JP2000160495A - Production of coated paper for offset printing and coated paper for offset printing - Google Patents
Production of coated paper for offset printing and coated paper for offset printingInfo
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- JP2000160495A JP2000160495A JP34074998A JP34074998A JP2000160495A JP 2000160495 A JP2000160495 A JP 2000160495A JP 34074998 A JP34074998 A JP 34074998A JP 34074998 A JP34074998 A JP 34074998A JP 2000160495 A JP2000160495 A JP 2000160495A
- Authority
- JP
- Japan
- Prior art keywords
- paper
- coated paper
- offset printing
- base paper
- coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、面状（微小光沢ム
ラ）、表面性及び不透明度に優れるオフセット印刷用塗
被紙の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a coated paper for offset printing, which is excellent in planarity (fine gloss unevenness), surface properties and opacity.
【0002】[0002]
【従来の技術】近年、印刷物のビジュアル化、カラー
化、高級化指向に伴い、特に印刷用塗被紙においては、
塗被面の光沢度及び平滑性の向上が要望されている。ま
た、雑誌或いはダイレクトメールの多様化に伴い、オフ
セット印刷用塗被紙においては軽量であり、不透明度に
優れた製品が要望されている。一般に、印刷用塗被紙
は、高い平滑性と光沢を得るためにスーパーカレンダー
処理するが、そのために、一方で塗被紙が圧縮されて、
密度が高くなり不透明度が低下する傾向にある。その上
に塗被紙の軽量化による紙厚の低下と相まって、不透明
度の低下を余儀なくされているのが現状である。2. Description of the Related Art In recent years, with the trend toward visualization, colorization, and upgrading of printed matter, especially in coated paper for printing,
Improvements in gloss and smoothness of the coated surface have been demanded. Also, with the diversification of magazines or direct mail, there is a demand for a product that is lightweight and excellent in opacity in coated paper for offset printing. In general, coated paper for printing is subjected to a super calendering process to obtain high smoothness and gloss.
The density tends to increase and the opacity tends to decrease. In addition, the reduction in opacity is inevitably accompanied by the reduction in paper thickness due to the weight reduction of coated paper.
【0003】従って、高い白紙光沢度、平滑性を維持したま
ま、より嵩高（低密度）な紙を製造する技術が求められ
ている。[0003] Therefore, there is a need for a technique for producing bulkier (lower density) paper while maintaining high white paper gloss and smoothness.
【0004】一般的に、不透明度を改善する方法としては、
原紙内添用填料や塗被液用顔料として屈折率の大きな二
酸化チタンや針状などの形状を有した軽質炭酸カルシウ
ムを用いたり、微粒化顔料を用いる等の方法が提案され
ている。[0004] Generally, as a method of improving the opacity,
Methods have been proposed, such as using titanium dioxide having a large refractive index, light calcium carbonate having a needle-like shape, or a finely divided pigment as a filler for internal base paper or a pigment for a coating liquid.
【0005】また塗工層を嵩高にして不透明度を改善すると
ともに白紙光沢度を向上する技術としては、比重が小さ
く嵩高な塗被層を形成し、かつ変形性、熱可塑性の高い
プラスチックピグメントやバインダーピグメントを用い
る方法、及び耐熱・耐圧性に優れるプラスチックの弾性
ロールを有するソフトカレンダーを高温下で使用する方
法等が知られている。[0005] Further, as a technique for improving the opacity by increasing the bulk of the coating layer and improving the glossiness of white paper, a plastic pigment having a low specific gravity and a bulky coating layer, and having high deformability and thermoplasticity, is used. A method using a binder pigment and a method using a soft calender having a plastic elastic roll having excellent heat resistance and pressure resistance at a high temperature are known.
【0006】しかしながら、前者においてはこれら顔料の単
価が高いため、少量しか配合できず、実用上十分な効果
が出ておらず、また、後者については高温で塗被紙をソ
フトカレンダー処理すると、原紙の坪量ムラや塗被量ム
ラ等が塗被面に微小な光沢ムラとなって現れるため、塗
被紙の外観を損なう問題があった。[0006] However, in the former, since the unit price of these pigments is high, only a small amount can be blended, and the effect is not practically sufficient. In the latter, when the coated paper is soft calendered at a high temperature, the base paper The unevenness of the basis weight and the unevenness of the coating amount appear as minute unevenness in gloss on the coated surface, and thus there is a problem that the appearance of the coated paper is impaired.
【0007】[0007]
【発明が解決しようとする課題】以上のような状況に鑑
み、本発明の課題は、顔料塗被紙に光沢付与するための
高温ソフトカレンダー処理において問題となる微小光沢
ムラを改善し、白紙光沢度及び不透明度に優れ、かつ印
刷表面強度に優れる軽量オフセット印刷用塗被紙の製造
方法を提供することにある。SUMMARY OF THE INVENTION In view of the above situation, an object of the present invention is to improve fine gloss unevenness, which is a problem in high-temperature soft calendering for imparting gloss to pigment-coated paper, and to improve white paper gloss. An object of the present invention is to provide a method for producing a lightweight coated paper for offset printing, which is excellent in degree and opacity and excellent in printing surface strength.
【0008】[0008]
【課題を解決するための手段】上記課題をいろいろな角
度から研究を進めた結果、本発明者等は原紙に内添する
填料が、原紙上の塗被層の微小光沢ムラに大きな影響を
及ぼすことを見出し本発明を完成した。すなわち、本発
明は、原紙に顔料と接着剤を含有する塗被液を塗被する
オフセット印刷用塗被紙において、原紙製造時に填料と
して、硫酸塩法またはソーダ法によるパルプ製造工程の
苛性化工程で、生石灰を水または弱液で消和した後、緑
液で苛性化反応することによって製造された長径５．０
〜１０．０ μm、短径０．２〜０．５μmの範囲内にあ
る針状または柱状の軽質炭酸カルシウムを含有した原紙
に塗被液を塗被・乾燥した後、塗被面を金属ロール表面
温度１３０℃以上のソフトカレンダー処理することを特
徴とするオフセット印刷用塗被紙の製造方法である。本
発明者らはこの製造方法を用いることにより、初めて、
ソフトカレンダー処理での微小光沢ムラを改善し、白紙
光沢度及び不透明度が高い軽量オフセット印刷用塗被紙
を得ることを見出した。本発明においては、従来の製法
に従った石灰乳と炭酸ガスとの反応で製造されたもの
（炭酸ガス法）と比較してパルプ製造工程で製造された
軽質炭酸カルシウムを使用する方が塗被紙の密度が低く
なるため、不透明度に優れ、かつ軽度のカレンダー処理
で所望の光沢を得やすくなることを認めた。As a result of studying the above problem from various angles, the present inventors have found that the filler internally added to the base paper has a great effect on the minute gloss unevenness of the coating layer on the base paper. The inventors have found that the present invention has been completed. That is, the present invention provides a coated paper for offset printing in which a base paper is coated with a coating liquid containing a pigment and an adhesive. The sludge was prepared by quenching quicklime with water or weak liquor, followed by a caustic reaction with green liquor.
