JP2013202921A - Decorative sheet for carbon fiber-reinforced plastic, decorative composite material, and method of manufacturing the same - Google Patents
Decorative sheet for carbon fiber-reinforced plastic, decorative composite material, and method of manufacturing the same Download PDFInfo
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本発明は特定のバインダー樹脂を用いた着色層を有する炭素繊維強化プラスチック用加飾シート、並びに加飾複合材料及びその製造方法に関する。 The present invention relates to a decorative sheet for carbon fiber reinforced plastic having a colored layer using a specific binder resin, a decorative composite material, and a method for producing the same.
近年、大きな衝撃や変形応力を受けるスポーツ用具、自動車、船舶、航空機などの部材として、炭素繊維強化プラスチック（ＣＦＲＰ）複合材料を用いた成形品が提案されており、特に軽量かつ高い力学特性が求められる分野において積極的に採用されている。このＣＦＲＰ複合材料は、炭素繊維に対して熱可塑性樹脂や熱硬化性樹脂といったマトリックス樹脂を含浸させ、必要に応じて硬化させることで製造され、炭素繊維によって強化されているため物性が著しく向上し、比較的軽量でありながら強靭な部材である。
一方、意匠性の観点からは、マトリックス樹脂の美麗な光沢や、炭素繊維の織目模様を活かした精巧な立体的な意匠が好まれ、特にスポーツ用具、スポーツカー等の分野においては、ＣＦＲＰが本来有する意匠性を活かした成形品が嗜好されている。
このようなＣＦＲＰの意匠性を活かした成形品の一例として、特許文献１には、ＣＦＲＰを表面材に用いた成形品が開示されている。
In recent years, molded products using carbon fiber reinforced plastic (CFRP) composite materials have been proposed as components for sports equipment, automobiles, ships, aircraft, etc. that are subject to large impacts and deformation stresses. Has been actively adopted in certain fields. This CFRP composite material is manufactured by impregnating a carbon fiber with a matrix resin such as a thermoplastic resin or a thermosetting resin, and curing it as necessary. It is a tough member that is relatively lightweight.
On the other hand, from the viewpoint of designability, elaborate three-dimensional designs that take advantage of the beautiful luster of the matrix resin and the texture of the carbon fiber are preferred. Especially in the field of sports equipment and sports cars, CFRP is Molded products that take advantage of their inherent design are preferred.
As an example of a molded product that takes advantage of such design properties of CFRP, Patent Document 1 discloses a molded product using CFRP as a surface material.
しかしながら、こういったＣＦＲＰ複合材料の意匠は、炭素繊維の織目の凹凸パターンと黒色の組合せのみに限定されているため、例えば織目の凹凸パターンを活かしつつ色のみを変更することはできない。
また、ＣＦＲＰ複合材料の表面に塗装を施す方法も考えられるが、不透明な塗料を用いると炭素繊維の織目が隠蔽されてしまうため、ＣＦＲＰ複合材料が本来有する良好な意匠性が失われてしまう。一方、透明性の高い塗料を用いると炭素繊維の黒色により望むような色が得られない。
本発明は、このような状況下で、ＣＦＲＰ複合材料が織目の凹凸パターンなどの本来有する良好な意匠性を活かしつつ、優れた加飾を簡便に施すことのできる炭素繊維強化プラスチック用加飾シート、並びに加飾複合材料及びその製造方法を提供することを課題とする。
However, since the design of such a CFRP composite material is limited only to a combination of a carbon fiber texture uneven pattern and a black color, for example, it is not possible to change only the color while utilizing the texture uneven pattern.
Although a method of coating the surface of the CFRP composite material is also conceivable, if an opaque paint is used, the texture of the carbon fiber is concealed, so that the good design property inherent in the CFRP composite material is lost. . On the other hand, when a highly transparent paint is used, the desired color cannot be obtained due to the black color of the carbon fiber.
Under such circumstances, the present invention is a decoration for carbon fiber reinforced plastic that can be easily easily decorated while taking advantage of the good design properties that the CFRP composite material originally has, such as a textured uneven pattern. It is an object to provide a sheet, a decorative composite material, and a manufacturing method thereof.
本発明者は、前記課題を解決するために鋭意研究を重ねた結果、特定のバインダー樹脂を用いた着色層を有する炭素繊維強化プラスチック用加飾シートを用いてＣＦＲＰに加飾を施すと、着色層が炭素繊維の立体形状に追従し、得られる加飾複合材料に新規な意匠を与えることを見出した。本発明は、かかる知見に基づいて完成したものである。 As a result of intensive studies to solve the above problems, the present inventor colored CFRP using a decorative sheet for carbon fiber reinforced plastic having a colored layer using a specific binder resin. It has been found that the layer follows the three-dimensional shape of the carbon fiber and gives a new design to the resulting decorative composite material. The present invention has been completed based on such findings.
