JP2788298B2 - Papermaking method - Google Patents
Papermaking methodInfo
- Publication number
- JP2788298B2 JP2788298B2 JP1223874A JP22387489A JP2788298B2 JP 2788298 B2 JP2788298 B2 JP 2788298B2 JP 1223874 A JP1223874 A JP 1223874A JP 22387489 A JP22387489 A JP 22387489A JP 2788298 B2 JP2788298 B2 JP 2788298B2
- Authority
- JP
- Japan
- Prior art keywords
- starch
- weight
- paper
- urea
- present
- 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
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/54—Starch
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
- D21H17/28—Starch
Landscapes
- Paper (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は紙または板紙の抄紙時に、紙表面強度、紙層
内強度および／もしくは紙層間強度等を向上させるため
に改善されたスプレー用澱粉を使用する抄紙方法に関す
る。Description: FIELD OF THE INVENTION The present invention relates to an improved starch for spraying to improve paper surface strength, paper layer strength and / or paper layer strength during papermaking of paper or paperboard. And a papermaking method using the same.
（従来の技術） 製紙工場において一般的に使用されているスプレー用
澱粉は大きく二つに分けられ、一つは生澱粉（例えばコ
ーンスターチ、馬鈴薯澱粉、タピオカ等）であり、もう
一つは加工澱粉（例えば、尿素・リン酸澱粉、アセチル
化澱粉等）である。(Prior Art) Spray starch generally used in paper mills is roughly divided into two types, one is raw starch (for example, corn starch, potato starch, tapioca, etc.) and the other is processed starch. (Eg, urea / phosphate starch, acetylated starch, etc.).
前者は糊化開始温度が高く、通常の抄紙機では十分に
糊化しえず、例えば多層抄合板紙の場合、層間剥離の問
題を生じている。又、澱粉の粒子径は馬鈴薯澱粉を除き
一般に小さいので紙に塗布した場合、紙を透過してしま
い十分に紙層内に生澱粉を担持出来ない（即ち歩留りが
低い。）。この結果十分な強度を紙に付与することが出
来ず、又抄紙機の用具汚れや廃水負荷上昇の原因になる
という問題を有する。The former has a high gelatinization starting temperature and cannot be sufficiently gelatinized by an ordinary paper machine. For example, in the case of a multilayer composite paperboard, a problem of delamination occurs. In addition, since the particle size of starch is generally small except for potato starch, when it is applied to paper, it penetrates the paper and cannot fully support raw starch in the paper layer (that is, the yield is low). As a result, there is a problem that sufficient strength cannot be imparted to the paper and that the paper machine tool becomes dirty and the wastewater load increases.
後者に於いて、尿素・リン酸エステル化澱粉は生澱粉
より５〜20℃糊化開始温度を低下させてあるので、広い
範囲のより多くの抄紙機乾燥工程において十分糊化する
ことが出来、又上記歩留りも十分であるので紙の強度向
上に貢献している。しかしながら尿素・リン酸エステル
化澱粉には従来より、大きな欠点があることが知られて
いる。すなわち、尿素・リン酸エステル化澱粉は屡々抄
紙機ワイヤーの目詰を発生し、運転停止という重大なト
ラブルを引き起こす。特にパルプスラリー中のpHが低い
場合にこの現象が顕著に現れる。尿素・リン酸エステル
化澱粉はこの欠点のため低pH領域の抄紙機には使用でき
ないという制限があった。しかしながら、どうしても紙
強度ということに重点を置いた場合に尿素・リン酸エス
テル化澱粉を使わざるを得ず、その場合、頻繁にワイヤ
ーの洗浄、交換等で対処してきたのが実状であり、その
度に抄紙機を停止せねばならず、又、ワイヤーの洗浄、
交換等の操作自体も大変な労力を要する。代表的な市販
の尿素・リン酸エステル化澱粉の結合リン原子および可
溶性リン原子含有量はそれぞれ0.3〜1.5重量％及び0.15
〜1.5重量％である。又、尿素・リン酸エステル化澱粉
以外の加工澱粉、例えばアセチル化澱粉のようなものに
ついては、糊化開始温度を低くすれば、抄紙機乾燥工程
において十分糊化させることは出来るが、歩留りが低
く、強度も不十分であるという問題が有する。In the latter, the urea / phosphate esterified starch has a lower gelatinization onset temperature of 5-20 ° C than the raw starch, so that it can be gelatinized sufficiently in a wider range of more paper machine drying steps, Further, since the above-mentioned yield is sufficient, it contributes to the improvement of paper strength. However, it has been known that urea / phosphate esterified starch has a major drawback. That is, the urea / phosphate esterified starch often causes clogging of the paper machine wire, causing a serious trouble of shutting down the operation. This phenomenon is particularly noticeable when the pH in the pulp slurry is low. Due to this disadvantage, urea / phosphate esterified starch has a limitation that it cannot be used in a paper machine in a low pH range. However, if the emphasis is on paper strength, urea / phosphate esterified starch must be used, and in that case, the actual situation has been to frequently deal with such issues as washing and replacing wires. Each time the paper machine must be shut down,
The operation itself such as replacement also requires a great deal of labor. Typical commercially available urea-phosphate esterified starch has a bound phosphorus atom and soluble phosphorus atom content of 0.3-1.5% by weight and 0.15%, respectively.
