JP2012149142A - Polyurethane resin molded article - Google Patents
Polyurethane resin molded article Download PDFInfo
- Publication number
- JP2012149142A JP2012149142A JP2011007513A JP2011007513A JP2012149142A JP 2012149142 A JP2012149142 A JP 2012149142A JP 2011007513 A JP2011007513 A JP 2011007513A JP 2011007513 A JP2011007513 A JP 2011007513A JP 2012149142 A JP2012149142 A JP 2012149142A
- Authority
- JP
- Japan
- Prior art keywords
- polyurethane resin
- resin molded
- powder
- molded product
- bamboo
- 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.)
- Granted
Links
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 63
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 57
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 57
- 241001330002 Bambuseae Species 0.000 claims abstract description 57
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 57
- 239000011425 bamboo Substances 0.000 claims abstract description 57
- 239000003610 charcoal Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 15
- 241000196324 Embryophyta Species 0.000 claims description 23
- 238000000465 moulding Methods 0.000 claims description 23
- 239000011162 core material Substances 0.000 claims description 17
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 abstract description 13
- 239000004814 polyurethane Substances 0.000 abstract description 13
- 230000008961 swelling Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 8
- 239000010410 layer Substances 0.000 abstract description 7
- 230000035515 penetration Effects 0.000 abstract description 7
- 238000002347 injection Methods 0.000 abstract description 3
- 239000007924 injection Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000011247 coating layer Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
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- 238000004332 deodorization Methods 0.000 abstract 1
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- 239000002994 raw material Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 12
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- 150000003077 polyols Chemical class 0.000 description 12
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 11
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 11
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 11
- 239000005642 Oleic acid Substances 0.000 description 11
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 11
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 11
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
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- 239000004970 Chain extender Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
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- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
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- ZFQOKLYYNBBPHT-UHFFFAOYSA-N 3,4,5-triethylbenzene-1,2-diamine Chemical compound CCC1=CC(N)=C(N)C(CC)=C1CC ZFQOKLYYNBBPHT-UHFFFAOYSA-N 0.000 description 1
- NPZVJXUOSPGWEW-UHFFFAOYSA-N 3,4-diethylbenzene-1,2-diamine Chemical compound CCC1=CC=C(N)C(N)=C1CC NPZVJXUOSPGWEW-UHFFFAOYSA-N 0.000 description 1
- ZYCRBOCGBKATBL-UHFFFAOYSA-N 3-tert-butyl-6-methylbenzene-1,2-diamine Chemical compound CC1=CC=C(C(C)(C)C)C(N)=C1N ZYCRBOCGBKATBL-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 1
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- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
Description
この発明は、ポリウレタン樹脂成形品、例えば自動車用ステアリングホイール、トランスミッションコントロール用ノブなどの把持操作部品、インストルメントパネル、ピラーガーニッシュなどの内装パネル等に適用可能なポリウレタン樹脂成形品に関する。 The present invention relates to a polyurethane resin molded product, for example, a polyurethane resin molded product applicable to an interior panel such as an instrument panel and a pillar garnish, for example, a steering operation part for an automobile, a knob for transmission control, and the like.
ポリウレタン樹脂成形品は、ソフトな触感が得られ、また一体の表皮の下に発泡層を形成する、いわゆるインテグラルスキンフォームの形式とすれば一層ソフトな感触となって、人が触れあるいは把持操作などする部分、例えば、ステアリングホィール、アシストグリップやノブ、内装トリム材であるインストルメントパネル、アッパーパネルやピラーガーニッシュ、ドアトリムなどに適用して、好ましい感触を実現することができる。
一方、ポリウレタン樹脂では、油分の含侵による膨潤の課題もある。
上記の用途にあっては、手油、手入れ用ワックス剤などの油がポリウレタン樹脂成形品の表面に付着し、それが長期的に成形品内部に浸透して、成形品を膨張させることがある。そのため、寸法変化や、組み合わされる他の部品との合わせ品質の問題や、芯材の外側を覆う形態では、芯材との密着性にも影響を及ぼすことがあり、例えば、ステアリングホイールではグリップ部が空転するおそれもある。
Polyurethane resin molded products provide a soft tactile sensation, and a so-called integral skin foam type that forms a foamed layer under the integral skin provides a softer sensation that can be touched or gripped by humans. For example, a steering wheel, an assist grip and a knob, an instrument panel which is an interior trim material, an upper panel, a pillar garnish, a door trim, and the like can be used to achieve a preferable feel.
On the other hand, polyurethane resins also have a problem of swelling due to impregnation of oil.
In the above applications, oils such as hand oil and care wax may adhere to the surface of polyurethane resin molded products, which may penetrate into the molded product for a long time and cause the molded product to expand. . For this reason, dimensional changes, quality problems with other components to be combined, and the form of covering the outside of the core material may affect the adhesion to the core material. May run idle.
ステアリングホィールの芯材との密着性を向上する方法としては、たとえば芯材にポリウレタン表皮との機械的結合を向上させるような形状を設定する、というものがある（特許文献１）。
しかしながら、触感を重視する観点からは、芯材を異型等にしてアンカー作用を生じさせるため、内部の凹凸形状が表面から握ったときの感触を悪化させるとの懸念がある。すなわち、例えば中空の芯材の表面部に開口を形成すると、開口部ではウレタン表皮を下支えするものがなくなり、開口しない部分との圧縮に対する反力差を生ずることがある。また、型内の囲まれた空間で発泡する樹脂の発泡力が変化するので発泡の均一性が損なわれる懸念もある。すなわち、空間に向かって未反応樹脂が本流である外周リム部の反応液フローから分岐するため、下流に向かって流れる反応液の金型内面による押さえこまれかたに変化を生ずる。下流に流れる反応液を押送する力も減少し、反応液のスムーズな流れが阻害される惧れがある。また芯材を断面略三角管状とするなどの断面周方向で顕著に芯材の形状を変える場合にあっては角部と辺部とで感触が異なりゴツゴツ感やエッジ感（角当たり感）が出やすい。
As a method for improving the adhesion of the steering wheel to the core material, for example, there is a method of setting the core material so as to improve the mechanical coupling with the polyurethane skin (Patent Document 1).
