JP2014218769A - Pitch control agent - Google Patents

Pitch control agent Download PDF

Info

Publication number
JP2014218769A
JP2014218769A JP2014081361A JP2014081361A JP2014218769A JP 2014218769 A JP2014218769 A JP 2014218769A JP 2014081361 A JP2014081361 A JP 2014081361A JP 2014081361 A JP2014081361 A JP 2014081361A JP 2014218769 A JP2014218769 A JP 2014218769A
Authority
JP
Japan
Prior art keywords
control agent
pitch
pitch control
degree
mol
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
JP2014081361A
Other languages
Japanese (ja)
Inventor
木村　知裕
Tomohiro Kimura
知裕 木村
規之 福島
Noriyuki Fukushima
規之 福島
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.)
Toho Chemical Industry Co Ltd
Original Assignee
Toho Chemical Industry Co 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 Toho Chemical Industry Co Ltd filed Critical Toho Chemical Industry Co Ltd
Priority to JP2014081361A priority Critical patent/JP2014218769A/en
Publication of JP2014218769A publication Critical patent/JP2014218769A/en
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/08—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching
    • 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
    • D21H17/53—Polyethers; Polyesters
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a pitch control agent which reduces adhesiveness of pitch particles in a step of producing pulp and paper so as to suppress and reduce pitch troubles.SOLUTION: A pitch control agent is used in a step of producing pulp and paper and contains a polyvinyl acetal resin synthesized by acetalization reaction of polyvinyl alcohol with an aldehyde.

Description

本発明はパルプ又は紙の製造工程におけるピッチ障害を抑制・防止するためのピッチコントロール剤に関するものである。   The present invention relates to a pitch control agent for suppressing / preventing a pitch failure in a pulp or paper manufacturing process.

パルプ又は紙の製造工程におけるピッチとは、原料の木材やパルプに含まれる天然樹脂や脂肪酸類、古紙由来で混入する接着剤やラテックスなどの粘着性物質、更には、パルプ及び製紙工程で使用される添加薬品等によって生じる有機物などを主体とした非水溶性の粘着性物質の総称である。これらピッチは製紙工程のスラリー中でコロイド状となって分散しているが、せん断力、急激なｐＨ変化、イオン性薬剤の添加などの何らかの外的作用により、そのコロイド状態が破壊されて、凝集・粗大化すると考えられている。   The pitch in the pulp or paper manufacturing process is a natural resin or fatty acids contained in raw wood or pulp, sticky substances such as adhesives and latex mixed from waste paper, and also used in pulp and paper manufacturing processes. It is a general term for water-insoluble adhesive substances mainly composed of organic substances produced by added chemicals. These pitches are dispersed in a colloidal form in the papermaking process slurry, but the colloidal state is destroyed and agglomerated by some external action such as shearing force, rapid pH change, and addition of an ionic drug.・ It is considered to be coarse.

凝集したピッチは、その粘着性によりファンポンプ、配管、チェスト、フェルト、ロール等の製造設備へ付着して生産性を阻害するだけでなく、パルプや紙へ付着して断紙の発生や製品の品質低下を招く。近年、紙の多様化に伴う使用薬品の増加と、公害規制に伴う工程での水のクローズド化により、ピッチ障害は増大する傾向になっている。   Aggregated pitch adheres to the manufacturing equipment such as fan pumps, pipes, chests, felts, rolls, etc. due to its adhesiveness, which not only impedes productivity, but also adheres to pulp and paper, causing paper breaks and product Incurs quality degradation. In recent years, pitch obstacles tend to increase due to an increase in chemicals used due to diversification of paper and the closure of water in processes associated with pollution regulations.

従来ピッチ障害を抑制、防止するため、種々の方策が講じられてきた。例えばタルクやクレイにピッチを吸着させる事によってピッチの粘着性を低下させるとともに紙に抄き込ませる方法（特許文献１）、カチオン性ポリマーを用いてアニオン電荷を有するピッチと結合させて紙へ抄き込む方法（特許文献２）、界面活性剤やアニオン性ポリマーによってピッチを微粒子の状態に分散して凝集・集塊化を防止する方法（特許文献３、４）等が提案されている。   Conventionally, various measures have been taken to suppress and prevent pitch disturbance. For example, a method of reducing the tackiness of the pitch by adsorbing the pitch to talc or clay and embedding it on paper (Patent Document 1). There have been proposed a method (Patent Document 2) and a method (Patent Documents 3 and 4) for preventing pitch and agglomeration by dispersing the pitch in a fine particle state using a surfactant or an anionic polymer.

