JP2014234446A - Transparent elastic body and method for stabilizing the same - Google Patents
Transparent elastic body and method for stabilizing the same Download PDFInfo
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- JP2014234446A JP2014234446A JP2013116342A JP2013116342A JP2014234446A JP 2014234446 A JP2014234446 A JP 2014234446A JP 2013116342 A JP2013116342 A JP 2013116342A JP 2013116342 A JP2013116342 A JP 2013116342A JP 2014234446 A JP2014234446 A JP 2014234446A
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- Prior art keywords
- elastic body
- transparent elastic
- liquid
- edetate
- oil
- Prior art date
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Abstract
Description
本発明は、透明弾性体及びその粒状体の安定化方法に関し、詳しくは、薬剤を含有した、膨潤した吸液性ポリマーからなる透明弾性体において、経時的に発生する褐変及び離水が共に防止された、安定した透明弾性体、および前記透明弾性体の安定化方法に関する。 The present invention relates to a transparent elastic body and a method for stabilizing the granular body, and more specifically, in a transparent elastic body comprising a swollen liquid-absorbing polymer containing a drug, both browning and water separation occurring with time are prevented. The present invention also relates to a stable transparent elastic body and a method for stabilizing the transparent elastic body.
従来、吸液性ポリマーは、紙おむつや生理用ナプキン、ネコ砂等において、体液や排泄物を吸収することを目的として使用されている。また別の用途として、薬剤担体として使用することが検討されている。例えば、匍匐害虫の防除器において、殺虫剤の担体として吸液性ポリマーを使用すること(例えば、特許文献1参照。)や、害虫防除剤が保持された、膨潤させた吸液性ポリマーからなる粒状体をアリ用ベイト剤として用いること(例えば、特許文献2参照。)等が知られている。 Conventionally, liquid-absorbing polymers are used for the purpose of absorbing body fluids and excrement in paper diapers, sanitary napkins, cat sands, and the like. As another application, use as a drug carrier has been studied. For example, in a pest control device, a liquid-absorbing polymer is used as an insecticide carrier (see, for example, Patent Document 1), or a swollen liquid-absorbing polymer in which a pest-control agent is held is used. It is known to use a granular material as a bait agent for ants (for example, see Patent Document 2).
ところが上記のように、吸液性ポリマーに薬剤を含有させて用いた場合、経時的に褐変が生じたり、離水が発生することがある。
離水の発生を抑制する方法については、ゲル製剤において種々検討がなされており、例えば、消臭薬剤と共に離水防止剤としてデンプンを用いたゲル型消臭剤(例えば、特許文献3参照。)や、ネイティブジェランガムを含有させた、カラギーナンやジェランガム等のゲル化剤を用いたゲル組成物の離水抑制方法(例えば、特許文献4参照。)等が知られている。
However, as described above, when a liquid-absorbing polymer is used by containing a drug, browning may occur over time or water separation may occur.
Various methods for suppressing the generation of water separation have been studied in gel preparations. For example, a gel-type deodorant using starch as a water separation inhibitor together with a deodorant (for example, see Patent Document 3), A method for suppressing water separation of a gel composition using a gelling agent such as carrageenan or gellan gum containing native gellan gum is known (for example, see Patent Document 4).
一方、褐変を防止する方法としては、例えば、ウレタン化合物を用いた透明な芳香ゲル組成物において、紫外線吸収剤や還元剤を用いることが有用であること(例えば、特許文献5参照。)等が知られている。 On the other hand, as a method for preventing browning, for example, in a transparent aromatic gel composition using a urethane compound, it is useful to use an ultraviolet absorber or a reducing agent (see, for example, Patent Document 5). Are known.
しかしながら上記の従来技術は、特定のゲル組成物における離水又は褐変を防止しようとするものであって、膨潤した吸液性ポリマーからなる透明弾性体において、経時的に発生する褐変及び離水を共に防止するといった課題については何ら示されていない。また、この課題を解決しうる有効な手段は知られていないのが現状である。
そこで本発明は、薬剤を含有した、膨潤した吸液性ポリマーからなる透明弾性体において、経時的に発生する褐変及び離水を共に防止した、安定した透明弾性体を提供すると共に、その透明弾性体の安定化方法を提供するものである。
However, the above prior art is intended to prevent water separation or browning in a specific gel composition, and prevents both browning and water separation that occur over time in a transparent elastic body composed of a swollen liquid-absorbing polymer. There is no indication of issues such as doing. Moreover, the present condition is that the effective means which can solve this subject is not known.
Therefore, the present invention provides a stable transparent elastic body that prevents both browning and water separation that occur with time in a transparent elastic body that contains a drug and contains a swollen liquid-absorbing polymer. The stabilization method is provided.