~ 1.5% by weight. Also, processed starches other than urea / phosphate esterified starch, such as acetylated starch, can be sufficiently gelatinized in the paper machine drying step if the gelatinization start temperature is lowered, but the yield is low. There is a problem that the strength is low and the strength is insufficient.
（発明が解決しようとする課題） 本発明は、糊化開始温度が低く、高い歩留りを示し、
どのようなpH領域のパルプスラリーにおいても網汚れを
起こさず、且つ紙に十分な強度（例えば、紙表面、紙層
内及び紙層間強度等）を付与出来るスプレー用澱粉を用
いる抄紙方法を提供することを目的とする。(Problems to be Solved by the Invention) The present invention has a low gelatinization start temperature and a high yield,
Provided is a papermaking method using a starch for spraying that does not cause mesh staining in a pulp slurry in any pH range and can impart sufficient strength (for example, strength on a paper surface, in a paper layer, and between paper layers) to paper. The purpose is to:
（課題を解決するための手段） 上記目的を達成するため、鋭意研究を重ねた結果、特
定の尿素・リン酸エステル化澱粉を使用すれば優れた巧
を奏することを見出した。即ち抄紙機ワイヤーの目詰
は、尿素・リン酸エステル化澱粉に含まれる可溶性のリ
ン化合物がパルプスラリー中の硫酸アルミニウムと反応
して不溶性のリン酸アルミニウムの沈澱を析出する結果
発生するものであることを、その付着物の元素分析の結
果から突き止めた。言い替えれば、澱粉に含まれる可溶
性のリン化合物の含有量を極力減少さすことが肝要であ
る事を見出だした。又、澱粉に結合したリン化合物が紙
の強度を向上し、且つ歩留を改善することも明らかにし
た。更に又、澱粉の糊化開始温度と紙強度の関係を見出
だした。その結果、本発明を成すに至った。(Means for Solving the Problems) In order to achieve the above object, as a result of diligent research, it has been found that the use of a specific urea / phosphoric esterified starch is excellent. That is, clogging of the paper machine wire occurs as a result of the soluble phosphorus compound contained in the urea / phosphate esterified starch reacting with the aluminum sulfate in the pulp slurry to precipitate an insoluble aluminum phosphate precipitate. This was ascertained from the results of elemental analysis of the deposit. In other words, it has been found that it is important to minimize the content of the soluble phosphorus compound contained in the starch. It has also been clarified that the phosphorus compound bound to the starch improves the strength of the paper and improves the yield. Furthermore, the relationship between the gelatinization start temperature of starch and the paper strength was found. As a result, the present invention has been accomplished.
即ち本発明は澱粉に結合したリン原子の含有量が0.4
重量％以上であり、冷水に可溶なリン化合物のリン原子
としての含有量が0.1重量％以下であり、且つ糊化開始
温度が35〜55℃を有する尿素リン酸エステル化澱粉の水
スラリーをスプレーすることを特徴とする抄紙方法を提
供する。That is, in the present invention, the content of phosphorus atoms bonded to starch is 0.4
Water slurry of a urea phosphorylated starch having a phosphorus compound content of 0.1% by weight or less and a gelatinization start temperature of 35 to 55 ° C. There is provided a papermaking method characterized by spraying.
上記澱粉に結合したリン原子の含有量は0.4重量％以
上であることが必須である。なお、その最大含有量につ
いては特に制限は無いが、使用するリン酸及びその塩等
の添加量が増加すると、必然的に未反応リン化合物が増
加する傾向にあるから、自ずから５重量％を超えること
は無い。一方、含有量が0.4重量％より少ないと十分な
歩留りが得られず、紙に十分な接着強度を付与出来な
い。リン原子の含有量は好ましくは0.4〜３重量％であ
る。It is essential that the content of phosphorus atoms bonded to the starch is 0.4% by weight or more. There is no particular limitation on the maximum content, but if the added amount of phosphoric acid or its salt used increases, the amount of unreacted phosphorus compounds tends to increase, and naturally exceeds 5% by weight. There is nothing. On the other hand, if the content is less than 0.4% by weight, sufficient yield cannot be obtained, and sufficient adhesive strength cannot be imparted to paper. The content of phosphorus atoms is preferably 0.4 to 3% by weight.
又尿素・リン酸エステル化澱粉中の冷水に可溶なリン
化合物、例えばリン酸、亜リン酸等のナトリウム塩、カ
リウム塩、アンモニウム塩等の含有量は、リン原子とし
て0.1重量％以下であることが必須であり、含有量が0.1
重量％より多いとパルプスリラー中に不溶性物質が生成
し、抄紙機ワイヤーの目詰を発生するので好ましくな
い。The content of phosphorus compounds soluble in cold water in the urea / phosphate esterified starch, for example, sodium, potassium, ammonium salts such as phosphoric acid and phosphorous acid is 0.1% by weight or less as phosphorus atoms. It is essential that the content is 0.1
If the amount is more than the weight percentage, an insoluble substance is formed in the pulp chiller, which causes clogging of the paper machine wire, which is not preferable.
