CN111315352A - 口腔用组合物 - Google Patents
口腔用组合物 Download PDFInfo
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- CN111315352A CN111315352A CN201880072376.XA CN201880072376A CN111315352A CN 111315352 A CN111315352 A CN 111315352A CN 201880072376 A CN201880072376 A CN 201880072376A CN 111315352 A CN111315352 A CN 111315352A
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- oral composition
- extract
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- oil
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- 239000000284 extract Substances 0.000 claims abstract description 44
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- 150000003839 salts Chemical class 0.000 claims abstract description 26
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- YKPUWZUDDOIDPM-SOFGYWHQSA-N capsaicin Chemical compound COC1=CC(CNC(=O)CCCC\C=C\C(C)C)=CC=C1O YKPUWZUDDOIDPM-SOFGYWHQSA-N 0.000 claims abstract description 18
- OJYLAHXKWMRDGS-UHFFFAOYSA-N zingerone Chemical compound COC1=CC(CCC(C)=O)=CC=C1O OJYLAHXKWMRDGS-UHFFFAOYSA-N 0.000 claims abstract description 18
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Abstract
本发明提供一种抑制由温感剂、冷感剂等感官刺激成分引起的口腔刺激且香味显现性良好的口腔用组合物。一种口腔用组合物,其含有(A)重均分子量为1,000以上20,000以下的聚丙烯酸盐,和(B)选自山椒提取物、辣椒提取物、姜提取物、金纽扣提取物、山椒醇、辣椒素、姜辣素、姜烯酚、姜油酮、千日菊酰胺和薄荷脑衍生物中的1种以上。上述口腔用组合物进一步含有(C)非离子型表面活性剂。
Description
技术领域
本发明涉及抑制由温感剂、冷感剂等感官刺激成分引起的口腔刺激且香味显现性良好的口腔用组合物。
背景技术
口腔用组合物中,提高其使用实感影响到继续使用,从可期待提高效果方面考虑,通常,混合香料,例如多存在使用薄荷脑等清凉剂给予清爽使用实感的市售产品。进一步地,作为上述香料的增香剂,混合各种感官刺激成分,例如混合辣椒提取物等温感剂、非薄荷脑系冷感剂,更加改善香料的效果,但是有担心来自于这些感官刺激成分的刺激显现的问题。
以往,研究作为来自于构成香料的香料成分的苦味、刺激的缓和剂,使用甜味剂、无机盐,进一步地使用非离子型表面活性剂。此外,作为降低由香料成分的薄荷脑等引起的刺激、苦味的方法,建议了甜味成分、无机盐的添加等方法(专利文献1:日本特开2000-178152号公报,专利文献2:日本特开2002-212041号公报),也有通过糖精等甜味剂来掩蔽降低刺激、苦味的方法,但是这些方法有由于混合量的增加而过于强调味道的担忧,抑制刺激的效果难以说是充分的。
另一方面,聚氧乙烯系等非离子型表面活性剂也有作为香料成分的增溶剂、稳定剂的作用,也有提出将其作为乳化剂应用的技术的方案(专利文献3:日本特开2011-168506号公报)。此外,人们建议:组合混合聚氧乙烯系非离子型表面活性剂时,可得到不损害香料的清凉感、稳定化、也不具有苦味的使用性高的口腔用组合物(专利文献4;日本特开2013-241378号公报)。但是,非离子型表面活性剂中,有具有特有苦味的非离子型表面活性剂,此外,混合过多非离子型表面活性剂时,有时会导致香料的香味发散、使用感的恶化。
