WO2011132675A1 - Water absorbent material - Google Patents

Water absorbent material Download PDF

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WO2011132675A1
WO2011132675A1 PCT/JP2011/059629 JP2011059629W WO2011132675A1 WO 2011132675 A1 WO2011132675 A1 WO 2011132675A1 JP 2011059629 W JP2011059629 W JP 2011059629W WO 2011132675 A1 WO2011132675 A1 WO 2011132675A1
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water
soft tissue
oil palm
trunk
water absorption
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PCT/JP2011/059629
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French (fr)
Japanese (ja)
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昭彦 小杉
▲隆▼ 森
隆益 荒井
善則 村田
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独立行政法人国際農林水産業研究センター
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Priority to CN201180030545.1A priority Critical patent/CN102946992B/en
Publication of WO2011132675A1 publication Critical patent/WO2011132675A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/485Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/50Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/68Superabsorbents

Definitions

  • the present invention relates to a naturally derived water-absorbing material.
  • a highly water-absorbing material is a material that can absorb water from several tens to several thousand times its own weight.
  • a highly water-absorbing resin having a water absorption performance of 10 g or more per 1 g of resin. It stipulates.
  • a resin obtained by cross-linking sodium polyacrylate with N—N′-methylenebisacrylamide is widely used as a typical synthetic superabsorbent resin.
  • Synthetic superabsorbent resins are widely used in disposable hygiene products and the like, but their biodegradability is low, and their disposal method is problematic.
  • Starch which is a naturally derived material, or cellulose such as pulp or paper has water absorbency, and is superior to synthetic superabsorbent resins in terms of biodegradability.
  • the water absorption of cellulose is due to the capillary phenomenon between the fibers, and does not reach the synthetic high water absorption resin.
  • the water-absorbing material derived from starch has low water absorption performance and is not classified as high water absorption. Furthermore, since starch becomes slurry when absorbed, it is difficult to handle.
  • xanthan gum-derived polymers (Patent Document 1) and Karaya gum-derived polymers (Patent Document 2) are known as highly water-absorbing materials mainly composed of naturally occurring polysaccharides.
  • xanthan gum and karaya gum which are naturally derived polysaccharides, are water-soluble and, like starch, dissolve when water is absorbed and are difficult to handle.
  • Patent Document 1 heats xanthan gum at 90 ° C. to 120 ° C. or mixes it with a poor solvent for xanthan gum.
  • Patent Document 2 polycarboxylic acid is added to Karaya gum and then heated at 120 ° C. to 180 ° C. for surface crosslinking.
  • it is generally necessary to perform extraction and purification operations from natural materials, and further, in order to insolubilize the materials, such as Karaya gum and xanthan gum. Need.
  • Today there is a demand for naturally-derived water-absorbing materials that can reduce the running cost without adding the availability and processing of the materials.
  • the present invention provides a water-absorbing material that is obtained from an oil palm trunk and is mainly composed of a fine particulate material called a soft tissue in the trunk.
  • the soft tissue in the oil palm trunk is a fine particulate material present in the woody part inside the trunk.
  • the water-absorbing material of the present invention can be obtained, for example, by drying the felled oil palm trunk and separating the soft tissue from the solid content in the wood part.
  • the water-absorbing material of the present invention is a naturally-derived material and can be used in various fields such as animal excreta treatment, feed additives, agricultural and horticultural materials.
  • animal excreta treatment e.g., cowpoxa treatment
  • feed additives e.g., talc, karaya gum
  • heat treatment or the like e.g., heat treatment or the like
  • Oil palm is a plant of the palm family that is cultivated to collect palm oil, and is cut and replanted approximately every 25 years in order to maintain oil and fat productivity.
  • about 40 million hectares of replanting is currently being carried out annually, so about 30 million tons of oil palm has been harvested.
  • the trunk is hardly reused and it is left as it is. ing.
  • FIG. 2 is a cross-sectional view of the oil palm trunk cut in the longitudinal direction as indicated by broken lines in FIG.
  • the oil palm trunk constitutes a woody part composed of a soft tissue 1, a vascular bundle 2 and a bark 3. Since the outer layer portion near the bark 3 has a relatively low water content, the outer layer portion is used for plywood only in the outer layer portion.
  • the soft tissue 1 and the vascular bundle 2 it has only been studied to hydrolyze and use as a raw material for ethanol fermentation, and its use has not been established yet.
  • the oil palm trunk can be easily divided into fine powdery solid solids and acicular solids with a sieve after drying the water-insoluble component after collecting the sap, that is, the juice residue.
  • the powdery fine particulate solid is called soft tissue. It is also possible to dry the felled oil palm trunk without squeezing the sap and separate the soft tissue from the woody part.
  • the soft structure of oil palm that is, the water-absorbing material of the present invention has a porous structure in which fine pores are densely packed, and this porous structure is considered to play an important role in water absorption performance.
