JPH0769868A - Water-soluble solid-containing composition - Google Patents

Water-soluble solid-containing composition

Info

Publication number
JPH0769868A
JPH0769868A JP21295193A JP21295193A JPH0769868A JP H0769868 A JPH0769868 A JP H0769868A JP 21295193 A JP21295193 A JP 21295193A JP 21295193 A JP21295193 A JP 21295193A JP H0769868 A JPH0769868 A JP H0769868A
Authority
JP
Japan
Prior art keywords
water
lactic acid
soluble solid
acid oligomer
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.)
Pending
Application number
JP21295193A
Other languages
Japanese (ja)
Inventor
Konosuke Kishida
孝之助 岸田
Fumiko Sakano
史子 坂野
Yoshiaki Yamaguchi
義昭 山口
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.)
Musashino Chemical Laboratory Ltd
Original Assignee
Musashino Chemical Laboratory Ltd
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 Musashino Chemical Laboratory Ltd filed Critical Musashino Chemical Laboratory Ltd
Priority to JP21295193A priority Critical patent/JPH0769868A/en
Publication of JPH0769868A publication Critical patent/JPH0769868A/en
Pending legal-status Critical Current

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  • Medicinal Preparation (AREA)
  • Cosmetics (AREA)

Abstract

PURPOSE:To obtain a composition containing a coated water-soluble solid capable of delaying dissolution of the water-soluble solid and successively developing effects caused by dissolution of the solid in water. CONSTITUTION:This composition contains a substance prepared by coating a water-soluble solid with a lactic acid polycondensate having 200-1,500 number- average molecular weight. The composition is widely usable for a bathing agent or a germicide for swimming pools.

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、溶解を遅延させるべく
被覆した水溶性の固体を含有し、水中において持続的な
作用を有する組成物に関する。
FIELD OF THE INVENTION The present invention relates to a composition containing a water-soluble solid coated to delay dissolution and having a sustained action in water.

【0002】[0002]

【従来の技術】水溶性の固体を含有する組成物やその成
形物を水中に投入、あるいは水分含有物と混合すると、
多くの場合、水溶性の固体は速やかに溶解する。したが
って、水溶性の固体が溶解することによる効果を徐々
に、あるいは持続的に発現させたい場合には、繰り返し
投入あるいは混合する必要があった。
2. Description of the Related Art When a composition containing a water-soluble solid or a molded product thereof is put into water or mixed with a water-containing material,
In many cases, water-soluble solids dissolve quickly. Therefore, in order to gradually or continuously develop the effect of the dissolution of the water-soluble solid, it was necessary to repeatedly add or mix.

【0003】例えば、炭酸ガスの発生を伴う浴用剤で
は、ガスの発生が少なくとも数十分間程度は持続するこ
とが望ましいが、従来市販されているものはおよそ数分
間でガスの発生が終わってしまう。また、プール用殺菌
剤では、有効成分が消費されるのに伴って徐々に溶解す
ることが望ましいが、従来市販されているものは、投入
直後には、濃度が高すぎて目などを刺激することが多
く、その弊害を避けるためには少量を繰り返し投入する
必要がある。したがって、このような場合には、成分の
一部あるいは全部が徐々に溶解することが望ましいもの
である。
For example, in the case of a bath agent accompanied by the generation of carbon dioxide gas, it is desirable that the gas generation lasts for at least several tens of minutes, but in the conventional commercial products, the gas generation ends in about several minutes. I will end up. Further, in the pool bactericidal agent, it is desirable that the active ingredient gradually dissolves as the active ingredient is consumed, but the conventional commercially available ones have a too high concentration immediately after the introduction and irritate the eyes and the like. In many cases, it is necessary to repeatedly add a small amount in order to avoid the adverse effect. Therefore, in such a case, it is desirable that some or all of the components be gradually dissolved.

【0004】また、水への溶解を遅延させる目的で、水
溶性固体を油脂類で被覆することが行われることもある
が、油脂類は水に溶けずに残るので困る場合も多い。
[0004] In addition, the water-soluble solid may be coated with fats and oils for the purpose of delaying the dissolution in water, but the fats and oils do not dissolve in water and remain, which is often a problem.