すなわち、本発明は、以下の発明を提供するものである。
［１］基材上に着色層を有する炭素繊維強化プラスチック用加飾シートであって、該着色層におけるバインダー樹脂の軟化点が１００℃未満であることを特徴とする炭素繊維強化プラスチック用加飾シート。
［２］前記着色層の厚みが０．１〜２０μｍである［１］に記載の炭素繊維強化プラスチック用加飾シート。
［３］炭素繊維にマトリックス樹脂を含浸させてなるプリプレグを１層以上配置し、該プリプレグ上に、［１］又は［２］に記載の炭素繊維強化プラスチック用加飾シートを、着色層側がプリプレグ側を向くように積層した後、一体成形することを特徴とする加飾複合材料の製造方法。
［４］前記一体成形が、加熱加圧成形により行われる［３］に記載の加飾複合材料の製造方法。
［５］炭素繊維強化プラスチック層、該炭素繊維強化プラスチック層に含まれる炭素繊維の立体形状に追従した模様を有する着色層及び基材をこの順に有することを特徴とする加飾複合材料。
That is, the present invention provides the following inventions.
[1] A decorative sheet for carbon fiber reinforced plastic having a colored layer on a substrate, wherein the softening point of the binder resin in the colored layer is less than 100 ° C. Sheet.
[2] The decorative sheet for carbon fiber reinforced plastic according to [1], wherein the colored layer has a thickness of 0.1 to 20 μm.
[3] One or more layers of a prepreg obtained by impregnating a carbon fiber with a matrix resin are arranged, and the carbon fiber reinforced plastic decorative sheet according to [1] or [2] is disposed on the prepreg, and the colored layer side is a prepreg. A method for producing a decorative composite material, wherein the layers are laminated so as to face side, and then integrally molded.
[4] The method for producing a decorative composite material according to [3], wherein the integral molding is performed by heat and pressure molding.
[5] A decorative composite material comprising a carbon fiber reinforced plastic layer, a colored layer having a pattern following the three-dimensional shape of the carbon fiber contained in the carbon fiber reinforced plastic layer, and a base material in this order.
本発明の炭素繊維強化プラスチック用加飾シートによれば、ＣＦＲＰが織目の凹凸パターンなどの本来有する良好な意匠性を活かしつつ、優れた加飾を施すことのできる炭素繊維強化プラスチック用加飾シート、並びに加飾複合材料及びその製造方法を提供することができる。 According to the decorative sheet for carbon fiber reinforced plastic of the present invention, the decorative for carbon fiber reinforced plastic that can be excellently decorated while taking advantage of the good design properties that CFRP originally has, such as an uneven pattern of a texture. A sheet, a decorative composite material, and a method for producing the same can be provided.
＜炭素繊維強化プラスチック用加飾シート＞
本発明の炭素繊維強化プラスチック用加飾シートは、基材上に着色層を有する炭素繊維強化プラスチック用加飾シートであって、該着色層におけるバインダー樹脂の軟化点が１００℃未満であることを特徴とする。
<Decoration sheet for carbon fiber reinforced plastic>
The decorative sheet for carbon fiber reinforced plastic of the present invention is a decorative sheet for carbon fiber reinforced plastic having a colored layer on a substrate, and the softening point of the binder resin in the colored layer is less than 100 ° C. Features.
［基材］
基材としては、代表的には熱可塑性樹脂からなる樹脂シートが使用される。該熱可塑性樹脂としては、一般的には、アクリロニトリル−ブタジエン−スチレン樹脂（以下「ＡＢＳ樹脂」という）、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート（ＰＥＮ）等のポリエステル樹脂、アクリル樹脂、ポリプロピレン，ポリエチレン等のポリオレフィン系樹脂、ポリカーボネート樹脂、塩化ビニル樹脂などが使用され、透明性、硬度、耐熱性等の観点からポリエステル樹脂が好ましく用いられる。また、基材は、これら樹脂の単層シート、あるいは同種又は異種樹脂による複層シートとして使用することができる。
基材を構成する熱可塑性樹脂としては、軟化点が８０℃超（より好ましくは１００℃超）のものであると、これを用いて得られる加飾複合材料には、炭素繊維の織目に由来する凹凸が表面に浮き出てこないことから、平滑性に優れた加飾複合材料が得られるため好ましい。
基材の厚さは、用途に応じて選定され、特に限定されないが、操作性、加工性、コスト等を考慮すると、１０〜５００μｍが好ましく、３０〜３００μｍがより好ましく、５０〜２５０μｍが更に好ましい。
[Base material]
As the base material, a resin sheet made of a thermoplastic resin is typically used. The thermoplastic resin is generally a polyester resin such as acrylonitrile-butadiene-styrene resin (hereinafter referred to as “ABS resin”), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), or the like. Polyolefin resins such as acrylic resin, polypropylene and polyethylene, polycarbonate resin, vinyl chloride resin and the like are used, and polyester resin is preferably used from the viewpoint of transparency, hardness, heat resistance and the like. Moreover, a base material can be used as a single layer sheet | seat of these resin, or a multilayer sheet | seat by the same kind or different resin.
