JPH0920629A - Sterilized calcium carbonate composition, its aqueous suspension composition and their production - Google Patents
Sterilized calcium carbonate composition, its aqueous suspension composition and their productionInfo
- Publication number
- JPH0920629A JPH0920629A JP7168701A JP16870195A JPH0920629A JP H0920629 A JPH0920629 A JP H0920629A JP 7168701 A JP7168701 A JP 7168701A JP 16870195 A JP16870195 A JP 16870195A JP H0920629 A JPH0920629 A JP H0920629A
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- Japan
- Prior art keywords
- calcium carbonate
- sterilized
- aqueous suspension
- calcium
- composition
- 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
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- Coloring Foods And Improving Nutritive Qualities (AREA)
- Apparatus For Disinfection Or Sterilisation (AREA)
- Cosmetics (AREA)
- Colloid Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、食品に添加してカルシ
ウムの強化および歯磨き用基剤などの化粧品にソフトな
研磨性を付与するのに利用される高懸濁安定性を有する
滅菌炭酸カルシウム組成物、特にその水懸濁液組成物及
びそれらの製造方法に関する。FIELD OF THE INVENTION The present invention relates to a sterilized calcium carbonate having high suspension stability, which is used for adding calcium to foods to enhance calcium and to impart soft abrasiveness to cosmetics such as toothpaste bases. The present invention relates to compositions, especially aqueous suspension compositions thereof and processes for their preparation.
【０００２】[0002]
【従来の技術】カルシウムは、骨や歯を形成する、生体
に欠かすことのできないミネラルであるが、最近カルシ
ウムの摂取量不足が高齢者の骨粗鬆症の増加や若年者の
骨折の多発などに関連して問題視されている。このカル
シウムの摂取量不足を補うために、食品へのカルシウム
強化が試みられており、特に、カルシウムの生体吸収性
が比較的良いとされている牛乳へのカルシウム強化が増
えてきている。2. Description of the Related Art Calcium is a mineral that forms bones and teeth and is indispensable to the living body. Recently, insufficient intake of calcium has been associated with increased osteoporosis in the elderly and frequent fractures in the young. Is regarded as a problem. In order to make up for this shortage of calcium intake, attempts have been made to enhance calcium in foods, and in particular, increase in calcium to milk, which is said to have relatively good bioabsorption of calcium, is increasing.
【０００３】例えば、牛乳に添加するカルシウム強化剤
としては、乳酸カルシウム、グルコン酸カルシウムなど
の有機酸カルシウムがあるが、有機酸カルシウムは水溶
性であるため、牛乳中の蛋白質と反応して加熱滅菌時に
凝固物を生じやすい。また、有機酸カルシウム自身のカ
ルシウム成分比が小さいため、牛乳への添加量が必然的
に多くなり、食味上にも問題がある。[0003] For example, calcium enhancers added to milk include organic acid calcium such as calcium lactate and calcium gluconate. Since organic acid calcium is water-soluble, it reacts with proteins in milk and is heat sterilized. Occasionally coagulates occur. In addition, since the calcium component ratio of the organic acid calcium itself is small, the amount added to milk is inevitably large and there is a problem in taste.
【０００４】一方、炭酸カルシウム、リン酸カルシウム
などの水難溶性カルシウム塩は、牛乳中のタンパク質と
の凝固物を生じることはなく、また無味無臭で食味に及
ぼす影響も少なく、有機酸カルシウムよりカルシウム含
量が多いことから、少ない添加量でカルシウム強化がで
きるなどカルシウム強化剤として好ましい。このため、
最近炭酸カルシウムをカルシウム強化剤として牛乳に添
加する応用例が増えているが、炭酸カルシウムは液中で
短時間に沈殿し、懸濁安定性に問題がある。この問題点
を解決する方法として、炭酸カルシウムに結晶性セルロ
ースを添加する方法、あるいはショ糖脂肪酸エステルな
どのＨＬＢが１０以上の親水性乳化剤を添加する方法な
どが提案されている。しかし、結晶性セルロースを用い
た場合は牛乳の粘度が高くなり、食味にも影響する。ま
た、親水性乳化剤を用いた場合は、超音波照射などの特
殊な分散方法が必要であり、製造効率が悪いなどの問題
がある。On the other hand, poorly water-soluble calcium salts such as calcium carbonate and calcium phosphate do not produce a coagulation product with proteins in milk, have no taste and odor and have little effect on taste, and have a higher calcium content than organic acid calcium. Therefore, it is preferable as a calcium strengthening agent because it can strengthen calcium with a small amount of addition. For this reason,
Recently, applications of adding calcium carbonate to milk as a calcium enhancer are increasing, but calcium carbonate precipitates in a liquid in a short time, and there is a problem in suspension stability. As a method for solving this problem, a method of adding crystalline cellulose to calcium carbonate or a method of adding a hydrophilic emulsifier having an HLB of 10 or more such as sucrose fatty acid ester has been proposed. However, when crystalline cellulose is used, the viscosity of milk becomes high and the taste is also affected. Further, when a hydrophilic emulsifier is used, a special dispersion method such as ultrasonic irradiation is required, which causes a problem such as poor production efficiency.
【０００５】滅菌炭酸カルシウム水懸濁液を食品添加物
として使用する場合、一般細菌等の発生を防止する衛生
面の管理が特に重要であり、その処理方法として加熱滅
菌を行う必要がある。しかし、炭酸カルシウムの分散剤
として最も効果のあるメタリン酸ナトリウムは炭酸カル
シウムの共存下に加熱すると反応して不溶性のリン酸カ
ルシウムが生成し、分散効果が著しく低下する。When a sterile calcium carbonate aqueous suspension is used as a food additive, it is particularly important to control hygiene in order to prevent the generation of general bacteria and the like, and heat sterilization must be performed as a treatment method. However, sodium metaphosphate, which is most effective as a dispersant for calcium carbonate, reacts when heated in the presence of calcium carbonate to form insoluble calcium phosphate, resulting in a marked decrease in the dispersing effect.