现有技术文献
专利文献
【专利文献1】日本特开2000-178152号公报
【专利文献2】日本特开2002-212041号公报
【专利文献3】日本特开2011-168506号公报
【专利文献4】日本特开2013-241378号公报
【专利文献5】日本特公平7-29907号公报
【专利文献6】日本特开2000-247851号公报
发明内容
发明要解决的课题
本发明鉴于上述情况而完成,目的在于提供抑制由温感剂、冷感剂等感官刺激成分引起的口腔刺激且香味显现性良好的口腔用组合物。
【解决课题的手段】
为了达到上述目的,本发明人进行深入研究,结果发现:重均分子量为特定值以下的聚丙烯酸盐具有使由特定的感官刺激物质引起的口腔刺激降低的作用,将上述特定的聚丙烯酸盐和特定的感官刺激物质组合混合入口腔用组合物时,由上述感官刺激物质引起的口腔刺激得到抑制,且香味显现性良好,香味发散优异,此外,外观稳定性也良好。
即,发现:根据本发明,通过将(A)重均分子量为1,000以上20,000以下的聚丙烯酸盐和(B)选自山椒(Zanthoxylum piperitum)提取物、辣椒提取物、姜提取物、金纽扣(Spilanthes acmella var.oleracea)提取物、山椒醇(sanshool)、辣椒素(capsaicin)、姜辣素(gingerol)、姜烯酚(shogaol)、姜油酮(zingerone)、千日菊酰胺(spilanthol)和薄荷脑衍生物中的1种以上混合入口腔用组合物中,可以抑制由作为感官刺激成分的(B)成分引起的口腔刺激,且香味显现性良好,此外,也可良好地维持外观稳定性,从而完成本发明。
作为口腔用组合物用的粘结剂,聚丙烯酸或其盐为公知的,通常,使用重均分子量10万以上、通常为30万左右的交联型聚丙烯酸或其盐。与此相对地,本发明中知晓了:重均分子量为20,000以下的(A)成分的聚丙烯酸盐发挥了抑制由(B)成分引起的口腔刺激例如口腔内的粘膜感受到的刺激这样的迄今为止未知的作用效果。进一步地,组合(A)和(B)成分时,可给予由混合香料带来的香味的显现性未恶化、香味发散良好、味道也良好的使用感。此外,知晓:进一步地混合(C)非离子型表面活性剂时,上述作用效果更优异,而且,即使随着时间流逝,制剂的外观稳定性也优异。由此,本发明中,可得到使用重均分子量大于20,000的聚丙烯酸盐时所不能得到的格外显著的作用效果。
如后述的表5中的比较例所示,包含(B)成分,不含(A)成分时,即使包含重均分子量大于20,000的聚丙烯酸盐,口腔刺激性(刺激的抑制效果)也差,香味显现性和外观稳定性也差(比较例3),即使进一步地包含作为非离子型表面活性剂的聚氧乙烯氢化蓖麻油,口腔刺激性和香味显现性也差(比较例4)。另外,不含(A)成分而包含(B)成分时,即使包含非离子型表面活性剂,香味显现性和味道(无异味)也差,使用感降低(比较例2)。与此相对地,如表1~4、6中的实施例所示,本发明的含有(A)和(B)成分的口腔用组合物的口腔刺激性(刺激的抑制效果)优异,香味显现性、味道(无异味)和外观稳定性也良好。
有人建议将分子量较低的聚丙烯酸聚合物应用于牙结石抑制、应用于抑制由污渍引起的牙齿着色的涂布剂的技术(专利文献5:日本特公平7-29907号公报,专利文献6:日本特开2000-247851号公报)。但是,根据专利文献5、6并不能想到本发明中的将(A)成分组合入(B)成分而带来的口腔刺激的抑制。
因此,本发明提供下述的口腔用组合物。
〔1〕一种口腔用组合物,其含有:
(A)重均分子量为1,000以上20,000以下的聚丙烯酸盐,和
(B)选自山椒提取物、辣椒提取物、姜提取物、金纽扣提取物、山椒醇、辣椒素、姜辣素、姜烯酚、姜油酮、千日菊酰胺和薄荷脑衍生物中的1种以上。
〔2〕根据〔1〕所述的口腔用组合物,其中,(A)成分的聚丙烯酸盐的重均分子量为1,000以上10,000以下。
〔3〕根据〔1〕或〔2〕所述的口腔用组合物,其中,薄荷脑衍生物选自薄荷酯(menthylester)、薄荷烷甲酰胺(menthane carboxamide)和薄荷醚(menthyl ether)中的1种以上。
