JP5770619B2 - Method for producing deinked pulp - Google Patents
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- JP5770619B2 JP5770619B2 JP2011271886A JP2011271886A JP5770619B2 JP 5770619 B2 JP5770619 B2 JP 5770619B2 JP 2011271886 A JP2011271886 A JP 2011271886A JP 2011271886 A JP2011271886 A JP 2011271886A JP 5770619 B2 JP5770619 B2 JP 5770619B2
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- 229920001131 Pulp (paper) Polymers 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 71
- 239000011787 zinc oxide Substances 0.000 claims description 35
- 239000010893 paper waste Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 description 53
- 230000008569 process Effects 0.000 description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 239000013055 pulp slurry Substances 0.000 description 22
- 239000002761 deinking Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000004061 bleaching Methods 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- 238000005188 flotation Methods 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 239000007844 bleaching agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- -1 washer Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000002791 soaking Methods 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
- 238000003756 stirring Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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)
Description
本発明は、脱インキパルプの製造方法に関する。 The present invention relates to a method for producing deinked pulp.
古紙の再生は古紙原料からインキを剥離し、剥離したインキを除去するいわゆる脱インキ処理を施すことで、再生パルプを得て再生紙を製造することにより行われる。近年、美しく見栄えのよい印刷に対する需要の増大とそれに伴う印刷技術の進展により、紙とインキの結合が強固になってきている。また、夏場には熱や紫外線の影響で紙からインキが剥離しにくくなる現象（難剥離化）がより顕著になる。 The recycling of used paper is carried out by removing the ink from the used paper raw material and performing a so-called deinking process for removing the peeled ink to obtain recycled pulp and producing recycled paper. In recent years, the bond between paper and ink has become stronger due to the increasing demand for beautiful and good-looking printing and the accompanying advances in printing technology. In summer, the phenomenon that ink becomes difficult to peel off from paper due to the influence of heat and ultraviolet rays (hard peeling) becomes more prominent.
これら印刷技術の進展や夏場の古紙原料の難剥離化に関わらず、安定した品質が得られる脱インキパルプの製造方法への期待が増大している。 Regardless of the progress of these printing technologies and the difficulty of exfoliating used paper raw materials in summer, there is an increasing expectation for a method for producing deinked pulp that can provide stable quality.
一般的に脱インキパルプは、インキ剥離工程、インキ除去工程、パルプ洗浄工程を実施できる装置を備えた脱インキ設備にて製造される。脱インキパルプの製造工程は、具体的には、パルパー、ニーダー、ケミカルミキサー、ディスパーザー等によるインキ剥離工程、フローテーター等によるインキ除去工程、シックナー、ウオッシャー、エキスト等による洗浄工程により構成され、所望の脱インキパルプ品質を得るために各製紙会社は、様々に各設備の配列、導入を実施している。 In general, deinked pulp is produced in a deinking facility equipped with an apparatus capable of performing an ink peeling process, an ink removing process, and a pulp washing process. The deinked pulp manufacturing process is specifically composed of an ink peeling process using a pulper, kneader, chemical mixer, disperser, etc., an ink removing process using a flowator, etc., and a cleaning process using a thickener, washer, extract, etc. In order to obtain the deinked pulp quality, each paper manufacturing company has variously arranged and introduced various facilities.
とりわけ、インキ剥離工程では、機械力だけでは満足のいく性能が得られ難く、アルカリ剤（ＮａＯＨ）の使用が必要であるが、それによる繊維の脆化や微細化、黄変等の弊害も問題となっている。特許文献１には、インキ剥離処理を弱アルカリ性から中性領域の条件で行うことにより、異物の微細化を防ぎ、排水のＣＯＤを低下させ、残留インキ量の少ない脱墨パルプを製造することを目的として、脱インキ工程において結晶性層状珪酸塩の無水物を添加し、ｐＨ７．０〜９．９でパルプからインキを剥離し、かつ、インキ除去工程において脱墨剤を添加し、インキを除去することを特徴とする脱墨パルプの製造方法が開示されている。 In particular, in the ink stripping process, it is difficult to obtain satisfactory performance with mechanical force alone, and it is necessary to use an alkaline agent (NaOH). However, problems such as embrittlement, refinement, and yellowing of the fiber are also problems. It has become. Patent Document 1 states that by performing the ink peeling process under weak alkaline to neutral conditions, it is possible to prevent the debris from being made finer, to reduce the COD of waste water, and to produce deinked pulp with a small amount of residual ink. The purpose is to add crystalline layered silicate anhydride in the deinking process, peel the ink from the pulp at pH 7.0-9.9, and add the deinking agent in the ink removing process to remove the ink. A method for producing deinked pulp is disclosed.
