JP4801478B2 - How to treat broke pulp - Google Patents
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- JP4801478B2 JP4801478B2 JP2006084927A JP2006084927A JP4801478B2 JP 4801478 B2 JP4801478 B2 JP 4801478B2 JP 2006084927 A JP2006084927 A JP 2006084927A JP 2006084927 A JP2006084927 A JP 2006084927A JP 4801478 B2 JP4801478 B2 JP 4801478B2
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 90
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 54
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 45
- 239000001569 carbon dioxide Substances 0.000 claims description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000010893 paper waste Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 239000011268 mixed slurry Substances 0.000 claims description 2
- 238000005360 mashing Methods 0.000 claims 1
- 239000013055 pulp slurry Substances 0.000 description 18
- 239000000945 filler Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 208000004434 Calcinosis Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- Paper (AREA)
Description
本発明は塗工紙の製造中に発生する損紙由来のブロークパルプを改質する方法に関するものであり、さらに詳しくは損紙由来のパルプ・無機物混合の水スラリーに二酸化炭素を含有するガスを吹き込むことによって改質する方法に関するものである。 The present invention relates to a method for modifying broke pulp derived from broken paper generated during the manufacture of coated paper, and more specifically, a gas containing carbon dioxide in a water slurry of a mixed pulp / inorganic matter derived from broken paper. The present invention relates to a method for reforming by blowing.
塗工紙の製造工程においては紙切れ時や仕上げ時等に必ず損紙が発生してしまう。この損紙はパルパー等で粗離解された後、さらにブローク離解機・ブローク叩解機等で離解され、粗大部分を除いた後にブロークパルプと呼ばれる紙原料として再利用されている。一般的にはブロークパルプが発生する工場では紙中の無機填料の約10〜40％、場合によって100％がブロークパルプ中の無機成分由来となっている。これらのブロークパルプ由来の無機成分は損紙中の塗工顔料、内添填料からなるが、塗工顔料由来の無機成分の割合が非常に高い場合が多い。 In the manufacturing process of coated paper, damaged paper is always generated when the paper is cut or finished. The waste paper is roughly disaggregated by a pulper or the like, further disaggregated by a broke disintegrator / broke beater, etc., and is reused as a paper raw material called broke pulp after removing coarse portions. Generally, in a factory where broke pulp is generated, about 10 to 40%, and in some cases 100% of the inorganic filler in the paper is derived from the inorganic components in the broke pulp. These inorganic components derived from broke pulp are composed of coating pigments and internal fillers in waste paper, but the proportion of inorganic components derived from coating pigments is often very high.
一方で、一般に使用される填料は塗工用顔料よりも平均粒子径が大きく、紙の不透明度などの光学品質が良好である。また、近年の省資源の観点から嵩高な紙が求められているが、この場合もある程度の大きさ（例えば2〜5μm）の粒子を用いた方がより嵩高な紙が得られる傾向にある。 On the other hand, generally used fillers have an average particle size larger than that of the coating pigment and have good optical quality such as paper opacity. In addition, a bulky paper is demanded from the viewpoint of resource saving in recent years. In this case, a bulky paper tends to be obtained by using particles of a certain size (for example, 2 to 5 μm).
ブロークパルプ中の塗工用顔料由来の無機成分は微細（例えば0.5〜1.0μm）なクレーや炭酸カルシウムからなるため、上記の填料に求められる良好な光学品質や紙の嵩高化への効果はほとんどない。
以上のようにブロークパルプは紙の品質の面からは使用する事は好ましくないが、ブロークパルプを廃棄すると膨大な廃棄物が発生し、また、紙資源の無駄使いにもなることから低品質でも使用しなければならないのが現状である。
Inorganic components derived from coating pigments in broke pulp are composed of fine (for example, 0.5 to 1.0 μm) clay and calcium carbonate, so there is little effect on the good optical quality required for the above fillers and the bulk of paper. Absent.
