JPH05311599A - Filler for paper and paper using the same - Google Patents

Filler for paper and paper using the same

Info

Publication number
JPH05311599A
JPH05311599A JP4109636A JP10963692A JPH05311599A JP H05311599 A JPH05311599 A JP H05311599A JP 4109636 A JP4109636 A JP 4109636A JP 10963692 A JP10963692 A JP 10963692A JP H05311599 A JPH05311599 A JP H05311599A
Authority
JP
Japan
Prior art keywords
paper
filler
weight
silicate
pore
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.)
Granted
Application number
JP4109636A
Other languages
Japanese (ja)
Other versions
JP3084125B2 (en
Inventor
Yoshiaki Koga
義明 古賀
Genji Taga
玄治 多賀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokuyama Corp
Original Assignee
Tokuyama Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tokuyama Corp filed Critical Tokuyama Corp
Priority to JP04109636A priority Critical patent/JP3084125B2/en
Priority to US07/922,837 priority patent/US5262142A/en
Priority to SE9202276A priority patent/SE504446C2/en
Priority to CA002075314A priority patent/CA2075314A1/en
Priority to DE4225927A priority patent/DE4225927A1/en
Priority to US08/067,003 priority patent/US5336477A/en
Publication of JPH05311599A publication Critical patent/JPH05311599A/en
Application granted granted Critical
Publication of JP3084125B2 publication Critical patent/JP3084125B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Abstract

PURPOSE:To obtain a filler for paper having high absorption of ink and print through preventing effect. CONSTITUTION:The objective filler for paper is characterized in that the filler consists of a water-containing silicic acid or a silicic acid salt and integrated volume of pores having <=5X10<10>Angstrom pore radius is 1.9-4.0cc/g and integrated volume of pares having pare radius in the range of 100-1000Angstrom is >=0.6cc/g.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、インクの吸収性および
裏抜け防止効果の良好な紙用填料に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paper filler having good ink absorbency and strike-through prevention effect.

【0002】[0002]

【従来の技術】紙用填料としては、含水ケイ酸、尿素ホ
ルムアルデヒドポリマー及びケイ酸アルミニウム等が知
られている。これらの紙用填料は、紙の白色度、白紙不
透明度の向上及びインクの裏抜け防止のために紙に含有
させる方法で良く使用されている。しかし、これら填料
は、紙の軽量化のために紙への混合量を減少させ、例え
ば、坪量を40g/m2 以下とすると裏抜け防止効果が
悪くなるという問題があった。
2. Description of the Related Art As fillers for paper, hydrous silicic acid, urea formaldehyde polymer, aluminum silicate and the like are known. These paper fillers are often used in a method of incorporating them in paper in order to improve whiteness and opacity of white paper and prevent strike-through of ink. However, these fillers have a problem that the amount of mixing into the paper is reduced in order to reduce the weight of the paper and, for example, if the basis weight is 40 g / m 2 or less, the strike-through prevention effect is deteriorated.

【0003】[0003]

【発明が解決しようとする課題】本発明は、紙中の填料
の含有量を少なくしても、インクの吸収性及び裏抜け防
止効果の優れた紙用填料を提供するものである。
SUMMARY OF THE INVENTION The present invention provides a paper filler having excellent ink absorbency and strike-through prevention effect even when the content of the filler in the paper is reduced.

【0004】[0004]

【課題を解決するための手段】そこで、本発明者らは、
インクの吸収性及び裏抜け防止効果の高い紙用填料を開
発することを目的とし、填料の物性とインクの吸収性及
び裏抜け防止効果の関係について鋭意研究を重ねた。そ
の結果、従来、インクの裏抜け防止効果は填料の吸油量
の大小に依存すると考えられていたが、本発明者らの研
究の結果、填料の細孔径分布とその細孔容積が重要であ
ることがわかった。即ち、インクは顔料とビヒクルによ
って構成されているが、顔料とビヒクルの吸収及び吸着
される填料の細孔半径がそれぞれ異なることがわかっ
た。顔料は、細孔半径が3000〜4×104オングス
トロームの範囲である細孔に吸収及び吸着され、ビヒク
ルは、細孔半径が100〜1000オングストロームの
範囲である細孔に吸収されることが、本発明者らの実験
により明らかになった。
Therefore, the present inventors have
For the purpose of developing a paper filler with high ink absorbency and strike-through prevention effect, we have conducted intensive studies on the relationship between the physical properties of the filler and the ink absorbency and strike-through prevention effect. As a result, it has been conventionally considered that the ink strike-through prevention effect depends on the oil absorption amount of the filler, but as a result of the research conducted by the present inventors, the pore size distribution of the filler and its pore volume are important. I understood it. That is, it was found that the ink is composed of the pigment and the vehicle, but the pore radii of the filler absorbed and adsorbed by the pigment and the vehicle are different. The pigment is absorbed and adsorbed in the pores having a pore radius in the range of 3000 to 4 × 10 4 angstroms, and the vehicle is absorbed in the pores having a pore radius in the range of 100 to 1000 angstroms. It became clear by the experiments of the present inventors.

【0005】本発明者らは、インクを吸収するに十分な
細孔分布を有する含水ケイ酸又はケイ酸塩が本発明の目
的を達成する紙用填料となり得ることを見い出し、本発
明を提案するに到った。
The present inventors have found that hydrous silicic acid or silicate having a pore distribution sufficient to absorb ink can be a paper filler for achieving the object of the present invention, and propose the present invention. Came to.

【0006】即ち、本発明は、含水ケイ酸またはケイ酸
塩よりなり、細孔半径が5×104オングストローム以
下である細孔の積算容積が1.9〜4.0cc/gであ
り、3000〜4×104オングストロームの範囲であ
る細孔の積算容積が0.5cc/g以上であり、かつ、
細孔半径が100〜1000オングストロームの範囲で
ある細孔の積算容積が0.6cc/g以上であることを
特徴とする紙用填料である。
That is, according to the present invention, the cumulative volume of pores made of hydrous silicic acid or silicate and having a pore radius of 5 × 10 4 Å or less is 1.9 to 4.0 cc / g, and 3000. The cumulative volume of pores in the range of 4 × 10 4 angstroms is 0.5 cc / g or more, and
It is a paper filler characterized in that the cumulative volume of pores having a pore radius in the range of 100 to 1000 angstroms is 0.6 cc / g or more.

