evaluated an aromatic polycarbonate injection molded lens. Thus, a new functional sheet with a protective film was found.
- a functional sheet with a protective film comprising a functional film formed by laminating a functional layer, which is a polyvinyl alcohol polarizing film layer, a light control layer, or a combination thereof, sandwiched between aromatic polycarbonate sheets or films, and a protective film.
- the protective film is a base material layer made of polypropylene having a melting point equal to or higher than the glass transition temperature of the aromatic polycarbonate, and has a melting point lower than the glass transition temperature at a temperature 15 ° C. lower than the glass transition temperature on one side.
- a functional sheet with a protective film which is a polyolefin-based resin film comprising at least two layers of an adhesive layer comprising a resin composition of polyolefin and polyolefin rubber.
- the polypropylene of the base material layer has a low density, a melting point of 150 to 170 ° C., and a thickness of 10 to 60 ⁇ m; (3).
- the polyolefin of the adhesive layer has a low density, a melting point of 135 to 145 ° C., and a thickness of the adhesive layer of 5 to 30 ⁇ m, (4).
- a functional sheet with a protective film is formed by laminating a functional film selected from a polyvinyl alcohol polarizing film layer, a light control layer or a combination thereof with an aromatic polycarbonate sheet or film and laminating the functional film.
- This is a functional fragrance made by punching this into the desired shape, heat-bending the punched piece, peeling off the protective film, attaching it to the mold, injection molding the aromatic polycarbonate resin, and taking out the molded product.
- the protective film comprises a base material layer made of polypropylene having a melting point equal to or higher than the glass transition temperature of the aromatic polycarbonate, and at least 15 ° C.
- a method for producing an aromatic polycarbonate injection molded lens which is a polyolefin resin film comprising at least two layers of a pressure-sensitive adhesive layer comprising the resin composition of the Ngomu.
- the hot bending process is to gradually deform the punched piece at a temperature 15 to 5 ° C. lower than the glass transition temperature of the aromatic polycarbonate; (8).
- the polypropylene of the base material layer has a low density, a melting point of 150 to 170 ° C., and a thickness of 10 to 60 ⁇ m; (9).
- the adhesive layer has a low-density polyolefin and a melting point of 135 to 145 ° C., and the adhesive layer has a thickness of 5 to 30 ⁇ m. (10).
- the polyolefin resin layer has a low density, a melting point of 120 to 145 ° C., and a thickness of 20 to 60 ⁇ m.
- the protective film of this invention consists of at least 3 layers which provided the intermediate
- the thickness of the protective film is preferably selected from 50 to 100 ⁇ m.
- the base material layer is a layer for mainly achieving the original role of the protective film, that is, the role of protecting the surface of the functional sheet from scratches, dirt and foreign matters during handling in the distribution stage and processing step. And select a film having an appropriate film strength.
- the base material layer does not generate cracks in the punching process, does not peel from the adhesive layer, and is exposed to an atmosphere having a glass transition temperature of the aromatic polycarbonate in the heat bending process. Also, it is a layer that does not melt and adhere, and that maintains the adhesive state with the adhesive layer or the adhesive layer that is substantially in a molten state.
- the base material layer does not melt in the heat bending step, and has a melting point (peak temperature by DSC measurement) higher than the glass transition temperature of the aromatic polycarbonate, preferably 150 to 170 ° C., more preferably 155 to 155 ° C.
- the temperature is 165 ° C., preferably selected from low density polypropylene, and the thickness is preferably selected from 10 to 60 ⁇ m, preferably 10 to 50 ⁇ m, more preferably 10 to 40 ⁇ m.
- the density is high, the material becomes brittle and a cutting residue due to cracking or the like is likely to occur.
- the melting point is low, a problem of a decrease in shape retention due to a decrease in strength as a base material layer is likely to occur.
- this protective film may not show an obvious melting
- the resin of the adhesive layer has a lower density and a small thickness ratio, it is usually measured with a low and gentle melting point peak shape.
- it since it is a composition with a polyolefin rubber, it is necessary to pay attention to the distinction from the rising portion on the low temperature side of the melting point peak of the base material layer.
- the pressure-sensitive adhesive layer retains the adhesion of the protective film to the base material layer or the intermediate layer, adheres to the surface of the aromatic polycarbonate, and peels off without any residue.
- it shows adhesion that does not peel off from the surface of the aromatic polycarbonate that is the protective surface and does not peel off from the base material layer, and also maintains a state of sticking to the base material layer even in a molten state
- Examples thereof include those having a low melt viscosity temperature dependency or an unclear melting point, such as a low-density product having poor regularity, a branched structure, and the like.
- the pressure-sensitive adhesive layer is made of a resin composition of a polyolefin and a polyolefin rubber having a melting point that is 15 ° C. lower than the glass transition temperature of the aromatic polycarbonate and lower than the glass transition temperature.
- the melting point of the polyolefin is preferably 135 to 145 ° C.
- the polyolefin is preferably a low density polyolefin. Further, the polyolefin is preferably polypropylene.
- the thickness of the adhesive layer is not particularly limited, but it is usually preferable to select from 5 to 30 ⁇ m. When the polyolefin of the adhesive layer is used alone, the adhesiveness to the aromatic polycarbonate is insufficient when it is pressure-bonded at room temperature.
- the melting point is too low, tackiness is exhibited even when used alone, the tackiness is greatly increased during hot bending, and even if cooled to room temperature, the decrease in tackiness is insufficient, which is not preferable.
- the melting point is too high, more polyolefin rubber component, which is a composition component for expressing the required tackiness, is required, and also the adhesion to the base material layer or the decrease in the adhesive force occurs. It is not preferable.
- adhesion to the intermediate layer that is a constituent element of the protective film or a decrease in adhesive strength is also undesirable.
- the polyolefin rubber of the present invention is obtained by copolymerizing ⁇ -olefin (such as 1-butene) and non-conjugated diene as appropriate using ethylene or propylene as main monomers.
- ⁇ -olefin such as 1-butene
- propylene as main monomers.
- EPDM ethylene-propylene rubber
- 1-butene or the like which is usually used as a third component as a special one, as one of the main components, such as propylene-butene rubber.
- ozone resistance, weather resistance, and heat resistance are excellent, but poor adhesiveness and slow vulcanization speed are considered to be disadvantageous, but excellent adhesives and vulcanizing agents have been developed.
- the composition ratio of the low-density polyolefin and polyolefin rubber in the adhesive layer is selected from the range of 20 to 60%, preferably 28 to 52% of the resin composition of the olefin rubber component.
- the adhesive strength of the present invention is a small value compared to the value of an ordinary adhesive and does not usually cause a problem, but consideration is essential.
- the protective film of the present invention requires at least two layers of a base material layer and an adhesive layer (or temporary adhesive layer), but between the base material layer and the adhesive layer (or temporary adhesive layer), or You may provide the auxiliary
- the polyolefin resin layer constituting the intermediate layer is made of a polyolefin having a melting point not lower than 40 ° C. lower than the glass transition temperature of the aromatic polycarbonate and not higher than 5 ° C. lower than the glass transition temperature.
