JP2008239465A - Slurry containing light calcium carbonate-silica composite and aluminum-based water-soluble inorganic compound - Google Patents
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Abstract
Description
本発明は、軽質炭酸カルシウム−シリカ複合物及びアルミニウム系水溶性無機化合物を含むスラリーの沈降、凝集によるハードケーキの形成を抑制することに関する。 The present invention relates to suppressing the formation of a hard cake due to sedimentation and aggregation of a slurry containing a light calcium carbonate-silica composite and an aluminum-based water-soluble inorganic compound.
シリカの水性懸濁液は非常に多くの分野で、特に製紙及びコンクリート工業において使用されている。これらの種々の用途のためには、特にコンクリートの分野においては、高い固形分を有する懸濁液を利用できることが有益である。 Aqueous suspensions of silica are used in numerous fields, especially in the paper and concrete industries. For these various applications, it is beneficial to be able to utilize suspensions with high solids, especially in the concrete field.
しかし、このような懸濁液は一般に過度に高い粘度を有し、このためにポンプ輸送上の難点を有し、従って工業的な用途の可能性を低下させる。さらにこれらの懸濁液、特に大きい粒度のシリカの懸濁液は貯蔵中に沈殿、または沈降する傾向がある。事実数日間の貯蔵期間後に、固い層が形成され、その上に固形分が減少した流動性スラリーが存在することがしばしば観察される。従って、たいていの場合には、シリカを再懸濁させること、または均一でしかも容易にポンプ輸送でき、かつ工業的に使用するのに十分に低い粘度のスラリーを得ることは不可能であった。 However, such suspensions generally have excessively high viscosities and thus have pumping difficulties, thus reducing the potential for industrial applications. Furthermore, these suspensions, especially suspensions of large particle size silica, tend to settle or settle during storage. In fact, after a storage period of several days, it is often observed that there is a fluidized slurry on which a hard layer has formed and on which solids have been reduced. Thus, in most cases it was not possible to resuspend the silica or to obtain a slurry that was homogeneous and easily pumpable and of sufficiently low viscosity for industrial use.
特許文献では、この欠点を示さない新規なシリカ含有懸濁液の製造方法が記載されている。その懸濁液は、シリカと硫酸アルミニウム、塩基性硫酸アルミニウム、明礬及びそれらの混合物から選択されるアルミニウム化合物との水性懸濁液で、4以下のpH、10〜50重量％の固形分を有し、これを静止したままにしておくとゲルを形成する傾向をもつ。このことが貯蔵中の物質の沈殿又は沈降を防止させ、数週間又は数ヶ月でさえも懸濁液の安定性を確保させるので、この懸濁液はこのような期間中にわたってその均質性を事実上保持する。さらに形成されたゲルは弱い応力の下で完全に可逆性であり、従って弱い剪断又は攪拌の下では低粘度であって容易にポンプ輸送ができる均質な懸濁液に変換される。 The patent literature describes a novel process for producing a silica-containing suspension that does not exhibit this drawback. The suspension is an aqueous suspension of silica and an aluminum compound selected from aluminum sulfate, basic aluminum sulfate, alum and mixtures thereof, having a pH of 4 or less and a solids content of 10-50% by weight. However, if this is left stationary, it tends to form a gel. This prevents sedimentation or settling of the substance during storage and ensures the stability of the suspension for weeks or even months, so that the suspension will demonstrate its homogeneity over these periods. Hold on. Furthermore, the gel formed is completely reversible under low stress and is therefore converted into a homogeneous suspension that is low in viscosity and easily pumpable under weak shear or agitation.
しかしながら、この場合ゲルを形成させるために、pHを低くせねばならない。軽カル−シリカ複合物は酸性下では核の軽カルが分解してしまい、この酸性条件下では適用できない。
軽質炭酸カルシウム−シリカ複合物及びアルミニウム系水溶性無機化合物を含むスラリーの沈降、凝集によるハードケーキの形成を抑制することにより、循環ポンプを装備していないローリーでの、軽カル−シリカ複合物の長距離輸送や、スムーズな払い出しを可能とし、長期間の貯蔵後の再分散も容易とするスラリーを提供することである。 Suppression of slurry containing light calcium carbonate-silica composite and aluminum-based water-soluble inorganic compound prevents formation of hard cake by agglomeration, thereby reducing light cal-silica composite in a lorry not equipped with a circulation pump. The object is to provide a slurry that enables long-distance transportation, smooth dispensing, and easy redispersion after long-term storage.
本発明により、軽質炭酸カルシウム−シリカ複合物及びアルミニウム系水溶性無機化合物を含むスラリーにおいて、固形分1〜50重量％を有し、pHが7以上であり、1週間以上静置した後もハードケーキを形成せず、低剪断下で再分散が可能な前記スラリーが提供される。 According to the present invention, a slurry containing a light calcium carbonate-silica composite and an aluminum-based water-soluble inorganic compound has a solid content of 1 to 50% by weight, has a pH of 7 or more, and is hard even after standing for more than one week. A slurry is provided that does not form a cake and is redispersible under low shear.
