Top > Search of International Patents > POLYMER DISPERSANT FOR CELLULOSE, AQUEOUS DISPERSION TREATMENT AGENT CONTAINING SAME, READILY DISPERSIBLE CELLULOSE COMPOSITION, CELLULOSE DISPERSION RESIN COMPOSITION, AND DISPERSANT-CONTAINING RESIN COMPOSITION FOR CELLULOSE DISPERSION

POLYMER DISPERSANT FOR CELLULOSE, AQUEOUS DISPERSION TREATMENT AGENT CONTAINING SAME, READILY DISPERSIBLE CELLULOSE COMPOSITION, CELLULOSE DISPERSION RESIN COMPOSITION, AND DISPERSANT-CONTAINING RESIN COMPOSITION FOR CELLULOSE DISPERSION

Foreign code F200010101
File No. 4595
Posted date May 18, 2020
Country WIPO
International application number 2015JP060028
International publication number WO 2015152188
Date of international filing Mar 30, 2015
Date of international publication Oct 8, 2015
Priority data
  • P2014-072482 (Mar 31, 2014) JP
Title POLYMER DISPERSANT FOR CELLULOSE, AQUEOUS DISPERSION TREATMENT AGENT CONTAINING SAME, READILY DISPERSIBLE CELLULOSE COMPOSITION, CELLULOSE DISPERSION RESIN COMPOSITION, AND DISPERSANT-CONTAINING RESIN COMPOSITION FOR CELLULOSE DISPERSION
Abstract The purposes of the present invention are to provide a high-performance polymer dispersant that can be applied to cellulose that is a hydrophilic substance and to achieve a practical technique for obtaining a cellulose dispersion resin composition that, when the polymer dispersant for cellulose is applied to cellulose and the result is dispersed within a thermoplastic resin, makes it easier to achieve a stable dispersion of cellulose using a method that does not use a large amount of an organic solvent and that is environmentally friendly. This objective is achieved by configuring a polymer dispersant for cellulose that is a polymer compound that has a block copolymer structure that includes a segment (A) that has resin affinity and a segment (B) that has cellulose-adsorbing properties, said polymer dispersant for cellulose being synthesized by reversible chain transfer catalyzed polymerization (RTCP) in which no heavy metals, nitroxide compounds, or sulfur-based compounds are used, an organic iodine compound is used as a starting compound, and a phosphorus compound, a nitrogen compound, an oxygen compound, or a carbon compound is used as a catalyst.
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 on earth and accumulation, can be reproduced by resource acid described above, 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, (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 obtained by treating cellulosic fibers as the defibration, known (CNC). 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, the surfactant () by adsorption, the organic solvent-dispersible is improved. In non-patent document 2, the 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.
Both with the above described prior example, a low molecular weight compound as a dispersant using attempting to improve the dispersibility of nano-cellulose. On the other hand, the inventors of the present invention, a fine pigment with a resin or a hydrophobic material, dispersed in the aqueous medium has been developed for high-molecular dispersant, simple, a large amount of organic solvent is not employed environment in a manner is also taken into consideration, cellulose with a hydrophilic substance can be applied to, are very useful in practical and has resulted in the recognition. However, as described above, the polymer dispersant is a conventional, fine hydrophobic material such as a pigment dispersing resin for the purpose of moderate whereas, cellulose, hydrophilic substances, in addition, light and easy to agglomerate, especially commodity and is hard to be dispersed in the resin, in order to disperse a pigment in the same manner as conventional of the polymeric dispersant cannot be applied. That is, in order to achieve the object described above, having the characteristics as described above with respect to the cellulose, capable of exhibiting the desired functionality of the polymeric dispersant structure development is required.
Here, a general-purpose resin to the dispersion of the cellulose, if it is possible to use a polymeric dispersant, such as those listed below are considered to be technically advantageous. First, a wide variety of structural design of the polymer of the monomer can be designed so that, for the purpose, the use of the molecule and it becomes possible to design point. That is, an infinite number of design of the structure of the polymer as a dispersant and thus it is possible, by the design of the monomer, e.g. the type of the dispersing adapted, synthesis of the dispersant of the higher performance can be expected. The polymeric dispersant may include, olefin-based polymer, acrylic polymer, ester-based polymer, a urethane-based polymer or the like, various types of contemplated for use. In which, in particular acrylic polymer, polymerized at mild conditions the polymer can be obtained relatively easily, in addition, a wide variety due to the presence of acryl-based monomer, the formulation of infinite compositions selected, purpose, the use of molecular design and can be easily, expected to be more useful.
Therefore, the inventors of the present invention, the acrylic polymer and cellulose polymer dispersant for review are performed. Further, in this case, has a hydroxyl group rich, hydrophobic polarity not inferior in compatibility with general-purpose resin useful for dispersion of the cellulose, an acrylic polymer having a specific structure in order to obtain, precise synthesis methods is expected to be necessary. Therefore, an acrylic polymer having a specific structure can be produced by living radical polymerization known synthetic method was considered to be suitable to use. That is, in living radical polymerization method, by stabilized terminated radicals, the radical polymerization side reaction to prevent a coupling or disproportionation, or adjusting the molecular weight, molecular weight distribution can be narrowed. In addition, terminated radicals can be stabilized in order, after which polymerizes the monomers, followed by the addition of another monomer, polymerization is allowed to proceed can be again, can be different structure respectively, express a different functionality than the block copolymer having a polymer segment can be synthesized.
On the other hand, for the purposes of this invention in the cellulose polymer dispersant, from the following reason, functionality in its structure having different polymer segment of the block copolymer structure is believed to be useful. The block copolymer may contain, two or more different 2 component of the polymer chains of the polymeric segments is included in the present 1 structure and hence, can be adjusted so that the monomer composition, the polymer segment of each of the different functions have the advantage that the property can be given. For example, made of a different monomer composition (component) chain A and chain B A-B type block copolymers can be described by way of example, a polymer segment A (A chain), a general-purpose resin having high affinity with the component and, on the other hand, the polymer segment B (B chain), having a component adsorbed cellulose so as to form a block copolymer A-B is designed, the copolymer can be used as the dispersing agent, chain A and chain B may effectively act, versatility to the suppression of aggregation of cellulose in the resin, dispersion stability can be expected. That is, the adsorptive cellulose resin affinity segment A and segment B A-B block copolymer having a cellulose dispersion of the resin composition when used as the dispersing agent, such as a molded body of various general-purpose resin used into the cellulose dispersion becomes excellent, the mechanical strength of the molded body as the filler is expected to be enhanced sufficiently.
As described above, such in the synthesis of the block copolymer, living radical polymerization method would be suitable. As living radical polymerization, specifically, a variety of methods such as those listed below have been reported. For example, by utilizing the binding and dissociation of the method (Nitroxide mediated polymerization hereinafter, abbreviated as NMP method), copper or ruthenium, nickel, a heavy metal such as iron, then, it can form a complex with using ligands, halogen compound atom transfer radical polymerization as a polymerization initiator compound (Atom Transfer Radical Polymerization, hereinafter abbreviated as ATRP method), dithiocarboxylic acid esters as the starting compound, the addition polymerizable monomer using a radical polymerization and reversible addition-cleavage type photopolymerization initiator and chain transfer polymerization (Reversible addition fragmentation chain transfer polymerization hereinafter, abbreviated as RAFT method), organometallic or organic tellurium, an organic antimony, antimony halide, organic germanium, a germanium halide such as a method of using a heavy metal compound (or less Degenerative transfer, abbreviated DT method) and the like are developed, extensive research is being performed.
Scope of claims (In Japanese)[請求項1]
 セルロースを分散させるためのセルロース用高分子分散剤であって、該高分子分散剤が、重金属、ニトロキサイド化合物又は硫黄系化合物のいずれについても用いない、リビングラジカル重合法である、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、可逆連鎖移動触媒重合(RTCP)法により合成された、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化合物であることを特徴とするセルロース用高分子分散剤。

