JP2021055225A - Water permeability improver - Google Patents
Water permeability improver Download PDFInfo
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- JP2021055225A JP2021055225A JP2019181095A JP2019181095A JP2021055225A JP 2021055225 A JP2021055225 A JP 2021055225A JP 2019181095 A JP2019181095 A JP 2019181095A JP 2019181095 A JP2019181095 A JP 2019181095A JP 2021055225 A JP2021055225 A JP 2021055225A
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
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- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、通水性向上剤に関し、詳しくは、紙の製造工程においてワイヤーやフェルトなどの水分を除去するための製紙用設備の通水性を向上させる通水性向上剤に関する。 The present invention relates to a water permeability improver, and more particularly to a water permeability improver for improving the water permeability of a papermaking facility for removing water such as wires and felts in a paper manufacturing process.
紙の製造は、木材などの繊維を水に懸濁させたパルプをワイヤーの上にのせて脱水し、更にフェルトで水を吸い取り搾水し、その後に乾燥させて行なわれている。ワイヤーやフェルトなどの製紙用設備は、ナイロンやポリエステルなどの疎水性の樹脂から一般にできており、必要に応じて界面活性剤などで親水化されている。しかし、パルプの原料中に含まれる樹脂などに由来する疎水性の汚れがこれら製紙用設備に堆積し、目詰まりを起こすと、表面が疎水性となり、水を通す能力（通水性）が低下する。 Paper is produced by placing pulp in which fibers such as wood are suspended in water on a wire to dehydrate it, sucking water with felt to squeeze it, and then drying it. Papermaking equipment such as wire and felt is generally made of hydrophobic resin such as nylon and polyester, and is hydrophilized with a surfactant or the like as needed. However, when hydrophobic stains derived from resins contained in the raw material of pulp accumulate on these papermaking equipment and cause clogging, the surface becomes hydrophobic and the ability to allow water to pass through (water permeability) decreases. ..
そのため、紙の通水性向上を目的として、（１）シャワー水などによる連続的な洗浄、（２）ピッチコントロール剤を添加したシャワー水による洗浄などが行われている。
上記（１）の例としては、例えば非特許文献１に示す洗浄方法が挙げられ、この方法ではフェルトに付着した汚れを高圧の水（シャワー）で洗浄を行う。上記（２）の例としては、ジメチルアミンとエピクロルヒドリンとの重合体および界面活性剤を外添し、ワイヤーやフェルトへの汚れの付着を防止することを特徴とする方法（例えば、特許文献１参照）などが挙げられる。これら（１）および（２）の方法でも、ある程度は通水性が向上していた。
Therefore, for the purpose of improving the water permeability of the paper, (1) continuous washing with shower water or the like, (2) washing with shower water to which a pitch control agent is added, or the like is performed.
Examples of the above (1) include, for example, the cleaning method shown in Non-Patent Document 1, in which the dirt adhering to the felt is cleaned with high-pressure water (shower). As an example of the above (2), a method characterized by externally adding a polymer of dimethylamine and epichlorohydrin and a surfactant to prevent adhesion of stains to wires and felt (see, for example, Patent Document 1). ) And so on. Even with these methods (1) and (2), water permeability was improved to some extent.
しかしながら、白水のクローズド化、古紙利用率の増加、ワイヤーやフェルトの織り構造の多重化などに起因して、通水性に由来するトラブルも増加傾向にある。特に、古紙および損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、または紙を製造する際に使用されるサイズ剤や紙の表面コートに使用されるワックスなど疎水性の汚れが増加することにより、ワイヤーやフェルトは表面が通常よりも疎水性となり、通水性が極端に低下する。このような状況下では、ワイヤー上での脱水、更にフェルトによる搾水が不十分となり、紙（湿紙）の水分量が増え、断紙などのトラブルが発生するおそれがある。また、従来技術によって通水性がある程度向上しても、薬剤の剥離や汚れの付着により使用中に再度、通水性（再通水性）が低下するおそれもある。
このように強い疎水性の汚れが多く付着し易い状況で、通水性向上効果が高く、その効果を維持することができる通水性向上剤は開発されていないのが現状である。
However, problems caused by water permeability are also increasing due to the closure of white water, the increase in the utilization rate of used paper, and the multiplexing of the woven structure of wire and felt. In particular, hydrophobic stains such as adhesives and adhesives such as latex mixed from waste paper and waste paper, or sizing agents used in paper production and wax used for surface coating of paper increase. As a result, the surface of the wire or felt becomes more hydrophobic than usual, and the water permeability is extremely reduced. Under such circumstances, dehydration on the wire and water squeezing with felt become insufficient, the amount of water in the paper (wet paper) increases, and problems such as paper breakage may occur. Further, even if the water permeability is improved to some extent by the conventional technique, the water permeability (re-water permeability) may be lowered again during use due to the peeling of the chemical agent or the adhesion of dirt.
In such a situation where a lot of strongly hydrophobic stains are easily attached, a water permeability improving agent having a high water permeability improving effect and capable of maintaining the effect has not been developed at present.
本発明は、上記事情に鑑みなされたものであり、紙の製造工程においてワイヤーやフェルトなどの水分を除去するための製紙用設備に強い疎水性の汚れが多く付着し易い状況であっても、通水性向上効果が高く、その効果を維持することを目的とする。 The present invention has been made in view of the above circumstances, and even in a situation where a large amount of strong hydrophobic stains are likely to adhere to a papermaking facility for removing water such as wires and felt in a paper manufacturing process. The effect of improving water permeability is high, and the purpose is to maintain that effect.
