JP4170129B2 - Deinking agent - Google Patents

Description

（式中、Ｒは水素または炭素数１から３０のアシル基、ＡＯは炭素数２から４のオキシアルキレン基を示し、ｎは３から８の整数であり、ｘ＋ｙ＋ｚは５〜２５０の整数である。）
【０００７】
本発明にかかわるポリグリセリンを主骨格とした界面活性剤については公知の方法で容易に得ることができる。すなわち、特に限定されるものではないが、ポリグリセリンに高級脂肪酸およびアルキレンオキサイドを反応させる事により得ることができる。反応モル比は重合数３〜８のポリグリセリン１．０モルに対し高級脂肪酸１．５〜５．０モル、炭素数２〜４のアルキレンオキサイド５〜２５０モルである。
ポリグリセリンの重合数が１０以上であるとフローテーション法での脱墨方法において発泡量が多すぎ、パルプの歩留まり率の低下など、発泡トラブルが多発する傾向が見られる。
高級脂肪酸の仕込量が１．５モルを下回れば未反応のポリグリセリンが多量に存在し、フローテーション法等による脱墨方法において、インキ捕集性の低下が見られ、５．０モルを超えればフローテーション法での脱墨方法で、発泡量の低下が見られる。
アルキレンオキサイドの付加モル数が５モルを下回ればインキの剥離性が低下し、２５０モルを超えれば高分子量化による泡沫の安定化が起こり、フローテーション法等による脱墨方法において発泡トラブルの原因となる。
他の製造方法として、高級脂肪酸にグリシドールを付加する方法もあるが、経済性の面からポリグリセリンと高級脂肪酸との脱水縮合によるものが好ましい。
【０００８】
ポリグリセリンとは、具体的にはトリグリセリン、テトラグリセリン、ペンタグリセリン、ヘキサグリセリン、ヘプタグリセリン、オクタグリセリン等が挙げられる。
これらの中でも重合数３〜８のポリグリセリンが好ましく使用できる。この範囲内で重合数の異なるポリグリセリンを使用しても問題ない。
【０００９】
本発明にかかわる化合物の原料として用いられる炭素数１〜３０の脂肪酸としては、蟻酸、酢酸、プロピオン酸、吉草酸、イソ吉草酸、カプリル酸、カプリン酸、２−エチルヘキサン酸、ノナン酸、カプロン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、オレイン酸、リノール酸、リノレン酸、ドコサン酸、ベヘン酸等が挙げられる。
これらの中でもカプロン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ドコサン酸、ベヘン酸等が好ましく使用でき、特に好ましくは炭素数８〜２２の飽和脂肪酸が使用できる。
【００１０】
アルキレンオキサイドとしてはエチレンオキサイド（以下ＥＯと省略）、プロピレンオキサイド（以下ＰＯと省略）、ブチレンオキサイド（以下ＢＯと省略）が挙げられる。その付加形態はブロック付加、ランダム付加のいずれの付加形態でもかまわず、また付加順序も特に限定されない。
【００１１】
一般式（ＩＩ）で表される化合物は高温、アルカリ存在下において、脂肪酸石鹸とポリオキシアルキレンポリグリセリルエーテルに加水分解される。加水分解して得られた脂肪酸石鹸がインキの凝集を促し、フローテーション法等による脱墨方法において、インキの速やかな除去が可能となる。
さらに、該化合物は浸透力に優れており、パルプとインキの界面に速やかに浸透し、良好なインキ剥離性を発揮する。
【００１２】
本発明の脱墨剤は一般式（ＩＩ）で表される界面活性剤を含有することを特徴とし、古紙離解工程、漂白工程、フローテーション工程等の各工程で添加することができる。また、従来の方法と同様、アルカリ類は苛性ソーダ、ケイ酸ソーダ、炭酸ソーダ及びリン酸ソーダ等が使用できる。また、過酸化水素等の漂白剤を併用し、脱墨パルプの白色度を上げるのも好ましい。更にＥＤＴＡ等のキレート剤を使用しても構わない。
本発明の脱墨剤の使用量は古紙に対し、０．００１〜２重量％の割合で使用できるが、好ましくは０．００５〜０．５重量％の割合で使用する。
【００１３】
本発明品は新聞古紙、色上古紙、雑誌古紙、ＣＰＯ等のＯＡ古紙等、いずれの古紙に対しても、インキの凝集及び未剥離インキの減少効果の両方を解決できる。
【００１４】
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、撹拌装置を備えた四つ口フラスコに、ステアリン酸２８０ｇ（１．０モル）、テトラグリセリン３３０ｇ（０．５モル）及び苛性カリ３ｇを仕込み、２３０℃で４時間脱水縮合させた後、ステンレス製オートクレープに１７４ｇ（０．２モル）移送した。反応槽内を十分に窒素置換した後、１２０±５℃、１〜５ｋｇ／ｃｍ^２を保つようにＰＯ１１６ｇ（２モル）を徐々に添加し付加反応を行った。添加終了後、１２０±５℃を２時間保持しながら熟成を行なった。次にＥＯ１７６ｇ（４モル）を徐々に添加し付加反応を行なった。添加終了後１２０±５℃を２時間保持しながら熟成を行なった。次にＰＯ１１６ｇ（２モル）徐々に添加し付加反応を行なった。添加終了後酢酸１ｇで触媒を中和し、本発明品Ｎｏ．１の化合物を得た。
【００１５】
製造例１と同様の方法で表１に示す発明品Ｎｏ．１〜３０の化合物を得た。
【表１】

