JP4543757B2 - Discrimination method of printed matter - Google Patents
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- JP4543757B2 JP4543757B2 JP2004163633A JP2004163633A JP4543757B2 JP 4543757 B2 JP4543757 B2 JP 4543757B2 JP 2004163633 A JP2004163633 A JP 2004163633A JP 2004163633 A JP2004163633 A JP 2004163633A JP 4543757 B2 JP4543757 B2 JP 4543757B2
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Description
本発明は、印刷物を形成するクリアコートした樹脂やインキの種類を判別する方法に関するものであり、これを用いて古紙を選別する方法に関する。更に詳しくは、印刷物にクリアコートした樹脂あるいは印刷インキ中の樹脂の溶剤に対する溶解性によりUVクリアコートやポリプロピレンコート、プレスコート、ビニール引き、ニス引き等の表面加工・コート印刷物及びUVインキ、トナー、オフセットインキ、グラビアインキ等について判別し、古紙再生工程で再生し難い印刷物を選別、除去する方法、及び古紙の再生方法に関する。 The present invention relates to a method for discriminating the types of clear-coated resins and inks that form printed matter, and to a method for sorting used paper using the method. More specifically, surface processing such as UV clear coating, polypropylene coating, press coating, vinyl drawing, varnishing, coated ink, UV ink, toner, The present invention relates to a method for discriminating offset ink, gravure ink, and the like, and selecting and removing printed matter that is difficult to recycle in a used paper recycling process, and a used paper recycling method.
近年、省資源あるいは環境問題といった観点から古紙の利用が拡大している。一方で印刷物の高品質化、多様化が進み、古紙として回収される印刷物の中に、再生し難いUVクリアコートした印刷物やポリプロピレンコートした印刷物等の混入が頻発するようになり、操業や品質の面で問題を生じている。この対策として、機械的負荷や薬品使用量を増加して対応した場合、繊維の劣化やコストの増加など新たな問題を生じる。最も効率の良い対策は、再生し難い印刷物を古紙再生工程に持込む前に選別することであるが、UVクリアコート等は既存の水性クリアコート等と違和感のないように作られており、目視での判別は困難であるため、FT−IR、GC−MSといった機器分析による判別を行う必要があった。これらの機器分析は高価な装置を利用するだけでなく、分析場所が限られており、更に分析に時間及び熟練を要することから、実際の古紙選別作業を行う段階で利用することは不可能であった。 In recent years, the use of waste paper has expanded from the viewpoint of resource saving or environmental problems. On the other hand, the quality and diversification of printed materials has progressed, and in the printed materials collected as used paper, UV clear-coated printed materials and polypropylene-coated printed materials that are difficult to recycle frequently become mixed. Is causing problems. As a countermeasure, when the mechanical load and the amount of chemicals used are increased, new problems such as fiber deterioration and cost increase arise. The most efficient measure is to sort printed materials that are difficult to recycle before bringing them into the used paper recycling process, but UV clear coats are made so that they do not feel uncomfortable with existing water-based clear coats. Since it is difficult to discriminate with FT, it is necessary to discriminate by instrumental analysis such as FT-IR and GC-MS. These instrument analyzes not only use expensive equipment, but also have limited analysis locations, and further time and skill are required for analysis, so it is impossible to use them at the stage of actual waste paper sorting work. there were.
特開平10−149473号公報(特許文献1)にはフーリエ変換近赤外線分析装置(FTNIR)を用いた印刷物の識別方法が提案されているが、これは有価証券などの判別をするものであり、印刷物に光ファイバープローブを密着させてスペクトルを測定するため、汚染、しわの少ないきれいな印刷物しか判別することができないので、古紙のような複雑かつ損傷の著しい印刷物の判別は困難であった。 Japanese Patent Laid-Open No. 10-149473 (Patent Document 1) proposes a printed matter identification method using a Fourier transform near-infrared analyzer (FTNIR), which is used to discriminate securities and the like. Since the optical fiber probe is closely attached to the printed matter and the spectrum is measured, only clean printed matter with less contamination and wrinkles can be discriminated. Therefore, it is difficult to discriminate complicated and severely printed matter such as waste paper.