本発明者らは、前記課題を解決するために鋭意検討した結果、薬剤を含有した、膨潤した吸液性ポリマーからなる透明弾性体に、エデト酸及びエデト酸塩の少なくともいずれか一方を含有させることで、該透明弾性体において、経時的に発生する褐変及び離水を共に有効に防止することができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the inventors of the present invention include at least one of edetic acid and edetate in a transparent elastic body comprising a swollen liquid-absorbing polymer containing a drug. Thus, the present inventors have found that the transparent elastic body can effectively prevent both browning and water separation occurring with time, and have completed the present invention.
すなわち本発明は以下の(1)又は(2)によって達成されるものである。
(1)原料から吸液させることによって膨潤した吸液性ポリマーからなる透明弾性体であって、前記透明弾性体が、薬剤とエデト酸及びエデト酸塩の少なくともいずれか一方とを含有することを特徴とする透明弾性体。
(2)薬剤を含有した、膨潤した吸液性ポリマーからなる透明弾性体の安定化方法であって、前記透明弾性体にエデト酸及びエデト酸塩の少なくともいずれか一方を含有させることを特徴とする、透明弾性体の安定化方法。
That is, the present invention is achieved by the following (1) or (2).
(1) A transparent elastic body comprising a liquid-absorbing polymer swollen by absorbing liquid from a raw material, wherein the transparent elastic body contains a drug and at least one of edetic acid and edetate. Characteristic transparent elastic body.
(2) A method for stabilizing a transparent elastic body comprising a swollen liquid-absorbing polymer containing a drug, characterized in that the transparent elastic body contains at least one of edetic acid and edetate. A method for stabilizing a transparent elastic body.
本発明によって、薬剤を含有した、膨潤した吸液性ポリマーからなる透明弾性体において、経時的に発生する褐変及び離水を共に有効に防止して安定化することができる。そのため所期の薬剤を用いて、長期間にわたり安定して使用可能な、芳香剤、消臭剤、虫よけ剤等の各種製品を提供することができる。 According to the present invention, in a transparent elastic body comprising a swollen liquid-absorbing polymer containing a drug, both browning and water separation that occur with time can be effectively prevented and stabilized. Therefore, it is possible to provide various products such as fragrances, deodorants, and insect repellents that can be used stably over a long period of time using the intended drugs.
本発明は、芳香剤、消臭剤、虫よけ剤等の各種製品として用いることができる、離水及び褐変が共に防止された、安定した透明弾性体およびその安定化方法に関するものである。すなわち、原料から吸液させることによって膨潤した吸液性ポリマーからなる透明弾性体であって、前記透明弾性体が、薬剤とエデト酸及びエデト酸塩の少なくともいずれか一方とを含有することを特徴とする透明弾性体を提供するものである。
また本発明は、薬剤を含有した、膨潤した吸液性ポリマーからなる透明弾性体の安定化方法であって、前記透明弾性体にエデト酸及びエデト酸塩の少なくともいずれか一方を含有させることを特徴とする、該透明弾性体の安定化方法を提供するものである。
前記透明弾性体は、エデト酸及びエデト酸塩の少なくともいずれか一方を含有することにより、褐変及び離水を共に有効に防止することができるようになる。
The present invention relates to a stable transparent elastic body that can be used as various products such as fragrances, deodorants, insect repellents, and the like, both prevented from water separation and browning, and a method for stabilizing the same. That is, a transparent elastic body comprising a liquid-absorbing polymer swollen by absorbing liquid from a raw material, wherein the transparent elastic body contains a drug and at least one of edetic acid and edetate. A transparent elastic body is provided.
Further, the present invention is a method for stabilizing a transparent elastic body comprising a swollen liquid-absorbing polymer containing a drug, wherein the transparent elastic body contains at least one of edetic acid and edetate. The present invention provides a method for stabilizing the transparent elastic body.
The transparent elastic body can effectively prevent both browning and water separation by containing at least one of edetic acid and edetate.
本発明において、膨潤した吸液性ポリマーからなる透明弾性体とは、原料の吸液性ポリマーが溶液(薬液)を吸って膨潤し、そのままの状態で流動性がなく、弾性的な透明のかたまりとなっている状態のものをいう。また透明とは、光を透過し、前記弾性体を通して向こう側が見えればよく、褐変が生じたことが分かる程度の透明性を有していれば、色素等によって着色されていたり、弾性体の一部が不透明になっていてもよい。
本発明の透明弾性体は、原料から吸液させることによって膨潤した吸液性ポリマーの1つ1つからなることから、分子量が小さく水に溶けるポリマーを用いて、液体を増粘、固化させて形成された塊状からなるものと比べ、単位容積あたりの表面積が大きくなり、その内部構造にも違いがあると推測される。そのため、経時的に、離水の発生や、紫外線による影響を受けた褐変の発生が起こりやすくなるものと考えられ、これらは膨潤した吸液性ポリマーの1つ1つからなる、本発明に特有な課題であると言うことができる。
In the present invention, the transparent elastic body composed of the swollen liquid-absorbing polymer means that the raw liquid-absorbing polymer swells by sucking the solution (chemical solution) and has no fluidity and remains an elastic transparent mass. The thing of the state which becomes. Transparent means that light can be transmitted and the other side can be seen through the elastic body. If it is transparent enough to show that browning has occurred, it is colored by a pigment or the like, The part may be opaque.
