JP2004299384A - Decorative sheet with protecting sheet and method for manufacturing decorative molding - Google Patents
Decorative sheet with protecting sheet and method for manufacturing decorative molding Download PDFInfo
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- JP2004299384A JP2004299384A JP2003430034A JP2003430034A JP2004299384A JP 2004299384 A JP2004299384 A JP 2004299384A JP 2003430034 A JP2003430034 A JP 2003430034A JP 2003430034 A JP2003430034 A JP 2003430034A JP 2004299384 A JP2004299384 A JP 2004299384A
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- 238000000465 moulding Methods 0.000 title claims description 23
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- 239000012948 isocyanate Substances 0.000 claims abstract description 6
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 6
- 125000005641 methacryl group Chemical group 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims description 44
- 239000011241 protective layer Substances 0.000 claims description 40
- 239000010410 layer Substances 0.000 claims description 30
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- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 claims description 7
- 238000001746 injection moulding Methods 0.000 claims description 6
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- 208000027418 Wounds and injury Diseases 0.000 abstract 2
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 7
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 5
- 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 5
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- MAHNDIUOLBEJMG-UHFFFAOYSA-N 1-chloropenta-1,4-dien-3-one Chemical compound ClC=CC(=O)C=C MAHNDIUOLBEJMG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- 238000007598 dipping method Methods 0.000 description 2
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- 238000007666 vacuum forming Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- IPZIVCLZBFDXTA-UHFFFAOYSA-N ethyl n-prop-2-enoylcarbamate Chemical compound CCOC(=O)NC(=O)C=C IPZIVCLZBFDXTA-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
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- 239000013557 residual solvent Substances 0.000 description 1
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- 229910052814 silicon oxide Inorganic materials 0.000 description 1
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- 239000004575 stone Substances 0.000 description 1
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Images
Landscapes
- Laminated Bodies (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
Description
本発明は、保護シート付き加飾シートおよびこれを用いた加飾成形品の製造方法に関する。 The present invention relates to a decorative sheet with a protective sheet and a method for manufacturing a decorative molded product using the same.
先行公知文献として、深い絞りの３次元形状のインサート成形品表面に耐磨耗性および耐薬品性を付与するための積層フィルムおよび表面に耐磨耗性および耐薬品性を付与された深い絞りの３次元形状のインサート成形品の製造方法という特許文献１がある。この発明の積層フィルムは、耐熱性の離型フィルムと、離型フィルムの離型面上に形成された特定の材質からなる転写層と、賦形性フィルムとからなるものであり、離型フィルムの離型面と接する転写層表面には柔軟性に富んだ未硬化樹脂成分を含む表面保護層が形成されている。 As a prior known document, a laminated film for imparting abrasion resistance and chemical resistance to the surface of a deep drawn three-dimensional insert molded product and a deep drawn surface provided with abrasion resistance and chemical resistance on the surface are disclosed. Patent Document 1 discloses a method for producing a three-dimensional insert molded product. The laminated film of the present invention is composed of a heat-resistant release film, a transfer layer made of a specific material formed on a release surface of the release film, and a shape-forming film. A surface protective layer containing an uncured resin component having high flexibility is formed on the surface of the transfer layer in contact with the release surface.
そして、この積層フィルムから耐磨耗性および耐薬品性を付与された深い絞りの３次元形状のインサート成形品を製造する方法は、積層フィルムから離型フィルムを剥離除去し、残された転写層と賦形性フィルムとからなるインサートフィルムを、成形金型面と表面保護層とが接するように成形金型内に挿入配置し、インサート成形した後、インサート成形品の表面保護層に活性エネルギー線を照射することにより表面保護層を硬化させ耐磨耗性および耐薬品性を付与するものである。 A method of manufacturing a three-dimensional insert molded product of a deep drawing imparted with abrasion resistance and chemical resistance from the laminated film is to peel off the release film from the laminated film and remove the remaining transfer layer. An insert film consisting of a film and a shape-forming film is inserted and arranged in a molding die so that the molding die surface and the surface protective layer are in contact with each other, and after insert molding, the active energy ray is applied to the surface protective layer of the insert molded product. Irradiation cures the surface protective layer to impart abrasion resistance and chemical resistance.
