JPS5823997A - Papermaking method - Google Patents

Papermaking method

Info

Publication number
JPS5823997A
JPS5823997A JP57131080A JP13108082A JPS5823997A JP S5823997 A JPS5823997 A JP S5823997A JP 57131080 A JP57131080 A JP 57131080A JP 13108082 A JP13108082 A JP 13108082A JP S5823997 A JPS5823997 A JP S5823997A
Authority
JP
Japan
Prior art keywords
polymer
cellulose fibers
anionic
cationic polymer
cationic
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.)
Pending
Application number
JP57131080A
Other languages
Japanese (ja)
Inventor
デビツド・クリフオ−ド・ベインズ
エドワ−ド・ウイリアム・バウア−
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bip Chemicals Ltd
Original Assignee
Bip Chemicals Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bip Chemicals Ltd filed Critical Bip Chemicals Ltd
Publication of JPS5823997A publication Critical patent/JPS5823997A/en
Pending legal-status Critical Current

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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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
    • D21H23/765—Addition of all compounds to the pulp
    • 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
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D21H17/51—Triazines, e.g. melamine
    • 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
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
    • 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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Making Paper Articles (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 本発明は製紙方法、特に改良された乾燥強度を有する紙
の製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for making paper, and more particularly to a process for making paper with improved dry strength.

紙を製造する場合には、セルロース繊維を水性懸濁液か
ら−９の層として沈積させ、次いでその層を脱水して固
めてから乾燥させる。製造された紙の湿潤強度を改善す
るために紘、ホルム　アル−ヒト含有量が比較的高いア
ミツブ２スト樹脂の酸性溶液であるメラミンの酸性コロ
イドによってセルロース繊維を処理することが公知でＴ
ｏ！り、この処理によって乾燥強度もかなシ改善される
。しかしながら、このような樹脂を普通の方法で用いる
と、作業環境内の遊離のホルム　アルデヒドの濃度が許
容限度を超えるという欠点がある。In making paper, cellulose fibers are deposited as a -9 layer from an aqueous suspension, and the layer is then dehydrated, consolidated, and dried. It is known to treat cellulose fibers with an acidic colloid of melamine, an acidic solution of Amitsub2-st resin with a relatively high formal acid content, in order to improve the wet strength of the paper produced.
o! This treatment also significantly improves dry strength. However, the conventional use of such resins has the disadvantage that the concentration of free formaldehyde in the working environment exceeds acceptable limits.

本発明は、作業環境内に許容限度を超える遊離のホルム
　アルデヒドを生じることなく、有効に改善され九乾燥
強度を有する紙を生産するのに利用できる方法を提供す
るものである。The present invention provides a method that can be used to effectively produce paper with improved dry strength without creating unacceptable levels of free formaldehyde in the working environment.

水性懸濁液からセルロース繊維を１層に沈積させ、セし
て峡セルロース繊維層を脱水して行う製紙方法であって
、製造後の紙の乾燥強度を高めるため、ホルム　アルデ
ヒドから誘導されたも９でないカチオン性。のポリマー
と、反復単位がアニオン性のアミ７ノラスト樹脂である
アニオン性のポリマーとを用いてセルロース繊維を順次
処理する方法が本発明によって提供される。A papermaking process in which cellulose fibers are deposited in a single layer from an aqueous suspension, and then the cellulose fiber layer is dehydrated. Cationicity that is not 9. Provided by the present invention is a method for sequentially treating cellulose fibers with an anionic polymer in which the repeating unit is an anionic amine 7 nolast resin.

反復単位が「アニオン性」であるという性質は、単位内
に塩の形の酸性基、例えば−ｏ、ｓｏｙ又は−８０「が
含まれることによって生じる。（塩のカチオンについて
捻、水に対する塩の溶解又は分散を妨げるものでない限
シ重要な要素とならない。The "anionic" nature of a repeating unit arises from the inclusion within the unit of an acidic group in the form of a salt, e.g. -o, soy or -80. It is not an important factor unless it interferes with dissolution or dispersion.

