JP6933331B1 - Shoe cleaner composition - Google Patents
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- JP6933331B1 JP6933331B1 JP2021046716A JP2021046716A JP6933331B1 JP 6933331 B1 JP6933331 B1 JP 6933331B1 JP 2021046716 A JP2021046716 A JP 2021046716A JP 2021046716 A JP2021046716 A JP 2021046716A JP 6933331 B1 JP6933331 B1 JP 6933331B1
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- 239000000203 mixture Substances 0.000 title claims abstract description 37
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 235000001510 limonene Nutrition 0.000 claims abstract description 20
- 229940087305 limonene Drugs 0.000 claims abstract description 20
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 16
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 16
- -1 polyoxyethylene Polymers 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000003599 detergent Substances 0.000 claims description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 239000004907 Macro-emulsion Substances 0.000 claims 1
- 239000012459 cleaning agent Substances 0.000 abstract description 12
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 28
- 230000000694 effects Effects 0.000 description 17
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 13
- 235000020971 citrus fruits Nutrition 0.000 description 6
- 241000207199 Citrus Species 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000004061 bleaching Methods 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 235000005979 Citrus limon Nutrition 0.000 description 3
- 244000248349 Citrus limon Species 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241001672694 Citrus reticulata Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229930003658 monoterpene Natural products 0.000 description 2
- 150000002773 monoterpene derivatives Chemical class 0.000 description 2
- 235000002577 monoterpenes Nutrition 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000545 (4R)-limonene group Chemical group 0.000 description 1
- QBUKAFSEUHGMMX-MTJSOVHGSA-N (5z)-5-[[3-(1-hydroxyethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical compound C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1C(C)O QBUKAFSEUHGMMX-MTJSOVHGSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004909 Moisturizer Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- VIBDJEWPNNCFQO-UHFFFAOYSA-N ethane-1,1,2-triol Chemical compound OCC(O)O VIBDJEWPNNCFQO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000015205 orange juice Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
Abstract
【課題】本発明は、安定した洗浄力、特に油落としと泡切れの良さを兼ね備え、組成物の経時的安定性にすぐれた靴洗浄剤組成物およびその製造方法を提供することを目的とする【解決手段】本発明によれば、（ａ）８乃至１２重量％のリモネンオイル、（ｂ）１２乃至１８重量％の多価アルコール、（ｃ）２０乃至３０重量％のポリオキシエチレングリコールを（ｄ）４０乃至６０重量％の水中に均一に分散させたことを特徴とするマイクロエマルション製剤が提供され、強固な油汚れに対する優れた洗浄力と長期間分離がない安定性を有するものである。【選択図】なしPROBLEM TO BE SOLVED: To provide a shoe-cleaning agent composition having stable detergency, particularly good oil removal and defoaming property, and excellent in stability over time of the composition, and a method for producing the same. According to the present invention, (a) 8 to 12% by weight of limonene oil, (b) 12 to 18% by weight of polyhydric alcohol, and (c) 20 to 30% by weight of polyoxyethylene glycol are used. d) A microemulsion preparation characterized by being uniformly dispersed in 40 to 60% by weight of water is provided, which has excellent detergency against strong oil stains and stability without long-term separation. [Selection diagram] None
Description
本発明は、洗浄効果と経時的安定性にすぐれた特定組成の靴洗浄剤組成物およびその製造方法に関するものである。
さらに詳細には、（ａ）８乃至１２重量％のリモネンオイル、（ｂ）１２乃至１８重量％の多価アルコール、（ｃ）２０乃至３０重量％のポリオキシエチレングリコールを（ｄ）４０乃至６０重量％の水中に均一に分散させたことを特徴とする油落としと泡切れのバランス機能及び経時的安定性にすぐれた洗浄剤組成物とその製造方法に関するものである。
The present invention relates to a shoe detergent composition having a specific composition excellent in cleaning effect and stability over time, and a method for producing the same.
More specifically, (a) 8 to 12% by weight of limonene oil, (b) 12 to 18% by weight of polyhydric alcohol, (c) 20 to 30% by weight of polyoxyethylene glycol (d) 40 to 60%. The present invention relates to a detergent composition having an excellent balance function of oil removal and defoaming and stability over time, which is characterized by being uniformly dispersed in% by weight of water, and a method for producing the same.
