JPS625165B2 - - Google Patents
Info
- Publication number
- JPS625165B2 JPS625165B2 JP54023958A JP2395879A JPS625165B2 JP S625165 B2 JPS625165 B2 JP S625165B2 JP 54023958 A JP54023958 A JP 54023958A JP 2395879 A JP2395879 A JP 2395879A JP S625165 B2 JPS625165 B2 JP S625165B2
- Authority
- JP
- Japan
- Prior art keywords
- starch
- graft
- acid
- modified starch
- hydrogen
- 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
Links
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- Graft Or Block Polymers (AREA)
Description
本発明は皮膜強度および接着力が改善され更に
金属に対する密着性、防食性、繊維に使用した場
合の防炎性の改善されたグラフト変性澱粉の製造
法に関する。
従来から澱粉は接着剤、繊維や紙のサイジング
剤、各種水溶性フイルムおよび成型素材に広く用
いられている。しかしながら、皮膜強度、接着
力、柔軟性更に金属に対する密着性、防食性、繊
維に使用した場合の防炎性の優れた澱粉が見い出
せないまま今日に至つている。
本発明者らはこれらの欠点を改良すべく鋭意研
究を重ねた結果、澱粉類に下記なる一般式よりな
るリン原子を含有するアクリル酸および／または
メタアクリル酸エステルより選ばれる１種または
２種以上を必須モノマーとしてグラフト共重合す
ることにより得られることを見い出し本発明を完
成した。
〔式中、R1は水素またはメチル、R2、R3は水素ま
たは炭素数１〜５のアルキルもしくはそのハロゲ
ン化物またはアルカリ金属、アルカリ土類金属、
および１級、２級、３級脂肪族アミンを意味す
る〕
該グラフト変性澱粉に用いる原料澱粉としては
通常この種のものに用いられているものでよく、
馬鈴薯澱粉、甘藷澱粉、トウモロコシ澱粉、モチ
トウモロコシ澱粉、高アミローストウモロコシ澱
粉、小麦澱粉、米澱粉、タピオカ澱粉、サゴ澱粉
などの天然澱粉やこれらの分解物、アミロースや
アミロペクチン分画物、架橋澱粉、エーテル化澱
粉、エステル化澱粉、酸化澱粉、酸処理澱粉、グ
ラフト変性澱粉、酵素処理澱粉、デキストリンな
どの化工澱粉、小麦粉、トウモロコシ粉、切干甘
藷、切干タピオカなどの澱粉含有物が挙げられ
る。
これらの原料澱粉とモノマーのグラフト重合反
応は水を溶媒として、第二セリウム塩、過硫酸
塩、過硫酸塩−亜硫酸塩、過酸化水素−モール塩
などの通常のグラフト重合開始剤を用い、10〜
100℃、好ましくは15〜45℃で常法に従つて行う
ことができる。グラフト率は0.01〜100％、好ま
しくは0.01〜50％とし、かかるグラフト率にする
ことにより水溶性のグラフト変性澱粉が製造でき
る。グラフト率が0.01％以下の場合、澱粉の十分
なる改質が行なえず、100％を越えると不溶性と
なり好ましくない。ここに言うグラフト率とはグ
ラフト重合による重量増加の用いた原料澱粉重量
に対する百分率を意味する。
本発明で用いるグラフト変性澱粉はグラフト側
鎖に、常法に従つてグラフト重合の前または後、
あるいはグラフト重合と同時に他の共重合可能な
モノマー、例えば酢酸ビニル、アクリルアミド、
アクリル酸、アクリル酸アルキルエステル、メタ
アクリル酸、メタアクリル酸アルキルエステル、
アクリロニトリル、スチレン、無水マレイン酸、
イタコン酸等の不飽和結合性モノマーなどと共重
合してもよい。かかるモノマーを共重合させる場
合、本発明の必須とするモノマーに対する割合は
適宜選択できるが、該エステルの重量と同じかま
たはそれ以下が好ましい。
また、該グラフト変性澱粉は水溶性であること
が必要で、用いる原料澱粉やモノマーによつては
そのグラフト側鎖の部分を塩酸、硝酸、硫酸など
の鉱酸あるいは水酸化ナトリウム、水酸化カリウ
ムなどのアルカリ金属水酸化物、アンモニア、ア
ルキルアミンなどのアルカリを触媒とし、メタノ
ール、エタノール、プロパノール、ブタノールな
どのアルコール、アセトン、アセトニトリルなど
の有機溶媒、水またはこれらの混合溶媒中で加水
分解、エステル交換、ケン化などしてグラフト側
鎖に親水基を導入することも本発明に含まれる。
また本発明の必須とするモノマーにアクリル酸
またはメタアクリル酸をグラフト共重合の前また
は同時あるいは後に共重合させても同様の水溶性
