JP5480575B2 - Anti-darkening stain - Google Patents
Anti-darkening stain Download PDFInfo
- Publication number
- JP5480575B2 JP5480575B2 JP2009220862A JP2009220862A JP5480575B2 JP 5480575 B2 JP5480575 B2 JP 5480575B2 JP 2009220862 A JP2009220862 A JP 2009220862A JP 2009220862 A JP2009220862 A JP 2009220862A JP 5480575 B2 JP5480575 B2 JP 5480575B2
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- acid
- polyuronic acid
- crystallinity
- oxidation
- 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.)
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- 239000002253 acid Substances 0.000 claims description 61
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- 229920002678 cellulose Polymers 0.000 claims description 44
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 35
- 238000004140 cleaning Methods 0.000 claims description 34
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- 239000000203 mixture Substances 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 28
- 230000003647 oxidation Effects 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 19
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- 239000002689 soil Substances 0.000 claims description 7
- 238000011109 contamination Methods 0.000 claims description 6
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- 239000002519 antifouling agent Substances 0.000 claims 1
- -1 alkali metal salt Chemical class 0.000 description 31
- 238000004519 manufacturing process Methods 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 239000004744 fabric Substances 0.000 description 19
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- 238000000034 method Methods 0.000 description 15
- 230000002265 prevention Effects 0.000 description 15
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- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 4
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
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- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical class C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910052811 halogen oxide Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229940041615 kanuma Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical group O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、生分解性が良好で、煤汚れや粉塵汚れの再汚染防止能に優れた黒ずみ汚れ防止剤、及びそれを含有する洗浄剤組成物に関する。 The present invention relates to an anti-darkening agent having excellent biodegradability and excellent ability to prevent re-contamination of wrinkle dirt and dust dirt, and a cleaning composition containing the same.
ポリカルボン酸等の水溶性高分子薬剤は、粒子の分散・安定化、凝集、粘度調整、接着等の機能を有し、様々な分野に応用されている。しかしながら、水溶性高分子材料の多くは、使用後の回収が困難であるため、環境負荷を低減するために生分解性であることが求められている。
一方、衣類の洗浄においては、古くから泥や煤等による固体汚れの洗浄は難しいことが知られており、特に近年、洗濯機の節水化の進展により、洗濯する毎に、被洗浄物が黒ずんでいくという問題が大きくなってきている。
洗濯毎に被洗浄物が黒ずんでいく主な要因として、洗浄過程で被洗浄物から離脱した汚れ（固体着色成分）が、再び洗濯水中の被洗浄物に再付着する現象が挙げられる。洗濯水量が少なくなると、洗濯水中の汚れ濃度が高くなるため、汚れの再付着は起こり易くなる。一方、洗濯水量が少なくなれば、洗濯液中の洗浄剤、分散剤の濃度が高くなり、洗浄剤等による再付着防止効果は向上するが、それ以上に汚れ濃度が高くなることによる汚れの再付着が大きいために、被洗浄物の「黒ずみ」が促進されていく。
環境負荷の低減、経済性向上等の観点から、洗濯水の節減は好ましいものの、被洗浄物の「黒ずみ」は使用水量が少ないこと自体に起因しているため、洗濯機自体による改善は困難である。したがって、使用水量の少ない洗浄システムにおいても高い洗浄力を発揮するだけでなく、被洗浄物の黒ずみを抑制できる洗浄剤組成物が強く求められている。
Water-soluble polymer drugs such as polycarboxylic acids have functions such as particle dispersion / stabilization, aggregation, viscosity adjustment, and adhesion, and are applied in various fields. However, since many water-soluble polymer materials are difficult to recover after use, they are required to be biodegradable in order to reduce the environmental burden.
On the other hand, in washing clothes, it has been known that it is difficult to wash solid dirt due to mud and straw for a long time. The problem of going out is growing.
The main factor that the washed object becomes darker every time washing is performed is a phenomenon in which dirt (solid coloring component) detached from the washed object in the washing process is reattached to the washed object in the washing water. When the amount of washing water decreases, the dirt concentration in the washing water increases, so that the redeposition of dirt tends to occur. On the other hand, if the amount of washing water decreases, the concentration of the cleaning agent and the dispersing agent in the washing liquid increases, and the anti-reattachment effect by the cleaning agent etc. is improved, but the soil reconstitution due to the increase in the concentration of the soil is further increased. Since the adhesion is large, “darkening” of the object to be cleaned is promoted.
Although it is preferable to reduce washing water from the viewpoints of reducing environmental impact and improving economic efficiency, it is difficult to improve with the washing machine itself because the “darkness” of the object to be washed is due to the small amount of water used. is there. Therefore, there is a strong demand for a cleaning composition that not only exhibits high cleaning power even in a cleaning system that uses a small amount of water, but can suppress darkening of the object to be cleaned.
従来、汚れの再付着防止技術として、高分子等の分散／再付着防止剤を含む洗剤ビルダー組成物（特許文献１参照）、ノニオン界面活性剤、スメクタイト型粘土鉱物、及び吸油性担体を含む粒状ノニオン洗剤組成物（特許文献２参照）、イオン性ポリマー主鎖と、それと反対電荷のイオン性ポリマー側鎖とが連結してなるグラフトコポリマーからなる皮脂汚れ等の汚れ放出剤を含む洗浄剤組成物（特許文献３参照）等が知られている。
しかしながら、特許文献１〜３では、黒ずみ汚れの防止効果が十分でない。
特許文献４には、煤汚れや粉塵汚れの再汚染防止を課題として、Ｎ−ビニルピロリドン由来の構成単位と酢酸ビニル由来の構成単位とを有する共重合体を含む洗剤組成物が開示されている。しかしながら、この共重合体は天然原料からは製造できず、また生分解性が極めて低いという問題がある。
Conventionally, as a technique for preventing redeposition of dirt, a detergent builder composition containing a dispersion / anti-deposition agent such as a polymer (see Patent Document 1), a nonionic surfactant, a smectite clay mineral, and a granular containing an oil-absorbing carrier Nonionic detergent composition (see Patent Document 2), detergent composition comprising a soil release agent such as sebum soil comprising a graft copolymer in which an ionic polymer main chain and an ionic polymer side chain of the opposite charge are linked to each other (See Patent Document 3) and the like are known.
However, in Patent Documents 1 to 3, the effect of preventing dark stains is not sufficient.
Patent Document 4 discloses a detergent composition containing a copolymer having a structural unit derived from N-vinylpyrrolidone and a structural unit derived from vinyl acetate for the purpose of preventing recontamination of scumming and dust soiling. . However, this copolymer has a problem that it cannot be produced from natural raw materials and has extremely low biodegradability.
一方、酸化セルロースの製造方法として、特許文献５には、マーセル化セルロース又は再生セルロースを、Ｎ−オキシル化合物の存在下で酸化するほぼ完全酸化されたセルロース誘導体の製造方法が開示されている。
しかしながら、この完全酸化セルロースはII型結晶構造を有する高結晶性の酸化セルロースであり、その調製には溶剤、金属等が必要となり、コスト的にも環境的にも不利であるという問題がある。
特許文献６には、重量平均分子量が３０，０００以上の非晶性ポリグルクロン酸が開示され、ガスバリア性コーティング剤として好適であることが記載されている。また、特許文献７には、カルボキシル基含有量が０．１〜２ｍｍｏｌ／ｇで、平均繊維径が２００ｎｍ以下のセルロース繊維を含むガスバリア用材料が開示されており、その比較例６には低結晶性セルロースを酸化して得たポリウロン酸が記載されている。
しかしながら、特許文献６及び７で得られる酸化セルロースは、酸化度が低いため、水への溶解性は低く、洗浄剤成分として使用した場合、衣類へ付着して性能が低下する等の問題がある。
On the other hand, as a method for producing oxidized cellulose, Patent Document 5 discloses a method for producing a substantially completely oxidized cellulose derivative in which mercerized cellulose or regenerated cellulose is oxidized in the presence of an N-oxyl compound.
However, this completely oxidized cellulose is a highly crystalline oxidized cellulose having a type II crystal structure, and its preparation requires a solvent, a metal, etc., and is disadvantageous in terms of cost and environment.
Patent Document 6 discloses amorphous polyglucuronic acid having a weight average molecular weight of 30,000 or more and describes that it is suitable as a gas barrier coating agent. Patent Document 7 discloses a gas barrier material containing cellulose fibers having a carboxyl group content of 0.1 to 2 mmol / g and an average fiber diameter of 200 nm or less. Polyuronic acid obtained by oxidizing water-soluble cellulose is described.
However, since the oxidized cellulose obtained in Patent Documents 6 and 7 has a low degree of oxidation, the solubility in water is low, and when used as a cleaning agent component, there is a problem such as adhesion to clothing and performance deterioration. .
本発明は、生分解性が良好で、煤汚れや粉塵汚れの再汚染を防止できる黒ずみ汚れ防止剤、及びそれを含有する洗浄剤組成物を提供することを課題とする。 An object of the present invention is to provide a dark stain preventing agent that has good biodegradability and can prevent re-contamination of scum and dust stains, and a cleaning composition containing the same.