However, from the viewpoint of emphasizing the tactile sensation, there is a concern that the feel when the inner concavo-convex shape is grasped from the surface is deteriorated because the anchoring material is generated by making the core material atypical. That is, for example, when an opening is formed in the surface portion of the hollow core material, there is no support for the urethane skin in the opening, and there may be a difference in reaction force against compression with the portion that does not open. In addition, since the foaming force of the foaming resin changes in the enclosed space in the mold, there is a concern that the uniformity of foaming may be impaired. That is, since the unreacted resin branches from the reaction liquid flow in the outer peripheral rim portion which is the main stream toward the space, a change occurs in how the reaction liquid flowing toward the downstream is held down by the inner surface of the mold. The force for pushing the reaction liquid flowing downstream also decreases, and there is a concern that the smooth flow of the reaction liquid may be hindered. In addition, when the shape of the core material is remarkably changed in the circumferential direction of the cross section, such as the core material having a substantially triangular tubular shape, the feel is different between the corner and the side, and the ruggedness and edge feeling (feel per corner) is different. Easy to come out.
油分の浸透による膨潤では、芯材とウレタン表皮の間でさらにミクロのズレを生ずるが、そのような場合に芯材の異型化による効果は限定的であり、または、長期に亘る安定性を与えるものとは言い難い。
芯材と表皮ウレタンとの密着性を向上する方法として、プライマーや接着層を形成する方法もある。しかし、この密着性向上手段も、厳重に行うことは、塗布工程、乾燥工程に大きなエネルギー消費や溶剤の放散を伴い、地球環境に及ぼす負荷が増大する惧れがある。もちろん、このような工程を簡略化または廃止することができなければ、安価にウレタン表皮付き部材を市場に提供することは難しくなる。
Swelling due to oil penetration causes further micro-displacement between the core material and the urethane skin, but in such a case, the effect of deforming the core material is limited or provides long-term stability. It's hard to say.
As a method for improving the adhesion between the core material and the skin urethane, there is a method of forming a primer or an adhesive layer. However, if this adhesion improving means is also performed strictly, there is a possibility that the burden on the global environment will increase with great energy consumption and solvent dissipation in the coating process and drying process. Of course, if such a process cannot be simplified or eliminated, it will be difficult to provide a member with a urethane skin to the market at a low cost.
本発明は、油分が浸透することによる成形品の膨潤を防止して、その寸法変化や被覆層（表皮ポリウレタン層）とインサート材等の内部部材との密着性の低減を解消して、成形品の経時的安定性を向上させることを目的としている。
また、安全性に優れ、環境負荷を少なくして膨潤抑制効果の付与された表皮付ポリウレタン製品を提供することを目的としている。
The present invention prevents the swelling of the molded product due to the permeation of oil, eliminates the dimensional change and the reduction of the adhesion between the coating layer (skin polyurethane layer) and the internal member such as the insert material, and the molded product. The purpose is to improve the stability over time.
Another object of the present invention is to provide a polyurethane product with a skin that is excellent in safety, has a reduced environmental burden, and is imparted with a swelling suppression effect.
本発明者らは、鋭意検討した結果、ＲＩＭ成形によるポリウレタン樹脂成形品に対して、竹粉と竹炭と乾留竹粉から選択した植物粉体の一種または二種以上を配合することが前記課題解決に有効であることを知見して、本発明に至った。
すなわち、本発明は、
１．竹粉と竹炭粉と乾留竹粉から選択した植物粉体の一種または二種以上を含有する射出反応ポリウレタン樹脂からなり、該植物粉体の粒径Ｄが、１０≦Ｄ≦３００μｍ であるポリウレタン樹脂成形品。
２．該植物粉体の粒径Ｄが、１０≦Ｄ≦１００μｍ である（１）記載のポリウレタン樹脂成形品。
３．該植物粉体の添加量Ｃは、０＜Ｃ≦２０重量％ である（１）または（２）記載のポリウレタン樹脂成形品。
４．（１）ないし（３）いずれか１項に記載のポリウレタン樹脂成形品である表皮で芯材を覆った、乗り物の把持操作部品。
に関する。
As a result of intensive studies, the present inventors have solved the above problem by blending one or more plant powders selected from bamboo powder, bamboo charcoal, and dry-distilled bamboo powder into a polyurethane resin molded product by RIM molding. As a result, the present invention has been found.
That is, the present invention
1. A polyurethane resin comprising an injection-reacting polyurethane resin containing one or more plant powders selected from bamboo powder, bamboo charcoal powder and dry-distilled bamboo powder, and the particle size D of the plant powder is 10 ≦ D ≦ 300 μm Molding.
2. The polyurethane resin molded product according to (1), wherein the particle size D of the plant powder is 10 ≦ D ≦ 100 μm.
3. The polyurethane resin molded product according to (1) or (2), wherein the addition amount C of the plant powder is 0 <C ≦ 20 wt%.
4). (1) thru | or (3) The holding | grip operation component of a vehicle which covered the core material with the skin which is the polyurethane resin molded product of any one of (1) thru | or.
About.
本発明によれば、ポリウレタン樹脂成形品は、配合した前記特定の植物粉体の多孔質構造が浸透する油分を吸収するため、油分による樹脂の膨張を防止することができ、その結果、寸法変化をきたすことなく、また、ポリウレタン樹脂と芯材などの内部部材との密着性の低下を防止することができる。
また、前記植物粉体は、天然物であり、これが配合されたポリウレタン樹脂成形品は、アレルギー発症などの人体への悪影響もなく、安全性にも優れている。
加えて、特定の植物粉体の抗菌、脱臭作用も同時に発揮され、衛生的で乗り物内などポリウレタン樹脂成形品を備えた室内を快適にすることができる。
更に、こうした効果を発現する一方で、配合した特定の植物粉体による樹脂成形品の機械的物性への影響もない。
According to the present invention, the polyurethane resin molded article absorbs the oil that penetrates into the porous structure of the specific plant powder that has been blended, and therefore can prevent the resin from expanding due to the oil, resulting in a dimensional change. In addition, it is possible to prevent a decrease in adhesion between the polyurethane resin and an internal member such as a core material.
The plant powder is a natural product, and a polyurethane resin molded product in which the plant powder is blended has no adverse effects on the human body such as the development of allergies and is excellent in safety.
In addition, the antibacterial and deodorizing actions of specific plant powders are also exhibited at the same time, and it is hygienic and can make a room equipped with a polyurethane resin molded product such as a vehicle comfortable.
Furthermore, while exhibiting such effects, there is no influence on the mechanical properties of the resin molded product by the blended specific plant powder.
