JPH04222285A - Deinking agent for recycling waste paper - Google Patents
Deinking agent for recycling waste paperInfo
- Publication number
- JPH04222285A JPH04222285A JP3086032A JP8603291A JPH04222285A JP H04222285 A JPH04222285 A JP H04222285A JP 3086032 A JP3086032 A JP 3086032A JP 8603291 A JP8603291 A JP 8603291A JP H04222285 A JPH04222285 A JP H04222285A
- Authority
- JP
- Japan
- Prior art keywords
- component
- deinking agent
- waste paper
- deinking
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002761 deinking Substances 0.000 title claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 32
- 239000010893 paper waste Substances 0.000 title claims abstract description 22
- 238000004064 recycling Methods 0.000 title claims abstract description 12
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 abstract description 22
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 21
- 229930195729 fatty acid Natural products 0.000 abstract description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 18
- 150000004665 fatty acids Chemical class 0.000 abstract description 16
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 15
- -1 fatty acid ester Chemical class 0.000 abstract description 13
- 238000005188 flotation Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- 229920001131 Pulp (paper) Polymers 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005406 washing Methods 0.000 abstract description 2
- 230000003311 flocculating effect Effects 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 26
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000005187 foaming Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 239000001384 succinic acid Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000005480 straight-chain fatty acid group Chemical group 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000004711 α-olefin Substances 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
Landscapes
- Paper (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は新聞、情報用紙、雑誌、
書籍等の古紙再生時に用いられる脱墨剤に関する。更に
詳しくは、新聞、情報用紙、雑誌、書籍等をフローテー
ション方式及びフローテーション並びに水洗折衷方式で
脱墨する場合に、高白色度で残インキ数の少ない脱墨パ
ルプを製造できる、インキ捕集性、凝集性、インキ剥離
性の優れた脱墨剤に関する。[Industrial Application Field] The present invention is applicable to newspapers, information sheets, magazines,
This invention relates to a deinking agent used when recycling used paper such as books. More specifically, when deinking newspapers, information sheets, magazines, books, etc. using the flotation method and a combination of flotation and washing, we will introduce an ink collection method that can produce deinked pulp with high whiteness and a small number of residual inks. The present invention relates to a deinking agent with excellent properties, cohesive properties, and ink removal properties.
【０００２】0002
【従来の技術】新聞、雑誌等印刷古紙の再生利用は古く
から行われてきているが、特に最近脱墨パルプの高度利
用が促進される一方、製紙コストの低廉化を図るため、
古紙の有効利用はますます重要性を増してきている。[Prior Art] Recycling of used printed paper such as newspapers and magazines has been carried out for a long time, but in recent years, the advanced use of deinked pulp has been promoted, and in order to reduce paper manufacturing costs,
Effective use of waste paper is becoming more and more important.
【０００３】古紙再生利用は、省エネルギー対策、都市
ゴミ対策、森林資源保護対策の観点から見ても利点が多
い。[0003] The recycling of waste paper has many advantages from the viewpoint of energy saving, urban waste, and forest resource protection.
【０００４】一方、最近の古紙は印刷技術・印刷方式の
変化、印刷インキ成分の変化等、脱墨という観点から見
ると一層厳しい条件下になりつつあり、より以上脱墨を
促進させるため装置にも改良が加えられてきている。[0004] On the other hand, recently, used paper has become subject to increasingly severe conditions from the viewpoint of deinking due to changes in printing technology and printing methods, changes in printing ink components, etc. Improvements have also been made.
【０００５】脱墨剤には、大別して、脱離したインキを
細かく分散させた状態で系外に除去することを目的とし
た分散系脱墨剤（主に非イオン系界面活性剤）と、脱離
したインキをある程度凝集させた状態で系外に除去する
ことを目的とした凝集系脱墨剤とがある。[0005] Deinking agents can be roughly divided into dispersion type deinking agents (mainly nonionic surfactants), which are used to remove detached ink from the system in a finely dispersed state; There is an agglomerating type deinking agent whose purpose is to remove detached ink from the system in a somewhat agglomerated state.
