JPH08100373A - Resin composite containing fine particle of naturally occurring substance whose surface is modified and formed article obtained by using the same - Google Patents
Resin composite containing fine particle of naturally occurring substance whose surface is modified and formed article obtained by using the sameInfo
- Publication number
- JPH08100373A JPH08100373A JP26116894A JP26116894A JPH08100373A JP H08100373 A JPH08100373 A JP H08100373A JP 26116894 A JP26116894 A JP 26116894A JP 26116894 A JP26116894 A JP 26116894A JP H08100373 A JPH08100373 A JP H08100373A
- Authority
- JP
- Japan
- Prior art keywords
- fine powder
- natural organic
- modified
- resin
- resin composition
- 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.)
- Pending
Links
- 239000000126 substance Substances 0.000 title claims abstract description 16
- 239000010419 fine particle Substances 0.000 title abstract 7
- 239000000805 composite resin Substances 0.000 title 1
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 239000011342 resin composition Substances 0.000 claims abstract description 31
- 239000011159 matrix material Substances 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 71
- 239000003607 modifier Substances 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 230000000704 physical effect Effects 0.000 claims description 7
- 239000005416 organic matter Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 229920005992 thermoplastic resin Polymers 0.000 claims description 5
- 102000008186 Collagen Human genes 0.000 abstract description 9
- 108010035532 Collagen Proteins 0.000 abstract description 9
- 229920001436 collagen Polymers 0.000 abstract description 9
- 108010022355 Fibroins Proteins 0.000 abstract description 6
- 239000002649 leather substitute Substances 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229920001169 thermoplastic Polymers 0.000 abstract 1
- 239000004416 thermosoftening plastic Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 229920002635 polyurethane Polymers 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920006264 polyurethane film Polymers 0.000 description 6
- -1 etc. Substances 0.000 description 5
- 239000011368 organic material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は表面改質された天然有機
物微粉末を含有する樹脂組成物、および、その成形品に
関する。さらに詳しくは、繊維処理剤，塗料，インク等
に好適に用いられる表面改質された天然有機物微粉末を
含有する樹脂組成物、およびフィルム，シート，合成皮
革，型物，樹脂コンパウンド成形品等に好適に用いられ
る表面改質された天然有機物微粉末を含有する樹脂組成
物の成形品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing a surface-modified fine powder of a natural organic substance, and a molded product thereof. More specifically, for resin compositions containing surface-modified fine powders of natural organic substances, which are suitable for use in fiber treatment agents, paints, inks, etc., as well as films, sheets, synthetic leather, molds, resin compound molded products The present invention relates to a molded article of a resin composition containing a surface-modified fine powder of a natural organic substance which is preferably used.
【０００２】[0002]
【従来の技術】天然有機物の微粉末とマトリックス樹脂
（熱可塑性樹脂、熱硬化性樹脂）とをコンパウンド化す
ることにより、マトリックス樹脂に吸放湿性、透湿性、
および良触感等の付加価値を与えることができる。近年
このような技術を用いて、人工皮革等のさまざまな用途
における開発が進められている。2. Description of the Related Art By compounding a fine powder of a natural organic substance and a matrix resin (thermoplastic resin, thermosetting resin), the matrix resin has a moisture absorbing / releasing property, a moisture permeability,
It is possible to provide added value such as a good touch. In recent years, development of various applications such as artificial leather has been promoted using such a technique.
【０００３】[0003]
【発明が解決しようとする課題】しかし、一般的に、天
然有機物微粉末をポリマー中に分散させた場合、両者の
親和性が低いため、たとえば耐熱性や機械的強度等のプ
ラスチックが有する一般的物性が低下するという問題が
あった。However, in general, when a fine powder of a natural organic substance is dispersed in a polymer, the affinity between them is low. There was a problem that the physical properties deteriorate.
