JP2005281906A - Defibration promoting agent for used paper and waste paper - Google Patents
Defibration promoting agent for used paper and waste paper Download PDFInfo
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- JP2005281906A JP2005281906A JP2004098178A JP2004098178A JP2005281906A JP 2005281906 A JP2005281906 A JP 2005281906A JP 2004098178 A JP2004098178 A JP 2004098178A JP 2004098178 A JP2004098178 A JP 2004098178A JP 2005281906 A JP2005281906 A JP 2005281906A
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- 239000010893 paper waste Substances 0.000 title claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 title abstract description 12
- 230000001737 promoting effect Effects 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 7
- 239000002253 acid Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000000123 paper Substances 0.000 description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- -1 phosphate ester compound Chemical class 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000005187 foaming Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 229940035429 isobutyl alcohol Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004078 waterproofing Methods 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 1
- 229940122930 Alkalising agent Drugs 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004440 Isodecyl alcohol Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- 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
Abstract
Description
本発明は、古紙または損紙を効率よく離解させる離解促進剤、およびこれを用いた古紙または損紙の再生方法に関する。 The present invention relates to a disaggregation accelerator that efficiently disaggregates used paper or damaged paper, and a method for recycling used paper or damaged paper using the same.
資源の有効利用や環境保護などの観点から古紙の再利用の重要性が増加しており、わが国においては古紙の紙への利用率は６０％に迫ろうとしている。古紙の再生は、通常はまずパルパーにおいて回収された古紙を水あるいは温水で分散させて古紙パルプスラリーを得ることで行う。この時必要に応じて、水酸化ナトリウム、炭酸ナトリウム、ケイ酸ナトリウム等のアルカリを使用する。一方抄紙機周辺で発生する損紙はブロークチェスに投入され、水あるいは温水でスラリーに再度調製される。
近年、紙は益々高度に加工されており、古紙原料には多種多様な性質を付与するための物質が含まれている。これらの中には紙の表面あるいは内部まで化学薬品で処理され、離解が困難な紙も多く含まれている。このような場合、離解を容易にするために、先の酸やアルカリをはじめ、次亜塩素酸塩や過酸化水素などの酸化剤や界面活性剤などの化学薬剤の使用が以下のように提案されている。
すなわち、特許文献１には界面活性剤と水酸化ナトリウムの併用が提案され、また、特許文献２にはグラシン紙に対し酸性物質が、特許文献３には分子内に窒素を含む界面活性剤が、特許文献４には非イオン性界面活性剤がそれぞれ提案されている。
The importance of reusing used paper is increasing from the viewpoint of effective use of resources and environmental protection, and in Japan, the utilization rate of used paper is approaching 60%. The recycling of used paper is usually performed by first dispersing used paper recovered by a pulper with water or hot water to obtain a used paper pulp slurry. At this time, an alkali such as sodium hydroxide, sodium carbonate or sodium silicate is used as necessary. On the other hand, the waste paper generated around the paper machine is put into a broke chess and prepared again into a slurry with water or hot water.
In recent years, paper has been increasingly processed, and waste paper materials contain substances for imparting a wide variety of properties. Among these, many papers which are treated with chemicals up to the surface or inside of the paper and are difficult to disaggregate are included. In such cases, in order to facilitate disaggregation, the use of chemical agents such as acids and alkalis as well as oxidizing agents and surfactants such as hypochlorite and hydrogen peroxide is proposed as follows. Has been.
That is, Patent Document 1 proposes a combination of a surfactant and sodium hydroxide, Patent Document 2 discloses an acidic substance for glassine paper, and Patent Document 3 includes a surfactant containing nitrogen in the molecule. Patent Document 4 proposes a nonionic surfactant.
