JP4401144B2 - Skin material - Google Patents
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- JP4401144B2 JP4401144B2 JP2003376621A JP2003376621A JP4401144B2 JP 4401144 B2 JP4401144 B2 JP 4401144B2 JP 2003376621 A JP2003376621 A JP 2003376621A JP 2003376621 A JP2003376621 A JP 2003376621A JP 4401144 B2 JP4401144 B2 JP 4401144B2
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Description
本発明は車両内装用に好適な表皮材に関し、詳細には、車両のドア、インナーパネルなど、加熱成形される成形材料の表面に用いられる表皮材であって、外観、触感に優れた表皮材に関する。 TECHNICAL FIELD The present invention relates to a skin material suitable for use in vehicle interiors, and in particular, a skin material used on the surface of a molding material to be heat-molded, such as a vehicle door and an inner panel, and having excellent appearance and touch. About.
近年、車両の高級化に伴い、内装表皮材についても高級感を付与させることが重要になってきている。具体的には、不自然な光沢がなく、なめらかで、しっとり感が付与された、天然の皮革に近い感触をもつ内装表皮材が切望されている。
表皮材の艶を調整する方法は種々提案されており、例えば、カルボン酸亜鉛を樹脂材料に相溶させたのち、溶剤で希釈し、外部離型剤として金型に塗布した後、樹脂材料を成形することで、樹脂成形体の表面の艶消しを行う技術が知られている（例えば、特許文献１参照。）。この方法では、つや消しのための粉体は、金型に外部離型剤とともに付着させているため、添加量に制限があり、十分な艶消し効果が得られなかった。
In recent years, with the upgrading of vehicles, it has become important to provide a high-class feeling to the interior skin material. Specifically, there is a strong demand for an interior skin material that has no unnatural luster, is smooth, has a moist feel, and has a feel similar to natural leather.
Various methods for adjusting the luster of the skin material have been proposed. For example, zinc carboxylate is dissolved in a resin material, diluted with a solvent, and applied to a mold as an external mold release agent. A technique for matting the surface of a resin molded body by molding is known (for example, see Patent Document 1). In this method, since the powder for matting is adhered to the mold together with the external release agent, the addition amount is limited, and a sufficient matting effect cannot be obtained.
これに対し、艶消し効果の向上の観点から、表皮材の最表面部に微細粒子を一定量散布し、表皮材の最表面部をメルトし、上記微細粒子を加圧して表皮材の最表面部に埋没させることで、微細粒子を表皮材の最表面部に保持させる技術が提案されている（例えば、特許文献２参照。）。この方法では、充填材として不定形の微粉末状シリカが用いられ、この表面処理によれば、確かに不自然な光沢は抑えられるものの、表面の感触は充填されたシリカの硬さや形状の影響を受けてしまい、指で触れた場合には、乾いた、硬い触感を感じるなど、表面の感触を満足させるには至っていないのが現状であった。
本発明は上記課題を考慮してなされたものであり、本発明の目的は、車両、特に高級乗用車などの内装材に好適に使用される、光沢がなく、なめらかで、しっとり感が付与された、表皮材を提供することにある。 The present invention has been made in consideration of the above-mentioned problems, and the object of the present invention is a glossy, smooth and moist feeling that is suitably used for interior materials such as vehicles, particularly luxury passenger cars. To provide skin material.
本発明者らは、検討の結果、基材との密着性に優れるウレタン系樹脂を主成分とし、そこに、感触向上のための柔軟な球状微粒子と重量平均分子量が１５００〜３０００であるシリコーンとを含有させることで上記問題点を解決しうることを見いだし、本発明を完成した。
即ち、本発明の表皮材は、基材上に表面処理層を設けた表皮材であって、該表面処理層が、ウレタン樹脂１００質量部に対して、平均粒子径１〜３０μｍの球状樹脂粒子１００〜２５０質量部、微粒子シリカ５〜３０質量部、及び、重量平均分子量が１５００〜３０００であるシリコーンオイル２〜５質量部を添加してなるウレタン樹脂組成物からなることを特徴とする。
ここで、前記表面処理層に含まれる球状樹脂微粒子の１０％圧縮硬さは０．１〜２０ＭＰａであることが好ましく、また、添加量としては、主成分であるウレタン樹脂１００質量部に対して１００〜２５０質量部の範囲であることが好ましい。
また、表面処理層の主成分であるウレタン樹脂は、分子内に、ウレタン結合を有する構造単位を含むものであれば、単独重合体であっても共重合体であってもよく、硬化後の硬さが、１００％モジュラスで２５〜１５０ｋｇ／ｃｍ２であることが効果の観点から好ましい。
As a result of the study, the inventors have, as a main component, a urethane-based resin excellent in adhesiveness with a base material, and there are soft spherical fine particles for improving the touch and silicone having a weight average molecular weight of 1500 to 3000. It was found that the above-mentioned problems can be solved by adding bismuth, and the present invention was completed.
