JP6298788B2 - Patterned paper manufacturing method - Google Patents
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- JP6298788B2 JP6298788B2 JP2015048783A JP2015048783A JP6298788B2 JP 6298788 B2 JP6298788 B2 JP 6298788B2 JP 2015048783 A JP2015048783 A JP 2015048783A JP 2015048783 A JP2015048783 A JP 2015048783A JP 6298788 B2 JP6298788 B2 JP 6298788B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 239000013055 pulp slurry Substances 0.000 claims description 54
- 230000015572 biosynthetic process Effects 0.000 claims description 40
- 229920002401 polyacrylamide Polymers 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims 1
- 238000007710 freezing Methods 0.000 claims 1
- 239000000123 paper Substances 0.000 description 140
- 238000000034 method Methods 0.000 description 21
- 229920001131 Pulp (paper) Polymers 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 125000000129 anionic group Chemical group 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004513 sizing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 7
- 239000013054 paper strength agent Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000001771 impaired effect Effects 0.000 description 5
- 239000010893 paper waste Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 239000011121 hardwood Substances 0.000 description 4
- 239000002655 kraft paper Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000011122 softwood Substances 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- 240000000907 Musa textilis Species 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000004931 aggregating effect Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 244000144992 flock Species 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
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Description
本発明は模様紙の製造方法に関し、更に詳しくは、多層抄き紙における最表層となる層の地合を調整することにより模様を形成した模様紙の製造方法に関するものである。 The present invention relates to a pattern paper manufacturing method, and more particularly, to a pattern paper manufacturing method in which a pattern is formed by adjusting the formation of the outermost layer of a multilayer paper.
模様紙は意匠性の高い紙で、カード用紙、ダイレクトメールなどの印刷用紙や、包装・ラベル用紙などに用いられ様々な種類の紙が上市されている。例えば、レーヨン繊維と木材繊維を混在させて作られる大礼紙、雲龍紙と呼ばれる模様加工紙（特許文献１）、全幹ケナフパルプと木材パルプとを組み合わせ、エンボス処理を行い、和紙と同様の風合いを持たせたエンボス模様紙（特許文献２）、最外層となる層にフロックを形成させた模様形成体が抄き込まれた模様紙（特許文献３）、各種植物の茎、葉、種実、殻、皮、繊維などを添加した模様紙（特許文献４）などがある。 Pattern paper is highly designed paper, and various types of paper are marketed for printing paper such as card paper and direct mail, and packaging and label paper. For example, Daisen paper made by mixing rayon fiber and wood fiber, patterned processed paper called Yunlong paper (Patent Document 1), combining main stem kenaf pulp and wood pulp, embossing, and giving the same texture as Japanese paper Embossed pattern paper (Patent Document 2), Pattern paper (Patent Document 3) in which a pattern forming body in which flocks are formed in the outermost layer (Patent Document 3), stems, leaves, seeds, shells of various plants In addition, there is a pattern paper (Patent Document 4) to which leather, fibers and the like are added.
しかしながら、特許文献１に開示された模様加工紙は、レーヨン繊維を使用するために製造コストが割高となる。また、特許文献２に開示されたエンボス模様紙を製造するには、エンボス処理を行うための設備が必要であり、さらに得られる模様も規則的な固定された模様となる。また、特許文献３に開示された模様紙においては、フロックを形成させるための手段が煩雑となる。さらに、特許文献４に開示された模様紙は茎、葉、種実、殻、皮、繊維などの粉砕に手間がかかり、その収集も容易ではないことが多く、大量生産には適さないという問題があった。 However, since the patterned paper disclosed in Patent Document 1 uses rayon fibers, the manufacturing cost is high. Moreover, in order to manufacture the embossed pattern paper disclosed by patent document 2, the equipment for performing an embossing process is required, and also the pattern obtained becomes a regular fixed pattern. Further, in the pattern paper disclosed in Patent Document 3, the means for forming a flock becomes complicated. Furthermore, the pattern paper disclosed in Patent Document 4 is troublesome to grind stems, leaves, seeds, shells, skins, fibers, and the like, and is often not easy to collect and is not suitable for mass production. there were.
このような問題を鑑み、本発明の目的は、パルプを主体とし、模様を形成するための特別な材料を用いず、生産性の良い模様紙の製造方法を提供することにある。 In view of such a problem, an object of the present invention is to provide a method for producing a pattern paper having good productivity without using a special material mainly for forming a pattern.
本発明の模様紙の製造方法は、ｐＨ５．０〜７．０に調整したパルプスラリーに、パルプの固形分に対してポリアルクリアミド系樹脂を０．０８〜１．０質量％添加してパルプを凝集処理して凝集パルプスラリーとし、該凝集パルプスラリーを少なくとも一方の最外層となる紙層用の紙料として多層抄きで抄紙を行い、該凝集パルプスラリーを用いて抄紙した紙層の地合指数を０．７以上とすることを特徴とする。 In the method for producing the patterned paper of the present invention, 0.08 to 1.0% by mass of a polyacrylamide resin is added to the pulp slurry adjusted to pH 5.0 to 7.0 with respect to the solid content of the pulp. The pulp is agglomerated to form an agglomerated pulp slurry, and the agglomerated pulp slurry is used as a paper material for a paper layer that is at least one of the outermost layers. The formation index is 0.7 or more.
また、本発明においては、前記パルプスラリー含まれるパルプの２８質量％以上がＮＢＫＰであることが好ましい。 Moreover, in this invention, it is preferable that 28 mass% or more of the pulp contained in the said pulp slurry is NBKP.
また、本発明においては、前記パルプスラリーの濾水度（ＣＳＦ）が４８０〜７７０ｍｌであることが好ましい。また、本発明においては、前記ポリアクリルアミド系樹脂の重量平均分子量が１０００万以上であることが好ましい。また、本発明においては、前記紙料の凝集パルプスラリーの濃度が０．０５〜０．２５質量％であることが好ましい。 Moreover, in this invention, it is preferable that the freeness (CSF) of the said pulp slurry is 480-770 ml. In the present invention, the polyacrylamide resin preferably has a weight average molecular weight of 10 million or more. Moreover, in this invention, it is preferable that the density | concentration of the aggregate pulp slurry of the said stock is 0.05-0.25 mass%.
さらに、本発明は、上記製造方法により製造された該凝集パルプスラリーを用いて抄紙した紙層の地合指数が０．７以上２．０以下である模様紙に関する。 Furthermore, this invention relates to the pattern paper whose formation index of the paper layer paper-made using this aggregated pulp slurry manufactured by the said manufacturing method is 0.7-2.0.
