JP2000109897A - Fragrant detergent for flush toilet and its production - Google Patents

Fragrant detergent for flush toilet and its production

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Publication number
JP2000109897A
JP2000109897A JP10285374A JP28537498A JP2000109897A JP 2000109897 A JP2000109897 A JP 2000109897A JP 10285374 A JP10285374 A JP 10285374A JP 28537498 A JP28537498 A JP 28537498A JP 2000109897 A JP2000109897 A JP 2000109897A
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JP
Japan
Prior art keywords
layer
detergent
fragrance
layers
mold
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP10285374A
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Japanese (ja)
Other versions
JP4398523B2 (en
Inventor
Eiji Kunitomo
栄治 国友
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.)
Kobayashi Pharmaceutical Co Ltd
Original Assignee
Kobayashi Pharmaceutical Co Ltd
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Application filed by Kobayashi Pharmaceutical Co Ltd filed Critical Kobayashi Pharmaceutical Co Ltd
Priority to JP28537498A priority Critical patent/JP4398523B2/en
Publication of JP2000109897A publication Critical patent/JP2000109897A/en
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Publication of JP4398523B2 publication Critical patent/JP4398523B2/en
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Expired - Lifetime legal-status Critical Current

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Abstract

PROBLEM TO BE SOLVED: To provide a fragrant detergent for flush toilets which can solve such conventional problems that a color is easily attached during handling and that the amt. of a liq. ingredient compounded can not be increased and which enables the fragrance to be controlled and a reactive ingredient to be compounded, and to provide a method for producing the same. SOLUTION: This detergent is a solid detergent at least contg. a surfactant, a colorant, and a perfume and has at least two-layered structure wherein a central axis layer is present; the outside surface of each layer is covered with the next layer one after another; and at least one ingredient contained in two layers of at least one combination is different from each other. The detergent is obtd. by arranging hollow partial metal molds concentrically one after another and by extruding with a metal mold having such a structure that the outlet part of each partial metal mold of the outer side is made tapered at near the outlet of the adjacent inner-side partial metal mold.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、水洗トイレ用芳香
洗浄剤及びその製造方法、特に、中心軸層とその周囲を
順次覆う２以上の層からなる水洗トイレ用芳香洗浄剤及
びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fragrance detergent for flush toilets and a method for producing the same, and more particularly, to a fragrance detergent for flush toilets comprising a central shaft layer and two or more layers sequentially covering the periphery thereof and a method for producing the same. .

【０００２】[0002]

【従来の技術】従来の水洗トイレ用芳香洗浄剤は、主に
界面活性剤、香料、色素からなる組成物であって、単一
層の固形層で形成されているため、次のような不都合が
あった。例えば、これらの洗浄剤は、水洗タンク上の容
器に設置して使用されるが、通常これらの洗浄剤は包装
フィルムに包まれており、詰め替え時には包装フィルム
を破いて取りだし前記容器に設置することになる。しか
し、袋から出にくい柔らかい洗浄剤を取り出す場合や、
また袋から出した洗浄剤が倒れるとそれを起こす場合
に、洗浄剤に直接手が触れることがあり、その場合、手
に付着した洗浄剤の色素は、石鹸等で洗浄しても取れに
くいため、不快感が使用者に長期間残る問題があった。2. Description of the Related Art A conventional fragrance detergent for flush toilets is a composition mainly composed of a surfactant, a fragrance, and a pigment, and is formed of a single solid layer. there were. For example, these cleaning agents are used by being installed in a container on a washing tank.However, these cleaning agents are usually wrapped in a packaging film. become. However, when taking out a soft cleaning agent that is difficult to get out of the bag,
Also, if the cleaning agent that has been taken out of the bag falls down and causes it, the hand may directly touch the cleaning agent, in which case the dye of the cleaning agent attached to the hand is difficult to remove even if it is washed with soap etc. However, there is a problem that discomfort remains for the user for a long time.

【０００３】次に、液体成分の配合量を多くすると、保
形性が悪くかつ洗浄剤が柔らかくベトツク問題があり、
また香料を配合する場合は、固形層全体にほぼ均一に配
合されるため、使用初期の香りを多くしたり、使用後期
の香りを多くする対応が困難であった。さらに、色素を
有する洗浄剤の場合、キレ−ト剤や酵素といった微量成
分を配合しても、その配合状態を使用者に認識させ、商
品価値を高めることが困難であり、また便器の黄ばみを
除去するための漂白剤と色素等は化学反応するため、単
一の洗浄剤に配合することができなかった。[0003] When the amount of the liquid component is increased, the shape retention is poor, the detergent is soft, and there is a sticky problem.
In addition, when a fragrance is mixed, it is almost uniformly mixed in the entire solid layer, so that it is difficult to increase the scent in the early stage of use or to increase the scent in the late stage of use. Furthermore, in the case of a detergent containing a pigment, even if a minor component such as a chelating agent or an enzyme is blended, it is difficult for the user to recognize the blended state, and to increase the commercial value, and to reduce the yellowing of the toilet bowl. Since the bleaching agent and the pigment for removal chemically react with each other, they cannot be blended in a single detergent.

【０００４】[0004]

【発明が解決しようとする課題】そこで、本発明は、取
扱い時に色素の付着しやすい問題や液体成分の配合量を
多くできない問題を解決できると共に、前記香りのコン
トロ−ルが可能であって、しかも前記微量成分の配合に
よる商品価値の向上と相互に化学反応する複数の成分の
配合が可能な水洗トイレ用芳香洗浄剤及びその製造方法
を提供することを目的とする。SUMMARY OF THE INVENTION Accordingly, the present invention can solve the problem that the dye is easily attached during handling and the problem that the amount of the liquid component cannot be increased, and the control of the scent is possible. Moreover, it is an object of the present invention to provide a fragrance cleaner for flush toilets and a method for producing the fragrance detergent, which is capable of improving a commercial value by blending the trace components and blending a plurality of components which chemically react with each other.

【０００５】[0005]

【課題を解決するための手段】かかる目的を達成するた
め、鋭意研究した結果、中心軸を有する複数の層からな
る洗浄剤とし、任意の複数の層間で、層中の成分が異な
るようにすれば、前記問題を解決できる洗浄剤が得られ
ることを見出だし、また複数の中空の金型の組み合わせ
を工夫すれば、これらの洗浄剤を機械的に簡単に製造し
得ることを見出だし、本発明を完成させた。Means for Solving the Problems In order to achieve the above object, as a result of intensive studies, a cleaning agent comprising a plurality of layers having a central axis has been prepared. For example, they have found that a cleaning agent that can solve the above-mentioned problems can be obtained, and it has been found that if a combination of a plurality of hollow molds is devised, these cleaning agents can be easily manufactured mechanically. Completed the invention.