That is, the skin material of the present invention is a skin material in which a surface treatment layer is provided on a substrate, and the surface treatment layer is a spherical resin particle having an average particle diameter of 1 to 30 μm with respect to 100 parts by mass of a urethane resin. It is characterized by comprising a urethane resin composition obtained by adding 100 to 250 parts by mass, 5 to 30 parts by mass of fine-particle silica, and 2 to 5 parts by mass of silicone oil having a weight average molecular weight of 1500 to 3000 .
Here, the 10% compression hardness of the spherical resin fine particles contained in the surface treatment layer is preferably 0.1 to 20 MPa, and the addition amount is based on 100 parts by mass of the urethane resin as the main component. It is preferable that it is the range of 100-250 mass parts .
Also, the urethane resin is the main component of the surface treatment layer in the molecule, as long as it contains a structural unit having a urethane bond, may be also copolymers be a homopolymer, after curing The hardness is preferably 25 to 150 kg / cm 2 at 100% modulus from the viewpoint of effects.
本発明の作用は明確ではないが、本発明においては、表皮材における表面処理層に、ウレタン樹脂に重量平均分子量が１５００〜３０００であるシリコーンを併用することで、ベースとなるウレタン樹脂の分子量を膜性に問題が生ずる程に低下させることなく、優れた柔軟性と柔らかな表面感触を実現している。さらに、充填材として、特定粒径の柔軟な球状微粒子と微粒子シリカとをバランスよく用いているために、しっとりした感触と艶消しの優れた外観とが両立され、さらに、表面の傷付きも効果的に抑制しうるものと考える。また、これらの充填材の機能により、真空成形などの加熱２次加工後にも艶変化が少なく、触感と成形性が共に優れた表面処理剤層を有する高級感のある表皮材を得ることができた。 Although the action of the present invention is not clear, in the present invention, the surface treatment layer in the skin material is used together with silicone having a weight average molecular weight of 1500 to 3000 in the urethane resin, so that the molecular weight of the base urethane resin can be increased. Excellent softness and soft surface feel are achieved without degrading the film properties to such an extent that problems arise. In addition, soft spherical fine particles with a specific particle size and fine particle silica are used in a well-balanced manner as a filler, providing both a moist feel and an excellent appearance with a matte effect, as well as surface scratches. I think that it can be suppressed. In addition, the function of these fillers makes it possible to obtain a high-quality skin material having a surface treatment agent layer that has little change in gloss after heat secondary processing such as vacuum forming and has both excellent tactile feel and formability. It was.
本発明によれば、車両、特に高級乗用車などの内装材に好適に使用され、不自然な光沢がなく、なめらかで、しっとり感が付与された、表皮材を提供することができる。本発明の表皮材の表面処理層は、光沢などの外観、触感に優れ、且つ、表皮材に用いられる一般的な基材との密着性も良好で、その応用範囲は広い。 ADVANTAGE OF THE INVENTION According to this invention, it can use suitably for interior materials, such as a vehicle, especially a high-class passenger car, and can provide the skin material without the unnatural glossiness, the smoothness and the moist feeling provided. The surface treatment layer of the skin material of the present invention is excellent in appearance such as gloss and touch, and has good adhesion to a general base material used for the skin material, and its application range is wide.
