JP5387313B2 - Manufacturing method of molded body, molded body, glasses and protective product - Google Patents
Manufacturing method of molded body, molded body, glasses and protective product Download PDFInfo
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- JP5387313B2 JP5387313B2 JP2009234591A JP2009234591A JP5387313B2 JP 5387313 B2 JP5387313 B2 JP 5387313B2 JP 2009234591 A JP2009234591 A JP 2009234591A JP 2009234591 A JP2009234591 A JP 2009234591A JP 5387313 B2 JP5387313 B2 JP 5387313B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 33
- 230000001681 protective effect Effects 0.000 title claims description 13
- 239000011521 glass Substances 0.000 title description 10
- 238000000034 method Methods 0.000 claims description 99
- 238000004043 dyeing Methods 0.000 claims description 67
- 229920005992 thermoplastic resin Polymers 0.000 claims description 59
- 239000002344 surface layer Substances 0.000 claims description 43
- 238000000465 moulding Methods 0.000 claims description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 28
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
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- 238000007493 shaping process Methods 0.000 claims description 7
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- 239000000975 dye Substances 0.000 description 35
- 238000011156 evaluation Methods 0.000 description 29
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- 229920003023 plastic Polymers 0.000 description 12
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- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 5
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- 239000007921 spray Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
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- 229920001342 Bakelite® Polymers 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000004420 Iupilon Substances 0.000 description 2
- 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 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
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- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004593 Epoxy Substances 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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000022563 Rema Species 0.000 description 1
- DEXKHGVSCDMMLD-UHFFFAOYSA-N [ClH]1N=CC=C1 Chemical compound [ClH]1N=CC=C1 DEXKHGVSCDMMLD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- WLDHEUZGFKACJH-UHFFFAOYSA-K amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1N=NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-UHFFFAOYSA-K 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
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- 238000007766 curtain coating Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- PBOIUUROGJVVNC-UHFFFAOYSA-L disodium 2-hydroxy-5-[[4-[[2-methoxy-4-[(3-sulfonatophenyl)diazenyl]phenyl]carbamoylamino]phenyl]diazenyl]benzoate Chemical compound [Na+].[Na+].COc1cc(ccc1NC(=O)Nc1ccc(cc1)N=Nc1ccc(O)c(c1)C([O-])=O)N=Nc1cccc(c1)S([O-])(=O)=O PBOIUUROGJVVNC-UHFFFAOYSA-L 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- MPCYPRXRVWZKGF-UHFFFAOYSA-J tetrasodium 5-amino-3-[[4-[4-[(8-amino-1-hydroxy-3,6-disulfonatonaphthalen-2-yl)diazenyl]phenyl]phenyl]diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(N=NC3=CC=C(C=C3)C3=CC=C(C=C3)N=NC3=C(C=C4C=C(C=C(C4=C3O)N)S([O-])(=O)=O)S([O-])(=O)=O)=C(O)C2=C1N MPCYPRXRVWZKGF-UHFFFAOYSA-J 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Respiratory Apparatuses And Protective Means (AREA)
- Eyeglasses (AREA)
Description
本発明は、成形体の製造方法、成形体、眼鏡、および防護製品に関する。 The present invention relates to a method for manufacturing a molded body, a molded body, glasses, and a protective product.
近年、眼鏡、ゴーグル、サングラス、バイザーに使用されるプラスチックレンズやヘルメットシールド、風防、防護面などに使用されるプラスチック防護体はガラス製品と比較して耐衝撃性が高いこと、透明であり軽量であることなどからガラス製品に代わり多方面で使用されている。（例えば、特許文献１参照。）
特にそれらは紫外線遮断効果やファッション性などから着色されて使用されることも多い。またレンズ上部の透過率が低く、レンズ下部の透過率を高くすることで着色濃度に階調をつけたレンズは遠方や空を見る際は防眩性が高く、手元の視界は明るく作業性が良いなどの機能性も付与される。
プラスチックをレンズや防護体などの成形体に加工する方法として、熱硬化製の液状プラスチック材料を所望の形状の金型に流し込み、熱硬化させる方法や、所望の形状の金型に対して熱可塑性樹脂を射出する方法などが挙げられる。
前述の方法で用意されたプラスチックレンズや防護体などの成形体を染色する方法は、これまで様々な方法が実施されている。代表的な方法として、
（１）気相中にて染料を昇華させ基材表面を染色する方法
（２）染料をスプレーやインクジェットなどで噴霧する方法
などが挙げられる。
（３）染料を分散させた染液を加熱し、プラスチックを浸漬させ染色する方法、
（４）染色困難なプラスチックに染色されやすい表面層を設け、該プラスチックを前記（１）の方法で染める方法、
In recent years, plastic lenses used for glasses, goggles, sunglasses, visors, helmet shields, windshields, protective surfaces, etc. have higher impact resistance than glass products, are transparent and lightweight. For some reasons, it is used in many ways in place of glass products. (For example, refer to Patent Document 1.)
In particular, they are often used because they are colored due to their UV blocking effect and fashionability. In addition, the lens with a low transmittance at the top of the lens and a high gradation at the bottom of the lens to give gradations to the coloring density is highly anti-glare when looking far away or in the sky, and the visibility at hand is bright and workable. Functionality such as good is also given.
As a method of processing plastics into molded bodies such as lenses and protective bodies, a liquid plastic material made of thermosetting is poured into a mold with a desired shape and thermally cured, or thermoplastic with respect to a mold with a desired shape Examples include a method of injecting resin.
Various methods have been used so far for dyeing molded articles such as plastic lenses and protective bodies prepared by the aforementioned methods. As a representative method,
(1) A method of dyeing the surface of a substrate by sublimating the dye in the gas phase (2) A method of spraying the dye with a spray or an ink jet.
(3) A method in which a dye solution in which a dye is dispersed is heated and the plastic is immersed and dyed,
(4) A method of providing a surface layer that is easily dyed on a difficult-to-dye plastic, and dyeing the plastic by the method of (1),
染色方法（１）は染料の色味によって昇華する条件がことなるため任意の色をプラスチック表面に付着させる工程が効率的ではなく、量産性に適していない。
染色方法（２）のスプレー法は噴霧範囲が広く、比較的小さな眼鏡レンズなどの色調を細かくコントロールすることは難しい。またインクジェット法を用いる際には染料の細かな吐出量などを設定できる専用のプリンターなどが必要となる。
染色方法（３）では、プラスチックを染色させるために染料を分散助剤などで分散させた染色液の中に浸漬させる。染色後、場合によっては染料を抜けにくくするために加熱処理などを行う。しかしこの方法ではプラスチック材料が染色されやすい材質に限られる。染色困難であるプラスチックを染色する場合、一般的には濃色まで染めることが困難であった。
染色方法（４）は、前述した染色困難な材料に用いられる。染色困難な材料の表面に染色可能な表面層を設けた後に染色方法（１）と同様の方法を用いて基材の染色を行う。しかしこの染色方法においては形状加工、成形後に、基材に対して表面処理を施す必要があり経済上有利ではないという問題点があった。
このように現状では染色されたプラスチック体を得るためには、染色方法が限られる、染色される材料が限られる、染色困難な材料を染色する際は成形後に染色可能な表面処理を施す工程が必要であることなどの問題があった。
In the dyeing method (1), the conditions for sublimation vary depending on the color of the dye, so the process of attaching an arbitrary color to the plastic surface is not efficient and is not suitable for mass production.
