JP4652198B2 - Synthetic resin sheet - Google Patents
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- JP4652198B2 JP4652198B2 JP2005286117A JP2005286117A JP4652198B2 JP 4652198 B2 JP4652198 B2 JP 4652198B2 JP 2005286117 A JP2005286117 A JP 2005286117A JP 2005286117 A JP2005286117 A JP 2005286117A JP 4652198 B2 JP4652198 B2 JP 4652198B2
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Description
本発明は、室内環境浄化材料として使用される、特にソファー、応接セット、車両内装材、車両シート等に使用される合成皮革等の合成樹脂シートに関する。 The present invention relates to a synthetic resin sheet such as a synthetic leather used as an indoor environment purification material, in particular, a sofa, a reception set, a vehicle interior material, a vehicle seat and the like.
近年、シックハウス症候群、シックビル症候群が大きな社会問題となっている。環境に対する問題意識が重要視され、各種製品の製造、開発に際して原料中に含まれる有機溶媒の大気中への放出、拡散が規制されるようになってきている。
このような社会情勢から、本発明者らは各種用途に用いられる合成皮革から有機溶剤の揮散を抑えるために検討を重ね、有機溶剤を用いない合成皮革について提案した（特願２００５−１３８３３１）。
In recent years, sick house syndrome and sick building syndrome have become major social problems. Awareness of environmental issues is regarded as important, and the release and diffusion of organic solvents contained in raw materials into the atmosphere during the manufacture and development of various products has been regulated.
From such a social situation, the present inventors have repeatedly studied to suppress the volatilization of the organic solvent from the synthetic leather used for various applications, and proposed synthetic leather that does not use the organic solvent (Japanese Patent Application No. 2005-138331).
また、自動車などの車内も室内と同様であり、車内で発生するホルムアルデヒドの低減について提案されている。特許文献１は、車内で接着剤や内装材から発生する揮発性有機物質のホルムアルデヒドを吸着するために多孔質の消臭剤を配合した接着剤組成物に関する。特許文献２は、自動車の天井材等の内装材に使用されるフェノール樹脂から発生するホルムアルデヒドを生地シートの片面に存在させた吸着剤で抑制しようとするものである。 In addition, the interior of a vehicle such as an automobile is the same as that in a room, and reduction of formaldehyde generated in the vehicle has been proposed. Patent Document 1 relates to an adhesive composition containing a porous deodorant to adsorb formaldehyde, a volatile organic substance generated from an adhesive or interior material in a vehicle. Patent Document 2 intends to suppress formaldehyde generated from a phenol resin used for an interior material such as a ceiling material of an automobile with an adsorbent that is present on one side of a fabric sheet.
しかしながら、特許文献１は、有機溶剤系接着剤で、しかもフェノール系樹脂を用いた汎用される接着剤の改良であって、それ自体からのホルムアルデヒドの発生を抑えることを主眼としたものであり、また、特許文献２は、自動車の天井材等の内装材に使用されるフェノール樹脂から発生するホルムアルデヒドを生地シートの片面に存在させた吸着剤で抑制しようとするものであって、両者は内装材から発生することを前提として、発生する材料の直近にある接着剤で吸収しようとするものである。 However, Patent Document 1 is an organic solvent-based adhesive, and is an improvement of a general-purpose adhesive using a phenolic resin, and mainly aims to suppress the generation of formaldehyde from itself. Patent Document 2 tries to suppress formaldehyde generated from a phenol resin used for interior materials such as automobile ceiling materials with an adsorbent that is present on one side of a fabric sheet, both of which are interior materials. It is intended to be absorbed by the adhesive immediately adjacent to the generated material.
吸着材料を含む接着剤は接着対象相互間に存在するから、空気中に存在する揮発性有機物質は材料を透過しないと吸着されない。従って環境浄化の観点から、大きな効果は期待できない。
本発明は、表面に揮発性有機物質を吸着する表面層を設けることで、柔軟な風合いや物性を損なうことなく吸着性を向上させた合成樹脂シートを提供することを課題とする。
Since the adhesive containing the adsorbing material exists between the objects to be bonded, volatile organic substances present in the air are not adsorbed unless they pass through the material. Therefore, a great effect cannot be expected from the viewpoint of environmental purification.
