JP5663183B2 - Toilet cleaning composition - Google Patents
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- JP5663183B2 JP5663183B2 JP2010078723A JP2010078723A JP5663183B2 JP 5663183 B2 JP5663183 B2 JP 5663183B2 JP 2010078723 A JP2010078723 A JP 2010078723A JP 2010078723 A JP2010078723 A JP 2010078723A JP 5663183 B2 JP5663183 B2 JP 5663183B2
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- 239000000203 mixture Substances 0.000 title claims description 45
- 238000004140 cleaning Methods 0.000 title claims description 40
- 229920002413 Polyhexanide Polymers 0.000 claims description 42
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 26
- -1 polyoxyethylene Polymers 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 150000005215 alkyl ethers Chemical class 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 64
- 229940126062 Compound A Drugs 0.000 description 27
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000002736 nonionic surfactant Substances 0.000 description 10
- 241000894006 Bacteria Species 0.000 description 8
- 239000000417 fungicide Substances 0.000 description 8
- 230000000855 fungicidal effect Effects 0.000 description 7
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 6
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 6
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 5
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 5
- 229940123208 Biguanide Drugs 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
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- 238000000034 method Methods 0.000 description 4
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- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LQXBZWFNAKZUNM-UHFFFAOYSA-N 16-methyl-1-(16-methylheptadecoxy)heptadecane Chemical compound CC(C)CCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC(C)C LQXBZWFNAKZUNM-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
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- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- 102000001708 Protein Isoforms Human genes 0.000 description 2
- 108010029485 Protein Isoforms Proteins 0.000 description 2
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- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 2
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- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002504 physiological saline solution Substances 0.000 description 2
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- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 1
- SYSZENVIJHPFNL-UHFFFAOYSA-N (alpha-D-mannosyl)7-beta-D-mannosyl-diacetylchitobiosyl-L-asparagine, isoform B (protein) Chemical compound COC1=CC=C(I)C=C1 SYSZENVIJHPFNL-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
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- 102000004190 Enzymes Human genes 0.000 description 1
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- 235000010254 Jasminum officinale Nutrition 0.000 description 1
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- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- 244000246386 Mentha pulegium Species 0.000 description 1
- 235000016257 Mentha pulegium Nutrition 0.000 description 1
- 235000004357 Mentha x piperita Nutrition 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical class C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
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- 241000018646 Pinus brutia Species 0.000 description 1
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- 241000191967 Staphylococcus aureus Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
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- 239000002781 deodorant agent Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 229940067606 lecithin Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002953 phosphate buffered saline Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
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- 239000008213 purified water Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
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- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
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- Detergent Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は、ポリヘキサメチレンビグアナイド塩酸塩の抗菌活性を、特定のノニオン性界面活性剤によって向上させたトイレ洗浄用組成物に関する。 The present invention relates to a toilet cleaning composition in which the antibacterial activity of polyhexamethylene biguanide hydrochloride is improved by a specific nonionic surfactant.
一般にトイレの便器内部のような一時的に水が流れる環境においては、無機質及び有機質が不溶性の塩を形成し、そのまま汚れとなる場合や、それらを基質として細菌やカビに由来する黒ずみ汚れが生じる。そのため、水洗トイレタンクに手洗い水を利用して自動的に洗浄水を水タンクに投入するトイレ洗浄用組成物に抗菌・殺菌作用を付与することが一般的に行われており、例えば、抗菌剤として第4級アンモニウム塩化合物が使用されている。
しかしながら、第4級アンモニウム塩化合物は、低濃度における抗菌活性が殆ど認められないため、大過剰の水に希釈して用いるようなトイレ洗浄用組成物等の用途においては、細菌やカビに由来する黒ずみ汚れを抑制する効果に対して満足できる抗菌・殺菌作用を得ることは困難であった。
In general, in an environment where water flows temporarily, such as inside a toilet bowl, inorganic and organic substances form insoluble salts and become dirty as they are, or dark stains derived from bacteria and mold occur using them as a substrate. . Therefore, it is generally performed to give antibacterial and bactericidal action to a toilet cleaning composition in which washing water is automatically poured into a water tank using hand-washing water in a flush toilet tank. A quaternary ammonium salt compound is used.
However, since quaternary ammonium salt compounds have almost no antibacterial activity at low concentrations, they are derived from bacteria and molds in applications such as toilet cleaning compositions that are diluted in a large excess of water. It was difficult to obtain a satisfactory antibacterial and bactericidal action for the effect of suppressing darkening stains.