以下、本発明を詳細に説明する。
本発明の表皮材は、ウレタン樹脂１００質量部に対して、平均粒子径１〜３０μｍの球状樹脂粒子１００〜２５０質量部、微粒子シリカ５〜３０質量部、及び、重量平均分子量が１５００〜３０００であるシリコーンオイル２〜５質量部を含有させたウレタン樹脂組成物からなる表面処理層を有することを特徴とする。以下、表面処理層を構成するウレタン樹脂組成物に含まれる各成分について説明する。
Hereinafter, the present invention will be described in detail.
The skin material of the present invention has 100 to 250 parts by weight of spherical resin particles having an average particle diameter of 1 to 30 μm, 5 to 30 parts by weight of fine silica, and a weight average molecular weight of 1500 to 3000 with respect to 100 parts by weight of urethane resin. It has a surface treatment layer made of a urethane resin composition containing 2 to 5 parts by mass of a certain silicone oil. Hereinafter, each component contained in the urethane resin composition constituting the surface treatment layer will be described.
〔ウレタン樹脂〕
本発明に係る表面処理層の主成分であるウレタン樹脂には特に制限はなく、分子内に、ウレタン結合を有する構造単位を含むものであれば、１種類のウレタン結合を含む構造単位のみからなる重合体であっても、２種以上の異なるウレタン結合を含む構造単位を含む共重合体であっても、ウレタン結合を含む構造単位と、目的に応じて併用される他の構造単位との共重合体であってもよい。
ここで、ウレタン結合を含む構造単位と併用しうる他の共重合成分としては、シリコーンなどが挙げられる。また、共重合比（モル比）は、ウレタン結合を含む構造単位に対して１０モル％以下であることが好ましい。
通常、本発明の如き表皮材は、表面処理層における樹脂表面が傷付きやすく、この傷付きを抑制するためにも、柔軟なウレタン樹脂をベースに用いることが好ましく、また、積層される基材との接着性の観点からも、ウレタン樹脂が好適である。表皮材の多くが、表面の傷付き抑制のためにウレタン樹脂を表面処理層に用いているが、本発明で用いるウレタン樹脂もこれら公知のものを適宜選択して使用することができる。
[Urethane resin]
There is no restriction | limiting in particular in the urethane resin which is a main component of the surface treatment layer which concerns on this invention, If it contains the structural unit which has a urethane bond in a molecule | numerator, it will consist only of a structural unit containing one type of urethane bond. Whether it is a polymer or a copolymer containing structural units containing two or more different urethane bonds, the structural unit containing urethane bonds and other structural units used in combination depending on the purpose. It may be a polymer.
Here, examples of other copolymerization components that can be used in combination with the structural unit containing a urethane bond include silicone. Moreover, it is preferable that a copolymerization ratio (molar ratio) is 10 mol% or less with respect to the structural unit containing a urethane bond.
Usually, the skin material as in the present invention is easily scratched on the resin surface in the surface treatment layer, and in order to suppress this scratch, it is preferable to use a flexible urethane resin as a base, and a substrate to be laminated From the viewpoint of adhesiveness, urethane resin is preferable. Many of the skin materials use a urethane resin for the surface treatment layer in order to suppress scratches on the surface, but the urethane resin used in the present invention can also be appropriately selected and used.
ウレタン樹脂のさらに好ましい物性としては、ＪＩＳ Ｋ−６３０１に準じて測定した硬さが、１００％モジュラスで２５〜１５０ｋｇ／ｃｍ2であることが挙げられ、さらに好ましくは、５０〜１００ｋｇ／ｃｍ2の範囲である。 More preferable physical properties of the urethane resin include a hardness measured according to JIS K-6301 of 25 to 150 kg / cm 2 at 100% modulus, and more preferably 50 to 100 kg / cm 2 . It is a range.
〔重量平均分子量が１５００〜３０００であるシリコーンオイル〕
本発明に係る表面処理層には、感触改良の目的で重量平均分子量が１５００〜３０００であるシリコーンオイルが添加される。通常用いられる分子量１００前後のシリコーンオイルでは感触向上効果が得られず、また、経時的なブリードも懸念されるため、本発明には適切ではなく、また、シリコーンオイルの分子量が大きすぎるとウレタン樹脂との均一混合が困難となる懸念がある。
シリコーンオイルは、分子量が上記好ましい範囲であれば、いずれのものも使用することができ、ジメチルポリシロキサン、メチルフェニルポリシロキサンなどの一般的なシリコーンオイルの他、アミノ変性シリコーンオイルなどの変性シリコーンオイルを用いることもできる。
[Silicone oil having a weight average molecular weight of 1500 to 3000 ]
A silicone oil having a weight average molecular weight of 1500 to 3000 is added to the surface treatment layer according to the present invention for the purpose of improving the feel . Not feel improving effect is obtained in passing customary There are molecular weight 100 before and after the silicone oil, also, since the temporal bleeding is a concern, it is not suitable for the present invention, also, the molecular weight of the silicone oil is too large urethane There is a concern that uniform mixing with the resin becomes difficult.