The spray method of the dyeing method (2) has a wide spray range, and it is difficult to finely control the color tone of a relatively small spectacle lens. Further, when using the ink jet method, a dedicated printer or the like that can set a fine discharge amount of the dye is required.
In the dyeing method (3), in order to dye the plastic, the dye is immersed in a dyeing solution in which the dye is dispersed with a dispersion aid or the like. After dyeing, in some cases, heat treatment or the like is performed to make it difficult to remove the dye. However, in this method, the plastic material is limited to materials that are easily dyed. When dyeing plastics that are difficult to dye, it is generally difficult to dye to a deep color.
The dyeing method (4) is used for the aforementioned difficult-to-dye material. After providing a dyeable surface layer on the surface of the material that is difficult to dye, the substrate is dyed using the same method as the dyeing method (1). However, this dyeing method has a problem that it is not economically advantageous because it is necessary to perform surface treatment on the base material after shape processing and molding.
As described above, in order to obtain a dyed plastic body, the dyeing method is limited, the material to be dyed is limited, and when dyeing difficult-to-dye material, there is a step of performing a surface treatment that can be dyed after molding. There were problems such as being necessary.
本発明は、上記課題に顧みてなされたものであり、熱可塑性樹脂シートまたは積層体に対して、染色可能な表面層を設ける工程、染色処理する工程、成形加工する工程を含むことによって、一般的な染色方法によって任意の色合い、濃度に効率よく染色できる成形体の製造方法を提供するものである。 The present invention has been made in view of the above problems, and generally includes a step of providing a dyeable surface layer, a step of dyeing, and a step of forming a thermoplastic resin sheet or laminate. The present invention provides a method for producing a molded product that can be efficiently dyed to an arbitrary shade and density by a typical dyeing method.
上記課題は、下記（１）〜（１１）に記載の本発明により達成される。
（１） 平板状の熱可塑性樹脂シートまたは積層体を用いて成形加工する成形体の製造方法であって、
平板状に加工された熱可塑性樹脂シートまたは積層体に対して、
少なくとも片面に染色可能な表面層を設ける工程、
成形加工する工程、
染色処理する工程を含む成形体の製造方法。
（２） 染色可能な表面層を設けられた工程、成形加工する工程、染色処理する工程の順に製造する前記（１）に記載の成形体の製造方法。
（３） 表染色可能な表面層を設けられた工程、染色処理をする工程、成形加工する工程の順に製造する前記（１）に記載の成形体の製造方法。
（４） 前記染色可能な表面層がアクリレート重合体を含む前記（１）〜（３）項のいずれか１項に記載の成形体の製造方法。
（５） 前記アクリレート重合体が、少なくとも炭素数２以上５以下、繰り返し単位が６以上であるアルキレングリコールを一種以上有するアクリレートモノマーまたはアクリレートオリゴマーである前記（４）に記載の成形体の製造方法。
（６） 前記熱可塑性樹脂シートまたは積層体に用いる熱可塑性樹脂が、ポリカーボネート樹脂、ポリエステル樹脂、ポリオレフィン樹脂、ポリアミド樹脂を含む前記（１）〜（５）項のいずれか１項に記載の成形体の製造方法。
（７） 前記熱可塑性樹脂積層体が、偏光性薄膜を含む積層体である前記（１）〜（６）項のいずれか１項に記載の成形体の製造方法。
（８） 前記成形体が、成形加工する工程、染色処理する工程の後に硬化性塗膜を成形体表面に形成していない成形体である前記（１）〜（７）項のいずれか１項に記載の成形体の製造方法。
（９） 前記（１）〜（８）項のいずれか１項に記載の成形体の製造方法により製造された成形体。
（１０） 前記（９）項に記載の成形体を用いて作製した眼鏡。
（１１） 前記（９）項に記載の成形体を用いて作製した防護製品。
The said subject is achieved by this invention as described in following (1)-(11).
(1) A method for producing a molded body that is molded using a flat-plate thermoplastic resin sheet or laminate,
For the thermoplastic resin sheet or laminate processed into a flat plate,
Providing a surface layer capable of being dyed on at least one side;
Molding process,
The manufacturing method of the molded object including the process of dyeing-processing.
(2) The method for producing a molded body according to (1), wherein the step of providing a dyeable surface layer, the step of forming, and the step of dyeing are produced in this order.
(3) The method for producing a molded article according to (1), wherein the process is performed in the order of a process provided with a surface layer capable of surface dyeing, a dyeing process, and a molding process.
(4) The method for producing a molded article according to any one of (1) to (3), wherein the dyeable surface layer contains an acrylate polymer.
(5) The method for producing a molded article according to (4), wherein the acrylate polymer is an acrylate monomer or an acrylate oligomer having at least one alkylene glycol having 2 to 5 carbon atoms and 6 or more repeating units.
(6) The molded article according to any one of (1) to (5), wherein the thermoplastic resin used in the thermoplastic resin sheet or laminate includes a polycarbonate resin, a polyester resin, a polyolefin resin, and a polyamide resin. Manufacturing method.
(7) The method for producing a molded article according to any one of (1) to (6), wherein the thermoplastic resin laminate is a laminate including a polarizing thin film.
(8) Any one of the items (1) to (7), wherein the molded body is a molded body in which a curable coating film is not formed on the surface of the molded body after the molding process and the dyeing process. The manufacturing method of the molded object of description.
(9) A molded product produced by the method for producing a molded product according to any one of (1) to (8).
(10) Glasses produced using the molded article according to (9).
(11) A protective product produced using the molded article described in (9) above.
本発明によれば、熱可塑性樹脂シートまたは積層体に対して染色可能な表面層を設ける工程、染色処理する工程、成形加工する工程の順序を問わず、染色された成形体を製造することが可能となる。 According to the present invention, a dyed molded article can be produced regardless of the order of the step of providing a surface layer that can be dyed to the thermoplastic resin sheet or laminate, the step of dyeing treatment, and the step of molding. It becomes possible.
本発明は、平板状の熱可塑性樹脂シートまたは積層体を用いて成形加工する成形体の製造方法であって、平板状に加工された熱可塑性樹脂シートまたは積層体に対して、
少なくとも片面に染色可能な表面層を設ける工程、
成形加工する工程、
染色処理する工程を含む成形体の製造方法を用いることで染色された成形体を得ることができる。
The present invention is a method for producing a molded article that is molded using a flat thermoplastic resin sheet or laminate, and the thermoplastic resin sheet or laminate processed into a flat shape,
Providing a surface layer capable of being dyed on at least one side;
Molding process,
A dyed molded article can be obtained by using a method for producing a molded article including a step of dyeing.
本発明で用いる平板状に加工された熱可塑性樹脂シートとは、透明な熱可塑性樹脂を溶液キャスト成形、押出成形、カレンダー成形、溶融キャスト成形など成形加工して作製した平板状の熱可塑性樹脂シートである。
熱可塑性樹脂積層体としては、異なる種類の熱可塑性樹脂を用いた積層体や熱可塑性樹脂と偏光性薄膜を有する積層体である。
The flat-plate-shaped thermoplastic resin sheet used in the present invention is a flat-plate-shaped thermoplastic resin sheet produced by molding a transparent thermoplastic resin such as solution cast molding, extrusion molding, calender molding, and melt cast molding. It is.