【０００４】本発明は、上述の問題に鑑みなされたもの
であり、耐熱性に優れた表面改質された天然有機物微粉
末を含有する樹脂組成物を提供し、また機械的特性に優
れた表面改質された天然有機物微粉末を含有する樹脂組
成物の成形品を提供することを目的とする。The present invention has been made in view of the above problems, and provides a resin composition containing surface-modified natural organic fine powder having excellent heat resistance and a surface having excellent mechanical properties. It is an object of the present invention to provide a molded article of a resin composition containing a modified fine powder of natural organic matter.
【０００５】[0005]
【課題を解決するための手段】上記目的を達成するため
本発明によれば、マトリックス樹脂としての熱可塑性樹
脂または熱硬化性樹脂と、天然有機物微粉末とを混合す
ることによって得られる樹脂組成物において、前記天然
有機物微粉末の表面が、改質材によって被覆されている
ことを特徴とする表面改質された天然有機物微粉末を含
有する樹脂組成物が提供される。To achieve the above object, according to the present invention, a resin composition obtained by mixing a thermoplastic resin or a thermosetting resin as a matrix resin and a natural organic fine powder. In the above, there is provided a resin composition containing the surface-modified natural organic matter fine powder, characterized in that the surface of the natural organic matter fine powder is coated with a modifier.
【０００６】また、その好ましい態様として、前記改質
材による被覆が、反応性活性基を有するポリマー，モノ
マー，オリゴマーまたはコポリマーを前記天然有機物微
粉末表面上で、重合、または天然有機物微粉末と共重合
することによって得られるものであることを特徴とする
表面改質された天然有機物微粉末を含有する樹脂組成物
が提供される。[0006] In a preferred embodiment, the coating with the modifying agent polymerizes or co-polymerizes a polymer, a monomer, an oligomer or a copolymer having a reactive active group on the surface of the natural organic fine powder. Provided is a resin composition containing a surface-modified natural organic fine powder, which is obtained by polymerization.
【０００７】また、前記改質材による被覆が、前記マト
リックス樹脂と、そのマトリックス樹脂と物性が近似し
たポリマー，モノマー，オリゴマーまたはコポリマーと
を共粉砕することによって得られるものであることを特
徴とする表面改質された天然有機物微粉末を含有する樹
脂組成物が提供される。Further, the coating with the modifying material is obtained by co-milling the matrix resin and a polymer, monomer, oligomer or copolymer having physical properties similar to those of the matrix resin. Provided is a resin composition containing a surface-modified natural organic fine powder.
【０００８】さらに、前記表面改質された天然有機物微
粉末を含有する樹脂組成物をさらに成形処理することに
よって得られるものであることを特徴とする表面改質さ
れた天然有機物微粉末を含有する樹脂組成物の成形品が
提供される。Furthermore, the surface-modified natural organic fine powder is obtained by further subjecting the resin composition containing the surface-modified natural organic fine powder to a molding treatment. A molded article of a resin composition is provided.
【０００９】以下、本発明を具体的に説明する。 １．表面改質された天然有機物微粉末を含有する樹脂組
成物 本発明の表面改質された天然有機物微粉末を含有する樹
脂組成物は、マトリックス樹脂と、その表面が改質材に
よって被覆された天然有機物微粉末とを混合することに
よって得られるものである。The present invention will be specifically described below. 1. Resin Composition Containing Surface-Modified Natural Organic Fine Powder The resin composition containing the surface-modified natural organic fine powder of the present invention comprises a matrix resin and a natural resin whose surface is coated with a modifier. It is obtained by mixing with an organic substance fine powder.
【００１０】（１）マトリックス樹脂 本発明に用いられるマトリックス樹脂としては、熱可塑
性樹脂および熱硬化性樹脂を挙げることができる。(1) Matrix Resin Examples of the matrix resin used in the present invention include thermoplastic resins and thermosetting resins.