しかし、タルク等の無機物を使用する方法では、薬剤自体が凝集や沈殿を生じやすいことに加え、ワイヤーなどの摩耗、損傷を引き起こす問題がある。またカチオン性ポリマーを用いてアニオン電荷を有するピッチと結合させて紙に抄き込ませる方法では、系内のコロイド粒子の電荷のバランスを崩す可能性があるため添加量が制限されることに加え、イオン性基を持たないピッチ粒子には効果が得られにくいという欠点もある。界面活性剤やアニオンポリマーを用いた方法は、一般的には短期間での効果は認められるものの、用水の循環再使用が進み水中のピッチ量が増加し限界に達すると、急激なピッチ障害を引き起こす場合がある。この方法には多くの改善が提案されており、例えばけん化度７０〜８０モル％のポリビニルアルコールをピッチ分散剤として用いる方法などが提案されている（特許文献５）が、いずれの方法も必ずしも満足できる結果は得られておらず、更なる改善が望まれている。   However, in the method using an inorganic substance such as talc, there is a problem that the drug itself tends to aggregate and precipitate, and also causes wear and damage of the wire. In addition, in the method in which a cationic polymer is used to bind to a pitch having an anionic charge and the paper is made into paper, the amount of the colloidal particles in the system may be unbalanced, so that the addition amount is limited. Further, there is a drawback that it is difficult to obtain an effect on pitch particles having no ionic group. Although the method using a surfactant or an anionic polymer is generally effective in a short period of time, if the circulation and reuse of water increases and the amount of pitch in the water increases and reaches the limit, a sudden pitch failure is caused. May cause. Many improvements have been proposed for this method. For example, a method using polyvinyl alcohol having a saponification degree of 70 to 80 mol% as a pitch dispersant has been proposed (Patent Document 5), but both methods are not necessarily satisfactory. No results have been obtained and further improvements are desired.

特開昭６０−９４６８７号公報JP-A-60-94687 特許第２６１８４９６号公報Japanese Patent No. 2,618,496 特公昭５９−２８６７６号公報Japanese Patent Publication No.59-28676 特公昭６３−２３２０号公報Japanese Patent Publication No. 63-2320 特公平２−１４４７９号公報Japanese Patent Publication No. 2-14479

本発明の目的は、パルプ又は紙を製造する際のピッチの凝集、及び製造設備へのピッチの付着を著しく抑制し、かつ断紙の発生や製品の品質低下を防ぎ、生産性及び作業性を向上させることのできるピッチコントロール剤を提供することにある。   The object of the present invention is to remarkably suppress pitch agglomeration during the production of pulp or paper and the adhesion of the pitch to the production equipment, and prevent the occurrence of paper breaks and product quality deterioration, thereby improving productivity and workability. An object of the present invention is to provide a pitch control agent that can be improved.

本発明者らは、前記課題を解決するために鋭意検討を重ねた結果、ポリビニルアセタール樹脂からなるピッチコントロール剤が上記課題を解決できることを見出し、本発明を完成するに至った。すなわち本発明は、
（１）ポリビニルアセタール樹脂を含有することを特徴とするピッチコントロール剤、
（２）前記ポリビニルアセタール樹脂が平均重合度３００〜５，０００、けん化度７０〜９９．５モル％のポリビニルアルコールと下記一般式[１]で示されるアルデヒドとのアセタール化反応によって合成されるポリビニルアセタール樹脂である、上記（１）に記載のピッチコントロール剤、
Ｒ１−ＣＨＯ [１]
(ただし、Ｒ１は水素原子または炭素数１〜１０の炭化水素基を表す。)
（３）前記ポリビニルアルコールが平均重合度３００〜３，５００、けん化度７２〜９９．５モル％である、上記（２）に記載のピッチコントロール剤、
（４）前記一般式[１]のアルデヒドがアセトアルデヒド、プロピオンアルデヒド、ブチルアルデヒド、ヘキシルアルデヒドおよびベンズアルデヒドからなる群から選ばれる少なくとも１種である上記（２）または（３）に記載のピッチコントロール剤、
（５）前記ポリビニルアセタール樹脂のアセタール化度が０．１から４０モル％である上記（１）〜（４）のいずれか１項に記載のピッチコントロール剤、
を提供するものである。 As a result of intensive studies to solve the above problems, the present inventors have found that a pitch control agent comprising a polyvinyl acetal resin can solve the above problems, and have completed the present invention. That is, the present invention
(1) A pitch control agent comprising a polyvinyl acetal resin,
(2) Polyvinyl acetal resin synthesized by acetalization reaction of polyvinyl alcohol having an average polymerization degree of 300 to 5,000 and a saponification degree of 70 to 99.5 mol% with an aldehyde represented by the following general formula [1] The pitch control agent according to (1) above, which is an acetal resin,
R 1 —CHO [1]
(However, R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)
(3) The pitch control agent according to (2), wherein the polyvinyl alcohol has an average degree of polymerization of 300 to 3,500 and a degree of saponification of 72 to 99.5 mol%,
(4) The pitch control agent according to (2) or (3), wherein the aldehyde of the general formula [1] is at least one selected from the group consisting of acetaldehyde, propionaldehyde, butyraldehyde, hexylaldehyde, and benzaldehyde,
(5) The pitch control agent according to any one of (1) to (4), wherein the degree of acetalization of the polyvinyl acetal resin is 0.1 to 40 mol%,
Is to provide.