Examples of the thermoplastic resin laminate include a laminate using different types of thermoplastic resins and a laminate having a thermoplastic resin and a polarizing thin film.
熱可塑性樹脂としては、例えば、ポリカーボネート樹脂、ポリアミド樹脂、ポリウレタン樹脂、ポリエステル樹脂、環状ポリオレフィン樹脂などのオレフィン類の樹脂、ポリメチルメタクリレートなどのメタクリル樹脂、ポリジエチレングリコールビスアリルカーボネートなどのポリジアリルグリコールカーボネート類、ポリスチレン、アクリロニトリル−スチレン共重合体、メチルメタクリレート−スチレン共重合体、ゴム強化メタクリル樹脂、セルロースアセテートなどのセルロースエステル類、ポリ塩化ビニル、ＡＢＳ（アクリルニトリル−ブタジエン−スチレン）樹脂などを挙げることができる。
またこれら樹脂からなる混合物を用いた熱可塑性樹脂シートや異なる種類の熱可塑性樹脂を積層した積層体を用いても良い。さらに、樹脂自体を濃色に染色することが困難な樹脂である、ポリカーボネート樹脂、ポリアミド樹脂、ポリエステル樹脂、環状ポリオレフィン樹脂などのオレフィン類の樹脂が、特に適している。
なお、前記熱可塑性樹脂には、着色剤、離型剤、酸化防止剤、光安定剤、紫外線吸収剤、蛍光増白剤、エステル交換防止剤、帯電防止剤などの各種添加剤を適宜配合してもよい。
Examples of the thermoplastic resin include polycarbonate resins, polyamide resins, polyurethane resins, polyester resins, olefin resins such as cyclic polyolefin resins, methacrylic resins such as polymethyl methacrylate, and polydiallyl glycol carbonates such as polydiethylene glycol bisallyl carbonate. , Polystyrene, acrylonitrile-styrene copolymer, methyl methacrylate-styrene copolymer, rubber reinforced methacrylic resin, cellulose esters such as cellulose acetate, polyvinyl chloride, ABS (acrylonitrile-butadiene-styrene) resin, and the like. it can.
Moreover, you may use the laminated body which laminated | stacked the thermoplastic resin sheet using the mixture which consists of these resin, and a different kind of thermoplastic resin. Further, olefin resins such as polycarbonate resin, polyamide resin, polyester resin, and cyclic polyolefin resin, which are difficult to dye the resin itself in a deep color, are particularly suitable.
The thermoplastic resin is appropriately mixed with various additives such as a colorant, a release agent, an antioxidant, a light stabilizer, an ultraviolet absorber, a fluorescent whitening agent, a transesterification agent, and an antistatic agent. May be.
本発明で用いる熱可塑性樹脂積層体は、偏光性薄膜を有する積層体であってもよい。
偏光性薄膜としては、偏光機能を有する薄膜であれば特に限定されず、例えばポリビニルアルコール系フィルムなどの高分子フィルムに、二色性色素を吸着させて配向せしめたものなどが挙げられる。二色性色素としては、ヨウ素系染料、二色性染料などが用いられる。特に耐熱性の観点から二色性染料などの二色性色素を吸着させて配向せしめたものなどが好ましい。
二色性染料としては、例えばアゾ系、アントラキノン系などの染料が挙げられ、具体的にはクロラチンファストレッド、コンゴーレッド、ブリリアントブルー６Ｂ、ベンゾパープリン、クロラゾールブラックＢＨ、ダイレクトブルー２Ｂ、ジアミングリーン、クリソフェノン、シリウスイエロー、ダイレクトファーストレッド、アシドブラックなどが挙げられる。
上記方法によって得られた偏光性薄膜に、熱可塑性樹脂シートを片面または両面に貼り合わせて熱可塑性樹脂積層体を作製することができる。
また、熱可塑性樹脂シートと熱可塑性樹脂積層体は、シートや積層体にされた後、金型などにより、ある形状に加工されたものであっても構わない。
The thermoplastic resin laminate used in the present invention may be a laminate having a polarizing thin film.
The polarizing thin film is not particularly limited as long as it has a polarizing function, and examples thereof include a film obtained by adsorbing and orienting a dichroic dye on a polymer film such as a polyvinyl alcohol film. As the dichroic dye, iodine dyes, dichroic dyes and the like are used. In particular, from the viewpoint of heat resistance, those obtained by adsorbing and orienting a dichroic dye such as a dichroic dye are preferred.
Examples of the dichroic dye include azo dyes and anthraquinone dyes. Specifically, chloratin fast red, congo red, brilliant blue 6B, benzoperpurine, chlorazole black BH, direct blue 2B, and diamine green. , Chrysophenone, Sirius yellow, direct first red, acid black and the like.
A thermoplastic resin laminate can be produced by attaching a thermoplastic resin sheet to one or both sides of the polarizing thin film obtained by the above method.
In addition, the thermoplastic resin sheet and the thermoplastic resin laminate may be formed into a sheet or a laminate, and then processed into a certain shape by a mold or the like.
熱可塑性樹脂シートまたは積層体の少なくとも片面に染色可能な表面層を設ける工程としては、表面層に樹脂組成物をコートして表面塗膜を設ける方法や、転写法、プレス法、ラミネーター法が挙げられる。特に樹脂組成物をコートし表面塗膜を設ける方法には浸漬法、フローコート法、ナイフコート法、カーテンコート法、スプレーコート法、スピンコート法、ロールコート法、ダイコート法、バーコート塗布法などが挙げられる。十分な密着性が得られやすく、成形時の熱によって不具合が生じにくい樹脂組成物をコートした後に硬化させて表面塗膜を設ける方法が好ましい。
上記熱可塑性樹脂シートまたは積層体に染色可能な表面層を形成する樹脂組成物を塗布し、その後、硬化処理を行うことで、表面層とする。
上記熱可塑性樹脂シートまたは積層体に塗布する樹脂組成物の厚みは１μｍ〜２０μｍになるのが好ましい。１μｍ以下では、濃色まで染めることが困難となり、また２０μｍ以上では耐熱成形性や熱可塑性樹脂シートまたは積層体への密着性が得られにくい。特に、表面層は熱可塑性樹脂シートまたは積層体の片面もしくは、両面に層を設けてもよい。
Examples of the step of providing a dyeable surface layer on at least one surface of the thermoplastic resin sheet or laminate include a method of coating the surface layer with a resin composition to provide a surface coating film, a transfer method, a press method, and a laminator method. It is done. In particular, methods for coating a resin composition and providing a surface coating include immersion, flow coating, knife coating, curtain coating, spray coating, spin coating, roll coating, die coating, bar coating, etc. Is mentioned. A method in which sufficient adhesion is easily obtained and a surface coating film is provided by coating a resin composition that is less likely to cause problems due to heat during molding and then cured is preferable.
A resin composition for forming a dyeable surface layer is applied to the thermoplastic resin sheet or the laminate, and then a curing treatment is performed to obtain a surface layer.