- the melting point thereof is preferably 120 ° C. to 145 ° C., and the thickness thereof is 20 to 60 ⁇ m.
- This intermediate layer becomes a molten state at the time of hot bending, absorbs local stress load, and is sandwiched and constrained by the base material layer and the adhesive layer (or temporary adhesive layer), so it flows independently. It is difficult to separate from the protective film body.
- the melting point of the intermediate layer polyolefin When the melting point of the intermediate layer polyolefin is lowered to about 120 ° C., it is difficult to separate from the film body by reducing the thickness to about 20 ⁇ m. Further, when the melting point of the intermediate layer polyolefin is increased to about 140 ° C., the effect of absorbing stress is increased when the thickness is about 40 ⁇ m, but it can be appropriately selected in consideration of the heat bending process conditions and the working environment. . When the melting point of the intermediate layer is higher than the melting point range, since the intermediate layer melts and does not flow during the hot bending process of the punched piece, the stress absorption is not sufficient, and the peeling wrinkles, unevenness, melamel, etc. are not eliminated.
- the intermediate layer melted during the hot bending process flows only due to the pressure of the reduced pressure or the pressurization during the hot bending, and the protective film base layer or the adhesive layer It sticks to the cross section of the heat-bent product by sticking or separating.
- a heat-bending protective film is peeled off and injection molding is performed, it is not desirable because it causes the same problems as white stripes.
- the protective film of the present invention is usually produced by a coextrusion method. Add at least two extruders for the base layer (core layer) and adhesive layer (or adhesive layer), and further add an extruder for the intermediate layer, and use at least three extruders.
- the film is melt-extruded under the conditions described above, in a molten state with a co-extrusion die, brought into layer contact, extruded from a die lip, and taken up with a roll to form a protective film.
- a small amount of a stabilizer, a release agent, a lubricant and the like can be appropriately added to perform more uniform extrusion, control of adhesion to a roll, and the like.
- the above protective film is temporarily adhered to the surface by adhesion or adhesion, and the functional sheet to be surface-protected is a functional layer selected from a polyvinyl alcohol polarizing film layer, a light control layer, or a combination thereof. It is formed by sandwiching between aromatic polycarbonate sheets or films.
- the functional layer which is a polyvinyl alcohol polarizing film layer, is usually a polarizing film obtained by adsorbing and orienting a dichroic organic dye while uniaxially stretching a polyvinyl alcohol resin film in an aqueous solution.
- the light control layer is a layer made of a transparent resin mixed with a photochromic compound (photochromic material).
- Photochromic materials include spirooxazine materials, spiropyran materials, fulgide materials, diarylethene materials, and salicylideneaniline materials, which are used as appropriate.
- the aromatic polycarbonate sheet or film has a thickness of 0.1 to 1 mm, preferably 0.2 to 0.5 mm, and has a uniaxially stretched retardation of 2,000 nm or more, usually 10,000 nm or less. preferable.
- aromatic polycarbonate resin 2,2-bis (4-hydroxyphenyl) alkane and bisphenol compounds represented by 2,2-bis (4-hydroxy-3,5-dihalogenophenyl) alkane are used in a known manner.
- the manufactured polymer may be used, and a structural unit having an ester bond in which a structural unit derived from a fatty acid diol is included in the polymer skeleton may be included.
- Bisphenol A polycarbonate resins derived from 2,2-bis (4-hydroxyphenyl) propane are preferred.
- the molecular weight is 17,000 to 40,000, preferably 22,000 to 34,000 in terms of viscosity average molecular weight from the viewpoint of formability and mechanical strength.
- aromatic polycarbonate resin for example, trade name: Iupilon (glass transition temperature: 145 to 150 ° C.) manufactured by Mitsubishi Engineering Plastics can be suitably used.
- the functional sheet of the present invention is produced by laminating the above functional layer with an aromatic polycarbonate sheet or film.
- Lamination is usually produced by laminating an aromatic polycarbonate sheet or film on both sides of a functional layer via an adhesive layer, press-bonding, and appropriately curing the adhesive layer.
- An example of an implementation method using a polyvinyl alcohol polarizing film as a functional layer is to apply and dry an adhesive on a long polyvinyl alcohol polarizing film continuously, and then press and bond the adhesive surface to a long aromatic polycarbonate sheet.
- the adhesive film is continuously coated again on the surface of the polarizing film and dried, and the adhesive surface is laminated and pressure-bonded to a long aromatic polycarbonate sheet, wound on a roll or cut into a predetermined size, and post-cured appropriately.
- the functional sheet with a protective film of the present invention is usually obtained by pressure-bonding a protective film, which is a continuous film, on both sides of the continuous or single-layer functional sheet. Crimping is usually by passing between two rolls. By appropriately heating the surface temperature to 60 ° C. to 80 ° C. at a pressure of 10 kg / cm or less.
- stacking the protective film of this invention will not be specifically limited if it is a lamination
- the present invention also includes a protective film attached to a functional sheet obtained by laminating a functional layer selected from a polyvinyl alcohol polarizing film layer, a light control layer, or a combination thereof with an aromatic polycarbonate sheet or film.
- a functional sheet with a protective film is formed, punched into a desired shape, heat-bending the punched piece, peeled off the protective film, attached to a mold, and injection molded with aromatic polycarbonate resin.
- the protective film comprises a base material layer made of polypropylene having a melting point equal to or higher than the glass transition temperature of the aromatic polycarbonate, and the glass on one side thereof.
- a method for producing an aromatic polycarbonate injection-molded lens which is a polyolefin-based resin film comprising at least two layers of a point polyolefin and an adhesive layer comprising a polyolefin rubber resin composition, and further comprising the thermal bending
- the process is a process for producing an aromatic polycarbonate injection-molded lens, wherein the punched piece is gradually deformed at a temperature 15 to 5 ° C. lower than the glass transition temperature of the aromatic polycarbonate.
- the present invention provides the method for producing an aromatic polycarbonate injection-molded lens, wherein the protective film is a base material layer made of polypropylene having a melting point equal to or higher than the glass transition temperature of the aromatic polycarbonate.
- An adhesive layer comprising a resin composition of a polyolefin and a polyolefin rubber having a melting point of 15 ° C. lower than the glass transition temperature and lower than the glass transition temperature, and the aromatic polycarbonate between the substrate layer and the adhesive layer
- An aromatic resin characterized by being a polyolefin-based resin film comprising at least three layers with an intermediate layer composed of a polyolefin having a melting point not lower than 40 ° C. and not higher than 5 ° C. below the glass transition temperature. This is a method for producing a polycarbonate injection molded lens.
- the functional sheet with the protective film is punched into a desired shape, for example, a disk having a diameter of 80 mm, and a slit shape in which both sides (upper and lower sides) of the disk are cut parallel to a certain width.
- a functional sheet with a protective film and a backing plate are placed on a press machine having a desired punching blade, for example, a Thomson blade, in consideration of the direction thereof.