以上の通り、本発明で示した、軽カル−シリカ複合物にアルミニウム系水溶性無機化合物をpH7以上の範囲で添加することにより、軽カル−シリカ複合物スラリーの沈降、凝集によるハードケーキの形成を抑制することができる。これにより、循環ポンプを装備していないローリーでの、軽カル−シリカ複合物の長距離輸送、スムーズな払い出しが可能となる。また、長期間の貯蔵後の再分散も容易となった。アルミニウム系水溶性無機化合物を添加した際、pH7以上とすることで、軽カル−シリカ複合物の品質を損なうことなく、物性の変化はなく、紙に配合したときの不透明度の発現にも影響がない。 As described above, by adding an aluminum-based water-soluble inorganic compound to the light cal-silica composite in the range of pH 7 or more shown in the present invention, a hard cake is formed by sedimentation and aggregation of the light cal-silica composite slurry. Can be suppressed. Thereby, long-distance transportation and smooth dispensing of the light cal-silica composite can be performed with a lorry that is not equipped with a circulation pump. In addition, redispersion after long-term storage became easy. When adding an aluminum-based water-soluble inorganic compound, adjusting the pH to 7 or higher does not impair the quality of the light cal-silica composite, there is no change in physical properties, and it affects the expression of opacity when blended with paper. There is no.
以下、本発明について具体的に説明する。
本発明で対象となる軽質炭酸カルシウム−シリカ複合物における、軽質炭酸カルシウムの製造方法は、以下の方法のどれであっても構わない。
Hereinafter, the present invention will be specifically described.
Any of the following methods may be sufficient as the manufacturing method of the light calcium carbonate in the light calcium carbonate-silica composite used as object in this invention.
軽質炭酸カルシウムの製造方法としては、（１）石灰の焼成装置その他から得られる二酸化炭素を含有したガスと石灰乳との反応、（２）アンモニアソーダ法における炭酸アンモニウムと塩化カルシウムとの反応、（３）炭酸ナトリウムの苛性化によって水酸化ナトリウムを製造する石灰乳と炭酸ナトリウムとの反応等が知られている。 As a light calcium carbonate production method, (1) a reaction between carbon dioxide-containing gas obtained from a lime baking apparatus and others and lime milk, (2) a reaction between ammonium carbonate and calcium chloride in an ammonia soda method, ( 3) Reaction of lime milk and sodium carbonate, which produces sodium hydroxide by causticization of sodium carbonate, is known.
本発明で対象となる軽質炭酸カルシウム−シリカ複合物の製造方法を以下に述べる。
（軽質炭酸カルシウム−シリカ複合物）
本発明の紙用の軽質炭酸カルシウム−シリカ複合物の製造では、まず軽質炭酸カルシウムを水中に分散させる。この軽質炭酸カルシウムの結晶形態はカルサイト、アラゴナイトのいずれでも良く、また形状についても針状、柱状、紡錘状、球状、立方体状、ロゼッタ型のいずれでも良い。この中でも特にロゼッタ型のカルサイト系の軽質炭酸カルシウムを用いた場合に、特に優れた嵩高、不透明度改善効果が高い軽質炭酸カルシウム−シリカ複合物が得られる。なお、ロゼッタ型とは、紡錘状の軽質炭酸カルシウム一次粒子がいがくり状に凝集した形状を指し、他の軽質炭酸カルシウムより高い比表面積と吸油性を示す特徴がある。また、軽質炭酸カルシウムは粉砕処理を施して使用しても良い。
（ケイ酸濃度）
この軽質炭酸カルシウムの反応原液中濃度は、後述の軽質炭酸カルシウムとケイ酸の配合比率が重要であるため、ケイ酸濃度の影響も加味しなくてはならないが、1〜20固形分重量%が好ましい。1%未満の低濃度であると１バッチ当たりの生産量が少なく、生産性に問題がある。また、20%を超える高濃度とすると分散性が悪く、また軽質炭酸カルシウム量と比例して、反応に用いるケイ酸アルカリの濃度が高くなるため、反応時の粘度が上昇し、操業性に問題がある。
（配合比率）
ついで、この軽質炭酸カルシウムのスラリーに、ナトリウム、カリウムのようなアルカリ溶液中に溶解した形のケイ酸を加える。一般的に工業用に用いられるものは、ケイ酸ソーダ(ナトリウム)もしくはケイ酸カリウムであるが、本発明である複合物を形成するためには、ケイ酸とアルカリのモル比はいずれでも良い。3号ケイ酸はSiO2：Na2O＝3〜3.4：1程度のモル比のものであるが、一般に入手しやすく、好適に使用される。軽質炭酸カルシウムとケイ酸アルカリとの仕込重量比は、生成する軽質炭酸カルシウム−シリカ複合物中の炭酸カルシウムとシリカの重量比が目標とする範囲に入るように仕込む。軽質炭酸カルシウム−シリカ複合物の炭酸カルシウムとシリカの重量比は、CaCO3/SiO2＝30/70〜70/30である。
（攪拌分散）
このスラリーをアジテータ、ホモミキサー、ミキサー等で攪拌、分散させるが、これは軽質炭酸カルシウムが水に十分に分散し、軽質炭酸カルシウムの粒子が極端に凝集してなければ問題なく、特に時間やアジテーションの強さ等の制限はない。
（中和反応）
次に、酸を用いた中和反応を行う。この場合、酸は鉱酸ならいずれでも良く、さらには鉱酸中に硫酸バンドや硫酸マグネシウムのような酸性金属塩を含む酸でも使用できる。工業的には硫酸、塩酸等の比較的安価に購入できる酸が好ましい。高濃度の酸を用いた場合、酸による中和時の攪拌が不十分であると、高濃度の酸の添加により部分的にpHの低い部分ができ、軽質炭酸カルシウムが分解するため、酸添加口でホモミキサー等を用いた強攪拌を行う必要がある。一方、あまりに希薄な酸を用いると、酸添加により全体的な容量が極端に増えてしまうので好ましくない。この面からも、0.05N以上の濃度の酸を用いることが適当である。鉱酸または酸性金属塩水溶液の添加は、アルカリ性であるケイ酸金属塩水溶液と軽質炭酸カルシウムとの混合物の沸点以下の温度で行う。この中和処理によりケイ酸分を析出させ、非晶質ケイ酸を形成し、これが軽質炭酸カルシウム粒子の表面を被覆する。
A method for producing a light calcium carbonate-silica composite which is an object of the present invention will be described below.