Any silicone oil can be used as long as the molecular weight is within the above-mentioned preferable range. In addition to general silicone oils such as dimethylpolysiloxane and methylphenylpolysiloxane, modified silicone oils such as amino-modified silicone oils can be used. Can also be used .
〔平均粒子径１〜３０μｍの球状樹脂粒子〕
本発明に係る表面処理層には、充填材として、平均粒子径１〜３０μｍの球状樹脂粒子を用いることを要する。
この球状微粒子は、その大きさ、添加量、粒子の硬さが最適範囲内であることが重要であり、感触の観点からは、球状粒子の大きさを上記範囲にするとともに、粒子を構成する樹脂の硬さを可能な限り軟らかくし、且つ、表皮材の表面に均一に存在させることで、表面を指で触れた時に、充填材である球状の軟らかい粒子の感触により、柔らかく、しっとりとした触感を達成することができる。
この観点から、球状樹脂粒子の大きさは平均粒子径が１〜３０μｍの範囲であることを要し、さらに好ましくは２〜２０μｍの範囲である。粒子の大きさが小さくなりすぎると触感に及ぼす影響が小さくなり過ぎて添加の効果を十分に得られないことがある。また、過度に大きすぎるとザラツキ感を感じてしまうため、いずれも好ましくない。
[Spherical resin particles having an average particle diameter of 1 to 30 μm]
In the surface treatment layer according to the present invention, it is necessary to use spherical resin particles having an average particle diameter of 1 to 30 μm as a filler.
It is important for the spherical fine particles that the size, the amount added, and the hardness of the particles are within the optimum range. From the viewpoint of feel, the size of the spherical particles is within the above range and the particles are constituted. By making the hardness of the resin as soft as possible and evenly present on the surface of the skin material, when touching the surface with a finger, it feels soft and moist due to the feeling of spherical soft particles that are fillers A tactile sensation can be achieved.
From this viewpoint, the size of the spherical resin particles requires that the average particle diameter is in the range of 1 to 30 μm, and more preferably in the range of 2 to 20 μm. If the size of the particles is too small, the effect on the tactile sensation may be too small to obtain the effect of addition sufficiently. Moreover, since it will feel a rough feeling when too large, neither is preferable.
柔らかさの観点からは、球状樹脂微粒子の、微小圧縮試験機ＭＣＴ−Ｗ５０１、（株）島津製作所製）にて測定した１０％圧縮硬さが０．１〜１０ＭＰａの範囲にあることが好ましく、１〜１０ＭＰａの範囲であることがさらに好ましい。この観点から、球状樹脂微粒子を形成する樹脂としては、柔軟なウレタン樹脂、シリコーン樹脂などが挙げられる。
このような球状樹脂粒子は、乳化重合法などにより容易に得ることができ、また、根上工業（株）製、アートパールＣ−８００などの市販品としても入手可能である。
球状樹脂微粒子の添加量は、ウレタン樹脂１００質量部に対して、１００〜２５０質量部であることが触感、均一分散、保持性の観点から好ましく、１５０〜２００質量部の範囲であることがさらに好ましい。
From the viewpoint of softness, it is preferable that the 10% compression hardness of the spherical resin fine particles measured with a micro compression tester MCT-W501 (manufactured by Shimadzu Corporation) is in the range of 0.1 to 10 MPa. More preferably, it is in the range of 1-10 MPa. From this viewpoint, examples of the resin that forms the spherical resin fine particles include a flexible urethane resin and a silicone resin.
Such spherical resin particles can be easily obtained by an emulsion polymerization method or the like, and are also available as commercial products such as those manufactured by Negami Kogyo Co., Ltd. and Art Pearl C-800.