〔4〕根据〔3〕所述的口腔用组合物,其中,薄荷脑衍生物选自乳酸薄荷酯、琥珀酸单薄荷酯、N-乙基-对薄荷烷-3-甲酰胺、N-{(乙氧羰基)甲基}-对薄荷烷-3-甲酰胺、N-(4-氰甲基苯基)-2-异丙基-5-甲基环己烷甲酰胺、N-(2-(2-吡啶基)乙基)-2-异丙基-5-甲基环己烷甲酰胺和3-l-薄荷氧基丙烷-1,2-二醇中的1种以上。
〔5〕根据〔1〕~〔4〕中任一项所述的口腔用组合物,其中,(B)成分选自山椒提取物、金纽扣提取物、山椒醇、千日菊酰胺、N-乙基-对薄荷烷-3-甲酰胺、N-{(乙氧羰基)甲基}-对薄荷烷-3-甲酰胺、N-(4-氰甲基苯基)-2-异丙基-5-甲基环己烷甲酰胺和N-(2-(2-吡啶基)乙基)-2-异丙基-5-甲基环己烷甲酰胺中的1种以上。
〔6〕根据〔1〕~〔5〕中任一项所述的口腔用组合物,其中,所述口腔用组合物含有0.01~2质量%的(A)成分和以纯成分计为0.000001~0.2质量%的(B)成分。
〔7〕根据〔1〕~〔6〕中任一项所述的口腔用组合物,其中,所述口腔用组合物还含有0.01~10质量%的(C)非离子型表面活性剂。
〔8〕根据〔7〕所述的口腔用组合物,其中,非离子型表面活性剂选自聚氧乙烯烷基醚、聚氧乙烯氢化蓖麻油和烷基糖苷(烷基配糖体;alkyl glucoside)中的1种以上。
〔9〕根据〔1〕~〔8〕中任一项所述的口腔用组合物,其中,所述口腔用组合物为洁齿剂或漱口剂。
【发明效果】
本发明可提供:抑制由感官刺激成分引起的口腔刺激,此外,香味显现性良好,外观稳定性也优异的口腔用组合物。本发明中,由感官刺激成分引起的口腔刺激得到抑制,香味发散也良好,因此,可期待效果实感的提高。
具体实施方式
以下,进一步地详细叙述本发明。本发明的口腔用组合物含有:(A)重均分子量为1,000以上20,000以下的聚丙烯酸盐,和(B)选自山椒提取物、辣椒提取物、姜提取物、金纽扣提取物、山椒醇、辣椒素、姜辣素、姜烯酚、姜油酮、千日菊酰胺和薄荷脑衍生物中的1种以上。
(A)成分的聚丙烯酸盐的重均分子量(Mw)为1,000以上20,000以下。此时,特别是从口腔刺激的抑制效果和香味显现性的角度考虑,重均分子量为1,000以上,优选2,000以上,此外,为20,000以下,优选10,000以下,更优选8,000以下。重均分子量小于1,000时,口腔刺激的抑制效果和香味显现性差。重均分子量大于20,000时,口腔刺激的抑制效果和香味显现性降低,不能得到充分的效果。
通过GPC(凝胶渗透色谱法),在日本专利第5740859号公报记载的方法和测定条件下进行上述重均分子量的测定。具体而言,如下述所示(以下相同)。
重均分子量的测定方法;
重均分子量为使用凝胶渗透色谱仪/多角度激光散射检测器(GPC-MALLS)测定的值,条件如下。
流动相:0.3M NaClO4
NaN3水溶液色谱柱:TSKgelα-M 2根
预柱:TSKguardcolumn α
标准物质:聚乙二醇
从口腔刺激的抑制效果的角度考虑,(A)成分的聚丙烯酸盐优选直链状的聚丙烯酸盐。
作为盐,优选一价盐,更优选碱金属盐或铵盐,进一步优选碱金属盐,可列举钠盐、钾盐,特别优选钠盐。
作为这样的聚丙烯酸盐,可使用Polyscience公司、东亚合成株式会社销售的市售品。
作为具体的市售品,可使用聚丙烯酸钠(Mw:1,000):直链状,Polyscience公司制造;聚丙烯酸钠(Mw:6,000):直链状,东亚合成株式会社制造,AC-10NP、AC-10NPD、Aron T-50;聚丙烯酸钠(Mw:8,000):直链状,Polyscience公司制造;聚丙烯酸钠(Mw:20,000):直链状,东亚合成株式会社制造,Aron A-20UN等。
另外,通常,(A)成分的聚丙烯酸盐,其重均分子量比作为洁齿剂中使用的粘结剂的交联型聚丙烯酸盐低,与作为粘结剂而公知的聚丙烯酸盐不同。
使用(A)成分以外的聚丙烯酸盐代替(A)成分时,口腔刺激的抑制效果差,不能达到本发明的目的。
(A)成分的混合量优选整个组合物的0.01~2%(质量%,以下相同),更优选0.01~1%,进一步优选0.05~0.5%。该混合量为0.01%以上时,可得到充分的口腔刺激的抑制效果和香味显现性。该混合量为2%以下时,可良好且充分地维持香味显现性、味道。
(B)成分选自山椒提取物、辣椒提取物、姜提取物、金纽扣提取物、山椒醇、辣椒素、姜辣素、姜烯酚、姜油酮、千日菊酰胺和薄荷脑衍生物。它们,为作为温感剂或冷感剂而被知晓的感官刺激成分,可以单独使用1种,也可以2种以上并用。