しかし、上記の方法では高度に加工された紙に対して離解性能が不足であったり、離解された古紙または損紙を製紙原料として使用するにあたり、パルプ繊維が脆化していたり、更にｐＨ等の調整が必要であったりして十分満足のいくものは得られなかった。特に抄紙工程付近で行われる損紙の離解処理においては、抄紙原料としてそのまま戻せるように強酸や強アルカリ、その他抄紙条件に大きな影響を与える薬剤の使用は好ましくない。また古紙を再利用するために離解に長時間を要することは、多大な動力エネルギーを必要とし、経済性の面からも好ましくない。
本発明の目的は、酸やアルカリなどの薬剤と併用しなくても、あるいはそれらが存在する場合においてもパルパーなどにおける機械的負荷を低減し効率よく離解を促進することができる離解促進剤を提供することにある。特に、本発明は、水への濡れ性が悪く機械によるせん断が可能となるまでに長時間を要するような撥水性の高い紙を迅速に湿潤させることができ、これにより機械によるせん断を早期に可能とし離解を促進することを目的とする。
However, in the above method, the disaggregation performance is insufficient with respect to highly processed paper, or when using disaggregated waste paper or waste paper as a papermaking raw material, pulp fibers become brittle, and further, such as pH Something that needs to be adjusted is not satisfactory. In particular, in the disaggregation treatment of damaged paper performed in the vicinity of the papermaking process, it is not preferable to use a strong acid, a strong alkali, or other chemicals that greatly affect the papermaking conditions so that the papermaking raw material can be returned as it is. In addition, it takes a long time for disaggregation to reuse waste paper, which requires a large amount of motive energy and is not preferable from the viewpoint of economy.
An object of the present invention is to provide a disaggregation promoter that can efficiently promote disaggregation by reducing the mechanical load on a pulper or the like even when they are not used in combination with chemicals such as acids and alkalis or when they are present. There is to do. In particular, the present invention can quickly wet highly water-repellent paper that has a poor wettability with water and takes a long time before it can be sheared by a machine. It aims to be possible and promote disaggregation.
本発明者らは、上記課題に鑑みて鋭意検討を行なった結果、これら古紙または損紙の離解において、特定のリン酸エステル化合物の使用が紙に対する水の浸透を促進し、離解機などの機械力を補助する点において有効であることを見出し、本発明に至った。即ち本発明は、
（イ）式（１）で示される化合物及び式（２）で示される化合物を含有する古紙用または損紙用の離解促進剤、
As a result of intensive studies in view of the above problems, the present inventors have found that in the disaggregation of these waste paper or waste paper, the use of a specific phosphate ester compound promotes the penetration of water into the paper, and a machine such as a disaggregator It was found that the method is effective in assisting the force, and the present invention has been achieved. That is, the present invention
(I) A disaggregation accelerator for used paper or waste paper containing the compound represented by the formula (1) and the compound represented by the formula (2),
（Ｒは炭素数４〜１２の炭化水素基であり、ＡＯは炭素数２〜４のオキシアルキレン基である。Ｘはアンモニウム、アルカノールアンモニウム又はアルカリ金属であり、ｎは２〜１０の整数を示す。）
（ロ）式（１）で示される化合物と式（２）で示される化合物の合計に対し、式（１）で示される化合物をモル比で３５〜９８％含有し、かつ式（２）で示される化合物をモル比で２〜６５％含有する上記（イ）の離解促進剤、
（ハ）４．５以上のｐＨ値を有する上記（イ）または（ロ）の離解促進剤、及び
（ニ）上記（イ）〜（ハ）のいずれかに記載の離解促進剤を、式（１）で示される化合物及び式（２）で示される化合物の合計量として５０〜５０，０００ｐｐｍの濃度で使用する古紙または損紙の再生方法、
を提供するものである。
(R is a hydrocarbon group having 4 to 12 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms. X is ammonium, alkanol ammonium or alkali metal, and n is an integer of 2 to 10. .)
(B) The compound represented by the formula (1) is contained in a molar ratio of 35 to 98% with respect to the total of the compound represented by the formula (1) and the compound represented by the formula (2), and the formula (2) The disaggregation accelerator of (a) above containing 2 to 65% of the compound shown by mole,
(C) The disaggregation accelerator according to (i) or (b) above having a pH value of 4.5 or more, and (d) the disaggregation accelerator according to any one of (a) to (c) above, A method for recycling used paper or waste paper, which is used at a concentration of 50 to 50,000 ppm as a total amount of the compound represented by 1) and the compound represented by formula (2);
Is to provide.