表中、アルキレンオキサイドの付加形態について、『−』はブロック付加、『／』はランダム付加を示す。
【００１６】
上記発明品との比較を行うために下記非イオン系界面活性剤を試験に供した。構造式中の『／』はランダム付加を表し、『−』はブロック付加を表す。
【００１７】
【表２】

【００１８】
（脱墨試験１）新聞古紙での脱墨試験
オフセット新聞古紙６０％、折り込み広告４０％からなる原料古紙を３ｃｍ×３ｃｍに切断し、卓上離解機に入れ、苛性ソーダを１．５％（対古紙）、３号ケイ酸ソーダを３％（対古紙）、３５％過酸化水素水を３％（対古紙）及び表１に示した脱墨剤０．２％（対古紙）を加えた後、水を加え、古紙濃度５％とし、５５℃に昇温後１５分間離解した。離解後同温度で１時間熟成してからパルプ濃度１％に希釈してフローテーターに移し、フローテーション処理を１０分間行った。得られたパルプを０．５％濃度にした後、硫酸アルミニウムにてｐＨ５．０に調整した後、ＪＩＳ Ｐ−８２０９に規定したシートマシンにて手抄きした。さらにフローテーション処理を行ったパルプを２００倍量のイオン交換水で３回洗浄を行った。このパルプについて同様の方法で手抄きした。
【００１９】
（性能評価試験）
フローテーターでの発泡性：フローテーション１分後の液面からの泡高（ｍｍ）を測定した。
また、手抄き紙は乾燥後、次の測定を行い、脱墨効果を評価した。
白色度：ＪＩＳ Ｐ−８１２３に規定した方法に準じて測定を行った。
残インキ数及び面積率：完全洗浄パルプについて、画像解析装置を使用し、視野１００ｍｍ^２中に存在する径２０μｍ以上のインキ個数及び全視野中におけるインキ総面積率（％）を測定した。
測定結果を表３に示す。
【００２０】
【表３】