しかし、上記方法でインサート成形を繰り返すと、表面保護層が成形金型面に常時触れたままの状態にさらされているため、表面保護層に含まれる未硬化樹脂成分が成形金型面に徐々に付着、堆積して成形金型面の平滑性を損ない、インサート成形品表面にその堆積物の凹凸形状が転移してしまう不具合があり、頻繁に成形金型面を掃除しなければならないという問題があった。また未硬化樹脂成分を含む表面保護層は非常に傷付きやすく、成形工程において取り扱いが難しいという問題もあった。 However, when insert molding is repeated by the above method, since the surface protective layer is always kept in contact with the molding die surface, the uncured resin component contained in the surface protective layer is gradually applied to the molding die surface. There is a problem that the smoothness of the molding die surface is impaired by depositing on the surface of the molding die, and the irregularities of the deposit are transferred to the surface of the insert molded product, and the molding die surface must be frequently cleaned. was there. In addition, the surface protective layer containing the uncured resin component is very easily damaged and has a problem that it is difficult to handle in the molding process.
そこで、本発明者は、上記問題点を解決するため、加飾層が形成された賦形性シート上に、メタアクリル当量１００〜３００ｇ／ｅｑ、水酸基価２０〜５００、重量平均分子量５０００〜５００００のポリマーと多官能イソシアネートとを有効成分として含有する熱または活性エネルギー線硬化性樹脂組成物からなる厚み３〜７０μｍの表面保護層が形成され、該表面保護層の上に厚み２０〜２００μｍの保護シートが貼付された保護シート付き加飾シートを発明した。 Then, in order to solve the above-mentioned problems, the present inventor has stated that a methacryl equivalent of 100 to 300 g / eq, a hydroxyl value of 20 to 500, and a weight average molecular weight of 5,000 to 50,000 are formed on a shape-forming sheet on which a decorative layer is formed. Of a heat or active energy ray-curable resin composition containing the polymer of the formula (1) and a polyfunctional isocyanate as active ingredients, and a protective layer having a thickness of 3 to 70 μm is formed. We have invented a decorative sheet with a protective sheet to which a sheet is attached.
すなわち、本発明は、特定材質および特定膜厚の表面保護層を選定し、特定膜厚の保護シートを設けた高い表面硬度を持った深い絞りの３次元形状のインサート成形品を得るための保護シート付き加飾シートであり、表面保護層の未硬化樹脂成分が成形金型面に付着しないため、頻繁に成形金型面を掃除するという手間がかからなくなる。また、保護シートが表面保護層に傷が付くのを防止しているため、取り扱いがしやすくなる。 That is, the present invention selects a surface protection layer of a specific material and a specific thickness, and provides protection for obtaining a deep drawn three-dimensional insert molded product having a high surface hardness provided with a protection sheet of a specific thickness. Since it is a decorative sheet with a sheet and the uncured resin component of the surface protective layer does not adhere to the molding die surface, it is not necessary to frequently clean the molding die surface. Further, since the protective sheet prevents the surface protective layer from being damaged, the handling becomes easy.
また、本発明は、保護シートが、ポリエチレンシート上にエチレンビニルアルコール樹脂を主成分とする粘着層が形成された保護シートである保護シート付き加飾シートであってもよい。また、本発明は、賦形性シートが、鉛筆硬度Ｆ以上で厚み５０〜３００μｍの賦形性シートである保護シート付き加飾シートであってもよい。 Further, the present invention may be a decorative sheet with a protective sheet, wherein the protective sheet is a protective sheet in which an adhesive layer mainly composed of an ethylene vinyl alcohol resin is formed on a polyethylene sheet. Moreover, the present invention may be a decorative sheet with a protective sheet, wherein the shape-forming sheet is a shape-forming sheet having a pencil hardness of F or more and a thickness of 50 to 300 μm.
また、本発明は、保護シート付き加飾シートを射出成形金型に挿入し、該射出成形金型に成形樹脂を射出して加飾成形品を得た後、保護シートを剥離し、加飾成形品表面の表面保護層に活性エネルギー線を照射して表面保護層を硬化させることを特徴とする加飾成形品の製造方法である。 The present invention also provides a decorative sheet with a protective sheet, which is inserted into an injection mold, and a molding resin is injected into the injection mold to obtain a decorative molded product. A method for producing a decorative molded product, characterized in that the surface protective layer on the surface of the molded product is irradiated with active energy rays to cure the surface protective layer.
したがって、本発明の保護シート付き加飾シートは、表面保護層の未硬化樹脂成分が成形金型面に付着したりすることがなく、頻繁に成形金型面を掃除するという手間がかからなくなる効果がある。また、保護シートが表面保護層に傷が付くのを防止しているため、取り扱いがしやすくなり、高い表面硬度を持った所望の加飾成形品を容易に得られる効果がある。 Therefore, in the decorative sheet with a protective sheet of the present invention, the uncured resin component of the surface protective layer does not adhere to the molding die surface, and the trouble of frequently cleaning the molding die surface is eliminated. effective. In addition, since the protective sheet prevents the surface protective layer from being damaged, it is easy to handle, and there is an effect that a desired decorative molded product having high surface hardness can be easily obtained.