更に本発明の尿素リン酸エステル化澱粉の糊化開始温
度は35〜55℃、好ましくは40〜50℃である。35℃よりも
低いと高温の工場、特に夏場においては屡々スラリーの
貯蔵中に温度が35℃以上にあがることがあり、その場合
澱粉は糊化し使用に耐えず、又55℃よりも高いと通常の
抄紙機では十分に糊化しないので好ましくない。Further, the gelatinization start temperature of the urea phosphorylated starch of the present invention is 35 to 55 ° C, preferably 40 to 50 ° C. If the temperature is lower than 35 ° C, the temperature may increase to 35 ° C or more during storage of the slurry in high temperature factories, especially in summer, in which case the starch does not gelatinize and cannot be used. Is not preferable because the papermaking machine does not sufficiently gelatinize.
本発明の尿素・リン酸エステル化澱粉の製造方法につ
いては、本質的には、通常の方法の中から適宜選択され
るが、代表的な市販の尿素・リン酸エステル化澱粉の結
合リン原子及び可溶性リン原子含有量はそれぞれ0.3〜
1.5重量％および0.15〜1.5重量％であり、その可溶性リ
ン原子含有量は、本発明の尿素・リン酸エステル化澱粉
の可溶性リン原子含有量0.1重量％を大きく上回ってい
る。従来の尿素・リン酸エステル化澱粉は、その製造上
の容易さと、本発明のように可溶性リン原子含有量を低
下させるという点に着目されていないために、上記のよ
うになったものである。従って、澱粉に結合したリン原
子の含有量が0.4重量％以上であり、冷水に可溶なリン
化合物のリン原子としての含有量が0.1重量％以下であ
り、且つ糊化開始温度が35〜55℃を有するような尿素・
リン酸エステル化澱粉を製造するためには、通常の方法
よりも、やや過酷な条件を選択しなければならない。通
常の方法として例えば、澱粉をリン酸やリン酸塩及び尿
素と混合し、加熱焙焼する乾式反応がある。その反応条
件は、反応温度80〜150℃、反応時間30分〜５時間、尿
素（対澱粉100重量部当たり）２〜20重量部、リン酸
（対澱粉100重量部当たり）１〜15重量部程度を使用す
るものがある。The method for producing the urea / phosphorylated starch of the present invention is essentially selected from ordinary methods as appropriate, but the typical phosphorus and phosphatized atoms of commercially available urea / phosphorylated starch are selected. Soluble phosphorus atom content is 0.3 ~
It is 1.5% by weight and 0.15 to 1.5% by weight, and its soluble phosphorus atom content is much higher than the soluble phosphorus atom content of the urea / phosphorylated starch of the present invention of 0.1% by weight. The conventional urea / phosphate esterified starch is as described above because it is not focused on its ease of production and on the point of reducing the soluble phosphorus atom content as in the present invention. . Therefore, the content of the phosphorus atom bonded to the starch is 0.4% by weight or more, the content of the phosphorus compound soluble in cold water as the phosphorus atom is 0.1% by weight or less, and the gelatinization start temperature is 35 to 55%. Urea with a temperature of
In order to produce a phosphorylated starch, conditions that are somewhat harsher than those of a conventional method must be selected. As a usual method, for example, there is a dry reaction in which starch is mixed with phosphoric acid, a phosphate, and urea, followed by heating and roasting. The reaction conditions are a reaction temperature of 80 to 150 ° C., a reaction time of 30 minutes to 5 hours, 2 to 20 parts by weight of urea (per 100 parts by weight of starch), and 1 to 15 parts by weight of phosphoric acid (per 100 parts by weight of starch). Some use degrees.
この場合、使用するリン酸及びリン酸塩の種類につい
ては特に制限はないが、リン酸、亜リン酸等及びそれら
の第１、２及び／又は３ナトリウム、カリウム、及び／
またはアンモニウム塩等が例示される。In this case, the type of phosphoric acid and phosphate used is not particularly limited, but phosphoric acid, phosphorous acid and the like, and their first, second and / or trisodium, potassium, and / or
Or an ammonium salt is exemplified.
又、上記のリン酸等以外の酸とその塩等を併用するこ
とができる。例えば、塩酸、硫酸、硝酸、スルファミン
酸、マレイン酸、コハク酸及び酢酸とそれらの塩が例示
される。又、酸化剤を併用することもできる。例えば、
過酸化水素、過硫酸アンモニウムなどが例示される。Further, an acid other than the above phosphoric acid and the like and a salt thereof can be used in combination. For example, hydrochloric acid, sulfuric acid, nitric acid, sulfamic acid, maleic acid, succinic acid, acetic acid and salts thereof are exemplified. Further, an oxidizing agent can be used in combination. For example,
Examples include hydrogen peroxide and ammonium persulfate.
