JP7039121B2 - Antiseptic antibacterial agent for cosmetics - Google Patents
Antiseptic antibacterial agent for cosmetics Download PDFInfo
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- JP7039121B2 JP7039121B2 JP2017108061A JP2017108061A JP7039121B2 JP 7039121 B2 JP7039121 B2 JP 7039121B2 JP 2017108061 A JP2017108061 A JP 2017108061A JP 2017108061 A JP2017108061 A JP 2017108061A JP 7039121 B2 JP7039121 B2 JP 7039121B2
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- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- ZNVKGUVDRSSWHV-UHFFFAOYSA-L zinc;4-hydroxybenzenesulfonate Chemical compound [Zn+2].OC1=CC=C(S([O-])(=O)=O)C=C1.OC1=CC=C(S([O-])(=O)=O)C=C1 ZNVKGUVDRSSWHV-UHFFFAOYSA-L 0.000 description 1
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 description 1
- 239000002446 δ-tocopherol Substances 0.000 description 1
Landscapes
- Cosmetics (AREA)
Description
本発明は、化粧料用防腐抗菌剤に関する。より詳しくは、皮膚化粧料、皮膚外用剤及び頭髪化粧料等に有用な化粧料用防腐抗菌剤に関する。 The present invention relates to an antiseptic and antibacterial agent for cosmetics. More specifically, the present invention relates to an antiseptic and antibacterial agent for cosmetics useful for skin cosmetics, external skin preparations, hair cosmetics and the like.
従来より化粧品や医薬品、医薬部外品、食品などの人体施用組成物には、防腐殺菌剤として、パラベン、安息香酸及びその塩類、サリチル酸及びその塩類等が用いられている。
しかしながら、上記従来の防腐殺菌剤は皮膚刺激性が高いなど安全性が低いため、使用濃度範囲が制限されやすいという欠点を有しており、例えば、パラベンや安息香酸塩の使用制限濃度は1%、安息香酸やサリチル酸の使用制限濃度は0.2%とされている。
また、近年これらの防腐殺菌剤に対しアレルギー反応を示す人が増えているため、安全性に対する志向がより高まり、防腐殺菌剤を全く配合していないか、又は、その配合量を軽減させた化粧料組成物の需要が高まっている。
そこで、従来の防腐殺菌剤の欠点が克服され、且つ安全性の高い抗菌物質の探索や、防腐殺菌剤の効力を高めることにより防腐殺菌剤の使用量を軽減しようという試みが種々行われている。例えば、より人体に安全な1,2-アルカンジオールを用いる技術(特許文献1参照)や、グリセロールモノアルキルエーテルを用いる技術(特許文献2参照)、4-ヒドロキシフェニル酢酸エチルを用いる技術(特許文献3参照)等が報告されている。
Conventionally, parabens, benzoic acid and its salts, salicylic acid and its salts and the like have been used as antiseptic and bactericidal agents in human body application compositions such as cosmetics, pharmaceuticals, quasi-drugs and foods.
However, the above-mentioned conventional preservatives and bactericides have a drawback that the range of concentration used is easily limited because they are highly irritating to the skin and have low safety. For example, the restricted concentration of paraben or benzoate is 1%. , The restricted concentration of benzoic acid and salicylic acid is 0.2%.
In addition, since the number of people who have an allergic reaction to these preservatives and fungicides has increased in recent years, the safety consciousness has increased, and makeup that does not contain any preservatives or fungicides or has a reduced amount of them. The demand for composition is increasing.
Therefore, various attempts have been made to overcome the drawbacks of conventional antiseptic and bactericidal agents, search for highly safe antibacterial substances, and reduce the amount of antiseptic and bactericidal agents used by increasing the efficacy of the antiseptic and bactericidal agents. .. For example, a technique using 1,2-alkanediol, which is safer for the human body (see Patent Document 1), a technique using a glycerol monoalkyl ether (see Patent Document 2), and a technique using ethyl 4-hydroxyphenylacetate (Patent Document). 3) etc. have been reported.
上記のように、1,2-アルカンジオール、グリセロールモノアルキルエーテルや4-ヒドロキシフェニル酢酸エチル等の従来の防腐抗菌剤では、ある程度の防腐抗菌効果が得られるものの、より高い防腐抗菌効果を発揮する防腐抗菌剤の開発が望まれている。 As described above, conventional antiseptic and antibacterial agents such as 1,2-alkanediol, glycerol monoalkyl ether and 4-hydroxyphenylacetate have some antiseptic and antibacterial effects, but exhibit higher antiseptic and antibacterial effects. The development of antiseptic and antibacterial agents is desired.
本発明は、上記現状に鑑みてなされたものであり、従来の防腐抗菌剤よりも高い防腐抗菌効果を発揮する化粧料用防腐抗菌剤を提供することを目的とする。 The present invention has been made in view of the above situation, and an object of the present invention is to provide a preservative antibacterial agent for cosmetics, which exhibits a higher antiseptic antibacterial effect than conventional antiseptic antibacterial agents.
本発明者は、化粧料用防腐抗菌剤について種々検討したところ、特定の構造のアミノ基含有単量体(A)由来の構造単位(a)と疎水性単量体(B)由来の構造単位(b)とを有し、重量平均分子量が4000~20万である共重合体が、従来の防腐抗菌剤よりも高い防腐抗菌効果を発揮することを見いだし、上記課題をみごとに解決することができることに想到し、本発明に到達したものである。 As a result of various studies on antiseptic and antibacterial agents for cosmetics, the present inventor has found that a structural unit (a) derived from an amino group-containing monomer (A) having a specific structure and a structural unit derived from a hydrophobic monomer (B) have a specific structure. It has been found that a copolymer having (b) and having a weight average molecular weight of 4000 to 200,000 exhibits a higher antiseptic and antibacterial effect than conventional antiseptic and antibacterial agents, and can solve the above-mentioned problems brilliantly. I came up with what I could do and arrived at the present invention.
すなわち本発明は、アミノ基含有単量体(A)由来の構造単位(a)と疎水性単量体(B)由来の構造単位(b)とを有し、重量平均分子量が4000~20万であり、
該アミノ基含有単量体(A)は、下記式(4)~(6);
以下に本発明を詳述する。
なお、以下において記載する本発明の個々の好ましい形態を2つ以上組み合わせたものもまた、本発明の好ましい形態である。
That is, the present invention has a structural unit (a) derived from the amino group-containing monomer (A) and a structural unit (b) derived from the hydrophobic monomer (B), and has a weight average molecular weight of 4000 to 200,000. And
The amino group-containing monomer (A) has the following formulas (4) to (6);
The present invention will be described in detail below.
It should be noted that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.
本発明における化粧料は人体の皮膚に直接施用する化粧品、医薬品、医薬部外品を意味し、化粧料には皮膚化粧料、皮膚外用剤及び頭髪化粧料等が含まれる。
本発明における化粧料用防腐抗菌剤とは、化粧料用途に用いられ、防腐性能及び/又は抗菌性能を有する剤のことをいう。防腐性能とは、微生物の侵入・発育・増殖を防止して、腐敗・発酵が起こらないようにする性能であり、抗菌性能とは、殺菌(微生物を殺す)、静菌(微生物の繁殖を抑える)滅菌、消毒、制菌、除菌、防カビ等の性能をいい、対象となる微生物は、細菌、真菌である。
The cosmetics in the present invention mean cosmetics, pharmaceuticals, quasi-drugs that are directly applied to the skin of the human body, and the cosmetics include skin cosmetics, external skin preparations, hair cosmetics and the like.
The antiseptic and antibacterial agent for cosmetics in the present invention refers to an agent that is used for cosmetics and has antiseptic and / or antibacterial performance. Antiseptic performance is the performance to prevent the invasion, growth and proliferation of microorganisms to prevent rot and fermentation, and antibacterial performance is sterilization (killing microorganisms) and bacteriostatic (suppressing the growth of microorganisms). ) It has good performance such as sterilization, disinfection, sterilization, sterilization, and antifungal properties, and the target microorganisms are bacteria and fungi.
上記細菌としては、大腸菌、緑膿菌、サルモネラ菌、モラクセラ菌、レジオネラ菌等のグラム陰性菌;黄色ブドウ球菌、クロストリジウム属細菌等のグラム陽性菌が挙げられる。上記真菌としてはカンジダ菌、ロドトルラ、パン酵母等の酵母類;赤カビ、黒カビ(クロコウジカビ、クロカワカビ)等のカビ類が挙げられる。 Examples of the above-mentioned bacteria include Gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, Salmonella, Moraxella, and Regionella; and Gram-positive bacteria such as Staphylococcus aureus and Clostridium. Examples of the fungus include yeasts such as Candida, Rhodotorula, and baker's yeast; and molds such as red mold and black mold (Aspergillus niger, Aspergillus niger).
本発明の化粧料用防腐抗菌剤(以下、単に本発明の防腐抗菌剤ともいう。)は、アミノ基含有単量体由来の構造単位と疎水性単量体由来の構造単位とを有する共重合体を含むものである。このような共重合体を含むことで防腐・抗菌性が発揮される理由は以下のように推定される。本発明の化粧料用防腐抗菌剤を、微生物に作用させると、共重合体が有するアミノ基含有単量体由来のアミノ基がマイナスの電荷を有する微生物の表面に吸着する。さらに共重合体が有する疎水基が細胞膜部分と親和性を示し、細胞膜と相互作用することにより、細胞膜を構成する脂質等の間の相互作用を破壊し、及び/又は、膜に結合しているタンパク質等の機能を阻害することにより、細胞が破壊され、及び/又は、細胞の生理活性が阻害され、微生物が死滅することが推定される。
上記共重合体は、高分子であるため、低分子化合物からなる従来のものよりも安全性が高く、また、水溶性であるため、化粧料への配合の制限が少ない。
さらに、本発明の化粧料用防腐抗菌剤は、化粧料に配合することによって、化粧料を乳化させる作用や、化粧料の粘度を増加させる作用も有し、乳化剤や増粘剤としての効果も発揮することができる。
The antiseptic antibacterial agent for cosmetics of the present invention (hereinafter, also simply referred to as the antiseptic antibacterial agent of the present invention) has a co-weight having a structural unit derived from an amino group-containing monomer and a structural unit derived from a hydrophobic monomer. It includes coalescence. The reason why the antiseptic and antibacterial properties are exhibited by including such a copolymer is presumed as follows. When the antiseptic antibacterial agent for cosmetics of the present invention is allowed to act on a microorganism, the amino group derived from the amino group-containing monomer of the copolymer is adsorbed on the surface of the microorganism having a negative charge. Furthermore, the hydrophobic group of the copolymer exhibits affinity with the cell membrane portion and interacts with the cell membrane to disrupt the interaction between lipids and the like constituting the cell membrane and / or bind to the membrane. It is presumed that by inhibiting the function of a protein or the like, the cell is destroyed and / or the physiological activity of the cell is inhibited and the microorganism is killed.
Since the copolymer is a polymer, it is safer than the conventional one made of a small molecule compound, and since it is water-soluble, there are few restrictions on its incorporation into cosmetics.
Further, the antiseptic antibacterial agent for cosmetics of the present invention has an effect of emulsifying the cosmetic and an effect of increasing the viscosity of the cosmetic by being blended with the cosmetic, and also has an effect as an emulsifier and a thickener. Can be demonstrated.
本発明の化粧料用防腐抗菌剤に含まれる共重合体は、アミノ基含有単量体(A)由来の構造単位(a)を有している。上記アミノ基含有単量体は、エチレン性不飽和基と、下記式(1); The copolymer contained in the antiseptic antibacterial agent for cosmetics of the present invention has a structural unit (a) derived from the amino group-containing monomer (A). The amino group-containing monomer has an ethylenically unsaturated group and the following formula (1);
(式中、R1及びR2は、同一又は異なって、水素原子、炭素数1~12の炭化水素基を表す。)で表される第1~3級アミノ基、又は、第1~3級アミノ基の酸による中和物、若しくは、第4級アンモニウム塩基とを有する単量体である。
上記炭化水素基は、鎖状構造であっても、環構造を有していてもよいが、鎖状構造であることが好ましい。炭化水素基が鎖状構造である場合、直鎖状であっても分岐を有していてもよい。
上記炭化水素基としては、アルキル基、アルケニル基、アリール基が好ましく、より好ましくはアルキル基、アルケニル基であり、更に好ましくはアルキル基である。
また、上記炭化水素基の炭素数としては、1~10が好ましく、より好ましくは1~8であり、更に好ましくは1~5であり、特に好ましくは1~2である。
上記R1及びR2のうち少なくともいずれか一方は、炭素数1~12の炭化水素基であることが好ましく、R1及びR2の両方が炭化水素基であることがより好ましい。すなわち、第1~3級アミノ基の中でも、第3級アミノ基が好ましい。
(In the formula, R 1 and R 2 are the same or different and represent a hydrogen atom and a hydrocarbon group having 1 to 12 carbon atoms.) The first to third-order amino groups or the first to third amino groups. It is a monomer having a neutralized product of a secondary amino group with an acid or a quaternary ammonium base.
The hydrocarbon group may have a chain structure or a ring structure, but a chain structure is preferable. When the hydrocarbon group has a chain structure, it may be linear or have a branch.
The hydrocarbon group is preferably an alkyl group, an alkenyl group or an aryl group, more preferably an alkyl group or an alkenyl group, and even more preferably an alkyl group.
The number of carbon atoms of the hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 5, and particularly preferably 1 to 2.
At least one of R 1 and R 2 is preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably both R 1 and R 2 are hydrocarbon groups. That is, among the primary to tertiary amino groups, a tertiary amino group is preferable.
上記第1~3級アミノ基としては、下記式(2); The primary to tertiary amino groups include the following formula (2);
(式中、R1、R2は、同一又は異なって、水素原子又は炭素数1~12の炭化水素基を表す。Y-は、陰イオンを表す。)で表される構造であることが好ましい。炭化水素基の具体例及び好ましい形態は、上述のとおりである。 (In the formula, R 1 and R 2 represent the same or different hydrocarbon atoms or hydrocarbon groups having 1 to 12 carbon atoms. Y − represents an anion.) preferable. Specific examples and preferred forms of the hydrocarbon group are as described above.
上記第4級アンモニウム塩基としては、下記式(3); As the quaternary ammonium base, the following formula (3);
(式中、R3~R5は、同一又は異なって、炭素数1~12の炭化水素基を表す。Y-は、陰イオンを表す。)で表される構造であることが好ましい。炭化水素基の具体例及び好ましい形態は、上述のとおりである。
上記炭素数1~12の炭化水素基としては、炭素数1~12のアルキル基、炭素数2~12のアルケニル基であることが好ましい。
R3~R5の炭素数としては、より好ましくは1~10であり、更に好ましくは1~7であり、特に好ましくは1~5である。
R3~R5の炭化水素基としては、メチル基又はエチル基が最も好ましい。
(In the formula, R 3 to R 5 represent the same or different hydrocarbon groups having 1 to 12 carbon atoms. Y − represents an anion.) It is preferable that the structure is represented by. Specific examples and preferred forms of the hydrocarbon group are as described above.
The hydrocarbon group having 1 to 12 carbon atoms is preferably an alkyl group having 1 to 12 carbon atoms and an alkenyl group having 2 to 12 carbon atoms.
The number of carbon atoms of R 3 to R 5 is more preferably 1 to 10, still more preferably 1 to 7, and particularly preferably 1 to 5.
As the hydrocarbon group of R 3 to R 5 , a methyl group or an ethyl group is most preferable.
上記式(2)及び(3)におけるY-は、特に制限されないが、例えば、塩素イオン、臭素イオン、ヨウ素イオン等のハロゲン化物イオン;硫酸メチルイオン等の硫酸アルキルイオン;酢酸イオン等の有機酸のイオン等が挙げられる。
上記式(2)におけるY-は、有機酸のイオンが好ましい。
上記式(3)におけるY-は、ハロゲン化物イオン、硫酸アルキルイオンが好ましい。
Y − in the above formulas (2) and (3) is not particularly limited, but is, for example, a halide ion such as a chlorine ion, a bromine ion or an iodine ion; an alkyl sulfate ion such as a methyl sulfate ion; an organic acid such as an acetate ion. Ions and the like can be mentioned.
For Y − in the above formula (2), an ion of an organic acid is preferable.
The Y − in the above formula (3) is preferably a halide ion or an alkyl sulfate ion.
上記アミノ基としては、第1~3級アミノ基、第1~3級アミノ基の酸による中和物及び第4級アンモニウム塩基の中でも、第3級アミノ基、第3級アミノ基の酸による中和物又は第4級アンモニウム塩基が好ましい。第3級アミノ基又は第3級アミノ基の酸による中和物としてはジメチルアミノ基、ジエチルアミノ基又はこれらの塩酸、酢酸等の酸による中和物が好ましい。 The amino groups include the acids of the tertiary amino group and the tertiary amino group among the neutralized products of the primary to tertiary amino groups and the acids of the primary to tertiary amino groups and the quaternary ammonium bases. Neutralized or quaternary ammonium bases are preferred. As the neutralized product of the tertiary amino group or the tertiary amino group with an acid, a dimethylamino group, a diethylamino group or a neutralized product of these with an acid such as hydrochloric acid or acetic acid is preferable.
上記アミノ基含有単量体(A)としては、下記式(4)~(6); The amino group-containing monomer (A) includes the following formulas (4) to (6);
(式(4)~(6)中、R6~R8は、同一又は異なって、水素原子又は炭素数1~5のアルキル基を表す。Xは、直接結合又は2価の連結基を表す。式(4)及び(5)中、R1、R2は、同一又は異なって、炭素数1~12の炭化水素基を表す。式(6)中、R3~R5は、同一又は異なって、炭素数1~12の炭化水素基を表す。Y-は、陰イオンを表す。)で表される構造であることが好ましい。 (In formulas (4) to (6), R 6 to R 8 represent the same or different alkyl groups having a hydrogen atom or 1 to 5 carbon atoms, and X represents a direct bond or a divalent linking group. In formulas (4) and (5), R 1 and R 2 represent the same or different hydrocarbon groups having 1 to 12 carbon atoms. In formula (6), R 3 to R 5 are the same or different. Differently, it represents a hydrocarbon group having 1 to 12 carbon atoms. Y − represents an anion.) It is preferable that the structure is represented by an anion.
上記R8における炭素数1~5のアルキル基は、メチル基であることが好ましい。上記R8としては、水素原子又はメチル基が好ましい。抗菌性及び耐加水分解性の観点からR8としてはメチル基がより好ましい。
上記R6、R7は、水素原子であることが好ましい。
The alkyl group having 1 to 5 carbon atoms in R8 is preferably a methyl group. The R 8 is preferably a hydrogen atom or a methyl group. From the viewpoint of antibacterial properties and hydrolysis resistance, a methyl group is more preferable as R8 .
It is preferable that R 6 and R 7 are hydrogen atoms.
上記式(4)及び(5)における2価の連結基としては、特に制限されないが、例えば、下記式(7); The divalent linking group in the above formulas (4) and (5) is not particularly limited, but for example, the following formula (7);
(式中、mは、0~12の整数を表す。)、下記式(8); (In the formula, m represents an integer from 0 to 12.), The following formula (8);
(式中、lは、0~4の整数を表す。)及び下記式(9); (In the formula, l represents an integer of 0 to 4) and the following formula (9);
(式中、kは、1~10の整数を表す。)で表される構造が挙げられる。 (In the formula, k represents an integer of 1 to 10).
上記式(6)における2価の連結基としては、上記式(7)~(9)で表される構造及び炭素数1~12のアルキレン基が挙げられる。
上記式(7)におけるmは、1~8であることが好ましく、より好ましくは1~5である。
上記式(9)におけるkは、1~8であることが好ましく、より好ましくは1~5である。
Examples of the divalent linking group in the above formula (6) include structures represented by the above formulas (7) to (9) and alkylene groups having 1 to 12 carbon atoms.
The m in the above formula (7) is preferably 1 to 8, and more preferably 1 to 5.
The k in the above formula (9) is preferably 1 to 8, and more preferably 1 to 5.
上記アミノ基含有単量体(A)として、具体的には、N,N-ジメチルアミノエチル(メタ)アクリレート、N,N-ジエチルアミノエチル(メタ)アクリレート、N,N-ジメチルアミノプロピル(メタ)アクリレート、N,N-ジエチルアミノプロピル(メタ)アクリレート等のN,N-ジアルキルアミノ基含有(メタ)アクリレート類及び上記モノマーに4級化剤を付加させたモノマー若しくはこれらの塩酸、酢酸等の酸による中和物;N,N-ジメチルアミノエチル(メタ)アクリルアミド、N,N-ジエチルアミノエチル(メタ)アクリルアミド、N,N-ジメチルアミノプロピル(メタ)アクリルアミド、N,N-ジエチルアミノプロピル(メタ)アクリルアミド等のN,N-ジアルキルアミノ基含有(メタ)アクリルアミド類及び上記モノマーに4級化剤を付加させたモノマー若しくはこれらの塩酸、酢酸等の酸による中和物;モノメチルアミノエチル(メタ)アクリレート、モノエチルアミノエチル(メタ)アクリレート、モノメチルアミノプロピル(メタ)アクリレート、モノエチルアミノプロピル(メタ)アクリレート、(メタ)アクリル酸2-(tert-ブチルアミノ)エチル等のモノアルキルアミノ基含有(メタ)アクリレート類及びこれらの塩酸、酢酸等の酸による中和物;モノメチルアミノエチル(メタ)アクリルアミド、モノエチルアミノエチル(メタ)アクリルアミド、モノメチルアミノプロピル(メタ)アクリルアミド、モノエチルアミノプロピル(メタ)アクリルアミド等のモノアルキルアミノ基含有(メタ)アクリルアミド類及びこれらの塩酸、酢酸等の酸による中和物;(メタ)アクリル酸-2-アミノエチル等の(メタ)アクリル酸とアルカノールアミンとのエステル類及びこれらの塩酸、酢酸等の酸による中和物;N,N-ジアリルメチルアミン及びこれに4級化剤を付加させたモノマー若しくはこれの塩酸、酢酸等の酸による中和物;アリルアミン及びこれの塩酸、酢酸等の酸による中和物;1-アリルオキシ-3-ジブチルアミノ-2-オール、1-アリルオキシ-3-ジエタノールアミノ-2-オール等の炭素数2~8の環状エーテル含有基を有する不飽和単量体と炭素数1~24のアミン化合物との付加反応物及びこれに4級化剤を付加させたモノマー若しくはこれの塩酸、酢酸等の酸による中和物等が挙げられる。 Specific examples of the amino group-containing monomer (A) include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth). N, N-dialkylamino group-containing (meth) acrylates such as acrylates and N, N-diethylaminopropyl (meth) acrylates, monomers having a quaternizing agent added to the above monomers, or acids such as hydrochloric acid and acetic acid thereof. Neutralized products; N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, etc. N, N-dialkylamino group-containing (meth) acrylamides and monomers obtained by adding a quaternizing agent to the above monomers or neutralized products of these with acids such as hydrochloric acid and acetic acid; monomethylaminoethyl (meth) acrylate, mono. Monoalkylamino group-containing (meth) acrylates such as ethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate, 2- (tert-butylamino) ethyl (meth) acrylate. Kinds and neutralized products of these with acids such as hydrochloric acid and acetic acid; monomethylaminoethyl (meth) acrylamide, monoethylaminoethyl (meth) acrylamide, monomethylaminopropyl (meth) acrylamide, monoethylaminopropyl (meth) acrylamide, etc. Monoalkylamino group-containing (meth) acrylamides and neutralized products of these with acids such as hydrochloric acid and acetic acid; esters of (meth) acrylic acids such as (meth) acrylic acid-2-aminoethyl and alkanolamines and these. Neutralized product with acid such as hydrochloric acid and acetic acid; N, N-diallylmethylamine and monomer added with a quaternizing agent or neutralized product with acid such as hydrochloric acid and acetic acid; Allylamine and hydrochloric acid thereof. , Neutralized with acid such as acetic acid; 1-allyloxy-3-dibutylamino-2-ol, 1-allyloxy-3-diethanolamino-2-ol, etc. Examples thereof include an addition reaction product of a saturated monomer and an amine compound having 1 to 24 carbon atoms, a monomer having a quaternizing agent added thereto, or a neutralized product thereof with an acid such as hydrochloric acid or acetic acid.
上記炭素数1~24のアミン化合物は、アミノ基を有し、炭素数2~8の環状エーテル含有基を有する不飽和単量体の環状エーテル構造と反応することができる限り特に制限されない。炭素数1~24のアミン化合物の炭素数は、1~20が好ましく、1~16がより好ましい。炭素数1~24のアミン化合物としては、第1級アミン、第2級アミンが挙げられ、例えば、炭素数1~24の(ジ)アルキルアミン、炭素数1~24の(ジ)アルカノールアミン、炭素数1~24のアルキルアルカノールアミン等が挙げられる。
炭素数1~24の(ジ)アルキルアミンとしては、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、ペンチルアミン、ジペンチルアミン、ヘキシルアミン、ジヘキシルアミン、ヘプチルアミン、ジヘプチルアミン、オクチルアミン、ジオクチルアミン、ドデシルアミン、ジドデシルアミン等が好ましい。
炭素数1~24の(ジ)アルカノールアミンとしては、メタノールアミン、エタノールアミン、プロパノールアミン、ブタノールアミン、ジメタノールアミン、ジエタノールアミン、ジプロパノールアミン、ジブタノールアミン、ヘキサノールアミン等が好ましい。
炭素数1~24のアルキルアルカノールアミンとしては、メチルエタノールアミン等が好ましい。
The amine compound having 1 to 24 carbon atoms is not particularly limited as long as it can react with the cyclic ether structure of the unsaturated monomer having an amino group and having a cyclic ether-containing group having 2 to 8 carbon atoms. The carbon number of the amine compound having 1 to 24 carbon atoms is preferably 1 to 20 and more preferably 1 to 16. Examples of the amine compound having 1 to 24 carbon atoms include primary amines and secondary amines, for example, (di) alkylamines having 1 to 24 carbon atoms, (di) alkanolamines having 1 to 24 carbon atoms, and the like. Examples thereof include alkylalkanolamines having 1 to 24 carbon atoms.
Examples of the (di) alkylamine having 1 to 24 carbon atoms include methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine and heptylamine. , Diheptylamine, octylamine, dioctylamine, dodecylamine, didodecylamine and the like are preferable.
As the (di) alkanolamine having 1 to 24 carbon atoms, methanolamine, ethanolamine, propanolamine, butanolamine, diethanolamine, diethanolamine, dipropanolamine, dibutanolamine, hexanolamine and the like are preferable.
As the alkylalkanolamine having 1 to 24 carbon atoms, methylethanolamine or the like is preferable.
上記アミノ基含有単量体(A)は、式(4)~(6)におけるR8が、メチル基であり、Xが、上記式(7)で表される構造であることが好ましい。 The amino group-containing monomer (A) preferably has a structure in which R8 in the formulas (4) to (6) is a methyl group and X is a structure represented by the above formula (7).
上記アミノ基含有単量体(A)として、好ましくは、N,N-ジアルキルアミノ基含有(メタ)アクリレート類及びこれらの塩酸、酢酸等の酸による中和物やこれらに4級化剤を付加させたモノマー、N,N-ジアルキルアミノ基含有(メタ)アクリルアミド類及びこれらの塩酸、酢酸等の酸による中和物やこれらに4級化剤を付加させたモノマー、中でもN,N-ジメチルアミノエチル(メタ)アクリレート、N,N-ジエチルアミノエチル(メタ)アクリレート、N,N-ジメチルアミノプロピル(メタ)アクリルアミド及びこれらの塩酸、酢酸等の酸による中和物やこれらに4級化剤を付加させたモノマーがより好ましい。
上記4級化剤としては、特に制限されるものではないが、塩化メチル、塩化エチル、臭化メチル、ヨウ化メチル等のハロゲン化アルキル;硫酸ジメチル、硫酸ジエチル、硫酸ジ-n-プロピル等のアルキル硫酸等の一般的なアルキル化剤が挙げられる。
アミノ基含有単量体は、第3級アミンでも第4級アンモニウムカチオンでもよいが、第3級アミンではグラム陰性菌、第4級アンモニウムカチオンではグラム陽性菌に対してより高い抗菌性を示すことになる。
As the amino group-containing monomer (A), N, N-dialkylamino group-containing (meth) acrylates, neutralized products of these with acids such as hydrochloric acid and acetic acid, and quaternizing agents are added thereto. Monomers, N, N-dialkylamino group-containing (meth) acrylamides and neutralized products of these with acids such as hydrochloric acid and acetic acid, and monomers with a quaternizing agent added to them, especially N, N-dimethylamino. Ethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, neutralized products of these with acids such as hydrochloric acid and acetic acid, and quaternizing agents are added thereto. The neutralized monomer is more preferable.
The quaternizing agent is not particularly limited, but is an alkyl halide such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide; dimethyl sulfate, diethyl sulfate, di-n-propyl sulfate and the like. Examples thereof include general alkylating agents such as alkyl sulfate.
The amino group-containing monomer may be a tertiary amine or a quaternary ammonium cation, but the tertiary amine exhibits higher antibacterial activity against Gram-negative bacteria and the quaternary ammonium cation against Gram-positive bacteria. become.
本発明の共重合体は、疎水性単量体(B)由来の構造単位(b)を有するものであり、疎水性単量体(B)は、単独重合を行って得られた単独重合体(ホモポリマー)の溶解性パラメータが15以下である。なお、溶解性パラメータが15以下であっても、アミノ基を有するものについては、アミノ基含有単量体(A)に含まれるものとする。
ここで、上記溶解性パラメータは、「POLYMER ENGINEERING AND SCIENCE」(1974年、Vol.14、No.2)の147~154ページに記載の方法によって計算される値である。
以下にその方法を概説する。単独重合体の溶解性パラメータ(δ)(cal/cm3)1/2は、該重合体を形成している構成単位の蒸発エネルギー(△ei)及びモル体積(△vi)に基づいて、下記の計算法により算出される。
δ=(△ei/△vi)1/2 (cal/cm3)1/2
The copolymer of the present invention has a structural unit (b) derived from the hydrophobic monomer (B), and the hydrophobic monomer (B) is a homopolymer obtained by homopolymerization. The solubility parameter of (homopolymer) is 15 or less. Even if the solubility parameter is 15 or less, those having an amino group are included in the amino group-containing monomer (A).
Here, the solubility parameter is a value calculated by the method described on pages 147 to 154 of "POLYMER ENGINEERING AND SCIENCE" (1974, Vol. 14, No. 2).