本発明の離解促進剤を使用することにより、古紙および損紙から紙を再生する際に機械的負荷を低減し、効率よく離解を行なうことができ、しかも後工程において中和などの追加の処理を必要とせず、再生紙を製造することが可能となる。 By using the disaggregation accelerator of the present invention, it is possible to reduce the mechanical load when recycling paper from waste paper and waste paper, to efficiently disaggregate, and to perform additional processing such as neutralization in the subsequent process This makes it possible to produce recycled paper.
以下、本発明を更に詳細に説明する。
本願発明の離解促進剤は、前記式（１）で示される化合物及び式（２）で示される化合物を含有するが、ここで、Ｒで表わされる炭素数４〜１２の炭化水素基としては、例えば、ブチル基、イソブチル基、ヘキシル基、イソヘキシル基、オクチル基、２−エチルヘキシル基、デシル基、イソデシル基、ラウリル基などが挙げられる。本発明においては、上記炭化水素基として、好ましくは炭素数６〜１０で分岐の炭化水素基を有するものが好ましい。炭素数が上記範囲内にある炭化水素基であれば、泡立ちを生じることなく十分な性能が得られる。
Hereinafter, the present invention will be described in more detail.
The disaggregation accelerator of the present invention contains the compound represented by the formula (1) and the compound represented by the formula (2). Here, as the hydrocarbon group having 4 to 12 carbon atoms represented by R, For example, butyl group, isobutyl group, hexyl group, isohexyl group, octyl group, 2-ethylhexyl group, decyl group, isodecyl group, lauryl group and the like can be mentioned. In the present invention, the hydrocarbon group preferably has a branched hydrocarbon group having 6 to 10 carbon atoms. If the hydrocarbon group has a carbon number within the above range, sufficient performance can be obtained without causing foaming.
式（１）及び式（２）において、ＡＯは炭素数２〜４のオキシアルキレン基である。このようなオキシアルキレン基としては、アルキレンオキサイドの付加により得られるものが好ましく、例えば、エチレンオキサイド、プロンピレンオキサイド、ブチレンオキサイドが使用できる。これらは単独でも２種以上を組みあわせて使用してもよい。組みあわせて使用する場合は、ブロックでもランダムでも使用できる。
本発明においては、前記Ｒで表わされる炭化水素基の炭素数が多い場合はエチレンオキサイドが好ましく用いられる。これらオキシアルキレン基のモル数ｎは２〜１０であり、好ましくは２〜８である。ｎが上記範囲内であれば、発泡による実用上の問題が生じることもなく優れた効果が得られる。
In Formula (1) and Formula (2), AO is an oxyalkylene group having 2 to 4 carbon atoms. As such an oxyalkylene group, those obtained by addition of alkylene oxide are preferable, and for example, ethylene oxide, prompylene oxide, and butylene oxide can be used. These may be used alone or in combination of two or more. When used in combination, it can be used either in blocks or randomly.
In the present invention, ethylene oxide is preferably used when the hydrocarbon group represented by R has a large number of carbon atoms. The number of moles n of these oxyalkylene groups is 2 to 10, preferably 2 to 8. When n is within the above range, a practical effect due to foaming does not occur and an excellent effect is obtained.
式（１）又は式（２）で表わされる化合物において、Ｘはアンモニウム、アルカノールアンモニウム又はアルカリ金属であり、該化合物はアンモニア、アルカノールアミン、アルカリ金属などの中和塩である。このように化合物が中和塩の形態であることにより、離解時にアルカリを添加する必要がなく、十分な浸透性が得られ、離解温度による効果の変動も少ない。本発明においては、具体的には、アンモニア水、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、水酸化ナトリウム、水酸化カリウムなどを用いて中和を行うことができる。 In the compound represented by formula (1) or formula (2), X is ammonium, alkanol ammonium or an alkali metal, and the compound is a neutralized salt of ammonia, alkanolamine, alkali metal or the like. Thus, since the compound is in the form of a neutralized salt, it is not necessary to add an alkali at the time of disaggregation, sufficient penetrability is obtained, and fluctuations in the effect due to the disaggregation temperature are small. In the present invention, specifically, neutralization can be performed using ammonia water, monoethanolamine, diethanolamine, triethanolamine, sodium hydroxide, potassium hydroxide, or the like.