【００２１】
（脱墨試験２）上質古紙での脱墨試験
色上古紙５０％、模造古紙５０％からなる原料古紙を３ｃｍ×３ｃｍに切断し、卓上離解機に入れ、苛性ソーダを１．５％（対古紙）、３号ケイ酸ソーダを３％（対古紙）、３５％過酸化水素水を３％（対古紙）及び表−１に示した脱墨剤を０．２％（対古紙）を加えた後、水を加え、古紙濃度５％とし、５５℃に昇温後１５分間離解した。離解後同温度で１時間熟成してからパルプ濃度１％に希釈してフローテーターに移し、フローテーション処理を１０分間行った。得られたパルプを０．５％濃度にした後、硫酸アルミニウムにてｐＨ５．０に調整した後、ＪＩＳ Ｐ−８２０９に規定したシートマシンにて手抄きした。さらにフローテーション処理を行ったパルプを２００倍量のイオン交換水で３回洗浄を行った。このパルプについて同様の方法で手抄きした。
【００２２】
（性能評価試験）
フローテーターでの発泡性：フローテーション１分後の液面からの泡高（ｍｍ）を測定した。
また、手抄き紙は乾燥後、次の測定を行い脱墨効果を評価した。
白色度：ＪＩＳ Ｐ−８１２３に規定した方法に準じて測定を行った。
残インキ数及び面積率：完全洗浄パルプについて、画像解析装置を使用し、視野１００ｍｍ^２中に存在する径２０μｍ以上のインキ個数及び全視野中におけるインキ総面積率（％）を測定した。
測定結果を表４に示す。
【００２３】
【表４】

【００２４】
【発明の効果】
本発明では、未剥離インキの低減効果により高品質の脱墨パルプが得られ、さらにフローテーション法による脱墨工程においてインキ捕集性に優れる脱墨剤が提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a deinking agent, and more particularly to a deinking agent characterized by using a surfactant having polyglycerin as a main skeleton when deinking waste paper.
[0002]
[Prior art]
So far, nonionic surfactants obtained by adding alkylene oxide to higher alcohols have been mainly used as deinking agents (see Patent Document 1, Patent Document 2, and Patent Document 3). However, as the printing technology has improved and the number of low-grade used paper has increased, the use of higher alcohol-based nonionic surfactant type deinking agents does not sufficiently remove the ink, and the quality of the deinked pulp deteriorates. There was a problem of being connected to. Further, the finely dispersed ink cannot be aggregated to an appropriate particle size, and it is difficult to quickly remove the ink by a deinking method such as a flotation method.
[0003]
[Patent Document 1]
JP 55-51891 A
[Patent Document 2]
JP 55-51892 A
[Patent Document 3]
JP-A-8-284087
[0004]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to provide a deinking agent that solves both the reduction of unpeeled ink and the aggregation of ink in a deinking method such as a flotation method.
[0005]
[Means for solving problems]
The present inventors have found that the above problem can be solved by using a deinking agent comprising a compound represented by the following general formula (II).
[0006]
[Chemical 2]

