JP4912493B2 - Synthetic leather for automotive interior materials - Google Patents
Synthetic leather for automotive interior materials Download PDFInfo
- Publication number
- JP4912493B2 JP4912493B2 JP2010217355A JP2010217355A JP4912493B2 JP 4912493 B2 JP4912493 B2 JP 4912493B2 JP 2010217355 A JP2010217355 A JP 2010217355A JP 2010217355 A JP2010217355 A JP 2010217355A JP 4912493 B2 JP4912493 B2 JP 4912493B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- synthetic leather
- fine particles
- resin
- leather
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002649 leather substitute Substances 0.000 title claims description 85
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- 230000011164 ossification Effects 0.000 description 1
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- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
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- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
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- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
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Description
本発明は、合成皮革でありながら、掌内湿度の上昇レベルを本革と同等に抑え、本革並みにべたつき感が少なく、且つサラサラした感触を持つ自動車内装材用合成皮革に関する。 The present invention relates to a synthetic leather for automobile interior materials, which is a synthetic leather, but suppresses an increase in the humidity level in the palm of the same level as that of genuine leather, has less stickiness as genuine leather, and has a smooth feel.
自動車内装材に一般的に用いられている合成皮革、いわゆる塩ビレザーは、皮革調外観や価格、耐磨耗性、成形性などに優れており、現在、車両用途、特に自動車内装材、例えば大衆自動車の天井表皮材、ドアトリム材、インパネ材、カーシート表皮材などとして、大量に利用されている。 Synthetic leather commonly used for automobile interior materials, so-called PVC leather, is excellent in leather-like appearance, price, wear resistance, moldability, etc., and is currently used in vehicles, especially automobile interior materials such as the masses. It is used in large quantities as automotive ceiling skin materials, door trim materials, instrument panel materials, and car seat skin materials.
しかしながら、塩ビレザーは、ポリ塩化ビニルを構成成分とすることから、廃棄後焼却の際のダイオキシン発生が懸念されており、近年の環境問題の高まりから、使用が制限されつつある。 However, since vinyl chloride leather contains polyvinyl chloride as a constituent component, there is a concern about generation of dioxins during incineration after disposal, and its use is being restricted due to an increase in environmental problems in recent years.
また、塩ビレザー以外の合成皮革も検討されている。例えば、不織布などの基材層上に、合成樹脂からなる表皮層を形成し、吸放湿吸水発熱性繊維又は吸放湿吸水発熱性粉末を含有する層を少なくとも１層以上有する人造皮革（特許文献１（請求項１）参照）；繊維質基体にセリシンを含む合成樹脂層を積層した合成皮革（特許文献２（請求項１）参照）；基布に、熱可塑性ポリウレタン系エラストマー発泡層及び熱可塑性ポリウレタン系エラストマー非発泡層を順次に設けてなる合成皮革（特許文献３（請求項１）参照）；金属めっき合成繊維を含有する合成繊維ウエブを交絡結合して成る不織布基材に、導電性パウダーを含むポリウレタン樹脂を含浸、発泡して成る合成皮革（特許文献４（請求項１）参照）；所定の単位面積当りの重量引張強さを有し、多成分連続フィラメントが繊度＜０．２ｄｔｅｘを有する極細連続フィラメントに分割されかつ固定されている不織布にポリマーを含浸した合成皮革（特許文献５（請求項１）参照）などが提案されている。 Synthetic leather other than PVC leather is also being studied. For example, an artificial leather having a skin layer formed of a synthetic resin on a base material layer such as a nonwoven fabric and having at least one layer containing moisture-absorbing / releasing moisture-absorbing exothermic fiber or moisture-absorbing / releasing moisture-absorbing exothermic powder (patent Reference 1 (see claim 1)); synthetic leather in which a synthetic resin layer containing sericin is laminated on a fibrous base (see patent document 2 (claim 1)); a thermoplastic polyurethane elastomer foam layer and heat Synthetic leather in which non-foamed layers of plastic polyurethane elastomer are sequentially provided (refer to Patent Document 3 (Claim 1)); a non-woven fabric base material formed by entanglement of a synthetic fiber web containing a metal-plated synthetic fiber; Synthetic leather impregnated and foamed with a polyurethane resin containing powder (see Patent Document 4 (Claim 1)); has a predetermined weight tensile strength per unit area, and a multicomponent continuous filament has a fineness <0 Synthetic leather impregnated with polymer nonwoven fabric that is divided into ultra-fine continuous filaments and fixed with 2 dtex (see Patent Document 5 (claim 1)) has been proposed.
しかしながら、従来の一般的な合成皮革からなる自動車内装材は、手や脚など肌で触れた際の触感が好ましくなく、べたつきを感じ、肌への貼り付きさえ感じる、という点で十分ではなかった。すなわち、合成皮革でありながら、掌内湿度の上昇レベルを本革と同等に抑え、本革並みにべたつき感が少なく、且つサラサラした触感を持つ自動車内装材用合成皮革はこれまで得られていなかった。 However, conventional automotive interior materials made of synthetic leather are not satisfactory in that they do not feel the touch when touched with skin such as hands and legs, and feel sticky and even stick to the skin. . In other words, synthetic leather for automobile interior materials has been not obtained so far, although it is a synthetic leather, it has the same level of increase in humidity inside the palm as that of genuine leather, has less stickiness than genuine leather, and has a smooth texture. It was.
本発明の目的は、前記の従来の問題点を解決することにあり、合成皮革でありながら掌内湿度の上昇レベルを本革と同等に抑え、本革並みにべたつき感が少なく、且つサラサラした触感を持つ自動車内装材用合成皮革を提供することにある。 The object of the present invention is to solve the above-mentioned conventional problems, and although it is a synthetic leather, it suppresses the rise level of the humidity in the palm to the same level as that of genuine leather, and is less sticky than genuine leather. It is to provide a synthetic leather for automobile interior materials having a tactile sensation.
本発明の自動車内装材用合成皮革は、単層あるいは多層構造を有する不織布または織編物の基材層上に、単層あるいは多層の合成樹脂からなる樹脂層を形成した合成皮革であって、前記樹脂層が吸湿性微粒子を含有し、かつ発汗シミュレーション装置測定による掌内湿度の発汗開始１分後の上昇（ΔＨ）が２０％ＲＨ以下であることを特徴とする。これにより、べたつき感が少なく、サラサラした触感を有する合成皮革が得られる。 The synthetic leather for automobile interior material of the present invention is a synthetic leather in which a resin layer made of a single layer or a multilayer synthetic resin is formed on a base layer of a nonwoven fabric or a woven or knitted fabric having a single layer or a multilayer structure, The resin layer contains hygroscopic fine particles, and the increase (ΔH) in the palm moisture 1 minute after the start of sweating as measured by a sweating simulation apparatus is 20% RH or less. Thereby, there is little stickiness and a synthetic leather having a smooth feel can be obtained.
前記樹脂層が多層である場合、樹脂層の最表層が吸湿性微粒子を含有することが好ましい。最表層が吸湿性微粒子を含有することにより、合成皮革のべたつき感をより少なくでき、よりサラサラした触感を付与できる。 When the resin layer is a multilayer, the outermost layer of the resin layer preferably contains hygroscopic fine particles. When the outermost layer contains hygroscopic fine particles, the stickiness of the synthetic leather can be reduced, and a more smooth feel can be imparted.
本発明の合成皮革は、１．４７Ｎ／ｃｍ2荷重時の平均表面摩擦係数（ＭＩＵ）が０．２５以下であることが好ましい。平均表面摩擦係数が上記範囲内であれば、合成皮革のサラサラ感がより優れたものとなる。 The synthetic leather of the present invention preferably has an average surface friction coefficient (MIU) of 0.25 or less at a load of 1.47 N / cm 2 . If the average surface friction coefficient is within the above range, the smoothness of the synthetic leather will be more excellent.
前記吸湿性微粒子の平均粒子径は１μｍ〜５０μｍが好ましい。また、前記樹脂層の吸湿性微粒子の含有量は、２ｇ／ｍ2〜５０ｇ／ｍ2であることが好ましい。前記吸湿性微粒子としては、その５０質量％以上がアクリル系架橋重合体を原料としたものが好適である。 The average particle diameter of the hygroscopic fine particles is preferably 1 μm to 50 μm. The content of the hygroscopic fine particles in the resin layer is preferably 2 g / m 2 to 50 g / m 2 . As the hygroscopic fine particles, those using 50% by mass or more of an acrylic crosslinked polymer as a raw material are suitable.
前記基材層は、上層を構成する繊維構造体と下層を構成する繊維構造体とが機械的交絡により積層された２層構造を有する不織布であって、上層の目付量が４０ｇ／ｍ2〜１５０ｇ／ｍ2、上層を構成する繊維の繊度が０．０００１ｄｔｅｘ〜０．５ｄｔｅｘであり、下層の目付量が４０ｇ／ｍ2〜２００ｇ／ｍ2、下層を構成する繊維の繊度が１．５ｄｔｅｘ〜１０．０ｄｔｅｘであるものが好ましい。 The base material layer is a nonwoven fabric having a two-layer structure in which a fiber structure constituting an upper layer and a fiber structure constituting a lower layer are laminated by mechanical entanglement, and the basis weight of the upper layer is 40 g / m 2 to 150 g / m 2 , the fineness of the fibers constituting the upper layer is 0.0001 dtex to 0.5 dtex, the basis weight of the lower layer is 40 g / m 2 to 200 g / m 2 , and the fineness of the fibers constituting the lower layer is 1.5 dtex to What is 10.0 dtex is preferable.
前記基材層が単層あるいは多層構造を有する不織布である場合、該不織布は、密度が１２０ｋｇ／ｍ3〜２５０ｋｇ／ｍ3、破裂強度が４００Ｎ〜１０００Ｎかつ剛軟度が１ｍｍ〜１２０ｍｍであることが好ましい。 When the base material layer is a nonwoven fabric having a single layer or a multilayer structure, the nonwoven fabric has a density of 120 kg / m 3 to 250 kg / m 3 , a burst strength of 400 N to 1000 N, and a bending resistance of 1 mm to 120 mm. Is preferred.
本発明の自動車内装材用合成皮革は、樹脂層が吸湿性微粒子を含有し、かつ発汗シミュレーション装置測定による掌内湿度の発汗開始１分後の上昇を２０％ＲＨ以下に抑えているため、本革並みにべたつき感が少なく、且つサラサラした触感を実現することができる。 In the synthetic leather for automobile interior materials of the present invention, the resin layer contains hygroscopic fine particles, and the increase in the palmar moisture of 1 minute after the start of sweating measured by the sweating simulation apparatus is suppressed to 20% RH or less. There is little stickiness like leather and a smooth touch can be achieved.
以下、本発明の詳細を説明する。
本発明の自動車内装材用合成皮革は、単層あるいは多層構造を有する不織布または織編物の基材層上に、単層あるいは多層の合成樹脂からなる樹脂層を形成した合成皮革であって、前記樹脂層が吸湿性微粒子を含有し、かつ発汗シミュレーション装置測定による掌内湿度の発汗開始１分後の上昇（ΔＨ）が２０％ＲＨ以下であることを特徴とする。なお、本明細書において、「多層」とは２層以上を意味する。
Details of the present invention will be described below.
The synthetic leather for automobile interior material of the present invention is a synthetic leather in which a resin layer made of a single layer or a multilayer synthetic resin is formed on a base layer of a nonwoven fabric or a woven or knitted fabric having a single layer or a multilayer structure, The resin layer contains hygroscopic fine particles, and the increase (ΔH) in the palm moisture 1 minute after the start of sweating as measured by a sweating simulation apparatus is 20% RH or less. In the present specification, “multilayer” means two or more layers.
実際に人が自動車内装材を触った際に感じるべたつき感は、肌と内装材の間に介在する水分（汗）が処理されないことが原因と推定される。そのため、出願人は、発汗シミュレーション装置試験法（スキンモデル試験法）を使用し、実用との対応関係を検討した。その結果、樹脂層に吸湿性微粒子を含有させ、掌内湿度の発汗開始１分後の上昇（ΔＨ）を２０％ＲＨ以下に抑えることにより、べたつき感が少なく、サラサラした触感を有する合成皮革が得られることを見出し本発明を完成した。 The sticky feeling that a person actually feels when touching an automobile interior material is presumed to be caused by the fact that moisture (sweat) intervening between the skin and the interior material is not processed. Therefore, the applicant used a sweating simulation device test method (skin model test method) and examined the correspondence with practical use. As a result, a synthetic leather having less stickiness and a smooth feel can be obtained by containing hygroscopic fine particles in the resin layer, and suppressing the increase (ΔH) in 1 minute after the start of sweating within 20% RH or less. As a result, the present invention was completed.