The method is outlined below. The solubility parameter (δ) (cal / cm 3 ) 1/2 of the homopolymer is as follows, based on the evaporation energy (Δei) and molar volume (Δvi) of the constituent units forming the polymer. It is calculated by the calculation method of.
δ = (△ ei / △ vi) 1/2 (cal / cm 3 ) 1/2
疎水性単量体を単独で重合した際に得られた単独重合体(ホモポリマー)に対する溶解性パラメータが15以下であれば、本発明の共重合体における疎水性が充分なものとなり、微生物の細胞膜に対する親和性が向上し、細胞膜との相互作用が増大することで、細胞膜の生理活性にダメージを与えるため、従来のポリマー型抗菌剤よりも抗菌性能に優れる。上記溶解性パラメータとして好ましくは14以下であり、より好ましくは13以下であり、更に好ましくは12以下である。上記溶解性パラメータとしては通常5以上である。 If the solubility parameter for the homopolymer obtained by polymerizing the hydrophobic monomer alone is 15 or less, the hydrophobicity in the copolymer of the present invention is sufficient, and the hydrophobicity of the microorganism is sufficient. By improving the affinity for the cell membrane and increasing the interaction with the cell membrane, the physiological activity of the cell membrane is damaged, so that the antibacterial performance is superior to that of the conventional polymer-type antibacterial agent. The solubility parameter is preferably 14 or less, more preferably 13 or less, and further preferably 12 or less. The solubility parameter is usually 5 or more.
上記疎水性単量体(B)としては、単独重合体での溶解性パラメータが15以下であれば特に制限されないが、(メタ)アクリル酸と置換基を有していてもよいアルコールとのエステル(置換基を有していてもよい(メタ)アクリレート)類;(メタ)アクリル酸、クロトン酸、α-アリルオキシアクリル酸及びこれらの塩等の不飽和モノカルボン酸類;スチレン等の芳香族ビニル系単量体;プロピレン等のオレフィン系単量体;酢酸ビニル等の不飽和アルコールとカルボン酸とのエステル;塩化ビニル等のハロゲン化ビニル;メチルビニルエーテル、エチルビニルエーテル等のアルキルビニルエーテル類;1-アリルオキシ-3-ブトキシプロパン-2-オール等の炭素数2~8の環状エーテル含有基を有する不飽和単量体と炭素数1~20のアルコールとの付加反応物;アリルアルコールのエチレンオキシド付加物、メタリルアルコールのエチレンオキシド付加物、イソプレノールのエチレンオキシド付加物等の炭素数2~20の不飽和アルコールのアルキレンオキシド付加物及びそれらの末端疎水変性物;N-ビニルピロリドン等の環状ビニル系単量体が挙げられる。
上記溶解性パラメータが15以下の疎水性単量体の中でも、炭素数が2以上のアルキル基を有するものが好ましい。疎水性単量体が、炭素数2以上のアルキル基を有することにより、微生物の細胞膜との親和性が増し、抗菌性がより向上する。
The hydrophobic monomer (B) is not particularly limited as long as the solubility parameter in the homopolymer is 15 or less, but it is an ester of (meth) acrylic acid and an alcohol which may have a substituent. ((Meta) acrylates that may have substituents); unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-allyloxyacrylic acid and salts thereof; aromatic vinyl such as styrene System monomers; Olefin-based monomers such as propylene; Esters of unsaturated alcohols such as vinyl acetate and carboxylic acids; Vinyl halides such as vinyl chloride; Alkyl vinyl ethers such as methyl vinyl ethers and ethyl vinyl ethers; 1-allyloxy Addition reaction product of unsaturated monomer having a cyclic ether-containing group having 2 to 8 carbon atoms such as -3-butoxypropane-2-ol and alcohol having 1 to 20 carbon atoms; ethylene oxide adduct of allyl alcohol, meta. Ester adducts of unsaturated alcohols having 2 to 20 carbon atoms such as ethylene oxide adducts of lyl alcohols and ethylene oxide adducts of isoprenol and their terminal hydrophobic modified products; cyclic vinyl monomers such as N-vinylpyrrolidone are mentioned. Be done.
Among the hydrophobic monomers having a solubility parameter of 15 or less, those having an alkyl group having 2 or more carbon atoms are preferable. When the hydrophobic monomer has an alkyl group having 2 or more carbon atoms, the affinity with the cell membrane of the microorganism is increased, and the antibacterial property is further improved.
上記不飽和モノカルボン酸の塩としては、金属塩が挙げられる。上記金属塩の金属としては、リチウム、ナトリウム、カリウム等のアルカリ金属が挙げられる。 Examples of the unsaturated monocarboxylic acid salt include metal salts. Examples of the metal of the metal salt include alkali metals such as lithium, sodium and potassium.
上記(メタ)アクリレートにおける置換基としては、水酸基;メトキシ基、エトキシ基等の炭素数1~18のアルコキシ基;オキシアルキレン基、スルホン酸基、リン酸基等のオキソ基含有基;フルオロ基等のハロゲノ基;グリシジル基等のエポキシ基;アルデヒド基等のカルボニル基等が挙げられる。 Examples of the substituent in the (meth) acrylate include a hydroxyl group; an alkoxy group having 1 to 18 carbon atoms such as a methoxy group and an ethoxy group; an oxo group-containing group such as an oxyalkylene group, a sulfonic acid group and a phosphoric acid group; a fluoro group and the like. Harogeno group; epoxy group such as glycidyl group; carbonyl group such as aldehyde group and the like.
上記のような置換基を有していてもよい(メタ)アクリレートとしては、特に制限されないが、下記一般式(10); The (meth) acrylate which may have the above-mentioned substituent is not particularly limited, but the following general formula (10);
(式中、R9は、水素原子又はメチル基を表す。R10は、置換基を有していてもよい炭化水素基を表す。)で表される化合物であることが好ましい。
置換基を有していてもよい炭化水素基とは、炭化水素基の水素原子の1つ又は2つ以上が、炭化水素基以外の基で置換された基をいう。置換基を有する炭化水素基であって、置換基が(ポリ)オキシアルキレン基を有する場合、該炭化水素基の炭素数は、3~200であることが好ましい。少なくとも置換基が(ポリ)オキシアルキレン基を有しない場合、置換基を有していてもよい炭化水素基の炭素数は1~30であることが好ましい。上記置換基を有していてもよい炭化水素基の炭素数は、置換基を有している場合には、置換基に含まれる炭素の数も上記炭素数に入れるものとする。
(In the formula, R 9 represents a hydrogen atom or a methyl group. R 10 represents a hydrocarbon group which may have a substituent.) It is preferably a compound represented by.
The hydrocarbon group which may have a substituent means a group in which one or two or more hydrogen atoms of the hydrocarbon group are substituted with a group other than the hydrocarbon group. When the hydrocarbon group has a substituent and the substituent has a (poly) oxyalkylene group, the number of carbon atoms of the hydrocarbon group is preferably 3 to 200. At least when the substituent does not have a (poly) oxyalkylene group, the hydrocarbon group which may have a substituent preferably has 1 to 30 carbon atoms. The number of carbon atoms of the hydrocarbon group which may have the above-mentioned substituent shall include the number of carbons contained in the substituent when the above-mentioned substituent is included in the above-mentioned carbon number.
上記炭化水素基としては、特に制限されず、アルキル基、アルケニル基、アルキニル基等の鎖状炭化水素基、芳香族炭化水素基、シクロアルキル基、シクロアルケニル基等の環状炭化水素基が挙げられる。
上記アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、2-エチルヘキシル基、イソオクチル基、ノニル基、2,3,5-トリメチルヘキシル基、デシル基、ウンデシル基、4-エチル-5-メチルオクチル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基等の直鎖又は分岐鎖のアルキル基が挙げられる。
上記アルケニル基としては、例えば、ビニル基、アリル基、1-ブテニル基、2-ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ドデセニル基、オクタデセニル基、イコセニル基等が挙げられる。
上記アルキニル基としては、例えば、エチニル基、1-プロピニル基、2-プロピニル基、ブチニル基、ペンチニル基、ヘキシニル基、ヘプチニル基、オクチニル基、ノニニル基、デシニル基、ドデシニル基、オクタデシニル基、イコシニル基等が挙げられる。
The hydrocarbon group is not particularly limited, and examples thereof include a chain hydrocarbon group such as an alkyl group, an alkenyl group, and an alkynyl group, and a cyclic hydrocarbon group such as an aromatic hydrocarbon group, a cycloalkyl group, and a cycloalkenyl group. ..
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and a hexyl group. Heptyl group, octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, 2,3,5-trimethylhexyl group, decyl group, undecyl group, 4-ethyl-5-methyloctyl group, dodecyl group, tridecyl group, tetradecyl Examples thereof include a linear or branched alkyl group such as a group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group.
Examples of the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, an octadecenyl group and an icosenyl group. And so on.
Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, a dodecynyl group, an octadecynyl group and an icocinyl group. And so on.
上記芳香族炭化水素基としては、例えば、フェニル基、ベンジル基、トリル基、o-キシリル基等が挙げられる。
上記シクロアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等が挙げられる。
上記シクロアルケニル基としては、例えば、シクロプロペニル基、シクロブテニル基、シクロペンテニル基、シクロヘキセニル基等が挙げられる。
Examples of the aromatic hydrocarbon group include a phenyl group, a benzyl group, a tolyl group, an o-kisilyl group and the like.
Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group and the like.
上記のような置換基を有しないアルキル(メタ)アクリレートとしては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、sec-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、n-オクチル(メタ)アクリレート、トリデシル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート等のシクロアルキル(メタ)アクリレート、n-ラウリル(メタ)アクリレート、ドデシル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソボルニルメタクリレート等が挙げられる。 Examples of the alkyl (meth) acrylate having no substituent as described above include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. ) Acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) ) Cycloalkyl (meth) acrylates such as acrylates, n-lauryl (meth) acrylates, dodecyl (meth) acrylates, stearyl (meth) acrylates, isobornyl methacrylates and the like.
水酸基含有(メタ)アクリレートとしては、例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレートなどのエステル基の炭素数が1~18の水酸基含有(メタ)アクリレート等が挙げられる。 Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxy. Examples thereof include hydroxyl group-containing (meth) acrylates having 1 to 18 carbon atoms in ester groups such as butyl (meth) acrylates.
アルコキシ基含有(メタ)アクリレートとしては、例えば、メトキシエチル(メタ)アクリレート、メトキシプロピル(メタ)アクリレート、メトキシブチル(メタ)アクリレート、エトキシブチル(メタ)アクリレート、トリメチロールプロパントリプロポキシ(メタ)アクリレート等が挙げられる。 Examples of the alkoxy group-containing (meth) acrylate include methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, methoxybutyl (meth) acrylate, ethoxybutyl (meth) acrylate, and trimethylolpropane tripropoxy (meth) acrylate. Can be mentioned.
オキソ基含有(メタ)アクリレートとしては、例えば、スルホプロピル(メタ)アクリレート;(メタ)アクリロイルオキシエチルホスフェート等が挙げられる。 Examples of the oxo group-containing (meth) acrylate include sulfopropyl (meth) acrylate; (meth) acryloyloxyethyl phosphate and the like.
フルオロ基含有(メタ)アクリレートとしては、例えば、トリフルオロエチル(メタ)アクリレート、テトラフルオロプロピル(メタ)アクリレート、オクタフルオロペンチル(メタ)アクリレートなどのエステル基の炭素数が2~6のフルオロ基含有アルキル(メタ)アクリレート等が挙げられる。 Examples of the fluorogroup-containing (meth) acrylate include a fluorogroup having 2 to 6 carbon atoms in an ester group such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and octafluoropentyl (meth) acrylate. Examples thereof include alkyl (meth) acrylate.
エポキシ基含有(メタ)アクリレートとしては、例えば、グリシジル(メタ)アクリレート、α-メチルグリシジル(メタ)アクリレート等が挙げられる。 Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate.
カルボニル基含有(メタ)アクリレートとしては、例えば、アセトニル(メタ)アクリレート、ジアセトン(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレートアセチルアセテート、ブタンジオール-1,4-アクリレートアセチルアセテート、2-(アセトアセトキシ)エチル(メタ)アクリレート、(メタ)アクリロイルオキシアルキルプロペナール等が挙げられる。 Examples of the carbonyl group-containing (meth) acrylate include acetoxy (meth) acrylate, diacetone (meth) acrylate, 2-hydroxypropyl (meth) acrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate, and 2- (aceto). Examples thereof include acetoxy) ethyl (meth) acrylate and (meth) acryloyloxyalkylpropenal.
上記疎水性単量体(B)は、少なくとも1種の(メタ)アクリル酸エステルを含むものが好ましい。
上記(メタ)アクリル酸エステルとしては、上記式(10)で表される化合物であって、式(10)のR10の炭化水素基の炭素数が、1~20である化合物であることが好ましい。
上記式(10)のR10の炭化水素基の炭素数は、より好ましくは1~16であり、更に好ましくは1~12であり、特に好ましくは1~8であり、最も好ましくは2~8である。
上記炭化水素基の炭素数が1~20であれば、重合体の水溶性、粘度を好適な範囲とすることができ、取扱いに優れるものとなる。上記炭化水素基の炭素数が1~12であれば、重合体の製造が容易となり、さらに、抗菌性に加えて安全性にも優れるものとなる。さらに上記炭化水素基の炭素数が2~8であれば、重合体の製造が容易であるだけでなく、安全性に優れ、かつ微生物の細胞膜との親和性が増し、抗菌性がより向上するものとなる。
上記炭化水素基として、好ましくはアルキル基、アルケニル基であり、より好ましくはアルキル基である。
すなわち上記(メタ)アクリル酸エステルとしては、(メタ)アクリル酸アルキルエステル(アルキル(メタ)アクリレート)が好ましく、疎水性単量体(B)は、少なくとも1種の(メタ)アクリル酸アルキルエステルを含むことが好ましい。
The hydrophobic monomer (B) preferably contains at least one (meth) acrylic acid ester.
The (meth) acrylic acid ester may be a compound represented by the above formula (10) and having a hydrocarbon group of R10 of the formula ( 10 ) having 1 to 20 carbon atoms. preferable.
The hydrocarbon group of R10 of the above formula ( 10 ) has more preferably 1 to 16 carbon atoms, further preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and most preferably 2 to 8 carbon atoms. Is.
When the number of carbon atoms of the hydrocarbon group is 1 to 20, the water solubility and viscosity of the polymer can be in a suitable range, and the handling is excellent. When the hydrocarbon group has 1 to 12 carbon atoms, the polymer can be easily produced, and the safety is excellent in addition to the antibacterial property. Further, when the hydrocarbon group has 2 to 8 carbon atoms, not only the polymer can be easily produced, but also the safety is excellent, the affinity with the cell membrane of the microorganism is increased, and the antibacterial property is further improved. It becomes a thing.
The hydrocarbon group is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.
That is, the (meth) acrylic acid ester is preferably a (meth) acrylic acid alkyl ester (alkyl (meth) acrylate), and the hydrophobic monomer (B) is at least one (meth) acrylic acid alkyl ester. It is preferable to include it.
アルキル(メタ)アクリレートとして好ましくはメチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、sec-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、n-オクチル(メタ)アクリレートであり、より好ましくは、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-プロピル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、sec-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレートである。 The alkyl (meth) acrylate is preferably methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-. Butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, more preferably methyl (meth) acrylate, ethyl (meth) acrylate, n- With propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate. be.
本発明の防腐抗菌剤に含まれる共重合体はまた、疎水性単量体(B)として、(メタ)アクリル酸アルキルエステル由来の構造単位と、更に溶解性パラメータが15以下であって、カルボキシル基、水酸基及びエーテル基からなる群より選択される少なくとも1種の官能基を有するモノマー由来の構造単位とを有するものであることが好ましい。このような構造単位を有する共重合体もまた、本発明の好適な実施形態の1つである。
上記カルボキシル基、水酸基及びエーテル基からなる群より選択される少なくとも1種の官能基を有するモノマーは、溶解性パラメータが15以下であって、カルボキシル基、水酸基及びエーテル基のいずれかの官能基を有しているものであればよく、(メタ)アクリル酸エステル構造を有しているものであっても、カルボキシル基、水酸基及びエーテル基からなる群より選択される少なくとも1種の官能基を有するモノマーに分類するものとする。
本発明において、疎水性単量体(B)として、上記(メタ)アクリル酸アルキルエステルとカルボキシル基、水酸基及びエーテル基からなる群より選択される少なくとも1種の官能基を有するモノマーとを共重合することにより、得られる共重合体の水溶性が向上し、また、塩やpHによる共重合体の析出、抗菌性の低下等の影響をより充分に緩和することができるため、幅広いpH領域において共重合体を使用することができ、弱酸性のものが多い化粧品用途に好適に用いることができる。
上記カルボキシル基、水酸基及びエーテル基からなる群より選択される少なくとも1種の官能基を有するモノマーとしては、上述の不飽和モノカルボン酸類;水酸基含有(メタ)アクリレート;アルキルビニルエーテル類;炭素数2~20の不飽和アルコールのアルキレンオキシド付加物;炭素数2~8の環状エーテル含有基を有する不飽和単量体と炭素数1~20のアルコールとの付加反応物等が挙げられる。
The copolymer contained in the antiseptic antibacterial agent of the present invention also has a structural unit derived from a (meth) acrylic acid alkyl ester as a hydrophobic monomer (B) and a solubility parameter of 15 or less, and is carboxyl. It preferably has a structural unit derived from a monomer having at least one functional group selected from the group consisting of a group, a hydroxyl group and an ether group. Copolymers having such structural units are also one of the preferred embodiments of the present invention.
The monomer having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group has a solubility parameter of 15 or less and has any functional group of a carboxyl group, a hydroxyl group and an ether group. It may have at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group, even if it has a (meth) acrylic acid ester structure. It shall be classified as a monomer.
In the present invention, as the hydrophobic monomer (B), the above (meth) acrylic acid alkyl ester is copolymerized with a monomer having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group. By doing so, the water solubility of the obtained copolymer is improved, and the influences such as precipitation of the copolymer due to salt and pH and deterioration of antibacterial property can be more sufficiently mitigated. Therefore, in a wide pH range. A copolymer can be used, and it can be suitably used for cosmetic applications in which many are weakly acidic.
Examples of the monomer having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group include the above-mentioned unsaturated monocarboxylic acids; hydroxyl group-containing (meth) acrylates; alkyl vinyl ethers; 2 to 2 carbon atoms. Examples thereof include an alkylene oxide adduct of 20 unsaturated alcohols; an addition reaction product of an unsaturated monomer having a cyclic ether-containing group having 2 to 8 carbon atoms and an alcohol having 1 to 20 carbon atoms.
カルボキシル基、水酸基及びエーテル基からなる群より選択される少なくとも1種の官能基を有するモノマーとしては、不飽和モノカルボン酸類;水酸基含有(メタ)アクリレート;炭素数2~20の不飽和アルコールのアルキレンオキシド付加物;炭素数2~8の環状エーテル含有基を有する不飽和単量体と炭素数1~20のアルコールとの付加反応物が好ましい。
上記不飽和モノカルボン酸類としては、(メタ)アクリル酸及びこれらの塩が好ましい。
上記水酸基含有(メタ)アクリレートとしては、2-ヒドロキシエチル(メタ)アクリレートが好ましい。
Examples of the monomer having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group include unsaturated monocarboxylic acids; hydroxyl group-containing (meth) acrylates; and alkylenes of unsaturated alcohols having 2 to 20 carbon atoms. Oxide adduct; an addition reaction product of an unsaturated monomer having a cyclic ether-containing group having 2 to 8 carbon atoms and an alcohol having 1 to 20 carbon atoms is preferable.
As the unsaturated monocarboxylic acids, (meth) acrylic acid and salts thereof are preferable.
As the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate is preferable.
上記炭素数2~20の不飽和アルコールの炭素数は、2~18であることが好ましく、炭素数2~20の不飽和アルコールとしては、ビニルアルコール、アリルアルコール、イソプレニルアルコール(イソプレノール)等が挙げられる。
上記炭素数2~20の不飽和アルコールのアルキレンオキシド付加物におけるアルキレンオキシドの炭素数は、2~20であることが好ましく、より好ましくは、2~8であり、更に好ましくは2~6であり、特に好ましくは2~4であり、最も好ましくは2~3である。上記アルキレンオキシドとしては、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、イソブチレンオキシド、1-ブテンオキシド、2-ブテンオキシド、スチレンオキシド等が挙げられる。より好ましくは、エチレンオキシド、プロピレンオキシド、ブチレンオキシドであり、更に好ましくは、エチレンオキシド、プロピレンオキシドである。
上記アルキレンオキシドの平均付加モル数は、1~100であることが好ましい。より好ましくは、1~80であり、更に好ましくは、1~70であり、特に好ましくは、1~50である。
上記炭素数2~20の不飽和アルコールのアルキレンオキシド付加物としては、イソプレノールのエチレンオキシド付加物が好ましい。
The unsaturated alcohol having 2 to 20 carbon atoms preferably has 2 to 18 carbon atoms, and examples of the unsaturated alcohol having 2 to 20 carbon atoms include vinyl alcohol, allyl alcohol, and isoprenil alcohol (isoprenol). Can be mentioned.
The carbon number of the alkylene oxide in the unsaturated alcohol alkylene oxide adduct having 2 to 20 carbon atoms is preferably 2 to 20, more preferably 2 to 8, and further preferably 2 to 6. , Particularly preferably 2 to 4, and most preferably 2 to 3. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, and styrene oxide. Ethylene oxide, propylene oxide and butylene oxide are more preferable, and ethylene oxide and propylene oxide are more preferable.
The average number of moles of the alkylene oxide added is preferably 1 to 100. It is more preferably 1 to 80, still more preferably 1 to 70, and particularly preferably 1 to 50.
As the alkylene oxide adduct of the unsaturated alcohol having 2 to 20 carbon atoms, an ethylene oxide adduct of isoprenol is preferable.
上記炭素数1~20のアルコールとしては、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール等のアルキルアルコールが挙げられる。好ましくはエタノール、プロパノール、ブタノール等の炭素数2~16のアルキルアルコールである。
上記炭素数2~8の環状エーテル含有基を有する不飽和単量体と炭素数1~20のアルコールとの付加反応物としては1-アリルオキシ-3-ブトキシプロパン-2-オールが好ましい。
Examples of the alcohol having 1 to 20 carbon atoms include alkyl alcohols such as methanol, ethanol, propanol, butanol, pentanol and hexanol. It is preferably an alkyl alcohol having 2 to 16 carbon atoms such as ethanol, propanol and butanol.
As the addition reaction product of the unsaturated monomer having a cyclic ether-containing group having 2 to 8 carbon atoms and the alcohol having 1 to 20 carbon atoms, 1-allyloxy-3-butoxypropane-2-ol is preferable.
本発明の共重合体は、上記アミノ基含有単量体(A)及び疎水性単量体(B)以外のその他の単量体由来の構造単位を有していてもよい。その他の単量体としては、アミノ基を有しないものであって、アミノ基含有単量体及び疎水性単量体と共重合できるものである限り特に制限されない。その他の単量体の単独重合体での溶解性パラメータは、15以下であっても、15を超えるものであってもよい。その他の単量体の溶解性パラメータが15以下であっても、15を超えるものであっても、上記疎水性単量体を好ましい割合で重合している限り、共重合体としての疎水性は充分に維持されることとなる。
また、粘度を調整する観点から溶解性パラメータの値にかかわらずエチレン性不飽和基を2個以上有する単量体が含まれていてもよい。エチレン性不飽和基を2個以上有する単量体としては、エチレングリコール、プロピレングリコール、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、グリセリン、ポリグリセリン、トリメチロールプロパン、ペンタエリスリトール、サッカロース、ソルビトール、1,4-ブタンジオール等のポリオールの2置換以上の水酸基と(メタ)アクリル酸とのエステル類;上記ポリオールの2置換以上のメタクリル酸エステル類;上記ポリオールの2置換以上の水酸基とアリルアルコール、ビニルアルコール等の不飽和アルコールとのエーテル類;フタル酸ジアリル、リン酸トリアリル、メタクリル酸アリル、テトラアリルオキシエタン、トリアリルシアヌレート、アジピン酸ジビニル、クロトン酸ビニル、1,5-ヘキサジエン、ジビニルベンゼン等が挙げられる。これらのその他の単量体は、単独で用いてもよく、2種以上を併用してもよい。
抗菌性を向上させる観点から、本発明はその他の単量体として重合性金属塩を共重合していてもよい。重合性金属塩としてはアクリル酸亜鉛、メタクリル酸亜鉛、α-アリルオキシアクリル酸亜鉛等の不飽和カルボン酸の重金属塩が挙げられる。
The copolymer of the present invention may have a structural unit derived from other monomers other than the amino group-containing monomer (A) and the hydrophobic monomer (B). The other monomer is not particularly limited as long as it does not have an amino group and can be copolymerized with the amino group-containing monomer and the hydrophobic monomer. The solubility parameter of the other monomer in the homopolymer may be 15 or less or more than 15. Regardless of whether the solubility parameter of the other monomer is 15 or less or more than 15, the hydrophobicity as a copolymer is as long as the above hydrophobic monomer is polymerized at a preferable ratio. It will be sufficiently maintained.
Further, from the viewpoint of adjusting the viscosity, a monomer having two or more ethylenically unsaturated groups may be contained regardless of the value of the solubility parameter. Examples of the monomer having two or more ethylenically unsaturated groups include ethylene glycol, propylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, polyglycerin, trimethylolpropane, pentaerythritol, saccharose, sorbitol, 1, Esters of 2-substituted or more hydroxyl groups of polyols such as 4-butanediol and (meth) acrylic acid; 2-substituted or more methacrylic acid esters of the above polyols; 2-substituted or more hydroxyl groups of the polyols and allyl alcohols, vinyl alcohols Ethers with unsaturated alcohols such as diallyl phthalate, triallyl phosphate, allyl methacrylate, tetraallyloxyetane, triallyl cyanurate, divinyl adipate, vinyl crotonate, 1,5-hexadiene, divinylbenzene, etc. Can be mentioned. These other monomers may be used alone or in combination of two or more.
From the viewpoint of improving the antibacterial property, the present invention may copolymerize a polymerizable metal salt as another monomer. Examples of the polymerizable metal salt include heavy metal salts of unsaturated carboxylic acids such as zinc acrylate, zinc methacrylate and zinc α-allyloxyacrylate.
本発明の共重合体は、共重合体における疎水性単量体(B)由来の構造単位の含有割合が、共重合体におけるアミノ基含有単量体(A)由来の構造単位(a)100質量%に対して、0.1~99.9質量%であることが好ましい。より好ましくは0.5~90質量%、更に好ましくは1~80質量%であり、一層好ましくは2~70質量%であり、より一層好ましくは3~64質量%であり、更に一層好ましくは4~60質量%であり、特に好ましくは5~50質量%であり、特に一層好ましくは5~40質量%であり、最も好ましくは5~30質量%である。本発明の共重合体における疎水性単量体(B)由来の構造単位の含有割合がこのような範囲であれば、上記共重合体の抗菌性能が向上し、特に、外膜を有する大腸菌や緑膿菌等のグラム陰性菌に対して高い抗菌性能を示す傾向にある。 In the copolymer of the present invention, the content ratio of the structural unit derived from the hydrophobic monomer (B) in the copolymer is the structural unit (a) 100 derived from the amino group-containing monomer (A) in the copolymer. It is preferably 0.1 to 99.9% by mass with respect to the mass%. It is more preferably 0.5 to 90% by mass, further preferably 1 to 80% by mass, still more preferably 2 to 70% by mass, still more preferably 3 to 64% by mass, and even more preferably 4 It is about 60% by mass, particularly preferably 5 to 50% by mass, still more preferably 5 to 40% by mass, and most preferably 5 to 30% by mass. When the content ratio of the structural unit derived from the hydrophobic monomer (B) in the copolymer of the present invention is within such a range, the antibacterial performance of the above-mentioned copolymer is improved, and in particular, Escherichia coli having an outer membrane and Escherichia coli. It tends to show high antibacterial performance against gram-negative bacteria such as Pseudomonas aeruginosa.
本発明の共重合体は上述のとおり、疎水性単量体(B)として、(メタ)アクリル酸アルキルエステル由来の構造単位と、更にカルボキシル基、水酸基及びエーテル基からなる群より選択される少なくとも1種の官能基を有するモノマー由来の構造単位とを有していてもよく、上記共重合体におけるカルボキシル基、水酸基及びエーテル基からなる群より選択される少なくとも1種の官能基を有するモノマー由来の構造単位の割合は、(メタ)アクリル酸アルキルエステル由来の構造単位100質量%に対して、0~100質量%であることが好ましい。より好ましくは0~50質量%である。 As described above, the copolymer of the present invention is selected as the hydrophobic monomer (B) from at least a group consisting of a structural unit derived from a (meth) acrylic acid alkyl ester and a carboxyl group, a hydroxyl group and an ether group. It may have a structural unit derived from a monomer having one kind of functional group, and may be derived from a monomer having at least one kind of functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group in the above copolymer. The ratio of the structural unit of is preferably 0 to 100% by mass with respect to 100% by mass of the structural unit derived from the (meth) acrylic acid alkyl ester. More preferably, it is 0 to 50% by mass.
本発明の共重合体は、共重合体を形成する構造単位の総量100質量%に対して、アミノ基含有単量体(A)由来の構造単位(a)を0.01~99.9質量%の割合で有することが好ましい。より好ましくは0.1~99質量%、更に好ましくは1~98質量%であり、一層好ましくは10~97質量%であり、より一層好ましくは30~96質量%であり、更に一層好ましくは36~96質量%であり、特に好ましくは50~95質量%であり、特に一層好ましくは60~95質量%であり、最も好ましくは70~95質量%である。
本発明の共重合体は、共重合体を形成する構造単位の総量100質量%に対して、疎水性単量体(B)由来の構造単位(b)を0.01~90質量%の割合で有することが好ましい。より好ましくは0.05~80質量%、更に好ましくは0.1~70質量%であり、一層好ましくは0.2~64質量%であり、より一層好ましくは0.5~60質量%であり、更に一層好ましくは1~50質量%であり、特に好ましくは3~50質量%であり、特に一層好ましくは4~40質量%であり、最も好ましくは5~30質量%である。
The copolymer of the present invention contains 0.01 to 99.9 mass of the structural unit (a) derived from the amino group-containing monomer (A) with respect to 100% by mass of the total amount of the structural units forming the copolymer. It is preferable to have it in a ratio of%. It is more preferably 0.1 to 99% by mass, still more preferably 1 to 98% by mass, still more preferably 10 to 97% by mass, still more preferably 30 to 96% by mass, and even more preferably 36. It is ~ 96% by mass, particularly preferably 50 to 95% by mass, more preferably 60 to 95% by mass, and most preferably 70 to 95% by mass.