【０００６】本発明は、食品、特に牛乳などの飲料添加
用のカルシウム強化剤として使用するに当たって、液中
で沈殿しにくく、懸濁安定性及び保存安定性に優れ、ま
た歯磨きなどの化粧品に使用して歯質を損傷することの
ないソフトな研磨性に優れた滅菌炭酸カルシウム水懸濁
液組成物を提供することを目的とする。[0006] The present invention, when used as a calcium enhancer for the addition of foods, especially milk and other beverages, is unlikely to precipitate in a liquid, has excellent suspension stability and storage stability, and is used for cosmetics such as toothpaste. It is an object of the present invention to provide a sterilized calcium carbonate aqueous suspension composition which is soft and has excellent abrasiveness without damaging the tooth structure.
【０００７】[0007]
【課題を解決するための手段】本発明者は、上記課題に
鑑み検討を重ねた結果、炭酸カルシウムの水懸濁液とメ
タリン酸ナトリウムの水溶液をあらかじめ個別に加熱滅
菌した後に混合して湿式粉砕するか、又はポリペプチド
を添加した炭酸カルシウムの水懸濁液とメタリン酸ナト
リウムの水溶液をあらかじめ個別に加熱滅菌した後に混
合して湿式粉砕することにより、液中で沈降しにくく、
懸濁安定性及び保存安定性に優れた滅菌炭酸カルシウム
水懸濁液が得られることを見出した。Means for Solving the Problems As a result of extensive studies in view of the above-mentioned problems, the present inventor has found that an aqueous suspension of calcium carbonate and an aqueous solution of sodium metaphosphate are individually heat-sterilized in advance and then mixed and wet-milled. Or, by water-suspending calcium carbonate to which the polypeptide is added and an aqueous solution of sodium metaphosphate are individually heat-sterilized in advance and then mixed and wet-milled, it is difficult to settle in the liquid,
It was found that a sterile calcium carbonate aqueous suspension having excellent suspension stability and storage stability can be obtained.
【０００８】すなわち、本発明は、以下の滅菌炭酸カル
シウム組成物、その水懸濁液組成物及びそれらの製造方
法に関する。That is, the present invention relates to the following sterilized calcium carbonate composition, its aqueous suspension composition, and a method for producing them.
【０００９】項１． 炭酸カルシウム及びメタリン酸ナ
トリウムを含有し、リン酸カルシウムを実質的に含まな
い滅菌炭酸カルシウム組成物。Item 1. A sterile calcium carbonate composition containing calcium carbonate and sodium metaphosphate and substantially free of calcium phosphate.
【００１０】項２． 炭酸カルシウム及びメタリン酸ナ
トリウムを含有し、リン酸カルシウムを実質的に含まな
い滅菌炭酸カルシウム水懸濁液組成物。Item 2. A sterile calcium carbonate aqueous suspension composition containing calcium carbonate and sodium metaphosphate and substantially free of calcium phosphate.
【００１１】項３． 炭酸カルシウム、ポリペプチド及
びメタリン酸ナトリウムを含有する滅菌炭酸カルシウム
水懸濁液組成物。Item 3. A sterile calcium carbonate aqueous suspension composition comprising calcium carbonate, a polypeptide and sodium metaphosphate.
【００１２】項４． ポリペプチドがカゼインホスホペ
プチドおよびカゼインカルシウムペプチドからなる群か
ら選ばれる少なくとも１種である項３に記載の滅菌炭酸
カルシウム水懸濁液組成物。Item 4. Item 4. The sterile calcium carbonate aqueous suspension composition according to Item 3, wherein the polypeptide is at least one selected from the group consisting of casein phosphopeptides and casein calcium peptides.
【００１３】項５． 炭酸カルシウムの水懸濁液とメタ
リン酸ナトリウムの水溶液をあらかじめ個別に加熱滅菌
した後に混合して湿式粉砕することを特徴とする滅菌炭
酸カルシウム水懸濁液組成物の製造方法。Item 5. A method for producing a sterile calcium carbonate aqueous suspension composition, which comprises individually sterilizing an aqueous suspension of calcium carbonate and an aqueous solution of sodium metaphosphate in advance by heating, then mixing and wet pulverizing.
【００１４】項６． 炭酸カルシウムの水懸濁液を加熱
滅菌し、湿式粉砕した後に別に加熱滅菌したメタリン酸
ナトリウムの水溶液を添加、攪拌混合することを特徴と
する滅菌炭酸カルシウム水懸濁液組成物の製造方法。Item 6. A method for producing a sterilized calcium carbonate aqueous suspension composition, which comprises sterilizing an aqueous suspension of calcium carbonate with heat, wet pulverizing, and then separately adding an aqueous solution of sodium metaphosphate that has been sterilized with heat, and stirring and mixing.
【００１５】項７． ポリペプチドを添加した炭酸カル
シウムの水懸濁液とメタリン酸ナトリウムの水溶液をあ
らかじめ個別に加熱滅菌した後に混合して湿式粉砕する
ことを特徴とする滅菌炭酸カルシウム水懸濁液組成物の
製造方法。Item 7. A method for producing a sterilized calcium carbonate aqueous suspension composition, which comprises individually heating and sterilizing an aqueous suspension of calcium carbonate to which a polypeptide is added and an aqueous solution of sodium metaphosphate, and then mixing and wet pulverizing.