本発明によれば、地合を模様として認識できる模様紙を製造することができ、さらに、模様を形成するための特別な材料を用いず、模様紙を低コストで効率よく生産することができる。本発明の方法は、特に模様紙の大量生産に適している。 According to the present invention, it is possible to produce a pattern paper that can recognize the texture as a pattern, and further, it is possible to efficiently produce the pattern paper at a low cost without using a special material for forming the pattern. . The method of the present invention is particularly suitable for mass production of patterned paper.
本発明の模様紙の製造方法は、凝集パルプスラリーを最外層となる紙層用の紙料として用い、多層抄きで抄紙を行い、該凝集パルプスラリーを用いて抄紙した紙層（以下、凝集パルプ層ということがある）の地合指数を０．７以上とすることで、表面に地合模様を有する模様紙を製造するものである。すなわち、本発明の模様紙の製造方法は、多層抄き紙の最外層となる紙層の地合を、模様として認識できる程度に意図的に崩した模様紙の製造方法である。さらに、本発明は、当該製造方法により製造された模様紙に関する。 The method for producing a patterned paper of the present invention uses a coagulated pulp slurry as a paper material for a paper layer that is the outermost layer, performs paper making by multilayer paper making, and makes a paper layer (hereinafter referred to as an agglomerated paper) using the coagulated pulp slurry. A pattern paper having a formation pattern on the surface is produced by setting the formation index of the pulp layer to 0.7 or more. That is, the pattern paper manufacturing method of the present invention is a pattern paper manufacturing method in which the texture of the paper layer that is the outermost layer of the multilayer paper is intentionally broken to such an extent that it can be recognized as a pattern. Furthermore, this invention relates to the pattern paper manufactured by the said manufacturing method.
まず、凝集パルプスラリーの調製方法について説明する。最初に、水中にパルプを分散させてパルプスラリーを得る。ここでパルプスラリーに用いるパルプとしては特に限定するものではなく、針葉樹晒クラフトパルプ（ＮＢＫＰ）、針葉樹晒サルファイトパルプ（ＮＢＳＰ）、広葉樹晒クラフトパルプ（ＬＢＫＰ）、広葉樹晒サルファイトパルプ（ＬＢＳＰ）に代表される木材漂白化学パルプを使用することができる。また、必要に応じて、ＧＰ（砕木パルプ）、ＴＭＰ（サーモメカニカルパルプ）、ＢＣＴＭＰ（晒ケミサーモメカニカルパルプ）等の機械パルプや、雑誌古紙、チラシ古紙、色上古紙、新聞古紙等の古紙パルプを適宜配合することもできる。更には、本発明の目的とする効果を損なわない範囲で、木材パルプ以外に、楮や三椏、アバカ等の非木材パルプ、合成パルプ、合成繊維などを適宜配合することもできる。 First, a method for preparing the agglomerated pulp slurry will be described. First, a pulp slurry is obtained by dispersing pulp in water. Here, the pulp used for the pulp slurry is not particularly limited, and it may be softwood bleached kraft pulp (NBKP), softwood bleached sulfite pulp (NBSP), hardwood bleached kraft pulp (LBKP), or hardwood bleached sulfite pulp (LBSP). Representative wood bleached chemical pulp can be used. If necessary, waste paper pulp such as GP (crushed wood pulp), TMP (thermomechanical pulp), BCTMP (bleached chemithermomechanical pulp), etc., magazine waste paper, leaflet waste paper, colored waste paper, newspaper waste paper, etc. Can also be suitably blended. Furthermore, non-wood pulp, such as straw, trifoam, and abaca, synthetic pulp, synthetic fiber, and the like can be appropriately blended in addition to the wood pulp as long as the intended effect of the present invention is not impaired.
本発明においては、この凝集パルプスラリー用に調製するパルプスラリーに含まれるパルプの２８質量％以上をＮＢＫＰとすることが好ましい。より好ましくは３０質量％以上であり、さらに５０質量％以上９５質量％以下であり、更に好ましくは７０質量％以上である。ＮＢＫＰは比較的容易に入手することができるパルプであるが、繊維が太く長いため、後述するパルプの凝集処理を行うことで撚れたような繊維束が生じやすく、ＮＢＫＰを一定量配合することで凝集パルプ層の地合指数を高くすることが容易となる。 In the present invention, it is preferable that 28% by mass or more of the pulp contained in the pulp slurry prepared for the agglomerated pulp slurry is NBKP. More preferably, it is 30 mass% or more, Furthermore, 50 mass% or more and 95 mass% or less, More preferably, it is 70 mass% or more. NBKP is a pulp that can be obtained relatively easily. However, because the fibers are thick and long, fiber bundles that are twisted are easily produced by aggregating the pulp described later, and a certain amount of NBKP is blended. This makes it easy to increase the formation index of the aggregated pulp layer.
また、凝集パルプスラリー用に調製するパルプスラリーの濾水度（ＣＳＦ）は、４８０〜７７０ｍｌ、例えば、５００〜７５０ｍｌであることが好ましい。このような濾水度の範囲とすることでポリアクリルアミドによるパルプの凝集をより促進することができる。より好ましくは５００〜７００ｍｌ、例えば、５８０〜７００ｍｌまたは６００〜７００ｍｌである。濾水度（ＣＳＦ）が４８０ｍｌ未満では目的とする地合指数を得にくくなる。一方、で７７０ｍｌを超えると模様紙の各種強度を損ねるおそれがあり、特に凝集パルプ層の表面強度が弱くなりすぎるおそれがある。ここで、濾水度とは、ＪＩＳ Ｐ ８１２１「パルプのろ水度試験方法」に規定されるカナダ標準濾水度（ＣＳＦ）を言う。 Moreover, it is preferable that the freeness (CSF) of the pulp slurry prepared for the agglomerated pulp slurry is 480 to 770 ml, for example, 500 to 750 ml. By setting the freeness within such a range, aggregation of pulp by polyacrylamide can be further promoted. More preferably, it is 500-700 ml, for example, 580-700 ml or 600-700 ml. If the freeness (CSF) is less than 480 ml, it is difficult to obtain the desired formation index. On the other hand, if it exceeds 770 ml, the various strengths of the pattern paper may be impaired, and particularly the surface strength of the aggregated pulp layer may be too weak. Here, the freeness refers to the Canadian standard freeness (CSF) defined in JIS P 8121 “Pulp Freeness Test Method”.
