JP4273210B2 - Oil-based inkjet printing decorative sheet and laminate decorative material - Google Patents
Oil-based inkjet printing decorative sheet and laminate decorative material Download PDFInfo
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Abstract
Description
本発明は、特に真空成形積層法、射出成形積層法等の熱圧により成形して被着体に積層する成形同時化粧シート用に好適な油性インクジェット印刷用化粧シートおよびラミネート化粧材に関する。 The present invention relates to a decorative sheet for oil-based ink jet printing and a laminate decorative material, particularly suitable for a molded simultaneous decorative sheet that is molded by hot pressure such as vacuum molding lamination method or injection molding lamination method and laminated on an adherend.
従来から、樹脂成形品の被着体に加熱加圧により化粧シートを熱成形して積層する方法として真空成形積層法(特許文献1)、射出成形積層法(特許文献2)等が知られている。代表的なものの1種として、熱可塑性樹脂からなる基材シートに印刷層および接着剤層を順次積層してなる化粧シートがあり、このような構成とする事で被着体に表面物性や塗装感等を付与することが知られている。また、化粧シートの印刷層を形成する方法としては通常のグラビヤ印刷、オフセット印刷、シルク印刷、インクジェット印刷等公知の印刷技術が用いられているが、中でもインクジェット印刷は出力方式の簡便さ、印字品質、小ロットで印刷する場合は低コストである等の特徴があり、近年急速に普及している。しかし、水性インクジェットで印刷して得られた化粧シートを使用した場合、印刷層すなわちインク受容層は水性インクを受容するために比較的耐水性が低い材料が用いられることから、最終製品の耐水性は十分なものではなかった(特許文献3)。また、一般的に水系インクを用いたインクジェット方式で高画質の印刷が得られる印刷層すなわちインク受容層はシリカやアルミナ等の無機顔料を高比率で含有してなる場合が多く、熱成形性が必要な化粧シートの用途に使用した場合、印刷層に亀裂、割れが生じる不具合が発生することがあった。 Conventionally, a vacuum molding lamination method (Patent Document 1), an injection molding lamination method (Patent Document 2), and the like are known as methods for thermoforming and laminating a decorative sheet by heat and pressure on an adherend of a resin molded product. Yes. As one of the typical types, there is a decorative sheet in which a printing layer and an adhesive layer are sequentially laminated on a base material sheet made of a thermoplastic resin. By adopting such a configuration, surface physical properties and coating are applied to an adherend. It is known to give a feeling and the like. In addition, as a method for forming the printing layer of the decorative sheet, known printing techniques such as normal gravure printing, offset printing, silk printing, and ink jet printing are used. Among them, ink jet printing is simple in output method, print quality. In the case of printing in a small lot, there is a feature such as low cost, and it has been rapidly spread in recent years. However, when a decorative sheet obtained by printing with water-based ink jet is used, the printed layer, i.e., ink receiving layer, uses a relatively low water-resistant material to receive the water-based ink. Was not sufficient (Patent Document 3). In general, a printing layer that can obtain high-quality printing by an ink jet method using a water-based ink, that is, an ink receiving layer, often contains a high proportion of inorganic pigments such as silica and alumina, and has a thermoformability. When used for a necessary decorative sheet application, there may be a problem that the printed layer is cracked or broken.
したがって、本発明の課題は真空成形積層法、射出成形同時積層法の成形同時加飾法のように熱圧により成形して被着体に接着積層する成形同時化粧シート用に適しており、化粧シートの絵柄はインクジェット方式で記録可能でかつ耐水性に優れた化粧シートおよびラミネート化粧材を提供することが本発明の課題である。 Therefore, the object of the present invention is suitable for a simultaneous molding decorative sheet that is molded by hot pressure and bonded and laminated to an adherend, such as vacuum molding lamination method and injection molding simultaneous lamination method. It is an object of the present invention to provide a decorative sheet and a laminate decorative material in which the pattern of the sheet can be recorded by an inkjet method and has excellent water resistance.