【0007】本発明の紙用填料は、含水ケイ酸またはケ
イ酸塩からなる。含水ケイ酸は、一般式SiO2・nH2
O(nは正の数である。)で示される化合物であり、少
量の、例えば、2重量%未満の不純物が含まれていても
よい。ケイ酸塩は、ケイ素以外の金属を酸化物換算で2
〜30重量%含む化合物が好適である。具体的には、ケ
イ酸カルシウム、ケイ酸マグネシウム、ケイ酸アルミニ
ウム、ケイ酸チタニウム、ケイ酸アルミニウムチタニウ
ム等の化合物を挙げることができる。
The paper filler of the present invention comprises hydrous silicic acid or silicate. Hydrous silicic acid has the general formula SiO 2 · nH 2
It is a compound represented by O (n is a positive number), and may contain a small amount of impurities, for example, less than 2% by weight. Silicate is a metal other than silicon in terms of oxide 2
Compounds containing up to 30% by weight are preferred. Specific examples thereof include compounds such as calcium silicate, magnesium silicate, aluminum silicate, titanium silicate, and aluminum titanium silicate.

【0008】本発明の紙用填料は、特定の細孔分布を有
する。まず、細孔半径が5×104オングストローム以
下である細孔の積算容積が1.9〜4.0cc/gであ
る。上記の細孔容積が1.9cc/gより小さいとき
は、吸油量が小さくなり、そのような化合物を紙の填料
として使用してもインクの吸収性、着肉性に乏しいため
にインクの裏抜防止効果に欠ける。一方、細孔半径が5
×104オングストローム以下である細孔の積算容積が
4.0cc/gよりも大きいものは製造が困難である。
上記の細孔半径が5×104オングストローム以下であ
る細孔の積算容積は、吸油量を大きくしかも製造を容易
にするためには、2.0〜3.6cc/gの範囲である
ことが好ましい。
The paper filler of the present invention has a specific pore distribution. First, the cumulative volume of pores having a pore radius of 5 × 10 4 angstroms or less is 1.9 to 4.0 cc / g. When the pore volume is smaller than 1.9 cc / g, the oil absorption becomes small, and even if such a compound is used as a filler for paper, the ink absorbency and inking property are poor and the ink backing is poor. Lack of pull-out prevention effect. On the other hand, the pore radius is 5
If the cumulative volume of pores of 10 4 Å or less is larger than 4.0 cc / g, it is difficult to manufacture.
The cumulative volume of the pores having a pore radius of 5 × 10 4 angstroms or less is in the range of 2.0 to 3.6 cc / g in order to increase the oil absorption and to facilitate the production. preferable.

【0009】また、本発明の紙用填料は、細孔半径が3
000〜4×104オングストロームの範囲である細孔
の積算容積が0.5cc/g以上である。上記の細孔半
径の細孔にはインクの成分のうち顔料が吸収される。し
たがって、上記の細孔半径の細孔容積が0.5cc/g
未満のときには、インクの成分のうち顔料の吸収性に劣
るために、インクの吸収性の良好な紙用填料となり得な
い。上記の細孔半径の細孔容積は、インクの吸収性の十
分な紙用填料とするためには、0.6〜1.5cc/g
の範囲であることが好ましい。
The paper filler of the present invention has a pore radius of 3
The cumulative volume of pores in the range of 000 to 4 × 10 4 angstroms is 0.5 cc / g or more. Pigments of the ink components are absorbed in the pores having the above-described pore radii. Therefore, the pore volume of the above-mentioned pore radius is 0.5 cc / g
When the amount is less than the above range, the pigment cannot be used as a paper filler having good ink absorbency because the pigment absorbability is poor among the ink components. The pore volume of the above-mentioned pore radius is 0.6 to 1.5 cc / g in order to obtain a paper filler having sufficient ink absorbency.
The range is preferably.

【0010】さらに、本発明の紙用填料は、細孔半径が
100〜1000オングストロームの範囲である細孔に
積算容積が0.6cc/g以上である。上記の細孔半径
の細孔にはインクの成分のうちビヒクルが吸収される。
したがって、上記の細孔半径の細孔容積が0.6cc/
g未満のときには、インクの成分のうちビヒクルの吸収
性に劣るために、インクの吸収性及び裏抜け防止効果の
良好な紙用填料となり得ない。上記の細孔半径の細孔容
積は、インクの吸収性の十分な填料を得るためには、
0.7〜1.6cc/gの範囲であることが好ましい。
Further, the paper filler of the present invention has a cumulative volume of 0.6 cc / g or more in pores having a pore radius of 100 to 1000 angstroms. Vehicles of the ink components are absorbed in the pores having the above-described pore radii.
Therefore, the pore volume of the above-mentioned pore radius is 0.6 cc /
When the amount is less than g, the ink cannot be used as a paper filler having good ink absorbency and strike-through prevention effect, because the ink absorbency of the vehicle is poor. The pore volume of the above-mentioned pore radius is in order to obtain a filler having sufficient ink absorbency.
It is preferably in the range of 0.7 to 1.6 cc / g.

【0011】なお、本発明において、細孔の積算容積
は、水銀ポロシメーターを用いて測定した値である。
In the present invention, the cumulative volume of pores is a value measured using a mercury porosimeter.

【0012】本発明の紙用填料は、通常、粒子径8〜5
0nmの一次粒子が凝集して形成された、粒子径1〜5
00μmの凝集粒子であり、水に分散させたスラリー状
態で測定された平均凝集粒子径は10〜25μmの範囲
である。また、本発明の紙用填料の表面積は、通常、1
00〜300m2 /gの範囲である。
The paper filler of the present invention usually has a particle size of 8-5.
Particle size 1 to 5 formed by agglomeration of 0 nm primary particles
The agglomerated particles are 00 μm, and the average agglomerated particle diameter measured in a slurry state of being dispersed in water is in the range of 10 to 25 μm. The surface area of the paper filler of the present invention is usually 1
The range is from 00 to 300 m 2 / g.