次に、凝集パルプスラリー用に調製するパルプスラリーをｐＨ５．０〜７．０に調整する。ｐＨとは水素イオン指数である。パルプスラリーをｐＨ５．０〜７．０に調整する方法については特に限定するものではないが、抄紙薬品として慣用されている硫酸バンドを適宜添加して調整することが望ましい。重曹や水酸化ナトリウム等のアルカリ性の薬品を添加して調整することもできる。硫酸バンド、重曹や水酸化ナトリウム等は、所望するｐＨに合わせて適宜添加すればよい。好ましくはｐＨ５．５〜６．８であり、更に好ましくはｐＨ５．９〜６．６である。パルプスラリーをｐＨ５．０〜７．０に調整することで後述するポリアクリルアミド系樹脂によるパルプの凝集処理を効率よく行うことができる。しかしながら、ｐＨ５．０未満又はｐＨ７．０を超えると凝集処理を効率よく行うことができず、本発明に必要な範囲の地合指数を達成することが困難となる。 Next, the pulp slurry prepared for the agglomerated pulp slurry is adjusted to pH 5.0 to 7.0. pH is the hydrogen ion index. The method of adjusting the pulp slurry to pH 5.0 to 7.0 is not particularly limited, but it is desirable to adjust by appropriately adding a sulfuric acid band commonly used as a papermaking chemical. It can also be adjusted by adding an alkaline chemical such as sodium bicarbonate or sodium hydroxide. A sulfuric acid band, sodium bicarbonate, sodium hydroxide, and the like may be appropriately added in accordance with a desired pH. Preferably it is pH 5.5-6.8, More preferably, it is pH 5.9-6.6. By adjusting the pulp slurry to pH 5.0 to 7.0, pulp agglomeration treatment with a polyacrylamide resin described later can be performed efficiently. However, if the pH is less than 5.0 or exceeds 7.0, the aggregation treatment cannot be performed efficiently, and it is difficult to achieve the formation index within the range necessary for the present invention.
次に、このｐＨ５．０〜７．０に調整したパルプスラリーにポリアクリルアミド系樹脂をパルプスラリー中のパルプ（固形分）に対して０．０８〜１．０質量％添加してパルプを凝集処理し、凝集パルプスラリーを得る。ポリアクリルアミド系樹脂の添加量が０．０８質量％未満ではパルプの凝集が弱く、模様を形成するに適した凝集パルプスラリーが得られない。逆に１．０質量％を超えると抄紙系で工程汚れが発生するなど抄紙の操業性が悪くなり、また、模様紙に異物が混入しやすくなる。ポリアクリルアミド系樹脂の添加量は、好ましくは０．２〜０．９質量％であり、更に好ましくは０．４〜０．８質量％である。 Next, 0.08 to 1.0 mass% of polyacrylamide resin is added to the pulp slurry adjusted to pH 5.0 to 7.0 with respect to the pulp (solid content) in the pulp slurry, and the pulp is agglomerated. To obtain an agglomerated pulp slurry. When the addition amount of the polyacrylamide resin is less than 0.08% by mass, the aggregation of the pulp is weak, and an agglomerated pulp slurry suitable for forming a pattern cannot be obtained. On the other hand, if it exceeds 1.0% by mass, the operability of papermaking deteriorates because process stains occur in the papermaking system, and foreign matters are likely to be mixed into the pattern paper. The addition amount of the polyacrylamide resin is preferably 0.2 to 0.9 mass%, more preferably 0.4 to 0.8 mass%.
ここで、パルプの凝集処理に用いるポリアクリルアミド系樹脂としては、分子量の大きいものほど凝集能が高くなる傾向にあるため、重量平均分子量が１０００万以上であることが好ましい。より好ましくは重量平均分子量が１２００万以上である。凝集能の観点からは上限は特にないが、分子量が高くなりすぎると、抄紙において工程汚れが発生するなど抄紙の操業性が悪くなり、また、模様紙に異物が混入しやすくなる可能性があるため、重量平均分子量は１６００万未満とすることが好ましい。 Here, as the polyacrylamide resin used for the pulp agglomeration treatment, the higher the molecular weight, the higher the aggregating ability. Therefore, the weight average molecular weight is preferably 10 million or more. More preferably, the weight average molecular weight is 12 million or more. There is no particular upper limit from the viewpoint of agglomeration ability. However, if the molecular weight is too high, process operability of papermaking deteriorates due to process contamination in papermaking, and foreign matter may be easily mixed into the pattern paper. For this reason, the weight average molecular weight is preferably less than 16 million.
このようにして得た凝集パルプスラリーには、本発明の目的とする効果を損ねない範囲で、各種公知の製紙用薬品を含有させてもよい。製紙用薬品としては、サイズ剤、紙力剤、分散助剤、歩留向上剤、填料、染料、顔料、蛍光増白剤などが挙げられる。 The coagulated pulp slurry thus obtained may contain various known papermaking chemicals as long as the effects of the present invention are not impaired. Examples of papermaking chemicals include sizing agents, paper strength agents, dispersion aids, yield improvers, fillers, dyes, pigments, and fluorescent whitening agents.
例えば、サイズ剤として、ロジン系エマルジョンサイズ剤をパルプスラリー中のパルプ（固形分）に対して０．０５〜０．５質量部添加すればよく、例えば、紙力剤として、グラフト化澱粉をパルプスラリー中のパルプ（固形分）に対して０．０５〜１．５質量部添加すればよい。 For example, as a sizing agent, a rosin-based emulsion sizing agent may be added in an amount of 0.05 to 0.5 parts by mass based on the pulp (solid content) in the pulp slurry. For example, grafted starch is pulped as a paper strength agent. What is necessary is just to add 0.05-1.5 mass parts with respect to the pulp (solid content) in a slurry.
次に、多層抄きでの抄紙について説明する。本発明では、前述のようにして得た凝集パルプスラリーを、少なくとも一方の最外層となる紙層用の紙料として用い、多層抄きで抄紙を行う。そして、凝集パルプスラリーを用いて抄紙した凝集パルプ層の地合指数を０．７以上とすることで、凝集パルプ層に模様を形成する。本発明における地合指数は、ベータ線の透過率を測定することにより得られる値である。すなわち、本発明における地合指数は、低坪量であるほどベータ線の透過率が高いことを利用することで一定の面積の坪量ムラを測定する装置を使用し、坪量規格化標準偏差を指標として算出したものである。 Next, the paper making by the multi-layer paper making will be described. In the present invention, the agglomerated pulp slurry obtained as described above is used as a paper material for a paper layer that is at least one outermost layer, and papermaking is performed by multilayer papermaking. And a pattern is formed in an aggregate pulp layer by making the formation index of the aggregate pulp layer paper-made using the aggregate pulp slurry into 0.7 or more. The formation index in the present invention is a value obtained by measuring the transmittance of beta rays. That is, the formation index in the present invention uses a device that measures the basis weight unevenness of a certain area by utilizing the fact that the lower the basis weight, the higher the transmittance of beta rays, and the basis weight standardization standard deviation. Is calculated as an index.
