JP2020026587A - Starch composition, papermaking additive, and method for producing starch composition - Google Patents
Starch composition, papermaking additive, and method for producing starch composition Download PDFInfo
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 46
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- 239000004202 carbamide Substances 0.000 claims abstract description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 24
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
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- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、新規なでん粉組成物、製紙用添加剤及びでん粉組成物の製造方法に関する。 The present invention relates to a novel starch composition, a papermaking additive, and a method for producing a starch composition.
でん粉は、製紙用薬品としては填料に次ぐ需要（国内年間約40〜50万トン）があり、早くから自家変性の対象とされてきた。自家変性とは、製紙会社で使用直前に用途に応じた化工や反応を施すことで、自製化とも称する。自家変性で得られたでん粉は、市販のあらかじめ加工されたものに比べて品質的に劣るものの安価な原料（未加工でん粉など）を用いることから、経済的メリットが期待できるため、大手製紙会社を中心に広く採用されている。でん粉の自家変性は、カチオン化、エステル化なども知られているが、最も需要が多いのは表面サイズ用途を対象とした低粘度化である。 Starch has the second highest demand for papermaking chemicals after fillers (approximately 400,000 to 500,000 tons per year in Japan), and has been an object of self-modification from an early age. The self-modification is referred to as self-manufacturing by applying a chemical treatment or reaction according to the use immediately before use by a papermaking company. Starch obtained by self-modification is inferior in quality to commercially available pre-processed one, but it uses cheap raw materials (such as unprocessed starch). Widely adopted in the center. Self-modification of starch is also known as cationization, esterification, etc., but the most in demand is viscosity reduction for surface size applications.
表面サイズとは紙の印刷適正や紙力の向上、板紙のカール防止などの目的で水溶性ポリマーの溶液を紙に塗布することをいい、コスト面よりでん粉を加熱糊化した糊液が最も一般的に使用される。 Surface size refers to the application of a water-soluble polymer solution to paper for the purpose of improving the printability and strength of paper, preventing curling of paperboard, etc. Is used regularly.
でん粉の塗布量は、紙の種類、塗布条件などで変わるが、いずれの場合も操業と効果のバランスを考慮して適当な濃度と粘度に調整された糊液が用いられる。 The amount of starch to be applied varies depending on the type of paper, application conditions, and the like. In any case, a size liquid adjusted to an appropriate concentration and viscosity in consideration of the balance between operation and effect is used.
でん粉は、もともと重量平均分子量が数千万から数億の巨大分子であり、そのままでは糊液の粘度が高すぎて塗布が困難となる。逆に、粘度を下げるために糊液の濃度を下げれば、塗布量が低くなりすぎて目的の効果が得られなくなる。そこで、通常10％濃度で60℃の測定条件下で10〜150mPa・sの粘度に低粘度化される。 Starch is originally a macromolecule having a weight-average molecular weight of tens of millions to hundreds of millions, and as it is, the viscosity of the size liquid is too high to apply. Conversely, if the concentration of the size liquid is reduced in order to lower the viscosity, the applied amount becomes too low and the desired effect cannot be obtained. Therefore, the viscosity is usually reduced to 10 to 150 mPa · s under a measurement condition of 60 ° C. at a concentration of 10%.
上記において、粘度を下げる、すなわち低分子化する方法としては、酵素処理、酸加水分解や熱化学変性等の化学処理が知られている。 In the above, chemical treatments such as enzymatic treatment, acid hydrolysis and thermochemical denaturation are known as methods for lowering the viscosity, that is, reducing the molecular weight.
酵素処理は、一部の製紙会社で酵素変性としてでん粉の自家変性に採用されている。酵素としては、一般にでん粉分子をランダムに分解するα−アミラーゼが用いられる。酵素はその活性の安定化のため、一定のpH範囲に管理した状態で低粘度化を進める必要がある。また、酵素は触媒的に働くので、低粘度化が完了した時点で酵素を失活させないと、保存中に糊液の低粘度化など糊液品質の低下が進行するおそれがある。 Enzymatic treatment is used by some paper companies for the in-house modification of starch as enzymatic modification. As the enzyme, α-amylase that generally degrades starch molecules at random is used. In order to stabilize the activity of the enzyme, it is necessary to reduce the viscosity while controlling the pH within a certain range. In addition, since the enzyme acts as a catalyst, if the enzyme is not deactivated at the time when the viscosity reduction is completed, the quality of the size liquid such as the reduction of the viscosity of the size liquid may be reduced during storage.
また、酵素変性は、酵素の添加量が微量で済み、経済的ではあるが、いわば生き物の酵素による変性のため、原料でん粉の品質やわずかな処理条件の変化により糊液粘度がバラツキやすいこと、夾雑するタンパク質がスカムとして沈殿し、抄紙機、用具、紙を汚染しがちなことなどの潜在的な問題がある。 In addition, enzymatic denaturation requires only a small amount of enzyme and is economical.However, because of the denaturation of living organisms by enzymes, the viscosity of paste liquid tends to vary due to the quality of raw starch and slight changes in processing conditions. There are potential problems such as contaminating proteins precipitating as scum and tending to contaminate paper machines, utensils, and paper.