以下に本発明を詳細に説明する。   The present invention is described in detail below.

本発明に言うポリビニルアセタール樹脂とは、ポリビニルアルコールとアルデヒドとのアセタール化反応によって合成することができるポリビニルアセタール樹脂である。具体的には、一般的に、水、アルコール、水とアルコールとの混合溶媒、ジメチルスルホキシド（ＤＭＳＯ）中などで、ポリビニルアルコールとアルデヒドとを酸触媒の存在下にて反応させることにより合成される。   The polyvinyl acetal resin referred to in the present invention is a polyvinyl acetal resin that can be synthesized by an acetalization reaction between polyvinyl alcohol and an aldehyde. Specifically, it is generally synthesized by reacting polyvinyl alcohol and an aldehyde in the presence of an acid catalyst in water, alcohol, a mixed solvent of water and alcohol, dimethyl sulfoxide (DMSO), or the like. .

本発明で用いることができるポリビニルアルコールとしては特に限定されず、ポリ酢酸ビニルをアルカリ、酸、アンモニア水等によりけん化することにより製造されたもの等の従来公知のポリビニルアルコールを用いることができ、一部カルボン酸基などのイオン性基を導入した変性ポリビニルアルコール等も用いることができる。
上記ポリビニルアルコールの重合度は、その平均重合度が３００〜５０００が好ましく、更に好ましくは３００〜３５００である。重合度が上記範囲における下限値以上であれば、反応後のポリビニルアセタール樹脂に十分なピッチコントロール効果が得られ、重合度が上記範囲における上限値以下であれば、反応後のポリビニルアセタール樹脂のハンドリング性も良好である。
また上記ポリビニルアルコールのけん化度は、７０〜９９．５モル％が好ましく、更に好ましくは７２〜９９．５モル％である。 The polyvinyl alcohol that can be used in the present invention is not particularly limited, and a conventionally known polyvinyl alcohol such as one produced by saponifying polyvinyl acetate with alkali, acid, aqueous ammonia, or the like can be used. Modified polyvinyl alcohol and the like into which an ionic group such as a partial carboxylic acid group is introduced can also be used.
The average polymerization degree of the polyvinyl alcohol is preferably 300 to 5000, more preferably 300 to 3500. If the degree of polymerization is equal to or higher than the lower limit in the above range, a sufficient pitch control effect can be obtained for the polyvinyl acetal resin after the reaction. The property is also good.
Moreover, 70-99.5 mol% is preferable and, as for the saponification degree of the said polyvinyl alcohol, More preferably, it is 72-99.5 mol%.

本発明で用いることができるアルデヒドは特に限定されないが、一般式[１]で示されるアルデヒドが好ましく、Ｒ１は水素原子、炭素数１〜１０の直鎖状、分岐状、環状の飽和、不飽和または芳香族の炭化水素基が挙げられる。このようなアルデヒドとしては例えばホルムアルデヒド、アセトアルデヒド、プロピオニルアルデヒド、ｎ−ブチルアルデヒド、イソブチルアルデヒド、tert−ブチルアルデヒド、ヘキシルアルデヒド、シクロヘキシルアルデヒド、ベンズアルデヒド、オクチルアルデヒドなどが挙げられる。中でもｎ−ブチルアルデヒド、イソブチルアルデヒド、tert−ブチルアルデヒド、ベンズアルデヒドが更に好ましい。これらアルデヒドは単独で用いてもよく、２種以上を併用してもよい。 The aldehyde that can be used in the present invention is not particularly limited, but an aldehyde represented by the general formula [1] is preferable, and R 1 is a hydrogen atom, a linear, branched, cyclic saturated or unsaturated group having 1 to 10 carbon atoms. A saturated or aromatic hydrocarbon group is mentioned. Examples of such aldehydes include formaldehyde, acetaldehyde, propionyl aldehyde, n-butyraldehyde, isobutyraldehyde, tert-butyraldehyde, hexyl aldehyde, cyclohexyl aldehyde, benzaldehyde, octyl aldehyde, and the like. Of these, n-butyraldehyde, isobutyraldehyde, tert-butyraldehyde, and benzaldehyde are more preferable. These aldehydes may be used alone or in combination of two or more.

上記酸触媒としては特に限定されず、有機酸、無機酸のどちらでも使用可能であり、例えば酢酸、パラトルエンスルホン酸、硝酸、硫酸、塩酸などが挙げられる。また、合成反応を中止するために、通常、アルカリ中和を行うが、その際に使用されるアルカリとしては、例えば、水酸化ナトリウム、水酸化カリウム、アンモニア、酢酸ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウムなどが挙げられる。   The acid catalyst is not particularly limited, and either an organic acid or an inorganic acid can be used. Examples thereof include acetic acid, paratoluenesulfonic acid, nitric acid, sulfuric acid, and hydrochloric acid. In order to stop the synthesis reaction, alkali neutralization is usually performed. Examples of the alkali used in this case include sodium hydroxide, potassium hydroxide, ammonia, sodium acetate, sodium carbonate, and sodium bicarbonate. , Potassium carbonate, potassium hydrogen carbonate and the like.