The copolymer of the present invention contains 0.01 to 90% by mass of the structural unit (b) derived from the hydrophobic monomer (B) with respect to 100% by mass of the total amount of the structural units forming the copolymer. It is preferable to have it in. It is more preferably 0.05 to 80% by mass, further preferably 0.1 to 70% by mass, still more preferably 0.2 to 64% by mass, and even more preferably 0.5 to 60% by mass. It is even more preferably 1 to 50% by mass, particularly preferably 3 to 50% by mass, even more preferably 4 to 40% by mass, and most preferably 5 to 30% by mass.
本発明の共重合体の疎水性単量体(B)由来の構造単位として(メタ)アクリル酸アルキルエステル由来の構造単位を有する場合、共重合体を形成する構造単位の総量100質量%に対して、(メタ)アクリル酸アルキルエステル由来の構造単位の割合が、0.01~60質量%であることが好ましい。より好ましくは1~50質量%、更に好ましくは3~40質量%である。 When the structural unit derived from the (meth) acrylic acid alkyl ester is used as the structural unit derived from the hydrophobic monomer (B) of the copolymer of the present invention, the total amount of the structural units forming the copolymer is 100% by mass. The ratio of the structural unit derived from the (meth) acrylic acid alkyl ester is preferably 0.01 to 60% by mass. It is more preferably 1 to 50% by mass, still more preferably 3 to 40% by mass.
本発明の防腐抗菌剤は、共重合体を形成する構造単位の総量100質量%に対して、その他の単量体(E)由来の構造単位(e)の含有割合が、0~10質量%であることが好ましい。より好ましくは、0~8質量%、更に好ましくは0~5質量%である。その他の単量体の中でもエチレン性不飽和基を2個以上有する単量体由来の構造単位の含有割合は、共重合体を形成する構造単位の総量100質量%に対して0~1質量%であることが好ましく、より好ましくは、0~0.5質量%、更に好ましくは0~0.1質量%である。 In the antiseptic antibacterial agent of the present invention, the content ratio of the structural unit (e) derived from the other monomer (E) is 0 to 10% by mass with respect to the total amount of the structural unit forming the copolymer of 100% by mass. Is preferable. It is more preferably 0 to 8% by mass, still more preferably 0 to 5% by mass. Among other monomers, the content ratio of the structural unit derived from the monomer having two or more ethylenically unsaturated groups is 0 to 1% by mass with respect to the total amount of 100% by mass of the structural units forming the copolymer. It is preferably 0 to 0.5% by mass, more preferably 0 to 0.1% by mass.
本発明の防腐抗菌剤に含まれる共重合体としては、アミノ基含有単量体(A)由来の構造単位(a)と疎水性単量体(B)由来の構造単位(b)のみからなる共重合体もまた、好ましい形態の1つである。この場合、構造単位(a)と(b)の割合の合計は、100質量%であり、構造単位(a)又は(b)の割合は、100質量%から上述の構造単位(b)又は(a)の割合を差し引いた値となる。 The copolymer contained in the antiseptic antibacterial agent of the present invention comprises only the structural unit (a) derived from the amino group-containing monomer (A) and the structural unit (b) derived from the hydrophobic monomer (B). Copolymers are also one of the preferred forms. In this case, the total of the ratios of the structural units (a) and (b) is 100% by mass, and the ratio of the structural units (a) or (b) is from 100% by mass to the above-mentioned structural unit (b) or ( It is the value obtained by subtracting the ratio of a).
本発明の化粧料用防腐抗菌剤が含む共重合体の重量平均分子量は、4000~100万である。上記共重合体の重量平均分子量がこのような範囲であれば、防腐抗菌剤を使用する素材に対する防腐抗菌剤の吸着性が向上するため、洗浄した際に洗い流されることを充分に抑制し、上記素材に対する抗菌作用が向上する。
上記重量平均分子量として好ましくは4000~80万であり、より好ましくは5000~60万であり、更に好ましくは6000~40万であり、一層好ましくは7000~20万であり、更に一層好ましくは7000~10万であり、特に好ましくは7000~8万である。共重合体の重量平均分子量は、実施例に記載の方法により測定することができる。
The weight average molecular weight of the copolymer contained in the antiseptic antibacterial agent for cosmetics of the present invention is 40 to 1 million. When the weight average molecular weight of the copolymer is in such a range, the adsorptivity of the antiseptic antibacterial agent to the material using the antiseptic antibacterial agent is improved. The antibacterial effect on the material is improved.
The weight average molecular weight is preferably 40,000 to 800,000, more preferably 5,000 to 600,000, still more preferably 6,000 to 400,000, still more preferably 7,000 to 200,000, and even more preferably 7,000 to 7,000. It is 100,000, particularly preferably 7,000 to 80,000. The weight average molecular weight of the copolymer can be measured by the method described in Examples.
本発明の化粧料用防腐抗菌剤が含む共重合体の構造はランダム共重合体構造、グラフト構造、ブロック共重合体構造、グラジエント共重合体構造、星形構造、デンドリマー構造などが挙げられるが、いずれの構造であってもよい。 Examples of the copolymer structure contained in the antiseptic antibacterial agent for cosmetics of the present invention include a random copolymer structure, a graft structure, a block copolymer structure, a gradient copolymer structure, a star-shaped structure, and a dendrimer structure. Any structure may be used.
<共重合体の製造方法>
本発明の共重合体の製造は特に制限されないが、単量体成分を重合することにより製造することができ、単量体成分の具体例及び好ましい例は、上述のとおりである。また、単量体成分における単量体(A)、(B)及び(E)の好ましい含有割合は、上述の共重合体における構造単位(a)、(b)及び(e)の好ましい割合と同様である。
<Method for producing copolymer>
The production of the copolymer of the present invention is not particularly limited, but it can be produced by polymerizing the monomer component, and specific examples and preferable examples of the monomer component are as described above. Further, the preferable content ratios of the monomers (A), (B) and (E) in the monomer component are the preferable ratios of the structural units (a), (b) and (e) in the above-mentioned copolymer. The same is true.
上記共重合体は、上記単量体成分を重合開始剤の存在下で重合する方法により製造することが好ましい。単量体成分を重合させる際には、重合方法に応じて重合開始剤を適宜用いることができる。上記重合開始剤としては、通常用いられるものを使用することができ、例えば、過酸化水素;過硫酸ナトリウム、過硫酸アンモニウム等の過硫酸塩;ジメチル2,2’-アゾビス(2-メチルプロピオネート)、2,2’-アゾビス(イソブチロニトリル)、2,2’-アゾビス(2-メチルブチロニトリル)、2,2’-アゾビス(イソ酪酸)ジメチル、4,4’-アゾビス(4-シアノ吉草酸)、2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩、2,2’-アゾビス[N-(2-カルボキシエチル)-2-メチルプロピオンアミジン]n水和物、2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]二塩酸塩、2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]二硫酸塩二水和物、1,1’-アゾビス(シクロヘキサン-1-カルボニトリル)、2,2’-アゾビス[N-(2-プロペニル)-2-メチルプロピオンアミド]等のアゾ系化合物;過酸化ベンゾイル、過酸化ラウロイル、過酢酸、ジ-t-ブチルパーオキサイド等の有機過酸化物等が好適である。これらの重合開始剤のうち、アゾ系化合物が好ましい。上記重合開始剤としては、かかる例示のみに限定されるものではない。これらの重合開始剤は、それぞれ単独で用いてもよく、2種類以上を併用してもよい。 The copolymer is preferably produced by a method of polymerizing the monomer component in the presence of a polymerization initiator. When polymerizing the monomer component, a polymerization initiator can be appropriately used depending on the polymerization method. As the polymerization initiator, commonly used ones can be used, for example, hydrogen peroxide; persulfate such as sodium persulfate, ammonium persulfate; dimethyl 2,2'-azobis (2-methylpropionate). ), 2,2'-Azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (isobutyric acid) dimethyl, 4,4'-azobis (4) -Cyanovaleric acid), 2,2'-azobis (2-methylpropion amidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropion amidine] n hydrate, 2,2'-Azobisisobuty [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydration Azobisisobuty, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis [N- (2-propenyl) -2-methylpropionamide] and other azo compounds; benzoyl peroxide, peroxidation. Organic peroxides such as lauroyl, peracetic acid, and di-t-butyl peroxide are suitable. Of these polymerization initiators, azo compounds are preferable. The polymerization initiator is not limited to these examples. These polymerization initiators may be used alone or in combination of two or more.
上記重合開始剤の使用量は、上記単量体成分の重合を開始できる量であれば特に制限されないが、全単量体成分100質量部に対して、通常0.01~50質量部であり、好ましくは0.05~30質量部、より好ましくは0.05~20質量部であることが好ましい。 The amount of the polymerization initiator used is not particularly limited as long as it can initiate the polymerization of the monomer component, but is usually 0.01 to 50 parts by mass with respect to 100 parts by mass of all the monomer components. It is preferably 0.05 to 30 parts by mass, more preferably 0.05 to 20 parts by mass.
本発明で用いるアミノ基含有単量体の使用方法としては、それらを酸により中和した酸中和物、又は、4級化剤により4級化した4級アンモニウム塩として用いてもよい。アミノ基含有単量体を4級化して用いることにより、黄色ブドウ球菌等のグラム陽性菌に対して、より高い抗菌性能を示すことになる。
アミノ基含有単量体の中和に用いる酸としては、特に制限されるものではないが、塩酸、硫酸等の無機酸;酢酸、クエン酸、酒石酸、トルエンスルホン酸、乳酸、コハク酸、グリコール酸等の有機酸が挙げられる。
アミノ基含有単量体の4級化剤としては、上述のとおりである。
As a method of using the amino group-containing monomer used in the present invention, it may be used as an acid neutralized product obtained by neutralizing them with an acid or as a quaternary ammonium salt quaternized with a quaternary agent. By quaternizing the amino group-containing monomer and using it, higher antibacterial performance is exhibited against gram-positive bacteria such as Staphylococcus aureus.
The acid used for neutralizing the amino group-containing monomer is not particularly limited, but is not limited to inorganic acids such as hydrochloric acid and sulfuric acid; acetic acid, citric acid, tartaric acid, toluenesulfonic acid, lactic acid, succinic acid and glycolic acid. Organic acids such as.
The quaternizing agent for the amino group-containing monomer is as described above.
上記酸、又は、4級化剤を用いる場合、これらの使用量としては、上記アミノ基含有単量体の一部又は全部が中和又は4級化される限り特に制限されないが、重合反応に用いるアミノ基含有単量体1モルに対して、酸、又は、4級化剤は0.1~1モルであることが好ましい。 When the acid or the quaternizing agent is used, the amount of these used is not particularly limited as long as a part or all of the amino group-containing monomer is neutralized or quaternized, but the polymerization reaction is not limited. The acid or quaternizing agent is preferably 0.1 to 1 mol with respect to 1 mol of the amino group-containing monomer used.
上記共重合方法において、単量体成分や重合開始剤等の反応容器への添加方法としては、反応容器に単量体成分の全てを仕込み、重合開始剤を反応容器内に添加することによって共重合を行う方法;反応容器に単量体成分の一部を仕込み、重合開始剤と残りの単量体成分を反応容器内に連続してあるいは段階的に(好ましくは連続して)添加することによって共重合を行う方法;反応容器に重合溶媒を仕込み、単量体成分と重合開始剤の全量を添加する方法;単量体のうちの一(例えば、アミノ基含有単量体)の一部を反応容器に仕込み、重合開始剤と残りの単量体成分を反応容器内に(好ましくは連続して)添加することによって共重合を行う方法等が好適である。このような方法の中でも、得られる共重合体の分子量分布を狭く(シャープに)することができることから、重合開始剤と単量体成分を反応容器に逐次滴下する方法で共重合を行うことが好ましい。 In the above-mentioned copolymerization method, as a method of adding the monomer component, the polymerization initiator, etc. to the reaction vessel, all the monomer components are charged in the reaction vessel, and the polymerization initiator is added into the reaction vessel. Method of performing polymerization: A part of the monomer component is charged in a reaction vessel, and the polymerization initiator and the remaining monomer component are added continuously or stepwise (preferably continuously) into the reaction vessel. Method of performing polymerization by the method; a method of charging a polymerization solvent in a reaction vessel and adding the entire amount of the monomer component and the polymerization initiator; Is preferable, and the polymerization initiator and the remaining monomer component are added into the reaction vessel (preferably continuously) to carry out the copolymerization. Even in such a method, since the molecular weight distribution of the obtained copolymer can be narrowed (sharpened), the copolymerization can be carried out by sequentially dropping the polymerization initiator and the monomer component into the reaction vessel. preferable.
上記共重合方法としては、例えば、溶液重合やバルク重合、懸濁重合、乳化重合、リビング重合やグラフト重合等の方法で行うことができ、特に限定されるものではないが、溶液重合が好ましい。この際使用できる溶媒は、水であることが好ましい。水のみを使用する場合には、脱溶剤工程を省略できる点で好適である。 The copolymerization method can be carried out by, for example, solution polymerization, bulk polymerization, suspension polymerization, emulsification polymerization, living polymerization, graft polymerization and the like, and is not particularly limited, but solution polymerization is preferable. The solvent that can be used at this time is preferably water. When only water is used, it is preferable in that the solvent removal step can be omitted.
上記共重合方法は、回分式でも連続式でも行うことができる。また、共重合の際、必要に応じて使用される溶媒としては、公知のものを使用でき、水;メチルアルコール、エチルアルコール、イソプロピルアルコール、ブタノール、THF(テトラヒドロフラン)等の1価のアルコール類;グリセリン、(ポリ)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、ジプロピレングリコール等の多価アルコール;ベンゼン、トルエン、キシレン、シクロヘキサン、n-ヘプタン等の芳香族又は脂肪族炭化水素類;酢酸エチル等のエステル類;アセトン、メチルエチルケトン等のケトン類;ジメチルホルムアミド等のアミド類;ジエチルエーテル、ジオキサン等のエーテル類等が好適である。これらは単独で用いてもよく、2種以上を併用してもよい。これらの中でも、単量体成分及び得られる共重合体の溶解性の点から、水及び炭素数1~4の低級アルコールからなる群より選択される1種又は2種以上の溶媒を用いることが好ましい。上記溶媒は、比較的安価なものであり、本発明の製造方法は、経済的にも優れる。また、上記共重合方法においては、水にプロピレングリコールやエチレングリコール等の多価アルコール溶媒を加えて重合してもよい。上記多価アルコール溶媒は水と併用することによって、ポリマーの溶解性を高めることができ、ソープフリー重合をより充分に抑制することができる。これにより、水溶性に乏しいポリマーの生成をより充分に抑制し、溶液の透明性をより向上させることができる。
上記多価アルコール溶媒と水とを併用する場合、水100質量%に対する多価アルコール溶媒の割合は、0~200質量%であることが好ましい。
本発明の共重合体の製造方法は、必要に応じて、任意の連鎖移動剤、pH調節剤、緩衝剤などを用いることができる。
The above-mentioned copolymerization method can be carried out by either a batch method or a continuous method. In addition, known solvents can be used as the solvent used in the copolymerization as needed, and water; monohydric alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butanol, and THF (tetratetra); Polyhydric alcohols such as glycerin, (poly) ethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene glycol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, n-heptane; acetic acid Esters such as ethyl; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide; ethers such as diethyl ether and dioxane are suitable. These may be used alone or in combination of two or more. Among these, one or more solvents selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms may be used from the viewpoint of the solubility of the monomer component and the obtained copolymer. preferable. The solvent is relatively inexpensive, and the production method of the present invention is economically excellent. Further, in the above-mentioned copolymerization method, polyhydric alcohol solvent such as propylene glycol or ethylene glycol may be added to water for polymerization. When the polyhydric alcohol solvent is used in combination with water, the solubility of the polymer can be enhanced and soap-free polymerization can be suppressed more sufficiently. As a result, the formation of a polymer having poor water solubility can be more sufficiently suppressed, and the transparency of the solution can be further improved.
When the polyhydric alcohol solvent and water are used in combination, the ratio of the polyhydric alcohol solvent to 100% by mass of water is preferably 0 to 200% by mass.
In the method for producing a copolymer of the present invention, any chain transfer agent, pH adjuster, buffer, or the like can be used, if necessary.
重合の際の温度は特に限定されないが、通常50~120℃であり、好ましくは60~110℃である。重合時の温度が上記範囲であれば、残存単量体成分が少なくなる傾向にある。なお、重合時の温度は、重合反応の進行中において、常に一定に保持する必要はなく、例えば、室温から重合を開始し、適当な昇温時間又は昇温速度で設定温度まで昇温し、その後、設定温度を保持するようにしてもよいし、単量体成分や開始剤等の滴下方法に応じて、重合反応の進行中に経時的に重合温度を変動(昇温又は降温)させてもよい。また、単量体成分を重合させる際には、単量体成分が均一に重合するようにするために、適宜、撹拌することが好ましい。 The temperature at the time of polymerization is not particularly limited, but is usually 50 to 120 ° C, preferably 60 to 110 ° C. When the temperature at the time of polymerization is in the above range, the residual monomer component tends to decrease. It is not necessary to keep the temperature at the time of polymerization constant during the progress of the polymerization reaction. For example, the polymerization is started from room temperature and the temperature is raised to a set temperature at an appropriate temperature rise time or rate. After that, the set temperature may be maintained, or the polymerization temperature may be changed (increased or lowered) with time during the progress of the polymerization reaction depending on the dropping method of the monomer component, the initiator and the like. May be good. Further, when polymerizing the monomer component, it is preferable to appropriately stir the monomer component so that the monomer component is polymerized uniformly.
重合時間は特に制限されず、重合反応の進行状況に応じて適宜設定すればよいが、通常、2~9時間程度である。
なお、本発明において、「重合時間」とは単量体の滴下前の加熱撹拌を行っている時間、単量体を添加している時間及び単量体の滴下後の熟成時間を表す。
The polymerization time is not particularly limited and may be appropriately set according to the progress of the polymerization reaction, but is usually about 2 to 9 hours.
In the present invention, the "polymerization time" represents the time during which the monomer is heated and stirred before the dropping, the time during which the monomer is added, and the aging time after the dropping of the monomer.
反応系内の圧力としては、常圧(大気圧)下、減圧下、加圧下のいずれであってもよい。反応系内の雰囲気としては、空気雰囲気でも不活性雰囲気でもどちらでもよい。 The pressure in the reaction system may be normal pressure (atmospheric pressure), reduced pressure, or pressurized. The atmosphere in the reaction system may be either an air atmosphere or an inert atmosphere.
上記重合反応系における重合反応が終了した時点での水溶液中の固形分濃度(すなわち単量体の重合固形分濃度)は、20質量%以上が好ましく、25~80質量%であることがより好ましい。このように重合反応終了時の固形分濃度が20質量%以上と高ければ、高濃度かつ一段で重合を行うことができる。そのため、従来の製造方法では場合によっては必要であった濃縮工程を省略することができるなど、効率よく共重合体を含む防腐抗菌剤を得ることができる。それゆえ、その製造効率を大幅に上昇させたものとすることができ、その結果、本発明の防腐抗菌剤の生産性を大幅に向上し、製造コストの上昇も抑制することが可能となる。 The solid content concentration in the aqueous solution (that is, the polymerized solid content concentration of the monomer) at the time when the polymerization reaction in the above polymerization reaction system is completed is preferably 20% by mass or more, more preferably 25 to 80% by mass. .. As described above, when the solid content concentration at the end of the polymerization reaction is as high as 20% by mass or more, the polymerization can be carried out at a high concentration and in one step. Therefore, an antiseptic antibacterial agent containing a copolymer can be efficiently obtained, for example, the concentration step which is necessary in some cases in the conventional production method can be omitted. Therefore, the production efficiency can be significantly increased, and as a result, the productivity of the antiseptic and antibacterial agent of the present invention can be significantly improved, and the increase in production cost can be suppressed.
本発明の共重合体の製造方法は、全ての使用原料の添加が終了した以降に、単量体の重合率を上げること等を目的として熟成工程を設けても良い。熟成時間は、通常1~240分間、好ましくは1~180分間、より好ましくは1~120分間である。熟成時間が1分未満の場合には、熟成不十分につき単量体成分が残ることがあり、残存単量体に起因する毒性や臭気などが問題となる。 In the method for producing a copolymer of the present invention, an aging step may be provided for the purpose of increasing the polymerization rate of the monomer after the addition of all the raw materials used is completed. The aging time is usually 1 to 240 minutes, preferably 1 to 180 minutes, and more preferably 1 to 120 minutes. If the aging time is less than 1 minute, the monomer component may remain due to insufficient aging, and toxicity and odor caused by the remaining monomer become a problem.
また、熟成工程における好ましい重合体溶液の温度は、上記重合温度と同様の範囲である。したがって、ここでの温度も一定温度(好ましくは上記滴下が終了した時点での温度)で保持してもよいし、熟成中に経時的に温度を変化させてもよい。 Further, the temperature of the polymer solution preferable in the aging step is in the same range as the above-mentioned polymerization temperature. Therefore, the temperature here may be maintained at a constant temperature (preferably the temperature at the time when the dropping is completed), or the temperature may be changed over time during aging.
本発明の防腐抗菌剤は、本発明の共重合体以外のその他の成分を含んでいてもよい。
上記その他の成分としては、防腐抗菌剤の抗菌性能を阻害するものでない限り特に制限されないが、例えば、アルカリ調整剤、アニオン界面活性剤、相溶化剤や安定化剤等の添加剤等が挙げられる。
また、本発明の防腐抗菌剤は、抗菌性を向上させる観点から、更に金属塩や金属酸化物、金属水酸化物などを含んでいてもよい。金属塩又は金属酸化物、金属水酸化物における金属としては、銅や、亜鉛、銀等の重金属が好ましい。
上記その他の成分の含有量は、防腐抗菌剤の抗菌性能を阻害しなければ、特に制限されないが、上記共重合体100質量%に対して、0~20質量%であることが好ましい。
The antiseptic antibacterial agent of the present invention may contain other components other than the copolymer of the present invention.
The other components are not particularly limited as long as they do not inhibit the antibacterial performance of the antiseptic antibacterial agent, and examples thereof include additives such as alkali adjusting agents, anionic surfactants, compatibilizers and stabilizers. ..
Further, the antiseptic antibacterial agent of the present invention may further contain a metal salt, a metal oxide, a metal hydroxide and the like from the viewpoint of improving the antibacterial property. As the metal in the metal salt, metal oxide, or metal hydroxide, heavy metals such as copper, zinc, and silver are preferable.
The content of the other components is not particularly limited as long as it does not inhibit the antibacterial performance of the antiseptic antibacterial agent, but is preferably 0 to 20% by mass with respect to 100% by mass of the copolymer.
本発明の防腐抗菌剤は、皮膚化粧料、皮膚外用剤又は頭髪(毛髪)化粧料等の化粧料用途に用いられることが好ましい。
上記皮膚化粧料としては特に制限されないが、例えば、化粧水、クリーム、乳液、美容液等の基礎化粧料;リキッドファンデーション、下地乳液、チークカラー、アイシャドウ、マスカラ、口紅等のメイクアップ化粧料;クレンジングクリーム、洗顔フォーム、液状洗顔料等の洗浄用化粧料;日焼け止め化粧料等の化粧料(医薬部外品を含む);浴用剤等の浴用化粧料が挙げられる。皮膚外用剤としては、リニメント剤、ローション剤、軟膏剤等の外用医薬品等が挙げられる。
上記頭髪化粧料としては特に制限されないが、例えば、シャンプー、リンス、トリートメント、ワックス、スプレー、ジェル、ミスト等が挙げられる。
The antiseptic and antibacterial agent of the present invention is preferably used for cosmetic applications such as skin cosmetics, external skin preparations, and hair (hair) cosmetics.
The skin cosmetics are not particularly limited, but for example, basic cosmetics such as lotion, cream, milky lotion, and beauty liquid; makeup cosmetics such as liquid foundation, base milky lotion, teak color, eye shadow, mascara, and lipstick; Cleaning cosmetics such as cleansing creams, facial cleansing foams, and liquid washing pigments; cosmetics such as sunscreen cosmetics (including non-medicinal products); bath cosmetics such as bathing agents. Examples of the external skin preparation include external medicines such as liniment agents, lotions and ointments.
The hair cosmetics are not particularly limited, and examples thereof include shampoos, conditioners, treatments, waxes, sprays, gels, and mists.
本発明はまた、本発明の化粧料用防腐抗菌剤を含む化粧料でもある。
上記化粧料における防腐抗菌剤の含有割合としては特に制限されないが、化粧料100質量%に対して5質量%以下、より好ましくは3質量%以下、更に好ましくは1質量%以下である。
The present invention is also a cosmetic containing the antiseptic antibacterial agent for cosmetics of the present invention.
The content ratio of the antiseptic antibacterial agent in the above cosmetics is not particularly limited, but is 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less with respect to 100% by mass of the cosmetics.
また、本発明の化粧料及び皮膚外用剤には、必要に応じて水及び一般的に化粧料及び皮膚外用剤に配合される添加成分、例えば油性基剤、保湿剤、感触向上剤、界面活性剤、高分子、増粘・ゲル化剤、溶剤、噴射剤、酸化防止剤、還元剤、酸化剤、本発明の防腐抗菌剤以外の防腐剤・抗菌剤、キレート剤、pH調整剤、酸、アルカリ、粉体類、無機塩、紫外線吸収剤、美白剤、ビタミン類及びその誘導体類、消炎剤、抗炎症剤、育毛用薬剤、血行促進剤、刺激剤、ホルモン類、抗しわ剤、抗老化剤、ひきしめ剤、冷感剤、温感剤、創傷治癒促進剤、刺激緩和剤、鎮痛剤、細胞賦活剤、植物・動物・微生物エキス、鎮痒剤、角質剥離・溶解剤、制汗剤、清涼剤、収れん剤、酵素、核酸、香料、色素、着色剤、染料、顔料、水等を配合することができる。 In addition, the cosmetics and skin external preparations of the present invention include, if necessary, water and additive components generally added to cosmetics and skin external preparations, such as oily bases, moisturizers, feel enhancers, and surface activity. Agents, polymers, thickening / gelling agents, solvents, propellants, antioxidants, reducing agents, oxidizing agents, preservatives / antibacterial agents other than the antiseptic / antibacterial agents of the present invention, chelating agents, pH adjusters, acids, Alkali, powders, inorganic salts, UV absorbers, whitening agents, vitamins and their derivatives, anti-inflammatory agents, anti-inflammatory agents, hair growth agents, blood circulation promoters, stimulants, hormones, anti-wrinkle agents, anti-aging Agents, tightening agents, cooling sensitizers, warming agents, wound healing promoters, stimulants, painkillers, cell activators, plant / animal / microbial extracts, antipruritic agents, keratin exfoliating / dissolving agents, antiperspirants, refreshing agents Agents, astringents, enzymes, nucleic acids, fragrances, pigments, colorants, dyes, pigments, water and the like can be blended.