【００１１】本発明に用いられる熱可塑性樹脂として
は、たとえば塩化ビニル樹脂、酢酸ビニル樹脂、ポリス
チレン、ＡＢＳ樹脂、アクリル樹脂、ポリエチレン樹
脂、ポリプロピレン、フッ素樹脂、ポリアミド樹脂、ア
セタール樹脂、ポリカーボネート、ウレタン系，エステ
ル系等の熱可塑性エラストマー、セルロース系プラスチ
ック等を挙げることができる。Examples of the thermoplastic resin used in the present invention include vinyl chloride resin, vinyl acetate resin, polystyrene, ABS resin, acrylic resin, polyethylene resin, polypropylene, fluororesin, polyamide resin, acetal resin, polycarbonate, urethane resin, Examples thereof include ester-based thermoplastic elastomers, cellulosic plastics and the like.
【００１２】本発明に用いられる熱硬化性樹脂として
は、たとえばフェノール系樹脂等を挙げることができ
る。Examples of the thermosetting resin used in the present invention include phenolic resins.
【００１３】（２）天然有機物微粉末 本発明に用いられる天然有機物微粉末としては、たとえ
ばコラーゲン微粉末，絹フィブロイン微粉末，セルロー
ス微粉末，キチン，キトサン微粉末，ウール微粉末等を
挙げることができる。(2) Natural organic substance fine powder Examples of the natural organic substance fine powder used in the present invention include collagen fine powder, silk fibroin fine powder, cellulose fine powder, chitin, chitosan fine powder, and wool fine powder. it can.
【００１４】その粒径は用途にもよるが、一般的に粒径
が大きいと、フィルム等の成形品に加工した場合、ざら
つき感が発現したり、強度が低下するため、細かければ
細かい程好ましい。たとえば人工皮革に用いられる場
合、平均粒径が３０μ以下、中でも１０μ以下が好まし
い。The particle size depends on the use, but generally, when the particle size is large, a rough feeling is exhibited or the strength is lowered when processed into a molded product such as a film, so the finer the particle size, the finer the particle size. preferable. For example, when used for artificial leather, the average particle size is preferably 30 μm or less, and more preferably 10 μm or less.
【００１５】（３）天然有機物微粉末表面の改質材によ
る被覆 本発明に用いられる天然有機物微粉末表面の改質材によ
る被覆の手段としては、化学的改質手段および物理的改
質手段を挙げることができる。換言すれば、天然有機物
微粉末表面の改質材による被覆とは、具体的に、改質材
が天然有機物微粉末表面と化学的結合を形成し、または
物理的に絡み合いながら天然有機物微粉末表面を被覆す
ることをいう。(3) Coating of Natural Organic Fine Powder Surface with Modifying Agent As means for coating the surface of the natural organic fine powder used with the modifying agent, there are a chemical modifying means and a physical modifying means. Can be mentioned. In other words, the coating of the surface of the natural organic fine powder with the modifier specifically means that the modifier forms a chemical bond with the surface of the natural organic fine powder, or the surface of the natural organic fine powder is physically entangled. Is to be covered.
【００１６】化学的改質手段 この改質手段に用いられる改質材として、反応性活性基
を有するポリマー，モノマー，オリゴマーまたはコポリ
マーを挙げることができる。例えば、イソシアネート基
を有するウレタン、アミド基を持つアクリルアミド等を
挙げることができる。これらを天然有機物微粉末表面上
で重合、または微粉末と共重合させることにより、改質
材が微粉末表面を被覆し、その表面は改質されることに
なる。なお、微粉末と可溶性蛋白等とを同時に用いるこ
とにより、共重合が起こる際、改質材と微粉末とを可溶
性蛋白がより強固につなぐため、さらに、成形品として
のフィルム等の物性の向上を図ることができる。Chemical Modification Means The modifying material used in this modification means may be a polymer, monomer, oligomer or copolymer having a reactive active group. Examples thereof include urethane having an isocyanate group and acrylamide having an amide group. By polymerizing these on the surface of the natural organic fine powder or copolymerizing with the fine powder, the modifier covers the surface of the fine powder and the surface is modified. By using the fine powder and the soluble protein at the same time, when the copolymerization occurs, the modifier and the fine powder are more firmly connected to the soluble protein, further improving the physical properties of the film or the like as a molded article. Can be achieved.