【０００６】すなわち、本発明のうち請求項１記載の発
明は、少なくとも、界面活性剤、色素、香料からなる固
形の水洗トイレ用芳香洗浄剤において、中心軸層を有
し、各層の軸回りの周囲を次の層が順次覆う、２以上の
層からなり、少なくとも一つの組合わせの二層間で、層
中の少なくとも一つの成分が異なることを特徴とする水
洗トイレ用芳香洗浄剤である。That is, the present invention according to claim 1 of the present invention relates to a solid fragrance detergent for flush toilets comprising at least a surfactant, a pigment, and a fragrance, which has a central shaft layer, and a layer around the axis of each layer. An aromatic detergent for flush toilets, comprising two or more layers whose surroundings are successively covered by a next layer, wherein at least one component in the layers is different between at least one combination of two layers.

【０００７】ここで、「少なくとも一つの組合わせの二
層間」の二層は、任意に選択でき、隣接する二層であっ
ても、二層が離れていてもよい。例えば中心軸層と最外
層であってもよい。また、「少なくとも一つの組合わせ
の二層」であるから、三つ以上の層で成分が異なってい
てもよいし、複数の組合わせの二層間で成分が異なって
いてもよい。一方、「一つの成分が異なる」とは、その
成分の種類が異なる場合のみならず、種類が同じであっ
ても、その成分の性質若しくは配合量が異なる場合も含
む。その成分の有無による相違は勿論含まれる。また、
「少なくとも一つ」であるから、複数の成分が異なって
いてもよいのは勿論である。なお、２以上の層（好まし
くは２以上であって数個〜数十個までの層）からなる洗
浄剤の断面形状は問わない。例えば、円形、楕円形、三
角形、四角形、多角形、星型、ハ−ト型等を含む。ま
た、洗浄剤の各層の断面形状は、これらの断面形状の二
以上の組合わせであってもよい。例えば、中心軸層が星
型でその外側層が円形、中心軸層が星型でその次の層が
三角でそのまた次の層が円形、中心軸層がハ−ト型でそ
の次の層が四角形等が例示される。Here, the two layers of "at least one combination of two layers" can be arbitrarily selected, and may be adjacent two layers or separated from each other. For example, the central axis layer and the outermost layer may be used. Further, since it is “two layers of at least one combination”, the components may be different between three or more layers, or the components may be different between two layers of a plurality of combinations. On the other hand, “one component is different” includes not only the case where the types of the components are different, but also the case where the types or the amounts of the components are different even if the types are the same. The difference depending on the presence or absence of the component is of course included. Also,
Since it is "at least one", it goes without saying that a plurality of components may be different. The cross-sectional shape of the cleaning agent composed of two or more layers (preferably, two or more layers and several to several tens of layers) does not matter. For example, a circle, an ellipse, a triangle, a quadrangle, a polygon, a star, a heart, and the like are included. Further, the cross-sectional shape of each layer of the cleaning agent may be a combination of two or more of these cross-sectional shapes. For example, the central axis layer is star-shaped and its outer layer is circular, the central axis layer is star-shaped, the next layer is triangular, the next layer is circular, and the central axis layer is heart-shaped and the next layer Is a quadrangle or the like.

【０００８】本発明に用いる界面活性剤は、いわゆる、
非イオン界面活性剤、アニオン界面活性剤、カチオン界
面活性剤、両性イオン界面活性剤、その他の界面活性剤
のいずれであってもよいが、非イオン界面活性剤、アニ
オン界面活性剤が好ましい。なお、これらの界面活性剤
は、単独で用いてもよいし、２種以上を混合して用いて
もよい。The surfactant used in the present invention is a so-called surfactant.
Nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and other surfactants may be used, but nonionic surfactants and anionic surfactants are preferred. These surfactants may be used alone or in combination of two or more.

【０００９】本発明に用いる色素は、水溶性の色素であ
れば特に限定されないが、具体的には、青色１号、青色
２号、青色３号、黄色３号、黄色４号、黄色２０２号、
赤色１０６号、赤色２号、赤色３号などが例示される。The dye used in the present invention is not particularly limited as long as it is a water-soluble dye, and specifically, blue No. 1, blue No. 2, blue No. 3, yellow No. 3, yellow No. 4, yellow No. 202 ,
Red No. 106, Red No. 2 and Red No. 3 are exemplified.

【００１０】本発明に用いる香料は、特に限定されない
が、具体的には、ロ−ズ油、グレ−プフル−ツ油、パイ
ン油などの天然香料又はリモネンなどの合成香料及びこ
れらの混合物が例示される。The fragrance used in the present invention is not particularly limited, but specific examples thereof include natural fragrances such as rose oil, grapefruit oil and pine oil, synthetic fragrances such as limonene, and mixtures thereof. Is done.

【００１１】本発明には、また、ビルダ−、溶解調節
剤、その他微量成分として、キレ−ト剤、酵素、消臭
剤、撥水剤等が配合されていてもよい。さらに、滑沢
剤、離型剤等の他の配合剤が配合されていてもよい。In the present invention, a chelating agent, an enzyme, a deodorant, a water repellent and the like may be blended as a builder, a dissolution regulator and other minor components. Further, other compounding agents such as a lubricant and a release agent may be compounded.