昨今のコロナ禍において、いわゆるフットケアは、衛生管理の面からハンドケア及びマウスケアと並んでその重要度は増しており、一連の抗菌・抗ウィルス対策として今後も大変重要な課題である。靴についた汚れの室内持ち込みは厳禁であり、その衛生管理としてのこまめな洗浄は必須である。 In the recent corona illness, so-called foot care is becoming more important along with hand care and mouse care from the aspect of hygiene management, and it will continue to be a very important issue as a series of antibacterial and antiviral measures. It is strictly forbidden to bring dirt on shoes into the room, and frequent cleaning is essential for hygiene management.
一方、スニーカー等の靴汚れに目立つ黒ずみは、ホコリや泥・砂などの不溶性粒子が付着したものが多い。また、油性の混在した汚れが表面に付着し、その表面に塵や微粒子がさらに少しずつ蓄積され黒ずんだ汚れを形成する。スニーカー用の洗浄剤は、このような不溶性の汚れに適した成分で構成されることが多いため、水に溶けない汚れを溶かす化学的作用や、研磨剤等の摩擦による物理的作用で洗浄する機能を有するものが多い。 On the other hand, many of the dark spots that are conspicuous on shoe stains such as sneakers have insoluble particles such as dust, mud, and sand attached to them. In addition, oily mixed stains adhere to the surface, and dust and fine particles are gradually accumulated on the surface to form darkened stains. Since cleaning agents for sneakers are often composed of components suitable for such insoluble stains, they are cleaned by a chemical action that dissolves stains that are insoluble in water or a physical action by friction such as an abrasive. Many have functions.
ここで、靴やスニーカー用の洗剤に求められる重要な条件は３つ挙げられる。1つ目は靴表面の素材の損傷防止、２つ目は高い洗浄力の保持、そして3つ目は早い泡切れである。 Here, there are three important conditions required for detergents for shoes and sneakers. The first is to prevent damage to the material on the shoe surface, the second is to maintain high detergency, and the third is to break bubbles quickly.
特に高い洗浄力と泡切れのバランスは難易度が高いが、少ない水資源利用の観点からも大変重要である。素材を重視すれば、洗浄力は低下し、自ずと洗剤の使用量が増える。使用量が増えると泡立ちが増し、消泡のために大量の水を使用することになる。 The balance between high detergency and defoaming is particularly difficult, but it is also very important from the viewpoint of using less water resources. If the material is emphasized, the detergency will decrease and the amount of detergent used will naturally increase. As the amount used increases, foaming increases, and a large amount of water is used for defoaming.
したがって、これら３点のバランス考量と実効性のある最適な洗浄剤組成の選択が極めて重要である。
しかしながら、従来技術によれば、この点に着目した有用な靴洗浄剤組成物の提供はなされていないのが実情である。
Therefore, it is extremely important to consider the balance of these three points and select the optimum cleaning agent composition that is effective.
However, according to the prior art, the actual situation is that a useful shoe detergent composition focusing on this point has not been provided.
汚れを効果的に落とするために漂白剤が使用されることもあるが、洗浄剤の効果を低下させる等の問題がある他、特有の臭気を伴う等の環境的・健康的に問題があった。これを解消すべく特定の選択成分で構成された洗浄剤の試みがされている。例えば、特許文献１にその解決策が開示されている。 Bleach may be used to effectively remove stains, but there are problems such as reducing the effectiveness of the cleaning agent, as well as environmental and health problems such as having a peculiar odor. rice field. In order to solve this problem, attempts have been made to use a cleaning agent composed of a specific selective component. For example, Patent Document 1 discloses the solution.
すなわち、当該特許文献１によれば、界面活性剤に加え、特定のポリマーと特定の構造を有する化合物を組み合わせ配合することによって、漂白剤特有のにおいを発生させることなく十分な漂白効果が得られる技術が提供されている。 That is, according to Patent Document 1, by blending a specific polymer and a compound having a specific structure in combination with a surfactant, a sufficient bleaching effect can be obtained without generating an odor peculiar to a bleaching agent. Technology is provided.