【0013】本発明の紙用填料を水に分散させた分散液
のpHは5〜7の範囲であり、ほぼ中性である。また、
本発明の紙用填料を水中に分散させてもほとんど水に溶
出することはない。
The pH of the dispersion obtained by dispersing the paper filler of the present invention in water is in the range of 5 to 7, which is almost neutral. Also,
Even if the paper filler of the present invention is dispersed in water, it hardly elutes in water.

【0014】本発明の紙用填料はどのような方法によっ
て製造されてもよい。一般には、次に述べる方法によっ
て好適に製造することができる。
The paper filler of the present invention may be manufactured by any method. Generally, it can be suitably produced by the method described below.

【0015】塩類の存在下にシリカ換算濃度7〜10重
量%のケイ酸アルカリ水溶液に10〜45℃で中和率2
0〜40%となるように鉱酸及び/又はケイ酸アルカリ
と反応してケイ酸塩を形成し得る塩の酸性水溶液を添加
する第1工程と、該第1工程で得られた反応液を95℃
〜該反応液の沸点以下の温度に昇温して熟成し、該反応
液のpHが3〜5になるように鉱酸及び/又はケイ酸ア
ルカリと反応してケイ酸塩を形成し得る塩の酸性水溶液
を添加する第2工程よりなる方法である。
Neutralization rate of 2 at 10 to 45 ° C. in an aqueous solution of alkali silicate having a silica conversion concentration of 7 to 10% by weight in the presence of salts.
A first step of adding an acidic aqueous solution of a salt capable of reacting with a mineral acid and / or an alkali silicate to form a silicate so as to be 0 to 40%, and the reaction solution obtained in the first step 95 ° C
~ A salt capable of forming a silicate by reacting with a mineral acid and / or an alkali silicate so as to have a pH of the reaction liquid of 3 to 5 by aging by heating to a temperature not higher than the boiling point of the reaction liquid. The method comprises the second step of adding the acidic aqueous solution.

【0016】まず、上記方法の第1工程では、塩類の存
在下にシリカ換算濃度が7〜10重量%のケイ酸アルカ
リ水溶液に10〜45℃で中和率が20〜40%となる
ように鉱酸及び/又はケイ酸アルカリと反応してケイ酸
塩を形成し得る塩の酸性水溶液が添加される。
First, in the first step of the above method, the neutralization rate is adjusted to 20 to 40% at 10 to 45 ° C. in an alkaline silicate aqueous solution having a silica conversion concentration of 7 to 10% by weight in the presence of salts. An acidic aqueous solution of a salt capable of reacting with a mineral acid and / or an alkali silicate to form a silicate is added.

【0017】ケイ酸アルカリとしては、通常、ケイ酸ナ
トリウムが使用される。ケイ酸アルカリ水溶液の濃度
は、シリカ換算濃度で7〜10重量%の範囲でなければ
ならず、8〜9重量%であることが好ましい。ケイ酸ア
ルカリ水溶液の濃度が上記の範囲をはずれた場合には、
得られる紙用填料の細孔容積が小さくなるために好まし
くない。
As the alkali silicate, sodium silicate is usually used. The concentration of the aqueous alkali silicate solution must be in the range of 7 to 10% by weight in terms of silica, and preferably 8 to 9% by weight. If the concentration of the aqueous alkali silicate solution is out of the above range,
It is not preferable because the resulting paper filler has a small pore volume.

【0018】ケイ酸アルカリ水溶液に添加される鉱酸と
しては、公知のものが何等制限なく採用される。具体的
には、塩酸、硫酸、硝酸等が採用されるが、通常は硫酸
が使用される。鉱酸の濃度は特に制限されないが、一般
には10〜30重量/体積%の範囲から選べばよい。
As the mineral acid to be added to the aqueous solution of alkali silicate, known ones can be adopted without any limitation. Specifically, hydrochloric acid, sulfuric acid, nitric acid or the like is adopted, but sulfuric acid is usually used. The concentration of the mineral acid is not particularly limited, but it may be generally selected from the range of 10 to 30% by weight / volume.

【0019】また、ケイ酸アルカリ水溶液に添加される
塩の酸性水溶液としては、ケイ酸アルカリと反応してケ
イ酸塩を形成し得る塩の酸性水溶液が何ら制限なく使用
される。例えば、硫酸マグネシウム、硫酸アルミニウ
ム、硫酸チタニウム等の硫酸塩の酸性水溶液を好適に使
用し得る。
As the acidic aqueous solution of the salt added to the aqueous alkaline silicate solution, an acidic aqueous solution of a salt capable of reacting with an alkaline silicate to form a silicate is used without any limitation. For example, an acidic aqueous solution of sulfate such as magnesium sulfate, aluminum sulfate and titanium sulfate can be preferably used.

【0020】特に硫酸チタニウム等のチタン化合物の酸
性水溶液を使用したときは、得られる紙用填料の成形性
と隠蔽力を向上させることができるため、紙の強度と不
透明性を向上させることができる。上記の塩の酸性水溶
液の濃度は、酸化物換算濃度で3〜8重量%の範囲であ
ることが好ましい。また、上記に例示した塩を溶解した
水溶液はそのままで酸性を示すが、さらに、塩酸や硫酸
を添加しても良い。酸性水溶液の酸濃度は、一般には1
0〜30重量/体積%の範囲であることが、良好な紙用
填料を得るために好適である。
In particular, when an acidic aqueous solution of a titanium compound such as titanium sulfate is used, the moldability and hiding power of the resulting paper filler can be improved, so that the strength and opacity of the paper can be improved. .. The concentration of the acidic aqueous solution of the above salt is preferably in the range of 3 to 8% by weight in terms of oxide concentration. The aqueous solution in which the salts exemplified above are acidic as they are, but hydrochloric acid or sulfuric acid may be further added. The acid concentration of the acidic aqueous solution is generally 1
The range of 0 to 30% by weight / volume is suitable for obtaining a good paper filler.