特許文献1には、トイレ等の床や器具などに使用できる殺菌洗浄剤として、硬質表面用固形殺菌洗浄剤組成物が開示されている。
この硬質表面用固形殺菌洗浄剤組成物は、カチオン系殺菌剤0.05〜20重量%およびノニオン性界面活性剤0.5〜30重量%を含有する非発泡性の硬質表面用固形殺菌洗浄剤組成物であり、特許文献1には、ノニオン性界面活性剤であるポリオキシエチレンアルキル(C12〜18)エーテルを含有することによりカチオン系殺菌剤であるビグアナイド系殺菌剤の浸透性が向上し、殺菌作用が向上することが記載されている。
しかしながら、ノニオン性界面活性剤によるビグアナイド系殺菌剤の殺菌作用の向上効果は2倍程度にすぎず、また、黒ずみ汚れを抑制する効果も期待できなかった。
Patent Document 1 discloses a solid sterilization detergent composition for hard surfaces as a sterilization detergent that can be used for floors and appliances such as toilets.
This hard sterilization detergent composition for hard surfaces is a non-foaming solid sterilization detergent for hard surfaces containing 0.05 to 20% by weight of a cationic fungicide and 0.5 to 30% by weight of a nonionic surfactant. In Patent Document 1, the permeability of the biguanide fungicide that is a cationic fungicide is improved by containing polyoxyethylene alkyl (C12-18) ether that is a nonionic surfactant in Patent Document 1, It is described that the bactericidal action is improved.
However, the effect of improving the bactericidal action of the biguanide fungicide by the nonionic surfactant is only about twice, and the effect of suppressing dark stains could not be expected.
特許文献2には、ポリヘキサメチレンビグアナイド塩酸塩を含むビグアナイド系殺菌剤、および、アルキルフェノール系化合物とエチレンオキサイドとの付加重合物を含有するトイレ洗浄水添加剤組成物が開示されている。
しかしながら、このトイレ洗浄水添加剤組成物は、ビグアナイド系殺菌剤の濃度が3重量%(希釈時60ppm)未満では、殺菌力が不充分であり、殺菌剤を低濃度にして使用することが困難であった。
Patent Document 2 discloses a toilet wash water additive composition containing a biguanide fungicide containing polyhexamethylene biguanide hydrochloride and an addition polymer of an alkylphenol compound and ethylene oxide.
However, this toilet cleaning water additive composition has insufficient bactericidal activity when the concentration of the biguanide fungicide is less than 3% by weight (60 ppm when diluted), and it is difficult to use the fungicide at a low concentration. Met.
本発明は、抗菌・殺菌作用を奏するポリヘキサメチレンビグアナイド塩酸塩の抗菌・殺菌作用を向上させ、低濃度での効果的な抗菌・殺菌作用を実現するとともに、黒ずみ汚れを抑制することができるトイレ洗浄用組成物を提供することを目的とする。 The present invention improves the antibacterial and bactericidal action of polyhexamethylene biguanide hydrochloride having antibacterial and bactericidal action, realizes an effective antibacterial and bactericidal action at a low concentration, and can suppress dark stains An object is to provide a cleaning composition.
上記課題を解決すべく検討したところ、ポリヘキサメチレンビグアナイド塩酸塩に、特定のノニオン性界面活性剤を配合すると、ポリヘキサメチレンビグアナイド塩酸塩の抗菌・殺菌作用を向上させることができるので低濃度で使用でき、また、トイレの黒ずみ汚れの防止に有効であることを見出した。 In order to solve the above problems, polyhexamethylene biguanide hydrochloride can be combined with a specific nonionic surfactant to improve the antibacterial and bactericidal action of polyhexamethylene biguanide hydrochloride. It was found that it can be used and is effective in preventing darkening stains on the toilet.
すなわち、本発明は、
ポリヘキサメチレンビグアナイド塩酸塩、および、
下記一般式(1):
で表され、式中R1で表される置換基が、直鎖又は分岐状の炭素数16〜18のアルキル基である化合物を含有することを特徴とするトイレ洗浄用組成物に関する。
That is, the present invention
Polyhexamethylene biguanide hydrochloride, and
The following general formula (1):
And a substituent represented by R 1 in the formula contains a linear or branched compound having a carbon number of 16 to 18 and a toilet cleaning composition.
本発明において、一般式(1)で表される化合物は、R1の炭素数が16〜18であるポリオキシエチレンアルキルエーテルであることが好ましい。
また、一般式(1)で表される化合物は、HLBが5〜18であることが好ましい。
In the present invention, the compound represented by the general formula (1) is preferably a polyoxyethylene alkyl ether in which R 1 has 16 to 18 carbon atoms.
Moreover, it is preferable that the compound represented by General formula (1) has HLB 5-18.
本発明において、ポリヘキサメチレンビグアナイド塩酸塩の重量濃度は、0.3〜3.0ppmであることが好ましい。 In the present invention, the weight concentration of polyhexamethylene biguanide hydrochloride is preferably 0.3 to 3.0 ppm.
また、本発明では、ポリヘキサメチレンビグアナイド塩酸塩1重量部に対して、一般式(1)で表される化合物が5重量部以上50重量部以下であることが好ましい。 Moreover, in this invention, it is preferable that the compound represented by General formula (1) is 5 to 50 weight part with respect to 1 weight part of polyhexamethylene biguanide hydrochloride.