【００１６】項８． ポリペプチドを添加した炭酸カル
シウムの水懸濁液を加熱滅菌し、湿式粉砕した後に別に
加熱滅菌したメタリン酸ナトリウムの水溶液を添加、攪
拌混合することを特徴とする滅菌炭酸カルシウム水懸濁
液組成物の製造方法。Item 8. Sterilized calcium carbonate aqueous suspension composition, characterized in that an aqueous suspension of calcium carbonate to which a polypeptide is added is sterilized by heating, wet-milled, and then an aqueous solution of sodium metaphosphate that has been separately sterilized by heating is added and mixed with stirring. Manufacturing method.
【００１７】項９． 炭酸カルシウムとメタリン酸ナト
リウムをあらかじめ個別に加熱滅菌した後に攪拌混合す
ることを特徴とする滅菌炭酸カルシウム組成物の製造方
法。Item 9. A method for producing a sterilized calcium carbonate composition, which comprises individually sterilizing calcium carbonate and sodium metaphosphate in advance by heating and then stirring and mixing them.
【００１８】項10． 項１に記載の滅菌炭酸カルシウム
組成物を配合してなる練り歯磨き。Item 10. A toothpaste containing the sterile calcium carbonate composition according to Item 1.
【００１９】本発明の滅菌炭酸カルシウム組成物は、蒸
留水などの滅菌水を加えることにより容易に安定な滅菌
炭酸カルシウム水懸濁液組成物に変換することができ
る。従って、輸送時ないし保存時には水を含まない組成
物の形態とし、使用時に水を加えて懸濁液としてもよ
い。又、本発明の滅菌炭酸カルシウム組成物は、水を少
し含んだペースト状あるいは濃厚懸濁液においても炭酸
カルシウムを安定に存在させることができるので、例え
ば練り歯磨きに加えると研磨剤としての炭酸カルシウム
が歯質を損傷することはなく、研磨を円滑に行うことが
でき、歯磨き後の練り歯磨きの除去も容易に行うことが
できる。また、傷を付けずに汚れを落とすクレンザータ
イプの食器用、台所用などの液状洗剤にも適用できる。The sterile calcium carbonate composition of the present invention can be easily converted into a stable sterile calcium carbonate aqueous suspension composition by adding sterile water such as distilled water. Therefore, it may be in the form of a composition containing no water at the time of transportation or storage and may be made into a suspension by adding water at the time of use. Further, the sterilized calcium carbonate composition of the present invention allows calcium carbonate to be stably present even in a paste form or a concentrated suspension containing a small amount of water, and therefore, when added to toothpaste, calcium carbonate as an abrasive is used. Does not damage the tooth substance, the polishing can be performed smoothly, and the toothpaste after the tooth brushing can be easily removed. It can also be applied to cleanser-type tableware, kitchen and other liquid detergents that remove dirt without scratching.
【００２０】さらに、本発明の組成物を固体、液状又は
半固形状の食品に加えた場合にも、該食品を摂取したと
きに炭酸カルシウムの微細粒子が十分に分散された状態
で存在するために吸収されやすい。本発明の組成物が配
合される食品としては例えば牛乳、乳飲料、アイスクリ
ーム、練乳などの乳製品、コーヒー、飲料水、豆乳等が
挙げられる。Furthermore, when the composition of the present invention is added to a solid, liquid or semi-solid food, fine particles of calcium carbonate are present in a sufficiently dispersed state when the food is ingested. Easily absorbed by. Examples of foods containing the composition of the present invention include milk, milk drinks, dairy products such as ice cream and condensed milk, coffee, drinking water, soy milk and the like.
【００２１】本発明の組成物は、炭酸カルシウムとメタ
リン酸ナトリウムをあらかじめ個別に加熱滅菌した後に
混合・攪拌して製造することができる。The composition of the present invention can be produced by individually heating and sterilizing calcium carbonate and sodium metaphosphate, then mixing and stirring.
【００２２】本発明において、「リン酸カルシウムを実
質的に含まない」とは、リン酸カルシウムの存在により
炭酸カルシウム水懸濁液の懸濁安定性が損なわれないこ
とを意味するものであり、炭酸カルシウム水懸濁液が十
分に安定である限り、リン酸カルシウムを含んでもよい
ことを意味する。In the present invention, the phrase "substantially free of calcium phosphate" means that the presence of calcium phosphate does not impair the suspension stability of the calcium carbonate aqueous suspension. It means that calcium phosphate may be included as long as the suspension is sufficiently stable.
【００２３】例えば、本発明の水懸濁液１００ｍｌ（炭
酸カルシウム濃度＝０．２％）を４週間放置したときの
沈降物の見かけ容積が１ｍｌ以下であれば、「リン酸カ
ルシウムを実質的に含まない」に該当する。For example, when the apparent volume of the sediment when the 100 ml of the water suspension of the present invention (calcium carbonate concentration = 0.2%) is allowed to stand for 4 weeks is 1 ml or less, "substantially no calcium phosphate is contained. It corresponds to.
【００２４】炭酸カルシウムは、食品添加物規格または
化粧品原料基準に適合した合成品または粉砕品が用いら
れ、好ましくは、ＢＥＴ比表面積７ｍ2／ｇ以上、平均
粒子径５μｍ以下であり、より好ましくは、ＢＥＴ比表
面積７〜１００ｍ2／ｇ程度、平均粒子径０．０２〜５
μｍ程度である。As the calcium carbonate, a synthetic product or a pulverized product which conforms to the food additive standard or the cosmetic raw material standard is used, and preferably has a BET specific surface area of 7 m 2 / g or more and an average particle diameter of 5 μm or less, more preferably , BET specific surface area of about 7 to 100 m 2 / g, average particle diameter of 0.02 to 5
It is about μm.
