JP2018058813A - Antisepsis antimicrobial agent for cosmetics - Google Patents
Antisepsis antimicrobial agent for cosmetics Download PDFInfo
- Publication number
- JP2018058813A JP2018058813A JP2017108061A JP2017108061A JP2018058813A JP 2018058813 A JP2018058813 A JP 2018058813A JP 2017108061 A JP2017108061 A JP 2017108061A JP 2017108061 A JP2017108061 A JP 2017108061A JP 2018058813 A JP2018058813 A JP 2018058813A
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Landscapes
- Cosmetics (AREA)
Abstract
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 a preservative antibacterial agent for cosmetics. More specifically, the present invention relates to a preservative antibacterial agent for cosmetics useful for skin cosmetics, skin external 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。
2. Description of the Related Art Conventionally, parabens, benzoic acid and salts thereof, salicylic acid and salts thereof, and the like are used as antiseptic fungicides in human body compositions such as cosmetics, pharmaceuticals, quasi drugs, and foods.
However, the above-mentioned conventional antiseptic disinfectant has a drawback that the use concentration range is easily limited because of its low safety such as high skin irritation. For example, the use restriction concentration of paraben and benzoate is 1%. The limit concentration of benzoic acid and salicylic acid is 0.2%.
In recent years, an increasing number of people have an allergic reaction to these antiseptic disinfectants, so the safety consciousness has increased and cosmetics with no or no preservative antiseptics have been added. There is an increasing demand for coating compositions.
Therefore, various attempts have been made to overcome the disadvantages of conventional antiseptics and to reduce the amount of antiseptics used by searching for highly safe antibacterial substances and increasing the effectiveness of antiseptics. . For example, a technique using 1,2-alkanediol, which is safer for the human body (see Patent Document 1), a technique using glycerol monoalkyl ether (see Patent Document 2), a technique using ethyl 4-hydroxyphenylacetate (Patent Document) 3)) has 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 antibacterial agents such as 1,2-alkanediol, glycerol monoalkyl ether and ethyl 4-hydroxyphenylacetate can provide a certain level of antibacterial antibacterial effect but exhibit higher antiseptic antibacterial effect. Development of antiseptic 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。 This invention is made | formed in view of the said present condition, and aims at providing the antiseptic antibacterial agent for cosmetics which exhibits the antiseptic antibacterial effect higher than the conventional antiseptic antibacterial agent.
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 antibacterial agents for cosmetics, the present inventors have found that a structural unit derived from an amino group-containing monomer (A) having a specific structure (a) and a structural unit derived from a hydrophobic monomer (B) It is found that a copolymer having (b) and a weight average molecular weight of 4,000 to 200,000 exhibits a higher antiseptic antibacterial effect than a conventional antiseptic antibacterial agent, and can solve the above-mentioned problems brilliantly. The present inventors have arrived at the present invention by conceiving what can be done.
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) is represented by the following formulas (4) to (6);
The present invention is described in detail below.
A combination of two or more 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, and quasi-drugs that are directly applied to the human skin. Cosmetics include skin cosmetics, skin external preparations, hair cosmetics, and the like.
The antiseptic antibacterial agent for cosmetics in the present invention refers to an agent used for cosmetics and having antiseptic performance and / or antibacterial performance. Antiseptic performance is the ability to prevent the invasion, growth and proliferation of microorganisms and prevent rot and fermentation. Antibacterial performance refers to sterilization (killing microorganisms) and bacteriostatic (suppressing the growth of microorganisms). ) Performance such as sterilization, disinfection, sterilization, sterilization, and mold prevention. 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 bacterium include Gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, Salmonella, Moraxella, Legionella, and Gram-positive bacteria such as Staphylococcus aureus and Clostridium bacteria. Examples of the fungi include yeasts such as Candida, Rhodotorula, and baker's yeast; molds such as red mold and black mold (black mold and black mold).
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) is a co-polymer having a structural unit derived from an amino group-containing monomer and a structural unit derived from a hydrophobic monomer. Includes coalescence. The reason why 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 microorganisms, 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 shows affinity with the cell membrane part, and by interacting with the cell membrane, the interaction between lipids constituting the cell membrane is broken and / or bound to the membrane. By inhibiting the function of protein or the like, it is presumed that 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 conventional ones made of low molecular weight compounds, and since it is water-soluble, there are few restrictions on blending into cosmetics.