上記従来技術は、洗濯水量が少ないことにより汚れ濃度が増加した洗濯水中における汚れの再付着防止、及び環境負荷の低減に対しては不十分である。
洗濯液中の着色汚れ成分として代表的なものは、泥粒子のような親水性微粒子と、煤のような疎水性微粒子であるが、黒ずみを防止するためには、これらの異なる物性を有する汚れ微粒子に対して、高い再付着防止性をもつ洗浄剤が必要である。
本発明者らは、セルロースＩ型結晶化度が１０％未満の粉末セルロースを酸化して得られた重量平均分子量３０，０００以上のポリウロン酸が生分解性が良好で、かつ優れた黒ずみ汚れ防止性能を有することを見出した。
すなわち、本発明は次の（１）及び（２）を提供する。
（１）セルロースＩ型結晶化度が１０％未満である粉末セルロースを酸化して得られた、重量平均分子量が３０，０００以上であり、酸化度が７０％以上であるポリウロン酸を含む黒ずみ汚れ防止剤。
（２）前記（１）の黒ずみ汚れ防止剤を含有する洗浄剤組成物。
The above prior art is insufficient for preventing the reattachment of dirt in the wash water in which the dirt concentration is increased due to a small amount of wash water and reducing the environmental load.
Typical coloring stain components in the washing liquid are hydrophilic fine particles such as mud particles and hydrophobic fine particles such as wrinkles. In order to prevent darkening, stains having these different physical properties are used. A cleaning agent having high anti-redeposition property for fine particles is required.
The present inventors have demonstrated that polyuronic acid having a weight average molecular weight of 30,000 or more obtained by oxidizing powdered cellulose having a cellulose I-type crystallinity of less than 10% has good biodegradability and excellent blackening stain prevention. It was found to have performance.
That is, the present invention provides the following (1) and (2).
(1) Dark stain containing polyuronic acid having a weight average molecular weight of 30,000 or more and an oxidation degree of 70% or more obtained by oxidizing cellulose powder having a cellulose I type crystallinity of less than 10% Inhibitor.
(2) A cleaning composition containing the dark stain preventing agent of (1).
本発明によれば、生分解性が良好で、洗濯中に機械力で衣類から除去された煤汚れや粉塵汚れの再汚染を防止できる黒ずみ汚れ防止剤、及びそれを含有する洗浄剤組成物を提供することができる。 According to the present invention, there is provided a dark stain preventing agent having good biodegradability and capable of preventing recontamination of wrinkle stains and dust stains removed from clothing by mechanical force during washing, and a cleaning composition containing the same. Can be provided.
本発明の黒ずみ汚れ防止剤は、セルロースＩ型結晶化度が１０％未満である粉末セルロースを酸化して得られた、重量平均分子量が３０，０００以上であり、酸化度が７０％以上であるポリウロン酸を含むことを特徴とする。また、本発明の洗浄剤組成物は、前記の黒ずみ汚れ防止剤を含有することを特徴とする。
以下、本発明に用いられるポリウロン酸、原料セルロース等について説明する。
The dark stain preventing agent of the present invention has a weight average molecular weight of 30,000 or more and an oxidation degree of 70% or more obtained by oxidizing powdered cellulose having a cellulose I type crystallinity of less than 10%. It contains polyuronic acid. Moreover, the cleaning composition of the present invention is characterized by containing the above-mentioned darkening stain preventing agent.
Hereinafter, polyuronic acid, raw material cellulose and the like used in the present invention will be described.
［ポリウロン酸］
本発明におけるポリウロン酸は、Ｄ−グルクロン酸やＤ−ガラクツロン酸等のウロン酸のアルカリ金属塩がグリコシド結合で糖ユニットと連結した重合体で、代表的には下記構造式（１）で表され、その重量平均分子量は３０，０００以上のものである。
[Polyuronic acid]
The polyuronic acid in the present invention is a polymer in which an alkali metal salt of uronic acid such as D-glucuronic acid or D-galacturonic acid is linked to a sugar unit by a glycosidic bond, and is typically represented by the following structural formula (1). The weight average molecular weight is 30,000 or more.
構造式（１）中、Ｘは、水素又はアルカリ金属を示す。Ｘが、水素又はナトリウムであれば、構造式（１）で表されるポリウロン酸（塩）は、２５℃の蒸留水に対して、１０％以上の溶解性を示す。
構造式（１）中のｍは、ポリウロン酸（塩）中のＤ−グルクロン酸（塩）ユニットのモル分率を示し、ポリウロン酸の酸化度と同義である。該モル分率ｍ、即ちポリウロン酸の酸化度は、７０％以上であり、好ましくは７５％以上、より好ましくは８５〜１００％である。該モル分率ｍ（酸化度）を７０％以上にすることで、煤又は粉塵微粒子に吸着したポリウロン酸の電荷反発により洗濯液中でより安定に分散することが可能となる。
構造式（１）中のｎは、ポリウロン酸塩中の糖ユニットのモル分率を示し、ｎは好ましくは３０％未満、より好ましくは２５％未満、更に好ましくは１５〜０％である。
これらの観点から、ウロン酸塩ユニットｍと糖ユニットｎとのモル分率比（ｍ／ｎ）は、好ましくは７０〜１００／３０〜０、より好ましくは７５〜１００／２５〜０、更に好ましくは８５〜１００／１５〜０である。
In the structural formula (1), X represents hydrogen or an alkali metal. When X is hydrogen or sodium, the polyuronic acid (salt) represented by the structural formula (1) exhibits a solubility of 10% or more in distilled water at 25 ° C.
M in the structural formula (1) indicates the molar fraction of D-glucuronic acid (salt) units in polyuronic acid (salt), and is synonymous with the degree of oxidation of polyuronic acid. The molar fraction m, that is, the degree of oxidation of polyuronic acid is 70% or more, preferably 75% or more, more preferably 85 to 100%. By setting the molar fraction m (oxidation degree) to 70% or more, it becomes possible to disperse more stably in the washing liquid by charge repulsion of polyuronic acid adsorbed on the soot or dust fine particles.
N in the structural formula (1) represents a mole fraction of sugar units in the polyuronic acid salt, and n is preferably less than 30%, more preferably less than 25%, and further preferably 15 to 0%.
From these viewpoints, the molar fraction ratio (m / n) between the uronic acid salt unit m and the sugar unit n is preferably 70 to 100/30 to 0, more preferably 75 to 100/25 to 0, and still more preferably. Is 85-100 / 15-0.
ここで、ポリウロン酸の酸化度は、ポリウロン酸単位中のカルボキシ基の当量数に対して中和に用いた塩基性化合物の当量数の比として算出される。具体的には、実施例記載の滴定法により、測定されたポリウロン酸塩単位重量当りのカルボン酸量から、下記計算式（２）によって求められた値である。
酸化度（％）＝〔（１６２．１×Ａ）／（１−１４．０×Ａ）〕×１００ （２）
ここで、Ａは滴定によって求めたカルボン酸量（ｍｏｌ／ｇ）である。
なお、中和に用いられる塩基性化合物としては、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム等のアルカリ金属又はアルカリ土類金属水酸化物、アンモニアやアミン化合物等が挙げられる。
Here, the oxidation degree of polyuronic acid is calculated as the ratio of the number of equivalents of the basic compound used for neutralization to the number of equivalents of carboxy groups in the polyuronic acid unit. Specifically, it is a value determined by the following formula (2) from the amount of carboxylic acid per unit weight of polyuronic acid salt measured by the titration method described in the examples.
Oxidation degree (%) = [(162.1 × A) / (1-14.0 × A)] × 100 (2)
Here, A is the amount of carboxylic acid (mol / g) determined by titration.
Examples of the basic compound used for neutralization include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide, ammonia, and amine compounds.
本発明の黒ずみ汚れ防止剤を構成するポリウロン酸の重量平均分子量は、３０，０００以上である。ここで重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）における水に可溶な成分のプルラン換算分子量である。重量平均分子量を３０，０００以上にすることで、衣料から除去された煤又は粉塵微粒子を十分に洗濯液中に分散させることができ、泥粒子が衣料に再付着するのを防止することができる。また、重量平均分子量の上限は特に制限されないが、１８０，０００以下にすることが好ましい。重量平均分子量が１８０，０００以下であれば、煤微粒子表面に吸着したポリウロン酸同士が煤又は粉塵微粒子間で結合して、煤又は粉塵微粒子の凝集塊を形成するのを防止することができ、また配合時の粘度増加を抑制することができる。ポリウロン酸の重量平均分子量は、好ましくは３０，０００〜１８０，０００、より好ましくは３１，０００〜１２０，０００、更に好ましくは３２，０００〜１００，０００である。
ポリウロン酸の酸化度や重量平均分子量は、原料多糖類の種類、酸化剤量等の反応条件によって、適宜調整することができ、泥汚れ洗浄性能を変化させることができる。
The weight average molecular weight of the polyuronic acid constituting the darkening stain preventing agent of the present invention is 30,000 or more. Here, the weight average molecular weight is a pullulan equivalent molecular weight of a water-soluble component in gel permeation chromatography (GPC). By setting the weight average molecular weight to 30,000 or more, the cocoons or dust particles removed from the clothing can be sufficiently dispersed in the washing liquid, and mud particles can be prevented from reattaching to the clothing. . The upper limit of the weight average molecular weight is not particularly limited, but is preferably 180,000 or less. If the weight average molecular weight is 180,000 or less, it is possible to prevent the polyuronic acids adsorbed on the surface of the soot fine particles from being combined between the soot or dust fine particles to form the aggregate of the soot or dust fine particles, Moreover, the viscosity increase at the time of a mixing | blending can be suppressed. The weight average molecular weight of polyuronic acid is preferably 30,000 to 180,000, more preferably 31,000 to 120,000, and still more preferably 32,000 to 100,000.