选自山椒提取物、辣椒提取物、姜提取物、金纽扣提取物、山椒醇、辣椒素、姜辣素、姜烯酚、姜油酮和千日菊酰胺中的成分(B1)作为温感剂而被知晓。上述提取物可使用通过市售溶剂等而得的该植物的提取物,可使用提取物、精油等。此外,分别地,山椒醇可使用公知方法从山椒提取物中分离;辣椒素可使用公知方法从辣椒提取物中分离,姜辣素、姜烯酚、姜油酮均可使用公知方法从姜提取物中分离,千日菊酰胺提取物可使用公知方法从金纽扣提取物中分离,并可使用它们。
另外,具体而言,原料可使用市售的水蒸气蒸馏得到的精油、通过溶剂等得到的提取物、使用二氧化碳的超临界提取物。
作为提取溶剂,可使用水、乙醇等低级1元醇,作为提取条件、后处理,可使用通常的方法。
作为(B1)成分,其中,从更有效地给予口腔刺激的抑制效果和香味显现性两者的角度考虑,优选山椒提取物、金纽扣提取物、山椒醇、千日菊酰胺,更优选山椒提取物、山椒醇、千日菊酰胺,特别优选山椒提取物、山椒醇,进一步优选山椒提取物,特别优选山椒的使用二氧化碳的超临界提取物。
这些市售品,具体而言可使用Sichuan Pepper Absolute CO2 Extract(夏拉波(Charabot)株式会社制造)、辣椒提取物(株式会社永广堂本店制造)、千日菊酰胺(高砂香料工业株式会社制造)、姜油树脂(盐野香料株式会社制造)等。
此外,薄荷脑衍生物(B2)作为冷感剂被知晓,优选选自薄荷酯、薄荷烷甲酰胺和薄荷醚中的1种以上。可列举例如乳酸薄荷酯、琥珀酸单薄荷酯等薄荷酯;N-乙基-对薄荷烷-3-羧基酰胺、N-{(乙氧羰基)甲基}-对薄荷烷-3-羧基酰胺、N-(4-氰甲基苯基)-2-异丙基-5-甲基环己烷甲酰胺、N-(2-(2-吡啶基)乙基)-2-异丙基-5-甲基环己烷甲酰胺等薄荷烷甲酰胺;3-l-薄荷氧基丙烷-1,2-二醇等薄荷醚。其中,优选薄荷烷羧酰胺、特别优选N-乙基-对薄荷烷-3-甲酰胺、N-{(乙氧羰基)甲基}-对薄荷烷-3-甲酰胺、N-(4-氰甲基苯基)-2-异丙基-5-甲基环己烷甲酰胺、N-(2-(2-吡啶基)乙基)-2-异丙基-5-甲基环己烷甲酰胺。
薄荷脑衍生物(B2),可使用市售品。具体而言,可列举下述物质。
乳酸薄荷酯(Frescolat(注册商标)ML,德之馨公司制造)
琥珀酸单薄荷酯(Physcool(注册商标),V.MANE FILS公司制造)
N-乙基-对薄荷烷-3-甲酰胺(WS-3,德之馨公司制造)
N-{(乙氧羰基)甲基}-对薄荷烷-3-甲酰胺(WS-5,德之馨公司制造)
N-(4-氰甲基苯基)-2-异丙基-5-甲基环己烷甲酰胺(Evercool(注册商标)G-180,奇华顿日本公司制造)
N-(2-(2-吡啶基)乙基)-2-异丙基-5-甲基环己烷甲酰胺(Evercool(注册商标)G-190,奇华顿日本公司制造)
3-l-薄荷氧基丙烷-1,2-二醇(Cooling Agent 10,高砂香料工业株式会社制造)
(B1)、(B2)成分可分别单独使用,或可组合(B1)和(B2)成分使用。
(B)成分的混合量优选整个组合物的0.000001~0.2%(提取物的情况下为除去溶剂的提纯取纯成分量),更优选0.00001~0.04%,进一步优选0.00002~0.02%。该混合量为0.000001%以上时,可得到满意的混合效果,香味显现性也良好。该混合量为0.2%以下时,可充分地得到口腔刺激的抑制效果,此外,其自身引起的异味(苦味、涩味)被充分抑制,味为也良好。
进一步地,(B)成分的总混合量在上述范围内,(B1)成分的优选混合量为整个组合物的0.000001~0.2%,特别优选为0.00001~0.02%。各成分的优选混合量分别为整个组合物的0.000001~0.2%,特别优选为0.00001~0.02%。
此外,(B)成分的总混合量在上述范围内,(B2)成分的优选混合量为整个组合物的0.00001~0.2%,特别优选为0.002~0.02%。
本发明中,(B)成分相对于(A)成分的混合比例无特别限定,可在满足上述各成分的混合量的范围内设定。
本发明的口腔用组合物,可进一步地含有(C)非离子型表面活性剂。除了(A)和(B)成分之外,还混合(C)成分时,(C)成分作为增溶剂和刺激缓和的提高剂发挥作用,进一步地提高由(A)成分引起的口腔刺激的抑制效果和外观稳定性。
作为(C)非离子型表面活性剂,可列举例如聚氧乙烯烷基醚、聚氧乙烯-聚氧丙烯嵌段共聚物、聚氧乙烯氢化蓖麻油、甘油酯的聚氧乙烯醚、烷基糖苷、蔗糖脂肪酸酯、甘油脂肪酸酯、脱水山梨糖醇脂肪酸酯、聚氧乙烯脱水山梨糖醇脂肪酸酯等。它们中,从防止香味显现性和使用感(味道)的恶化的角度考虑,优选聚氧乙烯烷基醚、聚氧乙烯氢化蓖麻油、烷基糖苷、蔗糖脂肪酸酯、甘油脂肪酸酯、脱水山梨糖醇脂肪酸酯、聚氧乙烯脱水山梨糖醇脂肪酸酯,更优选聚氧乙烯烷基醚、聚氧乙烯氢化蓖麻油、烷基糖苷、脱水山梨糖醇脂肪酸酯、聚氧乙烯脱水山梨糖醇脂肪酸酯,尤其优选聚氧乙烯烷基醚、聚氧乙烯氢化蓖麻油、烷基糖苷。