上記ポリビニルアセタール樹脂のアセタール化度は０．１〜４０モル％が好ましく、更に好ましくは１．０〜２０モル％である。アセタール化度が４０％を超えるとポリビニルアセタール樹脂の水溶性もしくは水分散性が著しく低下し、ピッチコントロール剤で使用する際の効果が低下する。   The acetalization degree of the polyvinyl acetal resin is preferably 0.1 to 40 mol%, more preferably 1.0 to 20 mol%. If the degree of acetalization exceeds 40%, the water-solubility or water-dispersibility of the polyvinyl acetal resin is remarkably lowered, and the effect when used as a pitch control agent is lowered.

本発明のピッチコントロール剤は、必要に応じポリビニルアセタール樹脂に加え、界面活性剤、ポリマー、キレート剤、溶剤、消泡剤、防腐剤などを配合することができる。   The pitch control agent of the present invention can contain a surfactant, a polymer, a chelating agent, a solvent, an antifoaming agent, an antiseptic, and the like in addition to the polyvinyl acetal resin as necessary.

本発明のピッチコントロール剤をパルプ原料や製紙原料に使用する場合は、通常、本発明のポリビニルアセタール樹脂をパルプ重量に対して１０〜１００００ｐｐｍ、好ましくは１００〜５０００ｐｐｍの範囲から適宜選択し、パルプ原料系や製紙原料系に対して添加し使用する。また、パルプもしくは紙を製造する工程において製造装置類、例えばワイヤー、フェルト、カンバス、ロール等の洗浄シャワーラインに圧入してシャワー水とともに噴霧し使用する場合は、使用する水に対して０．５〜２０００ｐｐｍ、好ましくは２〜５００ｐｐｍの範囲で添加し使用する。   When the pitch control agent of the present invention is used as a pulp raw material or papermaking raw material, the polyvinyl acetal resin of the present invention is usually appropriately selected from the range of 10 to 10000 ppm, preferably 100 to 5000 ppm, based on the pulp weight. Add to the system and papermaking raw material system. In addition, in the process of producing pulp or paper, when used by being pressed into a washing shower line such as a wire, felt, canvas, roll, etc. and sprayed with shower water, the amount of water used is 0.5. It is added in the range of -2000 ppm, preferably 2-500 ppm.

また、本発明のピッチコントロール剤を使用する際にその効果を損なわない範囲において、他の工程添加剤、例えば、歩留り剤、スケール防止剤、スライムコントロール剤、消泡剤、紙力剤、および他のピッチコントロール剤を併用することに何ら制限を加えるものではない。   In addition, other process additives such as a retention agent, a scale inhibitor, a slime control agent, an antifoaming agent, a paper strength agent, and the like, as long as the effect of the pitch control agent of the present invention is not impaired. No limitation is imposed on the combined use of the pitch control agent.

以下、本発明の実施例を示すが、これに限定されるものではない。
製造例１
温度計、撹拌装置を備えたフラスコに平均重合度３００、けん化度９８．２モル％のポリビニルアルコール４４重量部、及びイオン交換水３９６重量部を添加し、加温溶解させ、ポリビニルアルコール水溶液を作製した。この水溶液を２０℃に保持しつつ、３５重量％塩酸を４重量部添加し、更にブチルアルデヒド４．３重量部を滴下した。その後同温度にて１７時間撹拌保持した。得られた反応物を２０重量％水酸化ナトリウム水溶液７．３重量部で中和し、精製することにより本発明品Ｎｏ．１のピッチコントロール剤の１０重量％水溶液を得た。得られた水溶液をポリエチレンテレフタレートフィルム上に流涎し、乾燥させて透明なフィルムを得た。このフィルムをＤＭＳＯ−ｄ６溶液に溶解し、１Ｈ−ＮＭＲによって測定したブチラール化度は１０モル％であった。 Examples of the present invention are shown below, but are not limited thereto.
Production Example 1
44 parts by weight of polyvinyl alcohol having an average polymerization degree of 300 and a saponification degree of 98.2 mol% and 396 parts by weight of ion-exchanged water are added to a flask equipped with a thermometer and a stirrer, and heated and dissolved to prepare a polyvinyl alcohol aqueous solution. did. While maintaining this aqueous solution at 20 ° C., 4 parts by weight of 35% by weight hydrochloric acid was added, and 4.3 parts by weight of butyraldehyde was further added dropwise. Thereafter, the mixture was kept stirred for 17 hours at the same temperature. The reaction product obtained was neutralized with 7.3 parts by weight of a 20% by weight aqueous sodium hydroxide solution and purified, thereby purifying the product of the present invention. A 10 wt% aqueous solution of 1 pitch control agent was obtained. The obtained aqueous solution was poured onto a polyethylene terephthalate film and dried to obtain a transparent film. This film was dissolved in DMSO-d6 solution, and the degree of butyralization measured by 1 H-NMR was 10 mol%.