本発明の離解促進剤においては、含有される式（１）で示される化合物と式（２）で示される化合物の合計に対し、式（１）で示されるジエステルをモル比で３５〜９８％、また式（２）で表わされるモノエステルをモル比で２〜６５％含有することが好ましい。本発明においては、更に、ジエステルをモル比で４０〜９５％、モノエステルのモル比をで５〜６０％含むことが好ましい。ジエステルの含有量が上記範囲内であれば、パルプに対する浸透性が十分でしかも起泡性が低く好ましい。
このようなジエステルとモノエステルの比率は電位差を利用した滴定や、ガスクロマトグラフィー（ＧＣ）やゲルパーミエーションクロマトグラフィー（ＧＰＣ）などの方法によって容易に求めることが可能である。
In the disaggregation accelerator of the present invention, the diester represented by the formula (1) is contained in a molar ratio of 35 to 98% with respect to the total of the compound represented by the formula (1) and the compound represented by the formula (2). Moreover, it is preferable to contain 2-65% of monoesters represented by Formula (2) by molar ratio. In the present invention, it is further preferable that the diester is contained in a molar ratio of 40 to 95% and the monoester in a molar ratio of 5 to 60%. If the content of the diester is within the above range, it is preferable that the permeability to the pulp is sufficient and the foaming property is low.
Such a ratio between the diester and the monoester can be easily determined by titration using a potential difference, gas chromatography (GC), gel permeation chromatography (GPC), or the like.
本発明の式（１）あるいは式（２）で表わされる化合物は、その製造方法については特に制限はなく、たとえば、アルコールにアルキレンオサイドを付加重合させた後に五酸化ニリンやピロリン酸、オキシ塩化リン、三塩化リンなどを用いてエステル化する方法などを用いることが出来る。得られたエステル化物から必要に応じ未反応物を取り除き、アンモニア、アルカノールアミン、アルカリ金属等のいずれかで中和することにより本発明の上記化合物を得ることができる。
上記アルコールの例としては、炭素数４〜１２、好ましくは６〜１０のものが挙げられ、例えば、ブチルアルコール、イソブチルアルコール、ヘキシルアルコール、イソヘキシルアルコール、オクチルアルコール、２−エチルヘキシルアルコール、デシルアルコール、イソデシルアルコール、ラウリルアルコールなどが使用できる。
アルキレンオキサイドの付加には、エチレンオキサイド、プロンピレンオキサイド、ブチレンオキサイドを単独あるいは二種以上を組みあわせて使用することができる。上記アルコールとして炭素数が多いものを用いる場合は、アルキレンオキサイドとしてエチレンオキサイドが好ましい。
The compound represented by the formula (1) or the formula (2) of the present invention is not particularly limited in its production method. For example, after addition-polymerization of an alkylene oxide to an alcohol, niline pentoxide, pyrophosphoric acid, oxychloride A method of esterification using phosphorus, phosphorus trichloride or the like can be used. The above-mentioned compound of the present invention can be obtained by removing unreacted substances from the obtained esterified product as necessary and neutralizing with any of ammonia, alkanolamine, alkali metal and the like.
Examples of the alcohol include those having 4 to 12 carbon atoms, preferably 6 to 10 carbon atoms, such as butyl alcohol, isobutyl alcohol, hexyl alcohol, isohexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, Isodecyl alcohol, lauryl alcohol, etc. can be used.
For the addition of alkylene oxide, ethylene oxide, prompyrene oxide, or butylene oxide can be used alone or in combination of two or more. When the alcohol having a large number of carbon atoms is used, ethylene oxide is preferable as the alkylene oxide.