- the punched piece uses a mold having a desired shape, usually a partially spherical mold, and is preheated to a temperature that is 15 ° C. to 5 ° C. lower than the glass transition temperature, preferably 130 ° C. or higher as appropriate. Then, it is placed in a female mold for hot bending and subjected to reduced pressure or pressurization, so that the maximum temperature of the punched piece is 15 to 5 ° C. lower than the glass transition temperature of the aromatic polycarbonate, usually 135 to 145 ° C. Gradually, it is usually deformed over 0.5 to 10 minutes, and the hot bending process is completed by pressing the male mold during this time.
- the adhesive layer of the present protective film partially melts at the temperature of this hot bending process.
- the polyolefin used for the pressure-sensitive adhesive layer of this protective film alone has a melting point peak in the maximum temperature range of almost heat bending, but when the resin composition for the pressure-sensitive adhesive layer is used, the melting point peak cannot be confirmed.
- the adhesive layer of the conventional protective film shows a clear melting point peak.
- the pressure-sensitive adhesive layer of the present invention is very unclear compared to the conventional one and has a difference that a high melting point peak can be confirmed.
- the pressure-sensitive adhesive layer of the present invention does not flow out from the base material layer because of its high viscosity even during hot bending, and is considered to be difficult to melt and adhere to the punched end surface.
- the punched piece that has been heat-bended is removed from its protective film, placed in the mold of an injection molding machine at a predetermined temperature, and an aromatic polycarbonate resin molding material is injected to produce an aromatic polycarbonate injection molded lens.
- the resin temperature is usually 260 to 340 ° C., preferably 270 to 310 ° C., the injection pressure 50 to 200 MPa, preferably 80 to 150 MPa, the mold temperature 60 to 130 ° C., preferably 80 to 125 ° C. ° C.
- the aromatic polycarbonate injection-molded lens produced above is appropriately subjected to a hard coat treatment, and further subjected to a mirror coat, an antireflection coat or the like to obtain a product.
- the material or processing conditions of the hard coat must be excellent in adhesion to the appearance and the underlying aromatic polycarbonate, or to an inorganic layer such as a mirror coat or antireflection coat that is subsequently coated.
- the firing temperature is preferably a temperature that is 50 ° C. lower than the glass transition point and lower than the glass transition point of the aromatic polycarbonate sheet, and particularly, a temperature that is 40 ° C. lower than the glass transition point and 15 ° C. lower than the glass transition point.
- the time required for baking the hard coat at a temperature of about 120 ° C. is about 0.5 to 2 hours.
- Functional sheet A functional sheet with a total thickness of 0.6 mm, width of 300 mm, and length of 340 mm (Mitsubishi Corporation), in which an aromatic polycarbonate sheet with a thickness of 0.3 mm is laminated on both sides of a polarizing film with a thickness of 30 ⁇ m using a thermosetting polyurethane adhesive layer Gas Chemical Co., Ltd., Iupilon Polar) was used and pressure-bonded (load 9 kg / cm) to both surfaces with a roll (roll surface temperature 65 ° C.) heated with the protective film described in Table 1 below. (Examples 1 and 2, Comparative Examples 1 and 2) Next, the functional sheet with a protective film was punched out.
- punching was performed by press punching using a Thomson blade, but as described in the above-mentioned problem section, for the purpose of manufacturing a punched piece with a significantly increased white stripe occurrence frequency, A Thomson blade with a single blade was adopted, the single blade was arranged outwardly, and the blade edge was removed by 5 ⁇ m.
- Shape of punched piece A disk with a diameter of 80 mm is cut in the same amount on both sides of a straight line passing through the center of the disk, and has a slit shape with a width of 55 mm, or a longitudinal cross-sectional shape of a capsule or a bag, and has small protrusions for positioning on the arc portions on both sides that are not cut. .
- the longitudinal direction of the punched piece was taken as the absorption axis direction of the polarizing film.
- the punched piece produced above was subjected to hot bending.
- thermal bending the punched piece is preheated with a preheater, placed on a partial spherical female mold with a predetermined temperature and a predetermined curvature, and pressed with a male mold made of silicon rubber.
- a continuous hot bending apparatus comprising a step of picking up, pulling up the male mold, holding the punched piece adsorbed by the female mold in a hot air atmosphere at a predetermined temperature for a predetermined time, and then taking it out was used.
- preheating of the punched piece is performed at an ambient temperature of 136 ° C.
- the female die is a partial spherical surface equivalent to 8R (radius of about 65.6 mm)
- the surface temperature is 138 ° C.
- the pressing time by the silicone rubber male die is 4 seconds
- the female die Adsorption to was carried out for 9 minutes in an atmosphere where the hot air temperature was 166 ° C.
- this thermal bending condition is set and selected as a condition with a high frequency of white stripes, like the punching blade condition.
- the hot bending punching piece it observed (henceforth end surface observation) regarding the protective film of a punch cut end surface. Furthermore, the wrinkles and cloudiness of the protective film, and the occurrence of melamella were observed, and the peelability was also confirmed.
- the method is shown below, and the results are shown in Table 1.
- the heat-bending punched piece protective film produced above was peeled off, mounted on a mold cavity of an injection molding machine, and injection molded using an aromatic polycarbonate (containing an ultraviolet absorber, trade name;).
- the injection molding conditions were set such that the resin temperature was 310 ° C., the injection pressure was 125 MPa, the holding pressure was 63 MPa, the mold temperature was 80 ° C., and the injection cycle was 70 seconds.
- Table 1 The results of observing the occurrence of white streaks with respect to the obtained injection molded lens are shown in Table 1 below.
- Shape of punched piece A disk with a diameter of 80 mm is cut in the same amount on both sides of a straight line passing through the center of the disk, and has a slit shape with a width of 55 mm, or a longitudinal cross-sectional shape of a capsule or a bag, and has small protrusions for positioning on the arc portions on both sides that are not cut. .
- the longitudinal direction of the punched piece was taken as the absorption axis direction of the polarizing film.
- Injection molding resin Aromatic polycarbonate resin (viscosity average molecular weight 23000, trade name: Iupilon CLS3400, Mitsubishi Engineering Plastics)
- the mold cavity is a partial spherical surface equivalent to 8R with a diameter of less than about 80 mm, with a total thickness of 2 mm including aberration-corrected mounting (insert) sheet, and a through hole used for post-processing of the lens at the opposite end of the gate. It is the shape where the projection part was provided.
- the sheet mounting portion has a recess for receiving a positioning small projection of the punched piece so that a slit or a bowl-shaped linear portion is perpendicular to the opposite end direction from the gate on the concave surface side.
- the molten resin moves while spreading in a partial spherical shape from the gate, hits the straight part of the punched piece on the concave side, gets over the punched piece, and reaches the protrusion at the opposite end of the gate while shrinking.