Furthermore, the antiseptic antibacterial agent for cosmetics of the present invention has an effect of emulsifying the cosmetics and an effect of increasing the viscosity of the cosmetics when blended in the cosmetics, and also has an effect as an emulsifier and a thickener. It 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 includes 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。
(Wherein R 1 and R 2 are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms) or a primary to tertiary amino group represented by It is a monomer having a neutralized product of a quaternary amino group with an acid or a quaternary ammonium base.
The hydrocarbon group may have a chain structure or a ring structure, but preferably has a chain structure. When the hydrocarbon group has a chain structure, it may be linear or branched.
As said hydrocarbon group, an alkyl group, an alkenyl group, and an aryl group are preferable, More preferably, they are an alkyl group and an alkenyl group, More preferably, it is an alkyl group.
Moreover, as carbon number of the said hydrocarbon group, 1-10 are preferable, More preferably, it is 1-8, More preferably, it is 1-5, Most preferably, it is 1-2.
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, tertiary amino groups are preferred.
上記第1〜3級アミノ基としては、下記式(2); Examples of 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。 (Wherein R 1 and R 2 are the same or different and each represents a hydrogen atom or a hydrocarbon group 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 said quaternary ammonium base, 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 formula, R < 3 > -R < 5 > is the same or different and represents a C1-C12 hydrocarbon group. Y < - > represents an anion.). 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 or an alkenyl group having 2 to 12 carbon atoms.
As carbon number of R < 3 > -R < 5 >, More preferably, it is 1-10, More preferably, it is 1-7, Most preferably, it is 1-5.
The hydrocarbon group for R 3 to R 5 is most preferably a methyl group or an ethyl group.
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. For example, halide ions such as chlorine ion, bromine ion and iodine ion; alkyl sulfate ions such as methyl sulfate ion; organic acids such as acetate ion And the like.
Y − in the above formula (2) is preferably an organic acid ion.
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。 Among the amino groups, among the primary to tertiary amino groups, neutralized products of acids of the primary to tertiary amino groups and quaternary ammonium bases, tertiary amino groups and acids of tertiary amino groups are used. Neutralized products or quaternary ammonium bases are preferred. The neutralized product of the tertiary amino group or the tertiary amino group with an acid is preferably a dimethylamino group, a diethylamino group or a neutralized product thereof with an acid such as hydrochloric acid or acetic acid.
上記アミノ基含有単量体(A)としては、下記式(4)〜(6); As said amino group containing monomer (A), following formula (4)-(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 Formula (4)-(6), R < 6 > -R < 8 > is the same or different, and represents a hydrogen atom or a C1-C5 alkyl group. X represents a direct bond or a bivalent coupling group. In formulas (4) and (5), R 1 and R 2 are the same or different and represent a hydrocarbon group having 1 to 12 carbon atoms, and in formula (6), R 3 to R 5 are the same or Differently, it represents a hydrocarbon group having 1 to 12 carbon atoms, and Y − represents 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 R 8 is preferably a methyl group. R 8 is preferably a hydrogen atom or a methyl group. From the viewpoint of antibacterial properties and hydrolysis resistance, R 8 is more preferably a methyl group.
R 6 and R 7 are preferably 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); Although it does not restrict | limit especially as a bivalent coupling group in the said Formula (4) and (5), For example, following formula (7);
(式中、mは、0〜12の整数を表す。)、下記式(8); (Wherein m represents an integer of 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); (Wherein, 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。 (Wherein, 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。
As a bivalent coupling group in the said Formula (6), the structure represented by the said Formula (7)-(9) and a C1-C12 alkylene group are mentioned.
M in the above formula (7) is preferably 1 to 8, and more preferably 1 to 5.