聚氧乙烯烷基醚的烷基链的碳原子数为12~30,特别优选12~20,氧化乙烯的平均加成摩尔数(平均加成EO)优选3~30。聚氧乙烯氢化蓖麻油的平均加成EO优选10~100。烷基糖苷的烷基的碳原子数为8~16,特别优选12~14。脱水山梨糖醇脂肪酸酯的脂肪酸的碳原子数优选12~18。聚氧乙烯脱水山梨糖醇脂肪酸酯的脂肪酸的碳原子数优选16~18,平均加成EO优选10~40,优选为饱和脂肪酸。
混合(C)非离子型表面活性剂时,其混合量优选整个组合物的0.01~10%,更优选0.01~5%。其混合量在该范围内时,更加提高口腔刺激的抑制效果,外观稳定性更优异。此外,香料的香味显现性也良好。
本发明的口腔用组合物,特别适宜制造为膏状洁齿剂、液状洁齿剂、液体洁齿剂、润制洁齿剂(tooth wet-powder)等洁齿剂;漱口剂,其中,适宜制造为洁齿剂,尤其适宜制造为膏状洁齿剂。此时,除了上述成分之外,可在不损害本发明效果的范围内添加、混合其他公知成分作为任意成分。例如可混合表面活性剂、研磨剂、粘结剂、增稠剂,进一步地,根据需要,可混合甜味剂、防腐剂、着色剂、香料、各种有效成分等,可将这些成分和水混合以制造。
表面活性剂,除了(C)成分,可混合这以外的表面活性剂,例如阴离子型表面活性剂、两性表面活性剂。
阴离子型表面活性剂,可列举具有碳原子数优选12~14、特别优选12的烷基的烷基硫酸盐;酰基氨基酸盐;酰基牛磺酸盐等。酰基氨基酸盐和酰基牛磺酸盐的酰基的碳原子数分别优选12~14,更优选12。具体而言,作为烷基硫酸盐,可列举月桂基硫酸盐、肉豆蔻基硫酸盐等。作为酰基氨基酸盐,可列举月桂酰基谷氨酸盐、肉豆蔻酰基谷氨酸盐等酰基谷氨酸盐;月桂酰基肌氨酸盐等酰基肌氨酸盐等。作为酰基牛磺酸盐,可列举月桂酰基甲基牛磺酸盐等。盐优选钠盐、钾盐等碱金属盐。它们可以单独使用1种,也可以2种以上组合使用,特别优选烷基硫酸盐、酰基肌氨酸盐、酰基牛磺酸盐。其中,优选具有碳原子数12的烃基(月桂基)的阴离子型表面活性剂,特别是烷基硫酸盐(钠盐)在味道、使用感等方面比其他表面活性剂优异,因此,更优选。
两性表面活性剂,可列举具有碳原子数12~14的酰基的酰基氨基乙酸甜菜碱、脂肪酸酰胺丙基甜菜碱。作为酰基氨基乙酸甜菜碱,可列举月桂酰基二甲基氨基乙酸甜菜碱;作为脂肪酸酰胺丙基甜菜碱,可列举椰油脂肪酸酰胺丙基甜菜碱。它们可以单独使用1种,也可以2种以上组合使用,特别优选酰基氨基乙酸甜菜碱。其中,优选具有碳原子数12的烃基(月桂基)的酰基氨基乙酸甜菜碱,更优选月桂基二甲基氨基乙酸甜菜碱。
这些除(C)成分以外的表面活性剂的混合量通常为0.01~10%,特别优选0.01~5%。
研磨剂,可列举例如硅酸酐、晶体性二氧化硅、非晶性二氧化硅、硅胶(silicagel)、硅酸铝等二氧化硅系研磨剂,磷酸氢钙无水合物、磷酸氢钙二水合物、磷酸四钙、磷酸三钙等磷酸钙系研磨剂;沸石;焦磷酸钙;碳酸钙;碳酸氢钠;氢氧化铝;氧化铝;碳酸镁;磷酸三镁;硅酸锆;羟基磷灰石;合成树脂系研磨剂。它们可以单独使用1种,也可以2种以上组合使用,其中,从口腔刺激的抑制和使用性的观点考虑,优选硅酸酐等二氧化硅系研磨剂;磷酸钙系研磨剂之类的无机研磨剂,特别优选硅酸酐。
研磨剂的混合量优选0~50%,特别优选3~30%,尤其优选5~20%。从口腔刺激的抑制的角度考虑,优选不混合过多研磨剂。另外,漱口剂中,研磨剂的混合量优选0~10%,特别优选0~5%。
粘结剂,例如为海藻酸衍生物、黄原胶等胶类、重均分子量大于20,000的交联型聚丙烯酸盐、卡拉胶、羧甲基纤维素钠等纤维素衍生物之类的有机粘结剂;硅胶、铝硅胶等无机粘结剂(通常,混合量为0.3~10%)。
增稠剂,可列举山梨糖醇、赤藓糖醇、木糖醇等糖醇;丙二醇、丙三醇、聚乙二醇等多元醇(通常,混合量为5~70%)。
甜味剂可列举糖精钠、甜菊苷、甘草酸二钾、紫苏葶、索马甜(thaumatin)、新橙皮苷二氢查尔酮、天冬氨酰基苯丙氨酸甲酯,防腐剂可列举对羟基苯甲酸酯、苯甲酸钠。着色剂可列举蓝色1号、黄色4号、二氧化钛。