【００２５】最も好ましい炭酸カルシウムは多孔質炭酸
カルシウムであり、該多孔質炭酸カルシウムは、例えば
以下の工程(i)〜(iii)により製造される。The most preferred calcium carbonate is porous calcium carbonate, and the porous calcium carbonate is produced, for example, by the following steps (i) to (iii).
【００２６】(i)水酸化カルシウム水懸濁液に炭酸ガス
濃度１５容量％以上の炭酸ガス含有気体を水酸化カルシ
ウム１ｋｇ当たり２５リットル／分以上で吹き込み、炭
酸化率６０〜９０％まで炭酸化反応を行う第一炭酸化工
程、(ii)第一炭酸化工程終了後の水懸濁液に、水酸化カ
ルシウム水懸濁液を加えて、炭酸ガス濃度１０容量％以
上の炭酸ガス含有気体を水酸化カルシウム１ｋｇ当たり
１５リットル／分以上で吹き込み、炭酸化率７０〜９０
％まで炭酸化反応を行う第二炭酸化工程、及び(iii)第
二炭酸化工程終了後に、さらに第二炭酸化工程と同じ炭
酸化工程を１回以上繰り返し、次いで当該炭酸化工程終
了後の水懸濁液に、水酸化カルシウム水懸濁液を加え
て、炭酸ガス濃度１０容量％以上の炭酸ガス含有気体を
水酸化カルシウム１ｋｇ当たり１５リットル／分以上で
吹き込み、ｐＨ６．５〜７．５となるまで炭酸化反応を
行う最終炭酸化工程。(I) Carbon dioxide-containing gas having a carbon dioxide concentration of 15% by volume or more is blown into the calcium hydroxide aqueous suspension at a rate of 25 liter / min or more per 1 kg of calcium hydroxide to carbonate the carbonation rate to 60 to 90%. The first carbonation step of carrying out the reaction, (ii) calcium hydroxide aqueous suspension is added to the water suspension after the completion of the first carbonation step to give a carbon dioxide-containing gas having a carbon dioxide concentration of 10% by volume or more. Blow at a rate of 15 liters / minute or more per 1 kg of calcium hydroxide, and a carbonation rate of 70 to 90
% Of the second carbonation step, and (iii) after the second carbonation step is completed, the same carbonation step as the second carbonation step is repeated one or more times. An aqueous suspension of calcium hydroxide is added to the aqueous suspension, and a carbon dioxide-containing gas having a carbon dioxide concentration of 10% by volume or more is blown at a rate of 15 liter / min or more per 1 kg of calcium hydroxide to have a pH of 6.5 to 7.5. The final carbonation step of performing the carbonation reaction until
【００２７】なお、工程(i)〜(iii)の炭酸化率は、式：
炭酸化率（％）＝１００×Ｗ／（Ｗ＋Ｗ1）（但し、Ｗ
は反応液中の炭酸カルシウムの重量、Ｗ1は反応液中の
水酸化カルシウムの重量である。）により表わされるも
のである。The carbonation rate in steps (i) to (iii) is calculated by the formula:
Carbonation rate (%) = 100 × W / (W + W1) (however, W
Is the weight of calcium carbonate in the reaction solution, and W1 is the weight of calcium hydroxide in the reaction solution. ).
【００２８】炭酸カルシウムの固形分濃度は５〜５０重
量％程度、好ましくは１０〜４５重量％程度である。炭
酸カルシウムの固形分濃度が上記範囲にあると製造効率
が高く、低コストで製造できるため好ましい。The solid content concentration of calcium carbonate is about 5 to 50% by weight, preferably about 10 to 45% by weight. When the solid content concentration of calcium carbonate is within the above range, the production efficiency is high and the production can be performed at low cost, which is preferable.
【００２９】メタリン酸ナトリウムの添加量は、炭酸カ
ルシウム１００重量部に対し０．５〜５重量部程度、好
ましくは０．８〜４重量部程度である。The amount of sodium metaphosphate added is about 0.5 to 5 parts by weight, preferably about 0.8 to 4 parts by weight, based on 100 parts by weight of calcium carbonate.
【００３０】ポリペプチドは、好ましくはアミノ酸残基
の数が１０〜５０である。なお、該アミノ酸残基の数
は、会合性のタンパク質の場合には単量体のアミノ酸の
数である。該ポリペプチドは、リン酸残基を構造中に含
むホスホペプチドが好ましい。このようなホスホペプチ
ドとしては、カゼインホスホペプチド（ＣＰＰ）、カゼ
インカルシウムペプチド（ＣＣＰ）等が挙げられる。Ｃ
ＰＰおよびＣＣＰはいずれもカゼインまたはカゼインカ
ルシウムを酵素分解して得られるものであり、市販品と
して入手できる。The polypeptide preferably has 10 to 50 amino acid residues. The number of amino acid residues is the number of monomeric amino acids in the case of an associative protein. The polypeptide is preferably a phosphopeptide containing a phosphate residue in the structure. Examples of such phosphopeptides include casein phosphopeptide (CPP) and casein calcium peptide (CCP). C
Both PP and CCP are obtained by enzymatically decomposing casein or casein calcium, and are commercially available.
【００３１】ポリペプチドの添加量としては、炭酸カル
シウム１００重量部に対し０．０５〜１重量部程度、好
ましくは０．１〜０．８重量部程度である。The amount of polypeptide added is about 0.05 to 1 part by weight, preferably about 0.1 to 0.8 part by weight, based on 100 parts by weight of calcium carbonate.
【００３２】本発明の製造方法において、湿式粉砕工程
に用いられる湿式粉砕装置としては、コロイドミル、サ
ンドミル、ボールミルなどが挙げられる。In the manufacturing method of the present invention, examples of the wet crushing device used in the wet crushing step include a colloid mill, a sand mill, a ball mill and the like.