そこで本発明は、印刷物を形成するクリアコートした樹脂やインキについて、古紙選別作業時に利用することが可能な簡便、迅速な判別方法と、それを用いた古紙の選別方法、及びそれに基づいて選別された古紙を原料とした古紙の再生方法を提供することを目的とする。 Therefore, the present invention provides a simple and quick discriminating method that can be used for sorting used paper and clear-coated resins and inks that form printed matter, a used paper sorting method using the same, and a sorting method based thereon. An object of the present invention is to provide a method for recycling used paper from recycled paper.
本発明者らは、印刷物を形成するクリアコートした樹脂やインキに含まれる樹脂が古紙の再生し易さに大きな影響を与えていることに着目し、この樹脂を簡便に判別する方法について鋭意研究した結果、性質の異なる溶剤を用いて樹脂の溶解性を調べることで印刷物の再生の容易の程度を予測でき、更には再生の困難な古紙を選別できることを見出し、この知見に基づいて本発明を完成するに至った。 The inventors of the present invention have paid attention to the fact that the clear-coated resin that forms the printed matter and the resin contained in the ink have a great influence on the ease with which the used paper can be recycled. As a result, it was found that by examining the solubility of the resin using solvents having different properties, it is possible to predict the degree of easy reproduction of the printed matter, and furthermore, it is possible to select used paper that is difficult to regenerate. It came to be completed.
すなわち、本発明は、溶解度パラメーターの異なる有機溶剤を印刷物に一定時間接触させた後、印刷物を形成するクリアコート用樹脂やインキの溶剤に対する溶解性を判定し、これに基づいて樹脂及びインキを判別すると共に印刷物の再生し易さを予測し、パルプ品質を損なうような再生し難い印刷物を古紙から簡便、迅速に選別することで、パルプ中の異物の少ない高品質な再生パルプを得ることを特徴とするものである。 In other words, the present invention determines the solubility of a clearcoat resin or ink for forming a printed matter in a solvent after contacting an organic solvent with a different solubility parameter for a certain period of time, and discriminates the resin and ink based on this. In addition, it predicts the ease with which printed matter can be regenerated, and easily and quickly sorts out hard-to-regenerate printed matter that impairs pulp quality from waste paper, resulting in high-quality recycled pulp with less foreign matter in the pulp. It is what.
本発明による印刷物の判別方法によれば高価な分析装置や高度な分析技術を必要とせずに、古紙回収ヤードや脱墨パルプ製造工場等において、簡便・迅速に印刷物を判別することが可能となり、これに基づいて古紙を選別することにより高品質の脱墨パルプを製造することができる。 According to the method for discriminating printed matter according to the present invention, it becomes possible to discriminate the printed matter easily and quickly in a used paper collection yard or a deinked pulp manufacturing factory without requiring an expensive analyzer or advanced analysis technology. High quality deinked pulp can be produced by sorting waste paper based on this.
本発明は、印刷物として、例えば、新聞用紙、中質紙、上質紙、塗工紙、微塗工紙、感熱記録紙、ノーカーボン紙、色上質紙、PPC用紙、紙器、シール・ラベル、帳票、段ボール、白板紙などに印刷した紙に適用できるが、特に光沢のある印刷物や表面加工処理した印刷物の判別に有効である。印刷物を形成するクリアコート用樹脂及びインキとしては、「古紙リサイクルにおける阻害性要確認資材等に関する調査報告書」(平成14年度国庫補助事業、財団法人古紙再生促進センター発行)における光沢加工及び光沢インキが挙げられる。また、インキとしては公知の印刷インキ(相原次郎「印刷インキ入門増補版」第4版、印刷学会出版部、1999年発行)が挙げられる。 The present invention is a printed material, for example, newsprint paper, medium-quality paper, high-quality paper, coated paper, fine-coated paper, heat-sensitive recording paper, carbonless paper, colored high-quality paper, PPC paper, paper container, sticker / label, form Although it can be applied to paper printed on corrugated cardboard, white paperboard, etc., it is particularly effective for discriminating glossy printed matter and surface-treated printed matter. As the clear coat resin and ink that form printed matter, the glossy processing and glossy ink in the “Survey Report on Inhibition Necessary Confirmation Materials for Recycled Paper Recycling” (issued in 2002 by the National Treasury Aid Project, Recycled Paper Recycling Promotion Center) Is mentioned. Examples of the ink include known printing inks (Jiro Aihara “4th edition of Introductory Printing Ink”, 4th edition, published by the Japan Society of Printing Science, 1999).