【0005】さらに、医薬の分野では、有効成分を徐々
に体内に放出させるために乳酸の重縮合物(ポリ乳酸)
などに含有させたりする方法が開発されているが、これ
らに用いられるポリ乳酸は分子量が少なくとも数千以
上、通常は数万以上のものであり、高価なものである。
Further, in the field of medicine, a polycondensate of lactic acid (polylactic acid) is used to gradually release the active ingredient into the body.
For example, polylactic acid used for these has a molecular weight of at least several thousands, usually tens of thousands or more, and is expensive.

【0006】[0006]

【発明が解決しようとする課題】したがって、本発明の
目的は、水溶性の固体の溶解を遅延することができ、か
つ水中において水溶性の固体の溶解による効果を持続的
に発現することのできる安価な水溶性固体を含有する組
成物を提供することにある。
Therefore, the object of the present invention is to delay the dissolution of a water-soluble solid and to continuously exhibit the effect of the dissolution of the water-soluble solid in water. An object is to provide a composition containing an inexpensive water-soluble solid.

【0007】[0007]

【課題を解決するための手段】本発明者らは、水溶性の
固体の溶解速度を制御する方法を種々検討した結果、水
溶性固体を数平均分子量200〜1500の乳酸重縮合
物の比較的少量で被覆することにより目的が達せられる
ことを見出し、本発明を完成させた。
As a result of various studies on the method for controlling the dissolution rate of water-soluble solids, the present inventors have found that water-soluble solids can be converted into lactic acid polycondensates having a number average molecular weight of 200 to 1500 relatively. It was found that the purpose can be achieved by coating with a small amount, and the present invention has been completed.

【0008】すなわち、本発明は数平均分子量200〜
1500の乳酸重縮合物で水溶性固体を被覆したものを
含有することを特徴とする組成物により達成される。
That is, the present invention has a number average molecular weight of 200 to
Achieved by a composition characterized by containing a water-soluble solid coated with 1500 lactic acid polycondensates.

【0009】[0009]

【作用】以下、本発明につき、より詳細に説明する。The present invention will be described in more detail below.

【0010】まず、本発明において、乳酸乳酸重縮合物
(以下、乳酸オリゴマーともいう)で水溶性固体を被覆
するとは、すなわち、水溶性の固体と加熱溶融した乳酸
オリゴマーとを混合したり、水溶性固体に乳酸オリゴマ
ーの溶液を含浸させた後、溶媒を蒸発させて除去するこ
と、あるいは水溶性の固体を成形したものに乳酸オリゴ
マーの溶融物を含浸させたり、乳酸オリゴマーの溶液を
含浸させた後、溶媒を蒸発させたりすることを意味す
る。
First, in the present invention, coating a water-soluble solid with a lactic acid-lactic acid polycondensate (hereinafter, also referred to as a lactic acid oligomer) means that a water-soluble solid and a lactic acid oligomer melted by heating are mixed or water-soluble solid is mixed. A solid solid by impregnating it with a solution of lactic acid oligomer and then removing the solvent by evaporation, or by molding a water-soluble solid with a melt of lactic acid oligomer, or by impregnating a solution of lactic acid oligomer. After that, it means to evaporate the solvent.

【0011】上記乳酸オリゴマー溶液の溶媒としては、
アセトン、トルエン、ベンゼン、酢酸エチルなどが挙げ
られる。
As the solvent for the lactic acid oligomer solution,
Acetone, toluene, benzene, ethyl acetate and the like can be mentioned.

【0012】また、本発明で用いる数平均分子量200
〜1500の乳酸オリゴマーは、常温では粘稠な液体な
いしは軟らかい固体状であるが、40〜100℃の比較
的低温で流動性の良い溶融物となるので、上記溶媒を用
いなくても加熱溶融により容易に混合できる場合が多
い。
The number average molecular weight used in the present invention is 200.
The lactic acid oligomers of up to 1500 are a viscous liquid or a soft solid at room temperature, but become a melt having good fluidity at a relatively low temperature of 40 to 100 ° C., so that they can be melted by heating without using the above solvent. Often can be mixed easily.