Since the transparent elastic body of the present invention consists of each of the liquid-absorbing polymers swollen by absorbing liquid from the raw material, the liquid is thickened and solidified using a polymer having a small molecular weight and soluble in water. It is estimated that the surface area per unit volume is larger than that of the formed lump, and the internal structure is also different. For this reason, it is considered that the occurrence of water separation and the occurrence of browning affected by ultraviolet rays are likely to occur over time, which are unique to the present invention, each consisting of a swollen liquid-absorbing polymer. It can be said that it is a problem.
このような透明弾性体とするには、原料として、水に不溶であり、かつ水に対して膨潤するような高吸水性樹脂を用いることで調製される。具体的にはアクリル酸系ポリマーを用いることができ、その重量平均分子量が1000万以上の高分子のものが好適である。
これよりも分子量が低くなると、分子量の低下につれて水に溶けやすくなっていき、水に溶けて増粘性を付与するように作用して、弾性体としての形態を保つことができなくなる。
前記のアクリル酸系ポリマーとしては、例えば、澱粉−アクリル酸ソーダグラフト重合体の架橋物、ポリアクリル酸ソーダの架橋物、ポリビニルアルコールアクリル酸ソーダグラフト重合体の架橋物、長鎖アルキルアクリレート架橋重合体、等が挙げられ、好ましくは、アクリルアミド−アクリル酸架橋重合体、ポリアクリル酸架橋重合体(例えばポリアクリル酸ナトリウム共重合体;2−Propenoic acid,polymer with sodium 2−propenoate(1:1))を挙げることができる。
In order to obtain such a transparent elastic body, it is prepared by using, as a raw material, a highly water-absorbent resin that is insoluble in water and swells in water. Specifically, an acrylic acid polymer can be used, and a polymer having a weight average molecular weight of 10 million or more is preferable.
If the molecular weight is lower than this, it becomes easier to dissolve in water as the molecular weight decreases, so that it becomes soluble in water and imparts thickening, so that the form as an elastic body cannot be maintained.
Examples of the acrylic acid polymer include, for example, a starch-sodium acrylate graft polymer cross-linked product, a polyacrylic acid soda cross-linked product, a polyvinyl alcohol sodium acrylate graft polymer cross-linked product, and a long-chain alkyl acrylate cross-linked polymer. Preferably, acrylamide-acrylic acid cross-linked polymer, polyacrylic acid cross-linked polymer (for example, sodium polyacrylate copolymer; 2-propenic acid, polymer with sodium 2-propenoate (1: 1)) Can be mentioned.
この他にも、吸液性を有する公知のポリマーを用いることができ、例えば、澱粉−アクリロニトリルグラフト重合体の加水分解物、イソブチレン−マレイン酸共重合体の架橋物及びその塩、ポリ酢酸ビニル−エチレン系不飽和カルボン酸共重合体の鹸化物の架橋物の塩、ポリソルボルネン、アルキルスチレン−ジビニルベンゼン共重合体、メタクレート系架橋重合体、等が挙げられる。 In addition, a known polymer having a liquid absorbing property can be used, for example, a hydrolyzate of starch-acrylonitrile graft polymer, a cross-linked product of isobutylene-maleic acid copolymer and a salt thereof, polyvinyl acetate, Examples thereof include a salt of a saponified product of an ethylenically unsaturated carboxylic acid copolymer, polysorbene, an alkylstyrene-divinylbenzene copolymer, and a methacrylate cross-linked polymer.