The thermoplastic resin constituting the base material has a softening point of more than 80 ° C. (more preferably more than 100 ° C.), and the decorative composite material obtained using this has a carbon fiber texture. Since the unevenness | corrugation originating in does not float on the surface, since the decorative composite material excellent in smoothness is obtained, it is preferable.
The thickness of the substrate is selected according to the application and is not particularly limited. However, in consideration of operability, workability, cost, etc., 10 to 500 μm is preferable, 30 to 300 μm is more preferable, and 50 to 250 μm is still more preferable. .
これらの基材はその上に設けられる層との密着性を向上させるために、所望により、片面又は両面に酸化法や凹凸化法などの物理的又は化学的表面処理を施すことができる。
上記酸化法としては、例えばコロナ放電処理、クロム酸化処理、火炎処理、熱風処理、オゾン・紫外線処理法などが挙げられ、凹凸化法としては、例えばサンドブラスト法、溶剤処理法などが挙げられる。これらの表面処理は、基材の種類に応じて適宜選択されるが、一般にはコロナ放電処理法が効果及び操作性などの面から好ましく用いられる。
また該基材は色彩を整えるための塗装や、デザイン的な観点での模様があらかじめ形成されていても良いし、予め炭素繊維を隠蔽しない範囲において着色材を含有させた有色のものであってもよい。
These base materials can be subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides, if desired, in order to improve the adhesion with the layer provided thereon.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
In addition, the base material may be preliminarily formed with a paint for adjusting the color or a design in terms of design, and may be a colored material containing a colorant in a range not concealing the carbon fiber in advance. Also good.
［着色層］
本発明の炭素繊維強化プラスチック用加飾シートは、これを用いて製造される加飾複合材料に装飾性を与える着色層を有する。着色層は、種々のインキを用いて、基材に塗工することで設けたり、印刷機を使用して印刷することにより形成することができ、また、基材の全面に設けられていてもよいし、基材上に部分的に設けられていてもよい。
着色層を形成する方法としては、グラビア印刷などの通常の印刷方法や、グラビアコート、グラビアリバースコート、グラビアオフセットコート、スピンナーコート、ロールコート、リバースロールコートなどの通常の塗工方法が挙げられる。
[Colored layer]
The decorative sheet for carbon fiber reinforced plastic of the present invention has a colored layer that gives decorativeness to a decorative composite material produced using the decorative sheet. The colored layer can be formed by coating on a substrate using various inks, or can be formed by printing using a printing machine, and can also be formed on the entire surface of the substrate. It may be provided partially on the substrate.
Examples of the method for forming the colored layer include ordinary printing methods such as gravure printing, and ordinary coating methods such as gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, and reverse roll coating.
着色層は、絵柄層及び／又は着色ベタ層として形成されるものであり、絵柄層に形成される模様としては、木目模様、大理石模様（例えばトラバーチン大理石模様）などの岩石の表面を模した石目模様、布目や布状の模様を模した布地模様、タイル貼模様、煉瓦積模様などがあり、これらを複合した寄木、パッチワークなどの模様もある。これらの模様は通常の黄色、赤色、青色、及び黒色のプロセスカラーによる多色印刷によって形成される他、模様を構成する個々の色の版を用意して行う特色による多色印刷などによっても形成される。
また着色ベタ層としては、基材上に均一一様な着色層として形成され、基材の表面の全面に意図した色彩を与えるものである。通常不透明色で形成することが多いが、着色透明色で形成し、下地が持っている模様を活かすこともできる。
着色層の厚みは、０．１〜２０μｍが好ましく、０．１〜１５μｍがより好ましく、０．３〜１０μｍがさらに好ましい。着色層の厚みが０．１μｍ以上であると、加飾複合材料に対する加飾効果が良好となり、２０μｍ以下であると、炭素繊維の立体形状が見易くなる。
The colored layer is formed as a picture layer and / or a colored solid layer, and the pattern formed on the picture layer is a stone imitating the surface of a rock such as a wood grain pattern or a marble pattern (for example, a travertine marble pattern). There are eye patterns, fabric patterns simulating cloth and cloth-like patterns, tiled patterns, brickwork patterns, etc. There are also patterns such as parquet and patchwork that combine these. These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates constituting the pattern. Is done.
The colored solid layer is formed as a uniform and uniform colored layer on the base material, and gives the intended color to the entire surface of the base material. Usually, it is formed with an opaque color, but it can also be formed with a colored transparent color and make use of the pattern of the base.
The thickness of the colored layer is preferably from 0.1 to 20 μm, more preferably from 0.1 to 15 μm, still more preferably from 0.3 to 10 μm. When the thickness of the colored layer is 0.1 μm or more, the decoration effect on the decorative composite material is good, and when it is 20 μm or less, the three-dimensional shape of the carbon fiber is easy to see.