本発明者らは、上記課題を解決するために鋭意検討を行った結果、ビニルピロリドン（以下「ＶＰ」と表記することがある。）と炭素数が４〜６のカルボン酸ビニル（以下「ＶＳｃ」と表記することがある。）とのモル比を所定範囲に調整して得られた共重合体（以下「ＰＶＰ／ＶＳｃ」と表記することがある。）を使用することにより、疎水性のワイヤーやフェルトの表面を親水化し、通水性の向上およびその効果の維持（再通水性の向上）に有効であることを見出した。 As a result of diligent studies to solve the above problems, the present inventors have conducted diligent studies on vinylpyrrolidone (hereinafter sometimes referred to as "VP") and vinyl carboxylate having 4 to 6 carbon atoms (hereinafter "VSc"). (May be referred to as “PVP / VSc”) obtained by adjusting the molar ratio with (may be referred to as “PVP / VSc”) to a predetermined range. It was found that the surface of the wire or felt is made hydrophilic, which is effective in improving the water permeability and maintaining the effect (improving the water permeability).
すなわち本発明の通水性向上剤は、ＶＰとＶＳｃとを重合して得られるＰＶＰ／ＶＳｃからなり、ＶＰ：ＶＳｃのモル比が４０：６０〜９９．５：０．５であることを特徴とする。 That is, the water permeability improver of the present invention is composed of PVP / VSc obtained by polymerizing VP and VSc, and is characterized in that the molar ratio of VP: VSc is 40:60 to 99.5: 0.5. To do.
本発明の通水性向上剤は、ワイヤーやフェルト、ロールなどの製造設備に接触させる外添型の薬剤である。内添型の薬剤がパルプスラリー全量を処理するのに対して、外添型の薬剤は任意の製造設備および製造設備表面近傍を選択的に処理することから、薬剤使用量が少量で済み、パルプスラリーおよび紙製品へ及ぼす悪影響が少なく、高い通水性向上性が得られるなど、多数のメリットが得られる。また、疎水性の汚れが多い状況であっても、その効果（再通水性) を維持することができる。 The water permeability improving agent of the present invention is an externally added type agent that comes into contact with manufacturing equipment such as wire, felt, and roll. While the internal chemicals process the entire amount of pulp slurry, the external chemicals selectively treat any manufacturing equipment and the vicinity of the surface of the manufacturing equipment, so the amount of chemicals used can be small and the pulp can be used. There are many merits such as less adverse effect on slurry and paper products and high water permeability improvement. In addition, the effect (reperfusion) can be maintained even in a situation where there are many hydrophobic stains.
本発明の通水性向上剤は、紙の製造工程において、疎水性かつ構造が複雑な製紙用具・製紙装置への付着と親水化効果が充分であるので、ワイヤーやフェルトなどの通水性が要求される製紙用設備の通水性を向上することができる。 The water-permeable improver of the present invention is required to have water permeability of wires, felts, etc. because it has sufficient adhesion and hydrophilicity to papermaking tools and papermaking devices having a hydrophobic and complicated structure in the paper manufacturing process. It is possible to improve the water permeability of papermaking equipment.
本発明の通水性向上剤は、ワイヤーやフェルト、ロールなどの製造設備に接触させる外添型の薬剤である。内添型の薬剤がパルプスラリー全量を処理するのに対して、外添型の薬剤は任意の製造設備および製造設備表面近傍を選択的に処理することから、薬剤使用量が少量で済み、パルプスラリーおよび紙製品へ及ぼす悪影響が少ないとうメリットがある。したがって、本発明の通水性向上剤を含有する水溶液の所定量を製紙用具や製紙装置に外添することによって、製紙用具や製紙装置が汚れていた場合でも高い通水性が得られるうえ、薬剤使用量の低減によるコスト削減、パルプスラリーおよび紙製品へ及ぼす悪影響が少ないという効果も得られる。更に、シャワーによる濯ぎや抄紙工程を経ても、その通水性の維持（再通水性の向上）に有効である。 The water permeability improving agent of the present invention is an externally added type agent that comes into contact with manufacturing equipment such as wire, felt, and roll. While the internal chemicals process the entire amount of pulp slurry, the external chemicals selectively treat any manufacturing equipment and the vicinity of the surface of the manufacturing equipment, so the amount of chemicals used can be small and the pulp can be used. It has the advantage of having little adverse effect on slurries and paper products. Therefore, by externally adding a predetermined amount of the aqueous solution containing the water permeability improving agent of the present invention to the papermaking tool or the papermaking apparatus, high water permeability can be obtained even when the papermaking tool or the papermaking apparatus is dirty, and the chemicals are used. It also has the effect of reducing costs by reducing the amount and having less adverse effect on pulp slurry and paper products. Further, it is effective in maintaining the water permeability (improving the water permeability) even after rinsing with a shower or performing a papermaking process.
以下、本発明の実施形態について説明するが、これにより本発明が制限されるものではない。なお、本明細書において記号「〜」を用いて規定された数値範囲は「〜」の両端（上限および下限）の数値を含むものとする。例えば「２〜５」は２以上５以下を表す。 Hereinafter, embodiments of the present invention will be described, but this does not limit the present invention. In addition, the numerical range defined by using the symbol "~" in this specification shall include the numerical values at both ends (upper limit and lower limit) of "~". For example, "2 to 5" represents 2 or more and 5 or less.