前記試験法は、常に一定の水蒸気と熱が内装材表層に供給されるという実用環境を考慮したモデル評価法である。この評価法は、発汗シミュレーション測定装置（東洋紡績株式会社製）を用い、水供給量：１４０ｇ／ｍ2・ｈ、熱板温度：３７℃、試料−熱板距離：０．５ｃｍ、環境温湿度：２０℃×６５％ＲＨ、発汗パターン：試験開始より５分発汗を実施し、熱板と試料間の空間の温湿度を測定するものである。 The test method is a model evaluation method considering a practical environment in which constant water vapor and heat are always supplied to the interior material surface layer. This evaluation method uses a sweating simulation measuring device (manufactured by Toyobo Co., Ltd.), water supply amount: 140 g / m 2 · h, hot plate temperature: 37 ° C., sample-hot plate distance: 0.5 cm, environmental temperature and humidity : 20 ° C. × 65% RH, sweat pattern: sweating is performed for 5 minutes from the start of the test, and the temperature and humidity of the space between the hot plate and the sample are measured.
本発明の自動車内装材用合成皮革のΔＨは、２０％ＲＨ以下であり、好ましくは１８％ＲＨ以下、より好ましくは１６％ＲＨ以下である。前記ΔＨが２０％ＲＨを超えると、自動車内装材用合成皮革のべたつき感が悪いものとなる。なお、前記ΔＨの下限は、特に限定されないが０％ＲＨである。 The ΔH of the synthetic leather for automobile interior material of the present invention is 20% RH or less, preferably 18% RH or less, more preferably 16% RH or less. When the ΔH exceeds 20% RH, the feeling of stickiness of the synthetic leather for automobile interior materials becomes poor. The lower limit of ΔH is not particularly limited, but is 0% RH.
また、自動車内装材用合成皮革の１．４７ｋｇｆ／ｃｍ2荷重時の平均表面摩擦係数（ＭＩＵ）は０．２５以下が好ましく、より好ましくは０．２０以下、さらに好ましくは０．１８以下である。平均表面摩擦係数とは、合成皮革の風合い（例えば、サラサラ感、ザラツキ）を示す指標であり、値が小さい程表面が滑らかであることを示す。前記平均表面摩擦係数が０．２５以下であれば、自動車内装材用合成皮革のサラサラ感がより優れたものとなる。前記平均表面摩擦係数の下限は特に限定されないが、通常０．１０である。 Moreover, the average surface friction coefficient (MIU) at 1.47 kgf / cm 2 load of the synthetic leather for automobile interior materials is preferably 0.25 or less, more preferably 0.20 or less, and further preferably 0.18 or less. . The average surface friction coefficient is an index indicating the texture of the synthetic leather (for example, smooth feeling, roughness), and the smaller the value, the smoother the surface. When the average surface friction coefficient is 0.25 or less, the smoothness of the synthetic leather for automobile interior materials becomes more excellent. The lower limit of the average surface friction coefficient is not particularly limited, but is usually 0.10.
自動車内装材用合成皮革の目付量は、２５０ｇ／ｍ2以上が好ましく、より好ましくは３００ｇ／ｍ2以上、さらに好ましくは３５０ｇ／ｍ2以上であり、５５０ｇ／ｍ2以下が好ましく、より好ましくは５００ｇ／ｍ2以下、さらに好ましくは４５０ｇ／ｍ2以下である。目付量が上記範囲内であれば、機械的特性に優れ、軽量な自動車内装材用合成皮革となる。 The basis weight of the synthetic leather for automobile interior materials is preferably 250 g / m 2 or more, more preferably 300 g / m 2 or more, still more preferably 350 g / m 2 or more, and preferably 550 g / m 2 or less, more preferably. It is 500 g / m 2 or less, more preferably 450 g / m 2 or less. When the weight per unit area is within the above range, the synthetic leather is excellent in mechanical characteristics and lightweight for automobile interior materials.
基材
単層あるいは多層構造を有する不織布または織編物の基材層を構成する繊維としては、熱可塑性樹脂からなる合成繊維が好ましい。また、構成繊維として、必要に応じて天然繊維や再生繊維、半合成繊維、無機繊維などを混綿、あるいは混繊してもよい。
Base Material As the fibers constituting the base layer of the nonwoven fabric or knitted fabric having a single layer or multilayer structure, a synthetic fiber made of a thermoplastic resin is preferable. Further, as a constituent fiber, natural fiber, regenerated fiber, semi-synthetic fiber, inorganic fiber, or the like may be blended or mixed as necessary.
前記合成繊維を形成する熱可塑性樹脂としては、繊維形成能を有するものであれば特に限定されず、例えば、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリブチレンテレフタレート、およびこれらを主体とし、さらにイソフタル酸を共重合成分として用いた低融点ポリエステルなどのポリエステル類；ポリプロピレン、高密度ポリエチレン、中密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレン、プロピレンと他のα−オレフィンとの二〜三元共重合体などのポリオレフィン類；ポリアミド６、ポリアミド６６などのポリアミド類；もしくはこれらの混合物や共重合体などを用いることができる。 The thermoplastic resin forming the synthetic fiber is not particularly limited as long as it has fiber-forming ability. For example, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and the main components thereof, and further isophthalic acid is used. Polyesters such as low-melting polyester used as a copolymerization component; polypropylene, high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, binary to ternary copolymerization of propylene and other α-olefins Polyolefins such as coalescence; polyamides such as polyamide 6 and polyamide 66; or a mixture or copolymer thereof can be used.
このような熱可塑性樹脂から得られる合成繊維は、単一成分系のものの他、芯鞘型や偏心芯鞘型、並列型、海島型などの多成分系であってもよく、繊維断面の形状にも特に制限はない。また、必要に応じてつや消し剤、顔料、酸化防止剤、紫外線吸収剤、光安定剤、結晶核剤、難燃剤、防ダニ剤などの各種添加剤を含有させることも可能である。 Synthetic fibers obtained from such thermoplastic resins may be multi-component systems such as a core-sheath type, an eccentric core-sheath type, a parallel type, and a sea-island type in addition to those of a single component type, and the cross-sectional shape of the fiber There are no particular restrictions. In addition, various additives such as a matting agent, a pigment, an antioxidant, an ultraviolet absorber, a light stabilizer, a crystal nucleating agent, a flame retardant, and an acaricide may be contained as necessary.
前記基材層の目付量は、５０ｇ／ｍ2以上が好ましく、より好ましくは１００ｇ／ｍ2以上、さらに好ましくは１５０ｇ／ｍ2以上であり、３５０ｇ／ｍ2以下が好ましく、より好ましくは４００ｇ／ｍ2以下、さらに好ましくは４５０ｇ／ｍ2以下が好ましい。基材層の目付量が上記範囲内であれば、機械的特性に優れ、軽量な自動車内装材用合成皮革が得られる。 The basis weight of the base material layer is preferably 50 g / m 2 or more, more preferably 100 g / m 2 or more, still more preferably 150 g / m 2 or more, preferably 350 g / m 2 or less, more preferably 400 g / m 2. m 2 or less, more preferably 450 g / m 2 or less. When the basis weight of the base material layer is within the above range, a lightweight synthetic leather for automobile interior materials is obtained that is excellent in mechanical properties.
前記基材層として不織布を用いる場合、上層を構成する繊維構造体と下層を構成する繊維構造体とが機械的交絡により積層された２層構造を有する不織布が好適である。特に、上層の目付量が４０ｇ／ｍ2〜１５０ｇ／ｍ2、上層を構成する繊維の繊度が０．０００１ｄｔｅｘ〜０．５ｄｔｅｘであり、下層の目付量が４０ｇ／ｍ2〜２００ｇ／ｍ2、下層を構成する繊維の繊度が１．５ｄｔｅｘ〜１０．０ｄｔｅｘである２層構造を有する不織布が好ましい。 When using a nonwoven fabric as the base material layer, a nonwoven fabric having a two-layer structure in which a fiber structure constituting an upper layer and a fiber structure constituting a lower layer are laminated by mechanical entanglement is preferable. In particular, the basis weight of the upper layer is 40g / m 2 ~150g / m 2 , the fineness of the fibers constituting the upper layer is 0.0001Dtex～0.5Dtex, basis weight of the lower layer 40g / m 2 ~200g / m 2 , A nonwoven fabric having a two-layer structure in which the fineness of the fibers constituting the lower layer is 1.5 dtex to 10.0 dtex is preferable.
前記基材層に用いられる原料不織布は、上層、下層共に、短繊維不織布あるいは長繊維不織布のいずれでもよいが、より良好な機械的特性を確保する点から長繊維不織布が好ましい。その製造方法については特に限定されないが、好ましい方法としては、長繊維不織布であればスパンボンド法やメルトブロー法などが、短繊維不織布であればカーディング法やエアレイ法などが挙げられる。 The raw material nonwoven fabric used for the base material layer may be either a short fiber nonwoven fabric or a long fiber nonwoven fabric for both the upper layer and the lower layer, but a long fiber nonwoven fabric is preferable from the viewpoint of securing better mechanical properties. The production method is not particularly limited, but preferred methods include a spunbond method and a melt blow method for a long-fiber nonwoven fabric, and a carding method and an airlay method for a short-fiber nonwoven fabric.
前記基材層となる原料不織布の上層は繊度を０．５ｄｔｅｘ以下とすることにより、緻密性が高く、骨立ちが殆どない、消費者が好む風合い、柔軟性に優れた基材となる。上層基材の繊度の下限は特に限定されないが、０．０００１ｄｔｅｘ以上であることが強度を保つという観点から好ましい。また、生産性などを考慮した場合、上層基材のより好ましい繊度は０．０１ｄｔｅｘ〜０．４ｄｔｅｘ、更に好ましくは０．１ｄｔｅｘ〜０．３ｄｔｅｘの範囲である。 The upper layer of the raw material non-woven fabric used as the base material layer has a fineness of 0.5 dtex or less, so that it becomes a base material with high density, almost no skeletal texture, excellent in texture and flexibility preferred by consumers. Although the minimum of the fineness of an upper layer base material is not specifically limited, It is preferable from a viewpoint of maintaining intensity | strength that it is 0.0001 dtex or more. Moreover, when productivity etc. are considered, the more preferable fineness of an upper layer base material is the range of 0.01 dtex-0.4 dtex, More preferably, it is the range of 0.1 dtex-0.3 dtex.
しかしながら、上層を構成する不織布のみでは、重厚感、高級感に欠け、自動車用内装材としての強度などの基本的な機械的性能にも欠ける。そのため、下層として繊度１．５ｄｔｅｘ〜１０．０ｄｔｅｘの不織布を積層し、一体化することで機械的特性に優れ、柔軟・軽量で骨立ちが極めて少なく、重厚感、高級感のある自動車内装材用合皮が得られるものである。下層基材の繊度は、１．５ｄｔｅｘ〜１０．０ｄｔｅｘの範囲であれば、嵩高性と柔軟性を兼ね備えた基材が得られる。よりバランスの良い基材を得るには、下層基材の繊度は１．５ｄｔｅｘ〜８．０ｄｔｅｘ、更には２．０ｄｔｅｘ〜６．０ｄｔｅｘの範囲であることが好ましい。 However, only the nonwoven fabric constituting the upper layer lacks a profound feeling and luxury, and lacks basic mechanical performance such as strength as an automobile interior material. For this reason, non-woven fabric with a fineness of 1.5 dtex to 10.0 dtex is laminated and integrated as a lower layer, and it has excellent mechanical properties, is flexible and lightweight, has very little suspicion, and has a profound and high-class feeling. Synthetic leather is obtained. When the fineness of the lower layer base material is in the range of 1.5 dtex to 10.0 dtex, a base material having both bulkiness and flexibility can be obtained. In order to obtain a more balanced substrate, the fineness of the lower layer substrate is preferably in the range of 1.5 dtex to 8.0 dtex, and more preferably in the range of 2.0 dtex to 6.0 dtex.
上層基材の目付量は、４０ｇ／ｍ2〜１５０ｇ／ｍ2であることが好ましく、より好ましくは５０ｇ／ｍ2〜１４０ｇ／ｍ2、更に好ましくは６０ｇ／ｍ2〜１２０ｇ／ｍ2である。目付量が４０ｇ／ｍ2以上であれば、緻密化による骨立ち防止効果が極めて有効に発揮され、１５０ｇ／ｍ2を超えない範囲では、下層とのニードルパンチやウォーターパンチ等による機械的交絡が効果的になされるからである。 Basis weight of the upper substrate is preferably 40g / m 2 ~150g / m 2 , more preferably 50g / m 2 ~140g / m 2 , more preferably is at 60g / m 2 ~120g / m 2 . If the weight per unit area is 40 g / m 2 or more, the effect of preventing bone formation due to densification is very effectively exhibited, and within a range not exceeding 150 g / m 2 , mechanical entanglement with the needle punch or water punch with the lower layer is possible. Because it is done effectively.