本発明の一の特徴は、ポリウレタン樹脂成形品を、竹粉と竹炭粉と乾留竹粉から選択した植物粉体の一種または二種以上を含有する射出反応ポリウレタン樹脂から形成したもので、該植物粉体の粒径Ｄが、１０≦Ｄ≦３００μｍ としたものである。好ましくは、該植物粉体の粒径Ｄが、１０≦Ｄ≦１００μｍ とする。 One feature of the present invention is that a polyurethane resin molded article is formed from an injection-reacting polyurethane resin containing one or more plant powders selected from bamboo powder, bamboo charcoal powder, and dry-distilled bamboo powder. The particle diameter D of the powder is 10 ≦ D ≦ 300 μm. Preferably, the particle size D of the plant powder is 10 ≦ D ≦ 100 μm.
選択された植物粉体は、ヒトの分泌油（高級脂肪酸エステル類を含む）やハンドクリーム、化粧品に含まれるエタノールやオレイン酸エステル等の付着浸透に対して、好ましく成形品内に分散されて配され、これらを吸着・吸収して深部への浸透を抑制する。そのため、長期に亘るヒトの接触によっても深部からの膨潤を抑制して有意な形状変化、寸法変化が防止される。
本件発明のポリウレタン樹脂成形品は、表皮で芯材を覆った、乗り物の把持操作部品として、好適に使用できるものである。
The selected plant powder is preferably dispersed and distributed in the molded product against adhesion penetration of human secretory oil (including higher fatty acid esters), hand creams, ethanol and oleate contained in cosmetics. These are adsorbed and absorbed to suppress penetration into the deep part. Therefore, significant shape change and dimensional change are prevented by suppressing swelling from the deep part even by long-term human contact.
The polyurethane resin molded product of the present invention can be suitably used as a vehicle gripping operation part having a core covered with a skin.
本発明のポリウレタン樹脂成形品は、前記特定の植物粉体を所定量含むことが重要であり、その他の成形条件は特に制限はなく、一般的なＲＩＭ成形と同様にして行うことができる。
すなわち、ポリオール、触媒、鎖延長剤、及びその他の助剤を含むポリオール混合物と、ポリイソシアネート化合物から製造することができる。
好ましくは、表層に低発泡の緻密なスキン層を備えたポリウレタンインテグラルスキンフォームが形成される。
It is important that the polyurethane resin molded product of the present invention contains a predetermined amount of the specific plant powder, and other molding conditions are not particularly limited, and can be performed in the same manner as general RIM molding.
That is, it can be produced from a polyol mixture containing a polyol, a catalyst, a chain extender, and other auxiliary agents, and a polyisocyanate compound.
Preferably, a polyurethane integral skin foam having a dense low-foam skin layer on the surface layer is formed.
本発明に使用する前記特定の植物粉体は、竹粉と竹炭粉と乾留竹粉から選択される。
本発明において使用する竹粉は、その竹の種類については特に制限はないが、真竹、孟宗竹が好ましい。竹の粉末化は、グラインダーなどで粉末化処理したものでよく、必要に応じてふるい、大きい粒子を除き、１０μｍ〜３００μｍの粒径の範囲を使用するのが好ましい。また、ポリウレタン樹脂原料への配合の際には乾燥処理を行うことが好ましい。乾燥により竹粉の表面にはミクロな開口が形成されて多孔質構造となる。
The specific plant powder used in the present invention is selected from bamboo powder, bamboo charcoal powder and dry-distilled bamboo powder.
The bamboo powder used in the present invention is not particularly limited with respect to the kind of the bamboo, but is preferably true bamboo or bamboo shoot. Bamboo powdering may be powdered with a grinder or the like, and it is preferable to use a particle size range of 10 μm to 300 μm except for large particles by sieving as necessary. Moreover, it is preferable to perform a drying process in the case of mix | blending with a polyurethane resin raw material. By drying, a microscopic opening is formed on the surface of the bamboo powder to form a porous structure.
本発明に使用する竹炭粉は、竹を６５０〜７００℃の温度で炭化処理して得られるが、例えばバン株式会社などの市販品を使用してもよい。竹炭は好ましくは、粒径１０〜３００μｍに粉砕される。
また、本発明に使用する乾留竹粉は、圧力釜を使用して、５〜１０気圧の状態で例えば１２０〜１７０℃の温度で竹粉を１〜５時間程乾留したものであり、これも例えばバン株式会社製などの市販品を使用することができる。竹炭も乾留竹粉もその粒子表面には図１に示すようにミクロ孔が開口して多孔質構造となっている。この多孔質構造により、脱臭、吸着・吸収効果を発現することができるとともに、抗菌作用を示す成分による効果も発現することができる。なお、乾留竹紛は上記の処理温度であるため該抗菌性成分が残存するが、竹炭では処理温度が高いために有機系の有効成分はほとんど分解し、無機系の有効成分による作用となるので、その抗菌作用は乾留竹紛よりも低くなる。しかし、ミクロな開口構造は、竹炭の方がより緻密になり吸着性は竹炭の方が優れている。
The bamboo charcoal powder used in the present invention is obtained by carbonizing bamboo at a temperature of 650 to 700 ° C., but a commercial product such as Van Co., Ltd. may be used. Bamboo charcoal is preferably ground to a particle size of 10-300 μm.
The dry-distilled bamboo powder used in the present invention is obtained by dry-distilling bamboo powder for about 1 to 5 hours at a temperature of 120 to 170 ° C. in a state of 5 to 10 atm using a pressure cooker. For example, commercially available products such as those manufactured by Van Co., Ltd. can be used. Bamboo charcoal and dry-distilled bamboo powder have a porous structure with micropores open on the particle surface as shown in FIG. With this porous structure, deodorizing and adsorbing / absorbing effects can be exhibited, and effects due to components exhibiting antibacterial action can also be exhibited. In addition, dry-distilled bamboo powder has the above-mentioned treatment temperature, so the antibacterial component remains. However, bamboo charcoal has a high treatment temperature, so the organic active ingredient is almost decomposed and acts as an inorganic active ingredient. The antibacterial action is lower than dry-distilled bamboo powder. However, the micro-opening structure is more dense with bamboo charcoal, and the adsorption is better with bamboo charcoal.