The degree of oxidation and the weight average molecular weight of polyuronic acid can be appropriately adjusted depending on reaction conditions such as the type of raw material polysaccharide and the amount of oxidizing agent, and mud dirt cleaning performance can be changed.
（原料セルロース）
ポリウロン酸の製造原料となるセルロースは、セルロースＩ型結晶化度が１０％未満の粉末セルロースであればよく、その種類、分子量は特に限定されない。原料セルロースのセルロースＩ型結晶化度は８％未満が好ましく、６％未満がより好ましい。結晶化度が高いセルロース用いてポリウロン酸を製造した場合、水に不溶な部分が生じるが、この水に不溶な部分も含めることにより高い黒ずみ汚れ防止性能が発現する。
セルロースには幾つかの結晶構造が知られており、結晶部とアモルファス部との全量に対する結晶部の割合から、一般に結晶化度が算出される。
本発明においては、「セルロースＩ型結晶化度」とは、天然セルロースの結晶構造に由来するＩ型の結晶化度を意味し、粉末Ｘ線結晶回折スペクトル法による回折強度値か
らＳｅｇａｌ法により算出したもので、下記計算式（３）により定義される。
セルロースＩ型結晶化度（％）＝〔（Ｉ22.6−Ｉ18.5）／Ｉ22.6〕×１００ （３）
〔式中、Ｉ22.6は、Ｘ線回折における格子面（００２面）（回折角２θ＝２２．６°）の回折強度を示し、Ｉ18.5は、アモルファス部（回折角２θ＝１８．５°）の回折強度を示す。〕
通常の粉末セルロースは、少量のアモルファス部を有し、それらの結晶化度は、上記式（３）によれば概ね６０〜８０％の範囲に含まれるいわゆる結晶性セルロースである。
(Raw cellulose)
The cellulose used as a raw material for producing polyuronic acid may be powdered cellulose having a cellulose I-type crystallinity of less than 10%, and the type and molecular weight are not particularly limited. The cellulose type I crystallinity of the raw material cellulose is preferably less than 8%, more preferably less than 6%. When polyuronic acid is produced using cellulose having a high degree of crystallinity, a part insoluble in water is produced, but by including this part insoluble in water, a high darkness stain prevention performance is exhibited.
Several crystal structures are known for cellulose, and the degree of crystallinity is generally calculated from the ratio of crystal parts to the total amount of crystal parts and amorphous parts.
In the present invention, “cellulose type I crystallinity” means type I crystallinity derived from the crystal structure of natural cellulose, and is calculated by the Segal method from the diffraction intensity value by the powder X-ray crystal diffraction spectrum method. It is defined by the following calculation formula (3).
Cellulose type I crystallinity (%) = [(I 22.6 -I 18.5 ) / I 22.6 ] × 100 (3)
Wherein, I 22.6, the lattice plane in X-ray diffraction (002 plane) indicates the diffraction intensity of the (diffraction angle 2θ = 22.6 °), I 18.5 is amorphous portion (angle of diffraction 2 [Theta] = 18.5 °) The diffraction intensity is shown. ]
Ordinary powdered cellulose has a small amount of amorphous part, and the crystallinity thereof is so-called crystalline cellulose included in the range of approximately 60 to 80% according to the above formula (3).
原料セルロースとして結晶性の高いパルプをそのまま使用すると、結晶性部位の酸化反応は進み難い。そのため、メカノケミカル処理等によりセルロースＩ型結晶化度を１０％未満に低下させた粉末セルロースを使用する。結晶化度が低下するに従い、セルロースの酸化反応は極めて良好に進行し、高い酸化度を有するポリウロン酸を効率的に得ることができる。
また、低結晶性セルロースの重合度は、１３０以上が好ましく、１５０以上が好ましく、３００以上が更に好ましい。
このようなセルロースＩ型結晶化度を低下させた粉末セルロースは、汎用原料として得られるシート状やロール状のセルロース純度の高いパルプから簡便に調製することができる。結晶化度を低下させた粉末セルロースの調製方法は特に限定されない。例えば、特開昭６２−２３６８０１号公報、特開２００３−６４１８４号公報、特開２００４−３３１９１８号公報等に記載の方法を挙げることができる。これらの中では、メカノケミカル処理により結晶化度を低下させた粉末セルロースを使用することがより好ましい。
If a highly crystalline pulp is used as the raw material cellulose as it is, the oxidation reaction of the crystalline part is difficult to proceed. Therefore, powdered cellulose having a cellulose I-type crystallinity reduced to less than 10% by mechanochemical treatment or the like is used. As the degree of crystallinity decreases, the oxidation reaction of cellulose proceeds very well, and polyuronic acid having a high degree of oxidation can be efficiently obtained.
Further, the degree of polymerization of the low crystalline cellulose is preferably 130 or more, preferably 150 or more, and more preferably 300 or more.
Such cellulose powder with reduced cellulose I-type crystallinity can be easily prepared from sheet-like or roll-like pulp with high cellulose purity obtained as a general-purpose raw material. There is no particular limitation on the method for preparing the powdered cellulose having a reduced crystallinity. For example, methods described in JP-A-62-236801, JP-A-2003-64184, JP-A-2004-331918 and the like can be mentioned. Among these, it is more preferable to use powdered cellulose whose crystallinity is lowered by mechanochemical treatment.
（メカノケミカル処理）
特に好適なメカノケミカル処理によるセルロースＩ型結晶化度が１０％未満の粉末セルロースの製造方法としては、例えばシート状パルプを粗粉砕して得られるチップ状パルプを、押出機で処理した後、更にボールミルで処理することによる方法が挙げられる。
この方法に用いられる押出機としては、単軸又は二軸の押出機、好ましくは二軸押出機が挙げられるが、強い圧縮せん断力を加える観点から、スクリューのいずれかの部分に、いわゆるニーディングディスク部を備えるものが好ましい。
ニーディングディスク部とは、複数のニーディングディスクで構成され、これらを連続して、一定の位相でずらしながら組み合わせたものである。例えば３〜２０枚、好ましくは６〜１６枚のニーディングディスクを９０°の位相で互い違いにずらしながら組み合わせたものが挙げられる。ニーディングディスク部は、スクリューの回転にともなって、その狭い隙間にチップ状パルプ等を強制的に通過させることで極めて強いせん断力を付与しながら、連続的に処理することができる。押出機処理におけるせん断速度としては、６００〜３０００ｓｅｃ-1が好ましく、６０００〜２０００ｓｅｃ-1がより好ましい。
押出機を用いる処理方法としては、特に制限はないが、チップ状パルプを押出機に投入し、連続的に処理する方法が好ましい。
(Mechanochemical treatment)
As a method for producing a cellulose powder having a cellulose I type crystallinity of less than 10% by a particularly suitable mechanochemical treatment, for example, after treating a chip-like pulp obtained by roughly pulverizing a sheet-like pulp with an extruder, The method by processing with a ball mill is mentioned.
Examples of the extruder used in this method include a single-screw or twin-screw extruder, preferably a twin-screw extruder. From the viewpoint of applying a strong compressive shear force, a so-called kneading is applied to any part of the screw. A thing provided with a disk part is preferred.
The kneading disc portion is composed of a plurality of kneading discs, which are combined while being shifted at a constant phase. For example, a combination of 3 to 20 kneading disks, preferably 6 to 16 kneading disks, which are staggered at a phase of 90 °. The kneading disk portion can be continuously processed while applying a very strong shearing force by forcibly passing chip-like pulp through the narrow gap as the screw rotates. As a shear rate in an extruder process, 600-3000 sec < -1 > is preferable and 6000-2000 sec < -1 > is more preferable.
Although there is no restriction | limiting in particular as a processing method using an extruder, The method of throwing a chip-form pulp into an extruder and processing continuously is preferable.
また、ボールミルとしては、公知の振動ボールミル、媒体攪拌ミル、転動ボールミル、遊星ボールミル等を用いることができる。
媒体として用いるボールの材質には特に制限はなく、例えば、鉄、ステンレス、アルミナ、ジルコニア等が挙げられる。ボールの外径は、効率的にセルロースを非晶化させる観点から、好ましくは０．１〜１００ｍｍ、より好ましくは１〜５０ｍｍである。媒体としては、ボール以外にも、ロッド状やチューブ状のものを用いることができる。
またボールミル処理の際には、発生する熱による変性や劣化を最小限に抑えるために、好ましくは２５０℃以下、より好ましくは５〜２００℃の範囲で処理を行うことが望ましい。
As the ball mill, a known vibration ball mill, medium stirring mill, rolling ball mill, planetary ball mill, or the like can be used.
There is no restriction | limiting in particular in the material of the ball | bowl used as a medium, For example, iron, stainless steel, an alumina, a zirconia etc. are mentioned. The outer diameter of the ball is preferably 0.1 to 100 mm, more preferably 1 to 50 mm, from the viewpoint of efficiently amorphizing cellulose. As a medium, besides a ball, a rod-shaped or tube-shaped medium can be used.
In the ball mill treatment, the treatment is preferably performed at a temperature of preferably 250 ° C. or less, more preferably 5 to 200 ° C., in order to minimize denaturation and deterioration due to generated heat.