【００３３】また、本発明の攪拌混合工程において用い
られる攪拌混合装置としては、ホモジナイザー、ディス
パーなどが挙げられる。湿式粉砕、攪拌混合等の条件
は、特に限定されず、当業者であれば容易に決定でき
る。Further, examples of the stirring and mixing apparatus used in the stirring and mixing step of the present invention include a homogenizer and a disper. Conditions such as wet pulverization and stirring and mixing are not particularly limited, and can be easily determined by those skilled in the art.
【００３４】加熱滅菌は、６０〜１２０℃程度で１５〜
６０分程度の条件で行えばよい。Heat sterilization is carried out at about 60 to 120 ° C. for 15 to
It may be performed under the condition of about 60 minutes.
【００３５】本発明の製造方法は、炭酸カルシウム（ポ
リペプチドを含んでいてもよい）とメタリン酸ナトリウ
ムをあらかじめ別々に加熱滅菌処理し、次いでこれらを
混合する点に特徴がある。これらを混合後に加熱滅菌処
理を行うと、不溶性のリン酸カルシウムが生じるため、
好ましくない。The production method of the present invention is characterized in that calcium carbonate (which may contain a polypeptide) and sodium metaphosphate are separately heat-sterilized in advance and then these are mixed. When heat sterilization is performed after mixing these, insoluble calcium phosphate is generated,
Not preferred.
【００３６】[0036]
【実施例】以下、本発明を実施例に基づいて説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.
【００３７】実施例１ ３０％多孔質炭酸カルシウム（ＢＥＴ比表面積３０ｍ2
／ｇ、平均粒子径３μｍ、ｐＨ＝９．５）水懸濁液を８
５℃で３０分間加熱滅菌した。これとは別に１５％メタ
リン酸ナトリウム水溶液を９５℃で５分間加熱滅菌し
た。これらを各々３０℃まで冷却した後炭酸カルシウム
１００重量部に対しメタリン酸ナトリウムが３重量部に
なるように両者を混合し、ダイノーミルで湿式粉砕して
懸濁液を得た。Example 1 30% porous calcium carbonate (BET specific surface area 30 m 2
/ G, average particle diameter 3 μm, pH = 9.5) 8 water suspension
Heat sterilization was performed at 5 ° C for 30 minutes. Separately from this, a 15% aqueous sodium metaphosphate solution was sterilized by heating at 95 ° C. for 5 minutes. After cooling each to 30 ° C., both were mixed so that sodium metaphosphate was 3 parts by weight with respect to 100 parts by weight of calcium carbonate, and wet milled with a Dyno-mill to obtain a suspension.
【００３８】実施例２ ２０％炭酸カルシウム（ＢＥＴ比表面積１１ｍ2／ｇ、
平均粒子径１μｍ、ｐＨ＝１０．５）水懸濁液を８５℃
で３０分間加熱滅菌し、３０℃まで冷却した後、ダイノ
ーミルで湿式粉砕した。これとは別に、１５％メタリン
酸ナトリウム水溶液を９５℃で５分間加熱滅菌し、３０
℃まで冷却した。次いで、炭酸カルシウム１００重量部
に対しメタリン酸ナトリウムが４重量部になるように両
者を混合して懸濁液を得た。Example 2 20% calcium carbonate (BET specific surface area 11 m 2 / g,
Average particle size 1 μm, pH = 10.5) Water suspension at 85 ° C
It was sterilized by heat for 30 minutes, cooled to 30 ° C., and wet-ground with a Dyno-mill. Separately, heat sterilize a 15% sodium metaphosphate aqueous solution at 95 ° C. for 5 minutes, and
Cooled to ° C. Next, both were mixed so that sodium metaphosphate was 4 parts by weight with respect to 100 parts by weight of calcium carbonate, to obtain a suspension.
【００３９】実施例３ ３５％多孔質炭酸カルシウム（ＢＥＴ比表面積３０ｍ2
／ｇ、平均粒子径３μｍ、ｐＨ＝９．５）水懸濁液に、
１０％ＣＰＰを、炭酸カルシウム１００重量部に対し
０．３重量部になるように添加し、８５℃で３０分間加
熱滅菌し、３０℃まで冷却した。これとは別に、１５％
メタリン酸ナトリウム水溶液を９５℃で５分間加熱滅菌
し、３０℃まで冷却した。次いで、炭酸カルシウム１０
０重量部に対しメタリン酸ナトリウムが３重量部になる
ように両者を混合し、ダイノーミルで湿式粉砕して懸濁
液を得た。Example 3 35% porous calcium carbonate (BET specific surface area 30 m 2
/ G, average particle size 3 μm, pH = 9.5)
10% CPP was added to 0.3 parts by weight to 100 parts by weight of calcium carbonate, sterilized by heating at 85 ° C for 30 minutes, and cooled to 30 ° C. Apart from this, 15%
The aqueous sodium metaphosphate solution was sterilized by heating at 95 ° C for 5 minutes and cooled to 30 ° C. Then calcium carbonate 10
Both were mixed so that sodium metaphosphate was 3 parts by weight with respect to 0 part by weight, and wet-ground with a dyno mill to obtain a suspension.
【００４０】実施例４ ３０％多孔質炭酸カルシウム（ＢＥＴ比表面積３０ｍ2
／ｇ、平均粒子径３μｍ、ｐＨ＝９．５）水懸濁液に、
１０％ＣＣＰを、炭酸カルシウム１００重量部に対し
０．１重量部になるように添加し、８５℃で３０分間加
熱滅菌し、３０℃まで冷却した。これとは別に、１５％
メタリン酸ナトリウム水溶液を９５℃で５分間加熱滅菌
し、３０℃まで冷却した。次いで、炭酸カルシウム１０
０重量部に対しメタリン酸ナトリウムが１重量部になる
ように両者を混合し、ダイノーミルで湿式粉砕して懸濁
液を得た。Example 4 30% porous calcium carbonate (BET specific surface area 30 m 2
/ G, average particle size 3 μm, pH = 9.5)
10% CCP was added to 0.1 part by weight to 100 parts by weight of calcium carbonate, heat sterilized at 85 ° C for 30 minutes, and cooled to 30 ° C. Apart from this, 15%
The aqueous sodium metaphosphate solution was sterilized by heating at 95 ° C for 5 minutes and cooled to 30 ° C. Then calcium carbonate 10
Both were mixed so that sodium metaphosphate was 1 part by weight with respect to 0 part by weight, and wet pulverized with a dyno mill to obtain a suspension.