香料,除了(B)成分以外,可使用通常的口腔用香料成分。可以使用口腔用组合物中使用的公知的香料原材料,并不限定于实施例的香料,可以使用例如胡椒薄荷油(peppermint oil)、留兰香油、茴香油、桉叶油、冬青油、肉桂油、丁香油、百里香油、鼠尾草油、柠檬油、橙油、薄荷油、小豆蔻油、芫荽油、橘子油、白柠檬油、熏衣草油、迷迭香油、月桂油、洋甘菊油、页蒿子油、马郁兰油、月桂叶油、柠檬草油、牛至油、松针油、橙花油、玫瑰油、茉莉油、鸢尾浸膏、胡椒薄荷净油、玫瑰净油、橙花净油等天然香料,和这些天然香料的加工处理(前馏分切割、后馏分切割、分馏、液液萃取、精制化、香料粉末化等)后的香料,以及薄荷脑、香芹酮、茴香脑、水杨酸甲酯、肉桂醛、芳樟醇、乙酸芳樟酯、柠檬烯、薄荷酮、蒎烯、辛醛、柠檬醛、胡薄荷酮、乙酸香芹酯(carvyl acetate)、茴香醛、乙酸乙酯、丁酸乙酯、环己基丙酸烯丙酯、邻氨基苯甲酸甲酯、甲基苯基缩水甘油酸乙酯、香兰素、十一内酯、己醛、异戊醇、己烯醇、二甲基硫醚、甲基环戊烯醇酮(cyclotene)、糠醛、三甲基吡嗪、乳酸乙酯、硫代乙酸乙酯等单品香料,进一步地,草莓风味香精、苹果风味香精、香蕉风味香精、菠萝风味香精、葡萄风味香精、芒果风味香精、黄油风味香精、牛奶风味香精、混合水果风味香精、热带水果风味香精等调和香料等。
上述的香料原材料根据成分而不同,优选在整个口腔用组合物的0.000001~1%的范围内使用。尤其优选:含有选自胡椒薄荷油(含精油)、留兰香油(含精油)、日本薄荷油(含精油)、薄荷脑和香芹酮中的成分的1种以上的香料。上述成分,在口腔用组成中优选0.05~1%的范围内使用,更优选在0.1~0.8%的范围使用。
使用上述香料原材料的赋香用香料优选在组合物中混合0.001~2%,更优选0.1~2%。
另外,以含(B)成分的香料混合入口腔用组合物时,可在上述(B)成分记载的范围内使用(B)成分。
作为任意的有效成分,可列举异丙基甲基苯酚等非离子性杀菌剂;西吡氯铵(cetylpyridinium chloride)等阳离子性杀菌剂;葡聚糖酶(dextranase)、非水溶性葡聚糖酶(mutanase)、溶菌酶(lysozyme)、淀粉酶、蛋白酶、溶菌酶、SOD(超氧化物歧化酶)等酶;单氟磷酸钠、单氟磷酸钾等碱金属单氟磷酸盐;氟化钠、氟化亚锡等氟化物;氨甲环酸、ε-氨基己酸、尿囊素、尿囊素氯羟基铝、二氢胆固醇、甘草酸、甘草次酸等抗炎剂;硝酸钾、乳酸铝等感觉过敏改善剂;甘油磷酸盐;叶绿素;氯化钠;氯化锌、氧化锌、柠檬酸锌等锌化合物;葡萄糖酸酮、硫酸铜等铜化合物;聚磷酸钠等水溶性无机磷氧化物;维生素A、B族维生素、维生素C、维生素E等维生素类;黄柏、茶等生药。这些有效成分可以使用1种或2种以上,此外,在不妨碍本发明效果的范围内,可以混合有效量的这些有效成分。
口腔用组合物的pH(25℃)可为通常范围,pH优选5~9,特别优选6~8。另外,可添加公知的pH调节剂进行pH调节,可使用盐酸、氢氧化钠等碱金属的氢氧化物。
【实施例】
以下,示出实施例和比较例具体地说明本发明,但是本发明并不受限于下述的实施例。另外,除非另有说明,否则下述的例中,%均表示质量%。
此外,使用凝胶渗透色谱仪/多角度激光散射检测器(GPC-MALLS),在与上述相同的方法和测定条件下测定重均分子量(Mw)。
[实施例、比较例]
根据通常的方法制造表1~6所示组成的口腔用组合物(漱口剂或膏状洁齿剂),将它们作为试验组合物使用,用下述方法进行评价。将结果一并记于表1~6。
(1)使用感(口腔刺激性)的评价方法
作为按照下述方法使用试验组合物时的使用感,10名受试者评论员分别按照下述评分标准评价口腔刺激性。根据10人的评分的平均值,按照下述判定标准进行判定。
·漱口剂:评价将试验组合物含于口中清洁口腔内时的口腔刺激。
·膏状洁齿剂:评价将1g试验组合物载置于牙刷上刷牙3分钟而清洁口腔内时的口腔刺激。
口腔刺激性的评分标准
4分:口腔内几乎感觉不到刺激
3分:口腔内稍微能感觉到刺激,但是没有问题
2分:口腔内能感觉到刺激
1分:口腔内非常能感觉到刺激
口腔刺激性的判定标准
◎:平均分3.5分以上4.0分以下
○:平均分3.0分以上且小于3.5分
△:平均分2.0分以上且小于3.0分
×:平均分1.0分以上且小于2.0分
(2)使用感(味道)的评价方法
作为按照下述方法使用试验组合物时的使用感,10名受试者评论员分别按照下述评分标准评价味道(无异味)。根据10人的评分的平均值,按照下述判定标准进行判定。
·漱口剂:评价将试验组合物含于口中清洁口腔内时的味道(异味)的有无。
·膏状洁齿剂:评价将1g试验组合物载置于牙刷上刷牙3分钟而清洁口腔内时的味道(异味)的有无。
味道(无异味)的评分标准