【0013】上記混合に用いられる混合撹拌機として
は、特に限定されるものでなく、例えば、リボンミキサ
ー、ナウターミキサーなど、従来より用いられている混
合機をそのまま利用することができるものである。な
お、固体の成形物を被覆する場合は、乳酸オリゴマーの
溶融物あるいは溶液中に当該成形物を浸漬した後、引き
上げるだけでもよい。
The mixing stirrer used for the above mixing is not particularly limited, and for example, a conventionally used mixer such as a ribbon mixer or a Nauta mixer can be used as it is. . In the case of coating a solid molded product, the molded product may be immersed in a melt or solution of a lactic acid oligomer and then pulled up.

【0014】上記被覆操作により、水溶性固体の表面の
一部あるいは全部が乳酸オリゴマーの薄膜で被覆され
る。したがって、乳酸オリゴマーで被覆された水溶性の
固体は、水中に投入してもすぐには水に溶解しない。す
なわち、乳酸オリゴマーが溶解し除去されるか、あるい
は水が乳酸オリゴマーの被覆層を透過して水溶性固体と
接するかして初めて溶解する。
By the above coating operation, a part or all of the surface of the water-soluble solid is coated with the thin film of lactic acid oligomer. Therefore, the water-soluble solid coated with the lactic acid oligomer is not immediately dissolved in water even when it is put into water. That is, the lactic acid oligomer is dissolved and removed, or is dissolved only when water permeates the coating layer of the lactic acid oligomer and comes into contact with the water-soluble solid.

【0015】次に、本発明を適用することのできる水溶
性固体としては、浴用剤やプール用殺菌剤など水中に投
入、あるいは水分含有物と混合した際に、直ちに溶解す
るよりもむしろ徐々に溶解することが望まれる用途に用
いられるものであればよく、具体的には、炭酸ナトリウ
ム、重炭酸ナトリウムセスキ炭酸ナトリウム、炭酸カリ
ウム、炭酸アンモニウムなどの塩基性物質、コハク酸、
フマル酸、リンゴ酸、酒石酸、クエン酸、マレイン酸、
マロン酸などの酸性物質、硫酸ナトリウム、塩化マグネ
シウムなどの中性物質などの固体が挙げられるが、水溶
性の固体であれば、これらに限られるわけではない。ま
た2種類以上の水溶性固体が併用される場合も多い。
Next, as a water-soluble solid to which the present invention can be applied, when it is put into water such as a bath agent or a bactericide for a pool or when it is mixed with a water-containing substance, it is gradually dissolved rather than immediately dissolved. Any substance may be used as long as it is desired to be dissolved. Specifically, basic substances such as sodium carbonate, sodium bicarbonate sodium sesquicarbonate, potassium carbonate and ammonium carbonate, succinic acid,
Fumaric acid, malic acid, tartaric acid, citric acid, maleic acid,
Examples thereof include solid substances such as acidic substances such as malonic acid and neutral substances such as sodium sulfate and magnesium chloride, but are not limited thereto as long as they are water-soluble solids. In addition, two or more kinds of water-soluble solids are often used in combination.

【0016】また、上記水溶性固体の大きさは、特に限
定されるものでなく、上述の乳酸オリゴマーの被覆方法
等により異なるものであるが、通常市販されている程度
の粉体あるいは粒体、またはこれらを錠剤、ケーキ状に
成形したものであればよい。
The size of the water-soluble solid is not particularly limited and may vary depending on the coating method of the lactic acid oligomer described above and the like. Alternatively, these may be formed into tablets or cakes.

【0017】さらに本発明では、乳酸オリゴマーの分子
量と使用量によって水溶性固体の溶解速度を調節するこ
とが可能であり、この場合、乳酸オリゴマーの分子量は
高い方が、また使用量は多い方が水溶性固体の溶解を遅
延する効果が大きい。したがって、本発明で用いられる
乳酸オリゴマーの数平均分子量は、通常200〜150
0、好ましくは300〜1100である。該数平均分子
量が200未満では乳酸オリゴマーが速やかに溶解する
ので遅延効果が得られず、また1500を越える場合に
は、乳酸オリゴマーの溶解が遅く、一部が長時間経って
も溶けずに残ってしまうので好ましくない。
Further, in the present invention, it is possible to control the dissolution rate of the water-soluble solid depending on the molecular weight and the amount of the lactic acid oligomer used. In this case, the higher the molecular weight of the lactic acid oligomer and the higher the amount of the lactic acid oligomer used. The effect of delaying the dissolution of the water-soluble solid is great. Therefore, the number average molecular weight of the lactic acid oligomer used in the present invention is usually 200 to 150.
It is 0, preferably 300 to 1100. When the number average molecular weight is less than 200, the lactic acid oligomer is rapidly dissolved, so that the retarding effect cannot be obtained. When it exceeds 1500, the lactic acid oligomer is slowly dissolved and a part of the lactic acid oligomer remains undissolved even after a long time. It is not preferable because it will end up.