  • Oil palm soft tissue can be obtained by simply defibrating and drying the wood part of the oil palm trunk tree, and does not require additional treatment such as heat treatment at high temperatures. Therefore, the running cost can be reduced as compared with the extraction and purification of polysaccharides.
  • the soft tissue of oil palm swells when water is added, but is not gel-like when it does not contain water.
  • a major feature is that even if salts and organic components are contained in the moisture, the water absorption capacity of the soft tissue hardly changes. For this reason, soft tissue is applied to water-absorbing articles intended to absorb body fluids such as urine, sweat, saliva and blood, such as paper diapers, portable toilets, pet urine absorbing materials, meat and fish freshness-retaining materials, etc. can do.
  • water-absorbing articles for civil engineering materials that absorb mud, river water, seawater, soil and fertilizers can be used as soil improvement materials, or agricultural and horticultural materials such as water retention materials in dry land It can be used in a wide range, for example, as a water-absorbing article.
  • the soft tissue may be used alone, for example, by wrapping it with a cloth or non-woven fabric to form a water-absorbing article.
  • the water-absorbing material of the present invention may be preliminarily mixed with water and mixed with inorganic matter, soil or fertilizer.
  • the oil palm trunk is divided into a hard bark surrounding the outside and a yellowish white wood part.
  • the bark of the felled oil palm was removed, the woody part was squeezed, and the solid residue after squeezing the sap was dried at 60 ° C. for 1 to 3 days.
  • the dried product was lightly pulverized in a mortar and fractionated with a sieve, it could be divided into fine powdery particles, ie soft tissue (diameter of about 30 ⁇ m to 50 ⁇ m), and needle-like solid solids, ie vascular bundles. .
  • a soft tissue image is shown in FIG. 3, and a vascular bundle image is shown in FIG. It can be seen that the soft tissue is fine powdery particles and the vascular bundle is in a needle-like form.
  • about 50 to 60% of the wood part was soft tissue and the rest was vascular bundle.
  • Soft tissue and vascular bundles were dried at 70 ° C. for 1 day. 1 g of each solid content was weighed and placed in a tea bag under conditions that allow free swelling (size of bag that does not rupture even if it absorbs water 100 times) and was immersed in 1 liter of distilled water at 20 ° C. for 1 hour. Thereafter, the tea bag was suspended for 3 hours to drain water, then weighed (20 ° C.), and the water absorption capacity was determined from the following formula from the weight difference before and after immersion. The results are shown in Table 1.
  • microcrystalline cellulose powder (Sigma Cell; Sigma Aldrich), cellulose powder (Whatman), starch (from corn; Wako Pure Chemical), silica gel (Wako Pure Chemical), agar (for microbial culture; Wako Pure Chemical), 1 g each of duran gum (Wako Pure Chemical Industries) was weighed, placed in a tea bag under conditions that allow free swelling (size of bag that does not burst even if it absorbs water 100 times), and was immersed in 1 liter of distilled water at 20 ° C. for 1 hour.
  • the tea bag was suspended for 3 hours to drain water, and then weighed (20 ° C.) (this was referred to as the resin amount after immersion), and the water absorption ratio was determined from the weight difference from the resin amount before immersion. The results are shown in Table 1.
  • the solid content obtained from the oil palm trunk, particularly the soft tissue has very high water absorption performance.
  • the vascular bundle had a water absorption ratio of 1.4 times, while the soft tissue showed a water absorption ratio of about 20 times. That is, it can be seen that the water-absorbing material of the present invention has performance comparable to that of the highly water-absorbent resin specified in JIS Method-K-7223.
  • the solid content from oil palm trunk is known to contain cellulose and hemicellulose as a constituent component, and a small amount of starch, but it is extremely high compared to the commercially available cellulose and starch components listed as comparative examples. It showed water absorption ability. Therefore, the water-absorbing performance of this soft tissue has shown that it has the water-absorbing ability by the function or structure different from the water-absorbing ability which a cellulose and starch have. Moreover, it turns out that the water absorption capacity
  • FIG. 5 reveals that the soft tissue has a structure in which fine porous structures such as egg shells are densely packed.
  • FIG. 6 it can be seen that fine pores are not densely packed in the vascular part, and that the structure is completely heterogeneous.
  • the soft tissue was immersed in 0.05M phosphate buffer pH 5.5, and then excess water was removed with gauze and transferred to a petri dish, and the soil containing microorganisms was reduced to about 0. Mixed with 5 g, spread flat to make a solid medium and cultured at 30 ° C. Vigorous growth of filamentous fungi was mainly confirmed on the second day of culture.
  • 1 ml of commercially available mold enzyme (Sigma, Cellulase) is added to 1 g of soft tissue and reacted in an acetate buffer (pH 5.0) for 48 hours. I let you.
  • the decomposition solution was centrifuged at 14,000 rpm at 4 ° C. for 5 minutes, and the supernatant was diluted with distilled water to an appropriate concentration, and the sugar composition was measured.