本発明における溶剤とは、「化学大辞典」(東京化学同人、1989年発行)における有機溶媒を意味し、脂肪族溶媒や芳香族溶媒、あるいは無極性溶媒、極性溶媒、または、プロトン性溶媒、非プロトン性溶媒等として分類される物質の総称であり、更に加えて、これら物質の混合物、あるいはこれらの物質が含まれる精製度の低い石油製品などの工業製品を含むものである。 The solvent in the present invention means an organic solvent in the “Chemical Dictionary” (Tokyo Kagaku Dojin, published in 1989), an aliphatic solvent, an aromatic solvent, a nonpolar solvent, a polar solvent, or a protic solvent, It is a general term for substances classified as aprotic solvents and the like, and further includes industrial products such as a mixture of these substances or a petroleum product with a low degree of purification containing these substances.
本発明における溶解度パラメーターとは、理化学辞典(第5版、岩波書店)にあるように液体のモル蒸発熱とモル体積から定義される量δをいい、2成分系での溶解度は両者の溶解度パラメーターの差が小さくなるほど大きくなる。δは溶剤の極性を表わす指標であり、一般に樹脂の溶解性を評価するために使用されている指標である。δはモル蒸発熱ΔHとモル体積Vからδ=(ΔH/V)1/2として求められる値であり、単位は(cal/cm3)1/2である(新高分子文庫8 接着百科(上)(高分子刊行会、第9版、p24−35、1988年)。他の参考文献として例えば有機合成化学協会編の新板溶剤ポケットブックp22−25が挙げられ、その間接的な評価法などの求め方が記載されている。ここではδの単位が(MPa)1/2となっており、(cal/cm3)1/2=2.046(MPa)1/2となる。 The solubility parameter in the present invention refers to the quantity δ defined by the molar heat of vaporization and the molar volume of the liquid as described in the physics and chemistry dictionary (5th edition, Iwanami Shoten). The smaller the difference, the larger. δ is an index representing the polarity of the solvent, and is generally an index used for evaluating the solubility of the resin. δ is a value obtained as δ = (ΔH / V) 1/2 from the heat of molar evaporation ΔH and the molar volume V, and the unit is (cal / cm 3 ) 1/2 (New Polymer Library 8 Adhesion Encyclopedia (above ) (Polymer Publications, 9th edition, p24-35, 1988) Other references include, for example, the new board solvent pocket book p22-25 edited by the Society of Synthetic Organic Chemistry, and its indirect evaluation methods, etc. Here, the unit of δ is (MPa) 1/2 and (cal / cm 3 ) 1/2 = 2.046 (MPa) 1/2 .
本発明において、溶解度パラメーターを溶剤の樹脂溶解性を表わす指標として用いていることが好ましいが、混合物や不純物を含む精製度の低い石油製品については、例えば、石油エーテルやベンジン等、その性質が一定であり、大きく無極性溶媒や極性溶媒といった分類が推定可能であれば溶解度パラメーターが未知のものであってもよい。好ましくは溶解度パラメーターの差が少なくとも0.2程度である複数の有機溶剤を用いて、各々の有機溶剤に対する溶解性により、印刷物を判別する。 In the present invention, it is preferable to use the solubility parameter as an index representing the resin solubility of the solvent. However, for petroleum products having a low purity including a mixture and impurities, for example, properties such as petroleum ether and benzine are constant. So long as the classification such as a nonpolar solvent or polar solvent can be estimated, the solubility parameter may be unknown. Preferably, using a plurality of organic solvents having a solubility parameter difference of at least about 0.2, the printed matter is discriminated based on the solubility in each organic solvent.
