JPH0753761B2 - Method for producing modified starch - Google Patents
Method for producing modified starchInfo
- Publication number
- JPH0753761B2 JPH0753761B2 JP61063659A JP6365986A JPH0753761B2 JP H0753761 B2 JPH0753761 B2 JP H0753761B2 JP 61063659 A JP61063659 A JP 61063659A JP 6365986 A JP6365986 A JP 6365986A JP H0753761 B2 JPH0753761 B2 JP H0753761B2
- Authority
- JP
- Japan
- Prior art keywords
- starch
- water
- modified
- mixed
- stirring
- 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.)
- Expired - Fee Related
Links
- 229920000881 Modified starch Polymers 0.000 title claims description 15
- 239000004368 Modified starch Substances 0.000 title claims description 15
- 235000019426 modified starch Nutrition 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920002472 Starch Polymers 0.000 claims description 40
- 235000019698 starch Nutrition 0.000 claims description 39
- 239000008107 starch Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 23
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 23
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 11
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 10
- 150000004645 aluminates Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229920001592 potato starch Polymers 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910001388 sodium aluminate Inorganic materials 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 229920002261 Corn starch Polymers 0.000 description 4
- 239000008120 corn starch Substances 0.000 description 4
- 229940099112 cornstarch Drugs 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 240000003183 Manihot esculenta Species 0.000 description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920000856 Amylose Polymers 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DJVJZONPMOOVCU-UHFFFAOYSA-N n-(hydroxymethyl)propanamide Chemical compound CCC(=O)NCO DJVJZONPMOOVCU-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229940116317 potato starch Drugs 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、変性ジメチルポリシロキサンを用いる変性澱
粉の製造方法に関するものであり、この変性澱粉は、耐
水性および耐油性を有する接着剤、バインダー、サイズ
剤、コーティング剤等に用いることができ、また、ポリ
マー用のてん料としても用いることができる。TECHNICAL FIELD The present invention relates to a method for producing a modified starch using a modified dimethylpolysiloxane, which comprises an adhesive and a binder having water resistance and oil resistance. It can also be used as a sizing agent, a coating agent, etc., and can also be used as a filler for polymers.
（従来の技術） 澱粉に耐水性を付与する方法として、エピクロルヒドリ
ンによるエーテル化、重合リン酸塩によるエステル化、
アルデヒドによるアセタール化等によって澱粉を架橋さ
せる方法がある。これらの架橋澱粉は、ある程度の耐水
性を有するが充分ではなく、糊になりにくく通常の塗布
方法を用いることが困難であり、また、造膜性がなく被
膜を形成しないという欠点がある。(Prior Art) As a method for imparting water resistance to starch, etherification with epichlorohydrin, esterification with polymerized phosphate,
There is a method of cross-linking starch by acetalization with aldehyde. These crosslinked starches have a certain degree of water resistance, but they are not sufficient, they are difficult to form into a paste, and it is difficult to use an ordinary coating method. Further, they have the disadvantage that they do not form a film and do not form a film.
また、Ｎ−メチロールプロピオンアミドエーテル化澱粉
（米国特許第3101330号公報）は、Ｎ−メチロール基を
有するので、塗布後、加熱または酸触媒によって三次元
化させ耐水性を発現させることができる。しかし、その
製造中において、酸アミド基が加水分解し、カルボキシ
エチル化物が生成するため耐水性を阻害したり、反応中
にＮ−メチロール基が縮合しゲル化するという問題点が
ある。Since N-methylolpropionamide etherified starch (US Pat. No. 3,101,330) has an N-methylol group, it can be made three-dimensional by heating or an acid catalyst after coating to exhibit water resistance. However, during its production, the acid amide group is hydrolyzed to form a carboxyethylated product, which impairs the water resistance and causes a problem that the N-methylol group is condensed and gels during the reaction.