製造例２
製造例１と同様の方法で平均重合度５００、けん化度９８．４モル％のポリビニルアルコール４４重量部とベンズアルデヒド３．２重量部を反応させ、本発明品Ｎｏ．２のピッチコントロール剤の１０重量％水溶液を得た。１Ｈ−ＮＭＲによって測定したベンザール化度は５モル％であった。 Production Example 2
In the same manner as in Production Example 1, 44 parts by weight of polyvinyl alcohol having an average degree of polymerization of 500 and a degree of saponification of 98.4 mol% were reacted with 3.2 parts by weight of benzaldehyde. A 10% by weight aqueous solution of the pitch control agent of No. 2 was obtained. The degree of benzalization measured by 1 H-NMR was 5 mol%.

製造例３
製造例１と同様の方法で平均重合度１７００、けん化度９８．９モル％のポリビニルアルコール４４重量部をイオン交換水５０６重量部に加温溶解させ、ブチルアルデヒド１．４重量部とを反応させ、本発明品Ｎｏ．３のピッチコントロール剤の８重量％水溶液を得た。１Ｈ−ＮＭＲによって測定したブチラール化度は３モル％であった。 Production Example 3
In the same manner as in Production Example 1, 44 parts by weight of polyvinyl alcohol having an average degree of polymerization of 1700 and a degree of saponification of 98.9 mol% was dissolved by heating in 506 parts by weight of ion-exchanged water and reacted with 1.4 parts by weight of butyraldehyde. The product No. of the present invention. An 8 wt% aqueous solution of the pitch control agent of No. 3 was obtained. The degree of butyralization measured by 1 H-NMR was 3 mol%.

製造例４
製造例１と同様の方法で平均重合度３３００、けん化度９９．１モル％のポリビニルアルコール４４重量部をイオン交換水１０５６重量部に加温溶解させ、ホルムアルデヒド４．５重量部を反応させ、本発明品Ｎｏ．４のピッチコントロール剤４重量％の水溶液を得た。このホルマール化度は２４モル％であった。 Production Example 4
In the same manner as in Production Example 1, 44 parts by weight of polyvinyl alcohol having an average degree of polymerization of 3300 and a saponification degree of 99.1 mol% was dissolved by heating in 1056 parts by weight of ion-exchanged water and reacted with 4.5 parts by weight of formaldehyde. Invention No. An aqueous solution of 4% by weight of the pitch control agent 4 was obtained. The degree of formalization was 24 mol%.

製造例５
製造例１と同様の方法で平均重合度５００、けん化度８９．０モル％のポリビニルアルコール４４重量部とブチルアルデヒド３．６重量部を反応させ、本発明品Ｎｏ．５のピッチコントロール剤の１０重量％水溶液を得た。１Ｈ−ＮＭＲによって測定したブチラール化度は７モル％であった。 Production Example 5
In the same manner as in Production Example 1, 44 parts by weight of polyvinyl alcohol having an average degree of polymerization of 500 and a degree of saponification of 89.0 mol% and 3.6 parts by weight of butyraldehyde were reacted. A 10 wt% aqueous solution of 5 pitch control agent was obtained. The butyralization degree measured by 1 H-NMR was 7 mol%.

製造例６
製造例１と同様の方法で平均重合度５００、けん化度８０．３モル％のポリビニルアルコール４４重量部とベンズアルデヒド３．０重量部を反応させ、本発明品Ｎｏ．６のピッチコントロール剤の１０重量％水溶液を得た。１Ｈ−ＮＭＲによって測定したベンザール化度は４モル％であった。 Production Example 6
In the same manner as in Production Example 1, 44 parts by weight of polyvinyl alcohol having an average polymerization degree of 500 and a saponification degree of 80.3 mol% were reacted with 3.0 parts by weight of benzaldehyde. A 10 wt% aqueous solution of No. 6 pitch control agent was obtained. The benzalization degree measured by 1 H-NMR was 4 mol%.

製造例７
製造例１と同様の方法で平均重合度５００、けん化度７３．０モル％のポリビニルアルコール４４重量部とブチルアルデヒド０.３重量部を反応させ、本発明品Ｎｏ．７のピッチコントロール剤１０重量％の水溶液を得た。このブチラール化度は０．６モル％であった。 Production Example 7
In the same manner as in Production Example 1, 44 parts by weight of polyvinyl alcohol having an average polymerization degree of 500 and a saponification degree of 73.0 mol% were reacted with 0.3 part by weight of butyraldehyde. Thus, a 10% by weight aqueous solution of No. 7 pitch control agent was obtained. The degree of butyralization was 0.6 mol%.