本発明のトイレ洗浄用組成物によれば、ポリヘキサメチレンビグアナイド塩酸塩に、特定のノニオン性界面活性剤を配合することにより、ポリヘキサメチレンビグアナイド塩酸塩の抗菌・殺菌作用を向上させることができることから、低濃度でも効果的な抗菌・殺菌作用を発揮することができる。
また、黒ずみ汚れの発生を抑制することもできる。
According to the toilet cleaning composition of the present invention, the antibacterial / bactericidal action of polyhexamethylene biguanide hydrochloride can be improved by blending a specific nonionic surfactant with polyhexamethylene biguanide hydrochloride. Therefore, an effective antibacterial and bactericidal action can be exhibited even at a low concentration.
In addition, the occurrence of dark stains can be suppressed.
本発明のトイレ洗浄用組成物は、
ポリヘキサメチレンビグアナイド塩酸塩(以下、PHMBともいう)、および、
下記一般式(1):
で表され、式中R1で表される置換基が、直鎖又は分岐状の炭素数16〜18のアルキル基である化合物(以下、化合物Aともいう)を含有する。
The toilet cleaning composition of the present invention comprises:
Polyhexamethylene biguanide hydrochloride (hereinafter also referred to as PHMB), and
The following general formula (1):
In which the substituent represented by R 1 is a linear or branched alkyl group having 16 to 18 carbon atoms (hereinafter also referred to as compound A).
PHMBは、ビグアナイド系殺菌剤の1つであり、トイレ洗浄用組成物において抗菌・殺菌作用を奏する有効成分として機能する。 PHMB is one of the biguanide fungicides, and functions as an active ingredient having antibacterial and bactericidal action in the toilet cleaning composition.
上記化合物Aは、ノニオン性界面活性剤であり、R1は直鎖又は分岐状(イソ型)のいずれでも使用することができる。 The compound A is a nonionic surfactant, and R 1 can be used in any of linear or branched (iso form).
上記一般式(1)において、R1は直鎖又は分岐状(イソ型)の炭素数16〜18のアルキル基を示す。R1が炭素数16〜18のアルキル基であれば、PHMBの抗菌・殺菌作用を好適に向上させることができる。 In the general formula (1), R 1 represents a linear or branched (isoform) alkyl group having 16 to 18 carbon atoms. When R 1 is an alkyl group having 16 to 18 carbon atoms, the antibacterial and bactericidal action of PHMB can be preferably improved.
上記化合物AはHLB(Hydrophile-Lipophile Balance)が、5〜18であることが好ましい。HLBがこの範囲にあると、PHMBの抗菌・殺菌作用を好適に向上させることができる。上記化合物AのHLBは、8〜18であることがより好ましく、10〜18であることがさらに好ましい。
ここで、化合物Aにおいて、エチレンオキシド(EO)やプロピレンオキシド(PO)の付加モル数とHLBは概ね相関することが知られており、HLBの調整のためにEOやPOの付加モル数を変更することは、当該分野で周知の方法により行うことができる。また、HLB値は、当該分野で周知のいくつかの方法により算出することができるが、本発明においてはグリフィン法により算出した。
The compound A preferably has an HLB (Hydrophile-Lipophile Balance) of 5 to 18. When the HLB is in this range, the antibacterial and bactericidal action of PHMB can be preferably improved. The HLB of the compound A is more preferably 8-18, and further preferably 10-18.
Here, in Compound A, it is known that the addition mole number of ethylene oxide (EO) or propylene oxide (PO) and HLB are generally correlated, and the addition mole number of EO or PO is changed for the adjustment of HLB. This can be done by methods well known in the art. The HLB value can be calculated by several methods well known in the art. In the present invention, the HLB value was calculated by the Griffin method.
一般式(1)において、nおよびmは任意の整数であるが、とくにR1が直鎖である場合、nは2〜17の整数であることが好ましく、mは0〜24であることが好ましい。また、n+m=2〜30を満たすことがより好ましい。化合物Aにおいて、エチレンオキシドとプロピレンオキシドはランダム又はブロック付加体のいずれであってもよく、R1にプロピレンオキシドが直接結合したものも含まれる。 In the general formula (1), n and m are arbitrary integers. Particularly, when R 1 is linear, n is preferably an integer of 2 to 17, and m is 0 to 24. preferable. Further, it is more preferable that n + m = 2 to 30 is satisfied. In compound A, ethylene oxide and propylene oxide may be either random or block adducts, and those in which propylene oxide is directly bonded to R 1 are also included.
