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PRODUCTION METHOD FOR READILY DISPERSIBLE CELLULOSE COMPOSITION, READILY DISPERSIBLE CELLULOSE COMPOSITION, CELLULOSE DISPERSION RESIN COMPOSITION, AND PRODUCTION METHOD FOR WATER-BASED DISPERSANT FOR CELLULOSE

Foreign code F200010100
File No. 4596
Posted date May 18, 2020
Country WIPO
International application number 2015JP060029
International publication number WO 2015152189
Date of international filing Mar 30, 2015
Date of international publication Oct 8, 2015
Priority data
  • P2014-072483 (Mar 31, 2014) JP
Title PRODUCTION METHOD FOR READILY DISPERSIBLE CELLULOSE COMPOSITION, READILY DISPERSIBLE CELLULOSE COMPOSITION, CELLULOSE DISPERSION RESIN COMPOSITION, AND PRODUCTION METHOD FOR WATER-BASED DISPERSANT FOR CELLULOSE
Abstract The purpose of the present invention is to provide technology for facilitating the dispersion of cellulose within a hydrophobic substance such as a resin without performing nano-cellulose surface modification or the like by using a simple and effective method to treat cellulose (which is a hydrophilic substance) with a polymer dispersant that was developed for dispersing a fine hydrophobic substance such as a pigment in a system in which water is the main medium. This objective is achieved by: a production method in which a polymer dispersant that has a block copolymer structure that includes a segment (A) that has resin affinity and a segment (B) that has cellulose-adsorbing properties is dissolved in a hydrophilic organic solvent solution, a surfactant is added to the result, a water-based dispersant that contains the polymer dispersant is subsequently produced by adding water, and the obtained water-based dispersant is added to cellulose that is in a hydrous state or a dry state in order to obtain a readily dispersible cellulose composition; a production method for the water-based dispersant that is used in the aforementioned production method; a readily dispersible cellulose composition; and a cellulose dispersion resin composition that uses the readily dispersible cellulose composition.
Outline of related art and contending technology BACKGROUND ART
Cellulose fibers, a substance having a basic skeleton of all plants, more than one trillion ton accumulation on earth and, tree planting from the fact that the resource can be reproduced by an, effective utilization thereof is desired. Cellulose fibers, the lightness of the steel regardless of whether or not in 1/5, the strength of the steel 5 times or more, low coefficient of linear thermal expansion of 1/50 glass fibers having. Therefore, cellulose fibers, as a filler in the matrix of a resin or the like containing, provide mechanical strength has been proposed a technique (patent document 1). In addition, cellulose fibers have the purpose of enhancing the mechanical strength, steaming and cellulosic fibers, cellulose nanofibers (CNF, the microfibrillated plant fiber) in the additive is present in a dispersed state for the agent fibrous reinforcing resin has been proposed (patent document 2). In addition, in the same manner as CNF defibration as obtained by treating cellulosic fibers, cellulose nanocrystals (CNC) is known. Is CNF, mechanical solution of the cellulose fibers produced on the pasteboard and the fibers obtained, about 4-100 nm fiber width, fiber length 5 μm more than that of the fiber. Is CNC, such as acid hydrolysis of cellulose fibers obtained by performing a chemical treatment of a crystal, the crystal width about 10-50 nm, about 500 nm crystal length of crystal. And these CNF is CNC, collectively referred to as nano-cellulose. Nano-cellulose, a high specific surface area (250-300m2 /g) and, compared to steel and light in weight and high strength.
Nano-cellulose, and the thermal deformation is small compared to the glass. High strength and low thermal expansion nano-cellulose, and is therefore useful as sustained resource material, for example, nano-cellulose polymer materials such as resins in combination with high strength, low thermal expansion for a composite material, aerogel material, by self-organization of the chiral nematic liquid crystal phase CNC using the optical anisotropic material, the functional group is introduced into the nano-cellulose high development and of the functional material has been created. On the other hand, nano-cellulose, since the hydroxyl group-rich, strong polar hydrophilic, hydrophobic polarity versatility not inferior in view of compatibility with a resin. For this reason, the development of nano-cellulose material, by chemical treatment, surface modification of cellulose nano or nano and a functional group introduced to the cellulose, the versatility of the nano-cellulose resin to improve the compatibility of the have been studied. In other words, the versatility of the nano-cellulose to improve the dispersion property with respect to the resin has been studied.
In addition, cellulose fibers as a filler in the preparation of the resin composition can be a general purpose, and a dispersant, the dispersibility of the cellulose fibers and general-purpose resin, it is possible to improve the compatibility has been studied. In non-patent document 1, a surfactant () cellulose nanocrystals by adsorption, organic solvent dispersion of the cellulose nanocrystals is improved. In non-patent document 2, the cellulose nanocrystals adsorbed surfactant isotactic polypropylene (iPP) as a reinforcement material and the production of composite materials, less than about 1.4 times alone iPP and the tensile strength is improved. In the above-mentioned Patent Document 2, of the thermoplastic resin in the case of using cellulose as a reinforcing material, thereby suppressing generation of aggregates of cellulose, for the purpose of uniformly dispersing the cellulose resin, and a hydrophilic cellulose fiber and a specific HLB and (hydrophilic-lipophilic balance) value additive having used (low-molecular-weight surfactant), a cellulose fiber in the additive is causing a dispersed state.
Scope of claims (In Japanese)[請求項1]
 セルロースの樹脂中への分散性を高めた易分散性セルロース組成物の製造方法であって、樹脂親和性セグメントAと、セルロース吸着性セグメントBとを有するブロック共重合体構造を有する高分子分散剤を親水性有機溶剤溶液に溶解し、これに界面活性剤を添加し、その後に水を添加することで前記高分子分散剤を含有した水系の分散処理剤を作製し、得られた水系の分散処理剤を、含水状態又は乾燥状態のセルロースに添加して易分散性セルロース組成物を得ることを特徴とする易分散性セルロース組成物の製造方法。