［ポリウロン酸の製造］
本発明においては、セルロースＩ型結晶化度が１０％未満の粉末セルロースを溶媒に溶解又は分散させ、触媒、及び必要に応じて更に共酸化剤や助触媒の存在下で酸化反応させることにより、重量平均分子量が３０，０００以上であり、酸化度が７０％以上であるポリウロン酸を製造することができる。ここで、酸化反応とは、セルロースの構成成分であるグルコース単位の一級水酸基、すなわちＣ６位の一級水酸基を選択的に酸化し、カルボキシ基を有するグルクロン酸（前記構造式（１）で表される左側部分）を生成させる反応である。
一級水酸基の選択的酸化反応としては、白金触媒を用いる酸素による酸化反応、窒素酸化物による酸化反応、硝酸による酸化反応、Ｎ−オキシル化合物による酸化反応が挙げられる。これらの中では、反応の高選択性、均質性、及びより温和な条件で酸化反応を円滑に進行させる観点から、Ｎ−オキシル化合物を触媒としてその存在下で、さらに必要に応じて共酸化剤や助触媒を用いて酸化反応を行うことにより、重量平均分子量３０，０００以上のポリウロン酸を製造することが好ましい。
ポリウロン酸の重量平均分子量の調整は、酸化反応のｐＨ及び温度の調整、原料である低結晶性セルロースの分子量の調整等により行うことができる。
[Production of polyuronic acid]
In the present invention, powdered cellulose having a cellulose I type crystallinity of less than 10% is dissolved or dispersed in a solvent, and an oxidation reaction is performed in the presence of a catalyst, and if necessary, a co-oxidant or a co-catalyst. A polyuronic acid having a weight average molecular weight of 30,000 or more and an oxidation degree of 70% or more can be produced. Here, the oxidation reaction refers to glucuronic acid having a carboxy group (expressed by the above structural formula (1)) by selectively oxidizing a primary hydroxyl group of a glucose unit which is a constituent component of cellulose, that is, a primary hydroxyl group of C6 position. This is a reaction for generating a left portion.
Examples of the selective oxidation reaction of the primary hydroxyl group include an oxidation reaction with oxygen using a platinum catalyst, an oxidation reaction with nitrogen oxides, an oxidation reaction with nitric acid, and an oxidation reaction with an N-oxyl compound. Among these, in view of high selectivity of the reaction, homogeneity, and smooth progress of the oxidation reaction under milder conditions, an N-oxyl compound is used as a catalyst in the presence thereof, and if necessary, a co-oxidant. It is preferable to produce a polyuronic acid having a weight average molecular weight of 30,000 or more by carrying out an oxidation reaction using a cocatalyst.
The weight average molecular weight of the polyuronic acid can be adjusted by adjusting the pH and temperature of the oxidation reaction, adjusting the molecular weight of the low crystalline cellulose that is the raw material, or the like.
（Ｎ−オキシル化合物）
前記Ｎ−オキシル化合物は、ヒンダードアミンのＮ−酸化物であり、特にアミノ基のα位に嵩高い基を有するヒンダードアミンのＮ−酸化物である。Ｎ−オキシル化合物としては、２，２，６，６−テトラアルキルピペリジン−１−オキシル、４−ヒドロキシ−２，２，６，６−テトラアルキルピペリジン−１−オキシル、４−アルコキシ−２，２，６，６−テトラアルキルピペリジン−１−オキシル等のジ−ターシャリーアルキルニトロキシル化合物が挙げられる。これらの中では、２，２，６，６−テトラメチルピペリジン−１−オキシル、４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−１−オキシル、４−メトキシ−２，２，６，６−テトラメチルピペリジン−１−オキシルが好ましく、２，２，６，６−テトラメチルピペリジン−１−オキシル（ＴＥＭＰＯ）がより好ましい。
なお、Ｎ−オキシル化合物としてＴＥＭＰＯを用いる酸化反応では、ニトロキシラジカルの酸化活性種であるオキソアンモニウム部が酸化剤として機能すると考えられる。
反応系におけるＮ−オキシル化合物の量は、触媒量であればよく、低結晶性の粉末セルロースに対して、好ましくは０．００１〜５質量％、より好ましくは０．１〜４質量％、更に好ましくは０．５〜３質量％である。
(N-oxyl compound)
The N-oxyl compound is a hindered amine N-oxide, particularly a hindered amine N-oxide having a bulky group at the α-position of the amino group. Examples of N-oxyl compounds include 2,2,6,6-tetraalkylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetraalkylpiperidine-1-oxyl, 4-alkoxy-2,2 Di-tertiary alkyl nitroxyl compounds such as 6,6-tetraalkylpiperidine-1-oxyl. Among these, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6 , 6-Tetramethylpiperidine-1-oxyl is preferred, and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) is more preferred.
In the oxidation reaction using TEMPO as the N-oxyl compound, it is considered that the oxoammonium moiety, which is an oxidation active species of the nitroxy radical, functions as an oxidizing agent.
The amount of the N-oxyl compound in the reaction system may be a catalytic amount, and is preferably 0.001 to 5% by mass, more preferably 0.1 to 4% by mass, and more preferably 0.1 to 4% by mass, based on the low crystalline powdery cellulose. Preferably it is 0.5-3 mass%.
（共酸化剤及び助触媒）
共酸化剤としては、酸素又は空気、過酸化物、ハロゲン、次亜ハロゲン酸、亜ハロゲン酸、過ハロゲン酸又はそれらの塩、ハロゲン酸化物、窒素酸化物等が挙げられる。
助触媒としては、臭化ナトリウム、臭化カリウム等の臭化物や、ヨウ化ナトリウム、ヨウ化カリウム等のヨウ化物等が挙げられる。
共酸化剤及び助触媒の量は、それらの機能を発揮できる有効量であればよく、特に制限はない。
(Co-oxidizer and cocatalyst)
Examples of the co-oxidant include oxygen or air, peroxide, halogen, hypohalous acid, halous acid, perhalogen acid or salts thereof, halogen oxide, nitrogen oxide and the like.
Examples of the cocatalyst include bromides such as sodium bromide and potassium bromide, and iodides such as sodium iodide and potassium iodide.
The amount of the co-oxidant and the co-catalyst is not particularly limited as long as it is an effective amount capable of exhibiting these functions.
（反応条件）
酸化反応の温度は、反応の選択性、副反応の抑制の観点から、反応温度は、好ましくは５０℃以下、より好ましくは４０℃以下、更に好ましくは２０℃以下であり、その下限は、好ましくは−５℃以上である。
反応系のｐＨは共酸化剤の性質に合わせることが好ましく、例えば、次亜塩素酸ナトリウムの場合、反応系のｐＨはアルカリ側が好ましい。
本発明における酸化反応は、低結晶性の粉末セルロースを水又は有機溶媒に分散させて行うのが好ましい。その有機溶媒としては、メタノール、エタノール等のアルコール、アセトン、メチルエチルケトン等のケトン、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド等が挙げられる。これらの中では、環境負荷低減の観点から、水又は水を主成分とし有機溶媒を含む水系媒体に分散させて酸化反応を行うことがより好ましい。水系媒体は水単独で、又は水と２種以上の有機溶媒を混合して用いることができる。
ポリウロン酸塩の製造においては、触媒として用いるＴＥＭＰＯ等のＮ−オキシル化合物等の残存や塩の副生が生じ易い。そこで、純度の高いポリウロン酸塩を得るためには、メタノール、エタノール、アセトン等への再沈殿、水に不溶な溶媒へのＮ−オキシル化合物等の抽出及び塩のイオン交換、透析等による精製を行うことが好ましい。精製法は、酸化反応における溶媒の種類、生成物の酸化の程度、精製の程度により最適な方法を採用することができる。
(Reaction conditions)
The temperature of the oxidation reaction is preferably 50 ° C. or less, more preferably 40 ° C. or less, further preferably 20 ° C. or less, and the lower limit is preferably from the viewpoint of reaction selectivity and side reaction suppression. Is −5 ° C. or higher.
The pH of the reaction system is preferably matched to the properties of the cooxidant. For example, in the case of sodium hypochlorite, the pH of the reaction system is preferably on the alkali side.
The oxidation reaction in the present invention is preferably carried out by dispersing low crystalline powdered cellulose in water or an organic solvent. Examples of the organic solvent include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, N, N-dimethylformamide, and dimethyl sulfoxide. Among these, from the viewpoint of reducing environmental burden, it is more preferable to carry out the oxidation reaction by dispersing in water or an aqueous medium containing water as a main component and containing an organic solvent. The aqueous medium can be water alone or a mixture of water and two or more organic solvents.
In the production of polyuronic acid salts, residual N-oxyl compounds such as TEMPO used as a catalyst and salt by-products are likely to occur. Therefore, in order to obtain a highly pure polyuronic acid salt, reprecipitation into methanol, ethanol, acetone, etc., extraction of N-oxyl compounds into a solvent insoluble in water, ion exchange of salts, purification by dialysis, etc. Preferably it is done. As the purification method, an optimum method can be adopted depending on the kind of solvent in the oxidation reaction, the degree of oxidation of the product, and the degree of purification.