本発明の透明弾性体は、エデト酸及びエデト酸塩の少なくともいずれか一方を含有することによって、褐変及び離水を共に防ぐことができ、安定化することができる。
エデト酸塩としては、エデト酸二ナトリウム(エチレンジアミン四酢酸二ナトリウム・二水和物)やエデト酸四ナトリウム(エチレンジアミン四酢酸四ナトリウム・四水和物)、エデト酸三ナトリウム(エチレンジアミン四酢酸三ナトリウム・三水和物)、エデト酸二カリウム(エチレンジアミン四酢酸二カリウム・二水和物)、エデト酸三カリウム(エチレンジアミン四酢酸三カリウム・二水和物)、エデト酸マグネシウム二ナトリウム(エチレンジアミン四酢酸マグネシウム(II)二ナトリウム・四水和物)、エデト酸カルシウム二ナトリウム(エチレンジアミン四酢酸カルシウム(II)二ナトリウム・二水和物)、エデト酸鉄ナトリウム(エチレンジアミン四酢酸鉄(III)ナトリウム・三水和物)、エデト酸亜鉛二ナトリウム(エチレンジアミン四酢酸亜鉛(II)二ナトリウム・四水和物)、エデト酸コバルト二ナトリウム(エチレンジアミン四酢酸コバルト(II)二ナトリウム・四水和物)、エデト酸銅二ナトリウム(エチレンジアミン四酢酸銅(II)二ナトリウム・四水和物)、エデト酸マンガン二ナトリウム(エチレンジアミン四酢酸マンガン(II)二ナトリウム・三水和物)、エデト酸二リチウム(エチレンジアミン四酢酸二リチウム・水和物)、エデト酸二アンモニウム(エチレンジアミン四酢酸二アンモニウム)等が挙げられる。なお、本明細書において、「エデト酸及びエデト酸塩の少なくともいずれか一方」のことを、単に「エデト酸等」と表記することがある。
By containing at least one of edetic acid and edetate, the transparent elastic body of the present invention can prevent both browning and water separation and can be stabilized.
Edetate includes disodium edetate (disodium ethylenediaminetetraacetate, dihydrate), tetrasodium edetate (tetrasodium ethylenediaminetetraacetate, tetrahydrate), trisodium edetate (trisodium ethylenediaminetetraacetate)・ Trihydrate), dipotassium edetate (dipotassium ethylenediaminetetraacetate, dihydrate), tripotassium edetate (tripotassium ethylenediaminetetraacetate, dihydrate), magnesium disodium edetate (ethylenediaminetetraacetate) Magnesium (II) disodium tetrahydrate), edetate calcium disodium (ethylenediaminetetraacetate calcium (II) disodium dihydrate), edetate sodium iron (ethylenediaminetetraacetate iron (III) sodium Hydrate), disodium zinc edetate Ethylenediaminetetraacetic acid zinc (II) disodium tetrahydrate), cobalt edetate disodium (ethylenediaminetetraacetic acid cobalt (II) disodium tetrahydrate), edetate copper disodium (ethylenediaminetetraacetate copper (II ) Disodium tetrahydrate), disodium manganese edetate (ethylenediaminetetraacetate manganese (II) disodium trihydrate), dilithium edetate (dilithium ethylenediaminetetraacetate hydrate), edetic acid And diammonium (ethyleneammonium tetraacetate diammonium). In the present specification, “at least one of edetic acid and edetate” may be simply referred to as “edetic acid and the like”.
本発明の透明弾性体にエデト酸等を含有させるには、例えば、エデト酸等を含有した溶液を調製して、原料である吸液性ポリマーに吸収、膨潤させることができる。
前記溶液を調製するに際しては、例えば、アルコール類、多価アルコール類、ケトン類、エステル類、エーテル類などの有機溶媒、水、これらの混合溶媒等を用いることができる。
溶液全体に対するエデト酸等の含有量は特に制限されないが、0.01〜1質量%が好ましい。
溶液は、吸液性ポリマーの吸液能に対して最大まで吸液させることが好ましいが、その吸液能はポリマーによって異なることから、必ずしも最大まで吸液させる必要はなく、膨潤さえしていればよい。
In order to contain edetic acid or the like in the transparent elastic body of the present invention, for example, a solution containing edetic acid or the like can be prepared and absorbed and swollen in the liquid absorbent polymer as a raw material.
In preparing the solution, for example, alcohols, polyhydric alcohols, ketones, esters, ethers and other organic solvents, water, a mixed solvent thereof and the like can be used.
Although content in particular of edetic acid with respect to the whole solution is not restrict | limited, 0.01-1 mass% is preferable.
It is preferable to absorb the solution up to the maximum with respect to the liquid absorption capacity of the liquid-absorbing polymer. However, since the liquid absorption capacity varies depending on the polymer, it is not always necessary to absorb the liquid to the maximum, and it may even swell. That's fine.
さらに前記溶液に所期の薬剤を含有させて薬液とし、同時に原料である吸液性ポリマーに吸収、膨潤させて含有させてもよい。
また、薬液のみを原料である吸液性ポリマーに吸収、膨潤させて、膨潤した吸液性ポリマーからなる透明弾性体の表面に、エデト酸等を含む溶液を塗布したり、スプレー(噴霧)により付着させたりして含有させてもよい。
Furthermore, the desired chemical | medical agent may be contained in the said solution to make a chemical | medical solution, and you may make it absorb and swell and contain in the liquid-absorbing polymer which is a raw material simultaneously.