上記課題を解決すべく本発明の化粧シートは、少なくとも熱可塑性樹脂からなる基材シートと感熱接着剤層とを積層した印刷シートの感熱接着剤層に油性インクジェット方式で絵柄を印刷してなる化粧シートであって、前記感熱接着剤層が塩化ビニル‐酢酸ビニル共重合体を20%〜100%重量部含有することを特徴とする油性インクジェット印刷用化粧シートとする。
また、本発明は、更に基材シートおよび感熱接着剤層が実質的に透明であることを特徴とする。
さらに、本発明は、前記の化粧シートの感熱接着剤層表面を熱可塑性樹脂からなる被着体の表面に熱接着積層してなるラミネート化粧材とする。
In order to solve the above-mentioned problems, the decorative sheet of the present invention is formed by printing a pattern by an oil-based ink jet method on a heat-sensitive adhesive layer of a printed sheet in which a base sheet composed of at least a thermoplastic resin and a heat-sensitive adhesive layer are laminated. A decorative sheet for oil-based ink jet printing, wherein the heat-sensitive adhesive layer contains 20% to 100% by weight of vinyl chloride-vinyl acetate copolymer.
The present invention is further characterized in that the base sheet and the heat-sensitive adhesive layer are substantially transparent.
Furthermore, the present invention provides a laminate decorative material obtained by thermally bonding and laminating the heat-sensitive adhesive layer surface of the decorative sheet to the surface of an adherend made of a thermoplastic resin.
本発明の化粧シート構成とすることで、真空成形積層法、射出成形同時積層法の成形同時加飾法のように熱圧により成形して被着体に接着積層する成形同時化粧シート用途に適しており、化粧シートの絵柄はインクジェット方式で記録されており、かつ耐水性に優れた化粧シートおよびラミネート化粧材が得られる。
By using the decorative sheet configuration of the present invention, it is suitable for use in simultaneous decorative sheet applications that are molded by hot pressure and adhesively laminated to the adherend, such as the simultaneous molding and decoration method of the vacuum molding lamination method and injection molding simultaneous lamination method. The decorative sheet pattern is recorded by an ink jet method , and a decorative sheet and a laminate decorative material excellent in water resistance can be obtained.
以下、本発明の実施の形態を説明する。
基材シートには真空成形積層法、射出成形同時積層法において成形可能な熱可塑性樹脂からなるシートを用いる。基材シートを構成する熱可塑性樹脂としては、例えば、ポリエチレン、ポリプロピレン、ポリブテン、エチレンプロピレン共重合体、エチレン‐酢酸ビニル共重合体、ポリエチレンテレフタレート、アクリル、塩化ビニル、ポリカーボネート、ポリアミド等が使用可能である。特に好ましくはメチルメタクリレート等のメタクリル酸エステルを主成分とする樹脂であって、着色やシート物性改善の目的で着色剤や添加剤を含有する事も差し支えない。また、基材シートの厚みは、加工性や印刷適正面で20μm〜300μmが望ましい。
Embodiments of the present invention will be described below.
As the base sheet, a sheet made of a thermoplastic resin that can be molded by a vacuum molding lamination method or an injection molding simultaneous lamination method is used. As the thermoplastic resin constituting the base sheet, for example, polyethylene, polypropylene, polybutene, ethylene propylene copolymer, ethylene-vinyl acetate copolymer, polyethylene terephthalate, acrylic, vinyl chloride, polycarbonate, polyamide, etc. can be used. is there. Particularly preferred is a resin mainly composed of a methacrylic acid ester such as methyl methacrylate, and it may contain a colorant or an additive for the purpose of coloring or improving sheet physical properties. Further, the thickness of the base sheet is desirably 20 μm to 300 μm in terms of workability and proper printing.