- white streaks A white streak extending between the punched piece and the injection resin from the cut end face of the punched piece in the flow direction of the injection resin was visually observed and determined. Normally noticeable white streaks are generated with a length of about 1 to 2 cm, but small white streaks of 1 mm or less and several mm are also selected as defective. Occurrence of peeling wrinkles: Protective film with a length of about 5 to 10 mm, and a gap between the protective film adhesive layer and the protective layer of the functional sheet. The film was peeled off and visually observed for determination. Peelability: It was determined whether or not the protective film could be easily peeled off manually by hot bending.
- Unevenness The shape of the surface of the protective layer of the functional layer after heat bending is changed, and the dents with a depth of about 20-100 ⁇ m and the lengths or widths of about 100-600 ⁇ m are visually observed with the reflected light of the fluorescent lamp.
- Melamela The change in the shape of the protective sheet surface of the functional layer after the heat bending process was judged by visually observing the heat bent product through a fluorescent lamp.
- the melting point of the adhesive layer in the table is the melting point of the low-density polypropylene component.
- PPOR1 Composition of low-density polypropylene having a melting point of about 140 ° C. and an ethylene-propylene-diene terpolymer
- PPOR2 Composition of low-density polypropylene having a melting point of about 140 ° C. and a propylene- (1-butene) copolymer
- PP1 low density polypropylene near melting point 160 ° C.
- PP2 low density polypropylene near melting point 140 ° C .: high density polyethylene PE near melting point 120 ° C .: high density polyethylene near melting point 100 ° C.
- White streak ⁇ There is no white streak in the lens.
- White streak x A white streak is generated on the lens by several mm.
- Peeling ⁇ No peeling flaw has occurred on the protective film.
- Peeling wrinkles ⁇ Peeling wrinkles are generated in the protective film.
- Peelability ⁇ The protective film can be peeled without problems. Peelability x: It is difficult to peel off the protective film.
- Unevenness ⁇ Unevenness is not generated on the protective sheet of the functional layer after the protective film is peeled off.
- Unevenness x Unevenness occurs on the protective sheet of the functional layer after the protective film is peeled off.
- Cloudiness ⁇ No cloudiness is present in the injection molded lens.
- Cloudiness x Cloudiness is present in the injection molded lens.
- the present invention it is possible to provide a functional sheet with a protective film capable of manufacturing an aromatic polycarbonate injection-molded lens in which defects such as white streaks, peeling wrinkles, and irregularities resulting from the manufacturing environment at the time of processing the functional sheet are significantly reduced. It became.
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Abstract
Description
また、特許文献2は、保護フィルムとして、105~130℃の融解ピーク(A)と160~175℃の融解ピーク(B)とを持ち、融解ピークの面積比[(A)/(B)]が35/65~80/20である共押し出しのポリオレフィン系フィルムを開示する。
特許文献1、2は、熱曲げ加工を行った後の評価(効果)までは記載するが、熱曲げ品を射出成形金型に装着してなる射出成形レンズに関する記載はなく、射出成形レンズとしての評価はない。
特に、生産性の向上の要請から、機器の使用効率の一層の向上やより短時間での製造への要求はますます厳しくなってきており、そのような問題への対応に伴って、「白スジ」の欠陥の発生頻度の増加傾向が見られ、早急の解決が望まれている。
