JP2020029631A - Pulp washing agent - Google Patents
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Abstract
Description
本発明はパルプ用洗浄剤に関する。 The present invention relates to a pulp detergent.
パルプを製造する工程は、木材チップを蒸解してパルプを得る蒸解手順と、このパルプとリグニンを含む黒液とを分離し、分離されたパルプを洗浄する洗浄手順と、洗浄されたパルプを漂白する漂白手順と、を有する（例えば、特許文献１参照）。このようにして製造される漂白されたパルプは、製紙等に使用されることになる。 The process of producing pulp includes a cooking procedure in which wood chips are digested to obtain pulp, a rinsing procedure in which the pulp and black liquor containing lignin are separated and the separated pulp is washed, and the washed pulp is bleached. (See, for example, Patent Document 1). The bleached pulp produced in this manner is used for papermaking and the like.
パルプの洗浄系（酸素脱リグニン工程を含む）において、リグニン等の抽出成分を効率よくパルプから除去することは、プロセスの生産性向上に大きく寄与する。これまでは、主に洗浄機の改良によってパルプの洗浄効率の改善がなされてきたが、これには多くのコストがかかることから、設備改造を伴わない薬品による実用的な改善も試みられている。 In the pulp washing system (including the oxygen delignification step), efficiently removing extracted components such as lignin from the pulp greatly contributes to improving the productivity of the process. Until now, pulp washing efficiency has been improved mainly by improving the washing machine.However, since this requires a lot of cost, practical improvement by chemicals without equipment modification is also being attempted. .
例えば、パルプの洗浄効率の高める薬品としては界面活性剤が挙げられるが、その中でも、非イオン系界面活性剤が広く適用されている（例えば、特許文献２及び３参照）。 For example, surfactants are listed as chemicals that improve the pulp washing efficiency, and among them, nonionic surfactants are widely applied (for example, see Patent Documents 2 and 3).
しかしながら、特許文献２及び３に記載の非イオン性界面活性剤のリグニンに対する洗浄性は、満足のいくものではなく、また、樹脂等の有機物（汚れ成分）に対する洗浄性も十分でないという問題があった。
そこで、本発明は、従来の非イオン性界面活性剤に比して、パルプに付着しているリグニン分解物及び樹脂等の有機物（汚れ成分）を取り除く機能に優れた界面活性剤を含有するパルプ洗浄剤を提供することを目的とする。
However, the detergency of the nonionic surfactants described in Patent Documents 2 and 3 against lignin is not satisfactory, and the detergency against organic substances (dirt components) such as resins is not sufficient. Was.
Accordingly, the present invention provides a pulp containing a surfactant excellent in removing organic substances (dirt components) such as lignin decomposition products and resins adhering to the pulp as compared with conventional nonionic surfactants. It is intended to provide a cleaning agent.
本発明者はこれらの問題を解決すべく誠意検討した結果、本発明に到達した。即ち本発明は、下記一般式（１）で表される非イオン性界面活性剤（Ｘ）を含むパルプ用洗浄剤である。
Ｒ１Ｏ［（Ｃ２Ｈ４Ｏ）ｐ／（Ｃ３Ｈ６Ｏ）ｑ］Ｈ （１）
［一般式（１）中、Ｒ１は炭素数８〜９の分岐のアルキル基を表し；ｐはエチレンオキシ基の数平均付加モル数で、１〜５の数であり；ｑはプロピレンオキシ基の数平均付加モル数で、１〜１０の数であり；［（Ｃ２Ｈ４Ｏ）ｐ／（Ｃ３Ｈ６Ｏ）ｑ］はエチレンオキシ基とプロピレンオキシ基の付加形式がランダム状又はブロック状であることを表す。］
The present inventor has made sincere studies to solve these problems, and as a result, has arrived at the present invention. That is, the present invention is a pulp detergent containing a nonionic surfactant (X) represented by the following general formula (1).
R 1 O [(C 2 H 4 O) p / (C 3 H 6 O) q] H (1)
[In the general formula (1), R 1 represents a branched alkyl group having 8 to 9 carbon atoms; p is a number-average addition mole number of an ethyleneoxy group, and is a number of 1 to 5; q is a propyleneoxy group. the number average addition number of moles is a number of 1~10; [(C 2 H 4 O) p / (C 3 H 6 O) q] is the additional form of ethyleneoxy group and propyleneoxy group random form or Indicates a block shape. ]
本発明のパルプ用洗浄剤は、パルプ洗浄工程に用いることで白色度が高く、かつ汚れ成分である有機物の付着量が少ないパルプを得ることができるという効果を奏する。 The pulp detergent of the present invention has an effect that, when used in the pulp washing step, pulp having a high degree of whiteness and a small amount of organic matter as a stain component can be obtained.
本発明のパルプ用洗浄剤は、下記一般式（１）で表される非イオン性界面活性剤（Ｘ）を含む。
なお、非イオン性界面活性剤（Ｘ）は、１種を単独で使用しても、２種以上を併用しても良い。
Ｒ１Ｏ［（Ｃ２Ｈ４Ｏ）ｐ／（Ｃ３Ｈ６Ｏ）ｑ］Ｈ （１）
The pulp detergent of the present invention contains a nonionic surfactant (X) represented by the following general formula (1).