一方、離解工程で無機粉体を添加する技術として、特許文献２には、原料古紙に混在する粘着異物を、古紙のパルプ化の過程で系外に除去する目的で、原料古紙を機械的に離解するに際して、吸水量が０．４ｍｌ／０．５ｇ以下であり、平均粒子径が８〜２０μｍの範囲にあるタルクを、原料古紙に対して０．１〜５重量％、さらにタルクと共に酸化亜鉛を古紙原料に対して０．０１〜１重量％の範囲で添加することを特徴とする古紙のパルプ化方法が開示されている。 On the other hand, as a technique for adding inorganic powder in the disaggregation process, Patent Document 2 discloses that raw material waste paper is mechanically removed for the purpose of removing the adhering foreign matter mixed in the material waste paper out of the system during the pulping process of the waste paper. When disaggregating, talc having a water absorption of 0.4 ml / 0.5 g or less and an average particle diameter of 8 to 20 μm is 0.1 to 5% by weight based on the raw paper, and zinc oxide together with talc. Is disclosed in a method for pulping used paper, characterized by adding 0.01 to 1% by weight to the used raw material.
離解工程でアルカリ剤を用いると得られた脱インキパルプが黄変等の変色をすることがあり、また、特許文献１に挙げられているように排水のＣＯＤの低減等を達成するために、中性付近で離解工程を行うことが望まれる。 When an alkaline agent is used in the disaggregation step, the deinked pulp obtained may be discolored such as yellowing, and in order to achieve reduction in COD of wastewater as mentioned in Patent Document 1, It is desirable to perform the disaggregation process near neutrality.
本発明の課題は、離解工程で水酸化ナトリウム等のアルカリ剤を用いることなく、インキ剥離性が良好な脱インキパルプの製造方法を提供することである。 The subject of this invention is providing the manufacturing method of deinked pulp with favorable ink peelability, without using alkaline agents, such as sodium hydroxide, at a disaggregation process.
本発明は、原料古紙を水中で離解する離解工程を有する脱インキパルプの製造方法であって、離解工程で、原料古紙１００重量部に対して、平均粒子径が１．０〜５．０μｍの酸化亜鉛を０．３〜６．０重量部の範囲で添加して離解し、離解工程を水のｐＨ６〜１０の範囲で行う、脱インキパルプの製造方法に関する。 The present invention is a method for producing deinked pulp having a disaggregation step of disaggregating raw waste paper in water, and the average particle size is 1.0 to 5.0 μm with respect to 100 parts by weight of the raw waste paper in the disaggregation step. The present invention relates to a method for producing deinked pulp, in which zinc oxide is added in a range of 0.3 to 6.0 parts by weight and disaggregated, and the disaggregation step is performed in a range of pH 6 to 10 of water.
本発明によれば、離解工程で水酸化ナトリウム等のアルカリ剤を用いることなく、インキ剥離性が良好な脱インキパルプの製造方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of deinked pulp with favorable ink peelability is provided, without using alkaline agents, such as sodium hydroxide, at a disaggregation process.
本発明での効果を発現する機構は定かでないが、以下の様に推定される。水へ溶解した酸化亜鉛は、水酸イオンを生じてセルロース同士の水素結合を弱める効果を発現し、繊維の膨潤を促しインキを剥離しやすくさせていると考えられる。また、水へ溶解していない酸化亜鉛粒子は研磨剤のように働き、さらにインキの剥離を向上させていると考えている。 The mechanism for producing the effect of the present invention is not clear, but is estimated as follows. Zinc oxide dissolved in water is thought to produce an effect of weakening hydrogen bonds between celluloses by generating hydroxyl ions, promoting the swelling of the fibers and making the ink easy to peel off. Further, it is considered that zinc oxide particles not dissolved in water work like an abrasive and further improve the peeling of ink.
一般に、脱インキパルプは、（１）原料古紙をスラリー状にする離解工程（パルパー）、（２）離解工程で剥離したインクをパルプスラリーから排出する脱水工程、（３）強い剪断力を与えてインクを剥離させるニーディング工程、（４）漂白工程、（５）剥離したインクを効率よく系外に排出するフローテーション工程及び（６）洗浄工程等を適宜組み合わせて製造される。本発明の製造方法は、少なくとも離解工程を含む、原料古紙からの脱インキパルプの製造方法に関する。 In general, deinked pulp consists of (1) a disaggregation step (pulper) that makes raw raw paper into a slurry state, (2) a dehydration step that discharges ink separated in the disaggregation step from the pulp slurry, and (3) gives a strong shearing force. A kneading step for peeling the ink, (4) a bleaching step, (5) a flotation step for efficiently discharging the peeled ink out of the system, and (6) a washing step are appropriately combined. The manufacturing method of this invention is related with the manufacturing method of the deinking pulp from raw material used paper including a disaggregation process at least.