酸加水分解では、酸が触媒として働き、でん粉分子をほぼランダムに分解する。でん粉自家変性においては、でん粉の水懸濁液もしくは加熱糊化した糊液に酸を添加し、一定時間保持して加水分解を進めた後、アルカリで中和する方法が考えられる。しかしながら、この方法では、変性時のでん粉濃度や温度の変動、中和のタイミングのわずかなズレなどで、糊液粘度などの糊液品質が大きくばらつく欠点があり、実用的とはいいがたい。 In acid hydrolysis, the acid acts as a catalyst to break down the starch molecules almost randomly. In the starch self-modification, a method in which an acid is added to an aqueous suspension of starch or a paste solution heated and gelatinized, the hydrolysis is carried out for a certain period of time, and then neutralization with an alkali is considered. However, this method has a disadvantage that the size of the sizing liquid such as the viscosity of the sizing liquid greatly varies due to fluctuations in starch concentration and temperature during denaturation, slight deviations in the timing of neutralization, etc., and is not practical.
ペルオキソ二硫酸アンモニウム（過硫酸アンモニウム）は、でん粉自家変性としては最も普及している熱化学変性（TCC法、Thermochemical conversion）に使用される。熱化学変性は、薬品による低粘度化と熱機械作用による低粘度化を組み合わせた方法であり、一般に薬品を添加したでん粉の懸濁液をジェットクッカーに連続的に送り込み同時に蒸気を吹き込んで150℃前後に加熱して5分間ほど保持して変性を進めた後、蒸気を分離してついで希釈水を連続的に添加することにより、目的の低粘度糊液を得る。高温で高いせん断を受けるためでん粉分子の分散が進み、比較的安定な品質の糊液が得られることが特徴である。 Ammonium peroxodisulfate (ammonium persulfate) is used for thermochemical conversion (TCC method), which is the most widely used starch self-modification. Thermochemical denaturation is a method that combines viscosity reduction with chemicals and viscosity reduction with thermomechanical action.Generally, a starch suspension containing chemicals is continuously fed into a jet cooker and steam is simultaneously blown at 150 ° C. After heating before and after and holding for about 5 minutes for denaturation, the vapor is separated, and then the dilution water is continuously added to obtain the desired low-viscosity paste liquid. It is characterized by the fact that starch molecules are subjected to high shear at a high temperature and the dispersion of starch molecules progresses, and a size liquid of relatively stable quality is obtained.
しかし、ペルオキソ二硫酸アンモニウムなどの過硫酸塩を用いた場合、その添加量に応じて希望の粘度の糊液を簡単に得ることができる反面、変性により硫酸が副生するため苛性ソーダで中和する必要があること（作業性が悪い）、変性時に褐色に着色すること（変性度が高く、中和pHが高いほど著しい）、変性時の温度や時間の変動で糊液の粘度などの糊液品質がばらつきやすいことなどの欠点を持つ。また、ペルオキソ二硫酸水溶液は、PRTR制度の第一種指定化学リストに収載されており、環境への負荷が懸念される。 However, when a persulfate such as ammonium peroxodisulfate is used, a paste liquid having a desired viscosity can be easily obtained according to the amount of addition, but it is necessary to neutralize with caustic soda because sulfuric acid is by-produced due to denaturation. Size (the workability is poor), brown color during denaturation (the higher the degree of denaturation and the higher the neutralization pH), the size of the sizing liquid such as the viscosity of the sizing liquid due to temperature and time fluctuations during the denaturation Have disadvantages such as easy variation. In addition, peroxodisulfuric acid aqueous solution is included in the first-class designated chemical list of the PRTR system, and there is a concern that it will affect the environment.
なお、熱分解、せん断による機械的分解、放射線などの物理的にでん粉を低粘度化する方法も知られている。例えば、熱機械変性はジェットクッカーを用いて高温高圧の蒸気を吹き込み、水蒸気が水に凝縮する際に起こる強いせん断力を利用してでん粉を低粘度化する方法である。しかしながら、物理的なでん粉自家変性は、その低粘度化の程度の不十分さやコスト面から表面サイズに応用されていない。 In addition, a method of physically lowering the viscosity of starch by thermal decomposition, mechanical decomposition by shearing, or radiation is also known. For example, thermomechanical modification is a method in which high-temperature and high-pressure steam is blown using a jet cooker, and the starch is reduced in viscosity by using a strong shear force generated when the steam condenses into water. However, physical starch self-modification has not been applied to the surface size due to insufficient degree of viscosity reduction and cost.