これらの添加成分を例示すると、油性基剤としては、セタノール、ミリスチルアルコール、オレイルアルコール、ラウリルアルコール、セトステアリルアルコール、ステアリルアルコール、アラキルアルコール、ベヘニルアルコール、ホホバアルコール、キミルアルコール、セラキルアルコール、バチルアルコール、ヘキシルデカノール、イソステアリルアルコール、2-オクチルドデカノール、ダイマージオール等の高級アルコール類;ベンジルアルコール等のアラルキルアルコール及び誘導体;ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、ベヘン酸、ウンデシレン酸、12-ヒドロキシステアリン酸、パルミトオレイン酸、オレイン酸、リノール酸、リノレイン酸、エルカ酸、ドコサヘキサエン酸、エイコサペンタエン酸、イソヘキサデカン酸、アンテイソヘンイコサン酸、長鎖分岐脂肪酸、ダイマー酸、水素添加ダイマー酸等の高級脂肪酸類及びそのアルミニウム塩、カルシウム塩、マグネシウム塩、亜鉛塩、カリウム塩等の金属石けん類、及びアミド等の含窒素誘導体類;流動パラフィン(ミネラルオイル)、重質流動イソパラフィン、軽質流動イソパラフィン、α-オレフィンオリゴマー、ポリイソブテン、水添ポリイソブテン、ポリブテン、スクワラン、オリーブ由来スクワラン、スクワレン、ワセリン、固型パラフィン、水添ポリデセン等の炭化素類;キャンデリラワックス、カルナウバワックス、ライスワックス、木ろう、みつろう、モンタンワックス、オゾケライト、セレシン、パラフィンワックス、マイクロクリスタリンワックス、ペトロラタム、フィッシャートロプシュワックス、ポリエチレンワックス、エチレン・プロピレンコポリマー等のワックス類;ヤシ油、パーム油、パーム核油、サフラワー油、オリーブ油、ヒマシ油、アボカド油、ゴマ油、茶油、月見草油、小麦胚芽油、マカデミアナッツ油、ヘーゼルナッツ油、ククイナッツ油、ローズヒップ油、メドウフォーム油、パーシック油、ティートリー油、ハッカ油、トウモロコシ油、ナタネ油、ヒマワリ油、小麦胚芽油、アマニ油、綿実油、大豆油、落花生油、コメヌカ油、カカオ脂、シア脂、水素添加ヤシ油、水素添加ヒマシ油、ホホバ油、水素添加ホホバ油等の植物油脂類;牛脂、乳脂、馬脂、卵黄油、ミンク油、タートル油等の動物性油脂類;鯨ロウ、ラノリン、オレンジラッフィー油等の動物性ロウ類; To exemplify these additive components, examples of the oily base include cetanol, myristyl alcohol, oleyl alcohol, lauryl alcohol, cetostearyl alcohol, stearyl alcohol, araquil alcohol, behenyl alcohol, jojoba alcohol, kimil alcohol, seraquil alcohol, and bacillus. Higher alcohols such as alcohol, hexyldecanol, isostearyl alcohol, 2-octyldodecanol, dimerdiol; aralkyl alcohols and derivatives such as benzyl alcohol; lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, undecylene Acid, 12-hydroxystearic acid, palmitooleic acid, oleic acid, linoleic acid, linoleic acid, erucic acid, docosahexaenoic acid, eikosapentaenoic acid, isohexadecanoic acid, anteisohenicosanoic acid, long chain branched fatty acid, dimer acid , Higher fatty acids such as hydrogenated dimer acid and metal soaps such as aluminum salt, calcium salt, magnesium salt, zinc salt and potassium salt, and nitrogen-containing derivatives such as amide; liquid paraffin (mineral oil), heavy Carbides such as liquid isoparaffin, light liquid isoparaffin, α-olefin oligomer, polyisobutene, hydrogenated polyisobutene, polybutene, squalane, olive-derived squalane, squalane, vaseline, solid paraffin, hydrogenated polydecene; candelilla wax, carnauba wax. , Rice wax, wood wax, mitsuro, montan wax, ozokelite, ceresin, paraffin wax, microcrystallin wax, petrolatum, fisher tropsh wax, polyethylene wax, ethylene / propylene copolymer and other waxes; palm oil, palm oil, palm kernel oil , Saflower oil, olive oil, castor oil, avocado oil, sesame oil, brown oil, evening primrose oil, wheat germ oil, macadamia nut oil, hazelnut oil, kukui nut oil, rose hip oil, meadow foam oil, persic oil, tea tree oil, peppermint oil , Corn oil, rapeseed oil, sunflower oil, wheat germ oil, flaxseed oil, cottonseed oil, soybean oil, peanut oil, rice bran oil, cacao butter, shea butter, hydrogenated palm oil, hydrogenated castor oil, jojoba oil, hydrogenated hojoba Vegetable oils and fats such as oils; animal oils and fats such as beef oil, milk fat, horse fat, egg yolk oil, mink oil, turtle oil; animal products such as whale wax, lanolin, and orange raffy oil. Rows;
液状ラノリン、還元ラノリン、吸着精製ラノリン、酢酸ラノリン、酢酸液状ラノリン、ヒドロキシラノリン、ポリオキシエチレンラノリン、ラノリン脂肪酸、硬質ラノリン脂肪酸、ラノリンアルコール、酢酸ラノリンアルコール、酢酸(セチル・ラノリル)エステル等のラノリン類;レシチン、ホスファチジルコリン、ホスファチジルエタノールアミン、ホスファチジルセリン、ホスファチジルグリセロール、ホスファチジルイノシトール、スフィンゴミエリン等のスフィンゴリン脂質、ホスファチジン酸、リゾレシチン等のリン脂質類;水素添加大豆リン脂質、部分水素添加大豆リン脂質、水素添加卵黄リン脂質、部分水素添加卵黄リン脂質等のリン脂質誘導体類;コレステロール、ジヒドロコレステロール、ラノステロール、ジヒドロラノステロール、フィトステロール、コール酸等のステロール類;サポゲニン類;サポニン類;酢酸コレステリル、ノナン酸コレステリル、ステアリン酸コレステリル、イソステアリン酸コレステリル、オレイン酸コレステリル、N-ラウロイル-L-グルタミン酸ジ(コレステリル/ベヘニル/オクチルドデシル)、N-ラウロイル-L-グルタミン酸ジ(コレステリル/オクチルドデシル)、N-ラウロイル-L-グルタミン酸ジ(フィトステリル/ベヘニル/オクチルドデシル)、N-ラウロイル-L-グルタミン酸ジ(フィトステリル/オクチルドデシル)、N-ラウロイルサルコシンイソプロピル等のアシルサルコシンアルキルエステル、12-ヒドロキシステアリン酸コレステリル、マカデミアナッツ油脂肪酸コレステリル、マカデミアナッツ油脂肪酸フィトステリル、イソステアリン酸フィトステリル、軟質ラノリン脂肪酸コレステリル、硬質ラノリン脂肪酸コレステリル、長鎖分岐脂肪酸コレステリル、長鎖α-ヒドロキシ脂肪酸コレステリル等のステロールエステル類;リン脂質・コレステロール複合体、リン脂質・フィトステロール複合体等の脂質複合体; Lanolins such as liquid lanolin, reduced lanolin, adsorption purified lanolin, acetate lanolin, acetate liquid lanolin, hydroxylanolin, polyoxyethylene lanolin, lanolin fatty acid, hard lanolin fatty acid, lanolin alcohol, acetate lanolin alcohol, acetic acid (cetyl lanolyl) ester, etc. Sphingo phospholipids such as lecithin, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, sphingomyelin, phospholipids such as phosphatidic acid, lysolecithin; hydrogenated soybean phospholipids, partially hydrogenated soybean phospholipids, hydrogen Phosphorus derivatives such as added egg yolk phospholipids and partially hydrogenated egg yolk phospholipids; sterols such as cholesterol, dihydrocholesterol, lanosterol, dihydrolanosterol, phytosterol, and choleacid; sapogenins; saponins; cholesteryl acetate, cholesteryl nonanoate, Cholesteryl stearate, Cholesteryl isostearate, Cholesteryl oleate, Di-lauroyl-L-glutamate (cholesteryl / behenyl / octyldodecyl), di-lauroyl-L-glutamate (cholesteryl / octyldodecyl), N-lauroyl-L- Acylsarcosine alkyl esters such as diglutamate (phytosteryl / behenyl / octyldodecyl), di-lauroyl-L-glutamate (phytosteryl / octyldodecyl), N-lauroylsarcosin isopropyl, cholesteryl 12-hydroxystearate, fatty acid cholesteryl of macadamia nuts, Sterol esters such as macadamia nut oil fatty acid phytosteryl, phytosteryl isostearate, soft lanolin fatty acid cholesteryl, hard lanolin fatty acid cholesteryl, long-chain branched fatty acid cholesteryl, long-chain α-hydroxy fatty acid cholesteryl; phospholipid-cholesterol complex, phospholipid-phytosterol complex Fatty acid complex such as body;
ミリスチン酸オクチルドデシル、ミリスチン酸ヘキシルデシル、イソステアリン酸オクチルドデシル、パルミチン酸セチル、パルミチン酸オクチルドデシル、オクタン酸セチル、オクタン酸ヘキシルデシル、イソノナン酸イソトリデシル、イソノナン酸イソノニル、イソノナン酸オクチル、イソノナン酸イソトリデシル、ネオペンタン酸イソデシル、ネオペンタン酸イソトリデシル、ネオペンタン酸イソステアリル、ネオデカン酸オクチルドデシル、オレイン酸オレイル、オレイン酸オクチルドデシル、リシノレイン酸オクチルドデシル、ラノリン脂肪酸オクチルドデシル、ジメチルオクタン酸ヘキシルデシル、エルカ酸オクチルドデシル、イソステアリン酸硬化ヒマシ油、オレイン酸エチル、アボカド油脂肪酸エチル、ミリスチン酸イソプロピル、パルミチン酸イソプロピル、パルミチン酸オクチル、イソステアリン酸イソプロピル、ラノリン脂肪酸イソプロピル、セバチン酸ジエチル、セバチン酸ジイソプロピル、セバチン酸ジオクチル、アジピン酸ジイソプロピル、セバチン酸ジブチルオクチル、アジピン酸ジイソブチル、コハク酸ジオクチル、クエン酸トリエチル等のモノアルコールカルボン酸エステル類;乳酸セチル、リンゴ酸ジイソステアリル、モノイソステアリン酸水添ヒマシ油等のオキシ酸エステル類; Octyldodecyl myristite, hexyldecyl myristate, octyldodecyl isostearate, cetyl palmitate, octyldodecyl palmitate, cetyl octanate, hexyldecyl octanoate, isotrideyl isononanoate, isononyl isononanoate, octyl isononanoate, isononenate Isodecyl acid, isotridecyl neopentate, isostearyl neopentate, octyldodecyl neodecanoate, oleyl oleate, octyldodecyl oleate, octyldodecyl ricinoleate, octyldodecyl lanolin fatty acid, hexyldecyl dimethyloctanoate, octyldodecyl erucate, cured isostearate. Himasi oil, ethyl oleate, ethyl avocado oil fatty acid, isopropyl myristate, isopropyl palmitate, octyl palmitate, isopropyl isostearate, isopropyl lanolin fatty acid, diethyl sebatate, diisopropyl sebatate, dioctyl sebatate, diisopropyl adipate, sebatic acid Monoalcohol carboxylic acid esters such as dibutyloctyl, diisobutyl adipate, dioctyl succinate, triethyl citrate; oxyacid esters such as cetyl lactate, diisostearyl malate, hydrogenated castor oil monoisostearate;
トリエチルヘキサノイン、トリオクタン酸グリセリル、トリオレイン酸グリセリル、トリイソステアリン酸グリセリル、ジイソステアリン酸グリセリル、トリ(カプリル酸/カプリン酸)グリセリル、トリ(カプリル酸/カプリン酸/ミリスチン酸/ステアリン酸)グリセリル、水添ロジントリグリセリド(水素添加エステルガム)、ロジントリグリセリド(エステルガム)、ベヘン酸エイコサン二酸グリセリル、トリオクタン酸トリメチロールプロパン、トリイソステアリン酸トリメチロールプロパン、ジオクタン酸ネオペンチルグリコール、ジカプリン酸ネオペンチルグリコール、ジオクタン酸2-ブチル-2-エチル-1,3-プロパンジオール、ジオレイン酸プロピレングリコール、テトラオクタン酸ペンタエリスリチル、水素添加ロジンペンタエリスリチル、トリエチルヘキサン酸ジトリメチロールプロパン、(イソステアリン酸/セバシン酸)ジトリメチロールプロパン、トリエチルヘキサン酸ペンタエリスリチル、(ヒドロキシステアリン酸/ステアリン酸/ロジン酸)ジペンタエリスリチル、ジイソステアリン酸ジグリセリル、テトライソステアリン酸ポリグリセリル、ノナイソステアリン酸ポリグリセリル-10、デカ(エルカ酸/イソステアリン酸/リシノレイン酸)ポリグリセリル-8、(ヘキシルデカン酸/セバシン酸)ジグリセリルオリゴエステル、ジステアリン酸グリコール(ジステアリン酸エチレングリコール)等の多価アルコール脂肪酸エステル類; Triethylhexanoin, glyceryl trioctanoate, glyceryl trioleate, glyceryl triisostearate, glyceryl diisostearate, tri (capric acid / capric acid) glyceryl, tri (capric acid / capric acid / myristic acid / stearic acid) glyceryl, hydrogenated Rozine triglyceride (hydrogenated ester gum), rosin triglyceride (ester gum), glyceryl dicosanate behenate, trimethylol propane trioctanoate, trimethylol propane triisostearate, neopentylglycol dioctanoate, neopentyl glycol dicaprate, dioctanoic acid 2-Butyl-2-ethyl-1,3-propanediol, propylene glycol dioleate, pentaerythrityl tetraoctanoate, hydrogenated rosin pentaerythrityl, ditrimethylolpropane triethylhexanoate, ditrimethylol (isostearic acid / sebacic acid) Propane, pentaerythrityl triethylhexanoate, (hydroxystearic acid / stearic acid / logonic acid) dipentaerythrityl, diglyceryl diisostearate, polyglyceryl tetraisostearate, polyglyceryl-10 nonaisostearate, deca (erucic acid / isostearic acid / ricinoleic acid) Polyhydric alcohol fatty acid esters such as polyglyceryl-8, (hexyldecanoic acid / sebacic acid) diglyceryl oligoester, glycol distearate (ethylene glycol distearate);
ダイマージリノール酸ジイソプロピル、ダイマージリノール酸ジイソステアリル、ダイマージリノール酸ジ(イソステアリル/フィトステリル)、ダイマージリノール酸(フィトステリル/ベヘニル)、ダイマージリノール酸(フィトステリル/イソステアリル/セチル/ステアリル/ベヘニル)、ダイマージリノール酸ダイマージリノレイル、ジイソステアリン酸ダイマージリノレイル、ダイマージリノレイル水添ロジン縮合物、ダイマージリノール酸硬化ヒマシ油、ヒドロキシアルキルダイマージリノレイルエーテル等のダイマー酸若しくはダイマージオールの誘導体;ヤシ油脂肪酸モノエタノールアミド(コカミドMEA)、ヤシ油脂肪酸ジエタノールアミド(コカミドDEA)、ラウリン酸モノエタノールアミド(ラウラミドMEA)、ラウリン酸ジエタノールアミド(ラウラミドDEA)、ラウリン酸モノイソプロパノールアミド(ラウラミドMIPA)、パルミチン酸モノエタノールアミド(パルタミドMEA)、パルミチン酸ジエタノールアミド(パルタミドDEA)、ヤシ油脂肪酸メチルエタノールアミド(コカミドメチルMEA)等の脂肪酸アルカノールアミド類;ジメチコン(ジメチルポリシロキサン)、高重合ジメチコン(高重合ジメチルポリシロキサン)、シクロメチコン(環状ジメチルシロキサン、デカメチルシクロペンタシロキサン)、フェニルトリメチコン、ジフェニルジメチコン、フェニルジメチコン、ステアロキシプロピルジメチルアミン、(アミノエチルアミノプロピルメチコン/ジメチコン)コポリマー、ジメチコノール、ジメチコノールクロスポリマー、シリコーン樹脂、シリコーンゴム、アミノプロピルジメチコン及びアモジメチコン等のアミノ変性シリコーン、カチオン変性シリコーン、ジメチコンコポリオール等のポリエーテル変性シリコーン、ポリグリセリン変性シリコーン、糖変性シリコーン、カルボン酸変性シリコーン、リン酸変性シリコーン、硫酸変性シリコーン、アルキル変性シリコーン、脂肪酸変性シリコーン、アルキルエーテル変性シリコーン、アミノ酸変性シリコーン、ペプチド変性シリコーン、フッ素変性シリコーン、カチオン変性及びポリエーテル変性シリコーン、アミノ変性及びポリエーテル変性シリコーン、アルキル変性及びポリエーテル変性シリコーン、ポリシロキサン・オキシアルキレン共重合体等のシリコーン類;パーフルオロデカン、パーフルオロオクタン、パーフルオロポリエーテル等のフッ素系油剤類が、好ましいものとして挙げられる。 Diisopropyl dimergilinolate, diisostearyl dimergilinolate, dimersielyl dimergilinolate (isostearyl / phytosteryl), dimerjilinolic acid (phytosteryl / behenyl), dimerjilinol acid (phytosteryl / isostearyl / cetyl / stearyl /) Dimericicic acid or dimer such as behenyl), dimerjilinoleic acid dimergylinoleil, diisostearate dimergelinoleil, dimergylinoleil hydrogenated rosin condensate, dimerjilinol acid-cured castor oil, hydroxyalkyl dimergylinoleil ether, etc. Derivatives of diols; coconut oil fatty acid monoethanolamide (cocamide MEA), coconut oil fatty acid diethanolamide (cocamide DEA), lauric acid monoethanolamide (lauramide MEA), lauric acid diethanolamide (lauramide DEA), lauric acid monoisopropanolamide (lauramic acid monoisopropanolamide). Lauramide MIPA), palmitic acid monoethanolamide (partamide MEA), palmitic acid diethanolamide (partamide DEA), palm oil fatty acid methylethanolamide (cocamidemethyl MEA) and other fatty acid alkanolamides; dimethicone (dimethylpolysiloxane), highly polymerized dimethicone. (Highly polymerized dimethylpolysiloxane), cyclomethicone (cyclic dimethylsiloxane, decamethylcyclopentasiloxane), phenyltrimethicone, diphenyldimethicone, phenyldimethicone, stearoxypropyldimethylamine, (aminoethylaminopropylmethicone / dimethicone) copolymer, dimethiconol , Dimethiconol crosspolymer, silicone resin, silicone rubber, amino-modified silicone such as aminopropyl dimethicone and amodimethicone, polyether-modified silicone such as cation-modified silicone and dimethiconecopolypoly, polyglycerin-modified silicone, sugar-modified silicone, carboxylic acid-modified silicone. , Phosphate-modified silicone, sulfuric acid-modified silicone, alkyl-modified silicone, fatty acid-modified silicone, alkyl ether-modified silicone, amino acid-modified silicone, peptide-modified silicone, fluorine-modified silicone, cationic-modified and polyether-modified silicone, amino-modified and polyether-modified silicone. , Alkyl-modified and polyether-modified silicone, silicones such as polysiloxane / oxyalkylene copolymer; perfluorodecane, pa -Fluorine-based oils such as fluorooctane and perfluoropolyether are preferable.
保湿剤・感触向上剤としては、グリセリン、1,3-ブチレングリコール、プロピレングリコール、3-メチル-1,3-ブタンジオール、1,3-プロパンジオール、2-メチル-1,3-プロパンジオール、トリメチロールプロパン、ペンタエリスリトール、ヘキシレングリコール、ジグリセリン、ポリグリセリン、ジエチレングリコール、ポリエチレングリコール、ジプロピレングリコール、ポリプロピレングリコール、エチレングリコール・プロピレングリコール共重合体等のポリオール類及びその重合体;ジエチレングリコールモノエチルエーテル(エトキシジグリコール)、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールジブチルエーテル等のグリコールアルキルエーテル類;ソルビトール、キシリトール、エリスリトール、マンニトール、マルチトール等の糖アルコール類;グルコース、フルクトース、ガラクトース、マンノース、トレオース、キシロース、アラビノース、フコース、リボース、デオキシリボース、マルトース、トレハロース、ラクトース、ラフィノース、グルコン酸、グルクロン酸、シクロデキストリン類(α-、β-、γ-シクロデキストリン、及び、マルトシル化、ヒドロキシアルキル化等の修飾シクロデキストリン)、β-グルカン、キチン、キトサン、ヘパリン及び誘導体、ペクチン、アラビノガラクタン、デキストリン、デキストラン、グリコーゲン、エチルグルコシド、メタクリル酸グルコシルエチル重合物若しくは共重合物等の糖類及びその誘導体類;ヒアルロン酸、ヒアルロン酸ナトリウム;コンドロイチン硫酸ナトリウム;ムコイチン硫酸、カロニン硫酸、ケラト硫酸、デルマタン硫酸;シロキクラゲ抽出物、シロキクラゲ多糖体;フコイダン;チューベロース多糖体、天然由来多糖体;クエン酸、酒石酸、乳酸等の有機酸及びその塩;尿素;2-ピロリドン-5-カルボン酸及びそのナトリウム等の塩; Examples of the moisturizing agent / feeling improving agent include glycerin, 1,3-butylene glycol, propylene glycol, 3-methyl-1,3-butanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, and the like. Polypolymers such as trimethylolpropane, pentaerythritol, hexylene glycol, diglycerin, polyglycerin, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, ethylene glycol / propylene glycol copolymer and its polymers; diethylene glycol monoethyl ether Glycol alkyl ethers such as (ethoxydiglycol), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dibutyl ether; sugar alcohols such as sorbitol, xylitol, erythritol, mannitol, martitol; glucose, fructose, galactose, mannose , Treose, xylose, arabinose, fucose, ribose, deoxyribose, maltose, trehalose, lactose, raffinose, gluconic acid, glucuronic acid, cyclodextrins (α-, β-, γ-cyclodextrin, and maltosylated, hydroxyalkyl. Modifications such as cyclodextrin), β-glucan, chitin, chitosan, heparin and derivatives, pectin, arabinogalactan, dextrin, dextran, glycogen, ethyl glucoside, glucosyl ethyl methacrylate polymer or copolymer and other saccharides thereof. Derivatives; hyaluronic acid, sodium hyaluronate; sodium chondroitin sulfate; mucoitin sulfate, caronine sulfate, keratosulfate, dermatane sulfate; white jellyfish extract, white jellyfish polysaccharide; fucoidan; tuberose polysaccharide, naturally derived polysaccharide; citric acid, tartrate, Organic acids such as lactic acid and salts thereof; urea; salts such as 2-pyrrolidext-5-carboxylic acid and sodium thereof;
ベタイン(トリメチルグリシン)、プロリン、ヒドロキシプロリン、アルギニン、リジン、セリン、グリシン、アラニン、フェニルアラニン、チロシン、β-アラニン、スレオニン、グルタミン酸、グルタミン、アスパラギン、アスパラギン酸、システイン、シスチン、メチオニン、ロイシン、イソロイシン、バリン、トリプトファン、ヒスチジン、タウリン等のアミノ酸類及びその塩;コラーゲン、魚由来コラーゲン、アテロコラーゲン、ゼラチン、エラスチン、コラーゲン分解ペプチド、加水分解コラーゲン、塩化ヒドロキシプロピルアンモニウム加水分解コラーゲン、エラスチン分解ペプチド、ケラチン分解ペプチド、加水分解ケラチン、コンキオリン分解ペプチド、加水分解コンキオリン、シルク蛋白分解ペプチド、加水分解シルク、ラウロイル加水分解シルクナトリウム、大豆蛋白分解ペプチド、小麦蛋白分解ペプチド、加水分解小麦蛋白、カゼイン分解ペプチド、アシル化ペプチド等の蛋白ペプチド類及びその誘導体;パルミトイルオリゴペプチド、パルミトイルペンタペプチド、パルミトイルテトラペプチド等のアシル化ペプチド類;シリル化ペプチド類;乳酸菌培養液、酵母抽出液、卵殻膜タンパク、牛顎下腺ムチン、ヒポタウリン、ゴマリグナン配糖体、グルタチオン、アルブミン、乳清;塩化コリン、ホスホリルコリン;胎盤抽出液、エアラスチン、コラーゲン、アロエ抽出物、ハマメリス水、ヘチマ水、カモミラエキス、カンゾウエキス、コンフリーエキス、シルクエキス、イザヨイバラエキス、セイヨウノコギリソウエキス、ユーカリエキス、メリロートエキス等の動物・植物抽出成分、天然型セラミド(タイプ1、2、3、4、5、6)、ヒドロキシセラミド、疑似セラミド、スフィンゴ糖脂質、セラミド及び糖セラミド含有エキス等のセラミド類が好ましいものとして挙げられる。 Betain (trimethylglycine), proline, hydroxyproline, arginine, lysine, serine, glycine, alanine, phenylalanine, tyrosine, β-alanine, threonine, glutamate, glutamine, asparagine, aspartic acid, cysteine, cystine, methionine, leucine, isoleucine, Amino acids such as valine, tryptophan, histidine, taurine and salts thereof; collagen, fish-derived collagen, atelocollagen, gelatin, elastin, collagen-degrading peptide, hydrolyzed collagen, hydroxypropylammonium chloride hydrolyzed collagen, elastin-degrading peptide, keratin-degrading peptide , Hydrolyzed keratin, conchiolin-degrading peptide, hydrolyzed conchiolin, silk proteolytic peptide, hydrolyzed silk, lauroyl-hydrolyzed silk sodium, soybean proteolytic peptide, wheat proteolytic peptide, hydrolyzed wheat protein, casein-degrading peptide, acylated peptide Protein peptides and derivatives thereof; acylated peptides such as palmitoyl oligopeptide, palmitoyl pentapeptide, palmitoyl tetrapeptide; silylated peptides; lactic acid bacteria culture solution, yeast extract, eggshell membrane protein, bovine submandibular gland mutin, etc. Hippotaurin, sesame lignan glycoside, glutathione, albumin, lactose; choline chloride, phosphorylcholine; placenta extract, aerastin, collagen, aloe extract, hamamelis water, hechima water, chamomile extract, kanzo extract, confree extract, silk extract, Animal / plant extracts such as Izayoibara extract, Seiyo-no-kogiri-sou extract, Eucalyptus extract, Merilot extract, natural ceramides (types 1, 2, 3, 4, 5, 6), hydroxyceramides, pseudo-ceramides, sphingoglycolipids, ceramides and Ceramides such as sugar ceramide-containing extracts are preferred.
界面活性剤としては、陰イオン性界面活性剤、非イオン界面活性剤、陽イオン性界面活性剤、両性界面活性剤、高分子界面活性剤等が好ましいものとして挙げられる。界面活性剤のHLBには特に制限はなく、1程度の低いものから20程度の高いものまで使用でき、HLB低いものと高いものを組み合わせることも好ましい。
界面活性剤として好ましいものを例示すると、陰イオン性界面活性剤では、ラウリン酸カリウム、ミリスチン酸カリウム等の脂肪酸塩;ラウリル硫酸ナトリウム、ラウリル硫酸トリエタノールアミン、ラウリル硫酸アンモニウム等のアルキル硫酸エステル塩;ラウレス硫酸ナトリウム、ラウレス硫酸トリエタノールアミン等のポリオキシエチレンアルキル硫酸塩;ココイルメチルタウリンナトリウム、ココイルメチルタウリンカリウム、ラウロイルメチルタウリンナトリウム、ミリストイルメチルタウリンナトリウム、ラウロイルメチルアラニンナトリウム、ラウロイルサルコシンナトリウム、ラウロイルサルコシントリエタノールアミン、ラウロイルグルタミン酸メチルアラニンナトリウム等のアシルN-メチルアミノ酸塩;ココイルグルタミン酸ナトリウム、ココイルグルタミン酸トリエタノールアミン、ラウロイルグルタミン酸ナトリウム、ミリストイルグルタミン酸ナトリウム、ステアロイルグルタミン酸ナトリウム、パルミトイルアスパラギン酸ジトリエタノールアミン、ココイルアラニントリエタノールアミン等のアシルアミノ酸塩;ラウレス酢酸ナトリウム等のポリオキシエチレンアルキルエーテル酢酸塩;ラウロイルモノエタノールアミドコハク酸ナトリウム等のコハク酸エステル塩;脂肪酸アルカノールアミドエーテルカルボン酸塩;アシル乳酸塩;ポリオキシエチレン脂肪アミン硫酸塩;脂肪酸アルカノールアミド硫酸塩;硬化ヤシ油脂肪酸グリセリン硫酸ナトリウム等の脂肪酸グリセリド硫酸塩;アルキルベンゼンポリオキシエチレン硫酸塩;α-オレフィンスルホン酸ナトリウム等のオレフィンスルホン酸塩;スルホコハク酸ラウリル2ナトリウム、スルホコハク酸ジオクチルナトリウム等のアルキルスルホコハク酸塩;スルホコハク酸ラウレス2ナトリウム、モノラウロイルモノエタノールアミドポリオキシエチレンスルホコハク酸ナトリウム、ラウリルポリプロピレングリコールスルホコハク酸ナトリウム等のアルキルエーテルスルホコハク酸塩;テトラデシルベンゼンスルホン酸ナトリウム、テトラデシルベンゼンスルホン酸トリエタノールアミン等のアルキルベンゼンスルホン酸塩;アルキルナフタレンスルホン酸塩;アルカンスルホン酸塩;α-スルホ脂肪酸メチルエステル塩;アシルイセチオン酸塩;アルキルグリシジルエーテルスルホン酸塩;アルキルスルホ酢酸塩;ラウレスリン酸ナトリウム、ジラウレスリン酸ナトリウム、トリラウレスリン酸ナトリウム、モノオレスリン酸ナトリウム等のアルキルエーテルリン酸エステル塩;ラウリルリン酸カリウム等のアルキルリン酸エステル塩;カゼインナトリウム;アルキルアリールエーテルリン酸塩;脂肪酸アミドエーテルリン酸塩;ホスファチジルグリセロール、ホスファチジルイノシトール、ホスファチジン酸等のリン脂質類;カルボン酸変性シリコーン、リン酸変性シリコーン、硫酸変性シリコーン等のシリコーン系陰イオン性界面活性剤等;
Preferred examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and polymer surfactants. The HLB of the surfactant is not particularly limited and can be used from a low HLB of about 1 to a high HLB of about 20, and it is also preferable to combine a low HLB and a high HLB.