製造例８
温度計、撹拌装置を備えたフラスコに平均重合度１０００、けん化度９８．２モル％のポリビニルアルコール４４重量部、及びイオン交換水２９４重量部を添加し、加温溶解させ、ポリビニルアルコール水溶液を作製した。この水溶液を２０℃に保持しつつ、イソプロピルアルコール３３重量部、及び３５重量％塩酸を６重量部添加し、更にアセトアルデヒド４．０重量部を滴下した。その後同温度にて１７時間撹拌保持した。得られた反応物を２０．０重量％水酸化ナトリウム水溶液１１．６重量部で中和し、精製することにより本発明品Ｎｏ．８のピッチコントロール剤の１１．２重量％水溶液を得た。１Ｈ−ＮＭＲによって測定したアセタール化度は１５モル％であった。 Production Example 8
44 parts by weight of polyvinyl alcohol having an average degree of polymerization of 1000 and a degree of saponification of 98.2 mol% and 294 parts by weight of ion-exchanged water are added to a flask equipped with a thermometer and a stirrer, and heated to dissolve to prepare a polyvinyl alcohol aqueous solution. did. While maintaining this aqueous solution at 20 ° C., 33 parts by weight of isopropyl alcohol and 6 parts by weight of 35% by weight hydrochloric acid were added, and 4.0 parts by weight of acetaldehyde was further added dropwise. Thereafter, the mixture was kept stirred for 17 hours at the same temperature. The obtained reaction product was neutralized with 11.6 parts by weight of a 20.0% by weight aqueous sodium hydroxide solution and purified, thereby purifying the product of the present invention. An 11.2 wt% aqueous solution of 8 pitch control agents was obtained. The degree of acetalization measured by 1 H-NMR was 15 mol%.

本発明品の効果を確かめるべく粘着テープ脱粘着試験、並びにピッチ制御試験を実施した。尚、比較としてポリビニルアルコール、市販のピッチコントロール剤及び界面活性剤を供試した。   In order to confirm the effect of the product of the present invention, an adhesive tape detack test and a pitch control test were conducted. For comparison, polyvinyl alcohol, a commercially available pitch control agent and a surfactant were used.

試験に使用した比較薬剤を表１に記す。   Table 1 shows the comparative drugs used in the test.

（湿潤時粘着テープ脱粘着試験）
本試験はワイヤーやフェルト等のウェットパートにおける粘着物質の粘着性の評価を想定したものである。１０００ｍＬのビーカーにイオン交換水で各薬剤を固形分３００ｐｐｍに調整した試験液９５０ｍＬを入れ、スターラーで撹拌しながら湯浴で４０℃に温調した。温調した試験液に市販の粘着テープを５×１２ｃｍに裁断したものを浸漬させ、浸漬から５分後に取り出した。粘着テープを鋼鈑に１２ｋｇの金属ローラーで圧着させ、引張試験器（東洋精機製作所製）を用いて２つを１８０°方向に引き離すのに必要な力を測定した。必要な力の減少は粘着物質の粘着性が軽減されたことを示す。 (Adhesive tape detack test when wet)
This test assumes the evaluation of the adhesiveness of adhesive substances in wet parts such as wires and felts. In a 1000 mL beaker, 950 mL of a test solution in which each drug was adjusted to a solid content of 300 ppm with ion-exchanged water was added, and the temperature was adjusted to 40 ° C. with a hot water bath while stirring with a stirrer. A commercially available pressure-sensitive adhesive tape cut to 5 × 12 cm was immersed in the temperature-controlled test solution and taken out 5 minutes after the immersion. The pressure-sensitive adhesive tape was pressed against a steel plate with a 12 kg metal roller, and the force required to separate the two in the 180 ° direction was measured using a tensile tester (manufactured by Toyo Seiki Seisakusho). A decrease in the required force indicates that the tackiness of the adhesive substance has been reduced.

湿潤時脱粘着率（％）を以下の式１によって計算する。
［式１］
The detacking rate (%) when wet is calculated by the following formula 1.
[Formula 1]

（乾燥時粘着テープ脱粘着試験）
本試験はドライパートにおける粘着物質の粘着性の評価を想定したものである。１０００ｍＬのビーカーにイオン交換水で各薬剤を固形分５０００ｐｐｍに調整した試験液９５０ｍＬを入れ、スターラーで撹拌しながら湯浴で４０℃に温調した。温調した試験液に市販の粘着テープを５×１２ｃｍに裁断したものを浸漬させ、浸漬から５分後に取り出し、水洗した後１０５℃の乾燥機で５分間乾燥させた。次いで粘着テープを鋼鈑に１２ｋｇの金属ローラーで圧着させ、引張試験器（東洋精機製作所製）を用いて２つを１８０°方向に引き離すのに必要な力を測定した。必要な力の減少は粘着物質の粘着性が軽減されたことを示す。 (Adhesive tape detack test when dry)
This test assumes the evaluation of the adhesiveness of the adhesive substance in the dry part. In a 1000 mL beaker, 950 mL of a test solution in which each drug was adjusted to a solid content of 5000 ppm with ion-exchanged water was added, and the temperature was adjusted to 40 ° C. with a hot water bath while stirring with a stirrer. A commercially available adhesive tape cut to 5 × 12 cm was immersed in the temperature-controlled test solution, taken out 5 minutes after the immersion, washed with water, and then dried with a dryer at 105 ° C. for 5 minutes. Next, the pressure-sensitive adhesive tape was pressed against a steel plate with a 12 kg metal roller, and the force required to separate the two in the 180 ° direction was measured using a tensile tester (manufactured by Toyo Seiki Seisakusho). A decrease in the required force indicates that the tackiness of the adhesive substance has been reduced.