上述のように、紙の表面サイズには未加工のでん粉を加熱糊化すると同時に、酵素処理、化学処理を適用することにより低粘度化する、いわゆる自家変性による低粘度化したものが大量に用いられている。なかでも、白色度を低下させることなく自家変性用でん粉を得る手法として、でん粉の水性懸濁液に酸性物質と水溶性窒素化合物を添加したうえ、高温で蒸煮し低粘度化する緩衝型酸加水分解方式による熱化学変性法が提案されている（特許文献１）。この熱化学変性用でん粉は、用いる酸の種類により長期保存する間に自家変性後のでん粉糊液粘度が変化し、実用上問題のあることが判明している。当該問題を解決するために、酸性物質として塩酸又は硝酸と硫酸を一定割合で配合して用いる熱化学変性法が提案されている（特許文献２）。当該方法により、長期間保存しても自家変性後のでん粉糊液粘度の変化を抑制し、一定な粘度の熱化学変性でん粉が得られる。 As described above, the raw starch is heated and gelatinized at the same time as the paper surface size, and at the same time, the viscosity is reduced by applying enzyme treatment and chemical treatment. Have been. Above all, as a method of obtaining starch for self-denaturing without reducing whiteness, an acidic suspension and a water-soluble nitrogen compound are added to an aqueous suspension of starch, and then a buffered acid solution that is steamed at a high temperature to reduce the viscosity. A thermochemical modification method using a decomposition method has been proposed (Patent Document 1). It has been found that the starch for thermochemical modification changes the viscosity of the starch paste liquid after self-denaturation during long-term storage depending on the type of acid used, and has a practical problem. In order to solve the problem, a thermochemical denaturation method has been proposed in which hydrochloric acid or nitric acid and sulfuric acid are blended in a fixed ratio as acidic substances (Patent Document 2). By this method, even if the starch paste is stored for a long period of time, a change in the viscosity of the starch paste liquid after self-denaturation is suppressed, and a thermochemically modified starch having a constant viscosity can be obtained.
しかしながら、上記手法において糊液の粘度についての記載はあり、確かに粘度は紙への表面サイズについて効果を上げるに重要な因子であるが、他の品質（糊液における沈殿やｐＨ）という観点での検討は一切行われておらず、品質改善の余地を残す設計であった。 However, in the above method, there is a description of the viscosity of the size liquid, and although the viscosity is certainly an important factor for increasing the effect on the surface size on paper, from the viewpoint of other quality (sedimentation and pH in the size liquid). The design was not done at all, leaving room for quality improvement.
上記のような状況に鑑み、本発明は、でん粉自体及び蒸煮後糊液のより品質の高いでん粉組成物を提供することを目的とする。 In view of the above situation, an object of the present invention is to provide a starch composition having higher quality of starch itself and paste liquid after steaming.
本発明者らは、上記目的達成のため、鋭意検討の結果、本発明を完成するに至った。
すなわち、本発明の１つは、でん粉１００質量部に対し、０．５〜３質量部の尿素と、０．１３〜０．３５質量部の酸とを含有するでん粉組成物であって、前記酸は、硫酸と、硝酸及び／又は塩酸とを含み、前記硫酸と、硝酸及び／又は塩酸との質量比が４２：５８〜８７：１３の範囲であり、前記でん粉組成物の８質量％糊液のｐＨが６．５〜８．３であることを特徴とするでん粉組成物を提供するものである。
The present inventors have conducted intensive studies to achieve the above object, and as a result, completed the present invention.
That is, one of the present invention is a starch composition containing 0.5 to 3 parts by mass of urea and 0.13 to 0.35 parts by mass of acid, based on 100 parts by mass of starch. The acid includes sulfuric acid, nitric acid and / or hydrochloric acid, the mass ratio of the sulfuric acid to nitric acid and / or hydrochloric acid is in the range of 42:58 to 87:13, and 8% by mass of the starch composition It is intended to provide a starch composition characterized in that the pH of the liquid is 6.5 to 8.3.
本発明のでん粉組成物は、自家変性処理に用いられることが好ましい。 The starch composition of the present invention is preferably used for an autologous modification treatment.
本発明のでん粉組成物においては、前記でん粉が未加工でん粉であることが好ましい。 In the starch composition of the present invention, it is preferable that the starch is a raw starch.
本発明のもう１つは、前記でん粉組成物を含有することを特徴とする製紙用添加剤を提供するものである。 Another object of the present invention is to provide a papermaking additive characterized by containing the starch composition.
本発明の更にもう１つは、でん粉１００質量部に対し、０．５〜３質量部の尿素と、０．１３〜０．３５質量部の酸とを含有するでん粉組成物の製造方法であって、前記酸として、硫酸と、硝酸及び／又は塩酸とを含み、前記硫酸と、硝酸及び／又は塩酸との質量比が４２：５８〜８７：１３の範囲であるものを用い、前記でん粉組成物の８質量％糊液のｐＨが６．５〜８．３となるように前記酸及び尿素を配合することを特徴とするでん粉組成物の製造方法を提供するものである。 Still another aspect of the present invention is a method for producing a starch composition containing 0.5 to 3 parts by mass of urea and 0.13 to 0.35 parts by mass of an acid based on 100 parts by mass of starch. The acid composition contains sulfuric acid, nitric acid and / or hydrochloric acid, and the mass ratio of sulfuric acid to nitric acid and / or hydrochloric acid is in the range of 42:58 to 87:13. It is an object of the present invention to provide a method for producing a starch composition, wherein the acid and urea are blended so that the pH of an 8% by mass paste liquid of the product is 6.5 to 8.3.