【0021】鉱酸及び/又はケイ酸アルカリと反応して
ケイ酸塩を形成し得る塩の酸性水溶液のケイ酸アルカリ
水溶液への添加は、中和率が20〜40%の範囲となる
ように行われる。ここで、中和率とは、ケイ酸アルカリ
水溶液の中和に必要な上記の鉱酸及び/又は酸性水溶液
の量を使用したときを100%とした、中和の程度を示
す指標である。中和率が20%よりも低いときは、一次
粒子が大きくなって粒子の凝集が弱くなるため細孔容積
が小さくなる。中和率が40%を越えるときは、粒子の
凝集が強くなり3000〜4×104オングストローム
の細孔が0.5cc/g未満となる。インクの吸収性と
及び裏抜け防止効果の優れた紙用填料を得るためには、
中和率は23〜35%の範囲であることが好ましい。
Addition of an acidic aqueous solution of a salt capable of reacting with a mineral acid and / or an alkali silicate to form a silicate to the aqueous alkali silicate solution has a neutralization ratio of 20 to 40%. Done. Here, the neutralization rate is an index showing the degree of neutralization, where 100% is the amount of the above-mentioned mineral acid and / or acidic aqueous solution necessary for neutralizing the alkaline silicate aqueous solution. When the neutralization rate is lower than 20%, the primary particles become large and the aggregation of the particles becomes weak, so that the pore volume becomes small. When the neutralization rate exceeds 40%, the aggregation of particles becomes strong and the number of pores of 3000 to 4 × 10 4 angstrom becomes less than 0.5 cc / g. To obtain a paper filler excellent in ink absorbency and strike-through prevention effect,
The neutralization rate is preferably in the range of 23 to 35%.

【0022】第1工程では塩類の存在下に反応が行われ
る。塩類は、公知の水溶性無機塩が何等制限なく採用さ
れるが、一般には核形成作用のある水溶性無機塩が好適
に採用される。具体的には、塩化ナトリウム、硫酸ナト
リウム、硝酸ナトリウム、塩化カリウム、硫酸カリウ
ム、硝酸カリウム等のアルカリ金属塩を例示することが
できる。上記の塩類の濃度は、特に制限されないが、通
常は酸化物換算濃度でケイ酸アルカリ水溶液中に0.5
〜5重量%の範囲から選ばれる。塩類は、鉱酸及び/又
は塩の酸性水溶液を添加する前に反応液中に添加してお
くことが、細孔分布、成形性が良好であり、スラリー状
態での粉砕による細孔容積の減少の小さい紙用填料が得
られるために好ましい。
In the first step, the reaction is carried out in the presence of salts. As the salt, a known water-soluble inorganic salt is used without any limitation, but generally, a water-soluble inorganic salt having a nucleating action is preferably used. Specific examples thereof include alkali metal salts such as sodium chloride, sodium sulfate, sodium nitrate, potassium chloride, potassium sulfate and potassium nitrate. The concentration of the above-mentioned salts is not particularly limited, but is usually 0.5 in terms of the oxide conversion concentration in the aqueous alkali silicate solution.
Is selected from the range of 5 wt%. It is preferable to add the salt to the reaction solution before adding the acidic aqueous solution of the mineral acid and / or the salt, because the pore distribution and moldability are good, and the volume of the pore is reduced by pulverization in a slurry state. It is preferable since a small paper filler can be obtained.

【0023】第1工程の反応は、10〜45℃で行われ
る。反応温度が、上記範囲をはずれた場合には、細孔容
積が小さくなるために好ましくない。
The reaction of the first step is carried out at 10 to 45 ° C. When the reaction temperature is out of the above range, the pore volume becomes small, which is not preferable.

【0024】次に本発明の方法の第2工程では、上記の
第1工程で得られた反応液が95℃〜該反応液の沸点以
下の温度に昇温される。反応液の温度が上記の範囲をは
ずれた場合には、細孔容積が小さくなるために好ましく
ない。そして、この温度で熟成される。熟成の時間は特
に制限されないが、通常は10〜30分間の範囲から選
択すればよい。
Next, in the second step of the method of the present invention, the temperature of the reaction liquid obtained in the first step is raised to 95 ° C. to a temperature not higher than the boiling point of the reaction liquid. When the temperature of the reaction solution is out of the above range, the pore volume becomes small, which is not preferable. Then, it is aged at this temperature. The aging time is not particularly limited, but it is usually selected from the range of 10 to 30 minutes.

【0025】第2工程においては、反応液のpHが3〜
5になるように鉱酸及び/又はケイ酸アルカリと反応し
てケイ酸塩を形成し得る塩の酸性水溶液が添加される。
反応液のpHが3未満の場合は、紙用填料の成分が液中
で溶解しやすくなり、また、成形性が悪化する。反応液
のpHが5を越えると紙用填料の成分の生成が不十分と
なり、満足する細孔容積のものが得られない。
In the second step, the pH of the reaction solution is 3 to
An acidic aqueous solution of a salt capable of reacting with a mineral acid and / or an alkali silicate to form a silicate so as to be 5 is added.
When the pH of the reaction liquid is less than 3, the components of the paper filler are easily dissolved in the liquid and the moldability is deteriorated. If the pH of the reaction liquid exceeds 5, the components of the paper filler will be insufficiently produced, and a product having a satisfactory pore volume cannot be obtained.

【0026】鉱酸及び/又は塩の酸性水溶液は徐々に添
加することが好ましく、通常は、これらを60〜120
の時間をかけて添加することが好ましい。
The acidic aqueous solution of the mineral acid and / or salt is preferably added slowly, and usually 60 to 120
It is preferable to add it over time.

【0027】本発明の紙用填料は、紙の原料パルプ繊維
中に分散させた内填剤として使用することもでき、ま
た、紙の表面コート剤として使用することもできる。上
記方法で紙用填料を製造後、余分な塩をろ過等の手段に
よって除去したのち、水に分散させたスラリー状態で保
管し、粉砕および分級を行った後スラリー状態のまま紙
の原料と混合して製紙することができ、また、上記方法
で製造した紙用填料を乾燥後、粉体として保管し、これ
を紙の原料と混合するときに水に再分散させて使用する
こともできる。本発明の紙用填料とパルプ繊維との配合
量は、特に制限されないが、本発明においては紙用填料
の少量の配合で十分なインクの裏抜け防止効果を発揮さ
せることができる。通常は、紙中に占める割合で0.1
〜2重量%、好ましくは0.3〜1.5重量%の範囲か
ら選べば十分である。
The paper filler of the present invention can be used as an internal filler dispersed in a raw pulp fiber of paper, or can be used as a surface coating agent for paper. After the paper filler is manufactured by the above method, excess salt is removed by means such as filtration, stored in a slurry state dispersed in water, crushed and classified, and then mixed with the paper raw material in the slurry state. Alternatively, the paper filler produced by the above-mentioned method may be dried and stored as a powder, which may be redispersed in water when mixed with a paper raw material. The amounts of the paper filler and pulp fiber of the present invention to be blended are not particularly limited, but in the present invention, a small amount of the paper filler can exhibit a sufficient ink strike-through prevention effect. Normally, it is 0.1 in the paper.
It is sufficient to select from the range of ˜2% by weight, preferably 0.3 to 1.5% by weight.