離解工程は、機械力等で印刷古紙等の原料古紙を繊維状に解きほぐすと共にパルプ繊維からインキを剥離する工程である。本発明では、所定平均粒子径の酸化亜鉛を所定量離解工程で添加する。すなわち、本発明では、原料古紙等の原料とは別に酸化亜鉛を用いて、水−パルプスラリー（以下、パルプスラリーという）中に存在させるものである。本発明では、特定の酸化亜鉛を別途存在させて原料古紙を離解するため、酸化亜鉛は、離解する以前又は離解する途中で添加することができる。具体的には、原料古紙を離解する前又は途中で、酸化亜鉛をパルプスラリーに添加する、水に酸化亜鉛を添加してから原料古紙を添加する、原料古紙と酸化亜鉛が共存したものに水を添加する、等により離解工程で用いるパルプスラリーを調製することができる。なお、酸化亜鉛をパルプスラリーに添加する場合、一括、連続、間欠など、種々の態様を採用することができる。 The disaggregation step is a step of unwinding the raw waste paper such as printed waste paper into a fiber shape by mechanical force or the like and peeling the ink from the pulp fiber. In the present invention, a predetermined amount of zinc oxide having a predetermined average particle diameter is added in a disaggregation step. That is, in the present invention, zinc oxide is used separately from raw materials such as raw paper, and is present in water-pulp slurry (hereinafter referred to as pulp slurry). In the present invention, since specific raw zinc paper is separately present to disaggregate the raw waste paper, the zinc oxide can be added before or during disaggregation. Specifically, before or during the disintegration of the raw waste paper, zinc oxide is added to the pulp slurry, the zinc oxide is added to the water, and then the raw waste paper is added. The pulp slurry used in the disaggregation step can be prepared by adding In addition, when adding zinc oxide to a pulp slurry, various aspects, such as lump, continuous, and intermittent, are employable.
離解工程での酸化亜鉛の添加量は、原料古紙１００重量部に対して、０．３〜６．０重量部であり、インキ剥離性の観点から好ましくは、０．５〜５．５重量部、より好ましくは１．０〜５．５重量部であり、更に好ましくは２．０〜５．５重量部であり、更に好ましくは４．０〜５．５重量部である。 The amount of zinc oxide added in the disaggregation step is 0.3 to 6.0 parts by weight with respect to 100 parts by weight of the raw waste paper, and preferably 0.5 to 5.5 parts by weight from the viewpoint of ink releasability. More preferably, it is 1.0-5.5 weight part, More preferably, it is 2.0-5.5 weight part, More preferably, it is 4.0-5.5 weight part.
酸化亜鉛の平均粒子径は１．０〜５．０μｍであり、インキ剥離性の観点から、好ましくは１．０〜４．０μｍ、より好ましくは１．０〜３．０μｍ、更に好ましくは１．５〜２．５μｍである。酸化亜鉛についての平均粒子径は、後述の実施例の粒子径の測定に示したレーザ回折により測定されたものである。 The average particle diameter of zinc oxide is 1.0 to 5.0 μm, and from the viewpoint of ink peelability, it is preferably 1.0 to 4.0 μm, more preferably 1.0 to 3.0 μm, and still more preferably 1. 5 to 2.5 μm. The average particle diameter of zinc oxide is measured by laser diffraction shown in the measurement of particle diameter in Examples described later.
また、本発明では、離解工程で水酸化ナトリウム等のアルカリ剤を使用しないことが好ましく、中性付近で離解工程を行うことができる。パルプスラリーのｐＨは原料パルプの組成等によって変動するが、アルカリ剤を用いない場合は、酸化亜鉛添加後のパルプスラリー中の水のｐＨは、通常ｐＨ６〜１０の範囲となる。本発明では、ＣＯＤの低減等の観点から、このｐＨ範囲のまま、つまりｐＨ６〜１０の範囲で離解工程を行う。得られるパルプの黄変等の変色を抑制する観点から離解工程のパルプスラリー中の水のｐＨは６〜９が好ましい。離解工程の全ての期間中、ｐＨはこれらの範囲内であることが好ましい。なお、アルカリ剤としては、水酸化ナトリウム、水酸化カリウム及び珪酸ナトリウム等が挙げられ、本発明では、離解工程でこれらアルカリ剤の添加を行わないことが好ましい。 Moreover, in this invention, it is preferable not to use alkaline agents, such as sodium hydroxide, at a disaggregation process, and a disaggregation process can be performed in neutral vicinity. The pH of the pulp slurry varies depending on the composition of the raw material pulp and the like, but when an alkali agent is not used, the pH of water in the pulp slurry after the addition of zinc oxide is usually in the range of pH 6-10. In the present invention, from the viewpoint of reducing COD, etc., the disaggregation process is performed in this pH range, that is, in the range of pH 6-10. From the viewpoint of suppressing discoloration such as yellowing of the obtained pulp, the pH of water in the pulp slurry in the disaggregation process is preferably 6-9. The pH is preferably within these ranges during all periods of the disaggregation process. Examples of the alkali agent include sodium hydroxide, potassium hydroxide and sodium silicate. In the present invention, it is preferable not to add these alkali agents in the disaggregation step.
このように、本発明は、離解工程で、原料古紙と、原料古紙１００重量部に対して０．３〜６．０重量部の平均粒子径が１．０〜５．０μｍの酸化亜鉛と、水とから調製したｐＨ６〜１０のパルプスラリーを用いるものである。 Thus, in the disaggregation step, the present invention is a raw waste paper, and zinc oxide having an average particle diameter of 1.0 to 5.0 μm of 0.3 to 6.0 parts by weight with respect to 100 parts by weight of the raw waste paper, A pulp slurry having a pH of 6 to 10 prepared from water is used.