本発明の離解促進剤においては、前述のように特定の中和剤を用いて中和されたものであるが、中和の程度については、例えば１％水溶液のｐＨで４．５以上であることが好ましい。ｐＨ値が４．５以上であれば紙への浸透性が十分得られ好ましい。このｐＨ値の上限は、製剤の安定性や離解時の条件を配慮したものであれば特に限定されないが、通常は、
１２である。
本発明の離解促進剤においては、式（１）で表わされる化合物及び式（２）で表わされる化合物の各々として、Ｒ、ＡＯ、ｎ及びＸの少なくとも一つが異なる化合物を二種以上含むものを使用することもできる。
本発明の離解促進剤は、式（１）あるいは式（２）で表わされる化合物を１０重量％以上含有することが好ましい。このような離解促進剤には、水などの希釈溶媒、リン酸やリン酸トリエステルといった副生物、他の界面活性剤などを含有することができる。
The disaggregation accelerator of the present invention is neutralized by using a specific neutralizing agent as described above, and the degree of neutralization is, for example, 4.5 or more at a pH of a 1% aqueous solution. It is preferable. A pH value of 4.5 or more is preferable because sufficient permeability to paper can be obtained. The upper limit of the pH value is not particularly limited as long as it takes into consideration the stability of the preparation and the conditions at the time of disaggregation.
12.
In the disaggregation accelerator of the present invention, the compound represented by the formula (1) and the compound represented by the formula (2) each include two or more compounds in which at least one of R, AO, n and X is different. It can also be used.
The disaggregation accelerator of the present invention preferably contains 10% by weight or more of the compound represented by formula (1) or formula (2). Such a disaggregation accelerator can contain a diluting solvent such as water, by-products such as phosphoric acid and phosphoric acid triester, other surfactants, and the like.
本発明は上記離解促進剤を使用した古紙または損紙の再生方法を提供する。すなわち、本発明の再生方法は、本発明の離解促進剤を式（１）で示される化合物及び式（２）で示される化合物の合計量として５０〜５０，０００ｐｐｍの濃度で使用するものである。
離解工程において用いる装置や処理条件については特に制限はないが、紙をなじませるに十分な水が存在することが好ましい。たとえば通常の離解機では３〜５％、高濃度パルパーでは約１０％、ニーダーでは２０％前後のパルプ濃度となるように水や温水が加えられることが好ましく、この際、離解の初期の段階から上記離解促進剤が添加されていることが好ましい。
本発明の離解促進剤の使用量が水溶液あるいは水分散液に対し上記範囲内であれば本発明の効果が十分に得られる。使用量が５０ｐｐｍ未満では古紙や損紙中に含まれる共雑物のために該促進剤が消費され、離解促進の効果は乏しくなる。また５０，０００ｐｐｍを超えると効果は更に高いが経済的な効果が薄れる。
The present invention provides a used paper or waste paper recycling method using the above-mentioned disaggregation accelerator. That is, the regeneration method of the present invention uses the disaggregation accelerator of the present invention at a concentration of 50 to 50,000 ppm as the total amount of the compound represented by the formula (1) and the compound represented by the formula (2). .
Although there is no restriction | limiting in particular about the apparatus and processing conditions which are used in a disaggregation process, It is preferable that sufficient water exists to make paper adapt. For example, water or warm water is preferably added so that the pulp concentration is about 3 to 5% for a normal disintegrator, about 10% for a high-concentration pulper, and about 20% for a kneader. In this case, from the initial stage of disaggregation It is preferable that the disaggregation accelerator is added.
If the amount of the disaggregation accelerator of the present invention is within the above range with respect to the aqueous solution or aqueous dispersion, the effects of the present invention can be obtained sufficiently. When the amount used is less than 50 ppm, the accelerator is consumed due to the compost contained in the waste paper and waste paper, and the effect of promoting disaggregation becomes poor. On the other hand, if it exceeds 50,000 ppm, the effect is further increased but the economic effect is reduced.