［洗浄剤組成物］
本発明の洗浄剤組成物は、セルロースＩ型結晶化度が１０％未満の粉末セルロースを酸化して得られた、重量平均分子量が３０，０００以上であり、酸化度が７０％以上であるポリウロン酸を含む黒ずみ汚れ防止剤を含有することを特徴とし、好ましくは更に界面活性剤を含有する。該ポリウロン酸を含む黒ずみ汚れ防止剤と界面活性剤を併用すると、汚れの再汚染を防止効果が増強される。
洗浄剤組成物中の該ポリウロン酸の含有量は、洗浄性能の観点から、０．１〜１５質量％が好ましく、０．５〜１０質量％がより好ましく、１．５〜１０質量％が更に好ましい。洗浄剤組成物中の界面活性剤の含有量は、洗浄性能と再汚染防止を効果的に発現する観点から、５〜６０質量％が好ましく、１０〜４０質量％がより好ましく、２０〜３０質量％が更に好ましい。
[Cleaning composition]
The detergent composition of the present invention is a polyuron having a weight average molecular weight of 30,000 or more and an oxidation degree of 70% or more obtained by oxidizing cellulose cellulose having a crystallinity of less than 10%. It is characterized by containing an anti-darkening stain containing acid, and preferably further contains a surfactant. When the darkening stain preventing agent containing the polyuronic acid and the surfactant are used in combination, the effect of preventing stain recontamination is enhanced.
From the viewpoint of cleaning performance, the content of the polyuronic acid in the cleaning composition is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1.5 to 10% by mass. preferable. The content of the surfactant in the cleaning composition is preferably 5 to 60% by mass, more preferably 10 to 40% by mass, and more preferably 20 to 30% by mass from the viewpoint of effectively expressing cleaning performance and re-contamination prevention. % Is more preferable.
界面活性剤としては、陰イオン性界面活性剤、陽イオン性界面活性剤、非イオン性界面活性剤、両性界面活性剤が挙げられる。
陰イオン性界面活性剤としては、例えば、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩、ジアルキルスルホコハク酸エステル塩、α−オレフィンスルホン酸塩、高級アルコール硫酸エステル塩、アルキルエーテル硫酸塩、ポリオキシエチレンアルキルフェニルエーテル硫酸塩、脂肪酸アルキロールアミドの硫酸エステル塩、アルキルエーテルリン酸エステル塩、アルキルリン酸エステル塩、アルキルエーテルカルボン酸塩、Ｎ−アシルアミノ酸塩、脂肪酸石ケン等が好適に用いられる。
上記の陰イオン性界面活性剤の中では直鎖アルキルベンゼンスルホン酸塩、アルキル硫酸エステル塩、ポリオキシアルキレンアルキルエーテル硫酸塩が好ましく、炭素数１０〜１８のアルキル鎖を持つ直鎖アルキルベンゼンスルホン酸ナトリウムがより好ましい。
Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonate, alkylnaphthalene sulfonate, dialkyl sulfosuccinate, α-olefin sulfonate, higher alcohol sulfate, alkyl ether sulfate, polyoxyethylene alkyl Phenyl ether sulfate, fatty acid alkylolamide sulfate ester, alkyl ether phosphate ester salt, alkyl phosphate ester salt, alkyl ether carboxylate, N-acyl amino acid salt, fatty acid soap and the like are preferably used.
Among the above anionic surfactants, linear alkyl benzene sulfonates, alkyl sulfate esters, and polyoxyalkylene alkyl ether sulfates are preferable, and linear alkyl benzene sulfonate sodium having an alkyl chain having 10 to 18 carbon atoms is preferable. More preferred.
陽イオン性界面活性剤としては、脂肪族アミン塩、脂肪族四級アンモニウム塩、ベンザルコニウム塩、塩化ベンゼトニウム、ピリジニウム塩、イミダゾリニウム塩等が好適に用いられる。
非イオン性界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンポリオキシプロピレンブロックポリマー、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレンヒマシ油、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、ポリエチレングリコール脂肪酸エステル、脂肪酸モノグリセリド、ポリグリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、高級脂肪酸アルカノールアミド又はそのアルキレンオキシド付加物、ポリオキシエチレンアルキルアミン、アルキルアミンオキシド等が好適に用いられる。
非イオン界面活性剤は、耐硬水性が良好であるうえに、皮脂汚れ等の油性汚れの洗浄力が優れており、その好適例としては、アルキル基の平均炭素数が１０〜２０、好ましくは１２〜１８、特に好ましくは１２〜１４でエチレンオキシドの平均付加モル数が６〜１４、好ましくは６〜１０のポリオキシエチレンアルキルエーテルが挙げられる。
両性界面活性剤としては、例えばカルボキシベタイン型化合物、アミノカルボン酸塩、イミダゾリニウムベタイン等が好適に用いられる。
As the cationic surfactant, aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts and the like are preferably used.
Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene Castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, higher fatty acid alkanolamide or its alkylene oxide adduct, polyoxyethylene alkylamine , Alkylamine oxide and the like are preferably used.
The nonionic surfactant has good hard water resistance and excellent detergency for oily dirt such as sebum dirt, and preferred examples thereof include an alkyl group having an average carbon number of 10 to 20, preferably Examples thereof include polyoxyethylene alkyl ethers having 12 to 18, particularly preferably 12 to 14, and an average added mole number of ethylene oxide of 6 to 14, preferably 6 to 10.
As the amphoteric surfactant, for example, carboxybetaine type compounds, aminocarboxylates, imidazolinium betaines and the like are preferably used.
界面活性剤は、陰イオン性界面活性剤及び非イオン性界面活性剤を主界面活性剤として使用することが好ましい。
洗浄剤組成物中の陰イオン性界面活性剤の含有量は、泥等の親水性固体粒子汚れに対する洗浄力の点から、５質量％以上が好ましく、７質量％以上がより好ましく、９質量％以上が更に好ましい。また、粉末物性の観点から、４０質量％以下が好ましく、３５質量％以下がより好ましく、３０質量％以下がより好ましく、２６質量％以下が更に好ましい。
洗浄剤組成物中の非イオン性界面活性剤の含有量は、起泡性やすすぎ性の観点から、１〜１５質量％が好ましく、５〜１５質量％がより好ましい。
As the surfactant, an anionic surfactant and a nonionic surfactant are preferably used as the main surfactant.
The content of the anionic surfactant in the cleaning composition is preferably 5% by mass or more, more preferably 7% by mass or more, and more preferably 9% by mass from the viewpoint of detergency against hydrophilic solid particle dirt such as mud. The above is more preferable. Moreover, from a viewpoint of powder physical properties, 40 mass% or less is preferable, 35 mass% or less is more preferable, 30 mass% or less is more preferable, and 26 mass% or less is still more preferable.
The content of the nonionic surfactant in the cleaning composition is preferably 1 to 15% by mass and more preferably 5 to 15% by mass from the viewpoint of foamability and rinsability.
本発明の洗浄剤組成物を製造する際には、本発明の黒ずみ汚れ防止剤と界面活性剤の他に、通常の洗浄剤組成物に用いられる種々の洗剤成分を配合することができる。
用いられる洗剤成分としては、例えば、アルカリ剤、金属イオン封鎖剤、その他の重合体の他、その他添加剤として、漂白剤（過炭酸塩、過ホウ酸塩等）、漂白活性化剤、再汚染防止剤（カルボキシメチルセルロース等）、柔軟化剤、還元剤（亜硫酸塩等）、蛍光増白剤、制泡剤（シリコーン等）、セルラーゼやプロテアーゼ等の酵素、染料、香料等が挙げられる。
アルカリ剤としては、洗浄性の点から、公知のアルカリ剤を使用することができる。例えば、デンス灰やライト灰と総称される炭酸ナトリウム等のアルカリ金属炭酸塩、並びにＪＩＳ１号、２号、３号珪酸ナトリウム等の非晶質のアルカリ金属珪酸塩、結晶性アルカリ金属珪酸塩等のアルカリ金属塩が挙げられる。皮脂等の油汚れに対する洗浄力を高める観点から、洗浄剤組成物中のアルカリ剤の含有量は、１〜４０質量％が好ましく、５〜３０質量％以上がより好ましい。
金属イオン封鎖剤としては、結晶性アルミノ珪酸塩、結晶性珪酸ナトリウム、アクリル酸重合体、アクリル酸−マレイン酸共重合体、トリポリリン酸ナトリウム、エチレンジアミン四酢酸、メチルグリシン二酢酸が挙げられる。
その他の重合体としては、例えば、重量平均分子量が３０００〜２万のアクリル酸、メタクリル酸、イタコン酸等の単独重合体又は共重合体カルボン酸系重合体、重量平均分子量は１０００〜２万のポリエチレングリコール、カルボキシメチルセルロース等が挙げられる。
上記の界面活性剤や洗剤成分は、単独で又は２種以上を適宜組み合わせて用いることができる。
本発明の洗浄剤組成物の用途に特に限定はないが、糸束、布帛、衣料等の繊維製品用洗浄剤組成物として特に好適に使用することができる。
In producing the cleaning composition of the present invention, various detergent components used in ordinary cleaning compositions can be blended in addition to the dark stain preventing agent and surfactant of the present invention.
Detergent components used include, for example, alkali agents, sequestering agents, other polymers, other additives, bleaching agents (percarbonate, perborate, etc.), bleach activators, recontamination Examples thereof include inhibitors (carboxymethyl cellulose and the like), softening agents, reducing agents (sulfite and the like), fluorescent whitening agents, antifoaming agents (silicone and the like), enzymes such as cellulase and protease, dyes and fragrances.
As the alkali agent, a known alkali agent can be used from the viewpoint of detergency. For example, alkali metal carbonates such as sodium carbonate collectively called dense ash and light ash, and amorphous alkali metal silicates such as JIS No. 1, No. 2 and No. 3 sodium silicate, crystalline alkali metal silicates, etc. Examples include alkali metal salts. From the viewpoint of increasing the detergency against oil stains such as sebum, the content of the alkaline agent in the cleaning composition is preferably 1 to 40% by mass, and more preferably 5 to 30% by mass or more.