4分:口腔内感觉不到异味
3分:口腔内稍微能感觉到异味,但是没有问题
2分:口腔内能感觉到异味
1分:口腔内非常能感觉到异味
味道(无异味)的判定标准
◎:平均分3.5分以上4.0分以下
○:平均分3.0分以上且小于3.5分
△:平均分2.0分以上且小于3.0分
×:平均分1.0分以上且小于2.0分
(3)香味显现性的评价方法
作为受试者,以10名专家评论员人为对象实施。专家评论员根据下述评分标准评价按照下述方法使用试验组合物时的香味显现性。根据10人的评分的平均值,按照下述判定标准进行判定。
·漱口剂:评价将试验组合物含于口中清洁口腔内时的香味显现性
·膏状洁齿剂:评价将1g试验组合物载置于牙刷上刷牙3分钟而清洁口腔内时的香味显现性
香味显现性的评分标准
4分:非常能感觉到香味
3分:能感觉到香味
2分:稍微能感觉到香味
1分:感觉不到香味
香味显现性的判定标准
◎:平均分3.5分以上4.0分以下
○:平均分3.0分以上且小于3.5分
△:平均分2.0分以上且小于3.0分
×:平均分1.0分以上且小于2.0分
(4)外观稳定性的评价方法
将450mL试验组合物(均为澄清外观)填充入容量500mL的无色透明PET(聚对苯二甲酸乙二醇酯)容器(株式会社吉野工业所制造)中,在50℃恒温槽中保存1个月后,按照下述4个等级的评分标准目视评价外观稳定性。对3瓶进行评价,根据这些评分的平均值,按照下述的判定标准进行判定,以◎、○、×表示。
外观稳定性的评分标准
4:完全不浑浊
3:几乎不浑浊
2:稍微浑浊
1:相当浑浊
外观稳定性的判定标准
◎:平均分3.5分以上4.0分以下
○:平均分3.0分以上且小于3.5分
△:平均分2.0分以上且小于3.0分
×:平均分1.0分以上且小于2.0分
使用的原料的详细情况如下所示。
(A)成分:
聚丙烯酸钠(Mw:1,000)
直链状,Polyscience公司制造
聚丙烯酸钠(Mw:6,000)
直链状,东亚合成株式会社制造,商品名:AC-10NP
聚丙烯酸钠(Mw:8,000)
直链状,Polyscience公司制造
聚丙烯酸钠(Mw:20,000)
直链状,东亚合成株式会社制造,商品名:Aron A-20UN
聚丙烯酸钠(Mw:300,000,比较成分)
交联型,Polyscience公司制造
(B)成分:
山椒提取物
商品名:Sichuan Pepper Absolute CO2 Extract,夏拉波株式会社制造辣椒提取物
商品名:辣椒提取物,株式会社永广堂本店制造
千日菊酰胺
高砂香料工业株式会社制造
姜提取物
商品名:姜油树脂,盐野香料株式会社制造
乳酸薄荷酯
商品名:Frescolat(注册商标)ML,德之馨公司制造
N-乙基-对薄荷烷-3-甲酰胺
商品名:WS-3,德之馨公司制造
N-{(乙氧羰基)甲基}-对薄荷烷-3-甲酰胺
商品名:WS-5,德之馨公司制造
N-(4-氰甲基苯基)-2-异丙基-5-甲基环己烷甲酰胺
商品名:Evercool(注册商标)G-180,奇华顿日本公司制造N-(2-(2-吡啶基)乙基)-2-异丙基-5-甲基环己烷甲酰胺
商品名:Evercool(注册商标)G-190,奇华顿日本公司制造3-l-薄荷氧基丙烷-1,2-二醇
商品名:Cooling Agent 10,高砂香料工业株式会社制造
琥珀酸单薄荷酯
商品名:Physcool(注册商标),V.MANE FILS公司制造
(C)成分
聚氧乙烯(60)氢化蓖麻油
商品名:Blaunon RCW-60,青木油脂工业株式会社制造
聚氧乙烯(20)氢化蓖麻油
商品名:Blaunon RCW-20,青木油脂工业株式会社制造
聚氧乙烯(30)十六烷基醚
商品名:NIKKOL BC-30,日光化学株式会社制造
月桂基糖苷
商品名:Mydol 12(烷基的碳原子数8~16),花王株式会社制造
聚乙二醇油酸酯
商品名:EMALEX OE-10(E.O.10),日本Emulsion株式会社制造
蔗糖脂肪酸酯
商品名:Ryoto Sugar Ester POS-135(脂肪酸的碳原子数16~18),三菱化学食品株式会社制造
十聚甘油月桂酸酯
商品名:SY Glyster ML-750,阪本药品工业株式会社制造
另外,表中的(B)成分为提取物时,表示其混合量的数值是除去溶剂的提取纯成分量。
此外,使用的香料组合物A~F的组成如后述的表7~13所示。
【表1】
【表2】
【表3】
【表4】
【表5】
【表6】