[請求項2]
 前記界面活性剤が、脂肪族アミン類のカルボン酸塩、無機酸塩及び4級アンモニウム塩からなる群から選ばれる少なくともいずれかである請求項1に記載の易分散性セルロース組成物の製造方法。

[請求項3]
 前記親水性有機溶剤が、アルコール系溶剤又はグリコール系溶剤である請求項1又は2に記載の易分散性セルロース組成物の製造方法。

[請求項4]
 前記セルロースが、セルロースナノファイバー、セルロースナノクリスタル、パルプ、リグノセルロース及び木粉からなる群から選ばれる少なくとも1種の、含水状態又は乾燥状態のセルロース繊維である請求項1~3のいずれか1項に記載の易分散性セルロース組成物の製造方法。

[請求項5]
 前記高分子分散剤が、更に、下記(1)~(5)の要件をすべて満たすブロック共重合体である請求項1~4のいずれか1項に記載の易分散性セルロース組成物の製造方法。
(1)前記A-Bブロック共重合体の構成成分の90質量%以上がメタクリレート系モノマーで構成されていること;
(2)前記セルロース吸着性セグメントBは、構成成分の50質量%以上が、水酸基を1個以上有するメタクリレート系モノマー及び/又は尿素基を有するメタクリレート系モノマーで構成されており、且つ、樹脂との相溶性がないこと;
(3)前記樹脂親和性セグメントAのゲルパーミエーションクロマトグラフィーにおけるポリスチレン換算の数平均分子量が500~20000であり、且つ、前記A-B共重合体全体に占める該樹脂親和性セグメントAの割合が5~95質量%であること;
(4)前記セルロース吸着性セグメントBのゲルパーミエーションクロマトグラフィーにおけるポリスチレン換算の数平均分子量が500~20000であり、且つ、前記A-B共重合体全体に占める該セルロース吸着性セグメントBの割合が5~95質量%であること;
(5)前記A-Bブロック共重合体のゲルパーミエーションクロマトグラフィーにおけるポリスチレン換算の数平均分子量が3500~40000であり、且つ、分子量分布指数(重量平均分子量/数平均分子量)が1.0~1.6であること。

[請求項6]
 前記(2)のセルロース吸着性セグメントBの構成成分の70質量%以上が、水酸基を1個以上有するメタクリレート系モノマー及び/又は尿素基を有するメタクリレート系モノマーで構成されており、更に、構成成分の3~15質量%が、アルカリで中和されたメタクリル酸及び/又はカルボキシ基を有するメタクリレート系モノマー又は第4級アンモニウム塩基を有するメタクリレート系モノマーで構成されている請求項5に記載の易分散性セルロース組成物の製造方法。

[請求項7]
 前記高分子分散剤が、有機ヨウ素化合物を開始化合物とし、リン化合物、窒素化合物、酸素化合物又は炭素化合物を触媒とするリビングラジカル重合法である可逆連鎖移動触媒重合(RTCP)法で合成されたものである請求項5又は6に記載の易分散性セルロース組成物の製造方法。

[請求項8]
 請求項1~7のいずれか1項に記載の易分散性セルロース組成物の製造方法により得られたことを特徴とする易分散性セルロース組成物。

[請求項9]
 請求項8に記載の易分散性セルロース組成物と、樹脂とを含む樹脂組成物を溶融混練して得られたものであることを特徴とするセルロース分散樹脂組成物。

[請求項10]
 前記樹脂組成物が、前記易分散性セルロース組成物に起因する液分を含んだまま溶融混練して得られたものである請求項9に記載のセルロース分散樹脂組成物。

[請求項11]
 前記樹脂が、熱可塑性樹脂である請求項9又は10に記載のセルロース分散樹脂組成物。

[請求項12]
 樹脂親和性セグメントAと、セルロース吸着性セグメントBとを有するブロック共重合体構造を有する高分子分散剤を親水性有機溶剤溶液に溶解し、これに界面活性剤を添加し、その後に水を添加することで高分子分散剤を含有した水系の分散処理剤を製造することを特徴とする、セルロースの樹脂中への分散性を高めた易分散性セルロース組成物の製造に用いる水系の分散処理剤の製造方法。
  • Applicant
  • ※All designated countries except for US in the data before July 2012
  • DAINICHISEIKA COLOR & CHEMICALS MFG. CO., LTD.
  • KYOTO UNIVERSITY
  • Inventor
  • IMAI Takahiro
  • AOYAGI Taiyo
  • SHIMANAKA Hiroyuki
  • TSUJII Yoshinobu
  • SAKAKIBARA Keita
  • GOTO Atsushi
IPC(International Patent Classification)
Specified countries National States: AE AG AL AM AO AT AU AZ BA BB BG BH BN BR BW BY BZ CA CH CL CN CO CR CU CZ DE DK DM DO DZ EC EE EG ES FI GB GD GE GH GM GT HN HR HU ID IL IN IR IS JP KE KG KN KP KR KZ LA LC LK LR LS LU LY MA MD ME MG MK MN MW MX MY MZ NA NG NI NO NZ OM PA PE PG PH PL PT QA RO RS RU RW SA SC SD SE SG SK SL SM ST SV SY TH TJ TM TN TR TT TZ UA UG US UZ VC VN ZA ZM ZW
ARIPO: BW GH GM KE LR LS MW MZ NA RW SD SL SZ TZ UG ZM ZW
EAPO: AM AZ BY KG KZ RU TJ TM
EPO: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR
OAPI: BF BJ CF CG CI CM GA GN GQ GW KM ML MR NE SN ST TD TG
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