従って、カチオンは反復単位に較べて小さなアルカリ金
属イオン、例えばナトリウムもしくはカリウム、又社有
機カチオン、例えばＮ（ＣＨ３）　４＋であるのが好都
合である。） カチオン性の非ホルム　アルデヒド系ポリマーとアニオ
ン性のポリマーとを順次水性懸濁液に加え、その水性懸
濁液からセルロース繊維を沈積させることによシ、セル
ロース繊維の処理を行うのが望ましい。これらのポリ１
−は水性懸濁液に溶解又拡分散し、そして繊維上に順次
沈積する。The cation is therefore advantageously a small alkali metal ion compared to the repeating unit, such as sodium or potassium, or an organic cation, such as N(CH3) 4+. Preferably, the cellulose fibers are treated by sequentially adding a cationic non-formaldehyde polymer and an anionic polymer to an aqueous suspension and depositing the cellulose fibers from the aqueous suspension. These poly 1
- is dissolved or dispersed in an aqueous suspension and then deposited on the fibers.

いかなる処理方法を採用するにせよ、カチオン性のポリ
マーがそれと接触するセルロース繊維によって実質上完
全に吸着されるように、カチオン性ポリマーを添加し九
後充分な時間（通常０．５分以上とするのが望ましい）
を置くことが必要である。アニオン性のポリマーの添加
が早すぎると、周囲の水性媒質中にまだかなシの濃度で
残っているカチオン性のポリマーと反応し、中性で水に
不溶性の−りｗ−錯体を形成する可能性がある。処理の
過程でこのようなポリマー錯体がセルロース繊維上に沈
積しても、その繊維から作られる紙の乾燥強度を高める
効果状ない。Whatever treatment method is used, the cationic polymer is added for a sufficient period of time (usually not less than 0.5 minutes) so that the cationic polymer is substantially completely adsorbed by the cellulose fibers in contact with it. (preferably)
It is necessary to put If the anionic polymer is added too early, it can react with the cationic polymer still remaining in small concentrations in the surrounding aqueous medium, forming a neutral, water-insoluble -w-complex. There is sex. When such polymer complexes are deposited on cellulose fibers during processing, they have no effect on increasing the dry strength of paper made from the fibers.

アニオン性のアミノシラスト樹脂は、囚メラミン　幅）
ホルム　アルデヒド　（Ｃ）亜硫酸のアルカリ金属塩の
縮合反応で誘導されたものであるのが望ましい、この種
の樹脂は、深井掘さく用の準さく液に加えると有効であ
るとして、本発明者による英国特許第７５１，５０１号
明細書に開示されている。縮合反応に用いるホルム　ア
ルデヒドの量はメラミン１そルに対して１．７５〜４モ
ルとするのが望ましい。Anionic aminosillast resin is made of melamine (width)
This type of resin, which is preferably derived from the condensation reaction of an alkali metal salt of formaldehyde (C) sulfite, has been proposed by the present inventors as being effective when added to a semi-drilling solution for deep well drilling. It is disclosed in British Patent No. 751,501. The amount of formaldehyde used in the condensation reaction is preferably 1.75 to 4 moles per 1 mole of melamine.

アニオン性のアミノプラスト樹脂の適量はセルロース繊
維の０．１〜５重量％である。A suitable amount of anionic aminoplast resin is 0.1 to 5% by weight of the cellulose fibers.