さらに、オルガノシランを用いる澱粉の変性方法（特開
昭59−179501号公報、特開昭59−207902号公報）も提案
されているが、ケイ素化合物がモノマー単位で結合して
いるため耐水性および耐油性が弱いという問題点があ
る。Further, a method for modifying starch using organosilane has been proposed (JP-A-59-179501 and JP-A-59-207902). However, since the silicon compound is bonded in a monomer unit, water resistance and There is a problem that the oil resistance is weak.
（発明が解決しようとする問題点） 上記のように、エピクロルヒドリン、重合リン酸塩、ア
ルデヒド等による架橋澱粉は耐水性が充分でなく、Ｎ−
メチルロールプロピオンアミドエーテル化澱粉は、加熱
または酸触媒によって三次元化しないと耐水性が得られ
ない。またオルガノシランを用いる方法では耐水性およ
び耐油性が弱いという問題点があり、未だ耐水性および
耐油性が強く、製造および使用のし易い変性澱粉がない
のが現状である。(Problems to be Solved by the Invention) As described above, the cross-linked starch formed by epichlorohydrin, polymerized phosphate, aldehyde, etc., has insufficient water resistance, and N-
Methyl roll propionamide etherified starch cannot obtain water resistance unless it is three-dimensionalized by heating or acid catalyst. In addition, the method using an organosilane has a problem that the water resistance and oil resistance are weak, and the present situation is that there is no modified starch that has high water resistance and oil resistance and is easy to manufacture and use.
（問題点を解決するための手段） 上記の問題点を解決するため鋭意研究した結果、澱粉を
アルミン酸アルカリまたは水酸化アルカリを触媒とし
て、ケイ素化合物のポリマーである変性ジメチルポリシ
ロキサンと反応することにより得られた変性澱粉が強い
耐水性および耐油性を有することが見出された。(Means for Solving Problems) As a result of earnest research to solve the above problems, it was found that starch is reacted with modified dimethylpolysiloxane which is a polymer of silicon compound, using alkali aluminate or alkali hydroxide as a catalyst. It has been found that the modified starch obtained according to (1) has strong water resistance and oil resistance.
本発明の変性澱粉の製造方法は、変性ジメチルポリシロ
キサンを水に懸濁させ、この懸濁液に澱粉を投入し、そ
の後、アルミン酸アルカリまたは水酸化アルカリを加
え、充分撹拌しながら反応を行なう。ただし、アルミン
酸アルカリまたは水酸化アルカリは、澱粉を投入する前
に添加してもよい。反応温度は室温でもよいが、澱粉の
糊化温度以下の温度（一般には40℃ぐらい）に加熱する
方が有利である。According to the method for producing a modified starch of the present invention, a modified dimethylpolysiloxane is suspended in water, starch is added to this suspension, and then alkali aluminate or alkali hydroxide is added, and the reaction is carried out with sufficient stirring. . However, alkali aluminate or alkali hydroxide may be added before adding the starch. The reaction temperature may be room temperature, but it is advantageous to heat it to a temperature below the gelatinization temperature of starch (generally about 40 ° C.).
上記のように湿式で反応した場合は、反応後、公知の方
法により、水洗、脱水、乾燥することにより本願発明の
変性澱粉を得ることができる。When the reaction is carried out in a wet manner as described above, the modified starch of the present invention can be obtained by washing with water, dehydration and drying by a known method after the reaction.
また、澱粉を加熱し、糊液の状態にして、これに変性ジ
メチルポリシロキサンおよびアルミン酸アルカリまたは
水酸化アルカリを加えて反応させることも可能である。
澱粉を糊化した後の反応温度は澱粉の糊化温度以下でよ
い。It is also possible to heat the starch to make it into a paste solution, and add the modified dimethylpolysiloxane and alkali aluminate or alkali hydroxide to it to react.
The reaction temperature after gelatinizing the starch may be equal to or lower than the gelatinization temperature of the starch.
このように糊化反応で得られた本発明の変性澱粉は、そ
のまま用いることができ、またドラム乾燥等により乾燥
し、粉末化することもできる。Thus, the modified starch of the present invention obtained by the gelatinization reaction can be used as it is, or can be dried by drum drying or the like to be pulverized.