本発明によれば、糊液とした際の品質が高くでん粉自体の保存安定性の変化が抑制されたでん粉組成物を提供することができる。具体的には、自家変性後の糊液の沈殿率が低く、でん粉組成物を長期間保存しても自家変性後の糊液の品質が変化し難いものを提供することが出来る。 Advantageous Effects of Invention According to the present invention, it is possible to provide a starch composition having a high quality as a size liquid and having a reduced storage stability of the starch itself. Specifically, it is possible to provide a paste liquid which has a low sedimentation rate of the size liquid after self-denaturation, and hardly changes the quality of the size liquid after self-denaturation even when the starch composition is stored for a long period of time.
当該でん粉組成物は、次亜塩素酸塩で低粘度化した酸化でん粉等と比べ、簡便かつ低コストで製造することが出来る。また、でん粉の糊化と同時に低分子化を行うため、酸化でん粉等と比べ加工（低分子化）処理後の洗浄・脱水・乾燥などの工程が不要なことや排水がないこと、加工処理後に別途糊化作業を行う必要がないことで環境負荷の低減に寄与することができる。 The starch composition can be produced simply and at low cost as compared to oxidized starch or the like whose viscosity is reduced by hypochlorite. In addition, since starch is gelatinized and depolymerized at the same time, compared to oxidized starch etc., there is no need for processes such as washing, dehydration and drying after processing (reduction of molecular weight), no drainage, and after processing, Since there is no need to separately perform gelatinization work, it is possible to contribute to reduction of environmental load.
本発明のでん粉組成物は、でん粉と、尿素と、酸とを含有する組成物であり、でん粉質量に対して、所定範囲の質量の尿素及び酸を含有し、酸として、硫酸と、硝酸及び／又は塩酸とを所定の割合で含有し、８質量％糊液のｐＨが６．５〜８．３であることを特徴とする。 The starch composition of the present invention is a composition containing starch, urea, and an acid, and contains urea and an acid in a predetermined range with respect to the starch mass.As the acid, sulfuric acid, nitric acid and And / or hydrochloric acid at a predetermined ratio, and the pH of the 8% by mass size liquid is 6.5 to 8.3.
本発明に用いるでん粉は、製紙、段ボール、繊維、塗料、その他工業用途などに用いられるでん粉であれば制限はなく、例えば、未加工のでん粉、湿熱処理や温水処理などの物理的処理が施されたでん粉、架橋処理、エステル化処理、カチオン化処理などの化学的処理が施されたでん粉、α-アミラーゼ処理などの酵素的処理が施されたでん粉を用いることができる。簡便、低コスト、低環境負荷で低粘度化でん粉を得ると言う本発明の趣旨を考慮すると、未加工のでん粉を用いるのが好ましい。 The starch used in the present invention is not limited as long as it is starch used for papermaking, cardboard, fiber, paint, and other industrial uses.For example, unprocessed starch, subjected to a physical treatment such as a wet heat treatment or a hot water treatment. Starch, starch subjected to chemical treatment such as crosslinking treatment, esterification treatment, cationization treatment, and starch subjected to enzymatic treatment such as α-amylase treatment can be used. In view of the purpose of the present invention of obtaining a low-viscosity starch with a simple, low cost and low environmental load, it is preferable to use unprocessed starch.
でん粉としては、コーンスターチ、タピオカでん粉、馬鈴薯でん粉、甘藷でん粉、小麦でん粉等を用いることができる。また、複数のでん粉を組み合わせて用いてもよい。 As starch, corn starch, tapioca starch, potato starch, sweet potato starch, wheat starch and the like can be used. Further, a plurality of starches may be used in combination.
本発明のでん粉組成物の調製には、酸として、硫酸と、塩酸及び硝酸のいずれか又は両者とが用いられる。これらは、市場で入手できる硫酸、塩酸、硝酸であれば、いずれも使用できる。 In preparing the starch composition of the present invention, sulfuric acid and either or both of hydrochloric acid and nitric acid are used as the acid. Any of these can be used as long as they are commercially available sulfuric acid, hydrochloric acid, and nitric acid.
酸の添加量は、でん粉１００質量部に対して、０．１３〜０．３５質量部となるように配合すればよく、上記範囲ででん粉８質量％糊液のｐＨが６．５〜８．３となるように調整すればよい。また、酸の添加量は、上記の範囲内において、所望とするでん粉糊液の粘度、でん粉の種類、熱化学変性の条件、尿素の添加量などに応じて適宜調整することができる。その効果を考慮すると、でん粉１００質量部に対して０．１５〜０．３質量部とするのが好ましく、０．１９〜０．２５質量部とするのがより好ましい。酸の量が過少であると、糊液のｐＨが所望の範囲であったとしても糊液に沈殿が生じやすく糊液の品質に問題が生じ、またでん粉糊液の調製時に加水分解が十分に進行しないため糊液の粘度も十分に低下しない。酸が過大である場合も、糊液のｐＨが所望の範囲であったとしても糊液に沈殿が生じやすく糊液の品質に問題が生じる。 The acid may be added in an amount of 0.13 to 0.35 parts by mass with respect to 100 parts by mass of the starch, and the pH of the starch 8% by mass size liquid is 6.5 to 8.0 in the above range. It may be adjusted so as to be 3. Further, the amount of the acid to be added can be appropriately adjusted within the above range according to the desired viscosity of the starch paste solution, the type of the starch, the conditions of thermochemical modification, the amount of the urea added, and the like. In consideration of the effect, the amount is preferably 0.15 to 0.3 part by mass, more preferably 0.19 to 0.25 part by mass, based on 100 parts by mass of the starch. If the amount of the acid is too small, even if the pH of the size liquid is in a desired range, precipitation tends to occur in the size liquid, causing a problem in the quality of the size liquid, and sufficient hydrolysis is required during preparation of the starch size liquid. Since it does not proceed, the viscosity of the size liquid does not decrease sufficiently. Even when the acid is excessive, even if the pH of the size liquid is in a desired range, precipitation tends to occur in the size liquid, which causes a problem in the quality of the size liquid.