下層基材の目付量は、４０ｇ／ｍ2〜２００ｇ／ｍ2であることが好ましく、より好ましくは５０ｇ／ｍ2〜１８０ｇ／ｍ2、更に好ましくは６０ｇ／ｍ2〜１６０ｇ／ｍ2である。目付量を４０ｇ／ｍ2以上とすることにより、基材の重厚感、高級感が得られ、２００ｇ／ｍ2を超えない範囲であれば、上層の緻密化による優れた骨立ち防止性を阻害せず、風合いに優れ、かつ重厚な基材が得られるからである。 Basis weight of the lower layer substrate is preferably 40g / m 2 ~200g / m 2 , more preferably 50g / m 2 ~180g / m 2 , more preferably is at 60g / m 2 ~160g / m 2 . By setting the basis weight to 40 g / m 2 or more, a solid feeling and high-quality feeling of the base material can be obtained, and if it is in a range not exceeding 200 g / m 2 , the superior anti-settling property due to densification of the upper layer is inhibited. This is because a substrate having an excellent texture and a heavy thickness can be obtained.
また、下層基材の初期応力は経、緯ともに０．１Ｎ／５ｃｍ〜４０Ｎ／５ｃｍであることが好ましい。上述の通り、繊度の小さい上層では自動車用内装材としての機械的性能を満たさないため、下層にて上層を補強する効果を得る必要がある。また、下層の初期応力が上記該当範囲にあれば、上層の柔軟性と相俟って、上層下層間に強い交絡が得られ、一体性の高い積層基材が得られる。より柔軟かつ重厚感、高級感のある積層基材を得るには、下層のより好ましい初期応力は１Ｎ／５ｃｍ〜２０Ｎ／５ｃｍ、更に好ましくは３Ｎ／５ｃｍ〜１０Ｎ／５ｃｍの範囲である。 The initial stress of the lower layer base material is preferably 0.1 N / 5 cm to 40 N / 5 cm for both warp and weft. As described above, since the upper layer having a small fineness does not satisfy the mechanical performance as an automobile interior material, it is necessary to obtain an effect of reinforcing the upper layer in the lower layer. Moreover, if the initial stress of the lower layer is in the above-mentioned range, combined with the flexibility of the upper layer, strong entanglement is obtained between the upper and lower layers, and a highly integrated laminated base material is obtained. In order to obtain a laminated base material that is more flexible, profound, and high-class, the initial stress of the lower layer is more preferably in the range of 1 N / 5 cm to 20 N / 5 cm, and more preferably 3 N / 5 cm to 10 N / 5 cm.
上層、下層が積層された基材としての密度は、１２０ｋｇ／ｍ3〜２５０ｋｇ／ｍ3であることが好ましく、より好ましくは１３０ｋｇ／ｍ3〜２４０ｋｇ／ｍ3、更に好ましくは１４０ｋｇ／ｍ3〜２３０ｋｇ／ｍ3の範囲である。基材の密度が１２０ｋｇ／ｍ3未満の場合、緻密性が不足するため骨立ち発生の要因となる。また２５０ｋｇ／ｍ3を超える場合、厚みが低下し、重厚感、高級感が損なわれるため、好ましくない。 Upper, the density of the groups lower layer are laminated material is preferably 120kg / m 3 ~250kg / m 3 , more preferably 130kg / m 3 ~240kg / m 3 , more preferably 140 kg / m 3 ~ The range is 230 kg / m 3 . When the density of the base material is less than 120 kg / m 3 , the denseness is insufficient, which causes the occurrence of erection. On the other hand, if it exceeds 250 kg / m 3 , the thickness is lowered, and the profound feeling and luxury feeling are impaired, which is not preferable.
また、上層、下層が積層された基材の破裂強度は４００Ｎ〜１０００Ｎが好ましく、より好ましくは５００Ｎ〜９００Ｎの範囲である。４００Ｎ以上あれば、例えば、合成皮革に加工後、自動車内装材のシート表皮材のとして用いられた場合においても、展張時に破れるという問題が生じ難く、用途範囲が拡大する。 Further, the burst strength of the base material on which the upper layer and the lower layer are laminated is preferably 400N to 1000N, and more preferably 500N to 900N. If it is 400 N or more, for example, even if it is used as a seat skin material for an automobile interior material after being processed into a synthetic leather, the problem of tearing at the time of expansion hardly occurs, and the application range is expanded.
さらに、上層、下層が積層された基材の剛軟度は１ｍｍ〜１２０ｍｍであることが好ましく、より好ましくは５０ｍｍ〜１２０ｍｍ、更に好ましくは７０ｍｍ〜１００ｍｍである。１ｍｍ〜１２０ｍｍの柔軟性を備えていれば、自動車内装材用合成皮革として加工した場合においても、基材の柔軟性を活かした最終製品に仕上がるからである。 Furthermore, the bending resistance of the base material on which the upper layer and the lower layer are laminated is preferably 1 mm to 120 mm, more preferably 50 mm to 120 mm, and still more preferably 70 mm to 100 mm. This is because if it has a flexibility of 1 mm to 120 mm, it will be finished into a final product utilizing the flexibility of the base material even when processed as a synthetic leather for automobile interior materials.
合成樹脂
樹脂層を形成する合成樹脂としては、例えば、ポリウレタン樹脂、ポリアミド樹脂、ポリアクリレート樹脂、酢酸ビニル樹脂、ポリアクリロニトリル樹脂などが挙げられる。これらの合成樹脂は、単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、ポリウレタン樹脂が好適である。
Synthetic resin Examples of the synthetic resin forming the resin layer include polyurethane resin, polyamide resin, polyacrylate resin, vinyl acetate resin, and polyacrylonitrile resin. These synthetic resins may be used alone or in combination of two or more. Among these, a polyurethane resin is preferable.
具体的なポリウレタン樹脂の構成成分としては、一般にポリウレタン樹脂、ポリウレタンウレア樹脂と呼ばれるものであり、分子量４００から４０００のポリアルキレンエーテルグリコールまたは、末端に水酸基を有するポリエステルポリオール、ポリε−カプロラクトンポリオール、またはポリカーボネートポリオールなどの単独あるいは混合物を有機ジイソシアネートと反応させて得られるものであり、必要に応じて２個の活性水素を有する化合物で鎖延長させて得られるものである。 As a specific component of the polyurethane resin, generally called a polyurethane resin or a polyurethane urea resin, a polyalkylene ether glycol having a molecular weight of 400 to 4000, a polyester polyol having a hydroxyl group at the terminal, a poly ε-caprolactone polyol, or It is obtained by reacting a polycarbonate polyol or the like alone or with a mixture with an organic diisocyanate, and is obtained by extending a chain with a compound having two active hydrogens if necessary.
前記ポリアルキレンエーテルグリコールとしては、例えば、ポリテトラメチレンエーテルグリコール、ポリプロピレングリコール、ポリエチレングリコール、グリセリンプロピレンオキシド付加物、末端にエチレンオキサイドを付加したポリエーテルポリオール、ビニルモノマーグラフト化ポリエーテルポリオールが挙げられる。前記ポリエステルポリオールとしては、例えば、エチレングリコール、ブチレングリコール、へキシレングリコール、ジエチレングリコール、ジプロピレングリコール、ネオペンチルグリコールなどのアルキレングリコールとコハク酸、グルタール酸、アジピン酸、セバシン酸、マレイン酸、フマール酸、フタル酸、トリメリット酸などのカルボン酸類とを末端がヒドロキシル酸となるように反応して与えられるものが挙げられる。ポリカーボネートポリオールとしては、例えば、ポリエチレンカーボネートジオール、ポリテトラメチレンカーボネートジオール、ポリヘキサメチレンカーボネートジオールが挙げられる。 Examples of the polyalkylene ether glycol include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, glycerin propylene oxide adduct, polyether polyol having ethylene oxide added to the terminal, and vinyl monomer grafted polyether polyol. Examples of the polyester polyol include ethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, and neopentyl glycol, and other alkylene glycols and succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, Examples thereof include those obtained by reacting carboxylic acids such as phthalic acid and trimellitic acid with hydroxyl acid at the end. Examples of the polycarbonate polyol include polyethylene carbonate diol, polytetramethylene carbonate diol, and polyhexamethylene carbonate diol.
有機ジイソシアネートとしては、例えば、２，４−及び２，６−トリレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、１，５−ナフタレンジイソシアネート、キシリレンジイソシアネートなどの芳香族イソシアネート；１，６−ヘキサメチレンジイソシアネート、ジシクロヘキシルメタン−４，４’−ジイソシアネート、３−イソシアネートメチルー３，５，５’−トリメチルシクロヘキシルイソシアネート、２，６−ジイソシアネートメチルカプロエートなどの脂肪族イソシアネート；が挙げられ、これらは単独で使用してもよいし、２種以上を併用してもよい。 Examples of the organic diisocyanate include aromatic isocyanates such as 2,4- and 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, and xylylene diisocyanate; 1,6-hexamethylene Aliphatic isocyanates such as diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 3-isocyanate methyl-3,5,5′-trimethylcyclohexyl isocyanate, 2,6-diisocyanate methyl caproate; Or two or more of them may be used in combination.
前記鎖延長剤としては、ヒドラジン、エチレンジアミン、テトラメチレンジアミン、水、ピペラジン、イソホロンジアミン、エチレングリコール、ブチレングリコール、へキシレングリコール、ジエチレングリコール、ジプロピレングリコール、ネオペンチルグリコールなど、あるいはジメチロールプロピオン酸、アミノエタンスルホン酸へのエチレンオキサイド付加物などの親水性向上を可能とするグリコール類、ジアミン類を単独あるいは混合して用いることができる。 Examples of the chain extender include hydrazine, ethylenediamine, tetramethylenediamine, water, piperazine, isophoronediamine, ethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, or dimethylolpropionic acid, amino acid. Glycols and diamines that can improve hydrophilicity such as ethylene oxide adducts to ethanesulfonic acid can be used alone or in combination.
前記ポリウレタン樹脂としては、耐加水分解性に優れることから、構成成分としてポリカーボネートポリオールを用いたポリカーボネート系ポリウレタン樹脂が好ましい。また、特に、合成皮革の最表面に存在する樹脂層には、合成皮革の風合いを向上させるために、シリコーン変性されたポリカーボネート系ポリウレタン樹脂を用いることが好ましい。 As the polyurethane resin, a polycarbonate-based polyurethane resin using a polycarbonate polyol as a constituent component is preferable because of excellent hydrolysis resistance. In particular, for the resin layer present on the outermost surface of the synthetic leather, it is preferable to use a silicone-modified polycarbonate polyurethane resin in order to improve the texture of the synthetic leather.
前記シリコーン変性型ポリカーボネート系ポリウレタンは、分子鎖中にオルガノポリシロキサン骨格を有するか、分子鎖末端にイソシアネート基と非反応性の官能基、例えば、トリアルキルシリル基、トリアリールシリル基等により封止されたオルガノポリシロキサン骨格を有するポリカーボネート系ポリウレタンである。 The silicone-modified polycarbonate-based polyurethane has an organopolysiloxane skeleton in the molecular chain, or is sealed with a functional group that is non-reactive with an isocyanate group at the molecular chain end, for example, a trialkylsilyl group or a triarylsilyl group. A polycarbonate-based polyurethane having an organopolysiloxane skeleton.
吸湿性微粒子
上記吸湿性微粒子とは、その名の通り、吸湿性を有する微粒子である。このような微粒子の好ましいものとしては、アクリル系架橋重合体を原料として得られるものがあり、本発明においては、吸湿性微粒子の５０質量％以上（好ましくは７０質量％以上、より好ましくは９０質量％以上）がアクリル系架橋重合体を原料としたものであることが好ましく、吸湿性微粒子がアクリル系架橋重合体を原料としたもののみからなることが好ましい。
Hygroscopic fine particles The hygroscopic fine particles are fine particles having hygroscopicity, as the name suggests. Preferred examples of such fine particles include those obtained using an acrylic crosslinked polymer as a raw material. In the present invention, 50% by mass or more (preferably 70% by mass or more, more preferably 90% by mass) of the hygroscopic fine particles. % Or more) is preferably made from an acrylic crosslinked polymer as a raw material, and the hygroscopic fine particles are preferably made only from an acrylic crosslinked polymer as a raw material.
この「アクリル系架橋重合体」とは、（メタ）アクリル酸；（メタ）アクリル酸メチル、（メタ）アクリル酸エチルなどの（メタ）アクリル酸エステル；（メタ）アクリル酸アミド；などのアクリル酸系モノマーや、（メタ）アクリロニトリルなどの少なくとも重合性ビニル基とニトリル基を有するアクリロニトリル系モノマーに、必要に応じて他の共重合単量体を加えた共重合単量体組成物を共重合したアクリル系重合体に、架橋構造を導入したものを意味する。 This “acrylic crosslinked polymer” refers to (meth) acrylic acid; (meth) acrylic acid ester such as methyl (meth) acrylate and ethyl (meth) acrylate; acrylic acid such as (meth) acrylic acid amide; A copolymer monomer composition in which another copolymer monomer is added to an acrylonitrile monomer having at least a polymerizable vinyl group and a nitrile group such as (meth) acrylonitrile, if necessary, is copolymerized It means what introduce | transduced the crosslinked structure into the acrylic polymer.