以下、図面を参照しながら詳細に説明する。図１は、この発明の保護シート付き加飾シートの一実施例を示す断面図である。図２は、この発明の保護シート付き加飾シートにより得られた加飾成形品の一実施例を示す断面図である。 Hereinafter, this will be described in detail with reference to the drawings. FIG. 1 is a sectional view showing one embodiment of a decorative sheet with a protective sheet according to the present invention. FIG. 2 is a cross-sectional view showing one embodiment of a decorative molded product obtained by using the decorative sheet with a protective sheet according to the present invention.
保護シートは、賦形性シートと同様の深絞り性を有するシート基材上に、高温高圧のかかる成形工程を経ても表面保護層と固着したり、反応したりしない粘着層が形成された構成からなる。ただし、シート基材自身が適度な粘着性を有する場合には粘着層を省略してもよい。 A structure in which a protective sheet is formed on a sheet substrate having the same deep drawability as a shapeable sheet, and an adhesive layer that does not adhere to or react with the surface protective layer even after a molding step of high temperature and high pressure is formed. Consists of However, when the sheet substrate itself has an appropriate adhesiveness, the adhesive layer may be omitted.
保護シートのシート基材の材質としては、ポリエチレン、ポリプロピレン、ウレタン、エチレン酢酸ビニル、エチレンビニルアルコール等の樹脂から選択される単層フィルム、または上記の中から選択された２種以上の樹脂による積層フィルムまたは共重合フィルム等がある。保護シートのシート基材の厚みとしては、１０〜１８０μｍにするのが好ましい。１０μｍより薄いとしわが入りやすく、１８０μｍより厚いと取り扱いにくいためである。 As the material of the sheet base material of the protective sheet, a single-layer film selected from resins such as polyethylene, polypropylene, urethane, ethylene vinyl acetate, and ethylene vinyl alcohol, or a laminate of two or more resins selected from the above A film or a copolymer film. The thickness of the sheet substrate of the protective sheet is preferably from 10 to 180 μm. When the thickness is less than 10 μm, wrinkles are easily formed, and when the thickness is more than 180 μm, it is difficult to handle.
保護シートの粘着層の材質としては、エチレンビニルアルコール、ポリエステル、アクリル、ウレタン等の樹脂がある。粘着層の厚みは５〜１００μｍにするのが好ましい。３０μｍより薄いと粘着性が不足することがあり、１００μｍより厚いと粘着層に含まれる残留溶剤が表面保護層等を侵すことがあるためである。 Examples of the material of the adhesive layer of the protective sheet include resins such as ethylene vinyl alcohol, polyester, acrylic, and urethane. The thickness of the adhesive layer is preferably 5 to 100 μm. If the thickness is less than 30 μm, the adhesion may be insufficient, and if the thickness is more than 100 μm, the residual solvent contained in the adhesion layer may attack the surface protective layer and the like.
保護シート全体の厚みとしては、２０〜２００μｍにするのが好ましい。２０μｍより薄いと成形工程の際に保護シートが破断することがあり、２００μｍより厚いと射出成形樹脂の熱および圧力を受けて保護シートが変形したり、穴が空いたりすることがあるためである。 The thickness of the entire protective sheet is preferably 20 to 200 μm. If the thickness is less than 20 μm, the protective sheet may be broken during the molding process. If the thickness is more than 200 μm, the protective sheet may be deformed or have holes due to the heat and pressure of the injection molding resin. .
その中でも、ポリエチレンシートを基材とし、エチレンビニルアルコール樹脂を粘着層とする保護シートが好ましい。他のものに比べてすぐれた粘着性とクッション性があり、取り扱いやすく容易に加飾成形品を得ることができるためである。 Among them, a protective sheet having a polyethylene sheet as a base material and an ethylene vinyl alcohol resin as an adhesive layer is preferable. This is because it has excellent adhesiveness and cushioning properties as compared with other products, and it is easy to handle and a decorative molded product can be easily obtained.