【００１２】本発明に用いるビルダ−としては、水溶性
の充填剤であればいずれも使用できるが、具体的には、
アルカリ金属の塩化物、炭酸塩、炭酸水素塩、硫酸塩、
リン酸塩、ホウ酸塩、ケイ酸塩等の水溶性無機充填剤、
及び炭素数が２〜１０のカルボン酸、炭素数が２〜１０
のヒドロキシカルボン酸、ポリカルボン酸やヒドロキシ
ポリカルボン酸等の有機酸並びにそれらの塩、炭素数が
２〜１０のアミノカルボン酸、アミノポリカルボン酸若
しくはポリアミノカルボン酸又はそれらの塩等水溶性有
機充填剤が例示できる。なお、これらのビルダ−は、単
独で用いてもよいし、２種以上を混合して用いてもよ
い。As the builder used in the present invention, any water-soluble filler can be used.
Alkali metal chlorides, carbonates, bicarbonates, sulfates,
Water-soluble inorganic fillers such as phosphates, borates and silicates,
And a carboxylic acid having 2 to 10 carbon atoms, 2 to 10 carbon atoms
Organic acids such as hydroxycarboxylic acids, polycarboxylic acids and hydroxypolycarboxylic acids and salts thereof, and water-soluble organic fillers such as aminocarboxylic acids having 2 to 10 carbon atoms, aminopolycarboxylic acids or polyaminocarboxylic acids or salts thereof. Agents can be exemplified. These builders may be used alone or as a mixture of two or more.

【００１３】本発明に用いる溶解調節剤としては、カル
ボキシメチルセルロ−ス塩、水溶性であって熱可塑性の
オリゴマ−やポリマ−、例えばゼラチン、寒天等を、例
示することができる。Examples of the dissolution regulator used in the present invention include carboxymethyl cellulose salts, water-soluble and thermoplastic oligomers and polymers such as gelatin and agar.

【００１４】このように構成すると、目的に応じ、各層
に配合する成分の種類、性質、量を変えることができる
ので、以下に示すように、前記課題が解決できる。例え
ば、(1) 二つ以上の同心軸層の最外層に色素を配さず、
それより内側の層に色素（例えば、青色）を配合すれ
ば、洗浄水の色（青色）は確保できて、しかもこの洗浄
剤に手が振れても、色素が付着しない効果が得られ、前
記使用者に与える長期の不快感の問題を解決できる。With this configuration, the types, properties and amounts of the components to be mixed in each layer can be changed according to the purpose, so that the above problems can be solved as described below. For example, (1) without disposing a dye on the outermost layer of two or more concentric layers,
If a pigment (for example, blue) is blended in the inner layer, the color of the washing water (blue) can be secured, and even if the hand is shaken with this cleaning agent, the effect that the pigment does not adhere is obtained. The problem of long-term discomfort given to the user can be solved.

【００１５】また、(2) 液体成分の配合量をより内側の
層で多くし、より外側の層に固形成分を多く配合するよ
うにすれば、液体成分は内層に閉じ込められるので、洗
浄剤の保形性とベトツキの問題が解決でき、(3) 香料を
配合する場合も、最外層により多くの香料を配合すれば
使用初期の香りを多くし、より内側の層により多くの香
料を配合すれば使用後期の香りを多くすることが可能で
ある。また、(4) 最外層に色素を配合せず、色の付いた
微量成分（キレ−ト剤や酵素等）を配合すれば、その配
合状態を使用者に認識させ、商品価値を高めることがで
き、(5) 二層の各層に化学反応成分を分離して配合し、
その成分による化学反応を防止できる。さらに、これら
(1) 〜(5) の配合の２以上の組み合わせも可能である。(2) If the amount of the liquid component is increased in the inner layer and the solid component is increased in the outer layer, the liquid component is confined in the inner layer. The problem of shape retention and stickiness can be solved. (3) When blending fragrances, blending more fragrances into the outermost layer will increase the fragrance at the beginning of use, and blend more fragrances into the inner layer. It is possible to increase the scent of late use. (4) If the outermost layer is compounded with a colored trace component (such as a chelating agent or an enzyme) without a dye, the user can recognize the state of the compound and increase the commercial value. (5) Separate and mix the chemical reaction components in each of the two layers,
A chemical reaction due to the component can be prevented. In addition, these
Combinations of two or more of the combinations of (1) to (5) are also possible.

【００１６】本発明のうち請求項２記載の発明は、請求
項１記載の発明のうち、少なくとも一つの組合わせの二
層間で、色素が異なることを特徴とする水洗トイレ用芳
香洗浄剤である。このように、構成すれば、各層に配合
する色が使用時の洗浄水中では混合色となり、商品には
色層分離による意匠的効果を付与しつつ、使用時には、
新鮮な混合色の洗浄水にすることができる。また、前記
したように、最外層に色素を配合せず、より内側層に色
素を配合すれば、洗浄剤に手が振れても、色素が付着し
ない効果が得られる。According to a second aspect of the present invention, there is provided the fragrance detergent for flush toilets according to the first aspect of the present invention, wherein the dye is different between at least one combination of the two layers. . With this configuration, the color blended in each layer becomes a mixed color in the wash water at the time of use, and the product has a design effect by color layer separation while being used.
It can be a fresh mixed color wash water. Further, as described above, if the dye is not blended in the outermost layer but is blended in the inner layer, an effect is obtained in which the pigment does not adhere even if the hand of the detergent is shaken.

【００１７】本発明のうち請求項３記載の発明は、請求
項１記載の発明のうち、少なくとも一つの組合わせの二
層間で、液体成分量及び／又は香料の量が異なることを
特徴とする水洗トイレ用芳香洗浄剤である。このよう
に、構成すれば、液体成分の配合量を通常より多くした
い場合でも、その成分をより内側の層に配合し、より外
側の層（例えば、最外層）に固形成分を多く配合するよ
うにすれば、従来の単一層の洗浄剤に生じた、柔らかく
ベトツク洗浄剤の問題が解決でる。香料については、例
えばより外側の層により多くの香料を配合すれば香りの
立上がりを早くし、より内側の層により多くの香料を配
合すれば香りの立上がりを遅くすることが可能である。
また、液体成分の配合量の異なる二層と香料の配合量の
異なる二層との組み合わも可能である。According to a third aspect of the present invention, in the first aspect of the present invention, the amount of the liquid component and / or the amount of the fragrance is different between at least one combination of the two layers. It is an aromatic detergent for flush toilets. With this configuration, even when it is desired to increase the amount of the liquid component, the component is added to the inner layer and the solid component is added to the outer layer (for example, the outermost layer). This solves the problem of the soft, sticky cleaning agent that occurs with conventional single-layer cleaning agents. As for the fragrance, for example, if more fragrance is blended in the outer layer, the rise of the fragrance can be made faster, and if more fragrance is blended in the inner layer, the rise of the fragrance can be made slow.
It is also possible to combine two layers with different amounts of the liquid component and two layers with different amounts of the fragrance.