本発明はサイズ剤や耐水化剤を含有し、あるいは表面コートした紙からなる損紙を処理する際に特に有用である。また性状等が不特定な古紙の離解にも使用することが出来る。いずれの場合においても、離解工程あるいはそれ以前の工程に本発明の離解促進剤を使用することが効果の面で好ましい。この際、必要に応じ水酸化ナトリウムや珪酸ナトリウム、酸化剤、界面活性剤等を添加することができる。本発明の離解促進剤は、そのまま使用することも可能であるが、またあらかじめ水や溶剤に溶解、乳化、分散して使用することも出来る。 The present invention is particularly useful when processing waste paper comprising a sizing agent, a water-proofing agent, or a surface-coated paper. It can also be used for disaggregating used paper whose properties are unspecified. In any case, the use of the disaggregation accelerator of the present invention in the disaggregation step or the previous step is preferable from the viewpoint of the effect. At this time, sodium hydroxide, sodium silicate, an oxidizing agent, a surfactant or the like can be added as necessary. The disaggregation accelerator of the present invention can be used as it is, but can also be used by dissolving, emulsifying and dispersing in water or a solvent in advance.
以下、実施例により本発明を更に具体的に説明する。
実施例１
攪拌装置、圧力計、温度計および窒素吹き込み管のついたオートクレーブ反応装置に、イソブチルアルコール７４ｇおよび水酸化カリウム１．５ｇを加え、窒素置換した後、１１０〜１３０℃まで加温する。そこへあらかじめ計量したエチレンオキサイド１３２ｇを滴下槽より４時間かけて圧入した。その後、０．２ＭＰａの圧力下で１時間反応を続けた後、塩酸にて中和し、９５〜１０５℃、０．００４ＭＰａ以下で３時間脱水処理を行った。その後７５〜８５℃に降温して濾過を行った。得られた化合物を分析したところ水酸基価２７２であった。
次に、得られたアルキレンオキサイドを付加したアルコール２００ｇに冷却しながら五酸化二リン９２ｇを滴下し反応を行った後、残存塩素を加水分解した。得られた燐酸エステル化物の酸価を測定し、水酸化ナトリウムを溶かした水溶液を加え中和した。発熱の後室温にまで冷却して、固形分５０％の離解促進剤の製剤を得た。
Hereinafter, the present invention will be described more specifically with reference to examples.
Example 1
In an autoclave reactor equipped with a stirrer, a pressure gauge, a thermometer, and a nitrogen blowing tube, 74 g of isobutyl alcohol and 1.5 g of potassium hydroxide are added, the atmosphere is replaced with nitrogen, and the mixture is heated to 110 to 130 ° C. Thereto, 132 g of ethylene oxide weighed in advance was injected from the dropping tank over 4 hours. Thereafter, the reaction was continued for 1 hour under a pressure of 0.2 MPa, then neutralized with hydrochloric acid, and dehydrated at 95 to 105 ° C. and 0.004 MPa or less for 3 hours. Thereafter, the temperature was lowered to 75 to 85 ° C. and filtration was performed. When the obtained compound was analyzed, it was hydroxyl group value 272.
Next, 92 g of diphosphorus pentoxide was dropped while cooling to 200 g of the alcohol to which the resulting alkylene oxide was added, and then the residual chlorine was hydrolyzed. The acid value of the obtained phosphoric acid ester was measured and neutralized by adding an aqueous solution in which sodium hydroxide was dissolved. After the exotherm, the mixture was cooled to room temperature to obtain a disaggregation accelerator preparation having a solid content of 50%.
評価１
ポリアミドエピクロルヒドリン樹脂を含有した坪量１６０ｇ/ｍ2の耐水紙を４ｃｍ四方の紙片に裁断し、この紙片約３０枚と水道水１００ｍｌ、さらに上記得られた離解促進剤の製剤０．１ｇを容量２００ｍｌのビーカーに入れ、直径５ｃｍのタービン羽をつけたスリーワンモーターを用い、室温で３００ｒｐｍにて攪拌した。１時間後に離解されていない大きな紙片から５枚サンプリングし、その平均粒径を求めた。また離解時の泡立ちの様子を目視観察し、次の判断を行った。
○：泡立ちが少なく問題なし
△：若干の泡立ちはあるがビーカーから泡が溢れることなく特に問題なし
×：泡立ちが多く、一部溢れるなどの問題がある
Evaluation 1
A water-resistant paper having a basis weight of 160 g / m 2 containing a polyamide epichlorohydrin resin is cut into a 4 cm square piece of paper, about 30 pieces of this piece of paper, 100 ml of tap water, and 0.1 g of the above-obtained disaggregation accelerator preparation in a volume of 200 ml. Was stirred at 300 rpm at room temperature using a three-one motor with a turbine blade having a diameter of 5 cm. Five sheets were sampled from a large piece of paper that had not been disaggregated after 1 hour, and the average particle size was determined. Moreover, the state of foaming at the time of disaggregation was visually observed to make the following judgment.