化合物Aの具体例としては、例えば、POEセチルエーテル、POEオレイルエーテル、POEステアリルエーテル、POEイソセチルエーテル、POEイソオレイルエーテル、POEイソステアリルエーテル、POEアルキル(C16〜18)エーテル、POE・POPセチルエーテル、POE・POPオレイルエーテル、POE・POPステアリルエーテル、POE・POPイソセチルエーテル、POE・POPイソオレイルエーテル、POE・POPイソステアリルエーテル、POPセチルエーテル、POPオレイルエーテル、POPステアリルエーテル、POPイソセチルエーテル、POPイソオレイルエーテル、POPイソステアリルエーテル等が挙げられる。
これらの中でも、PHMBの抗菌・殺菌作用がより向上される点で、POEセチルエーテル、POEオレイルエーテル、POEステアリルエーテル、POE・POPセチルエーテル、POE・POPオレイルエーテル、POE・POPステアリルエーテルが好ましく、
POEセチルエーテル、POEオレイルエーテル、POEステアリルエーテルが特に好ましい。
Specific examples of the compound A include, for example, POE cetyl ether, POE oleyl ether, POE stearyl ether, POE isocetyl ether, POE isooleyl ether, POE isostearyl ether, POE alkyl (C16-18) ether, POE · POP cetyl. Ether, POE / POP oleyl ether, POE / POP stearyl ether, POE / POP isocetyl ether, POE / POP isooleyl ether, POE / POP isostearyl ether, POP cetyl ether, POP oleyl ether, POP stearyl ether, POP isocetyl Examples include ether, POP isooleyl ether, and POP isostearyl ether.
Among these, POE cetyl ether, POE oleyl ether, POE stearyl ether, POE · POP cetyl ether, POE · POP oleyl ether, POE · POP stearyl ether are preferable in that the antibacterial and bactericidal action of PHMB is further improved.
POE cetyl ether, POE oleyl ether, and POE stearyl ether are particularly preferred.
ここで、「POE」はポリオキシエチレンを、「POP」はポリオキシプロピレンを示す。 Here, “POE” represents polyoxyethylene, and “POP” represents polyoxypropylene.
本発明においては、PHMBと化合物Aとを併用することで、PHMBの抗菌・殺菌作用を向上させることができる。
そのため、PHMBの重量濃度は、特に限定されないが、0.3〜3.0ppmであることが好ましく、0.3〜2.0ppmであることがより好ましい。下限は0.5ppmがさらに好ましい。上限は1.0ppmがさらに好ましく、0.8ppmが特に好ましい。
この範囲内であれば、化合物Aと併用したときのPHMBの抗菌・殺菌作用の向上効果がより顕著である。また、従来、この範囲内であれば、PHMBの抗菌・殺菌作用は見られなかったが、化合物Aと併用すると、このような低濃度の範囲内でも抗菌・殺菌作用に優れるトイレ洗浄用組成物とすることができる。このことから、従来、抗菌・殺菌作用がないとして使用されてこなかった低濃度であっても、本発明によれば使用可能である。そして、トイレ洗浄用組成物中への抗菌剤の配合量については、環境への影響を考慮して限りなく低濃度であることが求められるが、本発明によれば、低濃度でも抗菌性に優れるトイレ洗浄用組成物を得ることができる。
また、本発明のトイレ洗浄用組成物によれば、トイレ便器等の黒ずみ汚れの発生を抑制することもできる。黒ずみ汚れは、便器等に付着した有機又は無機付着物の上に細菌が付着した後、この細菌が細胞外ポリマーを生成し、その細胞外ポリマー表面にカビの胞子等が付着することで発生すると考えられるが、本発明では、抗菌・殺菌作用により有機又は無機付着物の上に付着した細菌を除去することで細胞外ポリマーの生成を抑制することができるため、黒ずみ汚れの発生を抑制することができると考えられる。
In the present invention, the combined use of PHMB and Compound A can improve the antibacterial / bactericidal action of PHMB.
Therefore, the weight concentration of PHMB is not particularly limited, but is preferably 0.3 to 3.0 ppm, and more preferably 0.3 to 2.0 ppm. The lower limit is more preferably 0.5 ppm. The upper limit is more preferably 1.0 ppm, and particularly preferably 0.8 ppm.
Within this range, the effect of improving the antibacterial / bactericidal action of PHMB when used in combination with Compound A is more remarkable. Conventionally, the antibacterial and bactericidal action of PHMB was not observed within this range, but when used in combination with Compound A, the toilet cleaning composition has excellent antibacterial and bactericidal action even within such a low concentration range. It can be. For this reason, even at a low concentration that has not been used in the past as having no antibacterial / bactericidal action, it can be used according to the present invention. And the amount of the antibacterial agent in the toilet cleaning composition is required to be as low as possible in consideration of the influence on the environment. An excellent toilet cleaning composition can be obtained.
Moreover, according to the toilet cleaning composition of the present invention, it is also possible to suppress the occurrence of dark stains on toilet toilets and the like. Black stains occur when bacteria adhere to organic or inorganic deposits attached to toilets, etc., and then these bacteria produce extracellular polymers and mold spores adhere to the extracellular polymer surface. Although it can be considered, in the present invention, the generation of extracellular polymer can be suppressed by removing bacteria attached on organic or inorganic deposits by antibacterial and bactericidal action. It is thought that you can.