The addition amount of the spherical resin fine particles is preferably 100 to 250 parts by mass with respect to 100 parts by mass of the urethane resin from the viewpoints of tactile sensation, uniform dispersion, and retainability, and further within the range of 150 to 200 parts by mass. preferable.
〔微粒子シリカ〕
本発明に係る表面処理層には、微粒子シリカを用いることを要する。
微粒子シリカは、艶消し用の充填材として一般的に用いられるものを使用することができる。具体的には、微粉末で不定形な酸化珪素（シリカ）を用いることができる。
ここで用いられる微粒子シリカの粒径は、一般的には、１〜３μｍ程度が好ましく、不定形、あるいは、表面に凹凸を有する多孔質粒子なども艶消し効果の観点から好ましく用いられる。
微粒子シリカの添加量は、仕上がり時における所望の艶の程度により適宜選択されるが、一般的には、ベースとなるウレタン樹脂１００質量部に対して、５〜３０質量部の範囲で添加されることを要し、１０〜２５質量部であることがさらに好ましい。また、前記した充填材である球状樹脂微粒子との比率に関しては、球状樹脂微粒子の感触を阻害しないという観点から、全充填材に占める微粒子シリカの割合は５〜１５質量％であることが好ましい。
[Fine particle silica]
The surface treatment layer according to the present invention requires the use of fine particle silica.
As the fine particle silica, those generally used as a filler for matting can be used. Specifically, finely powdered and amorphous silicon oxide (silica) can be used.
In general, the particle diameter of the fine particle silica used is preferably about 1 to 3 μm, and amorphous particles or porous particles having irregularities on the surface are also preferably used from the viewpoint of the matte effect.
The addition amount of the fine-particle silica is appropriately selected depending on the desired gloss level at the finish, but is generally added in the range of 5 to 30 parts by mass with respect to 100 parts by mass of the urethane resin as the base. More preferably, it is 10 to 25 parts by mass. Moreover, regarding the ratio with the spherical resin fine particles as the filler, the ratio of the fine particle silica in the total filler is preferably 5 to 15% by mass from the viewpoint of not inhibiting the feel of the spherical resin fine particles.
〔表面処理層の形成〕
本発明の表皮材を得るためには、基材となるシート状に前記各成分を含む表面処理層を設ける。表面処理層の形成方法としては、これらの成分を適切な溶剤に溶解して表面処理層塗布液を調整し、基材表面に塗布、乾燥する方法が一般的であるが、これに制限されず、表面処理層を予めシート状に成形し、基材に接着剤により接着したり、ラミネートしたりすることも可能である。
[Formation of surface treatment layer]
In order to obtain the skin material of the present invention, a surface treatment layer containing each of the above components is provided in the form of a sheet as a base material. As a method for forming the surface treatment layer, a method in which these components are dissolved in an appropriate solvent to prepare a surface treatment layer coating solution, which is applied to the substrate surface and dried, is not limited thereto. The surface treatment layer can be formed into a sheet shape in advance, and can be adhered to the substrate with an adhesive or laminated.
表面処理層塗布液に用いる溶剤は、これらの成分を均一に溶解、分散しうるものであれば特に制限はないが、具体的には、例えば、メチルエチルケトン（ＭＥＫ）、トルエン、テトラヒドロフラン（ＴＨＦ）、ジメチルアセトアミド（ＤＭＡＣ）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、イソプロピルアルコール（ＩＰＡ）などが挙げられる。
塗布液濃度には特に制限はないが、一般的には、２０〜５０質量％程度が好ましい。
また、基材上の表面処理層の塗布量としては、乾燥後の重量で１〜３０ｇ／ｍ2の範囲であることが効果の観点から好ましく、５〜２０ｇ／ｍ2の範囲であることがさらに好ましい。
The solvent used in the surface treatment layer coating solution is not particularly limited as long as these components can be uniformly dissolved and dispersed. Specifically, for example, methyl ethyl ketone (MEK), toluene, tetrahydrofuran (THF), Examples thereof include dimethylacetamide (DMAC), N, N-dimethylformamide (DMF), and isopropyl alcohol (IPA).