本発明に使用する竹粉、竹炭、乾留竹粉は、ポリウレタン樹脂原料のいずれに添加しても良いが、均一分散性の観点から、ポリオール原料に混合するのが好ましい。この場合、粒径が３００μｍを超えるとポリオールに対して比重差が大きいため沈降し易くなり分散性が低下する。また、分散性の低下により、均一な色味を出すことが難しくなる。粒径が１０μｍ未満になると飛散し易くなり、加工コストも高くなる。 The bamboo powder, bamboo charcoal and dry-distilled bamboo powder used in the present invention may be added to any polyurethane resin raw material, but are preferably mixed with the polyol raw material from the viewpoint of uniform dispersibility. In this case, when the particle diameter exceeds 300 μm, the specific gravity difference with respect to the polyol is large, so that the particles are easily settled and the dispersibility is lowered. Moreover, it becomes difficult to produce a uniform color due to a decrease in dispersibility. When the particle size is less than 10 μm, the particles are easily scattered and the processing cost is increased.
本発明において、前記特定の植物粉体の添加量は、ポリウレタン樹脂成形品に対して１〜２０重量％の範囲である。本発明の所期の効果を発現するためには少なくとも１重量％の配合は必要であり、また２０重量％を超えるとポリオールの粘度が上昇し、成形が困難となる。好ましくは２〜１０重量％である。成形に際して、原料をナチュラル（無着色）とし、透明なバリヤーコートを組み合わせると、添加した植物粉体の自然な色合いを製品に付与することができる。 In this invention, the addition amount of the said specific plant powder is the range of 1-20 weight% with respect to a polyurethane resin molded product. In order to exhibit the desired effect of the present invention, the blending of at least 1% by weight is necessary, and when it exceeds 20% by weight, the viscosity of the polyol increases and molding becomes difficult. Preferably it is 2 to 10% by weight. When molding, if the raw material is natural (uncolored) and a transparent barrier coat is combined, the natural color of the added plant powder can be imparted to the product.
本発明に使用するポリウレタン樹脂成形品は、原料としてポリオール、触媒、鎖延長剤、助剤からなるポリオール混合物とポリイソシアネート化合物を使用し、その表面部に、低発泡の緻密なスキン層を備えたポリウレタンインテグラルスキンフォームである。
本発明に使用するポリイソシアネート化合物としては、ジフェニルメタンジイソシアネート、ポリメチレンポリフェニルポリイソシアネート、トルエンジイソシアネート、これらのポリイソシアネートをウレタン変性、アロファネート変性、カルボジイミド変性、またはイソシアヌレート変性した変性ポリイソシアネート、これらの混合物などがある。
The polyurethane resin molded article used in the present invention uses a polyol mixture comprising a polyol, a catalyst, a chain extender and an auxiliary agent and a polyisocyanate compound as raw materials, and has a low-foaming dense skin layer on its surface. Polyurethane integral skin foam.
Examples of the polyisocyanate compound used in the present invention include diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, toluene diisocyanate, urethane-modified, allophanate-modified, carbodiimide-modified, or isocyanurate-modified polyisocyanate, and mixtures thereof. and so on.
また、本発明に使用するポリオールとしては、プロピレングリコール、ジエチレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、蔗糖などの水酸基含有化合物、トリエタノールアミン、ジエタノールアミンなどのアミノ基や水酸基を含有する化合物、あるいはエチレンジアミン、ジアミントルエンなどのアミノ基含有化合物にエチレンオキシド、プロピレンオキシドなどのアルキレンオキシドを付加した分子中に２〜６個の水酸基を含有し、平均水酸基当量が１００〜２４００（ＯＨ基５６１〜２３ｍｇＫＯＨ／ｇ）のポリエーテルポリオールあるいはこれらのポリエーテルポリオールにビニル化合物を付加重合したポリマーポリオールなどが用いられる。 In addition, as the polyol used in the present invention, a hydroxyl group-containing compound such as propylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sucrose, a compound containing an amino group and a hydroxyl group such as triethanolamine and diethanolamine, Alternatively, it contains 2 to 6 hydroxyl groups in a molecule obtained by adding an alkylene oxide such as ethylene oxide and propylene oxide to an amino group-containing compound such as ethylenediamine and diaminetoluene, and has an average hydroxyl equivalent weight of 100 to 2400 (OH groups 561 to 23 mgKOH / The polyether polyol of g) or a polymer polyol obtained by addition polymerization of a vinyl compound to these polyether polyols is used.
触媒としては、トリエチレンジアミン、ペンタメチルジエチレントリアミン、ジメチルアミノエタノール、テトラメチルエチレンジアミン、ジメチルベンジルアミン、テトラメチルヘキサメチレンジアミン、ビス（２−ジメチルアミノエチル）エーテル、１−メチルイミダゾール、１−イソブチルー２−メチルイミダゾールなどの第３級アミンやジブチル錫ジラウレート、オクタン酸錫、ジブチル錫ジアセテートなどの有機金属化合物が用いられる。触媒の使用量は、ポリオール混合物１００重量部に対して、０．１〜５．０重量部、好ましくは、０．３〜１．８重量部である。 Catalysts include triethylenediamine, pentamethyldiethylenetriamine, dimethylaminoethanol, tetramethylethylenediamine, dimethylbenzylamine, tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1-isobutyl-2-methyl Tertiary amines such as imidazole and organometallic compounds such as dibutyltin dilaurate, tin octoate and dibutyltin diacetate are used. The usage-amount of a catalyst is 0.1-5.0 weight part with respect to 100 weight part of polyol mixtures, Preferably, it is 0.3-1.8 weight part.
鎖延長剤としては、分子量が６１〜３００の２価アルコール、例えば、エチレングリコール、プロピレングリコール、ブタンジオール、１，３−ブタンジオール、ヘキサンジオール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ジプロピレングリコール、ポリプロピレングリコールや２価アミン、例えば、ジエチルトルエンジアミン、ｔ−ブチルトルエンジアミン、ジエチルジアミノベンゼン、トリエチルジアミノベンゼン、テトラエチルジアミノジフェニルメタン、などが必要に応じて用いられる。鎖延長剤の使用量は、ポリオール１００重量部に対して、１．０〜２０．０重量部、好ましくは５．０〜１０．０重量部である。 As the chain extender, a dihydric alcohol having a molecular weight of 61 to 300, for example, ethylene glycol, propylene glycol, butanediol, 1,3-butanediol, hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, Polypropylene glycol and divalent amines such as diethyltoluenediamine, t-butyltoluenediamine, diethyldiaminobenzene, triethyldiaminobenzene, tetraethyldiaminodiphenylmethane and the like are used as necessary. The amount of the chain extender used is 1.0 to 20.0 parts by weight, preferably 5.0 to 10.0 parts by weight, based on 100 parts by weight of the polyol.