In addition, as the nonionic surfactant (X), one type may be used alone, or two or more types may be used in combination.
R 1 O [(C 2 H 4 O) p / (C 3 H 6 O) q] H (1)
一般式（１）中、Ｒ１は炭素数８〜９の分岐のアルキル基を表す。
炭素数８〜９の分岐のアルキル基としては、炭素数８〜９の分岐のアルキル基であって、メチル基を２個有するアルキル基（ｒ１）、メチル基を３個有するアルキル基（ｒ２）、メチル基を４個有するアルキル基（ｒ３）及びメチル基を５個以上有するアルキル基（ｒ４）等が挙げられる。
In the general formula (1), R 1 represents a branched alkyl group having 8 to 9 carbon atoms.
Examples of the branched alkyl group having 8 to 9 carbon atoms include a branched alkyl group having 8 to 9 carbon atoms, and an alkyl group having two methyl groups (r1) and an alkyl group having three methyl groups (r2). And an alkyl group (r3) having four methyl groups and an alkyl group (r4) having five or more methyl groups.
前記のメチル基を２個有するアルキル基（ｒ１）としては、２−オクチル基、２−エチルヘキサン−１−イル基、６−メチルヘプタン−１−イル基、２−ノニル基、７−メチルオクタン−１−イル基等が挙げられる。 Examples of the alkyl group having two methyl groups (r1) include a 2-octyl group, a 2-ethylhexane-1-yl group, a 6-methylheptane-1-yl group, a 2-nonyl group, and a 7-methyloctane. -1-yl group and the like.
前記のメチル基を３個有するアルキル基（ｒ２）としては、３−メチルヘプタン−３−イル及び３，５−ジメチル−ヘキサン−１−イル等が挙げられる。 Examples of the alkyl group having three methyl groups (r2) include 3-methylheptane-3-yl and 3,5-dimethyl-hexane-1-yl.
前記のメチル基を４個有するアルキル基（ｒ３）としては、３，５，５−トリメチルヘキサン−１−イル基及び２，６−ジメチルヘプタン−４−イル基及び２，３，５−トリメチルヘキサン−１−イル等が挙げられる。 Examples of the alkyl group (r3) having four methyl groups include a 3,5,5-trimethylhexane-1-yl group, a 2,6-dimethylheptane-4-yl group and a 2,3,5-trimethylhexane -1-yl and the like.
前記のメチル基を５個以上有するアルキル基（ｒ４）としては、２，２−ジメチル−５−メチルヘキサン−４−イル等が挙げられる。 Examples of the alkyl group (r4) having five or more methyl groups include 2,2-dimethyl-5-methylhexane-4-yl and the like.
これらのＲ１の内、リグニン等に対する洗浄性の観点から好ましいのは、前記のメチル基を３個有するアルキル基（ｒ２）、メチル基を４個有するアルキル基（ｒ３）及びメチル基を５個以上有するアルキル基（ｒ４）であり、更に好ましいのは、メチル基を４個有するアルキル基（ｒ３）及びメチル基を５個以上有するアルキル基（ｒ４）であり、特に好ましいのは３，５，５−トリメチルヘキサン−１−イルである。 Among these R 1 , from the viewpoint of detergency against lignin and the like, the above-mentioned alkyl group (r2) having three methyl groups, alkyl group (r3) having four methyl groups, and five methyl groups are preferable. The alkyl group (r4) having at least four methyl groups is more preferable, and the alkyl group (r3) having four methyl groups and the alkyl group (r4) having five or more methyl groups are particularly preferable. 5-trimethylhexane-1-yl.
一般式（１）中、ｐはエチレンオキシ基の数平均付加モル数で、１〜５の数である。数平均付加モル数は整数の場合もあれば小数の場合もあり得る（以下、おなじ）。
ｐが１未満であるとリグニン等に対する洗浄性が悪化する。
ｐが５を超えるとリグニン等に対する洗浄性が悪化する。
また、ｐは、リグニン等に対する洗浄性の観点から１〜３の数であることが好ましい。
In the general formula (1), p is a number-average number of moles of the ethyleneoxy group, and is 1 to 5. The number-average number of moles added may be an integer or a decimal number (the same applies hereinafter).
When p is less than 1, the washing property for lignin and the like deteriorates.
When p is more than 5, the cleaning property against lignin and the like deteriorates.
Further, p is preferably a number of 1 to 3 from the viewpoint of detergency against lignin and the like.
一般式（１）中、ｑはプロピレンオキシ基の数平均付加モル数で、１〜１０の数である。
ｑが１未満であるとリグニン等に対する洗浄性が悪化する。
ｑが１０を超えるとリグニン等に対する洗浄性が悪化する。
また、ｑは、リグニン等に対する洗浄性の観点から２〜８の数であることが好ましく、３〜７の数であることが更に好ましい。
In the general formula (1), q is a number average addition mole number of the propyleneoxy group, and is a number of 1 to 10.
When q is less than 1, the washing property for lignin and the like is deteriorated.
When q exceeds 10, the washing property against lignin and the like deteriorates.