の高いグラフト変性澱粉が得られこれも本発明に
含まれる。
かくして得られるグラフト変性澱粉は柔軟性に
富みかつ優れた造膜性を示し皮膜強度、接着力に
優れ、金属に対する密着性、防食性、繊維に使用
した場合の防炎性が優れているので接着剤あるい
は繊維や紙のサイジング剤、コーテイング剤、内
添剤、各種の加工および成型素材に用いることが
でき、特に金属メツキ、塗装の前処理剤、抑制剤
として有用で、繊維の耐炎性仕上糊、耐炎性壁接
着剤として優れている。
次に実施例を挙げて本発明を更に詳しく説明す
る。
実施例 １
コーンスターチ３Kgを水10中に分散させ、40
℃にてモノ（２−ヒドロキシエチルメタアクリレ
ート）アシツドフオスフエート２Kg、硝酸第二セ
リウムアンモニウム10ml、硝酸５mlを加えて撹拌
下、40℃、５時間反応させる。反応後中和、水洗
を行ないグラフト率57％の澱粉−ポリモノ（２−
ヒドロキシエチルメタアクリレート）アシツドフ
オスフエートグラフト共重合体を得た。
実施例 ２
酸化澱粉３Kgを水10中に分散させ、80℃で20
分間加熱糊化させる。25℃に冷却し、モール塩10
ｇ、モノ（２−ヒドロキシエチルアクリレート）
アシツドフオスフエート１Kg、アクリル酸300
ｇ、過酸化水素25mlを加え、撹拌下25℃で５時間
反応させる。反応後水洗を行ないモノ（２−ヒド
ロキシエチルアクリレート）アシツドフオスフエ
ートのグラフト率48％、アクリル酸のグラフト率
６％の酸化澱粉−ポリモノ（２−ヒドロキシエチ
ルアクリレート）アシツドフオスフエート−ポリ
アクリル酸グラフト共重合体を得た。
実施例 ３
酸処理澱粉３Kgを水10中に分散させ、85℃で
30分間加熱糊化させ、35℃に冷却し、２−ジ（２
−クロロエチル）フオスフエートプロピルアクリ
レート1.0Kg、硝酸第二セリウムアンモニウム20
ｇ、硝酸10mlを加え撹拌下、35℃で３時間重合反
応させ、グラフト反応が終了した後、水酸化ナト
リウム30ｇ添加し、90℃で４時間側鎖のアクリル
酸エステル部分を部分ケン化し、塩酸にて中和を
行ない、２−ジ（２−クロロエチル）フオスフエ
ートプロピルアクリレートのグラフト率18％、ア
クリル酸ソーダのグラフト率２％の酸処理澱粉−
ポリ２−ジ（２−クロロエチル）フオスフエート
プロピルアクリレート−ポリアクリル酸ソーダグ
ラフト共重合体を得た。
実施例 ４
タピオカ澱粉３Kgを水10中に分散させ、モー
ル塩10ｇ、ジエチルフオスフエートエチルアクリ
レート300ｇ、２−ヒドロキシエチルメタクリレ
ート50ｇ、過酸化水素25mlを加え、撹拌下30℃で
２時間反応させる。反応後水洗を行ないジエチル
フオスフエートエチルアクリレートのグラフト率
7.6％、２−ヒドロキシエチルメタアクリレート
のグラフト率１％のタピオカ澱粉−ポリジエチル
フオスフエートエチルアクリレート−ポリ２−ヒ
ドロキシエチルアクリレートグラフト共重合体を
得た。
実施例 ５
実施例１〜４によつて得られたグラフト変性澱
粉および未変性のタピオカ澱粉より糊液を調整
し、10cm×10cmの枠でポリエステルフイルム上に
25℃にて皮膜を作り各種試験を行なつた。
The present invention relates to a method for producing graft-modified starch that has improved film strength and adhesive strength, and also has improved adhesion to metals, corrosion resistance, and flame resistance when used in fibers. Starch has been widely used in adhesives, fiber and paper sizing agents, various water-soluble films, and molding materials. However, to date, no starch has been found that has excellent film strength, adhesive strength, flexibility, adhesion to metals, corrosion resistance, and flame retardant properties when used in fibers. As a result of intensive research to improve these drawbacks, the present inventors have found that one or two types selected from acrylic acid and/or