本発明においては、多層抄きであれば抄紙方法は特に限定するものではなく、公知の抄紙機を用いることができる。たとえば、円網式抄紙機、長網式抄紙機、ツインワイヤー抄紙機によって２層以上の多層で抄紙される。これらの抄紙機のコンビネーションでもかまわない。また、抄合わせの際には抄合わせた各紙層の層間剥離を防止するために澱粉等の紙力剤を各紙層間にスプレー塗布しても良い。凝集パルプ層同士又は凝集パルプ層と他の任意の紙層とを湿紙の状態で抄き合わせた後、プレスにて脱水し、ドライヤーで乾燥させて紙匹を得ることができる。その後、必要に応じてサイズプレス液を塗布してもよい。サイズプレス液には、表面紙力剤や表面サイズ剤などの公知の抄紙薬品を使用することができる。また、抄紙後の模様紙にはカレンダー処理を行ってもよい。本発明に係る模様紙は、凝集パルプ層の地合により模様を形成するものであり、カレンダー処理により凝集パルプ層の表面の平滑性が高くなったとしても、模様自体を損なうものではない。ただし、凝集パルプ層の平滑性を低くすることで和紙のような手触り感を与えることも可能であるため、模様紙としての風合いを考慮すると、カレンダー処理は行わないことが好ましい。和紙の風合いを考慮した場合、凝集パルプ層表面のベック平滑度を１５秒以下とすることが好ましい。 In the present invention, the paper making method is not particularly limited as long as it is a multilayer paper making, and a known paper machine can be used. For example, the paper is produced in two or more layers by a circular net paper machine, a long net paper machine, or a twin wire paper machine. A combination of these paper machines is also acceptable. Further, at the time of papermaking, a paper strength agent such as starch may be spray-coated between the paper layers in order to prevent delamination of the paper layers after the papermaking. After agglomerated pulp layers or agglomerated pulp layers and other arbitrary paper layers are made together in the state of wet paper, they are dehydrated with a press and dried with a dryer to obtain a paper web. Then, you may apply | coat a size press liquid as needed. Known paper making chemicals such as surface paper strength agents and surface sizing agents can be used for the size press liquid. Moreover, you may perform a calendar process to the pattern paper after papermaking. The pattern paper according to the present invention forms a pattern by formation of the aggregated pulp layer, and even if the smoothness of the surface of the aggregated pulp layer is increased by calendering, the pattern itself is not impaired. However, since it is possible to give a hand feeling like Japanese paper by lowering the smoothness of the agglomerated pulp layer, it is preferable not to perform the calendar process in consideration of the texture as a pattern paper. In consideration of the texture of Japanese paper, the Beck smoothness on the surface of the aggregated pulp layer is preferably 15 seconds or less.
凝集パルプ層以外の層に用いる抄紙原料は、特に限定するものではなく、本発明の目的とする効果を損なわない範囲で、多層紙で用いられる各種公知の紙層用の抄紙原料を用いることができる。本発明の模様紙において、凝集パルプ層以外の層に用いるパルプとしては、特に限定はないが、例えば、針葉樹晒クラフトパルプ（ＮＢＫＰ）、針葉樹晒サルファイトパルプ（ＮＢＳＰ）、広葉樹晒クラフトパルプ（ＬＢＫＰ）、広葉樹晒サルファイトパルプ（ＬＢＳＰ）に代表される木材漂白化学パルプを使用することができる。また、必要に応じて、ＧＰ（砕木パルプ）、ＴＭＰ（サーモメカニカルパルプ）、ＢＣＴＭＰ（晒ケミサーモメカニカルパルプ）等の機械パルプや古紙パルプを適宜配合することもできる。更には、木材パルプ以外に、楮や三椏、アバカ等の非木材パルプ、合成パルプ、合成繊維などを適宜配合することもできる。パルプの濾水度は特に限定するものではないが、カナダ標準濾水度（フリーネス）で、４５０〜７００ｍｌＣＳＦとすることが好ましい。 The papermaking raw material used for layers other than the agglomerated pulp layer is not particularly limited, and various known papermaking raw materials for paper layers used in multilayer paper may be used as long as the intended effects of the present invention are not impaired. it can. In the pattern paper of the present invention, the pulp used for layers other than the agglomerated pulp layer is not particularly limited. For example, softwood bleached kraft pulp (NBKP), softwood bleached sulfite pulp (NBSP), hardwood bleached kraft pulp (LBKP) ), Wood bleached chemical pulp represented by hardwood bleached sulfite pulp (LBSP) can be used. If necessary, mechanical pulp such as GP (crushed wood pulp), TMP (thermomechanical pulp), BCTMP (bleached chemothermomechanical pulp), or used paper pulp can be appropriately blended. Furthermore, in addition to wood pulp, non-wood pulp such as cocoons, cocoons, and abaca, synthetic pulp, synthetic fibers, and the like can be appropriately blended. The freeness of the pulp is not particularly limited, but it is preferably a Canadian standard freeness (freeness) of 450 to 700 ml CSF.
本発明の模様紙においては、凝集パルプ層の地合指数を０．７以上とする。地合指数が０．７未満であると、凝集パルプ層の地合を模様としての認識することが困難となる。地合指数が大きいほど凝集パルプ層の地合を模様として認識しやすくなる。地合指数は０．９以上が好ましく、１．０以上がより好ましい。地合指数の上限は特に設けるものではないが、２．０を超えると極端に地合の悪い紙層となることから、抄紙過程における紙切れが生じやすくなり、操業上で問題が生じるおそれがあるため、地合指数は２．０以下とすることが好ましい。 In the patterned paper of the present invention, the formation index of the aggregated pulp layer is 0.7 or more. If the formation index is less than 0.7, it is difficult to recognize the formation of the aggregated pulp layer as a pattern. The larger the formation index, the easier it is to recognize the formation of the aggregated pulp layer as a pattern. The formation index is preferably 0.9 or more, and more preferably 1.0 or more. The upper limit of the formation index is not particularly set, but if it exceeds 2.0, the paper layer becomes extremely unfavorable, so paper breakage is likely to occur in the paper making process, which may cause problems in operation. Therefore, the formation index is preferably set to 2.0 or less.