上記のアクリル系重合体に用いるアクリル酸系モノマー、あるいはアクリロニトリル系モノマーは、１種を単独で使用してもよく、２種以上を同時に用いてもよい。また、上記の他の共重合単量体としては、最終的に得られる吸湿性微粒子の作用を損なうものでなければ特に限定されず、例えばハロゲン化ビニル、ハロゲン化ビニリデン、ｐ−スチレンスルホン酸塩などのスルホン酸含有モノマーおよびその塩、スチレン、酢酸ビニルなどのビニル系化合物やビニリデン系化合物などが使用可能である。 The acrylic acid monomer or acrylonitrile monomer used for the acrylic polymer may be used alone or in combination of two or more. Further, the above-mentioned other comonomer is not particularly limited as long as it does not impair the action of the finally obtained hygroscopic fine particles. For example, vinyl halide, vinylidene halide, p-styrene sulfonate And sulfonic acid-containing monomers such as styrene and vinyl acetate, vinylidene compounds such as vinyl acetate, and the like can be used.
架橋構造の導入は、上記の共重合単量体組成物に、さらに架橋構造を形成する共重合成分として２以上の重合性ビニル基を有する化合物を加え、これを共重合する方法が採用できる。２以上の重合性ビニル基を有する化合物としては、トリアリルイソシアヌレート、トリアリルシアヌレート、ジビニルベンゼン、エチレングリコールジ（メタ）アクリレート、メチレンビスアクリルアミドなどが好ましく用いられる。 For introducing the cross-linked structure, a method of adding a compound having two or more polymerizable vinyl groups as a copolymer component for forming a cross-linked structure to the above comonomer monomer composition and copolymerizing the compound can be employed. As the compound having two or more polymerizable vinyl groups, triallyl isocyanurate, triallyl cyanurate, divinylbenzene, ethylene glycol di (meth) acrylate, methylenebisacrylamide and the like are preferably used.
また、アクリル系重合体が、アクリロニトリル系モノマーに、必要に応じて他の共重合単量体を加えた共重合単量体組成物を共重合して得られるアクリロニトリル系重合体である場合は、ヒドラジン系化合物処理により、架橋構造を導入することも可能である。この場合に使用できるヒドラジン系化合物としては、ヒドラジン；水加ヒドラジン、硫酸ヒドラジン、塩酸ヒドラジン、硝酸ヒドラジン、臭素酸ヒドラジン、ヒドラジンカーボネートなどのヒドラジン塩類；エチレンジアミン、硫酸グアジニン、塩酸グアジニン、硝酸グアジニン、リン酸グアジニン、メラミンなどのヒドラジン誘導体などが挙げられる。 Further, when the acrylic polymer is an acrylonitrile polymer obtained by copolymerizing a copolymer monomer composition in which another copolymer monomer is added to an acrylonitrile monomer as required, It is also possible to introduce a crosslinked structure by treatment with a hydrazine compound. Examples of hydrazine compounds that can be used in this case include hydrazine; hydrated hydrazine, sulfate hydrazine, hydrazine hydrochloride, hydrazine nitrate, hydrazine bromate, hydrazine carbonate, and the like; ethylenediamine, sulfate guanidine, guanidine hydrochloride, guanidine nitrate, phosphate Examples include hydrazine derivatives such as guanidine and melamine.
上記の他の共重合単量体、２以上の重合性ビニル基を有する化合物、ヒドラジン系化合物は、夫々１種単独で、または２種以上を同時に使用することができる。 One of these other comonomer, compound having two or more polymerizable vinyl groups, and hydrazine compound can be used alone or in combination of two or more.
上記のアクリル系架橋重合体はいずれも、カルボキシル基を有するか、カルボキシル基に変性できる官能基を有するものであり、該カルボキシル基、あるいはカルボキシル基に変性できる官能基を塩型カルボキシル基に化学変換せしめることで、吸湿性微粒子が得られる。 Each of the above acrylic cross-linked polymers has a carboxyl group or a functional group that can be modified to a carboxyl group, and the carboxyl group or a functional group that can be modified to a carboxyl group is chemically converted to a salt-type carboxyl group. By causing it to absorb, hygroscopic fine particles are obtained.
このような吸湿性微粒子としては、例えば、アクリロニトリルを５０質量％以上含有する共重合単量体組成物を共重合したアクリロニトリル系重合体にヒドラジン系化合物により架橋構造を導入したアクリロニトリル系架橋重合体、あるいはアクリロニトリルを５０質量％以上含有し、さらに２以上の重合性ビニル基を有する化合物などを含有する共重合単量体組成物を共重合したアクリロニトリル系架橋重合体のニトリル基を加水分解により塩型カルボキシル基に化学変換せしめたものであって、該塩型カルボキシル基を１．０ｍｍｏｌ／ｇ以上含有するものなどが挙げられる。 Examples of such hygroscopic fine particles include, for example, an acrylonitrile-based crosslinked polymer in which a crosslinked structure is introduced by a hydrazine-based compound into an acrylonitrile-based polymer obtained by copolymerizing a comonomer composition containing 50% by mass or more of acrylonitrile, Alternatively, the nitrile group of an acrylonitrile-based crosslinked polymer obtained by copolymerizing a comonomer composition containing 50% by mass or more of acrylonitrile and further containing a compound having two or more polymerizable vinyl groups is converted into a salt form by hydrolysis. Examples thereof include those chemically converted to a carboxyl group and containing 1.0 mmol / g or more of the salt-type carboxyl group.
より好ましい態様としては、（Ａ）アクリロニトリルを８５質量％以上含有する共重合単量体組成物を共重合したアクリロニトリル系重合体に、窒素含有量の増加が０．１〜１５．０質量％となるようにヒドラジン系化合物処理により架橋構造を導入したアクリロニトリル系架橋重合体の残存しているニトリル基を加水分解により塩型カルボキシル基に化学変換せしめたものであって、該塩型カルボキシル基を１．０ｍｍｏｌ／ｇ以上有する吸湿性微粒子、（Ｂ）アクリロニトリルを５０質量％以上含有し、さらにジビニルベンゼンまたはトリアリルイソシアヌレート、および他の共重合単量体を含有する共重合単量体組成物を共重合して架橋構造を導入したアクリロニトリル系架橋重合体のニトリル基を加水分解により塩型カルボキシル基に化学変換せしめたものであって、該塩型カルボキシル基を２．０ｍｍｏｌ／ｇ以上含有する吸湿性微粒子、などが挙げられる。 As a more preferred embodiment, (A) an acrylonitrile-based polymer obtained by copolymerizing a comonomer composition containing 85% by mass or more of acrylonitrile has an increase in nitrogen content of 0.1 to 15.0% by mass. The remaining nitrile group of the acrylonitrile-based crosslinked polymer introduced with a crosslinked structure by treatment with a hydrazine compound is chemically converted to a salt-type carboxyl group by hydrolysis, and the salt-type carboxyl group is converted to 1 A comonomer composition comprising 0.0 mmol / g or more of hygroscopic fine particles, (B) containing 50% by mass or more of acrylonitrile, and further containing divinylbenzene or triallyl isocyanurate and other comonomer. Salt type carboxyl group by hydrolysis of nitrile group of acrylonitrile cross-linked polymer copolymerized and introduced with cross-linked structure Be those was allowed chemical transformation, hygroscopic fine particles containing salt-type carboxyl group 2.0 mmol / g or more, and the like.
なお、（Ａ）の吸湿性微粒子において「窒素含有量の増加」とは、原料となるアクリロニトリル系重合体中の窒素含有量（質量％）と、該樹脂にヒドラジン系化合物処理による架橋構造導入した後の窒素含有量（質量％）の差を意味する。この窒素含有量が上記範囲を下回ると、加水分解工程において有機微粒子が溶解し、塩型カルボキシル基を導入することができない。他方、上記範囲を超えるとニトリル基の１．０ｍｍｏｌ／ｇ以上を塩型カルボキシル基に変換できない。また、アクリロニトリル系重合体にヒドラジン系化合物による架橋を導入する方法は、該架橋による窒素含有量の増加が０．１〜１５．０質量％となる手段である限り特に限定されないが、ヒドラジン系化合物濃度１〜８０質量％、温度５０〜１２０℃で０．２〜１０時間処理する手段が工業的に好ましい。 In the hygroscopic fine particles of (A), “increase in nitrogen content” means that the nitrogen content (% by mass) in the acrylonitrile polymer used as a raw material and a crosslinked structure introduced into the resin by treatment with a hydrazine compound. It means the difference in the nitrogen content (mass%) after. When the nitrogen content is below the above range, the organic fine particles are dissolved in the hydrolysis step, and a salt-type carboxyl group cannot be introduced. On the other hand, when the above range is exceeded, 1.0 mmol / g or more of the nitrile group cannot be converted into a salt-type carboxyl group. In addition, the method of introducing a hydrazine-based crosslinking into the acrylonitrile-based polymer is not particularly limited as long as the increase in the nitrogen content by the crosslinking is 0.1 to 15.0% by mass, but the hydrazine-based compound is not limited. Means for treating at a concentration of 1 to 80% by mass and a temperature of 50 to 120 ° C. for 0.2 to 10 hours are industrially preferable.
吸湿性微粒子としては、上記のアクリロニトリル系架橋重合体を原料とするものの他、アクリル酸エステル５質量％以上含有し、さらにジビニルベンゼンまたはトリアリルイソシアヌレート、および他の共重合単量体を含有する共重合単量体組成物を共重合して架橋構造を導入したアクリル酸エステル系架橋重合体のメチルエステル部を加水分解により塩型カルボキシル基に化学変換せしめたものであって、該塩型カルボキシル基を１．０ｍｍｏｌ／ｇ以上含有する吸湿性微粒子なども好ましく使用できる。 As the hygroscopic fine particles, in addition to the acrylonitrile-based crosslinked polymer as a raw material, the hygroscopic fine particle contains 5% by mass or more of an acrylate ester, and further contains divinylbenzene or triallyl isocyanurate, and other comonomer. A methyl ester part of an acrylic ester cross-linked polymer obtained by copolymerizing a comonomer composition and introducing a cross-linked structure is chemically converted into a salt-type carboxyl group by hydrolysis, and the salt-type carboxyl Hygroscopic fine particles containing 1.0 mmol / g or more of groups can also be preferably used.
吸湿性微粒子の粒径は、自動車内装材用合成皮革の機械的性質などを損なうものでなければ、特に限定されるものではなく、用途に応じて適宜選択可能である。ただし、人が直接触れるハンドルやシートの表皮材へ用いられる場合、表面粗さが消費者に好まれない場合があるため、平均粒子径は５０μｍ以下であることが好ましい。より好ましくは３０μｍ以下、更に好ましくは２０μｍ以下である。なお、吸湿性微粒子の平均粒子径の下限は特に限定されないが、１μｍ以上が好適である。 The particle diameter of the hygroscopic fine particles is not particularly limited as long as it does not impair the mechanical properties of the synthetic leather for automobile interior materials, and can be appropriately selected according to the application. However, since the surface roughness may not be preferred by consumers when used on a handle or sheet skin material that is directly touched by a person, the average particle size is preferably 50 μm or less. More preferably, it is 30 micrometers or less, More preferably, it is 20 micrometers or less. The lower limit of the average particle size of the hygroscopic fine particles is not particularly limited, but 1 μm or more is preferable.
吸湿性微粒子の自動車内装材用合成皮革の樹脂層中の含有量（樹脂層が多層の場合は、全樹脂層に含まれる合計含有量）は２ｇ／ｍ2以上が好ましく、より好ましくは５ｇ／ｍ2以上である。２ｇ／ｍ2以上含有されていることにより、人が自動車内装材を触った際に、肌と内装材の間に介在する水分（汗）が素早く合成皮革に吸湿され、べたつき感を感じないものに仕上がる。前記含有量は特に限定されるものではないが、合成皮革の仕上がり、コストパフォーマンスなどから、５０ｇ／ｍ2以下であることが好ましいく、より好ましくは３０ｇ／ｍ2以下、さらに好ましくは、２０ｇ／ｍ2以下である。 The content of hygroscopic fine particles in the resin layer of the synthetic leather for automobile interior materials (when the resin layer is a multilayer, the total content contained in all resin layers) is preferably 2 g / m 2 or more, more preferably 5 g / m 2 or more. Containing 2 g / m 2 or more, when a person touches an automobile interior material, moisture (sweat) intervening between the skin and the interior material is quickly absorbed by the synthetic leather and does not feel sticky Finished. The content is not particularly limited, but is preferably 50 g / m 2 or less, more preferably 30 g / m 2 or less, and still more preferably 20 g / m 2 from the finish of synthetic leather, cost performance, and the like. m 2 or less.