しかしながら、当該技術では、特定の構造を有する金属ポリフィリンを構成として含むところ、当該化合物には重金属を含む場合があり、環境問題を十分に配慮したものではない。
また、すすぎ性も従来に比べて改善されているものの、洗浄時の泡切れが未だ不十分であり、結果的に排水量が多くなる欠点を有している。
さらに、安定な洗浄力を保持するためには、製剤中のエマルションが熱力学的に安定な連続層を構成する必要があるが、この点においても改善の余地がある。
However, in the present technology, when a metal porphyrin having a specific structure is included as a constitution, the compound may contain a heavy metal, and environmental problems are not sufficiently considered.
Further, although the rinsing property is improved as compared with the conventional case, there is a drawback that the foam breakage at the time of washing is still insufficient, and as a result, the amount of drainage is increased.
Further, in order to maintain a stable detergency, the emulsion in the formulation needs to form a thermodynamically stable continuous layer, and there is room for improvement in this respect as well.
このように、頑固な汚れが付着した被洗浄物に対し、環境面を考慮しつつ、短時間で一定の洗浄効果を備えながら経時的分離等のない安定性良好な構成をとる靴用の洗浄剤組成物の提供は実現されていない。 In this way, for the object to be cleaned with stubborn stains, while considering the environment, cleaning for shoes that has a constant cleaning effect in a short time and has a stable structure without separation over time. The provision of the agent composition has not been realized.
本発明は、上記の未達の問題に鑑みてなされたものであり、特に安定した洗浄力を発揮するために不可欠な洗浄剤の経時的安定性にすぐれた靴洗浄剤組成物とその製造方法を提供することを目的とする。 The present invention has been made in view of the above-mentioned problems that have not been achieved, and a shoe cleaning agent composition having excellent temporal stability of a cleaning agent, which is indispensable for exhibiting particularly stable cleaning power, and a method for producing the same. The purpose is to provide.
本発明者は、上記の課題を解決すべく、洗浄力を落とさず、かつ、経時的安定性が良好な成分のバランス調整を行ったところ、特定の成分組成で構成される洗浄剤組成物が所望の効果を発揮することを見出し、本発明を完成した。具体的には以下のとおりである。 In order to solve the above-mentioned problems, the present inventor adjusted the balance of components having good detergency and good stability over time, and found that a cleaning agent composition composed of a specific component composition was obtained. The present invention has been completed by finding that it exerts a desired effect. Specifically, it is as follows.
本発明者らは、環境面の配慮から、天然物由来であり、油汚れに洗浄効果及び抗菌効果を見込める素材を探索した結果、テルペン類のオイルに着目するに至った。もともとテルペン類は、悪臭を隠ぺいするマスキング性や種々の生物学的特性を有することが知られている。その中でも特に本洗浄組成物に適した素材として、ｄ−リモネンオイルが最適であるという結論に至り、本発明の課題解決のために鋭意研究を継続した。 From the viewpoint of the environment, the present inventors have searched for a material that is derived from a natural product and is expected to have a cleaning effect and an antibacterial effect on oil stains. As a result, the present inventors have focused on terpenes oil. Originally, terpenes are known to have masking properties that conceal malodors and various biological properties. Among them, we came to the conclusion that d-limonene oil is the most suitable material for the present cleaning composition, and continued diligent research to solve the problems of the present invention.
ここで、ｄ−リモネンは、ミカン皮やレモン皮の柑橘皮油中に多量に含まれており、例えば、ミカンジュースやレモンジュースの製造時に排出される柑橘皮を圧搾し蒸留することにより、比較的大量、かつ容易に得ることができる成分である。また、ｄ-リモネン自体に起因した殺菌効果を得ることも期待できる。柑橘臭は靴洗浄後の芳香としても最適である。 Here, d-limonene is contained in a large amount in the citrus peel oil of mandarin orange peel and lemon peel, and for example, the citrus peel discharged during the production of mandarin orange juice and lemon juice is squeezed and distilled for comparison. It is a component that can be easily obtained in a large amount. It can also be expected to obtain a bactericidal effect due to d-limonene itself. The citrus odor is also optimal as an aroma after washing shoes.