  • Each free sugar contained in the decomposition solution was measured by high performance liquid chromatography (Prominence, manufactured by Shimadzu Corporation) using a differential refraction detector with an Aminex HPX-87P column (Bio-Rad).
  • High performance liquid chromatography Prominence, manufactured by Shimadzu Corporation
  • Aminex HPX-87P column Bio-Rad
  • the high water absorption performance of the soft tissue prepared from the oil palm trunk depends on its unique porous structural characteristics, and further has biodegradability. . Therefore, the solid content prepared from the oil palm trunk, particularly the soft tissue, can be used as a highly water-absorbing material.
  • the water-absorbing material of the present invention may be wrapped in a water-permeable material such as paper or cloth to make a water-absorbing article.
  • a water-permeable material such as paper or cloth
  • water absorption performance hardly deteriorates even in solutions containing high salt concentrations such as seawater or flammable organic solvents. It can also be used as a poor environmental improvement material in the region. It can also be used as a soil conditioner that absorbs moisture and gradually releases the absorbed moisture.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

Disclosed is a water absorbent material—which has as a primary component a minute particulate material that is obtained from oil palm trunks and that is called parenchyma that is in the trunks—wherein the abovementioned parenchyma has porous structural characteristics, and has the excellent characteristic of water absorbing performance decreasing very little even with respect to liquids containing organic solvents or liquids with high salt concentration such as seawater.

Description

吸水性素材Water-absorbing material
 本発明は天然由来の吸水性素材に関する。 The present invention relates to a naturally derived water-absorbing material.
 高吸水性素材は、自重の数十倍から数千倍の水を吸水できる素材であり、JIS法-K-7223によれば、樹脂1gあたり10g以上の吸水性能を備えるものを高吸水性樹脂と規定している。現在、ポリアクリル酸ナトリウムをN-N’-メチレンビスアクリルアミドで架橋した樹脂が合成系高吸水性樹脂の代表的なものとして広く使われている。合成系高吸水性樹脂は、使い捨て衛生用品等に広く使用されているものの、生分解性が低く、その処分方法が問題となっている。 A highly water-absorbing material is a material that can absorb water from several tens to several thousand times its own weight. According to JIS-K-7223, a highly water-absorbing resin having a water absorption performance of 10 g or more per 1 g of resin. It stipulates. At present, a resin obtained by cross-linking sodium polyacrylate with N—N′-methylenebisacrylamide is widely used as a typical synthetic superabsorbent resin. Synthetic superabsorbent resins are widely used in disposable hygiene products and the like, but their biodegradability is low, and their disposal method is problematic.
 天然由来の素材である澱粉、又はパルプや紙等のセルロースは吸水性を有し、生分解性の観点で合成系高吸水樹脂より優れている。しかし、セルロースの吸水性は、繊維間の毛細管現象によるものであり、合成系高吸水性樹脂に到底及ばない。また、澱粉由来の吸水性素材も吸水性能が低く、高吸水性に分類されるものではない。さらに澱粉は、吸水した場合にスラリー状になるため、取り扱いが難しい。 Starch, which is a naturally derived material, or cellulose such as pulp or paper has water absorbency, and is superior to synthetic superabsorbent resins in terms of biodegradability. However, the water absorption of cellulose is due to the capillary phenomenon between the fibers, and does not reach the synthetic high water absorption resin. Also, the water-absorbing material derived from starch has low water absorption performance and is not classified as high water absorption. Furthermore, since starch becomes slurry when absorbed, it is difficult to handle.
 セルロースや澱粉以外に、天然由来の多糖を主成分とする高吸水性の素材として、キサンタンガム由来のポリマー(特許文献1)やカラヤガム由来のポリマー(特許文献2)が知られている。 In addition to cellulose and starch, xanthan gum-derived polymers (Patent Document 1) and Karaya gum-derived polymers (Patent Document 2) are known as highly water-absorbing materials mainly composed of naturally occurring polysaccharides.
特開2003-192703号JP 2003-192703 A 特開2005-246121号JP 2005-246121 A
 しかし、天然由来の多糖であるキサンタンガムやカラヤガムは水溶性であり、澱粉同様、水を吸水したときに溶解するため取り扱いが難しい。この問題を解決するために、特許文献1では、キサンタンガムを90℃~120℃で加熱するか又はキサンタンガムの貧溶媒に混合してから加熱処理を行っている。また、特許文献2では、カラヤガムにポリカルボン酸を添加してから120℃~180℃で加熱して表面架橋を行っている。このように、天然由来の多糖を吸水性素材として利用するためには、一般に、天然素材からの抽出、精製という操作を必要とし、さらにカラヤガムやキサンタンガムのように、素材を不溶化するために加工処理を必要としている。
 今日、天然由来の吸水素材に関して、素材の入手の容易さと加工処理を付加することなく、ランニングコストを低減できるものが求められている。
However, xanthan gum and karaya gum, which are naturally derived polysaccharides, are water-soluble and, like starch, dissolve when water is absorbed and are difficult to handle. In order to solve this problem, Patent Document 1 heats xanthan gum at 90 ° C. to 120 ° C. or mixes it with a poor solvent for xanthan gum. In Patent Document 2, polycarboxylic acid is added to Karaya gum and then heated at 120 ° C. to 180 ° C. for surface crosslinking. Thus, in order to use naturally-derived polysaccharides as water-absorbing materials, it is generally necessary to perform extraction and purification operations from natural materials, and further, in order to insolubilize the materials, such as Karaya gum and xanthan gum. Need.