本発明の尿素・リン酸エステル化澱粉を湿紙上にスプ
レーするに当たっては、未加工澱粉、ポリアクリルマイ
ド、PVA、ポリエチレンイミン、ポリエチレンオキサイ
ドなどと併用することができる。本発明に用いられる澱
粉としては、とうもろこし、タピオカ、馬鈴薯、かんし
ょ、小麦などいずれでもよく、また一部及び／又は全部
エーテル化、エステル化、酸化、酸処理などを受けてい
るものでもかまわない。In spraying the urea / phosphate esterified starch of the present invention onto wet paper, it can be used in combination with raw starch, polyacrylamide, PVA, polyethyleneimine, polyethylene oxide and the like. The starch used in the present invention may be corn, tapioca, potato, potato, wheat, or the like, and may be partially and / or entirely subjected to etherification, esterification, oxidation, acid treatment, or the like.
本発明によってスプレーを施す方法として、抄紙実機
上で行なう場合には通常通りワイヤー上に走行方向に対
し直角にスプレーノズルを設置し、0.1〜５％程度の濃
度範囲の澱粉スラリーをスプレーする。次にスプレーさ
れた湿紙を吸引脱水、プレス脱水した後、乾燥工程を経
て紙、板紙等を得る。一方、実験室的に実施する場合に
は、通常の手抄紙の場合と同様に、パルプをビーターで
叩解し、濾水度を調整し、市販実験用抄紙機で抄紙し、
その湿紙上に澱粉スラリーをスプレーし、第２の湿紙を
その上に重ね、パルプ濃度20重量％になるまで吸引脱
水、プレス脱水し、シリンダー乾燥機上にて所定の温度
にて乾燥し、紙、板紙等を得る。As a method for applying the spray according to the present invention, when performing on a papermaking machine, a spray nozzle is installed on a wire at right angles to the running direction as usual, and a starch slurry having a concentration range of about 0.1 to 5% is sprayed. Next, the sprayed wet paper is subjected to suction dehydration and press dehydration, and then subjected to a drying step to obtain paper, paperboard and the like. On the other hand, when carried out in a laboratory, the pulp is beaten with a beater, the freeness is adjusted, and the paper is made on a commercial laboratory paper machine, as in the case of ordinary hand papermaking.
A starch slurry is sprayed on the wet paper, a second wet paper is superimposed on the wet slurry, suction dehydration and press dehydration are performed until the pulp concentration reaches 20% by weight, and dried at a predetermined temperature on a cylinder dryer. Obtain paper, paperboard, etc.
本明細書中において、糊化開始温度とは第１図に示す
ように、ブラベンダーアミログラムで立上った粘度カー
ブの接線が基線に対し45゜の角度をなす点の温度を糊化
開始温度とした。その場合、澱粉濃度は25重量％にて測
定した。In the present specification, the gelatinization start temperature is, as shown in FIG. 1, the temperature at the point where the tangent of the viscosity curve rising in the Brabender amyogram forms an angle of 45 ° with the base line. And In that case, the starch concentration was measured at 25% by weight.
（発明の効果） 本発明によれば、紙に十分な接着力を付与し、低いpH
のパルプスラリー中でも不溶性物質を析出せず、抄紙機
の網汚れや目詰りを発生しない優れた抄紙方法を提供す
る。(Effects of the Invention) According to the present invention, sufficient adhesive strength is imparted to paper and low pH
The present invention provides an excellent papermaking method which does not precipitate insoluble substances even in pulp slurries and does not cause net stains and clogging of paper machines.
（実施例） 本発明を実施例により更に詳細に説明する。(Examples) The present invention will be described in more detail with reference to examples.
本発明はこれら実施例に限定されない。 The present invention is not limited to these examples.
参考例１ 尿素10部を水10部に溶解し、これに75％リン酸2.7部
を加えて撹拌溶解した後、コーンスターチ100部に散布
し、良く混合して均一にした。この混合物を熱風乾燥機
中で140℃、３時間加熱反応させた。反応物の25重量％
濃度でのアミログラムによる糊化開始温度は41℃であっ
た。Reference Example 1 10 parts of urea was dissolved in 10 parts of water, and 2.7 parts of 75% phosphoric acid was added thereto, followed by stirring and dissolving. Then, the mixture was sprayed on 100 parts of corn starch, mixed well, and uniformly mixed. This mixture was heated and reacted in a hot air drier at 140 ° C. for 3 hours. 25% by weight of reactants
The gelatinization onset temperature by amyogram at the concentration was 41 ° C.
元素分析による澱粉に結合したリン原子の量は乾物換
算で0.66重量％、冷水に可溶な物質のリン原子としての
量は0.08重量％であった。以後本製品を本発明品Ａと記
述する。According to elemental analysis, the amount of phosphorus atoms bound to starch was 0.66% by weight in terms of dry matter, and the amount of a substance soluble in cold water as phosphorus atoms was 0.08% by weight. Hereinafter, this product is referred to as product A of the present invention.