前記着色剤としては、例えばカーボンブラック、チタン白、亜鉛華、弁柄、紺青、カドミウムレッド、アゾ顔料、レーキ顔料、アントラキノン顔料、フタロシアニン顔料、キナクリドン顔料、イソインドリノン顔料、イミダゾロン顔料、ジオキサジン顔料、金粉、銀粉、銅粉、アルミニウム粉、魚鱗粉、パール顔料、蛍光顔料、夜光顔料、またはこれらから選ばれる2種以上の混合物を使用することができる。 Examples of the colorant include carbon black, titanium white, zinc white, dial, bitumen, cadmium red, azo pigment, lake pigment, anthraquinone pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, imidazolone pigment, dioxazine pigment, Gold powder, silver powder, copper powder, aluminum powder, fish scale powder, pearl pigment, fluorescent pigment, luminescent pigment, or a mixture of two or more selected from these can be used.
また、基材シートの表裏面には必要に応じ適宜公知の易接着処理、すなわちコロナ放電処理、プラズマ処理、オゾン処理、プライマー層塗工等の密着性強化処理を施しても良い。 Further, the front and back surfaces of the substrate sheet may be appropriately subjected to a known easy adhesion treatment, that is, an adhesion enhancing treatment such as corona discharge treatment, plasma treatment, ozone treatment, primer layer coating, etc., as necessary.
なお、基材シートの感熱接着剤層と反対面に射出成形樹脂やFRP補強層を設ける場合、前記射出成形樹脂やFRP補強層との密着性を確保するための易接着層を設けても良い。例えば、エチレン‐酢酸ビニル共重合体、アクリル樹脂、塩化ビニル樹脂、塩化ビニル‐酢酸ビニル共重合体、塩素化ポリプロピレン、エポキシ樹脂、セルロース、ウレタン樹脂、ポリエステル樹脂等が易接着層として使用可能である。 In the case where an injection molding resin or FRP reinforcing layer is provided on the surface opposite to the heat-sensitive adhesive layer of the base sheet, an easy adhesion layer may be provided to ensure adhesion with the injection molding resin or FRP reinforcing layer. . For example, ethylene-vinyl acetate copolymer, acrylic resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, chlorinated polypropylene, epoxy resin, cellulose, urethane resin, polyester resin, etc. can be used as an easily adhesive layer. .
感熱接着剤層は基材シート上に設けられ、被着体に対し熱接着性を有する必要があることから塩化ビニル‐酢酸ビニル共重合体を20%〜100%重量部含有する事を特徴とする。塩化ビニル‐酢酸ビニル共重合体を感熱接着剤層中に20%重量部未満であると、ABS、アクリル等各種熱可塑性樹脂材料に対し良好な接着性を得る事が出来ない。また、塩化ビニル‐酢酸ビニル共重合体を20%〜100%重量部含有する感熱接着剤層は加熱成形性が良好であり、化粧シート単独あるいは化粧シートを被着体表面に接着積層して得られるラミネート化粧材を熱成形性が必要な用途に使用した場合でも、感熱接着剤層に亀裂、割れが生じることがなく優れた成形性を示すものである。さらに、塩化ビニル‐酢酸ビニル共重合体を20%以上含有する感熱接着剤層は油性インクを用いたインクジェット方式で記録可能であることから、印字品質、小ロットで印刷する場合は低コストである等の特徴を生かした化粧シートを作成する事が出来る。 Since the heat-sensitive adhesive layer is provided on the base sheet and needs to have thermal adhesiveness to the adherend, it is characterized by containing 20% to 100% by weight of vinyl chloride-vinyl acetate copolymer. To do. When the vinyl chloride-vinyl acetate copolymer is less than 20% by weight in the heat-sensitive adhesive layer, good adhesion to various thermoplastic resin materials such as ABS and acrylic cannot be obtained. In addition, a heat-sensitive adhesive layer containing 20% to 100% by weight of vinyl chloride-vinyl acetate copolymer has good heat moldability, and is obtained by laminating a decorative sheet alone or a decorative sheet on the surface of an adherend. Even when the laminated decorative material obtained is used for an application requiring thermoformability, the heat-sensitive adhesive layer does not cause cracking or cracking and exhibits excellent moldability. Furthermore, since the heat-sensitive adhesive layer containing 20% or more of vinyl chloride-vinyl acetate copolymer can be recorded by an ink jet method using oil-based ink, the printing quality is low when printing in a small lot. It is possible to create a decorative sheet that takes advantage of the features such as.