Further, q is preferably a number of 2 to 8, more preferably 3 to 7, from the viewpoint of detergency against lignin and the like.
ｐとｑの関係としては、リグニン等に対する洗浄性の観点からｐ＋ｑが３〜１０の数であることが好ましく、ｐ＋ｑが４〜８の数であることが更に好ましい。
なお、ｐ又はｑで表される数平均付加モル数は、非イオン性界面活性剤（Ｘ）の分子集団における各付加モル数の分子当たりの数平均値である。
ｐ及びｑは、非イオン性界面活性剤（Ｘ）が後に詳述する通り、「Ｒ１に水酸基が結合したアルコール」に、エチレンオキサイド及びプロピレンオキサイドを付加反応させて製造した場合には、反応原料の仕込みモル数に基づいて算出することもできる。
また、ｐとｑの関係としては、リグニン等に対する洗浄性の観点からｑ≧ｐであることが好ましい。
As the relationship between p and q, from the viewpoint of detergency against lignin and the like, p + q is preferably a number of 3 to 10, and more preferably p + q is a number of 4 to 8.
In addition, the number average addition mole number represented by p or q is a number average value per molecule of each addition mole number in the molecular population of the nonionic surfactant (X).
As described in detail later, p and q represent a reaction when the nonionic surfactant (X) is produced by adding ethylene oxide and propylene oxide to “an alcohol having a hydroxyl group bonded to R 1 ”. It can also be calculated based on the charged mole number of the raw material.
In addition, the relationship between p and q is preferably q ≧ p from the viewpoint of detergency against lignin and the like.
一般式（１）中、（Ｃ２Ｈ４Ｏ）はエチレンオキシ基を表し、（Ｃ３Ｈ６Ｏ）はプロピレンオキシ基を表す。
［（Ｃ２Ｈ４Ｏ）ｐ／（Ｃ３Ｈ６Ｏ）ｑ］はエチレンオキシ基とプロピレンオキシ基の付加形式がランダム状又はブロック状であることを表す。
ここで、［（Ｃ２Ｈ４Ｏ）ｐ／（Ｃ３Ｈ６Ｏ）ｑ］のエチレンオキシ基とプロピレンオキシ基の付加形式は、リグニン等に対する洗浄性の観点からブロック状であることが好ましく、その場合、エチレンオキシ基とプロピレンオキシ基のブロック付加形式はエチレンオキシ基ブロック−プロピレンオキシブロックの順とその逆の場合もあり得るが、なかでも［（Ｃ３Ｈ６Ｏ）ｑ−（Ｃ２Ｈ４Ｏ）ｐ］であること［即ち、「Ｒ１Ｏ」に（Ｃ３Ｈ６Ｏ）ｑが結合し、続いて（Ｃ２Ｈ４Ｏ）ｐがブロック状に結合する付加形式］が更に好ましい。
In the general formula (1), (C 2 H 4 O) represents an ethyleneoxy group, and (C 3 H 6 O) represents a propyleneoxy group.
[(C 2 H 4 O) p / (C 3 H 6 O) q ] indicates that the addition form of the ethyleneoxy group and the propyleneoxy group is random or block.
Here, the addition form of the ethyleneoxy group and the propyleneoxy group of [(C 2 H 4 O) p / (C 3 H 6 O) q ] is preferably a block form from the viewpoint of detergency against lignin and the like. , in which case, block addition form of ethyleneoxy groups and propyleneoxy groups are ethyleneoxy groups block - there may be a case of the forward and reverse propyleneoxy blocks, among others [(C 3 H 6 O) q - (C 2 H 4 O) p] is that [i.e., the "R 1 O" (C 3 H 6 O) q is attached, followed by (C 2 H 4 O) additional form p binds to blocky ' Is more preferred.
本発明のパルプ用洗浄剤は、必要に応じて、水、有機溶剤、キレート剤、ビルダー、酵素、消泡剤、他の非イオン性界面活性剤等を含有しても良い。 The pulp detergent of the present invention may contain water, an organic solvent, a chelating agent, a builder, an enzyme, an antifoaming agent, other nonionic surfactants, and the like, if necessary.
前記のキレート剤は、金属を錯体化する作用を有する化合物を指す。使用できるキレート剤としては、特に限定されないが、ＥＤＴＡ（エチレンジアミン四酢酸）、ＤＴＰＡ（ジエチレントリアミン五酢酸）、ＨＥＤＴＡ（ヒドロキシエチレンジアミン四酢酸）、ＥＤＤＳ（エチレンジアミンコハク酸）、ＴＴＨＡ（トリエチレンテトラアミン六酢酸）、ＨＥＤＰ（ヒドロキシエタンホスホン酸）、ＮＴＭＰ（ニトリロトリスメチレンホスホン酸）及びＰＢＴＣ（ホスホノブタントリカルボン酸）等が挙げられる。
前記のキレート剤は、１種を単独で使用してもよく、２種以上を併用してもよい。
The above-mentioned chelating agent refers to a compound having an action of complexing a metal. The chelating agent that can be used is not particularly limited, but EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), HEDTA (hydroxyethylenediaminetetraacetic acid), EDDS (ethylenediaminesuccinic acid), TTHA (triethylenetetraaminehexaacetic acid) , HEDP (hydroxyethanephosphonic acid), NTMP (nitrilotrismethylenephosphonic acid) and PBTC (phosphonobutanetricarboxylic acid).