As mentioned above, it is not preferable to use broke pulp from the viewpoint of paper quality. However, disposal of broke pulp generates enormous waste and waste of paper resources. The current situation is that it must be used.
パルプ内にある炭酸カルシウムを再利用する技術としては、炭酸カルシウムを含有する製紙スラッジを、成形機により成形し、この成形体をキルン等で乾燥、炭化、焼成の処理をした焼却灰を、粉砕して高品質な製紙用填料を得る方法が開示されている。（特許文献１参照）このように、焼却灰から炭酸カルシウムを回収して填料として利用する技術は、他にもあり、従来から存在していたが、ブロークパルプ中に存在する炭酸カルシウムを直接、改質して高品質な填料にして利用する技術はなかった。 The technology for reusing calcium carbonate in pulp is to form paper sludge containing calcium carbonate with a molding machine, and then pulverize the incinerated ash that has been dried, carbonized, and fired in a kiln. Thus, a method for obtaining a high-quality paper filler is disclosed. (See Patent Document 1) Thus, there are other techniques for recovering calcium carbonate from incinerated ash and using it as a filler, which has existed in the past, but directly the calcium carbonate present in the broke pulp, There was no technology to modify and use it as a high quality filler.
また、パルプと炭酸カルシウムを含有するコートブロークに、炭酸カルシウムからのCa2+の溶出を抑えるために炭酸ガスを吹き込むことは開示されている。（特許文献２参照）
しかしながら、パルプと炭酸カルシウムを含有する無機物の混合物からなるスラリーに二酸化炭素を含有するガスを吹き込むことで該無機物を該スラリーへ溶解させ、さらに該無機物を該スラリーに析出させることからなる、ブロークパルプ中の炭酸カルシウムを含有する無機物を改質する方法は開示されていない。
However, the broke pulp which consists of melt | dissolving this inorganic substance in this slurry by blowing the gas containing a carbon dioxide into the slurry which consists of a mixture of an inorganic substance containing a pulp and calcium carbonate, and also depositing this inorganic substance in this slurry. A method for modifying the inorganic substance containing calcium carbonate therein is not disclosed.
以上のような状況に鑑み、塗工紙の製造工程において紙切れ時や仕上げ時等に発生するブロークパルプ中の無機成分、特に炭酸カルシウムを改質して高品質な填料にし、抄紙工程の紙原料へ利用することで、不透明度などの光学品質が良好で、嵩高な紙を製造することを本発明の課題とした。 In view of the situation as described above, the inorganic component in broke pulp, especially calcium carbonate, which is generated when the paper is cut or finished in the coated paper manufacturing process, is modified into a high-quality filler to make paper raw materials for the papermaking process. It was an object of the present invention to produce a bulky paper having good optical qualities such as opacity by being used.
これまでブロークパルプ中の無機成分の改質方法として公知の技術等を調査してきたが、ほとんどそれらに対する研究がなされていない。本発明者らはブロークパルプの中に炭酸カルシウムが多量に含まれており、この炭酸カルシウムが酸性では溶解し、中性・アルカリ性では析出しやすい特徴に着目した。ブロークパルプのスラリーのｐHを酸性にし、ブロークパルプ中の微細な炭酸カルシウムを一部溶解させた後、ブロークパルプのスラリーのｐHを中性以上にすることで目的とする大きさ・形態の粒子に再度、析出させることが可能であることを見出し、この知見に基づいて本発明をなすに至った。 So far, a known technique or the like has been investigated as a method for modifying inorganic components in broke pulp, but little research has been done on them. The present inventors paid attention to the feature that broke pulp contains a large amount of calcium carbonate, and this calcium carbonate dissolves when acidic, and easily precipitates when neutral and alkaline. After making the pH of the broke pulp slurry acidic and dissolving some of the fine calcium carbonate in the broke pulp, the pH of the broke pulp slurry is made neutral or higher to obtain particles of the desired size and form. Again, it was found that it was possible to cause precipitation, and the present invention was made based on this finding.