凝集パルプ層の地合指数のコントロール方法としては、前述した凝集パルプスラリーの調製方法により行うほか、一般的な抄紙条件としての地合を崩す方法を用いることができる。例えば、抄紙機のプレスパートで使用するフェルトとして表面が比較的粗いものを用いたり、ワイヤーパート上の原料上にシャワー水を噴霧して地合を崩す方法が挙げられる。また、円網抄紙機を用いて抄紙する場合は、円網バット内外のヘッド差（円網バット内外の液面の高低差）を小さくする方法もある。このヘッド差を小さくする具体的方法としては、例えば、バット内に添加する粘剤（ポリアクリルアミド樹脂やポリエチレンオキサイド樹脂など）を減量する方法がある。 As a method for controlling the formation index of the agglomerated pulp layer, in addition to the above-described method for preparing the agglomerated pulp slurry, a method for breaking the formation as a general papermaking condition can be used. For example, a felt having a relatively rough surface as a felt used in a press part of a paper machine, or a method in which shower water is sprayed on a raw material on a wire part to collapse the formation can be mentioned. In addition, when making paper using a circular paper machine, there is a method of reducing the head difference between the inside and outside of the net bat (the difference in height between the liquid level inside and outside the net bat). As a specific method of reducing the head difference, for example, there is a method of reducing the amount of a sticking agent (polyacrylamide resin, polyethylene oxide resin, etc.) added to the bat.
また、本発明においては、凝集パルプ層に用いる紙料の凝集パルプスラリーの濃度を０．０５〜０．２５質量％に調整して抄紙することで地合指数を向上させながら（地合を崩しながら）、抄紙操業性のよい紙層を形成することができる。紙料の当該濃度が０．０５質量％未満では地合指数の向上効果に乏しく、逆に０．２５質量％を超えると紙層の形成が難しくなり、抄紙操業性を悪化させるおそれがある。 In the present invention, the paper is made by adjusting the concentration of the aggregate pulp slurry of the stock used for the aggregate pulp layer to 0.05 to 0.25% by mass while improving the formation index (disintegrating the formation). However, a paper layer with good papermaking operability can be formed. If the concentration of the stock is less than 0.05% by mass, the effect of improving the formation index is poor. Conversely, if it exceeds 0.25% by mass, it is difficult to form a paper layer, which may deteriorate papermaking operability.
本発明に係る模様紙は、２層以上の多層構造である。例えば、２層構造であれば、両方の紙層が凝集パルプ層であってもよいが、一方の紙層のみを凝集パルプ層とし、もう一方の紙層を、例えば地合の良い紙層とすることで、全体的に単に地合の悪い多層紙ではなく、凝集パルプ層側の崩れた地合を模様として引き立たせることができる。また、３層以上の構造であれば、最外層の内側に位置する少なくとも１層の層を地合の良い紙層とすることで、最外層となる少なくとも一方の層の凝集パルプ層の崩れた地合を模様として引き立たせることができる。更には、凝集パルプ層は、その地合が崩れていることから、紙層としての強度は高くなく、凝集パルプ層のみで模様紙を形成した場合には、模様紙全体として強度が不足するおそれがある。そこで、凝集パルプ層と組み合わせた任意の紙層に強度を付与することにより、模様紙全体としての強度を向上させることもできる。 The patterned paper according to the present invention has a multilayer structure of two or more layers. For example, in the case of a two-layer structure, both paper layers may be agglomerated pulp layers, but only one paper layer is agglomerated pulp layer, and the other paper layer is a coherent paper layer, for example. By doing so, it is possible not only to make a multilayer paper with a poor formation as a whole, but also to bring out the collapsed formation on the side of the agglomerated pulp layer as a pattern. Moreover, if it is a structure of three or more layers, at least one layer located inside the outermost layer is used as a paper layer with good formation, and the aggregated pulp layer of at least one of the outermost layers has collapsed. You can enhance the formation as a pattern. Furthermore, since the aggregated pulp layer has collapsed, the strength of the paper layer is not high, and when the pattern paper is formed only with the aggregated pulp layer, the strength of the pattern paper as a whole may be insufficient. There is. Then, the intensity | strength as the whole pattern paper can also be improved by providing intensity | strength to the arbitrary paper layers combined with the aggregation pulp layer.
また、本発明に係る模様紙の模様をより引き立たせる方法として、最外層となる凝集パルプ層と、凝集パルプ層に接する任意の紙層とを異なる色彩に着色する方法がある。例えば、任意の紙層には着色染料や着色顔料を添加して有彩色に着色し、その上に最外層として着色していない又は任意の紙層とは異なる色に着色した凝集パルプ層を設けることで、凝集パルプ層の地合の崩れが模様として視認しやすくなり、模様としてより引き立たせることができる。 Further, as a method for further enhancing the pattern of the pattern paper according to the present invention, there is a method of coloring the aggregated pulp layer as the outermost layer and an arbitrary paper layer in contact with the aggregated pulp layer in different colors. For example, a colored dye or a pigment is added to an arbitrary paper layer and colored in a chromatic color, and an agglomerated pulp layer that is not colored as an outermost layer or colored differently from an arbitrary paper layer is provided thereon. Thus, the collapse of the formation of the aggregated pulp layer can be easily recognized as a pattern, and can be further enhanced as a pattern.
本発明に係る模様紙の坪量は、特に限定するものではなく、例えば５０〜２０００ｇ／ｍ２の範囲とすることができる。ただし、凝集パルプ層は地合の崩れが模様として認識しやすい坪量であることが好ましく、２０ｇ／ｍ２以上であることが好ましい。また、前述した凝集パルプ層と、凝集パルプ層に接する任意の紙層とを異なる色彩に着色して模様をより引き立たせる場合には、凝集パルプ層の坪量を大きくしすぎると模様をより引き立たせる効果に乏しくなるため、その坪量は１５０ｇ／ｍ２以下とすることが好ましい。 The basis weight of the pattern paper according to the present invention is not particularly limited, and can be, for example, in the range of 50 to 2000 g / m 2 . However, it is preferable that the aggregated pulp layer has a basis weight at which formation collapse is easily recognized as a pattern, and is preferably 20 g / m 2 or more. In addition, when the above-described aggregated pulp layer and an arbitrary paper layer in contact with the aggregated pulp layer are colored in different colors to further enhance the pattern, if the basis weight of the aggregated pulp layer is excessively increased, the pattern is further enhanced. The basis weight is preferably set to 150 g / m 2 or less, because the effect of making it becomes poor.