本発明において印刷物を判別し古紙を選別する場合、例えば、印刷物に対して前記溶剤を滴下、塗布、噴霧等の方法により表面に直接接触させ、一定時間後にウェスや紙、エアーブロー等によって除去する方法が簡便であるが、溶剤の接触・除去方法は、これらに限定するものではない。簡易な方法として、溶剤をスプレーにより印刷物に噴霧し、表面を観察する方法がある。 When discriminating printed matter and sorting used paper in the present invention, for example, the solvent is directly contacted with the surface by a method such as dripping, coating, or spraying on the printed matter, and then removed by waste, paper, air blow, or the like after a certain time. Although the method is simple, the method for contacting and removing the solvent is not limited to these. As a simple method, there is a method of spraying a solvent onto a printed material by spraying and observing the surface.
本発明による印刷物の判別は、例えば、以下のようにして行う。 The discrimination of the printed matter according to the present invention is performed as follows, for example.
1)溶解度パラメーターが9未満である溶剤に対する印刷面の溶解性を観察することにより、古紙として再生し難い印刷物を選別する。 1) By observing the solubility of the printed surface in a solvent having a solubility parameter of less than 9, a printed material that is difficult to recycle as used paper is selected.
2)テレピン油、ベンジン、石油エーテル、ヘキサンのいずれか、またはそれらの混合物に対する印刷面の溶解性を観察することにより、古紙として再生し難い印刷物を選別する。 2) The printed matter that is difficult to recycle as waste paper is selected by observing the solubility of the printing surface in turpentine oil, benzine, petroleum ether, hexane, or a mixture thereof.
3)少なくとも2種類以上の溶解度パラメーターの異なる溶剤を印刷物表面に一定時間接触させた後、除去することで、印刷物を形成するクリアコートした樹脂やインキを判別する。 3) After at least two kinds of solvents having different solubility parameters are brought into contact with the surface of the printed material for a certain period of time and then removed, the clear-coated resin or ink forming the printed material is determined.
4)溶解度パラメーターが9(cal/cm3)1/2未満である溶剤、及びアセトンまたはジメチルスルホキシドを用いて、クリアコートした印刷物を判別する。 4) Using a solvent having a solubility parameter of less than 9 (cal / cm 3 ) 1/2 and acetone or dimethyl sulfoxide, the clear-coated printed matter is discriminated.
5)前記4)において、さらに第3の溶剤としてジクロロメタンあるいはジメチルホルムアミドを用いて、UVクリアコート若しくはUVニス引きした印刷物を判別する。 5) In the above 4), using a dichloromethane or dimethylformamide as a third solvent, the printed matter obtained by UV clear coating or UV varnishing is discriminated.
6)印刷物の3種類の溶剤A〜Cに対する溶解性を観察し、溶剤A〜Cのいずれの溶剤にも可溶であるものをオフセット印刷またはグラビア印刷、溶剤Aに不溶で溶剤B及び溶剤Cに可溶であるものをプレスコートを含む再生に注意が必要である印刷物、溶剤A及び溶剤Bに不溶で溶剤Cに可溶であるものをUVコートを含む再生困難な印刷物、溶剤A〜Cのいずれの溶剤にも不溶であるものをポリプロピレンコートまたは高度に重合したアクリル樹脂を含む再生困難な印刷物と判別する。なお、ポリプロピレンコートは引裂き時に透明コート部分が紙から剥離して伸びることから、高重合アクリル樹脂と区別することができる。
溶剤A:テレピン油、ベンジン、石油エーテル、ヘキサンのいずれか
溶剤B:アセトンあるいはジメチルスルホキシド
溶剤C:ジクロロメタンあるいはジメチルホルムアミド
本発明の印刷物の判別方法に基づいて、UVコート、及びポリプロピレンコートを含む再生困難な印刷物を除去した古紙を原料として用いることにより、高品質の再生パルプの製造が可能となる。
6) Observe the solubility of the printed material in the three types of solvents A to C, and those that are soluble in any of the solvents A to C are offset printing or gravure printing, insoluble in solvent A, solvent B and solvent C Printed materials that are soluble in water and need to be regenerated including press coat, printed materials that are insoluble in solvent A and solvent B but soluble in solvent C, and difficult to regenerate including UV coat, solvents A to C Those that are insoluble in any of these solvents are identified as difficult-to-reproduce printed matter containing polypropylene coat or highly polymerized acrylic resin. The polypropylene coat can be distinguished from the highly polymerized acrylic resin because the transparent coat portion is peeled off from the paper and stretched during tearing.