(Light calcium carbonate-silica composite)
In the production of the light calcium carbonate-silica composite for paper of the present invention, first, the light calcium carbonate is dispersed in water. The crystal form of the light calcium carbonate may be either calcite or aragonite, and the shape may be any of acicular, columnar, spindle, spherical, cubic, and rosetta types. Among these, in particular, when a rosetta-type calcite-type light calcium carbonate is used, a light calcium carbonate-silica composite having a particularly high bulk and high opacity improvement effect can be obtained. The rosetta type refers to a shape in which spindle-shaped light calcium carbonate primary particles are aggregated in a corrugated shape, and is characterized by a higher specific surface area and oil absorption than other light calcium carbonates. Light calcium carbonate may be used after being pulverized.
(Silicic acid concentration)
The concentration of the light calcium carbonate in the reaction stock solution is important for the ratio of light calcium carbonate and silicic acid, which will be described later, so the influence of the silicic acid concentration must be taken into account. preferable. When the concentration is less than 1%, the production amount per batch is small, and there is a problem in productivity. In addition, if the concentration exceeds 20%, the dispersibility is poor, and the concentration of alkali silicate used in the reaction increases in proportion to the amount of light calcium carbonate. There is.
(Mixing ratio)
Next, silicic acid dissolved in an alkaline solution such as sodium or potassium is added to the light calcium carbonate slurry. Generally used for industrial use is sodium silicate (sodium) or potassium silicate, but in order to form the composite of the present invention, any molar ratio of silicic acid and alkali may be used. No. 3 silicic acid has a molar ratio of about SiO2: Na2O = 3 to 3.4: 1, but is generally easily available and is preferably used. The weight ratio of light calcium carbonate and alkali silicate is charged so that the weight ratio of calcium carbonate and silica in the resulting light calcium carbonate-silica composite falls within the target range. The weight ratio of calcium carbonate to silica in the light calcium carbonate-silica composite is CaCO 3 / SiO 2 = 30/70 to 70/30.
(Stir dispersion)
This slurry is stirred and dispersed with an agitator, homomixer, mixer, etc. This is fine as long as the light calcium carbonate is sufficiently dispersed in water and the light calcium carbonate particles are not extremely agglomerated, especially time and agitation. There is no limit on the strength of the.
(Neutralization reaction)
Next, a neutralization reaction using an acid is performed. In this case, the acid may be any mineral acid, and further, an acid containing an acidic metal salt such as a sulfate band or magnesium sulfate in the mineral acid can be used. Industrially preferred are acids that can be purchased relatively inexpensively, such as sulfuric acid and hydrochloric acid. When a high concentration acid is used, if the stirring during neutralization with the acid is insufficient, the addition of the high concentration acid will result in a portion with a low pH, and light calcium carbonate will decompose, so acid addition It is necessary to perform strong stirring using a homomixer or the like at the mouth. On the other hand, if a too dilute acid is used, the overall capacity is extremely increased by the acid addition, which is not preferable. From this aspect, it is appropriate to use an acid having a concentration of 0.05 N or more. The mineral acid or acidic metal salt aqueous solution is added at a temperature not higher than the boiling point of a mixture of the alkaline metal silicate aqueous solution and light calcium carbonate. By this neutralization treatment, silicic acid is precipitated to form amorphous silicic acid, which covers the surface of the light calcium carbonate particles.
さらに、この酸添加は数回に分けて行っても良い。酸添加後、熟成を行っても良い。なお、熟成とは酸添加を一時中止し、攪拌のみを施し放置しておくことを指す。この熟成中に強攪拌や粉砕を行い、粒子の形態をコントロールすることも可能である。 Furthermore, this acid addition may be performed in several times. Aging may be performed after the acid addition. The aging means that the acid addition is temporarily stopped, only stirred and left to stand. It is also possible to control the morphology of the particles by vigorous stirring and pulverization during this aging.
次に、上記酸添加によるスラリーの中和はpH＝7〜9を目標に行う。析出してきたケイ酸分により軽質炭酸カルシウムが被覆されていくが、酸性側(pH7未満)にすると、軽質炭酸カルシウムが分解してしまう。一方、pHが高い(9.0超)状態で中和を終了すると、ケイ酸分の析出が十分に行われず、スラリー中に未反応のケイ酸分が残り、ケイ酸分のロスが多くなり、工業的に好ましくない。そのため、目標pHは7〜9で中和を終了させる。
（後処理）
このようにして、製造された軽質炭酸カルシウム−ケイ酸の複合物は、軽質炭酸カルシウム粒子表面をシリカが被覆した懸濁液の状態となる。この懸濁液のまま抄紙工程等に使用しても良いが、生産規模が小規模の場合にはろ紙やメンブランフィルタ等のろ過設備、中規模以上の場合にはベルトフィルタやドラムフィルタ等を用いたろ過、または遠心分離機を用いた遠心分離を行うことによって固液分離を行い、中和反応で生成した余分な副生成物である塩を極力取り除いたほうが好ましい。これは、余分な塩が残存していると、抄紙工程においてこの塩が難溶性の金属塩(例えば、硫酸カルシウム)に変化し、これを原因としたスケーリングの問題を発生するおそれがあるためである。さらにこの固液分離を行った固形分濃度10〜50%のケーキ状複合物を、水またはエタノールにより再分散後、再び固液分離を行い、さらに余分なケイ酸や副生成物である塩を取り除いても良い。
Next, neutralization of the slurry by the above acid addition is carried out with the target of pH = 7-9. The light calcium carbonate is coated with the precipitated silicic acid component, but when it is on the acidic side (less than pH 7), the light calcium carbonate is decomposed. On the other hand, when neutralization is completed at a high pH (above 9.0), silicic acid is not sufficiently precipitated, unreacted silicic acid remains in the slurry, and the loss of silicic acid increases. Is not preferable. Therefore, neutralization is completed at a target pH of 7-9.