Today, there is a demand for naturally-derived water-absorbing materials that can reduce the running cost without adding the availability and processing of the materials.
 本発明者らは天然由来の吸水素材について研究を進めた結果、これまで利用されることなく廃棄されていたオイルパーム由来の樹木組織が、高い吸水性を有することを見出し、本発明を完成するに至った。 As a result of researches on naturally-derived water-absorbing materials, the present inventors have found that oil palm-derived tree tissues that have been discarded without being used so far have high water absorption, and complete the present invention. It came to.
 すなわち、本発明は、オイルパーム幹から得られる、幹中の柔組織と呼ばれる細かい粒子状の素材を主成分とする、吸水性素材を提供する。オイルパーム幹中の柔組織は、幹内部の木質部に存在する細かい粒子状の素材である。本発明の吸水性素材は、例えば、伐採されたオイルパーム幹を乾燥し、木質部中の固形分から柔組織を分離することにより得ることができる。 That is, the present invention provides a water-absorbing material that is obtained from an oil palm trunk and is mainly composed of a fine particulate material called a soft tissue in the trunk. The soft tissue in the oil palm trunk is a fine particulate material present in the woody part inside the trunk. The water-absorbing material of the present invention can be obtained, for example, by drying the felled oil palm trunk and separating the soft tissue from the solid content in the wood part.
 本発明の吸水性素材は、天然由来の素材であり、動物用のし尿処理、飼料添加剤、農園芸用資材等、種々の分野で利用可能である。
 なお、キサンタンガムやカラヤガムとは異なり、加熱処理等を行う必要がないので安価に製造することができる。
The water-absorbing material of the present invention is a naturally-derived material and can be used in various fields such as animal excreta treatment, feed additives, agricultural and horticultural materials.
In addition, unlike xanthan gum and karaya gum, it is not necessary to perform heat treatment or the like, and can be manufactured at low cost.
本発明に用いるオイルパーム幹の外観を示す像である。It is an image which shows the external appearance of the oil palm trunk used for this invention. 図1の破線に従って縦方向にオイルパーム幹を切断した断面図である。It is sectional drawing which cut | disconnected the oil palm trunk in the vertical direction according to the broken line of FIG. オイルパーム由来の柔組織の像(×1)を示す図である。It is a figure which shows the image (x1) of the soft tissue derived from oil palm. オイルパーム由来の維管束の像(×1)を示す図である。It is a figure which shows the image (x1) of the vascular bundle derived from an oil palm. オイルパーム由来の柔組織の拡大像(×150)を示す図である。It is a figure which shows the enlarged image (x150) of the soft tissue derived from oil palm. オイルパーム由来の維管束の像(×550)を示す図である。It is a figure which shows the image (x550) of the vascular bundle derived from an oil palm. オイルパーム由来の柔組織のボールミル処理後の拡大像(×370)を示す図である。It is a figure which shows the enlarged image (x370) after the ball mill process of the soft tissue derived from an oil palm.
 オイルパームは、パーム油を採取するために栽培されているヤシ科の植物であり、油脂生産性を維持するために約25年ごとに伐採、再植される。マレーシアでは、現在年間約4万ヘクタールの再植が行われるため約3,000万トンのオイルパームが伐採されているが、その幹の再利用はほとんどなされることなく、伐採されたまま放置されている。 Oil palm is a plant of the palm family that is cultivated to collect palm oil, and is cut and replanted approximately every 25 years in order to maintain oil and fat productivity. In Malaysia, about 40 million hectares of replanting is currently being carried out annually, so about 30 million tons of oil palm has been harvested. However, the trunk is hardly reused and it is left as it is. ing.
 図1にオイルパーム幹の外観を示す。図2は、図1に破線で示すようにオイルパーム幹を縦方向に切断した断面図である。図2に示すように、オイルパーム幹は柔組織1、維管束2及び樹皮3からなる木質部を構成している。樹皮3付近の外層部は、比較的水分含量が低いため、外層部に限り合板への利用が図られている。しかし、柔組織1、維管束2に関しては、加水分解して、エタノール発酵用の原料として用いることが検討されているだけで、その利用は未だ確立されていない。なお、伐採オイルパーム幹中に含まれる多量の樹液中にはエタノール発酵に適した発酵可能な六単糖が多く含まれるため、樹液を直接エタノール発酵の原料とできることが本発明者らにより報告されている。 Figure 1 shows the appearance of the oil palm trunk. FIG. 2 is a cross-sectional view of the oil palm trunk cut in the longitudinal direction as indicated by broken lines in FIG. As shown in FIG. 2, the oil palm trunk constitutes a woody part composed of a soft tissue 1, a vascular bundle 2 and a bark 3. Since the outer layer portion near the bark 3 has a relatively low water content, the outer layer portion is used for plywood only in the outer layer portion. However, regarding the soft tissue 1 and the vascular bundle 2, it has only been studied to hydrolyze and use as a raw material for ethanol fermentation, and its use has not been established yet. In addition, since a large amount of fermentable hexose suitable for ethanol fermentation is contained in a large amount of sap contained in the felled oil palm trunk, the present inventors have reported that the sap can be directly used as a raw material for ethanol fermentation. ing.