Examples of preferred surfactants include fatty acid salts such as potassium laurate and potassium myristate; alkyl sulphates such as sodium lauryl sulphate, triethanolamine lauryl sulphate and ammonium lauryl sulphate; laureth. Polyoxyethylene alkyl sulfates such as sodium sulphate, triethanolamine laures sulphate; sodium cocoylmethyl taurine, potassium cocoyl methyl taurine, sodium lauroyl methyl taurine, sodium myristylmethyl taurine, sodium lauroyl methyl alanine, sodium lauroyl sulcocin, sodium lauroyl sulcocin triethanol. Acyl N-methyl amino acid salts such as amines and sodium methylalanine lauroyl glutamate; sodium cocoyl glutamate, triethanolamine cocoyl glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium stearoyl glutamate, ditriethanolamine palmitoyl aspartate, cocoylalanine triethanolamine. Acylamino acid salts such as; polyoxyethylene alkyl ether acetates such as sodium laures acetate; succinic acid ester salts such as lauroyl monoethanolamide sodium succinate; fatty acid alkanolamide ether carboxylates; acyl lates; polyoxyethylene fatty amines. Sulfate; fatty acid alkanolamide sulfate; hardened coconut oil fatty acid fatty acid glyceride sulfate such as sodium glycerin sulfate; alkylbenzenepolyoxyethylene sulfate; olefin sulfonate such as α-olefin sulfonate sodium; lauryl lauryl sulfosuccinate disodium, sulfokohaku Alkyl sulfosuccinates such as sodium dioctyl sulphonate; alkyl ether sulfosuccinates such as laures disodium sulfosuccinate, monolauroyl monoethanolamide polyoxyethylene sulfosuccinate sodium, sodium lauryl polypropylene glycol sulfosuccinate; sodium tetradecylbenzene sulfonate, tetra Alkylbenzene sulfonates such as decylbenzenesulfonic acid triethanolamine; Alkylnaphthalene sulfonates; Alcan sulfonates; Alkyl ether phosphates such as sodium acid, sodium dilaures phosphate, sodium trilaures phosphate, sodium monoolesphosphate; alkyl phosphates such as potassium lauryl phosphate; sodium caseinate; alkylaryl ether phosphate; fatty acid amide ether Phosphate; Phosphatidylglycerol, phosphatidylinositol, phosphatidic acid and other phospholipids; carboxylic acid-modified silicone, phosphoric acid-modified silicone, sulfate-modified silicone and other silicone-based anionic surfactants;
非イオン界面活性剤では、ラウレス(ポリオキシエチレンラウリルエーテル)類、セテス(ポリオキシエチレンセチルエーテル)類、ステアレス(ポリオキシエチレンステアリルエーテル)類、ベヘネス類(ポリオキシエチレンベヘニルエーテル)、イソステアレス(ポリオキシエチレンイソステアリルエーテル)類、オクチルドデセス(ポリオキシエチレンオクチルドデシルエーテル)類等の種々のポリオキシエチレン付加数のポリオキシエチレンアルキルエーテル類;ポリオキシエチレンアルキルフェニルエーテル;ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンヒマシ油、ポリオキシエチレン硬化ヒマシ油モノイソステアレート、ポリオキシエチレン硬化ヒマシ油トリイソステアレート、ポリオキシエチレン硬化ヒマシ油モノピログルタミン酸モノイソステアリン酸ジエステル、ポリオキシエチレン硬化ヒマシ油マレイン酸等のヒマシ油及び硬化ヒマシ油誘導体;ポリオキシエチレンフィトステロール;ポリオキシエチレンコレステロール;ポリオキシエチレンコレスタノール;ポリオキシエチレンラノリン;ポリオキシエチレン還元ラノリン;ポリオキシエチレン・ポリオキシプロピレンセチルエーテル、ポリオキシエチレン・ポリオキシプロピレン2-デシルテトラデシルエーテル、ポリオキシエチレン・ポリオキシプロピレンモノブチルエーテル、ポリオキシエチレン・ポリオキシプロピレン水添ラノリン、ポリオキシエチレン・ポリオキシプロピレングリセリンエーテル等のポリオキシエチレン・ポリオキシプロピレンアルキルエーテル;ポリオキシエチレン・ポリオキシプロピレングリコール;PPG-9ジグリセリル等の(ポリ)グリセリンポリオキシプロピレングリコール;ステアリン酸グリセリル、イソステアリン酸グリセリル、パルミチン酸グリセリル、ミリスチン酸グリセリル、オレイン酸グリセリル、ヤシ油脂肪酸グリセリル、モノ綿実油脂肪酸グリセリン、モノエルカ酸グリセリン、セスキオレイン酸グリセリン、α,α’-オレイン酸ピログルタミン酸グリセリン、モノステアリン酸グリセリンリンゴ酸等のグリセリン脂肪酸部分エステル類;ステアリン酸ポリグリセリル-2、同3、同4、同5、同6、同8、同10、ジステアリン酸ポリグリセリル-6、同10、トリステアリン酸ポリグリセリル-2、デカステアリン酸ポリグリセリル-10、イソステアリン酸ポリグリセリル-2、同3、同4、同5、同6、同8、同10、ジイソステアリン酸ポリグリセリル-2(ジイソステアリン酸ジグリセリル)、同3、同10、トリイソステアリン酸ポリグリセリル-2、テトライソステアリン酸ポリグリセリル-2、デカイソステアリン酸ポリグリセリル-10、オレイン酸ポリグリセリル-2、同3、同4、同5、同6、同8、同10、ジオレイン酸ポリグリセリル-6、トリオレイン酸ポリグリセリル-2、デカオレイン酸ポリグリセリル-10等のポリグリセリン脂肪酸エステル;モノステアリン酸エチレングリコール等のエチレングリコールモノ脂肪酸エステル;モノステアリン酸プロピレングリコール等のプロピレングリコールモノ脂肪酸エステル;ペンタエリスリトール部分脂肪酸エステル;ソルビトール部分脂肪酸エステル;マルチトール部分脂肪酸エステル; Nonionic surfactants include laureth (polyoxyethylene lauryl ether), ceteth (polyoxyethylene cetyl ether), steares (polyoxyethylene stearyl ether), behenes (polyoxyethylene behenyl ether), and isosteares (poly). Polyoxyethylene alkyl ethers with various polyoxyethylene additions such as oxyethylene isostearyl ethers), octyldodeces (polyoxyethylene octyldodecyl ethers); polyoxyethylene alkylphenyl ethers; polyoxyethylene hydrogenated castor oil, poly Oxyethylene glycol oil, polyoxyethylene hydrogenated castor oil monoisostearate, polyoxyethylene hydrogenated castor oil triisostearate, polyoxyethylene hydrogenated castor oil monopyroglutamic acid monoisostearic acid diester, polyoxyethylene hydrogenated castor oil maleic acid, etc. Polyoxyethylene phytosterol; polyoxyethylene cholesterol; polyoxyethylene cholesterolol; polyoxyethylene lanolin; polyoxyethylene reduced lanolin; polyoxyethylene / polyoxypropylene cetyl ether, polyoxyethylene / Polyoxyethylene / polyoxypropylene alkyl such as polyoxypropylene 2-decyltetradecyl ether, polyoxyethylene / polyoxypropylene monobutyl ether, polyoxyethylene / polyoxypropylene hydrogenated lanolin, polyoxyethylene / polyoxypropylene glycerin ether, etc. Ether; Polyoxyethylene / Polyoxypropylene glycol; (Poly) glycerin such as PPG-9 diglyceryl Polyoxypropylene glycol; Glyceryl stearate, glyceryl isostearate, glyceryl palmitate, glyceryl myristate, glyceryl oleate, coconut oil fatty acid Glyceryl, monocotton oil fatty acid glycerin, monoerkaate glycerin, sesquioleate glycerin, α, α'-pyroglutamate oleate glycerin, monostearate glycerin apple acid and other glycerin fatty acid partial esters; polyglyceryl-2 stearate, 3, 4, 5, 6, 8, 10, Distearate Polyglyceryl-6, 10, Tristearate Polyglyceryl-2, Decastarate Polyglyceryl-10, Isostearate Polyglycerate Lil-2, 3, 4, 5, 5, 6, Polyglyceryl-2 diisostearate-2 (diglyceryl diisostearate), 3, 10, Polyglyceryl-2 triisostearate, Tetraisostearic acid. Polyglyceryl-2, polyglyceryl-10 decaisostearate, polyglyceryl-2 oleate, 3, 4, 5, 6, 6, 8, polyglyceryl-6 dioleate, polyglyceryl-2 trioleate, decaurenic acid Polyglycerin fatty acid ester such as polyglyceryl-10; ethylene glycol monofatty acid ester such as ethylene glycol monostearate; propylene glycol monofatty acid ester such as propylene glycol monostearate; pentaerythritol partial fatty acid ester; sorbitol partial fatty acid ester; martitol moiety Fatty acid ester;
マルチトールエーテル;ソルビタンモノオレエート、ソルビタンモノイソステアレート、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンセスキオレエート、ソルビタントリオレエート、ペンタ-2-エチルヘキシル酸ジグリセロールソルビタン、テトラ-2-エチルヘキシル酸ジグリセロールソルビタン等のソルビタン脂肪酸エステル;ショ糖脂肪酸エステル、メチルグルコシド脂肪酸エステル、ウンデシレン酸トレハロース等の糖誘導体部分エステル;カプリリルグルコシド等のアルキルグルコシド;アルキルポリグリコシド;ラノリンアルコール;還元ラノリン;ポリオキシエチレンジステアレート、ポリチレングリコールジイソステアレート、ポリオキシエチレンモノオレエート、ポリオキシエチレンジオレエート等のポリオキシエチレン脂肪酸モノ及びジエステル;ポリオキシエチレン・プロピレングリコール脂肪酸エステル;ポリオキシエチレングリセリンモノステアレート、ポリオキシエチレングリセリンモノイソステアレート、ポリオキシエチレングリセリントリイソステアレート等のポリオキシエチレンモノオレエート等のポリオキシエチレングリセリン脂肪酸エステル;ポリオキシエチレンソルビタンモノオレエート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタンモノオレート、ポリオキシエチレンソルビタンテトラオレエート等のポリオキシエチレンソルビタン脂肪酸エステル;ポリオキシエチレンソルビトールモノラウレート、ポリオキシエチレンソルビトールモノオレエート、ポリオキシエチレンソルビトールペンタオレエート、ポリオキシエチレンソルビトールモノステアレート等のポリオキシエチレンソルビトール脂肪酸エステル;ポリオキシエチレンメチルグルコシド脂肪酸エステル;ポリオキシエチレンアルキルエーテル脂肪酸エステル;ポリオキシエチレンソルビトールミツロウ等のポリオキシエチレン動植物油脂類;イソステアリルグリセリルエーテル、キミルアルコール、セラキルアルコール、バチルアルコール等のアルキルグリセリルエーテル類;多価アルコールアルキルエーテル;ポリオキシエチレンアルキルアミン;テトラポリオキシエチレン・テトラポリオキシプロピレン-エチレンジアミン縮合物類;サポニン、ソホロリピッド等の天然系界面活性剤;ポリオキシエチレン脂肪酸アミド;ヤシ油脂肪酸モノエタノールアミド(コカミドMEA)、ヤシ油脂肪酸ジエタノールアミド(コカミドDEA)、ラウリン酸モノエタノールアミド(ラウラミドMEA)、ラウリン酸ジエタノールアミド(ラウラミドDEA)、ラウリン酸モノイソプロパノールアミド(ラウラミドMIPA)、パルミチン酸モノエタノールアミド(パルタミドMEA)、パルミチン酸ジエタノールアミド(パルタミドDEA)、ヤシ油脂肪酸メチルエタノールアミド(コカミドメチルMEA)等の脂肪酸アルカノールアミド類; Multitoll ether; sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta-2-ethylhexyl diglycerol sorbitan, tetra Sorbitan fatty acid ester such as -2-ethylhexyl diglycerol sorbitan; sugar derivative partial ester such as sucrose fatty acid ester, methyl glucoside fatty acid ester, undosilenic acid trehalose; alkyl glucoside such as caprylyl glucoside; alkyl polyglycoside; lanolin alcohol; reduction Lanolin; Polyoxyethylene fatty acid mono and diesters such as polyoxyethylene distearate, polytylene glycol diisostearate, polyoxyethylene monooleate, polyoxyethylene dioleate; polyoxyethylene / propylene glycol fatty acid ester; poly Polyoxyethylene glycerin fatty acid esters such as polyoxyethylene monooleate such as oxyethylene glycerin monostearate, polyoxyethylene glycerin monoisostearate, polyoxyethylene glycerin triisostearate; polyoxyethylene sorbitan monooleate, poly Polyoxyethylene sorbitan fatty acid esters such as oxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tetraoleate; polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monooleate, polyoxyethylene sorbitol Polyoxyethylene sorbitol fatty acid esters such as pentaoleate and polyoxyethylene sorbitol monostearate; polyoxyethylene methyl glucoside fatty acid esters; polyoxyethylene alkyl ether fatty acid esters; polyoxyethylene animal and vegetable oils and fats such as polyoxyethylene sorbitol honeybees; Alkyl glyceryl ethers such as isostearyl glyceryl ether, kimil alcohol, seraquil alcohol, batyl alcohol; polyhydric alcohol alkyl ether; polyoxyethylene alkylamine; tetrapolyoxyethylene / tetrapolyoxypropylene-ethylenediamine condensate; saponin , Sophorolipid and other natural surfactants; polyoxyethylene fat Acid amide; coconut oil fatty acid monoethanolamide (cocamide MEA), coconut oil fatty acid diethanolamide (cocamide DEA), lauric acid monoethanolamide (lauramide MEA), lauric acid diethanolamide (lauramide DEA), lauric acid monoisopropanolamide (lauramide) MIPA), palmitic acid monoethanolamide (partamide MEA), palmitic acid diethanolamide (partamide DEA), coconut oil fatty acid methylethanolamide (cocamidomethyl MEA) and other fatty acid alkanolamides;
ラウラミンオキシド、コカミンオキシド、ステアラミンオキシド、ベヘナミンオキシド等のアルキルジメチルアミンオキシド;アルキルエトキシジメチルアミンオキシド;ポリオキシエチレンアルキルメルカプタン;ジメチコンコポリオール等のポリエーテル変性シリコーン、ポリシロキサン・オキシアルキレン共重合体、ポリグリセリン変性シリコーン、糖変性シリコーン等のシリコーン系非イオン性界面活性剤等;陽イオン性界面活性剤では、ベヘントリモニウムクロリド、ステアルトリモニウムクロリド、セトリモニウムクロリド、ラウリルトリモニウムクロリド等のアルキルトリメチルアンモニウムクロリド;ステアリルトリモニウムブロミド等のアルキルトリメチルアンモニウムブロミド;ジステアリルジモニウムクロリド、ジココジモニウムクロリド等のジアルキルジメチルアンモニウムクロリド;ステアラミドプロピルジメチルアミン、ステアラミドエチルジエチルアミン等の脂肪酸アミドアミン及びその塩;ステアロキシプロピルジメチルアミン等のアルキルエーテルアミン及びその塩または四級塩;エチル硫酸長鎖分岐脂肪酸(12~31)アミノプロピルエチルジメチルアンモニウム、エチル硫酸ラノリン脂肪酸アミノプロピルエチルジメチルアンモニウム等の脂肪酸アミド型四級アンモニウム塩;ポリオキシエチレンアルキルアミン及びその塩または四級塩;アルキルアミン塩;脂肪酸アミドグアニジウム塩;アルキルエーテルアミンモニウム塩;アルキルトリアルキレングリコールアンモニウム塩;ベンザルコニウム塩;ベンゼトニウム塩;塩化セチルピリジニウム等のピリジニウム塩;イミダゾリニウム塩;アルキルイソキノリニウム塩;ジアルキルモリホニウム塩;ポリアミン脂肪酸誘導体;アミノプロピルジメチコン及びアモジメチコン等のアミノ変性シリコーン、カチオン変性シリコーン、カチオン変性及びポリエーテル変性シリコーン、アミノ変性及びポリエーテル変性シリコーン等のシリコーン系陽イオン性界面活性剤等;両性界面活性剤では、ラウリルベタイン(ラウリルジメチルアミノ酢酸ベタイン)等のN-アルキル-N,N-ジメチルアミノ酸ベタイン;コカミドプロピルベタイン、ラウラミドプロピルベタイン等の脂肪酸アミドアルキル-N,N-ジメチルアミノ酸ベタイン;ココアンホ酢酸ナトリウム、ラウロアンホ酢酸ナトリウム等のイミダゾリン型ベタイン;アルキルジメチルタウリン等のアルキルスルホベタイン;アルキルジメチルアミノエタノール硫酸エステル等の硫酸型ベタイン;アルキルジメチルアミノエタノールリン酸エステル等のリン酸型ベタイン;ホスファチジルコリン、ホスファチジルエタノールアミン、ホスファチジルセリン、スフィンゴミエリン等のスフィンゴリン脂質、リゾレシチン、水素添加大豆リン脂質、部分水素添加大豆リン脂質、水素添加卵黄リン脂質、部分水素添加卵黄リン脂質、水酸化レシチン等のリン脂質類;シリコーン系両性界面活性剤等;高分子界面活性剤では、ポリビニルアルコール、アルギン酸ナトリウム、デンプン誘導体、トラガントガム、アクリル酸・メタアクリル酸アルキル共重合体;シリコーン系各種界面活性剤が好ましいものとして挙げられる。 Alkyldimethylamine oxides such as lauramine oxide, cocamine oxide, stearamine oxide, and behenamine oxide; alkylethoxydimethylamine oxides; polyoxyethylene alkyl mercaptans; polyether-modified silicones such as dimethicone copolyol, polysiloxanes and oxyalkylenes. Silicone-based nonionic surfactants such as copolymers, polyglycerin-modified silicones, and sugar-modified silicones; among cationic surfactants, behentrimonium chloride, stealtrimonium chloride, cetrimonium chloride, and lauryltrimonium chloride. Alkyltrimethylammonium chlorides such as; alkyltrimethylammonium bromides such as stearyltrimonium bromides; dialkyldimethylammonium chlorides such as distearyldimonium chlorides and dicocodimonium chlorides; fatty acid amide amines such as stealamidepropyldimethylamine and stearamideethyldiethylamine and The salt; an alkyl ether amine such as stearoxypropyl dimethylamine and its salt or a quaternary salt; ethyl sulfate long chain branched fatty acid (12-31) aminopropyl ethyldimethylammonium, ethyl sulfate lanolin fatty acid amino acid such as aminopropyl ethyldimethylammonium. Amido-type quaternary ammonium salt; polyoxyethylene alkylamine and its salt or quaternary salt; alkylamine salt; fatty acid amide guanidium salt; alkyl etheraminemonium salt; alkyltrialkylene glycol ammonium salt; benzalconium salt; benzethonium Salts; pyridinium salts such as cetylpyridinium chloride; imidazolinium salts; alkylisoquinolinium salts; dialkylmoriphonium salts; polyamine fatty acid derivatives; amino-modified silicones such as aminopropyldimethicone and amodimethicone, cation-modified silicones, cation-modified And silicone-based cationic surfactants such as polyether-modified silicones, amino-modified and polyether-modified silicones; for amphoteric surfactants, N-alkyl-N, N- such as lauryl betaine (lauryldimethylaminoacetic acid betaine). Dimethyl amino acid betaine; fatty acid amide alkyl-N, N-dimethylamino acid betaine such as cocamidopropyl betaine and lauramidopropyl betaine; imidazoline type betaine such as sodium cocoamphoacetate and sodium lauroamphoacetate; Alkyl sulfobetaine such as ledimethyltaurin; Sulfate-type betaine such as alkyldimethylaminoethanol sulfate ester; Phospholipid-type betaine such as alkyldimethylaminoethanol phosphate ester; Sphingoline such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, sphingomyelin Phospholipids such as lipids, lysolecithin, hydrogenated soybean phospholipids, partially hydrogenated soybean phospholipids, hydrogenated egg yolk phospholipids, partially hydrogenated egg yolk phospholipids, and hydroxylated lecithin; silicone-based amphoteric surfactants, etc .; Examples of the activator include polyvinyl alcohol, sodium alginate, starch derivative, tragant gum, acrylic acid / alkyl methacrylic acid copolymer; and various silicone-based surfactants are preferable.
高分子・増粘剤・ゲル化剤としては、グアーガム、ローカストビーンガム、クィーンスシード、カラギーナン、ガラクタン、アラビアガム、タラガム、タマリンド、ファーセレラン、カラヤガム、トロロアオイ、キャラガム、トラガントガム、ペクチン、ペクチン酸及びナトリウム塩等の塩、アルギン酸及びナトリウム塩等の塩、マンナン;コメ、トウモロコシ、バレイショ、コムギ等のデンプン;キサンタンガム、デキストラン、サクシノグルカン、カードラン、ヒアルロン酸及びその塩、ザンサンガム、プルラン、ジェランガム、キチン、キトサン、寒天、カッソウエキス、コンドロイチン硫酸塩、カゼイン、コラーゲン、ゼラチン、アルブミン;メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロース及びそのナトリウム等の塩、メチルヒドロキシプロピルセルロース、セルロース硫酸ナトリウム、ジアルキルジメチルアンモニウム硫酸セルロース、結晶セルロース、セルロース末等のセルロース及びその誘導体;可溶性デンプン、カルボキシメチルデンプン、メチルヒドロキシプロピルデンプン、メチルデンプン等のデンプン系高分子、塩化ヒドロキシプロピルトリモニウムデンプン、オクテニルコハク酸トウモロコシデンプンアルミニウム等のデンプン誘導体;アルギン酸ナトリウム、アルギン酸プロピレングリコールエステル等アルギン酸誘導体;ポリビニルピドリドン(PVP)、ポリビニルアルコール(PVA)、ビニルピドリドン・ビニルアルコール共重合体、ポリビニルメチルエーテル;ポリエチレングリコール、ポリプロピレングリコール、ポリオキシエチレン・ポリオキシプロピレン共重合体;(メタクリロイルオキシエチルカルボキシベタイン/メタクリル酸アルキル)コポリマー、(アクリレーツ/アクリル酸ステアリル/メタクリル酸エチルアミンオキシド)コポリマー等の両性メタクリル酸エステル共重合体;(ジメチコン/ビニルジメチコン)クロスポリマー、(アクリル酸アルキル/ジアセトンアクリルアミド)コポリマー、(アクリル酸アルキル/ジアセトンアクリルアミド)コポリマーAMP;ポリ酢酸ビニル部分けん化物、マレイン酸共重合体;ビニルピロリドン・メタクリル酸ジアルキルアミノアルキル共重合体;アクリル樹脂アルカノールアミン;ポリエステル、水分散性ポリエステル;ポリアクリルアミド;ポリアクリル酸エチル等のポリアクリル酸エステル共重合体、カルボキシビニルポリマー、ポリアクリル酸及びそのナトリウム塩等の塩、アクリル酸・メタアクリル酸エステル共重合体; Examples of the polymer / thickener / gelling agent include guar gum, locust bean gum, queens seed, carrageenan, galactan, arabic gum, tara gum, tamarind, farcerelan, karaya gum, trolley aoi, cara gum, tragant gum, pectin, pectic acid and sodium. Salts such as salts, salts such as alginic acid and sodium salts, mannan; starches such as rice, corn, potatoes, wheat; xanthan gum, dextran, succinoglucan, curdran, hyaluronic acid and its salts, zansan gum, purulan, gellan gum, chitin , Chitosan, agar, casso extract, chondroitin sulfate, casein, collagen, gelatin, albumin; methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose and salts such as sodium thereof, methylhydroxypropylcellulose, sodium cellulose sulfate, dialkyldimethyl Ammium sulfate cellulose, crystalline cellulose, cellulose such as cellulose powder and derivatives thereof; starch-based polymers such as soluble starch, carboxymethyl starch, methyl hydroxypropyl starch, methyl starch, hydroxypropyltrimonium chloride starch, octenyl succinate corn starch aluminum, etc. Alginic acid derivatives such as sodium alginate and propylene glycol alginate; polyvinylpyridone (PVP), polyvinyl alcohol (PVA), vinylpidridone / vinyl alcohol copolymer, polyvinylmethyl ether; polyethylene glycol, polypropylene glycol, polyoxyethylene. Polyoxypropylene copolymer; (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymer, (Acrylate / stearyl acrylate / ethylamine methacrylate) copolymer and other amphoteric methacrylic acid ester copolymers; (dimethicone / vinyldimethicone) cloth Polymers, (alkyl acrylate / diacetone acrylamide) copolymers, (alkyl acrylate / diacetone acrylamide) copolymers AMP; partially saponified polyvinyl acetates, maleic acid copolymers; vinylpyrrolidone / dialkylaminoalkyl methacrylate copolymers; Acrylic resin alkanolamine; polyester, water-dispersible polyester; polya Crylamide; polyacrylic acid ester copolymer such as ethyl polyacrylic acid, carboxyvinyl polymer, salt such as polyacrylic acid and sodium salt thereof, acrylic acid / methacrylic acid ester copolymer;
アクリル酸・メタアクリル酸アルキル共重合体;ポリクオタニウム-10等のカチオン化セルロース、ポリクオタニウム-7等のジアリルジメチルアンモニウムクロリド・アクリルアミド共重合体、ポリクオタニウム-22等のアクリル酸・ジアリルジメチルアンモニウムクロリド共重合体、ポリクオタニウム-39等のアクリル酸・ジアリルジメチルアンモニウムクロリド・アクリルアミド共重合体、アクリル酸・カチオン化メタアクリル酸エステル共重合体、アクリル酸・カチオン化メタアクリル酸アミド共重合体、ポリクオタニウム-47等のアクリル酸・アクリル酸メチル・塩化メタクリルアミドプロピルトリメチルアンモニウム共重合体、塩化メタクリル酸コリンエステル重合体;カチオン化オリゴ糖、カチオン化デキストラン、グアーヒドロキシプロピルトリモニウムクロリド等のカチオン化多糖類;ポリエチレンイミン;カチオンポリマー;ポリクオタニウム-51等の2-メタクリロイルオキシエチルホスホリルコリンの重合体及びメタクリル酸ブチル共重合体等との共重合体;アクリル樹脂エマルジョン、ポリアクリル酸エチルエマルジョン、ポリアクリルアルキルエステルエマルジョン、ポリ酢酸ビニル樹脂エマルジョン、天然ゴムラテックス、合成ラテックス等の高分子エマルジョン;ニトロセルロース;ポリウレタン類及び各種共重合体;各種シリコーン類;アクリル-シリコーングラフト共重合体等のシリコーン系各種共重合体;各種フッ素系高分子;12-ヒドロキシステアリン酸及びその塩;パルミチン酸デキストリン、ミリスチン酸デキストリン等のデキストリン脂肪酸エステル;無水ケイ酸、煙霧状シリカ(超微粒子無水ケイ酸)、ケイ酸アルミニウムマグネシウム、ケイ酸ナトリウムマグネシウム、金属石鹸、ジアルキルリン酸金属塩、ベントナイト、ヘクトライト、有機変性粘土鉱物、ショ糖脂肪酸エステル、フラクトオリゴ糖脂肪酸エステルが好ましいものとして挙げられる。 Acrylic acid / alkyl methacrylic acid copolymer; cationized cellulose such as polyquaternium-10, diallyldimethylammonium chloride / acrylamide copolymer such as polyquaternium-7, acrylic acid / diallyldimethylammonium chloride copolymer such as polyquaterium-22. , Polyquaternium-39 and other acrylic acid / diallyldimethylammonium chloride / acrylamide copolymers, acrylic acid / cationized methacrylic acid ester copolymers, acrylic acid / cationized methacrylic acid amide copolymers, polyquaterium-47 and the like. Acrylic acid / methyl acrylate / methacrylate propyltrimethylammonium chloride copolymer, choline chloride ester polymer; cationized oligosaccharides, cationized dextran, cationized polysaccharides such as guarhydroxypropyltrimonium chloride; polyethyleneimine; Cationic polymer; Polymer of 2-methacryloyloxyethyl phosphorylcholine such as polyquaternium-51 and polymer with butyl methacrylate copolymer; acrylic resin emulsion, ethyl polyacrylate emulsion, polyacrylic alkyl ester emulsion, vinyl acetate Polymer emulsions such as resin emulsions, natural rubber latex, synthetic latex; nitrocellulose; polyurethanes and various copolymers; various silicones; various silicone-based copolymers such as acrylic-silicone graft copolymers; various fluoropolymers; Polymers; 12-hydroxystearic acid and salts thereof; dextrin fatty acid esters such as dextrin palmitate and dextrin myristinate; silicic acid anhydride, fumigant silica (ultrafine anhydrous silicic acid), aluminum magnesium silicate, sodium magnesium silicate, metal. Preferred examples include soap, dialkyl phosphate metal salt, bentonite, hectrite, organically modified clay mineral, sucrose fatty acid ester, and fructo-oligosaccharide fatty acid ester.
溶剤・噴射剤類としては、エタノール、2-プロパノール(イソプロピルアルコール)、ブタノール、イソブチルアルコール等の低級アルコール類;プロピレングリコール、1,3-ブチレングリコール、ジエチレングリコール、ジプロピレングリコール、イソペンチルジオール等のグリコール類;ジエチレングリコールモノエチルエーテル(エトキシジグリコール)、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、トリエチレングリコールモノエチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノエチルエーテル等のグリコールエーテル類;エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等のグリコールエーテルエステル類;コハク酸ジエトキシエチル、エチレングリコールジサクシネート等のグリコールエステル類;ベンジルアルコール、ベンジルオキシエタノール、炭酸プロピレン、炭酸ジアルキル、アセトン、酢酸エチル、N-メチルピロリドン;トルエン;フルオロカーボン、次世代フロン;LPG、ジメチルエーテル、炭酸ガス等の噴射剤が好ましいものとして挙げられる。 Examples of solvents and propellants include lower alcohols such as ethanol, 2-propanol (isopropyl alcohol), butanol and isobutyl alcohol; glycols such as propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol and isopentyldiol. Kind: Diethylene glycol monoethyl ether (ethoxydiglycol), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether Glycol ethers such as; glycol ether esters such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate; glycol esters such as diethoxyethyl succinate, ethylene glycol dissuccinate; benzyl Preferred examples include propellants such as alcohol, benzyloxyethanol, propylene carbonate, dialkyl carbonate, acetone, ethyl acetate, N-methylpyrrolidone; toluene; fluorocarbon, next-generation freon; LPG, dimethyl ether, carbon dioxide gas and the like.
酸化防止剤としては、トコフェロール(ビタミンE)、酢酸トコフェロール等のトコフェロール誘導体;BHT、BHA;没食子酸プロピル等の没食子酸誘導体;ビタミンC(アスコルビン酸)および/またはその誘導体;エリソルビン酸及びその誘導体;亜硫酸ナトリウム等の亜硫酸塩;亜硫酸水素ナトリウム等の亜硫酸水素塩;チオ硫酸ナトリウム等のチオ硫酸塩;メタ亜硫酸水素塩;チオタウリン、ヒポタウリン;チオグリセロール、チオ尿素、チオグリコール酸、システイン塩酸塩が好ましいものとして挙げられる。
還元剤としては、チオグリコール酸、システイン、システアミン等が好ましいものとして挙げられる。
酸化剤としては、過酸化水素水、過硫酸アンモニウム、臭素酸ナトリウム、過炭酸等が好ましいものとして挙げられる。
Antioxidants include tocopherol derivatives such as tocopherol (vitamin E) and tocopherol acetate; BHT, BHA; asbestosic acid derivatives such as propyl bisulfate; vitamin C (ascorbic acid) and / or its derivatives; erythorbic acid and its derivatives; Sodium bisulfite and other sulfites; Sodium bisulfite and other sulfite hydrogen salts; Sodium bisulfite and other thiosulfates; Metahydrosulfite hydrogen salts; Thiotaurine, hypotaurine; Thioglycerol, thiourea, thioglycolic acid, cysteine hydrochloride are preferred. Is mentioned as.
As the reducing agent, thioglycolic acid, cysteine, cysteamine and the like are preferable.
As the oxidizing agent, hydrogen peroxide solution, ammonium persulfate, sodium bromate, percarbonate and the like are preferable.
本発明の防腐抗菌剤以外の防腐剤・抗菌剤としては、メチルパラベン、エチルパラベン、プロピルパラベン、ブチルパラベン等のヒドロキシ安息香酸及びその塩若しくはそのエステル;サリチル酸;安息香酸ナトリウム;フェノキシエタノール;1,2-ペンタンジオール、1,2-ヘキサンジオール等の1,2-ジオール;メチルクロロイソチアゾリノン、メチルイソチアゾリノン等のイソチアゾリンオン誘導体;イミダゾリニウムウレア;デヒドロ酢酸及びその塩;フェノール類;トリクロサン等のハロゲン化ビスフェノール類、酸アミド類、四級アンモニウム塩類;トリクロロカルバニド、ジンクピリチオン、塩化ベンザルコニウム、塩化ベンゼトニウム、ソルビン酸、クロルヘキシジン、グルコン酸クロルヘキシジン、ハロカルバン、ヘキサクロロフェン、ヒノキチオール;フェノール、イソプロピルフェノール、クレゾール、チモール、パラクロロフェノール、フェニルフェノール、フェニルフェノールナトリウム等のその他フェノール類;フェニルエチルアルコール、感光素類、抗菌性ゼオライト、銀イオンが好ましいものとして挙げられる。
キレート剤としては、EDTA、EDTA2Na、EDTA3Na、EDTA4Na等のエデト酸塩(エチレンジアミン四酢酸塩);HEDTA3Na等のヒドロキシエチルエチレンジアミン三酢酸塩;ペンテト酸塩(ジエチレントリアミン五酢酸塩);フィチン酸;エチドロン酸等のホスホン酸及びそのナトリウム塩等の塩類;シュウ酸ナトリウム;ポリアスパラギン酸、ポリグルタミン酸等のポリポリアミノ酸類;ポリリン酸ナトリウム、メタリン酸ナトリウム、リン酸;クエン酸ナトリウム、クエン酸、アラニン、ジヒドロキシエチルグリシン、グルコン酸、アスコルビン酸、コハク酸、酒石酸が好ましいものとして挙げられる。
pH調整剤・酸・アルカリとしては、クエン酸、クエン酸ナトリウム、乳酸、乳酸ナトリウム、グリコール酸、コハク酸、酢酸、酢酸ナトリウム、リンゴ酸、酒石酸、フマル酸、リン酸、塩酸、硫酸、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、イソプロパノールアミン、トリイソプロパノールアミン、2-アミノ-2-メチル-1,3ープロパンジオール、2-アミノ-2-ヒドロキシメチル-1,3ープロパンジオール、アルギニン、水酸化ナトリウム、水酸化カリウム、アンモニア水、炭酸グアニジン、炭酸アンモニウムが好ましいものとして挙げられる。
Examples of the antiseptic / antibacterial agent other than the antiseptic / antibacterial agent of the present invention include hydroxybenzoic acids such as methylparaben, ethylparaben, propylparaben and butylparaben and salts thereof or esters thereof; salicylic acid; sodium benzoate; phenoxyethanol; 1,2-. 1,2-diols such as pentandiol and 1,2-hexanediol; isothiazolinone derivatives such as methylchloroisothiazolinone and methylisothiazolinone; imidazolinium urea; dehydroacetic acid and its salts; phenols; triclosan and the like. Halogenized bisphenols, acid amides, quaternary ammonium salts; trichlorocarbanide, zincpyrythion, benzalconium chloride, benzethonium chloride, sorbic acid, chlorhexidine, chlorhexidine gluconate, halocarban, hexachlorophen, hinokithiol; phenol, isopropylphenol, Other phenols such as cresol, timole, parachlorophenol, phenylphenol, sodium phenylphenol; phenylethyl alcohol, photosensitizers, antibacterial zeolite, silver ion are preferred.