離解工程におけるパルプスラリー中のパルプ濃度は、好ましくは３．０〜１８重量％であり、より好ましくは３．０〜１０重量％、更に好ましくは３．０〜５．０重量％である。離解手段（離解機）としては、高濃度パルピングシステム（アイ・エイチ・アイフォイトペーパーテクノロジー社）、高濃度パルパー（相川鉄工社製）、デルタパルパー（低中濃度パルパー）（相川鉄工社製）、ファイバーフロー（アンドリッツ社製）、低濃度パルパー（熊谷理機工業（株）製）等が用いられる。パルプ繊維への浸透性及びインキ剥離性の観点から、アルコール系非イオン性界面活性剤をパルプ１００重量部に対して０．０１〜１重量部添加してもよい。離解時間は好ましくは５〜６０分、より好ましくは５〜３０分、更に好ましくは５〜１５分であり、離解温度は、好ましくは５〜６０℃、より好ましくは２０〜６０℃、更に好ましくは４０〜５５℃である。 The pulp density | concentration in the pulp slurry in a disaggregation process becomes like this. Preferably it is 3.0-18 weight%, More preferably, it is 3.0-10 weight%, More preferably, it is 3.0-5.0 weight%. As a disaggregation means (disaggregator), a high concentration pulping system (IH Itoit Paper Technology Co., Ltd.), a high concentration pulper (Aikawa Tekko Co., Ltd.), a delta pulper (low medium concentration pulper) (Aikawa Tekko Co., Ltd.) , Fiber flow (manufactured by Andritz), low-concentration pulper (manufactured by Kumagaya Rikyu Kogyo Co., Ltd.) and the like are used. From the viewpoint of permeability to pulp fibers and ink releasability, 0.01 to 1 part by weight of an alcohol-based nonionic surfactant may be added to 100 parts by weight of pulp. The disaggregation time is preferably 5 to 60 minutes, more preferably 5 to 30 minutes, still more preferably 5 to 15 minutes, and the disaggregation temperature is preferably 5 to 60 ° C, more preferably 20 to 60 ° C, still more preferably. 40-55 ° C.
本発明では、離解工程の後に脱水工程を行うことが好ましい。脱水工程は、離解工程で剥離したインクをパルプスラリーから排出する工程であり、ワイヤーで濾過する方法が挙げられる。脱水工程により、離解工程で用いた酸化亜鉛の少なくとも一部をパルプスラリーから排出させることができる。 In this invention, it is preferable to perform a dehydration process after a disaggregation process. A dehydration process is a process of discharging the ink peeled at the disaggregation process from a pulp slurry, and the method of filtering with a wire is mentioned. By the dehydration step, at least a part of the zinc oxide used in the disaggregation step can be discharged from the pulp slurry.
本発明では、さらに、脱水工程の後に洗浄工程を行うことが好ましい。洗浄工程は、パルプを洗浄する工程であり、パルプを水で希釈攪拌した後に、ワイヤーで濾過する方法が挙げられる。洗浄工程により、離解工程で用いた酸化亜鉛をパルプスラリーから排出することができる。 In the present invention, it is further preferable to perform a washing step after the dehydration step. A washing | cleaning process is a process of wash | cleaning a pulp, and after diluting and stirring a pulp with water, the method of filtering with a wire is mentioned. The zinc oxide used in the disaggregation process can be discharged from the pulp slurry by the washing process.
本発明の製造方法では、これらの工程の他に、必要に応じて、ニーディング工程、フローテーション工程、漂白工程、除塵するスクリーニング工程、希釈工程等を組み合わせることができる。 In the production method of the present invention, in addition to these steps, a kneading step, a flotation step, a bleaching step, a dust removing screening step, a dilution step, and the like can be combined as necessary.
ニーディング工程は、離解工程で得られた離解古紙に、より強い剪断力を与えて、パルプ繊維からインキを剥離する工程である。ニーディング工程は、通常、パルプスラリーを脱水してパルプ濃度を高めたスラリーに対して行われる。ニーディング工程において、パルプスラリー中のパルプ濃度は、好ましくは１８重量％以上５０重量％以下であり、機械的負荷によるインキ剥離性向上の観点から、より好ましくは２０重量％以上、更に好ましくは２２重量％以上であり、機械的剪断力の低下防止、搾水容易性の向上及び添加薬剤の反応性向上の観点から、好ましくは４０重量％以下、より好ましくは３５重量％以下である。したがって、インキ剥離性と機械的剪断力の低下防止、搾水容易性の向上及び添加薬剤の反応性向上の観点から、好ましくは２０〜５０重量％、より好ましくは２２〜３５重量％である。 The kneading step is a step of peeling ink from pulp fibers by giving a stronger shearing force to the old paper obtained by the disaggregation step. The kneading step is usually performed on a slurry in which the pulp slurry is dehydrated to increase the pulp concentration. In the kneading step, the pulp concentration in the pulp slurry is preferably 18% by weight or more and 50% by weight or less, more preferably 20% by weight or more, and still more preferably 22% from the viewpoint of improving the ink peelability due to mechanical load. It is preferably 40% by weight or less, more preferably 35% by weight or less, from the viewpoints of preventing reduction in mechanical shearing force, improving ease of squeezing, and improving the reactivity of the added drug. Therefore, it is preferably 20 to 50% by weight, more preferably 22 to 35% by weight, from the viewpoints of ink releasability and prevention of lowering mechanical shearing force, improvement of water squeezing ease and reactivity improvement of the added drug.