【００１８】本発明のうち請求項４記載の発明は、請求
項１記載の発明のうち、少なくとも一つの組合わせの二
層間のより外側部分の層に、水洗トイレ用芳香洗浄剤の
微量成分を配合したことを特徴とする水洗トイレ用芳香
洗浄剤である。このように、構成すれば、その配合状態
を使用者に認識させ、商品価値を高めることが可能であ
る。例えば、最外層に色の着いた微量成分（キレ−ト
剤、酵素消臭剤、撥水剤等）を配合し、その層に色素を
配合せず、より内側の層に色素を配合した場合である。
この場合、使用時の洗浄水の色を、内側層の色素により
確保しつつ、洗浄剤の意匠的効果を高めることになる。According to a fourth aspect of the present invention, in the first aspect of the present invention, a trace component of a fragrance detergent for flush toilet is added to the outermost layer between at least one combination of the two layers. A fragrance cleaner for flush toilets characterized by being blended. With this configuration, it is possible to make the user aware of the blending state and increase the commercial value. For example, when the outermost layer is blended with a colored trace component (a chelating agent, an enzyme deodorant, a water repellent, etc.), and the pigment is not blended in that layer, but is blended in the inner layer. It is.
In this case, the design effect of the cleaning agent is enhanced while the color of the cleaning water at the time of use is ensured by the pigment in the inner layer.

【００１９】本発明のうち請求項５記載の発明は、請求
項１記載の発明のうち、少なくとも一つの組合わせの二
層の一方と他方に、互いに化学反応する成分を分離して
配合したことを特徴とする請求項１記載の水洗トイレ用
芳香洗浄剤である。以上のように構成すると、互いに化
学反応する成分が洗浄剤中に含まれていても、それらの
成分は二層に分離されているため化学反応しない。その
結果、この洗浄剤は、化学反応による構成成分の機能変
化が生ぜず長期間の保存が可能であり、しかも使用時に
それらの成分が流水に溶解しても、瞬時の一部混合であ
るため、それら成分間の反応はあまり起こらず、各成分
の機能は維持される。例えば、漂白剤と色素を二つの層
に分離して配合した洗浄剤の場合、便器の黄ばみ除去の
漂白剤の機能と洗浄水に色をつける色素の機能がその洗
浄剤の長期の保存状態においても、またその洗浄剤の使
用時においても維持される。化学反応成分として、その
他、酸と塩基の組合わせ等が例示される。According to a fifth aspect of the present invention, in the first aspect of the present invention, at least one of the two layers is combined with one of the two layers by separating components chemically reacting with each other. The fragrance cleaning agent for flush toilets according to claim 1, characterized in that: With the above configuration, even if components that chemically react with each other are included in the cleaning agent, those components do not chemically react because they are separated into two layers. As a result, this cleaning agent can be stored for a long period of time without causing a change in the function of the constituent components due to chemical reactions, and even if those components are dissolved in running water during use, they are instantaneously partially mixed. The reaction between these components does not occur much, and the function of each component is maintained. For example, in the case of a detergent containing a bleach and a pigment separated in two layers, the function of the bleach for removing the yellowing of the toilet bowl and the function of the pigment for coloring the wash water may occur in the long-term storage of the detergent. Is also maintained during use of the cleaning agent. Other examples of the chemical reaction component include a combination of an acid and a base.

【００２０】本発明のうち請求項６記載の発明は、中心
軸となる、中空の部分金型（以下、単に部分金型とい
う）に、外側の部分金型の内径が隣接する内側の部分金
型の外径より大きくなるようにして、部分金型を順次配
置し、かつ前記外側の部分金型のそれぞれの出口部分が
隣接する内側の部分金型の出口付近で先細になっている
構成の金型を用い、押出成形することを特徴とする請求
項１、２、３、４又は５記載の水洗トイレ用芳香洗浄剤
の製造方法である。The invention according to claim 6 of the present invention is directed to an inner metal mold in which the inner diameter of an outer metal mold is adjacent to a hollow metal mold (hereinafter simply referred to as a metal mold) serving as a central axis. The configuration is such that the partial dies are sequentially arranged so as to be larger than the outer diameter of the die, and the respective outlet portions of the outer partial dies are tapered near the outlet of the adjacent inner partial dies. The method for producing a fragrance cleaner for flush toilet according to claim 1, wherein the mold is extruded using a mold.

【００２１】以上のように構成すると、各部分金型に、
押出機から洗浄剤原料が圧入されると、その原料は金型
内を通過して金型出口に達っするが、その際、外側の部
分金型のそれぞれの出口部分が隣接する内側の部分金型
の出口付近で先細になっているため、出口までは金型壁
で隔てられていた各層の原料は、出口付近で外側の層の
ものが内側の層へと圧縮されて成形されることになる。
その結果、それぞれの層が同心軸状に一体的に積層さ
れ、各層間に隙間のない洗浄剤が連続して容易に形成さ
れる。With the above configuration, each of the partial molds has:
When the detergent raw material is injected from the extruder, the raw material passes through the inside of the mold and reaches the mold outlet. At this time, the respective outlet portions of the outer part molds are adjacent to the inner part. The material of each layer separated by the mold wall until the outlet is tapered near the outlet of the mold, so that the material of the outer layer near the outlet is compressed and formed into the inner layer become.
As a result, the respective layers are integrally laminated concentrically, and a cleaning agent having no gap between the respective layers is easily formed continuously.

【００２２】[0022]

【発明の実施の形態】以下、本発明の実施の形態を、図
面に基づいて説明するが、本発明はこの実施の形態に示
す、洗浄剤とその製造方法に限定されるものではない。
図１は、本発明の第１の実施の形態に係るの二つの層
（中心軸層と外側層）を形成する洗浄剤の斜視図であ
る。図２は本発明の第２の実施の形態に係る製造方法に
用いる押出機の要部を示す概略図であり、１は金型、２
は押出機本体である。１ａは中心軸となる部分金型であ
り、１ｂはその外側の部分金型である。金型１ｂの内径
は金型１ａの外径より大きく、金型１ａの出口部分で先
細となっている。また２ａは金型１ａに連結された押出
機本体であり、２ｂは金型１ｂに連結された押出機本体
である。図３は原料成分の混練機と計量供給機を示す概
略図であり、３は二軸混練機、４は粉体成分の定量供給
器、５は液体成分の定量ポンプである。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the cleaning agent and the method of manufacturing the same as shown in the embodiments.
FIG. 1 is a perspective view of a cleaning agent forming two layers (a central axis layer and an outer layer) according to the first embodiment of the present invention. FIG. 2 is a schematic diagram showing a main part of an extruder used in a manufacturing method according to a second embodiment of the present invention, wherein 1 is a mold, 2
Is an extruder body. 1a is a partial mold serving as a central axis, and 1b is an outer partial mold. The inner diameter of the mold 1b is larger than the outer diameter of the mold 1a, and is tapered at the exit of the mold 1a. 2a is an extruder main body connected to the mold 1a, and 2b is an extruder main body connected to the mold 1b. FIG. 3 is a schematic view showing a kneader and a metering machine for the raw material components, 3 is a twin-screw kneader, 4 is a metering device for powder components, and 5 is a pump for metering liquid components.