着色層の形成に用いるインキとしては、バインダー樹脂と、顔料、染料などの着色剤とを含有するものが使用され、さらに必要に応じて体質顔料、溶剤、安定剤、可塑剤、触媒、硬化剤などを適宜混合してもよい。
着色剤のバインダー樹脂としては、軟化点が１００℃未満（好ましくは９０℃未満、さらに好ましくは３０℃以上９０℃未満）のものを用いる必要があり、例えば、ポリウレタン系樹脂、塩化ビニル／酢酸ビニル系共重合体樹脂、塩化ビニル／酢酸ビニル／アクリル系共重合体樹脂、塩素化ポリプロピレン系樹脂、アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ブチラール系樹脂、ポリスチレン系樹脂、ニトロセルロース系樹脂、酢酸セルロース系樹脂などの中から任意のものが、１種単独で又は２種以上を混合して用いられる。なお２種以上バインダー樹脂を混合して使用する場合は、混合比率に応じた平均軟化点温度が１００℃未満であればよい。
また軟化点が１００℃未満のバインダー樹脂であれば、ＣＦＲＰが織目の凹凸パターンなどの本来有する良好な意匠性を活かしつつ、プリプレグとの接着性を向上できる点で好ましい。ここで、上記軟化点は、ＪＩＳ Ｋ５６０１−２−２塗料成分試験方法−第２部の塗料成分の軟化点試験方法である環球法を用いて測定されるものである。バインダー樹脂の軟化点が１００℃以上であると、炭素繊維強化プラスチック用加飾シートを用いて加飾複合材料を製造しても、着色層が炭素繊維の立体形状に追従しないため、本発明の効果を発現せず、また軟化点が３０℃以上であると、加熱加圧成形により一体成形を行う場合に、熱圧で溶融しにくくなるため好ましい。さらに、上記意匠性や接着性の観点からは、塩化ビニル／酢酸ビニル系共重合体、アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂又はこれらの２種以上の混合物をバインダー樹脂として用いることが好ましく、塩化ビニル／酢酸ビニル系共重合体、アクリル系樹脂、又はこれらの混合物を用いることが特に好ましい。
着色剤としては、カーボンブラック（墨）、鉄黒、チタン白、アンチモン白、黄鉛、チタン黄、弁柄、カドミウム赤、群青、コバルトブルーなどの無機顔料、キナクリドンレッド、イソインドリノンイエロー、フタロシアニンブルーなどの有機顔料又は染料、アルミニウム、真鍮などの鱗片状箔片からなる金属顔料、二酸化チタン被覆雲母、塩基性炭酸鉛などの鱗片状箔片からなる真珠光沢（パール）顔料などが用いられる。
As the ink used for forming the colored layer, an ink containing a binder resin and a colorant such as a pigment or a dye is used. If necessary, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is used. Etc. may be mixed as appropriate.
As the binder resin of the colorant, it is necessary to use a resin having a softening point of less than 100 ° C. (preferably less than 90 ° C., more preferably 30 ° C. or more and less than 90 ° C.). For example, polyurethane resin, vinyl chloride / vinyl acetate Copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, Arbitrary things are used among cellulose acetate type resin etc. individually by 1 type or in mixture of 2 or more types. In addition, when mixing and using 2 or more types of binder resin, the average softening point temperature according to a mixing ratio should just be less than 100 degreeC.
In addition, a binder resin having a softening point of less than 100 ° C. is preferable in that the CFRP can improve the adhesiveness with the prepreg while taking advantage of the good design properties inherent in the texture pattern. Here, the softening point is measured using a ring and ball method which is a JIS K5601-2-2 paint component test method-part 2 paint component softening point test method. If the softening point of the binder resin is 100 ° C. or higher, even if a decorative composite material is manufactured using a decorative sheet for carbon fiber reinforced plastic, the colored layer does not follow the three-dimensional shape of the carbon fiber. When the effect is not exhibited and the softening point is 30 ° C. or higher, it is difficult to melt by heat pressure when performing integral molding by heat and pressure molding, which is preferable. Furthermore, from the viewpoints of the design properties and adhesiveness, it is preferable to use a vinyl chloride / vinyl acetate copolymer, an acrylic resin, a polyester resin, a polyamide resin, or a mixture of two or more thereof as a binder resin. It is particularly preferable to use a vinyl chloride / vinyl acetate copolymer, an acrylic resin, or a mixture thereof.
Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metal pigments made of scaly foil pieces such as aluminum and brass, pearlescent pigments made of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.