Examples of the sequestering agent include crystalline aluminosilicate, crystalline sodium silicate, acrylic acid polymer, acrylic acid-maleic acid copolymer, sodium tripolyphosphate, ethylenediaminetetraacetic acid, and methylglycine diacetic acid.
Examples of other polymers include homopolymers or copolymer carboxylic acid polymers such as acrylic acid, methacrylic acid, and itaconic acid having a weight average molecular weight of 3000 to 20,000, and a weight average molecular weight of 1,000 to 20,000. Examples include polyethylene glycol and carboxymethyl cellulose.
Said surfactant and detergent component can be used individually or in combination of 2 or more types as appropriate.
Although there is no limitation in particular in the use of the cleaning composition of this invention, it can use especially suitably as a cleaning composition for textiles, such as a yarn bundle, a fabric, and clothing.
以下の製造例、実施例及び比較例において、「％」は特記しない限り「質量％」である。なお、原料の低結晶性セルロース粉末の重合度と結晶化度の測定、ポリウロン酸塩の重量平均分子量と酸化度の測定、及び生分解性の評価は、以下の方法で行った。
また、実施例及び比較例で得られたポリウロン酸のナトリウム塩等についてのカーボンブラック再汚染防止性能及び泥洗浄性能の評価を以下の方法で行った。
In the following production examples, examples and comparative examples, “%” is “% by mass” unless otherwise specified. In addition, the measurement of the polymerization degree and crystallinity degree of the low crystalline cellulose powder of a raw material, the measurement of the weight average molecular weight and oxidation degree of a polyuronic acid salt, and evaluation of biodegradability were performed with the following method.
Moreover, evaluation of the carbon black recontamination prevention performance and mud washing performance of the sodium salt of polyuronic acid obtained in Examples and Comparative Examples was performed by the following methods.
＜粉末セルロースの重合度の測定＞
ＩＳＯ−４３１２に記載の銅アンモニア法により、粉末セルロースの重合度を測定した。
＜セルロースＩ型結晶化度の算出＞
株式会社リガク製「Rigaku RINT 2500VC X-RAY diffractometer」を用いて、以下の条件で測定した回折スペクトルのピーク強度から、前記式（３）によりセルロースＩ型結晶化度を算出した。
Ｘ線光源：Ｃｕ／Ｋα−ｒａｄｉａｔｉｏｎ、管電圧：４０ｋＶ、管電流：１２０ｍＡ
測定範囲：２θ＝５〜４５°、
測定サンプル：面積３２０ｍｍ2×厚さ１ｍｍのペレットを圧縮して作成
Ｘ線のスキャンスピード：１０°／ｍｉｎ
<Measurement of degree of polymerization of powdered cellulose>
The degree of polymerization of powdered cellulose was measured by the copper ammonia method described in ISO-4312.
<Calculation of cellulose I type crystallinity>
Using a “Rigaku RINT 2500VC X-RAY diffractometer” manufactured by Rigaku Corporation, the cellulose I type crystallinity was calculated from the peak intensity of the diffraction spectrum measured under the following conditions by the above formula (3).
X-ray light source: Cu / Kα-radiation, tube voltage: 40 kV, tube current: 120 mA
Measurement range: 2θ = 5-45 °,
Measurement sample: Prepared by compressing pellets with an area of 320 mm 2 × thickness 1 mm X-ray scanning speed: 10 ° / min
＜ポリウロン酸の重量平均分子量の測定＞
ゲルパーミエーションクロマトグラフィーを用いて、以下の条件で測定した。水に溶解しない部分は、０．４５μｍのフィルターを用いて除去し、水に溶解している部分のみを測定した。
カラム：東ソー株式会社製、G4000PWXL＋G2500PWXL
溶離液：０．２Ｍリン酸緩衝液／アセトニトリル（容量比）＝９／１
測定温度：４０℃、流速：１．０ｍＬ／ｍｉｎ、検出器：ＵＶ又はＲＩ
標準ポリマー：プルラン
<Measurement of weight average molecular weight of polyuronic acid>
It measured on condition of the following using gel permeation chromatography. The portion not dissolved in water was removed using a 0.45 μm filter, and only the portion dissolved in water was measured.
Column: Tosoh Corporation G4000PWXL + G2500PWXL
Eluent: 0.2M phosphate buffer / acetonitrile (volume ratio) = 9/1
Measurement temperature: 40 ° C., flow rate: 1.0 mL / min, detector: UV or RI
Standard polymer: Pullulan
＜ポリウロン酸の酸化度の測定＞
製造したポリウロン酸のナトリウム塩の２％水溶液又は水分散液を５０ｇ調製し、６Ｎ塩酸にてｐＨを1以下とした。この酸性水溶液をエタノール５００ｍＬに投入し、生じた沈殿物を回収、エタノールで数回洗浄した。得られたポリウロン酸を０．１ｇ精秤し、イオン交換水３０ｍＬに溶解又は分散させ、フェノールフタレインを指示薬として０．１Ｎ水酸化ナトリウム水溶液で滴定し、ポリウロン酸塩単位重量当りのカルボン酸量を求めた。さらにこのカルボン酸量から、下記計算式（２）により酸化度を求めた。
酸化度（％）＝〔（１６２．１×Ａ）／（１−１４．０×Ａ）〕×１００ （２）
ここで、Ａは滴定によって求めたカルボン酸量（ｍｏｌ／ｇ）である。
馬鈴薯澱粉の酸化度、カルボキシメチルセルロースのカルボキシルメチル化度も同様にして測定した。
<Measurement of oxidation degree of polyuronic acid>
50 g of a 2% aqueous solution or aqueous dispersion of sodium polyuronic acid produced was prepared, and the pH was adjusted to 1 or less with 6N hydrochloric acid. This acidic aqueous solution was poured into 500 mL of ethanol, and the resulting precipitate was recovered and washed several times with ethanol. 0.1 g of the resulting polyuronic acid is precisely weighed, dissolved or dispersed in 30 mL of ion exchange water, titrated with 0.1N aqueous sodium hydroxide solution using phenolphthalein as an indicator, and the amount of carboxylic acid per unit weight of polyuronic acid salt Asked. Furthermore, from the amount of carboxylic acid, the degree of oxidation was determined by the following formula (2).
Oxidation degree (%) = [(162.1 × A) / (1-14.0 × A)] × 100 (2)
Here, A is the amount of carboxylic acid (mol / g) determined by titration.
The degree of oxidation of potato starch and the degree of carboxyl methylation of carboxymethyl cellulose were also measured in the same manner.
＜生分解性の評価＞
３Ｌのビーカーに、ポリマー５０ｍｇ−炭素／Ｌ（約１００ｍｇ／Ｌ）、処理場汚泥２００ｍｇ／Ｌとなるように仕込み、空気をバブリング、攪拌しながら２５±１℃で試験を行った。試験開始２８日目にサンプルを採取し、０．２μｍのフィルターでろ過した後、溶存有機炭素濃度（ＤＯＣ）を測定した。
生分解率（％）は、試験開始時点のＤＯＣとの比により求めた。
<Evaluation of biodegradability>
A 3 L beaker was charged with 50 mg-carbon / L (about 100 mg / L) of polymer and 200 mg / L of treatment site sludge, and the test was conducted at 25 ± 1 ° C. while bubbling and stirring air. On the 28th day from the start of the test, a sample was collected and filtered through a 0.2 μm filter, and the dissolved organic carbon concentration (DOC) was measured.
The biodegradation rate (%) was determined by the ratio with the DOC at the start of the test.
＜カーボンブラック再汚染防止性能、及び泥洗浄性能の評価＞
以下に示す洗浄剤組成物を調製し、以下の方法によりカーボンブラック汚れ布、及び泥汚れ布の洗浄試験を行い、ポリウロン酸等のポリマーを配合していない洗浄剤に対し、実施例及び比較例のポリマーを配合した洗浄剤組成物の再汚染防止性能及び洗浄性能を評価した。
（洗浄剤組成物の組成）
ポリオキシエチレン（エチレンオキシドの平均付加モル数２．５）アルキル（炭素数１２〜１４）エーテル硫酸ナトリウム：２５％
ポリオキシエチレン（エチレンオキシドの平均付加モル数７）アルキル（炭素数１２〜１４）エーテル：１５％
ポリウロン酸のナトリウム塩等のポリマー：６％、水：バランス
<Evaluation of carbon black recontamination prevention performance and mud cleaning performance>
The cleaning composition shown below was prepared, and the carbon black soiled cloth and the mud soiled cloth were subjected to a cleaning test by the following method. Examples and Comparative Examples were applied to cleaning agents not containing a polymer such as polyuronic acid. The anti-recontamination performance and the cleaning performance of the cleaning composition containing the polymer were evaluated.