また、熱曲げ加工品についてサンプル観察したところ、打ち抜き断面に保護フィルム由来と思われる付着樹脂が確認される場合があり、この切断面をナイフなどにて清掃したものでは、白スジが見られなくなった。
熱曲げ加工品は、その保護フィルムを剥離してから金型に装着し、射出成形する。この時発生する白スジは、保護フィルムを剥離しても、打ち抜き断面にそのまま残存した付着樹脂が原因であり、剥離力にて切断分離するほどに切断面に強固に付着したものか、或いは、切断分離片となって付着していたものと推定される。なお、一連の試験は、後記の実施例記載の方法によった。
打ち抜き回数が少ない場合には、発生頻度は少なく、多くなると増加する。取り換え或いは研磨時期の迫った打ち抜き刃は、摩耗にてその鋭利な刃先を失ったものである。
鋭利な刃先を失った或いは刃が欠けたものでは、保護フィルムはある程度以上引き延ばされてから切断される。詳細には、ある程度以上刃先が侵入し、引き延ばしされた後に当て板との間に挟まれて切断され、その後、打ち抜き刃が後退して打ち抜きが完了する。これは、引き伸ばし部を形成した後に、押し切りされる。大きく引き延ばされた部分、ひび割れ状に引き伸ばされた部分、または破断して小片化した部分などが切断端に残存したものとなる。
熱曲げ加工は、機能層の保護シートを容易に、すなわち、小さい応力で曲げ加工できる温度に、最高温度として保護シートである芳香族ポリカーボネート樹脂のガラス転移温度より低い135~145℃に加熱した状態で、徐々に変形させることによる。
当然に、保護フィルムもこの温度となり、この結果、融点がこの温度未満の樹脂は溶融する。なお、溶融は、全面で起こるので、芳香族ポリカーボネート樹脂表面との接着力が溶融により大きく増加するものは不適切な粘着或いは接着層用の樹脂となる。
前記したように、切断端の引き延ばされた部分や小片或いはひび割れ状部分の樹脂も溶融し流動し、場合により流動先で固化し粘着或いは接着する。
そして、用いた保護フィルムの種類により、この突出倒れ込みは概ね100~600μmの範囲であった。
なお、保護フィルム剥離後の切断端面への付着残存物の有無は未確認である。
前記した溶融流動にて基材層と分離したものや、切断端の基材層との接続部分が細く薄くなり粘着或いは接着強度に耐えられず、金型への装着にあたって剥離される保護フィルム本体と分離して切断端に残存することとなる。突出倒れ込みの大きいものは、残渣が残りやすい。残渣が、射出された溶融芳香族ポリカーボネートにて溶融されて引きずられて移動した軌跡が白スジとして見えるものとなる。
そこで、白スジの発生頻度の高い条件、鋭利な刃先を失った打ち抜き刃を用い、さらに、熱曲げ条件を選択することにより、保護フィルムの評価を行い、白スジが生じないかまたは大幅に減少した芳香族ポリカーボネート射出成形レンズの得られる保護フィルム付き機能性シートを見出した。
凸凹のより詳細な表面観察から保護フィルムの表面にも凹みが観察される場合があり、この凹みと熱曲げ品の表面の凹みとの一致が認められた。作業環境の清浄化(無塵化)のレベルが低いとより多く発生するものであり、これらから、ゴミが原因と推定された。
ところが白スジ発生の無い開発品では凸凹が発生し観察される作業環境においても、白スジの発生する従来の二枚構成の保護フィルムでは、この凸凹は実質的に観察されなかった。また、白スジの発生しない保護フィルムの開発過程の一部の試作品でも同様にこの凸凹が殆ど観察されないものがあった。
このメラメラは、白スジの発生しない開発品の場合には程度が強く発生し、白スジの発生する従来の二枚構成の保護フィルムでは程度が弱いか、前記したメラメラとして観察されるほど発生しない。
この点においても両者の最も大きな相違点は、熱曲げ時に溶融流動する樹脂層を持つか否かである。詳細には、熱曲げ加工する際、溶融流動する樹脂層を持たない開発品保護フィルムは熱曲げ品の形状変化に追従しない為、局在応力負荷が発生し熱曲げ品表面を微小な範囲で歪めて、前記メラメラとなる。それに対し溶融流動層を持つ白スジ発生品では、熱曲げ時に溶融流動する粘着層が容易に熱曲げ品表面の形状変化に追従する為、前記メラメラを誘発させないものと推定される。
そこで、本発明者らは、白スジ発生頻度の高い条件で、中間層に熱曲げ条件下に溶融する樹脂層を設けた保護フィルムを試作し、芳香族ポリカーボネート射出成形レンズを製造し評価することにより新規な保護フィルム付き機能性シートを見出した。
(1).ポリビニルアルコール系偏光フィルム層、調光層またはこれらの組み合わせである機能層を芳香族ポリカーボネートシート或いはフィルムで挟んで積層してなる機能性シートに保護フィルムを貼り合わせてなる保護フィルム付き機能性シートおいて、前記保護フィルムが、前記芳香族ポリカーボネートのガラス転移温度以上の融点のポリプロピレンからなる基材層と、その片面に前記のガラス転移温度よりも15℃低い温度以上でガラス転移温度よりも低い融点のポリオレフィンとポリオレフィンゴムとの樹脂組成物からなる粘着層との少なくとも2層からなるポリオレフィン系樹脂フィルムであることを特徴とする保護フィルム付き機能性シートである。
(2).前記基材層のポリプロピレンが低密度でその融点が150~170℃で、厚みが10~60μmであること、
(3).前記粘着層のポリオレフィンが低密度でその融点が135~145℃で、前記粘着層の厚みが5~30μmであること、また、
(4).前記基材層と前記粘着層との間に、前記基材層よりも低融点のポリオレフィン系樹脂層を持つこと、さらに、
(5).前記ポリオレフィン系樹脂層が低密度でその融点が120~145℃であり、その厚みが20~60μmである保護フィルム付き機能性シートである。
(6).ポリビニルアルコール系偏光フィルム層、調光層またはこれらの組み合わせから選択した機能層を芳香族ポリカーボネートシート或いはフィルムで挟んで積層してなる機能性シートに保護フィルムを貼り合わせて保護フィルム付き機能性シートとし、これを所望形状に打ち抜きし、打ち抜き片を熱曲げ加工した後、保護フィルムを剥離して金型に装着し、芳香族ポリカーボネート樹脂を射出成形し、成形品を取り出すことからなる機能性の芳香族ポリカーボネート射出成形レンズの製造法において、前記保護フィルムが、前記芳香族ポリカーボネートのガラス転移温度以上の融点のポリプロピレンからなる基材層と、その片面に前記のガラス転移温度よりも15℃低い温度以上でガラス転移温度よりも低い融点のポリオレフィンとポリオレフィンゴムとの樹脂組成物からなる粘着層との少なくとも2層からなるポリオレフィン系樹脂フィルムであることを特徴とする芳香族ポリカーボネート射出成形レンズの製造法である。
(7).前記熱曲げ加工が、打ち抜き片の最高温度が前記芳香族ポリカーボネートのガラス転移温度よりも15~5℃低い温度にて徐々に変形させるものであること、
(8).前記基材層のポリプロピレンが低密度でその融点が150~170℃であり、厚みが10~60μmであること、
(9).前記粘着層のポリオレフィンが低密度でその融点が135~145℃であり、前記粘着層の厚みが5~30μmであること、
(10).前記基材層と前記粘着層との間に、前記基材層よりも低融点のポリオレフィン系樹脂層を持つこと、
(11).前記ポリオレフィン系樹脂層が低密度でその融点が120~145℃であり、その厚みが20~60μmである、芳香族ポリカーボネート射出成形レンズの製造法である。
本発明の保護フィルムは、基材層と粘着層(或いは接着層)との少なくとも2層、または基材層と粘着層との間に中間層を設けた少なくとも3層からなる。本保護フィルムの厚みは、50~100μmから選択することが好ましい。