Although there is no restriction | limiting in particular in a coating liquid density | concentration, Generally about 20-50 mass% is preferable.
Furthermore, it as the coating amount of the surface treatment layer on the substrate, from the viewpoint of the effect in the range of 1 to 30 g / m 2 in weight after drying is in the range of 5 to 20 g / m 2 Further preferred.
〔基材〕
本発明の表皮材のベースに用いられる基材には特に制限はなく、公知のものを目的に応じて使用することができる。具体的には、例えば、スチレン系エラストマー、オレフィン系エラストマー、ポリエステル系エラストマーなどをシート状に成形したものなどが挙げられ、なかでも、ＴＰＯと称される、ポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）の如きオレフィン系樹脂と、エチレン−プロピレンゴム（ＥＰＤＭ）、イソブチレン−イソプレンゴムなどの如きオレフィン系ゴムをブレンドしたオレフィン系熱可塑性エラストマーが好ましく用いられる。基材は単層であっても、目的に応じた物性を有するシートを積層した重層構造を有するものであってもよい。
なお、表面処理層の形成にあたっては、これらの基材表面に、接着性の向上のために、コロナ放電処理などの易接着処理を施したり、接着助剤層（プライマー層）を設けることもできる。
〔Base material〕
There is no restriction | limiting in particular in the base material used for the base of the skin material of this invention, A well-known thing can be used according to the objective. Specifically, for example, styrene elastomers, olefin elastomers, polyester elastomers and the like molded into a sheet shape can be mentioned. Among them, polypropylene (PP) and polyethylene (PE) called TPO are particularly mentioned. An olefinic thermoplastic elastomer obtained by blending such an olefinic resin with an olefinic rubber such as ethylene-propylene rubber (EPDM) or isobutylene-isoprene rubber is preferably used. Even if a base material is a single | mono layer, it may have a multilayer structure which laminated | stacked the sheet | seat which has a physical property according to the objective.
In forming the surface treatment layer, an easy adhesion treatment such as a corona discharge treatment or an adhesion assistant layer (primer layer) can be applied to the surface of these base materials in order to improve adhesion. .
本発明の表皮材は上記構成としたので、不自然な光沢がなく、外観に優れ、ソフトでしっとりとした感触を有しており、そのままでも好適に使用できるが、さらにシボ加工などを施してもよい。また、着色にあたっては、ベースとなるウレタン樹脂のみならず、添加する充填材も、予め着色されたものを用いることができる。 Since the skin material of the present invention has the above-described configuration, it has no unnatural luster, has an excellent appearance, has a soft and moist feel, and can be suitably used as it is. Also good. In addition, for coloring, not only the urethane resin as a base but also a pre-colored filler can be used.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらに制限されるものではない。
（実施例１）
オレフィン系熱可塑性エラストマー（ＰＰ／ＰＥ／ＥＰＤＭを混合比３６／２８／３６でブレンドした混合物）を厚さ８００μｍのシート状に成形したものを基材として用い、基材表面に、以下の表面処理層塗布液を乾燥後の重量が、２０ｇ／ｍ2となる塗布量で塗布後、１００℃、３分間、熱風乾燥炉で乾燥し、表面処理層を形成して実施例１の表皮材を得た。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these.
Example 1
An olefin-based thermoplastic elastomer (a mixture of PP / PE / EPDM blended at a mixing ratio of 36/28/36) formed into a sheet having a thickness of 800 μm is used as the substrate, and the following surface treatment is applied to the substrate surface. After coating the layer coating solution at a coating weight of 20 g / m 2 , it is dried in a hot air drying oven at 100 ° C. for 3 minutes to form a surface treatment layer to obtain the skin material of Example 1 It was.