乾燥時脱粘着率（％）を以下の式２によって計算する。
［式２］
The detackifying rate (%) at the time of drying is calculated by the following formula 2.
[Formula 2]

試験結果を表２に示す。   The test results are shown in Table 2.

（ピッチ制御試験）
（テスト例１）
クラフトパルプの製造工程より採取したピッチ（ピッチ１）を溶剤で抽出し、２％濃度に調整した。このピッチ溶液にＬＢＫＰを浸漬し、１１０℃で３時間乾燥して得たピッチ付着パルプ（ピッチ付着量：対パルプ１．５％）を、１５％濃度で離解後、３％濃度に希釈し試験用パルプスラリーとした。試験用パルプスラリーは、Ｊ．ＴＡＰＰＩ紙パルプ試験Ｎｏ．１１のパルプピッチの金網付着試験法（試験器…熊谷理機工業（株）製ピッチテスター）に従ってピッチ付着試験を行い、ワイヤーへのピッチ付着量より性能評価を行った。尚、各薬剤の添加量は対パルプ当たり０．０５重量％（固型分）であり、この時の試験温度は４０℃、使用した溶剤はベンゼン／エタノール（２／１）混合溶剤である。 (Pitch control test)
(Test example 1)
The pitch (pitch 1) collected from the kraft pulp manufacturing process was extracted with a solvent and adjusted to 2% concentration. Pitch-adhered pulp obtained by immersing LBKP in this pitch solution and drying at 110 ° C. for 3 hours (pitch adhesion amount: 1.5% of pulp) was disaggregated at 15% concentration and diluted to 3% concentration for testing. A pulp slurry was obtained. Test pulp slurries are described in J. TAPPI paper pulp test no. A pitch adhesion test was conducted in accordance with 11 pulp pitch wire mesh adhesion test method (tester: pitch tester manufactured by Kumagai Riki Kogyo Co., Ltd.), and performance was evaluated from the amount of pitch adhesion to the wire. The amount of each agent added is 0.05% by weight (solid content) per pulp, the test temperature at this time is 40 ° C., and the solvent used is a benzene / ethanol (2/1) mixed solvent.

（テスト例２）
ダンボール古紙を原料として中芯を製造している工程から採取したピッチ（ピッチ２）を用い、テスト例１と同様の試験を行った。この時、使用した溶剤はトルエンである。 (Test example 2)
A test similar to Test Example 1 was performed using a pitch (pitch 2) collected from the process of manufacturing the core using corrugated cardboard as a raw material. At this time, the solvent used was toluene.

ピッチ付着量はパルプ１００ｇ当たりのｍｇ数であり、付着防止率（％）は以下の式３によって計算される。
［式３］
The pitch adhesion amount is the number of mg per 100 g of pulp, and the adhesion prevention rate (%) is calculated by the following Equation 3.
[Formula 3]

この試験の結果を表３に示す。   The results of this test are shown in Table 3.

表２及び表３に示したように本発明のピッチコントロール剤は比較品と比べ、粘着性物質の粘着性低減効果が良好且つ、優れたピッチ抑制効果があることが判る。
As shown in Tables 2 and 3, it can be seen that the pitch control agent of the present invention has a better adhesiveness-reducing effect of the adhesive material and an excellent pitch-inhibiting effect than the comparative product.

Claims (5)