基材層は、保護フィルムの本来の役割、すなわち、流通段階や、加工工程などの取り扱いの際に機能性シートの表面をキズ、汚れや異物から保護するとの役割を主に達成するための層であり、適度なフィルム強度を持ったものを選択する。また、基材層は、打ち抜き工程にて、細片への割れを発生せず、粘着層と剥離せず、また、熱曲げ工程で前記芳香族ポリカーボネートのガラス転移温度程度の雰囲気に曝されても溶融接着などしないものであり、実質的に溶融状態となった粘着層或いは接着層との接着状態を保持する層である。
なお、本保護フィルムは、熱測定において、明白な融点ピークを示さない場合がある。特に、粘着層の樹脂は、より低密度であり、厚み比が小さいことから、通常、低くなだらかな融点ピーク形状で測定される。さらに、本発明では、ポリオレフィンゴムとの組成物であることから、基材層の融点ピークの低温側の立ち上がり部分との識別に注意が必要である。
粘着層のポリオレフィンは、単独使用では、室温での圧着では芳香族ポリカーボネートへの粘着性が不十分である。融点が低すぎると、単独使用でも粘着性を発現し、熱曲げ加工時に粘着性が大きく増加し、室温に冷却されても粘着性の低下が不十分なものとなるので好ましくない。他方、融点が高すぎると、必要とされる粘着性を発現させるための組成成分であるポリオレフィンゴム成分をより多く必要とするものとなり、また、基材層との粘着或いは接着力の低下も発生し好ましくない。他の態様においては、融点が高すぎると、保護フィルムの構成要素である中間層との粘着或いは接着力の低下も発生し好ましくない。
一般的に、耐オゾン性、耐候性、耐熱性が優れるが、接着性に劣り、加硫速度が遅いことが短所とされていたが、優れた接着剤や加硫剤が開発されている。これらはガラス転移温度が氷点下にあり、通常、架橋前には、室温で高粘度の液体から、室温より高く低密度ポリエチレンより低い融点をもち、架橋前の重量平均分子量が通常、10,000~200,000の範囲にある共重合体である。尚、非共役ジエンを含まないゴム状の重合体であるEPMの一種と思われる市販品の中には融点表示されたグレードもある。
粘着層の低密度のポリオレフィンとポリオレフィンゴムの組成比は、オレフィンゴム成分が、樹脂組成物の20~60%、好ましくは28~52%の範囲から選択する。
中間層ポリオレフィンの融点を120℃程度に低くする場合には、厚みを20μm程度に薄くする事でフィルム本体から分離しにくい。また、前記中間層ポリオレフィンの融点を140℃程度に高くする場合には、厚みを40μm程度にするとより応力吸収する効果が高まるが、熱曲げ加工条件や作業環境を考慮して適宜選択可能である。
中間層の融点が、前記融点範囲よりも高い場合には、打抜き片の熱曲げ加工時に中間層が溶融し流動しない為に応力吸収も十分でなく、剥離皺、凸凹及びメラメラなどが解消されない。中間層融点が前記融点範囲よりも低い場合には、熱曲げ加工時に溶融した中間層が熱曲げ時の減圧または加圧の応力により、中間層のみが流動して保護フィルム基材層や粘着層よりも突出した状態になり、熱曲げ品の断面に付着もしくは分離して固着する。そのような熱曲げ品の保護フィルムを剥離して射出成型を行った場合、白スジと同じような不具合になる為望ましくない。
基材層(コア層)用と粘着層(或いは接着層)との少なくとも2つの押出機を、さらに、中間層用の押出機を追加し少なくとも3つの押出機を用いて、それぞれの樹脂をそれぞれの条件にて溶融押出しし、共押出ダイにて溶融状態で層接触させてダイリップから押し出し、ロールにて引き取りして保護フィルムとする。なお、この共押出にあたって、安定剤、離型剤、滑剤などを、適宜、少量添加して、より均一な押出し、ロールなどへの付着の制御など行うことができる。
上記の保護フィルムをその表面に粘着或いは接着にて仮接着されて、表面保護される機能性シートは、ポリビニルアルコール系偏光フィルム層、調光層またはこれらの組み合わせから選択した機能層を芳香族ポリカーボネートシート或いはフィルムで挟んで積層してなるものである。
ポリビニルアルコール系偏光フィルム層である機能層は、通常、ポリビニルアルコール系樹脂フィルムを水溶液中で一軸延伸しつつ、二色性有機染料を吸着配向させてなる偏光フィルムであって、3.5~6.5倍に一軸延伸され、適宜、ホウ酸または金属化合物にて処理してなる偏光フィルムである。
調光層は、透明な樹脂にフォトクロミック化合物(フォトクロミック材料)を混合したものからなる層である。フォトクロミック材料としては、スピロオキサジン系材料、スピロピラン系材料、フルギド系材料、ジアリールエテン系材料、サリチリデンアニリン系材料があり適宜用いられる。
芳香族ポリカーボネート樹脂としては、2,2-ビス(4-ヒドロキシフェニル)アルカンや2,2-ビス(4-ヒドロキシ-3,5-ジハロゲノフェニル)アルカンで代表されるビスフェノール化合物から周知の方法で製造された重合体が用いられ、その重合体骨格に脂肪酸ジオールに由来する構造単位が含まれるエステル結合を持つ構造単位が含まれても良い。2,2-ビス(4-ヒドロキシフェニル)プロパンから誘導されるビスフェノールAポリカーボネート樹脂が好ましい。分子量は、賦型性や機械的強度の観点から粘度平均分子量で17,000~40,000、好ましくは22,000~34,000である。
芳香族ポリカーボネート樹脂としては、例えば、三菱エンジニアリングプラスチック社製、商品名:ユーピロン(ガラス転移温度・145~150℃)などを好適に用いることができる。
ポリビニルアルコール系偏光フィルムを機能層とする実施方法の一例は、長尺のポリビニルアルコール系偏光フィルムに連続的に接着剤を塗布乾燥し、接着剤面を長尺の芳香族ポリカーボネートシートに重ね圧着し、その偏光フィルム表面に再び連続的に接着剤を塗布乾燥し、接着剤面に長尺の芳香族ポリカーボネートシートに重ね圧着し、ロールに巻き取り或いは所定寸法に切断したものを、適宜、後硬化させる方法が挙げられる。
本発明の保護フィルム付き機能性シートは、通常、連続フィルムである保護フィルムを前記の連続或いは枚葉の機能性シートの両面に重ね圧着することによる。
圧着は、通常、2本のロール間を通過させることによる。圧力10kg/cm以下にて、適宜表面温度を60℃~80℃に加熱して用いる事による。
尚、本発明の保護フィルムを積層する方法は、最終的に本発明の保護フィルムの構成となるような積層方法であれば特に限定されるものではない。
また、本発明は、ポリビニルアルコール系偏光フィルム層、調光層またはこれらの組み合わせから選択した機能層を芳香族ポリカーボネートシート或いはフィルムで挟んで積層してなる機能性シートに保護フィルムを貼り合わせて保護フィルム付き機能性シートとし、これを所望形状に打ち抜きし、打ち抜き片を熱曲げ加工した後、保護フィルムを剥離して金型に装着し、芳香族ポリカーボネート樹脂を射出成形し、成形品を取り出すことからなる機能性の芳香族ポリカーボネート射出成形レンズの製造法において、前記保護フィルムが、前記芳香族ポリカーボネートのガラス転移温度以上の融点のポリプロピレンからなる基材層と、その片面に前記のガラス転移温度よりも15℃低い温度以上でガラス転移温度よりも低い融点のポリオレフィンとポリオレフィンゴムとの樹脂組成物からなる粘着層との少なくとも2層からなるポリオレフィン系樹脂フィルムであることを特徴とする芳香族ポリカーボネート射出成形レンズの製造法であり、さらに、前記熱曲げ加工が、打ち抜き片の最高温度が前記芳香族ポリカーボネートのガラス転移温度よりも15~5℃低い温度にて徐々に変形させるものであることからなる芳香族ポリカーボネート射出成形レンズの製造法である。
他の態様において、本発明は、前記芳香族ポリカーボネート射出成形レンズの製造法において、前記保護フィルムが、前記芳香族ポリカーボネートのガラス転移温度以上の融点のポリプロピレンからなる基材層、その片面に前記のガラス転移温度よりも15℃低い温度以上でガラス転移温度よりも低い融点のポリオレフィンとポリオレフィンゴムとの樹脂組成物からなる粘着層および前記の基材層と粘着層との間に、前記芳香族ポリカーボネートのガラス転移温度よりも40℃低い温度以上でガラス転移温度よりも5℃低い温度以下の融点のポリオレフィンからなる中間層との少なくとも3層からなるポリオレフィン系樹脂フィルムであることを特徴とする芳香族ポリカーボネート射出成形レンズの製造法である。