【００２３】第１の実施の形態に係る二つの層（中心軸
層と外側層）を形成する洗浄剤（以下、単に二層洗浄剤
という）は、図２の押出機を用い、第２の実施の形態に
係る次の方法にて製造する。すなわち、まず、原料の粉
体成分は定量供給器４で計量し、液体成分は定量ポンプ
５で計量して、二軸混練機３に送り、ここで十分攪拌混
練する。この場合、成分の種類、性質、量を変えると原
料組成の異なる種々の混練原料が得られる。次に、この
混練原料のうち、洗浄剤の中心軸層となる原料は二軸混
練機３から押出機本体２ａを経由して金型１ａに圧送さ
れ、外側層用の原料は二軸混練機３から押出機本体２ｂ
を経由して金型１ｂに圧送されるが、金型１ｂは金型１
ａの出口部分で先細となっているため、金型１ｂ内の原
料はそこで圧縮され、金型１ａから出た原料に押しつけ
られる。その結果、双方の原料により形成される二層
は、それまで双方を隔てていた金型１ａの金型壁に起因
する隙間が埋められることになり、二層間が密着した一
体成形体となる。この成形体は、所望の大きさに切断し
て使用する。The cleaning agent (hereinafter, simply referred to as a two-layer cleaning agent) for forming the two layers (the central axis layer and the outer layer) according to the first embodiment is formed by using the extruder shown in FIG. It is manufactured by the following method according to the embodiment. That is, first, the powder component of the raw material is measured by the metering device 4, and the liquid component is measured by the metering pump 5, sent to the twin-screw kneader 3, and sufficiently stirred and kneaded. In this case, various kinds of kneaded raw materials having different raw material compositions can be obtained by changing the types, properties and amounts of the components. Next, of the kneaded raw materials, the raw material to be the central axis layer of the detergent is sent from the twin-screw kneader 3 to the mold 1a via the extruder main body 2a, and the raw material for the outer layer is the biaxial kneader. 3 to the extruder body 2b
Is fed to the mold 1b through the mold 1, but the mold 1b is
Since the material is tapered at the outlet of a, the material in the mold 1b is compressed there and pressed against the material coming out of the mold 1a. As a result, the two layers formed by both the raw materials are filled with the gap caused by the mold wall of the mold 1a that has separated the two layers, and the two layers are formed into an integrated molded body in which the two layers are in close contact with each other. This molded body is used after being cut into a desired size.

【００２４】以上の如くして製造すれば、例えば、色素
を配合した原料と配合していない原料の組み合わせ、異
なる色素を配合した原料の組み合わせ、液体成分をより
多く配合した原料と液体成分の少ない原料の組み合わ
せ、又は微量成分を配合した原料と配合していない原料
の組み合わせによる、以下の実施例に示す二層洗浄剤を
得ることができる。When manufactured as described above, for example, a combination of a raw material containing a dye and a raw material not containing the dye, a combination of a raw material containing a different dye, a raw material containing a larger amount of a liquid component, and a mixture containing a smaller amount of a liquid component The two-layer detergent shown in the following examples can be obtained by a combination of raw materials or a combination of a raw material in which a trace component is blended and a raw material in which a trace component is not blended.

【００２５】[0025]

【実施例】以下、実施例を用いて本発明を更に具体的に
説明するが、本発明はこれらの実施例に限定されるもの
ではない。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

【００２６】（実施例１と比較例１）実施例１と比較例
１は、中心軸層（表１において中心層という、以下、他
の表において同じ）に色素を配合し、その外側層（表１
において外層という、以下、他の表において同じ）に色
素を配合しない二層洗浄剤に関するものである。実施例
１の試料は、界面活性剤として椰子油混合脂肪酸塩（第
一工業製薬株式会社製）とポリエチレングリコ−ル（第
一工業製薬株式会社製ＰＥＧ６０００Ｐ）、ビルダ−と
して中性無水芒硝（四国化成株式会社製）、溶解調節剤
としてカルボキシメチルセルロ−ス塩、色素として青色
１号（三国住友化学株式会社製）、香料として香料混合
物を用い、表１の如く配合して、前記第２の実施の形態
に示す方法にて製造したものである。比較例１の試料も
表１の配合に基づき、同様にして製造した。実施例１、
比較例１の各試料のいずれも、外側層縁径が３２ｍｍで
あり、中心軸層縁径が２２．６ｍｍ（体積比１：１）で
あって、長さ２２．０ｍｍのものが得られた。(Example 1 and Comparative Example 1) In Example 1 and Comparative Example 1, a dye was blended in a central axis layer (referred to as a central layer in Table 1, hereinafter the same in other tables), and an outer layer ( Table 1
In the following, the same applies to other tables). The sample of Example 1 was prepared by using a coconut oil mixed fatty acid salt (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and polyethylene glycol (PEG6000P manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as surfactants, and neutral anhydrous sodium sulfate (Shikoku) as a builder. Kasei Co., Ltd.), a carboxymethyl cellulose salt as a dissolution regulator, Blue No. 1 (manufactured by Mikuni Sumitomo Chemical Co., Ltd.) as a pigment, and a fragrance mixture as a fragrance. It was manufactured by the method described in the embodiment. The sample of Comparative Example 1 was manufactured in the same manner based on the formulation in Table 1. Example 1,
Each of the samples of Comparative Example 1 had an outer layer edge diameter of 32 mm, a central axis layer edge diameter of 22.6 mm (volume ratio 1: 1), and a length of 22.0 mm. .