(Post-processing)
Thus, the manufactured light calcium carbonate-silicic acid composite is in a suspension state in which the surface of the light calcium carbonate particles is coated with silica. This suspension may be used in the papermaking process, but if the production scale is small, filter equipment such as filter paper or membrane filter is used, and if it is medium or larger, a belt filter or drum filter is used. It is preferable to carry out solid-liquid separation by performing filtration or centrifugal separation using a centrifuge, and to remove as much as possible the salt which is an extra by-product generated by the neutralization reaction. This is because if excess salt remains, it may change into a poorly soluble metal salt (e.g., calcium sulfate) in the papermaking process, which may cause scaling problems. is there. Furthermore, after re-dispersing the cake-like composite having a solid content concentration of 10 to 50%, which has been subjected to the solid-liquid separation, with water or ethanol, the solid-liquid separation is performed again to further remove excess silicic acid and by-product salts. It may be removed.
得られた軽質炭酸カルシウム−ケイ酸の複合物は、目的粒子径より大きい粗粒物を取り除くため、振動篩やスクリーンを用いて、100μｍ以上の粒子を除去する。
本発明の軽質炭酸カルシウム−ケイ酸の複合物の平均粒子径の調整は、前述のように、熟成中に強攪拌や粉砕を行うことにより粒子の形態をコントロールすることも可能であるが、中和反応終了後または反応終了後の固液分離したものを、湿式粉砕機を用いて、目的の平均粒子径に調整しても良い。また、この組み合わせにより平均粒子径を調整しても良い。
The obtained light calcium carbonate-silicic acid composite removes particles of 100 μm or more using a vibrating sieve or a screen in order to remove coarse particles larger than the target particle size.
As described above, the average particle size of the light calcium carbonate-silicic acid composite of the present invention can be controlled by vigorous stirring and pulverization during ripening. What was solid-liquid separated after completion of the summation reaction or after completion of the reaction may be adjusted to the target average particle size using a wet pulverizer. Further, the average particle diameter may be adjusted by this combination.
粗大粒子を除去した後、あるいは粗大粒子除去後さらに強撹拌や粉砕処理を施した軽質炭酸カルシウム−ケイ酸の複合物の平均粒子径は、その用途が紙用の填料である場合には、30μｍ以下が良く、20μｍ以下が好ましく、10μｍ以下が更に好ましい。 After removing the coarse particles, or after removing the coarse particles, the average particle size of the light calcium carbonate-silicic acid composite that has been further stirred and pulverized is 30 μm when the use is a filler for paper. The following is preferable, preferably 20 μm or less, and more preferably 10 μm or less.
本発明において使用できるアルミニウム系水溶性無機化合物とは、硫酸アルミニウム、明礬など水溶性で、アルミニウム元素を含む化合物であればよい。
軽質炭酸カルシウム−シリカ複合物の製造において、1重量％未満の低濃度で製造することは生産性に問題がある。また、本発明は、軽質炭酸カルシウム−シリカ複合物スラリーの沈降、凝集によるハードケーキの形成を抑制することにより、循環ポンプを装備していないローリーでの、軽カル−シリカ複合物の長距離輸送や、スムーズな払い出しを可能とし、長期間の貯蔵後の再分散も容易とするスラリーを提供することである。貯蔵及び輸送効率の観点からも1重量％未満の低濃度にすることはほとんどない。また固形分が50重量％を超えるまで高濃度になると、軽質炭酸カルシウム−シリカ複合物スラリーの沈降、凝集を抑制するにはアルミニウム系水溶性無機化合物の添加量を多くせねばならず、アルミニウム系水溶性無機化合物によっては、pHを7以上に保つことができないものがある。また、製造段階における軽質炭酸カルシウムの反応原液中の濃度は20％を超えると分散性が悪く、また軽質炭酸カルシウムに比例して反応に用いるケイ酸アルカリの濃度が高くなるため、反応時の粘度が上昇し、操業性に問題がある。よって、製造段階で50％を超えることはなく、また反応後、軽質炭酸カルシウム−シリカ複合物50％を超えるまで濃度を絞ることはほとんどない。
The aluminum-based water-soluble inorganic compound that can be used in the present invention may be any compound that is water-soluble and contains an aluminum element such as aluminum sulfate and alum.
In the production of a light calcium carbonate-silica composite, production at a low concentration of less than 1% by weight has a problem in productivity. In addition, the present invention suppresses the formation of a hard cake due to sedimentation and aggregation of the light calcium carbonate-silica composite slurry, thereby allowing long-distance transportation of the light cal-silica composite in a lorry not equipped with a circulation pump. Another object of the present invention is to provide a slurry that enables smooth dispensing and facilitates redispersion after long-term storage. From the viewpoint of storage and transportation efficiency, the concentration is hardly reduced to less than 1% by weight. In addition, when the concentration becomes high until the solid content exceeds 50% by weight, the amount of the aluminum-based water-soluble inorganic compound must be increased in order to suppress sedimentation and aggregation of the light calcium carbonate-silica composite slurry. Some water-soluble inorganic compounds cannot maintain the pH at 7 or higher. Also, if the concentration of light calcium carbonate in the reaction stock solution in the production stage exceeds 20%, the dispersibility is poor, and the concentration of alkali silicate used in the reaction increases in proportion to the light calcium carbonate. As a result, there is a problem in operability. Therefore, it does not exceed 50% in the production stage, and after the reaction, the concentration is hardly reduced until it exceeds 50% of the light calcium carbonate-silica composite.