【０００６】これら古紙再生用脱墨剤として使用されて
いる従来公知の化学物資はアルキルベンゼンスルホネー
ト、アルキルサルフェート、α−オレフィンスルホネー
ト、ジアルキルスルホサクシネート、高級脂肪酸塩等の
陰イオン系界面活性剤、高級アルコールエチレンオキサ
イド付加物、アルキルフェノールエチレンオキサイド付
加物、脂肪酸エチレンオキサイド付加物、脂肪酸アミド
エチレンオキサイド付加物、ポリプロピレングリコール
エチレンオキサイド付加物、油脂のエチレンオキサイド
付加物、高級アルコールエチレンオキサイドプロピレン
オキサイド付加物等の非イオン系界面活性剤、アミンオ
キサイド、アルキルベタイン等の両性イオン系界面活性
剤等が挙げられる。Conventionally known chemical substances used as deinking agents for waste paper recycling include anionic surfactants such as alkylbenzene sulfonates, alkyl sulfates, α-olefin sulfonates, dialkyl sulfosuccinates, higher fatty acid salts, and higher Alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, fatty acid amide ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, ethylene oxide adducts of fats and oils, higher alcohol ethylene oxide propylene oxide adducts, etc. Examples include ionic surfactants, amine oxides, amphoteric ionic surfactants such as alkyl betaines, and the like.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、これら
の化学物質およびその配合物等では、フローテーション
工程での脱墨効率は必ずしも高くなく、高白色度かつ低
残インキの再生紙を得るという要求に対しては必ずしも
満足できうるものではない。[Problems to be Solved by the Invention] However, with these chemical substances and their compounds, the deinking efficiency in the flotation process is not necessarily high, and the demand for obtaining recycled paper with high brightness and low residual ink cannot be met. It is not always possible to be satisfied with this.
【０００８】特に常温で固体の脂肪酸を用いた場合、凝
集性は優れているが、未剥離インキ（いわゆるヒゲ）が
発生しやすく、溶融するためのエネルギー費用が非常に
高い。[0008] Particularly when a fatty acid that is solid at room temperature is used, the agglomeration property is excellent, but unreleased ink (so-called whiskers) is likely to occur, and the energy cost for melting is very high.
【０００９】また、脂肪酸の塩をそのままの形あるいは
水溶液の形で添加した場合には再生パルプの白色度が劣
り、さらに常温で液体の脂肪酸を用いた場合には、起泡
剤として用いる界面活性剤の泡立ちを抑制し、離脱した
インキを十分に系外に除去できないため、再生パルプの
白色度が上がらないという問題があった。[0009] Furthermore, when fatty acid salts are added as they are or in the form of an aqueous solution, the whiteness of the recycled pulp is inferior, and when fatty acids that are liquid at room temperature are used, the surfactant used as a foaming agent is Since foaming of the agent cannot be suppressed and the separated ink cannot be sufficiently removed from the system, there has been a problem that the whiteness of the recycled pulp cannot be increased.
【００１０】さらに、通常の非イオン系界面活性剤はイ
ンキの分散力、洗浄力および起泡力には優れているが、
インキの凝集力に劣るため、必ずしも再生パルプの白色
度が上らないという問題がある。Furthermore, although ordinary nonionic surfactants have excellent ink dispersing power, cleaning power, and foaming power,
There is a problem that the whiteness of the recycled pulp does not necessarily increase due to the poor cohesive force of the ink.
【００１１】このように古紙離解工程における紙からの
インキの剥離性、凝集性、フローテーション工程での高
起泡性および高インキ捕集性のすべてを兼ね備えた化学
物質は見出されておらず、ある特定の化学物質の２種類
以上を併用又は配合使用する方法が一般的である。しか
し、この配合物を用いた脱墨方法にしてもある程度の効
果は認められるものの、必ずしも満足のいく方法とは言
えない。[0011] As described above, no chemical substance has been found that has all of the properties of removing ink from paper in the waste paper disintegration process, cohesive property, high foaming property in the flotation process, and high ink collecting property. A common method is to use two or more specific chemical substances in combination or in combination. However, although a deinking method using this compound has a certain degree of effectiveness, it cannot necessarily be said to be a satisfactory method.
【００１２】さらに、最近のように脱墨パルプの用途拡
大、配合比率の増大に伴って、古紙から離脱していない
未剥離インキ（ヒゲ）の存在が問題になりつつあり、ま
た、トナーが使われている情報用紙古紙等難脱墨古紙が
増加している現在、よりインキ離脱性に優れた脱墨剤の
開発が要望されている。Furthermore, as the use of deinked pulp has recently expanded and its blending ratio has increased, the presence of unreleased ink (scratches) that has not separated from waste paper is becoming a problem, and the At present, as the amount of used paper that is difficult to deink, such as used information paper, is increasing, there is a demand for the development of a deinking agent that has better ink removal properties.
【００１３】[0013]
【課題を解決するための手段】そこで、本発明者らは、
上記欠点のない脱墨剤を見い出すべく鋭意研究した結果
、本発明を完成した。[Means for solving the problem] Therefore, the present inventors
As a result of intensive research to find a deinking agent that does not have the above drawbacks, the present invention was completed.