該酸中の硫酸と、塩酸及び／又は硝酸との割合は、硫酸：硝酸及び／又は塩酸の質量比が４２：５８〜８７：１３となるように配合する必要がある。すなわち、例えば酸として硫酸と硝酸を用いる場合、でん粉に添加する酸中の４２〜８７質量％が硫酸となる。硫酸だけ、又は塩酸及び／又は硝酸だけを配合すると、でん粉自体の保存安定性が損なわれるだけでなく、糊液のｐＨが所望の範囲であったとしても糊液に沈殿が生じやすく品質に問題が生じる。また、硫酸だけを配合すると糊液の粘度が十分に低下せず、塩酸及び／又は硝酸だけを配合するとでん粉がダマになりやすいという問題を有する。酸中の硫酸の割合が過少であっても過大であっても、糊液に沈殿が生じやすく品質に問題が生じる。塩酸と硝酸の両者を用いる場合、これら両者の割合は格別限定されることはなく任意でよい。なお、自家変性後糊液の良好な品質が達成される限り、塩酸、硝酸、硫酸以外の酸を少量併用してもよいが、概して好ましくない。なお、硫酸：硝酸及び／又は塩酸の質量比は、４５：５４〜８７：１３となるようにすることが好ましく、４５：５４〜８０：２０となるようにすることがより好ましく、５０：５０〜７０：３０となるようにすることが特に好ましい。 The ratio of sulfuric acid to hydrochloric acid and / or nitric acid in the acid must be blended so that the mass ratio of sulfuric acid: nitric acid and / or hydrochloric acid is 42:58 to 87:13. That is, for example, when sulfuric acid and nitric acid are used as the acid, the sulfuric acid accounts for 42 to 87% by mass of the acid added to the starch. Mixing only sulfuric acid or only hydrochloric acid and / or nitric acid not only impairs the storage stability of the starch itself, but also tends to cause sedimentation in the size liquid even if the pH of the size liquid is in a desired range, resulting in poor quality. Occurs. In addition, when only sulfuric acid is blended, the viscosity of the size liquid does not sufficiently decrease, and when only hydrochloric acid and / or nitric acid is blended, there is a problem that starch is easily lumped. Regardless of whether the proportion of sulfuric acid in the acid is too small or too large, sediment is likely to be formed in the size liquid, which causes quality problems. When both hydrochloric acid and nitric acid are used, the ratio between these two is not particularly limited and may be arbitrary. As long as good quality of the size liquid after self-denaturation is achieved, a small amount of an acid other than hydrochloric acid, nitric acid and sulfuric acid may be used in combination, but is generally not preferred. The mass ratio of sulfuric acid: nitric acid and / or hydrochloric acid is preferably 45:54 to 87:13, more preferably 45:54 to 80:20, and 50:50. It is particularly preferable that the ratio be up to 70:30.
本発明において酸とともに使用される尿素は、工業用、肥料用等のいずれも用いることができ、固形品のほか液状品（高濃度水溶液）も用いることができる。その添加量は、でん粉１００質量部に対して０．５〜３質量部となるように配合すればよく、上記範囲ででん粉糊液のｐＨが６．５〜８．３となるように調整すればよい。また、尿素の添加量は、所望とするでん粉糊液の粘度、でん粉の種類、自家変性の条件、酸の添加量などに応じて適宜調整することができる。その効果を考慮すると、でん粉１００質量部に対して１〜３質量部とするのが好ましく、１〜２質量部とするのがより好ましい。 The urea used together with the acid in the present invention can be used for industrial purposes, for fertilizers, and the like, and liquid products (high-concentration aqueous solutions) as well as solid products can be used. The amount of addition may be adjusted so as to be 0.5 to 3 parts by mass with respect to 100 parts by mass of starch, and the pH of the starch paste solution is adjusted to be 6.5 to 8.3 in the above range. I just need. The amount of urea to be added can be appropriately adjusted according to the desired viscosity of the starch paste liquid, the type of starch, the conditions for self-denaturation, the amount of acid added, and the like. In consideration of the effect, the amount is preferably 1 to 3 parts by mass, more preferably 1 to 2 parts by mass with respect to 100 parts by mass of the starch.