軽カル−シリカ複合物にアルミニウム系水溶性無機化合物を加えた際、pH7より小さくしてしまうと、軽カル−シリカ複合物の核の軽カルが分解してしまい、紙に配合した際、軽カル−シリカ複合物の軽カルが寄与する不透明度が著しく低下してしまう。pH7以上であればアルミニウム系水溶性無機化合物の添加による、軽カル−シリカ複合物の品質への影響はなく、粒子径、比表面積、吸油量などの物性は変化せず、紙に配合したときの不透明度の効果の発現にも影響がない。 When an aluminum-based water-soluble inorganic compound is added to a light cal-silica composite, if the pH is lower than 7, the light cal-core of the light cal-silica composite is decomposed. The opacity contributed by the light cal of the cal-silica composite is significantly reduced. When the pH is 7 or higher, the addition of an aluminum-based water-soluble inorganic compound has no effect on the quality of the light cal-silica composite, and the physical properties such as particle diameter, specific surface area, and oil absorption do not change. It does not affect the expression of the opacity effect.
抄紙填料として用いる場合には、おおよそ100μm以上の填料粒子は、粗大粒子として取り扱われ、紙の地合悪化や印刷時の粉落ちの要因となりやすい。用途が紙用の填料である場合には、30μm以下が良く、20μm以下が好ましく10μm以下であるのが更に好ましい。 When used as a papermaking filler, filler particles of about 100 μm or more are handled as coarse particles, and are liable to cause deterioration of paper formation and powder falling off during printing. When the use is a filler for paper, it is preferably 30 μm or less, preferably 20 μm or less, and more preferably 10 μm or less.
軽質炭酸カルシウム−シリカ複合物は、軽質炭酸カルシウム由来の高い比散乱係数（高不透明性）という性状と、シリカ由来の高吸油量、嵩高という性状を併せ持つ複合物である。軽質炭酸カルシウム−シリカ複合物の、軽質炭酸カルシウムの比率がケイ酸30に対し70よりも大きくなると、軽カルによる光学特性向上効果は期待できるが、吸油量向上及び嵩高効果は小さくなってしまう。逆に、軽質炭酸カルシウム−シリカ複合物の、軽質炭酸カルシウムの比率がケイ酸70に対し30よりも小さくなると、吸油量の向上、嵩高効果は期待できるが、軽カルによる光学特性向上効果は小さくなる。 The light calcium carbonate-silica composite is a composite having both properties of a high specific scattering coefficient (high opacity) derived from light calcium carbonate, a high oil absorption amount and bulkiness derived from silica. If the light calcium carbonate ratio of the light calcium carbonate-silica composite is greater than 70 with respect to silicic acid 30, the effect of improving the optical properties due to light calories can be expected, but the oil absorption improvement and bulky effect will be reduced. Conversely, when the light calcium carbonate ratio of the light calcium carbonate-silica composite is smaller than 30 with respect to silicic acid 70, an improvement in oil absorption and a bulky effect can be expected, but the effect of improving the optical properties by light calf is small. Become.
軽質炭酸カルシウム−シリカ複合物は、軽質炭酸カルシウムを核とし、その周囲の全てまたは一部をシリカ粒子で覆ったものであり、一般に、シリカは軽カルより吸油量が高いため、複合物とした場合にも軽カル比率が増加するに従って、吸油量は低くなる。 The light calcium carbonate-silica composite is composed of light calcium carbonate as a core, and all or part of the periphery thereof is covered with silica particles. Generally, silica has a higher oil absorption than light calcare and is therefore a composite. In some cases, the oil absorption decreases as the light cal ratio increases.
軽質炭酸カルシウム−シリカ複合物の製造に使用する軽質炭酸カルシウムの結晶形態は、カルサイト、アラゴナイトいずれでもよく、また形状についても針状、柱状、紡錘状、球状、立方体状、ロゼッタ型のいずれでも良い。この中でも特にロゼッタ型のカルサイト系の軽質炭酸カルシウムを用いた場合に、特に優れた嵩高、不透明度改善効果が高い軽質炭酸カルシウム−シリカ複合物が得られる。なお、ロゼッタ型とは、紡錘状の軽質炭酸カルシウム一次粒子がいがぐり状に凝集した形状を指し、他の軽質炭酸カルシウムより高い比表面積と吸油性を示す特徴がある。また、軽質炭酸カルシウムは粉砕処理を施して使用しても良い。
本発明で示される軽カル−シリカ複合物にアルミニウム系水溶性無機化合物を混合させたスラリーは、長時間静置後も多少の沈降は起こるものの、沈降層の粒子密度は小さく、したがってハードケーキを形成せず、再分散が容易であり、長時間の輸送、長期間の貯蔵を可能にすることができる。
The crystal form of the light calcium carbonate used for the production of the light calcium carbonate-silica composite may be either calcite or aragonite, and the shape may be any of acicular, columnar, spindle, spherical, cubic, and rosetta types. good. Among these, in particular, when a rosetta-type calcite-type light calcium carbonate is used, a light calcium carbonate-silica composite having a particularly high bulk and high opacity improvement effect can be obtained. The rosetta type refers to a shape in which spindle-shaped light calcium carbonate primary particles are aggregated in a corrugated shape, and is characterized by a higher specific surface area and oil absorption than other light calcium carbonates. Light calcium carbonate may be used after being pulverized.
The slurry obtained by mixing the light cal-silica composite according to the present invention with an aluminum-based water-soluble inorganic compound has some sedimentation even after standing for a long time, but the particle density of the sedimentation layer is small. It is not formed and can be easily redispersed, and can be transported for a long time and stored for a long time.