また、感熱接着剤層は室温環境下では実質的に接着性を発現しないものとする必要がある。インクジェット印刷工程で化粧シートを搬送する際、室温環境下で化粧シート表面に接着性があると化粧シート表面と接触する搬送ロール等に接着することで搬送不良等の不具合を引き起こすからである。 In addition, the heat-sensitive adhesive layer needs to substantially not exhibit adhesiveness in a room temperature environment. This is because, when a decorative sheet is conveyed in an ink jet printing process, if the decorative sheet surface has adhesiveness in a room temperature environment, adhesion to a conveying roll or the like in contact with the decorative sheet surface causes problems such as defective conveyance.
感熱接着剤層に含有する塩化ビニル‐酢酸ビニル共重合体は、感熱接着剤層が室温環境下では実質的に接着性を発現しない状態となるよう、ガラス転移点いわゆるTgが20℃以上のものを使用することが望ましいがこれに限定されるものではない。
感熱接着剤層に使用する塩化ビニル‐酢酸ビニル共重合体の塩化ビニル‐酢酸ビニルのポリマー組成重量比率は塩化ビニル:酢酸ビニルが50:50〜96:4の範囲である事が望ましい。上記比率よりも塩化ビニルの組成比率が高いと接着性が劣り、上記比率よりも塩化ビニルの組成比率が低いと、油性インクを用いたインクジェット方式での記録適正が劣るからである。
The vinyl chloride-vinyl acetate copolymer contained in the heat-sensitive adhesive layer has a glass transition point, so-called Tg of 20 ° C or higher, so that the heat-sensitive adhesive layer does not substantially exhibit adhesiveness at room temperature. However, the present invention is not limited to this.
The vinyl chloride-vinyl acetate polymer composition weight ratio of the vinyl chloride-vinyl acetate copolymer used in the heat-sensitive adhesive layer is preferably in the range of 50:50 to 96: 4 of vinyl chloride: vinyl acetate. This is because if the composition ratio of vinyl chloride is higher than the above ratio, the adhesiveness is inferior, and if the composition ratio of vinyl chloride is lower than the above ratio, the recording suitability in the ink jet system using oil-based ink is inferior.
前記感熱接着剤層には前記塩化ビニル‐酢酸ビニル共重合体以外に各種樹脂材料、微粒子、紫外線防止剤、帯電防止剤、滑剤等を添加することが可能である。添加可能な樹脂としては具体的には、アクリル樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、ウレタン樹脂、ポリエステル樹脂、エポキシ樹脂、エチレン‐酢酸ビニル樹脂、ポリアミド樹脂等が使用可能であるがこれに限定されるものではない。添加可能な添加剤としては例えばシリカ、アルミナ、炭酸カルシウム、炭酸マグネシウム、水酸化アルミニウム、水酸化マグネシウム、酸化亜鉛、酸化マグネシウム、珪酸アルミニウム、珪酸カルシウム、ゼオライト、雲母、カーボンブラック、チタン白、亜鉛華、弁柄、紺青、カドミウムレッド、アゾ顔料、レーキ顔料、アントラキノン顔料、フタロシアニン顔料、キナクリドン顔料、イソインドリノン顔料、イミダゾロン顔料、ジオキサジン顔料、金粉、銀粉、銅粉、アルミニウム粉、魚鱗粉、パール顔料、蛍光顔料、夜光顔料、またはこれらから選ばれる2種以上の混合物等を使用することができる。 In addition to the vinyl chloride-vinyl acetate copolymer, various resin materials, fine particles, ultraviolet light inhibitors, antistatic agents, lubricants, and the like can be added to the heat-sensitive adhesive layer. Specific examples of resins that can be added include acrylic resins, vinyl chloride resins, vinyl acetate resins, urethane resins, polyester resins, epoxy resins, ethylene-vinyl acetate resins, and polyamide resins, but are not limited thereto. It is not something. Examples of additives that can be added include silica, alumina, calcium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum silicate, calcium silicate, zeolite, mica, carbon black, titanium white, and zinc white. , Petal, bitumen, cadmium red, azo pigment, lake pigment, anthraquinone pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, imidazolone pigment, dioxazine pigment, gold powder, silver powder, copper powder, aluminum powder, fish scale powder, pearl pigment , Fluorescent pigments, luminescent pigments, or a mixture of two or more selected from these pigments can be used.