【００４１】実施例５ ２５％炭酸カルシウム（ＢＥＴ比表面積１１ｍ2／ｇ、
平均粒子径１μｍ、ｐＨ＝１０．５）水懸濁液に、１０
％ＣＰＰを、炭酸カルシウム１００重量部に対し０．４
重量部になるように添加し、８５℃で３０分間加熱滅菌
し、３０℃まで冷却し、ダイノーミルで湿式粉砕した。
これとは別に、１５％メタリン酸ナトリウム水溶液を９
５℃で５分間加熱滅菌し、３０℃まで冷却した。次い
で、炭酸カルシウム１００重量部に対しメタリン酸ナト
リウムが２重量部になるように両者を混合して懸濁液を
得た。Example 5 25% calcium carbonate (BET specific surface area 11 m 2 / g,
Average particle size 1 μm, pH = 10.5)
% CPP is 0.4 per 100 parts by weight of calcium carbonate
It was added in an amount of 1 part by weight, heat sterilized at 85 ° C. for 30 minutes, cooled to 30 ° C., and wet pulverized with a Dyno mill.
Separately, add 9% of 15% sodium metaphosphate aqueous solution.
It was heat-sterilized at 5 ° C for 5 minutes and cooled to 30 ° C. Then, both were mixed so that sodium metaphosphate was 2 parts by weight with respect to 100 parts by weight of calcium carbonate to obtain a suspension.
【００４２】比較例１ ３０％炭酸カルシウム（ＢＥＴ比表面積３０ｍ2／ｇ、
平均粒子径３μｍ、ｐＨ＝９．５）水懸濁液を８５℃で
３０分間加熱滅菌した。これとは別に１５％メタリン酸
ナトリウム水溶液を９５℃で５分間加熱滅菌した。これ
らを各々３０℃まで冷却した後炭酸カルシウム１００重
量部に対しメタリン酸ナトリウムが０．２重量部になる
ように両者を混合し、ダイノーミルで湿式粉砕して懸濁
液を得た。Comparative Example 1 30% calcium carbonate (BET specific surface area 30 m 2 / g,
The water suspension having an average particle diameter of 3 μm and pH = 9.5) was sterilized by heating at 85 ° C. for 30 minutes. Separately from this, a 15% aqueous sodium metaphosphate solution was sterilized by heating at 95 ° C. for 5 minutes. After cooling each to 30 ° C., both were mixed so that sodium metaphosphate would be 0.2 parts by weight with respect to 100 parts by weight of calcium carbonate, and wet-ground with a Dyno-mill to obtain a suspension.
【００４３】比較例２ ３０％炭酸カルシウム（ＢＥＴ比表面積３０ｍ2／ｇ、
平均粒子径３μｍ、ｐＨ＝９．５）水懸濁液に１５％メ
タリン酸ナトリウム水溶液を、炭酸カルシウム１００重
量部に対し３重量部を添加し、８５℃で３０分間加熱滅
菌した。３０℃まで冷却した後、ダイノーミルで湿式粉
砕して懸濁液を得た。Comparative Example 2 30% calcium carbonate (BET specific surface area 30 m 2 / g,
A 15% aqueous solution of sodium metaphosphate (3 parts by weight) was added to a water suspension having an average particle diameter of 3 μm and a pH of 9.5), and 3 parts by weight was added to 100 parts by weight of calcium carbonate, followed by heat sterilization at 85 ° C. for 30 minutes. After cooling to 30 ° C., it was wet-ground with a dyno mill to obtain a suspension.
【００４４】懸濁安定性試験 実施例１〜５及び比較例１〜２で得た滅菌炭酸カルシウ
ム水懸濁液を炭酸カルシウムの固形分濃度で０．２％に
なるまで水で希釈し、ディスパー攪拌機で１０００ｒｐ
ｍ×７分３０秒攪拌した後、遠心分離器で１５７Ｇ×４
分２０秒間遠心力をかけた。次に遠心沈降物を蒸発乾固
させ、電気炉で９５０℃×３時間焼成し、冷却後に重量
を測定して懸濁率を算出した。また、同様にして調製し
た０．２％希釈液を１００ｍｌの有栓メスシリンダーに
取り、常温で静置して希釈液の懸濁液面の高さ及び沈降
物の見掛け容積の経時変化を測定した。結果を表１〜表
３に示す。なお、表２中のｐＨ比、粘度比＝（１〜４週
間後の値）／（製造直後の値）で表される。 Suspension Stability Test The sterilized calcium carbonate aqueous suspensions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were diluted with water to a solid concentration of calcium carbonate of 0.2% and dispersed in a disperser. 1000 rp with a stirrer
m × 7 minutes and 30 seconds, and then centrifuge to 157G × 4
Centrifugal force was applied for 20 seconds. Next, the centrifugal sediment was evaporated to dryness, calcined in an electric furnace at 950 ° C. for 3 hours, and after cooling, the weight was measured to calculate the suspension rate. The 0.2% diluted solution prepared in the same manner was placed in a 100 ml graduated cylinder with a stopper and allowed to stand at room temperature to measure the height of the suspension surface of the diluted solution and the change with time of the apparent volume of sediment. did. The results are shown in Tables 1 to 3. The pH ratio and the viscosity ratio in Table 2 are expressed as (value after 1 to 4 weeks) / (value immediately after production).