本保護フィルムの粘着層に用いるポリオレフィンは、単独では略熱曲げ加工の最高温度範囲に融点ピークをもつものを用いるが、粘着層用の樹脂組成物とした場合、融点ピークは確認できないものではないが、不明確となる。従来の保護フィルムの粘着層は明白な融点ピークを示す。本発明の粘着層は、従来のものに比較して極めて不明確であり、また、高い融点ピークが確認できるとの相違点をもつものである。
本発明の粘着層は、熱曲げ加工時においても高い粘性から基材層から分離して流れ出さず、打ち抜き端面に溶融して付着しづらいものとなっているものと思われる。
本発明の射出成形は、通常は、樹脂温度は260~340℃、好ましくは270~310℃、射出圧力50~200MPa、好ましくは80~150MPa、金型温度60~130℃、好ましくは80~125℃である。
ハードコートの材質あるいは加工条件は、外観や下地の芳香族ポリカーボネートに対して、あるいは続いてコートされるミラーコートや反射防止コート等の無機層に対する密着性に優れている必要があり、この点から、焼成温度は芳香族ポリカーボネートシートのガラス転移点より50℃低い温度以上でガラス転移点未満の温度が好ましく、特に、ガラス転移点より40℃低い温度以上でガラス転移点より15℃低い温度未満で、120℃前後の温度で、ハードコートの焼成に要する時間は概ね0.5~2時間である。
以下に、本発明を実施例にて説明する。
厚み30μmの偏光フィルムの両面に熱硬化性ポリウレタン系接着層にて厚み0.3mmの芳香族ポリカーボネートシートを積層した全厚み0.6mm、幅300mm、長さ340mmの機能性シート(三菱瓦斯化学(株)製、ユーピロンポーラ)を用い、その両面に、下記表1記載の保護フィルムを加温したロール(ロール表面温度65℃)にて圧着(荷重9kg/cm)した。(実施例1および2、比較例1および2)
次に、保護フィルム付き機能性シートを打ち抜き加工した。
ここで、打ち抜きは、常法に従い、トムソン刃を用いるとプレス打ち抜きとしたが、上記の課題の項で説明したように、白スジ発生頻度を大幅に高くした打ち抜き片を製造するとの目的から、トムソン刃として片刃のものを採用し、片刃は外向き配置とし、さらに、刃先を5μm除いたものを用いた。
直径80mmの円盤をその中心を通る直線の両側を平行に同量切り取り幅55mmとしたスリット形状或いはカプセルや俵の縦断面形状であり、切り取られない両側の円弧部分に位置決め用の小突起を持つ。打ち抜き方向は、打ち抜き片の長手方向を偏光フィルムの吸収軸方向とした。
熱曲げは、打ち抜き片を予熱器にて予備加熱し、これを所定の温度、所定の曲率の部分球面雌型に乗せ、シリコンゴム製雄型にて押し付けると同時に減圧を開始して雌型に吸着させ、雄型を引き上げ、雌型に吸着された打ち抜き片を所定の時間、所定の温度の熱風雰囲気中で保持した後、取り出す工程からなる連続熱曲げ装置を使用した。
上記において、打ち抜き片の予備加熱は136℃雰囲気温度とし、雌型は8R相当(半径約65.6mm)の部分球面で表面温度138℃、シリコンゴム製雄型による押し付け時間は4秒、雌型への吸着は、吹き込み熱風温度が166℃である雰囲気下で9分間とした。
なお、この熱曲げ条件は、打ち抜き刃の条件と同様に、白スジの発生頻度の高い条件を設定選択したものである。
熱曲げ打ち抜き片について、打ち抜き切断端面の保護フィルムに関して観察(以下、端面観察と記す)した。さらに、保護フィルムのシワ及び白濁、メラメラの発生を観察し、剥離性も確認した。方法を下記に、結果を表1に示した。
得られた射出成形レンズに関して、白スジの発生を観察した結果を下記表1に示した。
直径80mmの円盤をその中心を通る直線の両側を平行に同量切り取り幅55mmとしたスリット形状或いはカプセルや俵の縦断面形状であり、切り取られない両側の円弧部分に位置決め用の小突起を持つ。
打ち抜き方向は、打ち抜き片の長手方向を偏光フィルムの吸収軸方向とした。
射出成形樹脂:
芳香族ポリカーボネート樹脂(粘度平均分子量23000、商品名:ユーピロンCLS3400、三菱エンジニアリングプラスチックス(株))
度数を持たないプラノレンズ用。金型キャビチーは、直径約80mm弱の8R相当の部分球面で、収差補正され装着(インサート)シートを含む総厚み2mmで、ゲートの反対端には、レンズの後加工などに使用する貫通穴付きの突起部が設けられた形状である。シート装着部は凹面側、ゲートからその反対端方向に対してスリット或いは俵形状の直線部が直交するように、打ち抜き片の位置決め小突起を受ける凹みを持つ。
従って、溶融樹脂は、ゲートから部分球面形状に広がりつつ移動し、凹面側では、打ち抜き片の直線部にぶつかり、打ち抜き片上を乗り越え、縮まりながらゲートの反対端の突起部に至る。
DSCによる。昇温速度10℃/分、サンプル量10mgにて測定。
端面観察:
熱曲げ打ち抜き片の端面において、保護フィルムは、機能性シート切断端面から突出して倒れ込んでおり、機能性シート切断壁に付着している状態が観察される。
顕微鏡観察し、保護フィルムの厚みを差し引いて、端面からの突出倒れ込み量をそれぞれ測定した。
射出樹脂の流れ方向に、打ち抜き片の切断端面から、打ち抜き片と射出樹脂との間に伸びる白いスジで、目視にて観察判定した。通常目立つ白スジは、1~2cm程度の長さで発生するが、1cm以下で数mm程度の小さな白スジも不良として選別した。
剥離皺の発生:
熱曲げ加工後に、熱曲げ品凹面に発生する保護フィルムの剥離皺で、5~10mm程度の長さがあり、保護フィルム粘着層と機能性シートの保護層との界面が空隙になっている保護フィルムの剥離皺を目視で観察判定した。
剥離性:
熱曲げ加工後の保護フィルムの剥がし易さで、人手で容易に剥がせるかどうか判定した。
凸凹:
熱曲げ加工後の機能層の保護シート表面の形状変化で、20~100μm程度の深さの凹みであり、長さ若しくは幅が100~600μm程度ある凸凹を、蛍光灯の反射光により目視で観察判定した。
メラメラ:
熱曲げ加工後の機能層の保護シート表面の形状変化で、目視にて蛍光灯越しに熱曲げ品を観察して判定した。
注)*表記載の粘着層の融点は、低密度ポリプロピレン成分の融点
PPOR1:融点140℃付近の低密度ポリプロピレンとエチレン-プロピレン-ジエン三元共重合体との組成物
PPOR2:融点140℃付近の低密度ポリプロピレンとプロピレン-(1-ブテン)共重合体との組成物
PP1 :融点160℃付近の低密度ポリプロピレン
PP2 :融点140℃付近の低密度ポリプロピレン
PE1 :融点120℃付近の高密度ポリエチレン
PE2 :融点100℃付近の高密度ポリエチレン
上記融点は示唆走査熱量計(DSC)を用いて測定した樹脂の融解ピークが、カタログ値付近にあることを確認して記載したものである。
白スジ ○:レンズに白スジが発生していない。
白スジ ×:レンズに白スジが数mm発生している。
剥離皺 ○:保護フィルムに剥離皺が発生していない。
剥離皺 ×:保護フィルムに剥離皺が発生している。
剥離性 ○:問題なく保護フィルムを剥離できる。
剥離性 ×:保護フィルムを剥離することが困難。
凸凹 ○:保護フィルム剥離後に、機能層の保護シート上に凸凹が発生していない。
凸凹 ×:保護フィルム剥離後に、機能層の保護シート上に凸凹が発生している。
白濁 ○:射出成型レンズに白濁が存在していない。
白濁 ×:射出成型レンズに白濁が存在している。
また、本発明は以上の詳細な説明により更に完全に理解できるであろう。しかしながら、詳細な説明および特定の実施例は、本発明の望ましい実施の形態であり、説明の目的のためにのみ記載されているものである。この詳細な説明から、種々の変更、改変が、当業者にとって明らかだからである。