感熱接着剤層の厚みは特に限定はないが、被着体との接着性を確保するため1μm以上とすることが望ましく、生産性を考慮し100μm以下とすることが望ましい。 The thickness of the heat-sensitive adhesive layer is not particularly limited, but is preferably 1 μm or more in order to ensure adhesion with the adherend, and is preferably 100 μm or less in consideration of productivity.
被着体が化粧シートと接着積層してラミネート化粧材として使用される場合、真空成形積層法、射出成形同時積層法において成形可能な熱可塑性樹脂からなるシートが被着体として使用可能である。その場合、被着体となるシートの厚みは50〜5000μm程度が使用できるが特に限定されるものではない。また、被着体となるシートも基材シートと同様、公知の易接着処理を行っても差し支えない。 When the adherend is bonded and laminated to a decorative sheet and used as a laminate decorative material, a sheet made of a thermoplastic resin that can be molded by a vacuum forming lamination method or an injection molding simultaneous lamination method can be used as the adherend. In that case, the thickness of the sheet to be the adherend can be about 50 to 5000 μm, but is not particularly limited. Moreover, the sheet | seat used as a to-be-adhered body may perform a well-known easy-adhesion process similarly to a base material sheet.
上記構成とすれば、感熱接着剤層に形成された絵柄は基材シートと被着体との間に位置し、表裏面から樹脂で保護される形となり、製造段階および最終製品状態での耐久性に優れたものとなる。例えば射出成形同時積層法の場合、基材シートの感熱接着剤層表面に被着体をラミネートしてなるラミネート化粧材を使用すれば、基材シートあるいは被着体の化粧シートと反対面に熱圧により射出される樹脂が接触する場合でも印刷層が流出したり損傷することを防止できる。 With the above configuration, the pattern formed on the heat-sensitive adhesive layer is located between the base sheet and the adherend, and is protected from the front and back by a resin, making it durable in the manufacturing stage and final product state. Excellent in properties. For example, in the case of the injection molding simultaneous lamination method, if a laminate decorative material is used, in which an adherend is laminated on the surface of the heat-sensitive adhesive layer of the base sheet, the surface opposite to the base sheet or the decorative sheet of the adherend is heated. Even when the resin injected by pressure comes into contact, the printed layer can be prevented from flowing out or being damaged.
基材シートと感熱接着剤層の間にはグラビア印刷、活版印刷、オフセット印刷、シルクスクリーン印刷、転写印刷、インクジェット印刷、手描き法等公知の印刷方法により全面ないし所望の部分に印刷層を形成しても良い。印刷で形成する柄は木目、石目、布目、砂目、文字、記号等特に限定されるものではない。 A printing layer is formed on the entire surface or a desired portion between the base sheet and the heat-sensitive adhesive layer by a known printing method such as gravure printing, letterpress printing, offset printing, silk screen printing, transfer printing, ink jet printing, and hand drawing method. May be. The pattern formed by printing is not particularly limited, such as wood grain, stone grain, cloth grain, sand grain, letters, symbols, and the like.