尿素の量が過少であると、でん粉の自家変性に際し加水分解が過度にすすむとともに、酸の中和が不完全になり、でん粉糊液のｐＨが所望の範囲よりも低くなりやすい。また、でん粉糊液のｐＨが所望の範囲となるよう酸の添加量を併せて減らすと、熱化学変性時に加水分解が十分に進行しないため、糊液の沈殿が増えて粘度も十分に低下しない。更に、尿素の量が過少であると、でん粉組成物自体の保存中に安定性の低下、自家変性後の糊液の沈殿の増加と粘度の低下を招く。 If the amount of urea is too small, hydrolysis proceeds excessively during self-denaturation of the starch, acid neutralization becomes incomplete, and the pH of the starch paste liquid tends to be lower than a desired range. In addition, when the amount of the acid added is also decreased so that the pH of the starch paste is in a desired range, hydrolysis does not proceed sufficiently during thermochemical denaturation, so that precipitation of the paste is increased and the viscosity is not sufficiently reduced. . Furthermore, when the amount of urea is too small, the stability of the starch composition itself during storage is reduced, the precipitation of the size liquid after auto-denaturation and the viscosity are reduced.
一方、尿素の量が過大である場合は、コストの点やその後の製紙工程などへ残留尿素が持ち込まれてしまう点で好ましくない。加えて、でん粉組成物自体の保存中に尿素が分解してアンモニアが発生し、添加した酸を消費してしまうため、結果として得られる糊液の粘度、沈殿率が高くなってしまう傾向がある。更に、尿素の量が過大であると、でん粉組成物自体の保存中に安定性の低下、自家変性後の糊液粘度、沈殿率の上昇を招く。 On the other hand, if the amount of urea is excessive, it is not preferable in terms of cost and in that residual urea is brought into the subsequent papermaking process. In addition, during storage of the starch composition itself, urea is decomposed and ammonia is generated, and the added acid is consumed, so that the viscosity of the resulting size liquid and the precipitation rate tend to increase. . Further, if the amount of urea is excessive, the stability of the starch composition itself during storage is reduced, and the viscosity of the paste liquid after self-denaturation and the precipitation rate are increased.
でん粉に上記酸と尿素とを添加してでん粉組成物を調製する方法は、格別限定されない。例えば、酸と尿素を含む水溶液を調製し、それをでん粉に混合することができる。酸と尿素とを含む水溶液の調製に際しては、なるべく少量の水に攪拌しながら尿素、次いで所定の割合の、硫酸と、塩酸及び／又は硝酸とを順次添加し、溶解せしめることが好ましい。調製された混合水溶液を、所定の添加割合になるように、でん粉の粉体に添加、混合する。混合には、例えば、リボンミキサー、パドルミキサー、コニカルミキサー、スクリューブレンダー、ジェットミキサーなどバッチ式、連続式のいずれの混合機も用いることができる。水溶液の添加により水含有量がでん粉の平衡点より高くなるので、気流乾燥機などにより平衡水分量の近辺まで乾燥する。多量の水を用いると最終的に得られるでん粉組成物の水分量を平衡点付近にもっていくための乾燥負荷が増大するので好ましくない。 The method for preparing a starch composition by adding the above-mentioned acid and urea to starch is not particularly limited. For example, an aqueous solution containing an acid and urea can be prepared and mixed with the starch. In preparing an aqueous solution containing an acid and urea, it is preferable that urea is added to a small amount of water while stirring, and then a predetermined ratio of sulfuric acid and hydrochloric acid and / or nitric acid are sequentially added and dissolved. The prepared mixed aqueous solution is added to and mixed with starch powder so as to have a predetermined addition ratio. For mixing, any of a batch-type mixer and a continuous-type mixer such as a ribbon mixer, a paddle mixer, a conical mixer, a screw blender, and a jet mixer can be used. Since the water content becomes higher than the equilibrium point of the starch by the addition of the aqueous solution, the water content is dried to a value near the equilibrium water content by a flash dryer or the like. If a large amount of water is used, the drying load for bringing the water content of the finally obtained starch composition to near the equilibrium point increases, which is not preferable.
本発明のでん粉組成物から目的とする低粘度のでん粉糊液を得るには常法に従って自家変性すればよい。自家変性の好ましい具体例を挙げると、でん粉濃度が３０重量％以上となるようにでん粉組成物に水を加えて水性懸濁液とし、これを滞留装置付きのでん粉変性装置に連続的に供給し、同時に蒸気を連続的に加えて１４０〜１６０℃で２〜７分間保持した後、大気中に放出して蒸気を分離し、次いで適当な温度の希釈水を連続的に添加することにより、目的の濃度及び粘度に調整された沈殿率の低い低粘度でん粉糊液を得ることができる。 In order to obtain the desired low-viscosity starch paste liquid from the starch composition of the present invention, the starch paste may be self-modified according to a conventional method. As a preferred specific example of the self-modification, water is added to the starch composition so that the starch concentration becomes 30% by weight or more to form an aqueous suspension, which is continuously supplied to a starch denaturing device equipped with a retention device. At the same time, the steam is continuously added and kept at 140 to 160 ° C. for 2 to 7 minutes, then released to the atmosphere to separate the steam, and then the dilution water at an appropriate temperature is continuously added to achieve the purpose. A low-viscosity starch paste liquid having a low sedimentation rate adjusted to the concentration and viscosity of the above can be obtained.