【００１７】物理的改質手段 この改質手段において、マトリックス樹脂と、そのマト
リックス樹脂と物性が近似したポリマー，モノマー，オ
リゴマーまたはコポリマーとを共粉砕するために用いら
れる改質装置としては、転動ボールミル，遊星ボールミ
ル，振動ボールミル，ジェットミル等の粉砕装置、ハイ
ブリダイザー等の一般的改質装置を挙げることができ
る。また、改質材としては、上述の化学的改質手段に用
いたものを用いることができる。この場合、マトリック
ス樹脂と同系統のポリマー等を用いることが樹脂と改質
された微粉末との親和性をより向上させることができる
ため好ましい。たとえば、ポリウレタンをマトリックス
樹脂として用いる場合、ポリウレタン系の改質材を用い
ることが好ましい。なお、改質に際しては乾式でもよい
し、ＤＭＦ，ＭＥＫ等の溶媒中で湿式にて行なってもよ
い。Physical Modifying Means In this modifying means, as a modifying device used for co-milling a matrix resin and a polymer, monomer, oligomer or copolymer having physical properties similar to those of the matrix resin, a rolling device is used. A ball mill, a planetary ball mill, a vibrating ball mill, a crushing device such as a jet mill, and a general reforming device such as a hybridizer can be mentioned. Further, as the modifying material, those used in the above-mentioned chemical modifying means can be used. In this case, it is preferable to use a polymer of the same type as the matrix resin because the affinity between the resin and the modified fine powder can be further improved. For example, when polyurethane is used as the matrix resin, it is preferable to use a polyurethane modifier. The reforming may be performed by a dry method or a wet method in a solvent such as DMF or MEK.
【００１８】（４）マトリックス樹脂と表面改質天然有
機物微粉末との混合 マトリックス樹脂と表面改質された天然有機物微粉末と
を混合（コンパウンド）する手段としては特に制限はな
く、たとえば溶液系のマトリックス樹脂を用いる場合に
は、単に攪拌するだけで天然有機物微粉末を分散させる
ことができる。また、溶融系のマトリックス樹脂を用い
る場合には、バンバリー，ニーダー，ロール，押出機等
の混練機を用いて分散することができる。(4) Mixing of Matrix Resin and Surface-Modified Natural Organic Material Fine Powder There is no particular limitation on the means for mixing (compounding) the matrix resin and the surface-modified natural organic material fine powder. When the matrix resin is used, the natural organic fine powder can be dispersed by simply stirring. When a molten matrix resin is used, it can be dispersed using a kneader such as Banbury, kneader, roll, and extruder.
【００１９】また、マトリックス樹脂と微粉末との混合
割合（重量比）は用途によって定められるが、たとえば
人工皮革の場合、９９〜５０：１〜５０とすることが好
ましく、中でも９５〜８０：５〜２０とすることがさら
に好ましい。The mixing ratio (weight ratio) of the matrix resin and the fine powder is determined depending on the use. For example, in the case of artificial leather, it is preferably 99 to 50: 1 to 50, especially 95 to 80: 5. It is more preferable to set it to 20.
【００２０】２．表面改質された天然有機物微粉末を含
有する樹脂組成物の成形品 上記のように得られた表面改質された天然有機物微粉末
を含有する樹脂組成物を成形する手段としては特に制限
はなく、通常の、ペーストコート，ペーストカレンダー
法、またはカレンダー，インフレ，Ｔダイ，射出成形等
を用いることができる。このような成形品としては、フ
ィルム，シート，型物等の形状を有するものを挙げるこ
とができる。2. Molded Article of Resin Composition Containing Surface-Modified Natural Organic Material Fine Powder There is no particular limitation on means for molding the resin composition containing the surface-modified natural organic material fine powder obtained as described above. Ordinary paste coating, paste calendering method, calendering, inflation, T-die, injection molding or the like can be used. Examples of such a molded product include those having a shape such as a film, a sheet, and a mold.