［接着剤層］
本発明の炭素繊維強化プラスチック用加飾シートは、着色層や炭素繊維強化プラスチック層との密着性を向上させるため、所望により、基材と着色層との間や、着色層上に接着剤層を設けることができ、さらに、基材上に着色層が部分的に設けられている場合、基材が露出している部分に着色層と並列に接着剤層を設けることもできる。
接着剤層には、熱可塑性樹脂又は熱硬化性樹脂が用いられる。熱可塑性樹脂としては、アクリル樹脂、アクリル変性ポリオレフィン樹脂、塩素化ポリオレフィン樹脂、塩化ビニル−酢酸ビニル共重合体、熱可塑性ウレタン樹脂、熱可塑性ポリエステル樹脂、ポリアミド樹脂、ゴム系樹脂などが挙げられ、また、熱硬化性樹脂としては、ウレタン樹脂、エポキシ樹脂などが挙げられ、これらは１種又は２種以上を混合して用いることができる。
[Adhesive layer]
The decorative sheet for carbon fiber reinforced plastic according to the present invention improves the adhesion between the colored layer and the carbon fiber reinforced plastic layer, so that an adhesive layer is formed between the base material and the colored layer or on the colored layer as desired. Furthermore, when the colored layer is partially provided on the base material, an adhesive layer can be provided in parallel with the colored layer in a portion where the base material is exposed.
A thermoplastic resin or a thermosetting resin is used for the adhesive layer. Examples of the thermoplastic resin include acrylic resin, acrylic-modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, and rubber resin. Examples of thermosetting resins include urethane resins and epoxy resins, which can be used alone or in combination of two or more.
＜加飾複合材料の製造方法＞
上述の炭素繊維強化プラスチック用加飾シートは、加飾複合材料の製造に用いることができる。
本発明の加飾複合材料の製造方法は、炭素繊維にマトリックス樹脂を含浸させてなるプリプレグを１層以上配置し、該プリプレグ上に、上述の炭素繊維強化プラスチック用加飾シートを、着色層側がプリプレグ側を向くように積層した後、一体成形することを特徴とする。
<Method for producing decorative composite material>
The above-mentioned decorative sheet for carbon fiber reinforced plastic can be used for the production of a decorative composite material.
In the method for producing a decorative composite material of the present invention, one or more layers of a prepreg obtained by impregnating a carbon fiber with a matrix resin are disposed, and the above-mentioned decorative sheet for carbon fiber reinforced plastic is placed on the prepreg, After lamination so as to face the prepreg side, it is integrally formed.
［マトリックス樹脂］
マトリックス樹脂としては、炭素繊維のプリプレグに使用可能なものであれば特に限定されないが、例えば、エポキシ樹脂、不飽和ポリエステル樹脂、フェノール樹脂、シリコーン樹脂、ウレタン樹脂、ポリイミド樹脂等の熱硬化性樹脂や、ポリスルホン、ポリエーテルスルホン、ポリエーテルイミド、ポリイミド等の熱可塑性樹脂や各種熱可塑性エラストマーより一種又は二種以上を組み合わせて用いることができ、特にエポキシ樹脂が好ましい。
[Matrix resin]
The matrix resin is not particularly limited as long as it can be used for a carbon fiber prepreg. For example, a thermosetting resin such as an epoxy resin, an unsaturated polyester resin, a phenol resin, a silicone resin, a urethane resin, or a polyimide resin, , Polysulfone, polyethersulfone, polyetherimide, polyimide and other thermoplastic resins and various thermoplastic elastomers can be used alone or in combination of two or more, and epoxy resins are particularly preferred.
［炭素繊維］
本発明において使用される炭素繊維については特に限定されず、ポリアクリロニトリル（ＰＡＮ）系、ピッチ系等のいずれを用いても良く、またそれらが混合されているものを用いても良い。また炭素繊維の織目としては、一方向に引き揃えられた長繊維、二方向織物、多軸織物、不織布、マット、ニット、組み紐などのいずれのものであってもよい。ここでいう長繊維とは、実質的に１０ｍｍ以上連続な単繊維もしくは繊維束を意味する。
[Carbon fiber]
The carbon fiber used in the present invention is not particularly limited, and any of polyacrylonitrile (PAN) type, pitch type and the like may be used, and those in which they are mixed may be used. Further, the carbon fiber weave may be any one of long fibers arranged in one direction, bi-directional woven fabric, multiaxial woven fabric, non-woven fabric, mat, knit, braided string, and the like. The long fiber here means a single fiber or a fiber bundle substantially continuous for 10 mm or more.
［プリプレグ］
プリプレグとは、強化繊維にマトリックス樹脂を含浸させた成形中間基材であり、本発明においては、強化繊維として炭素繊維が用いられる。こういったプリプレグを必要に応じて積層、硬化することで炭素繊維強化プラスチック層が得られる。もちろん、プリプレグは単層で使用してもよいが、複数枚のプリプレグを積層して用いることもできる。
[Prepreg]
The prepreg is a molded intermediate base material in which a reinforcing fiber is impregnated with a matrix resin. In the present invention, a carbon fiber is used as the reinforcing fiber. A carbon fiber reinforced plastic layer can be obtained by laminating and curing these prepregs as necessary. Of course, the prepreg may be used as a single layer, but a plurality of prepregs may be laminated and used.