ニーディング工程でニーダー処理する手段としては、ニーダー（山本百馬製作所社製）、マイカプロセッサー（アイ・エイチ・アイフォイトペーパーテクノロジー社製）、ディスパーザー（相川鉄工社製）、ホットディスパーザー（ファイバーテック社製）、コニディスク（相川鉄工社製）等が用いられる。 The kneading process in the kneading process includes a kneader (manufactured by Yamamoto Hyakuma Mfg. Co., Ltd.), a mica processor (manufactured by IH Itoit Paper Technology Co., Ltd.), a disperser (manufactured by Aikawa Tekko), and a hot disperser (fiber). Technic Co., Ltd.), Koni Disc (manufactured by Aikawa Tekko Co., Ltd.) and the like are used.
フローテーション工程は、剥離したインキを系外に除去する工程であり、特に限定されないが、好ましくは、パルプ濃度は０．１〜３重量％、処理温度は５〜６５℃である。フローテーション工程を行う手段として、OKフローテーター（王子エンジニアリング社製）、MTフローテータ、EcoCellフローテーター（何れもアイ・エイチ・アイフォイトペーパーテクノロジー社製）、MAC CELLフローテーター（相川鉄工社製）、バーチカルフローテーター（アゼッタ社製）等の装置が一般的に用いられている。 The flotation step is a step of removing the peeled ink out of the system and is not particularly limited, but preferably the pulp concentration is 0.1 to 3% by weight and the treatment temperature is 5 to 65 ° C. As a means of performing the flotation process, OK Floatator (Oji Engineering Co., Ltd.), MT Floatator, EcoCell Floatator (all manufactured by IH Itoit Paper Technology Co., Ltd.), MAC CELL Floatator (Aikawa Tekko Co., Ltd.) An apparatus such as a vertical flotator (Azetta) is generally used.
漂白工程は、漂白剤添加後にソーキング処理する工程を意味する工程である。ソーキング処理は、漂白剤添加後のパルプスラリーを、４０〜９０℃で３０〜３６０分保持することにより行うのが好ましい。漂白工程ではパルプスラリーには剪断力をかけてもかけなくても良い。漂白剤としては過酸化水素、ハイドロサルファイド、二酸化チオ尿素、ハイポ等が使用されるが、過酸化水素が好ましい。漂白工程におけるパルプスラリー中のパルプ濃度は、通常、１８〜５０重量％であるが、漂白性向上及びインキ剥離性向上の観点から、好ましくは２０〜４０重量％、より好ましくは２２〜３５重量％である。漂白工程は、インキ剥離性向上の観点から、離解工程より後でフローテーション工程より前に行うことが好ましい。 A bleaching process is a process which means the process of performing a soaking process after bleaching agent addition. The soaking treatment is preferably performed by holding the pulp slurry after the addition of the bleaching agent at 40 to 90 ° C. for 30 to 360 minutes. In the bleaching step, the pulp slurry may or may not be subjected to a shearing force. Hydrogen peroxide, hydrosulfide, thiourea dioxide, hypo, etc. are used as the bleaching agent, but hydrogen peroxide is preferred. The pulp concentration in the pulp slurry in the bleaching step is usually 18 to 50% by weight, but preferably 20 to 40% by weight, more preferably 22 to 35% by weight from the viewpoint of improving bleachability and improving ink peelability. It is. The bleaching step is preferably performed after the disaggregation step and before the flotation step from the viewpoint of improving the ink peelability.
本発明において原料古紙として用いられる印刷古紙は、新聞古紙（新聞紙とチラシの混合物）、雑誌古紙、模造色上古紙など、一般的に用いられている原料古紙が使用できる。 As the used waste paper for use in the present invention, generally used waste paper such as newspaper waste paper (mixture of newspaper and leaflet), magazine waste paper, and imitation color waste paper can be used.