【００２１】なお、成形時における成形安定性の向上、
成形品の物性改良、および増量等のため、一般的に知ら
れている酸化防止剤，紫外線吸収剤，滑剤等の添加剤、
炭酸カルシウム，タルク等の充填剤、および酸化チタン
等の顔料等を加えてもよい。Incidentally, improvement of molding stability during molding,
Additives such as generally known antioxidants, UV absorbers, lubricants, etc. for improving the physical properties of molded articles and increasing the amount
Fillers such as calcium carbonate and talc, and pigments such as titanium oxide may be added.
【００２２】[0022]
【作用】従来のこの種の樹脂組成物においては、マトリ
ックス樹脂と天然有機物微粉末との界面における親和性
は低いものであった。本発明においては、天然有機物微
粉末の表面が改質され、すなわち、その表面が改質材に
よって被覆されているため、その樹脂組成物においてマ
トリックス樹脂と天然有機物微粉末の界面に改質材が存
在することとなる。この改質材が、マトリックス樹脂と
天然有機物微粉末の界面において接着剤的な役割を果た
すため、樹脂組成物、成形品の耐熱性，フィルム強度
等、プラスチックのもつ一般物性が向上することにな
る。In the conventional resin composition of this type, the affinity at the interface between the matrix resin and the fine powder of the natural organic material was low. In the present invention, the surface of the natural organic fine powder is modified, that is, since the surface is covered with the modifier, the modifier is present at the interface between the matrix resin and the natural organic fine powder in the resin composition. Will exist. Since this modifier plays a role of an adhesive at the interface between the matrix resin and the fine powder of natural organic matter, general physical properties of the plastic, such as resin composition, heat resistance of molded products, film strength, etc., will be improved. .
【００２３】[0023]
【実施例】本発明を実施例によって、さらに具体的に説
明する。 実施例１ ３００ｍｌ三角フラスコにコラーゲン微粉末（５μ）１
０．０ｇと０．０５ＮＮａＯＨ水溶液２００ｍｌをい
れ、室温でマグネチックスターラーで１時間攪拌し、５
５℃で５分浸漬処理し、試料を得た。この試料４．
０ｇを１，４−ブタンジオール１６ｇに分散させ、ボー
ルミル中に投入し、直径６ｍｍのガラス製ボール１００
個を用いて３時間ボールミルを作動させた後、８０００
ｒｐｍで１５分遠心分離を行い、５０℃温風乾燥機で１
時間乾燥させ、試料を得た。次にフラスコに試料１
０．０ｇとクロロベンゼン１００ｍｌを加え、３０分窒
素置換した。滴下漏斗に、ヘキサメチレンジイソシアネ
ート５．６ｇとクロロベンゼン５２ｍｌを入れ、９０℃
に昇温後、滴下漏斗からその半量を一度に滴下し、残り
半量を３時間かけて滴下し、さらに１時間加熱し、ポリ
ウレタンによる表面重付加を行い、改質コラーゲン微粉
末（改質試料）を得た。次に、この改質試料の性質を調
べるために、ポリウレタン膜を作成した。まずＤＭＦ中
に改質試料を分散させ、そこに一液性ポリウレタン（大
日精化社製、レザミンＭＥ−３６１２ＬＰ）を加え、５
分間乳鉢で混練した。混合割合（重量部）は、改質試
料：ＤＭＦ：一液性ポリウレタン＝１：５：１０とし
た。この混合ペーストからフィルムアプリケーターを用
いて膜を作成した。次に、この膜を幅１０ｍｍの短冊状
の形状とし、引っ張り試験機を用いて、チャック間隔８
０ｍｍ、チャートスピード５００ｍｍ／分で引っ張り試
験を行った。また、組成物と成形品の耐熱性を測定する
ため、改質試料（微粉末自体）と前記ポリウレタン膜
（フィルム）について１０（Ｋ／分）の昇温速度で熱重
量分析（ＴＧ）測定を行い微粉末およびポリウレタン膜
の５０％重量減少温度を測定した。EXAMPLES The present invention will be described more specifically by way of examples. Example 1 Collagen fine powder (5μ) 1 in a 300 ml Erlenmeyer flask
Add 0.0 g and 200 ml of 0.05N NaOH aqueous solution and stir at room temperature with a magnetic stirrer for 1 hour.