[請求項2]
 前記高分子化合物が、更に、下記(1)~(5)の要件をすべて満たすA-Bブロック共重合体である請求項1に記載のセルロース用高分子分散剤。
(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、熱可塑性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3]
 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、
 前記(3)の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1000~8000であり、且つ、前記A-B共重合体全体に占める樹脂親和性セグメントAの割合が30~70質量%であり、
 前記(4)の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1000~8000であり、且つ、前記A-B共重合体全体に占めるセルロース吸着性セグメントBの割合が30~70質量%であり、
 前記(5)のA-B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2000~16000であり、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である請求項2に記載のセルロース用高分子分散剤。

[請求項4]
 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2又は3に記載のセルロース用高分子分散剤。

[請求項5]
 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種である請求項1~4のいずれか1項に記載のセルロース用高分子分散剤。

[請求項6]
 前記セルロースに対する分散性を向上させた高分子分散剤を含有する水系分散処理剤であって、請求項4に記載のセルロース用高分子分散剤を、水系媒体中に分散処理してなることを特徴とする高分子分散剤含有の水系分散処理剤。

[請求項7]
 セルロースに対する分散性を向上させた高分子分散剤を含有する水系分散処理剤であって、請求項1~4のいずれか1項に記載のセルロース用高分子分散剤を、界面活性剤によって水系媒体中に分散処理されてなることを特徴とする高分子分散剤含有の水系分散処理剤。

[請求項8]
 前記界面活性剤が、カチオン性界面活性剤である請求項5に記載の水系分散処理剤。

[請求項9]
 請求項1~5のいずれか1項に記載のセルロース用高分子分散剤と、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種のセルロースとを含んでなることを特徴とする易分散性セルロース組成物。

[請求項10]
 請求項6又は7に記載の水系分散処理剤と、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種のセルロースとを含んでなることを特徴とする易分散性セルロース組成物。

[請求項11]
 請求項9又10に記載の易分散性セルロース組成物と、熱可塑性樹脂とを含んでなることを特徴とするセルロース分散樹脂組成物。

[請求項12]
 請求項1~5のいずれか1項に記載のセルロース用高分子分散剤と、熱可塑性樹脂とを含んでなることを特徴とするセルロース分散用分散剤含有樹脂組成物。

[請求項13]
 請求項6又は7に記載の水系分散処理剤と、熱可塑性樹脂とを含んでなることを特徴とするセルロース分散用分散剤含有樹脂組成物。

[請求項14]
 請求項12又は13に記載のセルロース分散用分散剤含有樹脂組成物と、セルロースとを含んでなることを特徴とするセルロース分散樹脂組成物。
  • 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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