なお、印刷層のインキはバインダー等からなるビヒクル、着色剤、添加剤を主成分とし、バインダー樹脂にはエチレン‐酢酸ビニル共重合体、アクリル樹脂、ポリエステル樹脂、塩化ビニル樹脂、塩化ビニル‐酢酸ビニル共重合体、塩素化ポリプロピレン、エポキシ樹脂、セルロース、ウレタン樹脂等が使用可能である。また、着色剤には公知の顔料、染料が使用可能であり、例えば、前述した基材シートの説明で列挙した着色剤が使用可能である。 The ink for the printing layer is mainly composed of a vehicle consisting of a binder, colorant, and additives. The binder resin is ethylene-vinyl acetate copolymer, acrylic resin, polyester resin, vinyl chloride resin, vinyl chloride-vinyl acetate. Copolymers, chlorinated polypropylene, epoxy resins, cellulose, urethane resins and the like can be used. Moreover, a well-known pigment and dye can be used for a coloring agent, for example, the coloring agent enumerated by description of the base material sheet mentioned above can be used.
化粧シートを被着体に積層する方法について以下に記す。
(1)真空成形積層方法;特公昭56−45768号公報に記載されるように成形品等の立体形状の被着体表面と化粧シートとの間に接着剤層を介して対向し、被着体側からの真空吸引による圧力差により化粧シートを被着体に積層する方法。
(2)射出成形同時積層方法;特公昭50−19132号公報に記載されるように化粧シートを射出成形の雄雌両金型間に配置した後、流動状態の樹脂を型内に射出充填し、樹脂成形物の成形と同時にその表面に化粧シートを一体成形する射出成形同時加飾方法がある。化粧シートの絞りが深い場合は、化粧シートを真空成形法により予備成形する事が望ましい形態である。
(3)真空成形後に補強部材を積層する方法;特開平5−237924に記載されるように化粧シートを真空成形した後、ハンドレイアップ法やスプレーアップ法によってガラス繊維強化不飽和ポリエステル樹脂(以下、FRPという)等の補強部材を積層する方法が知られている。
図1は、本発明の化粧シートの形態を示す模式断面図である。
図2は、本発明のラミネート化粧材の形態を示す模式断面図である。
図3は、本発明のラミネート化粧材を真空成形装置にセットした図である。
図4は、図3においてヒーター6でラミネート化粧材を加熱軟化させた後、真空吸気孔7により減圧し、ラミネート化粧材を金型9の表面に沿って成形した状態を示す図である
以下、実施例及び比較例により本発明を更に記述する。
The method for laminating the decorative sheet on the adherend will be described below.
(1) Vacuum forming and laminating method; as described in Japanese Patent Publication No. 56-45768, the surface of a three-dimensional adherend such as a molded article and the decorative sheet are opposed to each other with an adhesive layer and attached. A method of laminating a decorative sheet on an adherend by a pressure difference due to vacuum suction from the body side.
(2) Simultaneous injection molding method: As described in Japanese Patent Publication No. 50-19132, a decorative sheet is placed between both male and female molds for injection molding, and then a resin in a fluid state is injected and filled into the mold. There is an injection molding simultaneous decorating method in which a decorative sheet is integrally formed on the surface of a resin molded product at the same time. When the decorative sheet is deeply drawn, it is desirable to preform the decorative sheet by vacuum forming.
(3) A method of laminating a reinforcing member after vacuum forming; after a decorative sheet is vacuum-formed as described in JP-A-5-237924, a glass fiber reinforced unsaturated polyester resin (hereinafter referred to as a glass fiber reinforced unsaturated polyester resin) A method of laminating reinforcing members such as FRP) is known.