〔通水性向上剤〕
本発明の通水性向上剤は、ＶＰとＶＳｃとを重合して得られるＰＶＰ／ＶＳｃからなる。
ＶＳｃとしては飽和カルボン酸ビニルが好ましい。炭素数が４〜６の飽和脂肪族カルボン酸ビニルとしては、酢酸ビニル、プロピオン酸ビニル、酪酸ビニルが挙げられ、入手の容易性の点から、酢酸ビニルが好ましい。
[Water permeability improver]
The water permeability improver of the present invention comprises PVP / VSc obtained by polymerizing VP and VSc.
Saturated vinyl carboxylate is preferable as VSc. Examples of the saturated aliphatic carboxylate vinyl having 4 to 6 carbon atoms include vinyl acetate, vinyl propionate, and vinyl butyrate, and vinyl acetate is preferable from the viewpoint of easy availability.
ＶＰ：ＶＳｃのモル比は、４０：６０〜９９．５：０．５であり、好ましくは５０：５０〜９５：５、より好ましくは６０：４０〜９０：１０である。ＶＰ：ＶＳｃのモル比がこれらの範囲から外れると、通水性の向上やその効果の維持（再通水性の向上）が期待できなくなることがある。 The molar ratio of VP: VSc is 40:60 to 99.5: 0.5, preferably 50:50 to 95: 5, and more preferably 60:40 to 90:10. If the molar ratio of VP: VSc deviates from these ranges, improvement in water permeability and maintenance of the effect (improvement in water permeability) may not be expected.
なお、ＰＶＰ／ＶＳｃには、本発明の効果を減じない範囲で、他の単量体由来の構造体を含んでいても良い。言い換えれば、ＶＰとＶＳｃを含む単量体混合物は、本発明の効果を減じない範囲で、他の単量体を含んでいてもよい。
他の単量体としては、例えば、スチレン、ビニルトルエン、α−メチルスチレンなどの芳香族ビニル系単量体；（メタ）アクリロイルオキシエチルトリメチルアンモニウムクロリド、（メタ）アクリロイルアミノプロピルトリメチルアンモニウムクロリドなどの４級アンモニウム塩を含むビニル系単量体；フェノキシエチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、イソボルニル（メタ）アクリレートなどの脂環アクリル系単量体；（メタ）アクリル酸、イタコン酸、クロトン酸、マレイン酸などのカルボキシ基含有単量体、およびこれらのアンモニウム塩、有機アミン塩、アルカリ金属塩；スチレンスルホン酸、ビニルスルホン酸、メタリルスルホン酸、２−（メタ）アクリルアミド−２−メチルプロパンスルホン酸、３−スルホプロピル（メタ）アクリレートなどのスルホン酸基含有ビニル系単量体、およびこれらのアンモニウム塩、有機アミン塩、アルカリ金属塩；２−（メタ）アクリロイルオキシエチルアシッドホスフェートなどのリン酸基含有ビニル系単量体、およびこれらのアンモニウム塩、有機アミン塩、アルカリ金属塩などが使用できる。
In addition, PVP / VSc may contain a structure derived from another monomer as long as the effect of the present invention is not diminished. In other words, the monomer mixture containing VP and VSc may contain other monomers as long as the effects of the present invention are not diminished.
Other monomers include, for example, aromatic vinyl-based monomers such as styrene, vinyltoluene, α-methylstyrene; (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride and the like. Vinyl-based monomers containing quaternary ammonium salts; alicyclic acrylic monomers such as phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate; (meth) acrylic acid, itaconic acid , Carboxy group-containing monomers such as crotonic acid and maleic acid, and their ammonium salts, organic amine salts, alkali metal salts; styrene sulfonic acid, vinyl sulfonic acid, metalyl sulfonic acid, 2- (meth) acrylamide-2 -Sulfonic acid group-containing vinyl monomers such as methylpropanesulfonic acid and 3-sulfopropyl (meth) acrylate, and ammonium salts, organic amine salts, and alkali metal salts of these; 2- (meth) acryloyloxyethyl acid phosphate. Such sulfonic acid group-containing vinyl-based monomers, and ammonium salts, organic amine salts, alkali metal salts and the like thereof can be used.
単量体混合物中、他の単量体の含有割合は、発明の効果を減じない範囲で任意に選ぶことができるが、モル比で１０％以下であることが好ましく、５質量％以下であることがより好ましい。 The content ratio of the other monomer in the monomer mixture can be arbitrarily selected as long as the effect of the invention is not diminished, but the molar ratio is preferably 10% or less and 5% by mass or less. Is more preferable.
ＰＶＰ／ＶＳｃの構造としては、ランダム共重合体、交互共重合体、ブロック共重合体およびグラフト共重合体のいずれの構造であってもよい。
共重合体を得るための重合方法としては、例えば、ラジカル重合法、リビングラジカル重合法などの公知の各種重合方法が採用される。また、熱の除去や取り扱い上の理由から、重合には溶剤として水や有機溶剤を用いることができる。
The structure of PVP / VSc may be any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer.
As the polymerization method for obtaining the copolymer, for example, various known polymerization methods such as a radical polymerization method and a living radical polymerization method are adopted. Further, for reasons of heat removal and handling, water or an organic solvent can be used as the solvent for the polymerization.