次に実施例を挙げて本発明を具体的に説明するが、本発明はこれらの例に限定されるものではない。また、例中の「部」、「％」は、特に断らない限りそれぞれ固形分換算での質量部又は質量％を示す。 EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these examples. Further, “parts” and “%” in the examples respectively represent parts by mass or mass% in terms of solid content unless otherwise specified.
（実施例１）
＜凝集パルプ層用の紙料の調整＞
ＮＢＫＰ７０部とＬＢＫＰ３０部からなるパルプ（フリーネス６００ｍｌＣＳＦ）を水中に分散してパルプスラリーを得た。該パルプスラリーにサイズ剤としてロジン系エマルジョンサイズ剤（商品名：ＡＬ１２００／星光ＰＭＣ社製）０．３部、紙力剤としてグラフト化澱粉（商品名：ＤＧ４２０４／星光ＰＭＣ株式会社製）１部をそれぞれ添加して撹拌し、更にｐＨ６．４となるように硫酸バンドを加えた後、重量平均分子量１２００万のアニオン性ポリアクリルアミド（商品名：ハイモロックＳＳ−１００／ハイモ社製）０．５部を添加して凝集パルプスラリーを得た。該凝集パルプスラリーの濃度を０．１５％に調整して凝集パルプ層用の紙料を得た。
＜非凝集パルプ層用の紙料の調製＞
ＮＢＫＰ（フリーネス５００ｍｌＣＳＦ）１００部を水中に分散してパルプスラリーとし、該パルプスラリーに紙力増強剤（商品名：ＤＧ４２０４／星光ＰＭＣ社製）１部と、サイズ剤（商品名：星光ＡＬ１２００／星光ＰＭＣ社製）０．３部とを添加して撹拌し、非凝集パルプ層用の紙料を得た。
＜模様紙の抄紙＞
これらの２種類の紙料を用い、円網式抄紙機にて、凝集パルプ層／非凝集パルプ層の構成となるように２層抄合わせで湿紙を抄紙し、プレスにて脱水後、乾燥させた。その後、２本ロールサイズプレスにてポリアクリルアミド紙力剤（商品名：ＳＴ５０００／星光ＰＭＣ株式会社製）８％水溶液を、用紙の両面あたり５０ｃｃ／ｍ２塗布した後、シリンダードライヤーにて乾燥し、坪量１８０ｇ／ｍ２、含有水分率７％の模様紙を得た。尚、抄紙の際の凝集パルプ層用の紙料の円網バット内外のヘッド差は２０ｍｍであった。また、各層の坪量はそれぞれ９０ｇ／ｍ２であった。
Example 1
<Adjustment of paper stock for agglomerated pulp layer>
Pulp consisting of 70 parts NBKP and 30 parts LBKP (freeness 600 ml CSF) was dispersed in water to obtain a pulp slurry. As a sizing agent, 0.3 parts of rosin emulsion sizing agent (trade name: AL1200 / manufactured by Seiko PMC) and 1 part of grafted starch (trade name: DG4204 / manufactured by Seiko PMC) as a paper strength agent are added to the pulp slurry. After adding and stirring each, and adding a sulfuric acid band so that it might become pH 6.4, 0.5 part of anionic polyacrylamide (trade name: Hymolock SS-100 / made by Hymo Co., Ltd.) having a weight average molecular weight of 12 million was added. Addition to obtain an agglomerated pulp slurry. The concentration of the aggregated pulp slurry was adjusted to 0.15% to obtain a stock for the aggregated pulp layer.
<Preparation of paper for non-aggregated pulp layer>
100 parts of NBKP (freeness 500 ml CSF) is dispersed in water to form a pulp slurry, and 1 part of a paper strength enhancer (trade name: DG4204 / manufactured by Seiko PMC) and a sizing agent (trade name: Seiko AL1200 / Starlight) PMC) 0.3 parts) was added and stirred to obtain a paper material for a non-aggregated pulp layer.
<Making paper pattern>
Using these two types of paper stock, a wet paper is made by two-layer composition so as to form an agglomerated pulp layer / non-agglomerated pulp layer with a circular net paper machine, dehydrated with a press, and dried. I let you. Then, after applying an 8% aqueous solution of polyacrylamide paper strength agent (trade name: ST5000 / manufactured by Seiko PMC Co., Ltd.) with a two roll size press, 50 cc / m 2 per both sides of the paper, and drying with a cylinder dryer, A pattern paper having a basis weight of 180 g / m 2 and a moisture content of 7% was obtained. In addition, the head difference inside and outside the circular net bat of the stock for the aggregated pulp layer at the time of papermaking was 20 mm. The basis weight of each layer was 90 g / m 2 .
（実施例２）
凝集パルプ層用の紙料の調整において、ＮＢＫＰ３０部とＬＢＫＰ７０部からなるパルプ（フリーネス６００ｍｌＣＳＦ）を用いてパルプスラリーを得た以外は実施例１と同様にして模様紙を得た。
(Example 2)
Pattern paper was obtained in the same manner as in Example 1 except that pulp slurry was obtained using pulp (freeness 600 ml CSF) consisting of 30 parts NBKP and 70 parts LBKP in the adjustment of the stock for the aggregated pulp layer.
（実施例３）
凝集パルプ層用の紙料の調整において、パルプのフリーネスを５００ｍｌＣＳＦとした以外は実施例１と同様にして模様紙を得た。
(Example 3)
Pattern paper was obtained in the same manner as in Example 1 except that the pulp freeness was changed to 500 ml CSF in the adjustment of the stock for the agglomerated pulp layer.
（実施例４）
凝集パルプ層用の紙料の調整において、パルプのフリーネスを７５０ｍｌＣＳＦとした以外は実施例１と同様にして模様紙を得た。
Example 4
Pattern paper was obtained in the same manner as in Example 1, except that the pulp freeness was changed to 750 ml CSF in the adjustment of the stock for the aggregated pulp layer.
（実施例５）
凝集パルプ層用の紙料の調整において、重量平均分子量１２００万のアニオン性ポリアクリルアミド（商品名：ハイモロックＳＳ−１００／ハイモ社製）０．５部を、重量平均分子量１０００万のアニオン性ポリアクリルアミド（商品名：ハイモロックＦＡ−２３０／ハイモ社製）０．５部に変更した以外は実施例１と同様にして模様紙を得た。
(Example 5)
In the adjustment of the stock for the agglomerated pulp layer, 0.5 part of an anionic polyacrylamide having a weight average molecular weight of 12 million (trade name: Hymolock SS-100 / manufactured by Hymo Co., Ltd.) was added to the anionic polyacrylamide having a weight average molecular weight of 10 million. (Trade name: Hymo Lock FA-230 / manufactured by Hymo Co.) A pattern paper was obtained in the same manner as in Example 1 except that the amount was changed to 0.5 part.