本発明の製造方法では、必要に応じて、従来から一般に用いられている公知の脱インキ剤、例えばアルコール系非イオン性界面活性剤、高級アルコール硫酸塩、ポリオキシアルキレン高級アルコール硫酸塩、アルキルベンゼンスルホン酸塩、高級脂肪酸あるいはその塩等を、脱インキ剤として使用することも可能である。脱インキ剤を用いる場合、例えば、離解工程で添加することができる。 In the production method of the present invention, a known deinking agent that has been conventionally used, for example, an alcohol-based nonionic surfactant, a higher alcohol sulfate, a polyoxyalkylene higher alcohol sulfate, an alkylbenzene sulfone, is used as necessary. It is also possible to use acid salts, higher fatty acids or salts thereof as deinking agents. When using a deinking agent, it can add in a disaggregation process, for example.
アルコール系非イオン性界面活性剤としては、例えば、総炭素数８〜２４の飽和もしくは不飽和の第１級もしくは第２級アルコールのアルキレンオキサイド付加物又は総炭素数８〜１２のアルキルフェノールのアルキレンオキサイド付加物が挙げられる。構成アルコールとしては、ミリスチルアルコール、ステアリルアルコールが好ましい。また、アルコールに付加するＡＯは、エチレンオキサイド（以下、ＥＯと略記する）、プロピレンオキサイド（以下ＰＯと略記する）、ブチレンオキサイドが挙げられ、特にＥＯを必須とするのが望ましい。ＡＯの付加モル数は、アルコール又はアルキルフェノール１モルに対し３〜２００モル、特に１０〜８０モルが好ましく、この範囲において特にインキ剥離性が良好で液状化が容易な非イオン性界面活性剤が得られる。付加形態はランダム付加又はブロック付加どちらでも良い。 Examples of alcohol-based nonionic surfactants include alkylene oxide adducts of saturated or unsaturated primary or secondary alcohols having a total carbon number of 8 to 24 or alkylphenols having a total carbon number of 8 to 12. Addenda may be mentioned. As the constituent alcohol, myristyl alcohol and stearyl alcohol are preferable. Examples of AO added to alcohol include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), and butylene oxide, and it is particularly desirable to make EO essential. The number of moles of AO added is preferably 3 to 200 moles, particularly 10 to 80 moles per mole of alcohol or alkylphenol. In this range, a nonionic surfactant having particularly good ink releasability and easy liquefaction is obtained. It is done. The addition form may be either random addition or block addition.
更に本発明の製造方法では、過酸化水素、次亜塩素酸塩、次亜硫酸塩等の漂白剤、スケール防止剤等、ピッチコントロール剤、消泡剤、スライムコントロール剤等の公知のパルプ製造薬品を併用することもできる。また、得られる脱インキパルプの黄変を抑制する観点から、水酸化ナトリウムや珪酸ナトリウム等のアルカリ剤を使用しないことが好ましい。また、本発明の脱インキパルプの製造方法は、少なくとも離解工程を含むものであるが、離解工程以外のいずれの工程でもアルカリ剤を使用しないことが好ましい。 Furthermore, in the production method of the present invention, known pulp manufacturing chemicals such as bleaching agents such as hydrogen peroxide, hypochlorite, and hyposulfite, scale inhibitors, pitch control agents, antifoaming agents, slime control agents, etc. It can also be used together. Moreover, it is preferable not to use alkali agents, such as sodium hydroxide and sodium silicate, from a viewpoint of suppressing yellowing of the deinked pulp obtained. Moreover, although the manufacturing method of the deinked pulp of this invention includes a disaggregation process at least, it is preferable not to use an alkaline agent in any processes other than a disaggregation process.
本発明の製造方法で得られる脱インキパルプは、黄変等の変色が抑制され白色度が向上しており、該パルプを用いた再生紙の好適に用いることができる。 The deinked pulp obtained by the production method of the present invention is suppressed in discoloration such as yellowing and has improved whiteness, and can be suitably used for recycled paper using the pulp.
実施例１及び比較例１
下記の原料古紙に対して、表１に示す化合物を添加して離解工程及び抄紙を行い、得られたパルプシートの残インキ量と変色を測定した。すなわち、関東化学（株）製の酸化亜鉛（平均粒子径２．３μｍ、関東化学（株）社製）又は水酸化ナトリウムを添加剤として用いて、乾燥シートを作成し、残インキ量と変色の度合いを測定した。結果を表１に示した。比較例１−５は、添加剤として酸化亜鉛と水酸化ナトリウムとを併用しｐＨを本発明の範囲外としたものである。なお、酸化亜鉛の平均粒子径は（株）堀場製作所社製のレーザ回折／散乱式 粒度分布測定装置ＬＡ−９２０にて測定して得られた、メジアン径を示した（他の実施例、比較例でも同様）。
Example 1 and Comparative Example 1
The compound shown in Table 1 was added to the following raw paper to perform a disaggregation process and paper making, and the residual ink amount and discoloration of the obtained pulp sheet were measured. That is, a dry sheet was prepared using zinc oxide (average particle size 2.3 μm, manufactured by Kanto Chemical Co., Ltd.) or sodium hydroxide as an additive from Kanto Chemical Co., Ltd. The degree was measured. The results are shown in Table 1. In Comparative Example 1-5, zinc oxide and sodium hydroxide are used in combination as additives and the pH is outside the range of the present invention. In addition, the average particle diameter of zinc oxide showed the median diameter obtained by measuring with the laser diffraction / scattering type particle size distribution measuring device LA-920 made by Horiba Ltd. (other examples, comparison) The same applies to the example).