【００４５】[0045]
【表１】 [Table 1]
【００４６】[0046]
【表２】 [Table 2]
【００４７】[0047]
【表３】 [Table 3]
【００４８】懸濁液の高懸濁安定性の評価基準を以下に
示す。The evaluation criteria for the high suspension stability of the suspension are shown below.
【００４９】(1)懸濁率：６０％以上 (2)懸濁液面の高さ：７０ｍｌ以上（４週間後） (3)ｐＨ比：０．９０〜１．１０（４週間後） (4)粘度比：０．８０〜１．２５（４週間後） 上記評価基準によれば、本発明の懸濁液組成物が高懸濁
安定性を有することは明らかである。このことは、実施
例１〜５で得られた懸濁液は、リン酸カルシウムは実質
的に含まないことを示している。(1) Suspension rate: 60% or more (2) Height of suspension surface: 70 ml or more (after 4 weeks) (3) pH ratio: 0.90 to 1.10 (after 4 weeks) ( 4) Viscosity ratio: 0.80 to 1.25 (after 4 weeks) According to the above evaluation criteria, it is clear that the suspension composition of the present invention has high suspension stability. This indicates that the suspensions obtained in Examples 1 to 5 are substantially free of calcium phosphate.
【００５０】製造例１ 練り歯磨き 以下の処方により、常法に従い練り歯磨きを製造した。Production Example 1 Toothpaste A toothpaste was produced according to a conventional method according to the following formulation.
【００５１】 炭酸カルシウム １００重量部 メタリン酸ナトリウム ２重量部 ラウリル硫酸ナトリウム（発泡剤） ４重量部 ソルビット（湿潤剤） ２０重量部 カラギーナン（粘結剤） ２重量部 香料 適量 保存剤 適量Calcium carbonate 100 parts by weight Sodium metaphosphate 2 parts by weight Sodium lauryl sulfate (foaming agent) 4 parts by weight Solbit (wetting agent) 20 parts by weight Carrageenan (caking agent) 2 parts by weight Perfume Suitable amount Preservatives Suitable amount
【００５２】[0052]
【発明の効果】以上のように、本発明で得られる滅菌炭
酸カルシウム水懸濁液組成物は懸濁安定性が高く、食品
用カルシウム強化剤として適しており、食品中への分散
性及び保存安定性に優れている。また、化粧品用基剤へ
の分散性、安定性にも優れている。INDUSTRIAL APPLICABILITY As described above, the sterilized calcium carbonate aqueous suspension composition obtained by the present invention has high suspension stability and is suitable as a calcium enhancer for food, dispersibility in food and storage. It has excellent stability. It also has excellent dispersibility in a cosmetic base and stability.
【００５３】本発明のポリペプチドは、水懸濁液製造の
どの時点で加えても効果がある。The polypeptides of the present invention are effective when added at any point during the production of the aqueous suspension.
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Claims (10)
を含有し、リン酸カルシウムを実質的に含まない滅菌炭
酸カルシウム組成物。1. A sterile calcium carbonate composition containing calcium carbonate and sodium metaphosphate and substantially free of calcium phosphate.
を含有し、リン酸カルシウムを実質的に含まない滅菌炭
酸カルシウム水懸濁液組成物。2. A sterile calcium carbonate aqueous suspension composition containing calcium carbonate and sodium metaphosphate and substantially free of calcium phosphate.
ン酸ナトリウムを含有する滅菌炭酸カルシウム水懸濁液
組成物。3. A sterile calcium carbonate aqueous suspension composition containing calcium carbonate, a polypeptide and sodium metaphosphate.
よびカゼインカルシウムペプチドからなる群から選ばれ
る少なくとも１種である請求項３に記載の滅菌炭酸カル
シウム水懸濁液組成物。4. The sterile calcium carbonate aqueous suspension composition according to claim 3, wherein the polypeptide is at least one selected from the group consisting of casein phosphopeptides and casein calcium peptides.
トリウムの水溶液をあらかじめ個別に加熱滅菌した後に
混合して湿式粉砕することを特徴とする滅菌炭酸カルシ
ウム水懸濁液組成物の製造方法。5. A method for producing a sterile calcium carbonate aqueous suspension composition, which comprises individually sterilizing an aqueous suspension of calcium carbonate and an aqueous solution of sodium metaphosphate in advance by heating, then mixing and wet pulverizing.
湿式粉砕した後に別に加熱滅菌したメタリン酸ナトリウ
ムの水溶液を添加、攪拌混合することを特徴とする滅菌
炭酸カルシウム水懸濁液組成物の製造方法。6. An aqueous suspension of calcium carbonate is heat-sterilized,
A method for producing a sterilized calcium carbonate aqueous suspension composition, which comprises adding an aqueous solution of sodium metaphosphate sterilized by heating after wet pulverizing, and mixing with stirring.
水懸濁液とメタリン酸ナトリウムの水溶液をあらかじめ
個別に加熱滅菌した後に混合して湿式粉砕することを特
徴とする滅菌炭酸カルシウム水懸濁液組成物の製造方
法。7. A sterile calcium carbonate aqueous suspension composition, characterized in that an aqueous suspension of calcium carbonate to which a polypeptide is added and an aqueous solution of sodium metaphosphate are individually sterilized by heating in advance, then mixed and wet-milled. Method of manufacturing things.