Moreover, a solution containing edetic acid or the like is applied to the surface of a transparent elastic body made of a swollen liquid-absorbing polymer by absorbing and swelling only the chemical liquid into the liquid-absorbing polymer as a raw material, or by spraying You may make it adhere and contain.
本発明の透明弾性体におけるエデト酸等の含有量は、吸液性ポリマーの吸液性を損なわず、また褐変及び離水を共に防ぐ効果を発揮できれば特に制限されない。
例えば、通常の室内において用いる場合、透明弾性体に対するエデト酸等の含有量は0.2質量%以上とするのがよい。また多量に含有させると吸液性ポリマーの吸液力の低下を引き起こすことがあるので、25質量%以下とするのが好ましく、2〜20質量%とするのがより好ましい。
The content of edetic acid and the like in the transparent elastic body of the present invention is not particularly limited as long as it does not impair the liquid absorbability of the liquid absorbent polymer and can exhibit the effect of preventing both browning and water separation.
For example, when used in a normal room, the content of edetic acid or the like with respect to the transparent elastic body is preferably 0.2% by mass or more. Moreover, since it may cause the fall of the liquid absorption power of a liquid absorbing polymer when it contains abundantly, it is preferable to set it as 25 mass% or less, and it is more preferable to set it as 2-20 mass%.
膨潤した透明弾性体のサイズとしては、例えば、植物抽出物等の揮散性薬剤を用いる場合、薬剤が周辺雰囲気中に十分に拡散するための表面積を確保する必要がある。そのため、透明弾性体は、球状である場合には、直径2〜20mm程度が好ましい。また同等の表面積が得られるのであれば、その他の立体形状としてもよい。 As the size of the swollen transparent elastic body, for example, when a volatile drug such as a plant extract is used, it is necessary to secure a surface area for the drug to sufficiently diffuse into the surrounding atmosphere. Therefore, when the transparent elastic body is spherical, the diameter is preferably about 2 to 20 mm. Further, as long as an equivalent surface area can be obtained, other three-dimensional shapes may be used.
本発明の透明弾性体は、原料の形状が略反映されることから、原料となるポリマーの製造時に所期の形状に整えることで、例えば、球状、楕円状、棒状、多角状、金平糖状、中空状、等の各種形状とし、膨潤させて、視覚的な価値を付与することができる。 Since the shape of the raw material is substantially reflected in the transparent elastic body of the present invention, for example, spherical, elliptical, rod-shaped, polygonal, confetti, Various shapes such as a hollow shape can be formed and swollen to give visual value.
本発明に用いられる薬剤としては、例えば、消臭剤、芳香剤、虫よけ剤、害虫防除剤、等の各種用途で用いられる植物抽出物、精油、香料、化学物質等が挙げられ、単独で用いても複数を組み合わせて用いてもよい。 Examples of the drug used in the present invention include plant extracts, essential oils, fragrances, chemical substances, etc. used in various applications such as deodorants, fragrances, insect repellents, pest control agents, etc. Or may be used in combination.
例えば、モウソウチク、グレープフルーツ、茶、ユッカ、オリーブ、ブドウ、ムルレイヤ、カンゾウ、シソ、からし、ショウガ、エゴノキ、カワラヨモギ、ホオノキ、レンギョウ、モミガラ、ペッパー、ダイズ、ピメンタ、アロエ、エイジツ、オウゴン、オウバク、オトギリソウ、オレンジ、海藻、カモミラ、キイチゴ、キウイ、キューカンバ、クチナシ、クララ、クワ、ゴボウ、ササ、ザボンソウ、サンザシ、サンショウ、ジオウ、シコン、シナノキ、シャクヤク、ショウブ、シラカバ、スイガズラ、アルニカ、ヨクイニン、スギナ、セイヨウキズタ、セイヨウノコギリソウ、セージ、センキュウ、センブリ、タイソウ、チョウジ、チンピ、トウキ、トウキセンカ、トウヒ、ドクダミ、ニンジン、ノバラ、ハマメリス、ヒキオコシ、ビワ、ブクリョウ、ヘチマ、ベニバナ、ボダイジュ、ホップ、マツ、マツカサ、マロニエ、ムクロジ、モモ、ヤグルマギク、アルニカ、オトギソウ、ユリ、ヨモギ、リンゴ、レモン、ローズ、ワレモコウ等の植物抽出物、そのエキス又は乾留物; For