After coating and drying the coating liquid on the base paper containing needle-like or columnar light calcium carbonate having a diameter of about 10.0 μm and a minor diameter of 0.2 to 0.5 μm, the coating surface is coated with a metal roll. A method for producing a coated paper for offset printing, characterized by performing a soft calender treatment at a surface temperature of 130 ° C. or more. The present inventors, for the first time by using this manufacturing method,
It has been found that a fine coated paper for offset printing with high gloss and opacity of white paper is improved by improving the minute gloss unevenness in the soft calender treatment. In the present invention, the use of light calcium carbonate manufactured in the pulp manufacturing process is more coated than that manufactured by the reaction of milk of lime and carbon dioxide according to the conventional manufacturing method (carbon dioxide method). It was recognized that the density of the paper was low, so that the opacity was excellent and the desired gloss could be easily obtained by a light calendering treatment.
【0009】また、液浸法により針状或いは柱状の苛性化軽
質炭酸カルシウムの屈折率を測定したところ、炭酸ガス
法で製造された炭酸カルシウムと比較して若干大きいこ
とが明らかとなり、この屈折率が高いことも不透明度向
上効果に少なからず寄与しているものと考えられる。When the refractive index of acicular or columnar causticized light calcium carbonate was measured by the liquid immersion method, it was found that the refractive index was slightly larger than that of calcium carbonate produced by the carbon dioxide gas method. Is also considered to have contributed to the opacity improving effect to a considerable extent.
【0010】また、この軽質炭酸カルシウムは原紙の窪みを
剛直な微細繊維の如く埋めることで、原紙表面の凹凸を
減少させる効果もあり、高温ソフトカレンダー処理によ
る微小光沢ムラ発生を抑制しているものと推測される。[0010] The light calcium carbonate also has the effect of reducing irregularities on the surface of the base paper by filling the pits of the base paper as rigid fine fibers, thereby suppressing the occurrence of minute gloss unevenness due to high-temperature soft calendering. It is presumed.
【0011】この事実より、本法で得られたものを使用した
原紙の表面は水に対するサイズ性が向上しており、塗被
液の原紙中への浸透が抑制されるため、比較的密度の低
い塗被紙が製造でき、続く高温ソフトカレンダー処理に
より、白紙光沢度、不透明度が高く、かつ微小光沢ムラ
のない顔料塗被紙が得られるものと考えられる。苛性化
反応することによって製造された針状または柱状の軽質
炭酸カルシウムは、長径が５．０〜１０．０μｍ、短径
が０．２〜０．５μｍの範囲にあることが必要であり、
より好ましくは長径が６．０〜８．０μｍ、短径が０．
２〜０．４μｍである。針状または柱状の軽質炭酸カル
シウムの長径が５．０μｍより小さいものを使用する
と、原紙表面のサイズ度が低下し、塗被液の浸透が促進
されるために塗被紙の密度が大きくなり、塗被紙の不透
明度、及び白紙光沢度発現性が低下すると共に面状が悪
化する。また、長径が１０．０μｍより大きいものでは
不透明度は向上するが、原紙表面付近にこのような大き
な粒子径を有するものが存在すると塗被紙の表面性が低
下するため、微小光沢ムラが生じやすく、白紙光沢度の
発現性も悪くなるだけでなく、オフセット印刷時に大き
な顔料ピックとなって現れドライ強度が著しく低下す
る。一方、短径が０．２μｍより小さいものは不透明度
が低下し、微小光沢ムラも発生する。短径が０．５μｍ
より大きいものを使用すると、不透明度が低下し、ドラ
イ強度が低下し、微小光沢ムラも発生する。本発明にお
いて、原紙中に含まれる針状または柱状の軽質炭酸カル
シウムの量は４〜１０重量％であることが必要であり、
より好ましくは６〜８重量％である。４重量％より低く
なると、十分な白紙光沢度及び不透明度が得られず、微
小光沢ムラも改善しない。逆に１０重量％より高くなる
と、不透明度は向上するものの、原紙表面のサイズ度が
高くなり、極めて撥水性が向上するために塗被液の浸透
性が極度に阻害されることで塗工層と原紙間の強度が低
下し、印刷時の顔料ピックやベッセルピックが多発し、
ドライ強度が劣り、かつ原紙の表面粗さが顕著となり、
塗工後の白紙光沢が発現しにくく、微小光沢ムラが発生
する。[0011] From this fact, the surface of the base paper obtained by using the method obtained by the present method has improved sizing properties with respect to water, and the penetration of the coating liquid into the base paper is suppressed. It is considered that a low-coated paper can be manufactured, and the subsequent high-temperature soft calendering can provide a pigment-coated paper having high white paper glossiness and opacity and no fine gloss unevenness. Needle-like or columnar light calcium carbonate produced by the caustic reaction needs to have a major axis in a range of 5.0 to 10.0 μm and a minor axis in a range of 0.2 to 0.5 μm,
More preferably, the major axis is 6.0 to 8.0 μm, and the minor axis is 0.1 μm.