［一体成形方法］
プリプレグと、上述の炭素繊維強化プラスチック用加飾シートとを一体成形する際には、加熱加圧成形により一体成形を行うことが好ましい。加熱加圧成形を行うことで、マトリックス樹脂としてエポキシ樹脂等の熱硬化性樹脂を使用する場合には、一体成形と同時にマトリックス樹脂を加熱硬化することができ、マトリックス樹脂として熱可塑性樹脂を使用する場合には、マトリックス樹脂を軟化させつつ一体成形することができるため、生産効率に優れる。
ここで加熱加圧成形法としては、プレス成形法、オートクレーブ成形法、バッギング成形法、ラッピングテープ法および内圧成形法等が採用できるが、一体成形と同時に、マトリックス樹脂と着色層との密着性を高める観点から、プレス成形法が好ましい。
加熱加圧成形法における成形温度（又は硬化時間）は、選択したマトリクス樹脂により適宜選択してよく、例えば、エポキシ樹脂組成物の場合、含まれる硬化剤の種類などにもよるが、通常８０〜２２０℃の温度が好ましい。かかる成形温度が低すぎると、十分な速硬化性が得られない場合があり、逆に高すぎると、熱歪みによる反りが発生しやすくなったりする場合がある。
また、プレス成形法で成形する圧力としては、プリプレグの厚みなどにより異なるが、通常０．１〜１ＭＰａの圧力が好ましい。かかる成形圧力が低すぎると、プリプレグの内部まで十分に熱が伝わらず、局所的に未硬化となったり、反りが発生する場合がある。逆に高すぎると、樹脂が硬化する前に周囲に流れ出してしまい、炭素繊維強化プラスチック中にボイドが発生する場合がある。
[Integrated molding method]
When integrally forming the prepreg and the above-mentioned decorative sheet for carbon fiber reinforced plastic, it is preferable to perform integral molding by heat and pressure molding. When thermosetting resin such as epoxy resin is used as the matrix resin by performing heat and pressure molding, the matrix resin can be heat-cured simultaneously with integral molding, and a thermoplastic resin is used as the matrix resin. In this case, since the matrix resin can be integrally molded while being softened, the production efficiency is excellent.
Here, press molding method, autoclave molding method, bagging molding method, wrapping tape method, internal pressure molding method, etc. can be adopted as the heat and pressure molding method, but at the same time as the integral molding, the adhesion between the matrix resin and the colored layer is improved. From the viewpoint of enhancing, a press molding method is preferable.
The molding temperature (or curing time) in the heat and pressure molding method may be appropriately selected depending on the selected matrix resin. For example, in the case of an epoxy resin composition, depending on the type of curing agent contained, etc. A temperature of 220 ° C. is preferred. If the molding temperature is too low, sufficient rapid curability may not be obtained. Conversely, if the molding temperature is too high, warping due to thermal strain may be likely to occur.
Moreover, as a pressure shape | molded by the press molding method, although it changes with thickness of a prepreg etc., the pressure of 0.1-1 Mpa is preferable normally. If the molding pressure is too low, heat may not be sufficiently transmitted to the inside of the prepreg, resulting in uncured locally or warping. On the other hand, if it is too high, the resin will flow out before it hardens, and voids may be generated in the carbon fiber reinforced plastic.
＜加飾複合材料＞
上述の製造方法により得られる本発明の加飾複合材料は、炭素繊維強化プラスチック層、該炭素繊維強化プラスチック層に含まれる炭素繊維の立体形状に追従した模様を有する着色層及び基材をこの順に有することを特徴とする。
本発明の加飾複合材料の構成について図１を用いて詳細に説明する。図１に示す例では、炭素繊維強化プラスチック層１１上に着色層１２及び基材１３が順次積層されている。
<Decorative composite material>
The decorative composite material of the present invention obtained by the above-described manufacturing method includes a carbon fiber reinforced plastic layer, a colored layer having a pattern following the three-dimensional shape of the carbon fiber contained in the carbon fiber reinforced plastic layer, and a base material in this order. It is characterized by having.
The structure of the decorative composite material of this invention is demonstrated in detail using FIG. In the example shown in FIG. 1, a colored layer 12 and a base material 13 are sequentially laminated on a carbon fiber reinforced plastic layer 11.
［炭素繊維強化プラスチック層］
炭素繊維強化プラスチック層は、上述のように、プリプレグを必要に応じて積層、硬化することで形成される。
[Carbon fiber reinforced plastic layer]
As described above, the carbon fiber reinforced plastic layer is formed by laminating and curing a prepreg as necessary.