水懸濁液を加熱滅菌し、湿式粉砕した後に別に加熱滅菌
したメタリン酸ナトリウムの水溶液を添加、攪拌混合す
ることを特徴とする滅菌炭酸カルシウム水懸濁液組成物
の製造方法。8. A sterilized calcium carbonate aqueous solution characterized in that an aqueous suspension of calcium carbonate to which a polypeptide is added is sterilized by heating, wet-milled, and then an aqueous solution of sodium metaphosphate separately sterilized by heating is added and mixed with stirring. A method for producing a suspension composition.
あらかじめ個別に加熱滅菌した後に攪拌混合することを
特徴とする滅菌炭酸カルシウム組成物の製造方法。9. A method for producing a sterilized calcium carbonate composition, wherein calcium carbonate and sodium metaphosphate are individually sterilized by heating in advance and then mixed with stirring.
成物を配合してなる練り歯磨き。10. A toothpaste comprising the sterilized calcium carbonate composition according to claim 1.
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| JPH10330233A (en) * | 1997-06-03 | 1998-12-15 | Sunstar Inc | Composition for oral cavity |
| JPH1112145A (en) * | 1997-06-19 | 1999-01-19 | Sunstar Inc | Composition for oral cavity |
| JPH11215958A (en) * | 1997-11-21 | 1999-08-10 | Sono Kosakusho:Kk | Konjak (paste made from starch of devil's-tongue) food and its production |
| JPH11310522A (en) * | 1997-04-24 | 1999-11-09 | Sunstar Inc | Composition for application to oral cavity |
| JP2000050833A (en) * | 1998-08-05 | 2000-02-22 | Lotte Co Ltd | Material having function for improving flavor and taste, drink, food and composition for oral cavity, using the same |
| JP2002521415A (en) * | 1998-07-29 | 2002-07-16 | パシフィック バイオリンク ピーティーワイ．リミテッド | Casein compositions for delivery of bioactive ingredients |
| JP2003520040A (en) * | 2000-01-21 | 2003-07-02 | ザ プロクター アンド ギャンブル カンパニー | Method of using a beverage composition for treating tooth erosion |
| JP2004033712A (en) * | 2002-06-14 | 2004-02-05 | Sang-Kee Han | Interdental toothbrush |
| EP1341864A4 (en) * | 2000-08-18 | 2005-09-07 | Huber Corp J M | Method for making abrasive compositions and products thereof |
| KR100517188B1 (en) * | 1997-04-24 | 2006-05-12 | 선스타 가부시키가이샤 | Oral composition |
| JP2008529564A (en) * | 2005-01-26 | 2008-08-07 | オムヤ・デベロツプメント・アー・ゲー | Method for controlling microbial contamination, resulting inorganic suspension and use thereof |
| JP2017517472A (en) * | 2014-05-30 | 2017-06-29 | コーニング インコーポレイテッド | Ball milling method of aluminum metaphosphate |
| CN113056438A (en) * | 2019-02-01 | 2021-06-29 | Omya国际股份公司 | Production of surface-reacted calcium salts by milling-induced transformation |
-
1995
- 1995-07-04 JP JP7168701A patent/JP2981595B2/en not_active Expired - Lifetime
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100517188B1 (en) * | 1997-04-24 | 2006-05-12 | 선스타 가부시키가이샤 | Oral composition |
| JPH11310522A (en) * | 1997-04-24 | 1999-11-09 | Sunstar Inc | Composition for application to oral cavity |
| JPH10330233A (en) * | 1997-06-03 | 1998-12-15 | Sunstar Inc | Composition for oral cavity |
| JPH1112145A (en) * | 1997-06-19 | 1999-01-19 | Sunstar Inc | Composition for oral cavity |
| JPH11215958A (en) * | 1997-11-21 | 1999-08-10 | Sono Kosakusho:Kk | Konjak (paste made from starch of devil's-tongue) food and its production |
| JP2002521415A (en) * | 1998-07-29 | 2002-07-16 | パシフィック バイオリンク ピーティーワイ．リミテッド | Casein compositions for delivery of bioactive ingredients |
| JP2000050833A (en) * | 1998-08-05 | 2000-02-22 | Lotte Co Ltd | Material having function for improving flavor and taste, drink, food and composition for oral cavity, using the same |
| JP2003520040A (en) * | 2000-01-21 | 2003-07-02 | ザ プロクター アンド ギャンブル カンパニー | Method of using a beverage composition for treating tooth erosion |
| US9585827B2 (en) | 2000-01-21 | 2017-03-07 | The Procter & Gamble Company | Kits comprising a beverage composition and information for use |
| EP1341864A4 (en) * | 2000-08-18 | 2005-09-07 | Huber Corp J M | Method for making abrasive compositions and products thereof |
| JP2004033712A (en) * | 2002-06-14 | 2004-02-05 | Sang-Kee Han | Interdental toothbrush |
| JP2008529564A (en) * | 2005-01-26 | 2008-08-07 | オムヤ・デベロツプメント・アー・ゲー | Method for controlling microbial contamination, resulting inorganic suspension and use thereof |
| US8877127B2 (en) | 2005-01-26 | 2014-11-04 | Omya International Ag | Process for control of microbial contamination, mineral suspensions obtained and their uses |
| US8889068B2 (en) | 2005-01-26 | 2014-11-18 | Omya International Ag | Method for controlling microbial contamination, mineral suspensions obtained and uses thereof |
| JP2017517472A (en) * | 2014-05-30 | 2017-06-29 | コーニング インコーポレイテッド | Ball milling method of aluminum metaphosphate |
| CN113056438A (en) * | 2019-02-01 | 2021-06-29 | Omya国际股份公司 | Production of surface-reacted calcium salts by milling-induced transformation |
| CN113056438B (en) * | 2019-02-01 | 2024-01-26 | Omya国际股份公司 | Production of surface-reacted calcium salts by milling-induced transformation |
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| JP2981595B2 (en) | 1999-11-22 |
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