2 to 0.4 μm. When a needle or columnar light calcium carbonate having a major axis smaller than 5.0 μm is used, the sizing degree of the base paper surface is reduced, and the penetration of the coating liquid is promoted, so that the density of the coated paper is increased. The opacity of the coated paper and the glossiness of white paper are reduced, and the surface condition is deteriorated. When the major axis is larger than 10.0 μm, the opacity is improved. However, when there is one having such a large particle diameter near the surface of the base paper, the surface properties of the coated paper are reduced. Not only is it easy to develop the glossiness of white paper, but also a large pigment pick appears during offset printing, and the dry strength is significantly reduced. On the other hand, when the minor axis is smaller than 0.2 μm, the opacity is reduced and minute gloss unevenness also occurs. The minor axis is 0.5 μm
When a larger one is used, the opacity is reduced, the dry strength is reduced, and unevenness in fine gloss occurs. In the present invention, the amount of needle-like or columnar light calcium carbonate contained in the base paper needs to be 4 to 10% by weight,
More preferably, it is 6 to 8% by weight. If the content is less than 4% by weight, sufficient white paper gloss and opacity cannot be obtained, and fine gloss unevenness does not improve. Conversely, if the content is higher than 10% by weight, the opacity is improved, but the size of the base paper surface is increased, and the water repellency is extremely improved. The strength between the base paper and the paper decreases, and pigment picks and vessel picks during printing frequently occur.
The dry strength is inferior, and the surface roughness of the base paper becomes remarkable,
The glossiness of white paper after coating is hardly developed, and minute gloss unevenness occurs.
【0012】本発明で用いるソフトカレンダー処理は、金属
ロール温度が１３０℃以上で行う必要があるが、高い表
面性印刷品質を得るために１５０〜２５０℃で行うこと
が好ましい。１３０℃より低い場合は、微小光沢ムラは
良化傾向になるが、白紙光沢の向上も不十分である。ま
た、塗被液中の共重合体ラテックスは、平均粒子径が５
０〜９０μｍの共重合体を含有することが好ましい。平
均粒子径が９０ｎｍより大きい場合には、印刷表面強度
が劣る傾向にある。平均粒子径が５０ｎｍより小さい場
合には、乳化剤の影響により印刷湿潤時（印刷機の湿し
水が付いた際）の印刷表面強度が低下しやすい。また、
平均粒子径が５０〜９０μｍの共重合体ラテックスの含
有量は４〜８重量部が好ましい。４重量部より少なくな
ると、印刷表面強度が低下しやすく、８重量部より多く
なると印刷表面強度は向上するが、白紙光沢度が低下
し、微小光沢ムラも改善されない傾向にある。また、本
願発明では、密度が１．００ｇ／ｃｍ3以下の塗被紙に
することが好ましく、密度が１．００ｇ／ｃｍ3を越え
る場合は、潰れ過ぎによる不透明度が低下する傾向にあ
り、好ましくない。[0012] The soft calendering treatment used in the present invention must be performed at a metal roll temperature of 130 ° C or higher, but is preferably performed at 150 to 250 ° C in order to obtain high surface print quality. When the temperature is lower than 130 ° C., the fine gloss unevenness tends to be improved, but the improvement in the gloss of the white paper is insufficient. The copolymer latex in the coating liquid has an average particle diameter of 5%.
It preferably contains a copolymer of 0 to 90 μm. When the average particle size is larger than 90 nm, the printing surface strength tends to be inferior. When the average particle size is smaller than 50 nm, the printing surface strength at the time of printing wetness (when a fountain solution is attached to a printing press) tends to decrease due to the influence of the emulsifier. Also,
The content of the copolymer latex having an average particle diameter of 50 to 90 μm is preferably 4 to 8 parts by weight. When the amount is less than 4 parts by weight, the printing surface strength tends to decrease, and when the amount is more than 8 parts by weight, the printing surface strength is improved, but the glossiness of the white paper is reduced and the minute gloss unevenness does not tend to be improved. Further, in the present invention, it is preferable that the coated paper has a density of 1.00 g / cm 3 or less, and if the density exceeds 1.00 g / cm 3 , the opacity due to excessive crushing tends to decrease, Not preferred.
【0013】[0013]
【発明の実施の形態】本発明で規定する特定の形状を有
する軽質炭酸カルシウムは、硫酸塩法またはソーダ法に
よるパルプ製造工程の苛性化工程で製造されたものを使
用する。硫酸塩法またはソーダ法によるパルプ製造工程
においては、木材中の繊維素を単離するために水酸化ナ
トリウムと硫化ナトリウムとを混合した薬液を用いて高
温、高圧下で蒸解する。そして繊維素は固層として分離
精製されてパルプとなり、薬液及び木材からの繊維素以
外の溶出成分はパルプ廃液（黒液）として回収され、回
収ボイラーで燃焼可能な濃度まで濃縮される。さらに、
一連の過程で失われたナトリウム分と硫黄分を補給する
ために硫酸ナトリウムが添加された後、回収ボイラーで
燃焼される。その際、黒液中の有機物質は熱源として、
無機物質は主として炭酸ナトリウム及び硫化ナトリウム
として回収されるが、これらの無機物はスメルトと呼ば
れ溶融状態で回収ボイラーから取り出される。回収ボイ
ラーから取り出されたスメルトは、水または弱液（炭酸
カルシウムを水洗浄した後に得られる、白液成分を微量
含んだ液）で溶解されて緑液となる。BEST MODE FOR CARRYING OUT THE INVENTION Light calcium carbonate having a specific shape as defined in the present invention is produced by a causticizing step of a pulp producing step by a sulfate method or a soda method. In the pulp production process by the sulfate method or the soda method, in order to isolate fibrous material in wood, digestion is performed at high temperature and high pressure using a chemical solution in which sodium hydroxide and sodium sulfide are mixed. Then, the fibrous material is separated and purified into a pulp as a solid layer, and components eluted from the chemical solution and the wood other than the fibrous material are recovered as pulp waste liquid (black liquor) and concentrated to a concentration that can be burned by the recovery boiler. further,
Sodium sulfate is added to make up for the sodium and sulfur lost in the series of processes and then burnt in a recovery boiler. At that time, the organic matter in the black liquor is used as a heat source,
Inorganic substances are mainly recovered as sodium carbonate and sodium sulfide, and these inorganic substances are called smelt and are taken out of the recovery boiler in a molten state. The smelt removed from the recovery boiler is dissolved in water or a weak liquid (a liquid containing a small amount of a white liquor component obtained after washing calcium carbonate with water) to become a green liquor.