【0028】[0028]

【効果】本発明の紙用填料は良好な細孔分布を有する。
このため、本発明の紙用填料は、インクの吸収性に優れ
るためにインクの裏抜防止効果が十分である。さらに、
本発明の紙用填料は、優れた隠蔽力を有するために紙の
不透明性を向上させることもできる。
[Effect] The paper filler of the present invention has a good pore distribution.
Therefore, the paper filler of the present invention is excellent in ink absorbency and therefore has a sufficient ink strike-through prevention effect. further,
Since the paper filler of the present invention has excellent hiding power, it can also improve the opacity of paper.

【0029】さらに、本発明の紙用填料は、スラリー状
態で粉砕を行っても細孔半径が3000〜4×104
ングストロームの細孔の容積の減少が小さく、したがっ
て、インクを構成する顔料およびビヒクルの吸収性が共
に良好で、インクの裏抜防止効果が優れる。
Further, the paper filler of the present invention has a small decrease in the volume of the pores having a pore radius of 3000 to 4 × 10 4 angstroms even if it is pulverized in a slurry state. The vehicle absorbency is good, and the ink strike-through prevention effect is excellent.

【0030】[0030]

【実施例】本発明をさらに詳細に説明するために、以下
に実施例及び比較例を掲げるが、本発明はこれら実施例
に限定されるものではない。
EXAMPLES In order to explain the present invention in more detail, examples and comparative examples are given below, but the present invention is not limited to these examples.

【0031】なお、本発明において種々の物性は、次の
方法により測定した。
Various physical properties in the present invention were measured by the following methods.

【0032】(1)化学組成 蛍光X線分析装置(理学電機(株)製)を使用して測定
した。
(1) Chemical composition It was measured using a fluorescent X-ray analyzer (manufactured by Rigaku Denki Co., Ltd.).

【0033】(2)細孔容積 水銀ポロシメーター(カルロエルバ社製2000型)を
使用して測定した。尚、細孔半径が5×104オングス
トローム以下の細孔の細孔容積は、細孔半径が37.5
〜5×104オングストロームの細孔について測定し
た。
(2) Pore volume Measured using a mercury porosimeter (2000 type, manufactured by Carlo Erba Co.). The pore volume of pores having a pore radius of 5 × 10 4 angstroms or less has a pore radius of 37.5.
Measured for ˜5 × 10 4 Angstrom pores.

【0034】(3)比表面積 BET法により測定した。(3) Specific surface area Measured by the BET method.

【0035】(4)吸油量 JIS K5101に準拠。(4) Oil absorption amount According to JIS K5101.

【0036】(5)平均粒径 コールターマルチサイザー(コールターエレクトロニク
ス社製)使用。
(5) Average particle size Coulter Multisizer (manufactured by Coulter Electronics) is used.

【0037】(6)pH測定 反応液をサンプリングし、pHメーター(堀場製作所
製)により測定。
(6) pH measurement The reaction solution was sampled and measured with a pH meter (manufactured by Horiba Ltd.).

【0038】(7)抄紙 パルプとして、NBKP(ニードルリーフ・ブリーチン
グ・クラフト・パルプ)10重量部、TMP(サーモメ
カニカル・パルプ)45重量部およびDIP(デインキ
ング・パルプ)45重量部が配合された混合物をビータ
ーで5〜6分攪拌した後、本発明の紙用填料を乾燥パル
プ基準で2重量%添加し、15分攪拌した。その後、硫
酸アルミニウムでスラリーpHを4.5に調整した。次
に角型シートマシン(300mm×300mm)にて抄
紙し、プレス脱水を行って得た湿紙を表面温度110℃
の回転ドライヤーで乾燥を行った後、相対湿度65%、
温度25℃にて24時間シーズニングを行って、坪量4
0g/m2 の紙を得た。
(7) Papermaking As pulp, 10 parts by weight of NBKP (needle leaf bleaching craft pulp), 45 parts by weight of TMP (thermo-mechanical pulp) and 45 parts by weight of DIP (deinking pulp) are blended. After stirring the mixture with a beater for 5 to 6 minutes, 2% by weight of the paper filler of the present invention was added based on the dry pulp, and the mixture was stirred for 15 minutes. Then, the slurry pH was adjusted to 4.5 with aluminum sulfate. Next, the wet paper obtained by making paper with a square sheet machine (300 mm x 300 mm) and performing press dehydration has a surface temperature of 110 ° C.
After drying with a rotary dryer of 65% relative humidity,
Seasoning is carried out at a temperature of 25 ° C for 24 hours, and the basis weight is 4
0 g / m 2 of paper was obtained.

【0039】(8)印刷後の紙の不透明性 市販の印刷機(RICOH PRIPORT SS88
0:(株)リコー製)を用いて紙の片面に80×120
mmのベタ印刷を行った後に印刷後不透明性を測定し
た。
(8) Opacity of paper after printing Commercially available printer (RICOH PRIPORT SS88)
0: 80 × 120 on one side of paper using Ricoh Co., Ltd.
After performing solid printing of mm, the opacity was measured after printing.