表面保護層は、熱及び活性エネルギー線硬化性樹脂組成物からなる。熱及び活性エネルギー線硬化性樹脂組成物とは、ポリマーと多官能イソシアネートとを有効成分として含有する樹脂組成物のことである。とくに、メタアクリル等量１００〜３００ｇ／ｅｑ、水酸基価２０〜５００、重量平均分子量５０００〜５００００の熱及び活性エネルギー線硬化性樹脂組成物は、未硬化時は柔軟性に富み充分な深絞り加工が可能で、硬化後は耐磨耗性等にすぐれたハードコート塗膜を形成できる特長がある。 The surface protective layer is made of a heat and active energy ray-curable resin composition. The heat and active energy ray-curable resin composition is a resin composition containing a polymer and a polyfunctional isocyanate as active ingredients. In particular, a heat and active energy ray-curable resin composition having a methacryl equivalent of 100 to 300 g / eq, a hydroxyl value of 20 to 500, and a weight average molecular weight of 5,000 to 50,000 has sufficient flexibility and sufficient deep drawing when uncured. After curing, there is a feature that a hard coat film having excellent abrasion resistance and the like can be formed.
表面保護層の厚みは３〜７０μｍが好ましい。厚みが３μｍ未満であると所望の耐磨耗性、耐擦傷性等が得られず、厚みが７０μｍを超えると乾燥が困難となり生産性が大きく低下する。さらに、４０〜７０μｍの間は厚みを厚くしても耐磨耗性、耐擦傷性等がほとんど変わらないため、生産性の向上の点から表面保護層の厚みを３〜４０μｍにする方がより好ましい。
The thickness of the surface protective layer is preferably from 3 to 70 μm. If the thickness is less than 3 μm, desired abrasion resistance, scratch resistance and the like cannot be obtained, and if the thickness exceeds 70 μm, drying becomes difficult and productivity is greatly reduced. Furthermore, since the abrasion resistance and the abrasion resistance hardly change even if the thickness is increased between 40 and 70 μm, it is more preferable to make the thickness of the surface
表面保護層を形成する理由は、表面の耐磨耗性、耐擦傷性等を向上させるためであり、賦形性シートのみでは硬度を高くするにしても２Ｈ程度が限界で耐磨耗性や耐擦傷性等が従来のハードコート被膜に比べて劣るためである。 The reason for forming the surface protective layer is to improve the abrasion resistance and abrasion resistance of the surface. Even if the hardness is increased only by the shape-forming sheet, about 2H is a limit and the abrasion resistance and the like are limited. This is because the scratch resistance and the like are inferior to those of the conventional hard coat film.
賦形性シートは、一定水準以上の硬度と充分な深絞り性、その他基材としての諸機能を有することが求められる。 The shapeable sheet is required to have a certain level of hardness or more, sufficient deep drawability, and other various functions as a base material.
賦形性シートの硬度は、ＪＩＳ−Ｋ−５４００の測定方法において鉛筆硬度Ｆ以上であることが好ましい。鉛筆硬度Ｆ以上とするのは、下地の賦形性シートに硬度があるほどハードコート性のある表面保護層が形成されるためであり、例えば鉛筆硬度Ｆの賦形性シートを用いて本発明を実施すれば鉛筆硬度２Ｈ〜８Ｈの加飾成形品が得られるためである。 The hardness of the shape-forming sheet is preferably equal to or more than pencil hardness F in the measuring method of JIS-K-5400. The reason why the hardness is higher than the pencil hardness F is because the surface protective layer having a hard coat property is formed as the hardness of the underlying shapeable sheet is increased. Is carried out to obtain a decorative molded product having a pencil hardness of 2H to 8H.
賦形性シートの厚みは１０〜２０００μｍが好ましい。厚みが１０未満であると剛性がなく表面保護層等を設けるのが困難となり、厚みが２０００μｍを超えると深絞り加工に時間がかかり生産性が低下する。 The thickness of the shape-forming sheet is preferably from 10 to 2000 μm. If the thickness is less than 10, it is difficult to provide a surface protective layer or the like due to lack of rigidity, and if the thickness exceeds 2000 μm, deep drawing takes a long time and productivity is reduced.
賦形性シートとしては、ポリカーボネート、ポリアミド、ポリイミド、ポリエステル、アクリル、オレフィン、ウレタン、アクリロニトリルブタジエンスチレン等の樹脂から選択される単層シート、または上記の中から選択された２種以上の樹脂による積層シートまたは共重合シートが挙げられるが、耐光性などの点からアクリルシートが最も好ましい。 As the shape-forming sheet, a single-layer sheet selected from a resin such as polycarbonate, polyamide, polyimide, polyester, acrylic, olefin, urethane, acrylonitrile butadiene styrene, or a laminate of two or more resins selected from the above A sheet or a copolymer sheet may be mentioned, but an acrylic sheet is most preferable in terms of light resistance and the like.