前記樹脂層が多層である場合、最表層が吸湿性微粒子を含有することが好ましい。最表層が吸湿性微粒子を含有することにより、合成皮革のべたつき感をより少なくでき、よりサラサラした触感を付与できる。この場合、最表層中の吸湿性微粒子の含有量は２ｇ／ｍ2以上が好ましく、より好ましくは５ｇ／ｍ2以上であり、４０ｇ／ｍ2以下であることが好ましく、さらに好ましくは２０ｇ／ｍ2以下である。 When the resin layer is a multilayer, the outermost layer preferably contains hygroscopic fine particles. When the outermost layer contains hygroscopic fine particles, the stickiness of the synthetic leather can be reduced, and a more smooth feel can be imparted. In this case, the content of the hygroscopic fine particles in the outermost layer is preferably 2 g / m 2 or more, more preferably 5 g / m 2 or more, preferably 40 g / m 2 or less, more preferably 20 g / m 2. 2 or less.
本発明の自動車内装材用合成皮革は、基材層上に樹脂層を形成することで製造できる。樹脂層を形成する方法は特に限定されず、溶剤によって、液状化した合成樹脂を塗布した後に溶剤を乾燥させて樹脂層を形成する方法、液状の樹脂を塗布した後にその樹脂を反応させて形成する方法などの乾式法；合成樹脂からなる樹脂フィルムを貼り付けるラミネート法；液状の樹脂を塗布した後に凝固浴に導き凝固させる湿式法；などが挙げられる。また、合成皮革の表面に必要に応じてエンボス加工やシボ加工を施し、所望の外観を得ることが可能である。 The synthetic leather for automobile interior materials of the present invention can be produced by forming a resin layer on a base material layer. The method of forming the resin layer is not particularly limited, and a method of forming a resin layer by applying a liquefied synthetic resin with a solvent and then drying the solvent, and forming by reacting the resin after applying a liquid resin For example, a dry method such as a method for laminating; a laminating method for attaching a resin film made of a synthetic resin; a wet method for applying a liquid resin to a coagulation bath and coagulating it. In addition, the surface of the synthetic leather can be embossed or textured as necessary to obtain a desired appearance.
なお、上記ラミネート法を採用する場合には、樹脂フィルムを貼り付けるために用いる接着剤としては、表皮層との接着力を考慮し、ポリウレタン系接着剤を用いるのが好ましい。ポリウレタン系接着剤は、例えば、ポリエーテル系、ポリエステル系、ポリカーボネート系、又は、これらの複合型が挙げられる。接着剤は、硬化物の１００％モジュラスが０．５ＭＰａ〜５ＭＰａであるものが好ましく、耐屈曲性を考慮すると、０．５ＭＰａ〜３ＭＰａであるものが特に好ましい。 In addition, when employ | adopting the said lamination method, it is preferable to use a polyurethane-type adhesive as an adhesive used for affixing a resin film in consideration of the adhesive force with an outer skin layer. Examples of the polyurethane-based adhesive include polyether-based, polyester-based, polycarbonate-based, or a composite type thereof. The adhesive preferably has a 100% modulus of the cured product of 0.5 MPa to 5 MPa, and is preferably 0.5 MPa to 3 MPa in consideration of bending resistance.
本発明の自動車内装材用合成皮革は、合成皮革でありながら、本革と同等の掌内湿度の上昇レベルに抑えるほど吸湿特性に優れており、べたつき感が無くサラサラした触感を有する自動車内装材用合成皮革である。そのため上記特性を活かし、自動車用内装材、特にステアリング表皮、コンソールＢＯＸ表皮、シフトカバー材、インパネ材、ドアトリム材、天井表皮材、カーシート表皮材などに有用である。無論、用途との関係で要求性能に合うべき他の素材と組み合わせで用いることもでき、本発明の性能を低下させない範囲で加工を施し、形状を付与することもできる。さらに、製品化させる任意の段階で難燃化、防虫抗菌化、耐熱化、撥水撥油化、着色、芳香性などの機能を薬剤添加などにより付与することも可能である。 The synthetic leather for automobile interior materials according to the present invention is a synthetic leather, and has excellent moisture absorption properties so as to suppress the increase in palm moisture equivalent to that of genuine leather, and has no sticky feeling and a smooth feel. Synthetic leather. Therefore, taking advantage of the above characteristics, it is useful for automobile interior materials, particularly steering skins, console BOX skins, shift cover materials, instrument panel materials, door trim materials, ceiling skin materials, car seat skin materials and the like. Of course, it can also be used in combination with other materials that should meet the required performance in relation to the application, and can be processed and given a shape within a range that does not degrade the performance of the present invention. Furthermore, functions such as flame retardancy, insecticidal and antibacterial properties, heat resistance, water and oil repellency, coloring, and aromaticity can be imparted by adding chemicals at any stage of commercialization.
以下に実施例を挙げて本発明をより具体的に説明するが、本発明は、下記実施例によって限定されるものではなく、前・後記の趣旨に適合しうる範囲で適宜変更して実施することも可能であり、それらはいずれも本発明の技術的範囲に包含される。実施例において用いた測定方法は下記のとおりである。以下において、含有量ないし使用量を表す「％」及び「部」は、特記しないかぎり質量基準である。 The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples, and may be appropriately modified and implemented within a range that can meet the purpose described above and below. All of which are within the scope of the present invention. The measurement methods used in the examples are as follows. In the following, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.
１−１．掌内湿度
発汗シミュレーション測定装置を用い、水供給量：１４０ｇ／ｍ2・ｈ、熱板温度：３７℃、試料−熱板距離：０．５ｃｍ、環境温湿度：２０℃×６５％ＲＨ、発汗パターン：試験開始より５分発汗を実施し、熱板と試料間の空間の湿度を測定した。測定結果から、試験開始前の湿度に対する発汗１分経過時の湿度の上昇（ΔＨ）を求めた。
なお、発汗シミュレーション装置は、発汗孔を有する基体及び産熱体からなる産熱発汗機構、発汗孔に水を供給するための送水機構、産熱体の温度を制御する産熱制御機構、温湿度センサーから構成されている。基体は黄銅製で面積１２０ｃｍ2であり、発汗孔が６個設けられており、面状ヒーターからなる産熱体により一定温度に制御される。送水機構はチューブポンプを用いており、一定水量を基体の発汗孔に送り出す。基体表面には、厚み０．１ｍｍのポリエステルマルチフィラメント織物からなる模擬皮膚が貼り付けられており、これにより発汗孔から吐出された水が基体表面に広げられ、発汗状態が作り出される。基体の周囲には高さ０．５ｃｍの外枠が設けられており、試料を基体から０．５ｃｍ離れた位置にセットできる。温湿度センサーは基体と試料（合成皮革）との間の空間に設置され、基体が発汗状態の時の「基体と試料と外枠で囲まれた空間」の湿度を測定する。
1-1. Humidity inside the palm Using a sweating simulation measurement device, water supply amount: 140 g / m 2 · h, hot plate temperature: 37 ° C., sample-hot plate distance: 0.5 cm, environmental temperature and humidity: 20 ° C. × 65% RH, sweat Pattern: Sweating was carried out for 5 minutes from the start of the test, and the humidity of the space between the hot plate and the sample was measured. From the measurement results, the increase in humidity (ΔH) after one minute of sweating with respect to the humidity before the start of the test was determined.
The sweating simulation device includes a heat-producing sweating mechanism comprising a substrate having a sweating hole and a heat-producing body, a water-feeding mechanism for supplying water to the sweating hole, a heat-producing control mechanism for controlling the temperature of the heat-producing body, and temperature and humidity. It consists of sensors. The substrate is made of brass, has an area of 120 cm 2 , is provided with six sweat holes, and is controlled at a constant temperature by a heat-producing body composed of a planar heater. The water supply mechanism uses a tube pump, and sends out a constant amount of water to the sweat holes of the substrate. Simulated skin made of a polyester multifilament woven fabric having a thickness of 0.1 mm is affixed to the surface of the base, whereby water discharged from the perspiration holes is spread on the surface of the base and a sweating state is created. An outer frame having a height of 0.5 cm is provided around the substrate, and the sample can be set at a position 0.5 cm away from the substrate. The temperature / humidity sensor is installed in a space between the substrate and the sample (synthetic leather), and measures the humidity of the “space surrounded by the substrate, the sample and the outer frame” when the substrate is in a sweating state.
１−２．平均表面摩擦係数（特殊法）
カトーテック（株）製の表面摩擦係数測定器（ＫＥＳ−ＳＥ）を用いて、平均表面摩擦係数（ＭＩＵ）を測定した。測定条件は、標準摩擦子（指紋タイプ）、摩擦時の荷重１．４７Ｎ／ｃｍ2（１５０ｇｆ／ｃｍ2）、測定感度Ｌ（高感度１００ｇ／Ｖ）とした。摩擦距離、摩擦速度などその他の条件は装置仕様通りである（摩擦距離３０ｍｍ、解析距離２０ｍｍ、試料移動速度１ｍｍ／ｓｅｃ）。
1-2. Average surface friction coefficient (special method)
The average surface friction coefficient (MIU) was measured using a surface friction coefficient measuring device (KES-SE) manufactured by Kato Tech Co., Ltd. The measurement conditions were a standard friction element (fingerprint type), a load at friction of 1.47 N / cm 2 (150 gf / cm 2 ), and a measurement sensitivity L (high sensitivity 100 g / V). Other conditions such as the friction distance and the friction speed are as specified in the apparatus specification (friction distance 30 mm, analysis distance 20 mm, sample moving speed 1 mm / sec).
１−３．モニターによるべたつき感、サラサラ感、ザラツキ感の一対比較評価
１０人のモニターにより、試料のべたつき感、サラサラ感及びザラツキ感を一対比較法により判定した。
２５℃、６０％ＲＨの環境下に制御した恒温恒湿室に設置したカーシートにモニターを座らせ、カーシートの左右座面に比較対象となる２種の試料を各々敷いた。次いで、カーシート座面上にある左右各試料上に、モニターの左右の掌を１分間置いた。そして、１分後のべたつき感、サラサラ感、ザラツキ感を判定させた。左右どちらの試料がよりべたつかないか、サラサラしているか、ザラザラしていないかを判定し、全試料の組合せにて一対比較判定後、サーストンの一対比較法に準拠し、べたつき感、サラサラ感、ザラツキ感を−２〜＋２点で標準化して得点化した。なお、べたつき感は得点が高いほどべたつかず、サラサラ感は得点が高いほどサラサラしている感覚が高く、ザラツキ感は得点が高いほどザラザラしていないことを示す。
1-3. Paired Comparative Evaluation of Stickiness, Smoothness, and Roughness with a Monitor Using 10 monitors, the stickiness, smoothness, and roughness of a sample were determined by a paired comparison method.
The monitor was seated on a car seat installed in a constant temperature and humidity chamber controlled in an environment of 25 ° C. and 60% RH, and two types of samples to be compared were laid on the left and right seat surfaces of the car seat. Next, left and right palms of the monitor were placed on the left and right samples on the car seat seat for 1 minute. Then, a sticky feeling, a smooth feeling, and a rough feeling after 1 minute were judged. Determine whether the left or right sample is more sticky, smooth, or not rough, and after a paired comparison with all the sample combinations, according to Thurston's paired comparison method, stickiness, smoothness, The graininess was scored by standardizing from -2 to +2 points. In addition, the sticky feeling is not sticky as the score is high, and the smooth feeling is higher as the score is higher, and the feeling of smoothness is higher, and the rough feeling is higher as the score is higher.
１−４．外観
目視にて、合成皮革の表面状態を確認し、欠点、凹凸ムラ、塗りむらがないかを確認した。
1-4. Appearance Visually, the surface condition of the synthetic leather was confirmed, and it was confirmed that there were no defects, unevenness, and uneven coating.
１−５．平均粒子径
島津製作所製レーザー回折式粒度分布測定装置「ＳＡＬＤ−２００Ｖ」を使用して水を分散媒として測定し、体積基準で表した粒子径分布から、平均粒子径を求めた。
1-5. Average Particle Diameter Using a laser diffraction particle size distribution analyzer “SALD-200V” manufactured by Shimadzu Corporation, water was measured as a dispersion medium, and the average particle diameter was determined from the particle diameter distribution expressed on a volume basis.