One of the above chelating agents may be used alone, or two or more thereof may be used in combination.
前記のビルダーとしては、特に限定されないが、例えば、アクリル酸系ポリマー、マレイン酸系ポリマーが使用できる。
前記のビルダーは、１種を単独で使用してもよく、２種以上を併用してもよい。
The builder is not particularly limited, and for example, an acrylic acid-based polymer and a maleic acid-based polymer can be used.
One of the above builders may be used alone, or two or more may be used in combination.
本発明のパルプ用洗浄剤が含有する前記の非イオン性界面活性剤（Ｘ）の重量割合は、リグニン等に対する洗浄性の観点から、６０〜１００重量％であることが好ましい。 The weight ratio of the nonionic surfactant (X) contained in the pulp detergent of the present invention is preferably from 60 to 100% by weight from the viewpoint of detergency against lignin and the like.
前記の非イオン性界面活性剤（Ｘ）は、公知の方法により製造することができる。例えば、前記のＲ１に水酸基が結合したアルコールに、アルカリ触媒（水酸化カリウム等）又は酸触媒（三フッ化ホウ素等）を加え窒素雰囲気下にてエチレンオキサイド及びプロピレンオキサイドを付加反応させて製造することができる。 The nonionic surfactant (X) can be produced by a known method. For example, it is produced by adding an alkali catalyst (such as potassium hydroxide) or an acid catalyst (such as boron trifluoride) to an alcohol in which a hydroxyl group is bonded to R 1 and subjecting ethylene oxide and propylene oxide to an addition reaction under a nitrogen atmosphere. can do.
＜パルプ洗浄方法＞
パルプの洗浄工程は、向流多段洗浄が一般的である。真空型フィルターや加圧型フィルター、プレスフィルター等様々な洗浄装置を２台〜６台連結してパルプを洗浄する方法である。最後段の洗浄装置にのみ、ボイラー回収温水を使用し、その洗浄ろ液を一段前の洗浄装置の洗浄水として用い、その洗浄ろ液を更にもう一段前の洗浄装置の洗浄水として用いるので、向流洗浄と呼ぶ。この場合、リグニン等の汚れ成分有機物は、最前段のろ液に濃縮される事となり、回収が容易になる。また、洗浄装置の中間に、酸素脱リグニン反応塔を設置し、リグニンの脱離を促進する例もある。
<Pulp washing method>
In the pulp washing process, countercurrent multistage washing is generally performed. This is a method of washing pulp by connecting two to six various washing devices such as a vacuum filter, a pressure filter, and a press filter. Only the last-stage washing device uses boiler-recovered hot water, and uses the washing filtrate as washing water for the preceding washing device, and uses the washing filtrate as washing water for the further preceding washing device. Called countercurrent cleaning. In this case, the organic matter of the dirt component such as lignin is concentrated in the filtrate at the forefront, and the recovery is easy. There is also an example in which an oxygen delignification reaction tower is installed in the middle of the cleaning device to promote lignin desorption.
＜パルプ洗浄剤＞
パルプ洗浄剤はこの洗浄工程に添加する。具体的には、パルプ移送ライン及びろ液循環ライン等への添加であり、上記の向流多段洗浄では、最後段の洗浄機入口に添加する事が効率的である。ただし、最後段の洗浄機への添加に限定するものではなく、パルプの滞留時間及び洗浄機形式等の因子によっては、すべての洗浄機入口への添加が効率的な場合もある。パルプ洗浄剤の添加量は、０．１〜１．５ｋｇ／パルプｔ（この場合のパルプは乾燥パルプを指す）であることが好ましい。
<Pulp detergent>
Pulp detergent is added to this washing step. Specifically, it is an addition to a pulp transfer line, a filtrate circulation line, and the like. In the above-described countercurrent multistage washing, it is efficient to add it to the inlet of the last washing machine. However, addition to the last washing machine is not limited, and addition to all washing machine inlets may be efficient depending on factors such as pulp residence time and washing machine type. The added amount of the pulp detergent is preferably 0.1 to 1.5 kg / t (pulp in this case indicates dry pulp).
以下、実施例により本発明を更に説明するが、本発明はこれに限定されるものではない。 Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto.