FIG. 1 is a schematic cross-sectional view showing the form of the decorative sheet of the present invention.
FIG. 2 is a schematic cross-sectional view showing the form of the laminated decorative material of the present invention.
FIG. 3 is a diagram in which the laminated decorative material of the present invention is set in a vacuum forming apparatus.
FIG. 4 is a view showing a state in which the laminated decorative material is heated and softened by the heater 6 in FIG. 3 and then decompressed by the
アクリル樹脂からなる厚さ75μmの透明基材シートに、塩化ビニル‐酢酸ビニル共重合体をMEKに溶解した塗液をメイヤーバーコーターにて乾燥時で10μmとなるように塗布、乾燥することで感熱接着剤層を積層して印刷シートを作成した。次いで得られた印刷シートの感熱接着剤層表面に油性インクを用いたインクジェット方式で絵柄を形成し、絵柄が形成された化粧シートを作成した。
Heat is applied by applying a coating solution prepared by dissolving vinyl chloride-vinyl acetate copolymer in MEK to a transparent substrate sheet made of acrylic resin in a thickness of 10 μm with a Mayer bar coater, and drying to 10 μm. A printed sheet was prepared by laminating an adhesive layer. Next, a pattern was formed on the surface of the heat-sensitive adhesive layer of the obtained printing sheet by an ink jet method using an oil-based ink, thereby creating a decorative sheet on which the pattern was formed.
実施例1で得られた化粧シートの感熱接着剤層表面とアクリル樹脂からなる厚さ4mmの被着体シートの表面とを対向させ、130℃に加熱された2本のゴムロールを用いてラミネートし、ラミネート化粧材を作成した。 The surface of the heat-sensitive adhesive layer of the decorative sheet obtained in Example 1 and the surface of the adherend sheet made of acrylic resin having a thickness of 4 mm are opposed to each other and laminated using two rubber rolls heated to 130 ° C. A laminated decorative material was created.
実施例1に於いて感熱接着剤層として、塩化ビニル‐酢酸ビニル共重合体が20重量部とポリメタクリルメタクリレート樹脂が80重量部をMEKに溶解した塗液を使用した以外は実施例1と同様に絵柄が形成された化粧シートを作成した。 As in Example 1, except that a coating solution in which 20 parts by weight of vinyl chloride-vinyl acetate copolymer and 80 parts by weight of polymethacryl methacrylate resin was dissolved in MEK was used as the heat-sensitive adhesive layer. A decorative sheet with a pattern was created.
実施例1に於いて基材シートにA-PETの厚さ200μmを使用した以外は実施例1と同様に絵柄が形成された化粧シートを作成した。 A decorative sheet on which a pattern was formed was prepared in the same manner as in Example 1 except that A-PET thickness of 200 μm was used for the base sheet in Example 1.
実施例1に於いて感熱接着剤層として、塩化ビニル‐酢酸ビニル共重合体50重量部をMEKに溶解した樹脂溶液に酸化チタン50重量部を分散した塗液を使用した以外は実施例1と同様に絵柄が形成された化粧シートを作成した。 Example 1 is the same as Example 1 except that a coating solution in which 50 parts by weight of titanium oxide is dispersed in a resin solution in which 50 parts by weight of vinyl chloride-vinyl acetate copolymer is dissolved in MEK is used as the heat-sensitive adhesive layer. Similarly, a decorative sheet on which a pattern was formed was prepared.