本発明によりブロークパルプ中の微細な不定形の炭酸カルシウムを粒子径・形態を制御した高品質炭酸カルシウムに容易に再生することができ、これを中性抄紙における紙原料に用いることで不透明度などの光学品質が良好で、かつ嵩高な紙が製造できる。 According to the present invention, fine amorphous calcium carbonate in broke pulp can be easily regenerated into high-quality calcium carbonate with controlled particle size and form, and this can be used as a raw material for paper in neutral papermaking. This makes it possible to produce a paper that has good optical quality and is bulky.
二酸化炭素を含有するガスをブロークパルプのスラリーに導入する場合、二酸化炭素の水への溶解度が限定されるため、スラリーのpHは6前後までしか低下しない。そのため溶解できる炭酸カルシウム量は少なく、二酸化炭素を含有するガスを導入している間は炭酸カルシウムの飽和濃度となっている。しかし、この飽和濃度において炭酸カルシウムは水中への溶解と炭酸カルシウム粒子上への析出を繰り返しており、より小さい粒子は比表面積が大きいため大きい粒子より溶解しやすく、より大きい粒子は比表面積が小さいため溶解しにくい。一方で既に炭酸カルシウムが存在している状況では、炭酸カルシウムの微粒子が生成しにくいため、析出はより大きい粒子の方が起こりやすくなる。そのため、塗工用顔料由来の無機成分である微細な炭酸カルシウムでも粒子径を大きくし、高品質な填料として再利用することができる。 When a gas containing carbon dioxide is introduced into a broke pulp slurry, the solubility of carbon dioxide in water is limited, so the pH of the slurry is only reduced to around 6. Therefore, the amount of calcium carbonate that can be dissolved is small, and the saturated concentration of calcium carbonate is obtained while the gas containing carbon dioxide is introduced. However, at this saturation concentration, calcium carbonate repeatedly dissolves in water and precipitates on the calcium carbonate particles. Smaller particles are easier to dissolve than larger particles because of their larger specific surface area, while larger particles have a smaller specific surface area. Therefore, it is difficult to dissolve. On the other hand, in a situation where calcium carbonate already exists, fine particles of calcium carbonate are less likely to be formed, and thus precipitation is more likely to occur with larger particles. Therefore, even fine calcium carbonate that is an inorganic component derived from the coating pigment can be reused as a high-quality filler by increasing the particle diameter.
本発明のブロークパルプは、塗工紙の製造工程において紙切れ時や仕上げ時に発生する損紙が、パルパー等で粗離解された後、さらにブローク離解機やブローク叩解機等で離解され、粗大部分を除いた後のブロークパルプのことである。 In the broke pulp of the present invention, in the coated paper manufacturing process, after the paper breakage or finishing, the broken paper is roughly disaggregated with a pulper, etc., and further disaggregated with a broke disintegrator or broke beater, etc. It is the broke pulp after removing.
本発明では、パルプと無機物の混合スラリーの濃度が0.01〜10重量％、好ましくは、0.１〜3重量％に調製されたブロークパルプスラリーに二酸化炭素を含有するガスを吹き込むことにより、スラリーのｐHを酸性にしてブロークパルプ中の炭酸カルシウムを一部、溶解させる。 In the present invention, the concentration of the mixed slurry of pulp and inorganic matter is 0.01 to 10% by weight, preferably 0.1 to 3% by weight, by blowing a gas containing carbon dioxide into the broke pulp slurry prepared, Acidify the pH to dissolve some of the calcium carbonate in the broke pulp.