［着色層］
本発明に係る加飾複合材料の着色層は、上述の一体成形により炭素繊維の立体形状に追従した模様を形成する。より具体的には、例えば、ベタ塗りの着色層を有する炭素繊維強化プラスチック用加飾シートと、織物状の炭素繊維にマトリックス樹脂を含浸させたものとを用いて、ホットプレス成形により一体成形した場合、得られる加飾複合材料は、着色層に模様を有するものとなる。この模様は、炭素繊維の立体形状（織目）に追従するものであり、従来のＣＦＲＰ複合材料とは全く異なる新規な意匠性を有するものである。
[Colored layer]
The colored layer of the decorative composite material according to the present invention forms a pattern that follows the three-dimensional shape of the carbon fiber by the above-described integral molding. More specifically, for example, by using a decorative sheet for carbon fiber reinforced plastic having a solid colored layer and a fabric-like carbon fiber impregnated with a matrix resin, it is integrally formed by hot press molding. In this case, the resulting decorative composite material has a pattern on the colored layer. This pattern follows the three-dimensional shape (texture) of the carbon fiber, and has a novel design that is completely different from the conventional CFRP composite material.
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこの例によってなんら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
＜測定方法＞
（１）軟化点
ＪＩＳ Ｋ５６０１−２−２塗料成分試験方法−第２部の塗料成分の軟化点試験方法である環球法を用いて軟化点試験方法である環球法を用いて測定した。
＜評価方法＞
（１）意匠性
各実施例・比較例で得られた加飾複合材料の外観を目視で確認し、以下の基準で評価した。
○：着色層が炭素繊維の立体形状に追従した模様を示した。
×：着色層が炭素繊維の立体形状に追従した模様を示さなかったか、又は炭素繊維の織目が隠蔽されて見えなくなった。
（２）表面平滑性
各実施例・比較例で得られた加飾複合材料に映った蛍光灯の形状を目視で確認し、その鮮鋭性を以下の基準で評価した。
◎：蛍光灯が歪むことなくきれいに映った。
○：炭素繊維の織目に沿って、軽微な凹凸が表面に浮かび上がったが、蛍光灯はきれいに映った。
×：炭素繊維の織目に沿って凹凸、ピンホール状の欠点が表面に存在し、蛍光灯もぼやけて見えた。
<Measurement method>
(1) Softening point JIS K5601-2-2 Paint component test method—Measured using the ring and ball method which is the softening point test method using the ring and ball method which is the softening point test method of the paint component in Part 2.
<Evaluation method>
(1) Designability The appearance of the decorative composite material obtained in each Example / Comparative Example was visually confirmed and evaluated according to the following criteria.
A: The colored layer showed a pattern following the three-dimensional shape of the carbon fiber.
X: The colored layer did not show a pattern following the three-dimensional shape of the carbon fiber, or the texture of the carbon fiber was hidden and disappeared.
(2) Surface smoothness The shape of the fluorescent lamp reflected in the decorative composite material obtained in each of the examples and comparative examples was visually confirmed, and the sharpness was evaluated according to the following criteria.
A: The fluorescent lamp was clearly reflected without distortion.
○: A slight unevenness emerged on the surface along the texture of the carbon fiber, but the fluorescent lamp appeared fine.
X: Concavities and convexities and pinhole-like defects were present on the surface along the carbon fiber weave, and the fluorescent lamps were also blurred.
実施例１
（炭素繊維強化プラスチック用加飾シートの製造）
ポリエチレンテレフタレート基材（厚み：１８８μｍ、軟化点：１８０℃超）に、アクリル系樹脂（軟化点：６７℃）とアルミ顔料とを含むインキを用いて、全面ベタ印刷を行って着色層を形成し、炭素繊維強化プラスチック用加飾シートを得た。
Example 1
(Manufacture of decorative sheets for carbon fiber reinforced plastics)
Using an ink containing an acrylic resin (softening point: 67 ° C) and an aluminum pigment on a polyethylene terephthalate substrate (thickness: 188 µm, softening point: over 180 ° C), a solid color printing is performed to form a colored layer. A decorative sheet for carbon fiber reinforced plastic was obtained.
（加飾複合材料の製造）
炭素繊維に未硬化のエポキシ樹脂を含浸させてなるプリプレグを６層積層し、該積層プリプレグ上に、上記の炭素繊維強化プラスチック用加飾シートを、着色層側がプリプレグ側を向くように積層した後、加熱加圧成形（硬化温度：１３０℃、硬化時間：２時間、圧力：０．４９ＭＰａ）により一体成形し、板状の加飾複合材料を得た。
得られた加飾複合材料について、上記評価方法に基づいて意匠性及び表面平滑性を評価した結果を第１表に示す。
(Manufacture of decorative composite materials)
After laminating 6 layers of a prepreg obtained by impregnating carbon fiber with an uncured epoxy resin, and laminating the above-mentioned decorative sheet for carbon fiber reinforced plastic on the laminated prepreg so that the colored layer side faces the prepreg side Then, it was integrally molded by heat and pressure molding (curing temperature: 130 ° C., curing time: 2 hours, pressure: 0.49 MPa) to obtain a plate-like decorative composite material.
Table 1 shows the results of evaluating the designability and surface smoothness of the obtained decorative composite material based on the above evaluation method.