本発明のでん粉組成物は、その特徴を発揮するために、自家変性に用いられるものであることが好ましい。「自家変性」とは、上記に例示されたようなでん粉の糊化と低分子化を同時に行う処理を意味する。上記に例示されるようなでん粉自家変性装置を用いて自家変性することででん粉の糊化、酸によるでん粉の加水分解及び尿素の熱分解で生じるアンモニアによる酸の中和を同時に行うことが出来る。 The starch composition of the present invention is preferably used for self-modification in order to exhibit its characteristics. The “self-modification” means a treatment for simultaneously performing starch gelatinization and molecular weight reduction as exemplified above. By self-denaturing using a starch self-denaturing device as exemplified above, gelatinization of starch, hydrolysis of starch with acid, and neutralization of acid with ammonia generated by thermal decomposition of urea can be simultaneously performed.
本発明のでん粉組成物は、簡便・安価に沈殿率が低く低粘度のでん粉糊液を調整することができるため、様々な用途に用いることができる。その用途に限定はなく、例えば、製紙用、繊維用、塗料用などに用いることができる。すなわち、本発明のでん粉組成物は、例えば、製紙用添加剤、繊維用添加剤、塗料用添加剤として用いることができ、その糊液としての性質を考慮すると製紙用添加剤とするのが好ましい。上記各添加剤は、その使用方法にも特に制限はなく、通常用いられる添加剤と同様に用いることができる。 INDUSTRIAL APPLICABILITY The starch composition of the present invention can be easily and inexpensively prepared for a starch paste liquid having a low sedimentation rate and a low viscosity, so that it can be used for various applications. The use is not limited, and for example, it can be used for papermaking, fiber, paint and the like. That is, the starch composition of the present invention can be used, for example, as an additive for papermaking, an additive for fiber, and an additive for paint, and is preferably used as a papermaking additive in view of its properties as a paste liquid. . Each of the above-mentioned additives is not particularly limited in its use method, and can be used in the same manner as a commonly used additive.
本発明のでん粉組成物によれば、自家変性後の糊液に一定の粘度を与え、沈殿が少なく、ｐＨが中性付近という、品質が安定化された糊液を得ることが出来る。具体的には、後述の実施例に示したとおり、糊液に沈殿が生じにくい。糊液に沈殿が生じると、例えば製紙用に用いる場合、沈殿物がストレーナーやフィルターに詰まる、塗工ロールに汚れが付着する等の不具合が生じるため、大きな問題となる。また、糊液における沈殿生成は、糊液の老化性の指標であり、沈殿が生じやすい糊液ほど老化しやすい糊液といえ、糊液が老化することにより不均質となる、歩留まりが低下するといった問題が生じる。一方、糊液の粘度を低く保つことができれば、種々の作業効率を高めることができ、例えば製紙用に用いる場合は表面サイズ剤として使用しやすくなる。 ADVANTAGE OF THE INVENTION According to the starch composition of this invention, the paste liquid which gave fixed viscosity to the paste liquid after self-denaturation, has few precipitations, and is pH-neutral, and can obtain the paste liquid of stabilized quality is obtained. Specifically, as shown in Examples described later, sediment hardly occurs in the size liquid. If sedimentation occurs in the size liquid, for example, when used for papermaking, there is a problem in that the sediment is clogged in a strainer or a filter, or a coating roll is stained. In addition, the generation of precipitate in the size liquid is an index of the aging property of the size liquid, and the size liquid that easily precipitates can be said to be an easily sized size liquid. Such a problem arises. On the other hand, if the viscosity of the size liquid can be kept low, various work efficiencies can be enhanced. For example, when used for papermaking, it becomes easy to use as a surface sizing agent.
以下に実施例を挙げて本発明の詳細を説明するが、本発明は以下の実施例に限定されるものではない。
実施例
＜試料の調製＞
表１に示した配合で、尿素及び酸（硫酸、硝酸、塩酸）を少量の水に溶解した水溶液を、コーンスターチに均一に添加、混合した後、気流乾燥により水分量約１３％のでん粉組成物を得た。なお、試料１０は、糊液のｐＨが表１に記載した通りとなるように糊化時に苛性ソーダをインラインで添加して調製した。
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.
Example <Preparation of sample>
An aqueous solution prepared by dissolving urea and an acid (sulfuric acid, nitric acid, hydrochloric acid) in a small amount of water in the composition shown in Table 1 is uniformly added to corn starch, mixed, and then flash dried to obtain a starch composition having a water content of about 13%. I got Sample 10 was prepared by adding caustic soda in-line during gelatinization so that the pH of the size liquid was as shown in Table 1.