軽カル−シリカ複合物にアルミニウム系水溶性無機化合物を混合させた後のpHを7以上にすることを特徴とし、コスト、効果を考慮した場合、好ましくは、軽カル−シリカ複合物に対し1〜2重量部のアルミニウム系水溶性無機化合物を添加する。これは、pH7近辺においてアルミニウム系水溶性無機化合物として添加したアルミニウムは水酸化アルミニウムとして存在し、その水酸化アルミニウムは軽カル−シリカ複合物の表面のシリカ粒子を吸着し、間隙の多い三次元網目構造に凝集させる。この凝集は、間隙が多く、また粒子同士の結合が弱いため、低剪断下での再分散が容易となると考えられる。 The pH after mixing the aluminum-based water-soluble inorganic compound with the light cal-silica composite is 7 or more, and considering the cost and effect, preferably 1 for the light cal-silica composite. Add ~ 2 parts by weight of an aluminum based water soluble inorganic compound. This is because aluminum added as an aluminum-based water-soluble inorganic compound in the vicinity of pH 7 exists as aluminum hydroxide, and the aluminum hydroxide adsorbs silica particles on the surface of the light cal-silica composite and has a three-dimensional network with many gaps. Aggregate into structure. This aggregation is thought to facilitate redispersion under low shear because there are many gaps and the bonds between particles are weak.
また軽カル−シリカ複合物のBET比表面積が10〜70m2/gであり、シリカ単体と比較して低く、そのため軽カル−シリカ複合物に対して、アルミニウム系水溶性無機化合物の添加が比較的少量で、軽カル−シリカ複合物の沈降、凝集によるハードケーキの形成を抑制できると考えられる。
本発明によるスラリーにおいては、軽カル−シリカ複合物の品質への影響はなく、粒子径、比表面積、吸油量などの物性は変化せず、紙に配合したときの不透明度の効果の発現にも影響がない。
The light cal-silica composite has a BET specific surface area of 10 to 70 m 2 / g, which is lower than that of silica alone. Therefore, the addition of an aluminum-based water-soluble inorganic compound is compared to the light cal-silica composite. It is considered that the formation of a hard cake due to precipitation and aggregation of the light cal-silica composite can be suppressed with a small amount.
In the slurry according to the present invention, there is no influence on the quality of the light cal-silica composite, the physical properties such as the particle diameter, specific surface area, and oil absorption amount do not change, and the effect of opacity when blended in paper is exhibited. Has no effect.
（物性評価方法）
本発明における軽カルーシリカ複合物の各特性値は、下記の測定方法により得られた値を用いるものとする。
（1) 吸油量：JIS K5101の方法による。
（2）粒度分布測定（レーザー法）：試料スラリーを分散剤ヘキサメタリン酸ソーダ0.2重量％添加した純水中で滴下混合して均一分散体とし、レーザー法粒度測定機（使用機器：マルバーン社製マスターサイザーS型）を使用して粒度測定する。
（3）紙の不透明度の測定：熊谷理機工業（株）製の配向性抄紙機により、抄紙原料としてLBKPスラリーを用い、各実施例において得られた填料スラリーを填料として、その添加率を対パルプ5、10、15％として坪量60g/m2になるように抄造して、プレスにより脱水後、送風乾燥機にて乾燥し、各添加率のシートサンプルを作製した。このシートサンプルをJIS−P8138に準じ、色差計(村上色彩研究所製)を用い、不透明度を測定した。ま今回の試験では、紙中填料7％で比較を行っているため、各シートサンプルを525℃にて焼成し、残渣分の灰分量を求めた後、紙中填料7％時の測定値を算出している。
（4）再分散性の評価：静置一日後のケーキ高さを測った。またラボ攪拌機250rpmで攪拌し、ケーキがなくなり、均一に分散するまでの時間で、再分散性を評価した。◎：30秒以内、○：30秒〜1分、△：1分〜3分、×：3分以上。以上の評価を静置三日後、七日後につても同様に行った。
〔実施例１〕
200mlビーカーに入れた、固形分30重量％の軽カル−シリカ複合物スラリー100mlをラボ攪拌機250rpmで分散した。攪拌しながら軽カル−シリカ複合物スラリーのpHが9になるように硫酸バンド（固形分42％）を加えた。その後静置し、一日後のケーキ高さを測った。またラボ攪拌機250rpmで攪拌し、ケーキがなくなり、均一に分散するまでの時間で、再分散性を評価した。三日後、七日後も同様に再分散性の評価を行った。また、粒径、吸油量を測定し、結果を表１に記した。
(Physical property evaluation method)
The values obtained by the following measuring methods are used as the characteristic values of the light calo-silica composite in the present invention.
(1) Oil absorption: According to JIS K5101 method.
(2) Particle size distribution measurement (laser method): The sample slurry is dropped and mixed in pure water added with 0.2% by weight of sodium hexametaphosphate dispersant to form a uniform dispersion. Particle size is measured using Sizer S type.
(3) Measurement of opacity of paper: Using an orientation paper machine manufactured by Kumagai Riki Kogyo Co., Ltd., using LBKP slurry as a papermaking raw material, and using the filler slurry obtained in each example as a filler, the addition rate was determined. Paper sheets were made so as to have a basis weight of 60 g / m 2 with respect to 5, 10 and 15% of pulp, dehydrated with a press, and then dried with a blow dryer to prepare sheet samples of each addition rate. The opacity of this sheet sample was measured using a color difference meter (manufactured by Murakami Color Research Laboratory) in accordance with JIS-P8138. In this test, since the comparison was made with 7% paper filler, each sheet sample was baked at 525 ° C, and the ash content of the residue was calculated. Calculated.