This invention makes it a subject to provide the synthetic resin sheet which improved the adsorptivity without impairing a soft texture and physical property by providing the surface layer which adsorb | sucks a volatile organic substance on the surface.
すなわち、本発明は、（１）合成樹脂と基布からなる合成樹脂シートを基材としてその表面に、ガス成分を吸着する表面層が形成された合成樹脂シート状物であって、該表面層がアミノアルキルトリアルコキシシランを含むシリコン変性ウレタン樹脂組成物からなることを特徴とする合成樹脂シート状物、（２）アミノアルキルトリアルコキシシランが、アミノプロピルトリメトキシシラン、アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、Ｎ−フェニルγアミノプロピルトリメトキシシランから選ばれた少なくとも１種のアミノアルキルトリアルコキシシランであることを特徴とする（１）記載の合成樹脂シート状物、（３）（１）又は（２）記載の合成樹脂シート状物において、前記合成樹脂がポリウレタン樹脂であることを特徴とする合成皮革、に関する。
That is, the present invention provides (1) a synthetic resin sheet-like product in which a surface layer that adsorbs a gas component is formed on the surface of a synthetic resin sheet comprising a synthetic resin and a base fabric, and the surface layer A synthetic resin sheet-like material characterized by comprising a silicon-modified urethane resin composition containing aminoalkyltrialkoxysilane, (2) aminoalkyltrialkoxysilane is aminopropyltrimethoxysilane, aminopropyltriethoxysilane , N At least one aminoalkyltrialkoxy selected from -β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-phenylγaminopropyltrimethoxysilane characterized in that it is a silane (1) a synthetic resin sheet according , (3) in (1) or (2) a synthetic resin sheet as claimed, synthetic leather, wherein the synthetic resin is a polyurethane resin, about.
本発明の合成樹脂シート状物は、ＶＯＣの吸着能力に優れ、しかも表面強度にも優れた環境浄化材料として好適である。 The synthetic resin sheet-like material of the present invention is suitable as an environmental purification material having excellent VOC adsorption capability and excellent surface strength.
本発明の合成樹脂シート状物は、ガス成分を吸着する表面層が形成された合成樹脂シート状物であり、表面層はシリコン変性ウレタン樹脂とアミノアルキルトリアルコキシシランからなる。
本発明の表面層に使用されるシリコン変性ウレタン樹脂としては、レザミンＳＰ２００、レザミンＳＰ３００、レザロイドＬＵ４３４７、レザロイドＬＵ４３０５（大日精化工業（株）製）が挙げられる。
The synthetic resin sheet-like material of the present invention is a synthetic resin sheet-like material on which a surface layer that adsorbs gas components is formed, and the surface layer is composed of a silicon-modified urethane resin and an aminoalkyltrialkoxysilane.
Examples of the silicon-modified urethane resin used in the surface layer of the present invention include Rezamin SP200, Rezamin SP300, Rezaroid LU4347, Rezaroid LU4305 (manufactured by Dainichi Seika Kogyo Co., Ltd.).
本発明に使用されるアミノアルキルトリアルコキシシランとしては、アミノアルキルトリアルコキシシランが、アミノプロピルトリメトキシシラン、アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、Ｎ−フェニルγアミノプロピルトリメトキシシラン等が挙げられる。具体的には、ＴＳＬ８３３１、ＴＳＬ８３３０、ＴＳＬ８３４０、ＴＳＬ８３４５（ＧＥ東芝シリコーン（株）製）が挙げられる。
As the aminoalkyltrialkoxysilane used in the present invention, aminoalkyltrialkoxysilane is aminopropyltrimethoxysilane, aminopropyltriethoxysilane , N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-phenylγaminopropyltrimethoxysilane and the like can be mentioned. Specifically, TSL8331, TSL8330, TSL8340, TSL8345 (made by GE Toshiba Silicone Co., Ltd.) are mentioned.