本発明において求められる洗浄機能は、ｄ−リモネンのみでは劣ることから、相溶性と洗浄効果の面から検討したところ、ポリオキシアルキレングリコール系の界面活性剤が相性の良いことがわかり、第二成分として選定した。 Since the cleaning function required in the present invention is inferior only with d-limonene, it was found that the polyoxyalkylene glycol-based surfactant has good compatibility when examined from the viewpoint of compatibility and cleaning effect, and the second component. Was selected as.
一方、これら選定の両成分は油汚れの洗浄効果として優れるが、泡立ちが良すぎて消泡しづらいこと、また靴などの深い汚れ部位に対しては、浸透力を高める必要があることから第三成分の選定を要した。同時に、製剤構成として水を加えて適度の粘度に調整することが必要であり、経時的にも安定な均一のエマルションを構成する成分の選択を要することとなった。
検討の結果、多価アルコールの併用が最適であることが判明し、本発明を完成するに至った。
On the other hand, both of these selected components are excellent in cleaning oil stains, but the foaming is too good and it is difficult to defoam, and it is necessary to increase the penetrating power for deeply soiled parts such as shoes. It was necessary to select the three components. At the same time, it is necessary to add water as a pharmaceutical composition to adjust the viscosity to an appropriate level, and it is necessary to select a component that constitutes a uniform emulsion that is stable over time.
As a result of the study, it was found that the combined use of a polyhydric alcohol was optimal, and the present invention was completed.
すなわち、本発明によれば、（ａ）８乃至１２重量％のリモネンオイル、（ｂ）１２乃至１８重量％の多価アルコール、（ｃ）２０乃至３０重量％のポリオキシエチレングリコールを（ｄ）４０乃至６０重量％の水中に均一に分散させたことを特徴とする油落としと泡切れのバランス機能及び経時的安定性にすぐれた靴専用の洗浄剤組成物とその製造方法が提供されるものである。 That is, according to the present invention, (a) 8 to 12% by weight of limonene oil, (b) 12 to 18% by weight of polyhydric alcohol, and (c) 20 to 30% by weight of polyoxyethylene glycol are (d). Provided are a detergent composition for shoes and a method for producing the same, which is characterized by being uniformly dispersed in 40 to 60% by weight of water, having an excellent balance function of oil removal and foam breakage, and excellent stability over time. Is.
本発明の靴用洗浄剤組成物は、上記のとおり、特定量の（ａ）リモネンオイル、（ｂ）多価アルコール及び（ｃ）ポリオキシエチレングリコールを特定量の（ｄ）水中に均一に分散させたことを特徴とするものであり、これらの特定の成分種と量の組合せによって、強固な油汚れに対しても十分な洗浄力と泡切れ力を発揮し、長期間に安定な洗浄効果を奏し得るものである。 As described above, the shoe cleaning composition of the present invention uniformly disperses a specific amount of (a) limonene oil, (b) polyhydric alcohol and (c) polyoxyethylene glycol in a specific amount of (d) water. It is characterized by the fact that, by combining these specific component types and amounts, it exerts sufficient detergency and defoaming power even against strong oil stains, and has a stable cleaning effect for a long period of time. Can be played.
そして、本発明の靴洗浄剤組成物は、その製造方法にも注目すべき特徴がある。
すなわち、本発明の靴洗浄剤組成物の製造方法は、第１工程として予め上記（ｂ）及び（ｃ）の混液を調製しておき、当該混液を（a）に徐々に添加して撹拌混合させ、第２工程として、当該（ａ）、（ｂ）及び（ｃ）の混合液を（ｄ）に徐々に添加混合することによって、課題解決に最適な所望のマイクロエマルション製剤を得ることができるものである。当該マイクロエマルションは熱力学的に安定な連続層を形成することから、長期間保存によっても常に安定な洗浄力が期待できるものである。
The shoe detergent composition of the present invention also has a remarkable feature in its production method.
That is, in the method for producing a shoe detergent composition of the present invention, a mixed solution of the above (b) and (c) is prepared in advance as a first step, and the mixed solution is gradually added to (a) and stirred and mixed. Then, as the second step, the mixed solution of (a), (b) and (c) is gradually added to and mixed with (d) to obtain a desired microemulsion preparation optimal for solving the problem. It is a thing. Since the microemulsion forms a thermodynamically stable continuous layer, stable detergency can always be expected even after long-term storage.