methacrylic acid esters containing a phosphorus atom represented by the following general formula are added to starch. It was discovered that the above can be obtained by graft copolymerization using essential monomers, and the present invention was completed. [In the formula, R 1 is hydrogen or methyl, R 2 and R 3 are hydrogen, alkyl having 1 to 5 carbon atoms, or a halide thereof, an alkali metal, an alkaline earth metal,
and primary, secondary, and tertiary aliphatic amines] The raw material starch used for the graft-modified starch may be those normally used for this type of starch,
Natural starches such as potato starch, sweet potato starch, corn starch, waxy corn starch, high amylose corn starch, wheat starch, rice starch, tapioca starch, sago starch and their decomposition products, amylose and amylopectin fractions, cross-linked starches, ethers Examples include modified starch, esterified starch, oxidized starch, acid-treated starch, graft-modified starch, enzyme-treated starch, modified starch such as dextrin, and starch-containing substances such as wheat flour, corn flour, dried sweet potato, and dried tapioca. Graft polymerization reactions between these raw material starches and monomers are carried out using water as a solvent and common graft polymerization initiators such as ceric salts, persulfates, persulfate-sulfites, and hydrogen peroxide-Mohr's salts. ~
It can be carried out according to a conventional method at 100°C, preferably 15 to 45°C. The grafting rate is 0.01 to 100%, preferably 0.01 to 50%, and by setting this grafting rate, water-soluble graft-modified starch can be produced. When the grafting rate is less than 0.01%, the starch cannot be sufficiently modified, and when it exceeds 100%, it becomes insoluble, which is not preferable. The graft ratio referred to herein means the percentage of weight increase due to graft polymerization relative to the weight of the raw material starch used. The graft-modified starch used in the present invention is added to the graft side chain by a conventional method before or after graft polymerization.