 オイルパーム幹は、樹液を採取した後の水不溶成分、すなわち、搾汁残渣を乾燥後、篩等により、パウダー状の細かい粒子状固形分と針状固形分とに容易に分けることができる。本明細書中では、パウダー状の細かい粒子状固形分を柔組織という。なお、樹液を搾汁せずに、伐採したオイルパーム幹を乾燥して、木質部から柔組織を分離することも可能である。 The oil palm trunk can be easily divided into fine powdery solid solids and acicular solids with a sieve after drying the water-insoluble component after collecting the sap, that is, the juice residue. In the present specification, the powdery fine particulate solid is called soft tissue. It is also possible to dry the felled oil palm trunk without squeezing the sap and separate the soft tissue from the woody part.
 オイルパームの柔組織、すなわち、本発明の吸水性素材は、微細な孔が密集した多孔質構造を有しており、この多孔質構造が吸水性能に重要な役割を果たしていると考えられる。 The soft structure of oil palm, that is, the water-absorbing material of the present invention has a porous structure in which fine pores are densely packed, and this porous structure is considered to play an important role in water absorption performance.
 オイルパームの柔組織は、オイルパーム幹の樹木中の木質部を解繊し、乾燥するだけで得ることができ、高温での加熱処理等の付加的な処理を必要としないので、製造に当たり、必要とするエネルギー量も少なく、多糖の抽出、精製に比べ、ランニングコストを低減することができる。 Oil palm soft tissue can be obtained by simply defibrating and drying the wood part of the oil palm trunk tree, and does not require additional treatment such as heat treatment at high temperatures. Therefore, the running cost can be reduced as compared with the extraction and purification of polysaccharides.
 オイルパームの柔組織は、水を加えると膨潤するが、水を含んでいない状態ではゲル状ではない。 The soft tissue of oil palm swells when water is added, but is not gel-like when it does not contain water.
 水分中に、塩類や有機成分が含まれていても、柔組織の吸水能はほとんど変化しないことも大きな特徴である。このため、柔組織を尿、汗、唾液、血液等の体液を吸収することを目的とした吸水物品、例えば紙おむつ、携帯用トイレ、ペット用のし尿吸収材、肉や魚の鮮度保持材などに適用することができる。また、体液だけでなく、泥水、河川水、海水を吸収する土木工事資材の吸水物品、土壌や肥料と混ぜて土壌改良材とする、あるいは、乾燥地での保水材のような農園芸資材の吸水物品として使用するなど、広範囲での利用が可能である。 A major feature is that even if salts and organic components are contained in the moisture, the water absorption capacity of the soft tissue hardly changes. For this reason, soft tissue is applied to water-absorbing articles intended to absorb body fluids such as urine, sweat, saliva and blood, such as paper diapers, portable toilets, pet urine absorbing materials, meat and fish freshness-retaining materials, etc. can do. In addition to bodily fluids, water-absorbing articles for civil engineering materials that absorb mud, river water, seawater, soil and fertilizers can be used as soil improvement materials, or agricultural and horticultural materials such as water retention materials in dry land It can be used in a wide range, for example, as a water-absorbing article.
 柔組織は、単独で、例えば布、不織布で包んで吸水物品としてもよいが、必要に応じ、吸水物品中に香料、消臭剤、無機物等を混合してもよい。 The soft tissue may be used alone, for example, by wrapping it with a cloth or non-woven fabric to form a water-absorbing article.
 本発明の吸水性素材は、あらかじめ水を含ませて、無機物、土壌あるいは肥料と混合してもよい。 The water-absorbing material of the present invention may be preliminarily mixed with water and mixed with inorganic matter, soil or fertilizer.
 以下に、本発明に係る吸水性素材及びその製造方法を実施例に基づき説明する。なお、本発明は下記の実施例に限定されるものではない。 Hereinafter, the water-absorbing material and the manufacturing method thereof according to the present invention will be described based on examples. In addition, this invention is not limited to the following Example.