前述のとおり、本発明は、特定の成分構成・配合組成によって、強固な靴の油汚れに対しても十分な洗浄力を発揮し、長期間に渡って安定な洗浄効果を奏し得る靴専用の洗浄剤組成物とその製造方法を提供するものである。 As described above, the present invention is exclusively for shoes, which can exert a sufficient detergency against oil stains on strong shoes and can exert a stable detergency effect for a long period of time due to a specific composition and composition. It provides a cleaning agent composition and a method for producing the same.
すなわち、本発明によれば、第一に、好適には８乃至１２重量％の（ａ）リモネンオイル、１２乃至１８重量％の（ｂ）多価アルコール、２０乃至３０重量％の（ｃ）ポリオキシエチレングリコール及び４０乃至６０重量％の（ｄ）水で構成される靴洗浄剤組成物が提供され、第二に、好適には第１工程として、予め１２乃至１８重量％の（ｂ）多価アルコール及び２０乃至３０重量％の（ｃ）ポリオキシエチレングリコールの混液を調製し、当該混液を８乃至１２重量％の（ａ）リモネンオイルに徐々に添加して撹拌混合させ、第２工程として、当該（ａ）リモネンオイル（ｂ）多価アルコール及び（ｃ）ポリオキシエチレングリコールの混合液を４０乃至６０重量％の（ｄ）水に添加混合することによって、靴洗浄用の澄明なマイクロエマルション製剤を製造する方法が提供される。 That is, according to the present invention, firstly, preferably 8 to 12% by weight (a) limonene oil, 12 to 18% by weight (b) polyhydric alcohol, 20 to 30% by weight (c) poly. A shoe cleaning composition composed of oxyethylene glycol and 40-60% by weight (d) water is provided, secondly, preferably as a first step, 12-18% by weight (b) in advance. A mixed solution of a valent alcohol and 20 to 30% by weight of (c) polyoxyethylene glycol is prepared, and the mixed solution is gradually added to 8 to 12% by weight of (a) limonene oil and mixed by stirring. A clear microemulsion for washing shoes by adding and mixing a mixture of (a) limonene oil (b) polyhydric alcohol and (c) polyoxyethylene glycol to 40 to 60% by weight (d) water. A method of manufacturing a formulation is provided.
本発明における（ａ）リモネンオイルは、柑橘系由来のオイルであり、油に対する親和性が高く、靴の汚れに対する漂白と洗浄に効果を発揮する。リモネン自体は、柑橘類に含まれる代表的な単環式のモノテルペンであり、化学式がＣ10Ｈ16で表され、その分子量は136.23である。常温常圧では無色透明の液体として存在する。キラル化合物であり、いずれのエナンチオマーも生合成されるものの、強いレモン臭がするのはｄ-リモネンである。本発明で好適に使用されるのは当該ｄ−リモネンのオイルであり、柑橘系の果皮から抽出されるもの、合成によって得られるものであればいずれを使用してもよい。
また、単離精製物に限らず、前記果実の果皮から抽出したオレンジ色のものをそのまま使用することも任意であるが、この場合、性能に支障はないが、紫外線によって経時的に退色が進む場合があり、遮光できる容器の選定を考慮する必要がある。
さらに、一定の洗浄効果を得るために、少なくとも８乃至１２重量％のｄ−リモネンを含有することが好ましい。リモネンには芳香があることに加え、一定の殺菌作用も知られていることから、靴洗浄用の機能性と併せ、トリプルの効果が期待できる。そして、主として天然物由来のものを用いることから環境の面からも広く許容される有用な素材である。
The (a) limonene oil in the present invention is a citrus-derived oil, has a high affinity for oil, and is effective for bleaching and washing stains on shoes. Limonene itself is a typical monoterpene of the monoterpene type contained in citrus fruits, its chemical formula is represented by C 10 H 16 , and its molecular weight is 136.23. It exists as a colorless and transparent liquid at normal temperature and pressure. Although it is a chiral compound and all enantiomers are biosynthesized, it is d-limonene that has a strong lemon odor. The oil of d-limonene is preferably used in the present invention, and any oil extracted from citrus peel or synthetically obtained may be used.