１−６．塩型カルボキシル基量
十分乾燥した試料１ｇを精秤し（Ｘ（ｇ））、これに２００ｍｌの水を加えた後、５０℃に加温しながら１ｍｏｌ／ｌ塩酸水溶液を添加してｐＨ２とすることで、試料に含まれるカルボキシル基を全てＨ型カルボキシル基とした。次いで、０．１ｍｏｌ／ｌＮａＯＨ水溶液で常法に従って滴定曲線を求めた。該滴定曲線からＨ型カルボキシル基に消費されたＮａＯＨ水溶液消費量（Ｙ（ｍｌ））を求め、次式によって試料中に含まれる全カルボキシル基量を算出した。
（全カルボキシル基量（ｍｍｏｌ／ｇ））＝０．１×Ｙ／Ｘ
別途、上述の全カルボキシル基量測定操作中の１ｍｏｌ／ｌ塩酸水溶液添加によるｐＨ２への調整をすることなく同様に滴定曲線を求め、試料中に含まれるＨ型カルボキシル基量を求めた。これらの結果から次式により塩型カルボキシル基量を算出した。
（塩型カルボキシル基量（ｍｍｏｌ／ｇ））＝（全カルボキシル基量）−（Ｈ型カルボキシル基量）
1-6. Amount of salt-type carboxyl group 1 g of a sufficiently dried sample is precisely weighed (X (g)), 200 ml of water is added thereto, and then a 1 mol / l aqueous hydrochloric acid solution is added while heating to 50 ° C. to adjust the pH to 2. Thus, all the carboxyl groups contained in the sample were H-type carboxyl groups. Then, a titration curve was obtained according to a conventional method using a 0.1 mol / l NaOH aqueous solution. From the titration curve, the consumption amount of NaOH aqueous solution consumed in the H-type carboxyl groups (Y (ml)) was determined, and the total amount of carboxyl groups contained in the sample was calculated by the following formula.
(Total amount of carboxyl groups (mmol / g)) = 0.1 × Y / X
Separately, a titration curve was similarly obtained without adjusting to pH 2 by adding a 1 mol / l hydrochloric acid aqueous solution during the above-described total carboxyl group amount measurement operation, and the amount of H-type carboxyl groups contained in the sample was obtained. From these results, the salt-type carboxyl group amount was calculated by the following formula.
(Amount of salt-type carboxyl groups (mmol / g)) = (Total amount of carboxyl groups) − (Amount of H-type carboxyl groups)
１−７．不織布の密度
ＪＩＳ−Ｌ １９１３（２０１０）に準拠して求められた目付量及び厚みから１ｍ3当りの重量に換算しｇ／ｍ3として密度とした。具体的には、厚さ測定器により荷重２ｋＰａにて厚さを測定し、目付量を厚さで除することにより密度を求めた。
1-7. Density of non-woven fabric The weight per 1 m 3 was converted from the weight per unit area and thickness determined according to JIS-L 1913 (2010), and the density was defined as g / m 3 . Specifically, the thickness was measured by a thickness measuring instrument with a load of 2 kPa, and the density was determined by dividing the basis weight by the thickness.
１−８．不織布の初期応力
ＪＩＳ−Ｌ １９１３（２０１０）に準拠して測定された引張強度における５％伸長時の応力を初期応力とした。具体的には、幅５ｃｍ、長さ３０ｃｍの試験片を５枚準備し、それぞれについて引張試験を行い平均値を求めた。引張試験は、定速伸長形引張試験機につかみ間隔を２０ｃｍにして取り付け、１０ｃｍ／ｍｉｎの引張速度で試験片が切断するまで荷重を加えた。
1-8. Initial stress of nonwoven fabric The stress at 5% elongation in the tensile strength measured in accordance with JIS-L 1913 (2010) was defined as the initial stress. Specifically, five test pieces having a width of 5 cm and a length of 30 cm were prepared, and a tensile test was performed for each to obtain an average value. The tensile test was performed by attaching to a constant speed extension type tensile tester with a grip interval of 20 cm, and applying a load until the test piece was cut at a tensile speed of 10 cm / min.
１−９．不織布の破裂強度
ＪＩＳ−Ｌ １９１３（２０１０）破裂強さＢ法（定速伸長形法）に準拠した。具体的には直径８ｃｍの試験片を５枚採取し、先端曲率半径が１．２５ｃｍ、直径２．５ｃｍの押し棒を１００ｍｍ／ｍｉｎの定速加圧させた際の試験片を突き破る強さを測定しこれらの平均値を算出した。
1-9. Burst strength of nonwoven fabric JIS-L 1913 (2010) Burst strength B method (constant speed extension method) was used. Specifically, five specimens having a diameter of 8 cm were collected, and the strength to break through the specimen when a push rod having a tip radius of curvature of 1.25 cm and a diameter of 2.5 cm was pressed at a constant speed of 100 mm / min. The average value of these was calculated.
１−１０．不織布の剛軟度
ＪＩＳ−Ｌ １９１３（２０１０）に準拠した。具体的には、ＭＤ方向に２０ｃｍ、ＣＤ方向に２．５ｃｍ角の試験片をＣＤ方向の試験片全幅１ｍ当たり、６箇所において採取し４１．５°カンチレバー法に基づき裏表、計１２点にて測定しこれらの平均値を算出した。該方法はＭＤ方向の剛軟度結果であり、ＣＤ方向に関しては試験片方向を直交させ上述の如く、測定した結果である。
1-10. Bending softness of nonwoven fabric It conformed to JIS-L 1913 (2010). Specifically, test specimens of 20 cm in the MD direction and 2.5 cm square in the CD direction were sampled at 6 points per 1 m of the test piece full width in the CD direction, and the back and front sides based on the 41.5 ° cantilever method, a total of 12 points. The average value of these was calculated. This method is a result of bending resistance in the MD direction, and is a result of measurement as described above with the specimen direction orthogonal to the CD direction.
２．基材の作製
２−１．不織布（製造例１、比較例１の基材）
上層基材として、ポリアミド６とポリエチレンテレフタレートから構成される割繊前繊度０．２４ｄｔｅｘ中空花弁型割繊複合繊維である目付量８０ｇ／ｍ2である未割繊の短繊維複合割繊不織布を準備した。下層基材として、公知のスパンボンド法によりポリブチレンテレフタレート樹脂（以下「ＰＢＴ」と略す。）を、繊度が２．０ｄｔｅｘとなるようエアー元圧を調整し延伸させたフィラメント群を目付量が１００ｇ／ｍ2となるよう速度調整された樹脂ネット上に堆積させ、その後エンボスローラーにより仮接着加工を施しスパンボンド不織布を得た。得られたスパンボンド不織布の初期応力はタテ方向１８．０Ｎ／５ｃｍ、ヨコ方向７．５Ｎ／５ｃｍであった。
その後、公知のニードルパンチ法により、下層スパンボンド不織布からニードルが挿入されるように、上層分割繊維不織布と下層のスパンボンド不織布を繊維交絡させることによって、複合不織布を得た。さらに、その後、該上層基材と該下層基材とをウォーターパンチにより、高水圧処理を行い、割繊繊維を分割および積層させることができ、かつ剥離することなく上層と下層を交絡して目的の積層不織布を得た。得られた積層不織布の密度は１７２ｋｇ／ｍ3、破裂強度は７６０Ｎ、剛軟度はタテ方向１１０ｍｍ、ヨコ方向８１ｍｍであった。
2. 2. Production of substrate 2-1. Nonwoven fabric (base material of Production Example 1 and Comparative Example 1)
As an upper layer base material, an unbroken short fiber composite split nonwoven fabric with a basis weight of 80 g / m 2, which is a hollow petal split fiber composite fiber having a split fiber size of 0.24 dtex composed of polyamide 6 and polyethylene terephthalate, is prepared. did. As a lower layer base material, a filament group in which a polybutylene terephthalate resin (hereinafter abbreviated as “PBT”) is stretched by adjusting the air source pressure to a fineness of 2.0 dtex by a known spunbond method has a basis weight of 100 g. / M 2 , deposited on a resin net whose speed was adjusted, and then temporarily bonded with an embossing roller to obtain a spunbonded nonwoven fabric. The initial stress of the obtained spunbonded nonwoven fabric was 18.0 N / 5 cm in the vertical direction and 7.5 N / 5 cm in the horizontal direction.
Then, the composite nonwoven fabric was obtained by carrying out the fiber entanglement of the upper layer division | segmentation fiber nonwoven fabric and the lower layer spunbond nonwoven fabric by the well-known needle punch method so that a needle may be inserted from a lower layer spunbond nonwoven fabric. Furthermore, the upper layer base material and the lower layer base material are then subjected to a high water pressure treatment by water punch, and the split fiber can be divided and laminated, and the upper layer and the lower layer can be entangled without peeling. A laminated nonwoven fabric was obtained. The density of the obtained laminated nonwoven fabric was 172 kg / m 3 , the burst strength was 760 N, the bending resistance was 110 mm in the vertical direction and 81 mm in the horizontal direction.
２−２．編物（製造例２〜８、比較例２〜８の基材）
８４ｄｔｅｘ／３６ｆのポリエステルフィラメントを使用し、目付量が３００ｇ／ｍ2のトリコット編物を得た。
2-2. Knitted fabric (base materials of Production Examples 2 to 8 and Comparative Examples 2 to 8)
Using a polyester filament of 84 dtex / 36f, a tricot knitted fabric with a basis weight of 300 g / m 2 was obtained.
３．微粒子
３−１．吸湿性微粒子Ｎｏ．１（平均粒子径；３μｍ）
アクリロニトリル４５０部、アクリル酸メチル５０部及び水１１８１部を２リットルのオートクレーブ内に仕込み、更に重合開始剤としてジ−ｔｅｒｔ−ブチルパーオキサイドを単量体全量に対して０．５％添加した後、密閉し、次いで攪拌下において１２０℃の温度にて３０分間重合した。反応終了後、攪拌を継続しながら９０℃まで冷却することにより平均粒子径が２μｍの重合体粒子を得た。次いで、得られた重合体粒子１００部に６０％水加ヒドラジン６０部および水８５０部を混合し、９０℃、３時間の条件でヒドラジン処理を行うことにより架橋を導入し、さらに、１１２部の水酸化ナトリウムを添加し、１２０℃、２時間反応を行った。得られた粒子を水洗、洗浄、乾燥後、分級し、平均粒子径３μｍのアクリル系架橋重合体微粒子を得た。該粒子の塩型カルボキシル基量は７．０ｍｍｏｌ／ｇであった。また、ヒドラジン処理による窒素含有量の増加は１．５質量％であった。
3. Fine particles 3-1. Hygroscopic fine particles No. 1 (average particle size; 3 μm)
After charging 450 parts of acrylonitrile, 50 parts of methyl acrylate and 1181 parts of water into a 2 liter autoclave and further adding 0.5% of di-tert-butyl peroxide as a polymerization initiator with respect to the total amount of monomers, Sealed and then polymerized for 30 minutes at 120 ° C. under stirring. After completion of the reaction, the mixture was cooled to 90 ° C. while continuing stirring to obtain polymer particles having an average particle size of 2 μm. Next, 60 parts of 60% hydrazine and 850 parts of water were mixed with 100 parts of the obtained polymer particles, and crosslinking was introduced by performing hydrazine treatment at 90 ° C. for 3 hours. Sodium hydroxide was added and reacted at 120 ° C. for 2 hours. The obtained particles were washed, washed and dried, and then classified to obtain acrylic crosslinked polymer fine particles having an average particle diameter of 3 μm. The amount of the salt-type carboxyl group of the particles was 7.0 mmol / g. Moreover, the increase in nitrogen content by hydrazine treatment was 1.5% by mass.
３−２．吸湿性微粒子Ｎｏ．２（平均粒子径；３０μｍ）
アクリロニトリル５５部、アクリル酸メチル１０部、ジビニルベンゼン３５部からなるモノマー混合物を、０．５部の過硫酸アンモニウムを含む水溶液３００部に添加し、次いでピロ亜硫酸ナトリウム０．６部を加え、攪拌機つきの重合槽で６５℃、２時間重合した。得られた粒子１５部を水８５部中に分散し、これに水酸化ナトリウム１０部を添加し、９０℃で２時間加水分解反応を行った後、洗浄、脱水、乾燥を行い、アクリル系架橋重合体微粒子を得た。該粒子の平均粒子径は３０μｍ、塩型カルボキシル基量は６．３ｍｍｏｌ／ｇであった。
3-2. Hygroscopic fine particles No. 2 (average particle size; 30 μm)
A monomer mixture consisting of 55 parts of acrylonitrile, 10 parts of methyl acrylate, and 35 parts of divinylbenzene is added to 300 parts of an aqueous solution containing 0.5 part of ammonium persulfate, and then 0.6 part of sodium pyrosulfite is added, followed by polymerization with a stirrer. Polymerization was carried out in a tank at 65 ° C. for 2 hours. 15 parts of the obtained particles are dispersed in 85 parts of water, and 10 parts of sodium hydroxide is added thereto, followed by hydrolysis at 90 ° C. for 2 hours, followed by washing, dehydration and drying, and acrylic crosslinking. Polymer fine particles were obtained. The average particle size of the particles was 30 μm, and the amount of salt-type carboxyl groups was 6.3 mmol / g.
３−３．ＰＭＭＡ粒子Ｎｏ．１（平均粒子径；３μｍ）
メタクリル酸メチル９０部、エチレングリコールジメタクリレート１０部、２，２’−アゾビス（２，４−ジメチルバレロニトリル）１部、ポリビニルアルコール１０部、水３００部を混合、ホモミキサーで撹拌することによってモノマー分散液を作成し、５０℃で２時間重合した。得られた粒子を水洗、脱水、乾燥した後、分級処理することにより、平均粒子径３μｍのポリメタクリル酸メチル系微粒子を得た。
3-3. PMMA particle no. 1 (average particle size; 3 μm)
Monomer by mixing 90 parts of methyl methacrylate, 10 parts of ethylene glycol dimethacrylate, 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile), 10 parts of polyvinyl alcohol and 300 parts of water and stirring with a homomixer. A dispersion was prepared and polymerized at 50 ° C. for 2 hours. The obtained particles were washed with water, dehydrated, dried, and then classified to obtain polymethyl methacrylate-based fine particles having an average particle diameter of 3 μm.