発泡剤としては、クロロフロロカーボン以外の発泡剤が必要に応じて用いられる。例えば、水あるいはアミン化合物の炭酸塩又はギ酸が用いられる。
その他の助剤としては、例えば気泡安定剤、例えばシリコーン系整泡剤、界面活性剤、耐侯剤、酸化防止剤、紫外線吸収剤、光安定剤、着色剤などが必要に応じて用いられる。
As the foaming agent, a foaming agent other than chlorofluorocarbon is used as necessary. For example, water or an amine compound carbonate or formic acid is used.
As other auxiliaries, for example, cell stabilizers such as silicone-based foam stabilizers, surfactants, anti-mold agents, antioxidants, ultraviolet absorbers, light stabilizers, colorants and the like are used as necessary.
本発明のポリウレタン樹脂成形品の成形方法は、一般的に知られている上型をあけておいて下型にポリウレタン樹脂液を注入してから上型を閉じるオープン型注入や、予め上下型を閉じておいてポリウレタン樹脂液を型内に注入するクローズド型注入などの反応射出成形（ＲＩＭ）が用いられる。中でもステアリングホイールなど短時間成形サイクルが要求される、例えば注入後１分〜３分で型から取り出せるような反応性（ライズタイムが２０秒から６０秒）を有する自動車内装材用ポリウレタン樹脂原料の成形においては、反応射出成形法（ＲＩＭ）で成形するのが好ましい。
ＲＩＭによる植物粉体入りポリウレタン樹脂の製造（成形）にはＨｅｎｎｅｃｋｅ社製のＲ−ＲＩＭ用高圧ポリウレタン成形機などの反応射出成形機が用いられる。
The molding method of the polyurethane resin molded product of the present invention includes a generally known method of opening an upper mold, injecting a polyurethane resin liquid into the lower mold and then closing the upper mold, Reaction injection molding (RIM) such as closed mold injection in which a polyurethane resin liquid is injected into a mold while being closed is used. In particular, molding of polyurethane resin raw materials for automobile interior materials that require a short molding cycle such as a steering wheel, such as a reactivity (rise time of 20 to 60 seconds) that can be taken out from the
A reaction injection molding machine such as a high-pressure polyurethane molding machine for R-RIM manufactured by Hennecke is used for production (molding) of polyurethane resin containing plant powder by RIM.
本発明の植物粉体入りポリウレタン樹脂材料の製造（成形）には、ＮＣＯインデックスは９０から１３０がよく、好ましいＮＣＯインデックスは１００から１１５である。ＮＣＯインデックスが９０を下回ると、ポリオールが過剰であり、１００を上回るとイソシアネートが過剰になる。ステアリングホイールを例にとると、ＮＣＯがインデックスが９０を下回ると、耐摩耗性、耐候性などに問題が生じる可能性があり、１３０を上回ると表面が硬くなり、ポリウレタンステアリングホイールの特徴である弾性感とソフト感が損なわれる。
なお、ＮＣＯインデックスとは、ポリオール混合物中及び発泡剤として水を使用したときの、活性水素１つ当たりのポリオール混合物量及び水の量と、ポリイソシアネート中のイソシアネート基１つ当たりのポリイソシアネート量の比（当量比）×１００で示される。
以下、ステアリングホイール用ポリウレタン樹脂配合原料で、実施例、比較例を示し、本発明を具体的に説明するが、本発明は以下の実施例によって何ら限定されるものではない。
For the production (molding) of the polyurethane resin material containing plant powder of the present invention, the NCO index is preferably 90 to 130, and the preferred NCO index is 100 to 115. When the NCO index is below 90, the polyol is excessive, and when it exceeds 100, the isocyanate is excessive. Taking a steering wheel as an example, if the NCO index is less than 90, there may be a problem in wear resistance, weather resistance, etc., and if it exceeds 130, the surface becomes hard and the characteristic of the polyurethane steering wheel is Sexuality and softness are impaired.
The NCO index refers to the amount of the polyol mixture per active hydrogen and the amount of water when water is used in the polyol mixture and as a blowing agent, and the amount of polyisocyanate per isocyanate group in the polyisocyanate. Ratio (equivalent ratio) × 100.
EXAMPLES Hereinafter, examples and comparative examples will be shown with the polyurethane resin-blended raw materials for steering wheels, and the present invention will be specifically described. However, the present invention is not limited to the following examples.
ステアリングホイール用ポリウレタン樹脂配合原料（ポリオール混合物、発泡剤、ポリイソシアネート化合物）並びに成形条件
（１）ポリオール混合物
ポリエーテルポリオール ９０部（グリセリンにプロピレンオキシドとエチレンオキシドを付加した水酸基価３５ｍｇＫＯＨ／ｇ）
エチレングリコール ６．１部
トリエチレンジアミンの３３％エチレングリコール溶液 ０．１５部
ジブチル錫ラウレート ０．０１部
Ｔｏｙｏｃａｔ ＥＴ（東ソー株式会社製） １．３部
シリコーン整泡剤 ０．０２部
着色剤 １．８部
（２）水 ０．３５部
（３）ポリイソシアネート化合物
カルボジイミド変性ジフェニルメタンジイソシアネート
（ＮＣＯ含有２９％、粘度４０mＰａ・ｓ／２５℃）
（４）（１）ポリオール混合物と（２）水の合計１００部に対する（３）ポリイソシアネート化合物使用量は４５．８部（ＮＣＯインデックス１０５）
（５）反応性（ライズタイム） ３３秒
ハンドミキシング
ポリ容器発泡（フリーライズドフォーム）
ポリウレタン樹脂配合原料温度 ：２５℃
（６）成形条件
ハンドミキシングにてポリ容器で攪拌混合後、成形型へ注入
ポリウレタン樹脂配合原料温度 ：２５℃
成形型 ：スチール製平板状型（型サイズ２００×２００×１０ｍｍ）及びステアリングホイール実型
成形型温度 ：６０℃
脱型時間 ：型に原料を注入してから１２０秒後に脱型（離型）
成形品密度 ：０．５ｇ／ｃｍ３
Polyurethane resin blending raw material for steering wheel (polyol mixture, foaming agent, polyisocyanate compound) and molding conditions (1) Polyol mixture 90 parts of polyether polyol (Hydroxyl value 35 mgKOH / g with propylene oxide and ethylene oxide added to glycerin)
Ethylene glycol 6.1 parts 33% ethylene glycol solution of triethylenediamine 0.15 parts Dibutyltin laurate 0.01 parts Toyocat ET (manufactured by Tosoh Corporation) 1.3 parts Silicone foam stabilizer 0.02 parts Colorant 1.8 Part (2) water 0.35 parts
(3) Polyisocyanate compound Carbodiimide-modified diphenylmethane diisocyanate (NCO content 29%, viscosity 40 mPa · s / 25 ° C.)