【0014】苛性化工程とは、緑液中の炭酸ナトリウムを蒸
解薬品である水酸化ナトリウムに変えるための工程であ
り、生石灰を消石灰に変える消和反応(1)と、消石灰と
緑液を混合し水酸化ナトリウムと炭酸カルシウムを生成
する苛性化反応(2)よりなる。苛性化反応によって得ら
れた液は白液と呼ばれ、炭酸カルシウムと分離、清澄化
されて蒸解工程へ送られる。本発明では分離回収し、十
分に水洗浄された炭酸カルシウムを使用する。 ＣａＯ＋Ｈ２Ｏ→Ｃａ（ＯＨ）２ （１）：消和反応 Ｃａ（ＯＨ）２＋Ｎａ２ＣＯ３→ＣａＣＯ３＋２ＮａＯＨ（２）：苛性化反応 この炭酸カルシウムは主産物である白液を製造する際の
副産物であるため、従来の石灰乳と炭酸ガスとの反応に
よる方法で得られる軽質炭酸カルシウムに比べて非常に
低コストで製品を製造し得る。The causticizing step is a step for converting sodium carbonate in green liquor into sodium hydroxide as a cooking chemical, a slaking reaction (1) for converting quicklime into slaked lime, and mixing slaked lime and green liquor. Causticization reaction (2) that produces sodium hydroxide and calcium carbonate. The liquor obtained by the causticization reaction is called white liquor, separated from calcium carbonate, clarified and sent to the digestion step. In the present invention, calcium carbonate that has been separated and recovered and washed sufficiently with water is used. CaO + H 2 O → Ca (OH) 2 (1): slaking reaction Ca (OH) 2 + Na 2 CO 3 → CaCO 3 + 2NaOH (2): causticizing reaction This calcium carbonate is used when producing a white liquor which is a main product. Since it is a by-product, a product can be manufactured at a very low cost as compared with light calcium carbonate obtained by a conventional method of reacting milk of lime with carbon dioxide.
【0015】更に本発明において規定する針状または柱状の
軽質炭酸カルシウムは以下の製造法に従って初めて製造
される。すなわち、（１）苛性化工程で発生し、及び／
又は、苛性化工程外から導入した生石灰であって、
（２）０．１〜１０重量％の炭酸カルシウムを含有する
前記生石灰に対して、生石灰濃度が２０〜６０重量％に
なるようｐＨ５．５〜１４を有する液（水又は弱液）を
添加し、撹拌あるいは混和しながら消和させて石灰乳及
び／又は石灰泥を生成する第一段工程、次いで該石灰乳
及び／又は石灰泥に、前記苛性化工程で発生し、白液を
製造するのに必要な所定量の緑液を該石灰乳及び／又は
石灰泥に対して、反応温度２０〜１０５℃にて苛性化反
応を行うことによって製造するものである。Further, the needle-shaped or columnar light calcium carbonate specified in the present invention is produced for the first time according to the following production method. That is, (1) generated in the causticizing step, and / or
Or, quicklime introduced from outside the causticizing process,
(2) A liquid (water or weak liquid) having a pH of 5.5 to 14 is added to the quicklime containing 0.1 to 10% by weight of calcium carbonate such that the quicklime concentration becomes 20 to 60% by weight. The first step of producing milk of lime and / or lime mud by slaking with stirring or mixing, and then the lime milk and / or lime mud is generated in the causticizing step to produce white liquor. The lime milk and / or lime mud is subjected to a caustic reaction at a reaction temperature of 20 to 105 ° C. to produce a required amount of green liquor.
【0016】また上記軽質炭酸カルシウム以外に使用する填
料を特に規定するものではないが、一般的に原紙に使用
される重質炭酸カルシウム、その他の軽質炭酸カルシウ
ム、カオリン、クレー、タルク、シリカ、硫酸バリウム、
硫酸カルシウム、硫化亜鉛、二酸化チタンなどを本発明
の効果を損なわない範囲で１種以上併用することができ
る。[0016] The filler used other than the above-mentioned light calcium carbonate is not particularly limited, but heavy calcium carbonate generally used for base paper, other light calcium carbonate, kaolin, clay, talc, silica, sulfuric acid and the like. barium,
One or more of calcium sulfate, zinc sulfide, titanium dioxide and the like can be used in combination as long as the effects of the present invention are not impaired.
【0017】本発明で使用される原紙としては、メカニカル
パルプ、ケミカルパルプ及び故紙回収パルプ等を任意の
比率で混合して用いられ、必要に応じて通常の製紙用填
料、紙力増強剤、歩留まり向上剤及びサイズ剤等を添加
した製紙原料をシングルワイヤーあるいはツインワイヤ
ーを有する通常の抄紙機によって抄造される。As the base paper used in the present invention, a mechanical pulp, a chemical pulp, a waste paper recovery pulp and the like are mixed at an arbitrary ratio and used, and if necessary, a usual papermaking filler, a paper strength enhancer, a yield The papermaking raw material to which the improver, the sizing agent, and the like are added is formed by an ordinary paper machine having a single wire or a twin wire.
【0018】なお、本発明の場合、原紙としては軽量のもの
に特に効果が見られるものであり、好ましくは３０〜５
０ｇ／ｍ2の場合に本発明の効果が特に顕著に発揮され
る。In the case of the present invention, lightweight base paper is particularly effective, and preferably 30 to 5 weights.
In the case of 0 g / m 2 , the effect of the present invention is particularly remarkably exhibited.
【0019】本発明の原紙の製造において使用するデンプン
は、酸化デンプン、自家変性デンプン、リン酸エステル
化デンプン、ヒドロキシエチル化デンプン等があるが、
特に限定されるものではない。The starch used in the production of the base paper of the present invention includes oxidized starch, self-modified starch, phosphate esterified starch, hydroxyethylated starch, and the like.
There is no particular limitation.
【0020】本発明の原紙の製造において使用するサイズプ
レス方法としては、代表的には２本のプレスロール間に
紙を通し紙の両面からサイズプレス液を塗布する方式、
対になった３本ずつのロール（外からファウンテンロー
ル、メタリングロール、アプリケーターロール）を持
ち、サイズプレス液はファウンテンロールとメタリング
ロールの間に供給され、メタリングロールからアプリケ
ーターロールへ転写され、アプリケーターロール上のサ
イズプレス液層と紙がもう一方のアプリケーターロール
とのニップで接触して塗布される方式がある。その他タ
ブサイズプレス、カレンダーサイズプレス等があるがそ
の方式については、使用するデンプン濃度及び粘度を適
宜調整すれば使用可能なため特に限定されるものではな
い。[0020] The size press method used in the production of the base paper of the present invention is typically a method in which paper is passed between two press rolls and a size press liquid is applied from both sides of the paper.