Further, not limited to the isolated and purified product, it is also optional to use the orange one extracted from the peel of the fruit as it is, but in this case, the performance is not hindered, but the color fades with time due to ultraviolet rays. In some cases, it is necessary to consider the selection of a container that can block light.
Furthermore, in order to obtain a constant cleaning effect, it is preferable to contain at least 8 to 12% by weight of d-limonene. Since limonene has a fragrance and is known to have a certain bactericidal action, it can be expected to have a triple effect in addition to its functionality for washing shoes. And since it is mainly derived from natural products, it is a useful material that is widely accepted from the environmental point of view.
（ｂ）多価アルコールは、被洗浄物への浸透性が良いことから、本発明の組成物においては洗浄素材の洗浄効果を高める一方、本発明で使用する界面活性剤の気泡を抑制する効果もあることから、消泡効果による洗浄時間の短縮化を図ることが可能である。成分種としては、ｄ−リモネン及び界面活性剤との相溶性の点から、エチレングリコール、プロピレングリコール、１―３−ブチレングリコール及びグリセリンがあげられるが、最も好ましいものは、プロピレングリコール、グリセリンであり、配合量としては２０乃至３０重量％が好ましい。 (B) Since the polyhydric alcohol has good permeability to the object to be cleaned, the composition of the present invention enhances the cleaning effect of the cleaning material, while the effect of suppressing air bubbles of the surfactant used in the present invention. Therefore, it is possible to shorten the cleaning time due to the defoaming effect. Examples of the component species include ethylene glycol, propylene glycol, 1-3-butylene glycol and glycerin from the viewpoint of compatibility with d-lymonen and a surfactant, and the most preferable ones are propylene glycol and glycerin. The blending amount is preferably 20 to 30% by weight.
（ｃ）ポリオキシエチレングリコールは、油等の汚れ洗浄剤として機能する非イオン系界面活性剤である。具体的には、オキシエチレンの付加モル数が１乃至３０モル、好ましくは７-１５モルであるポリオキンエチレングリコールが例示できる。通常の配合量は、２５乃至３５重量％、本発明の洗浄剤を構成する各成分との相溶性と製剤全体の安定性を維持する上で好適には２０乃至３０重量％が使用される。 (C) Polyoxyethylene glycol is a nonionic surfactant that functions as a stain cleaning agent for oils and the like. Specifically, polyoxyethylene glycol having an addition molar number of 1 to 30 mol, preferably 7-15 mol, can be exemplified. The usual blending amount is 25 to 35% by weight, and preferably 20 to 30% by weight is used in order to maintain compatibility with each component constituting the cleaning agent of the present invention and stability of the entire preparation.
（ｄ）水は、上記（ａ）、（ｂ）及び（ｃ）の配合量に対する範囲でバランス調製される。特に本発明の製剤的特徴は、熱力学的に安定なマイクロエマルションを構成する点にあり、減圧下でホモジナイズする等の煩雑な工程を経ずに、常温で簡便な混合撹拌によって調製可能であるが、経時的により安定な連続層を得るためには、最終攪拌の時間は少なくとも３時間が必要であり、それ以下の時間であると、マイクロエマルションの経時的安定性が損なわれる場合がある。
また、本発明のマイクロエマルションは、外観的にも経時的にも安定な性状を維持するためには、好適な添加・撹拌の順序がある。
(D) Water is prepared in a balanced manner with respect to the blending amounts of (a), (b) and (c) above. In particular, the pharmaceutical feature of the present invention is that it constitutes a thermodynamically stable microemulsion, and can be prepared by simple mixing and stirring at room temperature without going through complicated steps such as homogenization under reduced pressure. However, in order to obtain a continuous layer that is more stable over time, the final stirring time needs to be at least 3 hours, and if it is less than that, the stability of the microemulsion over time may be impaired.
In addition, the microemulsion of the present invention has a suitable order of addition and stirring in order to maintain stable properties both in appearance and over time.