（原料古紙）
評価用の原料古紙は、新聞古紙６０重量％とコート系チラシ４０重量％を使用した。新聞古紙は発刊１ヶ月未満のものを８０℃の恒温槽で５時間保持し、強制熱劣化させたものを使用した。強制熱劣化は、夏場の劣化古紙を想定したものである。離解に際し、前記原料古紙を約５ｃｍ角に裁断した。
(Raw paper)
Used raw paper for evaluation was 60% by weight of used newspaper and 40% by weight of coated flyers. The newspaper used was one that had been published for less than one month and was forced-heat-deteriorated by holding it in a thermostatic bath at 80 ° C. for 5 hours. Forced heat deterioration is assumed to be deteriorated waste paper in summer. At the time of disaggregation, the raw material waste paper was cut into about 5 cm square.
（脱インキ処理方法）
下記の各工程を順に行い脱インキ処理を行った。
(Deinking method)
The following steps were performed in order to perform deinking treatment.
（１）離解工程（パルパー工程）
低濃度パルパー（熊谷理機工業（株）製）に４５℃の温水１９３０ｍＬおよび表中の添加剤を表中の量入れた後、７０ｇの原料古紙を入れた（パルプ濃度３．５重量％）。これを攪拌羽根（羽根３本、長さ各３５ｍｍ、回転数３０００ｒｐｍ）で７分間攪拌した。
(1) Disaggregation process (pulper process)
A low-concentration pulper (manufactured by Kumagaya Riki Kogyo Co., Ltd.) was charged with 1930 mL of warm water at 45 ° C. and the additives in the table, followed by 70 g of raw paper (pulp concentration 3.5% by weight) . This was stirred for 7 minutes with stirring blades (three blades, each length was 35 mm, rotation speed was 3000 rpm).
（２）脱水工程
離解後のパルプスラリー８５．７ｇ（絶乾重量３ｇ）を５Ｌの容器に入れ、それを４Ｌの水で希釈攪拌し８０メッシュのワイヤー（目開き１８０μｍ）で濾過した。
(2) Dehydration Step 85.7 g of pulp slurry after disaggregation (absolute dry weight 3 g) was placed in a 5 L container, diluted and stirred with 4 L of water, and filtered through an 80 mesh wire (opening 180 μm).
（３）洗浄工程
脱水工程で用いたメッシュ上のパルプを集め、再度５Ｌの容器へ入れ４Ｌの水で希釈した。これを（希釈→濾過）全４回繰り返し、剥離したインキを除去したパルプスラリーを得た。
(3) Washing process The pulp on the mesh used in the dehydration process was collected, put into a 5 L container again, and diluted with 4 L of water. This was repeated 4 times (dilution → filtration) to obtain a pulp slurry from which the peeled ink had been removed.
（抄紙方法）
洗浄工程後のパルプスラリーを用いて、丸型タッピーシートマシン（熊谷理機工業（株）製）にて抄紙し、２分間のプレス処理後、ドラム式回転ドライヤー（熊谷理機工業（株）製）にて乾燥し（１０５℃、２分間）乾燥シートを得た。
(Paper making method)
Paper is made with a round tappy sheet machine (manufactured by Kumagai Riki Kogyo Co., Ltd.) using the pulp slurry after the washing process, and after a 2-minute press treatment, a drum-type rotary dryer (manufactured by Kumagaya Rikyu Kogyo Co., Ltd.) ) (105 ° C., 2 minutes) to obtain a dry sheet.
（残インキ量の測定方法）
前記抄紙方法で得られたシートを用い、Ｔｅｃｈｎｉｄｙｎｅ（株）社製のＣｏｌｏｒ Ｔｏｕｃｈ ＰＣにてＥＲＩＣ ｎｕｍｂｅｒを測定し、未剥離残インキ量とした。測定はシートの表裏を各２視野ずつ測定しそれを平均した。同じ添加剤を用いた条件でも、用いた原料古紙によって残インキ量が異なるため、添加剤を用いない場合を基準として、残インキ率（％）〔（添加剤を用いた場合のＥＲＩＣ ｎｕｍｂｅｒ）／（添加剤を用いない場合のＥＲＩＣ ｎｕｍｂｅｒ）×１００〕を求めた。同じ基準に対して残インキ率が小さいほど残インキ量の低減効果が高いといえる。
(Measurement method of remaining ink amount)
Using the sheet obtained by the papermaking method, the ERIC number was measured by Color Touch PC manufactured by Technydine Co., Ltd. to obtain the unremoved residual ink amount. The measurement was performed by measuring the front and back of the sheet for each of two visual fields and averaging them. Even under the conditions using the same additive, the amount of residual ink varies depending on the used raw paper, so the residual ink ratio (%) [(ERIC number with additive) / (ERIC number when no additive is used) × 100]. It can be said that the smaller the residual ink ratio with respect to the same standard, the higher the effect of reducing the residual ink amount.