（実施例６）
凝集パルプ層用の紙料の調整において、重量平均分子量１２００万のアニオン性ポリアクリルアミド（商品名：ハイモロックＳＳ−１００／ハイモ社製）０．５部を、重量平均分子量１４００万のアニオン性ポリアクリルアミド（商品名：ハイモロックＶ−３３０／ハイモ社製）０．５部に変更した以外は実施例１と同様にして模様紙を得た。
(Example 6)
In the adjustment of the stock for the agglomerated pulp layer, 0.5 part of an anionic polyacrylamide having a weight average molecular weight of 12 million (trade name: Hymolock SS-100 / manufactured by Hymo Co., Ltd.) was added to the anionic polyacrylamide having a weight average molecular weight of 14 million. (Trade name: Hymo Lock V-330 / manufactured by Hymo Co.) A pattern paper was obtained in the same manner as in Example 1 except that the content was changed to 0.5 part.
（実施例７）
凝集パルプ層用の紙料の調整において、重量平均分子量１２００万のアニオン性ポリアクリルアミド（商品名：ハイモロックＳＳ−１００／ハイモ社製）の添加量を０．０８部に変更した以外は実施例１と同様にして模様紙を得た。
(Example 7)
Example 1 except that the amount of anionic polyacrylamide having a weight average molecular weight of 12 million (trade name: Hymolock SS-100 / manufactured by Hymo Co.) was changed to 0.08 parts in the adjustment of the stock for the aggregated pulp layer. Pattern paper was obtained in the same manner as above.
（実施例８）
凝集パルプ層用の紙料の調整において、重量平均分子量１２００万のアニオン性ポリアクリルアミド（商品名：ハイモロックＳＳ−１００／ハイモ社製）の添加量を０．９部に変更した以外は実施例１と同様にして模様紙を得た。
(Example 8)
Example 1 except that the amount of anionic polyacrylamide having a weight average molecular weight of 12 million (trade name: Hymolock SS-100 / manufactured by Hymo Co., Ltd.) was changed to 0.9 parts in adjusting the stock for the aggregated pulp layer. Pattern paper was obtained in the same manner as above.
（実施例９）
凝集パルプ層用の紙料の調整において、硫酸バンドを増添してｐＨ５．０に調整した以外は実施例１と同様にして模様紙を得た。
Example 9
Pattern paper was obtained in the same manner as in Example 1 except that in the adjustment of the stock for the agglomerated pulp layer, a sulfuric acid band was added to adjust the pH to 5.0.
（実施例１０）
凝集パルプ層用の紙料の調整において、硫酸バンドを減添してｐＨ７．０に調整した以外は実施例１と同様にして模様紙を得た。
(Example 10)
Pattern paper was obtained in the same manner as in Example 1 except that the sulfuric acid band was adjusted to pH 7.0 by adjusting the stock for the aggregated pulp layer.
（実施例１１）
凝集パルプ層用の紙料の調整において、凝集パルプスラリーの濃度を０．０７％に調整して凝集パルプ層用の紙料を得た以外は実施例１と同様にして模様紙を得た。
(Example 11)
Pattern paper was obtained in the same manner as in Example 1 except that in the adjustment of the paper for the aggregated pulp layer, the concentration of the aggregated pulp slurry was adjusted to 0.07% to obtain the paper for the aggregated pulp layer.
（実施例１２）
凝集パルプ層用の紙料の調整において、凝集パルプスラリーの濃度を０．２５％に調整して凝集パルプ層用の紙料を得た以外は実施例１と同様にして模様紙を得た。
(Example 12)
Pattern paper was obtained in the same manner as in Example 1 except that in the adjustment of the paper for the aggregated pulp layer, the concentration of the aggregated pulp slurry was adjusted to 0.25% to obtain the paper for the aggregated pulp layer.
（実施例１３）
凝集パルプ層用の紙料の調整を次のように変更した以外は実施例１と同様にして模様紙を得た。
＜凝集パルプ層用の紙料の調整＞
ＮＢＫＰ３０部とＬＢＫＰ７０部からなるパルプ（フリーネス５００ｍｌＣＳＦ）を水中に分散してパルプスラリーを得た。該パルプスラリーにサイズ剤としてロジン系エマルジョンサイズ剤（商品名：ＡＬ１２００／星光ＰＭＣ社製）０．３部、紙力剤としてグラフト化澱粉（商品名：ＤＧ４２０４／星光ＰＭＣ株式会社製）１部をそれぞれ添加して撹拌し、更にｐＨ５．０となるように硫酸バンドを加えた後、重量平均分子量１０００万のアニオン性ポリアクリルアミド（商品名：ハイモロックＦＡ−２３０／ハイモ社製）０．０８部を添加して凝集パルプスラリーを得た。該凝集パルプスラリーの濃度を０．０７％に調整して凝集パルプ層用の紙料を得た。
(Example 13)
A patterned paper was obtained in the same manner as in Example 1 except that the adjustment of the stock for the aggregated pulp layer was changed as follows.
<Adjustment of paper stock for agglomerated pulp layer>
Pulp consisting of 30 parts NBKP and 70 parts LBKP (freeness 500 ml CSF) was dispersed in water to obtain a pulp slurry. As a sizing agent, 0.3 parts of rosin emulsion sizing agent (trade name: AL1200 / manufactured by Seiko PMC) and 1 part of grafted starch (trade name: DG4204 / manufactured by Seiko PMC) as a paper strength agent are added to the pulp slurry. Each was added and stirred, and after adding a sulfuric acid band so that the pH was 5.0, an anionic polyacrylamide (trade name: Hymolock FA-230 / manufactured by Hymo Co.) having a weight average molecular weight of 10 million was added. Addition to obtain an agglomerated pulp slurry. The concentration of the aggregated pulp slurry was adjusted to 0.07% to obtain a stock for the aggregated pulp layer.
（実施例１４）
凝集パルプ層用の紙料の調整において、ＮＢＫＰ２０部とＬＢＫＰ８０部からなるパルプ（フリーネス６００ｍｌＣＳＦ）を水中に分散してパルプスラリーとし、また、模様紙の抄紙において、凝集パルプ層用の紙料の円網バット内外のヘッド差を１０ｍｍとした以外は実施例１と同様にして模様紙を得た。
(Example 14)
In the adjustment of the stock for the agglomerated pulp layer, a pulp (freeness 600 ml CSF) comprising 20 parts of NBKP and 80 parts of LBKP is dispersed in water to form a pulp slurry. Pattern paper was obtained in the same manner as in Example 1 except that the head difference inside and outside the net bat was 10 mm.