Solvent A: Any of turpentine oil, benzine, petroleum ether, hexane Solvent B: Acetone or dimethyl sulfoxide Solvent C: Dichloromethane or dimethylformamide Based on the method for discriminating printed matter of the present invention, it is difficult to regenerate including UV coat and polypropylene coat By using waste paper from which a printed matter is removed as a raw material, it is possible to produce high-quality recycled pulp.
本発明の印刷物の判別方法を用いて選別した古紙を原料とする古紙再生工程としては、例えば、新聞、チラシ、雑誌、色上、オフィス古紙、段ボール、白板紙などを再生する工程が挙げられるが、セルロース繊維として再生可能なシートを再生する工程であれば、これらに限定されるものではない。 Examples of the used paper recycling process using the used paper selected using the printed matter discrimination method of the present invention include a process of recycling newspapers, flyers, magazines, color, office waste paper, cardboard, white paperboard and the like. As long as it is a step of regenerating a sheet that can be regenerated as cellulose fiber, it is not limited thereto.
以下に実施例を挙げて本発明をより具体的に示すが、本発明はかかる実施例に限定されるものではない。表1に示した#1〜#11の試料、及び表3に示した#12〜15について、以下に示す方法にて溶剤に対する溶解性を調べた。 The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to such examples. The # 1 to # 11 samples shown in Table 1 and # 12 to 15 shown in Table 3 were examined for solubility in solvents by the following method.
<試料>
・コーティング組成の明らかな表面光沢コート見本品:5種(表1の#1〜5)
・色上古紙中の光沢コート系印刷物:5種(表1の#6〜10)
・トナー印刷物:1種(表1中の#11)
・組成未知の市中印刷物(表3の#12〜15)
<溶剤>
表2に示した溶解度パラメーター(以下δ)の異なる溶剤(13種)を用いた。δはモル蒸発熱ΔHとモル体積Vからδ=(ΔH/V)1/2として求められる値であり、新高分子文庫8 接着百科(上)(高分子刊行会、第9版、p24−35、1988年)から引用した。単位は(cal/cm3)1/2である。
<Sample>
・ Surface gloss coat sample with clear coating composition: 5 types (# 1 to 5 in Table 1)
・ Glossy coated printed matter in colored waste paper: 5 types (# 6 to 10 in Table 1)
-Toner print: 1 type (# 11 in Table 1)
・ Commercial print with unknown composition (# 12-15 in Table 3)
<Solvent>
Solvents (13 types) having different solubility parameters (hereinafter referred to as δ) shown in Table 2 were used. δ is a value obtained from the heat of molar evaporation ΔH and the molar volume V as δ = (ΔH / V) 1/2 . New Polymer Bunko 8 Adhesion Encyclopedia (above) (Polymer Press, 9th edition, p24-35 , 1988). The unit is (cal / cm 3 ) 1/2 .
<スポットテスト>
印刷物に溶剤を滴下し、30秒後、ティッシュ様の紙で擦り、目視で印面の剥離性を以下のように判定することにより、印面の溶剤に対する溶解性を判定した。○:良く剥離する、△:やや剥離する、×〜△:表面が薄くなり、インキが転写する、×:変化なし
<Spot test>
The solvent was dropped on the printed matter, and after 30 seconds, the surface was rubbed with a tissue-like paper, and the peelability of the stamping surface was visually determined as follows to determine the solubility of the stamping surface in the solvent. ○: Peel well, △: Slightly peel, × to △: Surface becomes thin, ink is transferred, X: No change
[実施例1]
スポットテストの結果を表2に示した。色上古紙から取り出した光沢コート系印刷物は、ほとんどの溶剤によく溶解した。一方、見本品(#1〜5)は、δが9〜10付近の溶剤に溶解すものが多かった。結果を元に図1に示すフローに従い、3種類の溶剤を用いることで印刷物を表3に示す分類A〜Dのグループ分けを行った。用いる溶剤としては、まず、テレピン油やトルエン、ベンジン、石油エーテル、ヘキサン等のδが9よりも小さい溶剤を用いて溶解性を判定し、次にアセトン、ジクロロメタンの順で溶解性を判定することで、表4に示す分類に判別することができた。
[Example 1]
The results of the spot test are shown in Table 2. The gloss-coated printed matter taken out of the old colored paper was well dissolved in most solvents. On the other hand, many of the sample products (# 1-5) were soluble in a solvent having a δ of 9-10. Based on the results, according to the flow shown in FIG. 1, the printed materials were classified into groups A to D shown in Table 3 by using three kinds of solvents. As the solvent to be used, first determine the solubility using a solvent having a δ smaller than 9 such as turpentine oil, toluene, benzine, petroleum ether, hexane, etc., and then determine the solubility in the order of acetone and dichloromethane. Thus, the classification shown in Table 4 could be made.