K in the formula (9) is preferably 1 to 8, 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 acrylate, N, N-diethylaminopropyl (meth) acrylate and the like, monomers obtained by adding a quaternizing agent to the above monomers, or acids such as hydrochloric acid and acetic acid. Neutralized product: 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 Monomers obtained by adding a quaternizing agent to the above monomers or neutralized products thereof with acids such as hydrochloric acid and acetic acid; monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) Monoalkylamino group-containing (meth) acrylates such as acrylate, monoethylaminopropyl (meth) acrylate, 2- (tert-butylamino) ethyl (meth) acrylate, and neutralized products thereof with acids such as hydrochloric acid and acetic acid Monoalkylamino group-containing (meth) acrylamides such as monomethylaminoethyl (meth) acrylamide, monoethylaminoethyl (meth) acrylamide, monomethylaminopropyl (meth) acrylamide, monoethylaminopropyl (meth) acrylamide, and the like; Neutralized products by acid such as hydrochloric acid and acetic acid; (meth) acrylic acid-2-aminoethyl and other (meth) acrylic acid and alkanolamine esters and neutralized products by acid such as hydrochloric acid and acetic acid; N , N-diallylmethylamine and a monomer obtained by adding a quaternizing agent thereto, or a neutralized product thereof with an acid such as hydrochloric acid or acetic acid; an allylamine or a neutralized product thereof with an acid such as hydrochloric acid or acetic acid; 1-allyloxy Unsaturated monomers having a cyclic ether-containing group having 2 to 8 carbon atoms such as -3-dibutylamino-2-ol, 1-allyloxy-3-diethanolamino-2-ol, and amine compounds having 1 to 24 carbon atoms And a monomer obtained by adding a quaternizing agent 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 an unsaturated monomer having an amino group and a cyclic ether-containing group having 2 to 8 carbon atoms. 1-20 are preferable and, as for carbon number of a C1-C24 amine compound, 1-16 are more preferable. Examples of the amine compound having 1 to 24 carbon atoms include primary amines and secondary amines, such as (di) alkylamines having 1 to 24 carbon atoms, (di) alkanolamines having 1 to 24 carbon atoms, Examples thereof include alkyl alkanolamines 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, 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, dimethanolamine, diethanolamine, dipropanolamine, dibutanolamine, hexanolamine and the like are preferable.
As the alkyl alkanolamine 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。 In the amino group-containing monomer (A), R 8 in the formulas (4) to (6) is preferably a methyl group, and X is preferably a structure represented by the 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。
The amino group-containing monomer (A) is preferably an N, N-dialkylamino group-containing (meth) acrylate and a neutralized product thereof with an acid such as hydrochloric acid or acetic acid or a quaternizing agent added thereto. Monomers, N, N-dialkylamino group-containing (meth) acrylamides and their neutralized products with acids such as hydrochloric acid and acetic acid, and monomers obtained by adding a quaternizing agent to these, particularly N, N-dimethylamino Neutralized products such as ethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, and acids such as hydrochloric acid and acetic acid, and quaternizing agents are added to these. More preferred is a monomer that has been allowed to react.
The quaternizing agent is not particularly limited, but alkyl halides such as methyl chloride, ethyl chloride, methyl bromide and methyl iodide; dimethyl sulfate, diethyl sulfate, di-n-propyl sulfate and the like. Common alkylating agents such as alkyl sulfuric acid may be mentioned.
The amino group-containing monomer may be a tertiary amine or a quaternary ammonium cation, but the tertiary amine exhibits higher antibacterial properties against gram-negative bacteria and 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 a hydrophobic monomer (B), and the hydrophobic monomer (B) is a homopolymer obtained by homopolymerization. The solubility parameter of (homopolymer) is 15 or less. In addition, even if a solubility parameter is 15 or less, what has an amino group shall be contained in an 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 based on the evaporation energy (Δei) and molar volume (Δvi) of the structural unit forming the polymer: It is calculated by the following calculation method.
δ = (Δei / Δvi) 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 copolymer of the present invention has sufficient hydrophobicity, and the Since the affinity for the cell membrane is improved and the interaction with the cell membrane is increased, the physiological activity of the cell membrane is damaged, so that the antibacterial performance is superior to the conventional polymer antibacterial agent. The solubility parameter is preferably 14 or less, more preferably 13 or less, and still more 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 is an ester of (meth) acrylic acid and an optionally substituted alcohol. ((Meth) acrylate optionally having a substituent); Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-allyloxyacrylic acid and salts thereof; Aromatic vinyl such as styrene Olefin monomers such as propylene; esters of unsaturated alcohols such as vinyl acetate with carboxylic acids; vinyl halides such as vinyl chloride; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; 1-allyloxy An unsaturated monomer having a cyclic ether-containing group having 2 to 8 carbon atoms such as -3-butoxypropan-2-ol and 1 to 2 carbon atoms Addition reaction product of alcohol with allyl alcohol; ethylene oxide adduct of allyl alcohol, ethylene oxide adduct of methallyl alcohol, ethylene oxide adduct of isoprenol, etc., and alkylene oxide adducts of unsaturated alcohols having 2 to 20 carbon atoms and terminal hydrophobic modification thereof And cyclic vinyl monomers such as N-vinylpyrrolidone.