得られた各試料（でん粉組成物）について、以下の手法で糊液の粘度及び沈殿率を測定した。
＜粘度の測定＞
各試料を３０質量％濃度になるように水に溶解して水性懸濁液を得た。これを定量ポンプで熱化学変性用の市販「日食でん粉変性装置」に連続的に供給し、同時に０．９Mpaの圧力を有する蒸気を連続的に供給して１５０℃に加熱して糊化させ、次いでホールディングコイルでこの温度に５分間滞留させて酸加水分解と酸の中和（尿素の加熱分解により生成するアンモニアによる）を進めた。背圧弁を通過させた直後に糊液をフラッシュチャンバーに導き、過剰の蒸気を分離した後、温水を連続的に供給して約６５℃の８質量％濃度の糊液を得た。この糊液について、６０℃、６０ｒｐｍの条件でＢ型粘度計（東機産業社製）を用いて測定した。
＜沈殿率の測定＞
上記粘度測定に用いた８質量％濃度糊液約１０ｇを遠沈管に採取し、約５０℃の温水約４０ｍｌにて希釈後に３０００ｒｐｍで１０分間遠心分離を行った。遠心後上澄みを捨て、沈殿を再度、温水約４０ｍｌに懸濁し、再度遠心分離した。上澄みを捨て、沈殿を重量既知のアルミカップに蒸留水で流し入れ、１０５℃で一夜乾燥した。乾燥後の重量を採取重量（沈殿重量）とし、糊液中のでん粉重量（糊液重量×８／１００）で割ることで沈殿率（糊液のでん粉のうち沈殿した割合）を求めた。
測定結果を表１に示した。
For each of the obtained samples (starch composition), the viscosity and sedimentation rate of the size liquid were measured by the following method.
<Measurement of viscosity>
Each sample was dissolved in water to a concentration of 30% by mass to obtain an aqueous suspension. This is continuously supplied to a commercially available "eclipse starch denaturing device" for thermochemical denaturation by a constant-rate pump, and at the same time, steam having a pressure of 0.9 Mpa is continuously supplied and heated to 150 ° C to gelatinize. Then, the mixture was kept at this temperature for 5 minutes in a holding coil to proceed with acid hydrolysis and acid neutralization (by ammonia generated by thermal decomposition of urea). Immediately after passing through the back pressure valve, the size liquid was led to the flash chamber, and after separating excess steam, hot water was continuously supplied to obtain an 8% by mass size liquid at about 65 ° C. The size liquid was measured at 60 ° C. and 60 rpm using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
<Measurement of precipitation rate>
About 10 g of the 8% by mass size liquid used in the above viscosity measurement was collected in a centrifuge tube, diluted with about 40 ml of warm water at about 50 ° C., and then centrifuged at 3000 rpm for 10 minutes. After centrifugation, the supernatant was discarded, and the precipitate was suspended again in about 40 ml of warm water and centrifuged again. The supernatant was discarded, and the precipitate was poured into an aluminum cup of known weight with distilled water and dried at 105 ° C. overnight. The weight after drying was taken as the collection weight (precipitation weight) and divided by the weight of starch in the size liquid (weight of the size liquid × 8/100) to obtain the precipitation rate (the ratio of starch in the size liquid that precipitated).
Table 1 shows the measurement results.
表１に示した通り、各酸の添加量が所望の範囲でありかつ糊液ｐＨが所望の範囲である変性でん粉（試料１１〜試料１７、試料１９、試料２２〜試料２５）は、糊液の粘度が十分に低く、沈殿率が１．０％以下と極めて低かった。ただし、尿素を４％添加した試料２４及び試料２５は、３ヶ月保存後のでん粉組成物について同様に糊液の粘度を測定したところ、表１に示した調整直後のものと比べ粘度が大きく上昇しており（データ省略）、保存安定性に問題があった。一方で、各酸の添加量や糊液ｐＨが所望の範囲を満たさない変性でん粉は、いずれも糊液の沈殿率が２％を越える高い値であった。でん粉糊液において沈殿が多いと、製紙工程においてフィルターやストレーナーに詰まりが生じる、糊液の均質性が大きく低下する、塗工ロールに汚れが付着するという点で大きな問題となる。また、糊液の沈殿率は、糊液老化安定性の指標であり、沈殿率の高い糊液は老化しやすいため糊液の保存安定性が低いといえる。 As shown in Table 1, denatured starch (samples 11 to 17, sample 19, and samples 22 to 25) in which the amount of each acid added is in the desired range and the pH of the size liquid is in the desired range is the size liquid. Had a sufficiently low viscosity and an extremely low precipitation rate of 1.0% or less. However, for the samples 24 and 25 to which 4% urea was added, the viscosity of the paste liquid was measured in the same manner for the starch composition after storage for 3 months. As a result, the viscosity greatly increased as compared with those immediately after the adjustment shown in Table 1. (Data omitted), there was a problem with storage stability. On the other hand, the modified starches in which the amount of each acid added and the pH of the sizing solution did not satisfy the desired ranges all had high precipitation rates of the sizing solution exceeding 2%. If the starch paste liquid has a large amount of sediment, it becomes a serious problem in that the filter and the strainer are clogged in the paper making process, the homogeneity of the paste liquid is greatly reduced, and the coating roll is stained. Further, the sedimentation rate of the size liquid is an index of the size liquid aging stability, and it can be said that the size liquid having a high precipitation rate is easily aged and thus the storage stability of the size liquid is low.
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