example, Mosouchiku, Grapefruit, Tea, Yucca, Olive, Grape, Mullayer, Licorice, Perilla, Mustard, Ginger, Egony, Kawaragigi, Honoki, Forsythia, Momiji, Pepper, Soybean, Pimenta, Aloe, Ages, Ogon, Ogiri, Otogiri , Orange, seaweed, chamomile, raspberry, kiwi, cucumber, gardenia, clara, mulberry, burdock, sasa, pomegranate, hawthorn, salamander, dianthus, shikon, linden, peonies, shobu, birch, honeysuckle, arnica, yakuinin, horsetail, Kizota, Achillea millefolium, Sage, Senkyu, Assembly, Taiso, Clove, Chimpi, Toki, Tokisenka, Spruce, Dokudami, Carrot, Novara, Hamamelis, Tobikoshi, Biwa, Kuryou, loofah, safflower, lime, hops, pine, pine cone, horse chestnut, Sapindaceae, peach, cornflower, arnica, Otogisou, lily, mugwort, apple, lemon, rose, plant extracts such as burnet, its extract or carbonization thereof;
ヒノキオイル、月桃オイル、ヒバオイル、スペアミントオイル、バジルオイル、バラオイル、ジャスミンオイル、ユーカリオイル、キュベバオイル、ハッカオイル、オレンジオイル、レモンオイル、グレープフルーツオイル、ライムオイル、ペチバーオイル、レモングラスオイル、ローズマリーオイル、ラベンダーオイル、イランイランオイル、ティートリーオイル、ボアドローズオイル、マジョラムオイル、ホップオイル、シソオイル、ベルガモットオイル、ゼラニウムオイル、ニームオイル、カモミールオイル等の精油; Cypress oil, moon peach oil, hiba oil, spearmint oil, basil oil, rose oil, jasmine oil, eucalyptus oil, cubaba oil, peppermint oil, orange oil, lemon oil, grapefruit oil, lime oil, pettibar oil, lemongrass oil, rosemary oil Essential oils such as lavender oil, ylang ylang oil, tea tree oil, bored rose oil, marjoram oil, hop oil, perilla oil, bergamot oil, geranium oil, neem oil, chamomile oil;
カルボン、リナロール、α―ピネン、β−ピネン、リモネン、ゲラニオール、シトラール、シトロネラール等の香料;等を挙げることができる。 Fragrances such as carvone, linalool, α-pinene, β-pinene, limonene, geraniol, citral, citronellal and the like.
その他、例えば、天然ピレトリン、プラレトリン、イミプロトリン、フタルスリン、アレスリン、トランスフルトリン、ビフェントリン、レスメトリン、フェノトリン、シフェノトリン、ペルメトリン、サイパーメスリン、シフルスリン、デルタメスリン、ビフェントリン、フェンプロパトリン、エムペンスリン、メトフルトリン、プロフルトリン等のピレスロイド系化合物、フェニトロチオン、ジクロルボス等の有機リン系化合物、カルバリル、チオジカルブ等のカーバメート系化合物、さらにメトキサジアゾン、フィプロニル、アミドフルメト、ジノテフラン、イミダクロプリド、メトプレン、ハイドロプレン、ピリプロキシフェン、クロルフェナピル、ディート、P−メンタン−3,8−ジオール、エチル−ブチルアセチルアミノプロピオネート、ベンジルアルコール、ハッカオイル、シトロネラオイル、ユーカリオイル、ゲラニウムオイル、蚊連草等が挙げられる。 Other examples include natural pyrethrin, praretrin, imiprothrin, phthalthrin, allethrin, transfluthrin, bifenthrin, resmethrin, phenothrin, ciphenothrin, permethrin, cypermethrin, cyfluthrin, deltamethrin, bifenthrin, fenpropatoline, empenthrin, methfluthrin, etc. Compounds, organophosphorus compounds such as fenitrothion and dichlorovos, carbamate compounds such as carbaryl and thiodicarb, methoxadiazone, fipronil, amidoflumet, dinotefuran, imidacloprid, metoprene, hydroprene, pyriproxyfen, chlorfenapyr, deto, P-menthane 3,8-diol, ethyl-butylacetylaminopro Onato, benzyl alcohol, peppermint oil, citronella oil, eucalyptus oil, galley iodonium oil, Karen grass, and the like.
この他にも、フェノキシエタノール、パラオキシ安息香酸エステル、デヒドロ酢酸、プロピオン酸、ε−ポリリジン、イソチアゾリノン又はこれらの誘導体、等の防腐剤、トウガラシエキス、安息香酸デナトニウム、等の誤食防止剤を用いることもできる。 In addition, anticorrosive agents such as preservatives such as phenoxyethanol, paraoxybenzoate, dehydroacetic acid, propionic acid, ε-polylysine, isothiazolinone or derivatives thereof, pepper extract, denatonium benzoate, etc. may be used. it can.