【0018】また乳酸オリゴマーの使用量は、多くの場
合、水溶性固体に対して、通常0.5〜30重量%、好
ましくは1〜20重量%である。該使用量が0.5重量
%未満の場合には、乳酸オリゴマーによる被覆が十分で
なく、水溶性固体が速やかに溶解するので遅延効果が得
られず、また30重量%を越える場合には、乳酸オリゴ
マーにより被覆層が厚く、水溶性固体の溶解が遅く、一
部が長時間経っても溶けずに残ってしまうので好ましく
ない。しかし、乳酸オリゴマーは被覆剤として働くだけ
でなく、それ自身が徐々に溶解して酸成分として働くの
で、組成物の用途によってはさらに多く配合することも
ある。
The amount of the lactic acid oligomer used is usually 0.5 to 30% by weight, preferably 1 to 20% by weight, based on the water-soluble solid. When the amount used is less than 0.5% by weight, the coating with the lactic acid oligomer is not sufficient, and the water-soluble solid dissolves quickly so that the retarding effect cannot be obtained. When it exceeds 30% by weight, The coating layer is thick due to the lactic acid oligomer, the dissolution of the water-soluble solid is slow, and a part thereof remains undissolved even after a long time, which is not preferable. However, the lactic acid oligomer not only acts as a coating agent, but also gradually dissolves itself and acts as an acid component, and therefore more lactic acid oligomer may be added depending on the use of the composition.

【0019】さらに乳酸オリゴマーの分子量や使用量を
変えて被覆した水溶性固体を混合すれば、溶解速度の範
囲をさらに拡げることができ、さらに長時間にわたって
徐々に作用する組成物を得ることができる。
Further, by mixing the water-soluble solid coated by changing the molecular weight and the amount of the lactic acid oligomer used, the range of the dissolution rate can be further expanded, and a composition which acts gradually over a long period of time can be obtained. .

【0020】また、水溶性固体の一部だけを乳酸オリゴ
マーで被覆し、残りは被覆しないで組成物を配合するこ
ともできる。こうすることによって、例えば、浴用剤の
場合、投入直後には被覆されていない水溶性固体の部分
が速やかに溶解して炭酸ガス(水溶性固体の一成分)が
勢いよく発生し、その後被覆された部分の水溶性固体が
徐々に溶解して炭酸ガスが少しずつ持続的に発生するよ
うにすることができる。また、水溶性固体を2種類以上
配合する場合には、その一部の種類だけを被覆すれば本
発明の目的とする持続的な効果が得られることもある。
It is also possible to formulate the composition by coating only part of the water-soluble solid with the lactic acid oligomer and leaving the rest uncoated. By doing so, for example, in the case of a bath agent, the portion of the water-soluble solid that has not been coated immediately dissolves immediately after being charged, and carbon dioxide gas (one component of the water-soluble solid) is vigorously generated, and then it is coated. It is possible to gradually dissolve the water-soluble solid in the other part and continuously generate carbon dioxide gas little by little. In addition, when two or more kinds of water-soluble solids are blended, it may be possible to obtain the lasting effect aimed at by the present invention by coating only a part of the kinds.

【0021】本発明の組成物には、前記水溶性固体の他
に、必要に応じて添加物を加えてもよい。また、本発明
の組成物は、目的や用途に応じて顆粒、錠剤またはケー
キ状に成形してもよい。この場合、乳酸オリゴマーは、
結合剤としても働くので、別に結合剤を必要としない場
合もある。
In addition to the above water-soluble solid, additives may be added to the composition of the present invention, if necessary. In addition, the composition of the present invention may be formed into granules, tablets or cakes depending on the purpose and application. In this case, the lactic acid oligomer is
In some cases, a separate binder is not required as it also acts as a binder.