【００２７】（実施例２、３、４）実施例２、３、４は
中心軸層と外側層に異なる色素を配合した二層洗浄剤に
関するものであり、各試料は、色素として黄色２０２号
（１）（三国住友化学株式会社製）、赤色１０６号（三
国住友化学株式会社製）を用い、表２に示す如く配合し
た以外は、前記実施例１の試料と同様にして製造した。
なお、各試料の寸法は、いずれも、実施例１の試料の寸
法と同じである。Examples 2, 3, and 4 Examples 2, 3, and 4 relate to a two-layer cleaning agent in which different dyes are blended in the central axis layer and the outer layer. (1) A sample was produced in the same manner as in the sample of Example 1 except that Red No. 106 (manufactured by Sumitomo Chemical Co., Ltd.) and Red No. 106 (manufactured by Sumitomo Chemical Co., Ltd.) were used and blended as shown in Table 2.
The size of each sample is the same as the size of the sample of Example 1.

【００２８】（実施例５と比較例２、３）実施例５と比
較例２、３は、液体成分の配合量を中心軸層に増やした
二層洗浄剤と、外側層に増やした二層洗浄剤に関するも
のであり、液体成分として椰子油脂肪酸ジエタノ−ルア
ミド（第一工業製薬株式会社製ダイヤノ−ルＣＤＥ）を
用い、表３の如く配合した以外は前記実施例１の場合と
同様にして製造した。なお、香料混合物も液体成分であ
る。また、各試料の寸法は、いずれも実施例１の試料の
寸法と同じである。(Example 5 and Comparative Examples 2 and 3) In Example 5 and Comparative Examples 2 and 3, a two-layer cleaning agent in which the mixing amount of the liquid component was increased in the central shaft layer and a two-layer cleaning agent in which the mixing amount of the liquid component was increased in the outer layer The present invention relates to a detergent and uses the same procedure as in Example 1 except that coconut oil fatty acid diethanolamide (Dianol CDE manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is used as a liquid component and blended as shown in Table 3. Manufactured. The fragrance mixture is also a liquid component. The dimensions of each sample are the same as the dimensions of the sample of Example 1.

【００２９】（実施例６）表１の実施例１の外側層の原
料組成に、微量成分として褐色の酵素（長瀬産業株式会
社製ビオプラ−ゼ）を該原料の１．０重量％の割合で配
合した以外は、実施例１と同様の組成、同様の方法にて
製造し、同様の寸法のものが得られた。(Example 6) In the raw material composition of the outer layer of Example 1 in Table 1, a brown enzyme (Bioprose manufactured by Nagase & Co., Ltd.) was added as a trace component at a ratio of 1.0% by weight of the raw material. Except for the compounding, the same composition and the same method as in Example 1 were used to produce the same size.

【００３０】（物性試験方法）表１の「洗浄剤による手
の汚れ」、「洗浄剤のベトツキ」は、洗浄剤を指で軽く
摘んだ時の、指への色素の着色の程度とベトツキ感で判
断した。(Method of Testing Physical Properties) "Hand stains with detergent" and "stickiness of detergent" in Table 1 indicate the degree of coloring of the pigment on the finger and the stickiness when the detergent is lightly picked with a finger. Judged by.

【００３１】表２の洗浄剤による洗浄水の色は、図４の
容器（上部及び下部に孔がある）に二層洗浄剤を入れ、
水洗トイレの貯水タンク上で使用した場合の便器に流れ
る洗浄水の色を目視観察で評価した。なお、図４の容器
を使用すると、上方からの流水は直接洗浄剤にかから
ず、容器の上部の孔から容器に入り内壁を伝って底部に
流れ、また底部の孔からも水は容器内に入るので、洗浄
剤は、水に漬かった底部の表面から溶け出すことにな
る。The color of the washing water with the detergent shown in Table 2 was obtained by placing the two-layer detergent in the container shown in FIG.
The color of the wash water flowing through the toilet when used on the water storage tank of the flush toilet was evaluated by visual observation. In addition, when the container of FIG. 4 is used, the flowing water from above does not directly hit the cleaning agent, but enters the container from the upper hole of the container, flows to the bottom along the inner wall, and the water also flows from the bottom hole into the container. As it enters, the cleaning agent will dissolve out of the bottom surface submerged in water.

【００３２】表３の「洗浄剤の保形性」は、１０名のモ
ニタ−者により、洗浄剤を指で軽く摘んだ時の変形度で
評価した。The "retainability of the detergent" in Table 3 was evaluated by the degree of deformation when the detergent was lightly picked with a finger by ten monitors.

【００３３】[0033]

【表１】 [Table 1]

【００３４】表１に示すように、外側層に色素を配合し
ていない実施例１は、明らかに手の汚れを生じないのに
対し、外側層に色素を配合している比較例１は手に汚れ
を生じる。また、実施例１は、比較例１よりビルダ−を
外側層に多く配合しているため、その表面が硬く、比較
例１がややベトツキ感を生じるのに対し、ベトツキ感を
生じない。As shown in Table 1, in Example 1 in which the outer layer was not mixed with a dye, the hands were clearly not stained, whereas in Comparative Example 1 in which the outer layer was mixed with a dye, hands were not mixed. Causes stains. In Example 1, since the builder was added to the outer layer more than in Comparative Example 1, the surface was hard, and Comparative Example 1 produced a slightly sticky feeling, but did not produce a sticky feeling.

【００３５】[0035]

【表２】 [Table 2]

【００３６】表２示すように、外側層に青色を中心軸層
に黄色の色素を配合した実施例２からは緑色の洗浄水
が、外側層に青色を中心軸層に赤色の色素を配合した実
施例３からは紫色の洗浄水が、外側層に赤色を中心軸層
に黄色の色素を配合した実施例４からはオレンジ色の洗
浄水が得られ、外側層と中心軸層の色素をそれぞれ置き
換えても同様の色の洗浄水が得られた。すなわち、各層
に異なる色素を配合すれば、使用時の洗浄水中ではそれ
らの混合色となるので、二層洗浄剤には色層分離による
意匠的効果を付与しつつ、使用時には、新鮮な混合色の
洗浄水にすることができる。As shown in Table 2, green washing water was used in Example 2 in which the outer layer was mixed with a yellow dye in the central axis layer, and blue was mixed in the outer layer with a red dye in the central axis layer. The washing water in purple was obtained from Example 3, and the washing water in orange was obtained from Example 4 in which the outer layer was mixed with a red dye and the yellow dye was mixed with the central axis layer. Even when the replacement was performed, washing water of the same color was obtained. In other words, if different pigments are blended in each layer, they will be mixed colors in the wash water at the time of use, so that the two-layer detergent will give a design effect by color layer separation, and at the time of use, a fresh mixed color Of washing water.