The thickness of the resin composition applied to the thermoplastic resin sheet or laminate is preferably 1 μm to 20 μm. If it is 1 μm or less, it becomes difficult to dye to a deep color, and if it is 20 μm or more, heat resistance moldability and adhesion to a thermoplastic resin sheet or laminate are difficult to obtain. In particular, the surface layer may be provided on one side or both sides of a thermoplastic resin sheet or laminate.
熱可塑性樹脂シートまたは積層体上に樹脂組成物を上記方法などにより塗布した後の硬化方法は、紫外線照射または電子線照射する方法が好ましい。
なお、溶剤を含む樹脂組成物を使用する場合は、硬化工程の前に熱可塑性樹脂シートおよび塗布された樹脂組成物の温度を上げ、充分に溶剤を蒸発させる工程を経ることが好ましい。また樹脂組成物の硬化に電子線照射装置を用いることもできる。このとき電子線は紫外線よりもエネルギーが高く、光重合開始剤の存在なしに重合開始種（ラジカル種）を発生でき、樹脂組成物の硬化が起こるため、光重合開始剤の添加はなくてもよい。
The curing method after applying the resin composition on the thermoplastic resin sheet or laminate by the above method is preferably a method of irradiating with ultraviolet rays or electron beams.
In addition, when using the resin composition containing a solvent, it is preferable to pass through the process of raising the temperature of a thermoplastic resin sheet and the apply | coated resin composition, and fully evaporating a solvent before a hardening process. An electron beam irradiation apparatus can also be used for curing the resin composition. At this time, the electron beam has higher energy than ultraviolet rays, and can generate a polymerization initiating species (radical species) without the presence of a photopolymerization initiator, and the resin composition is cured. Good.
前記熱可塑性樹脂シートまたは積層体を成形加工する工程としては、一般的な真空成形、プレス成形、圧空成形、または予め所望の形状にかたどられた成形型に密着させた後に成形可能な温度まで加熱し賦形する方法などが挙げられる。
なお、雄型と雌型によるプレス成形を行った後に真空吸引を行い賦形する方法など、これらの方法を組み合わせた方法を用いても良い。
また上記の成形加工は成形温度に耐えうる保護フィルムであれば用いてもよい。そのほかにシートまたは積層体の凹側に、インサートモールド射出成形法により樹脂を射出して、厚みのある積層体を作製する場合もある。もちろん用途によっては、樹脂を加熱せずに強制曲げあるいは平面状のシートのままでもよい。
The process of molding the thermoplastic resin sheet or laminate may be performed by general vacuum forming, press forming, pressure forming, or heating to a temperature at which it can be formed after being in close contact with a mold previously formed into a desired shape. And a method of shaping.
In addition, you may use the method which combined these methods, such as the method of vacuum-suctioning and shaping after performing the press molding by the male type | mold and the female type | mold.
Moreover, you may use said shaping | molding process if it is a protective film which can endure a shaping | molding temperature. In addition, a thick laminate may be produced by injecting resin on the concave side of the sheet or laminate by an insert mold injection molding method. Of course, depending on the application, the resin may be forcibly bent or a flat sheet without heating.
熱可塑性樹脂シートまたは該積層体を染色処理する工程としては、インクジェット法、スプレー法、着色したフィルムを用いた貼付法などの公知の染色方法を用いることができるが、染色可能な表面層を用いることにより、いかなる染色困難な熱可塑性樹脂シートまたは積層体を用いても浸漬法により実施することができ、任意の色調、濃度に効率よく染色することが可能となる。
浸漬法で使用する染料は分散染料などが挙げられ、場合によっては水中に染料を分散させるために分散助剤などを使用する。染色は全面的に均一な色調にする必要はなく、色調に濃度勾配があっても、複数の色調に染色してもよく、染色後にその表面に対して、他の耐摩耗性膜や反射防止膜、防曇性膜などを設けてもよい。
As a process of dyeing the thermoplastic resin sheet or the laminate, a known dyeing method such as an inkjet method, a spray method, or a sticking method using a colored film can be used, but a dyeable surface layer is used. Therefore, even if any difficult-to-dye thermoplastic resin sheet or laminate is used, it can be carried out by the dipping method, and it is possible to efficiently dye any color tone and density.
Examples of the dye used in the dipping method include disperse dyes. In some cases, a dispersion aid is used to disperse the dye in water. Dyeing does not have to be a uniform color on the entire surface, and even if there is a density gradient in the color tone, it may be dyed in multiple colors, and after the dyeing, other abrasion-resistant film and antireflection are applied to the surface A film, an antifogging film, or the like may be provided.
熱可塑性樹脂シートまたは積層体に対して、染色可能な表面層を設ける工程、成形加工する工程、染色処理する工程の順番は特に規定されず、いずれの工程順序でもよい。
染色可能な表面層を設ける工程、成形加工する工程、染色処理する工程の順に成形体を製造する製造方法、または、染色可能な表面層を設ける工程、染色処理をする工程、成形加工する工程の順に成形体を製造する製造方法であることが好ましい。
染色可能な表面層を設ける工程、成形加工する工程、染色処理する工程の順に成形体を製造する製造方法の場合は、複雑な染色方法、例えば色調に濃淡をつけたグラデーション染色や、複数色での染色など、個々の成形体に任意の色合いで染色、また所望の数量を生産する際に好適である。
また、染色可能な表面層を設ける工程、染色処理をする工程、成形加工する工程の順に成形体を製造する製造方法の場合は、熱可塑性樹脂シートまたは積層体を一括で染色した後に所望の形に成形する際に好ましい。従来であれば成形加工後に染色可能な表面処理を個々の成形体に対して施すのに対して、該工程順の通り染色可能な表面層を設ける工程を最初に行うことでシート状の熱可塑性樹脂に対し、一括で表面層を設けることができ、効率的に染色された成形体を得ることができる。
また従来通り成形加工後に表面処理工程を経て、染色工程を経る製造方法でも染色された成形体を得ることができる。なお、本発明で用いる表面層は染色性、成形性に影響がない範囲であれば、他の機能、例えば耐磨耗性や防曇性を付与させてもよい。
The order of the step of providing a dyeable surface layer, the step of forming, and the step of dyeing the thermoplastic resin sheet or laminate is not particularly defined, and any order may be used.
A process for providing a dyeable surface layer, a molding process, a manufacturing method for producing a molded article in the order of the dyeing process, or a process for providing a dyeable surface layer, a dyeing process, and a molding process. It is preferable that it is a manufacturing method which manufactures a molded object in order.
In the case of a manufacturing method for producing a molded product in the order of a process for providing a dyeable surface layer, a molding process, and a dyeing process, a complex dyeing method, for example, gradation dyeing with shades of shades or multiple colors This method is suitable for dyeing individual molded articles in an arbitrary color and producing a desired quantity.
In the case of a production method for producing a molded article in the order of a step of providing a surface layer capable of being dyed, a step of dyeing treatment, and a step of molding, the desired shape is obtained after dyeing the thermoplastic resin sheet or laminate in a lump. It is preferable when it is molded. Conventionally, surface treatment that can be dyed after molding processing is performed on individual molded products, whereas sheet-like thermoplasticity is performed by first performing a step of providing a dyeable surface layer in the order of the steps. A surface layer can be provided in a lump for the resin, and an efficiently dyed molded product can be obtained.