【0022】なお、本発明で用いる数平均分子量200
〜1500の乳酸オリゴマーは、乳酸の脱水縮合によっ
て容易に得られることから、医薬の分野などで利用され
ている分子量が少なくとも数千以上、通常は数万以上の
乳酸重縮合物(ポリ乳酸)などに比して安価である。ま
た、加熱により流動性のよい液体となるので、取扱いも
容易である。したがって、この乳酸オリゴマー液を用い
て水溶性固体を被覆する操作もごく容易に行える。
The number average molecular weight of 200 used in the present invention.
Since the lactic acid oligomers of up to 1500 are easily obtained by dehydration condensation of lactic acid, lactic acid polycondensates (polylactic acid) having a molecular weight of at least several thousands, usually tens of thousands, used in the field of medicine, etc. It is cheaper than. Further, since it becomes a liquid having good fluidity by heating, it is easy to handle. Therefore, the operation of coating the water-soluble solid with this lactic acid oligomer solution can be performed very easily.

【0023】[0023]

【実施例】以下に本発明の実施例を示すが、本発明の実
施の態様はこれらの実施例に限定されるものではない。
EXAMPLES Examples of the present invention will be shown below, but the embodiments of the present invention are not limited to these examples.

【0024】実施例1 数平均分子量1000の乳酸オリゴマーを70℃にて加
熱して溶融状態にした後、水溶性固体として酸性物質の
粉末を加えて約15分間よく混ぜて、乳酸オリゴマーで
水溶性固体(酸性物質粉末)を被覆してなる本発明の組
成物(粉末)を得た。比較例として、乳酸オリゴマーを
配合しない組成物についても同様に作製した。
Example 1 A lactic acid oligomer having a number average molecular weight of 1,000 was heated at 70 ° C. to be in a molten state, powder of an acidic substance was added as a water-soluble solid and mixed well for about 15 minutes to obtain a water-soluble lactic acid oligomer. A composition (powder) of the present invention obtained by coating a solid (acidic substance powder) was obtained. As a comparative example, a composition containing no lactic acid oligomer was similarly prepared.

【0025】続いて、炭酸水素ナトリウムを溶かした4
0℃の温水1000ml中に上記組成物を投入し、経過
時間毎の酸性物質の溶解率を測定した。用いた炭酸水素
ナトリウム、乳酸オリゴマーの量および酸性物質の種類
と量を表1に示す。また経過時間毎の溶解率の測定結果
を表2に示す。
Subsequently, 4 in which sodium hydrogen carbonate was dissolved
The above composition was put into 1000 ml of warm water at 0 ° C., and the dissolution rate of the acidic substance was measured at each elapsed time. Table 1 shows the amounts of sodium hydrogen carbonate and lactic acid oligomer used and the types and amounts of acidic substances used. Table 2 shows the measurement results of the dissolution rate for each elapsed time.

【0026】[0026]

【表1】 [Table 1]

【0027】[0027]

【表2】 [Table 2]

【0028】上記表1および表2の結果より、水溶性固
体(酸性物質粉末)として用いた各有機酸の溶解が乳酸
オリゴマーの配合により遅延し、さらに本実施例の配合
範囲内でその使用量の増加(水溶性固体に対して約12
重量%から約25重量%に増加)に応じて該有機酸の溶
解がより遅くなることも確認された。
From the results shown in Tables 1 and 2 above, the dissolution of each organic acid used as a water-soluble solid (acidic substance powder) was delayed by the blending of the lactic acid oligomer, and the amount used within the blending range of this example. Increase (about 12 for water-soluble solids)
It was also confirmed that the dissolution of the organic acid was slower in response to the increase from wt% to about 25 wt%).

【0029】実施例2 数平均分子量1000の乳酸オリゴマーは70〜110
℃に加熱し、また数平均分子量390の乳酸オリゴマー
が40〜70℃に加熱して溶融状態にし、これらに各成
分が表3に示す配分量となるように調整して水溶性固体
としてコハク酸、フマル酸および炭酸水素ナトリウム粉
末の混合物50gを加えて約30分間良く混ぜて、乳酸
オリゴマーで水溶性固体を被覆してなる本発明の組成物
(粉末)を得た。さらに該組成物を打錠して錠剤の入浴
剤とした。比較例として、乳酸オリゴマーを配合しない
入浴剤についても同様に作製した。
Example 2 A lactic acid oligomer having a number average molecular weight of 1,000 is 70 to 110.
The lactic acid oligomer having a number average molecular weight of 390 is heated to 40 to 70 ° C. to be in a molten state, and each component is adjusted to have a distribution amount shown in Table 3 to obtain succinic acid as a water-soluble solid. , 50 g of a mixture of fumaric acid and sodium hydrogencarbonate powder and well mixed for about 30 minutes to obtain a composition (powder) of the present invention in which a water-soluble solid is coated with a lactic acid oligomer. Further, the composition was compressed into a bath salt for tablets. As a comparative example, a bathing agent containing no lactic acid oligomer was similarly prepared.