３−４．ＰＭＭＡ粒子Ｎｏ．２（平均粒子径；３０μｍ）
メタクリル酸メチル９０部、エチレングリコールジメタクリレート１０部、２，２’−アゾビス（２，４−ジメチルバレロニトリル）１部、ポリビニルアルコール１０部、水３００部を混合、ホモミキサーで撹拌することによってモノマー分散液を作成し、５０℃で２時間重合した。得られた粒子を水洗、脱水、乾燥した後、分級処理することにより、平均粒子径３０μｍのポリメタクリル酸メチル系微粒子を得た。
3-4. PMMA particle no. 2 (average particle size; 30 μm)
Monomer by mixing 90 parts of methyl methacrylate, 10 parts of ethylene glycol dimethacrylate, 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile), 10 parts of polyvinyl alcohol and 300 parts of water and stirring with a homomixer. A dispersion was prepared and polymerized at 50 ° C. for 2 hours. The obtained particles were washed with water, dehydrated, dried, and then classified to obtain polymethyl methacrylate-based fine particles having an average particle diameter of 30 μm.
４．合成樹脂
４−１．ウレタン樹脂
ウレタン樹脂としては、１００％モジュラスが２〜１０ＭＰａである無黄変ポリカーボネート型ポリウレタンを使用した。
4). Synthetic resin 4-1. Urethane resin As the urethane resin, a non-yellowing polycarbonate type polyurethane having a 100% modulus of 2 to 10 MPa was used.
４−２．高滑性ウレタン樹脂
高滑性ウレタン樹脂としては、１００％モジュラスが５〜１０ＭＰａであるシリコーン変性無黄変ポリカーボネート型ポリウレタンを使用した。
4-2. High slip urethane resin As the high slip urethane resin, a silicone-modified non-yellowing polycarbonate polyurethane having a 100% modulus of 5 to 10 MPa was used.
５．合成皮革の製造
５−１．製造例１
上記にて得られた不織布を水性溶液のディップニップ法で質量比１８％のポリビニルアルコール（ＰＶＡ）樹脂を付着せしめた。これらはシート自身に寸法安定性を付与し、ウレタン樹脂との置換を実施するためである。
ポリウレタン樹脂溶液を、湿分付着７３０ｇ／ｍ2になるようにナイフコーターで塗布し、６０℃の温水でＰＶＡ樹脂を置換洗浄し、１２０℃の熱風で乾燥した。乾燥後ウレタン塗布目付量としては２２０ｇ／ｍ2となり、湿式合成皮革を得た。湿式合成皮革トータルで目付量４００ｇ／ｍ2、厚さ１．３ｍｍとした。さらに、離型紙上に溶剤に溶かしたウレタン樹脂をコンマコーターで、２５ｇ／ｍ2となるよう塗布し、乾燥させて作製した乾式層となるフィルムを、接着剤（約３０ｇ／ｍ2）を塗布した上記湿式合成皮革に張り合わせ、その後、エージング処理を行い、樹脂層を積層した。ここで、基材と樹脂層とのトータルで目付量４５５ｇ／ｍ2、厚さ１．６ｍｍとした。なお、接着剤には、ポリウレタン系接着剤を使用した。
前記高滑性ウレタン樹脂に吸湿性微粒子Ｎｏ．１を混合し、上記にて形成した樹脂層上にグラビアコートにて規定量付与し、最表層を形成した。離型紙を用い、本革様シボ加工を施し合成皮革を得た。
5. Manufacture of synthetic leather 5-1. Production Example 1
A polyvinyl alcohol (PVA) resin having a mass ratio of 18% was adhered to the nonwoven fabric obtained above by a dip nip method using an aqueous solution. These are for imparting dimensional stability to the sheet itself and for replacing it with a urethane resin.
The polyurethane resin solution was applied with a knife coater so as to have a moisture adhesion of 730 g / m 2 , the PVA resin was replaced with hot water at 60 ° C. and dried with hot air at 120 ° C. After drying, the urethane coating weight per unit area was 220 g / m 2 , and wet synthetic leather was obtained. The total weight of wet synthetic leather was 400 g / m 2 and the thickness was 1.3 mm. Further, apply a urethane resin dissolved in a solvent on the release paper with a comma coater so that it becomes 25 g / m 2, and dry it, and apply an adhesive (about 30 g / m 2 ) to form a dry layer. The wet synthetic leather was laminated, and then an aging treatment was performed to laminate a resin layer. Here, the total weight of the base material and the resin layer was 455 g / m 2 and the thickness was 1.6 mm. Note that a polyurethane adhesive was used as the adhesive.
The highly lubricious urethane resin has hygroscopic fine particles No. 1 was mixed, and a prescribed amount was applied by gravure coating on the resin layer formed above to form an outermost layer. Synthetic leather was obtained by applying a genuine leather-like texture using release paper.
５−２．製造例２
離型紙上に溶剤に溶かしたウレタン樹脂をコンマコーターで、２５ｇ／ｍ2となるよう塗布し、乾燥させて作製したフィルムを、接着剤（約３０ｇ／ｍ2）を塗布した上記編地に張り合わせ、その後、エージング処理を行い、樹脂層を形成した。ここで、基材と樹脂層とのトータルで、目付量３５５ｇ／ｍ2、厚さ０．９ｍｍとした。
前記高滑性ウレタン樹脂に吸湿性微粒子Ｎｏ．１を混合し、上記にて形成した樹脂層上にグラビアコートにて規定量付与し、最表層を形成した。離型紙を用い、本革様シボ加工を施し合成皮革を得た。
5-2. Production Example 2
A urethane resin dissolved in a solvent is applied onto a release paper with a comma coater so that it is 25 g / m 2, and the film produced by drying is bonded to the knitted fabric coated with an adhesive (about 30 g / m 2 ). Thereafter, an aging treatment was performed to form a resin layer. Here, the total weight of the base material and the resin layer was 355 g / m 2 and the thickness was 0.9 mm.
The highly lubricious urethane resin has hygroscopic fine particles No. 1 was mixed, and a prescribed amount was applied by gravure coating on the resin layer formed above to form an outermost layer. Synthetic leather was obtained by applying a genuine leather-like texture using release paper.
５−３．製造例３〜５
高滑性ウレタン樹脂に混合する吸湿性微粒子の含有量、又は、含有量と平均粒子径を変更したこと以外は製造例２と同様にして合成皮革を得た。
5-3. Production Examples 3-5
Synthetic leather was obtained in the same manner as in Production Example 2 except that the content of the hygroscopic fine particles to be mixed with the highly lubricious urethane resin, or the content and the average particle size were changed.
５−４．製造例６
溶剤に溶かしたウレタン樹脂に吸湿性微粒子Ｎｏ．１を混合し、離型紙上にコンマコーターで２５ｇ／ｍ2となるよう塗布し、乾燥させて作製したフィルムを、接着剤（約３０ｇ／ｍ2）を塗布した上記編地に張り合わせ、その後、エージング処理を行い、樹脂層を形成した。ここで、基材と樹脂層とのトータルで、目付量３５５ｇ／ｍ2、厚さ０．９ｍｍとした。
前記高滑性ウレタン樹脂に吸湿性微粒子Ｎｏ．１を混合し、上記にて形成した樹脂層上にグラビアコートにて規定量付与し、最表層を形成した。離型紙を用い、本革様シボ加工を施し合成皮革を得た。
5-4. Production Example 6
Hygroscopic fine particles No. in urethane resin dissolved in solvent. 1 was mixed and applied onto a release paper with a comma coater so as to be 25 g / m 2, and the film produced by drying was bonded to the knitted fabric coated with an adhesive (about 30 g / m 2 ), and then An aging treatment was performed to form a resin layer. Here, the total weight of the base material and the resin layer was 355 g / m 2 and the thickness was 0.9 mm.
The highly lubricious urethane resin has hygroscopic fine particles No. 1 was mixed, and a prescribed amount was applied by gravure coating on the resin layer formed above to form an outermost layer. Synthetic leather was obtained by applying a genuine leather-like texture using release paper.
５−５．製造例７
溶剤に溶かしたウレタン樹脂に吸湿性微粒子Ｎｏ．１を混合し、離型紙上にコンマコーターで２５ｇ／ｍ2となるよう塗布し、乾燥させて作製したフィルムを、接着剤（約３０ｇ／ｍ2）を塗布した上記編地に張り合わせ、その後、エージング処理を行い、樹脂層（最表層）を形成し、合成皮革を得た。
すなわち、高滑性ウレタン樹脂による最表層を形成しなかったこと以外は製造例６と同様にして合成皮革を得た。
5-5. Production Example 7
Hygroscopic fine particles No. in urethane resin dissolved in solvent. 1 was mixed and applied onto a release paper with a comma coater so as to be 25 g / m 2, and the film produced by drying was bonded to the knitted fabric coated with an adhesive (about 30 g / m 2 ), and then Aging treatment was performed to form a resin layer (outermost layer) to obtain a synthetic leather.
That is, a synthetic leather was obtained in the same manner as in Production Example 6 except that the outermost layer was not formed with a highly slippery urethane resin.
５−６．製造例８
ウレタン樹脂に混合する微粒子を、ＰＭＭＡ粒子Ｎｏ．１に変更したこと以外は製造例６と同様にして合成皮革を得た。
5-6. Production Example 8
The fine particles mixed with the urethane resin are designated as PMMA particles No. A synthetic leather was obtained in the same manner as in Production Example 6 except that it was changed to 1.
５−７．製造例９
高滑性ウレタン樹脂に混合する微粒子を、ＰＭＭＡ粒子Ｎｏ．１に変更したこと以外は製造例１と同様にして合成皮革を得た。
5-7. Production Example 9
Fine particles mixed with the highly lubricious urethane resin are designated as PMMA particles No. A synthetic leather was obtained in the same manner as in Production Example 1 except that it was changed to 1.
５−８．製造例１０
高滑性ウレタン樹脂に混合する微粒子を、ＰＭＭＡ粒子Ｎｏ．１に変更したこと以外は製造例２と同様にして合成皮革を得た。
5-8. Production Example 10
Fine particles mixed with the highly lubricious urethane resin are designated as PMMA particles No. A synthetic leather was obtained in the same manner as in Production Example 2 except that the number was changed to 1.
５−９．製造例１１
高滑性ウレタン樹脂に混合する微粒子を、ＰＭＭＡ粒子Ｎｏ．１に変更し、含有量を変更したこと以外は製造例２と同様にして合成皮革を得た。
5-9. Production Example 11
Fine particles mixed with the highly lubricious urethane resin are designated as PMMA particles No. A synthetic leather was obtained in the same manner as in Production Example 2 except that the content was changed to 1.
５−１０．製造例１２
高滑性ウレタン樹脂に混合する微粒子を、ＰＭＭＡ粒子Ｎｏ．２に変更し、含有量を変更したこと以外は製造例２と同様にして合成皮革を得た。
5-10. Production Example 12
Fine particles mixed with the highly lubricious urethane resin are designated as PMMA particles No. The synthetic leather was obtained in the same manner as in Production Example 2 except that the content was changed to 2.
５−１１．製造例１３
ウレタン樹脂に微粒子を混合しなかったこと以外は製造例７と同様にして合成皮革を得た。
5-11. Production Example 13
A synthetic leather was obtained in the same manner as in Production Example 7 except that the urethane resin was not mixed with fine particles.
５−１２．製造例１４
ウレタン樹脂に混合する微粒子及び高滑性ウレタン樹脂に混合する微粒子を、いずれもＰＭＭＡ粒子Ｎｏ．１に変更したこと以外は製造例６と同様にして合成皮革を得た。
5-12. Production Example 14
The fine particles mixed with the urethane resin and the fine particles mixed with the highly slippery urethane resin are both PMMA particles No. A synthetic leather was obtained in the same manner as in Production Example 6 except that it was changed to 1.
５−１３．製造例１５
ウレタン樹脂に混合する微粒子を、ＰＭＭＡ粒子Ｎｏ．１に変更したこと以外は製造例７と同様にして合成皮革を得た。
5-13. Production Example 15
The fine particles mixed with the urethane resin are designated as PMMA particles No. A synthetic leather was obtained in the same manner as in Production Example 7 except that the number was changed to 1.
５−１４．製造例１６
高滑性ウレタン樹脂に混合する微粒子を、ＰＭＭＡ粒子Ｎｏ．１に変更したこと以外は製造例６と同様にして合成皮革を得た。
5-14. Production Example 16
Fine particles mixed with the highly lubricious urethane resin are designated as PMMA particles No. A synthetic leather was obtained in the same manner as in Production Example 6 except that it was changed to 1.