また、適当な混合または捏和装置を用いて、変性ジメチ
ルポリシロキサンとアルミン酸アルカリまたは水酸化ア
ルカリとを２〜50％の水分で澱粉と混合することによっ
て、澱粉の糊化温度より高い温度で短時間に作業するこ
とも可能になる。Further, by using a suitable mixing or kneading device, the modified dimethylpolysiloxane and the alkali aluminate or the alkali hydroxide are mixed with the starch at a water content of 2 to 50%, so that the temperature is higher than the gelatinization temperature of the starch. It is also possible to work in a short time.
アルミン酸アルカリは、５〜15％水溶液として、または
固形物として使用され、アルミン酸ナトリウムが有利に
用いられる。添加量は、澱粉に対して0.005〜10％であ
る。The alkali aluminate is used as a 5 to 15% aqueous solution or as a solid, and sodium aluminate is advantageously used. The added amount is 0.005 to 10% with respect to starch.
水酸化アルカリは、水溶液（10％以下）として、または
固形物として使用され、水酸化ナトリウム、水酸化カリ
ウムが有利に用いられる。添加量は0.005〜４％であ
る。ただし、アルカリ濃度が高くて、澱粉が糊化してし
まう場合には、適量の硫酸ナトリウムをあらかじめ溶解
しておくとよい。Alkali hydroxide is used as an aqueous solution (10% or less) or as a solid, and sodium hydroxide and potassium hydroxide are advantageously used. The added amount is 0.005 to 4%. However, if the starch is gelatinized due to a high alkali concentration, it is preferable to dissolve an appropriate amount of sodium sulfate in advance.
本発明の変性澱粉を製造するのに使用されうる澱粉原料
としては、例えば、小麦澱粉、馬鈴薯澱粉、トウモロコ
シ澱粉、甘藷澱粉、タピオカ澱粉、サゴ澱粉、米澱粉、
モチトウモロコシ澱粉、高アミロース含有トウモロコシ
澱粉などの未処理澱粉もしくは小麦粉、タピオカ粉末、
コーンフラワー、米粉等の澱粉含有物、またはこれらの
エーテル化、エステル化、架橋化、酸化、酸処理化等を
行ったものも挙げられる。Examples of the starch raw material that can be used to produce the modified starch of the present invention include, for example, wheat starch, potato starch, corn starch, sweet potato starch, tapioca starch, sago starch, rice starch,
Waxy corn starch, untreated starch or wheat flour such as corn starch with high amylose content, tapioca powder,
Also included are starch-containing substances such as corn flour and rice flour, and those obtained by subjecting these to etherification, esterification, crosslinking, oxidation, acid treatment and the like.
本発明において、変性剤として用いることのできる変性
ジメチルポリシロキサンは下記の一般式で示される。In the present invention, the modified dimethylpolysiloxane that can be used as the modifier is represented by the following general formula.
〔式中Ｘは、場合により置換されたアミノ基、または−
Cl、−CH＝CH2および の群からの基を表わし、ｍは整数、ｎは１〜20の整数、
平均分子量は1000〜100000である。〕 また、変性ジメチルポリシロキサンの添加量は澱粉に対
して0.01〜10％である。 [Wherein X is an optionally substituted amino group, or-
Cl, -CH = CH 2 and Represents a group from the group of, m is an integer, n is an integer from 1 to 20,
The average molecular weight is 1000-100,000. The amount of the modified dimethylpolysiloxane added is 0.01 to 10% with respect to the starch.
（作用） 本発明の変性澱粉は、ごく少量の変性ジメチルポリシロ
キサンを使用されるだけで疎水性および疎油性を示す。
本発明の変性澱粉を紙や板に塗布、含浸等を行なうと、
その表面を澱粉に結合されたジメチルポリシロキサンが
おおうため、耐水性、耐油性が発現する。また、二次的
な効果として、紙の強度が向上する。(Function) The modified starch of the present invention exhibits hydrophobicity and oleophobicity even if only a small amount of modified dimethylpolysiloxane is used.