アミノアルキルトリアルコキシシランのシリコン変性ウレタン樹脂への添加量は樹脂１００重量部当たり１〜３０重量部が好ましく、３〜２０重量部がより好ましい。添加量が３０重量部を超えると無機性が強くなり、合成樹脂シートの風合いを損ねる虞があり、１重量部未満であると吸着能力に劣る。５〜１５重量部が最も好ましい範囲である。
本発明の合成樹脂シート状物において、基材は表面層を形成するベースであって、その表面に本発明の表面層を形成できる合成樹脂シート状物で有れば良く、家具や車両用の合成樹脂レザー、合成皮革が用いられる。中でも表面層との密着性の点でウレタン樹脂からなる合成皮革が好ましい。
The amount of aminoalkyltrialkoxysilane added to the silicon-modified urethane resin is preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight per 100 parts by weight of the resin. If the added amount exceeds 30 parts by weight, the inorganic property becomes strong, and the texture of the synthetic resin sheet may be impaired. 5 to 15 parts by weight is the most preferable range.
In the synthetic resin sheet-like material of the present invention, the base material is a base for forming a surface layer, and may be a synthetic resin sheet-like material that can form the surface layer of the present invention on the surface thereof. Synthetic resin leather and synthetic leather are used. Of these, synthetic leather made of urethane resin is preferable in terms of adhesion to the surface layer.
基材として最も好ましいのは、基材自体からの有機溶剤などの揮散を抑えた無溶剤型硬化性樹脂組成物からなる本発明者ら提案の合成皮革であって、そのウレタン樹脂を構成する原料の各成分をプレポリマーの状態で使用し、合成皮革製造の段階で硬化反応をさせて基布と複合一体させた合成皮革である。その無溶剤型硬化性ウレタン樹脂は分子量が１０００〜３０００程度の高分子量ポリオールとポリイソシアネートを反応硬化させたウレタン樹脂で、ポリイソシアネートが分子量２００以下の短鎖グリコールとジイソシアネートとの付加物からなるプレポリマーであってイソシアネート基含有率が１０〜２５％であり、かつ遊離ＮＣＯ基が１〜４％である。 The most preferable as the base material is a synthetic leather proposed by the present inventors consisting of a solventless curable resin composition that suppresses volatilization of organic solvents and the like from the base material itself, and is a raw material constituting the urethane resin. These components are used in the form of a prepolymer, and are subjected to a curing reaction at the synthetic leather production stage to be combined and integrated with the base fabric. The solvent-free curable urethane resin is a urethane resin obtained by reaction-curing a high molecular weight polyol having a molecular weight of about 1000 to 3000 and a polyisocyanate, and a prepolymer comprising an adduct of a short-chain glycol having a molecular weight of 200 or less and a diisocyanate. The polymer has an isocyanate group content of 10 to 25% and free NCO groups of 1 to 4%.
尚、本発明に用いる合成樹脂シートの基布としては、例えば、綿布、ポリエステル／レーヨン、ポリエステル、ポリアミドなどからなるメリヤス編布やニット、織布、およびこれらの起毛布、不織布等、従来から合成皮革などの製造加工に使用されるものを使用することができる。 As the base fabric of the synthetic resin sheet used in the present invention, for example, a knitted fabric, knit, woven fabric made of cotton, polyester / rayon, polyester, polyamide, etc. What is used for manufacturing processes, such as leather, can be used.
本発明の合成樹脂シート状物は、その表面層に可視光応答型光触媒を含有させることができる。吸着されたガス成分を分解促進することで、ソファー、応接セット、車両内装材、車両シート等に使用される合成皮革等の合成樹脂シートとして更に好適なものとなる。 The surface layer of the synthetic resin sheet-like product of the present invention can contain a visible light responsive photocatalyst. By promoting the decomposition of the adsorbed gas component, it becomes more suitable as a synthetic resin sheet such as synthetic leather used for sofas, reception sets, vehicle interior materials, vehicle seats and the like.
以下に本発明の実施例を挙げ本発明を具体的に説明する。ただし、本発明はこれに限定
されるものではない。
Hereinafter, the present invention will be specifically described with reference to examples of the present invention. However, the present invention is not limited to this.