A sample was obtained by immersion treatment at 5 ° C. for 5 minutes. This sample 4.
0 g was dispersed in 16 g of 1,4-butanediol, and the mixture was put into a ball mill to make a glass ball 100 having a diameter of 6 mm.
After operating the ball mill for 3 hours with
Centrifuge for 15 minutes at rpm and 1 at 50 ° C hot air dryer.
A sample was obtained by drying for an hour. Then sample 1 in the flask
0.0 g and 100 ml of chlorobenzene were added, and the atmosphere was replaced with nitrogen for 30 minutes. Put 5.6 g of hexamethylene diisocyanate and 52 ml of chlorobenzene in the dropping funnel, and keep at 90 ° C.
After raising the temperature to half, drop half of it at once from the dropping funnel, drop the remaining half over 3 hours, and heat for an additional hour to add surface polyaddition with polyurethane, and then modify collagen fine powder (modified sample). Got Next, a polyurethane film was formed to investigate the properties of this modified sample. First, the modified sample is dispersed in DMF, and one-component polyurethane (Resamine ME-3612LP manufactured by Dainichiseika Co., Ltd.) is added thereto, and the mixture is added.
Kneaded in a mortar for minutes. The mixing ratio (parts by weight) was modified sample: DMF: one-component polyurethane = 1: 5: 10. A film was made from this mixed paste using a film applicator. Next, this film was formed into a strip shape with a width of 10 mm, and a chuck interval of 8 was obtained using a tensile tester.
A tensile test was performed at 0 mm and a chart speed of 500 mm / min. In addition, in order to measure the heat resistance of the composition and the molded product, thermogravimetric analysis (TG) measurement was performed on the modified sample (fine powder itself) and the polyurethane film (film) at a heating rate of 10 (K / min). The 50% weight loss temperature of the fine powder and the polyurethane film was measured.
【００２４】実施例２ 前記フラスコに、１，４−ブタンジオール４．１ｇとク
ロロベンゼン１００ｍｌを入れ、滴下漏斗に、ヘキサメ
チレンジイソシアネート６．５ｇとクロロベンゼン５０
ｍｌを入れ、実施例１と同様にポリウレタンの重付加を
行った。二組のジルコニアポット各々に、前記コラーゲ
ン微粉末（５μ）４．０ｇと、上記で合成したポリウレ
タン粉０．７２ｇ、さらにジメチルホルムアミド（ＤＭ
Ｆ）４．０ｇ、アルミナボール３５ｇをいれ、遊星ボー
ルミルを用いて、３００ｒｐｍ、半湿式の状態で１時間
共粉砕した。ポリウレタン膜の形成、引っ張り試験およ
びＴＧ測定は実施例１と同様にした。Example 2 4.1 g of 1,4-butanediol and 100 ml of chlorobenzene were placed in the flask, and 6.5 g of hexamethylene diisocyanate and 50 ml of chlorobenzene were placed in a dropping funnel.
After adding ml, polyurethane polyaddition was carried out in the same manner as in Example 1. In two sets of zirconia pots, 4.0 g of the collagen fine powder (5 μ), 0.72 g of the polyurethane powder synthesized above, and dimethylformamide (DM) were added.
F) 4.0 g and 35 g of alumina balls were added and co-milled for 1 hour at 300 rpm in a semi-wet state using a planetary ball mill. The formation of the polyurethane film, the tensile test and the TG measurement were the same as in Example 1.