【００１４】即ち、本発明に係る古紙再生用脱墨剤は、
少なくとも下記Ａ成分、Ｂ成分、Ｃ成分を含有してなる
ことを特徴とする。（Ａ成分）下記一般式〔１〕で表さ
れる化合物That is, the deinking agent for waste paper recycling according to the present invention is
It is characterized by containing at least the following components A, B, and C. (Component A) Compound represented by the following general formula [1]
【００１５】[0015]
【化２】
［式中、Ｒ１ は炭素数５〜３０のアルキル基またはア
ルケニル基であり、ｈ，ｉ，ｊ，ｋは平均付加モル数を
示し、ｈ，ｉは０〜３０、ｊ，ｋは０〜２０である。た
だし、ｈ，ｉ，ｊ，ｋは同時に０であることはない。］
（Ｂ成分）下記一般式〔２〕及び／又は一般式〔３〕で
表される化合物
一般式〔２〕
Ｒ２ −ＣＯＯ（Ｃ２ Ｈ４ Ｏ）ｍ
（Ｃ３ Ｈ６ Ｏ）ｎ ＯＣ−Ｒ３ ［式中、Ｒ２
及びＲ３ は同一でも異なってもよく、炭素数６〜２１
のアルキル基またはアルケニル基であり、ｍ，ｎは平均
付加モル数を示し、ｍは８〜４５０、 ｎは０〜１００
である。］
一般式〔３〕
Ｒ４ −ＣＯＯ（Ｃ２ Ｈ４ Ｏ）ａ
（Ｃ３ Ｈ６ Ｏ）ｂ Ｈ［式中、Ｒ４ は炭素数６
〜２１のアルキル基またはアルケニル基であり、ａ，ｂ
は平均付加モル数を示し、ａは８〜２４０、 ｂは０〜
１００である。］（Ｃ成分）１−ヒドロキシエチリデン
−１，１−ジホスホン酸
本発明の好ましい態様としてはＡ成分が３０〜７０重量
％、Ｂ成分が５〜５０重量％、Ｃ成分が０．５〜１５重
量％であることである。[Formula, R1 is an alkyl group or alkenyl group having 5 to 30 carbon atoms, h, i, j, k represent the average number of added moles, h, i are 0 to 30, j, k is 0-20. However, h, i, j, and k are never 0 at the same time. ]
(Component B) Compound represented by the following general formula [2] and/or general formula [3] General formula [2] R2 -COO(C2 H4 O)m
(C3 H6 O)n OC-R3 [wherein, R2
and R3 may be the same or different, and have 6 to 21 carbon atoms.
is an alkyl group or alkenyl group, m and n indicate the average number of added moles, m is 8 to 450, and n is 0 to 100.
It is. ] General formula [3] R4 -COO(C2 H4 O)a
(C3 H6 O)b H [wherein, R4 has 6 carbon atoms
-21 alkyl or alkenyl group, a, b
indicates the average number of added moles, a is 8 to 240, b is 0 to
It is 100. ] (Component C) 1-hydroxyethylidene-1,1-diphosphonic acid In a preferred embodiment of the present invention, component A is 30 to 70% by weight, component B is 5 to 50% by weight, and component C is 0.5 to 15% by weight. %.
【００１６】[0016]
【作用】本発明における一般式〔１〕で表される化合物
（Ａ成分）の特徴は、二塩基酸のエチレンオキサキドな
いしはプロピレンオキサイド付加物であるので、インキ
の洗浄力、分散力に特に優れ、起泡力も優れている。ま
た二塩基酸系のため、インキの凝集力も通常の非イオン
系界面活性剤に比べ優れている。そのため本化合物単独
で使用しても優れた脱インキ性能を示すものである。ま
た、脂肪酸等と異なり液状であるため取り扱いが容易で
ある。[Action] The compound represented by the general formula [1] (component A) in the present invention is characterized by being an ethylene oxide or propylene oxide adduct of a dibasic acid, so it has particularly excellent ink detergency and dispersion power. , and has excellent foaming power. Furthermore, since it is a dibasic acid type, the cohesive force of the ink is also superior to that of ordinary nonionic surfactants. Therefore, even when this compound is used alone, it exhibits excellent deinking performance. Furthermore, unlike fatty acids and the like, it is liquid and therefore easy to handle.