（比較例１）
凝集パルプ層用の紙料の調整において、ＮＢＫＰ２０部とＬＢＫＰ８０部からなるパルプ（フリーネス６００ｍｌＣＳＦ）を水中に分散してパルプスラリーとした以外は実施例１３と同様にして模様紙を得た。
(Comparative Example 1)
Pattern paper was obtained in the same manner as in Example 13 except that pulp (freeness 600 ml CSF) composed of 20 parts of NBKP and 80 parts of LBKP was dispersed in water to prepare a pulp slurry.
（比較例２）
凝集パルプ層用の紙料の調整において、ＮＢＫＰ７０部とＬＢＫＰ３０部からなるパルプ（フリーネスを４００ｍｌＣＳＦ）を水中に分散してパルプスラリーとした以外は実施例１３と同様にして模様紙を得た。
(Comparative Example 2)
Pattern paper was obtained in the same manner as in Example 13 except that in the adjustment of the stock for the agglomerated pulp layer, pulp (freeness 400 mlCSF) consisting of 70 parts NBKP and 30 parts LBKP was dispersed in water to obtain a pulp slurry.
（比較例３）
凝集パルプ層用の紙料の調整において、重量平均分子量１０００万のアニオン性ポリアクリルアミド（商品名：ハイモロックＦＡ−２３０／ハイモ社製）０．０８部を、重量平均分子量８００万のアニオン性ポリアクリルアミド（商品名：ハイモロックＭＪ−５００／ハイモ社製）０．０８部に変更した以外は実施例１と同様にして模様紙を得た。
(Comparative Example 3)
In adjusting the stock for the agglomerated pulp layer, 0.08 part of an anionic polyacrylamide having a weight average molecular weight of 10 million (trade name: Hymo Lock FA-230 / manufactured by Hymo Co., Ltd.) was added to the anionic polyacrylamide having a weight average molecular weight of 8 million. (Trade name: Hymo Lock MJ-500 / manufactured by Hymo Co.) A pattern paper was obtained in the same manner as in Example 1 except that the content was changed to 0.08 part.
（比較例４）
凝集パルプ層用の紙料の調整において、重量平均分子量１０００万のアニオン性ポリアクリルアミド（商品名：ハイモロックＦＡ−２３０／ハイモ社製）の添加量を０．０５部に変更した以外は実施例１３と同様にして模様紙を得た。
(Comparative Example 4)
Example 13 except that the amount of anionic polyacrylamide having a weight average molecular weight of 10 million (trade name: Hymolock FA-230 / manufactured by Hymo Co.) was changed to 0.05 parts in the adjustment of the stock for the aggregated pulp layer. Pattern paper was obtained in the same manner as above.
（比較例５）
凝集パルプ層用の紙料の調整において、硫酸バンドを増添してｐＨ４．７に調整した以外は実施例１３と同様にして模様紙を得た。
(Comparative Example 5)
Pattern paper was obtained in the same manner as in Example 13 except that the pH of the aggregated pulp layer was adjusted to 4.7 by adding a sulfuric acid band.
（比較例６）
凝集パルプ層用の紙料の調整において、凝集パルプスラリーの濃度を０．０４％に調整して凝集パルプ層用の紙料を得た以外は実施例１３と同様にして模様紙を得た。
(Comparative Example 6)
Pattern paper was obtained in the same manner as in Example 13 except that the aggregated pulp slurry was adjusted to a concentration of 0.04% to obtain the aggregated pulp layer stock.
各実施例及び比較例で得た模様紙の評価結果を表１に示す。なお、評価については以下の方法で行った。
＜ベック平滑度＞
ＪＩＳ Ｐ ８１１９：１９９８に準拠して模様紙の凝集パルプ層の表面の平滑度を測定した。
＜風合い＞
手による感触と視覚により模様紙の凝集パルプ層の表面の風合いを判断し５段階で評価した。５が最も風合いが豊かであり、１が最も風合いに劣る。
＜地合指数＞
アンバーテック社製βフォーメーションテスターを用いて模様紙の単位坪量を下記の測定ピッチで測定し、下記の計算式に従い坪量規格化標準偏差（ｎ．ｓ．ｄ＝ｎｏｒｍａｌｉｚｅｄ ｓｔａｎｄａｒｄ ｄｅｖｉａｔｉｏｎ）を指標とし地合指数とした。
Table 1 shows the evaluation results of the pattern paper obtained in each Example and Comparative Example. The evaluation was performed by the following method.
<Beck smoothness>
The smoothness of the surface of the aggregated pulp layer of the pattern paper was measured according to JIS P 8119: 1998.
<Texture>
The texture of the agglomerated pulp layer of the pattern paper was judged by hand touch and vision and evaluated in five stages. 5 is the richest texture, and 1 is the least textured.
<Region index>
The unit basis weight of the pattern paper is measured with the following measurement pitch using a β formation tester manufactured by Amber Tech, and the basis weight standardized deviation (ns = normalized standard deviation) is used as an index according to the following formula. The formation index was used.
坪量規格化標準偏差（ｇ／ｍ）１／２＝坪量の標準偏差（ｇ／ｍ２）／坪量（ｇ／ｍ２）１／２
測定条件：測定面積７０ｍｍ×７０ｍｍ、測定ピッチ１ｍｍ×１ｍｍ
Basis weight normalized standard deviation (g / m) 1/2 = standard deviation of basis weight (g / m 2 ) / basis weight (g / m 2 ) 1/2
Measurement conditions: measurement area 70 mm × 70 mm, measurement pitch 1 mm × 1 mm
表１に示すとおり、実施例１〜１４で得られた模様紙は地合指数が０．７以上であり、凝集パルプ層の地合が模様として認識できるものであった。また、実施例１〜１４においては、模様紙としての風合いも豊かであった。これに対して各比較例で得られた模様紙は地合指数が低く、凝集パルプ層の地合を模様として認識することは困難であった。さらに、これら比較例においては、より平滑であり模様紙としての風合いも劣っていた。 As shown in Table 1, the pattern paper obtained in Examples 1 to 14 had a formation index of 0.7 or more, and the formation of the aggregated pulp layer could be recognized as a pattern. Moreover, in Examples 1-14, the texture as a pattern paper was also rich. On the other hand, the pattern paper obtained in each comparative example had a low formation index, and it was difficult to recognize the formation of the aggregated pulp layer as a pattern. Furthermore, in these comparative examples, it was smoother and the texture as a pattern paper was also inferior.
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