【００２５】実施例３ アクリルアミド３０ｇ、前記コラーゲン微粉末（５μ）
１０ｇ、可溶性コラーゲン１０ｇ、ＮａＨＳＯ3 ０．０
３８ｇ、Ｋ2 Ｓ2 Ｏ3 ０．１ｇを水２００ｍｌ中に入
れ、３０分窒素置換後、５５℃で２．５時間攪拌しなが
ら共重合を行った。ポリウレタン膜の形成、引張試験及
びＴＧ測定は実施例１と同様にした。Example 3 30 g of acrylamide, the collagen fine powder (5 μ)
10 g, soluble collagen 10 g, NaHSO 3 0.0
38 g and K 2 S 2 O 3 0.1 g were put in 200 ml of water, and after nitrogen substitution for 30 minutes, copolymerization was carried out while stirring at 55 ° C. for 2.5 hours. The formation of the polyurethane film, the tensile test and the TG measurement were the same as in Example 1.
【００２６】実施例４ 前記アクリルアミド３０ｇ、前記コラーゲン微粉末（５
μ）１０ｇ、ＮａＯＨ３ｇ、ＮａＨＳＯ3 ０．０３８
ｇ、Ｋ2 Ｓ2 Ｏ3 ０．１ｇを水２００ｍｌ中に入れ、３
０分窒素置換後、５５℃で２．５時間攪拌しながら共重
合を行った。ポリウレタン膜の形成、引張試験及びＴＧ
測定は実施例１と同様にした。Example 4 30 g of the acrylamide and the collagen fine powder (5
μ) 10 g, NaOH 3 g, NaHSO 3 0.038
g, K 2 S 2 O 3 0.1g into 200 ml of water,
After purging with nitrogen for 0 minutes, copolymerization was carried out while stirring at 55 ° C. for 2.5 hours. Polyurethane film formation, tensile test and TG
The measurement was the same as in Example 1.
【００２７】実施例５ 実施例１において、天然有機物微粉末として絹フィブロ
イン微粉末（５μ）を用いたこと以外は実施例１と同様
にした。Example 5 The same procedure was performed as in Example 1 except that silk fibroin fine powder (5 μ) was used as the natural organic fine powder.
【００２８】実施例６ 実施例２において、天然有機物微粉末として前記絹フィ
ブロイン微粉末（５μ）を用いたこと以外は実施例２と
同様にした。Example 6 The procedure of Example 2 was repeated, except that the silk fibroin fine powder (5 μ) was used as the natural organic fine powder.
【００２９】実施例７ 実施例４において、天然有機物微粉末として前記絹フィ
ブロイン微粉末（５μ）を用いたこと以外は実施例４と
同様にした。Example 7 Example 4 was performed in the same manner as in Example 4 except that the silk fibroin fine powder (5 μ) was used as the natural organic fine powder.
【００３０】比較例１ 実施例１において、天然有機物微粉末として前記コラー
ゲン微粉末（５μ）の表面改質を行なわないもの（ポリ
ウレタンによる表面重付加を施さないもの）を用いたこ
と以外は実施例１と同様にした。Comparative Example 1 An example except that the collagen fine powder (5 μ) which was not surface-modified (not subjected to surface polyaddition with polyurethane) was used as the natural organic fine powder in Example 1. Same as 1.
【００３１】比較例２ 実施例１において天然有機物微粉末として絹フィブロイ
ン微粉末（５μ）の表面改質を行なわないもの（ポリウ
レタンによる表面重付加を施さないもの）を用いたこと
以外は実施例１と同様にした。Comparative Example 2 Example 1 except that as the natural organic fine powder, silk fibroin fine powder (5 μ) which was not surface-modified (not subjected to surface polyaddition with polyurethane) was used. Same as.
【００３２】以上の結果を表１に示す。The above results are shown in Table 1.