When the modified starch of the present invention is applied to paper or a plate, impregnated, etc.,
Since its surface is covered with dimethylpolysiloxane bound to starch, water resistance and oil resistance are exhibited. Further, as a secondary effect, the strength of the paper is improved.
本発明の変性澱粉の糊液は、その原料澱粉よりも高い粘
度を示すが、顔料の分散に不利な作用をしない。The modified starch paste solution of the present invention has a higher viscosity than the starting starch, but does not adversely affect the dispersion of the pigment.
（実施例および発明の効果） （実施例１） エポキシ変性ジメチルポリシロキサン（KF−102 信越
化学工業（株）製造、エポキシ当量4000）0.4gを水400g
中に撹拌混合した。15分後、馬鈴薯澱粉200gを撹拌混合
した。アルミン酸ナトリウム0.82gを約10％の溶液にし
て撹拌混合した。この混合物を撹拌下に急速に40℃に加
熱し、引き続き６時間室温で撹拌しながら放置した。そ
の後、澱粉を瀘別、洗浄し、乾燥した。(Effects of Examples and Inventions) (Example 1) 0.4 g of epoxy-modified dimethylpolysiloxane (KF-102 manufactured by Shin-Etsu Chemical Co., Ltd., epoxy equivalent 4000) and 400 g of water
Stir-mixed in. After 15 minutes, 200 g of potato starch was mixed with stirring. 0.82 g of sodium aluminate was made into a solution of about 10% and mixed by stirring. The mixture was rapidly heated to 40 ° C. with stirring and then left to stir at room temperature for 6 hours. Then, the starch was filtered, washed and dried.
この方法で得られた澱粉のケイ素含有は0.0652％であ
り、澱粉の提供されたケイ素の約86％が澱粉により固定
された。The silicon content of the starch obtained by this method was 0.0652%, and about 86% of the provided silicon of the starch was fixed by the starch.
変性された澱粉の湿潤試験を行ない、少量の澱粉をビー
カー中に存在するイオン交換水に加えた。この場合、全
澱粉量は少なくとも24時間水に浮いたままであった。The modified starch was wet tested and a small amount of starch was added to the ion exchange water present in the beaker. In this case, the total amount of starch remained floating in water for at least 24 hours.
２％の濃度の糊液に瀘紙を浸した後、乾燥すると、瀘紙
は疎水性を示した。When the paper was soaked in a paste solution having a concentration of 2% and then dried, the paper showed a hydrophobic property.
５％の濃度で粘度を測定すると9660cps（30℃）であ
り、原料の馬鈴薯澱粉よりも著しい粘度上昇が認められ
た。When the viscosity was measured at a concentration of 5%, it was 9660 cps (30 ° C.), and a remarkable increase in viscosity was recognized as compared with the raw material potato starch.
（実施例２） エポキシ変性ジメチルポリシロキサン（KF−102）0.4g
を水400g中に撹拌混合した。15粉後、コーンスターチ20
0gを撹拌混合した。アルミン酸ナトリウム0.82gを約10
％の溶液にして撹拌混合した。この混合物を撹拌下に急
速に40℃に加熱し、引き続き６時間室温で撹拌しながら
放置した。その後、澱粉を瀘別、洗浄し、乾燥した。(Example 2) 0.4 g of epoxy-modified dimethylpolysiloxane (KF-102)
Was mixed with stirring in 400 g of water. After 15 powders, cornstarch 20
0 g was mixed with stirring. Sodium aluminate 0.82g about 10
% Solution and mixed with stirring. The mixture was rapidly heated to 40 ° C. with stirring and then left to stir at room temperature for 6 hours. Then, the starch was filtered, washed and dried.
湿潤試験において実施例１と同様の結果が得られた。In the wet test, the same results as in Example 1 were obtained.