すなわち、本発明によれば、好適には第１工程として、予め１２乃至１８重量％の（ｂ）多価アルコール及び２０乃至３０重量％の（ｃ）ポリオキシエチレングリコールの混液を調製し、当該混液を８乃至１２重量％の（ａ）リモネンオイルに徐々に添加して撹拌混合させる。次に、第２工程として、当該（ａ）リモネンオイル（ｂ）多価アルコール及び（ｃ）ポリオキシエチレングリコールの混合液を４０乃至６０重量％の（ｄ）水に添加混合することによって、所望の効果を発揮し得るマイクロエマルション製剤を得ることができる。
特に第２工程においては、（a）乃至（ｄ）を一度に混合、あるいは、（ｄ）を（a）乃至（ｃ）の混合物に添加混合すると、ミセル形成が不十分なために半透明あるいは懸濁が発生するので、注意が必要である。
That is, according to the present invention, preferably, as the first step, a mixed solution of 12 to 18% by weight (b) polyhydric alcohol and 20 to 30% by weight (c) polyoxyethylene glycol is prepared in advance. The mixed solution is gradually added to 8 to 12% by weight of (a) limonene oil and mixed by stirring. Next, as a second step, the desired mixture of (a) limonene oil (b) polyhydric alcohol and (c) polyoxyethylene glycol is added and mixed with 40 to 60% by weight (d) water. It is possible to obtain a microemulsion preparation capable of exerting the effect of.
In particular, in the second step, when (a) to (d) are mixed at once, or when (d) is added and mixed with the mixture of (a) to (c), it is translucent or translucent due to insufficient micelle formation. Care must be taken as suspension will occur.
ここで、マイクロエマルション（英語：Microemulsion）とは、一般に、エマルションに類似した分散系の一種であるが、ミセルの直径が100ナノメートル程度以下と小さく、熱力学的にも安定であり、また強い撹拌を要せず容易に形成されるものを指す。形成するミセルが小さいので可視光の散乱が少なく、目視的にも透明または半透明に見えるのが特徴である。 Here, a microemulsion (English: Microemulsion) is generally a kind of dispersion system similar to an emulsion, but the diameter of the micelle is as small as about 100 nanometers or less, and it is thermodynamically stable and strong. Refers to those that are easily formed without the need for stirring. Since the micelles formed are small, there is little scattering of visible light, and it is characterized by being transparent or translucent visually.
マイクロエマルションの応用面としては、上記のとおり透明な外観を呈し、分離することがないことに加え、親水性成分や疎水性成分のいずれにも親和性のある物質をも溶解しやすい特性があることから、多用途に利用されている。 As an application aspect of the microemulsion, it has a transparent appearance as described above, does not separate, and has a property of easily dissolving a substance having an affinity for both a hydrophilic component and a hydrophobic component. Therefore, it is used for many purposes.
本発明において、マイクロエマルション製剤を使用するメリットは、詳細は定かではないものの、およそ次の洗浄機能性の理論に基づいている。 In the present invention, the merit of using the microemulsion preparation is based on the following theory of cleaning functionality, although the details are not clear.
すなわち、多価アルコールに混和したリモネンオイルが被洗浄物に素早く浸透する結果、油汚れに親和して汚れを除去し、その後、マイクロエマルション系の組成バランスが崩れ、ミセルが乳化に移行し、界面活性剤ポリオキシエチレングリコールの力で二次的洗浄が始まる。先のリモネンオイルとの洗浄作用の協奏効果によって、汚れが落ちを加速させるとともに、助剤の多価アルコールが気泡の抑制を図ることで早い泡切れが達成されるものと推察される。 That is, as a result of the limonene oil mixed with the polyhydric alcohol quickly permeating into the object to be cleaned, the stain is removed in an affinity with oil stains, and then the composition balance of the microemulsion system is lost, the micelles shift to emulsification, and the interface. Secondary cleaning begins with the power of the activator polyoxyethylene glycol. It is presumed that the synergistic effect of the cleaning action with limonene oil accelerates the removal of dirt, and the polyhydric alcohol of the auxiliary agent suppresses air bubbles to achieve quick defoaming.
多価アルコールは、洗浄過程においては、被洗浄物への親和性を向上させるとともに、すすぎ排水後には、表面仕上がりのしなやかさを付与することが得られるものである。 The polyhydric alcohol can improve the affinity for the object to be cleaned in the cleaning process and impart the suppleness of the surface finish after rinsing and draining.