[実施例2]
実施例1の知見を元に未知試料として、光沢部と通常の印刷部を持つ中吊りと雑誌の表紙、写真つきパンフレットについてスポットテストを行った。アセトンは揮発性が高いこと、ジクロロメタンは含塩素化合物であることから、これらの代替物質として、それぞれジメチルスルホキシド(DMSO)及びジメチルホルムアミド(DMF)についてもテストを行った。
表4の#12及び#14については顕微FT−IR測定よりUV樹脂が検出されUVコートと判別できた。#15は同様にスチレンアクリル系樹脂が検出されプレスコートと判別でき、#13は炭化水素が検出されたことからオフセット印刷物と判別できた。
[Example 2]
Based on the knowledge of Example 1, as an unknown sample, a spot test was performed on a hanging cover having a glossy portion and a normal printing portion, a cover of a magazine, and a pamphlet with photographs. Since acetone is highly volatile and dichloromethane is a chlorine-containing compound, dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) were also tested as substitutes for these substances.
As for # 12 and # 14 in Table 4, UV resin was detected by microscopic FT-IR measurement, and could be distinguished from UV coating. Similarly, in # 15, a styrene acrylic resin was detected and could be discriminated as a press coat, and # 13 could be discriminated as an offset printed matter because hydrocarbons were detected.
これまでの実機での検討結果、及び「古紙リサイクルにおける阻害性要確認資材等に関する調査報告書」(平成14年度国庫補助事業、財団法人古紙再生促進センター発行)から、分類Aは再生が容易であり、分類Bは再生に注意が必要であること、分類C及びDは再生が極めて困難と判別される。 Based on the results of previous studies with actual machines and “Survey Report on Inhibition Required Materials for Used Paper Recycling” (FY2002 National Treasury Assistance Project, Waste Paper Recycling Promotion Center), Category A is easy to recycle. Yes, classification B is determined to require attention for reproduction, and classification C and D are determined to be extremely difficult to reproduce.
本発明による判別方法を古紙に対して用いることで、分類B〜Dに該当する印刷物を簡便、迅速に判別でき、これに基づき印刷物を選別することによって、パルプ中の異物の少ない高品質な再生パルプを得ることができ、これを用いて高品質な再生紙を得ることができる。 By using the discrimination method according to the present invention for waste paper, it is possible to easily and quickly discriminate prints corresponding to the classifications B to D, and by sorting the prints based on this, high quality reproduction with less foreign matter in the pulp. Pulp can be obtained, and a high-quality recycled paper can be obtained using this.
Claims (7)
溶剤A:テレピン油、ベンジン、石油エーテル、ヘキサンのいずれか
溶剤B:アセトンあるいはジメチルスルホキシド
溶剤C:ジクロロメタンあるいはジメチルホルムアミド Prints that are soluble in any of the solvents A to C include offset printing or gravure printing, and those that are insoluble in the solvent A but soluble in the solvent B and the solvent C include a press coat and require attention for regeneration. Printed materials that are insoluble in solvent A and solvent B but soluble in solvent C and that are difficult to regenerate because of UV coating, and those that are insoluble in any of solvents A to C are polypropylene coated or highly polymerized. A printed matter discriminating method, characterized in that it is discriminated from a printed matter that contains an acrylic resin that is difficult to regenerate.
Solvent A: turpentine, benzene, petroleum ether, or a solvent of hexane B: acetone or dimethyl sulfoxide solvent C: dichloromethane or dimethylformamidine de
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