（表面処理層塗布液１）
・ウレタン樹脂 １００質量部
（大日本インキ化学工業（株）製、クリスボンＮＹ−３２９、
硬度：１００％モジュラス ５６ｋｇ／ｃｍ２）
・球状樹脂微粒子 １００質量部
（ウレタン樹脂粒子、平均粒子径 ６μｍ、粒子１０％圧縮硬さ ５ＭＰａ）
・シリコーンオイル ２質量部
（シリコーンオイル、信越シリコーン（株）製、ＫＰ３４０
分子量２０００〜３０００の混合物）
・微粒子シリカ（不定形粒子） １２質量部
（日本シリカ工業（株）製、ニプシルＥ２２０、平均粒子径：１．５μｍ）
・溶剤 １０００質量部
（ＩＰＡ／ＤＭＦ／トルエン混合物、質量比：２９／４７／２４）
(Surface treatment layer coating solution 1)
・ Urethane resin 100 parts by mass (Dainippon Ink Chemical Co., Ltd., Crisbon NY-329,
Hardness: 100% modulus 56 kg / cm 2 )
・ Spherical resin fine particles 100 parts by mass (urethane resin particles, average particle size 6 μm, particles 10% compression hardness 5 MPa)
Shea recone oil 2 parts by weight (silicone oil, manufactured by Shin-Etsu Silicone Co., Ltd., KP340
(Mixture of molecular weight 2000-3000)
-Fine particle silica (amorphous particles) 12 parts by mass (manufactured by Nippon Silica Industry, Nipsil E220, average particle size: 1.5 μm)
-1000 parts by mass of solvent (IPA / DMF / toluene mixture, mass ratio: 29/47/24)
（性能評価）
得られた表皮材を以下の項目について性能評価した。各結果を下記表１に示す。
（１）触感の評価
触感については、官能評価を行った。
官能評価は２０〜３０才のパネラー１０名で各サンプルを指触し、しっとり感の有無を以下の基準で判定した。
○：柔らかく、しっとり感あり
△：柔らかいが、しっとり感はない
×：触感に違和感があり、しっとり感なし
(Performance evaluation)
The obtained skin material was evaluated for the following items. The results are shown in Table 1 below.
(1) Evaluation of tactile sensation The tactile sensation was evaluated.
The sensory evaluation was carried out by touching each sample with 10 panelists aged 20 to 30 years old, and the presence or absence of moist feeling was determined according to the following criteria.
○: Soft and moist △: Soft but moist ×: Uncomfortable to touch, no moist
（２）摩擦係数
摩擦係数測定は、カトーテック（株）製摩擦感テスターＫＥＳ−ＳＥにて荷重５０ｇ、測定速度２ｍｍ／秒の条件で実施した。
この数値が大きいほど、しっとり感があると評価する。
(2) Friction coefficient Friction coefficient measurement was carried out with a friction feeling tester KES-SE manufactured by Kato Tech Co., Ltd. under the conditions of a load of 50 g and a measurement speed of 2 mm / second.
It is evaluated that the larger this value is, the moist feeling is.
（３）艶の評価
（３−１）初期グロス値
得られた表皮材のグロス値をグロス測定機（スガ試験機（株）製、デジタル変角光沢計 ＵＧＶ−５Ｋ）で測定した。このグロス値が０．３〜１．０の範囲において、光沢のない良好な艶消し外観を有すると判定する。
（３−２）加熱後のグロス値
次に、得られた表皮材を、温度１７０℃で３分間加熱後し、上記と同様の条件でグロス値測定した。
（３−３）艶変化
前記初期のグロス値測定サンプルと、温度１７０℃で３分間で加熱した後のグロス値測定サンプルとを、目視にて比較し、艶の変化を官能評価により以下の基準で判定した。
○：加熱前後に艶の変化はみられない
△：加熱後にやや光沢が増した
×：加熱後に表面の光沢が著しく増した
(3) Evaluation of gloss (3-1) Initial gloss value The gloss value of the obtained skin material was measured with a gloss measuring device (manufactured by Suga Test Instruments Co., Ltd., Digital Variable Glossmeter UGV-5K). When the gloss value is in the range of 0.3 to 1.0, it is determined to have a good matte appearance with no gloss.
(3-2) Gloss value after heating Next, the obtained skin material was heated at a temperature of 170 ° C. for 3 minutes, and the gloss value was measured under the same conditions as described above.
(3-3) Gloss change The initial gloss value measurement sample and the gloss value measurement sample after heating at a temperature of 170 ° C. for 3 minutes are visually compared, and the gloss change is subjected to sensory evaluation according to the following criteria. Judged by.