(In the formula, R represents hydrogen or an acyl group having 1 to 30 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, n is an integer of 3 to 8 , and x + y + z is an integer of 5 to 250. .)
[0007]
The surfactant having polyglycerin as the main skeleton according to the present invention can be easily obtained by a known method. That is, although not particularly limited, it can be obtained by reacting polyglycerin with a higher fatty acid and an alkylene oxide. The reaction molar ratio is 1.5 to 5.0 mol of higher fatty acid and 5 to 250 mol of alkylene oxide having 2 to 4 carbon atoms with respect to 1.0 mol of polyglycerol having 3 to 8 polymerizations.
If the polymerization number of polyglycerin is 10 or more, the amount of foaming is too large in the deinking method by the flotation method, and foaming troubles such as a decrease in the yield rate of pulp tend to occur frequently.
If the amount of higher fatty acid charged is less than 1.5 mol, a large amount of unreacted polyglycerin is present, and in the deinking method such as the flotation method, the ink collecting property is reduced and the amount exceeds 5.0 mol. For example, the deinking method by the flotation method shows a decrease in the amount of foaming.
If the number of added moles of alkylene oxide is less than 5 moles, the ink peelability is lowered, and if it exceeds 250 moles, foam stabilization due to high molecular weight occurs, causing foaming troubles in deinking methods such as the flotation method. Become.
As another production method, there is a method of adding glycidol to a higher fatty acid, but from the viewpoint of economy, a method by dehydration condensation of polyglycerin and higher fatty acid is preferable.
[0008]
Specific examples of polyglycerin include triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin and the like.
Among these, polyglycerin having a polymerization number of 3 to 8 can be preferably used. There is no problem even if polyglycerin having a different polymerization number is used within this range.
[0009]
Examples of the fatty acid having 1 to 30 carbon atoms used as a raw material for the compound according to the present invention include formic acid, acetic acid, propionic acid, valeric acid, isovaleric acid, caprylic acid, capric acid, 2-ethylhexanoic acid, nonanoic acid, and capron. Examples thereof include acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, docosanoic acid, and behenic acid.
Among these, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, docosanoic acid, behenic acid and the like can be preferably used, and particularly preferably a saturated fatty acid having 8 to 22 carbon atoms can be used.
[0010]
Examples of the alkylene oxide include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), and butylene oxide (hereinafter abbreviated as BO). The addition form may be either block addition or random addition, and the addition order is not particularly limited.
[0011]
The compound represented by the general formula (II) is hydrolyzed into fatty acid soap and polyoxyalkylene polyglyceryl ether in the presence of alkali at high temperature. The fatty acid soap obtained by hydrolysis promotes the aggregation of the ink, and in the deinking method such as the flotation method, the ink can be removed promptly.
Further, the compound is excellent in penetrating power, quickly penetrates the interface between pulp and ink, and exhibits good ink peelability.
[0012]
The deinking agent of the present invention is characterized by containing a surfactant represented by the general formula (II) and can be added in each step such as a waste paper disaggregation step, a bleaching step, and a flotation step. As in the conventional method, caustic soda, sodium silicate, sodium carbonate, sodium phosphate and the like can be used as the alkali. It is also preferable to use a bleaching agent such as hydrogen peroxide to increase the whiteness of the deinked pulp. Further, a chelating agent such as EDTA may be used.
The amount of the deinking agent of the present invention can be used in a proportion of 0.001 to 2% by weight, preferably 0.005 to 0.5% by weight, based on the waste paper.
[0013]
The product of the present invention can solve both the ink aggregation and the reduction effect of the unpeeled ink for any used paper such as used newspaper, colored paper, magazine used paper, OA used paper such as CPO.
[0014]
Examples of the present invention are shown below, but are not limited thereto.
Production Example 1
A four-necked flask equipped with a thermometer and a stirrer was charged with 280 g (1.0 mol) of stearic acid, 330 g (0.5 mol) of tetraglycerin and 3 g of caustic potash and subjected to dehydration condensation at 230 ° C. for 4 hours. 174 g (0.2 mol) was transferred to a stainless steel autoclave. After sufficiently purging the inside of the reaction vessel with nitrogen, 116 g (2 mol) of PO was gradually added to carry out an addition reaction so as to maintain 120 ± 5 ° C. and 1 to 5 kg / cm ² . After completion of the addition, aging was performed while maintaining 120 ± 5 ° C. for 2 hours. Next, 176 g (4 mol) of EO was gradually added to carry out an addition reaction. After completion of the addition, aging was performed while maintaining 120 ± 5 ° C. for 2 hours. Next, 116 g (2 mol) of PO was gradually added to carry out an addition reaction. After completion of the addition, the catalyst was neutralized with 1 g of acetic acid. 1 compound was obtained.
[0015]
Invention No. shown in Table 1 in the same manner as in Production Example 1. 1-30 compounds were obtained.
[Table 1]

In the table, regarding the addition form of alkylene oxide, “-” indicates block addition and “/” indicates random addition.
[0016]
The following nonionic surfactants were used for the test in order to compare with the above invention products. “/” In the structural formula represents random addition, and “−” represents block addition.
[0017]
[Table 2]