アクリルシートは、メタクリル酸エステルやアクリル酸エステルなどの硬質のアクリル樹脂と軟質のアクリルゴムとからなる。その比率は重量％で６０：４０〜９０：１０の範囲内で、硬質のアクリル樹脂の割合が高いほど硬度が高くなり、より好ましい傾向にある。ただし、比率が重量％で９０：１０を超えるとシート化するのが困難となる。 The acrylic sheet is made of a hard acrylic resin such as a methacrylate or an acrylate and a soft acrylic rubber. The ratio is in the range of 60:40 to 90:10 by weight%, and the higher the ratio of the hard acrylic resin, the higher the hardness, which tends to be more preferable. However, when the ratio exceeds 90:10 by weight, it becomes difficult to form a sheet.
また、２種以上の樹脂シートの積層による賦形性シートの例としては、アクリルシートとアクリロニトリルブタジエンスチレンシートが積層されたものがある。これらの積層方法としては、熱ラミネート、ドライラミネートなどがある。 As an example of a shape-forming sheet formed by laminating two or more resin sheets, there is a laminate in which an acrylic sheet and an acrylonitrile-butadiene-styrene sheet are laminated. These laminating methods include thermal lamination and dry lamination.
加飾層は、木目柄、石目柄、布目柄、文字、幾何学模様、全面ベタ等の加飾したい絵柄を表現するための印刷層である。なお、加飾層は並列して複数形成してもよい。また、加飾層は賦形性シートの表面保護層形成面側に設けてもよいし、その反対側に設けてもよい。 The decorative layer is a print layer for expressing a pattern to be decorated such as a wood grain pattern, a stone grain pattern, a cloth grain pattern, a character, a geometric pattern, and a solid surface. Note that a plurality of decorative layers may be formed in parallel. The decorative layer may be provided on the surface protective layer forming surface side of the shape-forming sheet, or may be provided on the opposite side.
加飾層２の材質は、アクリル、塩化ビニル脂、硝化綿、ウレタン、塩化ゴム、アクリル−酢酸ビニル共重合、アクリル−塩化ビニル、アクリル−ウレタン等の樹脂などを挙げることができるが、特に限定されない。 Examples of the material of the decoration layer 2 include resins such as acrylic, vinyl chloride resin, nitrified cotton, urethane, chlorinated rubber, acryl-vinyl acetate copolymer, acryl-vinyl chloride, and acryl-urethane. Not done.
また、加飾層は、真空蒸着やメッキ等の方法によって、アルミニウム、クロム、銅、ニッケル、インジウム、錫、酸化珪素などの金属膜層を設けてもよい。この場合、金属膜層は全面でもパターン状でもよい。また、光輝性顔料を含んだインキや塗料を用いてパール調やメタリック調、金属光沢調等にしてもよい。 Further, as the decorative layer, a metal film layer of aluminum, chromium, copper, nickel, indium, tin, silicon oxide, or the like may be provided by a method such as vacuum evaporation or plating. In this case, the metal film layer may be in the entire surface or in a pattern. In addition, a pearl tone, a metallic tone, a metallic gloss tone, or the like may be performed by using an ink or a paint containing a glitter pigment.
加飾層の厚みは０．５μｍ〜５０μｍが好ましい。厚みが０．５μｍより薄いと、十分な意匠性が得られないという問題があり、５０μｍより厚いと、印刷後に乾燥し難いという問題があるためである。但し、金属膜層の場合は５０Å〜１２００Åが好ましい。金属膜層の膜厚が５０Åより薄いと、十分な金属光沢感が得られないという問題があり、１２００Åより厚いと、クラックが生じやすいという問題があるためである。 The thickness of the decorative layer is preferably 0.5 μm to 50 μm. If the thickness is less than 0.5 μm, there is a problem that sufficient design cannot be obtained. If the thickness is more than 50 μm, there is a problem that it is difficult to dry after printing. However, in the case of a metal film layer, the angle is preferably 50 ° to 1200 °. If the thickness of the metal film layer is less than 50 °, there is a problem that a sufficient metallic luster cannot be obtained, and if it is more than 1200 °, cracks tend to occur.
加飾層を設ける方法としては、グラビア印刷、スクリーン印刷、オフセット印刷法等の印刷法、各種コーティング法、蒸着、イオンプレーティング、スパッタ法等の金属薄膜形成法等がある。 Examples of the method for providing the decorative layer include printing methods such as gravure printing, screen printing, and offset printing, various coating methods, and metal thin film forming methods such as vapor deposition, ion plating, and sputtering.