ここでいう無機物とは、ブロークパルプ中の塗工顔料、内添填料由来の無機物であり、炭酸カルシウムの他に、カオリン、二酸化チタン、タルク、硫酸カルシウム、サチンホワイト等がある。ブロークパルプスラリー濃度が0.01重量％未満ではブロークパルプスラリー量が多くなりすぎるため、効率的な処理ができない。また、10重量％より高くなるとスラリー自体の流動性がなくなり、二酸化炭素を含有するガスが拡散しづらく、炭酸カルシウムの溶解が効率的にできない。 The term “inorganic material” as used herein refers to an inorganic material derived from a coating pigment in broke pulp and an internal filler. Examples of the inorganic material include kaolin, titanium dioxide, talc, calcium sulfate, and satin white in addition to calcium carbonate. If the broke pulp slurry concentration is less than 0.01% by weight, the amount of the broke pulp slurry becomes too large, so that efficient treatment cannot be performed. On the other hand, if it is higher than 10% by weight, the fluidity of the slurry itself is lost, the gas containing carbon dioxide is difficult to diffuse, and the calcium carbonate cannot be dissolved efficiently.
また、本技術はブロークパルプ中の炭酸カルシウムを改質することを目的としているため、ブロークパルプ中には炭酸カルシウムが含まれていることが必須である。ブロークパルプ中の炭酸カルシウム量は特に規定するものではないが、ブロークパルプ中の５重量％以上、好ましくは10重量％以上であることが好ましい。5重量％未満であると改質できる炭酸カルシウム量が少なく、光学品質、紙の嵩高化への効果が小さい場合がある。 Moreover, since this technique aims at modifying the calcium carbonate in the broke pulp, it is essential that the calcium carbonate is contained in the broke pulp. The amount of calcium carbonate in the broke pulp is not particularly specified, but it is preferably 5% by weight or more, preferably 10% by weight or more in the broke pulp. When the amount is less than 5% by weight, the amount of calcium carbonate that can be modified is small, and the optical quality and the effect of increasing the bulk of the paper may be small.
ブロークパルプスラリーに吹き込む二酸化炭素ガス濃度は1体積％以上、好ましくは５体積％以上であることが好ましい。１体積％未満では酸性側にするのに時間がかかりすぎるため効率的ではない。また、高純度な工業用炭酸ガスを使用することも可能であるので二酸化炭素ガス濃度の上限はない。二酸化炭素を含有するガスはどのような組成のガスでも構わないが、紙パルプ工場であれば、一般的なキルン、ボイラーで発生する排ガスが使用可能である。また、ブロークパルプのスラリーのpHを酸性にするためには二酸化炭素を含有するガス以外にも酸性を有する薬品も使用可能である。例えば、硫酸、塩酸、硝酸、硫酸バンドがある。 The carbon dioxide gas concentration blown into the broke pulp slurry is preferably 1% by volume or more, and preferably 5% by volume or more. If it is less than 1% by volume, it takes too much time to make it acidic, which is not efficient. Further, since it is possible to use high-purity industrial carbon dioxide, there is no upper limit of the carbon dioxide gas concentration. The gas containing carbon dioxide may have any composition, but in the case of a paper pulp factory, exhaust gas generated in a general kiln or boiler can be used. Further, in order to make the pH of the broke pulp slurry acidic, chemicals having acidity can be used in addition to the gas containing carbon dioxide. For example, there are sulfuric acid, hydrochloric acid, nitric acid, and sulfuric acid bands.
ブロークパルプスラリーに二酸化炭素を含むガスを導入する時間は処理後のブロークパルプの品質によって変更する必要があるが、短くともブロークパルプスラリーのｐHを6.5未満にできる時間は必要である。また、一般的にブロークパルプ中に塗工顔料が多く含まれている場合は二酸化炭素を含有するガスの導入時間は長い方が好ましい。 The time for introducing the carbon dioxide-containing gas into the broke pulp slurry needs to be changed depending on the quality of the broke pulp after the treatment, but at least it is necessary to have a time during which the pH of the broke pulp slurry can be made less than 6.5. In general, when a lot of coating pigment is contained in the broke pulp, it is preferable that the introduction time of the gas containing carbon dioxide is long.