【００１７】しかし、Ａ成分にＢ成分を添加し、さらに
相溶剤としてＣ成分を添加すると、両者の相乗効果によ
りＡ成分またはＢ成分を単独で使用した場合に比べ、イ
ンキの凝集力、捕集力、洗浄力、分散力、起泡力が顕著
に向上し、優れた脱墨剤となる。However, when component B is added to component A and component C is further added as a compatibilizer, the synergistic effect of the two improves the cohesive force and collection of the ink compared to when component A or component B is used alone. It has significantly improved power, detergency, dispersion power, and foaming power, making it an excellent deinking agent.
【００１８】以下、本発明について詳述する。The present invention will be explained in detail below.
【００１９】先ず、一般式〔１〕で表される化合物につ
いて説明する。First, the compound represented by the general formula [1] will be explained.
【００２０】本発明の一般式〔１〕で表される化合物（
Ａ成分）はアルキルコハク酸又はアルケニルコハク酸に
エチレンオキサイドおよびプロピレンオキサイドを付加
したものであるが、この場合用いるアルキルコハク酸又
はアルケニルコハク酸は、アルキル基又はアルケニル基
の炭素数の異なるものの混合物でも使用できるし、また
直鎖型でも分岐型でも使用できる。The compound represented by the general formula [1] of the present invention (
Component A) is an alkyl succinic acid or alkenyl succinic acid with ethylene oxide and propylene oxide added to it, but the alkyl succinic acid or alkenyl succinic acid used in this case may be a mixture of alkyl groups or alkenyl groups with different carbon numbers. It can be used in both linear and branched form.
【００２１】エチレンオキサイドおよびプロピレンオキ
サイドの付加は、混合して付加する（ランダム付加）か
、もしくは順次付加（ブロック付加）することによって
も行うことができる。The addition of ethylene oxide and propylene oxide can also be carried out by adding them in a mixed manner (random addition) or sequentially (block addition).
【００２２】また、さらに簡便に行なうためには、ポリ
エチレングリコールやポリプロピレングリコールでエス
テル化することもできる。[0022] Furthermore, in order to carry out the process more simply, esterification can be carried out using polyethylene glycol or polypropylene glycol.
【００２３】なお、一般式〔１〕において、Ｒ１ の炭
素数が３０を越える場合にはアルキレンオキサイド付加
物の固体化及び水溶性が劣り、また、ｈ，ｉが３１以上
、ｊ，ｋが２１以上の場合は脱墨効果が低下する傾向が
ある。In general formula [1], if the number of carbon atoms in R1 exceeds 30, solidification and water solubility of the alkylene oxide adduct will be poor; In the above cases, the deinking effect tends to decrease.
【００２４】次に、一般式〔２〕及び〔３〕で表される
化合物（Ｂ成分）について説明する。Next, the compounds represented by the general formulas [2] and [3] (component B) will be explained.
【００２５】本発明の一般式〔２〕で表される化合物は
脂肪酸にエチレンオキサイドやプロピレンオキサイドを
付加して得られるポリオキシアルキレン脂肪酸エステル
にさらに脂肪酸を反応させて得られるポリオキシアルキ
レンジ脂肪酸エステルであるが、その製造方法は、所定
の化合物が生成されればいかなる方法でもよく、例えば
あらかじめエチレンオキサイドおよびプロピレンオキサ
イドを重合させて得られたポリエチレングリコールまた
はポリエチレングリコールとポリプロピレングリコール
の共重合物（ランダム共重合でもブロック共重合でもよ
い。）１モルを脂肪酸２モルでジエステル化する方法も
あげられる。The compound represented by the general formula [2] of the present invention is a polyoxyalkylene difatty acid ester obtained by further reacting a fatty acid with a polyoxyalkylene fatty acid ester obtained by adding ethylene oxide or propylene oxide to a fatty acid. However, the manufacturing method may be any method as long as a predetermined compound is produced. For example, polyethylene glycol obtained by polymerizing ethylene oxide and propylene oxide in advance, or a copolymer of polyethylene glycol and polypropylene glycol (random Copolymerization or block copolymerization may be used.) A method in which 1 mole is diesterized with 2 moles of fatty acid is also mentioned.
【００２６】用いられる脂肪酸としては、ラウリン酸、
ステアリン酸等に代表される直鎖型脂肪酸、オレイン酸
等に代表される不飽和脂肪酸、イソステアリン酸等に代
表される分岐型脂肪酸などが挙げられる。この場合、脂
肪酸は飽和タイプでも不飽和タイプでも使用できるし、
また直鎖型でも分岐型でも使用できる。[0026] The fatty acids used include lauric acid,
Examples include straight-chain fatty acids such as stearic acid, unsaturated fatty acids such as oleic acid, and branched fatty acids such as isostearic acid. In this case, fatty acids can be used in either saturated or unsaturated types;
It can also be used in either a straight chain type or a branched type.