濃度２％の糊液に浸した後、乾燥した瀘紙も、実施例１
の場合と同様に疎水性を示した。Example 1 was also applied to the paper paper which was dried after being dipped in a paste solution having a concentration of 2%.
It showed hydrophobicity as in the case of.
（実施例３） エポキシ変性ジメチルポリシロキサン（分子量約1000
0）0.4gを水20mlの懸濁液にして馬鈴薯澱粉2000と混合
機中で混合し、これにアルミン酸ナトリウム0.82gを約1
0％の水溶液にして添加混合した。この混合物を40〜50
℃で３時間加熱した。冷却後、水に投入し瀘過、洗浄、
乾燥を行なった。(Example 3) Epoxy-modified dimethyl polysiloxane (molecular weight about 1000)
0) 0.4 g of water in 20 ml of suspension was mixed with potato starch 2000 in a mixer, to which 0.82 g of sodium aluminate was added to about 1 part.
A 0% aqueous solution was added and mixed. 40-50 this mixture
Heated at ° C for 3 hours. After cooling, put into water and filter, wash,
It was dried.
湿潤試験において実施例１と同様の結果が得られた。In the wet test, the same results as in Example 1 were obtained.
（実施例４） エポキシ変性ジメチルポリシロキサン（分子量約10000
0）0.4gを40℃のウォーターバス中で水800g中に撹拌混
合した。15分後、馬鈴薯澱粉400gを撹拌混合した。アル
ミン酸ナトリウム1.64gを約10％の水溶液にして撹拌混
合した。引き続き４時間撹拌した。その後、澱粉を瀘
別、洗浄し乾燥した。(Example 4) Epoxy-modified dimethylpolysiloxane (molecular weight of about 10,000
0) 0.4 g was stirred and mixed in 800 g of water in a 40 ° C. water bath. After 15 minutes, 400 g of potato starch was mixed with stirring. 1.64 g of sodium aluminate was made into an aqueous solution of about 10% and mixed with stirring. The mixture was subsequently stirred for 4 hours. Then, the starch was filtered, washed and dried.
湿潤試験、瀘紙の疎水性ともに実施例１と同様の結果が
得られた。The same results as in Example 1 were obtained in both the wet test and the hydrophobicity of the paper.
２％の濃度の糊液で浸含した瀘紙を乾燥し以下の試験を
行なった。The paper filter impregnated with a paste solution having a concentration of 2% was dried and subjected to the following test.
１）グラスマーカーペン（溶剤としてトルオールを用い
ている）で書くと、色はにじまず、紙の裏にはうつらな
かった。1) When I wrote with a glass marker pen (using toluol as a solvent), the color did not bleed and it was not transferred to the back of the paper.
２）瀘紙上に液状パラフィンを１滴滴下すると、液滴は
そのまま存在し、紙中にしみこんでいかない。2) When one drop of liquid paraffin is dropped on the paper, the drop remains and does not soak into the paper.
（実施例５） エポキシ変性ジメチルポリシロキサン（分子量約1000）
0.2gを40℃のウォーターバス中で水260g中に撹拌混合し
た。15分後、水酸化ナトリウム0.4gを約10％水溶液にし
て撹拌混合し、続いて馬鈴薯澱粉200gを撹拌混合した。
引き続き４時間撹拌した。その後、混合物を希塩酸でPH
6〜８に中和し、瀘過、洗浄し乾燥した。(Example 5) Epoxy-modified dimethylpolysiloxane (molecular weight about 1000)
0.2 g was stirred and mixed in 260 g of water in a 40 ° C. water bath. After 15 minutes, 0.4 g of sodium hydroxide was made into an aqueous solution of about 10% and mixed with stirring, and subsequently 200 g of potato starch was mixed with stirring.
The mixture was subsequently stirred for 4 hours. Then, the mixture is diluted with dilute hydrochloric acid to PH.
It was neutralized to 6-8, filtered, washed and dried.