実施例1
シリコン変性ウレタン樹脂（ＳＰ２００；大日精化工業（株）製）１００重量部に対してアミノアルキルトリアルコキシシラン（ＴＳＬ８３３１；ＧＥ東芝シリコーン（株）製）１０重量部を含むシリコン変性ウレタン樹脂組成物を、離型紙（旭ロール（株）製、ＡＲ−２２）上に、アミノアルキルトリアルコキシシランが０．２ｇ／ｍ２となるようにコーティングして、まず表面層を形成した。
Example 1
A silicon-modified urethane resin composition containing 10 parts by weight of aminoalkyltrialkoxysilane (TSL8331; manufactured by GE Toshiba Silicone) with respect to 100 parts by weight of silicon-modified urethane resin (SP200; manufactured by Dainichi Seika Kogyo Co., Ltd.) On the release paper (AR-22, manufactured by Asahi Roll Co., Ltd.), the aminoalkyltrialkoxysilane was coated at 0.2 g / m 2 to form a surface layer.
平均分子量８００の高分子量ポリオール（クラレポリオールＣ８００；（株）クラレ製）８００ｇ、ジプロピレングリコール／ヘキサメチレンジイソシアネート付加物（ＮＣＯ基含有率：２０％）５０４ｇ、ジブチル錫ジラウレート０．６８ｇを、遊離ＮＣＯ基を１．３％に調整して、表面層の上に厚さ０．４ｍｍに塗布し、８０℃の乾燥オーブン中を6分間通過させた。 800 g of high molecular weight polyol having an average molecular weight of 800 (Kuraray polyol C800; manufactured by Kuraray Co., Ltd.), dipropylene glycol / hexamethylene diisocyanate adduct (NCO group content: 20%) 504 g, dibutyltin dilaurate 0.68 g, and free NCO The base was adjusted to 1.3%, applied to a thickness of 0.4 mm on the surface layer, and passed through a drying oven at 80 ° C. for 6 minutes.
更にその上に、上記高分子量ポリオールを８００ｇ、上記ポリイソシアネートを５４６ｇ、上記触媒を０．２８ｇ混合し、厚さ０．１５ｍｍで塗布し、６０℃で２分間加熱した後、ポリエステル繊維製ニット生地に圧着し、室温で３日間熟成した後離型紙を剥離し合成皮革（合成樹脂シート状物）を得た。 Furthermore, 800 g of the above high molecular weight polyol, 546 g of the above polyisocyanate, and 0.28 g of the above catalyst were mixed, applied at a thickness of 0.15 mm, heated at 60 ° C. for 2 minutes, and then knit fabric made of polyester fiber. After being aged at room temperature for 3 days, the release paper was peeled off to obtain a synthetic leather (synthetic resin sheet).
この得られた合成皮革から１００ｃｍ２の試験サンプルを切り出し、ガス吸着試験と耐洗濯性試験を以下のように行った。アセトアルデヒド１００ｐｐｍのテドラーバッグ（容積５リットル）内に４８時間放置して後、ガス濃度を測定したところ初期濃度に対して６５％が吸着されていた。 A test sample of 100 cm 2 was cut out from the obtained synthetic leather, and a gas adsorption test and a washing resistance test were performed as follows. After standing in a Tedlar bag (volume 5 liters) of 100 ppm acetaldehyde for 48 hours and measuring the gas concentration, 65% of the initial concentration was adsorbed.
また、得られた合成皮革を縦横３０ｃｍの正方形に切り出し、市販の洗剤（アタック）３ｇ／リットルで連続１２０分間洗濯し、次いで３０分間通水して洗濯した。その後、脱水室温乾燥して、上記と同様に１００ｃｍ２の試験サンプルを得た。上記と同様にして吸着試験を行ったところ６３％が吸着されていた。 Further, the obtained synthetic leather was cut into a square of 30 cm in length and width, washed with a commercially available detergent (attack) 3 g / liter for 120 minutes continuously, and then washed by passing water for 30 minutes. Then, it dehydrated and dried at room temperature to obtain a 100 cm 2 test sample as described above. When an adsorption test was performed in the same manner as described above, 63% was adsorbed.