It has three pairs of rolls (fountain roll, metering roll, and applicator roll from the outside), and the size press liquid is supplied between the fountain roll and the metering roll, and is transferred from the metering roll to the applicator roll. There is a method in which the size press liquid layer on the applicator roll and the paper are applied in contact with each other at the nip of the other applicator roll. In addition, there are a tab size press, a calendar size press, and the like, but the method is not particularly limited since it can be used if the starch concentration and viscosity used are appropriately adjusted.
【0021】また、本発明に使用する塗被液中の顔料は一般
的に使用される重質炭酸カルシウム、カオリン、クレ
ー、タルク、サチンホワイト、シリカ、プラスチックピ
グメント、二酸化チタン等を１種以上使用する。As the pigment in the coating liquid used in the present invention, one or more commonly used heavy calcium carbonate, kaolin, clay, talc, satin white, silica, plastic pigment, titanium dioxide, etc. are used. I do.
【0022】本発明の塗被液に使用する接着剤は、ラテック
ス或いはその他の水性接着剤から必要に応じ２種或いは
３種以上を選択して使用する。ラテックスとしては、ス
チレン・ブタジエン共重合体、メタクリレート・ブタジ
エン共重合体等の共役ジエン系共重合ラテックス、アク
リル酸エステル及び／またはメタクリル酸エステルの共
重合体または共重合体等のビニル系共重合ラテックス、
あるいはこれらを更にカルボキシル基等の官能基含有単
量体で変性したものである。また、前記５０〜９０μｍ
の小粒径ラテックスに混合して使用するラテックスの平
均粒子径として１００〜１４０ｎｍが好ましい。トータ
ルのラテックスの配合量としては１０〜１５重量部が好
ましい。The adhesive used in the coating liquid of the present invention is selected from latex or other water-based adhesives, and two or more kinds are selected as necessary. Examples of the latex include conjugated diene copolymer latex such as styrene / butadiene copolymer and methacrylate / butadiene copolymer, and vinyl copolymer latex such as acrylate and / or methacrylate ester copolymer or copolymer. ,
Alternatively, these are further modified with a monomer containing a functional group such as a carboxyl group. In addition, the aforementioned 50 to 90 μm
The latex having an average particle diameter of 100 to 140 nm is preferably used as a mixture with the small particle size latex. The total amount of the latex is preferably 10 to 15 parts by weight.
【0023】またラテックス以外の水性接着剤としては、例
えば、酵素変性デンプン、冷水可溶性デンプン、リン酸
エステル化デンプン、エーテル化デンプン、酸化デンプ
ン等のデンプン類、カゼイン、大豆タンパク、合成タン
パク等のタンパク質類、ポリビニルアルコール、ポリビ
ニルピロリドン、オレフィン、無水マレイン酸樹脂、メ
ラミン樹脂等の合成樹脂系接着剤、カルボキシメチルセ
ルロース、ヒドロキシエチルセルロース、ヒドロキシメ
チルセルロース等のセルロース誘導体等の通常の塗工用
接着剤である。配合量としては、顔料１００重量部当た
り３〜１０重量部が好ましく、更に好ましくは３〜５重
量部である。Examples of aqueous adhesives other than latex include starches such as enzyme-modified starch, cold-water-soluble starch, phosphorylated esterified starch, etherified starch, and oxidized starch; protein such as casein, soybean protein, and synthetic protein. And ordinary adhesives for coating such as synthetic resins such as polyvinyl alcohol, polyvinylpyrrolidone, olefin, maleic anhydride resin and melamine resin, and cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose and hydroxymethylcellulose. The amount is preferably 3 to 10 parts by weight, more preferably 3 to 5 parts by weight, per 100 parts by weight of the pigment.
【0024】本発明の塗被液には分散剤、増粘剤、保水剤、
消泡剤、耐水化剤等通常の塗被紙用顔料に配合される各
種助剤を使用しても良い。The coating liquid of the present invention contains a dispersant, a thickener, a water retention agent,
Various auxiliaries, such as an antifoaming agent and a water-proofing agent, which are blended in a usual pigment for coated paper may be used.
【0025】かくして調製された塗被組成物は、一般の塗被
装置で塗被されるが、特に高速塗被に適した、ロールア
プリケーションやファウンテンノズルタイプのブレード
コータを使用することが好ましい。またその際の塗被液
濃度は６０〜６８％の範囲が好ましく、原紙上に単層あ
るいは多層塗被される。塗被量は、片面当たり２〜１２
ｇ／ｍ2が好ましい。The coating composition thus prepared is applied by a general coating apparatus, but it is preferable to use a roll application or a fountain nozzle type blade coater which is particularly suitable for high-speed coating. The concentration of the coating solution at that time is preferably in the range of 60 to 68%, and a single layer or a multilayer is coated on the base paper. The coating amount is 2 to 12 per side.
g / m 2 is preferred.
【0026】以上のように原紙に塗被液を塗被、乾燥された
塗被紙は、高温ソフトカレンダーで表面仕上げされる。
この時塗被紙は、圧力、スピード、表面温度及び塗被紙
の平衡水分などにより、種々の密度になる。本発明では
一対のロールのうち１本が弾性ロールであり、他の１本
が金属ロールからなる、いわゆるソフトカレンダーを用
いるが、線圧の上限は特に限定されないが１８０ｋｇ／
ｃｍ以下が望ましい。また、ニップ数・ロールの材質及
び温度等についても特に限定されるものではない。As described above, the base paper is coated with the coating liquid, and the dried coated paper is surface-finished by a high-temperature soft calender.
At this time, the coated paper has various densities depending on pressure, speed, surface temperature, equilibrium moisture of the coated paper, and the like. In the present invention, a so-called soft calender in which one of the pair of rolls is an elastic roll and the other one is a metal roll is used. The upper limit of the linear pressure is not particularly limited, but is 180 kg /.
cm or less is desirable. Further, the number of nips, the material and temperature of the roll, and the like are not particularly limited.