製造例１
撹拌機、温度計、圧力計、耐圧滴下ボンベ、減圧及び窒素導入ラインの付いた２Ｌオートクレーブ中に３，５，５−トリメチル−１−ヘキサノール１４４重量部（１モル部）、水酸化カリウム０．５重量部を加え撹拌を開始し窒素封入し１００℃に昇温した後、圧力−０．１ＭＰａＧで１時間脱水した。次いで１３０℃に昇温し、圧力０．３ＭＰａＧ以下でプロピレンオキサイド２３２重量部（４モル部）を５時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した（１段階目）。次いでエチレンオキサイド８８重量部（２モル部）を３時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した（２段階目）。その後６０℃に冷却し、酢酸０．５重量部で中和し、非イオン性界面活性剤（Ｘ−１）を得た。
Production Example 1
In a 2 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, reduced-pressure and nitrogen introduction line, 144 parts by weight (1 mol part) of 3,5,5-trimethyl-1-hexanol, 0.1 mol of potassium hydroxide. After adding 5 parts by weight, stirring was started, nitrogen was sealed, the temperature was raised to 100 ° C., and then dehydration was performed at a pressure of −0.1 MPaG for 1 hour. Then, the temperature was raised to 130 ° C., and 232 parts by weight (4 mol parts) of propylene oxide were sequentially dropped at a pressure of 0.3 MPaG or less over 5 hours, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached (first stage). . Next, 88 parts by weight (2 mol parts) of ethylene oxide were successively added dropwise over 3 hours, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached (second stage). Thereafter, the mixture was cooled to 60 ° C and neutralized with 0.5 parts by weight of acetic acid to obtain a nonionic surfactant (X-1).
製造例２
撹拌機、温度計、圧力計、耐圧滴下ボンベ、減圧及び窒素導入ラインの付いた２Ｌオートクレーブ中に３，５，５−トリメチル−１−ヘキサノール１４４重量部（１モル部）、水酸化カリウム０．５重量部を加え撹拌を開始し窒素封入し１００℃に昇温した後、圧力−０．１ＭＰａＧで１時間脱水した。次いで１３０℃に昇温し、圧力０．３ＭＰａＧ以下でエチレンオキサイド８８重量部（２モル部）を３時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した（１段階目）。次いでプロピレンオキサイド２３２重量部（４モル部）を５時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した（２段階目）。その後６０℃に冷却し、酢酸０．５重量部で中和し、非イオン性界面活性剤（Ｘ−２）を得た。
Production Example 2
In a 2 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, reduced-pressure and nitrogen introduction line, 144 parts by weight (1 mol part) of 3,5,5-trimethyl-1-hexanol, 0.1 mol of potassium hydroxide. After adding 5 parts by weight, stirring was started, nitrogen was sealed, the temperature was raised to 100 ° C., and then dehydration was performed at a pressure of −0.1 MPaG for 1 hour. Subsequently, the temperature was raised to 130 ° C., and 88 parts by weight (2 mol parts) of ethylene oxide was sequentially dropped at a pressure of 0.3 MPaG or less over 3 hours, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached (first stage). . Then, 232 parts by weight (4 mol parts) of propylene oxide were sequentially added dropwise over 5 hours, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached (second stage). Thereafter, the mixture was cooled to 60 ° C and neutralized with 0.5 parts by weight of acetic acid to obtain a nonionic surfactant (X-2).
製造例３
撹拌機、温度計、圧力計、耐圧滴下ボンベ、減圧及び窒素導入ラインの付いた２Ｌオートクレーブ中に３，５，５−トリメチル−１−ヘキサノール１４４重量部（１モル部）、水酸化カリウム０．５重量部を加え撹拌を開始し窒素封入し１００℃に昇温した後、圧力−０．１ＭＰａＧで１時間脱水した。次いで１３０℃に昇温し、圧力０．３ＭＰａＧ以下でエチレンオキサイド８８重量部（２モル部）及びプロピレンオキサイド２３２重量部（４モル部）を同時に５時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した。その後６０℃に冷却し、酢酸０．５重量部で中和し、非イオン性界面活性剤（Ｘ−３）を得た。
Production Example 3
In a 2 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, reduced-pressure and nitrogen introduction line, 144 parts by weight (1 mol part) of 3,5,5-trimethyl-1-hexanol, 0.1 mol of potassium hydroxide. After adding 5 parts by weight, stirring was started, nitrogen was sealed, the temperature was raised to 100 ° C., and then dehydration was performed at a pressure of −0.1 MPaG for 1 hour. Subsequently, the temperature was raised to 130 ° C., and at a pressure of 0.3 MPaG or less, 88 parts by weight (2 mol parts) of ethylene oxide and 232 parts by weight (4 mol parts) of propylene oxide were successively added dropwise over 5 hours, and pressure equilibration was performed at the same temperature. Stir for 1 hour until Thereafter, the mixture was cooled to 60 ° C and neutralized with 0.5 parts by weight of acetic acid to obtain a nonionic surfactant (X-3).
製造例４
製造例１において、プロピレンオキサイド２３２重量部（４モル）を１７４重量部（３モル部）に、エチレンオキサイド８８重量部（２モル部）を１３２重量部（３モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ−４）を得た。
Production Example 4
Production Example 1 was repeated except that 232 parts by weight (4 moles) of propylene oxide was changed to 174 parts by weight (3 moles) and 88 parts by weight (2 moles) of ethylene oxide was changed to 132 parts by weight (3 moles). Produced in the same manner as in Example 1 to obtain a nonionic surfactant (X-4).
製造例５
製造例１において、プロピレンオキサイド２３２重量部（４モル）を５８重量部（１モル部）に、エチレンオキサイド８８重量部（２モル部）を２２０重量部（５モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ−５）を得た。
Production Example 5
In Production Example 1, except that 232 parts by weight (4 mol) of propylene oxide was changed to 58 parts by weight (1 mol part) and 88 parts by weight (2 mol parts) of ethylene oxide was changed to 220 parts by weight (5 mol parts). Produced in the same manner as in Example 1 to obtain a nonionic surfactant (X-5).