ここで、PHMBの濃度は、使用時の濃度であって、例えば、使用時に水で希釈されることを想定したトイレ洗浄用組成物においては希釈後の濃度を意味する。例えば、トイレ洗浄用組成物のうち、容器に充填し、水洗トイレのタンク上部の手洗い部に備え付けて使用される、いわゆるオンタンク型のトイレ洗浄用組成物の場合、フラッシュによって水を流すと、容器内の組成物が一定量排出され、水と一緒にタンク内に溜まるが、この時のタンク内の濃度を意味する。 Here, the concentration of PHMB is a concentration at the time of use. For example, in a toilet cleaning composition that is assumed to be diluted with water at the time of use, it means the concentration after dilution. For example, in the case of a so-called on-tank type toilet cleaning composition that is filled in a container and used in a hand-washing portion at the top of a tank of a flush toilet, when the water is flushed, A certain amount of the composition inside is discharged and collected in the tank together with water, which means the concentration in the tank at this time.
また、本発明のトイレ洗浄用組成物は、PHMB1重量部に対して、化合物Aが5重量部以上50重量部以下配合されることが好ましい。
下限は、10重量部がより好ましい。一方、上限は、40重量部がより好ましく、30重量部が更に好ましく、20重量部が特に好ましい。
化合物Aの濃度が50重量部を超えると、トイレ洗浄用組成物としては優れた抗菌・殺菌作用を有するものの、化合物Aの配合量あたりの抗菌・殺菌作用の向上効果が抑えられる傾向がある。具体的には、PHMBの濃度が0.5ppmである場合、化合物Aを2.5〜25ppm程度配合することが好ましい。
In the toilet cleaning composition of the present invention, compound A is preferably blended in an amount of 5 to 50 parts by weight per 1 part by weight of PHMB.
The lower limit is more preferably 10 parts by weight. On the other hand, the upper limit is more preferably 40 parts by weight, still more preferably 30 parts by weight, and particularly preferably 20 parts by weight.
When the concentration of Compound A exceeds 50 parts by weight, the toilet cleaning composition has an excellent antibacterial and bactericidal action, but the effect of improving the antibacterial and bactericidal action per compounding amount of Compound A tends to be suppressed. Specifically, when the concentration of PHMB is 0.5 ppm, it is preferable to add about 2.5 to 25 ppm of Compound A.
本発明のトイレ洗浄用組成物には、必要に応じて、機能性成分、再付着防止剤、pH調整剤、キレート剤、粘度調整剤、懸濁剤、防腐剤、酸化防止剤、紫外線吸収剤、酵素、顔料、染料等の色素等の成分を適当量含有することもできる。機能性成分としては、たとえば芳香成分、消臭成分等が挙げられる。芳香成分としては、例えば、ラベンダー、レモン、オレンジ、ジャスミン、ペパーミント等の天然香料;リモネン、ターピノレン、ゲラニオール、シトロネロール、酢酸エチル等の合成香料; 及びこれらのブレンド香料等が挙げられる。また、消臭成分としては、例えば、イネ、松、ヒノキ、笹等の植物の抽出物; 脱塩型ベタイン化合物;変性有機酸化合物;トリエタノールアミン;安定化二酸化塩素;アルデヒド化合物等が挙げられる。これらの機能性成分は、1種単独で使用してもよく、また2種以上を組み合わせて使用してもよい。 In the toilet cleaning composition of the present invention, a functional component, an anti-redeposition agent, a pH adjuster, a chelating agent, a viscosity adjuster, a suspending agent, an antiseptic, an antioxidant, and an ultraviolet absorber as necessary. In addition, components such as enzymes, pigments, and pigments such as dyes may be contained in appropriate amounts. Examples of the functional component include an aromatic component and a deodorizing component. Examples of the aromatic component include natural fragrances such as lavender, lemon, orange, jasmine and peppermint; synthetic fragrances such as limonene, terpinolene, geraniol, citronellol and ethyl acetate; and blended fragrances thereof. In addition, examples of the deodorant component include extracts from plants such as rice, pine, hinoki and cocoon; desalted betaine compounds; modified organic acid compounds; triethanolamine; stabilized chlorine dioxide; . These functional components may be used individually by 1 type, and may be used in combination of 2 or more type.
本発明のトイレ洗浄用組成物は、例えば、容器に充填し、水洗トイレのタンク上部の手洗い部に備え付けて使用されるオンタンク型の液体洗浄組成物、容器に充填し、水洗トイレ便器のリム部に備え付けて使用される吊下げ型の液体洗浄組成物、容器に噴射剤と併せて充填して使用されるエアゾール型の液体洗浄組成物等として使用することができる。 The toilet cleaning composition of the present invention is, for example, an on-tank liquid cleaning composition that is used by being filled in a container and installed in a hand-washing unit at the top of a tank of a flush toilet. It can be used as a suspended liquid cleaning composition that is used in preparation, an aerosol liquid cleaning composition that is used by filling a container together with a propellant, and the like.