Moreover, the dyed molded object can be obtained also by the manufacturing method which passes a surface treatment process after a shaping | molding process as usual, and passes a dyeing process. In addition, as long as the surface layer used by this invention is a range which does not affect dyeability and a moldability, you may give other functions, for example, abrasion resistance and anti-fogging property.
本発明の染色可能な表面層に用いる樹脂組成物としては、アクリレート重合体を含むことで、成形性だけでなく、耐磨耗性や防曇性などを付与することが容易であるため好まし
い。
アクリレート重合体としては、例えば脂肪族（メタ）アクリレートモノマー（オリゴマー）、芳香族（メタ）アクリレートモノマー（オリゴマー）、ウレタン（メタ）アクリレートモノマー（オリゴマー）、エポキシ（メタ）アクリレートモノマー（オリゴマー）、ポリエステル（メタ）アクリレートモノマー（オリゴマー）ポリエーテル（メタ）アクリレートモノマー（オリゴマー）などを用いて重合させたアクリレート重合体が使用可能である。
上記のモノマーやオリゴマーの構造を分子中に複数含むアクリレート重合体が好ましく、例えば脂肪族ウレタン（メタ）アクリレートモノマー（オリゴマー）、または２種類以上のモノマー（オリゴマー）を用いてもよい。
なかでも炭素数２以上５以下、繰り返し単位が６以上であるアルキレングリコールを一種以上有する（メタ）アクリレートモノマーまたはオリゴマーを用いて重合させたアクリレート重合体が好ましい。
上記範囲内である（メタ）アクリレートモノマーまたはオリゴマーを用いることで染色性に寄与するために十分な親水性を有することができる。
それらのなかでも炭素数が２〜３のエチレン、プロピレングリコールを有し、繰り返し単位数が６〜１２であるアクリレートモノマーを用いて重合させたアクリレート重合体であることが好ましい。被染色層としての染色性を得やすいとともに、耐熱成形性を得ることができるからである。
また、４官能以上のアクリレートを用いて重合させたアクリレート重合体であることで耐磨耗性を付与することもできる。
As a resin composition used for the dyeable surface layer of the present invention, it is preferable to include an acrylate polymer because it is easy to impart not only moldability but also abrasion resistance and antifogging property.
Examples of the acrylate polymer include aliphatic (meth) acrylate monomer (oligomer), aromatic (meth) acrylate monomer (oligomer), urethane (meth) acrylate monomer (oligomer), epoxy (meth) acrylate monomer (oligomer), and polyester. An acrylate polymer polymerized using a (meth) acrylate monomer (oligomer) polyether (meth) acrylate monomer (oligomer) or the like can be used.
An acrylate polymer containing a plurality of the above monomer or oligomer structures in the molecule is preferable. For example, an aliphatic urethane (meth) acrylate monomer (oligomer) or two or more types of monomers (oligomer) may be used.
Among them, an acrylate polymer obtained by polymerization using a (meth) acrylate monomer or oligomer having at least one alkylene glycol having 2 to 5 carbon atoms and 6 or more repeating units is preferable.
By using a (meth) acrylate monomer or oligomer within the above range, it can have sufficient hydrophilicity to contribute to dyeability.
Among these, an acrylate polymer obtained by polymerization using an acrylate monomer having ethylene having 2 to 3 carbon atoms and propylene glycol and having 6 to 12 repeating units is preferable. This is because it is easy to obtain dyeability as a dyed layer and heat resistance moldability can be obtained.
Moreover, abrasion resistance can also be provided by being an acrylate polymer polymerized using a tetrafunctional or higher functional acrylate.
なお、本発明で用いる染色可能な表面層に用いられる樹脂組成物は、染色性、成形性を保つ範囲内であれば、他の添加剤を添加してもよい。
例えば、光重合開始剤、増粘剤、溶剤、表面調整剤、紫外線吸収剤、近赤外線吸収剤、フォトクロミック性色素などの添加剤が挙げられる。特に紫外線硬化型樹脂組成物を硬化させるため、光重合開始剤を添加することが望ましい。
なお、前出の電子線照射装置による重合を行う際には、上記光重合開始剤は用いなくてもよい。
The resin composition used for the dyeable surface layer used in the present invention may be added with other additives as long as the dyeability and moldability are maintained.
Examples thereof include additives such as a photopolymerization initiator, a thickener, a solvent, a surface conditioner, an ultraviolet absorber, a near infrared absorber, and a photochromic dye. In particular, it is desirable to add a photopolymerization initiator in order to cure the ultraviolet curable resin composition.
In addition, when performing the polymerization using the above-described electron beam irradiation apparatus, the photopolymerization initiator may not be used.
本発明で用いる染色可能な表面層に他の機能（例えば、耐摩耗性、防曇性、反射防止性）も付与していれば、染色処理する工程、成形加工する工程の後に、上記の他の機能を付与することは不要となる。
例えば、染色可能な表面層に用いる樹脂組成物に耐磨耗性を付与させるには、樹脂組成物に含まれるアクリレートモノマーやオリゴマーの官能基数を調整することで得られる。
特に耐摩耗性、防曇性に優れた表面層を用いることで染色された成形体を得た後に、耐摩耗性または防曇性改善を目的とした表面処理を行わなくてもよいため、成形体を得た後の工程を省くことができる。
また、上記の他の機能を付与することで染色可能な熱可塑性樹脂シートや積層体に対しても、表面層を設ける工程を最初に行い、後に順序は問わないが成形加工する工程、染色処理する工程行う製造方法により、効率的に染色された耐磨耗性、もしくは防曇性に優れた成形体を得ることができる。
If the dyeable surface layer used in the present invention has other functions (for example, abrasion resistance, antifogging properties, and antireflection properties), after the dyeing process and the molding process, It is not necessary to provide the function.
For example, in order to give abrasion resistance to the resin composition used for the surface layer which can be dyed, it can be obtained by adjusting the number of functional groups of acrylate monomers and oligomers contained in the resin composition.
In particular, after obtaining a molded product dyed by using a surface layer with excellent wear resistance and antifogging properties, it is not necessary to perform surface treatment for the purpose of improving wear resistance or antifogging properties. The process after obtaining the body can be omitted.
In addition, for the thermoplastic resin sheet or laminate that can be dyed by providing the other functions described above, the step of providing a surface layer is first performed, and the molding process and dyeing process are performed regardless of the order. By the manufacturing method to be performed, it is possible to obtain a molded body that is efficiently dyed and has excellent wear resistance or antifogging properties.
本発明の製造方法で作製される眼鏡としては、サングラス、ゴーグル、眼鏡、水中眼鏡、などが挙げられる。
本発明の製造方法で作製される防護製品としては、保護眼鏡、保護ゴーグル、ヘルメットシールド、防毒マスク用透視板、自動車のサンルーフ、船舶の窓板、各種監視カメラ用カバー、風防、防護面などの防眩性のある防護製品である
Examples of the glasses produced by the production method of the present invention include sunglasses, goggles, glasses, underwater glasses, and the like.