 オイルパーム幹は、外側を取り巻く固い樹皮と黄白色の木質部とに分けられる。
 伐採したオイルパームの樹皮を除いて、木質部を圧搾し、樹液を搾汁した後の固形残渣を60℃で1日から3日間乾燥させた。乾燥物を乳鉢で軽く粉砕後、篩により分画すると、パウダー状の細かい粒子、すなわち柔組織(直径約30μm~50μm)と、針状の固い固形分、すなわち維管束とに分けることができた。
 柔組織の像を図3に、維管束の像を図4に示す。柔組織は、パウダー状の細かい粒子であり、維管束は、針状の形態であることがわかる。柔組織と維管束の分量は、木質部の約50~60%が柔組織で、残りが維管束であった。
The oil palm trunk is divided into a hard bark surrounding the outside and a yellowish white wood part.
The bark of the felled oil palm was removed, the woody part was squeezed, and the solid residue after squeezing the sap was dried at 60 ° C. for 1 to 3 days. When the dried product was lightly pulverized in a mortar and fractionated with a sieve, it could be divided into fine powdery particles, ie soft tissue (diameter of about 30 μm to 50 μm), and needle-like solid solids, ie vascular bundles. .
A soft tissue image is shown in FIG. 3, and a vascular bundle image is shown in FIG. It can be seen that the soft tissue is fine powdery particles and the vascular bundle is in a needle-like form. Regarding the amount of soft tissue and vascular bundle, about 50 to 60% of the wood part was soft tissue and the rest was vascular bundle.
 柔組織及び維管束を70℃で1日間乾燥した。それぞれの固形分を1g秤量し、自由膨潤できる条件(100倍吸水しても破裂しない袋の大きさ)のティーバッグにそれぞれ入れ、20℃の蒸留水1リットルに1時間浸漬した。その後3時間、ティーバッグを吊り下げて水切りをした後、秤量(20℃)し、浸漬前後の重量差から下記式により吸水倍率を求めた。結果を表1に示す。 Soft tissue and vascular bundles were dried at 70 ° C. for 1 day. 1 g of each solid content was weighed and placed in a tea bag under conditions that allow free swelling (size of bag that does not rupture even if it absorbs water 100 times) and was immersed in 1 liter of distilled water at 20 ° C. for 1 hour. Thereafter, the tea bag was suspended for 3 hours to drain water, then weighed (20 ° C.), and the water absorption capacity was determined from the following formula from the weight difference before and after immersion. The results are shown in Table 1.
吸水倍率=(浸漬後の重量(g)-浸漬前の重量(g))/浸漬前の重量(g) Water absorption ratio = (weight after immersion (g) −weight before immersion (g)) / weight before immersion (g)
 比較のため、微結晶セルロース粉末(シグマセル;シグマアルドリッチ)、セルロース粉末(ワットマン社)、澱粉(トウモロコシ由来;和光純薬)、シリカゲル(和光純薬)、寒天(微生物培養用;和光純薬)、ジュランガム(和光純薬)をそれぞれ1g秤量し、自由膨潤できる条件(100倍吸水しても破裂しない袋の大きさ)のティーバッグに入れ、20℃の蒸留水1リットルに1時間浸漬した。その後3時間、ティーバッグを吊り下げて水切りをした後、秤量(20℃)(これを浸漬後の樹脂量という。)し、浸漬前の樹脂量との重量差から吸水倍率を求めた。結果を表1に示す。 For comparison, microcrystalline cellulose powder (Sigma Cell; Sigma Aldrich), cellulose powder (Whatman), starch (from corn; Wako Pure Chemical), silica gel (Wako Pure Chemical), agar (for microbial culture; Wako Pure Chemical), 1 g each of duran gum (Wako Pure Chemical Industries) was weighed, placed in a tea bag under conditions that allow free swelling (size of bag that does not burst even if it absorbs water 100 times), and was immersed in 1 liter of distilled water at 20 ° C. for 1 hour. Thereafter, the tea bag was suspended for 3 hours to drain water, and then weighed (20 ° C.) (this was referred to as the resin amount after immersion), and the water absorption ratio was determined from the weight difference from the resin amount before immersion. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 この結果から、オイルパーム幹から得られる固形分、特に柔組織が、非常に高い吸水性能を有することが明らかとなった。維管束は、1.4倍の吸水倍率であるが、柔組織は、その約20倍もの吸水倍率を示した。すなわち、本発明の吸水性素材は、JIS法-K-7223に規定する高吸水性樹脂に匹敵する性能を備えていることがわかる。 From this result, it became clear that the solid content obtained from the oil palm trunk, particularly the soft tissue, has very high water absorption performance. The vascular bundle had a water absorption ratio of 1.4 times, while the soft tissue showed a water absorption ratio of about 20 times. That is, it can be seen that the water-absorbing material of the present invention has performance comparable to that of the highly water-absorbent resin specified in JIS Method-K-7223.