本発明の方法に用いられるカチオン性の非ホルム　アル
デヒド系ポリマーは、脂肪族炭素原子に結合した塩の形
態のアミノ基が単位内に含まれることによって、反復単
位がカチオン性となっているポリマーであるのが望まし
い。該ポリマーは、ポリアミド、好適には英国特許８８
６５，７２７号明細書に開示されている１種のポリアミ
ド、すなわちｓ　（ｓ〜Ｃ工０飽和脂肪族二塩基酸（例
えば、マロン酸、こはく酸、アジピン酸、アゼ２イン酸
）と、２〜８個のアルキレン基を含むポリアルキレン　
ポリアミン（例えば、ジエチレン　トリアミン、トリエ
チレン　テトラミン、ナト２エチレンペンタアミン、ジ
ゾロｔレン　トリアミン）とを縮合させ、次に縮合生成
物をエビクロロヒドリンと反応させることによって誘導
されたものであるのが望ましい。このようなカチオン性
のポリマー拡、紙に湿潤強度を付与するのに常用されて
いる。The cationic non-formaldehyde polymer used in the method of the present invention is a polymer whose repeating units are cationic due to the inclusion of an amino group in the form of a salt bonded to an aliphatic carbon atom within the unit. It is desirable to have one. The polymer is a polyamide, preferably British Patent No. 88
No. 65,727 discloses one polyamide containing saturated aliphatic dibasic acids (e.g., malonic acid, succinic acid, adipic acid, azediic acid); Polyalkylene containing ~8 alkylene groups
Those derived by condensing polyamines (e.g., diethylene triamine, triethylene tetramine, diethylene pentaamine, dizolotrene triamine) and then reacting the condensation product with shrimp chlorohydrin. desirable. Such cationic polymer expansions are commonly used to impart wet strength to paper.

本発明を実施するに当ってのカチオン性ポリマーの適量
は、セルロース繊維の０．１〜５重量％である。A suitable amount of cationic polymer in the practice of this invention is 0.1 to 5% by weight of the cellulose fibers.

以下例をあげて本発明をさらに詳しく説明する。The present invention will be explained in more detail with reference to the following examples.

！Ｌ 漂白し大皿硫酸セルロース　パルプ〔モードク２りｙ　
（Ｍｏｄｏｃｒｏｗｎ　）　）をショツパー・リグ２−
直で３２＠の一水度まで叩解してから希釈して、セルロ
ース繊維の濃度を１．５重量％にした。! L Bleached platter cellulose sulfate pulp [MODOKU2RYY
(Modocrown)) Shopper Rig 2-
It was directly beaten to a water content of 32@1, and then diluted to give a cellulose fiber concentration of 1.5% by weight.

次にこのセルロース繊維の水性懸濁液に希硫酸を加えて
ｐＨ６とした後、攪拌しながらカチオン性ポリマーと７
ニオン性ポリマーとを順次添加した。Next, dilute sulfuric acid was added to this aqueous suspension of cellulose fibers to adjust the pH to 6, and the cationic polymer was added to the aqueous suspension while stirring.
and the ionic polymer were sequentially added.

令ｌリマー拡、水に溶解したものであ夛、懸濁液に含ま
れるセルロース繊維の２重量％（樹脂固形分）の量で用
いた。The first reamer was dissolved in water and used in an amount of 2% by weight (resin solids) of the cellulose fibers contained in the suspension.

このカチオン性ポリマーは、英国特許第８６５．７２７
号明細書の例１の方法におおむね準拠して、ジエチレン
　トリアミン（２，１モル）１アジピン酸（２モル）及
び工ぜクロロヒドリン、（２４５モル）から得られたポ
リアミド縮合物であ〕、その主要反復単位は、 ＋ →ＪＨ，ＣＨ２，ＣＨ，、ＮＨ，ＣＨ２，ＣＨ２，ＮＨ
，ＣＯ，ＣＨ２，ＣＨ２、ＣＨ２，ＣＨ，、ＣＯ，−Ｃ
Ｈ，、ＣＨ−ＯＨ２ ＼１ である。This cationic polymer is described in British Patent No. 865.727.
A polyamide condensate obtained from diethylene triamine (2.1 mol), adipic acid (2 mol) and engineered chlorohydrin (245 mol), generally according to the method of Example 1 of the specification. The main repeating units are + →JH, CH2, CH,, NH, CH2, CH2, NH
,CO,CH2,CH2,CH2,CH,,CO,-C
H,,CH-OH2\1.

アニオン性のアミノプラスト樹脂は、英国特許第７５１
．５０１号明細書の例１の方法におおむね準拠して、メ
ラミン（１モル）、ホルム　アルデヒド（６モル）及び
ピロ亜硫酸ナトリウム（１モルの亜硫酸２ジカル５ｏｌ
−となるのに充分な量）から得られる縮合物であって、
主要反復単位として を含むものであった。Anionic aminoplast resin is British Patent No. 751
．． 501, melamine (1 mol), formaldehyde (6 mol) and sodium pyrosulfite (1 mol of sulfite 5 ol
- a condensate obtained from
contained as the main repeating unit.