（変色の測定方法）
前記抄紙方法で得られた手すきシートを用い、Ｔｅｃｈｎｉｄｙｎｅ社製Ｃｏｌｏｒ Ｔｏｕｃｈ ＰＣ（分光光度計型測色計）を用い、ｂ値を測定した。原料の古紙の種類やロットの種類等により、得られる脱インキパルプのｂ値が異なるが、同じ評価条件での相対比較でｂ値が１％（１ポイント）違うと大きく差が認められるものである。添加剤を用いない場合のｂ値を基準として、その差を求めた。同じ基準に対して添加剤を用いない場合のｂ値から差が小さいほど、黄変等の変色が少ないといえる。
(Measurement method of discoloration)
Using the handsheet obtained by the papermaking method, b-value was measured using a Color Touch PC (Spectrophotometer-type colorimeter) manufactured by Technodyne. The b value of the deinked pulp obtained varies depending on the type of used paper and lot of raw materials, but a large difference is recognized when the b value is different by 1% (1 point) in relative comparison under the same evaluation conditions. is there. The difference was calculated | required on the basis of b value when an additive is not used. It can be said that the smaller the difference from the b value when no additive is used with respect to the same standard, the less discoloration such as yellowing.
酸化亜鉛の添加量を多くするにつれて、残インキ量が低減することがわかる。ｂ値は、酸化亜鉛を用いた場合が水酸化ナトリウムを用いた場合よりも、添加剤を用いない場合との差が小さく、変色がより少ないことがわかる。また、酸化亜鉛を使用してもｐＨが高いとｂ値の差が大きくなり、変色を十分に低減できないことがわかる。 It can be seen that the amount of residual ink decreases as the amount of zinc oxide added is increased. As for b value, when zinc oxide is used, it turns out that the difference with the case where an additive is not used is smaller than the case where sodium hydroxide is used, and there is less discoloration. It can also be seen that even when zinc oxide is used, if the pH is high, the difference in b value increases, and the discoloration cannot be reduced sufficiently.
実施例２及び比較例２
平均粒子径の違う酸化亜鉛（平均粒子径０．７３μｍ［カタログ値０．６８μｍ］、堺化学工業（株）製、平均粒子径０．１８μｍ［カタログ値０．０７μｍ］、和光純薬工業（株）製の酸化亜鉛分散溶液）及び酸化亜鉛とは異なる無機塩の酸化マグネシウム（平均粒子径１８．５μｍ、関東化学（株）製）を用いて、実施例１と同様に残インキ量及び変色を評価した。また、酸化亜鉛の添加量が０．１重量部の場合及び前記酸化亜鉛に代えて水酸化ナトリウムを用いた場合についても同様に評価した。結果を表２に示した。
Example 2 and Comparative Example 2
Zinc oxide with different average particle size (average particle size 0.73 μm [catalog value 0.68 μm], manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.18 μm [catalog value 0.07 μm], Wako Pure Chemical Industries, Ltd. ) Manufactured zinc oxide dispersion solution) and magnesium oxide of an inorganic salt different from zinc oxide (average particle size: 18.5 μm, manufactured by Kanto Chemical Co., Ltd.) evaluated. Further, the same evaluation was performed when the amount of zinc oxide added was 0.1 parts by weight and when sodium hydroxide was used instead of zinc oxide. The results are shown in Table 2.
平均粒子径が０．７３μｍ及び０．１８μｍの酸化亜鉛、並びに酸化マグネシウムでは、残インキ量は低減しなかった。 With zinc oxide having an average particle size of 0.73 μm and 0.18 μm, and magnesium oxide, the amount of residual ink was not reduced.
実施例３及び比較例３
平均粒子径２．３μｍの酸化亜鉛を分級して得られた平均粒子径１．２μｍの酸化亜鉛を用いて、実施例１と同様に残インキ量及び変色を評価した。また、前記酸化亜鉛に代えて水酸化ナトリウム又は平均粒子径０．７３μｍの酸化亜鉛を用いた場合についても同様に評価した。結果を表３に示した。
Example 3 and Comparative Example 3
Using zinc oxide having an average particle diameter of 1.2 μm obtained by classifying zinc oxide having an average particle diameter of 2.3 μm, the amount of residual ink and discoloration were evaluated in the same manner as in Example 1. Moreover, it evaluated similarly about the case where it replaced with the said zinc oxide and used the sodium hydroxide or the zinc oxide with an average particle diameter of 0.73 micrometer. The results are shown in Table 3.
平均粒子径１．２μｍの酸化亜鉛を所定ｐＨで用いることにより、平均粒子径２．３μｍの酸化亜鉛と同様に、残インキ量を低減させ、変色を抑制することができる。 By using zinc oxide having an average particle diameter of 1.2 μm at a predetermined pH, the amount of residual ink can be reduced and discoloration can be suppressed as in the case of zinc oxide having an average particle diameter of 2.3 μm.
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