【実施例】以下に、実施例を挙げて本発明をより具体的
に説明するが、もちろんその範囲に限定されるものでは
ない。なお、例中の部及び％は特に断らない限り、それ
ぞれ重量部及び重量％を示す。 ＜品質評価方法＞ （１）軽質炭酸カルシウム形態観察 製造した軽質炭酸カルシウムを水洗濾過し、乾燥後走査
電子顕微鏡（日本電子ＪＳＭ−５３００）で形状及び長
径・短径平均値を測定した。 （２）原紙灰分測定 填料の含有量は各手抄き紙をるつぼにつめて、電気コン
ロで予備的に燃焼した後、電気炉で９００℃、１時間灼
熱して測定した。また、原紙灰分は以下の計算式に従っ
て算出した。 原紙灰分（％）＝［原紙灰分実測量（ｇ）÷ 灼熱減量
（％）］÷原紙の絶乾重量（ｇ） （３）不透明度 ハンター白色度計を用いてＪＩＳ Ｐ−８１３８、Ａ法
に従い測定した。 （４）白紙光沢度 ＪＩＳ Ｐ−８１４２に従い角度７５度で測定した。 （５）微小光沢ムラ ソフトカレンダー処理後の塗被紙を以下の４段階で目視
評価した。The present invention will be described in more detail with reference to the following examples, but it should be understood that the present invention is by no means restricted to such specific ranges. In the examples, parts and% indicate parts by weight and% by weight, respectively, unless otherwise specified. <Quality Evaluation Method> (1) Observation of Light Calcium Carbonate Morphology The manufactured light calcium carbonate was washed with water, filtered, dried, and the shape and average value of major axis and minor axis were measured with a scanning electron microscope (JEOL JSM-5300). (2) Base paper ash measurement The content of filler was measured by placing each handmade paper in a crucible, preliminarily burning it with an electric stove, and burning in an electric furnace at 900 ° C for 1 hour. The base paper ash was calculated according to the following formula. Base paper ash content (%) = [Measured raw paper ash content (g) 減 Loss on burning (%)] 絶 Absolute dry weight of base paper (g) (3) Opacity According to JIS P-8138, Method A using Hunter whiteness meter It was measured. (4) Blank glossiness Measured at an angle of 75 degrees according to JIS P-8142. (5) Fine gloss unevenness The coated paper after the soft calender treatment was visually evaluated in the following four stages.
【0027】◎＝無し、○＝ほとんど無し、△＝若干有り、
×＝光沢ムラが非常に目立つ （６）ドライ強度 ＲＩ−ＩＩ型印刷機（明製作所製）を用い、東洋インキ
製ＴＶ−２４を使用し、インキ量０．３５ｃｃ一定で印
刷し、印刷面のピッキング程度を目視で相対評価した。◎ = none, ○ = almost none, Δ = somewhat,
× = Gloss unevenness is very conspicuous (6) Dry strength Using an RI-II type printing machine (manufactured by Meisho Seisakusho), using Toyo Ink TV-24, printing at a constant ink amount of 0.35 cc, The degree of picking was visually evaluated relative to each other.
【0028】◎＝全く発生しない、○＝ほとんど発生しな
い、△＝発生する、×＝発生が著しい ［実施例１］ 〔原紙製造のための原料と薬品〕 ＬＢＫＰ（濾水度：３２０ｍＬ） ８０部 ＮＢＫＰ（濾水度：４９０ ｍＬ） ２０部 硫酸バンド ０．８部 中性サイズ剤（アルキルケテンダイマー） ０．０３部 カチオン化デンプン ０．３部 カチオン化ポリアクリルアミド ０．０１２部 ベントナイト ０．４部 上記原料に対し、内添薬品と長径は７．０μｍ、短径は
０．３０μｍである苛性化針状軽質炭酸カルシウムを内
添し、原紙中の填料含有量が６．５重量％となるように
実験用手抄き器にて抄紙し、坪量４０ｇ／ｍ2の原紙を
得た。この原紙にヒシラコピー機（三菱製紙社製・ワン
ステッププロセッサーＳ−III型）を用いて表面サイズ
処理を行い、１０５℃にて１分間乾燥させた後、密度
０．７０ｇ／ｃｍ3となるようにマシンカレンダー処理
を行った。サイズプレスデンプン塗布量の調節はデンプ
ン濃度を３．５〜４％に希釈調整することで行い、デン
プン塗布量は１．０ｇ／ｍ2とした。◎ = not generated at all, ○ = not generated at all, Δ = produced, X = produced significantly [Example 1] [Raw materials and chemicals for base paper production] 80 parts of LBKP (freeness: 320 mL) NBKP (freeness: 490 mL) 20 parts Sulfuric acid band 0.8 parts Neutral sizing agent (alkyl ketene dimer) 0.03 parts Cationized starch 0.3 parts Cationized polyacrylamide 0.012 parts Bentonite 0.4 parts An internal additive and caustic needle-like light calcium carbonate having a major axis of 7.0 μm and a minor axis of 0.30 μm are internally added to the raw material so that the filler content in the base paper is 6.5% by weight. Was made with an experimental hand-making machine to obtain a base paper having a basis weight of 40 g / m 2 . The base paper is subjected to a surface sizing treatment using a Hishira copy machine (manufactured by Mitsubishi Paper Industries, Inc., one-step processor S-III), dried at 105 ° C. for 1 minute, and then adjusted to a density of 0.70 g / cm 3. Machine calendar processing was performed. The amount of size press starch applied was adjusted by diluting and adjusting the starch concentration to 3.5 to 4%, and the amount of starch applied was 1.0 g / m 2 .