[0018]
(Deinking test 1) Deinking test with waste newspaper waste paper waste paper consisting of 60% offset newspaper waste paper and 40% insert advertisement is cut into 3cm x 3cm, placed in a desktop disintegrator, 1.5% caustic soda (against waste paper) ) After adding 3% sodium silicate 3% (to old paper), 35% hydrogen peroxide 3% (to old paper) and 0.2% deinking agent (to old paper) shown in Table 1, Water was added to adjust the waste paper concentration to 5%, the temperature was raised to 55 ° C., and the mixture was disaggregated for 15 minutes. After disaggregation, the mixture was aged at the same temperature for 1 hour, diluted to a pulp concentration of 1%, transferred to a floatator, and subjected to a flotation treatment for 10 minutes. The obtained pulp was adjusted to 0.5% concentration, adjusted to pH 5.0 with aluminum sulfate, and then hand-drawn with a sheet machine defined in JIS P-8209. Further, the pulp subjected to the flotation treatment was washed three times with 200 times the amount of ion-exchanged water. This pulp was hand-made in the same manner.
[0019]
(Performance evaluation test)
Foamability with a flotator: The foam height (mm) from the liquid level after 1 minute of flotation was measured.
In addition, the hand-made paper was dried and then subjected to the following measurement to evaluate the deinking effect.
Whiteness: Measured according to the method defined in JIS P-8123.
Number of remaining inks and area ratio: For the completely washed pulp, the number of inks having a diameter of 20 μm or more existing in a visual field of 100 mm ² and the total ink area ratio (%) in the entire visual field were measured using an image analysis apparatus.
Table 3 shows the measurement results.
[0020]
[Table 3]

[0021]
(Deinking test 2) Deinking test with high-quality waste paper Raw material waste paper consisting of 50% colored waste paper and 50% imitation waste paper is cut into 3cm x 3cm, placed in a desktop disintegrator, and caustic soda 1.5% (against waste paper) 3% sodium silicate 3% (against old paper), 35% hydrogen peroxide 3% (against old paper) and 0.2% deinking agent shown in Table 1 (against old paper) After that, water was added to make the waste paper concentration 5%, and the temperature was raised to 55 ° C., and then disaggregated for 15 minutes. After disaggregation, the mixture was aged at the same temperature for 1 hour, diluted to a pulp concentration of 1%, transferred to a floatator, and subjected to a flotation treatment for 10 minutes. The obtained pulp was adjusted to 0.5% concentration, adjusted to pH 5.0 with aluminum sulfate, and then hand-drawn with a sheet machine defined in JIS P-8209. Further, the pulp subjected to the flotation treatment was washed three times with 200 times the amount of ion-exchanged water. This pulp was hand-made in the same manner.
[0022]
(Performance evaluation test)
Foamability with a flotator: The foam height (mm) from the liquid level after 1 minute of flotation was measured.
The handmade paper was dried and then subjected to the following measurements to evaluate the deinking effect.
Whiteness: Measured according to the method defined in JIS P-8123.
Number of remaining inks and area ratio: For the completely washed pulp, the number of inks having a diameter of 20 μm or more existing in a visual field of 100 mm ² and the total ink area ratio (%) in the entire visual field were measured using an image analysis apparatus.
Table 4 shows the measurement results.
[0023]
[Table 4]

[0024]
【The invention's effect】
In the present invention, a deinking pulp having a high quality can be obtained due to the effect of reducing the unpeeled ink, and further, a deinking agent having excellent ink collecting properties in a deinking process by a flotation method is provided.

Claims (1)

Formula (I)

(In the formula, R represents hydrogen or an acyl group having 1 to 30 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, n is an integer of 3 to 8 , and x + y + z is an integer of 5 to 250. A deinking agent comprising a compound represented by