【0040】印刷後不透明性=(印刷後の紙の裏面反射
率)/(未印刷の紙の裏面反射率)×100 実施例1 市販のケイ酸ソーダ(SiO2 26.50重量%、S
iO2/Na2Oモル比3.04)1811ml、ボウ硝
(Na2O 2.38重量%)2521ml、及び水1
668mlを10lの外部加熱方式の反応槽へ投入して
攪拌した(シリカ換算濃度8重量%)。第1工程におい
て、反応液温度35℃で、中和率を30%とするために
22%重量/体積%の硫酸351mlを投入した。その
後、第2工程において、95℃まで昇温し、昇温後、そ
のままの状態で10分間攪拌した。次に22%硫酸79
6mlを100分かけて投入し、反応液のpHを3.6
として反応を終了した。この反応液をろ過、水洗した
後、固形分濃度が13〜14%となるように水に再分散
させ、この分散液600mlを2lのポリ容器に入れ、
大きさ2mmのガラスビーズ1kgとともに回転数42
0rpmで5分間粉砕した後、145メッシュの篩で篩
分けし、篩下の分散液中の固形分について粒度分布を測
定した。次にこの分散液をろ過、水洗、乾燥し、この乾
燥物の細孔径分布を水銀ポロシメーターで測定した。そ
の結果を表1に示した。抄紙テストには上記の分散液を
使用した。
Opacity after printing = (back surface reflectance of paper after printing) / (back surface reflectance of unprinted paper) × 100 Example 1 Commercially available sodium silicate (26.50% by weight of SiO 2 , S)
iO 2 / Na 2 O molar ratio 3.04) 1811 ml, Glauber's salt (Na 2 O 2.38 wt%) 2521 ml, and water 1
668 ml was put into a 10 l external heating type reaction tank and stirred (silica conversion concentration 8% by weight). In the first step, 351 ml of 22% weight / volume% sulfuric acid was added at a reaction solution temperature of 35 ° C. in order to obtain a neutralization rate of 30%. Then, in the second step, the temperature was raised to 95 ° C., and after the temperature was raised, the mixture was stirred as it was for 10 minutes. Next, 22% sulfuric acid 79
Add 6 ml over 100 minutes to adjust the pH of the reaction solution to 3.6.
And the reaction was completed. After the reaction solution was filtered and washed with water, it was redispersed in water so that the solid content concentration became 13 to 14%, and 600 ml of this dispersion solution was put in a 2 l poly container,
Number of rotations 42 with 1 kg of glass beads of size 2 mm
After pulverizing at 0 rpm for 5 minutes, sieving was performed with a 145 mesh sieve, and the particle size distribution of the solid content in the dispersion liquid under the sieve was measured. Next, this dispersion was filtered, washed with water and dried, and the pore size distribution of this dried product was measured with a mercury porosimeter. The results are shown in Table 1. The above dispersion was used in the papermaking test.

【0041】[0041]

【表1】 [Table 1]

【0042】実施例2 実施例1において、市販のケイ酸ソーダ(SiO2
7.04重量%、SiO2/Na2O=3.06)155
3ml、ボウ硝(Na2O 2.47重量%)2429
ml、水酸化アルミニウム粉末68g及び水2018m
l(シリカ換算濃度7重量%)と第1工程で硫酸356
mlを投入して中和率を35%とし、第2工程の硫酸6
08mlを90分で投入した以外は同様に反応し、反応
液のpH=4.3として反応を終了した。これ以後は実
施例1と同様にした。その結果を表1に示した。また、
図1に細孔分布の測定結果を示した。図中、(A)は細
孔の積算容積を示す曲線であり、(B)はその微分曲線
である。
Example 2 In Example 1, commercially available sodium silicate (SiO 2 2
7.04% by weight, SiO 2 / Na 2 O = 3.06) 155
3 ml, Glauber's salt (2.47 wt% Na 2 O) 2429
ml, aluminum hydroxide powder 68g and water 2018m
1 (silica conversion concentration 7% by weight) and sulfuric acid 356 in the first step
Add ml to make the neutralization rate 35%, and add 6% sulfuric acid in the second step.
The reaction was carried out in the same manner except that 08 ml was charged in 90 minutes, and the reaction was terminated by setting the pH of the reaction solution to 4.3. After that, the same procedure as in Example 1 was performed. The results are shown in Table 1. Also,
The measurement result of the pore distribution is shown in FIG. In the figure, (A) is a curve showing the cumulative volume of pores, and (B) is its differential curve.

【0043】実施例3 実施例1において、ケイ酸ソーダ(SiO2 26.7
1重量%、SiO2/Na2O=3.05)1572m
l、ボウ硝(Na2O 1.97重量%)3045ml
及び水1383ml(シリカ換算濃度7重量%)と第1
工程に22重量/体積%の硫酸303mlを投入して中
和率30%とし、第2工程に硫酸濃度25.5重量/体
積%(TiO2 分6重量%)の硫酸チタン溶液586m
lを100分で投入した以外は同様に反応し、反応液の
pH=3.5として反応を終了した。これ以後は実施例
1と同様にした。その結果を表1に示した。
Example 3 In Example 1, sodium silicate (SiO 2 26.7) was used.
1% by weight, SiO 2 / Na 2 O = 3.05) 1572 m
1, Glauber's salt (1.97% by weight of Na 2 O) 3045 ml
And 1383 ml of water (concentration of silica 7% by weight) and first
Into the step, 303 ml of 22% by weight / volume% sulfuric acid was added to make the neutralization rate 30%, and in the second step, 586 m of titanium sulfate solution having a sulfuric acid concentration of 25.5% by weight (TiO 2 content 6% by weight).
The reaction was performed in the same manner except that 1 was added for 100 minutes, and the pH of the reaction solution was set to 3.5 to terminate the reaction. After that, the same procedure as in Example 1 was performed. The results are shown in Table 1.

【0044】実施例4 実施例1において、ケイ酸ソーダ(SiO2 27.0
4重量%、SiO2/Na2O=3.06)1775m
l、ボウ硝(Na2O 2.11重量%)2844ml
及び水1381ml(シリカ換算濃度8重量%)と第1
工程に硫酸濃度23重量/体積%(Al23 4重量
%)の硫酸アルミニウムの酸性溶液222ml(中和率
20%)及び第2工程で、同様の硫酸アルミニウム酸性
溶液745mlを120分かけて投入した以外は同様に
反応し、反応液のpH=3.3として反応を終了した。
これ以後は実施例1と同様にした。その結果を表1に示
した。
Example 4 In Example 1, sodium silicate (SiO 2 27.0) was used.
4% by weight, SiO 2 / Na 2 O = 3.06) 1775 m
l, Glauber's salt (Na 2 O 2.11 wt%) 2844 ml
And 1381 ml of water (concentration of silica 8% by weight) and first
In the step, 222 ml of an acidic solution of aluminum sulfate having a sulfuric acid concentration of 23% by weight (4% by weight of Al 2 O 3 ) (neutralization rate of 20%) and in the second step, 745 ml of the same acidic solution of aluminum sulfate was used for 120 minutes. The reaction was carried out in the same manner except that the reaction mixture was charged, and the pH of the reaction solution was adjusted to 3.3 to terminate the reaction.
After that, the same procedure as in Example 1 was performed. The results are shown in Table 1.