【0029】サイズプレス後の原紙に重質炭酸カルシウム６
５部、カオリン３５部に対して、ポリアクリル酸ソーダ
系分散剤０．３部を添加し、カウレス分散機を用いて水
に分散し、接着剤としてリン酸エステル化デンプン４部
と平均粒子径が７０ｎｍの共重合体ラテックス５部及び
平均粒子径が１１０ｎｍの共重合体ラテックス７部を配
合し、固形分濃度６５％の塗被液を絶乾の塗工量が両面
で２４ｇ／ｍ2となるようにブレードコータを用いて両
面塗工した。得られた塗工紙を金属ロール温度１５０
℃、線圧１２０ｋｇ／ｃｍ、１ニップのソフトカレンダ
ー処理を行い、密度０．９５ｇ／ｃｍ3の印刷用塗被紙
を得た。 ［実施例２］原紙中の填料含有量を４％とする以外は実
施例１と全く同一の方法で印刷用塗被紙を得た。 ［実施例３］原紙中の填料含有量を９％とする以外は実
施例１と全く同一の方法で印刷用塗被紙を得た。 ［実施例４］填料として長径が５．５μｍ、短径が０．
２５μｍである苛性化柱状軽質炭酸カルシウムを用いる
以外は実施例１と全く同一の方法で印刷用塗被紙を得
た。 ［比較例１］填料として長径が４．０μｍである苛性化
針状軽質炭酸カルシウムを用いる以外は実施例１全く同
一の方法で印刷用塗被紙を得た。 ［比較例２］填料として長径が１２μｍである苛性化針
状軽質炭酸カルシウムを用いる以外は実施例１と全く同
一の方法で印刷用塗被紙を得た。 ［比較例３］填料として短径が０．１５μｍである苛性
化針状軽質炭酸カルシウムを用いる以外は実施例１と全
く同一の方法で印刷用塗被紙を得た。 ［比較例４］填料として短径が０．７μｍである苛性化
針状軽質炭酸カルシウムを用いる以外は実施例１と全く
同一の方法で印刷用塗被紙を得た。 ［比較例５］原紙の填料灰分を３%とする以外は実施例
１と全く同一の方法で印刷用塗被紙を得た。 ［比較例６］原紙の填料灰分を１２％とする以外は実施
例１と全く同一の方法で印刷用塗被紙を得た。 ［比較例７］水酸化カルシウム水懸濁液に炭酸ガスを吹
き込むことにより得られた針状軽質炭酸カルシウムを用
いる以外は実施例１と全く同一の方法で印刷用塗被紙を
得た。 ［比較例８］紡錘状炭酸カルシウムを用いる以外は実施
例１と全く同一の方法で印刷用塗被紙を得た。 ［比較例９］ソフトカレンダー処理条件を温度１２０℃
とする以外は、実施例１と全く同一の方法で印刷用塗被
紙を得た。[0029] Heavy calcium carbonate 6 is added to the base paper after size pressing.
To 5 parts of kaolin and 35 parts of kaolin, 0.3 part of sodium polyacrylate dispersant was added, dispersed in water using a Cowles disperser, and 4 parts of phosphorylated ester starch and an average particle diameter were used as an adhesive. There copolymer latex 5 parts and the average particle size of 70nm is blended with copolymer latex 7 parts of 110 nm, a solid concentration of 65% coated liquid coating amount of bone dry it with 24 g / m 2 on both sides Coating was performed on both sides using a blade coater. The coated paper thus obtained was heated to a metal roll temperature of 150.
C., a linear pressure of 120 kg / cm, and one nip soft calendering were performed to obtain a coated paper for printing having a density of 0.95 g / cm 3 . Example 2 A coated paper for printing was obtained in exactly the same manner as in Example 1 except that the filler content in the base paper was 4%. Example 3 A coated paper for printing was obtained in exactly the same manner as in Example 1, except that the content of filler in the base paper was 9%. Example 4 A filler having a major axis of 5.5 μm and a minor axis of 0.5 μm was used.
A coated paper for printing was obtained in exactly the same manner as in Example 1 except that caustic columnar light calcium carbonate having a size of 25 μm was used. Comparative Example 1 A coated paper for printing was obtained in exactly the same manner as in Example 1 except that caustic needle-like light calcium carbonate having a major axis of 4.0 μm was used as a filler. Comparative Example 2 A coated paper for printing was obtained in exactly the same manner as in Example 1, except that caustic needle-like light calcium carbonate having a major axis of 12 μm was used as a filler. Comparative Example 3 A coated paper for printing was obtained in exactly the same manner as in Example 1 except that caustic needle-like light calcium carbonate having a minor axis of 0.15 μm was used as a filler. Comparative Example 4 A coated paper for printing was obtained in exactly the same manner as in Example 1, except that caustic needle-like light calcium carbonate having a minor axis of 0.7 μm was used as a filler. Comparative Example 5 A coated paper for printing was obtained in exactly the same manner as in Example 1 except that the filler ash content of the base paper was 3%. Comparative Example 6 A coated paper for printing was obtained in exactly the same manner as in Example 1 except that the filler ash content of the base paper was 12%. Comparative Example 7 A coated paper for printing was obtained in exactly the same manner as in Example 1, except that needle-like light calcium carbonate obtained by blowing carbon dioxide gas into an aqueous calcium hydroxide suspension was used. Comparative Example 8 A coated paper for printing was obtained in exactly the same manner as in Example 1 except that spindle-shaped calcium carbonate was used. [Comparative Example 9] A soft calendering condition was set to a temperature of 120 ° C.
A coated paper for printing was obtained in exactly the same manner as in Example 1, except for the following.
【0030】以上の評価結果を表１に示した。Table 1 shows the above evaluation results.
【0031】[0031]
【表１】 [Table 1]
【0032】表１の結果から明らかなように、実施例１〜４
は微小光沢ムラが無く、白紙光沢度、不透明度、及びド
ライ強度に優れる。これに対し、比較例１は、白紙光沢
度、不透明度が低く、微小光沢ムラが多い。比較例２
は、白紙光沢度、不透明度及びドライ強度が低く、微小
光沢ムラが多い。比較例３は、不透明度が低く、微小光
沢ムラが若干発生する。比較例４は、不透明度、ドライ
強度が低く、微小光沢ムラが多い。比較例５は、白紙光
沢度、不透明度が低く、微小光沢ムラが若干発生する。
比較例６は、白紙光沢度、ドライ強度が低く、微小光沢
ムラが多い。比較例７は、白紙光沢度、不透明度が低
く、微小光沢ムラが多い。比較例８は、白紙光沢度、不
透明度が低く、微小光沢ムラが多い。比較例９は、白紙
光沢度が低い。As is clear from the results in Table 1, Examples 1 to 4
Has no fine gloss unevenness, and is excellent in white paper glossiness, opacity, and dry strength. On the other hand, in Comparative Example 1, the glossiness and opacity of the blank sheet were low, and there were many minute gloss unevenness. Comparative Example 2
Has low white paper glossiness, opacity, and dry strength, and has many fine gloss unevenness. In Comparative Example 3, the opacity is low, and slight gloss unevenness occurs. Comparative Example 4 is low in opacity and dry strength, and has many fine gloss unevenness. In Comparative Example 5, the glossiness and opacity of the white paper were low, and slight gloss unevenness occurred.