(Composition of cleaning composition)
Polyoxyethylene (average addition mole number of ethylene oxide 2.5) alkyl (carbon number 12-14) ether sodium sulfate: 25%
Polyoxyethylene (average added mole number of ethylene oxide 7) alkyl (carbon number 12-14) ether: 15%
Polymer such as sodium salt of polyuronic acid: 6%, water: balance
（１）カーボンブラック再汚染防止性能の評価
（カーボンブラック汚れ試験布）
綿メリヤスニット（蛍光染料未染着布）を染色試材株式会社谷頭商店より入手した。
（カーボンブラック再汚染防止能試験）
再汚染防止効果の評価には、ターゴトメーターを使用して評価を行った。
上記の洗浄剤組成物を７２ｍｇ／Ｌ（ＣａＣＯ3換算）のカルシウム硬水１００ｍＬに各々溶解し、０．１５％になるように調製した。次いで洗浄剤溶液中に、０．１３ｇのカーボンブラックを入れ、超音波発振器（株式会社国際電気エルテック製、型式Ｕ０６００ＰＢ−Ｙ）の浴槽を用いて１５分間超音波照射し、分散させ、ターゴトメーターに移した。
３種の処理布をそれぞれサイズ４×５ｃｍとして、１種類を５枚組で計１５枚組にしたものターゴトメーター内の溶液中に投入し、２５℃、３０分間、回転速度１００回／分でターゴトメーターにて回転し洗浄を行った。５Ｌの水道水でためすすぎの後、アイロンプレス処理を行った。次いで、洗浄前の原布、再汚染試験布の５５０ｎｍにおける反射率を日本電色工業株式会社製、分光色差計ＳＥ２０００にて測定し、次式から再汚染防止率（％）及び再汚染防止増加率（％）を算出した。
再汚染防止率（％）＝［洗浄後の反射率／原布の反射率］×１００
再汚染防止増加率（％）＝［（ポリマー添加時の再汚染防止率−ポリマー未添加時の再汚染防止率）／ポリマー未添加時の再汚染防止率］×１００
(1) Evaluation of carbon black recontamination prevention performance (carbon black stain test cloth)
Cotton knitted fabric (fluorescent dye-undyed fabric) was obtained from Tanigami Shoten Co., Ltd.
(Carbon black recontamination prevention test)
For the evaluation of the effect of preventing recontamination, a targotometer was used.
The above detergent composition was dissolved in 100 mL of 72 mg / L (calculated in terms of CaCO 3 ) of calcium hard water to prepare 0.15%. Next, 0.13 g of carbon black is put into the detergent solution, and is irradiated with ultrasonic waves for 15 minutes using a bathtub of an ultrasonic oscillator (made by Kokusai Electric Eltech Co., Ltd., model U0600PB-Y), dispersed, and tergotometer Moved to.
Three kinds of treated cloths each having a size of 4 × 5 cm, each of which is a set of 15 pieces in a set of 5 pieces are put into a solution in a targotometer, and the rotation speed is 100 times / minute at 25 ° C. for 30 minutes. Then, it was rotated with a tartometer and washed. After rinsing with 5 L of tap water, an iron press treatment was performed. Next, the reflectance at 550 nm of the raw cloth before washing and the recontamination test cloth was measured with a spectrocolor difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. The rate (%) was calculated.
Recontamination prevention rate (%) = [reflectance after washing / reflectance of base fabric] × 100
Increase rate of prevention of recontamination (%) = [(recontamination prevention rate when polymer is added−recontamination prevention rate when polymer is not added) / recontamination prevention rate when polymer is not added] × 100
（２）泥洗浄性能の評価
（泥汚れ汚染布（人工汚染布））
鹿沼園芸用赤玉土を１２０℃±５℃で４時間乾燥後、粉砕し、１５０メッシュ（１００μｍ）パスのものを１２０℃±５℃で２時間乾燥後、±１５０ｇを１０００Ｌのパークレン中に分散して分散液を得た。得られた分散液に金巾＃２０２３布を接触させた後、ブラッシングし、分散液を除去した後、布表面に過剰に付着した泥を取り除いて泥汚れ評価用の汚染布を得た。得られた泥汚れ汚染布を顕微鏡で観察すると、繊維に泥粒子がめり込んだ形状で付着しているものが多く見られ、日常生活で汚れの付着状態に近いものが得られていることが確認された。
（泥汚れ汚染布の洗浄力試験）
洗浄剤水溶液１Ｌに１０ｃｍ×１０ｃｍの面の上記の泥汚れ汚染布（人工汚染布）を５枚入れ、かき混ぜ式洗浄力試験機（ターゴトメータ、株式会社上島製作所製）を用いて、以下の条件で洗浄した。
・洗浄条件
回転数：１００ｒｐｍ、洗浄時間：１０分、洗浄濃度：０．１３３％、
水の硬度：４°ＤＨ、水温：２０℃、濯ぎ：水道水にて５分間
洗浄力は汚染前の原布及び洗浄前後の汚染布の反射率を自記色彩計（株式会社島津製作所製）にて測定し、下記式により、洗浄率（％）（汚染布５枚の測定平均）及び洗浄率増加率（％）を算出した。
洗浄率（％）＝［（洗浄後の反射率−洗浄前の反射率）／（原布の反射率−洗浄前の反射率）］×１００
洗浄率増加率（％）＝［（ポリマー添加時の洗浄率−ポリマー未添加時の洗浄率）／ポリマー未添加時の洗浄率］×１００
(2) Evaluation of mud cleaning performance (mud soiled cloth (artificial soiled cloth))
Kanuma Horticultural Akadama soil is dried at 120 ° C ± 5 ° C for 4 hours and then pulverized, and 150 mesh (100 µm) passes are dried at 120 ° C ± 5 ° C for 2 hours, and then ± 150 g is dispersed in 1000 L of parkren. To obtain a dispersion. After the gold width # 2023 cloth was brought into contact with the obtained dispersion, brushing was performed and the dispersion was removed, and then the mud excessively adhered to the cloth surface was removed to obtain a contaminated cloth for evaluating mud dirt. When the obtained mud-stained cloth is observed with a microscope, it is confirmed that many of the fibers adhere to the fibers in a shape in which mud particles are embedded, and it is confirmed that there is a thing close to the state of dirt adhesion in daily life. It was done.
(Detergency test of mud soil contaminated cloth)
5 l of the above-mentioned mud-stained cloth (artificial soiled cloth) of 10 cm × 10 cm surface is put in 1 L of a cleaning agent aqueous solution, and using a stirring type detergency tester (Targometer, manufactured by Ueshima Seisakusho Co., Ltd.) Washed.
・ Cleaning conditions Rotation speed: 100 rpm, cleaning time: 10 minutes, cleaning concentration: 0.133%,
Water hardness: 4 ° DH, water temperature: 20 ° C., rinsing: 5 minutes with tap water Detergency is the self-recording color meter (manufactured by Shimadzu Corporation) with the reflectivity of the raw cloth before and after contamination. The cleaning rate (%) (measured average of 5 contaminated cloths) and the cleaning rate increase rate (%) were calculated according to the following formula.
Washing rate (%) = [(reflectance after washing−reflectance before washing) / (reflectance of base fabric−reflectivity before washing)] × 100
Increase rate of washing rate (%) = [(Washing rate when polymer is added−Washing rate when polymer is not added) / Washing rate when polymer is not added] × 100
製造例１（非晶化粉末セルロースの製造）
木材パルプシート（ボレガード社製、パルプシート、結晶化度７４％）をシュレッダー（株式会社明光商会製、「ＭＳＸ２０００−ＩＶＰ４４０Ｆ」）にかけてチップ状にした。
次に、得られたチップ状パルプをスクリューの中央部にニーディングディスク部を備えた二軸押出機（株式会社スエヒロＥＰＭ製、「ＥＡ−２０」）に２ｋｇ／ｈｒで投入し、せん断速度６６０ｓｅｃ-1、スクリュー回転数３００ｒｐｍの条件で、外部から冷却水を流しながら、１パス処理して粉末状にした。
次に、得られた粉末セルロースを、バッチ式媒体攪拌型ボールミル（三井鉱山株式会社製、「アトライタ」：容器容積８００ｍＬ、６ｍｍφ鋼球を１４００ｇ充填、攪拌翼の直径６５ｍｍ）に前記粉末状のセルロース１００ｇを投入した。容器ジャケットに冷却水を通しながら、攪拌回転数６００ｒｐｍで３時間粉砕処理を行い、非晶化粉末セルロース（結晶化度０％、重合度１５０、平均粒径４０μｍ）を得た。この粉末セルロースの反応には更に３２μｍ目開きの篩をかけた篩下品（投入量の９０％）を使用した。
Production Example 1 (Production of Amorphized Powdered Cellulose)
A wood pulp sheet (manufactured by Boleguard, pulp sheet, crystallinity 74%) was shredded (manufactured by Meiko Shokai, "MSX2000-IVP440F") to form a chip.
Next, the obtained chip-like pulp was charged at 2 kg / hr into a twin-screw extruder ("EA-20" manufactured by Suehiro EPM Co., Ltd.) equipped with a kneading disk at the center of the screw, and a shear rate of 660 sec. -1 and powdered by one pass treatment while flowing cooling water from the outside under the condition of screw rotation speed of 300 rpm.
Next, the powdered cellulose thus obtained is mixed into a batch-type medium stirring type ball mill (Mitsui Mine Co., Ltd., “Attritor”: container volume 800 mL, 6 mmφ steel ball 1400 g filled, stirring blade diameter 65 mm). 100 g was charged. While passing cooling water through the container jacket, pulverization was performed at a stirring rotational speed of 600 rpm for 3 hours to obtain amorphous powdered cellulose (crystallinity 0%, polymerization 150, average particle size 40 μm). For the reaction of the powdered cellulose, an unsieved product (90% of the input amount) with a sieve having an opening of 32 μm was used.