ＰＶＰ／ＶＳｃの分子量は、特に限定されないが、分子量に関連する物理量の動粘度で示される範囲が１０質量％の水溶液において、好ましくは１．０〜５０００ｍｍ２/ｓであり、より好ましくは１．１〜５００ｍｍ２/ｓであり、さらに好ましくは１．２〜１００ｍｍ２/ｓである。ＰＶＰ／ＶＳｃの動粘度が低すぎると通水性の向上効果が劣ることがあり、ＰＶＰ／ＶＳｃの動粘度が高すぎると薬液を調製した際の取扱いが難しくなることがある。
なお、ＰＶＰ／ＶＳｃ水溶液の動粘度は、ＪＩＳ Ｚ８８０３．６(２０１１)に基づき測定することができる。
The molecular weight of PVP / VSc is not particularly limited, but is preferably 1.0 to 5000 mm 2 / s, more preferably 1. It is 1 to 500 mm 2 / s, more preferably 1.2 to 100 mm 2 / s. If the kinematic viscosity of PVP / VSc is too low, the effect of improving water permeability may be inferior, and if the kinematic viscosity of PVP / VSc is too high, handling when preparing a chemical solution may be difficult.
The kinematic viscosity of the PVP / VSc aqueous solution can be measured based on JIS Z8803.6 (2011).
本発明の通水性向上剤は、少なくとも上記ＰＶＰ／ＶＳｃを含有する。
本発明の通水性向上剤中、ＰＶＰ／ＶＳｃの含有割合は、１〜４０質量％であることが好ましく、２〜３０質量％であることがより好ましく、３〜２０質量％であることがさら好ましい。
ＰＶＰ／ＶＳｃの含有割合が少なすぎると使用時の希釈倍率を高く設定することが難しくなることがあり、ＰＶＰ／ＶＳｃの含有割合が多すぎると通水性向上剤の取扱いが困難となることがある。
なお、通水性向上剤に含有されるＰＶＰ／ＶＳｃとして、共重合体の構造や分子量の異なる２種以上のＰＶＰ／ＶＳｃを用いることもできる。
The water permeability improver of the present invention contains at least the above PVP / VSc.
In the water permeability improver of the present invention, the content ratio of PVP / VSc is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and further preferably 3 to 20% by mass. preferable.
If the PVP / VSc content is too low, it may be difficult to set a high dilution ratio during use, and if the PVP / VSc content is too high, it may be difficult to handle the water permeability improver. ..
As the PVP / VSc contained in the water permeability improver, two or more types of PVP / VSc having different copolymer structures and molecular weights can also be used.
本発明の通水性向上剤は、取扱いなどの観点から、典型的には水溶液などの液状の形態をとる液剤である。例えば、ＰＶＰ／ＶＳｃを水中に混合し、溶解することによって本発明の通水性向上剤を調製することができる。使用する水としては、例えば、イオン交換水、蒸留水、ＲＯ水、水道水、工業用水が挙げられる。溶解に使用する水とともに、または水に代えて、本発明の効果を損なわない範囲で、エチルアルコールなどの有機溶剤を用いることもできる。 The water permeability improving agent of the present invention is a liquid agent that typically takes a liquid form such as an aqueous solution from the viewpoint of handling and the like. For example, the water permeability improver of the present invention can be prepared by mixing PVP / VSc in water and dissolving it. Examples of the water used include ion-exchanged water, distilled water, RO water, tap water, and industrial water. An organic solvent such as ethyl alcohol can also be used with or in place of the water used for dissolution as long as the effects of the present invention are not impaired.
本発明の通水性向上剤は、必要に応じて、界面活性剤、キレート剤、ＰＶＰ／ＶＳｃ以外の重合体、有機酸、ビルダー、ｐＨ調整剤、消泡剤、殺菌剤、防腐剤、着色料、香料などを含有してもよい。 The water permeability improver of the present invention is a surfactant, a chelating agent, a polymer other than PVP / VSc, an organic acid, a builder, a pH adjuster, an antifoaming agent, a bactericide, a preservative, and a coloring agent, if necessary. , Perfume and the like may be contained.
界面活性剤としては、陽イオン系界面活性剤、陰イオン系界面活性剤、両性界面活性剤、非イオン系界面活性剤などがあり、いずれの界面活性剤も好適に使用することかでき、１種を単独で、または２種以上を組み合わせて使用することができる。これら界面活性剤のうち、通水性を向上させる点から陽イオン系界面活性剤が好ましい。
また、陽イオン系界面活性剤の中でも特に、下記式１に示す陽イオン系界面活性剤から選ばれる１種または２種以上の界面活性剤を用いることがより好ましい。
Examples of the surfactant include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, and the like, and any of the surfactants can be preferably used. The seeds can be used alone or in combination of two or more. Among these surfactants, cationic surfactants are preferable from the viewpoint of improving water permeability.
Further, among the cationic surfactants, it is more preferable to use one or more kinds of surfactants selected from the cationic surfactants represented by the following formula 1.