Among the hydrophobic monomers having a solubility parameter of 15 or less, those having an alkyl group having 2 or more carbon atoms are preferred. 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 salt of the unsaturated monocarboxylic acid 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 halogeno group, an epoxy group such as a glycidyl group, a carbonyl group such as an 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); Although it does not restrict | limit especially as (meth) acrylate which may have the above substituents, 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。
(Wherein R 9 represents a hydrogen atom or a methyl group. R 10 represents a hydrocarbon group which may have a substituent).
The hydrocarbon group which may have a substituent refers to a group in which one or two or more hydrogen atoms of a hydrocarbon group are substituted with a group other than a hydrocarbon group. When it is a hydrocarbon group having a substituent and the substituent has a (poly) oxyalkylene group, the hydrocarbon group preferably has 3 to 200 carbon atoms. When at least the substituent does not have a (poly) oxyalkylene group, the hydrocarbon group which may have a substituent preferably has 1 to 30 carbon atoms. When the hydrocarbon group which may have the above substituent has a substituent, the number of carbons contained in the substituent is also included in the above 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 chain hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, and cyclic hydrocarbon groups such as aromatic hydrocarbon groups, cycloalkyl groups, and cycloalkenyl groups. .
Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, Heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, 2,3,5-trimethylhexyl, decyl, undecyl, 4-ethyl-5-methyloctyl, dodecyl, tridecyl, tetradecyl And linear or branched alkyl groups such as a group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group.
Examples of the alkenyl group include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, octadecenyl group, icocenyl group. Etc.
Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, dodecynyl group, octadecynyl group, icosinyl group. Etc.
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-xylyl 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, and a cyclohexenyl group.
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, 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) acrylate such as acrylate, n-lauryl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl methacrylate 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 a hydroxyl group-containing (meth) acrylate having 1 to 18 carbon atoms in an ester group such as butyl (meth) acrylate.
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, trimethylolpropane tripropoxy (meth) acrylate, and the like. Is 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.
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 fluoro group-containing (meth) acrylate include fluoro groups having 2 to 6 carbon atoms in an ester group such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and octafluoropentyl (meth) acrylate. Examples 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 acetonyl (meth) acrylate, diacetone (meth) acrylate, 2-hydroxypropyl (meth) acrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate, and 2- (acetoate). Acetoxy) ethyl (meth) acrylate, (meth) acryloyloxyalkylpropenal, and the like.
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.
As the (meth) acrylic acid ester, a compound represented by the above formula (10), that the carbon number of the hydrocarbon group R 10 of formula (10) is compound 1-20 preferable.
Carbon number of the hydrocarbon group of R 10 in the above formula (10) is more preferably 1 to 16, further preferably 1 to 12, particularly preferably 1 to 8, and most preferably 2 to 8. It is.
When the hydrocarbon group has 1 to 20 carbon atoms, the water solubility and viscosity of the polymer can be adjusted to suitable ranges, and the handling is excellent. When the hydrocarbon group has 1 to 12 carbon atoms, the production of the polymer is facilitated, and in addition to antibacterial properties, it is excellent in safety. 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 will be 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 composed of at least one (meth) acrylic acid alkyl ester. It is preferable to include.
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- Propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2 It is ethylhexyl (meth) acrylate.
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 is also a hydrophobic monomer (B) having a structural unit derived from (meth) acrylic acid alkyl ester, and further having a solubility parameter of 15 or less, And 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. A copolymer having such a structural unit is also one preferred embodiment of the present invention.