In Comparative Example 6, the glossiness of white paper and the dry strength were low, and there were many fine gloss unevenness. Comparative Example 7 is low in blank glossiness and opacity, and has many fine gloss unevenness. In Comparative Example 8, the glossiness and opacity of the blank sheet were low, and there was a lot of minute gloss unevenness. Comparative Example 9 has a low blank gloss level.
【0033】[0033]
【発明の効果】本発明により、微小光沢ムラが無く、白
紙光沢度、不透明度、及びドライ強度に優れたオフセッ
ト印刷用塗被紙を得ることができる。According to the present invention, it is possible to obtain a coated paper for offset printing which is free from minute gloss unevenness and excellent in blank gloss, opacity and dry strength.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 世見 勝則 山口県岩国市飯田町２丁目８番１号 日本 製紙株式会社岩国技術研究所内 (72)発明者 南里 泰徳 山口県岩国市飯田町２丁目８番１号 日本 製紙株式会社岩国技術研究所内 Ｆターム(参考） 4L055 AG11 AG12 AG27 AG48 AG89 AG94 AG97 AH01 AH02 AH37 AJ04 BC07 BE02 BE08 EA08 EA16 EA20 EA32 FA12 FA13 FA14 FA16 GA19 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Katsunori Semi 2-1-1, Iida-cho, Iwakuni-shi, Yamaguchi Japan Inside the Iwakuni Technical Research Laboratory, Paper Manufacturing Co., Ltd. (72) Yasutoku Minamisato 2-chome, Iida-cho, Iwakuni-shi, Yamaguchi No. 8-1 Nippon Paper Industries Co., Ltd. Iwakuni Technical Research Laboratory F-term (reference) 4L055 AG11 AG12 AG27 AG48 AG89 AG94 AG97 AH01 AH02 AH37 AJ04 BC07 BE02 BE08 EA08 EA16 EA20 EA32 FA12 FA13 FA14 FA16 GA19
Claims (4)
塗被するオフセット印刷用塗被紙において、原紙製造時
に填料として、硫酸塩法またはソーダ法によるパルプ製
造工程の苛性化工程で、生石灰を水または弱液で消和し
た後、緑液で苛性化反応することによって製造された長
径５．０〜１０．０ μm、短径０．２〜０．５μmの範
囲内にある針状または柱状の軽質炭酸カルシウムを、原
紙中に４〜１０重量％含有した原紙に、塗被液を塗被・
乾燥した後、１３０℃以上のソフトカレンダー処理する
ことを特徴とするオフセット印刷用塗被紙の製造方法。1. A coated paper for offset printing in which a base paper is coated with a coating liquid containing a pigment and an adhesive, in a causticizing step of a pulp manufacturing process by a sulfate method or a soda method as a filler during the manufacture of the base paper. A needle having a major axis of 5.0 to 10.0 μm and a minor axis of 0.2 to 0.5 μm manufactured by slaking quicklime with water or a weak liquid and then subjecting it to a caustic reaction with green liquor. A coating liquid is applied to base paper containing 4 to 10% by weight of base or columnar light calcium carbonate in base paper.
A method for producing coated paper for offset printing, wherein the coated paper is subjected to a soft calender treatment at 130 ° C. or more after drying.
重合体ラテックスを含有することを特徴とする請求項１
に記載のオフセット印刷用塗被紙の製造方法。2. The adhesive according to claim 1, wherein the adhesive in the coating liquid contains a copolymer latex of 50 to 90 nm.
3. The method for producing a coated paper for offset printing according to item 1.
ラテックスを顔料１００重量部に対して4〜８重量部含
有することを特徴とする請求項１または２に記載のオフ
セット印刷用塗被紙の製造方法。3. The coating for offset printing according to claim 1, wherein the coating composition contains 4 to 8 parts by weight of a copolymer latex having an average particle diameter of 50 to 90 nm based on 100 parts by weight of the pigment. Paper manufacturing method.
で製造された塗被紙の密度が１．００ｇ／ｃｍ3以下で
あることを特徴とするオフセット印刷用塗被紙。4. A coated paper for offset printing, wherein the density of the coated paper produced by the production method according to claim 1 is 1.00 g / cm 3 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34074998A JP3572969B2 (en) | 1998-11-30 | 1998-11-30 | Method for producing coated paper for offset printing and coated paper for offset printing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34074998A JP3572969B2 (en) | 1998-11-30 | 1998-11-30 | Method for producing coated paper for offset printing and coated paper for offset printing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000160495A true JP2000160495A (en) | 2000-06-13 |
| JP3572969B2 JP3572969B2 (en) | 2004-10-06 |
Family
ID=18339943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34074998A Expired - Fee Related JP3572969B2 (en) | 1998-11-30 | 1998-11-30 | Method for producing coated paper for offset printing and coated paper for offset printing |
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| Country | Link |
|---|---|
| JP (1) | JP3572969B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8382946B2 (en) | 2006-12-11 | 2013-02-26 | International Paper Company | Paper sizing composition, sized paper, and method for sizing paper |
| CN105155332A (en) * | 2015-09-15 | 2015-12-16 | 岳阳林纸股份有限公司 | Production method of top-grade book white offset printing paper |
-
1998
- 1998-11-30 JP JP34074998A patent/JP3572969B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8382946B2 (en) | 2006-12-11 | 2013-02-26 | International Paper Company | Paper sizing composition, sized paper, and method for sizing paper |
| CN105155332A (en) * | 2015-09-15 | 2015-12-16 | 岳阳林纸股份有限公司 | Production method of top-grade book white offset printing paper |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3572969B2 (en) | 2004-10-06 |
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