此外,使用香料组合物B、C、D、E或F代替香料组合物A,除此以外,同样地制造与上述实施例的组成相同的漱口剂或膏状洁齿剂,进行评价,分别得到与上述实施例相同的结果。
【表7】
【表8】
风味香料1组成 | |
薄荷呋喃(methofuran) | 1 |
茴香脑 | 1 |
薄荷酮 | 1 |
乙酸薄荷酯 | 1 |
合计 | 4份<sup>*</sup> |
*:表中的份为质量份(以下相同)。
【表9】
风味香料2组成 | |
橙油 | 1 |
橙子精油(前馏分80%切割) | 1 |
柠檬油 | 1 |
柠檬精油(前馏分95%切割) | 1 |
白柠檬油 | 1 |
橘子油 | 1 |
葡萄柚油 | 1 |
柚子油 | 1 |
柠檬醛 | 1 |
癸醛 | 1 |
合计 | 10份 |
【表10】
风味香料3组成 | |
茴香油 | 1 |
桉叶油 | 1 |
肉桂油 | 1 |
丁香油 | 1 |
百里香油 | 1 |
鼠尾草油 | 1 |
小豆蔻油 | 1 |
迷迭香油 | 1 |
月桂油 | 1 |
洋甘菊油 | 1 |
页蒿子油 | 1 |
罗勒油 | 1 |
合计 | 12份 |
【表11】
风味香料4组成 | |
冬青油 | 1 |
乳香油(mastic oil) | 1 |
柠檬草油 | 1 |
鸢尾油 | 1 |
香荚兰油 | 1 |
合计 | 5份 |
【表12】
风味香料5组成 | |
麦芽酚 | 1 |
乙基麦芽酚 | 1 |
香兰素 | 1 |
乙基香兰素 | 1 |
呋喃酮 | 1 |
乙基环戊烯醇酮 | 1 |
4,5-二甲基-3-羟基-2(5H)-呋喃酮 | 1 |
甲基环戊烯醇酮(cyclotene) | 1 |
2-甲基丁酸 | 1 |
乙酸 | 1 |
丙酸 | 1 |
合计 | 11份 |
【表13】
风味香料6组成 | |
对甲氧基肉桂醛 | 1 |
反式-2-己烯醛 | 1 |
十一内酯 | 1 |
癸内酯 | 1 |
丁酸乙酯 | 1 |
乙酸异戊酯 | 1 |
苯甲醛 | 1 |
乙酸己酯 | 1 |
2-甲基丁酸乙酯 | 1 |
苄醇 | 1 |
α-松油醇 | 1 |
苯基乙基缩水甘油酸酯 | 1 |
苯乙醇 | 1 |
己酸烯丙酯 | 1 |
辛醇 | 1 |
肉桂酸甲酯 | 1 |
庚炔碳酸甲酯 | 1 |
紫罗兰酮 | 1 |
β-甲基硫代丙酸乙酯 | 1 |
顺式-6-壬烯醇 | 1 |
甲基苯并二氧杂蒎酮 | 1 |
合计 | 21份 |
Claims (9)
1.一种口腔用组合物,其含有:
(A)重均分子量为1,000以上20,000以下的聚丙烯酸盐,和
(B)选自山椒提取物、辣椒提取物、姜提取物、金纽扣提取物、山椒醇、辣椒素、姜辣素、姜烯酚、姜油酮、千日菊酰胺和薄荷脑衍生物中的1种以上。
2.根据权利要求1所述的口腔用组合物,其中,(A)成分的聚丙烯酸盐的重均分子量为1,000以上10,000以下。
3.根据权利要求1或2所述的口腔用组合物,其中,薄荷脑衍生物选自薄荷酯、薄荷烷甲酰胺和薄荷醚中的1种以上。
4.根据权利要求3所述的口腔用组合物,其中,薄荷脑衍生物选自乳酸薄荷酯、琥珀酸单薄荷酯、N-乙基-对薄荷烷-3-甲酰胺、N-{(乙氧羰基)甲基}-对薄荷烷-3-甲酰胺、N-(4-氰甲基苯基)-2-异丙基-5-甲基环己烷甲酰胺、N-(2-(2-吡啶基)乙基)-2-异丙基-5-甲基环己烷甲酰胺和3-l-薄荷氧基丙烷-1,2-二醇中的1种以上。
5.根据权利要求1~4中任一项所述的口腔用组合物,其中,(B)成分选自山椒提取物、金纽扣提取物、山椒醇、千日菊酰胺、N-乙基-对薄荷烷-3-甲酰胺、N-{(乙氧羰基)甲基}-对薄荷烷-3-甲酰胺、N-(4-氰甲基苯基)-2-异丙基-5-甲基环己烷甲酰胺和N-(2-(2-吡啶基)乙基)-2-异丙基-5-甲基环己烷甲酰胺中的1种以上。
6.根据权利要求1~5中任一项所述的口腔用组合物,其中,所述口腔用组合物含有0.01~2质量%的(A)成分和以纯成分计为0.000001~0.2质量%的(B)成分。
7.根据权利要求1~6中任一项所述的口腔用组合物,其中,所述口腔用组合物还含有0.01~10质量%的(C)非离子型表面活性剂。
8.根据权利要求7所述的口腔用组合物,其中,非离子型表面活性剂选自聚氧乙烯烷基醚、聚氧乙烯氢化蓖麻油和烷基糖苷中的1种以上。
9.根据权利要求1~8中任一项所述的口腔用组合物,其中,所述口腔用组合物为洁齿剂或漱口剂。
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