【００２７】さらに、一般式〔３〕で表される化合物は
、脂肪酸にエチレンオキサイドおよびプロピレンオキサ
イドを付加したものであるが、Ａ成分同様ランダム付加
もしくはブロック付加することによって得られる。用い
られる脂肪酸は前記一般式〔２〕の化合物の場合と同様
である。Furthermore, the compound represented by the general formula [3] is obtained by adding ethylene oxide and propylene oxide to a fatty acid, and like component A, it can be obtained by random addition or block addition. The fatty acid used is the same as in the case of the compound of general formula [2] above.
【００２８】なお、一般式〔２〕及び〔３〕において、
Ｒ２ 、 Ｒ３ 、Ｒ４ の炭素数が５以下および２２
以上の場合、ｍが４５１以上およびｎが１０１以上の場
合、ａが２４１以上およびｂが１０１以上の場合はいず
れも脱墨効果が低下する傾向がある。[0028] In general formulas [2] and [3],
The number of carbon atoms in R2, R3, and R4 is 5 or less and 22
In the above cases, when m is 451 or more and n is 101 or more, when a is 241 or more and b is 101 or more, the deinking effect tends to decrease.
【００２９】また、Ｃ成分である１−ヒドロキシエチリ
デン−１，１−ジホスホン酸はそれ自身脱墨性能を高め
る効果はないが、製品の透明性を出すための相溶剤およ
びキレート剤として添加するとともに、凝固点降下剤と
しても効果を発揮する。In addition, 1-hydroxyethylidene-1,1-diphosphonic acid, which is component C, does not have the effect of improving the deinking performance by itself, but it is added as a compatibilizer and chelating agent to improve the transparency of the product. It is also effective as a freezing point depressant.
【００３０】もし、Ｃ成分を含まない場合には、透明性
が悪くなり、商品価値を低下させるとともに、凝固点が
上がり、冬期および寒冷地での操作性を低下させること
となる。したがって、このＣ成分は必須の重要な成分で
ある。[0030] If the C component is not contained, the transparency will deteriorate, reducing the commercial value, and the freezing point will increase, resulting in a decrease in operability in winter and in cold regions. Therefore, this C component is an essential and important component.
【００３１】本発明の脱墨剤の組成は、Ａ成分が３０〜
７０重量％、Ｂ成分が５〜５０重量％、Ｃ成分が０．５
〜１５重量％であることが好ましい。[0031] The composition of the deinking agent of the present invention is that the component A is 30 to 30%.
70% by weight, 5 to 50% by weight of B component, 0.5% of C component
Preferably it is 15% by weight.
【００３２】Ｂ成分が５０重量％を越える場合には凝固
点が上り、Ａ成分が３０重量％未満のときは、他の液状
有機成分が少ないか、Ｂ成分を増量するため、やはり凝
固点が上昇する傾向を生ずる。そのため、Ｃ成分を相当
量含有させても相溶し難いため、操作性を低下させ、商
品価値も低い。Ａ成分が７０重量％を越え、かつＢ成分
が５重量％未満の場合にはインキの凝集性がやや悪いた
め、当発明品に比べ性能的に劣る結果となる。Ｃ成分が
０．５重量％未満の場合には、前述のように透明性が悪
くなり、商品価値を低下させるとともに、凝固点を上昇
させる。また、Ｃ成分が１５重量％を越える場合、脱墨
剤の実質成分であるＡ成分、Ｂ成分の含有量が相対的に
減少するため、脱墨効果が低下するとともに、コストア
ップにもなるため好ましくない。[0032] If the B component exceeds 50% by weight, the freezing point will rise, and if the A component is less than 30% by weight, the freezing point will also rise because other liquid organic components are small or the amount of the B component is increased. give rise to a tendency. Therefore, even if a considerable amount of the C component is contained, it is difficult to be compatible with the C component, resulting in decreased operability and low commercial value. When the A component is more than 70% by weight and the B component is less than 5% by weight, the cohesiveness of the ink is somewhat poor, resulting in inferior performance compared to the product of the present invention. When the C component is less than 0.5% by weight, the transparency deteriorates as described above, lowering the commercial value and raising the freezing point. Furthermore, if the C component exceeds 15% by weight, the content of the A component and B component, which are the essential components of the deinking agent, will be relatively reduced, which will reduce the deinking effect and increase costs. Undesirable.