 オイルパーム幹からの固形分は、その構成成分としてセルロースやヘミセルロース、また少量の澱粉を含んでいることが知られているが、比較例として列挙した市販セルロースや澱粉成分に比較しても極めて高い吸水能を示した。従って本柔組織の吸水性能は、セルロースや澱粉の有する吸水能とは異なる機能又は構造による吸水能を有していることを示していた。また、商品化されている天然由来のジュランガムに匹敵する吸水倍率を示すことがわかる。 The solid content from oil palm trunk is known to contain cellulose and hemicellulose as a constituent component, and a small amount of starch, but it is extremely high compared to the commercially available cellulose and starch components listed as comparative examples. It showed water absorption ability. Therefore, the water-absorbing performance of this soft tissue has shown that it has the water-absorbing ability by the function or structure different from the water-absorbing ability which a cellulose and starch have. Moreover, it turns out that the water absorption capacity | capacitance comparable to the natural-derived duran gum commercialized is shown.
 柔組織の吸水特性を検討するため、高塩濃度を含む溶液や有機溶媒を含む溶液の吸水効果について試験を行った。
 柔組織1gをティーバッグに入れ、20℃の塩化ナトリウム5%(w%)、10%、20%溶液1リットルに浸漬した。結果を表2に示す。
 有機溶媒を含む溶液に関しては、メタノール(和光純薬 特級)-蒸留水10%、30%(v%)溶液、及びエタノール(和光純薬 特級)-蒸留水10%、30%(v%)溶液をそれぞれ調製し、柔組織の浸漬を行った。その結果を表3に示す。
In order to examine the water absorption characteristics of the soft tissue, the water absorption effect of a solution containing a high salt concentration or a solution containing an organic solvent was tested.
1 g of soft tissue was placed in a tea bag and immersed in 1 liter of a 20% sodium chloride 5% (w%), 10%, 20% solution. The results are shown in Table 2.
For solutions containing organic solvents, methanol (Wako Pure Chemical), distilled water 10%, 30% (v%) solution, and ethanol (Wako Pure Chemical), distilled water 10%, 30% (v%) solution Each was prepared and the soft tissue was immersed. The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 蒸留水に浸漬した柔組織の吸水倍率と比較し、5%、10%、20%塩化ナトリウム溶液に浸漬した柔組織の吸水倍率にはほとんど変化は認められなかった。また柔組織をメタノール、エタノール水溶液に浸漬した場合、吸水倍率の若干の低下は認められたが、ほぼ蒸留水と同等の吸水倍率を示した。これらの結果から、柔組織は、高塩濃度を含む溶液や有機溶媒を含む溶液に対しても蒸留水と同程度の吸湿能を有していることが明らかとなった。 Compared with the water absorption capacity of soft tissue immersed in distilled water, almost no change was observed in the water absorption capacity of soft tissue immersed in 5%, 10% and 20% sodium chloride solutions. Moreover, when the soft tissue was immersed in methanol or an ethanol aqueous solution, a slight decrease in the water absorption capacity was observed, but the water absorption capacity was almost the same as that of distilled water. From these results, it was clarified that the soft tissue has the same hygroscopicity as distilled water with respect to a solution containing a high salt concentration and a solution containing an organic solvent.
 オイルパーム幹の柔組織の吸水能に関して詳細に検討するため、調製された柔組織を電子顕微鏡で構造を観察した。その電子顕微鏡像を図5に示す。図5から、柔組織は、卵の殻のような微細な多孔性構造が密集した構造体を有していることが明らかとなった。これに対し、図6に示すように、維管束部分では微細な孔が密集しておらず、構造的に全く異質であることがわかる。 In order to examine in detail the water absorption ability of the soft tissue of the oil palm trunk, the structure of the prepared soft tissue was observed with an electron microscope. The electron microscope image is shown in FIG. FIG. 5 reveals that the soft tissue has a structure in which fine porous structures such as egg shells are densely packed. On the other hand, as shown in FIG. 6, it can be seen that fine pores are not densely packed in the vascular part, and that the structure is completely heterogeneous.
 この構造が、吸水性に関連しているかどうかを確認するため、ボールミル処理(5分間インターバル、6時間処理)を行い、柔組織の多孔質構造を破壊し、電子顕微鏡により確認した。その電子顕微鏡像を図7に示した。その結果、8割以上の多孔質が破れ、破壊されていることが確認できた。この多孔質構造が破壊された柔組織を用いて、蒸留水で浸漬処理を行った結果、吸水倍率は2.5倍と大幅に減少した。これらの結果から柔組織の吸水能はこの柔組織の持つ多孔質構造が重要であることが明らかとなった。 In order to confirm whether or not this structure is related to water absorption, ball mill treatment (5 minute interval, 6 hour treatment) was performed, the porous structure of the soft tissue was destroyed, and confirmed by an electron microscope. The electron microscope image is shown in FIG. As a result, it was confirmed that 80% or more of the porous material was broken and destroyed. As a result of immersion treatment with distilled water using the soft tissue in which the porous structure was destroyed, the water absorption ratio was significantly reduced to 2.5 times. From these results, it was revealed that the porous structure of the soft tissue is important for the water absorption capacity of the soft tissue.