ポリビニルアセタール樹脂を含有することを特徴とするピッチコントロール剤。 A pitch control agent comprising a polyvinyl acetal resin. 前記ポリビニルアセタール樹脂が、平均重合度３００〜５，０００、けん化度７０〜９９．５モル％のポリビニルアルコールと下記一般式[１]で示されるアルデヒドとのアセタール化反応によって合成されるポリビニルアセタール樹脂である請求項１に記載のピッチコントロール剤。
Ｒ１−ＣＨＯ [１]
(ただし、Ｒ１は水素原子または炭素数１〜１０の炭化水素基を表す。) The polyvinyl acetal resin is synthesized by an acetalization reaction between polyvinyl alcohol having an average polymerization degree of 300 to 5,000 and a saponification degree of 70 to 99.5 mol% and an aldehyde represented by the following general formula [1]. The pitch control agent according to claim 1.
R 1 —CHO [1]
(However, R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.) 前記ポリビニルアルコールが平均重合度３００〜３，５００、けん化度７２〜９９．５モル％である請求項２に記載のピッチコントロール剤。 The pitch control agent according to claim 2, wherein the polyvinyl alcohol has an average polymerization degree of 300 to 3,500 and a saponification degree of 72 to 99.5 mol%. 前記一般式[１]のアルデヒドがアセトアルデヒド、プロピオンアルデヒド、ブチルアルデヒド、ヘキシルアルデヒドおよびベンズアルデヒドからなる群から選ばれる少なくとも１種である請求項２または３に記載のピッチコントロール剤。 The pitch control agent according to claim 2 or 3, wherein the aldehyde of the general formula [1] is at least one selected from the group consisting of acetaldehyde, propionaldehyde, butyraldehyde, hexylaldehyde, and benzaldehyde. 前記ポリビニルアセタール樹脂のアセタール化度が０．１〜４０モル％である請求項１〜４のいずれか１項に記載のピッチコントロール剤。 The pitch control agent according to any one of claims 1 to 4, wherein the degree of acetalization of the polyvinyl acetal resin is 0.1 to 40 mol%.
JP2014081361A 2013-04-10 2014-04-10 Pitch control agent Pending JP2014218769A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014081361A JP2014218769A (en) 2013-04-10 2014-04-10 Pitch control agent

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2013082520 2013-04-10
JP2013082520 2013-04-10
JP2014081361A JP2014218769A (en) 2013-04-10 2014-04-10 Pitch control agent

Publications (1)

Publication Number Publication Date
JP2014218769A true JP2014218769A (en) 2014-11-20

Family

ID=51937489

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2014081361A Pending JP2014218769A (en) 2013-04-10 2014-04-10 Pitch control agent

Country Status (1)

Country Link
JP (1) JP2014218769A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01239194A (en) * 1988-03-21 1989-09-25 Kuraray Co Ltd Production of paper
JPH10158328A (en) * 1996-12-02 1998-06-16 Sekisui Chem Co Ltd Production of polyvinyl acetal resin
JP2000290886A (en) * 1999-04-09 2000-10-17 Nof Corp Pitch attaching suppressor
JP2006328560A (en) * 2005-05-23 2006-12-07 Nichiyu Solution Inc Method for producing paper
JP2010189779A (en) * 2009-02-16 2010-09-02 Hakuto Co Ltd Agent and method for preventing attachment of pitch

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01239194A (en) * 1988-03-21 1989-09-25 Kuraray Co Ltd Production of paper
JPH10158328A (en) * 1996-12-02 1998-06-16 Sekisui Chem Co Ltd Production of polyvinyl acetal resin
JP2000290886A (en) * 1999-04-09 2000-10-17 Nof Corp Pitch attaching suppressor
JP2006328560A (en) * 2005-05-23 2006-12-07 Nichiyu Solution Inc Method for producing paper
JP2010189779A (en) * 2009-02-16 2010-09-02 Hakuto Co Ltd Agent and method for preventing attachment of pitch

Similar Documents

Publication Publication Date Title
JP4503674B2 (en) Method for producing cellulose nanofiber and oxidation catalyst for cellulose
KR102269096B1 (en) Pitch inhibitor, pitch inhibition method, and process for producing deinked pulp
JP3612124B2 (en) Acetoacetate group-containing polyvinyl alcohol resin composition
JP5257933B2 (en) Paper making flocculant
JP4767645B2 (en) Papermaking aid
JP6442855B2 (en) Photosensitive composition and method for producing the same
JP2008115500A (en) Pitch adhesion inhibitor
JP2014218769A (en) Pitch control agent
WO2016002309A1 (en) Pitch inhibitor, pitch inhibition method, and paper production method
JP2006152206A (en) Polyvinyl alcohol-based resin and its use
KR101662981B1 (en) Method for producing paper, and pitch removal agent
JP2007204585A (en) Resin composition for filter
JP5084023B2 (en) Internal additive for papermaking and method of using the same
JP3199065B2 (en) Internal sizing method for paper
JP4275213B2 (en) Press roll water doctor paper dust adhesion prevention method and paper dust adhesion prevention method
EP3455404B1 (en) Tissue dust reduction
JP3717279B2 (en) Pitch inhibitor for papermaking
WO1992000417A1 (en) Papermaking process and papermaking additive
JP4201121B2 (en) Paperboard manufacturing method
JP2005350807A (en) Pitch control agent
JPS58115195A (en) Surface size agent
JP2019202434A (en) Laminate
JP4615098B2 (en) Pitch control method
JP2010236125A (en) Method for producing paper, and paper using the same
JPH0457992A (en) Additive for paper-making process and process for making paper

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20170327

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20180112

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20180130

A601 Written request for extension of time

Free format text: JAPANESE INTERMEDIATE CODE: A601

Effective date: 20180330

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20180731