出願人は、記載された実施の形態のいずれをも公衆に献上する意図はなく、開示された改変、代替案のうち、特許請求の範囲内に文言上含まれないかもしれないものも、均等論下での発明の一部とする。
本明細書あるいは請求の範囲の記載において、名詞及び同様な指示語の使用は、特に指示されない限り、または文脈によって明瞭に否定されない限り、単数および複数の両方を含むものと解釈すべきである。本明細書中で提供されたいずれの例示または例示的な用語(例えば、「等」)の使用も、単に本発明を説明し易くするという意図であるに過ぎず、特に請求の範囲に記載しない限り本発明の範囲に制限を加えるものではない。
Claims (11)
- ポリビニルアルコール系偏光フィルム層、調光層またはこれらの組み合わせである機能層を芳香族ポリカーボネートシート或いはフィルムで挟んで積層してなる機能性シートに保護フィルムを貼り合わせてなる保護フィルム付き機能性シートおいて、前記保護フィルムが、前記芳香族ポリカーボネートのガラス転移温度以上の融点のポリプロピレンからなる基材層と、その片面に前記のガラス転移温度よりも15℃低い温度以上でガラス転移温度よりも低い融点のポリオレフィンとポリオレフィンゴムとの樹脂組成物からなる粘着層との少なくとも2層からなるポリオレフィン系樹脂フィルムであることを特徴とする保護フィルム付き機能性シート。
- 前記基材層のポリプロピレンが低密度でその融点が150~170℃であり、厚みが10~60μmである請求項1記載の保護フィルム付き機能性シート。
- 前記粘着層のポリオレフィンが低密度でその融点が135~145℃であり、前記粘着層の厚みが5~30μmである請求項1記載の保護フィルム付き機能性シート。
- 前記基材層と前記粘着層との間に、前記基材層よりも低融点のポリオレフィン系樹脂層を持つ請求項1記載の保護フィルム付き機能性シート。
- 前記ポリオレフィン系樹脂層が低密度でその融点が120~145℃であり、その厚みが20~60μmである請求項4記載の保護フィルム付き機能性シート。
- ポリビニルアルコール系偏光フィルム層、調光層またはこれらの組み合わせから選択した機能層を芳香族ポリカーボネートシート或いはフィルムで挟んで積層してなる機能性シートに保護フィルムを貼り合わせて保護フィルム付き機能性シートとし、これを所望形状に打ち抜きし、打ち抜き片を熱曲げ加工した後、保護フィルムを剥離して金型に装着し、芳香族ポリカーボネート樹脂を射出成形し、成形品を取り出すことからなる機能性の芳香族ポリカーボネート射出成形レンズの製造法において、前記保護フィルムが、前記芳香族ポリカーボネートのガラス転移温度以上の融点のポリプロピレンからなる基材層と、その片面に前記のガラス転移温度よりも15℃低い温度以上でガラス転移温度よりも低い融点のポリオレフィンとポリオレフィンゴムとの樹脂組成物からなる粘着層との少なくとも2層からなるポリオレフィン系樹脂フィルムであることを特徴とする芳香族ポリカーボネート射出成形レンズの製造法。
- 前記熱曲げ加工が、打ち抜き片の最高温度が前記芳香族ポリカーボネートのガラス転移温度よりも15~5℃低い温度にて徐々に変形させるものである請求項6記載の芳香族ポリカーボネート射出成形レンズの製造法。
- 前記基材層のポリプロピレンが低密度でその融点が150~170℃であり、厚みが10~60μmである請求項6記載の芳香族ポリカーボネート射出成形レンズの製造法。
- 前記粘着層のポリオレフィンが低密度でその融点が135~145℃であり、前記粘着層の厚みが5~30μmである請求項6記載の芳香族ポリカーボネート射出成形レンズの製造法。
- 前記基材層と前記粘着層との間に、前記基材層よりも低融点のポリオレフィン系樹脂層を持つ請求項6記載の芳香族ポリカーボネート射出成形レンズの製造法。
- 前記ポリオレフィン系樹脂層が低密度でその融点が120~145℃であり、その厚みが20~60μmである請求項6記載の芳香族ポリカーボネート射出成形レンズの製造法。
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WO2020040189A1 (ja) * | 2018-08-21 | 2020-02-27 | 住友ベークライト株式会社 | 保護フィルム |
JP2020075512A (ja) * | 2018-08-21 | 2020-05-21 | 住友ベークライト株式会社 | 保護フィルム |
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TWI507785B (zh) | 2011-12-28 | 2015-11-11 | Toyo Boseki | 液晶顯示裝置 |
WO2016171223A1 (ja) | 2015-04-24 | 2016-10-27 | 株式会社トクヤマ | 光学積層体 |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2018199173A1 (ja) * | 2017-04-25 | 2018-11-01 | 住友ベークライト株式会社 | 保護フィルム |
JPWO2018199173A1 (ja) * | 2017-04-25 | 2019-06-27 | 住友ベークライト株式会社 | 保護フィルム |
CN110546002A (zh) * | 2017-04-25 | 2019-12-06 | 住友电木株式会社 | 保护膜 |
US11396615B2 (en) | 2017-04-25 | 2022-07-26 | Sumitomo Bakelite Co., Ltd. | Protective film |
WO2020040189A1 (ja) * | 2018-08-21 | 2020-02-27 | 住友ベークライト株式会社 | 保護フィルム |
JP2020037184A (ja) * | 2018-08-21 | 2020-03-12 | 住友ベークライト株式会社 | 保護フィルム |
JP2020075512A (ja) * | 2018-08-21 | 2020-05-21 | 住友ベークライト株式会社 | 保護フィルム |
US11584870B2 (en) | 2018-08-21 | 2023-02-21 | Sumitomo Bakelite Co., Ltd. | Protective film |
Also Published As
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EP3222420A1 (en) | 2017-09-27 |
JP6652929B2 (ja) | 2020-02-26 |
US10564325B2 (en) | 2020-02-18 |
KR20170086033A (ko) | 2017-07-25 |
US20170322344A1 (en) | 2017-11-09 |
TWI680055B (zh) | 2019-12-21 |
ES2822995T3 (es) | 2021-05-05 |
KR102404305B1 (ko) | 2022-05-31 |
CN107000415A (zh) | 2017-08-01 |
JPWO2016080445A1 (ja) | 2017-11-09 |
CN107000415B (zh) | 2020-06-26 |
TW201637864A (zh) | 2016-11-01 |
EP3222420A4 (en) | 2018-04-25 |
EP3222420B1 (en) | 2020-09-09 |
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