ブロークパルプスラリーに二酸化炭素を含むガスを導入する際のブロークパルプスラリー温度は5℃〜90℃、好ましくは20〜50℃である必要がある。二酸化炭素の水への溶解度は温度が低い方が大きくなるため、炭酸カルシウムの溶解を促進させるためには低温の方が好ましいが、5℃未満にするためには冷却が必要となるため、経済的ではない。また90℃よりも高くするためには加熱させる必要があるため、経済的ではない。 The temperature of the broke pulp slurry when introducing the gas containing carbon dioxide into the broke pulp slurry needs to be 5 ° C to 90 ° C, preferably 20 to 50 ° C. Since the solubility of carbon dioxide in water increases at lower temperatures, lower temperatures are preferred to promote the dissolution of calcium carbonate, but cooling is required to reduce the temperature below 5 ° C. Not right. Moreover, since it is necessary to heat in order to make it higher than 90 degreeC, it is not economical.
二酸化炭素を含有するガスをブロークパルプスラリーに一定時間導入した後は溶解した炭酸カルシウムを再度、析出させるが、これには加熱により水への二酸化炭素ガスの溶解度を低下させ、二酸化炭素ガスをスラリーから排出させて、さらにスラリーのpHを中性もしくは７以上にすることが好ましい。ここでの加熱時間は特に規定するものではない。この時、短時間で炭酸カルシウムを析出させるためにはアルカリ性の薬品を使用することも可能である。なお、炭酸カルシウムを溶解させるために酸性を有する液体の薬品を用いた場合、炭酸カルシウムが分解して炭酸ガスとしてスラリーから排出してしまうため、炭酸根を含有するアルカリ性の薬品、例えば炭酸ナトリウムなどを使用し、炭酸カルシウムを析出させる必要がある。 After introducing a gas containing carbon dioxide into the broke pulp slurry for a certain period of time, the dissolved calcium carbonate is precipitated again, but this reduces the solubility of the carbon dioxide gas in water by heating, and the carbon dioxide gas is slurried. It is preferable that the pH of the slurry is neutral or 7 or more. The heating time here is not particularly specified. At this time, alkaline chemicals can be used to precipitate calcium carbonate in a short time. In addition, when an acidic liquid chemical is used to dissolve calcium carbonate, calcium carbonate is decomposed and discharged from the slurry as carbon dioxide gas. Therefore, an alkaline chemical containing carbonate radical, such as sodium carbonate, etc. To deposit calcium carbonate.
攪拌や二酸化炭素を含有するガスの導入の装置は特に規定するものではないが、より二酸化炭素がスラリーに素早く溶解できるするようにすることが好ましい。 A device for introducing a gas containing agitation or carbon dioxide is not particularly defined, but it is preferable that carbon dioxide can be quickly dissolved in the slurry.
以上のような方法によってブロークパルプ中の微細な不定形の炭酸カルシウムを粒子径・形態を制御した高品質炭酸カルシウムに容易に再生することができ、これを紙原料に用いることで不透明度などの光学品質が良好で、かつ嵩高な紙が製造できる。 By the above method, fine amorphous calcium carbonate in broke pulp can be easily regenerated into high-quality calcium carbonate with controlled particle size and morphology. Paper with good optical quality and high bulk can be produced.
以下に、本発明を実施例により詳細に説明するが、本発明はこれに限定されるものではない。
［手抄き紙の作製］
パルプ分として紙重量あたり92重量％、填料分として紙重量当り8重量％、またはパルプ分として81重量％、填料分として19重量％になるようにブロークパルプとLBKP（濾水度CSF420ml）を混合してパルプスラリーを得た。このパルプスラリーを抄紙後のシート坪量が45g/m2になるように計り取り、配向性抄紙機にて抄紙した。次に、4.18kg/cm2で5分間、さらに4.18kg/cm2で2分間プレス機によりプレス脱水し、50℃で1時間緊張乾燥して手抄き紙を作成した。得られた手抄き紙は、23℃、湿度50％の条件で1日間調湿した。
［試験法］
（１）密度：JIS P 8118に準拠した。
（２）白色度：JIS P 8143に準拠し、高速分光光度計（村上色彩技術研究所製）で測定した。
（３）不透明度：JIS P 8138に準拠し、高速分光光度計（村上色彩技術研究所製）で測定した。
［実施例１］
以下の方法で得られたブロークパルプを用い、パルプ分として紙重量あたり92重量％、填料分として紙重量当り8重量％になるように、前記［手抄き紙の作製］の方法に従って手抄き紙を作製した。
Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.