本発明の透明弾性体において、離水及び褐変を防ぎ、安定化させる方法としては、薬剤を含有した、膨潤した吸液性ポリマーからなる透明弾性体に、エデト酸及びエデト酸塩の少なくともいずれか一方が含有されていればよく、以下の工程(a)〜(e)を含むことにより製造することができる。
(a)所期の薬剤を溶媒に溶解させて薬液を調製する工程
(b)吸液性ポリマーの原料に前記薬液を吸液させる工程
(c)吸液性ポリマーを膨潤させる工程
(d)エデト酸等を含む液剤を調製する工程
(e)吸液性ポリマーの粒状体に前記液剤を吸液させる工程
In the transparent elastic body of the present invention, as a method for preventing and stabilizing water separation and browning, a transparent elastic body comprising a swollen liquid-absorbing polymer containing a drug is added to at least one of edetic acid and edetate. May be contained, and can be produced by including the following steps (a) to (e).
(A) a step of dissolving a desired drug in a solvent to prepare a chemical solution (b) a step of absorbing the chemical solution into a raw material of the liquid-absorbing polymer (c) a step of swelling the liquid-absorbing polymer (d) edet A step of preparing a liquid containing an acid or the like (e) a step of absorbing the liquid into a granular material of a liquid-absorbing polymer;
なお、上記工程の順序は適宜変更することができ、また複数の工程を同時に行ってもよい。また、得られた透明弾性体に、さらに他の成分を含有させてもよい。 Note that the order of the above steps can be changed as appropriate, and a plurality of steps may be performed simultaneously. Further, the obtained transparent elastic body may further contain other components.
以下、実施例により本発明を具体的に説明する。ただし、本発明はこれらの実施例のみに限定されるものではない。 Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to only these examples.
(実施例1)
表1に示す薬剤及びエデト酸四ナトリウムをイオン交換水に溶解させ、消臭液を得た。
吸液性ポリマーとしてポリアクリル酸架橋重合体(2−Propenoic acid,polymer with sodium 2−propenoate(1:1);広州妙華国際有限会社製、平均粒径3〜4.5mm)4重量部に対して、前記消臭液を94.3重量部として吸液させて、前記吸液性ポリマーを膨潤させた。
次いでソープ系香料(調合香料)と紫外線吸収剤を質量比で99.5:0.5となるように混合した香料を前記膨潤した吸液性ポリマーの表面に1.7重量部を保持させ、本発明の透明弾性体を得た。得られた透明弾性体は、粒径約12mmの球状体を呈していた。
なお紫外線吸収剤は、商品名「Tinosorb S」(BASF社製)を用いた。
Example 1
The chemicals shown in Table 1 and tetrasodium edetate were dissolved in ion-exchanged water to obtain a deodorant solution.
As a liquid-absorbing polymer, polyacrylic acid cross-linked polymer (2-Propenic acid, polymer with sodium 2-propenoate (1: 1); manufactured by Guangzhou Myoka International Co., Ltd., average particle diameter: 3 to 4.5 mm) in 4 parts by weight On the other hand, the deodorizing liquid was absorbed as 94.3 parts by weight to swell the liquid absorbing polymer.
Subsequently, 1.7 parts by weight of the perfume prepared by mixing soap-based fragrance (prepared fragrance) and ultraviolet absorber so that the mass ratio is 99.5: 0.5 is held on the surface of the swollen liquid-absorbing polymer, A transparent elastic body of the present invention was obtained. The obtained transparent elastic body was a spherical body having a particle size of about 12 mm.
The trade name “Tinosorb S” (manufactured by BASF) was used as the ultraviolet absorber.
(実施例2〜4)
エデト酸四ナトリウムの配合濃度を表2に記載の濃度に変えた以外は、実施例1と同様にして透明弾性体を作製した。
(Examples 2 to 4)
A transparent elastic body was produced in the same manner as in Example 1 except that the blending concentration of tetrasodium edetate was changed to the concentration shown in Table 2.
(比較例1)
エデト酸四ナトリウムを含有しない以外は実施例1と同様にして透明弾性体を作製した。
(比較例2〜4)
エデト酸四ナトリウムに代えて、表2に記載の薬剤を含有(又は添加なし)させた以外は実施例1と同様にして透明弾性体を作製した。
(Comparative Example 1)
A transparent elastic body was produced in the same manner as in Example 1 except that it did not contain edetate tetrasodium.
(Comparative Examples 2 to 4)
A transparent elastic body was produced in the same manner as in Example 1 except that the chemicals shown in Table 2 were contained (or not added) instead of tetrasodium edetate.
比較例1は、イオン交換水を吸収、膨潤してなり、その表面に紫外線吸収剤が混合された香料が保持されている。
比較例2は安定化剤であるトリイソプロパノールアミンを用いた。
比較例3に含まれる没食子酸プロピルは、還元剤であって、褐変を防止するのに有用であることが知られている(特許文献5参照)。
比較例4に含まれるデンプンは、離水防止剤として知られている(特許文献3参照)。
Comparative Example 1 absorbs and swells ion-exchanged water, and a fragrance in which an ultraviolet absorber is mixed is held on its surface.