【0045】実施例5 実施例4において第1工程の中和率を25%とし、反応
液のpH3.1として反応を終了した以外は実施例1と
同様にした。結果を表1に示した。
Example 5 Example 5 was repeated except that the neutralization rate in the first step was 25% and the reaction solution was adjusted to pH 3.1 to terminate the reaction. The results are shown in Table 1.

【0046】比較例1 トクシールGu−N(徳山曹達株)の製造工程中の反応
液を実施例1の湿式粉砕処理方法と同様にして処理し
た。その結果を表1に示した。又、図2に細孔分布の測
定結果を示した。
Comparative Example 1 The reaction liquid in the manufacturing process of Tokseal Gu-N (Tokuyama Soda Co., Ltd.) was treated in the same manner as in the wet pulverization treatment method of Example 1. The results are shown in Table 1. In addition, FIG. 2 shows the measurement results of the pore distribution.

【0047】比較例2 市販の尿素ホルムアルデヒドポリマー(商品名、ユーパ
ール、三井東圧(株)製)のスラリーをろ過、乾燥した
ものの、細孔径分布を測定した。結果を表1に示した。
Comparative Example 2 A slurry of a commercially available urea-formaldehyde polymer (trade name, Eupearl, manufactured by Mitsui Toatsu Co., Ltd.) was filtered and dried, but the pore size distribution was measured. The results are shown in Table 1.

【0048】比較例3 実施例4において、中和率30%、反応温度90℃とし
た以外は実施例1と同様にした。その結果を表1に示し
た。
Comparative Example 3 The procedure of Example 1 was repeated except that the neutralization rate was 30% and the reaction temperature was 90 ° C. The results are shown in Table 1.

【図面の簡単な説明】[Brief description of drawings]

【図1】図1は、本発明の紙用填料の細孔分布を示すグ
ラフである。
FIG. 1 is a graph showing the pore distribution of the paper filler of the present invention.

【図2】図2は、比較例のホワイトカーボンの細孔分布
を示すグラフである。
FIG. 2 is a graph showing a pore distribution of white carbon of a comparative example.

─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───

【手続補正書】[Procedure amendment]

【提出日】平成4年8月20日[Submission date] August 20, 1992

【手続補正1】[Procedure Amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0040[Item name to be corrected] 0040

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0040】印刷後不透明性=(印刷後の紙の裏面反射
率)/(未印刷の紙の裏面反射率)×100 実施例1 市販のケイ酸ソーダ(SiO2 26.50重量%、S
iO2/Na2Oモル比3.04)1811ml、ボウ硝
(Na2O 2.38重量%)2521ml、及び水1
668mlを10lの外部加熱方式の反応槽へ投入して
攪拌した(シリカ換算濃度8重量%)。第1工程におい
て、反応液温度35℃で、中和率を30%とするために
22%重量/体積%の硫酸351mlを投入した。その
後、第2工程において、95℃まで昇温し、昇温後、そ
のままの状態で10分間攪拌した。次に22%硫酸79
6mlを100分かけて投入し、反応液のpHを3.6
として反応を終了した。この反応液をろ過、水洗した
後、固形分濃度が13〜14%となるように水に再分散
させ、この分散液600mlを2lのポリ容器に入れ、
大きさ2mmのガラスビーズ1kgとともに回転数42
0rpmで5分間粉砕した後、145メッシュの篩で篩
分けし、篩下の分散液中の固形分について粒度分布を測
定した。次に篩下の分散液100mlをブフナーロート
でろ過し、500mlの水で洗った後、得られたケーク
を熱風乾燥機を用いて105℃で24時間乾燥後、乾燥
されたケークについて細孔径分布を測定した。その結果
を表1に示した。抄紙テストには上記の分散液を使用し
た。
Opacity after printing = (back surface reflectance of paper after printing) / (back surface reflectance of unprinted paper) × 100 Example 1 Commercially available sodium silicate (26.50% by weight of SiO 2 , S)
iO 2 / Na 2 O molar ratio 3.04) 1811 ml, Glauber's salt (Na 2 O 2.38 wt%) 2521 ml, and water 1
668 ml was put into a 10 l reaction vessel of an external heating system and stirred (silica conversion concentration 8% by weight). In the first step, at a reaction liquid temperature of 35 ° C., 351 ml of 22% weight / volume% sulfuric acid was added in order to adjust the neutralization rate to 30%. Then, in the second step, the temperature was raised to 95 ° C., and after the temperature was raised, the mixture was stirred as it was for 10 minutes. Next, 22% sulfuric acid 79
Add 6 ml over 100 minutes to adjust the pH of the reaction solution to 3.6.
And the reaction was completed. After the reaction solution was filtered and washed with water, it was redispersed in water so that the solid content concentration became 13 to 14%, and 600 ml of this dispersion solution was put in a 2 l poly container,
Number of rotations 42 with 1 kg of glass beads of size 2 mm
After pulverizing at 0 rpm for 5 minutes, sieving was performed with a 145 mesh sieve, and the particle size distribution of the solid content in the dispersion liquid under the sieve was measured. Next, 100 ml of the dispersion under the sieve was filtered with a Buchner funnel, washed with 500 ml of water, and the cake obtained was dried at 105 ° C. for 24 hours using a hot air dryer. Was measured. The results are shown in Table 1. The above dispersion was used in the papermaking test.