カチオン性のポリマーを加えてから２分後にアニオン性
のアミノプラスト樹脂を加えた。Two minutes after adding the cationic polymer, the anionic aminoplast resin was added.

アニオン性のポリマーを加えた後水性懸濁液をに時間静
置し、次いでセルロース繊維の濃度が０．５重量％とな
るように希釈した。次に完全に在来飄の装置〔パルプ試
験用の製紙業協会標準装置（Ｐａｐｅｒｍａｋ＠ｒｓ　
Ａｓ５ｏｃｉａｔｉｏｎ　８ｔａｎ４ａｒｄ　Ａｐｐａ
ｒａｔｕｓｆｏｒ　Ｐｕ１ｐ　Ｅｖａｌｕａｔｉｏｎ　
）　）を用い、この希釈懸濁液から６０９７ｍ”の手す
亀紙を作夛、手すき紙を風乾してから１２７℃に１０分
間加熱して乾燥強度を充分高めるようｋした。After adding the anionic polymer, the aqueous suspension was allowed to stand for an hour and then diluted to a cellulose fiber concentration of 0.5% by weight. Next, a completely conventional device [Paper Industry Association standard device for pulp testing (Papermak@rs
As5ocation 8tan4ard Appa
ratusfor Pu1p Evaluation
)), 6097 m'' of handmade paper was prepared from this diluted suspension, and the handmade paper was air-dried and then heated to 127° C. for 10 minutes to sufficiently increase the dry strength.

比較のため、 （１）ポリマーの使用をやめ、また 個）　カチオン性ポリマーと７ニオン性ｆリマーとを順
次添加する代シに、湿潤及び乾燥強度を紙に付与するた
めに従来用いられてはいるが、作業製境内に高水準のホ
ルム　アルデヒド（５〜１０容量ｐｐｍ　）をも九らす
メラミン−ホルム　アルデヒドの酸性コロイドを用いて それぞれ上記の手順を繰返した。For comparison, (1) omitted the use of polymers, and instead of sequentially adding a cationic polymer and a 7-ionic f-rimer, conventionally used to impart wet and dry strength to paper. However, the above procedure was repeated using an acidic colloid of melamine-formaldehyde, which also introduced high levels of formaldehyde (5-10 ppm by volume) into the working environment.

次にそれぞれの方法による手すき紙の切断強度を測定し
友。Next, we measured the cutting strength of handmade paper using each method.

結果は次のとお〕であった： 製紙工場で上記のカチオン性／アニオン性手法を行った
ところ、工場の乾燥部門の付近におけるホルム　アルデ
ヒドの゛大気内濃度拡約０．５容量ｐｐｍ以下であるこ
とが認められた。The results were as follows: When the cationic/anionic method described above was carried out at a paper mill, the atmospheric concentration of formaldehyde near the drying section of the mill was below 0.5 ppm by volume. This was recognized.

代理人　浅村　皓 外４名Agent Hajime Asamura 4 other people

Claims (1)