(4) (3) Polyisocyanate compound usage is 45.8 parts (NCO index 105) based on 100 parts total of (1) polyol mixture and (2) water
(5) Reactivity (rise time) 33 seconds Hand mixing
Polycontainer foam (free rise foam)
Polyurethane resin compounding raw material temperature: 25 ° C
(6) Molding conditions Stir and mix in a plastic container by hand mixing, and then pour it into a mold. Polyurethane resin compounding raw material temperature: 25 ° C
Mold: Steel plate mold (mold size 200 × 200 × 10 mm) and steering wheel actual mold Mold temperature: 60 ° C.
Demolding time: Demolding (release) 120 seconds after injecting the raw material into the mold
Molded product density: 0.5 g / cm 3
ポリウレタン樹脂成形品の評価方法
１）耐オレイン酸膨潤性
成形品を１０×２０×４０ｍｍのサイズにカットし、テストピースとする。
オレイン酸原液中に４時間浸漬した後、ガーゼで表面をふき取り、８０℃のオ−ブンで４時間加熱する。
試験前後の重量変化及び寸法変化より、オイル分の含浸量、体積膨張率を求める。
寸法測定はデジタルノギス（寸法精度＝０．０００００１）を使用した。
２）耐オレイン酸グリップ密着度
ステアリングホイール成形品を図３の１〜４に示す部位において、６０ｍｍにカットして試験用サンプルとし、これをオレイン酸原液中に４時間浸漬した後、取り出してサンプルに付着したオレイン酸をガーゼでふき取り、６０℃のオーブン中で２時間放置する。オーブンより取り出し、直後に図４に示すような測定治具によりトルク負荷速度９０°／５〜１０ｓｅｃ、試験サンプル締め付け力１９６〜２４５Ｎ（２０〜２５ｋｇｆ）で各サンプルの耐オレイン酸グリップ密着度を測定した。なお、前記治具による測定は、図４中に図示しない裏面側において露出させた芯金部をクランプにて固定し、ポリウレタン表皮を締め付けながら回動させるようにトルクを負荷することにより行い、測定値は芯金から剥離（空転）したときの強度を示す。その測定結果を表６に示す。判定基準として、２．９Ｎ・ｍ以下で剥離・空転がないことを合格基準とする。
３）抗菌性試験
ＪＩＳ Ｚ ２８０１−２０００に準じて試験を実施した。
評価は、認定評価機関である大和化学工業（株）へ依頼した。
使用した供試細菌は下記２種類
ａ）大腸菌：Ｅｓｃｈｅｒｉｃｈｉａ Ｃｏｌｉ ＮＢＲＣ ３９７２
ｂ）ブドウ球菌：Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ Ａｕｒｅｕｓ ＮＢＲＣ １２７３２
生菌を製品表面に滴下し、２４時間後の生菌数を測定し、抗菌活性を求める。
抗菌活性値が２以上であれば、抗菌性を有すると判断される。
４）ＶＯＣ（揮発性有機化合物）放散量測定
以下の手順・操作により成形品から放散されるＶＯＣの量を測定する。
実施例３〜６、比較例１で成形された成形品を１００×１００×１０ｍｍにカットし、これをテストピースとする。
１．このテストピースを直ちにアルミホイルに包み更にサランラップで包む。
２．１週間後１０Ｌのテドラーバッグにテストピースを投入し、バッグの端末をラミネータで密閉した。
３．３Ｌの窒素を充填後、真空ポンプでバッグ内を真空にする。この操作を５回繰り返す。
４．次いで、バッグ内に５Ｌの窒素を充填し、８０℃恒温槽で２時間加熱する。
５．テストピースより発生したホルムアルデヒド、アセトアルデヒドは、島津製作所製ＨＰＬＣ測定システム：ＬＣ１０ＡＤ ＬＣソリューション解析システムにて測定し、トルエン、キシレン、エチルベンゼン、スチレン、テトラデカン、Ｔ−ＶＯＣ（全揮発性有機化合物）は、パーキンエルマー社製ＧＣ−ＭＳ測定システム：ＣＬＡＲＵＳ５００ 同社製ＴＤＡ加熱脱着装置：Ｔｕｒｂｏｍａｔｒｉｘ ６５０ＭＳ にて測定する。
５）機械的物性評価
島津オートグラフＡＧ５−ＫＥＮ使用
付加速度＝２００ｍｍ／ｍｉｎ
使用ダンベル：引っ張り強度＝ＪＩＳ２号ダンベル
引き裂き強度＝ＪＩＳＢ型ダンベル
Evaluation method of polyurethane resin molded product 1) Swelling resistance to oleic acid A molded product is cut into a size of 10 × 20 × 40 mm to obtain a test piece.
After dipping in the oleic acid stock solution for 4 hours, the surface is wiped off with gauze and heated in an oven at 80 ° C. for 4 hours.
The amount of oil impregnation and volume expansion coefficient are determined from the weight change and dimensional change before and after the test.
For the dimension measurement, a digital caliper (dimensional accuracy = 0.0001) was used.
2) Oleic acid grip adhesion degree The steering wheel molded product was cut into 60 mm at the site shown in FIGS. 1 to 4 to prepare a test sample, which was immersed in the oleic acid stock solution for 4 hours, then taken out and sampled The oleic acid adhering to is wiped off with gauze and left in an oven at 60 ° C. for 2 hours. Immediately after taking out from the oven, the oleic acid grip adhesion degree of each sample is measured at a torque load speed of 90 ° / 5 to 10 sec and a test sample fastening force of 196 to 245N (20 to 25 kgf) using a measuring jig as shown in FIG. did. The measurement with the jig is performed by fixing the cored bar exposed on the back side (not shown in FIG. 4) with a clamp, and applying a torque so as to rotate the polyurethane skin while tightening. The value indicates the strength when peeled (idling) from the cored bar. The measurement results are shown in Table 6. The acceptance criterion is that there is no peeling or idling at 2.9 N · m or less as a criterion.