Examples of protective products produced by the manufacturing method of the present invention include protective glasses, protective goggles, helmet shields, gas mask see-through plates, automobile sunroofs, ship window plates, various surveillance camera covers, windshields, protective surfaces, etc. It is an anti-glare protective product
次に、本発明の具体的な実施例および比較例について説明する。
＜実施例１＞
１）染色可能な表面層に用いられる樹脂組成物の調製
炭素数２以上５以下、繰り返し単位が６以上であるアルキレングリコールを一種以上有するアクリレートモノマーまたはアクリレートオリゴマーとして、ウレタンアクリレートモノマー（ダイセルサイテック社製、ＥＢＥＣＲＹＬ２０００）２．２５ｇ、ウレタンアクリレートオリゴマー（第一工業製薬社製、ＧＸ８６４４Ｄ）２．２５ｇ、その他のアクリレート成分として、ウレタンアクリレートオリゴマー（ダイセルサイテック社製、ＥＢＥＣＲＹＬ５１２９）、３．１５ｇ、アクリレートモノマー（新中村化学社製、ＮＫエステルＡ−ＴＭＭＴ）１．３５ｇ、を混合させ、混合物を得た。
この混合物に溶剤として２−プロパノール２．２５ｇ、１−メトキシ−２−プロパノール１５．５８ｇを使用、重合開始剤（ランベルティ社製、ＫＩＰ１００Ｆ） ０．６３ｇ
、レベリング剤（共栄社製、G４１０）を０．０１６ｇ、増粘剤（山一化学社製、Z４８
２）２．２５ｇを混合させ染色可能な表面層に用いられる樹脂組成物１を調製した。
Next, specific examples and comparative examples of the present invention will be described.
<Example 1>
1) Preparation of resin composition used for dyeable surface layer Urethane acrylate monomer (manufactured by Daicel Cytec Co., Ltd.) as an acrylate monomer or acrylate oligomer having at least one alkylene glycol having 2 to 5 carbon atoms and 6 or more repeating units , EBECRYL2000), 2.25 g, urethane acrylate oligomer (Daiichi Kogyo Seiyaku Co., Ltd., GX8644D) 2.25 g, other acrylate components, urethane acrylate oligomer (Daicel Cytec, EBECRYL5129), 3.15 g, acrylate monomer (new) Nakamura Chemical Co., Ltd. (NK Ester A-TMMT) 1.35 g was mixed to obtain a mixture.
In this mixture, 2.25 g of 2-propanol and 15.58 g of 1-methoxy-2-propanol were used as solvents, and a polymerization initiator (Lamberti KIP100F) 0.63 g
, 0.016 g of leveling agent (Kyoeisha, G410), thickener (Yamaichi Chemical Co., Ltd., Z48)
2) The resin composition 1 used for the dyeable surface layer was prepared by mixing 2.25 g.
２）平板状に加工された熱可塑性樹脂シートまたは積層体の少なくとも片面に染色可能な表面層を設ける工程
熱可塑性樹脂シートに用いられる熱可塑性樹脂として、ポリカーボネート樹脂（三菱エンジニアリングプラスチック社製、ユーピロンＥ−２０００ＦＮ）を押出成形して、厚み１．５ｍｍの熱可塑性樹脂シートを得た。得られた熱可塑性樹脂シートに対して、前記樹脂組成物をバーコーターを用い、均一になるように片面に塗布した。
その後に５０℃に保ったオーブン内に１０分間放置、乾燥させた。乾燥後、８０Ｗ／ｃｍメタルハライドランプ（ウシオ電機社製）にて紫外線積算照射量９００ｍＪ／ｃｍ２の紫外線を照射し、樹脂組成物を硬化させた。
熱可塑性樹脂シートのもう片面にも上記と同様の方法により、樹脂組成物の塗布、乾燥、紫外線照射による硬化を行い、厚さ１５μｍの樹脂組成物（塗膜）を両面に有する熱可塑性樹脂シートを得た。
2) A process of providing a dyeable surface layer on at least one surface of a thermoplastic resin sheet processed into a flat plate or a laminate. As a thermoplastic resin used in the thermoplastic resin sheet, polycarbonate resin (manufactured by Mitsubishi Engineering Plastics, Iupilon E) -2000FN) was extruded to obtain a thermoplastic resin sheet having a thickness of 1.5 mm. With respect to the obtained thermoplastic resin sheet, the said resin composition was apply | coated to single side | surface so that it might become uniform using the bar-coater.
Thereafter, it was left in an oven kept at 50 ° C. for 10 minutes and dried. After drying, the resin composition was cured by irradiating with an ultraviolet ray with an integrated UV irradiation dose of 900 mJ / cm 2 with an 80 W / cm metal halide lamp (manufactured by USHIO INC.).
A thermoplastic resin sheet having a resin composition (coating film) having a thickness of 15 μm on both sides is coated on the other side of the thermoplastic resin sheet by the same method as described above, dried and cured by ultraviolet irradiation. Got.
３）成形加工する工程と染色処理する工程
上記作製した表面層を設けた熱可塑性樹脂シートを７８Φの円形状に打ち抜き、成形機ＣＰＬ３２（レマ社製）を用いて１５０℃、８分間、０．０９ＭＰａで成形型中央から真空を引き、曲率半径８８ｍｍのレンズ状成形体を得た。
作製したレンズ状成形体を用いて、１Lの水中に染料（日本化薬製、ｋａｙａｒｏｎ
ｂｌａｃｋ）を２ｇ、ラウリル酸ナトリウムを３ｇ溶かし染液とした。この染液を９０℃に熱し、レンズ状成形体を２０分間浸漬させ、染色レンズを得た。
上記作製したレンズ状成形体、染色レンズを以下の評価方法で評価し、評価結果を表１に示した。
3) Molding process and dyeing process The thermoplastic resin sheet provided with the surface layer prepared above is punched into a circular shape of 78Φ, and is formed at 150 ° C. for 8 minutes using a molding machine CPL32 (manufactured by Rema). A vacuum was drawn from the center of the mold at 09 MPa to obtain a lens-shaped molded body having a radius of curvature of 88 mm.
Using the produced lens-shaped molded body, a dye (manufactured by Nippon Kayaku, Kayalon)
black) and 2 g of sodium laurate were dissolved to obtain a dyeing solution. This dyeing liquid was heated to 90 ° C., and the lens-shaped molded body was immersed for 20 minutes to obtain a dyed lens.
The produced lens-shaped molded body and dyed lens were evaluated by the following evaluation methods, and the evaluation results are shown in Table 1.
［評価方法］
１）染色性
上記作製した染色レンズを用いて染色後透過率によって評価した。
透過率測定はスガ試験機社製のＳＣ−２−ＳＣＨで測定し、評価基準は以下の通りとした。このときポリカーボネートシートの染色前透過率は９０％であった。
Ａ：染色後透過率が１５％以上３０％未満
Ｂ：染色後透過率が３０％以上５０％未満、または５％以上１５％未満
Ｃ：染色後透過率が５０％以上、または５％未満
評価基準「Ａ」は、目的の染色濃度へ効率よく染色を行う上で適している。
評価基準「Ｃ」は非常に染まりやすい、または染まりにくいため目的の染色濃度へ染色を行うのに適していない。
評価基準「Ｂ」は評価基準「Ａ」と比較して好適ではないが、使用上十分な染色性である
。
[Evaluation method]
1) Dyeability Evaluation was made based on the transmittance after dyeing using the produced dyeing lens.
The transmittance was measured with SC-2-SCH manufactured by Suga Test Instruments Co., Ltd., and the evaluation criteria were as follows. At this time, the transmittance before dyeing of the polycarbonate sheet was 90%.