参考例２ 尿素10部を水10部に溶解し、これに75％リン酸2.2部
を加えて撹拌溶解した後、タピオカ100部に散布し良く
混合して均一にした。この混合物を熱風乾燥機中で140
℃、２時間30分加熱反応させた。反応物の糊化開始温度
45℃であった。元素分析による澱粉に結合したリン原子
の量は0.51重量％（乾物ベース）、冷水に可溶なリン原
子としての量は0.06重量％（乾物ベース）であった。Reference Example 2 10 parts of urea was dissolved in 10 parts of water, and 2.2 parts of 75% phosphoric acid was added thereto and dissolved by stirring. Then, the mixture was sprayed on 100 parts of tapioca, mixed well, and made uniform. The mixture is placed in a hot air drier for 140
The mixture was heated for 2 hours and 30 minutes. Gelatinization start temperature of reactant
45 ° C. The amount of phosphorus atoms bound to starch by elemental analysis was 0.51% by weight (dry matter basis), and the amount of phosphorus atoms soluble in cold water was 0.06% by weight (dry matter basis).
以後本製品を本発明品Ｂと記述する。 Hereinafter, this product is referred to as product B of the present invention.
参考例３ 尿素10重量部を水10重量部に溶解し、これに75％リン
酸1.9重量部を加えて撹拌溶解したのち、ヒドロキシエ
チコル化コーンスターチ100部に散布し良く混合して均
一にした。この混合物を熱風乾燥機中で140℃、３時間
加熱反応させた。反応物の糊化開始温度は42℃であっ
た。元素分析により結合したリン原子含有量は0.43重量
％（乾物ベース）、冷水に可溶なリン原子含有量は0.06
重量％（乾物ベース）であった。以後本発明品を本発明
品Ｃと記述する。Reference Example 3 10 parts by weight of urea was dissolved in 10 parts by weight of water, 1.9 parts by weight of 75% phosphoric acid was added thereto, and the mixture was stirred and dissolved. Then, the mixture was sprayed and mixed well with 100 parts of hydroxyethylated corn starch to obtain a uniform mixture. . This mixture was heated and reacted in a hot air drier at 140 ° C. for 3 hours. The gelatinization start temperature of the reaction product was 42 ° C. Elemental analysis revealed a bound phosphorus atom content of 0.43% by weight (dry matter basis) and a cold water soluble phosphorus atom content of 0.06%
% By weight (dry matter basis). Hereinafter, the product of the present invention is referred to as product C of the present invention.
参考例４ 尿素８重量部を水８重量部に溶解し、これに75％リン
酸1.7重量部を加えて撹拌溶解したのち、コーンスター
チ100部に散布し良く混合して均一にした。この混合物
を熱風乾燥機中で140℃、２時間30分加熱反応させた。
反応物の糊化開始温度は53℃であった。元素分析により
結合したリン原子含有量は0.42重量％（乾物ベース）、
冷水に可溶なリン原子含有量は0.08重量％（乾物ベー
ス）であった。以後本発明品を本発明品Ｄと記述する。Reference Example 4 8 parts by weight of urea was dissolved in 8 parts by weight of water, 1.7 parts by weight of 75% phosphoric acid was added thereto, and the mixture was dissolved by stirring. Then, the mixture was sprayed on 100 parts of corn starch, mixed well, and uniformly mixed. This mixture was heated and reacted in a hot air dryer at 140 ° C. for 2 hours and 30 minutes.
The gelatinization start temperature of the reaction product was 53 ° C. The phosphorus atom content bound by elemental analysis is 0.42% by weight (dry matter basis),
The content of phosphorus atoms soluble in cold water was 0.08% by weight (dry matter basis). Hereinafter, the product of the present invention is referred to as product D of the present invention.
実施例１ 針葉樹クラフトパルプ（NBKP）100％、濾水度（CSF）
340mlからなる１％パルプスラリー375mlに、硫酸バンド
を対パルプ1.0％添加し、実験用角型抄紙機（25cm×25c
m）内で0.03％になるまで希釈した。次に脱水を開始し
マットが生成し始め、パルプスラリーの水面が金網より
2cm上に到達したところで一旦停止し、第一表の澱にな
るように粉の１％スラリーをパルプスラリー水面に澱粉
を乾物ベースで2g/m2スプレーした。その後再び脱水を
開始し、第一層目の湿紙（坪量60g/m2）を得た。次に、
第一層目の湿紙と同様にして得た第二層目の湿紙（但
し、NBKP/LBKP/段ボール故紙＝50/20/30、CSF390ml、澱
粉無塗布）を、第一層目の澱粉を塗布した面に重ね合わ
せ、吸引脱水、プレス脱水をして、シリンダー乾燥機で
75℃、60秒加熱乾燥し、試料とした。Example 1 Softwood Kraft Pulp (NBKP) 100%, Freeness (CSF)
To 375 ml of a 1% pulp slurry consisting of 340 ml, a sulfuric acid band was added at 1.0% to pulp, and a square paper machine for experiments (25 cm × 25 cm) was added.
m) to 0.03%. Next, dehydration starts, mats begin to form, and the water surface of the pulp slurry
When it reached 2 cm above, it was temporarily stopped, and a 1% slurry of the powder was sprayed on the water surface of the pulp slurry at a rate of 2 g / m 2 of starch on a dry matter basis so as to obtain the starch shown in Table 1. Thereafter, dehydration was started again to obtain a first layer of wet paper (basis weight 60 g / m 2 ). next,
The second-layer wet paper obtained in the same manner as the first-layer wet paper (NBKP / LBKP / cardboard waste paper = 50/20/30, CSF 390 ml, starch-free coating) was added to the first-layer starch. Is superimposed on the surface coated with
The sample was dried by heating at 75 ° C. for 60 seconds.