Alternatively, other monomers that can be copolymerized simultaneously with graft polymerization, such as vinyl acetate, acrylamide,
Acrylic acid, acrylic acid alkyl ester, methacrylic acid, methacrylic acid alkyl ester,
Acrylonitrile, styrene, maleic anhydride,
It may also be copolymerized with unsaturated bonding monomers such as itaconic acid. When such a monomer is copolymerized, the proportion of the monomer essential to the present invention can be selected as appropriate, but it is preferably the same as or less than the weight of the ester. In addition, the graft-modified starch must be water-soluble, and depending on the raw material starch and monomer used, the graft side chain may be treated with a mineral acid such as hydrochloric acid, nitric acid, or sulfuric acid, or with sodium hydroxide or potassium hydroxide. Hydrolysis and transesterification in alcohols such as methanol, ethanol, propanol, butanol, organic solvents such as acetone and acetonitrile, water, or a mixture of these using an alkali such as alkali metal hydroxide, ammonia, or an alkylamine as a catalyst. The present invention also includes introducing a hydrophilic group into the graft side chain by saponification or the like. Further, even if acrylic acid or methacrylic acid is copolymerized with the essential monomer of the present invention before, simultaneously, or after the graft copolymerization, a similar graft-modified starch with high water solubility can be obtained, and this is also included in the present invention. The graft-modified starch obtained in this way is highly flexible and has excellent film-forming properties, and has excellent film strength and adhesive strength, as well as adhesion to metals, corrosion resistance, and flame resistance when used on fibers, making it suitable for adhesion. It can be used as a sizing agent for fibers and paper, a coating agent, an internal additive, and various processing and molding materials.It is especially useful as a pretreatment agent and inhibitor for metal plating and painting, and as a flame-resistant finishing glue for fibers. , excellent as a flame-resistant wall adhesive. Next, the present invention will be explained in more detail with reference to Examples. Example 1 3 kg of corn starch was dispersed in 10 kg of water,
2 kg of mono(2-hydroxyethyl methacrylate) acid phosphate, 10 ml of ceric ammonium nitrate, and 5 ml of nitric acid were added at 40° C. and reacted with stirring for 5 hours at 40° C. After the reaction, the starch-polymono(2-
A hydroxyethyl methacrylate) acid phosphate graft copolymer was obtained. Example 2 3 kg of oxidized starch was dispersed in 10 kg of water and heated at 80°C for 20 min.
Heat for a minute to gelatinize. Cool to 25 °C and add Mohr salt 10
g, mono(2-hydroxyethyl acrylate)
Acid phosphate 1Kg, acrylic acid 300
g, and 25 ml of hydrogen peroxide were added, and the mixture was allowed to react at 25°C for 5 hours with stirring. After the reaction, washing with water was performed to obtain oxidized starch-polymono(2-hydroxyethyl acrylate) acid phosphate-polymer with a grafting rate of 48% of mono(2-hydroxyethyl acrylate) acid phosphate and a grafting rate of 6% of acrylic acid. An acrylic acid graft copolymer was obtained. Example 3 3 kg of acid-treated starch was dispersed in 10 ml of water and heated at 85°C.
Heat to gelatinize for 30 minutes, cool to 35℃,
-chloroethyl) phosphate propyl acrylate 1.0Kg, ceric ammonium nitrate 20
g, 10 ml of nitric acid was added, and the polymerization reaction was carried out at 35°C for 3 hours with stirring. After the grafting reaction was completed, 30 g of sodium hydroxide was added, and the acrylic ester part of the side chain was partially saponified at 90°C for 4 hours, and then hydrochloric acid Acid-treated starch with a grafting rate of 18% of 2-di(2-chloroethyl)phosphatepropyl acrylate and a grafting rate of 2% of sodium acrylate.
A poly 2-di(2-chloroethyl) phosphate propyl acrylate-sodium polyacrylate graft copolymer was obtained. Example 4 3 kg of tapioca starch is dispersed in 10 g of water, 10 g of Mohr's salt, 300 g of diethyl phosphate ethyl acrylate, 50 g of 2-hydroxyethyl methacrylate, and 25 ml of hydrogen peroxide are added, and the mixture is reacted at 30° C. for 2 hours with stirring. After the reaction, wash with water to determine the grafting rate of diethyl phosphate ethyl acrylate.
A tapioca starch-polydiethyl phosphate ethyl acrylate-poly 2-hydroxyethyl acrylate graft copolymer was obtained with a grafting rate of 7.6% and 2-hydroxyethyl methacrylate of 1%. Example 5 A size solution was prepared from the graft-modified starch obtained in Examples 1 to 4 and unmodified tapioca starch, and was spread on a polyester film in a 10 cm x 10 cm frame.
Films were made at 25°C and various tests were conducted.