○: Little foaming and no problem △: Slight bubbling but no problem with no foam overflowing from the beaker ×: Many foaming or partial overflow
評価２
サイズ剤としてＡＫＤ（ニューペルハード７６Ｇ、日本油脂（株）製）を含有した坪量２９０ｇ/ｍ2のサイズ紙を２×１０ｃｍの紙片に裁断し、この紙片の片端を０．１％の離解剤水溶液に浸漬した。浸漬３０秒後の紙片に浸透した水溶液重量（ｍｇ）を求めた。
実施例２〜８及び比較例１〜７
表１に示す化合物を用いて、実施例１と同様にして各種ポリオキシアルキレンアルキルフォスフェートの塩を得、その後実施例１と同様の評価を行った。結果を表２に示す。
Evaluation 2
A size paper having a basis weight of 290 g / m 2 containing AKD (New Perhard 76G, manufactured by Nippon Oil & Fats Co., Ltd.) as a sizing agent is cut into a 2 × 10 cm piece of paper, and one end of this piece of paper is 0.1% disaggregated It was immersed in the agent aqueous solution. The weight (mg) of the aqueous solution penetrating into the paper piece after 30 seconds of immersion was determined.
Examples 2-8 and Comparative Examples 1-7
Using the compounds shown in Table 1, various polyoxyalkylene alkyl phosphate salts were obtained in the same manner as in Example 1, and then the same evaluation as in Example 1 was performed. The results are shown in Table 2.
ここで、比較例２はＲで表わされるアルキル鎖が短く効果は得られず、比較例３は、アルキル鎖長が長いため泡立ち易い傾向で離解性能も十分ではなかった。比較例４は離解性に乏しい。比較例５では浸水量が少なく泡立ちも多い。比較例６、７は浸水量が不十分であり離解性も低かった。
以上より、本発明の離解促進剤は、水を容易に含浸させることができ泡立ちも少なく、優れた離解性能を示すことがわかる。
Here, in Comparative Example 2, the alkyl chain represented by R was short and the effect was not obtained, and in Comparative Example 3, the alkyl chain length was long, so that foaming was likely to occur and the disaggregation performance was not sufficient. Comparative Example 4 is poor in disaggregation. In Comparative Example 5, the amount of water immersion is small and foaming is also large. In Comparative Examples 6 and 7, the amount of water immersion was insufficient and the disaggregation property was low.
From the above, it can be seen that the disaggregation accelerator of the present invention can be easily impregnated with water, has less foaming, and exhibits excellent disaggregation performance.
本発明の離解促進剤は、古紙または損紙を効率よく離解させることができ、古紙または損紙の再生処理に有効に用いることができる。特に、サイズ剤や耐水化剤を含有し、あるいは表面コートした紙からなる損紙を処理する際に有効に適用することができる。
The disaggregation accelerator of the present invention can efficiently disaggregate waste paper or damaged paper, and can be effectively used for recycling treatment of waste paper or waste paper. In particular, the present invention can be effectively applied when processing damaged paper made of paper containing a sizing agent or water-proofing agent or having a surface coating.
Claims (4)
Waste paper or loss using the disaggregation promoter according to any one of claims 1 to 3 at a concentration of 50 to 50,000 ppm as a total amount of the compound represented by formula (1) and the compound represented by formula (2). How to recycle paper.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008169498A (en) * | 2007-01-10 | 2008-07-24 | San Nopco Ltd | Promoter for wastepaper disintegration |
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| JP2008169498A (en) * | 2007-01-10 | 2008-07-24 | San Nopco Ltd | Promoter for wastepaper disintegration |
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