【００３３】本発明の脱墨剤は古紙離解工程、熟成タワ
ーいずれの工程で添加してもよく、その添加量は古紙の
紙質、インキの種類により異なるが、一般的には原料古
紙に対して０．１〜０．８重量％使用するのが好適であ
り、より好ましくは０．２〜０．６重量％である。[0033] The deinking agent of the present invention may be added in either the waste paper disintegration process or the aging tower process, and the amount added varies depending on the quality of the waste paper and the type of ink, but it is generally added to the waste paper as a raw material. It is suitable to use 0.1-0.8% by weight, more preferably 0.2-0.6% by weight.
【００３４】本発明は、一般式〔１〕において、Ｒ１
の炭素数１２〜２０のアルキル基またはアルケニル基で
あり、エチレンオキサイドの平均付加モル数ｈ，ｉが４
〜２２、プロピレンオキサイドの平均付加モル数ｊ，ｋ
が０〜２０のものが本発明の目的を達成する上で特に優
れている。[0034] In the present invention, in general formula [1], R1
is an alkyl group or alkenyl group having 12 to 20 carbon atoms, and the average number of added moles of ethylene oxide h,i is 4
~22, average number of added moles of propylene oxide j, k
Those having a value of 0 to 20 are particularly excellent in achieving the object of the present invention.
【００３５】また、一般式〔２〕において、Ｒ２ 、Ｒ
３ の炭素数は１１〜１７のアルキル基またはアルケニ
ル基であり、エチレンオキサイドの平均付加モル数ｍが
２０〜１７０、 プロピレンオキサイドの平均付加モル
数ｎが０〜５０のものが、一般式〔３〕において、Ｒ４
の炭素数は１１〜１７のアルキル基またはアルケニル
基であり、エチレンオキサイドの平均付加モル数ａが２
０〜１７０、 プロピレンオキサイドの平均付加モル数
ｂが０〜５０のものが本発明の目的を達成する上で特に
優れている。Furthermore, in the general formula [2], R2, R
3 is an alkyl group or alkenyl group having 11 to 17 carbon atoms, the average number of added moles m of ethylene oxide is 20 to 170, and the average number of added moles n of propylene oxide is 0 to 50, the general formula [3 ], R4
is an alkyl group or alkenyl group having 11 to 17 carbon atoms, and the average number of added moles of ethylene oxide a is 2
0 to 170, and those in which the average added mole number b of propylene oxide is 0 to 50 are particularly excellent in achieving the objects of the present invention.
【００３６】また、本発明の脱墨剤は、上記Ａ成分、Ｂ
成分、Ｃ成分以外に第三の添加剤を含有することもでき
るし、また、本発明の脱墨剤の使用後に多価金属塩、例
えば塩化カルシウム、塩化マグネシウム、水酸化マグネ
シウム、水酸化カルシウム、硫酸アルミニウム等を使用
することも可能である。[0036] The deinking agent of the present invention also contains the above-mentioned A component, B
It is also possible to contain a third additive in addition to component C, and after using the deinking agent of the present invention, polyvalent metal salts such as calcium chloride, magnesium chloride, magnesium hydroxide, calcium hydroxide, It is also possible to use aluminum sulfate and the like.
【００３７】[0037]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれら実施例に限定されるものではない
。[Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.
【００３８】実施例１〜５８
脱墨剤として下記表１に示す本発明に係る化合物を使用
し、Ｊ．ＴＡＰＰＩ（紙パルプ技術協会）紙パルプ試験
方法（Ｎｏ．３９−８２、「古紙の脱インキ試験方法」
）に準ずる方法により脱墨試験を行った。Examples 1 to 58 The compounds according to the present invention shown in Table 1 below were used as deinking agents, and the compounds according to the present invention shown in Table 1 below were used as deinking agents. TAPPI (Paper and Pulp Technology Association) Paper Pulp Test Method (No. 39-82, "Deinking Test Method for Waste Paper")
) A deinking test was conducted using a method similar to that described in (1).
【００３９】試験方法は、毎日、朝日、読売の各新聞紙
（いずれも印刷後１〜３ヶ月経過したもの）７０重量％
とチラシ３０重量％とからなる古紙を裁断し、その一定
量を卓上離解機に入れ、その中に温水、水酸化ナトリウ
ム１．４重量％（対原料古紙）、３号けい酸ナトリウム
２．８重量％（対原料古紙）、過酸化水素（純分）１．
０重量％（対原料古紙）、表１に示す脱墨剤０．２重量
％（対原料古紙）を加え、パルプ濃度５重量％、６０℃
で１０分間離解した後、５０℃で１時間熟成した。[0039] The test method was to use 70% by weight of Mainichi, Asahi, and Yomiuri newspapers (all 1 to 3 months old after printing).