また、仕上がり後は被洗浄物に浸透し吸着したリモネンの芳香が続き、抗菌性をも付与し得ることから、例えばコロナ禍における環境対策の洗浄剤として大変有意義な製剤を提供しうるものである。 In addition, after finishing, the aroma of limonene that permeates and adsorbs to the object to be cleaned continues, and antibacterial properties can also be imparted. Therefore, for example, it is possible to provide a very meaningful preparation as an environmentally friendly cleaning agent for corona damage. ..
その他、本発明の洗浄剤組成物には、本発明の効果を損なわない範囲で、必要に応じて、保湿剤、柔軟仕上げ剤、溶剤、抗菌剤および香料等を添加することができる。 In addition, a moisturizer, a softening agent, a solvent, an antibacterial agent, a fragrance and the like can be added to the detergent composition of the present invention as needed, as long as the effects of the present invention are not impaired.
以下、実施例により、本発明を具体的に説明するが、本発明の範囲は当該実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the scope of the present invention is not limited to the Examples.
＜試験例１＞ 経時的安定性試験
（試験方法）
表１ の組成物を広口規格ビンに充填し、蓋をして、−５ ℃ 〜４０ ℃ のサイクル恒温槽に１年間保存し、３ヶ月毎に製剤の外観を目視評価した。
また、同時に１年間経過時点での洗浄効果面の評価を行った。
評価項目は、被洗浄物の汚れ落ちと表面の漂白の状態、消泡性の有無の３つである。
なお、表1の組成物（供試試料）は、いずれも本発明によって見出した以下の製造方法によって得たものである。
すなわち、第１工程として、（ｂ）多価アルコール及び（ｃ）ポリオキシエチレングリコールの混液を調製し、当該混液を（ａ）リモネンオイルに徐々に添加して撹拌混合させる。次に、第２工程として、当該（ａ）リモネンオイル（ｂ）多価アルコール及び（ｃ）ポリオキシエチレングリコールの混合液を（ｄ）水に添加混合することによって得たものである。
<Test Example 1> Stability test over time (test method)
The composition shown in Table 1 was filled in a wide-mouth standard bottle, covered, and stored in a cycle constant temperature bath at -5 ° C to 40 ° C for 1 year, and the appearance of the preparation was visually evaluated every 3 months.
At the same time, the cleaning effect was evaluated after one year had passed.
There are three evaluation items: the state of dirt removal of the object to be cleaned, the state of surface bleaching, and the presence or absence of defoaming property.
The compositions (test samples) in Table 1 were all obtained by the following production methods found by the present invention.
That is, as the first step, a mixed solution of (b) polyhydric alcohol and (c) polyoxyethylene glycol is prepared, and the mixed solution is gradually added to (a) limonene oil and mixed by stirring. Next, as a second step, it was obtained by adding and mixing the mixed solution of (a) limonene oil (b) polyhydric alcohol and (c) polyoxyethylene glycol to (d) water.
（結果と考察）
以下に示した通り、本発明品は、経時的な変化がなく、機能性も維持されていた。また、被洗浄物表面の汚れ落ちと漂白性も良好であり、本発明で特定された成分で構成されたマイクロエマルション組成物は優れた商品価値を有するものであることが明らかである。
As shown below, the product of the present invention did not change with time and its functionality was maintained. In addition, the surface of the object to be cleaned has good stain removal and bleaching properties, and it is clear that the microemulsion composition composed of the components specified in the present invention has excellent commercial value.
表２は、すべて本発明のマイクロエマルション組成物であり、上記と同様の製造方法で得た安定性試験を行って、所望の効果を有するものであること示したものである。
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| JPH05186798A (en) * | 1992-01-16 | 1993-07-27 | Raku:Kk | Water-soluble agent for dissolving resin |
| JP2001020000A (en) * | 1999-06-21 | 2001-01-23 | Atofina | Microemulsion type low-temperature detergent composition |
| JP2003238996A (en) * | 2002-02-22 | 2003-08-27 | Kao Corp | Concentrated liquid cleaning agent for flush toilet |
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