また、賦形性シートの表面保護層と反対側の面に、必要に応じて接着層を形成してもよい。接着層の材質は、アクリル、塩化ビニル、ウレタン、ポリエステル、ポリプロピレン、ポリエチレン、ポリスチレン、ポリカーボネート脂、ビニロン、アセテート、ポリアミド等の樹脂を挙げることができ、被着体との密着性に応じて適宜好ましい材料を選択する。とくに、塩化ビニルと酢酸ビニルとアクリルの樹脂からなる接着層は、接着できる被着体の適用範囲が広く有用である。 Further, an adhesive layer may be formed on the surface of the shaping sheet opposite to the surface protective layer, if necessary. The material of the adhesive layer may be a resin such as acrylic, vinyl chloride, urethane, polyester, polypropylene, polyethylene, polystyrene, polycarbonate resin, vinylon, acetate, or polyamide, and is preferably appropriate depending on the adhesion to the adherend. Select a material. In particular, an adhesive layer made of vinyl chloride, vinyl acetate, and an acrylic resin is useful because the applicable range of the adherend that can be bonded is wide.
接着層の膜厚は０．５μｍ〜５０μｍが好ましい。膜厚が０．５μｍより薄いと、十分な密着が得られないという問題があり、５０μｍより厚いと、印刷後に乾燥し難いという問題があるためである。接着層の形成方法は、グラビア印刷、オフセット印刷、スクリーン印刷などの方法でも、塗装、ディッピング、リバースコーターなどの方法がある。 The thickness of the adhesive layer is preferably 0.5 μm to 50 μm. If the thickness is less than 0.5 μm, there is a problem that sufficient adhesion cannot be obtained. If the thickness is more than 50 μm, there is a problem that it is difficult to dry after printing. As a method for forming the adhesive layer, there are methods such as gravure printing, offset printing, and screen printing, and methods such as painting, dipping, and reverse coater.
また、各層間の密着性が乏しい場合には必要に応じてアンカー層を設けてもよい。アンカー層の材質は、アクリル、塩化ビニル、ウレタン、ポリエステル、ポリプロピレン、ポリエチレン、ポリスチレン、ポリカーボネート、ビニロン、アセテート、ポリアミド等の樹脂を挙げることができ、各層との密着性に応じて適宜好ましい材料を選択する。 If the adhesion between the layers is poor, an anchor layer may be provided as necessary. Examples of the material of the anchor layer include resins such as acrylic, vinyl chloride, urethane, polyester, polypropylene, polyethylene, polystyrene, polycarbonate, vinylon, acetate, and polyamide, and a suitable material is appropriately selected according to the adhesiveness with each layer. I do.
アンカー層の膜厚は０．５μｍ〜５０μｍが好ましい。膜厚が０．５μｍより薄いと、十分な密着が得られないという問題があり、５０μｍより厚いと印刷後に乾燥し難いという問題があるためである。アンカー層５の形成方法は、グラビア印刷、オフセット印刷、スクリーン印刷などの方法のほか、塗装、ディッピング、リバースコーターなどの方法がある。 The thickness of the anchor layer is preferably 0.5 μm to 50 μm. If the thickness is less than 0.5 μm, there is a problem that sufficient adhesion cannot be obtained. If the thickness is more than 50 μm, there is a problem that it is difficult to dry after printing. Methods for forming the anchor layer 5 include methods such as gravure printing, offset printing, and screen printing, as well as methods such as painting, dipping, and reverse coater.
得られた保護シート付き加飾シートを射出成形金型に挿入し、該射出成形金型に成形樹脂を射出すれば加飾成形品が得られる。その後は、保護シートを剥離してから加飾成形品表面の表面保護層に活性エネルギー線を照射して表面保護層を硬化させるか、加飾成形品表面の表面保護層に活性エネルギー線を照射して表面保護層を硬化させてから保護シートを剥離する。このいずれかの方法により所望の表面硬度の高い加飾成形品が得られる。 The decorative sheet with the protective sheet obtained is inserted into an injection molding die, and a molding resin is injected into the injection molding die to obtain a decorative molded product. Thereafter, the protective sheet is peeled off, and the surface protective layer on the surface of the decorative molded product is irradiated with active energy rays to cure the surface protective layer, or the surface protective layer on the surface of the decorative molded product is irradiated with active energy rays. Then, the surface protective layer is cured, and then the protective sheet is peeled off. A decorative molded article having a desired high surface hardness can be obtained by any one of these methods.
活性エネルギー線の照射量は、表面保護層の材質や厚みによって変わるが積算光量５０〜１０００ｍＷ／平方センチメートルの範囲が好ましい。積算光量が５０ｍＷ／平方センチメートル未満であると硬化不足で表面保護層の機能が得られず、積算光量が１０００ｍＷ／平方センチメートルを超えると生産性が低下するためである。 The irradiation amount of the active energy ray varies depending on the material and thickness of the surface protective layer, but is preferably in the range of 50 to 1000 mW / cm 2. If the accumulated light amount is less than 50 mW / cm 2, the function of the surface protective layer cannot be obtained due to insufficient curing, and if the accumulated light amount exceeds 1000 mW / cm 2, the productivity is reduced.