Examples of the chelating agent include edetates (ethylenediamine tetraacetate) such as EDTA, EDTA2Na, EDTA3Na, and EDTA4Na; hydroxyethylethylenediamine triacetate such as HEDTA3Na; pentetate (diethylenetriaminepentaacetate); phytic acid; ethidronic acid and the like. Phosphonic acid and salts such as sodium salts thereof; Sodium oxalate; Polypolyamino acids such as polyaspartic acid and polyglutamic acid; Sodium polyphosphate, sodium metaphosphate, phosphate; sodium citrate, citric acid, alanine, dihydroxyethylglycine , Gluconic acid, ascorbic acid, succinic acid, tartrate acid are preferred.
pH adjusters / acids / alkalis include citric acid, sodium citrate, lactic acid, sodium lactate, glycolic acid, succinic acid, acetic acid, sodium acetate, malic acid, tartaric acid, fumaric acid, phosphoric acid, hydrochloric acid, sulfuric acid, monoethanol. Amine, diethanolamine, triethanolamine, isopropanolamine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, arginine, hydroxylated Preferred are sodium, potassium hydroxide, aqueous ammonia, guanidine carbonate and ammonium carbonate.
粉体類としては、マイカ、タルク、カオリン、セリサイト、モンモリロナイト、カオリナイト、雲母、白雲母、金雲母、合成雲母、紅雲母、黒雲母、パーミキュライト、炭酸マグネシウム、炭酸カルシウム、ケイ酸アルミニウム、ケイ酸バリウム、ケイ酸カルシウム、ケイ酸マグネシウム、ケイ酸ストロンチウム、タングステン酸金属塩、マグネシウム、ゼオライト、硫酸バリウム、焼成硫酸カルシウム、リン酸カルシウム、弗素アパタイト、ヒドロキシアパタイト、セラミックパウダー、ベントナイト、スメクタイト、粘土、泥、金属石鹸(例えば、ミリスチン酸亜鉛、パルミチン酸カルシウム、ステアリン酸アルミニウム)、炭酸カルシウム、ベンガラ、黄酸化鉄、黒酸化鉄、群青、紺青、カーボンブラック、酸化チタン、微粒子及び超微粒子酸化チタン、酸化亜鉛、微粒子及び超微粒子酸化亜鉛、アルミナ、シリカ、煙霧状シリカ(超微粒子無水ケイ酸)、雲母チタン、魚鱗箔、窒化ホウ素、ホトクロミック顔料、合成フッ素金雲母、微粒子複合粉体、金、アルミニウム等の各種の大きさ・形状の無機粉体、及び、これらをハイドロジェンシリコーン、環状ハイドロジェンシリコーン等のシリコーン若しくはその他のシラン若しくはチタンカップリング剤等の各種表面処理剤で処理を行って疎水化若しくは親水化した粉体等の無機粉体;デンプン、セルロース、ナイロンパウダー、ポリエチレン末、ポリメタクリル酸メチル末、ポリスチレン末、スチレンとアクリル酸の共重合体樹脂粉末、ポリエステル末、ベンゾグアナミン樹脂粉末、ポリエチレンテレフタレート・ポリメチルメタクリレート積層末、ポリエチレンテレフタレート・アルミニウム・エポキシ積層末等、ウレタン粉末、シリコーン粉末、テフロン(登録商標)粉末等の各種の大きさ・形状の有機系粉体及び表面処理粉体、有機無機複合粉体が好ましいものとして挙げられる。
無機塩類としては、食塩、並塩、岩塩、海塩、天然塩等の塩化ナトリウム含有塩類;塩化カリウム、塩化アルミニウム、塩化カルシウム、塩化マグネシウム、にがり、塩化亜鉛、塩化アンモニウム;硫酸ナトリウム、硫酸アルミニウム、硫酸アルミニウム・カリウム(ミョウバン)、硫酸アルミニウム・アンモニウム、硫酸バリウム、硫酸カルシウム、硫酸カリウム、硫酸マグネシウム、硫酸亜鉛、硫酸鉄、硫酸銅;リン酸1Na・2Na・3Na等のリン酸ナトリウム類、リン酸カリウム類、リン酸カルシウム類、リン酸マグネシウム類が好ましいものとして挙げられる。
Powders include mica, talc, kaolin, sericite, montmorillonite, kaolinite, mica, white mica, gold mica, synthetic mica, red mica, black mica, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, kei. Barium acid, calcium silicate, magnesium silicate, strontium silicate, metal salt of tungsten acid, magnesium, zeolite, barium sulfate, calcined calcium sulfate, calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder, bentonite, smectite, clay, mud, Metal soap (eg zinc myristate, calcium palmitate, aluminum stearate), calcium carbonate, red iron oxide, yellow iron oxide, black iron oxide, ultramarine, dark blue, carbon black, titanium oxide, fine powder and ultrafine titanium oxide, zinc oxide , Fine particles and ultrafine zinc oxide, alumina, silica, fumigant silica (ultrafine anhydrous silicic acid), mica titanium, fish scale foil, boron nitride, photochromic pigment, synthetic fluorine gold mica, fine particle composite powder, gold, aluminum, etc. Inorganic powders of various sizes and shapes, and these are treated with silicones such as hydrogen silicone and cyclic hydrogen silicone or other surface treatment agents such as silane or titanium coupling agents to make them hydrophobic. Inorganic powder such as hydrophilized powder; starch, cellulose, nylon powder, polyethylene powder, polymethylmethacrylate powder, polystyrene powder, styrene and acrylic acid copolymer resin powder, polyester powder, benzoguanamine resin powder, polyethylene terephthalate -Polymethylmethacrylate laminated powder, polyethylene terephthalate, aluminum, epoxy laminated powder, etc., urethane powder, silicone powder, Teflon (registered trademark) powder, and other organic powders and surface-treated powders of various sizes and shapes, organic and inorganic Composite powders are preferred.
Examples of inorganic salts include sodium chloride-containing salts such as salt, normal salt, rock salt, sea salt, and natural salt; potassium chloride, aluminum chloride, calcium chloride, magnesium chloride, ginger, zinc chloride, ammonium chloride; sodium sulfate, aluminum sulfate, etc. Aluminum / potassium sulfate (myoban), aluminum / ammonium sulfate, barium sulfate, calcium sulfate, potassium sulfate, magnesium sulfate, zinc sulfate, iron sulfate, copper sulfate; sodium phosphates such as 1Na / 2Na / 3Na phosphate, phosphoric acid Potassiums, calcium phosphates and magnesium phosphates are preferred.
紫外線吸収剤としては、パラアミノ安息香酸、パラアミノ安息香酸モノグリセリンエステル、N,N-ジプロポキシパラアミノ安息香酸エチルエステル、N,N-ジエトキシパラアミノ安息香酸エチルエステル、N,N-ジメチルパラアミノ安息香酸エチルエステル、N,N-ジメチルパラアミノ安息香酸ブチルエステル、N,N-ジメチルパラアミノ安息香酸エチルエステル等の安息香酸系紫外線吸収剤;ホモメンチル-N-アセチルアントラニレート等のアントラニル酸系紫外線吸収剤;サリチル酸及びそのナトリウム塩、アミルサリシレート、メンチルサリシレート、ホモメンチルサリシレート、オクチルサリシレート、フェニルサリシレート、ベンジルサリシレート、p-イソプロパノールフェニルサリシレート等のサリチル酸系紫外線吸収剤;オクチルシンナメート、エチル-4-イソプロピルシンナメート、メチル-2,5-ジイソプロピルシンナメート、エチル-2,4-ジイソプロピルシンナメート、メチル-2,4-ジイソプロピルシンナメート、プロピル-p-メトキシシンナメート、イソプロピル-p-メトキシシンナメート、イソアミル-p-メトキシシンナメート、2-エチルヘキシルp-メトキシシンナメート(パラメトキシケイヒ酸オクチル)、2-エトキシエチル-p-メトキシシンナメート(シノキサート)、シクロヘキシル-p-メトキシシンナメート、エチル-α-シアノ-β-フェニルシンナメート、2-エチルヘキシルα-シアノ-β-フェニルシンナメート(オクトクリン)、グリセリルモノ-2-エチルヘキサノイル-ジパラメトキシシンナメート、フェルラ酸及びその誘導体等の桂皮酸系紫外線吸収剤;2,4-ジヒドロキシベンゾフェノン、2,2’- ジヒドロキシ-4-メトキシベンゾフェノン、2,2’-ジヒドロキシ-4,4’-ジメトキシベンゾフェノン、2,2’,4,4’-テトラヒドロキシベンゾフェノン、2-ヒドロキシ-4- メトキシベンゾフェノン(オキシベンゾン-3)、2-ヒドロキシ-4-メトキシ-4’-メチルベンゾフェノン、2-ヒドロキシ-4-メトキシベンゾフェノン-5-スルホン酸塩、4-フェニルベンゾフェノン、2-エチルヘキシル-4’-フェニル-ベンゾフェノン-2-カルボキシレート、2-ヒドロキシ-4-n-オクトキシベンゾフェノン、4-ヒドロキシ-3-カルボキシベンゾフェノン等のベンゾフェノン系紫外線吸収剤;3-(4’-メチルベンジリデン)-d,l-カンファー、3-ベンジリデン-d,l-カンファー;2-フェニル-5-メチルベンゾキサゾール;2,2’-ヒドロキシ-5-メチルフェニルベンゾトリアゾール;2-(2’-ヒドロキシ-5’-t-オクチルフェニル)ベンゾトリアゾール;2-(2’-ヒドロキシ-5’-メチルフェニルベンゾトリアゾール;ジベンザラジン;ジアニソイルメタン;5-(3,3-ジメチル-2-ノルボルニリデン)-3-ペンタン-2-オン;4-t-ブチルメトキシジベンゾイルメタン等のジベンゾイルメタン誘導体;オクチルトリアゾン;ウロカニン酸及びウロカニン酸エチル等のウロカニン酸誘導体;2-(2'-ヒドロキシ-5'-メチルフェニル)ベンゾトリアゾール、1-(3,4-ジメトキシフェニル)-4,4-ジメチル-1,3-ペンタンジオン、ジメトキシベンジリデンジオキソイミダゾリジンプロピオン酸2-エチルヘキシル等のヒダントイン誘導体、フェニルベンズイミダソゾールスルホン酸、テレフタリリデンジカンフルスルホン酸、ドロメトリゾールトリシロキサン、アントラニル酸メチル、ルチン及びその誘導体、オリザノール及びその誘導体が好ましいものとして挙げられる。 Examples of the ultraviolet absorber include paraaminobenzoic acid, paraaminobenzoic acid monoglycerin ester, N, N-dipropoxyparaaminobenzoic acid ethyl ester, N, N-diethoxyparaaminobenzoic acid ethyl ester, and N, N-dimethylparaaminobenzoic acid ethyl. Anthranic acid-based UV absorbers such as esters, N, N-dimethylparaaminobenzoic acid butyl esters, N, N-dimethylparaaminobenzoic acid ethyl esters; Anthranilic acid-based UV absorbers such as homomentyl-N-acetylanthranilate; salicylic acid. And salicylic acid-based ultraviolet absorbers such as sodium salts, amilsalicylate, menthylsalicylate, homomentylsalicylate, octylsalicylate, phenylsalicylate, benzylsalicylate, p-isopropanolphenylsalicylate; octylcinnamate, ethyl-4-isopropylsinnate, methyl. -2,5-Diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p-methoxy cinnamate, isopropyl-p-methoxy cinnamate, isoamyl-p-methoxy Synnamete, 2-Ethylhexyl p-methoxysinamate (octyl paramethoxysilicate), 2-ethoxyethyl-p-methoxysinamate (sinoxate), cyclohexyl-p-methoxysinamate, ethyl-α-cyano-β-phenyl Ceramic acid-based ultraviolet absorbers such as cinnamate, 2-ethylhexyl α-cyano-β-phenyl cinnamate (octocrine), glycerylmono-2-ethylhexanoyl-diparamethoxycinnamate, ferulic acid and its derivatives; 2, 4-Dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy- 4-Methoxybenzophenone (oxybenzon-3), 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4' -Benzophes such as phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, etc. Non-ultraviolet absorber; 3- (4'-methylbenziliden) -d, l-phenyl, 3-benziliden-d, l-phenyl; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy- 5-Methylphenylbenzotriazole; 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole; 2- (2'-hydroxy-5'-methylphenylbenzotriazole; dibenzalazine; dianisoilmethane; 5- (3,3-Dimethyl-2-norbornylidene) -3-pentan-2-one; dibenzoylmethane derivatives such as 4-t-butylmethoxydibenzoylmethane; octylriazone; urocanic acid such as urocanic acid and ethyl urocanate Derivatives; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 1- (3,4-dimethoxyphenyl) -4,4-dimethyl-1,3-pentandione, dimethoxybenzilidendioxoimidazolidinepropion Preferred examples include hydrantin derivatives such as 2-ethylhexyl acid, phenylbenzimidazole sulfonic acid, terephthalylidenedicanfursulfonic acid, drometrizoletrisiloxane, methyl anthranilate, rutin and its derivatives, orizanol and its derivatives. ..
美白剤としては、アルブチン、α-アルブチン等のヒドロキノン配糖体及びそのエステル類;アスコルビン酸、アスコルビン酸リン酸エステルナトリウム塩及びアスコルビン酸リン酸エステルマグネシウム塩等のアスコルビン酸リン酸エステル塩、アスコルビン酸テトライソパルミチン酸エステル等のアスコルビン酸脂肪酸エステル、アスコルビン酸エチルエーテル等のアスコルビン酸アルキルエーテル、アスコルビン酸-2-グルコシド等のアスコルビン酸グルコシドおよびその脂肪酸エステル類、アスコルビン酸硫酸エステル、リン酸トコフェリルアスコルビル等のアスコルビン酸誘導体;コウジ酸、エラグ酸、トラネキサム酸及びその誘導体、フェルラ酸及びその誘導体、プラセンタエキス、グルタチオン、オリザノール、ブチルレゾルシノール、油溶性カモミラエキス、油溶性カンゾウエキス、西河柳エキス、ユキノシタエキス等植物エキスが好ましいものとして挙げられる。 Examples of the whitening agent include hydroquinone glycosides such as arbutin and α-albutin and their esters; ascorbic acid, ascorbic acid phosphate ester salts such as ascorbic acid, ascorbic acid phosphate sodium salt and ascorbic acid phosphate ester magnesium salt, and ascorbic acid. Ascorbic acid fatty acid ester such as tetraisopalmitic acid ester, ascorbic acid alkyl ether such as ascorbic acid ethyl ether, ascorbic acid glucoside such as ascorbic acid-2-glucoside and its fatty acid esters, ascorbic acid sulfate ester, tocopheryl ascorbyl phosphate Ascorbic acid derivatives such as; Etc. Plant extracts are preferred.
ビタミン類及びその誘導体類としては、レチノール、酢酸レチノール、パルミチン酸レチノール等のビタミンA類;チアミン塩酸塩、チアミン硫酸塩、リボフラビン、酢酸リボフラビン、塩酸ピリドキシン、ピリドキシンジオクタノエート、ピリドキシンジパルミテート、フラビンアデニンジヌクレオチド、シアノコバラミン、葉酸類、ニコチン酸アミド・ニコチン酸ベンジル等のニコチン酸類、コリン類等のビタミンB群類;アスコルビン酸及びそのナトリウム等の塩等のビタミンC類;ビタミンD;α、β、γ、δ-トコフェロール等のビタミンE類;パントテン酸、ビオチン等のその他ビタミン類;アスコルビン酸リン酸エステルナトリウム塩及びアスコルビン酸リン酸エステルマグネシウム塩等のアスコルビン酸リン酸エステル塩、アスコルビン酸テトライソパルミチン酸エステル・ステアリン酸アスコルビル・パルミチン酸アスコルビル・ジパルミチン酸アスコルビル等のアスコルビン酸脂肪酸エステル、アスコルビン酸エチルエーテル等のアスコルビン酸アルキルエーテル、アスコルビン酸-2-グルコシド等のアスコルビン酸グルコシド及びその脂肪酸エステル、リン酸トコフェリルアスコルビル等のアスコルビン酸誘導体;ニコチン酸トコフェロール、酢酸トコフェロール、リノール酸トコフェロール、フェルラ酸トコフェロール、トコフェロールリン酸エステル等のトコフェロール誘導体等のビタミン誘導体、トコトリエノール、その他各種ビタミン誘導体類が好ましいものとして挙げられる。 Examples of vitamins and derivatives thereof include vitamin A such as retinol, retinol acetate, and retinol palmitate; thiamine hydrochloride, thiamine sulfate, riboflavin, riboflavin acetate, pyridoxin hydrochloride, pyridoxin dioctanoate, pyridoxin dipalmitate, and the like. Flavin adenine dinucleotide, cyanocobalamine, folic acid, nicotinic acids such as nicotinic acid amide and benzyl nicotinate, vitamin B group such as choline; vitamin C such as ascorbic acid and its sodium salt; vitamin D; α, Vitamin E such as β, γ, δ-tocopherol; Other vitamins such as pantothenic acid and biotin; Ascorbic acid phosphate ester salt such as ascorbic acid phosphate sodium salt and ascorbic acid phosphate ester magnesium salt, ascorbic acid tetra Ascorbic acid fatty acid ester such as isopalmitic acid ester, ascorbic stearate, ascorbic palmitate, ascorbic dipalmitate, ascorbic acid alkyl ether such as ethyl ascorbic acid ether, ascorbic acid glucoside such as ascorbic acid-2-glucoside and its fatty acid ester. , Ascorbic acid derivatives such as tocopheryl phosphate ascorbic; vitamin derivatives such as tocopherol derivatives such as tocopherol nicotinate, tocopherol acetate, tocopherol linoleic acid, tocopherol ferulate, tocopherol phosphate ester, tocotrienol, and other various vitamin derivatives are preferable. Is mentioned as.
消炎剤・抗炎症剤としては、グリチルリチン酸及びその誘導体、グリチルレチン酸誘導体、サリチル酸誘導体、ヒノキチオール、グアイアズレン、アラントイン、インドメタシン、酸化亜鉛、酢酸ヒドロコーチゾン、プレドニゾン、塩酸ジフェドラミン、マレイン酸クロルフェニラミン;桃葉エキス、蓬葉エキス等の植物エキスが好ましいものとして挙げられる。 Anti-inflammatory and anti-inflammatory agents include glycyrrhizinic acid and its derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokithiol, guaiazulene, allantoin, indomethacin, zinc oxide, hydrocortisone acetate, prednison, diphedramine hydrochloride, chlorpheniramine maleate; peach leaf extract. , Plant extracts such as Honoha extract are preferred.
育毛用薬剤・血行促進剤・刺激剤としては、センブリエキス、トウガラシチンキ、ショウキョウチンキ、ショウキョウエキス、カンタリスチンキ等の植物エキス・チンキ類;カプサイシン、ノニル酸ワレニルアミド、ジンゲロン、イクタモール、タンニン酸、ボルネオール、シクランデレート、シンナリジン、トラゾリン、アセチルコリン、ベラパミル、セファランチン、γ-オリザノール、セファランチン、ビタミンE及びニコチン酸トコフェロール・酢酸トコフェロール等の誘導体、γ-オリザノール、ニコチン酸及びニコチン酸アミド・ニコチン酸ベンジルエステル・イノシトールヘキサニコチネート、ニコチンアルコール等の誘導体、アラントイン、感光素301、感光素401、塩化カプロニウム、ペンタデカン酸モノグリセリド、フラバノノール誘導体、スチグマステロール又はスチグマスタノール及びその配糖体、ミノキシジルが好ましいものとして挙げられる。
ホルモン類としては、エストラジオール、エストロン、エチニルエストラジオール、コルチゾン、ヒドロコルチゾン、プレドニゾン等が好ましいものとして挙げられる。
As hair growth agents, blood circulation promoters and stimulants, plant extracts and tinctures such as senburi extract, capsicum tincture, gypsum tincture, gypsum tincture, cantalis tincture; , Borneol, cyclanderate, cinnaridine, trazoline, acetylcholine, verapamil, cepharanthin, γ-orizanol, cepharanthin, vitamin E and derivatives such as tocopherol nicotinate / tocopherol acetate, γ-orizanol, nicotinic acid and nicotinic acid amide / benzyl nicotinate. Derivatives such as ester inositol hexanicotinate and nicotine alcohol, allantin, photosensitizer 301, photosensitizer 401, capronium chloride, pentadecanoic acid monoglyceride, flavanonol derivative, stigmasterol or stigmasterol and its glycosyl, minoxydil are preferable. Is mentioned as.
As the hormones, estradiol, estrone, ethinyl estradiol, cortisone, hydrocortisone, prednisone and the like are preferable.
抗しわ剤、抗老化剤、ひきしめ剤、冷感剤、温感剤、創傷治癒促進剤、刺激緩和剤、鎮痛剤、細胞賦活剤等のその他の薬効剤としては、レチノール類、レチノイン酸類、レチノイン酸トコフェリル;乳酸、グリコール酸、グルコン酸、フルーツ酸、サリチル酸及びその配糖体・エステル化物等の誘導体、ヒドロキシカプリン酸、長鎖α-ヒドロキシ脂肪酸、長鎖α-ヒドロキシ脂肪酸コレステリル等のα-又はβ-ヒドロキシ酸類及びその誘導体類;γ-アミノ酪酸、γ-アミノ-β-ヒドロキシ酪酸;カルニチン;クレアチン;セラミド類、スフィンゴシン類;カフェイン、キサンチン等及びその誘導体;コエンザイムQ10、カロチン、リコピン、アスタキサンチン、α-リポ酸等の抗酸化・活性酸素消去剤;カテキン類;ケルセチン等のフラボン類;イソフラボン類;没食子酸及びエステル糖誘導体;タンニン、セサミン、プロトアントシアニジン、クロロゲン酸、リンゴポリフェノール等のポリフェノール類;ルチン及び配糖体等の誘導体;ヘスペリジン及び配糖体等の誘導体;リグナン配糖体;グラブリジン、グラブレン、リクイリチン、イソリクイリチン等のカンゾウエキス関連物質;ラクトフェリン;ショウガオール、ジンゲロール;メントール、カンファー、セドロール等の香料物質及びその誘導体;カプサイシン、バニリン等及び誘導体;ジエチルトルアミド等の昆虫忌避剤;生理活性物質とシクロデキストリン類との複合体が好ましいものとして挙げられる。 Other medicinal agents such as anti-wrinkle agents, anti-aging agents, tightening agents, cold sensitizers, warming agents, wound healing promoters, stimulants, painkillers, cell activators, etc. include retinols, retinoic acids, retinoins. Tocopheryl acid; derivatives such as lactic acid, glycolic acid, gluconic acid, fruit acid, salicylic acid and glycosides / esterified products thereof, hydroxycapric acid, long-chain α-hydroxy fatty acid, long-chain α-hydroxy fatty acid cholesteryl and the like α-or β-Hydroxy acids and their derivatives; γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid; carnitine; creatin; ceramides, sphingosines; caffeine, xanthin and its derivatives; coenzyme Q10, carotene, lycopene, astaxanthin Antioxidants and active oxygen scavengers such as α-lipoic acid; catechins; flavones such as kelcetin; isoflavones; gallic acid and ester sugar derivatives; polyphenols such as tannin, sesamine, protoanthocyanidin, chlorogenic acid and apple polyphenols. Derivatives such as rutin and glycosides; Derivatives such as hesperidin and glycosides; Lignan glycosides; Perfume substances and derivatives thereof; capsaicin, vanillin and the like and derivatives; insect repellents such as diethyl toluamide; complexes of physiologically active substances and cyclodextrins are preferred.
植物・動物・微生物エキス類としては、アイリスエキス、アシタバエキス、アスナロエキス、アスパラガスエキス、アボガドエキス、アマチャエキス、アーモンドエキス、アルテアエキス、アルニカエキス、アロエエキス、アンズエキス、アンズ核エキス、イチョウエキス、インチコウエキス、ウイキョウエキス、ウコンエキス、ウーロン茶エキス、ウワウルシエキス、エイジツエキス、エチナシ葉エキス、エンメイソウエキス、オウゴンエキス、オウバクエキス、オウレンエキス、オオムギエキス、オタネニンジンエキス、オトギリソウエキス、オドリコソウエキス、オノニスエキス、オランダカラシエキス、オレンジエキス、海水乾燥物、海藻エキス、カキ葉エキス、カキョクエキス、加水分解エラスチン、加水分解コムギ末、加水分解シルク、カッコンエキス、カモミラエキス、油溶性カモミラエキス、カロットエキス、カワラヨモギエキス、カラスムギエキス、カルカデエキス、カンゾウエキス、油溶性カンゾウエキス、キウイエキス、キオウエキス、キクラゲエキス、キナエキス、キューカンバーエキス、キリ葉エキス、グアノシン、グアバエキス、クジンエキス、クチナシエキス、クマザサエキス、クララエキス、クルミエキス、クリエキス、グレープフルーツエキス、クレマティスエキス、黒米エキス、黒砂糖抽出物、黒酢、クロレラエキス、クワエキス、ゲンチアナエキス、ゲンノショウコエキス、紅茶エキス、酵母エキス、コウボクエキス、コーヒーエキス、ゴボウエキス、コメエキス、コメ発酵エキス、コメヌカ発酵エキス、コメ胚芽油、コンフリーエキス、コラーゲン、コケモモエキス、サイシンエキス、サイコエキス、サイタイ抽出液、サフランエキス、サルビアエキス、サボンソウエキス、ササエキス、サンザシエキス、サンシャエキス、サンショウエキス、シイタケエキス、ジオウエキス、シコンエキス、シソエキス、シナノキエキス、シモツケソウエキス、ジャトバエキス、シャクヤクエキス、ショウキュウエキス、ショウブ根エキス、シラカバエキス、白キクラゲエキス、スギナエキス、ステビアエキス、ステビア発酵物、西河柳エキス、セイヨウキズタエキス、セイヨウサンザシエキス、セイヨウニワトコエキス、セイヨウノコギリソウエキス、セイヨウハッカエキス、セージエキス、ゼニアオイエキス、センキュウエキス、センブリエキス、ソウハクヒエキス、ダイオウエキス、ダイズエキス、タイソウエキス、タイムエキス、タンポポエキス、地衣類エキス、茶エキス、チョウジエキス、チガヤエキス、チンピエキス、ティートリー油、甜茶エキス、トウガラシエキス、トウキエキス、トウキンセンカエキス、トウニンエキス、トウヒエキス、ドクダミエキス、トマトエキス、納豆エキス、ニンジンエキス、ニンニクエキス、ノバラエキス、ハイビスカスエキス、バクモンドウエキス、ハスエキス、パセリエキス、バーチエキス、蜂蜜、ハマメリスエキス、パリエタリアエキス、ヒキオコシエキス、ビサボロール、ヒノキエキス、ビフィズス菌エキス、ビワエキス、フキタンポポエキス、フキノトウエキス、ブクリョウエキス、ブッチャーブルームエキス、ブドウエキス、ブドウ種子エキス、プロポリス、ヘチマエキス、ベニバナエキス、ペパーミントエキス、ボダイジュエキス、ボタンエキス、ホップエキス、マイカイカエキス、マツエキス、マロニエエキス、ミズバショウエキス、ムクロジエキス、メリッサエキス、モズクエキス、モモエキス、ヤグルマギクエキス、ユーカリエキス、ユキノシタエキス、ユズエキス、ユリエキス、ヨクイニンエキス、ヨモギエキス、ラベンダーエキス、緑茶エキス、卵殻膜エキス、リンゴエキス、ルイボス茶エキス、レイシエキス、レタスエキス、レモンエキス、レンギョウエキス、レンゲソウエキス、ローズエキス、ローズマリーエキス、ローマカミツレエキス、ローヤルゼリーエキス、ワレモコウエキス等のエキスが好ましいものとして挙げられる。 Plant / animal / microbial extracts include iris extract, asitaba extract, asnalo extract, asparagus extract, avocado extract, flaxseed extract, almond extract, altea extract, arnica extract, aloe extract, apricot extract, apricot kernel extract, ginkgo biloba extract. , Inchkou extract, Uikyo extract, Ukon extract, Woolong tea extract, Uwaurushi extract, Agetsu extract, Echinashi leaf extract, Enmeisou extract, Ogon extract, Oubaku extract, Ouren extract, Omugi extract, Otaneninjin extract, Otogirisou extract, Odorikosou extract, Ononis extract , Dutch mustard extract, orange extract, dried seawater, seaweed extract, oyster leaf extract, oyster extract, hydrolyzed elastin, hydrolyzed wheat powder, hydrolyzed silk, cucumber extract, chamomile extract, oil-soluble chamomile extract, carrot extract, kawarayomogi Extract, crow wheat extract, karukade extract, kanzo extract, oil-soluble kanzo extract, kiwi extract, kiou extract, kikurage extract, kina extract, cucumber extract, kiri leaf extract, guanosine, guava extract, kujin extract, kuchinashi extract, kumazasa extract, clara extract, walnut Extract, chestnut extract, grapefruit extract, clematis extract, black rice extract, brown sugar extract, black vinegar, chlorella extract, quail extract, gentiana extract, gennoshoco extract, tea extract, yeast extract, koboku extract, coffee extract, gobo extract, rice extract, rice Fermented extract, fermented rice bran extract, rice germ oil, confree extract, collagen, kokemomo extract, saishin extract, psycho extract, saitai extract, saffron extract, salvia extract, sabonsou extract, sasa extract, sanzashi extract, sansha extract, sansho Extract, Shiitake extract, Jio extract, Shikon extract, Shiso extract, Shinanoki extract, Shimotsukesou extract, Jatoba extract, Shakuyaku extract, Shokyu extract, Shobu root extract, Shirakaba extract, White chrysanthemum extract, Sugina extract, Stevia extract, Stevia fermented product, Nishikawayanagi extract, Seiyoukizuta extract, Seiyousanzashi extract, Seiyouniwatoko extract, Seiyounokogirisou extract, Seiyouhakka extract, Sage extract, Zeniaoi extract, Senkyu extract, Senburi extract, Souhakuhi extract, Daiou extract, Die Zu extract, Taisou extract, Thyme extract, Dandelion extract, Local clothing extract, Tea extract, Chouji extract, Chigaya extract, Chinpi extract, Tea tree oil, Jincha extract, Togarashi extract, Touki extract, Tokinsenka extract, Tounin extract, Tohi extract, Dokudami extract, Tomato Extract, Natto extract, Carrot extract, Garlic extract, Novara extract, Hibiscus extract, Bakumondou extract, Hass extract, Parsley extract, Birch extract, Honey, Hamamelis extract, Parietaria extract, Hikiokoshi extract, Bisabolol, Hinoki extract, Bifizus bacterium extract, Biwa extract, Fukitanpopo extract, Fukinotou extract, Bukuryo extract, Butcher bloom extract, Grape extract, Grape seed extract, Propolis, Hechima extract, Benibana extract, Peppermint extract, Bodaiju extract, Button extract, Hop extract, Maikaika extract, Pine extract, Maronie extract , Mizubasho extract, Mukuroji extract, Melissa extract, Mozuku extract, Peach extract, Yagurumagiku extract, Eucalyptus extract, Yukinoshita extract, Yuzu extract, Yuri extract, Yokuinin extract, Yomogi extract, Lavender extract, Green tea extract, Eggshell membrane extract, Apple extract, Louis Boss tea extract , Reishi extract, lettuce extract, lemon extract, lotus extract, lotus extract, rose extract, rosemary extract, Roman chamomile extract, royal jelly extract, crackle extract and the like are preferable.