(4) Evaluation of redispersibility: The height of the cake after one day of standing was measured. Moreover, it stirred with the laboratory stirrer 250rpm, and redispersibility was evaluated by the time until a cake disappears and it disperse | distributes uniformly. ◎: Within 30 seconds, ○: 30 seconds to 1 minute, △: 1 minute to 3 minutes, ×: 3 minutes or more. The above evaluation was carried out in the same manner even after 7 days after standing.
[Example 1]
100 ml of a light cal-silica composite slurry having a solid content of 30% by weight in a 200 ml beaker was dispersed with a laboratory stirrer at 250 rpm. With stirring, a sulfuric acid band (solid content 42%) was added so that the pH of the light cal-silica composite slurry was 9. Then, it was left to stand and the cake height after one day was measured. Moreover, it stirred with the laboratory stirrer 250rpm, and redispersibility was evaluated by the time until a cake disappears and it disperse | distributes uniformly. The redispersibility was similarly evaluated after 3 days and after 7 days. The particle diameter and oil absorption were measured and the results are shown in Table 1.
さらに、手抄きを行い、再分散性評価を行った軽カル−シリカ複合物を紙に配合し紙質評価を行った結果を表２に記した。
七日間静置後も沈降層に硬い層はなく、再分散が容易であった（すべて◎）。さらに、紙に配合したとき、硫酸バンドを加えない軽カル−シリカ複合物と同等の不透明度であった。
〔実施例２〕
200mlビーカーに入れた、固形分30重量％の軽カル−シリカ複合物スラリー100mlをラボ攪拌機250rpmで分散した。攪拌しながら軽カル−シリカ複合物スラリーのpHが8になるように硫酸バンド（固形分42％）を加えた。その後静置し、一日後、三日後、七日後の再分散性の評価、粒径、吸油量の測定を行った。評価、測定に関しては実施例１と同様に行い、結果を表１に併載した。
Further, Table 2 shows the results of paper quality evaluation by blending a light cal-silica composite which has been hand-drawn and evaluated for redispersibility into paper.
Even after standing for 7 days, there was no hard layer in the sedimentation layer, and redispersion was easy (all ◎). Furthermore, when blended with paper, the opacity was equivalent to a light cal-silica composite without the addition of a sulfate band.
[Example 2]
100 ml of a light cal-silica composite slurry having a solid content of 30% by weight in a 200 ml beaker was dispersed with a laboratory stirrer at 250 rpm. With stirring, a sulfuric acid band (solid content 42%) was added so that the pH of the light cal-silica composite slurry was 8. Thereafter, the mixture was allowed to stand, and evaluation of redispersibility, particle size, and oil absorption after one day, three days, and seven days were performed. Evaluation and measurement were performed in the same manner as in Example 1, and the results are listed in Table 1.
さらに、手抄きを行い、再分散性評価を行った軽カル−シリカ複合物を紙に配合し紙質評価を行った結果を表２に併載した。
実施例１と同様、七日間静置後も沈降層に硬い層はなく、再分散が容易であった（すべて◎）。紙に配合したとき、硫酸バンドを加えない軽カル−シリカ複合物と同等の不透明度であった。
〔比較例１〕
200mlビーカーに入れた、固形分30重量％の軽カル−シリカ複合物スラリー100mlをラボ攪拌機250rpmで分散した。その後静置し、一日後、三日後、七日後の再分散性の評価、粒径、吸油量の測定を行った。評価、測定に関しては実施例１と同様に行い、結果を表１に併載した。
Further, Table 2 shows the results of paper quality evaluation by blending a light cal-silica composite which has been hand-drawn and evaluated for redispersibility into paper.
As in Example 1, there was no hard layer in the sedimented layer even after standing for 7 days, and redispersion was easy (all ◎). When blended with paper, it had an opacity equivalent to a light cal-silica composite with no sulfate band added.
[Comparative Example 1]
100 ml of a light cal-silica composite slurry having a solid content of 30% by weight in a 200 ml beaker was dispersed with a laboratory stirrer at 250 rpm. Thereafter, the mixture was allowed to stand, and evaluation of redispersibility, particle size, and oil absorption after one day, three days, and seven days were performed. Evaluation and measurement were performed in the same manner as in Example 1, and the results are listed in Table 1.
さらに、手抄きを行い、再分散性評価を行った軽カル−シリカ複合物を紙に配合し紙質評価を行った結果を表２に併載した。
静置期間が長くなるに従って、沈降層に固い層が形成され、再分散が困難になった（一日後：○、三日後：△、七日後：×）。
〔比較例２〕
200mlビーカーに入れた、固形分30重量％の軽カル−シリカ複合物スラリー100mlをラボ攪拌機250rpmで分散した。攪拌しながら軽カル−シリカ複合物スラリーのpHが8になるように25％硫酸を加えた。その後静置し、一日後、三日後、七日後の再分散性の評価、粒径、吸油量の測定を行った。評価、測定に関しては実施例１と同様に行い、結果を表１に併載した。
Further, Table 2 shows the results of paper quality evaluation by blending a light cal-silica composite which has been hand-drawn and evaluated for redispersibility into paper.
As the standing period became longer, a hard layer was formed in the sedimentation layer, and redispersion became difficult (after 1 day: ○, after 3 days: Δ, after 7 days: ×).
[Comparative Example 2]
100 ml of a light cal-silica composite slurry having a solid content of 30% by weight in a 200 ml beaker was dispersed with a laboratory stirrer at 250 rpm. While stirring, 25% sulfuric acid was added so that the pH of the light cal-silica composite slurry was 8. Thereafter, the mixture was allowed to stand, and evaluation of redispersibility, particle size, and oil absorption after one day, three days, and seven days were performed. Evaluation and measurement were performed in the same manner as in Example 1, and the results are listed in Table 1.