湿潤試験、瀘紙の疎水性ともに実施例１と同様の結果が
得られた。The same results as in Example 1 were obtained in both the wet test and the hydrophobicity of the paper.
（実施例６） エポキシ変性ジメチルポリシロキサン（分子量約4000）
0.4gを40℃のウォーターバス中で水260g中に撹拌混合し
た。これに硫酸ナトリウム100gを加え撹拌溶解した後、
水酸化ナトリウム4gを加えた。これにタピオカ酸化澱粉
200gを撹拌混合し、４時間撹拌し続けた。その後、混合
物を希塩酸でPH6〜８に中和し、瀘過、洗浄し乾燥し
た。(Example 6) Epoxy-modified dimethylpolysiloxane (molecular weight about 4000)
0.4 g was stirred and mixed in 260 g of water in a 40 ° C. water bath. After adding sodium sulfate 100 g to this and stirring to dissolve,
4 g of sodium hydroxide was added. Tapioca oxidized starch
200 g was mixed by stirring and the stirring was continued for 4 hours. Then, the mixture was neutralized to pH 6-8 with dilute hydrochloric acid, filtered, washed and dried.
湿潤試験、瀘紙の疎水性ともに実施例１と同様の結果が
得られた。The same results as in Example 1 were obtained in both the wet test and the hydrophobicity of the paper.
（実施例７） エポキシ変性ジメチルポリシロキサン（分子量約1000
0）0.4gを40℃のウォーターバス中で水260g中に撹拌混
合した。これにカチオン変性澱粉200gを撹拌混合した。
アルミン酸ナトリウム1.64gを約10％の水溶液にて撹拌
混合し、４時間撹拌し続けた。その後、瀘過、洗浄、乾
燥した。(Example 7) Epoxy-modified dimethyl polysiloxane (molecular weight of about 1000
0) 0.4 g was mixed with stirring in 260 g of water in a water bath at 40 ° C. To this, 200 g of cation-modified starch was mixed with stirring.
1.64 g of sodium aluminate was stirred and mixed in an aqueous solution of about 10%, and the stirring was continued for 4 hours. Then, it was filtered, washed and dried.
湿潤試験、瀘紙の疎水性ともに実施例１と同様の結果が
得られた。The same results as in Example 1 were obtained in both the wet test and the hydrophobicity of the paper.
（実施例８） 馬鈴薯澱粉10gを水400gに、85℃以上の温度で糊状に
し、エポキシ変性ジメチルポリシロキサン（分子量約10
000）0.1gを撹拌下に加え、水酸化ナトリウム0.4gを10
％の溶液にして加えて添加した。その後、室温に冷却し
た。得られた溶液について瀘紙試験を行なうと、疎水性
を示した。Example 8 10 g of potato starch was made into a paste at a temperature of 85 ° C. or higher in 400 g of water, and epoxy modified dimethyl polysiloxane (molecular weight of about 10) was used.
000) 0.1 g with stirring and 0.4 g of sodium hydroxide to 10
% Solution was added and added. Then, it cooled to room temperature. When a paper filter test was conducted on the obtained solution, it showed hydrophobicity.
中和後、全溶液をロータリーエバポレーターで蒸発乾固
した。その際に得られた粉末の２％の濃度の水溶液は、
再び同じ疎水性を示した。After neutralization, the whole solution was evaporated to dryness on a rotary evaporator. An aqueous solution having a concentration of 2% of the powder obtained at that time is
It again showed the same hydrophobicity.
（実施例９） 馬鈴薯澱粉10gを水400gに85℃以上の温度で糊化させた
後、ビニル変性ジメチルポリシロキサン（分子量約1000
0）0.1gを撹拌下に加え、アルミン酸ナトリウム0.12gを
水5mlに溶解して加えた。その後、室温に冷却した。Example 9 10 g of potato starch was gelatinized in 400 g of water at a temperature of 85 ° C. or higher, and then vinyl-modified dimethylpolysiloxane (molecular weight about 1000) was used.