 柔組織の生分解性を確認するため、柔組織を0.05Mリン酸緩衝液pH5.5に浸漬したのち、ガーゼで余分な水分を除いたものをシャーレに移し、微生物を含む土壌約0.5gと混合し、平らに広げて、固形培地を作成し、30℃で培養した。培養2日目で主に糸状菌の旺盛な生育が確認された。
 柔組織が、カビ酵素により分解可能かどうかを確認するため、市販カビ酵素(シグマ社、セルラーゼ)を柔組織1gに対し1ml加えて50℃、酢酸緩衝液(pH5.0)中で48時間反応させた。反応後、分解液を、14,000回転、4℃、5分間遠心したのち、上清を適当な濃度に蒸留水で希釈し糖組成について測定を行った。
 分解液に含まれる各遊離糖の測定には、アミネックスHPX-87Pカラム(バイオラッド)による示差屈折検出器を用いた高速液体クロマトグラフィー(島津製作所製、Prominence)により測定した。
 その結果、セロビオース、グルコース、キシロビオース、キシロース、アラビノースが検出され、柔組織が、酵素により分解していることが確認された。これらの結果から柔組織は、生分解能を持つ高吸水性素材であることが確認できた。
In order to confirm the biodegradability of the soft tissue, the soft tissue was immersed in 0.05M phosphate buffer pH 5.5, and then excess water was removed with gauze and transferred to a petri dish, and the soil containing microorganisms was reduced to about 0. Mixed with 5 g, spread flat to make a solid medium and cultured at 30 ° C. Vigorous growth of filamentous fungi was mainly confirmed on the second day of culture.
In order to confirm whether soft tissue can be decomposed by mold enzymes, 1 ml of commercially available mold enzyme (Sigma, Cellulase) is added to 1 g of soft tissue and reacted in an acetate buffer (pH 5.0) for 48 hours. I let you. After the reaction, the decomposition solution was centrifuged at 14,000 rpm at 4 ° C. for 5 minutes, and the supernatant was diluted with distilled water to an appropriate concentration, and the sugar composition was measured.
Each free sugar contained in the decomposition solution was measured by high performance liquid chromatography (Prominence, manufactured by Shimadzu Corporation) using a differential refraction detector with an Aminex HPX-87P column (Bio-Rad).
As a result, cellobiose, glucose, xylobiose, xylose and arabinose were detected, and it was confirmed that the soft tissue was degraded by the enzyme. From these results, it was confirmed that soft tissue is a highly water-absorbing material having biodegradability.
 以上の結果から、オイルパーム幹から調製される柔組織の持つ高い吸水性能は、その特有な多孔性構造特性に依っていることが明らかとなり、さらに生分解性能を有していることが判明した。
 従ってオイルパーム幹から調製した固形分、特に柔組織は、高吸水性素材として利用することが可能である。
From the above results, it became clear that the high water absorption performance of the soft tissue prepared from the oil palm trunk depends on its unique porous structural characteristics, and further has biodegradability. .
Therefore, the solid content prepared from the oil palm trunk, particularly the soft tissue, can be used as a highly water-absorbing material.
 本発明の吸水性素材は紙、布等の透水性素材で包み、吸水物品としてもよい。また、多孔性構造特性によるため海水など高塩濃度溶液や、可燃性の有機溶媒を含む溶液においても吸水性能はほとんど低下しないことから、これらの原因で環境汚染や被害を受けている、不良環境地域にける不良環境改善素材としても使用できる。また、水分を吸収させ、吸収した水分を徐々に放出する土壌改良材として用いることもできる。 The water-absorbing material of the present invention may be wrapped in a water-permeable material such as paper or cloth to make a water-absorbing article. In addition, because of its porous structure characteristics, water absorption performance hardly deteriorates even in solutions containing high salt concentrations such as seawater or flammable organic solvents. It can also be used as a poor environmental improvement material in the region. It can also be used as a soil conditioner that absorbs moisture and gradually releases the absorbed moisture.

Claims (4)

  1.  オイルパーム幹から得られる幹中の柔組織と呼ばれる細かい粒子状の素材を主成分とする、吸水性素材。 A water-absorbing material composed mainly of fine particulate material called soft tissue in the trunk obtained from oil palm trunk.
  2.  前記柔組織が、伐採されたオイルパーム幹から得られる粒子状の素材である、請求項1記載の吸水性素材。 The water-absorbing material according to claim 1, wherein the soft tissue is a particulate material obtained from a felled oil palm trunk.
  3.  前記柔組織が、前記オイルパーム幹を搾汁した後に得られる残渣である、請求項1記載の吸水性素材。 The water absorbent material according to claim 1, wherein the soft tissue is a residue obtained after squeezing the oil palm trunk.
  4.  オイルパーム幹又は伐採されたオイルパーム幹から得られる固形分から柔組織を分離することを特徴とする、吸水性素材の製造方法。 A method for producing a water-absorbing material, characterized in that soft tissue is separated from a solid content obtained from an oil palm trunk or a cut oil palm trunk.
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