鎮痒剤としては、塩酸ジフェンヒドラミン、マレイン酸クロルフェニラミン、カンファー、サブスタンス-P阻害剤等を例示することができる。
角質剥離・溶解剤としては、サリチル酸、イオウ、レゾルシン、硫化セレン、ピリドキシン等を例示することができる。
制汗剤としては、クロルヒドロキシアルミニウム、塩化アルミニウム、酸化亜鉛、パラフェノールスルホン酸亜鉛等を例示することができる。
清涼剤としては、メントール、サリチル酸メチル等を例示することができる。
収れん剤としては、クエン酸、酒石酸、乳酸、硫酸アルミニウム・カリウム、タンニン酸等を例示することができる。
酵素類としては、スーパーオキサイドディスムターゼ、カタラーゼ、塩化リゾチーム、リパーゼ、パパイン、パンクレアチン、プロテアーゼ等を例示することができる。
核酸類としては、リボ核酸及びその塩、デオキシリボ核酸及びその塩、アデノシン三リン酸二ナトリウムが好ましいものとして挙げられる。
Examples of the antipruritic agent include diphenhydramine hydrochloride, chlorpheniramine maleate, camphor, substance-P inhibitor and the like.
Examples of the exfoliating / dissolving agent include salicylic acid, sulfur, resorcin, selenium sulfide, pyridoxine and the like.
Examples of the antiperspirant include chlorohydroxyaluminum, aluminum chloride, zinc oxide, zinc paraphenolsulfonate and the like.
Examples of the refreshing agent include menthol and methyl salicylate.
Examples of the astringent include citric acid, tartaric acid, lactic acid, aluminum / potassium sulfate, tannic acid and the like.
Examples of the enzymes include superoxide dismutase, catalase, lysozyme chloride, lipase, papain, pancreatin, protease and the like.
Preferred examples of nucleic acids include ribonucleic acid and salts thereof, deoxyribonucleic acid and salts thereof, and disodium adenosine triphosphate.
香料としては、アセチルセドレン、アミルシンナムアルデヒド、アリルアミルグリコレート、β-イオノン、イソイースーパー、イソブチルキノリン、イリス油、イロン、インドール、イランイラン油、ウンデカナール、ウンデセナール、γ-ウンデカラクトン、エストラゴール、オイゲノール、オークモス、オポポナックスレジノイド、オレンジ油、オイゲノール、オーランチオール、ガラクソリッド、カルバクロール、L-カルボン、カンファー、キャノン、キャロットシード油、クローブ油、ケイヒ酸メチル、ゲラニオール、ゲラニルニトリル、酢酸イソボルニル、酢酸ゲラニル、酢酸ジメチルベンジルカルビニル、酢酸スチラリル、酢酸セドリル、酢酸テレピネル、酢酸p-t-ブチルシクロヘキシル、酢酸ベチベリル、酢酸ベンジル、酢酸リナリル、サリチル酸イソペンチル、サリチル酸ベンジル、サンダルウッド油、サンタロール、シクラメンアルデヒド、シクロペンタデカノリド、ジヒドロジャスモン酸メチル、ジヒドロミルセノール、ジャスミンアブソリュート、ジャスミンラクトン、cis-ジャスモン、シトラール、シトロネノール、シトロネラール、シナモンバーク油、1,8-シネオール、シンナムアルデヒド、スチラックスレジノイド、セダーウッド油、セドレン、セドロール、セロリシード油、タイム油、ダマスコン、ダマセノン、チモール、チュベローズアブソリュート、デカナール、デカラクトン、テルピネオール、γ-テルピネン、トリプラール、ネロール、ノナナール、2,6-ノナジエノール、ノナラクトン、パチョリアルコール、バニラアブソリュート、バニリン、バジル油、パチョリ油、ヒドロキシシトロネラール、α-ピネン、ピペリトン、フェネチルアルコール、フェニルアセトアルデヒド、プチグレン油、ヘキシルシンナムアルデヒド、cis-3-ヘキセノール、ペルーバルサム、ベチバー油、ベチベロール、ペパーミント油、ペパー油、ヘリオトロピン、ベルガモット油、ベンジルベンゾエート、ボルネオール、ミルレジノイド、ムスクケトン、メチルノニルアセトアルデヒド、γ-メチルヨノン、メントール、L-メントール、L-メントン、ユーカリ油、β-ヨノン、ライム油、ラベンダー油、D-リモネン、リナロール、リラール、リリアール、レモン油、ローズアブソリュート、ローズオキシド、ローズ油、ローズマリー油、各種精油等の合成香料及び天然香料並びに各種調合香料が好ましいものとして挙げられる。 As fragrances, acetylsedrene, amilcinnamaldehyde, allylamylglycolate, β-ionone, isoe super, isobutylquinoline, iris oil, iron, indole, ylang ylang oil, undecanal, undecenal, γ-undecalactone, Estragor, Eugenol, Oak Moss, Opoponax Resinoid, Orange Oil, Eugenol, Oranthiol, Galaxolid, Carbachlor, L-Carbon, Kamfer, Cannon, Carrot Seed Oil, Clove Oil, Methyl Caynate, Geraniol, Geranylnitrile , Isobornyl acetate, Geranyl acetate, Dimethylbenzylcarbyl acetate, Styralyl acetate, Sedrill acetate, Telepinel acetate, pt-butylcyclohexyl acetate, Vetiberyl acetate, benzyl acetate, Linaryl acetate, Isopentyl salicylate, benzyl salicylate, Sandalwood oil, Santa Roll, cyclamenaldehyde, cyclopentadecanolide, methyl dihydrojasmonate, dihydromilsenol, jasmine absolute, jasmine lactone, cis-jasmon, citral, citronenol, citroneral, cinnamon bark oil, 1,8-cineole, cinnamaldehyde, Stilax resinoid, cedarwood oil, sedren, sedrol, celery seed oil, thyme oil, damascon, damasenon, timol, tuberose absolute, decanal, decalactone, terpineol, γ-terpinen, triplar, nerol, nonanar, 2,6-nonadienol, nonalactone , Pacholi alcohol, vanilla absolute, vanillin, basil oil, pachori oil, hydroxycitronellal, α-pinene, piperitone, phenethyl alcohol, phenylacetaldehyde, petitgrain oil, hexylcinnamaldehyde, cis-3-hexenol, peruvian balsam, vetiver oil , Vetiberol, peppermint oil, pepper oil, heliotropin, bergamot oil, benzylbenzoate, borneol, millresinoid, muskketone, methylnonylacetaldehyde, γ-methylyonone, menthol, L-menthol, L-menthon, eucalyptus oil, β-yonon, Synthetic fragrances such as lime oil, lavender oil, D-lymonen, linalol, lylar, lilial, lemon oil, rose absolute, rose oxide, rose oil, rosemary oil, various essential oils and natural Fragrances and various blended fragrances are preferred.
色素・着色剤・染料・顔料としては、褐色201号、黒色401号、紫色201号、紫色401号、青色1号、青色2号、青色201号、青色202号、青色203号、青色204号、青色205号、青色403号、青色404号、緑色201号、緑色202号、緑色204号、緑色205号、緑色3号、緑色401号、緑色402号、赤色102号、赤色104-1号、赤色105-1号、赤色106号、赤色2号、赤色201号、赤色202号、赤色203号、赤色204号、赤色205号、赤色206号、赤色207号、赤色208号、赤色213号、赤色214号、赤色215号、赤色218号、赤色219号、赤色220号、赤色221号、赤色223号、赤色225号、赤色226号、赤色227号、赤色228号、赤色230-1号、赤色230-2号、赤色231号、赤色232号、赤色3号、赤色401号、赤色404号、赤色405号、赤色501号、赤色502号、赤色503号、赤色504号、赤色505号、赤色506号、橙色201号、橙色203号、橙色204号、橙色205号、橙色206号、橙色207号、橙色401号、橙色402号、橙色403号、黄色201号、黄色202-1号、黄色202-2号、黄色203号、黄色204号、黄色205号、黄色4号、黄色401号、黄色402号、黄色403-1号、黄色404号、黄色405号、黄色406号、黄色407号、黄色5号等の法定色素;Acid Red 14等のその他酸性染料; Dyes / colorants / dyes / pigments include brown 201, black 401, purple 201, purple 401, blue 1, blue 2, blue 201, blue 202, blue 203, and blue 204. , Blue 205, Blue 403, Blue 404, Green 201, Green 202, Green 204, Green 205, Green 3, Green 401, Green 402, Red 102, Red 104-1 , Red 105-1, Red 106, Red 2, Red 201, Red 202, Red 203, Red 204, Red 205, Red 206, Red 207, Red 208, Red 213. , Red 214, Red 215, Red 218, Red 219, Red 220, Red 221, Red 223, Red 225, Red 226, Red 227, Red 228, Red 230-1. , Red 230-2, Red 231, Red 232, Red 3, Red 401, Red 404, Red 405, Red 501, Red 502, Red 503, Red 504, Red 505. , Red 506, Orange 201, Orange 203, Orange 204, Orange 205, Orange 206, Orange 207, Orange 401, Orange 402, Orange 403, Yellow 201, Yellow 202-1 , Yellow 202-2, Yellow 203, Yellow 204, Yellow 205, Yellow 4, Yellow 401, Yellow 402, Yellow 403-1, Yellow 404, Yellow 405, Yellow 406, Yellow Legal dyes such as No. 407 and Yellow No. 5; Other acidic dyes such as Acid Red 14;
Arianor Sienna Brown、Arianor Madder Red、Arianor Steel Blue、Arianor Straw Yellow等の塩基染料;HC Yellow 2、HC Yellow5、HC Red 3、4-hydoxypropylamino-3-nitrophenol、N,N’bis(2-hydroxyethyl)-2-nitro-p- phenylenediamine、HC Blue 2、Basic Blue 26等のニトロ染料;分散染料;二酸化チタン、酸化亜鉛等の無機白色顔料;酸化鉄(ベンガラ)、チタン酸鉄等の無機赤色系顔料;γ-酸化鉄等の無機褐色系顔料;黄酸化鉄、黄土等の無機黄色系顔料;黒酸化鉄、低次酸化チタン等の無機黒色系顔料;マンゴバイオレット、コバルトバイオレット等の無機紫色系顔料;酸化クロム、水酸化クロム、チタン酸コバルト等の無機緑色系顔料;群青、紺青等の無機青色系顔料;酸化チタンコーテッドマイカ、酸化チタンコーテッドオキシ塩化ビスマス、酸化チタンコーテッドタルク、着色酸化チタンコーテッドマイカ、オキシ塩化ビスマス、魚鱗箔等のパール顔料;アルミニウムパウダー、カッパーパウダー、金等の金属粉末顔料;表面処理無機及び金属粉末顔料;赤色201号、赤色202号、赤色204号、赤色205号、赤色220号、赤色226号、赤色228号、赤色405号、橙色203号、橙色204号、黄色205号、黄色401号、青色404号、赤色3号、赤色104号、赤色106号、赤色227号、赤色230号、赤色401号、赤色505号、橙色205号、黄色4号、黄色5号、黄色202号、黄色203号、緑色3号、青色1号等のジルコニウム、バリウム又はアルミニウムレーキ等の有機顔料;表面処理有機顔料;アスタキサンチン、アリザリン等のアントラキノン類、アントシアニジン、β-カロチン、カテナール、カプサンチン、カルコン、カルサミン、クエルセチン、クロシン、クロロフィル、クルクミン、コチニール、シコニン等のナフトキノン類、ビキシン、フラボン類、ベタシアニジン、ヘナ、ヘモグロビン、リコピン、リボフラビン、ルチン等の天然色素・染料;p-フェニレンジアミン、トルエン-2,5-ジアミン、o-,m-,若しくはp-アミノフェノール、m-フェニレンジアミン、5-アミノ-2-メチルフェノール、レゾルシン、1-ナフトール、2,6-ジアミノピリジン等及びその塩等の酸化染料中間体及びカップラー;インドリン等の自動酸化型染料;ジヒドロキシアセトンが好ましいものとして挙げられる。 Basic dyes such as Arianor Sienna Brown, Arianor Madder Red, Arianor Steel Blue, Arianor Straw Yellow; HC Yellow 2, HC Yellow5, HC Red 3, 4-hydoxypolythrinth (4-hydoxypoly- Pigment-2-it. Nitro dyes such as 2-nitro-p-phenylenediamine, HC Blue 2, Basic Blue 26; Disperse dyes; Inorganic white pigments such as titanium dioxide and zinc oxide; Inorganic red pigments such as iron oxide (Bengala) and iron titanate; Inorganic brown pigments such as γ-iron oxide; Inorganic yellow pigments such as yellow iron oxide and ocher; Inorganic black pigments such as black iron oxide and lower titanium oxide; Inorganic purple pigments such as mango violet and cobalt violet; Inorganic green pigments such as chromium oxide, chromium hydroxide and cobalt titanate; Inorganic blue pigments such as ultramarine and dark blue; Titanium oxide coated mica, Titanium oxide coated bismuth oxide, Titanium oxide coated talc, Colored titanium oxide coated mica, Pearl pigments such as bismuth oxychloride and fish scale foil; metal powder pigments such as aluminum powder, copper powder and gold; surface-treated inorganic and metal powder pigments; red 201, red 202, red 204, red 205, red 220 No., Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401, Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Organics such as zirconium, barium or aluminum lake such as red 230, red 401, red 505, orange 205, yellow 4, yellow 5, yellow 202, yellow 203, green 3 and blue 1. Pigments; Surface-treated organic pigments; Anthracinones such as astaxanthin and alizarin, anthocyanidins, β-carotene, catenal, capsantine, chalcone, calsamine, quercetin, closin, chlorophyll, curcumin, cochineal, siconin and other naphthoquinones, bixins, flavones, etc. Natural pigments / dyes such as betacyanidine, henna, hemoglobin, lycopene, riboflavin, rutin; p-phenylenediamine, toluene-2,5-diamine, o-, m-, or p-aminophenol, m-phenylenedia Oxidation dye intermediates and couplers such as min, 5-amino-2-methylphenol, resorcin, 1-naphthol, 2,6-diaminopyridine and salts thereof; autoxidation dyes such as indoline; dihydroxyacetone is preferred. Can be mentioned.
水としては、常水、精製水の他、硬水、軟水、天然水、海洋深層水、電解アルカリイオ
ン水、電解酸性イオン水、イオン水、クラスター水が好ましいものとして挙げられる。
これらの他、化粧品原料基準、化粧品種別配合成分規格、日本化粧品工業連合会成分表
示名称リスト、INCI辞書(The International Cosmetic Ingredient Dictionary and Handbook)、医薬部外品原料規格、日本薬局方、医薬品添加物規格、食品添加物公定書等に記載されている成分、及び、国際特許分類IPCがA61K7の分類に属する日本国及び諸外国特許公報及び特許公開公報(公表公報・再公表を含む)に記載されている成分等、公知の化粧料成分、医薬品成分、食品成分などを、公知の組み合わせ及び配合比・配合量で含有させることが可能である。
As the water, in addition to normal water and purified water, hard water, soft water, natural water, deep ocean water, electrolytic alkaline ionized water, electrolytically acidic ionized water, ionized water, and cluster water are preferable.
In addition to these, cosmetic raw material standards, compounding ingredient standards by cosmetic type, Japan Cosmetic Industry Association ingredient display name list, INCI dictionary (The International Cosmetic Ingredient Handbook), non-pharmaceutical raw material standards, Japanese Pharmacy, pharmaceutical additives Ingredients described in standards, official standards for food additives, etc., and the international patent classification IPC is described in Japanese and foreign patent gazettes and patent publication gazettes (including published gazettes and republished gazettes) that belong to the A61K7 classification. It is possible to contain known cosmetic ingredients, pharmaceutical ingredients, food ingredients, etc. in known combinations, blending ratios, and blending amounts.
本発明の化粧料・皮膚外用剤の種類を更に詳細に説明すると、基礎化粧料としては、柔軟化粧水、収れん化粧水、洗浄用化粧水、多層式化粧水等の化粧水;エモリエントローション、モイスチャーローション、ミルキィーローション、ナリシングローション、ナリシングミルク、スキンモイスチャー、モイスャーエマルション、マッサージローション、クレンジングローション、プロテクトエマルション、サンプロテクト、サンプロテクター、UVケアミルク、サンスクリーン、メーキャップローション、角質スムーザー、エルボーローション、ハンドローション、ボディローション等の乳液;エモリエントクリーム、栄養クリーム、ナリシングクリーム、バニシングクリーム、モイスチャークリーム、ナイトクリーム、マッサージクリーム、クレンジングクリーム、メーキャップクリーム、ベースクリーム、プレメーキャップクリーム、サンスクリーンクリーム、サンタンクリーム、除毛クリーム、デオドラントクリーム、シェービングクリーム、角質軟化クリーム等のクリーム;モイスチャージェル等のジェル;保湿エッセンス、美白エッセンス、紫外線防止エッセンス等のエッセンス;リポソーム美容液、リポソーム化粧水等のリポソーム化粧品類;ピールオフパック、粉末パック、ウォッシングパック、オイルパック、クレンジングマスク等のパック・マスク類;クレンジングフォーム、クレンジングクリーム、クレンジングミルク、クレンジングローション、クレンジングジェル、クレンジングオイル、クレンジングマスク、洗粉、洗顔パウダー等の洗顔料;化粧石鹸、透明石鹸、薬用石鹸、液状石鹸、ひげそり石鹸、合成化粧石鹸等の石鹸が好ましいものとして挙げられる。 The types of cosmetics and external skin preparations of the present invention will be described in more detail. Basic cosmetics include soft cosmetics, astringent cosmetics, cleaning cosmetics, multi-layered cosmetics and the like; emollient lotion, moisture. Lotion, Milky Lotion, Nourishing Lotion, Nourishing Milk, Skin Moisture, Moisture Emulsion, Massage Lotion, Cleansing Lotion, Protect Emulsion, Sun Protect, Sun Protector, UV Care Milk, Sun Screen, Makeup Lotion, Horny Smoother, Elbow Emulsion such as lotion, hand lotion, body lotion; emollient cream, nourishing cream, nourishing cream, vanishing cream, moisture cream, night cream, massage cream, cleansing cream, makeup cream, base cream, pre-makeup cream, sunscreen cream, Creams such as suntan cream, hair removal cream, deodorant cream, shaving cream, and keratin softening cream; gels such as moisture gel; essences such as moisturizing essence, whitening essence, and UV protection essence; Kind: Peel-off pack, powder pack, washing pack, oil pack, cleansing mask, etc. Washing pigments; soaps such as cosmetic soaps, transparent soaps, medicated soaps, liquid soaps, shaving soaps, and synthetic cosmetic soaps are preferable.
メーキャップ化粧料としては、白粉・打粉類、ファンデーション類、口紅類、リップグロス、頬紅類、アイライナー、マスカラ、アイシャドー、眉墨、アイブロー、ネイルエナメル、エナメルリムーバー、ネイルトリートメントが好ましいものとして挙げられる。
芳香化粧料としては、香水、パフューム、パルファム、オードパルファム、オードトワレ、オーデコロン、練香水、芳香パウダー、香水石鹸、ボディローション、バスオイルが好ましいものとして挙げられる。
ボディ化粧料としては、ボディシャンプー等のボディ洗浄料;デオドラントローション、デオドラントパウダー、デオドラントスプレー、デオドラントスティック等の防臭化粧料;脱色剤、脱毛・除毛剤;浴用剤;虫よけスプレー等のインセクトリペラーが好ましいものとして挙げられる。
Preferred makeup cosmetics include white powder / dusting powder, foundations, lipsticks, lip gloss, blusher, eyeliner, mascara, eye shadow, eyebrow, eyebrow, nail enamel, enamel remover, and nail treatment.
Preferred fragrance cosmetics include perfumes, perfumes, parfum, eau de parfum, eau de toilette, eau de cologne, perfumes, fragrance powders, perfume soaps, body lotions and bath oils.
Body cosmetics include body cleaning agents such as body shampoo; deodorant cosmetics such as deodorant lotion, deodorant powder, deodorant spray, and deodorant stick; depigmenting agents, depilatory / depilatory agents; bathing agents; insect repellent sprays, etc. Repellers are preferred.
毛髪用化粧料としては、オイルシャンプー、クリームシャンプー、コンディショニングシャンプー、ふけ用シャンプー、ヘアカラー用シャンプー、リンス一体型シャンプー等のシャンプー;リンス、トリートメント、ヘアパック、カラーローション、枝毛コート、パーマネントウェーブ用剤、ストレートパーマ剤、酸化染毛剤、ヘアブリーチ、ヘアカラープレトリートメント、ヘアカラーアフタートリートメント、パーマプレトリートメント、パーマアフタートリートメント、ヘアマニキュア、ヘアトニック、育毛剤が好ましいものとして挙げられる。 Shampoos for hair include oil shampoos, cream shampoos, conditioning shampoos, indulgence shampoos, hair color shampoos, rinse-integrated shampoos, etc .; for rinses, treatments, hair packs, color lotions, split hair coats, permanent waves. Agents, straight perm agents, oxidative hair dyes, hair bleach, hair color pretreatment, hair color aftertreatment, perma pretreatment, perma aftertreatment, hair manicure, hair tonic, and hair restorer are preferred.
皮膚外用剤としては、軟膏剤、貼付剤、ローション剤、リニメント剤、液状塗布剤などの剤型でとしても用いることができる。また、歯磨き、マウスウォッシュ等の口腔内化粧料としても用いることが出来る。
本発明の化粧料又は皮膚外用剤の剤型としては、水中油(O/W)型、油中水(W/O)型、W/O/W型、O/W/O型等の乳化型化粧料、油性化粧料、固形化粧料、液状化粧料、練状化粧料、スティック状化粧料、揮発性油型化粧料、粉状化粧料、ゼリー状化粧料、ジェル状化粧料、ペースト状化粧料、乳化高分子型化粧料、シート状化粧料、ミスト状化粧料、スプレー型化粧料等の剤型が好ましいものとして挙げられる。
As the external skin preparation, it can also be used as a dosage form such as an ointment, a patch, a lotion, a liniment, and a liquid coating agent. It can also be used as an oral cosmetic such as toothpaste and mouthwash.
As the dosage form of the cosmetic or skin external preparation of the present invention, emulsification of oil-in-water (O / W) type, water-in-oil (W / O) type, W / O / W type, O / W / O type and the like. Type cosmetics, oil-based cosmetics, solid cosmetics, liquid cosmetics, paste-like cosmetics, stick-like cosmetics, volatile oil-type cosmetics, powder-like cosmetics, jelly-like cosmetics, gel-like cosmetics, paste-like Formulation types such as cosmetics, emulsified polymer type cosmetics, sheet-like cosmetics, mist-like cosmetics, and spray-type cosmetics are preferable.
本発明の防腐抗菌剤は、上述の構成よりなり、従来の防腐抗菌剤よりも高い防腐抗菌効果を発揮することができるため、基礎化粧料、メーキャップ化粧料、芳香化粧料、ボディ化粧料、軟膏等の皮膚外用剤、毛髪化粧料等に好適に用いることができる。 The antiseptic and antibacterial agent of the present invention has the above-mentioned constitution and can exhibit a higher antiseptic and antibacterial effect than the conventional antiseptic and antibacterial agents. It can be suitably used for skin external preparations such as, hair cosmetics and the like.
以下に実施例を掲げて本発明を更に詳細に説明するが、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。なお、特に断りのない限り、「部」は「重量部」を、「%」は「質量%」を意味するものとする。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" means "part by weight" and "%" means "mass%".
<ゲルパーミエーションクロマトグラフィー(GPC)>
共重合体の重量平均分子量(Mw)は、GPC(ゲルパーミュエーションクロマトグラフィー)により測定した。
測定条件、装置などは以下の通りである。
装置:東ソー社製 EcoSEC HLC-8320GPC
検出器:示差屈折率計(RI)検出器
カラム:東ソー社製 TSKgel α-M、α-2500
カラム温度:40℃
流速:0.4mL/min
注入量:20μL(試料濃度0.4wt%の溶離液調製溶液)
検量線:ジーエルサイエンス社製 ポリエチレングリコール
GPCソフト:東ソー社製 EcoSEC-WS
溶離液:0.5M酢酸+0.2M硝酸Na/アセトニトリル=50/50(v/v)
<Gel Permeation Chromatography (GPC)>
The weight average molecular weight (Mw) of the copolymer was measured by GPC (gel permeation chromatography).
The measurement conditions, equipment, etc. are as follows.
Equipment: Tosoh EcoSEC HLC-8320GPC
Detector: Differential Refractometer (RI) Detector Column: TSKgel α-M, α-2500 manufactured by Tosoh Corporation
Column temperature: 40 ° C
Flow velocity: 0.4 mL / min
Injection amount: 20 μL (sample concentration 0.4 wt% eluent preparation solution)
Calibration curve: Polyethylene glycol GPC software manufactured by GL Sciences: EcoSEC-WS manufactured by Tosoh Corporation
Eluent: 0.5M acetic acid + 0.2M Na nitrate / acetonitrile = 50/50 (v / v)
<最小発育阻止濃度(MIC)>
防腐抗菌剤を含む水溶液をミューラーヒントン培地中で2倍ずつ順次希釈していき、防腐抗菌剤含有培地の希釈系列を調製した。その後、各濃度の防腐抗菌剤を含有する培地をポリスチレン製96穴プレートに50μLずつ添加した。次に、18時間ミューラーヒントン寒天培地上で生育させた大腸菌(Escherichia coli、NBRC-15034、NBRC-3972)、黄色ブドウ球菌(Staphylococcus aureus、NBRC-15035、NBRC-13276)及び緑膿菌(Pseudomonas aeruginosa、NBRC-13275)のコロニーを、それぞれバターフィールド緩衝液に懸濁し、10×108個/mL程度の菌液を調製した。調製した菌液をミューラーヒントン培地中で10×106個/mL程度まで希釈し、上記で調製した希釈系列に対して50μLずつ添加した。35℃にて20時間静置後、菌が生育していない培地中の最小の防腐抗菌剤濃度(ppm)を最小発育阻止濃度(MIC)として決定した。菌の生育の有無は、目視にて濁度が上昇しているかによって判断した。
結果を表1及び2に示した。
<Minimum inhibitory concentration (MIC)>
An aqueous solution containing an antiseptic antibacterial agent was sequentially diluted 2-fold in Mueller-Hinton medium to prepare a dilution series of the antiseptic antibacterial agent-containing medium. Then, 50 μL of a medium containing each concentration of antiseptic and antibacterial agent was added to a polystyrene 96-well plate. Next, Escherichia coli (NBRC-15304, NBRC-3972), Staphylococcus aureus, NBRC-15035, NBRC-13276 and Pseudomonas aeruginosa grown on Mueller-Hinton agar medium for 18 hours. , NBRC-13275) were suspended in butterfield buffer to prepare a bacterial solution of about 10 × 10 8 cells / mL. The prepared bacterial solution was diluted to about 10 × 10 6 cells / mL in Mueller-Hinton medium, and 50 μL was added to each dilution series prepared above. After standing at 35 ° C. for 20 hours, the minimum antiseptic antibacterial agent concentration (ppm) in the medium in which the bacteria did not grow was determined as the minimum inhibitory concentration (MIC). The presence or absence of bacterial growth was visually determined by whether the turbidity had increased.
The results are shown in Tables 1 and 2.
<防腐試験1>
下記合成例1~5で合成した共重合体(防腐抗菌剤)を2000ppm含むポテトデキストロース寒天(PDA)培地を調製した。
予め前培養した培養液をAspergillus brasiliensis ATCC16404(クロコウジカビ)を約107個/mLに希釈したものを菌懸濁液として準備し、上記防腐抗菌剤を含むPDA培地15mlに上記懸濁液を0.15ml混釈して7日間25℃で静置培養し、培養後のPDA培地におけるコロニー形成の有無を確認した。
結果を表3に示した。
<Preservative test 1>
A potato dextrose agar (PDA) medium containing 2000 ppm of the copolymer (preservative antibacterial agent) synthesized in the following synthesis examples 1 to 5 was prepared.