【表１】 [Table 1]
【００３３】[0033]
【発明の効果】以上説明したように本発明によって、繊
維処理材，塗料，インク等に有効に用いられる耐熱性に
優れた表面改質された天然有機物微粉末を含有する樹脂
組成物を提供することができる。また、各種フィルム，
シート，人工皮革，型物等に有効に用いられる、機械的
特性に優れた表面改質された天然有機物微粉末を含有す
る樹脂組成物の成形品を提供することができる。INDUSTRIAL APPLICABILITY As described above, the present invention provides a resin composition containing surface-modified natural organic fine powder having excellent heat resistance, which is effectively used in fiber treatment materials, paints, inks and the like. be able to. In addition, various films,
It is possible to provide a molded article of a resin composition containing a surface-modified natural organic fine powder having excellent mechanical properties, which is effectively used for sheets, artificial leather, molds and the like.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 仙名 保 神奈川県横浜市港北区日吉３−14−１ 慶 応義塾大学理工学部内 (72)発明者 中島 義夫 神奈川県横浜市港北区日吉３−14−１ 慶 応義塾大学理工学部内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Ho Sena Ho 3-14-1, Hiyoshi, Kohoku Ward, Yokohama City, Kanagawa Prefecture Faculty of Science and Engineering, Keio University (72) Yoshio Nakajima, 3rd, Hiyoshi, Kohoku Ward, Yokohama City, Kanagawa Prefecture 14-1 Keio University Faculty of Science and Engineering
Claims (4)
または熱硬化性樹脂と、天然有機物微粉末とを混合する
ことによって得られる樹脂組成物において、 前記天然有機物微粉末の表面が、改質材によって被覆さ
れていることを特徴とする表面改質された天然有機物微
粉末を含有する樹脂組成物。1. A resin composition obtained by mixing a thermoplastic resin or a thermosetting resin as a matrix resin with a natural organic fine powder, wherein the surface of the natural organic fine powder is coated with a modifier. A resin composition containing a surface-modified fine powder of a natural organic substance.
を有するポリマー，モノマー，オリゴマーまたはコポリ
マーを前記天然物微粉末表面上で、重合、または天然有
機物微粉末と共重合することによって得られるものであ
ることを特徴とする請求項１記載の表面改質された天然
有機物微粉末を含有する樹脂組成物。2. The coating with the modifier is obtained by polymerizing a polymer, monomer, oligomer or copolymer having a reactive active group on the surface of the natural fine powder, or by copolymerizing with a natural organic fine powder. The resin composition containing the surface-modified natural organic fine powder according to claim 1, wherein the resin composition is a resin composition.
クス樹脂と、そのマトリックス樹脂と物性が近似したポ
リマー，モノマー，オリゴマーまたはコポリマーとを共
粉砕することによって得られるものであることを特徴と
する請求項１記載の表面改質された天然有機物微粉末を
含有する樹脂組成物。3. The coating with the modifier is obtained by co-grinding the matrix resin and a polymer, monomer, oligomer or copolymer having physical properties similar to those of the matrix resin. A resin composition containing the surface-modified fine powder of natural organic matter according to claim 1.
然有機物微粉末を含有する樹脂組成物をさらに成形処理
することによって得られるものであることを特徴とする
表面改質された天然有機物微粉末を含有する樹脂組成物
の成形品。4. A surface-modified product obtained by further subjecting a resin composition containing the surface-modified natural organic fine powder according to claim 1 to a molding treatment. A molded article of a resin composition containing a fine powder of natural organic matter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26116894A JPH08100373A (en) | 1994-09-30 | 1994-09-30 | Resin composite containing fine particle of naturally occurring substance whose surface is modified and formed article obtained by using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26116894A JPH08100373A (en) | 1994-09-30 | 1994-09-30 | Resin composite containing fine particle of naturally occurring substance whose surface is modified and formed article obtained by using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08100373A true JPH08100373A (en) | 1996-04-16 |
Family
ID=17358071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26116894A Pending JPH08100373A (en) | 1994-09-30 | 1994-09-30 | Resin composite containing fine particle of naturally occurring substance whose surface is modified and formed article obtained by using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08100373A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013039118A1 (en) * | 2011-09-16 | 2013-03-21 | メルクス株式会社 | Synthetic leather paste, and synthetic leather sheet and repair material using same |
-
1994
- 1994-09-30 JP JP26116894A patent/JPH08100373A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013039118A1 (en) * | 2011-09-16 | 2013-03-21 | メルクス株式会社 | Synthetic leather paste, and synthetic leather sheet and repair material using same |
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