【0030】上記入浴剤を温水5000ml中に投入し
て発泡が持続する時間を測定した。得られた結果を表3
に示す。
The above bathing agent was poured into 5000 ml of warm water and the time for which foaming lasted was measured. Table 3 shows the obtained results.
Shown in.

【0031】[0031]

【表3】 [Table 3]

【0032】表3の結果より、わずかな量の乳酸オリゴ
マーの配合によっても、発泡時間が大幅に延び、本実施
例の配合範囲内で該乳酸オリゴマーの使用量に比例して
発泡時間がより延びることも確認された。
From the results shown in Table 3, even when a small amount of the lactic acid oligomer was blended, the foaming time was significantly extended, and within the blending range of this example, the foaming time was further extended in proportion to the amount of the lactic acid oligomer used. It was also confirmed.

【0033】[0033]

【発明の効果】本発明により、水中に投入または水分含
有物と混合した際に、水溶性固体を含有する組成物の溶
解を遅延することができ、水中において該組成物中の有
効成分による効果(浴用剤での炭酸ガスによる血行促進
効果やプール用殺菌剤での殺菌効果)を持続的に発現す
ることができる水溶性固体を被覆したものを含有する組
成物を比較的安価に提供できるため、浴用剤やプール用
殺菌剤などに幅広く利用することができるものである。
INDUSTRIAL APPLICABILITY According to the present invention, the dissolution of a composition containing a water-soluble solid can be delayed when it is put into water or mixed with a water-containing substance, and the effect of the active ingredient in the composition in water is exerted. Since it is possible to provide a composition containing a material coated with a water-soluble solid capable of continuously exhibiting (the blood circulation promoting effect of carbon dioxide in a bath agent and the bactericidal effect of a pool bactericide) at a relatively low cost It can be widely used for bath agents and pool germicides.

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 数平均分子量200〜1500の乳酸重
縮合物で水溶性固体を被覆したものを含有することを特
徴とする組成物。
1. A composition comprising a water-soluble solid coated with a lactic acid polycondensate having a number average molecular weight of 200 to 1500.
JP21295193A 1993-08-27 1993-08-27 Water-soluble solid-containing composition Pending JPH0769868A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP21295193A JPH0769868A (en) 1993-08-27 1993-08-27 Water-soluble solid-containing composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP21295193A JPH0769868A (en) 1993-08-27 1993-08-27 Water-soluble solid-containing composition

Publications (1)

Publication Number Publication Date
JPH0769868A true JPH0769868A (en) 1995-03-14

Family

ID=16631001

Family Applications (1)

Application Number Title Priority Date Filing Date
JP21295193A Pending JPH0769868A (en) 1993-08-27 1993-08-27 Water-soluble solid-containing composition

Country Status (1)

Country Link
JP (1) JPH0769868A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007262083A (en) * 2007-06-11 2007-10-11 Medion Research Laboratories Inc Carbon dioxide percutaneous/transmucosal absorption composition
US20120023653A1 (en) * 2009-02-26 2012-02-02 Purac Biochem Bv Delayed-release shaped bodies for use in toilets
JP2013166779A (en) * 2013-04-26 2013-08-29 Medion Research Laboratories Inc Composition for carbon dioxide percutaneous-transmucosal absorption

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007262083A (en) * 2007-06-11 2007-10-11 Medion Research Laboratories Inc Carbon dioxide percutaneous/transmucosal absorption composition
US20120023653A1 (en) * 2009-02-26 2012-02-02 Purac Biochem Bv Delayed-release shaped bodies for use in toilets
JP2013166779A (en) * 2013-04-26 2013-08-29 Medion Research Laboratories Inc Composition for carbon dioxide percutaneous-transmucosal absorption

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