上記製造例１〜１６で得た合成皮革の構成及び掌内湿度、平均表面摩擦係数の評価結果を表１に示した。また、製造例１〜１６で得た合成皮革の平均表面摩擦係数と掌内湿度の発汗開始１分後の上昇分（ΔＨ）の関係を図１に示した。なお、参考例１として、実車に搭載されているカーシート用本革についても、同様の評価を行い、結果を図１に示した。 Table 1 shows the composition of the synthetic leather obtained in Production Examples 1 to 16, and the evaluation results of the humidity in the palm and the average surface friction coefficient. In addition, FIG. 1 shows the relationship between the average surface friction coefficient of the synthetic leather obtained in Production Examples 1 to 16 and the increase (ΔH) in the palm humidity one minute after the start of sweating. In addition, as Reference Example 1, the same evaluation was performed on the genuine leather for car seats mounted on an actual vehicle, and the results are shown in FIG.
また、モニターによるべたつき感、サラサラ感、ザラツキ感の主観評価結果を表２に示した。べたつき感は正の得点でべたつかない感覚、サラサラ感は正の得点でサラサラする感覚、ザラツキ感は正の得点でざらつかない感覚が得られることを示す。 Table 2 shows the subjective evaluation results of the stickiness, smoothness, and roughness of the monitor. A sticky sensation indicates that a positive score is not sticky, a smooth sensation is a positive score that feels smooth, and a rough sensation indicates that a positive score is not rough.
表１より、製造例２の掌内湿度の上昇が最も小さい傾向が見られ、次いで製造例６、１、３、５の順で掌内湿度の上昇が小さい傾向が見られた。製造例１〜８と参考例１（図１参照）に関しては、１分後の掌内湿度の上昇（ΔＨ）の値が、２０％ＲＨ以下であることが確認され、モニターの主観評価においても、べたつかない感覚が得られている。これらに対して、製造例９〜１６の試料は全て初期の段階から掌内湿度の上昇が早く、１分後のΔＨの値も２０％ＲＨ以上の値を示しており、モニターの主観評価でもべたつき感の評価は悪い傾向が見られている。 From Table 1, the tendency for the increase in the palm humidity in Production Example 2 to be the smallest was observed, and then the trend for the increase in palm moisture in the order of Production Examples 6, 1, 3, and 5 was observed. Regarding Production Examples 1 to 8 and Reference Example 1 (see FIG. 1), it was confirmed that the increase in palm humidity (ΔH) after 1 minute was 20% RH or less. , A non-sticky feeling is obtained. On the other hand, the samples in Production Examples 9 to 16 all showed a rapid increase in palm humidity from the initial stage, and the ΔH value after 1 minute also showed a value of 20% RH or more. There is a tendency for the evaluation of stickiness to be bad.
製造例２は、樹脂層が多層であり、最表層の吸湿性微粒子含有量が他の製造例よりも多く吸湿性能に優れたものと推察される。製造例６はウレタン樹脂層と高滑性ウレタン樹脂層の両方に吸湿性微粒子が含有されており、吸湿性に優れたものと推察される。そのため、これらの製造例２、６では、参考例１の本革よりも掌内湿度の上昇を抑え、べたつき感を感じにくい試料に仕上がっている。 In Production Example 2, the resin layer is multi-layered, and it is surmised that the outermost layer has a hygroscopic fine particle content higher than that of the other production examples and is excellent in moisture absorption performance. In Production Example 6, hygroscopic fine particles are contained in both the urethane resin layer and the highly slipping urethane resin layer, and it is assumed that the hygroscopic property is excellent. Therefore, in these production examples 2 and 6, the increase in the palm humidity is suppressed as compared with the genuine leather of Reference Example 1, and the samples are finished to be less sticky.
図１より、製造例１３は特殊法による平均表面摩擦係数が０．４以上、製造例１５は０．２あり、滑りにくい傾向が見られた。また、掌内湿度の１分後の上昇は製造例９〜１６の全試料でΔＨ２０％ＲＨを超え、参考例１の本革よりも５％ＲＨ以上高い値を示した。ちなみに通常、人は５％ＲＨ以上の差を体感できるといわれている。そのため、本革と比較し、製造例９〜１６の合成皮革は、べたつき感の大きいものと言え、中でも製造例１３、１５は表面摩擦抵抗も高く、サラサラ感も得られないものであることがわかる。 From FIG. 1, Production Example 13 had an average surface friction coefficient by a special method of 0.4 or more, Production Example 15 had 0.2, and a tendency to be slippery was observed. In addition, the increase in palm humidity after 1 minute exceeded ΔH20% RH in all the samples of Production Examples 9 to 16, and was 5% RH higher than the leather of Reference Example 1. Incidentally, it is usually said that a person can experience a difference of 5% RH or more. Therefore, compared with genuine leather, the synthetic leathers of Production Examples 9 to 16 can be said to have a great feeling of stickiness. Among them, Production Examples 13 and 15 have a high surface friction resistance and cannot have a smooth feeling. Recognize.
上記結果（ΔＨ：１分後の掌内湿度の上昇分、ＭＩＵ：特殊法による平均表面摩擦係数、べたつき感・サラサラ感・ザラツキ感：モニターによる主観結果）に加えて、外観、コストパフォーマンスを４段階（◎：大変良好、○：良好、△：普通、×：不良）で評価した。結果を表３に示す。 In addition to the above results (ΔH: increase in palm humidity after 1 minute, MIU: average surface friction coefficient by special method, stickiness, smoothness, roughness: subjective results by monitor), appearance and cost performance are 4 Evaluation was made at the stage (◎: very good, ○: good, Δ: normal, x: poor). The results are shown in Table 3.
表３より、べたつき感、サラサラ感、ザラツキ感以外の外観、コストパフォーマンスを考慮した場合、製造例３の構成が効果的であると推察される。しかし、製造例１〜８において１分後の掌内湿度の上昇は２０％ＲＨ以下であり、べたつき感が無く、サラサラした触感が得られていることから、製造例１〜８で得られた合成皮革は、いずれもべたつき感が少なく、且つサラサラした触感を持つ自動車内装材用合成皮革であるといえる。これに対して、製造例９〜１６で得られた合成皮革は、全て１分後の掌内湿度の上昇が２０％ＲＨを超えており、べたつき感が不良な自動車内装材用合成皮革であるといえる。 From Table 3, it is presumed that the configuration of Production Example 3 is effective when the appearance and cost performance other than stickiness, smoothness, and roughness are taken into consideration. However, in Production Examples 1 to 8, the increase in palm humidity after 1 minute was 20% RH or less, and there was no stickiness and a smooth feel was obtained. Thus, Production Examples 1 to 8 were obtained. Synthetic leather can be said to be a synthetic leather for automobile interior materials that has little stickiness and a smooth feel. On the other hand, the synthetic leathers obtained in Production Examples 9 to 16 are all synthetic leather for automobile interior materials in which the increase in palm humidity after 1 minute exceeds 20% RH and the stickiness is poor. It can be said.
また、本発明の合成皮革は、用いる吸湿性微粒子の量が少なく、微粒子を付与するための樹脂量も少ないため、従来の合成皮革と比較し、軽量化効果があり、コストパフォーマンスにも優れる自動車内装材用合成皮革であるといえる。 In addition, the synthetic leather of the present invention uses a small amount of hygroscopic fine particles and uses a small amount of resin for imparting fine particles, and therefore has an effect of reducing the weight and is excellent in cost performance compared to conventional synthetic leather. It can be said that it is a synthetic leather for interior materials.
本発明の自動車内装材用合成皮革は、自動車用内装材、特にステアリング表皮、コンソールＢＯＸ表皮、シフトカバー材、インパネ材、ドアトリム材、天井表皮材、カーシート表皮材などに有用である。 The synthetic leather for automobile interior materials of the present invention is useful for automobile interior materials, particularly steering skins, console BOX skins, shift cover materials, instrument panel materials, door trim materials, ceiling skin materials, car seat skin materials, and the like.
Claims (7)
該合成皮革の目付量が２５０ｇ／ｍ 2 以上であり、
前記樹脂層が吸湿性微粒子を含有し、かつ発汗シミュレーション装置測定による掌内湿度の発汗開始１分後の上昇（ΔＨ）が２０％ＲＨ以下であり、
１．４７Ｎ／ｃｍ2荷重時の平均表面摩擦係数（ＭＩＵ）が０．２５以下であることを特徴とする自動車内装材用合成皮革。 Synthetic leather for automobile interior materials in which a resin layer made of a single layer or multilayer synthetic resin is formed on a base layer of a nonwoven fabric or woven or knitted fabric having a single layer or multilayer structure,
The basis weight of the synthetic leather is 250 g / m 2 or more,
The resin layer contains hygroscopic fine particles, and the increase (ΔH) in 1 minute after the start of sweating in the palm by the sweating simulation apparatus measurement is 20% RH or less,
1. Synthetic leather for automobile interior material, having an average surface friction coefficient (MIU) of 0.25 or less at a load of 1.47 N / cm 2 .
上層の目付量が４０ｇ／ｍ2〜１５０ｇ／ｍ2、上層を構成する繊維の繊度が０．０００１ｄｔｅｘ〜０．５ｄｔｅｘであり、
下層の目付量が４０ｇ／ｍ2〜２００ｇ／ｍ2、下層を構成する繊維の繊度が１．５ｄｔｅｘ〜１０．０ｄｔｅｘである請求項１〜５のいずれか一項に記載の自動車内装材用合成皮革。 The base material layer is a nonwoven fabric having a two-layer structure in which a fiber structure constituting an upper layer and a fiber structure constituting a lower layer are laminated by mechanical entanglement,
The fineness of the fibers basis weight of the upper layer constitutes 40g / m 2 ~150g / m 2 , the upper layer is 0.0001Dtex～0.5Dtex,
Basis weight of the lower layer 40g / m 2 ~200g / m 2 , automotive interior materials for synthesis according to any one of claims 1-5 fineness of the fiber constituting the lower layer is 1.5dtex~10.0dtex leather.
該不織布は、密度が１２０ｋｇ／ｍ3〜２５０ｋｇ／ｍ3、破裂強度が４００Ｎ〜１０００Ｎかつ剛軟度が１ｍｍ〜１２０ｍｍである請求項１〜６のいずれか一項に記載の自動車内装材用合成皮革。 The base material layer is a nonwoven fabric having a single layer or a multilayer structure,
The nonwoven fabric had a density of 120kg / m 3 ~250kg / m 3 , burst strength 400N~1000N and bending resistance synthetic automotive interior material according to any one of claims 1 to 6 is 1mm~120mm leather.
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| JP6267016B2 (en) * | 2014-03-07 | 2018-01-24 | 東洋紡株式会社 | Synthetic leather |
| JP2016150972A (en) * | 2015-02-17 | 2016-08-22 | ユニチカトレーディング株式会社 | Moisture heat resistant film and blood/virus barrier laminated fabric using the same |
| CN110725136A (en) * | 2018-07-17 | 2020-01-24 | 安安(中国)有限公司 | Processing method of environment-friendly superfine fiber synthetic leather for automotive interior |
| JP7097292B2 (en) * | 2018-08-15 | 2022-07-07 | 日軽メタル株式会社 | Leather laminate and sheet material |
| JP6911215B1 (en) * | 2021-01-22 | 2021-07-28 | 大日精化工業株式会社 | Porous layer structure and method for manufacturing the porous layer structure |
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| JPH0754277A (en) * | 1993-08-10 | 1995-02-28 | Unitika Ltd | Production of moisture-permeable water-proofing coated cloth |
| JP4516204B2 (en) * | 2000-11-27 | 2010-08-04 | 東洋紡績株式会社 | Moisture permeable waterproof fabric |
| JP2002266113A (en) * | 2001-02-28 | 2002-09-18 | Mizuno Corp | Warmth-keeping product using artificial leather containing moisture-absorbing and releasing fiber generating heat by water-absorption |
| JP2002339215A (en) * | 2001-05-10 | 2002-11-27 | Toyobo Co Ltd | Moisture-absorbing/releasing leather like nonwoven fabric and method for producing the same |
| JP4352304B2 (en) * | 2002-09-12 | 2009-10-28 | 東洋紡績株式会社 | Humidity control automotive interior materials |
| JP4359818B2 (en) * | 2003-01-28 | 2009-11-11 | 東洋紡績株式会社 | Coated fabric |
| WO2006085522A1 (en) * | 2005-02-08 | 2006-08-17 | Tradik Co., Ltd. | Artificial leather and base therefor, and processes for production of both |
| JP4436917B2 (en) * | 2005-03-31 | 2010-03-24 | セーレン株式会社 | Synthetic leather manufacturing method |
| JP2007247079A (en) * | 2006-03-14 | 2007-09-27 | Toyobo Co Ltd | Laminated nonwoven fabric and synthetic leather using the same |
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