この試料の剥離強度と澱粉の歩留りを以下の方法にて
測定した。The peel strength and starch yield of this sample were measured by the following methods.
１）剥離強度（90゜剥離法） 試験片（10cm×1cm）の片面を金属プレートに接着固
定し、目的とする層間を２〜3cmあらかじめ剥離し、引
張試験機を用いて90゜方向に引張り剥離を行ない抵抗力
を測定した。1) Peeling strength (90 ° peeling method) One side of a test piece (10cm x 1cm) is fixedly adhered to a metal plate, the target layer is peeled off 2-3cm in advance, and pulled in 90 ° direction using a tensile tester. Peeling was performed and the resistance was measured.
２）歩留 アンスロン硫酸法により求めた製品に含有される澱粉
量をＡ、スプレーした澱粉の量をＢとし、次式より算出
した。2) Retention The amount of starch contained in the product obtained by the anthrone sulfate method was A, and the amount of sprayed starch was B, and the yield was calculated by the following equation.
第１表より、剥離強度の面からみると明らかに粘化開
始温度60℃以上の澱粉は不満足な値を示した。又、粘化
開始温度は低いが、結合リン原子の量が0.36％以下の尿
素・リン酸澱粉、あるいはアセチル化等の方法で粘化温
度を低下させた澱粉は、粘化開始温度60℃以上の澱粉に
較べると強度上昇は認められるがまだ不十分といえる。
本発明品を含む粘化開始温度が低く、結合リン原子含有
量が0.42％以上の尿素リン酸澱粉だけが満足のいく剥離
強度を示した。 From Table 1, it can be seen from the standpoint of the peel strength that the starch having a viscosity-onset temperature of 60 ° C. or higher showed an unsatisfactory value. In addition, the viscosifying onset temperature is low, but urea / phosphate starch having an amount of bound phosphorus atoms of 0.36% or less, or starch whose viscosifying temperature has been lowered by acetylation or the like, has a viscosifying onset temperature of 60 ° C or higher. Although the increase in strength is recognized as compared with the starch of No. 5, it can be said that it is still insufficient.
Only the urea phosphate starch containing the product of the present invention and having a low viscosity initiation temperature and a bound phosphorus atom content of 0.42% or more exhibited satisfactory peel strength.
一方、歩留は馬鈴薯澱粉あるいは馬鈴薯澱粉原料の加
工澱粉と、本発明品を含む結合リン原子の量が0.42％以
上の尿素リン酸澱粉が良好な値を示した。On the other hand, in the yield, potato starch or a modified starch of potato starch raw material and urea phosphate starch containing the present invention and having an amount of bound phosphorus atoms of 0.42% or more showed good values.
以上より、剥離強度、歩留共に満足のいく結果を得た
のは、本発明品を含む、粘化開始温度の低い、結合リン
原子の量が0.42％以上の尿素リン酸澱粉だけであること
が判る。From the above, satisfactory results in both peel strength and yield were obtained only with the urea phosphate starch containing the product of the present invention, having a low viscosity initiation temperature, and containing 0.42% or more of bound phosphorus atoms. I understand.
実施例２ 円網抄紙機（抄巾1660mm、抄速96m/分）を用い、表１
層（pH4.3）と表第２層（pH6.5）の層間に第２表の澱粉
を2g/m2スプレー塗布し、坪量450g/m2の抄合コート白ボ
ールを得た。Example 2 Table 1 was obtained using a round paper machine (paper width 1660 mm, paper speed 96 m / min).
The starch shown in Table 2 was spray-coated at 2 g / m 2 between the layer (pH 4.3) and the second layer (pH 6.5) to obtain a coated white ball having a basis weight of 450 g / m 2 .
第２表に示されるように、本発明を含む結合リン原子
の量が0.42％以上の尿素リン酸澱粉は、コーンスターチ
に比較して、良好な層間剥離強度を示した。しかし、可
溶性の物質のリン原子としての量を0.14％以上含有する
尿素リン酸澱粉、即ち、本発明品を除く尿素リン酸澱粉
は、運転開始３日から10日の間にワイヤーの目詰を生
じ、マシンの停止、洗浄を余儀なくされた。これに対
し、本発明品は１ケ月以上連続使用しても、ワイヤーの
目詰を生じさせなかった。 As shown in Table 2, the urea phosphate starch containing the present invention and having an amount of bound phosphorus atoms of 0.42% or more exhibited better delamination strength than corn starch. However, urea phosphate starch containing 0.14% or more of a soluble substance as a phosphorus atom, that is, urea phosphate starch excluding the product of the present invention, causes clogging of the wire between 3 and 10 days after the start of operation. As a result, the machine had to be stopped and cleaned. On the other hand, the product of the present invention did not cause wire clogging even when used continuously for one month or more.