【００３７】[0037]

【表３】 表３に示すように、液体成分である椰子油脂肪酸ジエタ
ノ−ルアミドを中心軸層に多く配合した実施例５の保形
性はよいが、それを外側層に配合した比較例３は不良と
なり、それを中心軸層と外側層に半分ずつ配した比較例
２はやや不良となっている。このことは、従来液体成分
が配合できなかった組成の原料でも、それを中心軸層に
配合すれば、保形性が維持できた。また、ベトツキ感も
実施例５には認められなかったが、比較例２、３には認
められ、特に比較例３は著しかった。[Table 3] As shown in Table 3, although the coconut oil fatty acid diethanolamide as a liquid component was blended in a large amount in the central shaft layer, the shape retaining property of Example 5 was good, but Comparative Example 3 in which it was blended in the outer layer was poor, Comparative Example 2 in which it was disposed half each in the central axis layer and the outer layer was slightly defective. This means that, even if a raw material having a composition in which a liquid component could not be blended conventionally, if it was blended in the central shaft layer, shape retention could be maintained. No stickiness was observed in Example 5, but was observed in Comparative Examples 2 and 3, and Comparative Example 3 was particularly remarkable.

【００３８】さらに、表１の外側層の原料組成（色素を
配合していない）に微量成分として褐色の酵素を配合し
た実施例６の試料は、褐色の酵素が斑点状に二層洗浄剤
の外側層の表面に表れ、その意匠的効果が認められた。Further, in the sample of Example 6 in which a brown enzyme was blended as a minor component in the raw material composition of the outer layer shown in Table 1 (no dye was blended), the brown enzyme was spotted in a two-layer cleaning agent. It appeared on the surface of the outer layer, and its design effect was recognized.

【００３９】[0039]

【発明の効果】以上説明したように、本発明の洗浄剤に
よれば、目的に応じ、各層に配合する成分の種類、性
質、量を変えることができるので、従来解決できなかっ
た前記課題を解決できる。例えば、 (1)二つ以上の層の
同心軸層の最外層に色素を配さず、それより内側の層に
色素（例えば、青色）を配合すれば、洗浄水の色（青
色）は確保できて、しかもこの洗浄剤に手が振れても、
色素が付着しない効果が得られ、前記使用者に与える長
期の不快感の問題を解決できる。As described above, according to the cleaning agent of the present invention, the types, properties and amounts of the components to be mixed in each layer can be changed according to the purpose. Solvable. For example, (1) If the dye is not arranged on the outermost layer of the concentric axis layer of two or more layers and the dye (for example, blue) is blended in the inner layer, the color of the washing water (blue) is secured. Even if you can do it and shake this hand,
The effect that the pigment does not adhere is obtained, and the problem of long-term discomfort given to the user can be solved.

【００４０】また、(2) 液体成分の配合量をより内側の
層で多くし、より外側の層に固形成分を多く配合するよ
うにすれば、液体成分は内層に閉じ込められるので、洗
浄剤の保形性が確保されると共に洗浄剤が柔らかくベト
ツク問題も解決でき、また(3) 最外層により多くの香料
を配合すれば使用初期の香りを多くし、より内側の層に
より多くの香料を配合すれば使用後期の香りを多くする
こと（又はその逆）が可能である。さらに、(4) 最外層
に色素を配合せず、色の付いた微量成分（キレ−ト剤や
酵素等）を配合すればその配合状態を使用者に認識させ
ることができ、商品価値を高めることや、(5) 二層の各
層に化学反応成分を分離して配合し、化学反応を防止し
て、その成分の機能を維持することができる。さらに、
これら(1) 〜(5) の配合の２以上の組み合わせも可能で
ある。(2) If the amount of the liquid component is increased in the inner layer and the solid component is increased in the outer layer, the liquid component is confined in the inner layer. As the shape retention is ensured, the detergent is soft and the tackiness problem can be solved. (3) If more fragrance is added to the outermost layer, the fragrance at the beginning of use is increased, and more fragrance is added to the inner layer. If so, it is possible to increase the scent in the later stage of use (or vice versa). In addition, (4) If a trace component (a chelating agent, an enzyme, etc.) is added without coloring in the outermost layer, the user can recognize the state of the compound and enhance the commercial value. (5) The chemical reaction components can be separated and blended in each of the two layers to prevent the chemical reaction and maintain the function of the components. further,
Combinations of two or more of these combinations of (1) to (5) are also possible.

【００４１】また、本発明の洗浄剤の製造方法によれ
ば、中心軸となる部分金型及びその回りに順次配置した
部分金型に、押出機から洗浄剤原料が圧入されると、そ
の原料は金型内を通過して金型出口に達っするが、その
際、外側の部分金型のそれぞれの出口部分が隣接する内
側の部分金型の出口付近で先細になっているため、出口
までは金型壁で隔てられていた各層の原料は、それぞれ
の出口付近で外側の層のものが内側の層へと圧縮されて
成形されることになる。その結果、それぞれの層が同心
軸状に一体的に積層され、各層間に隙間のない洗浄剤が
連続して容易に形成される。Further, according to the method for producing a detergent of the present invention, when a detergent material is press-fitted from an extruder into a partial mold serving as a central axis and partial molds arranged sequentially around the central mold, the material is removed. Passes through the mold to the mold outlet, where the respective outlets of the outer part molds are tapered near the outlet of the adjacent inner part mold, so the outlet Until now, the raw material of each layer separated by the mold wall is formed by compressing the material of the outer layer into the inner layer near each outlet. As a result, the respective layers are integrally laminated concentrically, and a cleaning agent having no gap between the respective layers is easily formed continuously.

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

【図１】 本発明の第１の実施の形態に係る二層の同心
軸層（中心軸層と外層）を形成する洗浄剤の斜視図であ
る。FIG. 1 is a perspective view of a cleaning agent forming two concentric axial layers (a central axial layer and an outer layer) according to a first embodiment of the present invention.