The monomer having at least one functional group selected from the group consisting of the carboxyl group, the hydroxyl group and the ether group has a solubility parameter of 15 or less, and has any functional group of the carboxyl group, the hydroxyl group and the ether group. What is necessary is just to have, Even if it has a (meth) acrylic acid ester structure, it has at least 1 sort (s) of functional group selected from the group which consists of a carboxyl group, a hydroxyl group, and an ether group 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. In this way, the water solubility of the resulting copolymer is improved, and the effects of precipitation of the copolymer due to salt and pH, reduction in antibacterial properties, etc. can be alleviated more sufficiently, so in a wide pH range. A copolymer can be used, and it can be suitably used for cosmetic applications that are often weakly acidic.
Examples of the monomer having at least one functional group selected from the group consisting of the carboxyl group, the hydroxyl group, and the ether group include the above-described unsaturated monocarboxylic acids; hydroxyl group-containing (meth) acrylates; alkyl vinyl ethers; 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, and the like.
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; alkylene 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 number of carbon atoms of the unsaturated alcohol having 2 to 20 carbon atoms is preferably 2 to 18, and examples of the unsaturated alcohol having 2 to 20 carbon atoms include vinyl alcohol, allyl alcohol, and isoprenyl alcohol (isoprenol). Can be mentioned.
The carbon number of alkylene oxide in the alkylene oxide adduct of unsaturated alcohol having 2 to 20 carbon atoms is preferably 2 to 20, more preferably 2 to 8, and further preferably 2 to 6. Particularly preferably, it is 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. More preferred are ethylene oxide, propylene oxide and butylene oxide, and still more preferred are ethylene oxide and propylene oxide.
It is preferable that the average added mole number of the said alkylene oxide is 1-100. More preferably, it is 1-80, More preferably, it is 1-70, Most preferably, it is 1-50.
As the alkylene oxide adduct of 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. Preferred are alkyl alcohols 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 an alcohol having 1 to 20 carbon atoms, 1-allyloxy-3-butoxypropan-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 another monomer other than the amino group-containing monomer (A) and the hydrophobic monomer (B). Other monomers are not particularly limited as long as they have no amino group and can be copolymerized with an amino group-containing monomer and a hydrophobic monomer. The solubility parameter of other monomer homopolymers may be 15 or less, or may exceed 15. Even if the solubility parameter of the other monomer is 15 or less or more than 15, as long as the hydrophobic monomer is polymerized at a preferred ratio, the hydrophobicity as a copolymer is It will be fully maintained.
Moreover, the monomer which has 2 or more of ethylenically unsaturated groups may be contained irrespective of the value of a solubility parameter from a viewpoint of adjusting a viscosity. Monomers 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 (meth) acrylic acid with two or more hydroxyl groups of a polyol such as 4-butanediol; Dimethacrylic acid esters with two or more substitutions of the polyol; Dihydroxy group with two or more substitutions of the polyol and allyl alcohol, vinyl alcohol Ethers with unsaturated alcohols such as diallyl phthalate, triallyl phosphate, allyl methacrylate, tetraallyloxyethane, triallyl cyanurate, divinyl adipate, vinyl crotonate, 1,5-hexadi Emissions, divinylbenzene and the like. These other monomers may be used alone or in combination of two or more.
From the viewpoint of improving antibacterial properties, the present invention may be copolymerized with 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 α-allyloxyzinc acrylate.
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 proportion of the structural unit derived from the hydrophobic monomer (B) in the copolymer is such that the structural unit (a) 100 derived from the amino group-containing monomer (A) in the copolymer. It is preferable that it is 0.1-99.9 mass% with respect to the mass%. More preferably, it is 0.5-90 mass%, More preferably, it is 1-80 mass%, More preferably, it is 2-70 mass%, More preferably, it is 3-64 mass%, More preferably, it is 4 It is -60 mass%, Especially preferably, it is 5-50 mass%, Most preferably, it is 5-40 mass%, Most preferably, it is 5-30 mass%. If the content ratio of the structural unit derived from the hydrophobic monomer (B) in the copolymer of the present invention is in such a range, the antibacterial performance of the copolymer is improved, and in particular, Escherichia coli having an outer membrane or It tends to exhibit 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 has at least a hydrophobic monomer (B) selected from the group consisting of a structural unit derived from an alkyl (meth) acrylate and a carboxyl group, a hydroxyl group and an ether group. A structural unit derived from a monomer having one type of functional group, and derived from a monomer having at least one type of functional group selected from the group consisting of a carboxyl group, a hydroxyl group and an ether group in the copolymer. The proportion of the structural unit 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 0-50 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。
In the copolymer of the present invention, the structural unit (a) derived from the amino group-containing monomer (A) is 0.01 to 99.9 mass% with respect to 100 mass% of the total amount of the structural units forming the copolymer. % Is preferable. More preferably, it is 0.1-99 mass%, More preferably, it is 1-98 mass%, More preferably, it is 10-97 mass%, More preferably, it is 30-96 mass%, More preferably, it is 36 It is -96 mass%, Most preferably, it is 50-95 mass%, Most preferably, it is 60-95 mass%, Most preferably, it is 70-95 mass%.