製造例６
製造例１において、プロピレンオキサイド２３２重量部（４モル）を１７４重量部（３モル部）に、エチレンオキサイド８８重量部（２モル部）を４４重量部（１モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ−６）を得た。
Production Example 6
Production Example 1 was repeated except that 232 parts (4 mol) of propylene oxide was changed to 174 parts (3 mol), and 88 parts (2 mol) of ethylene oxide was changed to 44 parts (1 mol). Produced in the same manner as in Example 1 to obtain a nonionic surfactant (X-6).
製造例７
製造例１において、プロピレンオキサイド２３２重量部（４モル）を５８０重量部（１０モル部）に、エチレンオキサイド８８重量部（２モル部）を４４重量部（１モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ−７）を得た。
Production Example 7
In Production Example 1, except that 232 parts by weight (4 mol) of propylene oxide was changed to 580 parts by weight (10 mol parts) and 88 parts by weight (2 mol parts) of ethylene oxide was changed to 44 parts by weight (1 mol part). Produced in the same manner as in Example 1 to obtain a nonionic surfactant (X-7).
製造例８
製造例１において、３，５，５−トリメチル−１−ヘキサノール１４４重量部（１モル部）を２−エチル−１−ヘキサノール１３０重量部（１モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ−８）を得た。
Production Example 8
Same as Production Example 1 except that in Preparation Example 1, 144 parts by weight (1 mol part) of 3,5,5-trimethyl-1-hexanol was changed to 130 parts by weight (1 mol part) of 2-ethyl-1-hexanol. To obtain a nonionic surfactant (X-8).
比較製造例１
製造例１において、３，５，５−トリメチル−１−ヘキサノール１４４重量部（１モル部）を２−デカノール１５８重量部（１モル部）に変更した以外は製造例１と同様に製造し、比較用の非イオン性界面活性剤（Ｘ’−１）を得た。
Comparative Production Example 1
In Production Example 1, it was produced in the same manner as in Production Example 1 except that 144 parts by weight (1 mol part) of 3,5,5-trimethyl-1-hexanol was changed to 158 parts by weight (1 mol part) of 2-decanol. A nonionic surfactant (X'-1) for comparison was obtained.
比較製造例２
製造例１において、３，５，５−トリメチル−１−ヘキサノール１４４重量部（１モル部）を４−メチル−１−ペンタノール１０２重量部（１モル部）に変更した以外は製造例１と同様に製造し、比較用の非イオン性界面活性剤（Ｘ’−２）を得た。
Comparative Production Example 2
Production Example 1 was the same as Production Example 1 except that 144 parts by weight (1 mol part) of 3,5,5-trimethyl-1-hexanol was changed to 102 parts by weight (1 mol part) of 4-methyl-1-pentanol. It produced similarly and obtained the nonionic surfactant (X'-2) for a comparison.
比較製造例３
製造例１において、３，５，５−トリメチル−１−ヘキサノール１４４重量部（１モル部）を１−オクタノール１３０重量部（１モル部）に変更した以外は製造例１と同様に製造し、比較用の非イオン性界面活性剤（Ｘ’−３）を得た。
Comparative Production Example 3
In Production Example 1, it was produced in the same manner as in Production Example 1 except that 144 parts by weight (1 mol part) of 3,5,5-trimethyl-1-hexanol was changed to 130 parts by weight (1 mol part) of 1-octanol. A nonionic surfactant (X'-3) for comparison was obtained.
比較製造例４
撹拌機、温度計、圧力計、耐圧滴下ボンベ、減圧及び窒素導入ラインの付いた２Ｌオートクレーブ中に２−エチル−１−ヘキサノール１３０重量部（１モル部）、水酸化カリウム０．５重量部を加え撹拌を開始し窒素封入し１００℃に昇温した後、圧力−０．１ＭＰａＧで１時間脱水した。次いで１３０℃に昇温し、圧力０．３ＭＰａＧ以下でプロピレンオキサイド２３２重量部（４モル部）を５時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した。その後６０℃に冷却し、酢酸０．５重量部で中和し、比較用の非イオン性界面活性剤（Ｘ’−４）を得た。
Comparative Production Example 4
130 parts by weight (1 mol part) of 2-ethyl-1-hexanol and 0.5 part by weight of potassium hydroxide were placed in a 2 L autoclave equipped with a stirrer, a thermometer, a pressure gauge, a pressure-resistant dropping cylinder, a reduced pressure and a nitrogen introduction line. After addition, stirring was started, nitrogen was sealed, the temperature was raised to 100 ° C., and then dehydration was performed at a pressure of −0.1 MPaG for 1 hour. Subsequently, the temperature was raised to 130 ° C., and 232 parts by weight (4 mol parts) of propylene oxide was sequentially dropped at a pressure of 0.3 MPaG or less over 5 hours, and the mixture was stirred at the same temperature for 1 hour until a pressure equilibrium was reached. Thereafter, the mixture was cooled to 60 ° C. and neutralized with 0.5 part by weight of acetic acid to obtain a nonionic surfactant (X′-4) for comparison.