式１中、Ｒ１はアルキル基またはアルケニル基であり、Ｒ１の炭素数は８〜２２が好ましく、１０〜１８がより好ましい。Ｒ１の炭素数が小さすぎると充分な親水化効果が得られ難いことがあり、Ｒ１の炭素数が大きすぎると通水性向上剤の外観を透明に維持し難くなったり、取り扱いが困難になったりすることがある。
Ｒ２〜Ｒ４は、それぞれ独立して、炭素数１〜２２、好ましくは炭素数１〜１０のアルキル基、炭素数１〜２２、好ましくは炭素数１〜１０のアルキレン基、分岐があっても良い炭素数２〜４のヒドロキシアルキレン基、またはベンジル基である。 炭素数１〜２２のアルキル基としては、例えばメチル基、エチル基、オクチル基、デシル基が挙げられる。
Ｒ１〜Ｒ４の炭素数の合計は２６以下であることが好ましく、これによって通水性向上剤の外観を透明に維持することや、取り扱いがより容易になる。
Ｘ−は陰イオンを示し、例えば塩素イオン、臭素イオン、メチル硫酸イオン、エチル硫酸イオン、エチル硫酸イオンおよびリン酸イオンなどが挙げられ、好ましくは塩素イオンである。
In the formula 1, R 1 is an alkyl group or an alkenyl group, and the carbon number of R 1 is preferably 8 to 22, more preferably 10 to 18. When the number of carbon atoms of R 1 is too small may be difficult sufficient hydrophilic effect can be obtained, or become difficult to maintain the appearance of the number of carbon atoms of R 1 is too large water permeability improver transparent, handling difficulties It may become.
R 2 to R 4 each have an alkyl group having 1 to 22 carbon atoms, preferably 1 to 10 carbon atoms, an alkylene group having 1 to 22 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and a branch. It is also a good hydroxyalkylene group having 2 to 4 carbon atoms, or a benzyl group. Examples of the alkyl group having 1 to 22 carbon atoms include a methyl group, an ethyl group, an octyl group and a decyl group.
The total number of carbon atoms of R 1 to R 4 is preferably 26 or less, which keeps the appearance of the water permeability improver transparent and makes it easier to handle.
X − represents an anion, and examples thereof include chlorine ion, bromine ion, methyl sulfate ion, ethyl sulfate ion, ethyl sulfate ion and phosphate ion, and chlorine ion is preferable.
本発明の通水性向上剤が界面活性剤を含有する場合、その含有量は特に制限されないが、好ましくは０．１〜４０質量％、より好ましくは０．５〜２０質量％、さらに好ましくは1 〜１０質量％である。通水性向上剤における界面活性剤の含有量が少なすぎると界面活性剤の添加による通水性向上効果のさらなる増大が期待できないことがあり、界面活性剤の含有量が多すぎると製品の取扱いが困難になることがある。
必要に応じ、非イオン界面活性剤などの他の界面活性剤を用いて２種以上の界面活性剤を用いる場合は、２種以上の界面活性剤の合計の含有量が上記範囲内であることが好ましい。
When the water permeability improver of the present invention contains a surfactant, the content thereof is not particularly limited, but is preferably 0.1 to 40% by mass, more preferably 0.5 to 20% by mass, still more preferably 1. It is 10% by mass. If the content of the surfactant in the water permeability improver is too small, it may not be possible to expect a further increase in the water permeability improving effect due to the addition of the surfactant, and if the content of the surfactant is too large, it is difficult to handle the product. May become.
If necessary, when two or more types of surfactants are used with other surfactants such as nonionic surfactants, the total content of the two or more types of surfactants must be within the above range. Is preferable.
キレート剤としては、アミノカルボン酸系キレート剤、ホスホン酸系キレート剤、グルコン酸などが好ましい。キレート剤は、使用する水由来の無機物がフェルトや装置に付着し難くすることや、付着した無機物の除去を行なう目的で使用することができる。キレート剤は、１種を単独で、または２種以上を組み合わせて使用することができる。 As the chelating agent, an aminocarboxylic acid-based chelating agent, a phosphonic acid-based chelating agent, gluconic acid and the like are preferable. The chelating agent can be used for the purpose of making it difficult for the water-derived inorganic substance to be used to adhere to the felt or the device, and for removing the adhered inorganic substance. The chelating agent may be used alone or in combination of two or more.
〔製紙方法〕
本発明の通水性向上剤は、製紙用具・製紙装置に接触させることによりワイヤーやフェルトに付着し、その表面を親水化することにより製紙用具・製紙装置に汚れが付着または堆積するのを抑制ないし防止し、その結果、ワイヤーやフェルトの通水性を向上させることができる。例えば、シャワー水などに通水性向上剤を添加して、製紙用具・製紙装置への散布、噴霧、浸漬などにより直接接触させることができる。
[Papermaking method]
The water permeability improver of the present invention adheres to the wire or felt when it comes into contact with the papermaking tool / device, and by making the surface hydrophilic, it does not prevent dirt from adhering or accumulating on the papermaking tool / device. It can be prevented and, as a result, the water permeability of the wire or felt can be improved. For example, a water permeability improver can be added to shower water or the like and brought into direct contact by spraying, spraying, dipping, or the like on a papermaking tool / device.