[Production of handmade paper]
Broke pulp and LBKP (freezing degree CSF 420 ml) are mixed so that the pulp content is 92% by weight per paper, the filler content is 8% by weight per paper weight, or the pulp content is 81% by weight and the filler content is 19% Thus, a pulp slurry was obtained. The pulp slurry was weighed so that the sheet basis weight after papermaking would be 45 g / m 2, and papermaking was performed with an oriented paper machine. Next, it was press-dehydrated with a press at 4.18 kg / cm 2 for 5 minutes and further at 4.18 kg / cm 2 for 2 minutes, and tension-dried at 50 ° C. for 1 hour to prepare handmade paper. The obtained handmade paper was conditioned for 1 day at 23 ° C. and 50% humidity.
[Test method]
(1) Density: Conforms to JIS P 8118.
(2) Whiteness: Measured with a high-speed spectrophotometer (Murakami Color Research Laboratory) according to JIS P 8143.
(3) Opacity: Measured with a high-speed spectrophotometer (Murakami Color Research Laboratory) in accordance with JIS P 8138.
[Example 1]
Using the broke pulp obtained by the following method, according to the method described in [Preparation of hand-made paper], the pulp content is 92% by weight per paper weight and the filler content is 8% by weight per paper weight. Paper was made.
ブロークパルプ中の全固形分に対して15重量％の炭酸カルシウムを含むブロークパルプのスラリー（濃度1重量％）1Lをセパラブルフラスコに入れ、20℃に調温した。これを300rpmの回転速度で攪拌しながら、工業用炭酸ガス（濃度99体積％）を200ml/minの流量で30分間導入した。このときのｐＨは8.0であった。導入後、スラリーを80℃で120分間保持した。最終のｐＨは7.9であった。
［実施例２］
以下の方法で得られたブロークパルプを用い、パルプ分として紙重量あたり92重量％、填料分として紙重量当り8重量％になるように、前記［手抄き紙の作製］の方法に従って手抄き紙を作製した。
1 L of a broke pulp slurry (concentration: 1 wt%) containing 15 wt% calcium carbonate based on the total solid content in the broke pulp was placed in a separable flask, and the temperature was adjusted to 20 ° C. While stirring this at a rotational speed of 300 rpm, industrial carbon dioxide (concentration 99% by volume) was introduced at a flow rate of 200 ml / min for 30 minutes. The pH at this time was 8.0. After introduction, the slurry was held at 80 ° C. for 120 minutes. The final pH was 7.9.
[Example 2]
Using the broke pulp obtained by the following method, according to the method described in [Preparation of hand-made paper], the pulp content is 92% by weight per paper weight and the filler content is 8% by weight per paper weight. Paper was made.
ブロークパルプ中の全固形分に対して15重量％の炭酸カルシウムを含むブロークパルプのスラリー（濃度1重量％）1Lをセパラブルフラスコに入れ、20℃に調温した。これを300rpmの回転速度で攪拌しながら、工業用炭酸ガス（濃度99体積％）を200ml/minの流量で30分間導入した。このときのｐＨは8.0であった。導入後、スラリーを９0℃で３0分間保持した。最終のｐＨは7.0であった。
［実施例３］
以下の方法で得られたブロークパルプを用い、パルプ分として紙重量あたり81重量％、填料分として紙重量当り19重量％になるように、前記［手抄き紙の作製］の方法に従って手抄き紙を作製した。
1 L of a broke pulp slurry (concentration: 1 wt%) containing 15 wt% calcium carbonate based on the total solid content in the broke pulp was placed in a separable flask, and the temperature was adjusted to 20 ° C. While stirring this at a rotational speed of 300 rpm, industrial carbon dioxide (concentration 99% by volume) was introduced at a flow rate of 200 ml / min for 30 minutes. The pH at this time was 8.0. After introduction, the slurry was held at 90 ° C. for 30 minutes. The final pH was 7.0.