このように、本発明品は剥離強度、ワイヤー目詰、共
に満足すべき性能を示し、理想的なスプレー用澱粉であ
るといえる。Thus, the product of the present invention shows satisfactory performance in both peel strength and wire clogging, and can be said to be an ideal starch for spraying.
実施例３ 長網抄紙機（抄巾3700mm、抄速420m/分）を用い、pH
4.4のパルプスラリーに対し、ワイヤー上にて第３表の
澱粉を0.5g/m2スプレーし、坪量82g/m2の中質紙を得
た。Example 3 Using a fourdrinier (3700 mm in width, 420 m / min speed),
The starch of Table 3 was sprayed on the wire at a rate of 0.5 g / m 2 to the pulp slurry of 4.4 to obtain a medium paper having a basis weight of 82 g / m 2 .
第３表の諸物性において、良好な結果を得、しかも、
ワイヤー目詰を発生させなかったのは本発明品Ｂ（粘化
温度45℃、結合リン原子0.51％、可溶性のリン原子0.06
％）だけであることが明白である。 In the physical properties shown in Table 3, good results were obtained.
The product B of the present invention which did not cause wire clogging (viscosity temperature: 45 ° C., bound phosphorus atom: 0.51%, soluble phosphorus atom: 0.06%)
%).
第１図は粘化開始温度を説明する温度と粘度との関係を
示すグラフである。FIG. 1 is a graph showing a relationship between temperature and viscosity for explaining a viscosity start temperature.
Claims (1)
量％以上であり、冷水に可溶なリン化合物のリン原子と
しての含有量が0.1重量％以下であり、且つ糊化開始温
度が35〜55℃を有する尿素リン酸エステル化糊粉の水ス
ラリーをスプレーすることを特徴とする抄紙方法。1. The content of phosphorus atoms bound to starch is 0.4% by weight or more, the content of phosphorus compounds soluble in cold water as phosphorus atoms is 0.1% by weight or less, and the gelatinization start temperature is A papermaking method characterized by spraying a water slurry of urea phosphorylated size powder having a temperature of 35 to 55 ° C.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1223874A JP2788298B2 (en) | 1989-08-30 | 1989-08-30 | Papermaking method |
| EP19900116567 EP0415385B1 (en) | 1989-08-30 | 1990-08-29 | Method of making paper |
| DE1990623436 DE69023436T2 (en) | 1989-08-30 | 1990-08-29 | Process for making paper. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1223874A JP2788298B2 (en) | 1989-08-30 | 1989-08-30 | Papermaking method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0390695A JPH0390695A (en) | 1991-04-16 |
| JP2788298B2 true JP2788298B2 (en) | 1998-08-20 |
Family
ID=16805064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1223874A Expired - Fee Related JP2788298B2 (en) | 1989-08-30 | 1989-08-30 | Papermaking method |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0415385B1 (en) |
| JP (1) | JP2788298B2 (en) |
| DE (1) | DE69023436T2 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6451121B2 (en) | 1993-07-30 | 2002-09-17 | National Starch And Chemical Investment Holding Corporation | Thermally-inhibited non-pregelatinized granular starches and flours and process for their preparation |
| US5932017A (en) * | 1993-07-30 | 1999-08-03 | National Starch And Chemical Investment Holding Corporation | Thermally-inhibited non-pregelatinized granular starches and flours and process for their preparation |
| US6221420B1 (en) | 1993-07-30 | 2001-04-24 | National Starch And Chemical Investment Holding Corporation | Foods containing thermally-inhibited starches and flours |
| US5720822A (en) | 1995-06-07 | 1998-02-24 | National Starch And Chemical Investment Holding Corporation | Thermally-inhibited pregelatinized non-granular starches and flours and process for their production |
| US5718770A (en) * | 1994-08-25 | 1998-02-17 | National Starch And Chemical Investment Holding Corporation | Thermally-inhibited pregelatinized granular starches and flours and process for their production |
| US5830884A (en) * | 1995-01-18 | 1998-11-03 | National Starch And Chemical Investment Holding Corporation | Pharmaceutical products containing thermally-inhibited starches |
| EP0804140A2 (en) * | 1995-01-18 | 1997-11-05 | National Starch and Chemical Investment Holding Corporation | Cosmetics containing thermally-inhibited starches |
| JPH10503803A (en) * | 1995-01-24 | 1998-04-07 | ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレイション | Aqueous adhesive containing heat-inhibited starch |
| EP0805898A1 (en) * | 1995-01-24 | 1997-11-12 | National Starch and Chemical Investment Holding Corporation | Paper containing thermally-inhibited starches |
| DE19829757A1 (en) | 1998-07-03 | 2000-01-05 | Stockhausen Chem Fab Gmbh | Aqueous adhesive dispersions and their use in the production of multilayer papers |