本発明の通水性向上剤を外添する対象の製紙用具・製紙装置は、紙やパルプが直接または間接的に接触する用具や装置であり、典型的には、抄紙工程におけるワイヤーパート、プレスパート、ドライヤーパートで用いられる用具や装置である。例えば、ワイヤー、フェルト、トランスファーベルト、シュープレス、テーブルロール、ブレストロール、ダンディロール、ワイヤーリターンロール、クーチロール、プレスロール、フェルトロール、ピックアップロール、サクションロール、ペーパーロール、バッキングロール、リップ、フォーミングボード、フォイル、ドクター、サクションボックス、ユールボックス、カンバスなどが挙げられ、中でも、ポリエステル樹脂やナイロン樹脂などの疎水性樹脂を主成分とするワイヤーやフェルトに特に有効である。本発明の通水性向上剤を外添する抄紙機に制限はなく、例えば円網、長網、短網、コンビネーション、オントップ、ツインワイヤーなどが挙げられる。 The papermaking tool / device to which the water permeability improving agent of the present invention is externally added is a tool or device with which paper or pulp comes into direct or indirect contact, and is typically a wire part or a press part in the papermaking process. , Tools and equipment used in the dryer part. For example, wire, felt, transfer belt, shoe press, table roll, breast roll, dandy roll, wire return roll, cooch roll, press roll, felt roll, pickup roll, suction roll, paper roll, backing roll, lip, forming board, etc. Examples thereof include foils, doctors, suction boxes, yule boxes, cambass, etc. Among them, it is particularly effective for wires and felts mainly composed of hydrophobic resins such as polyester resin and nylon resin. There is no limitation on the paper machine to which the water permeability improving agent of the present invention is externally added, and examples thereof include a circular net, a long net, a short net, a combination, an on-top, and a twin wire.
本発明の通水性向上剤を製紙用具・製紙装置に外添する方法としては、例えば抄紙機の稼動前または稼動中に、連続的にまたは間欠的に接触させる方法が挙げられるが、抄紙機の稼動中に連続的に接触させるのが好ましい。また、前記のように、本発明の通水性向上剤をシャワー水に添加して散布、噴霧、浸漬、接触させる方法が好ましいが、対象となる製紙用具・製紙装置以外のものに通水性向上剤を接触させることで、対象となる製紙用具・製紙装置に間接的に接触させても良い。 Examples of the method of externally adding the water permeability improving agent of the present invention to a papermaking tool / device include, for example, a method of continuously or intermittently contacting the papermaking machine before or during the operation of the papermaking machine. It is preferable to make continuous contact during operation. Further, as described above, a method of adding the water permeability improving agent of the present invention to shower water and spraying, spraying, dipping, and contacting the water permeability improving agent is preferable, but the water permeability improving agent is applied to other than the target papermaking tools and papermaking devices. May be indirectly brought into contact with the target papermaking tool / papermaking device.
本発明の通水性向上剤を添加するシャワー水などの水としては、本発明の効果を損なわない限り特に限定されず、例えば、井戸水など地下水、河川水または湖沼水などの表面水、工業用水などの新水、白水のいずれかまたはこれらを混合したものを使用することができる。ただし、水中の不純物と本発明の通水性向上剤との相互作用により充分な通水性が得られない場合がある点から、新水を使用するのが好ましい。 The water such as shower water to which the water permeability improving agent of the present invention is added is not particularly limited as long as the effect of the present invention is not impaired, and for example, groundwater such as well water, surface water such as river water or lake water, industrial water and the like. You can use either fresh water, white water, or a mixture of these. However, it is preferable to use fresh water because sufficient water permeability may not be obtained due to the interaction between impurities in water and the water permeability improver of the present invention.
本発明の通水性向上剤をシャワー水などに添加する場合の通水性向上剤の濃度は、例えば、通水性向上剤の固形分として好ましくは０．１〜２００ｐｐｍであり、より好ましくは０．３〜１００ｐｐｍ、さらに好ましくは０．５〜５０ｐｐｍである。通水性向上剤の濃度が低すぎると濡れ性の低下や汚れ付着を起こして通水性が不充分となることがあり、濃度が高すぎると泡立ちが生じ易くなり、得られる紙の品質や操業性が低下することがある。 When the water permeability improver of the present invention is added to shower water or the like, the concentration of the water permeability improver is preferably 0.1 to 200 ppm, more preferably 0.3, as the solid content of the water permeability improver, for example. It is ~ 100 ppm, more preferably 0.5 to 50 ppm. If the concentration of the water permeability improver is too low, the wettability may decrease or stains may adhere, resulting in insufficient water permeability. If the concentration is too high, foaming is likely to occur, and the quality and operability of the obtained paper May decrease.
本発明の通水性向上剤において、対象となるパルプの種類に制限はなく、クラフトパルプ、サルファイトパルプなどの晒または未晒化学パルプ；砕木パルプやサーモメカニカルパルプなどの晒または未晒機械パルプ；新聞古紙、雑誌古紙、段ボール古紙、雑古紙、脱墨古紙などの古紙パルプ；マシン損紙、コート損紙などのブロークパルプが挙げられる。 In the water permeability improver of the present invention, there is no limitation on the type of pulp, and bleached or unbleached chemical pulp such as kraft pulp and sulfite pulp; bleached or unbleached mechanical pulp such as crushed wood pulp and thermomechanical pulp; Waste paper pulp such as waste newspaper, waste magazine, waste cardboard, miscellaneous waste paper, and waste ink; broken pulp such as machine waste paper and coated waste paper.