In Comparative Example 2, triisopropanolamine as a stabilizer was used.
Propyl gallate contained in Comparative Example 3 is a reducing agent and is known to be useful for preventing browning (see Patent Document 5).
Starch contained in Comparative Example 4 is known as a water separation inhibitor (see Patent Document 3).
(離水試験)
上記で得られた実施例1〜4及び比較例1〜4の弾性体について、キセノンウェザーメーター(スガ試験機株式会社製)を用いて、63℃/50%RH/60W/m2の条件で、20時間(10時間×2回)の紫外線照射を行い、その後の離水した液をピペットにて回収し、その容量を離水量(mL)として測定した。試験は3回ずつ行い、その平均の離水量(mL)を求めた。
(Water separation test)
About the elastic bodies of Examples 1 to 4 and Comparative Examples 1 to 4 obtained above, using a xenon weather meter (manufactured by Suga Test Instruments Co., Ltd.), under the conditions of 63 ° C./50% RH / 60 W / m 2 . Then, ultraviolet irradiation was carried out for 20 hours (10 hours × 2 times), and then the separated water was collected with a pipette, and the volume was measured as the amount of water separation (mL). The test was performed three times, and the average water separation amount (mL) was determined.
(褐変試験)
離水試験と同様の紫外線照射を行い、照射後の弾性体の褐変レベルを、PANTONE(登録商標)プラスチック・補充用セレクターチップ(透明)(色番号T015−3−1〜T015−3−5)を指標として照らし合わせ目視で判定した。
褐変レベルは、色番号T015−3−1の1mm厚さ部分の色をレベル5とし、順に色番号T015−3−2の1mm厚さ部分の色をレベル4、色番号T015−3−3の1mm厚さ部分の色をレベル3、色番号T015−3−4の1mm厚さ部分の色をレベル2、色番号T015−3−5の1mm厚さ部分の色をレベル1とした。
なお、褐変レベルの数字が小さいほど、褐変していないということを表す。
(Browning test)
The same ultraviolet irradiation as in the water separation test was performed, and the browning level of the elastic body after irradiation was changed to PANTONE (registered trademark) plastic / replenishment selector chip (transparent) (color number T015-3-1 to T015-3-5). Judgment was made by visual inspection as an index.
As for the browning level, the color of the 1 mm thick part of the color number T015-3-1 is set to level 5, and the color of the 1 mm thick part of the color number T015-3-2 is sequentially set to level 4 and the color number T015-3-3. The color of the 1 mm thick portion is level 3, the color of the 1 mm thick portion of color number T015-3-4 is level 2, and the color of the 1 mm thick portion of color number T015-3-5 is level 1.
In addition, it represents that it has not browned, so that the number of browning levels is small.
離水試験及び褐変試験の結果を表3に表す。 Table 3 shows the results of the water separation test and the browning test.
比較例1、2、4では、いずれも15mL以上の離水が発生した。また比較例2及び比較例4では、褐変レベルが比較例1と同等であって、褐変が防止されてはいなかった。
また没食子酸プロピルを用いた弾性体(比較例3)では、離水の軽減が見られたが、褐変レベルは高く、弾性体では褐変の防止効果が得られない結果となった。
一方、エデト酸ナトリウムを用いた本発明の弾性体(実施例1〜4)では、エデト酸ナトリウムの配合濃度に関わらず離水が軽減され、かつ褐変の防止効果も十分であった。特に0.1〜0.5質量%の濃度においていずれの効果も優れていた。
In Comparative Examples 1, 2, and 4, water separation of 15 mL or more occurred. Moreover, in the comparative example 2 and the comparative example 4, the browning level was equivalent to the comparative example 1, and the browning was not prevented.
In addition, in the elastic body using propyl gallate (Comparative Example 3), water separation was reduced, but the browning level was high, and the elastic body did not have the effect of preventing browning.
On the other hand, in the elastic bodies (Examples 1 to 4) of the present invention using sodium edetate, water separation was reduced regardless of the blending concentration of sodium edetate, and the effect of preventing browning was sufficient. In particular, any effect was excellent at a concentration of 0.1 to 0.5% by mass.
なお、上記以外の、離水及び褐変が起こる他の薬剤に対しても、エデト酸ナトリウムを含有させることによって、離水及び褐変を防止する本願発明の効果が良好に作用する。 In addition, the effect of this invention which prevents water separation and browning acts favorably also with respect to the other chemical | medical agent in which water separation and browning generate | occur | produce other than the above by containing sodium edetate.
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