| JP4629833B2 (en) * | 2000-05-26 | 2011-02-09 | 王子コーンスターチ株式会社 | Interlayer adhesive for fiber sheet and paper making method |
| JP4585650B2 (en) * | 2000-05-26 | 2010-11-24 | 王子コーンスターチ株式会社 | Papermaking method using interlayer adhesive for fiber sheet |
| JP4527972B2 (en) * | 2003-12-22 | 2010-08-18 | 王子コーンスターチ株式会社 | Heat-saving adhesive for bonding |
| JP4594627B2 (en) * | 2004-02-10 | 2010-12-08 | 中外写真薬品株式会社 | Treatment method for fluorine-containing wastewater. |
| FR2940330B1 (en) | 2008-12-18 | 2017-06-23 | Georgia-Pacific France | PAPER SHEET DELITEABLE IN WATER, CHUCK FOR PAPER ROLL CONSISTING OF SUCH SHEET |
| FR2940331B1 (en) | 2008-12-18 | 2010-12-17 | Georgia Pacific France | METHOD FOR MANUFACTURING SINGLE PAPER SHEET, USE OF SHEET FOR MANUFACTURING ROLLER SUPPORTING CHUCK, DELIBERABLE PAPER SHEET, AND CHUCK MADE OF AT LEAST ONE OF SAID SHEETS |
| FR2948696A1 (en) | 2009-08-03 | 2011-02-04 | Georgia Pacific France | METHOD FOR MANUFACTURING A DELIBERABLE PAPER SHEET, DELICIOUS PAPER SHEET, CHUCK MADE OF AT LEAST ONE SUCH SHEET |
| WO2013026788A2 (en) * | 2011-08-19 | 2013-02-28 | Basf Se | Urea-containing aqueous papercoating slips, urea-containing aqueous papercoating slip components and use thereof |
| CN104878648B (en) * | 2014-02-28 | 2018-03-09 | 金东纸业（江苏）股份有限公司 | The manufacture method of paper |
| JP7439360B2 (en) * | 2019-12-05 | 2024-02-28 | 日本製紙株式会社 | Multilayer paper for food and beverages |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL134024C (en) * | 1965-11-17 | 1900-01-01 | ||
| JPS62116602A (en) * | 1985-11-18 | 1987-05-28 | Sanwa Denpun Kogyo Kk | Production of urea-phosphate starch |
-
1989
- 1989-08-30 JP JP1223874A patent/JP2788298B2/en not_active Expired - Fee Related
-
1990
- 1990-08-29 DE DE1990623436 patent/DE69023436T2/en not_active Expired - Fee Related
- 1990-08-29 EP EP19900116567 patent/EP0415385B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0390695A (en) | 1991-04-16 |
| EP0415385A1 (en) | 1991-03-06 |
| DE69023436T2 (en) | 1996-04-04 |
| EP0415385B1 (en) | 1995-11-08 |
| DE69023436D1 (en) | 1995-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2788298B2 (en) | Papermaking method | |
| EP1170418B1 (en) | Coating for paper products | |
| WO1999064467A1 (en) | Phosphate esters of starch | |
| JP4854901B2 (en) | Paper making method | |
| TW201821523A (en) | Dry strength composition, its use and method for increasing the strength properties of paper, board or the like | |
| JP2002521530A (en) | Oxidation of starch | |
| JPH09291103A (en) | Papermaking starch | |
| CA2334532C (en) | A process for making paper | |
| JP3876522B2 (en) | Papermaking paper strength enhancer and method for producing strong paper | |
| US7033426B2 (en) | Starch-based corrugating adhesive compositions | |
| JPH0778205B2 (en) | Improved starch-based cardboard adhesive | |
| KR101625408B1 (en) | Method for preparing modified starch with low viscosity, modified starch with low viscosity prepared thereby, composition comprising the modified starch for paper surface sizing, and paper having a surface treated with the composition | |
| US7217316B2 (en) | Coating compositions | |
| JPS62257498A (en) | Production of paper excellent in interlayer strength | |
| JP2001115121A (en) | Interlaminar adhesive and paper-manufacturing process using the same | |
| JP3921096B2 (en) | Surface-sized press paper using low-viscosity amphoteric starch | |
| JP4629833B2 (en) | Interlayer adhesive for fiber sheet and paper making method | |
| JP4061084B2 (en) | Amphoteric starch with reduced viscosity, method for producing the same and papermaking method | |
| JPS6111982B2 (en) | ||
| JPH01298296A (en) | Papermaking process | |
| JP3249281B2 (en) | Laminated paperboard | |
| JP2005232604A (en) | Bulkiness reduction inhibitor, paper making method, and paper | |
| WO1995011340A1 (en) | Manufacture and use of a zirconium-protein system | |
| JP4794224B2 (en) | Formulation for gelatinized paper strength enhancer, gelatinized paper strength enhancer, and papermaking method | |
| AU2004201151B2 (en) | Coating compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090605 Year of fee payment: 11 |
|
| LAPS | Cancellation because of no payment of annual fees |