In the copolymer of the present invention, the proportion of the structural unit (b) derived from the hydrophobic monomer (B) is 0.01 to 90% by mass with respect to 100% by mass of the total amount of the structural units forming the copolymer. It is preferable to have. More preferably, it is 0.05-80 mass%, More preferably, it is 0.1-70 mass%, More preferably, it is 0.2-64 mass%, More preferably, it is 0.5-60 mass% Still more preferably, it is 1-50 mass%, Most preferably, it is 3-50 mass%, Most preferably, it is 4-40 mass%, Most preferably, it is 5-30 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 structural units forming the copolymer is 100% by mass. The proportion of the structural unit derived from the (meth) acrylic acid alkyl ester is preferably 0.01 to 60% by mass. More preferably, it is 1-50 mass%, More preferably, it is 3-40 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 of the structural unit (e) derived from the other monomer (E) is 0 to 10% by mass with respect to 100% by mass of the total amount of the structural units forming the copolymer. It is preferable that More preferably, it is 0-8 mass%, More preferably, it is 0-5 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 100% by mass of the total amount of the structural units forming the copolymer. More preferably, it is 0-0.5 mass%, More preferably, it is 0-0.1 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 preferred form. In this case, the sum of the proportions of the structural units (a) and (b) is 100% by mass, and the proportion of the structural units (a) or (b) is from 100% by mass to the structural unit (b) or ( A 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 4,000 to 1,000,000. If the weight average molecular weight of the copolymer is in such a range, the antiseptic antibacterial agent adsorptivity to the material using the antiseptic antibacterial agent is improved, so that it is sufficiently suppressed from being washed away when washed, Antibacterial effect on the material is improved.
The weight average molecular weight is preferably 4,000 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, still more preferably 7,000. 100,000, particularly preferably 7000 to 80,000. The weight average molecular weight of a copolymer can be measured by the method as described in an Example.
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 structure of the copolymer 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 structure, a dendrimer structure, Any structure may be sufficient.
<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>
Although the production of the copolymer of the present invention is not particularly limited, it can be produced by polymerizing the monomer component, and specific examples and preferred examples of the monomer component are as described above. Moreover, the preferable content rate of the monomers (A), (B), and (E) in the monomer component is the preferable ratio of the structural units (a), (b), and (e) in the above-mentioned copolymer. It is the same.
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 in which the monomer component is polymerized in the presence of a polymerization initiator. When the monomer component is polymerized, a polymerization initiator can be appropriately used depending on the polymerization method. As the polymerization initiator, those usually used can be used, for example, hydrogen peroxide; persulfates such as sodium persulfate and 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-methylpropionamidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] n hydrate, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate object, , 1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], etc .; benzoyl peroxide, lauroyl peroxide, peroxy Organic peroxides such as acetic acid and di-t-butyl peroxide are preferred. Of these polymerization initiators, azo compounds are preferred. The polymerization initiator is not limited to such 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 start polymerization of the monomer component, but is usually 0.01 to 50 parts by mass with respect to 100 parts by mass of all monomer components. , Preferably it is 0.05-30 mass parts, More preferably, it is 0.05-20 mass parts.
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。
The amino group-containing monomer used in the present invention may be used as an acid neutralized product neutralized with an acid or a quaternary ammonium salt quaternized with a quaternizing agent. By using quaternized amino group-containing monomers, higher antibacterial performance is exhibited against Gram-positive bacteria such as Staphylococcus aureus.