A: Transmittance after dyeing is 15% or more and less than 30% B: Transmittance after dyeing is 30% or more and less than 50%, or 5% or more and less than 15% C: Transmittance after dyeing is 50% or more, or less than 5% The criterion “A” is suitable for efficient dyeing to a target dyeing density.
The evaluation standard “C” is not suitable for dyeing to a target dyeing density because it is very easily dyed or difficult to dye.
The evaluation standard “B” is not suitable as compared with the evaluation standard “A”, but has sufficient dyeability in use.
２）耐熱成形性
上記作製したレンズ状成形体の外観評価を行い塗膜面にクラックや、その他外観不良がないか目視で確認を行った。クラックやその他外観不良がある場合を不可、ない場合を良とした。
2) Heat-resistant moldability The appearance of the produced lens-shaped molded body was evaluated, and it was visually confirmed whether there were cracks or other appearance defects on the coating film surface. The case where there was a crack or other appearance defect was judged as unacceptable, and the case where there was no crack was judged good.
＜実施例２＞
炭素数２以上５以下、繰り返し単位が６以上であるアルキレングリコールを一種以上有するアクリレートモノマーとして、アクリレートモノマー（ダイセルサイテック社製、ＥＢＥＣＲＹＬ１１）４．０５ｇ、その他のアクリレート成分として、アクリレートモノマー（新中村化学社製、ＮＫエステルＡ−ＴＭＭＴ）０．９ｇ、アクリレートモノマー（新中村化学社製、ＮＫエステルＡ−９５５０）４．０５ｇ、を混合させ、この混合物を用いたこと以外は実施例１と同様の方法にて、溶剤、重合開始剤、レベリング剤、増粘剤を混合させ、染色可能な表面層に用いられる樹脂組成物２を調製した。
得られた樹脂組成物を用いたこと以外は実施例１と同様の方法にて、染色された成形体を作製し、実施例１同様の染色性評価、耐熱成形性評価を行った。
<Example 2>
As an acrylate monomer having one or more alkylene glycols having 2 to 5 carbon atoms and 6 or more repeating units, 4.05 g of an acrylate monomer (Deccel Cytec, EBECRYL11), an acrylate monomer (Shin Nakamura Chemical) NK Ester A-TMMT (0.9 g) and acrylate monomer (Shin Nakamura Chemical Co., Ltd., NK Ester A-9550) (4.05 g) were mixed and the same as in Example 1 except that this mixture was used. By the method, a solvent, a polymerization initiator, a leveling agent, and a thickener were mixed to prepare a resin composition 2 used for a dyeable surface layer.
A dyed molded body was prepared in the same manner as in Example 1 except that the obtained resin composition was used, and the dyeability evaluation and heat resistance moldability evaluation were performed in the same manner as in Example 1.
＜実施例３＞
炭素数２以上５以下、繰り返し単位が６以上であるアルキレングリコールを一種以上有するアクリレートオリゴマーとして、メタクリレートオリゴマー（新中村化学社製、ＢＰＥ−９００）を５．１５ｇ、その他のアクリレート成分として、ウレタンアクリレートオリゴマー（ダイセルサイテック社製、ＥＢＥＣＲＹＬ５１２９）を３．８５ｇ、混合させ、この混合物を用いたこと以外は実施例１と同様の方法にて、溶剤、重合開始剤、レベリング剤、増粘剤を混合させ、染色可能な表面層に用いられる樹脂組成物３を調製した。
得られた樹脂組成物を用いたこと以外は実施例１と同様の方法にて、染色された成形体を作製し、実施例１同様の染色性評価、耐熱成形性評価を行った
＜実施例４＞
炭素数２以上５以下、繰り返し単位が６以上であるアルキレングリコールを一種以上有するアクリレートモノマーとして、ウレタンアクリレートモノマー（ダイセルサイテック社製、ＥＢＥＣＲＹＬ２０００）を４．５ｇ、その他のアクリレート成分として、アクリレートモノマー（新中村化学社製、Ａ−ＴＭＭＴ）を４．５ｇ、混合させ、この混合物を用いたこと以外は実施例１と同様の方法にて、溶剤、重合開始剤、レベリング剤、増粘剤を混合させ、染色可能な表面層に用いられる樹脂組成物４を調製した。
得られた樹脂組成物を用いたこと以外は実施例１と同様の方法にて、染色された成形体を作製し、実施例１同様の染色性評価、耐熱成形性評価を行った。
<Example 3>
As an acrylate oligomer having at least one alkylene glycol having 2 to 5 carbon atoms and 6 or more repeating units, 5.15 g of a methacrylate oligomer (BPE-900, manufactured by Shin-Nakamura Chemical Co., Ltd.), urethane acrylate as another acrylate component 3.85 g of an oligomer (manufactured by Daicel Cytec Co., Ltd., EBECRYL5129) was mixed, and a solvent, a polymerization initiator, a leveling agent, and a thickener were mixed in the same manner as in Example 1 except that this mixture was used. A resin composition 3 used for the surface layer capable of being dyed was prepared.
A dyed molded body was prepared in the same manner as in Example 1 except that the obtained resin composition was used, and the dyeability evaluation and heat resistance moldability evaluation were performed in the same manner as in Example 1. <Example 4>
As an acrylate monomer having one or more alkylene glycols having 2 to 5 carbon atoms and 6 or more repeating units, 4.5 g of urethane acrylate monomer (EBECRYL2000, manufactured by Daicel Cytec Co., Ltd.), an acrylate monomer (new) A mixture of a solvent, a polymerization initiator, a leveling agent, and a thickener was prepared in the same manner as in Example 1 except that 4.5 g of Nakamura Chemical Co., Ltd. (A-TMMT) was mixed and this mixture was used. The resin composition 4 used for the surface layer which can be dyed was prepared.
A dyed molded body was prepared in the same manner as in Example 1 except that the obtained resin composition was used, and the dyeability evaluation and heat resistance moldability evaluation were performed in the same manner as in Example 1.
＜実施例５＞
熱可塑性樹脂として、ポリエステル樹脂（ＳＫケミカル社製、スカイグリーンＪ−２００３）６０重量部と、ポリカーボネート樹脂（三菱エンジニアリングプラスチック社製、ユーピロンＥ−２０００ＦＮ）４０重量部とをミキサーで混合しベント式単軸押出機により厚み１．５ｍｍの熱可塑性樹脂シートを得た。得られた熱可塑性樹脂シートを１１０℃で熱成形加工を行ったこと以外は実施例１と同様の方法にて、染色された成形体を作製し、実施例１同様の染色性評価、耐熱成形性評価を行った。
＜実施例６＞
熱可塑性樹脂として、環状ポリオレフィン樹脂（日本ゼオン社製、ゼオノア＃１０２０Ｒ）を押出成形し、厚み１．５ｍｍの熱可塑性樹脂シートを得た。得られた熱可塑性樹脂シートを１０５℃で熱成形加工したこと以外は実施例１と同様の方法にて、染色された成形体を作製し、実施例１同様の染色性評価、耐熱成形性評価を行った。
＜実施例７＞
熱可塑性樹脂として、透明ナイロン樹脂（ＥＭＳ社製、グリルアミドＸＥ３８０５）を押出成形し、厚み１．５ｍｍの熱可塑性樹脂シートを得たこと以外は実施例１と同様の方法にて、染色された成形体を作製し、実施例１同様の染色性評価、耐熱成形性評価を行った。
<Example 5>
As a thermoplastic resin, 60 parts by weight of a polyester resin (manufactured by SK Chemical Co., Ltd., Sky Green J-2003) and 40 parts by weight of a polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., Iupilon E-2000FN) are mixed with a mixer. A thermoplastic resin sheet having a thickness of 1.5 mm was obtained by a shaft extruder. A dyed molded article was prepared in the same manner as in Example 1 except that the obtained thermoplastic resin sheet was thermoformed at 110 ° C., and the dyeability evaluation and heat-resistant molding were the same as in Example 1. Sex evaluation was performed.