以下に、具体的な実施例を挙げて本発明をより詳細に説明するが、本発明は、下記実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.
実施例1
滅菌精製水(大塚製薬株式会社製)を用いて、ポリヘキサメチレンビグアナイド塩酸塩(アーチ・ケミカルズ・ジャパン社製、Proxel IB)の5000ppm水溶液を調製した。調製した5000ppm水溶液を100倍希釈して50ppm水溶液とした後、さらに100倍希釈して0.5ppm水溶液を調製した。その水溶液に、表1に記載したポリオキシエチレンセチルエーテル(一般式(1)において、R1=セチル基)(ブラウノンCH−310L、青木油脂工業株式会社製)を各濃度(6、8、10ppm)となるように添加、撹拌してトイレ洗浄用組成物を作製した。
Example 1
A sterilized purified water (manufactured by Otsuka Pharmaceutical Co., Ltd.) was used to prepare a 5000 ppm aqueous solution of polyhexamethylene biguanide hydrochloride (manufactured by Arch Chemicals Japan, Proxel IB). The prepared 5000 ppm aqueous solution was diluted 100 times to a 50 ppm aqueous solution, and further diluted 100 times to prepare a 0.5 ppm aqueous solution. The polyoxyethylene cetyl ether described in Table 1 (R 1 = cetyl group in the general formula (1)) (Brownon CH-310L, manufactured by Aoki Yushi Kogyo Co., Ltd.) in each aqueous solution was added at each concentration (6, 8, 10 ppm). ) Was added and stirred to prepare a toilet cleaning composition.
実施例2〜10および比較例1〜5
ブラウノンCH−310Lの代わりに、表1に記載した一般式(1)で表される化合物(ノニオン性界面活性剤、R1が直鎖状)を使用した(実施例2〜5、9〜10、比較例1〜2)、又は、表1に記載した一般式(1)で表される化合物(ノニオン性界面活性剤、R1が分岐状)を使用した(実施例6〜8、比較例3〜5)以外は、実施例1と同様の方法でトイレ洗浄用組成物を作製した。
Examples 2 to 10 and Comparative Examples 1 to 5
Instead of Braunone CH-310L, the compound represented by the general formula (1) described in Table 1 (nonionic surfactant, R 1 is linear) was used (Examples 2 to 5, 9 to 10). Comparative Examples 1 and 2) or a compound represented by the general formula (1) described in Table 1 (nonionic surfactant, R 1 is branched) (Examples 6 to 8, Comparative Examples) A toilet cleaning composition was prepared in the same manner as in Example 1 except for 3 to 5).
(評価方法)
得られたトイレ洗浄用組成物の殺菌効果を、以下の方法で評価した。
(Evaluation method)
The sterilizing effect of the obtained toilet cleaning composition was evaluated by the following method.
(1)被検菌株として黄色ブドウ球菌(Staphylococcus aureus NBRC12732)を用い、本菌株をSCD寒天培地(Soybean−Casein Digest Agar、日本製薬株式会社製)に白金耳で画線し、35℃で18〜24時間前培養した。 (1) Staphylococcus aureus NBRC12732 is used as a test strain, and this strain is streaked on a SCD agar medium (Soybean-Casein Digest Agar, manufactured by Nippon Pharmaceutical Co., Ltd.) with a platinum ear, Pre-cultured for 24 hours.
(2)前培養した被検菌株をニュートリエントブロス培地(日本ベクトン・ディッキンソン株式会社製)に約108cfu/mlとなるように懸濁した(以下、菌液とする)。 (2) The pre-cultured test strain was suspended in a Nutrient broth medium (manufactured by Nippon Becton Dickinson Co., Ltd.) so as to be about 10 8 cfu / ml (hereinafter referred to as a bacterial solution).
(3)50ml容の滅菌遠沈管(日本ベクトン・ディッキンソン株式会社製)に、以下のA〜Dの各溶液を9.9ml分注した。その後、各遠沈管に菌液0.1mlをそれぞれ接種して、10mlとし、25℃で3時間静置培養した。
A溶液:滅菌生理食塩水(大塚製薬株式会社製)のみ(ブランク)
B溶液:0.5ppmポリヘキサメチレンビグアナイド塩酸塩(PHMB)のみの水溶液
C溶液:各濃度の各種ノニオン性界面活性剤(上記一般式(1)で表される化合物)のみの水溶液
D溶液:実施例1〜10及び比較例1〜5の水溶液
(3) 9.9 ml of each of the following solutions A to D was dispensed into a 50 ml sterile centrifuge tube (manufactured by Nippon Becton Dickinson Co., Ltd.). Thereafter, 0.1 ml of the bacterial solution was inoculated into each centrifuge tube to make 10 ml, and statically cultured at 25 ° C. for 3 hours.