比較製造例５
製造例８において、エチレンオキサイド８８重量部（２モル部）を２６４重量部（６モル部）に変更した以外は製造例８と同様に製造し、比較用の非イオン性界面活性剤（Ｘ’−５）を得た。
Comparative Production Example 5
Production Example 8 was repeated except that 88 parts by weight (2 mol parts) of ethylene oxide was changed to 264 parts by weight (6 mol parts) to produce a nonionic surfactant (X ′) for comparison. -5) was obtained.
比較製造例６
撹拌機、温度計、圧力計、耐圧滴下ボンベ、減圧及び窒素導入ラインの付いた２Ｌオートクレーブ中に２−エチル−１−ヘキサノール１３０重量部（１モル部）、水酸化カリウム０．５重量部を加え撹拌を開始し窒素封入し１００℃に昇温した後、圧力−０．１ＭＰａＧで１時間脱水した。次いで１３０℃に昇温し、圧力０．３ＭＰａＧ以下でエチレンオキサイド８８重量部（２モル部）を５時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した。その後６０℃に冷却し、酢酸０．５重量部で中和し、比較用の非イオン性界面活性剤（Ｘ’−６）を得た。
Comparative Production Example 6
130 parts by weight (1 mol part) of 2-ethyl-1-hexanol and 0.5 part by weight of potassium hydroxide were placed in a 2 L autoclave equipped with a stirrer, a thermometer, a pressure gauge, a pressure-resistant dropping cylinder, a reduced pressure and a nitrogen introduction line. After addition, stirring was started, nitrogen was sealed, the temperature was raised to 100 ° C., and then dehydration was performed at a pressure of −0.1 MPaG for 1 hour. Subsequently, the temperature was raised to 130 ° C., and 88 parts by weight (2 mol parts) of ethylene oxide was sequentially added dropwise at a pressure of 0.3 MPaG or less over 5 hours, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached. Thereafter, the mixture was cooled to 60 ° C. and neutralized with 0.5 part by weight of acetic acid to obtain a nonionic surfactant (X′-6) for comparison.
比較製造例７
製造例８において、プロピレンオキサイド２３２重量部（２モル部）を６３８重量部（１１モル部）に変更した以外は製造例８と同様に製造し、比較用の非イオン性界面活性剤（Ｘ’−７）を得た。
Comparative Production Example 7
Production Example 8 was repeated, except that 232 parts by weight (2 mol parts) of propylene oxide was changed to 638 parts by weight (11 mol parts), and a nonionic surfactant for comparison (X ′) was produced. -7) was obtained.
＜実施例１〜８及び比較例１〜８＞
表１に記載の非イオン界面活性剤（Ｘ−１）〜（Ｘ−８）及び比較用の非イオン界面活性剤（Ｘ’−１）〜（Ｘ’−７）をパルプ用洗浄剤として用いて、以下の方法により、白色度及び溶剤抽出量を評価した。
なお、表１においてのみ、「（ＥＯ）」と「（ＰＯ）」との間の「−」は、「（ＥＯ）」及び「（ＰＯ）」がブロック状に結合していることを示し、また、「（ＥＯ）」と「（ＰＯ）」との間の「／」は、「（ＥＯ）」及び「（ＰＯ）」がランダム状に結合していることを示す。
<Examples 1 to 8 and Comparative Examples 1 to 8>
The nonionic surfactants (X-1) to (X-8) and the nonionic surfactants (X'-1) to (X'-7) for comparison used in Table 1 are used as pulp detergents. The whiteness and the amount of solvent extracted were evaluated by the following methods.
Only in Table 1, "-" between "(EO)" and "(PO)" indicates that "(EO)" and "(PO)" are combined in a block shape, In addition, “/” between “(EO)” and “(PO)” indicates that “(EO)” and “(PO)” are combined at random.
＜洗浄性試験＞
針葉樹未晒しパルプ製造工場提供の洗浄工程出口パルプを純水で２％濃度に希釈し、試験スラリーとした。試験スラリー５００部を恒温水槽で７０℃に加温後、対パルプとして１００ｐｐｍとなるよう０．００１部のパルプ用洗浄剤を添加し、ブレンダー（ブラウン社製ＭＲ５５５５ＭＣＡ 撹拌強度１０）で１分間撹拌した。このスラリーを−３０ｋＰａで吸引ろ過してシートを作成した。次にシートをろ紙で挟み、シートマシン用プレス［熊谷理機工業（株）製］を用いて、圧力０．３５ＭＰａで３分間プレスした後、２３℃、湿度２０％の恒温恒湿室で２４時間静置し、白色度測定装置（ＴＥＣＨＮＩＤＹＮＥ社製 カラータッチ２ＩＳＯモデル）で白色度を測定した。
<Washability test>
The pulp at the outlet of the washing step provided by the unbleached softwood pulp manufacturing plant was diluted with pure water to a concentration of 2% to prepare a test slurry. After heating 500 parts of the test slurry to 70 ° C. in a constant temperature water bath, 0.001 part of a pulp detergent was added so as to be 100 ppm as pulp, and the mixture was stirred for 1 minute with a blender (Brown MR5555MCA, stirring intensity 10). . This slurry was suction filtered at -30 kPa to form a sheet. Next, the sheet is sandwiched between filter papers and pressed at a pressure of 0.35 MPa for 3 minutes using a sheet machine press (manufactured by Kumagai Riki Kogyo Co., Ltd.), and then pressed in a constant temperature and humidity chamber at 23 ° C. and 20% humidity. After standing for a while, the whiteness was measured with a whiteness measuring device (a color touch 2ISO model manufactured by TECHNIDYNE).