本発明の通水性向上剤を用いた製紙方法は、酸性、中性およびアルカリ性条件下で行われる紙の製造工程に適用することができる。得られる紙の種類に制限はなく、例えば、新聞用紙、上質紙やコート紙などの印刷用紙；ＰＰＣ用紙や感熱紙原紙などの情報用紙；純白ロール紙や晒クラフト紙などの包装用紙；ティッシュペーパーやトイレットペーパーなどの衛生用紙；食品容器原紙や塗工印刷用原紙などの雑種紙；ライナーや中しん原紙などの段ボール原紙；白板紙や色板紙などの紙器用板紙；石こうボードや紙管原紙などの雑板紙などが挙げられる。 The papermaking method using the water permeability improver of the present invention can be applied to a paper manufacturing process performed under acidic, neutral and alkaline conditions. There are no restrictions on the types of paper that can be obtained, for example, printing paper such as newspaper, high-quality paper and coated paper; information paper such as PPC paper and heat-sensitive paper base paper; wrapping paper such as pure white roll paper and bleached kraft paper; tissue paper. Sanitary paper such as toilet paper; mixed paper such as food container base paper and coating printing base paper; cardboard base paper such as liner and medium shin base paper; paper container paper such as white paperboard and colored paperboard; gypsum board and paper tube base paper, etc. Examples include miscellaneous paperboard.
本発明の通水性向上剤を用いた製紙方法において、通水性向上剤とともに他の添加剤を併用することもできる。他の添加剤として、例えば、歩留り向上剤、凝結剤、乾燥紙力増強剤、湿潤紙力増強剤、柔軟剤、サイズ剤、染料、硫酸バンド、填料、他の外添型通水性向上剤、潤滑剤、剥離剤、洗浄剤、スライムコントロール剤、スケールコントロール剤、酸、アルカリなどの添加剤を併用することもできる。 In the papermaking method using the water permeability improving agent of the present invention, other additives can be used in combination with the water permeability improving agent. Other additives include, for example, yield improvers, coagulants, dry paper strength enhancers, wet paper strength enhancers, fabric softeners, sizing agents, dyes, sulfuric acid bands, fillers, other external water permeability improvers, Additives such as lubricants, release agents, cleaning agents, slime control agents, scale control agents, acids and alkalis can also be used in combination.
以下、実施例および比較例を挙げて本発明をさらに具体的に説明する。
表１および表２に示す原料を用いて、表３に示す実施例１〜４および比較例１の薬液（通水性向上剤）を調製した。得られた各薬液について以下の試験方法にて評価を行い、その結果を表３に示す。なお、対照として薬剤未添加の評価を併せて行った。また表１中の「％」はモル比基準である。共重合体Ａ１，Ａ２および重合体Ｂの動粘度は１０ｗｔ％水溶液を調製し、下記の方法にて測定を行った。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
Using the raw materials shown in Tables 1 and 2, the chemical solutions (water permeability improvers) of Examples 1 to 4 and Comparative Example 1 shown in Table 3 were prepared. Each of the obtained chemical solutions was evaluated by the following test method, and the results are shown in Table 3. As a control, the evaluation of no drug addition was also performed. In addition, "%" in Table 1 is a molar ratio standard. The kinematic viscosities of the copolymers A1 and A2 and the polymer B were measured by the following methods after preparing a 10 wt% aqueous solution.
［動粘度の測定］
共重合体及び重合体の水溶液について、ＪＩＳ Ｚ８８０３．６：２０１１（液体の粘度測定方法）に基づき４０℃での動粘度の測定を行なった。細管粘度計にはキャノン−フェンスケ粘度計を用いた。
[Measurement of kinematic viscosity]
The kinematic viscosity of the copolymer and the aqueous solution of the polymer was measured at 40 ° C. based on JIS Z8803.6: 2011 (method for measuring the viscosity of liquid). A Canon-Fenceke viscometer was used as the thin tube viscometer.
原料１（Ａ−１）の調製
機械かきまぜ機、還流冷却器、温度計および滴下漏斗を備えた２Ｌの４つ口フラスコにビニルピロリドン２８３ｇ（２．５５モル）、酢酸ビニル５６ｇ（０．６５モル）、イソプロパノール６０ｇ、蒸留水４８０ｇを入れ、１５分間窒素置換した。次にこの混合物を加熱して７８℃に昇温した。温度を保持しながら０．３ｍｌのｔ−ブチルペルオキシピバレートを添加し、１５分経過後、ビニルピロリドン２００ｇ（１．８０モル）を４時間かけて滴下した。滴下開始より１時間経過する度に０．３ｍｌのｔ−ブチルペルオキシピバレートを添加し、ビニルピロリドンの滴下中３回投入した。滴下が終わった後、２時間温度を維持し、ついで蒸留水を１００ｇ添加し、還流冷却器を蒸留器に換え、窒素気流下で１００℃まで温度を上げながらイソプロパノールを留去した。イソプロパノールの残存が無いことを確認後、冷却して生成物を取り出し、原料１（Ａ−１）とした。高分子溶液の固形分を測定し、蒸留水で固形分濃度を３０重量％とした後、以後の配合物の調製に使用した。
原料１（Ａ−２）、原料１（Ｂ）は市販の試薬を用いた。
Preparation of Raw Material 1 (A-1) 283 g (2.55 mol) of vinylpyrrolidone, 56 g (0.65 mol) of vinyl acetate in a 2 L four-necked flask equipped with a mechanical stirrer, a reflux condenser, a thermometer and a dropping funnel. ), 60 g of isopropanol and 480 g of distilled water were added, and the mixture was replaced with nitrogen for 15 minutes. The mixture was then heated to 78 ° C. While maintaining the temperature, 0.3 ml of t-butylperoxypivalate was added, and after 15 minutes, 200 g (1.80 mol) of vinylpyrrolidone was added dropwise over 4 hours. 0.3 ml of t-butylperoxypivalate was added every 1 hour after the start of the dropping, and the mixture was added 3 times during the dropping of vinylpyrrolidone. After the dropping was completed, the temperature was maintained for 2 hours, then 100 g of distilled water was added, the reflux condenser was replaced with a distiller, and isopropanol was distilled off while raising the temperature to 100 ° C. under a nitrogen stream. After confirming that there was no residual isopropanol, the product was cooled and the product was taken out and used as raw material 1 (A-1). The solid content of the polymer solution was measured, the solid content concentration was adjusted to 30% by weight with distilled water, and then the mixture was used for the subsequent preparation of the formulation.