Cut waste paper consisting of 30% by weight of leaflets and leaflets, put a certain amount of it into a tabletop disintegrator, and add warm water, 1.4% by weight of sodium hydroxide (based on raw waste paper), and 2.8% of No. 3 sodium silicate. Weight % (based on raw material waste paper), hydrogen peroxide (pure content) 1.
0% by weight (based on raw waste paper), 0.2% by weight (based on raw material waste paper) of the deinking agent shown in Table 1 was added, pulp concentration was 5% by weight, and 60°C.
After disintegrating for 10 minutes, the mixture was aged at 50°C for 1 hour.
【００４０】その後、水を加えてパルプ濃度を１重量％
に稀釈し、試験用フローテーターを用いて、３０℃で２
０分間フローテーション処理した。フローテーション後
のパルプスラリーを１０重量％に濃縮後、水を加えて１
重量％濃度に稀釈し、Ｊ．ＴＡＰＰＩスタンダードマシ
ンにて手抄きし、パルプシートを作製した。このパルプ
シートにつき、測色色差計（日本電色社製Ｚ−１００１
ＤＰ型）を用い白色度を、画像解析装置（ＫＳシステム
社製ドットアナライザーＤＡ−３０００型）（対物レン
ズ５倍）を用い残インキ数および残インキ面積を測定し
た。この場合、紙中に残っているインキ成分の中の樹脂
分まで検出できるシビアーな条件で測定した。[0040] After that, water was added to bring the pulp concentration to 1% by weight.
using a test floatator at 30℃ for 2 hours.
Flotation treatment was performed for 0 minutes. After concentrating the pulp slurry after flotation to 10% by weight, water was added to
Diluted to wt% concentration, J. A pulp sheet was produced by hand-sheeting using a TAPPI standard machine. For this pulp sheet, a colorimeter (Z-1001 manufactured by Nippon Denshoku Co., Ltd.) was used.
The number of remaining inks and the area of remaining ink were measured using an image analyzer (Dot Analyzer DA-3000, manufactured by KS System Co., Ltd.) (5x objective lens). In this case, measurements were made under severe conditions that allowed even the resin content of the ink components remaining in the paper to be detected.
【００４１】その評価結果をまとめて表１に示す。[0041] The evaluation results are summarized in Table 1.
【００４２】比較例１〜７ 市販品として一般によく用いられるComparative Examples 1 to 7 Commonly used as a commercial product
【００４３】[0043]
【化３】
Ｃ１２Ｈ２５Ｏ（ＥＯ）１０Ｈ、 ＨＯＯＣ（ＣＨ２
）４ ＣＯＯＨの４種類及びその他につき、前記実施例
と同様の条件及び方法により脱墨性を評価した。[Chemical 3] C12H25O(EO)10H, HOOC(CH2
) 4 The deinking properties of the four types of COOH and others were evaluated under the same conditions and methods as in the above examples.
【００４４】その結果をまとめて表２、表３に示す。The results are summarized in Tables 2 and 3.
【００４５】なお、表１〜３中において、ＥＯはエチレ
ンオキサイド単位、ＰＯはプロピレンオキサイド単位を
表す。In Tables 1 to 3, EO represents an ethylene oxide unit and PO represents a propylene oxide unit.
【００４６】[0046]
【表１】[Table 1]
【００４７】[0047]
【表２】[Table 2]
【００４８】[0048]
【表３】[Table 3]
【００４９】[0049]
【表４】[Table 4]
【００５０】実施例５９〜６２
実施例１、２９、３０及び３１において、脱墨剤の量を
０．６重量％に代えて同様に評価したところ、実施例１
、２９、３０及び３１よりも、各々更に良い効果が得ら
れた。Examples 59 to 62 Similar evaluations were made in Examples 1, 29, 30, and 31 except that the amount of deinking agent was changed to 0.6% by weight.
, 29, 30, and 31, each of which had better effects.
【００５１】[0051]
【発明の効果】本発明に係る脱墨剤は、二塩基酸のエチ
レンオキサイドないしはプロピレンオキサイド付加物お
よび脂肪酸のエチレンオキサイドないしはプロピレンオ
キサイドモノ付加物、ジ付加物であるため、優れたイン
キ捕集性、凝集性、インキ剥離性を有する。そのため、
再生紙は従来の脱墨剤使用時に比し、白色に仕上がり、
未剥離インキが少ない。Effects of the Invention The deinking agent according to the present invention is an ethylene oxide or propylene oxide adduct of a dibasic acid and an ethylene oxide or propylene oxide mono-adduct or di-adduct of a fatty acid, so it has excellent ink collection properties. , cohesive properties, and ink releasability. Therefore,
Recycled paper has a whiter finish than when using conventional deinking agents,
There is little unpeeled ink.