<Example 6>
As the thermoplastic resin, a cyclic polyolefin resin (Zeonor # 1020R, manufactured by Nippon Zeon Co., Ltd.) was extruded to obtain a thermoplastic resin sheet having a thickness of 1.5 mm. A dyed molded body was produced in the same manner as in Example 1 except that the obtained thermoplastic resin sheet was thermoformed at 105 ° C., and the dyeability evaluation and heat resistance moldability evaluation were the same as in Example 1. Went.
<Example 7>
As a thermoplastic resin, a transparent nylon resin (manufactured by EMS, Grillamide XE3805) was extruded and molded in the same manner as in Example 1 except that a thermoplastic resin sheet having a thickness of 1.5 mm was obtained. A body was prepared, and the same dyeability evaluation and heat resistance moldability evaluation as in Example 1 were performed.
＜実施例８＞
熱可塑性樹脂積層体として、偏光性薄膜を有する厚み０．８ｍｍのポリカーボネート樹脂製積層体（住友ベークライト社製、ＰＤＨ１４０１）を用いたこと以外は実施例１と同様の方法にて、染色された成形体を作製し、実施例１同様の染色性評価、耐熱成形性評価を行った。
なお、染色性評価については、実施例１〜７と染色前の透過率が異なるため評価基準は以下の通りとし、上記作製した染色レンズを用いて染色後透過率によって評価した。
Ａ：染色後透過率が７．５％以上１５％未満
Ｂ：染色後透過率が１５％以上２５％未満、または２％以上７．５％未満
Ｃ：染色後透過率が２５％以上、または２％未満
なお評価基準「Ａ」、「Ｂ」、「Ｃ」の優劣は実施例１〜７と同様とした。
評価基準「Ａ」は、目的の染色濃度へ効率よく染色を行う上で適している。
評価基準「Ｃ」は非常に染まりやすい、または染まりにくいため目的の染色濃度へ染色を行うのに適していない。
評価基準「Ｂ」は評価基準「Ａ」と比較して好適ではないが、使用上十分な染色性である。
＜実施例９＞
実施例１と同様の樹脂組成物を表面層に形成したポリカーボネート樹脂シートを用いて、実施例１の工程の順を染色処理する工程、その後成形加工する工程の順に行った以外は、実施例１と同じ方法にて染色された成形体を作製した。得られた成形体に対して実施例１と同様の染色性評価、耐熱成形性評価を行った。
<Example 8>
Molded dyed in the same manner as in Example 1 except that a 0.8 mm thick polycarbonate resin laminate (Sumitomo Bakelite, PDH1401) having a polarizing thin film was used as the thermoplastic resin laminate. A body was prepared, and the same dyeability evaluation and heat resistance moldability evaluation as in Example 1 were performed.
In addition, about dyeing | staining evaluation, since the transmittance | permeability before Example 1-7 differs from dyeing | staining, the evaluation criteria were as follows and evaluated by the transmittance | permeability after dyeing | staining using the produced said dyeing | staining lens.
A: Transmittance after dyeing is 7.5% or more and less than 15% B: Transmittance after dyeing is 15% or more and less than 25%, or 2% or more and less than 7.5% C: Transmittance after dyeing is 25% or more, or Less than 2% Evaluation criteria "A", "B", "C" superiority or inferiority was the same as in Examples 1-7.
The evaluation criterion “A” is suitable for efficient dyeing to a target dyeing density.
The evaluation standard “C” is not suitable for dyeing to a target dyeing density because it is very easily dyed or difficult to dye.
The evaluation standard “B” is not suitable as compared with the evaluation standard “A”, but has sufficient dyeability in use.
<Example 9>
Example 1 except that the polycarbonate resin sheet having the same resin composition as that of Example 1 formed on the surface layer was subjected to the dyeing process in the order of the process of Example 1 and then the molding process. The molded object dye | stained by the same method was produced. The obtained molded product was evaluated for dyeability and heat-resistant moldability in the same manner as in Example 1.
＜比較例1＞
２００ｍｍ×４００ｍｍ、厚み１．５ｍｍのポリカーボネート樹脂シート（住友ベークライト社製、ポリカエースＥＣ１００）に対して、実施例１と同様の成形する工程、染色処理する工程、を経た成形体を得た。得られた成形体を実施例１と同様の染色性評価、成形性評価を行った。
<Comparative Example 1>
For a polycarbonate resin sheet (Sumitomo Bakelite Co., Ltd., Polyace Ace EC100) having a size of 200 mm × 400 mm and a thickness of 1.5 mm, a molded body was obtained through the same molding process and dyeing process as in Example 1. The obtained molded product was evaluated for dyeability and moldability in the same manner as in Example 1.
実施例１〜９においては、用いた熱可塑性樹脂シートまたは積層体や染色可能な表面層の樹脂組成物が異なること、工程順が異なるが、いずれの実施例においても染色性、耐熱成形性に優れた成形体を得ることができた。
一方、比較例１においては、ポリカーボネート樹脂シートに対して、染色可能な表面層を設けずに染色を行ったため、成形性は優れるが、非常に染まりにくい結果となった。
In Examples 1 to 9, the thermoplastic resin sheet or laminate used and the resin composition of the surface layer that can be dyed are different and the order of the processes is different. An excellent molded product could be obtained.
On the other hand, in Comparative Example 1, because the polycarbonate resin sheet was dyed without providing a dyeable surface layer, the moldability was excellent, but the result was very difficult to dye.
Claims (11)
平板状に加工された熱可塑性樹脂シートまたは積層体に対して、少なくとも片面に染色可能な表面層を設ける工程、
成形加工する工程、
染色処理する工程を含む成形体の製造方法。 A method for producing a molded article that is molded using a flat-plate thermoplastic resin sheet or laminate,
A step of providing a surface layer that can be dyed on at least one side for a thermoplastic resin sheet or laminate processed into a flat plate shape,
Molding process,
The manufacturing method of the molded object including the process of dyeing-processing.
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| JPH0577277A (en) * | 1991-09-20 | 1993-03-30 | Sekisui Chem Co Ltd | Sheet for coating molding, coated molded form and manufacture of coated molded form |
| JPH05147097A (en) * | 1991-11-28 | 1993-06-15 | Mitsubishi Plastics Ind Ltd | Method for coloring drawings |
| MX9302953A (en) * | 1992-05-22 | 1994-05-31 | Avery Dennison Corp | PROCESS TO MANUFACTURE A PLASTIC PANEL PAINTED BY ELECTROSTATIC SPRAY. |
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