さらに、手抄きを行い、再分散性評価を行った軽カル−シリカ複合物を紙に配合し紙質評価を行った結果を表２に併載した。
比較例１同様、静置期間が長くなるに従って、沈降層に固い層が形成され、再分散が困難になった（一日後：○、三日後：△、七日後：×）。紙に配合したとき、硫酸を加えない軽カル−シリカ複合物と同等の不透明度であった。
〔比較例３〕
200mlビーカーに入れた、固形分30重量％の軽カル−シリカ複合物スラリー100mlをラボ攪拌機250rpmで分散した。攪拌しながら軽カル−シリカ複合物スラリーのpHが6になるように硫酸バンド（固形分42％）を加えた。その軽カル−シリカ複合物を手抄き紙に配合し紙質評価を行った結果を表２に併載した。
Further, Table 2 shows the results of paper quality evaluation by blending a light cal-silica composite which has been hand-drawn and evaluated for redispersibility into paper.
As in Comparative Example 1, as the standing period increased, a hard layer was formed in the sedimentation layer, and redispersion became difficult (after 1 day: ○, after 3 days: Δ, after 7 days: ×). When blended in paper, the opacity was equivalent to a light cal-silica composite without added sulfuric acid.
[Comparative Example 3]
100 ml of a light cal-silica composite slurry having a solid content of 30% by weight in a 200 ml beaker was dispersed with a laboratory stirrer at 250 rpm. With stirring, a sulfuric acid band (solid content 42%) was added so that the pH of the light cal-silica composite slurry was 6. Table 2 shows the results of blending the light cal-silica composite with hand-made paper and evaluating the paper quality.
実施例１と同様、七日間静置後も沈降層に硬い層はなく、再分散が容易であった（すべて◎）。しかし、硫酸バンド添加中、pHが酸性領域になると、軽カル−シリカ複合物の核の軽カルが溶解する現象が見られた。pH7より小さくなると、軽カル−シリカ複合物の品質を保持できなくなったと考えられた。実際、紙に配合したとき、ブランクである比較例１と比較し、不透明度は下がった。 As in Example 1, there was no hard layer in the sedimented layer even after standing for 7 days, and redispersion was easy (all ◎). However, when the pH was in the acidic range during the addition of the sulfuric acid band, a phenomenon was observed in which the light cal-core of the light cal-silica composite was dissolved. When the pH was lower than 7, it was considered that the quality of the light cal-silica composite could not be maintained. In fact, when blended with paper, the opacity decreased compared to Comparative Example 1 which was a blank.
Claims (4)
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| JP2007086767A Expired - Fee Related JP5096028B2 (en) | 2007-03-29 | 2007-03-29 | Slurry containing light calcium carbonate-silica composite and aluminum-based water-soluble inorganic compound |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012133797A1 (en) * | 2011-03-31 | 2012-10-04 | 日本たばこ産業株式会社 | Cigarrete paper effective in reducing amount of visible sidestream smoke and content of carbon monoxide in mainstream smoke, and cigarrete |
| JP2013096029A (en) * | 2011-10-31 | 2013-05-20 | Daio Paper Corp | Method for producing filler |
| CN114544442A (en) * | 2020-11-24 | 2022-05-27 | 立邦涂料（中国）有限公司 | Detection method for rapidly evaluating fineness of 700-mesh heavy calcium carbonate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003049389A (en) * | 2001-07-31 | 2003-02-21 | Nippon Paper Industries Co Ltd | Method for producing composite particle and method for producing loading material-added paper |
| JP2006088636A (en) * | 2004-09-27 | 2006-04-06 | Nippon Paper Industries Co Ltd | Inkjet recording medium |
| JP2006276478A (en) * | 2005-03-29 | 2006-10-12 | Nippon Paper Industries Co Ltd | Continuous recording paper |
| JP2007010930A (en) * | 2005-06-30 | 2007-01-18 | Nippon Paper Industries Co Ltd | Paper for recording information |
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2007
- 2007-03-29 JP JP2007086767A patent/JP5096028B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003049389A (en) * | 2001-07-31 | 2003-02-21 | Nippon Paper Industries Co Ltd | Method for producing composite particle and method for producing loading material-added paper |
| JP2006088636A (en) * | 2004-09-27 | 2006-04-06 | Nippon Paper Industries Co Ltd | Inkjet recording medium |
| JP2006276478A (en) * | 2005-03-29 | 2006-10-12 | Nippon Paper Industries Co Ltd | Continuous recording paper |
| JP2007010930A (en) * | 2005-06-30 | 2007-01-18 | Nippon Paper Industries Co Ltd | Paper for recording information |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012133797A1 (en) * | 2011-03-31 | 2012-10-04 | 日本たばこ産業株式会社 | Cigarrete paper effective in reducing amount of visible sidestream smoke and content of carbon monoxide in mainstream smoke, and cigarrete |
| JP5716087B2 (en) * | 2011-03-31 | 2015-05-13 | 日本たばこ産業株式会社 | Cigarette paper and cigarettes reduce visible sidestream smoke and carbon monoxide in mainstream smoke |
| JP2013096029A (en) * | 2011-10-31 | 2013-05-20 | Daio Paper Corp | Method for producing filler |
| CN114544442A (en) * | 2020-11-24 | 2022-05-27 | 立邦涂料（中国）有限公司 | Detection method for rapidly evaluating fineness of 700-mesh heavy calcium carbonate |
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|---|---|
| JP5096028B2 (en) | 2012-12-12 |
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