【手続補正2】[Procedure Amendment 2]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0041[Correction target item name] 0041

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0041】[0041]

【表1】 [Table 1]

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】含水ケイ酸またはケイ酸塩よりなり、細孔
半径5×104オングストローム以下である細孔の積算
容積が1.9〜4.0cc/gであり、3000〜4×
104オングストロームの範囲である細孔の積算容積が
0.5cc/g以上であり、かつ、細孔半径が100〜
1000オングストロームの範囲である細孔の積算容積
が0.6cc/g以上であることを特徴とする紙用填
料。
1. An integrated volume of pores made of hydrous silicic acid or silicate and having a pore radius of 5 × 10 4 angstroms or less is 1.9 to 4.0 cc / g, and 3000 to 4 ×.
The cumulative volume of pores in the range of 10 4 angstrom is 0.5 cc / g or more, and the pore radius is 100 to
A paper filler characterized in that the cumulative volume of pores in the range of 1000 Å is 0.6 cc / g or more.
【請求項2】請求項1記載の紙用填料がパルプ中に分散
されてなる紙。
2. A paper obtained by dispersing the paper filler according to claim 1 in pulp.
JP04109636A 1991-08-06 1992-04-28 Filler for paper and paper using it Expired - Lifetime JP3084125B2 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP04109636A JP3084125B2 (en) 1992-04-28 1992-04-28 Filler for paper and paper using it
US07/922,837 US5262142A (en) 1991-08-06 1992-07-31 Composite oxide of formula R2 O.Al2 O3.TiO2.SiO2.H2 O, where R is an alkali metal
SE9202276A SE504446C2 (en) 1991-08-06 1992-08-03 Oxide composition as filler for papermaking and method for its preparation
CA002075314A CA2075314A1 (en) 1991-08-06 1992-08-05 Composite oxide and process for producing same
DE4225927A DE4225927A1 (en) 1991-08-06 1992-08-05 COMPOSED OXIDE AND METHOD FOR THE PRODUCTION THEREOF
US08/067,003 US5336477A (en) 1991-08-06 1993-05-26 Process for producing a composite alkali metal oxide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP04109636A JP3084125B2 (en) 1992-04-28 1992-04-28 Filler for paper and paper using it

Publications (2)

Publication Number Publication Date
JPH05311599A true JPH05311599A (en) 1993-11-22
JP3084125B2 JP3084125B2 (en) 2000-09-04

Family

ID=14515311

Family Applications (1)

Application Number Title Priority Date Filing Date
JP04109636A Expired - Lifetime JP3084125B2 (en) 1991-08-06 1992-04-28 Filler for paper and paper using it

Country Status (1)

Country Link
JP (1) JP3084125B2 (en)

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JPH06166987A (en) * 1992-11-30 1994-06-14 Nippon Chem Ind Co Ltd Silicic acid hydrate filler for paper-making, its production and paper filled therewith
US5695730A (en) * 1994-09-26 1997-12-09 Nippon Paper Industries Co., Ltd. Process for preparing silicic acid hydrate
JPH11236208A (en) * 1998-02-25 1999-08-31 Nippon Silica Ind Co Ltd Hydrous silica for rubber reinforcement
JP2000007320A (en) * 1998-03-12 2000-01-11 Oji Paper Co Ltd Silica particle, its production and paper containing internally added silica particle
US6264907B1 (en) 1998-03-12 2001-07-24 Oji Paper Co., Ltd. Process for producing silica particles suitable for use as filler for paper
JP2002504881A (en) * 1997-06-13 2002-02-12 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Improved method for preparing low concentration polyaluminosilicate microgels
JP2004176196A (en) * 2002-11-25 2004-06-24 Seiko Pmc Corp Filler for paper and paper containing the filler
JP2006104016A (en) * 2004-10-05 2006-04-20 Tokuyama Corp Method for producing binary porous silica bead
JP2007284822A (en) * 2006-04-17 2007-11-01 Oji Paper Co Ltd Porous filler and method for producing the same, and porous filler slurry and paper
JP2008280234A (en) * 2007-04-10 2008-11-20 Oji Paper Co Ltd Hydrated silicate and method of manufacturing the same and paper
JP2009120997A (en) * 2007-11-16 2009-06-04 Oji Paper Co Ltd Light-weight bulky printing paper for offset printing

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JP5230135B2 (en) * 2007-08-06 2013-07-10 株式会社トクヤマ Calcium carbonate-silica composite material and method for producing the same

Cited By (16)

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Publication number Priority date Publication date Assignee Title
JPH06166987A (en) * 1992-11-30 1994-06-14 Nippon Chem Ind Co Ltd Silicic acid hydrate filler for paper-making, its production and paper filled therewith
US5695730A (en) * 1994-09-26 1997-12-09 Nippon Paper Industries Co., Ltd. Process for preparing silicic acid hydrate
JP2002504881A (en) * 1997-06-13 2002-02-12 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Improved method for preparing low concentration polyaluminosilicate microgels
JPH11236208A (en) * 1998-02-25 1999-08-31 Nippon Silica Ind Co Ltd Hydrous silica for rubber reinforcement
JP4568921B2 (en) * 1998-03-12 2010-10-27 王子製紙株式会社 Silica particles, method for producing the same, and silica particle-containing paper
JP2000007320A (en) * 1998-03-12 2000-01-11 Oji Paper Co Ltd Silica particle, its production and paper containing internally added silica particle
US6264907B1 (en) 1998-03-12 2001-07-24 Oji Paper Co., Ltd. Process for producing silica particles suitable for use as filler for paper
US6413373B1 (en) 1998-03-12 2002-07-02 Oji Paper Co., Ltd. Process for producing silica particles suitable for use as filler for paper
US6685907B2 (en) 1998-03-12 2004-02-03 Oji Paper Co., Ltd. Process for producing silica particles suitable for use as filler for paper
JP2004176196A (en) * 2002-11-25 2004-06-24 Seiko Pmc Corp Filler for paper and paper containing the filler
JP4559813B2 (en) * 2004-10-05 2010-10-13 株式会社トクヤマ Method for producing dual pore silica beads
JP2006104016A (en) * 2004-10-05 2006-04-20 Tokuyama Corp Method for producing binary porous silica bead
JP2007284822A (en) * 2006-04-17 2007-11-01 Oji Paper Co Ltd Porous filler and method for producing the same, and porous filler slurry and paper
JP4742963B2 (en) * 2006-04-17 2011-08-10 王子製紙株式会社 Porous filler and production method thereof, porous filler slurry and paper
JP2008280234A (en) * 2007-04-10 2008-11-20 Oji Paper Co Ltd Hydrated silicate and method of manufacturing the same and paper
JP2009120997A (en) * 2007-11-16 2009-06-04 Oji Paper Co Ltd Light-weight bulky printing paper for offset printing

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