Solution A: Only sterile physiological saline (Otsuka Pharmaceutical Co., Ltd.) (blank)
Solution B: Aqueous solution of 0.5 ppm polyhexamethylene biguanide hydrochloride (PHMB) only C solution: Aqueous solution D of various nonionic surfactants (compounds represented by the above general formula (1)) of various concentrations: Implementation Aqueous solutions of Examples 1-10 and Comparative Examples 1-5
(4)接種3時間後のA〜Dの各溶液から0.1mlずつを採取し、適宜リン酸緩衝生理食塩水(和光純薬工業株式会社製)を用いて希釈系列を調製した後、原液および各希釈液0.1mlをそれぞれSCDLP寒天培地(Soybean−Casein Digest Agar with Lecithin&Polysorbate 80、日本製薬株式会社製)に塗抹し、35℃で18時間培養して生菌数をそれぞれ測定した。 (4) 0.1 ml is taken from each of the solutions A to D 3 hours after inoculation, and a dilution series is appropriately prepared using phosphate buffered saline (manufactured by Wako Pure Chemical Industries, Ltd.), and then the stock solution Each 0.1 ml of the diluted solution was smeared on an SCDLP agar medium (Soybean-Casein Digest Agar with Lecithin & Polysorbate 80, manufactured by Nippon Pharmaceutical Co., Ltd.), and cultured at 35 ° C. for 18 hours to measure the number of viable cells.
(5)以下の式に従いB〜Dの各溶液の抗菌活性値を算出した。各溶液において、抗菌活性値が大きい、即ち、ブランクAに対して生菌数の減少が大きいほど、抗菌性が高いことを示す。
抗菌活性値=log[A(滅菌生理食塩水のみ)の菌数]―log[B〜Dの各溶液それぞれの菌数]
(5) The antibacterial activity value of each of the solutions B to D was calculated according to the following formula. In each solution, the larger the antibacterial activity value, that is, the greater the decrease in the number of viable bacteria relative to the blank A, the higher the antibacterial property.
Antibacterial activity value = log [number of bacteria in A (sterilized physiological saline only)]-log [number of bacteria in each solution of BD]
算出したB〜Dの各溶液の抗菌活性値を用いて、一般式(1)で表される化合物との併用による、PHMBの抗菌・殺菌作用の向上効果を算出した。D溶液(PHMBと一般式(1)で表される化合物とを含む水溶液)の抗菌活性値dからB溶液(PHMBのみの水溶液)の抗菌活性値bを差し引いた値(d−b)を「向上効果値」として求め、得られた向上効果値を以下の判定基準によって評価した。 Using the calculated antibacterial activity value of each of the solutions B to D, the effect of improving the antibacterial / bactericidal action of PHMB by the combined use with the compound represented by the general formula (1) was calculated. A value (db) obtained by subtracting the antibacterial activity value b of the B solution (aqueous solution containing only PHMB) from the antibacterial activity value d of the D solution (aqueous solution containing PHMB and the compound represented by the general formula (1)) "Improvement effect value" was obtained, and the obtained improvement effect value was evaluated according to the following criteria.
向上効果値の判定基準:
1未満 : ×
1以上1.5未満 : △
1.5以上2.0未満 : 〇
2.0以上 : ◎
Judgment criteria for improvement effect values:
Less than 1: ×
1 or more and less than 1.5: △
1.5 or more and less than 2.0: 〇2.0 or more: ◎
また、「向上効果値」をD溶液中の一般式(1)で表される化合物の各濃度で除算し、「一般式(1)で表される化合物1ppm当たりの抗菌活性値」を算出した。 Further, the “improvement effect value” was divided by the concentration of the compound represented by the general formula (1) in the D solution to calculate the “antibacterial activity value per 1 ppm of the compound represented by the general formula (1)”. .
表1に示したとおり、化合物Aと併用することで、PHMBの抗菌・殺菌作用を向上させることができた。
また、PHMB0.5ppmに対して、化合物Aを10ppm配合すると、「化合物1ppm当たりの抗菌活性値」が抑えられる傾向が見られたが、化合物Aの濃度が2.5〜25ppmである場合にとくに優れた抗菌・殺菌作用の向上効果が発揮された。すなわち、PHMB1重量部に対して、化合物A5〜50重量部である場合にとくに好ましかった。
なお、「向上効果値」とは、一般式(1)で表される化合物1ppm当りの抗菌活性値を示す。
As shown in Table 1, when used in combination with Compound A, the antibacterial / bactericidal action of PHMB could be improved.
In addition, when 10 ppm of Compound A was added to 0.5 ppm of PHMB, the “antibacterial activity value per 1 ppm of compound” tended to be suppressed, but particularly when the concentration of Compound A was 2.5 to 25 ppm. Excellent antibacterial and bactericidal activity was demonstrated. That is, it was particularly preferred when the compound A was 5 to 50 parts by weight relative to 1 part by weight of PHMB.