実施例２〜４及び比較例１〜３
基材や着色層を、第１表に示すものに変更した以外は、実施例１と同様にして炭素繊維強化プラスチック用加飾シート及び加飾複合材料を製造した。意匠性及び表面平滑性の評価結果を第１表に示す。
尚、比較例２では炭素繊維強化プラスチック用加飾シートを用いずに複合材料を製造したが、マトリックス樹脂が含浸しきれなかった部分でピンホール状の凹みが複数確認され、また、炭素繊維の織目に沿って艶ムラが生じた。
Examples 2 to 4 and Comparative Examples 1 to 3
A decorative sheet for carbon fiber reinforced plastic and a decorative composite material were produced in the same manner as in Example 1 except that the base material and the colored layer were changed to those shown in Table 1. Table 1 shows the evaluation results of the design properties and the surface smoothness.
In Comparative Example 2, the composite material was manufactured without using the decorative sheet for carbon fiber reinforced plastic, but a plurality of pinhole-shaped dents were confirmed in the portion where the matrix resin could not be impregnated. Uneven gloss occurred along the texture.
本発明の炭素繊維強化プラスチック用加飾シートは、自動車などの車両の内装材又は外装材、窓枠、扉枠等の建具、壁、床、天井等の建築物の内装材、テレビ受像機、空調機等の家電製品やパソコンの筐体、容器などの用途に用いられる加飾複合材料の製造に好適に用いられる。 The decorative sheet for carbon fiber reinforced plastic of the present invention is a vehicle interior material or exterior material such as an automobile, a window frame, a door frame and other building materials, a wall, a floor, a ceiling and other building interior materials, a television receiver, It is suitably used for the manufacture of decorative composite materials used for home appliances such as air conditioners, personal computer casings and containers.
１０．加飾複合材料
１１．炭素繊維強化プラスチック層
１２．着色層
１３．基材
10. 10. Decorative composite material Carbon fiber reinforced plastic layer 12. Colored layer 13. Base material
Claims (5)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013202922A (en) * | 2012-03-28 | 2013-10-07 | Dainippon Printing Co Ltd | Decorative sheet for carbon fiber reinforced plastic, decorative composite material, and method for manufacturing the same |
| JP2013226792A (en) * | 2012-03-28 | 2013-11-07 | Dainippon Printing Co Ltd | Carbon fiber-reinforced plastic laminate sheet, laminate composite material and method for manufacturing the laminate composite material |
| JP2020142487A (en) * | 2019-03-08 | 2020-09-10 | 大日本印刷株式会社 | Fiber-reinforced resin molding with hard coat layer |
| JP2021059036A (en) * | 2019-10-04 | 2021-04-15 | 和告 漆原 | Decorative sheet, method for producing the same, and molded article |
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| JPH0999510A (en) * | 1995-10-06 | 1997-04-15 | Nippon Shokubai Co Ltd | Laminate |
| JP2004098343A (en) * | 2002-09-05 | 2004-04-02 | Nissha Printing Co Ltd | Decorative sheet and manufacturing method for decorative frp molded product |
| JP2013202922A (en) * | 2012-03-28 | 2013-10-07 | Dainippon Printing Co Ltd | Decorative sheet for carbon fiber reinforced plastic, decorative composite material, and method for manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0999510A (en) * | 1995-10-06 | 1997-04-15 | Nippon Shokubai Co Ltd | Laminate |
| JP2004098343A (en) * | 2002-09-05 | 2004-04-02 | Nissha Printing Co Ltd | Decorative sheet and manufacturing method for decorative frp molded product |
| JP2013202922A (en) * | 2012-03-28 | 2013-10-07 | Dainippon Printing Co Ltd | Decorative sheet for carbon fiber reinforced plastic, decorative composite material, and method for manufacturing the same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013202922A (en) * | 2012-03-28 | 2013-10-07 | Dainippon Printing Co Ltd | Decorative sheet for carbon fiber reinforced plastic, decorative composite material, and method for manufacturing the same |
| JP2013226792A (en) * | 2012-03-28 | 2013-11-07 | Dainippon Printing Co Ltd | Carbon fiber-reinforced plastic laminate sheet, laminate composite material and method for manufacturing the laminate composite material |
| JP2020142487A (en) * | 2019-03-08 | 2020-09-10 | 大日本印刷株式会社 | Fiber-reinforced resin molding with hard coat layer |
| JP7225943B2 (en) | 2019-03-08 | 2023-02-21 | 大日本印刷株式会社 | Fiber reinforced resin molded product with hard coat layer |
| JP2021059036A (en) * | 2019-10-04 | 2021-04-15 | 和告 漆原 | Decorative sheet, method for producing the same, and molded article |
| JP7304259B2 (en) | 2019-10-04 | 2023-07-06 | 和告 漆原 | Decorative sheet, manufacturing method thereof, and molded article |
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|---|---|
| JP5928075B2 (en) | 2016-06-01 |
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