A pre-cultured culture solution diluted with Aspergillus brasiliensis ATCC16404 (Aspergillus niger) to about 107 cells / mL was prepared as a bacterial suspension, and the suspension was added to 15 ml of PDA medium containing the antiseptic antibacterial agent. .15 ml was mixed and statically cultured at 25 ° C. for 7 days, and the presence or absence of colony formation in the PDA medium after the culture was confirmed.
The results are shown in Table 3.
<防腐試験2:(O/Wクリームサンプル及び化粧水サンプルを用いたチャレンジテスト(保存効力試験))>
合成例1~3で合成した共重合体(防腐抗菌剤)及びその他の成分を表4のように配合し、クリームを調製した。
合成例4及び5で合成した共重合体(防腐抗菌剤)及びその他の成分を表6のように配合し、化粧水を調製した。
合成例8及び9で合成した共重合体(防腐抗菌剤)及びその他の成分を表8のように配合し、化粧水を調製した。
上記クリーム及び化粧水について、下記の方法によるチャレンジテストを行い、防腐力を評価した。
下記の菌種について、予め前培養した培養液を細菌及びカンジダは約108個/mLに、クロコウジカビは約107個/mLに希釈したものを菌懸濁液とした。尚、菌懸濁液の菌数はコロニーカウント法により確認した。
細菌:大腸菌(Escherichia coli、NBRC-3972)、黄色ブドウ球菌(Staphylococcus aureus、NBRC-13276)、緑膿菌(Pseudomonas aeruginosa、NBRC-13275)
酵母:カンジダ (Candia albicans ATCC10231)
カビ:クロコウジカビ(Aspergillus brasiliensis ATCC16404)
乾燥滅菌済みのガラス容器に調製したクリーム又は化粧水を20g入れ、上記菌懸濁液を0.2ml接種して、25℃で培養を行った。2、7、14、21日後に、各試料を1gずつ抜き取り、生理食塩水で希釈したものを寒天培地に混釈して細菌及びカンジダは48時間、クロコウジカビは7日間培養し、コロニーカウント法により、試料中の残存菌数を算出した。
結果を表5、7、9に示した。
<Preservative test 2: (Challenge test using O / W cream sample and lotion sample (preservative efficacy test))>
The copolymers (preservatives and antibacterial agents) synthesized in Synthesis Examples 1 to 3 and other components were blended as shown in Table 4 to prepare a cream.
The copolymer (preservative antibacterial agent) synthesized in Synthesis Examples 4 and 5 and other components were blended as shown in Table 6 to prepare a cosmetic water.
The copolymer (preservative antibacterial agent) synthesized in Synthesis Examples 8 and 9 and other components were blended as shown in Table 8 to prepare a cosmetic water.
For the above cream and lotion, a challenge test was conducted by the following method to evaluate the antiseptic power.
For the following bacterial species, a pre-cultured culture solution diluted to about 108 cells / mL for bacteria and Candida and to about 107 cells / mL for Aspergillus niger was used as a bacterial suspension. The number of bacteria in the bacterial suspension was confirmed by the colony counting method.
Bacteria: Escherichia coli (NBRC-3972), Staphylococcus aureus (NBRC-13276), Pseudomonas aeruginosa, NBRC-13275)
Yeast: Candida (Candida albicans ATCC10231)
Mold: Aspergillus brasiliensis ATCC16404
20 g of the prepared cream or lotion was put in a dry sterilized glass container, 0.2 ml of the above bacterial suspension was inoculated, and the cells were cultured at 25 ° C. After 2, 7, 14, and 21 days, 1 g of each sample was taken out, diluted with physiological saline and mixed with agar medium, and bacteria and candida were cultured for 48 hours, and Aspergillus niger was cultured for 7 days, and the colony counting method was performed. The number of residual bacteria in the sample was calculated.
The results are shown in Tables 5, 7 and 9.
<合成例1>
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、純水90.0gを仕込み、攪拌下、90℃に昇温した。次いで攪拌下、90℃一定状態の重合反応系中に、メタクリル酸2-(ジメチルアミノ)エチル(N,N-ジメチルアミノエチルメタクリレート)(和光純薬工業(株)製、以下DAMと称す)51.3g、酢酸18.6g及びメタクリル酸エチル(以下EMAと称す。)8.56gからなるモノマー溶液1;2,2'-アゾビス(2-メチルプロピオンアミジン)二塩酸塩(和光純薬工業(株)製、以下V-50と称す)2.5%水溶液29.3gからなる開始剤水溶液;DAM25.7g及び酢酸9.32gからなるモノマー溶液2をそれぞれ別々の滴下ノズルより滴下した。
滴下開始時間に関して、モノマー溶液1と開始剤水溶液は同時に滴下を開始し、モノマー溶液1は120分間、開始剤水溶液を210分間滴下した。モノマー溶液2はモノマー溶液1滴下終了後から60分間に渡って滴下した。全滴下終了後、さらに30分間反応溶液を90℃に保持して熟成し、重合を完結させ、共重合体1を得た。
得られた共重合体の固形分は36.8%、pHは6.41、重量平均分子量は44900であった。
<Synthesis example 1>
90.0 g of pure water was placed in a glass separable flask equipped with a thermometer, a reflux condenser and a stirrer, and the temperature was raised to 90 ° C. under stirring. Then, under stirring, 2- (dimethylamino) ethyl methacrylate (N, N-dimethylaminoethyl methacrylate) (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as DAM) 51 in a polymerization reaction system in a constant state at 90 ° C. Monomer solution 1 consisting of 0.3 g, 18.6 g of acetic acid and 8.56 g of ethyl methacrylate (hereinafter referred to as EMA); 2,2'-azobis (2-methylpropionamidine) dihydrochloride (Wako Pure Chemical Industries, Ltd.) ), Initiator aqueous solution consisting of 29.3 g of 2.5% aqueous solution; and monomer solution 2 composed of 25.7 g of DAM and 9.32 g of acetic acid were added dropwise from separate dropping nozzles.
Regarding the dropping start time, the monomer solution 1 and the initiator aqueous solution started dropping at the same time, the monomer solution 1 was dropped for 120 minutes, and the initiator aqueous solution was dropped for 210 minutes. The monomer solution 2 was dropped over 60 minutes after the completion of the dropping of the monomer solution 1. After the completion of all dropping, the reaction solution was kept at 90 ° C. for another 30 minutes and aged to complete the polymerization, and the copolymer 1 was obtained.
The solid content of the obtained copolymer was 36.8%, the pH was 6.41, and the weight average molecular weight was 44900.
<合成例2>
EMAをアクリル酸ブチル(以下BAと称す。)に変更したこと以外は合成例1と同様に重合し、共重合体2を得た。
得られた共重合体2の固形分は35.7%、pHは6.41、重量平均分子量は45200であった。
<Synthesis example 2>
Polymerization was carried out in the same manner as in Synthesis Example 1 except that EMA was changed to butyl acrylate (hereinafter referred to as BA) to obtain a copolymer 2.
The solid content of the obtained copolymer 2 was 35.7%, the pH was 6.41, and the weight average molecular weight was 45200.
<合成例3>
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、純水50g、プロピレングリコール22gを仕込み、攪拌下、90℃に昇温した。次いで攪拌下、90℃一定状態の重合反応系中に、DAM63g、酢酸24.1g及びBA22.5gからなるモノマー溶液1;V-50の5%水溶液31.9gからなる開始剤水溶液;18%アクリル酸(以下AAとも称す。)水溶液25.6gからなるモノマー溶液2をそれぞれ別々の滴下ノズルより滴下した。滴下開始時間に関して、モノマー溶液1は180分間、開始剤水溶液およびモノマー溶液2は210分間滴下した。
全滴下終了後、さらに30分間反応溶液を90℃に保持して熟成し、重合を完結させ、共重合体3を得た。
得られた共重合体3の固形分は34.9%、pHは6.15、重量平均分子量は49500であった。
<Synthesis example 3>
50 g of pure water and 22 g of propylene glycol were placed in a glass separable flask equipped with a thermometer, a reflux condenser and a stirrer, and the temperature was raised to 90 ° C. under stirring. Then, under stirring, in a polymerization reaction system in a constant state at 90 ° C., a monomer solution 1 consisting of 63 g of DAM, 24.1 g of acetic acid and 22.5 g of BA; an initiator aqueous solution consisting of 31.9 g of a 5% aqueous solution of V-50; 18% acrylic. A monomer solution 2 composed of 25.6 g of an aqueous acid (hereinafter also referred to as AA) aqueous solution was dropped from separate dropping nozzles. With respect to the dropping start time, the monomer solution 1 was dropped for 180 minutes, and the initiator aqueous solution and the monomer solution 2 were dropped for 210 minutes.
After the completion of all dropping, the reaction solution was kept at 90 ° C. for another 30 minutes for aging to complete the polymerization, and the copolymer 3 was obtained.
The solid content of the obtained copolymer 3 was 34.9%, the pH was 6.15, and the weight average molecular weight was 49500.
<合成例4>
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、1,3-ブタンジオール70gを仕込み、攪拌下、90℃に昇温した。次いで攪拌下、90℃一定状態の重合反応系中に、DAM73.8g、EMA13.5gからなるモノマー溶液1:V-50の7%水溶液21.9gからなる開始剤水溶液、18.3%アクリル酸水溶液14.7gからなるモノマー溶液2をそれぞれ別々の滴下ノズルより滴下した。
滴下開始時間に関して、モノマー溶液1及び2は180分間、開始剤水溶液及びモノマー溶液2は210分間滴下した。
全滴下終了後、さらに90分間反応溶液を90℃に保持して熟成し、重合を完結させた。純水50gを追加し、共重合体4を得た。
得られた共重合体4の固形分は35.2%、pHは9.0、重量平均分子量は30500であった。
<Synthesis example 4>
70 g of 1,3-butanediol was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 90 ° C. under stirring. Then, under stirring, in a polymerization reaction system at a constant state of 90 ° C., a monomer solution consisting of 73.8 g of DAM and 13.5 g of EMA 1: an initiator aqueous solution consisting of 21.9 g of a 7% aqueous solution of V-50 and 18.3% acrylic acid. The monomer solution 2 composed of 14.7 g of the aqueous solution was dropped from each of the separate dropping nozzles.
Regarding the dropping start time, the monomer solutions 1 and 2 were dropped for 180 minutes, and the initiator aqueous solution and the monomer solution 2 were dropped for 210 minutes.
After the completion of all dropping, the reaction solution was kept at 90 ° C. for another 90 minutes and aged to complete the polymerization. 50 g of pure water was added to obtain a copolymer 4.
The solid content of the obtained copolymer 4 was 35.2%, the pH was 9.0, and the weight average molecular weight was 30500.
<合成例5>
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、1,3-ブタンジオール60gを仕込み、攪拌下、90℃に昇温した。次いで攪拌下、90℃一定状態の重合反応系中に、DEAM 81gからなるモノマー溶液1:V-50の5%水溶液28.1gからなる開始剤水溶液、42.4%アクリル酸水溶液21.3gからなるモノマー溶液2をそれぞれ別々の滴下ノズルより滴下した。
滴下開始時間に関して、モノマー溶液1及び2は180分間、開始剤水溶液及びモノマー溶液2は210分間滴下した。
全滴下終了後、さらに90分間反応溶液を90℃に保持して熟成し、重合を完結させた。純水50gを追加し、共重合体5を得た。
得られた共重合体5の固形分は32.9%、pHは8.8、重量平均分子量は22000であった。
<Synthesis Example 5>
60 g of 1,3-butanediol was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 90 ° C. under stirring. Then, under stirring, in a polymerization reaction system in a constant state at 90 ° C., a monomer solution consisting of 81 g of DEAM 1: an initiator aqueous solution consisting of 28.1 g of a 5% aqueous solution of V-50, and 21.3 g of a 42.4% acrylic acid aqueous solution. The monomer solution 2 was dropped from separate dropping nozzles.
Regarding the dropping start time, the monomer solutions 1 and 2 were dropped for 180 minutes, and the initiator aqueous solution and the monomer solution 2 were dropped for 210 minutes.
After the completion of all dropping, the reaction solution was kept at 90 ° C. for another 90 minutes and aged to complete the polymerization. 50 g of pure water was added to obtain a copolymer 5.
The solid content of the obtained copolymer 5 was 32.9%, the pH was 8.8, and the weight average molecular weight was 22000.
<合成例6>
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、純水24.0g、プロピレングリコール(以下PGとも称す。)72gを仕込み、攪拌下、90℃に昇温した。次いで攪拌下、90℃一定状態の重合反応系中に、DAM54g、酢酸20.6gからなるモノマー溶液1;V-50の2.5%水溶液32.5gからなる開始剤水溶液;ブチルアクリレート(BA)36gからなるモノマー溶液2をそれぞれ別々の滴下ノズルより滴下した。滴下時間に関して、モノマー溶液1および2と開始剤水溶液は同時に滴下を開始し、モノマー溶液1、2は180分間、開始剤水溶液を210分間滴下した。全滴下終了後、さらに90分間反応溶液を90℃に保持して熟成し、重合を完結させ、共重合体6を得た。
得られた共重合体6の固形分は35.2%、重量平均分子量は22100であった。
<Synthesis example 6>
24.0 g of pure water and 72 g of propylene glycol (hereinafter, also referred to as PG) were placed in a glass separable flask equipped with a thermometer, a reflux condenser and a stirrer, and the temperature was raised to 90 ° C. under stirring. Then, under stirring, in a polymerization reaction system in a constant state at 90 ° C., a monomer solution 1 consisting of 54 g of DAM and 20.6 g of acetic acid; an initiator aqueous solution consisting of 32.5 g of a 2.5% aqueous solution of V-50; butyl acrylate (BA). The monomer solution 2 consisting of 36 g was dropped from each of the separate dropping nozzles. Regarding the dropping time, the monomer solutions 1 and 2 and the initiator aqueous solution started dropping at the same time, the monomer solutions 1 and 2 were dropped for 180 minutes, and the initiator aqueous solution was dropped for 210 minutes. After the completion of all dropping, the reaction solution was kept at 90 ° C. for another 90 minutes and aged to complete the polymerization, and the copolymer 6 was obtained.
The solid content of the obtained copolymer 6 was 35.2%, and the weight average molecular weight was 22100.
<合成例7>
合成例6のモノマー溶液2のBAを2-エチルヘキシルアクリレート(2EHA)に変えたこと以外は合成例6と同様にして重合を行い、共重合体7を得た。得られた共重合体7の固形分は36.4%、重量平均分子量は70700であった。
<Synthesis example 7>
Polymerization was carried out in the same manner as in Synthesis Example 6 except that the BA of the monomer solution 2 of Synthesis Example 6 was changed to 2-ethylhexyl acrylate (2EHA) to obtain a copolymer 7. The solid content of the obtained copolymer 7 was 36.4%, and the weight average molecular weight was 70,700.
<合成例8>
プロピレングリコールの変わりに純水50g、1,3-ブタンジオール(1,3-BG)30gを仕込み、撹拌下90℃に昇温した。次いで撹拌下、90℃一定状態の重合反応系中にDAM72g、酢酸27.52g、アクリル酸ブチル18gからなるモノマー溶液;V-50の5%水溶液29.9gからなる開始剤水溶液をそれぞれ別々の滴下ノズルより滴下した。モノマー溶液1、2は180分間、開始剤水溶液を210分間滴下した。全滴下終了後、さらに90分間反応溶液を90℃に保持して熟成し、純水50g添加して重合を完結させ、共重合体8を得た。得られた共重合体8の固形分は31.2%、重量平均分子量は24900であった。
<Synthesis Example 8>
Instead of propylene glycol, 50 g of pure water and 30 g of 1,3-butanediol (1,3-BG) were charged, and the temperature was raised to 90 ° C. with stirring. Then, under stirring, a monomer solution consisting of 72 g of DAM, 27.52 g of acetic acid, and 18 g of butyl acrylate; an initiator aqueous solution consisting of 29.9 g of a 5% aqueous solution of V-50 was separately added dropwise to the polymerization reaction system at a constant state of 90 ° C. Dropped from the nozzle. The monomer solutions 1 and 2 were added dropwise for 180 minutes, and the initiator aqueous solution was added dropwise for 210 minutes. After the completion of all dropping, the reaction solution was kept at 90 ° C. for another 90 minutes for aging, and 50 g of pure water was added to complete the polymerization to obtain a copolymer 8. The solid content of the obtained copolymer 8 was 31.2%, and the weight average molecular weight was 24900.
<合成例9>
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、純水42.0g、1,3-BG 28gを仕込み、攪拌下、90℃に昇温した。次いで攪拌下、90℃一定状態の重合反応系中に、DAM67.5g、酢酸25.8g、メタクリル酸エチル18gからなるモノマー溶液;V-50の7%水溶液22.6gからなる開始剤水溶液;27.3%AA水溶液16.5gからなるモノマー溶液2をそれぞれ別々の滴下ノズルより滴下した。滴下時間に関して、モノマー溶液1および2と開始剤水溶液は同時に滴下を開始し、モノマー溶液1、2は120分間、開始剤水溶液を150分間滴下した。全滴下終了後、さらに90分間反応溶液を90℃に保持して熟成し、純水50g添加して重合を完結させ、共重合体9を得た。
得られた共重合体9の固形分は32%、重量平均分子量は30200であった。
<Synthesis example 9>
42.0 g of pure water and 28 g of 1,3-BG were placed in a glass separable flask equipped with a thermometer, a reflux condenser and a stirrer, and the temperature was raised to 90 ° C. under stirring. Then, under stirring, in a polymerization reaction system at a constant state of 90 ° C., a monomer solution consisting of 67.5 g of DAM, 25.8 g of acetic acid, and 18 g of ethyl methacrylate; an initiator aqueous solution consisting of 22.6 g of a 7% aqueous solution of V-50; 27. A monomer solution 2 composed of 16.5 g of a 0.3% AA aqueous solution was dropped from separate dropping nozzles. Regarding the dropping time, the monomer solutions 1 and 2 and the initiator aqueous solution started dropping at the same time, the monomer solutions 1 and 2 were dropped for 120 minutes, and the initiator aqueous solution was dropped for 150 minutes. After the completion of all dropping, the reaction solution was kept at 90 ° C. for another 90 minutes for aging, and 50 g of pure water was added to complete the polymerization to obtain a copolymer 9.
The solid content of the obtained copolymer 9 was 32%, and the weight average molecular weight was 30200.
<実施例1~10及び比較例1、2:MIC>
合成例1~9で得られた共重合体1~9及び比較例としてのメチルパラベン、フェノキシエタノールについてMICを評価し、評価結果を表1及び2に示した。
<Examples 1 to 10 and Comparative Examples 1 and 2: MIC>
The MICs were evaluated for the copolymers 1 to 9 obtained in Synthesis Examples 1 to 9 and methylparaben and phenoxyethanol as comparative examples, and the evaluation results are shown in Tables 1 and 2.
<実施例11~15及び比較例3:防腐試験1>
合成例1~5で得られた共重合体1~5について防腐試験1を行い、評価結果を表3に示した。なお、比較例3では、防腐抗菌剤を用いずに同様に試験を行った。評価結果を表3に示した。
<Examples 11 to 15 and Comparative Example 3: Antiseptic test 1>
Antiseptic test 1 was performed on the copolymers 1 to 5 obtained in Synthesis Examples 1 to 5, and the evaluation results are shown in Table 3. In Comparative Example 3, the same test was conducted without using an antiseptic and antibacterial agent. The evaluation results are shown in Table 3.
<実施例16~18及び比較例4、5:防腐試験2>
表4のとおりに調製したクリームについて防腐試験2を行い、評価結果を表5に示した。
<Examples 16 to 18 and Comparative Examples 4 and 5: Antiseptic test 2>
The antiseptic test 2 was performed on the cream prepared as shown in Table 4, and the evaluation results are shown in Table 5.
<実施例19、20及び比較例6、7:防腐試験2>
表6のとおりに調製した化粧水について防腐試験2を行い、評価結果を表7に示した。
<Examples 19 and 20 and Comparative Examples 6 and 7: Antiseptic test 2>
The antiseptic test 2 was performed on the lotion prepared as shown in Table 6, and the evaluation results are shown in Table 7.
<実施例21、22及び比較例8:防腐試験2>
表8のとおりに調製した化粧水について防腐試験2を行い、評価結果を表9に示した。
<Examples 21 and 22 and Comparative Example 8: Antiseptic test 2>
The antiseptic test 2 was performed on the lotion prepared as shown in Table 8, and the evaluation results are shown in Table 9.
<実施例23及び比較例9:乳化性能試験>
(実施例23)
オリーブオイルを5g、水を44.4g、合成例2で得られた共重合体2を0.66g添加し、ホモミキサーにて回転数8000rpmで10分間撹拌して乳化した。乳化した液の粒子径を粒子径測定装置(濃厚系アナライザー FPAR-1000;大塚電子株式会社製)測定したところ、210nmであった。
(比較例9)
0.66gの共重合体2を0.25gのノニオン系界面活性剤NC2305(日本乳化剤製)に変更した以外は、実施例16と同様に乳化性能試験を行ったところ、乳化液の粒子径は450nmであった。
更に、実施例23及び比較例9の乳化液を1週間室温で放置した際の状態を観察したところ比較例9は分離しており、乳化状態が壊れていたのに対し、実施例23は乳化状態を維持していた。以上より、本発明の材料は既存の界面活性剤に比べて微分散することが可能であり、さらには分散安定性にも優れることが明らかとなった。
<Example 23 and Comparative Example 9: Emulsification performance test>
(Example 23)
5 g of olive oil, 44.4 g of water, and 0.66 g of the copolymer 2 obtained in Synthesis Example 2 were added, and the mixture was emulsified by stirring with a homomixer at a rotation speed of 8000 rpm for 10 minutes. The particle size of the emulsified liquid was measured by a particle size measuring device (concentrated analyzer FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.) and found to be 210 nm.
(Comparative Example 9)
When the emulsification performance test was carried out in the same manner as in Example 16 except that 0.66 g of the copolymer 2 was changed to 0.25 g of the nonionic surfactant NC2305 (manufactured by Nippon Emulsifier), the particle size of the emulsion was found. It was 450 nm.
Further, when the state of the emulsified liquids of Example 23 and Comparative Example 9 left at room temperature for one week was observed, Comparative Example 9 was separated and the emulsified state was broken, whereas Example 23 was emulsified. It was in good condition. From the above, it was clarified that the material of the present invention can be finely dispersed as compared with the existing surfactant, and is also excellent in dispersion stability.
以下の表10~17に本発明の化粧料の処方例を記載する。なお、これらの処方例における本発明の化粧品料組成物に防腐試験2を実施したところ、いずれの処方例でも抗菌活性値(抗菌活性値=log(接種時の生菌数)-log(7日後の生菌数、但し、クロコウジカビは14日後))は2.0以上であり、評価は「良好」と判定された。 Tables 10 to 17 below show examples of prescription of the cosmetics of the present invention. When the antiseptic test 2 was carried out on the cosmetic composition of the present invention in these formulation examples, the antibacterial activity value (antibacterial activity value = log (number of viable bacteria at the time of inoculation) -log (7 days later) in any of the formulation examples. However, the viable cell count of Aspergillus niger (14 days later)) was 2.0 or more, and the evaluation was judged to be "good".
処方例1~3 美白ローション Prescription example 1-3 Whitening lotion
*2 酵母エキス(山川貿易社製)
* 2 Yeast extract (manufactured by Yamakawa Trading Co., Ltd.)
(製法)Aに属する原料を70℃に加熱し、完全溶解した後、室温まで冷却した。その後、Bに属する原料を混合し、美白ローションを得た。 (Production method) The raw material belonging to A was heated to 70 ° C., completely dissolved, and then cooled to room temperature. Then, the raw materials belonging to B were mixed to obtain a whitening lotion.
処方例4~6 乳液
(製法)Aに属する油相部の原料及びBに属する水相部の原料を70℃に加熱し、完全溶解した後、油相部を水相部に混合し、ホモミキサーにて乳化した。乳化物を30℃まで冷却し、乳液を得た。 (Production method) The raw material of the oil phase portion belonging to A and the raw material of the aqueous phase portion belonging to B were heated to 70 ° C. and completely dissolved, and then the oil phase portion was mixed with the aqueous phase portion and emulsified with a homomixer. The emulsion was cooled to 30 ° C. to obtain an emulsion.
処方例7~9 モイスチャークリーム Prescription example 7-9 Moisture cream
(製法)Aに属する油相部の原料及びBに属する水相部の原料を70℃に加熱し、完全溶解した後、油相部を水相部に混合し、ホモミキサーにて乳化した。乳化物を30℃まで冷却し、モイスチャークリームを得た。 (Production method) The raw material of the oil phase portion belonging to A and the raw material of the aqueous phase portion belonging to B were heated to 70 ° C. and completely dissolved, and then the oil phase portion was mixed with the aqueous phase portion and emulsified with a homomixer. The emulsion was cooled to 30 ° C. to obtain a moisture cream.
処方例10~12 洗顔クリーム Prescription example 10-12 Facial cleansing cream
(製法)Aに属する油相部の原料及びBに属する水相部の原料を75℃に加熱し、溶解した後、水相部を油相部に混合し、その後攪拌した後、30℃まで冷却し、洗顔クリームを得た。 (Manufacturing method) The raw material of the oil phase portion belonging to A and the raw material of the aqueous phase portion belonging to B are heated to 75 ° C. and melted, the aqueous phase portion is mixed with the oil phase portion, and then stirred, and then up to 30 ° C. Cooled to get a face wash cream.
処方例13~15 サンスクリーンクリーム Prescription example 13-15 Sunscreen cream
(製法)Aに属する油相部の原料及びBに属する水相部の原料を75℃に加熱し、完全溶解した後、油相部を水相部に混合し、ホモミキサーにて乳化した。乳化物を30℃まで冷却し、サンスクリーンクリームを得た。 (Production method) The raw material of the oil phase portion belonging to A and the raw material of the aqueous phase portion belonging to B were heated to 75 ° C. to completely dissolve them, and then the oil phase portion was mixed with the aqueous phase portion and emulsified with a homomixer. The emulsion was cooled to 30 ° C. to give a sunscreen cream.
処方例16~18 リキッドファンデーション(シェイクウェルタイプ) Prescription example 16-18 Liquid foundation (Shakewell type)
(製法)Aに属する油相部を60℃まで加熱し、その後室温まで冷却する。Aに属する油相部の原料とBに属する水相部の原料を室温で混合し、ホモミキサーにて乳化し、シェイクウェルタイプのリキッドファンデーションを得た。 (Manufacturing method) The oil phase portion belonging to A is heated to 60 ° C. and then cooled to room temperature. The raw material of the oil phase portion belonging to A and the raw material of the aqueous phase portion belonging to B were mixed at room temperature and emulsified with a homomixer to obtain a shakewell type liquid foundation.
処方例19~21 シャンプー Prescription example 19-21 shampoo
(製法)Aに属する油相部を80℃まで加熱し、その後室温まで冷却し、シャンプーを得た。 (Production method) The oil phase portion belonging to A was heated to 80 ° C. and then cooled to room temperature to obtain a shampoo.
処方例22~24 コンディショナー Prescription example 22-24 Conditioner
(製法)A及びBに属する油相部を80℃まで加熱し、80℃に加温したCを80℃にて混合し、ホモミキサーにて乳化した。乳化物を室温まで冷却し、コンディショナーを得た。 (Production method) The oil phase portions belonging to A and B were heated to 80 ° C., C heated to 80 ° C. was mixed at 80 ° C., and emulsified with a homomixer. The emulsion was cooled to room temperature to obtain a conditioner.
Claims (6)
該共重合体は、アミノ基含有単量体(A)由来の構造単位(a)と疎水性単量体(B)由来の構造単位(b)とを有し、
重量平均分子量が4000~20万であり、
該アミノ基含有単量体(A)は、下記式(4)及び/又は(5);
ただし、qが0である場合、rは0であり、及び、qが1~30の範囲にある場合、rは1であり、(R 15 O) s は、炭素数2~4のオキシアルキレンユニットのホモポリマ、ランダムコポリマ、又は、ブロックコポリマであるポリオキシアルキレン基であり、ここで、R 15 は、C 2 H 4 、C 3 H 6 、C 4 H 8 又はそれらの混合物であり、sは、5~250の範囲の整数であり、Zは、-R 15 O-、-R 15 H-、-C(=O)-、-C(=O)NH-、-R 15 NHC(=O)NH-、又は、-C(=O)NHC(=O)-であり、かつ、R 16 は、炭素数8~40の直鎖アルキル基、炭素数8~40の分枝アルキル基、炭素数8~40の炭素環アルキル基、炭素数2~40のアルキル置換フェニル基、アリール置換の炭素数2~40アルキル基、及び、炭素数8~80の複合エステルからなる群より選択される置換又は非置換アルキル基であり、ここで、R 16 のアルキル基は任意で、ヒドロキシ基、アルコキシ基及びハロゲンからなる群より選択される1つ以上の置換基を含む。)で表される単量体を除く。)ことを特徴とする化粧料用防腐抗菌剤。 An antiseptic and antibacterial agent for cosmetics containing a copolymer.
The copolymer has a structural unit (a) derived from the amino group-containing monomer (A) and a structural unit (b) derived from the hydrophobic monomer (B).
The weight average molecular weight is 4000-200,000,
The amino group-containing monomer (A) has the following formulas (4) and / or (5);
However, when q is 0, r is 0, and when q is in the range of 1 to 30, r is 1, and (R 15 O) s is an oxyalkylene having 2 to 4 carbon atoms. A polyoxyalkylene group that is a homopolyma, random copolyma, or block copolyma of the unit, where R 15 is C 2 H 4 , C 3 H 6 , C 4 H 8 or a mixture thereof, where s is. It is an integer in the range of 5 to 250, where Z is -R 15 O-, -R 15 H- , -C (= O)-, -C (= O) NH-, -R 15 NHC (= O ). ) NH- or -C (= O) NHC (= O)-and R 16 is a linear alkyl group having 8 to 40 carbon atoms, a branched alkyl group having 8 to 40 carbon atoms, and carbon. Substitution selected from the group consisting of an alkyl ring group having 8 to 40 carbon atoms, an alkyl substituted phenyl group having 2 to 40 carbon atoms, an aryl substituted alkyl group having 2 to 40 carbon atoms, and a composite ester having 8 to 80 carbon atoms. Alternatively, it is an unsubstituted alkyl group, wherein the alkyl group of R 16 optionally comprises one or more substituents selected from the group consisting of hydroxy groups, alkoxy groups and halogens. ) Is excluded. ) An antiseptic and antibacterial agent for cosmetics.
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