＜溶剤抽出量測定＞
前記の白色度測定後のシートの重量を秤量し、ソックスレー抽出用円筒ろ紙に投入した。これを連続ソックスレー抽出装置［柴田科学（株）製Ｂ８１１型ＬＳＶタイプ］にセットし、溶媒（体積比ヘキサン：エタノール＝１：１）で抽出した。抽出条件は加熱時間４時間１０分、リンス時間は１時間とした。ヒーター設定は１６でエタノールの沸点以上を維持した。抽出液の溶媒を除去し、抽出物の重量を秤量した。溶剤抽出量はシート１０ｇに対する抽出物の固形分重量をｍｇで示した。
<Solvent extraction amount measurement>
The weight of the sheet after the whiteness measurement was weighed and put into a cylindrical filter paper for Soxhlet extraction. This was set in a continuous Soxhlet extractor [B811 LSV type manufactured by Shibata Kagaku Co., Ltd.], and extracted with a solvent (hexane: ethanol = 1: 1 by volume). The extraction conditions were a heating time of 4 hours and 10 minutes and a rinsing time of 1 hour. The heater setting was 16 to maintain above the boiling point of ethanol. The solvent of the extract was removed, and the weight of the extract was weighed. The solvent extraction amount was expressed in mg of the solid content of the extract per 10 g of the sheet.
表１に示されるように、本発明の非イオン界面活性剤（Ｘ−１）〜（Ｘ−８）を用いたパルプ用洗浄剤（実施例１〜８）は、本発明の非イオン界面活性剤（Ｘ）を用いないパルプ用洗浄剤（比較例１〜８）と比べ、大きく白色度が向上しており、また溶剤抽出量が少ないことから、汚れ成分が除去できていた。 As shown in Table 1, the pulp detergents (Examples 1 to 8) using the nonionic surfactants (X-1) to (X-8) of the present invention have the nonionic surfactants of the present invention. Compared with the pulp detergents not using the agent (X) (Comparative Examples 1 to 8), the whiteness was greatly improved, and the dirt components could be removed because the solvent extraction amount was small.
本発明のパルプ用洗浄剤は、パルプを洗浄する工程で用いることで、最終的に得られるパルプの白色度を大きく向上させることができ、また、パルプから汚れ成分を効率よく除去できることから、パルプ用洗浄剤として最適である。 The pulp detergent of the present invention can greatly improve the whiteness of the finally obtained pulp by being used in the step of washing the pulp, and can efficiently remove dirt components from the pulp. Ideal as a cleaning agent for
Claims (6)
Ｒ１Ｏ［（Ｃ２Ｈ４Ｏ）ｐ／（Ｃ３Ｈ６Ｏ）ｑ］Ｈ （１）
［一般式（１）中、Ｒ１は炭素数８〜９の分岐のアルキル基を表し；ｐはエチレンオキシ基の数平均付加モル数で、１〜５の数であり；ｑはプロピレンオキシ基の数平均付加モル数で、１〜１０の数であり；［（Ｃ２Ｈ４Ｏ）ｐ／（Ｃ３Ｈ６Ｏ）ｑ］はエチレンオキシ基とプロピレンオキシ基の付加形式がランダム状又はブロック状であることを表す。］ A pulp detergent containing a nonionic surfactant (X) represented by the following general formula (1).
R 1 O [(C 2 H 4 O) p / (C 3 H 6 O) q] H (1)
[In the general formula (1), R 1 represents a branched alkyl group having 8 to 9 carbon atoms; p is a number-average addition mole number of an ethyleneoxy group, and is a number of 1 to 5; q is a propyleneoxy group. the number average addition number of moles is a number of 1~10; [(C 2 H 4 O) p / (C 3 H 6 O) q] is the additional form of ethyleneoxy group and propyleneoxy group random form or Indicates a block shape. ]
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| JP2005531644A (en) * | 2002-07-04 | 2005-10-20 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Alkoxylate mixture and its use as a hard surface cleaner |
| JP2009270222A (en) * | 2008-05-07 | 2009-11-19 | Kao Corp | Method for producing deinked pulp |
| JP2011524940A (en) * | 2008-06-18 | 2011-09-08 | ダウ グローバル テクノロジーズ エルエルシー | Cleaning composition containing mid-range alkoxylate |
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| JP2005531644A (en) * | 2002-07-04 | 2005-10-20 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Alkoxylate mixture and its use as a hard surface cleaner |
| JP2009270222A (en) * | 2008-05-07 | 2009-11-19 | Kao Corp | Method for producing deinked pulp |
| JP2011524940A (en) * | 2008-06-18 | 2011-09-08 | ダウ グローバル テクノロジーズ エルエルシー | Cleaning composition containing mid-range alkoxylate |
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