○: No change in gloss before and after heating Δ: Gloss increased slightly after heating ×: Surface gloss increased significantly after heating
（参考例、実施例２、比較例１〜５）
前記実施例１で用いた表面処理層塗布液１において、各成分を下記表１に記載のように変更した他は、同様に調製した表面処理層塗布液を用いて、参考例、実施例２及び比較例１〜５の表皮材を得た。これらを実施例１と同様の条件で評価した。結果を下記表１に併記する。
( Reference Example, Example 2, Comparative Examples 1-5)
In the surface treatment layer coating solution 1 used in Example 1, except that each component was changed as shown in Table 1 below, a surface treatment layer coating solution prepared in the same manner was used, and Reference Example, Example 2 And the skin material of Comparative Examples 1-5 was obtained. These were evaluated under the same conditions as in Example 1. The results are also shown in Table 1 below.
表１に明らかなように、本発明の実施例１及び２のように、球状の充填剤とシリコンオイル及びシリカを最適範囲内で併用した表面処理層を設けた表皮材ではしっとり感があり、触感も良好で、加熱処理後の艶変化が少ないことから、真空成形などの加熱２次加工した後も艶消し効果に優れ、優れた外観を維持しうることがわかる。
一方、比較例１及び５のように充填剤として、球状樹脂微粒子のみを添加した表面処理層を設けた表皮材ではしっとり感は付与できるが成形後の艶変化が大きく、実用上問題のあるレベルであった。
微粒子シリカの含有量が本発明の範囲外である比較例２、球状樹脂微粒子を含有しない比較例３、及び、重量平均分子量が１５００〜３０００であるシリコーンオイルを含有しない比較例４では、いずれも、しっとり感が付与されないか、不十分であり、触感に問題があった。
As is apparent from Table 1, as in Examples 1 and 2 of the present invention, the skin material provided with the surface treatment layer in which the spherical filler, silicon oil and silica are used in the optimum range has a moist feeling, Since the tactile sensation is also good and the gloss change after heat treatment is small, it can be seen that the matte effect is excellent even after secondary heat processing such as vacuum forming, and an excellent appearance can be maintained.
On the other hand, a skin material provided with a surface treatment layer to which only spherical resin fine particles are added as a filler as in Comparative Examples 1 and 5 can give a moist feeling, but the gloss change after molding is large, and there is a practically problematic level. Met.
In Comparative Example 2 in which the content of the fine particle silica is outside the scope of the present invention, Comparative Example 3 in which the spherical resin fine particles are not included, and Comparative Example 4 in which the weight average molecular weight is 1500 to 3000 and no silicone oil is included, all , Moist feeling was not imparted or was insufficient, and there was a problem in tactile sensation.
上記各実施例、比較例の結果より、本発明の表皮材は、充填材として、球状樹脂粒子と微粒子シリカとをバランスよく含有する表面処理層を有することから、しっとり感のある優れた触感と、不自然な光沢のない艶消しの外観とを有し、その外観が、真空成形などの加熱２次加工後にも維持され、高級感のある車両などの内装材として有用であることがわかる。 From the results of each of the above Examples and Comparative Examples, the skin material of the present invention has a surface treatment layer containing spherical resin particles and fine particle silica in a balanced manner as a filler, and therefore has a moist and excellent tactile sensation. It has a matte appearance with no unnatural luster, and the appearance is maintained even after secondary heating processing such as vacuum forming, and is found to be useful as an interior material for high-grade vehicles.
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| JP7047399B2 (en) * | 2017-03-22 | 2022-04-05 | 三菱ケミカル株式会社 | Laminate |
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| JPS63264680A (en) * | 1987-04-21 | 1988-11-01 | Fujikura Kasei Kk | Coating composition for forming velvetlike paint film |
| JP2739435B2 (en) * | 1993-10-07 | 1998-04-15 | アキレス株式会社 | Leather-like sheet and method for producing the same |
| JPH0872179A (en) * | 1994-09-07 | 1996-03-19 | Mazda Motor Corp | Skin material and manufacture thereof |
| JP2000052494A (en) * | 1998-08-06 | 2000-02-22 | Sekisui Chem Co Ltd | Molding sheet and its production |
| JP2000302624A (en) * | 1999-04-22 | 2000-10-31 | Sekisui Plastics Co Ltd | Acrylic acid ester-based resin particle and external preparation containing the same |
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