成形樹脂としては、ポリプロピレン、ポリエチレン、ポリスチレン、アクリロニトリルブタジエンスチレン、ポリカーボネート、アクリル、ウレタン、ポリエステル、アセテート、ポリアミド等の樹脂を挙げることができる。 Examples of the molding resin include resins such as polypropylene, polyethylene, polystyrene, acrylonitrile butadiene styrene, polycarbonate, acryl, urethane, polyester, acetate, and polyamide.
なお、保護シート付き加飾シートを射出成形金型に挿入する前に、真空成形、圧空成形、プレス成形などの方法により保護シート付き加飾シートを所望の深絞り三次元形状に加工しておいてもよいし、トムソン打ち抜き、金型プレス、ルーター加工などの方法により保護シート付き加飾シートを所望の形状にカットしておいてもよい。 Before inserting the decorative sheet with the protective sheet into the injection mold, the decorative sheet with the protective sheet is processed into a desired deep-drawn three-dimensional shape by a method such as vacuum forming, pressure forming, or press forming. Alternatively, the decorative sheet with a protective sheet may be cut into a desired shape by a method such as Thomson punching, die pressing, or router processing.
厚み２００μｍで鉛筆硬度Ｈのアクリルシート上に、アクリル−塩化ビニル系樹脂からなる加飾層、ウレタン系樹脂からなるアンカー層をグラビア印刷によりそれぞれ厚み３μｍで形成し、メタアクリル等量２５０ｇ／ｅｑ、水酸基価４００、重量平均分子量４００００のポリマーと多官能イソシアネートとを有効成分として含有する熱または活性エネルギー線硬化性樹脂組成物からなる表面保護層をリバースコート法により厚み４０μｍで塗布し、加飾シートを得た。 On an acrylic sheet having a thickness of 200 μm and a pencil hardness of H, a decorative layer made of an acrylic-vinyl chloride resin and an anchor layer made of a urethane resin are formed to have a thickness of 3 μm by gravure printing, and a methacryl equivalent of 250 g / eq. A surface protective layer comprising a heat or active energy ray-curable resin composition containing a polymer having a hydroxyl value of 400 and a weight average molecular weight of 40,000 and a polyfunctional isocyanate as active ingredients is applied in a thickness of 40 μm by a reverse coating method, and the decorative sheet is provided. Got.
つぎに、厚み１００μｍのポリエチレンシートにエチレンビニルアルコール樹脂からなる厚み４０μｍの粘着層が形成された保護シートを用意し、共押し出しラミネート法によって上記加飾シートの表面保護層面に貼付し、保護シート付き加飾シートを得た。 Next, a protective sheet in which a 40 μm thick adhesive layer made of ethylene vinyl alcohol resin was formed on a 100 μm thick polyethylene sheet was prepared, and was adhered to the surface protective layer surface of the decorative sheet by a co-extrusion lamination method. A decorative sheet was obtained.
この保護シート付き加飾シートを圧空成形法により深絞り三次元形状に加工し、所望の形状にカットした後、射出成形金型面に保護シートが接するように載置してポリカーボネート樹脂で射出成形した。得られた加飾成形品の表面保護層面に積算光量３００ｍＷ／平方センチメートルの紫外線を照射し、保護シートを剥離すると鉛筆硬度３Ｈの所望の加飾成形品が得られた。 This decorative sheet with a protective sheet is processed into a deep drawn three-dimensional shape by a pressure forming method, cut into a desired shape, and then placed so that the protective sheet is in contact with an injection molding die surface and injection molded with a polycarbonate resin. did. When the surface of the surface protective layer of the obtained decorative molded product was irradiated with ultraviolet rays having an integrated light amount of 300 mW / cm 2 and the protective sheet was peeled off, a desired decorative molded product having a pencil hardness of 3H was obtained.