【特許請求の範囲】 （１）水４性懸濁液からセルロース繊維を１層に沈積さ
せ、そして該セルロース繊維層を脱水して行う製紙方法
において、仕上シ後の紙の乾燥強度を高めるため、カチ
オン性の非ホルム　アルデヒド系ポリマート、アニオン
性の反復単位を有するアミメゾ２スト樹脂であるアニオ
ン性のポリマーとを用いてセルロース繊維を順次処理す
ることを特徴とする方法。 （２）　　カチオン性のポリマーとアニオン性のポリマ
ーとを順次水性懸濁液に加え、該懸濁液からセルロース
繊維を沈積させることによって繊維の処理を行う特許請
求の範囲（１）に記載の方法。 （３）　　アミメゾ２スト樹脂が、（Ａ）メラミン、俤
）ポル８ムアルデヒド　（Ｃ）亜硫酸のアルカリ金属塩
の縮合反応で誘導されたものである特許請求の範囲（１
）又は（２）に記載の方法。 （４）　　メ２ミン１モル幽）１゜７５〜４モルの量で
ホルム　アルデヒドを用いる特許請求の範囲（３）に記
載の方法。 （５）セルロース繊維の０．１〜５重量％となる量でア
ニオン性ポリマーを用いる特許請求の範囲（１）〜（４
）のいずれか１項に記載の方法。 、（６）　　カチオン性のポリマ二がポリアミドである
特許請求の範囲（１）〜（５）のいずれか１項に記載の
方法。 曽　カチオン性のポリマーが、０３〜ＣＩＯ飽和脂肪族
二塩基カルボン酸と、２〜８個のアルキレン基を含むポ
リアルキレン　ポリアミンとを縮合させた後、縮合生成
物をエビクロロヒドリンと反応させることによって誘導
されたものである特許請求の範囲（６）に記載の方法。 （８）セルロース繊維の０８１〜５重量％となる量でカ
チオン性ポリマーを用いる特許請求の範囲（１）〜（７
）のいずれか１項に記載の方法。[Scope of Claims] (1) To increase the dry strength of paper after finishing in a paper manufacturing method in which cellulose fibers are deposited in a single layer from an aqueous suspension and the cellulose fiber layer is dehydrated. , a cationic non-formaldehyde polymer, and an anionic polymer which is an amimeso 2-st resin having anionic repeating units. (2) The method according to claim (1), wherein the fibers are treated by sequentially adding a cationic polymer and an anionic polymer to an aqueous suspension and depositing cellulose fibers from the suspension. . (3) The amimeso 2-st resin is derived from a condensation reaction of (A) melamine, 俤) pol-8-maldehyde, and (C) an alkali metal salt of sulfite (1).
) or the method described in (2). (4) A process according to claim (3), in which formaldehyde is used in an amount of 1.75 to 4 mol of meth2mine. (5) Claims (1) to (4) in which the anionic polymer is used in an amount of 0.1 to 5% by weight of the cellulose fibers.
). , (6) The method according to any one of claims (1) to (5), wherein the cationic polymer is a polyamide. Zeng The cationic polymer is obtained by condensing a 03-CIO saturated aliphatic dibasic carboxylic acid with a polyalkylene polyamine containing 2 to 8 alkylene groups, and then reacting the condensation product with shrimp chlorohydrin. The method according to claim (6), which is derived from. (8) Claims (1) to (7) in which the cationic polymer is used in an amount of 0.81 to 5% by weight of the cellulose fibers.
).
JP57131080A 1981-07-28 1982-07-27 Papermaking method Pending JPS5823997A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8123144 1981-07-28
GB8123144 1981-07-28

Publications (1)

Publication Number Publication Date
JPS5823997A true JPS5823997A (en) 1983-02-12

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JP57131080A Pending JPS5823997A (en) 1981-07-28 1982-07-27 Papermaking method

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EP (1) EP0071392A1 (en)
JP (1) JPS5823997A (en)
FI (1) FI822624L (en)
NO (1) NO822573L (en)
ZA (1) ZA825294B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4859527A (en) * 1986-05-29 1989-08-22 Air Products And Chemicals, Inc. Cellulosic nonwoven products of enhanced water and/or solvent resistance by pretreatment of the cellulosic fibers

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1270943B (en) * 1964-01-15 1968-06-20 Eastman Kodak Co Process for the production of wet-strength, formaldehyde-free papers
US3448005A (en) * 1965-01-04 1969-06-03 Weyerhaeuser Co Process of forming wet strength paper containing a cationic resin and fumarated unsaturated oil
US3704006A (en) * 1971-01-25 1972-11-28 Kenics Corp Dispersion producing method
DE2745709A1 (en) * 1976-10-14 1978-04-20 British Industrial Plastics BONDED FIBROUS MATERIAL

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ZA825294B (en) 1983-05-25
EP0071392A1 (en) 1983-02-09
NO822573L (en) 1983-01-31
FI822624A0 (en) 1982-07-27
FI822624L (en) 1983-01-29

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