3) Antibacterial test A test was carried out according to JIS Z 2801-2000.
Evaluation was requested from Daiwa Chemical Industry Co., Ltd., an accredited evaluation organization.
The following two types of test bacteria were used: a) Escherichia coli NBRC 3972
b) Staphylococcus: Staphylococcus Aureus NBRC 12732
Viable bacteria are dropped on the surface of the product, and the number of viable bacteria after 24 hours is measured to determine antibacterial activity.
If the antibacterial activity value is 2 or more, it is judged to have antibacterial properties.
4) VOC (volatile organic compound) emission measurement The amount of VOC emitted from the molded article is measured by the following procedure and operation.
The molded product molded in Examples 3 to 6 and Comparative Example 1 is cut into 100 × 100 × 10 mm, and this is used as a test piece.
1. Immediately wrap this test piece in aluminum foil and wrap it in Saran wrap.
2.1 weeks later, the test piece was put into a 10 L Tedlar bag, and the end of the bag was sealed with a laminator.
3. After filling with 3 L of nitrogen, the bag is evacuated with a vacuum pump. This operation is repeated 5 times.
4). Next, 5 L of nitrogen is filled in the bag and heated in an 80 ° C. constant temperature bath for 2 hours.
5. Formaldehyde and acetaldehyde generated from the test piece are measured by Shimadzu HPLC measurement system: LC10AD LC solution analysis system. Toluene, xylene, ethylbenzene, styrene, tetradecane, T-VOC (total volatile organic compounds) are perkin. Elmer GC-MS measurement system: LARUS500 Measured by TDA thermal desorption device: Turbomatrix 650MS.
5) Evaluation of mechanical properties Shimadzu Autograph AG5-KEN used Addition speed = 200mm / min
Dumbbell used: Tensile strength = JIS No. 2 dumbbell
Tear strength = JISB type dumbbell
実施例１
表１に示す竹炭をポリオール混合物１００部に対して３部（ポリウレタン樹脂成形品中約２．０％）添加し、先に示したステアリングホイール用ポリウレタン樹脂配合原料および成形条件にて成形品を得た。
実施例２
表１に示す竹粉をポリオール混合物１００部に対して３部（ポリウレタン樹脂成形品中約２．０％）を添加し、先に示したステアリングホイール用ポリウレタン樹脂配合原料および成形条件にて成形品を得た。
実施例３
表１に示す竹炭をポリオール混合物１００部に対して１０部（ポリウレタン樹脂成形品中約６．４％）添加し、先に示したステアリングホイール用ポリウレタン樹脂配合原料および成形条件にて成形品を得た。
実施例４
表１に示す乾留竹粉をポリオール混合物１００部に対して１０部（ポリウレタン樹脂成形品中約６．４％）添加し、先に示したステアリングホイール用ポリウレタン樹脂配合原料および成形条件にて成形品を得た。
実施例５
表１に示す竹炭をポリオール混合物１００重量部に対して５部（ポリウレタン樹脂成形品中約３．３％）添加し、先に示したステアリングホイール用ポリウレタン樹脂配合原料および成形条件にて成形品を得た。
実施例６
表１に示す乾留竹炭をポリオール混合物１００重量部に対して５部（ポリウレタン樹脂成形品中約３．３％）添加し、先に示したステアリングホイール用ポリウレタン樹脂配合原料および成形条件にて成形品を得た。
実施例７
表１に示す竹炭を１００℃のオーブン中に４時間放置して水分を蒸発させ、ポリオール混合物１００部に対して３部（ポリウレタン成形品中約２．０％）添加し、先に示したステアリングホイール用ポリウレタン樹脂配合原料及び成型条件にて成形品を得た。
参考例１
炭酸カルシウムの粉末をポリオール混合物１００部に対して３部（ポリウレタン樹脂成形品中約２．０％）添加し、先に示したステアリングホイール用ポリウレタン樹脂配合原料及び成型条件にて成形品を得た。
参考例２
ガラスパウダーをポリオール混合物１００部に対して３部（ポリウレタン樹脂成形品中約２．０％）添加し、先に示したステアリングホイール用ポリウレタン樹脂配合原料及び成型条件にて成形品を得た。
Example 1
3 parts of bamboo charcoal shown in Table 1 is added to 100 parts of the polyol mixture (about 2.0% in the polyurethane resin molded product), and a molded product is obtained by using the polyurethane resin compounding material for the steering wheel and the molding conditions described above. It was.
Example 2
3 parts of bamboo powder shown in Table 1 is added to 100 parts of the polyol mixture (about 2.0% in the polyurethane resin molded product), and the molded product is obtained by using the polyurethane resin blending raw material for steering wheel and the molding conditions described above. Got.
Example 3
10 parts of bamboo charcoal shown in Table 1 is added to 100 parts of the polyol mixture (about 6.4% in the polyurethane resin molded product), and a molded product is obtained using the polyurethane wheel compounding raw material and molding conditions for the steering wheel described above. It was.
Example 4
10 parts (about 6.4% of the polyurethane resin molded product) of the dry-distilled bamboo powder shown in Table 1 is added to 100 parts of the polyol mixture. Got.
Example 5
5 parts of bamboo charcoal shown in Table 1 is added to 100 parts by weight of the polyol mixture (about 3.3% in the polyurethane resin molded product). Obtained.
Example 6
5 parts of dry-distilled bamboo charcoal shown in Table 1 is added to 100 parts by weight of the polyol mixture (about 3.3% in the polyurethane resin molded product). Got.
Example 7
The bamboo charcoal shown in Table 1 was left in an oven at 100 ° C. for 4 hours to evaporate the water, and 3 parts (about 2.0% in the polyurethane molded product) were added to 100 parts of the polyol mixture. A molded product was obtained using the polyurethane resin blend raw material for the wheel and molding conditions.
Reference example 1
3 parts (about 2.0% of the polyurethane resin molded product) of calcium carbonate powder was added to 100 parts of the polyol mixture, and a molded product was obtained using the polyurethane resin compounding raw material and the molding conditions described above. .
Reference example 2
3 parts (about 2.0% of the polyurethane resin molded product) of glass powder was added to 100 parts of the polyol mixture, and a molded product was obtained using the above-described raw material and molding conditions for a polyurethane resin for a steering wheel.