【図２】 本発明の第２の実施の形態に係る製造方法に
用いる押出機の要部を示す概略図である。FIG. 2 is a schematic view illustrating a main part of an extruder used in a manufacturing method according to a second embodiment of the present invention.

【図３】 原料成分の混練機と計量供給機を示す概略図
である。FIG. 3 is a schematic diagram showing a kneading machine and a metering machine for raw material components.

【図４】 二層洗浄剤の使用状態を示す図である。FIG. 4 is a diagram illustrating a use state of a two-layer cleaning agent.

【符号の説明】[Explanation of symbols]

１・・・ 金型、１ａ・・・ 中心軸となる部分金型、１ｂ・・・
その外側の部分金型、２・・・ 押出機本体、２ａ・・・ 金型
１ａに連結された押出機本体、２ｂ・・・ 金型１ｂに連結
された押出機本体、３・・・ 混練機、４・・・ 粉体成分の定
量供給器、５・・・ 液体成分の定量ポンプ。DESCRIPTION OF SYMBOLS 1 ... Die, 1a ... Partial mold used as a central axis, 1b ...
Extruder body, 2 ... Extruder body, 2a ... Extruder body connected to mold 1a, 2b ... Extruder body connected to mold 1b, 3 ... Kneading Machine, 4 ... Powder component metering device, 5 ... Liquid component metering pump.

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】少なくとも、界面活性剤、色素、香料から
なる固形の水洗トイレ用芳香洗浄剤において、中心軸層
を有し、各層の軸回りの周囲を次の層が順次覆う、２以
上の層からなり、少なくとも一つの組合わせの二層間
で、層中の少なくとも一つの成分が異なることを特徴と
する水洗トイレ用芳香洗浄剤。Claims: 1. A solid flush toilet detergent comprising at least a surfactant, a pigment, and a fragrance, comprising a central axis layer, wherein the next layer sequentially covers the circumference of each layer around the axis. A fragrance cleaning agent for flush toilets, comprising at least one layer, wherein at least one component in the layer is different between at least one combination of the two layers. 【請求項２】少なくとも一つの組合わせの二層間で、色
素が異なることを特徴とする請求項１記載の水洗トイレ
用芳香洗浄剤。2. The fragrance detergent for flush toilets according to claim 1, wherein the pigment is different between at least one combination of the two layers. 【請求項３】少なくとも一つの組合わせの二層間で、液
体成分量及び／又は香料の量が異なることを特徴とする
請求項１記載の水洗トイレ用芳香洗浄剤。3. The fragrance detergent according to claim 1, wherein the amount of the liquid component and / or the amount of the fragrance is different between at least one combination of the two layers. 【請求項４】少なくとも一つの組合わせの二層間の外側
部分の層に、水洗トイレ用芳香洗浄剤の微量成分を配合
したことを特徴とする請求項１記載の水洗トイレ用芳香
洗浄剤。4. The fragrance detergent for flush toilet according to claim 1, wherein a minor component of the fragrance detergent for flush toilet is blended in the outer layer between at least one combination of two layers. 【請求項５】少なくとも一つの組合わせの二層の一方と
他方に、互いに化学反応する成分を分離して配合したこ
とを特徴とする請求項１記載の水洗トイレ用芳香洗浄
剤。5. The fragrance detergent for flush toilets according to claim 1, wherein components chemically reacting with each other are separated and blended into one and the other of at least one combination of two layers. 【請求項６】中心軸となる、中空の部分金型（以下、単
に部分金型という）に、外側の部分金型の内径が隣接す
る内側の部分金型の外径より大きくなるようにして、部
分金型を順次配置し、かつ前記外側の部分金型のそれぞ
れの出口部分が隣接する内側の部分金型の出口付近で先
細になっている構成の金型を用い、押出成形することを
特徴とする請求項１、２、３、４又は５記載の水洗トイ
レ用芳香洗浄剤の製造方法。6. A hollow partial mold (hereinafter, simply referred to as a partial mold) serving as a central axis so that an inner diameter of an outer partial mold is larger than an outer diameter of an adjacent inner mold. Extruding using a mold having a configuration in which the partial molds are sequentially arranged, and each outlet portion of the outer partial mold is tapered in the vicinity of the outlet of the adjacent inner partial mold. The method for producing an aromatic detergent for flush toilets according to claim 1, 2, 3, 4, or 5.
JP28537498A 1998-10-07 1998-10-07 Fragrance cleaning agent for flush toilet and manufacturing method thereof Expired - Lifetime JP4398523B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP28537498A JP4398523B2 (en) 1998-10-07 1998-10-07 Fragrance cleaning agent for flush toilet and manufacturing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP28537498A JP4398523B2 (en) 1998-10-07 1998-10-07 Fragrance cleaning agent for flush toilet and manufacturing method thereof

Related Child Applications (2)

Application Number Title Priority Date Filing Date
JP2009197519A Division JP5192465B2 (en) 2009-08-28 2009-08-28 Fragrance cleaning agent for flush toilet and manufacturing method thereof
JP2009197520A Division JP5192466B2 (en) 2009-08-28 2009-08-28 Fragrance cleaning agent for flush toilet and manufacturing method thereof

Publications (2)

Publication Number Publication Date
JP2000109897A true JP2000109897A (en) 2000-04-18
JP4398523B2 JP4398523B2 (en) 2010-01-13

Family

ID=17690731

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Application Number Title Priority Date Filing Date
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Country Link
JP (1) JP4398523B2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002088313A (en) * 2000-07-14 2002-03-27 Earth Chem Corp Ltd Solid coating agent for toilet and water-repelling coating method
JP2003052802A (en) * 2001-08-10 2003-02-25 Earth Chem Corp Ltd Liquid agent for on-tank type toilet aromatic and washing device
JP2006169270A (en) * 2004-12-10 2006-06-29 S T Chem Co Ltd Multilayer solid detergent and method for producing multilayer solid detergent

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002088313A (en) * 2000-07-14 2002-03-27 Earth Chem Corp Ltd Solid coating agent for toilet and water-repelling coating method
JP2003052802A (en) * 2001-08-10 2003-02-25 Earth Chem Corp Ltd Liquid agent for on-tank type toilet aromatic and washing device
JP2006169270A (en) * 2004-12-10 2006-06-29 S T Chem Co Ltd Multilayer solid detergent and method for producing multilayer solid detergent

Also Published As

Publication number Publication date
JP4398523B2 (en) 2010-01-13

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