Claims (5)
含有してなることを特徴とする古紙再生用脱墨剤。 （Ａ成分）下記一般式〔１〕で表される化合物【化１】 ［式中、Ｒ１ は炭素数５〜３０のアルキル基またはア
ルケニル基であり、ｈ，ｉ，ｊ，ｋは平均付加モル数を
示し、ｈ，ｉは０〜３０、ｊ，ｋは０〜２０である。た
だし、ｈ，ｉ，ｊ，ｋは同時に０であることはない。］
（Ｂ成分）下記一般式〔２〕及び／又は一般式〔３〕で
表される化合物 一般式〔２〕 Ｒ２ −ＣＯＯ（Ｃ２ Ｈ４ Ｏ）ｍ
（Ｃ３ Ｈ６ Ｏ）ｎ ＯＣ−Ｒ３ ［式中、Ｒ２
及びＲ３ は同一でも異なってもよく、炭素数６〜２１
のアルキル基またはアルケニル基であり、ｍ，ｎは平均
付加モル数を示し、ｍは８〜４５０、 ｎは０〜１００
である。］ 一般式〔３〕 Ｒ４ −ＣＯＯ（Ｃ２ Ｈ４ Ｏ）ａ
（Ｃ３ Ｈ６ Ｏ）ｂ Ｈ［式中、Ｒ４ は炭素数６
〜２１のアルキル基またはアルケニル基であり、ａ，ｂ
は平均付加モル数を示し、ａは８〜２４０、 ｂは０〜
１００である。］（Ｃ成分）１−ヒドロキシエチリデン
−１，１−ジホスホン酸1. A deinking agent for recycling used paper, comprising at least the following components A, B, and C. (Component A) A compound represented by the following general formula [1] [Formula 1] [wherein R1 is an alkyl group or alkenyl group having 5 to 30 carbon atoms, h, i, j, k are average added moles] h and i are 0 to 30, and j and k are 0 to 20. However, h, i, j, and k are never 0 at the same time. ]
(Component B) Compound represented by the following general formula [2] and/or general formula [3] General formula [2] R2 -COO(C2 H4 O)m
(C3 H6 O)n OC-R3 [wherein, R2
and R3 may be the same or different, and have 6 to 21 carbon atoms.
is an alkyl group or alkenyl group, m and n indicate the average number of added moles, m is 8 to 450, and n is 0 to 100.
It is. ] General formula [3] R4 -COO(C2 H4 O)a
(C3 H6 O)b H [wherein, R4 has 6 carbon atoms
-21 alkyl or alkenyl group, a, b
indicates the average number of moles added, a is 8 to 240, b is 0 to
It is 100. ] (Component C) 1-hydroxyethylidene-1,1-diphosphonic acid
５０重量％、Ｃ成分が０．５〜１５重量％であることを
特徴とする請求項１記載の古紙再生用脱墨剤。Claim 2: Component A is 30 to 70% by weight, and component B is 5 to 70% by weight.
The deinking agent for waste paper recycling according to claim 1, characterized in that the C component is 50% by weight and the C component is 0.5 to 15% by weight.
る請求項１又は２記載の古紙再生用脱墨剤。3. The deinking agent for waste paper recycling according to claim 1 or 2, which further contains another deinking agent.
する請求項１、２又は３記載の古紙再生用脱墨剤。4. The deinking agent for waste paper recycling according to claim 1, 2 or 3, wherein a polyvalent metal salt is subsequently used.
用されることを特徴とする請求項１〜４のいずれかに記
載の古紙再生用脱墨剤。5. The deinking agent for waste paper recycling according to claim 1, wherein the deinking agent is used in an amount of 0.1 to 0.8% by weight based on the base waste paper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3086032A JPH04222285A (en) | 1990-04-06 | 1991-03-26 | Deinking agent for recycling waste paper |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2-92884 | 1990-04-06 | ||
| JP9288490 | 1990-04-06 | ||
| JP28094690 | 1990-10-19 | ||
| JP2-280946 | 1990-10-19 | ||
| JP3086032A JPH04222285A (en) | 1990-04-06 | 1991-03-26 | Deinking agent for recycling waste paper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04222285A true JPH04222285A (en) | 1992-08-12 |
Family
ID=27305062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3086032A Pending JPH04222285A (en) | 1990-04-06 | 1991-03-26 | Deinking agent for recycling waste paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04222285A (en) |
-
1991
- 1991-03-26 JP JP3086032A patent/JPH04222285A/en active Pending
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