厚み２５μｍの離型処理がされたニ軸延伸ポリエチレンテレフタレートフィルム上に、メタアクリル等量１５０ｇ／ｅｑ、水酸基価１２０、重量平均分子量８０００のポリマーと多官能イソシアネートとを主成分として含有する熱または活性エネルギー線硬化性樹脂組成物からなる表面保護層をリップコート法により厚み２０μｍで塗布し、その上にウレタン系樹脂からなるアンカー層、アクリル−塩化ビニル系樹脂からなる加飾層、塩化ビニル系樹脂からなる接着層をグラビア印刷によりそれぞれ厚み４μｍで形成した転写シートを用意した。 Heat or activity containing, as main components, a polymer having a methacryl equivalent of 150 g / eq, a hydroxyl value of 120, and a weight average molecular weight of 8000 and a polyfunctional isocyanate on a release-treated biaxially stretched polyethylene terephthalate film having a thickness of 25 μm. A surface protective layer composed of an energy ray-curable resin composition is applied to a thickness of 20 μm by a lip coating method, and an anchor layer composed of a urethane resin, a decorative layer composed of an acryl-vinyl chloride resin, a vinyl chloride resin A transfer sheet was prepared in which an adhesive layer made of gravure was formed with a thickness of 4 μm by gravure printing.
この転写シートを、あらかじめ厚み５０μｍ、鉛筆硬度Ｆのアクリルシートと厚み２００μｍのアクリロニトリルブタジエンスチレンシートとが積層された賦形性シートに熱転写し、ニ軸延伸ポリエチレンテレフタレートフィルムを剥離した。一方、厚み２０μｍのポリエチレンシートにエチレンビニルアルコール樹脂からなる厚み４０μｍの粘着層が形成された保護シートを用意し、共押し出しラミネート法によってニ軸延伸ポリエチレンテレフタレートフィルムの剥離後の表面保護層面に貼付し、保護シート付き加飾シートとした。 This transfer sheet was thermally transferred in advance to a shape-forming sheet in which an acrylic sheet having a thickness of 50 μm and a pencil hardness of F and an acrylonitrile butadiene styrene sheet having a thickness of 200 μm were laminated, and the biaxially stretched polyethylene terephthalate film was peeled off. On the other hand, a protective sheet in which a 40 μm thick adhesive layer made of ethylene vinyl alcohol resin is formed on a 20 μm thick polyethylene sheet is prepared, and affixed to the surface of the surface protective layer after peeling off the biaxially stretched polyethylene terephthalate film by coextrusion lamination. , A decorative sheet with a protective sheet.
この保護シート付き加飾シートを真空成形法により深絞り三次元形状に加工し、所望の形状にカットした後、射出成形金型面に保護シートが接するように載置してポリカーボネート／アクリロニトリルブタジエンスチレン樹脂でインサート成形した。得られた加飾成形品から保護シートを剥離し、積算光量２００ｍＷ／平方センチメートルの紫外線を照射すると、鉛筆硬度２Ｈの所望の加飾成形品が得られた。 This decorative sheet with a protective sheet is processed into a deep drawn three-dimensional shape by a vacuum forming method, cut into a desired shape, and then placed so that the protective sheet is in contact with the surface of an injection mold, and the polycarbonate / acrylonitrile butadiene styrene is placed. Insert molding was performed with resin. When the protective sheet was peeled off from the obtained decorative molded product and irradiated with ultraviolet rays having an integrated light amount of 200 mW / cm 2, a desired decorative molded product having a pencil hardness of 2H was obtained.
本発明により得られた加飾シートは、家電製品、住宅機器、事務機器、自動車部品などに利用される成形品の加飾に用いられる。 The decorative sheet obtained by the present invention is used for decorating molded articles used for home electric appliances, home appliances, office equipment, automobile parts and the like.
Ａ 加飾シート
１ 保護シート
２ 表面保護層
３ 加飾層
４ 賦形性シート
５ 成形樹脂
A Decorative sheet
1 protection sheet
2 Surface protective layer
3 Decorative layers
4 Formable sheet
5 Molding resin
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006142698A (en) * | 2004-11-22 | 2006-06-08 | Shin Etsu Polymer Co Ltd | Manufacturing method of mulyilayer molded article and multilayer molded article |
| JP2010082963A (en) * | 2008-09-30 | 2010-04-15 | Nissha Printing Co Ltd | Transfer sheet having metal thin film in part of sheet surface and polyester based anchor layer and method of manufacturing the same |
| JP2012210755A (en) * | 2011-03-31 | 2012-11-01 | Nippon Paper Chemicals Co Ltd | Laminate hard coat film for molding, method for manufacturing the same, and method for manufacturing resin molding |
| JP2013139105A (en) * | 2011-12-30 | 2013-07-18 | Nippon Paper Industries Co Ltd | Laminate hard coat film for molding, method for manufacturing the same, and method for manufacturing resin molding |
| JP2014058161A (en) * | 2013-10-29 | 2014-04-03 | Toyobo Co Ltd | Hard coat film for molding with protective film |
| JP2016193494A (en) * | 2015-03-31 | 2016-11-17 | 大日本印刷株式会社 | Decorative sheet |
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