製造例２〜５（粉末セルロースの製造）
ボールミル処理における処理時間を変えた以外は、製造例１と同様にして、結晶化度０％、重合度６００の非晶化粉末セルロース（製造例２）、結晶化度２％、重合度８４５の低結晶性粉末セルロース（製造例３）、結晶化度０％、重合度３１の非晶化粉末セルロース（製造例４）、結晶化度０％、重合度６２の非晶化粉末セルロース（製造例５）を製造した。
製造例６（混合粉末セルロースの製造）
高結晶性粉末セルロース（日本製紙ケミカル株式会社製、商品名：ＫＣフロック４００Ｇ（登録商標）、結晶化度７０％、重合度２５０）と、製造例１で得られた非晶化粉末セルロースを、前者／後者（重量比）＝７／９３の割合で混合し、ボールミル処理における処理時間を変えた以外は、製造例１と同様にして、結晶化度５％、重合度１５７の混合粉末セルロースを製造した。
Production Examples 2 to 5 (Production of powdered cellulose)
Except for changing the treatment time in the ball mill treatment, in the same manner as in Production Example 1, non-crystallized powdered cellulose having a crystallinity of 0% and a polymerization degree of 600 (Production Example 2), a crystallinity of 2% and a polymerization degree of 845 Low crystalline powdered cellulose (Production Example 3), non-crystallized powdery cellulose (Production Example 4) with a degree of crystallinity of 0% and a degree of polymerization of 31 (Production Example) 5) was produced.
Production Example 6 (Production of mixed powder cellulose)
Highly crystalline powdered cellulose (manufactured by Nippon Paper Chemical Co., Ltd., trade name: KC Flock 400G (registered trademark), crystallinity 70%, polymerization degree 250) and the non-crystallized powdered cellulose obtained in Production Example 1, The mixed powdery cellulose having a crystallinity of 5% and a polymerization degree of 157 was prepared in the same manner as in Production Example 1 except that the former / the latter (weight ratio) = 7/93 and the treatment time in the ball mill treatment was changed. Manufactured.
実施例１（ポリウロン酸塩の製造と評価）
ｐＨメータを備え付けた５００ｍＬセパラブルフラスコに、製造例１で得られた非晶化粉末セルロース（重合度１５０）５ｇ及びイオン交換水９５ｇを仕込み、フットボール型攪拌子を用いて２００ｒｐｍの回転数で攪拌して非晶化セルロース粉末を分散させた。イオン交換水１５０ｇに２，２，６，６−テトラメチル−１−ピペリジン−Ｎ−オキシル（ＴＥＭＰＯ）０．０９５ｇ、臭化ナトリウム１．２５ｇを溶解させた水溶液を粉末セルロース分散液に投入し、氷冷下で攪拌し続けた。反応溶液の温度が５℃以下となった時点で、次亜塩素酸ナトリウム水溶液１５ｇを非晶化セルロース分散液に投入した。
酸化反応が進行するに従い、ｐＨが低下するため、非晶化セルロース分散液のｐＨを１０．８付近にするため、０．５Ｎ ＮａＯＨ（６１．７ｍＬ）をマイクロチューブポンプを用いて徐々に添加した。さらに次亜塩素酸ナトリウム水溶液（有効塩素濃度５％）４０ｇを１時間かけて添加し、ｐＨを１０．８付近に調整するために０．５Ｎ ＮａＯＨを添加した。
反応終了液をエタノール３Ｌに注ぎ、ポリウロン酸のナトリウム塩を沈殿させた。沈殿物をろ取し、アセトン／水（体積比）＝７／１の溶媒で洗浄後、さらにアセトンで洗浄した後、４０℃で乾燥して、微黄色のポリウロン酸のナトリウム塩６ｇを得た。
このポリウロン酸の酸化度は９０％、重量平均分子量は３２，８００であった。
得られたポリウロン酸塩によるカーボンブラック再汚染防止性能、及び泥洗浄性能を評価した結果を表１に示す。
Example 1 (Production and evaluation of polyuronic acid salt)
A 500 mL separable flask equipped with a pH meter is charged with 5 g of the amorphous powdered cellulose (polymerization degree 150) obtained in Production Example 1 and 95 g of ion-exchanged water, and stirred at a rotation speed of 200 rpm using a football-type stirrer. Then, the amorphous cellulose powder was dispersed. An aqueous solution prepared by dissolving 0.095 g of 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) and 1.25 g of sodium bromide in 150 g of ion-exchanged water was added to the powdered cellulose dispersion. Stirring was continued under ice cooling. When the temperature of the reaction solution became 5 ° C. or lower, 15 g of an aqueous sodium hypochlorite solution was added to the amorphous cellulose dispersion.
As the oxidation reaction progresses, the pH decreases, so 0.5N NaOH (61.7 mL) was gradually added using a microtube pump in order to bring the pH of the amorphous cellulose dispersion to around 10.8. . Furthermore, 40 g of sodium hypochlorite aqueous solution (effective chlorine concentration 5%) was added over 1 hour, and 0.5 N NaOH was added to adjust the pH to around 10.8.
The reaction-terminated liquid was poured into 3 L of ethanol to precipitate polyuronic acid sodium salt. The precipitate was collected by filtration, washed with a solvent of acetone / water (volume ratio) = 7/1, further washed with acetone, and then dried at 40 ° C. to obtain 6 g of slightly yellow sodium salt of polyuronic acid. .
The degree of oxidation of this polyuronic acid was 90%, and the weight average molecular weight was 32,800.
Table 1 shows the results of evaluating the carbon black recontamination prevention performance and mud washing performance with the polyuronic acid salt obtained.
実施例２〜４
実施例１において、製造例１で得られた非晶化粉末セルロースの代わりに、製造例２〜４で得られた粉末セルロース（実施例２：製造例２の非晶化粉末セルロース、実施例３：製造例３の低結晶性粉末セルロース、実施例４：製造例６の混合粉末セルロース）を用いた以外は、実施例１と同様にしてポリウロン酸のナトリウム塩を製造した。なお、実施例２で得られたポリウロン酸の生分解率は９４％であった。結果を表１に示す。
Examples 2-4
In Example 1, instead of the amorphous powdered cellulose obtained in Production Example 1, powdered cellulose obtained in Production Examples 2 to 4 (Example 2: Amorphized powdered cellulose of Production Example 2, Example 3) : Polyuronic acid sodium salt was produced in the same manner as in Example 1 except that the low crystalline powdery cellulose of Production Example 3 and Example 4: mixed powdered cellulose of Production Example 6) were used. The biodegradation rate of the polyuronic acid obtained in Example 2 was 94%. The results are shown in Table 1.
比較例１〜２
実施例１において、製造例１で得られた非晶化粉末セルロースの代わりに、製造例４〜５で得られた非晶化セルロース粉末を用いた以外は、実施例１と同様にしてポリウロン酸のナトリウム塩を製造した。結果を表１に示す。
比較例３
実施例１において、製造例１で得られた非晶化粉末セルロースの代わりに、馬鈴薯澱粉を用いた以外は、実施例１と同様にして酸化を行い、酸化澱粉を製造した。結果を表１に示す。
比較例４
市販のカルボキシルメチルセルロースナトリウム（ＣＭＣ、日本製紙ケミカル株式会社製、商品名：サンローズ（登録商標）ＡＰＰ−８４、生分解率：７４％）をそのまま使用してカーボンブラック再汚染防止性能、及び泥洗浄性能を評価した結果を表１に示す。
比較例５
再生セルロース繊維（旭化成株式会社製、ベンベルグ）を約５ｍｍの長さに切断したものを用いた以外は、実施例１と同様にして酸化を行い、ポリウロン酸ナトリウム塩を製造した。
比較例６
市販のポリアクリル酸ナトリウム（花王株式会社製、商品名：ポイズ（登録商標）５３６）をそのまま使用してカーボンブラック再汚染防止性能、及び泥洗浄性能を評価した結果を表１に示す。
Comparative Examples 1-2
In Example 1, polyuronic acid was used in the same manner as in Example 1 except that the amorphous cellulose powder obtained in Production Examples 4 to 5 was used instead of the amorphous powdered cellulose obtained in Production Example 1. The sodium salt of was prepared. The results are shown in Table 1.
Comparative Example 3
In Example 1, instead of the non-crystallized powder cellulose obtained in Production Example 1, oxidation was performed in the same manner as in Example 1 except that potato starch was used to produce oxidized starch. The results are shown in Table 1.
Comparative Example 4
Commercially available sodium carboxymethyl cellulose (CMC, manufactured by Nippon Paper Chemicals Co., Ltd., trade name: Sunrose (registered trademark) APP-84, biodegradation rate: 74%) is used as it is to prevent recontamination of carbon black, and mud washing The results of evaluating the performance are shown in Table 1.
Comparative Example 5
A polyuronic acid sodium salt was produced by oxidizing in the same manner as in Example 1 except that a regenerated cellulose fiber (Asahi Kasei Co., Ltd., Bemberg) was cut into a length of about 5 mm was used.
Comparative Example 6
Table 1 shows the results of evaluation of carbon black recontamination prevention performance and mud washing performance using a commercially available sodium polyacrylate (trade name: Poise (registered trademark) 536, manufactured by Kao Corporation) as it is.
表１の結果から、実施例のポリウロン酸のナトリウム塩は、比較例のものに比べて、カーボンブラック再汚染防止性能が特に優れており、泥洗浄性能についても満足いくレベルを達成することができ、両性能の両立が可能になることが分かる。 From the results of Table 1, the sodium salt of polyuronic acid of the example has particularly excellent carbon black recontamination prevention performance as compared with the comparative example, and can achieve a satisfactory level of mud cleaning performance. It can be seen that both performances are compatible.
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