【表】
透明性：皮膜の透明度の特に優れたもの◎、
優れたもの○、好ましくないもの△
実施例 ６
実施例１〜２によつて得られたグラフト変性澱
粉および未変性のタピオカ澱粉より糊液を調整
し、各種被接着体への接着性試験を行なつた。[Table] Transparency: Especially excellent film transparency◎,
Excellent ○, Unfavorable △
Example 6 A size solution was prepared from the graft-modified starch and unmodified tapioca starch obtained in Examples 1 and 2, and an adhesion test to various adherends was conducted.
【表】
接着性の特に優れたもの◎、優れたもの○、
接着性のあまりないもの△、ないもの×。
[Table] Particularly excellent adhesion ◎, Excellent ○,
Those with little adhesiveness △, those with no adhesiveness ×.
Claims (1)
選ばれる澱粉類にリン原子を含有するアクリル酸
エステルおよび／またはメタクリル酸エステルを
グラフト共重合することにより得られるグラフト
変性澱粉の製造法。 ２ 一般式 〔式中、R1は水素またはメチル、R2、R3は水素ま
たは炭素数１〜５のアルキルもしくはそのハロゲ
ン化物またはアルカリ金属、アルカリ土類金属、
および１級、２級、３級脂肪族アミンを意味す
る〕よりなるリン原子を含有するアクリル酸およ
び／またはメタアクリル酸エステルより選ばれる
１種または２種以上を必須モノマーとしてグラフ
ト共重合することにより得られる特許請求範囲第
１項のグラフト変性澱粉の製造法。[Scope of Claims] 1. Production of graft-modified starch obtained by graft copolymerizing phosphorus atom-containing acrylic ester and/or methacrylic ester to starch selected from naturally produced starches and/or various modified starches. Law. 2 General formula [In the formula, R 1 is hydrogen or methyl, R 2 and R 3 are hydrogen, alkyl having 1 to 5 carbon atoms, or a halide thereof, an alkali metal, an alkaline earth metal,
and primary, secondary, and tertiary aliphatic amines], as essential monomers, graft copolymerization with one or more selected from phosphorus atom-containing acrylic acid and/or methacrylic esters. A method for producing graft-modified starch according to claim 1 obtained by.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2395879A JPS55116715A (en) | 1979-02-28 | 1979-02-28 | Preparation of graft modified starch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2395879A JPS55116715A (en) | 1979-02-28 | 1979-02-28 | Preparation of graft modified starch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55116715A JPS55116715A (en) | 1980-09-08 |
| JPS625165B2 true JPS625165B2 (en) | 1987-02-03 |
Family
ID=12125047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2395879A Granted JPS55116715A (en) | 1979-02-28 | 1979-02-28 | Preparation of graft modified starch |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55116715A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120442118A (en) * | 2025-07-10 | 2025-08-08 | 国网安徽省电力有限公司电力科学研究院 | A flame retardant heat conductive polyacrylic acid fire retardant coating and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107558306B (en) * | 2017-08-08 | 2020-01-14 | 无锡海特新材料研究院有限公司 | Enhanced flame-retardant paperboard and manufacturing method thereof |
| CN107523245B (en) * | 2017-08-08 | 2019-08-27 | 无锡海特新材料研究院有限公司 | A kind of paperboard grade (stock) modified flame-retardant starch adhesive, preparation method and fire-retardant cardboard |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52138490A (en) * | 1976-05-17 | 1977-11-18 | Kurashiki Boseki Kk | Cellulose ion exchange fibers and manufacture |
-
1979
- 1979-02-28 JP JP2395879A patent/JPS55116715A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120442118A (en) * | 2025-07-10 | 2025-08-08 | 国网安徽省电力有限公司电力科学研究院 | A flame retardant heat conductive polyacrylic acid fire retardant coating and preparation method thereof |
| CN120442118B (en) * | 2025-07-10 | 2025-10-17 | 国网安徽省电力有限公司电力科学研究院 | A flame retardant heat conductive polyacrylic acid fire retardant coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55116715A (en) | 1980-09-08 |
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