Commercially available reagents were used as the raw material 1 (A-2) and the raw material 1 (B).
［フェルトの通水性評価］
１）板紙工場で使用したフェルトを直径５ｃｍの円形に切り取る。
２）中性ロジンサイズ剤（固形分５０％) を２％（固形分１％）に希釈し、液にフェルトを１時間浸漬する。
３）浸漬後、１０５℃で３時間乾燥し、放冷する。
４）調製した薬剤の１０００倍希釈液を３００ｍｌ準備する。
５）フェルトを図１に示す通水性評価器に固定する。
６）希釈した薬液を入れ、２００ｍｌの希釈液が排出されるまでの時間（通水時間）を計測する。
[Evaluation of felt water permeability]
1) Cut the felt used in the paperboard factory into a circle with a diameter of 5 cm.
2) Dilute the neutral rosin sizing agent (solid content 50%) to 2% (solid content 1%), and immerse the felt in the solution for 1 hour.
3) After immersion, dry at 105 ° C. for 3 hours and allow to cool.
4) Prepare 300 ml of a 1000-fold diluted solution of the prepared drug.
5) Fix the felt to the water permeability evaluator shown in FIG.
6) Add the diluted chemical solution and measure the time until 200 ml of the diluted solution is discharged (water flow time).
［フェルトの再通水性評価］
１）上記の通水性評価の液が抜けたことを確認する。
２）水を５００ｍｌ入れ、水が排出されるまで待ち、再度、水道水を５００ｍｌ入れる。
３）水が抜けたことを確認する。
４）水を５００ｍｌ入れ、３００ｍｌの目盛りから２００ｍｌの水が排出されるまでの時間（通水時間）を計測する。
[Evaluation of felt water permeability]
1) Confirm that the above water permeability evaluation liquid has drained.
2) Add 500 ml of water, wait until the water is discharged, and add 500 ml of tap water again.
3) Confirm that the water has drained.
4) Add 500 ml of water and measure the time from the 300 ml scale to the discharge of 200 ml of water (water flow time).
上記の通水時間の値に基づき、通水性および再通水性を各々以下の基準で評価した。 Based on the above values of water flow time, water flow and re-water flow were evaluated according to the following criteria.
［通水性の評価基準］
◎：通水時間が４０秒未満である。
○：通水時間が４０秒以上、６５秒未満である。
△：通水時間が６５秒以上、９０秒未満である。
×：通水時間が９０秒以上である。
[Evaluation criteria for water permeability]
⊚: Water flow time is less than 40 seconds.
◯: The water flow time is 40 seconds or more and less than 65 seconds.
Δ: Water flow time is 65 seconds or more and less than 90 seconds.
X: Water flow time is 90 seconds or more.
［再通水性の評価基準］
◎：通水時間が４０秒未満である。
○：通水時間が４０秒以上、５０秒未満である。
△：通水時間が５０秒以上、６０秒未満である。
×：通水時間が６０秒以上である。
[Evaluation criteria for re-water permeability]
⊚: Water flow time is less than 40 seconds.
◯: The water flow time is 40 seconds or more and less than 50 seconds.
Δ: Water flow time is 50 seconds or more and less than 60 seconds.
X: Water flow time is 60 seconds or more.
表３に示したように、本発明の通水性向上剤に係る実施例１〜３の薬液を用いることにより、比較例１の薬液と比べ、通水性および再通水性が向上していることがわかる。 As shown in Table 3, by using the chemical solutions of Examples 1 to 3 according to the water permeability improving agent of the present invention, the water permeability and re-water permeability are improved as compared with the chemical solution of Comparative Example 1. Understand.
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| JP2005272608A (en) * | 2004-03-24 | 2005-10-06 | Kohjin Co Ltd | Stain-preventing agent for impregnation roll and method for preventing impregnation roll from being stained |
| JP2008208187A (en) * | 2007-02-26 | 2008-09-11 | Kao Corp | Detergent composition containing specific polymer |
| JP2008240227A (en) * | 2007-02-26 | 2008-10-09 | Nisshin Kagaku Kenkyusho:Kk | Anti-staining agent composition for paper machine and method for preventing staining paper machine |
| JP2014098217A (en) * | 2012-11-13 | 2014-05-29 | Yuka Sangyo Kk | Spraying agent for paper making, and method of manufacturing paper |
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| JP2005272608A (en) * | 2004-03-24 | 2005-10-06 | Kohjin Co Ltd | Stain-preventing agent for impregnation roll and method for preventing impregnation roll from being stained |
| JP2008208187A (en) * | 2007-02-26 | 2008-09-11 | Kao Corp | Detergent composition containing specific polymer |
| JP2008240227A (en) * | 2007-02-26 | 2008-10-09 | Nisshin Kagaku Kenkyusho:Kk | Anti-staining agent composition for paper machine and method for preventing staining paper machine |
| JP2014098217A (en) * | 2012-11-13 | 2014-05-29 | Yuka Sangyo Kk | Spraying agent for paper making, and method of manufacturing paper |
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