The “improvement effect value” indicates an antibacterial activity value per 1 ppm of the compound represented by the general formula (1).
また、35名のモニターを選出し、何も使用しないグループ、PHMB(濃度0.5ppm)のみを使用するグループ、化合物A(濃度10ppm)のみを使用するグループ、実施例1のトイレ洗浄用組成物(化合物Aの濃度が10ppm)を使用するグループ、実施例4のトイレ洗浄用組成物(化合物Aの濃度が10ppm)を使用するグループ、実施例7のトイレ洗浄用組成物(化合物Aの濃度が10ppm)を使用するグループ、実施例9のトイレ洗浄用組成物(化合物Aの濃度が10ppm)を使用するグループとの7群に各5名ずつを分けた。モニター1人につき1日に2回の割合でトイレを使用し、トイレ便器に黒ずみ汚れが発生するまでの日数比較による黒ずみ汚れ抑制効果を確認した。
その結果、PHMBのみを使用するグループ、および、化合物Aのみを使用するグループにおいては、何も使用しないグループと同様の結果を示したのに対し、実施例に係る洗浄用組成物を使用するグループはトイレ便器での黒ずみ汚れを有意に抑制することができた。
また、他の実施例のトイレ洗浄用組成物も、黒ずみ汚れに対して同様の効果を示した。
In addition, 35 monitors were selected, a group using nothing, a group using only PHMB (concentration 0.5 ppm), a group using only compound A (concentration 10 ppm), and the toilet cleaning composition of Example 1 A group using (the concentration of Compound A is 10 ppm), a group using the toilet cleaning composition of Example 4 (the concentration of Compound A is 10 ppm), and the toilet cleaning composition of Example 7 (the concentration of Compound A is 5 groups each were divided into 7 groups: a group using 10 ppm) and a group using the toilet cleaning composition of Example 9 (compound A concentration of 10 ppm). The toilet was used twice a day for each monitor, and the effect of suppressing darkening stains was confirmed by comparing the number of days until darkening stains were generated on the toilet bowl.
As a result, the group using only the PHMB and the group using only the compound A showed the same result as the group not using anything, whereas the group using the cleaning composition according to the example Was able to significantly suppress darkening stains in toilet bowls.
In addition, the toilet cleaning compositions of other examples also showed the same effect on dark stains.
本発明のトイレ洗浄用組成物について、前述した実施例以外の処方例を、処方例1〜39として以下に示す。なお、表中の各成分の単位はppmである。 About the toilet cleaning composition of this invention, the prescription examples other than the Example mentioned above are shown below as prescription examples 1-39. The unit of each component in the table is ppm.
処方例1〜39においては、PHMBと各種化合物Aとが1:5〜1:50の割合になるように混合してトイレ洗浄用組成物を調製した。さらに、PHMBの濃度について、0.3ppm、0.8ppm、1.0ppm、2.0ppm、3.0ppmとし、表2〜4に記載した化合物Aと1:5〜1:50の割合になるように混合したトイレ洗浄用組成物も調製した。 In Formulation Examples 1 to 39, PHMB and various compounds A were mixed at a ratio of 1: 5 to 1:50 to prepare a toilet cleaning composition. Furthermore, about the density | concentration of PHMB, it is set as 0.3 ppm, 0.8 ppm, 1.0 ppm, 2.0 ppm, and 3.0 ppm so that it may become a ratio of 1: 5 to 1:50 with the compound A described in Tables 2-4. A toilet cleaning composition was also prepared.
いずれも抗菌活性について実施例と同様の効果を示し、とくにPHMBの濃度を0.3〜0.8ppmとしたときに、化合物Aとの併用による抗菌・殺菌作用の向上効果に優れていた。
また、トイレ便器での黒ずみ汚れ抑制効果についていずれも実施例と同様の効果を示し、とくにPHMBの濃度を0.3〜0.8ppmとしたときに、化合物Aとの併用による黒ずみ汚れ抑制効果に優れていた。
In any case, the antibacterial activity was the same as that of the example, and particularly when the PHMB concentration was 0.3 to 0.8 ppm, the antibacterial / bactericidal action was improved by the combined use with Compound A.
Moreover, all show the effect similar to an Example about the darkening stain | pollution | contamination suppression effect in a toilet bowl, especially when the density | concentration of PHMB is 0.3-0.8 ppm, it is in the darkening stain | pollution | contamination suppression effect by combined use with the compound A It was excellent.
Claims (5)
下記一般式(1):
で表され、式中R1で表される置換基が、直鎖又は分岐状の炭素数16〜18のアルキル基であるポリオキシアルキレンアルキルエーテル
を含有することを特徴とするトイレ洗浄用組成物。 Polyhexamethylene biguanide hydrochloride, and
The following general formula (1):
And a polyoxyalkylene alkyl ether having a linear or branched alkyl group having 16 to 18 carbon atoms, wherein the substituent represented by R 1 is a linear or branched alkyl group. Cleaning composition.
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