[Example 3]
Using the broke pulp obtained by the following method, it was hand-drawn according to the method of [Preparation of hand-made paper] so that the pulp content was 81% by weight per paper weight and the filler content was 19% by weight per paper weight. Paper was made.
ブロークパルプ中の全固形分に対して20重量％の炭酸カルシウムを含むブロークパルプのスラリー（濃度1重量％）1Lをセパラブルフラスコに入れ、40℃に調温した。これを300rpmの回転速度で攪拌しながら、工業用炭酸ガス（濃度99体積％）を200ml/minの流量で30分間導入した。このときのｐＨは8.1であった。導入後、スラリーを９0℃で３0分間保持した。最終のｐＨは7.1であった。
［比較例１］
ブロークパルプ中の全固形分に対して15重量％の炭酸カルシウムを含むブロークパルプを使用して、パルプ分として紙重量あたり92重量％、填料分として紙重量当り8重量％になるように、前記［手抄き紙の作製］の方法に従って手抄き紙を作製した。
［比較例２］
ブロークパルプ中の全固形分に対して20重量％の炭酸カルシウムを含むブロークパルプを使用して、パルプ分として紙重量あたり81重量％、填料分として紙重量当り19重量％になるように、前記［手抄き紙の作製］の方法に従って手抄き紙を作製した。
1 L of a broke pulp slurry (concentration: 1 wt%) containing 20 wt% calcium carbonate based on the total solid content in the broke pulp was placed in a separable flask, and the temperature was adjusted to 40 ° C. While stirring this at a rotational speed of 300 rpm, industrial carbon dioxide (concentration 99% by volume) was introduced at a flow rate of 200 ml / min for 30 minutes. The pH at this time was 8.1. After introduction, the slurry was held at 90 ° C. for 30 minutes. The final pH was 7.1.
[Comparative Example 1]
Using broke pulp containing 15 wt% calcium carbonate with respect to the total solid content in the broke pulp, the pulp content is 92 wt% per paper weight and the filler content is 8 wt% per paper weight. Hand-made paper was prepared according to the method of [Preparation of hand-made paper].
[Comparative Example 2]
Using broke pulp containing 20% by weight calcium carbonate based on the total solid content in the broke pulp, the pulp content is 81% by weight per paper weight and the filler content is 19% by weight per paper weight. Hand-made paper was prepared according to the method of [Preparation of hand-made paper].
表１の実施例１〜3に示す如く、本発明によってブロークパルプ中の炭酸カルシウムを改質でき、これを用いて手抄きシートを調製すると、未処理のものと比べて密度を低下させることができ、不透明度の光学品質も良好にすることができた。 As shown in Examples 1 to 3 in Table 1, when calcium carbonate in broke pulp can be modified according to the present invention and a handsheet is prepared using this, the density is reduced as compared with untreated ones. The optical quality of opacity could be improved.
Claims (4)
該スラリーに二酸化炭素を含有するガスを吹き込むことで該無機物を該スラリーへ溶解させる工程、
該無機物を該スラリーに析出させる工程、
を含む、ブロークパルプ中の炭酸カルシウムを含有する無機物を改質する方法。 From the mashing been Burokuparupu obtained from waste paper generated in the production of coated paper, the step of Luz rally concentrations of a mixture of inorganic substances containing pulp and calcium carbonate to prepare a 0.01 to 3% by weight of the slurry ,
Step Ru dissolving the inorganic to the slurry by blowing a gas containing carbon dioxide into the slurry,
Depositing the inorganic substance into the slurry ;
The method comprising, modifying the inorganic substance containing calcium carbonate in Burokuparupu a.
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