実施例2に於いて感熱接着剤層として、塩化ビニル‐酢酸ビニル共重合体50重量部をMEKに溶解した樹脂溶液に酸化チタン50重量部を分散した塗液を使用した以外は実施例1と同様に絵柄が形成されたラミネート化粧材を作成した。
実施例1から6で得られた化粧シートおよびラミネート化粧材を真空成形装置で真空成形したところ、化粧シートおよび形成された絵柄にクラックや割れの発生もなく、かつ得られた成形物は耐水性に優れるものであった。また、実施例1から6で得られた化粧シートおよびラミネート化粧材を真空成形装置で真空成形して作成した成形物は基材シート側から見た場合でも透明性が高く、印刷が鮮明であり意匠性が特に優れていた。
Example 2 is the same as Example 1 except that a coating solution in which 50 parts by weight of titanium oxide is dispersed in a resin solution in which 50 parts by weight of vinyl chloride-vinyl acetate copolymer is dissolved in MEK is used as the heat-sensitive adhesive layer. Similarly, a laminate decorative material having a pattern formed thereon was prepared.
When the decorative sheet and the laminate decorative material obtained in Examples 1 to 6 were vacuum-formed with a vacuum forming apparatus, the decorative sheet and the formed pattern were free from cracks and cracks, and the resulting molded product was water resistant. It was excellent. In addition, the molded product prepared by vacuum forming the decorative sheet and the laminate decorative material obtained in Examples 1 to 6 with a vacuum forming apparatus has high transparency even when viewed from the substrate sheet side, and printing is clear. The design was particularly excellent.
[比較例1]アクリル樹脂からなる厚さ75μmの透明基材シートに、塩化ビニル‐酢酸ビニル共重合体が10重量部とポリメタクリルメタクリレート樹脂が90重量部をMEKに溶解した塗液をメイヤーバーコーターにて乾燥時で10μmとなるように塗布、乾燥することで感熱接着剤層を積層して印刷シートを作成した。次いで得られた印刷シートの感熱接着剤層表面に油性インクを用いたインクジェット方式で絵柄を形成したところ、印刷適性が悪く、絵柄が滲んでおり意匠性に劣るものであった。
[比較例2]実施例1に於いて基材シートとして、2軸延伸PETの厚み75μmを使用した以外は実施例1と同様に絵柄が形成された化粧シートを作成した。得られた化粧シートおよびラミネート化粧材を真空成形装置で真空成形したところ、基材シートの成形性が悪く、所望の形状に成形することが不可能であった。
[Comparative Example 1] A Mayer bar is a coating solution prepared by dissolving 10 parts by weight of a vinyl chloride-vinyl acetate copolymer and 90 parts by weight of a polymethacryl methacrylate resin in MEK on a 75 μm thick transparent base sheet made of acrylic resin. A printed sheet was prepared by laminating a heat-sensitive adhesive layer by applying and drying to a thickness of 10 μm with a coater. Subsequently, when a pattern was formed on the surface of the heat-sensitive adhesive layer of the obtained print sheet by an ink jet method using an oil-based ink, the printability was poor, the pattern was blurred, and the design was poor.
[Comparative Example 2] A decorative sheet on which a pattern was formed was prepared in the same manner as in Example 1 except that a biaxially stretched PET thickness of 75 µm was used as the base sheet in Example 1. When the obtained decorative sheet and laminate decorative material were vacuum-formed with a vacuum forming apparatus, the base sheet was poorly moldable and could not be formed into a desired shape.
1・・・化粧シート
2・・・基材シート
3・・・感熱接着剤層(油性インクジェット方式で絵柄が印刷されている。)
4・・・被着体
5・・・ラミネート化粧材
6・・・ヒーター
7・・・真空吸気孔
8・・・クランプ
9・・・金型
DESCRIPTION OF
4 ...
Claims (3)
An oil-based inkjet system is used for a heat-sensitive adhesive layer of a printing sheet in which a base sheet made of at least a thermoplastic resin and a heat-sensitive adhesive layer containing 20% to 100% by weight of a vinyl chloride-vinyl acetate copolymer are laminated. A decorative sheet printed with a pattern .
A laminate decorative material obtained by thermally bonding and laminating the heat-sensitive adhesive layer surface of the decorative sheet according to any one of claims 1 and 2 on the surface of an adherend made of a thermoplastic resin.
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