実施例２
実施例１と同様にしてまず合成皮革を製造した。この合成皮革の表面にシリコン変性ウレタン樹脂（ＳＰ２００；大日精化工業（株）製）１００重量部に対してアミノアルキルトリアルコキシシラン（ＴＳＬ８３４０；ＧＥ東芝シリコーン（株）製）１０重量部を含むシリコン変性ウレタン樹脂組成物を、アミノアルキルトリアルコキシシランが０．２ｇ／ｍ２となるようにコーティングして表面層を形成した。
この合成皮革を用いて実施例１と同様に試験したところ、結果は５５％及び５４％であった。
Example 2
First, synthetic leather was produced in the same manner as in Example 1. Silicon containing 10 parts by weight of aminoalkyltrialkoxysilane (TSL8340; manufactured by GE Toshiba Silicone) with respect to 100 parts by weight of silicon-modified urethane resin (SP200; manufactured by Dainichi Seika Kogyo Co., Ltd.) on the surface of this synthetic leather A surface layer was formed by coating the modified urethane resin composition so that the aminoalkyltrialkoxysilane was 0.2 g / m 2 .
When this synthetic leather was tested in the same manner as in Example 1, the results were 55% and 54%.
実施例３
実施例１のＳＰ２００に替えてＮＥＳ９９５０を用いた以外は実施例１と同様にして合成皮革を製造した。この合成皮革について実施例１と同様に試験したところ６５％及び６４％であった。
Example 3
A synthetic leather was produced in the same manner as in Example 1 except that NES9950 was used instead of SP200 in Example 1. When this synthetic leather was tested in the same manner as in Example 1, it was 65% and 64%.
比較例１
実施例１のアミノアルキルトリアルコキシシランに替えてアジピン酸ジヒドラジドを吸着剤として用い、実施例と同様にして合成皮革を製造した。
実施例１と同様にして吸着試験を行った（但し、放置時間は９０時間）ところ６０％が吸着されていた。また実施例１と同様に洗濯乾燥後に試験を行ったところ初期ガス濃度の減少がみられなかった。
Comparative Example 1
Synthetic leather was produced in the same manner as in Example 1, except that adipic acid dihydrazide was used as an adsorbent in place of the aminoalkyltrialkoxysilane of Example 1.
An adsorption test was conducted in the same manner as in Example 1 (however, the standing time was 90 hours), and 60% was adsorbed. Further, when the test was carried out after washing and drying as in Example 1, no decrease in the initial gas concentration was observed.
Claims (3)
The synthetic resin sheet-like product according to claim 1 or 2, wherein the synthetic resin is a polyurethane resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005286117A JP4652198B2 (en) | 2005-09-30 | 2005-09-30 | Synthetic resin sheet |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005286117A JP4652198B2 (en) | 2005-09-30 | 2005-09-30 | Synthetic resin sheet |
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|---|---|
| JP2007090799A JP2007090799A (en) | 2007-04-12 |
| JP4652198B2 true JP4652198B2 (en) | 2011-03-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100969041B1 (en) * | 2008-03-25 | 2010-07-09 | 현대자동차주식회사 | Human skin feeling polyurethane artificial leather using non-organic solvent and Preparing method thereof |
| KR101466327B1 (en) * | 2012-10-30 | 2014-12-11 | 공주대학교 산학협력단 | Adsorbents Using Alum Sludges and Adsorbents Having Modified Surfaces |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000177088A (en) * | 1998-12-21 | 2000-06-27 | Dainippon Printing Co Ltd | Decoration sheet |
| JP2005076157A (en) * | 2003-09-02 | 2005-03-24 | Dainichiseika Color & Chem Mfg Co Ltd | Synthetic imitation leather and method for producing the same |
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- 2005-09-30 JP JP2005286117A patent/JP4652198B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000177088A (en) * | 1998-12-21 | 2000-06-27 | Dainippon Printing Co Ltd | Decoration sheet |
| JP2005076157A (en) * | 2003-09-02 | 2005-03-24 | Dainichiseika Color & Chem Mfg Co Ltd | Synthetic imitation leather and method for producing the same |
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| JP2007090799A (en) | 2007-04-12 |
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