0) 0.1 g was added with stirring, and 0.12 g of sodium aluminate was dissolved in 5 ml of water and added. Then, it cooled to room temperature.
瀘紙試験を行なうと、変性澱粉溶液で含浸した後も、蒸
発乾固した後の粉末による溶液で含浸した後も瀘紙は疎
水性を示した。When the paper filter test was carried out, the paper filter was hydrophobic both after impregnation with the modified starch solution and after impregnation with the solution of the powder after evaporation to dryness.
（比較例１） エポキシ変性ジメチルポリシロキサン（KF−102）0.4g
を馬鈴薯澱粉200gと混合した。この混合物について湿潤
試験を行なうと澱粉はただちに沈降し始めた。(Comparative Example 1) 0.4 g of epoxy-modified dimethylpolysiloxane (KF-102)
Was mixed with 200 g of potato starch. When a wet test was performed on this mixture, starch immediately began to settle.
また、この２％の濃度の糊液に瀘紙を浸した後乾燥して
も瀘紙は疎水性を示さなかった。Further, even when the paper was soaked in the paste solution having a concentration of 2% and then dried, the paper did not show hydrophobicity.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−27930（ＪＰ，Ａ) 特開 昭59−179501（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-59-27930 (JP, A) JP-A-59-179501 (JP, A)
Claims (4)
ルカリを触媒として、変性ジメチルポリシロキサンと反
応させることを特徴とする変性澱粉の製造方法。1. A method for producing a modified starch, which comprises reacting the starch with a modified dimethylpolysiloxane using an alkali aluminate or an alkali hydroxide as a catalyst.
せ、この懸濁液に澱粉を投入し、その後、アルミン酸ア
ルカリまたは水酸化アルカリを添加し、得られた懸濁液
を45℃までの温度で撹拌する、特許請求の範囲第（１）
項記載の方法。2. A modified dimethylpolysiloxane is suspended in water, starch is added to this suspension, and then an alkali aluminate or an alkali hydroxide is added, and the resulting suspension is heated to 45 ° C. Stirring at temperature, Claim (1)
Method described in section.
変性ジメチルポリシロキサンとアルミン酸アルカリまた
は水酸化アルカリを添加する、特許請求の範囲第（１）
項記載の方法。3. A starch solution and water are heated to form a paste solution, and the modified dimethylpolysiloxane and alkali aluminate or alkali hydroxide are added to the paste solution.
Method described in section.
ルポリシロキサンとアルミン酸アルカリまたは水酸化ア
ルカリとを２〜50％の水分で澱粉と混合する、特許請求
の範囲第（１）項記載の方法。4. The method according to claim 1, wherein the modified dimethylpolysiloxane and alkali aluminate or alkali hydroxide are mixed with the starch at a water content of 2 to 50% by using a mixing or kneading device. the method of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61063659A JPH0753761B2 (en) | 1986-03-19 | 1986-03-19 | Method for producing modified starch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61063659A JPH0753761B2 (en) | 1986-03-19 | 1986-03-19 | Method for producing modified starch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62218401A JPS62218401A (en) | 1987-09-25 |
| JPH0753761B2 true JPH0753761B2 (en) | 1995-06-07 |
Family
ID=13235695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61063659A Expired - Fee Related JPH0753761B2 (en) | 1986-03-19 | 1986-03-19 | Method for producing modified starch |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0753761B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5927930A (en) * | 1982-07-06 | 1984-02-14 | ダウ コ−ニング コ−ポレ−ション | Manufacture of silicone-treated starch and use |
| DE3310088A1 (en) * | 1983-03-21 | 1984-09-27 | Dynamit Nobel Ag, 5210 Troisdorf | METHOD FOR MODIFYING STARCH IN THE AQUEOUS MEDIUM |
-
1986
- 1986-03-19 JP JP61063659A patent/JPH0753761B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62218401A (en) | 1987-09-25 |
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