比較例１
先に示したステアリングホイール用ポリウレタン樹脂配合原料および成形条件にて成形品を得た。
比較例２
表１に示す乾留竹炭をポリオール混合物１００重量部に対して４０部（ポリウレタン樹脂成形品中約２１．５％）添加し、先に示したステアリングホイール用ポリウレタン樹脂配合原料および成形条件にて成形したが、混合不良のために成形品は得られなかった。
Comparative Example 1
A molded product was obtained using the above-mentioned raw material for blending polyurethane resin for a steering wheel and molding conditions.
Comparative Example 2
40 parts (about 21.5% of the polyurethane resin molded product) of dry-distilled bamboo charcoal shown in Table 1 was added to 100 parts by weight of the polyol mixture, and molded using the polyurethane resin blending raw material for steering wheel and molding conditions described above. However, no molded product was obtained due to poor mixing.
実施例１、２、７、参考例１、２及び比較例１のサンプル成形品について、前記オレイン酸膨潤試験結果を表２に示す。
注目すべき点は、乾留竹粉又は竹炭を添加することで、内部へのオイル分の浸透が抑制され、膨潤率が大きく低下することである。このように内部へのオイル分の浸透が抑制されることより材料の膨潤を防止して、芯材とこれを被覆する樹脂層との密着性への影響を排除することができ、グリップが空転する不安を解消することができる。これに対して炭酸カルシウムやガラスパウダーの添加ではオイル分の浸透抑制効果がなく、ポリウレタン樹脂の膨潤を防止することができない。
また、実際にステアリングホイールをオレイン酸に浸漬して、耐オレイン酸グリップ試験をした結果を表６に示す。乾留竹紛、及び竹炭は、炭酸カルシウムやガラスパウダー等の補強充填剤として一般に使用されている充填剤と対比して内部へのオイル浸透抑制効果があり、材料の膨潤を抑え、グリップ空転をきたすおそれを解消することができる。
Table 2 shows the oleic acid swelling test results of the sample molded products of Examples 1, 2, and 7, Reference Examples 1 and 2, and Comparative Example 1.
What should be noted is that by adding dry-distilled bamboo powder or bamboo charcoal, the penetration of oil into the interior is suppressed, and the swelling rate is greatly reduced. In this way, the penetration of the oil component into the inside is suppressed, so that the swelling of the material can be prevented, and the influence on the adhesion between the core material and the resin layer covering the core material can be eliminated, and the grip is idling. Can eliminate anxiety. On the other hand, the addition of calcium carbonate or glass powder has no effect of suppressing the permeation of the oil, and the polyurethane resin cannot be prevented from swelling.
Table 6 shows the results of an oleic acid grip test in which the steering wheel was actually immersed in oleic acid. Compared with fillers generally used as reinforcing fillers such as calcium carbonate and glass powder, dry-distilled bamboo powder and bamboo charcoal have the effect of suppressing oil penetration into the interior, suppressing material swelling and causing slipping of the grip. The fear can be resolved.
また、実施例３、実施例４と比較例１のサンプル成形品について、前記抗菌性試験結果を表３に示す。
乾留竹粉、竹炭とも抗菌活性値が２以上となり、抗菌性ありと判断できる。しかも、これらは、従来の銀ゼオライト、チオサルファイト銀錯体などの銀系抗菌剤のように、金属イオンによる抗菌作用ではないので、アレルギーを発症することもなく、人体への安全性は大幅に向上することができる。
また、実施例３、実施例４、実施例５、実施例６と比較例１のサンプル成形品について、前記ＶＯＣ放散量測定結果を表４に示す。
本発明の成形品では竹炭、あるいは乾留竹粉の吸着・吸収効果により、成形品中の揮発性成分が捕捉される結果、放散される揮発性成分の量は大幅に低減することができる。これにより車室内の空気汚染や異臭の度合いが大幅に軽減される。
実施例２、実施例５と比較例１のサンプル成形品について、前記機械的物性評価結果を表５に示す。引っ張り強度、引き裂き強度、伸びともに低下は認められない。
Table 3 shows the antibacterial test results of the sample molded products of Example 3, Example 4, and Comparative Example 1.
Both dry-distilled bamboo powder and bamboo charcoal have antibacterial activity values of 2 or more, and can be judged to have antibacterial properties. In addition, these silver antibacterial agents, such as conventional silver zeolite and thiosulfite silver complexes, are not antibacterial due to metal ions, so they do not develop allergies and greatly improve safety to the human body. Can be improved.
Table 4 shows the VOC emission measurement results for the sample molded products of Example 3, Example 4, Example 5, Example 6, and Comparative Example 1.
In the molded product of the present invention, as a result of trapping the volatile components in the molded product due to the adsorption / absorption effect of bamboo charcoal or dry-distilled bamboo powder, the amount of volatile components released can be greatly reduced. This greatly reduces the degree of air pollution and odor in the passenger compartment.
Table 5 shows the mechanical property evaluation results of the sample molded products of Example 2, Example 5 and Comparative Example 1. No decrease in tensile strength, tear strength, or elongation is observed.
Claims (4)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015000921A (en) * | 2013-06-14 | 2015-01-05 | 国立大学法人九州工業大学 | Composite molding |
| JP2018017647A (en) * | 2016-07-29 | 2018-02-01 | 国立研究開発法人 海上・港湾・航空技術研究所 | Neutron absorber and method for manufacturing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0455445A (en) * | 1990-06-25 | 1992-02-24 | Nippon Supeshiyaritei Prod Kk | Antimicrobial formed product |
| JP2001187574A (en) * | 1999-10-19 | 2001-07-10 | T S Tec Kk | Steering wheel, steering wheel cover, resin molding for automobile interior parts and steering wheel manufacturing method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0455445A (en) * | 1990-06-25 | 1992-02-24 | Nippon Supeshiyaritei Prod Kk | Antimicrobial formed product |
| JP2001187574A (en) * | 1999-10-19 | 2001-07-10 | T S Tec Kk | Steering wheel, steering wheel cover, resin molding for automobile interior parts and steering wheel manufacturing method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015000921A (en) * | 2013-06-14 | 2015-01-05 | 国立大学法人九州工業大学 | Composite molding |
| JP2018017647A (en) * | 2016-07-29 | 2018-02-01 | 国立研究開発法人 海上・港湾・航空技術研究所 | Neutron absorber and method for manufacturing the same |
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