Acids used for neutralization of amino group-containing monomers are not particularly limited, but include inorganic acids such as hydrochloric acid and sulfuric acid; acetic acid, citric acid, tartaric acid, toluenesulfonic acid, lactic acid, succinic acid, 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 quaternizing agent is used, the amount used thereof is not particularly limited as long as part or all of the amino group-containing monomer is neutralized or quaternized. It is preferable that an acid or a quaternizing agent is 0.1-1 mol with respect to 1 mol of an amino group-containing monomer to be 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 copolymerization method, monomer components, polymerization initiators, etc. can be added to the reaction vessel by charging all of the monomer components into the reaction vessel and adding the polymerization initiator into the reaction vessel. Method of performing polymerization: charging a part of the monomer component into the reaction vessel, and adding the polymerization initiator and the remaining monomer component continuously or stepwise (preferably continuously) into the reaction vessel. A method in which a polymerization solvent is charged into a reaction vessel and the whole amount of monomer components and a polymerization initiator is added; a part of one of the monomers (for example, an amino group-containing monomer) Is preferably carried out by adding a polymerization initiator and the remaining monomer component into the reaction vessel (preferably continuously). Among these methods, since the molecular weight distribution of the obtained copolymer can be narrowed (sharpened), it is possible to carry out copolymerization by a method in which a polymerization initiator and a monomer component are successively dropped into a 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。 Examples of the copolymerization method include solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, living polymerization, and graft polymerization, and are not particularly limited, but solution polymerization is preferable. The solvent that can be used in this case 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 copolymerization method can be carried out either batchwise or continuously. In addition, a known solvent can be used as necessary in the copolymerization, and water; monohydric alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butanol, and THF (tetrahydrofuran); 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 Suitable are esters such as ethyl; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide; ethers such as diethyl ether and dioxane. These may be used alone or in combination of two or more. Among these, from the viewpoint of the solubility of the monomer component and the resulting copolymer, one or more solvents selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms may be used. preferable. The solvent is relatively inexpensive, and the production method of the present invention is economically excellent. Moreover, in the said copolymerization method, you may superpose | polymerize by adding polyhydric alcohol solvents, such as propylene glycol and ethylene glycol, to water. When the polyhydric alcohol solvent is used in combination with water, the solubility of the polymer can be increased, and soap-free polymerization can be more sufficiently suppressed. Thereby, the production | generation of a polymer with poor water solubility can fully be suppressed, and the transparency of a solution can be improved more.
When using the said polyhydric alcohol solvent and water together, it is preferable that the ratio of the polyhydric alcohol solvent with respect to 100 mass% of water is 0-200 mass%.
In the method for producing the copolymer of the present invention, any chain transfer agent, pH adjuster, buffering agent, and the like can be used as 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。 Although the temperature in the case of superposition | polymerization is not specifically limited, Usually, it is 50-120 degreeC, Preferably it is 60-110 degreeC. If the temperature at the time of polymerization is in the above range, the residual monomer component tends to decrease. The temperature at the time of polymerization need not always be kept constant during the progress of the polymerization reaction. For example, the polymerization is started from room temperature, and the temperature is increased to a set temperature at an appropriate temperature increase time or temperature increase rate. Thereafter, the set temperature may be maintained, or the polymerization temperature may be varied (increased or decreased) over time during the course of the polymerization reaction, depending on the dropping method of the monomer component, initiator, and the like. Also good. Further, when the monomer component is polymerized, it is preferable to appropriately stir the monomer component so that the monomer component is uniformly polymerized.
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, “polymerization time” refers to the time during which heating and stirring is performed before dropping the monomer, 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 increased pressure. 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。 20 mass% or more is preferable and, as for the solid content concentration (namely, polymerization solid content concentration of a monomer) at the time of the completion | finish of the polymerization reaction in the said polymerization reaction system, it is more preferable that it is 25-80 mass%. . Thus, if 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 stage. Therefore, an antiseptic antibacterial agent containing a copolymer can be obtained efficiently, for example, the concentration step that is necessary in some cases in the conventional production method can be omitted. Therefore, the production efficiency can be greatly increased. As a result, the productivity of the antiseptic antibacterial agent of the present invention can be greatly improved, and an 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。 The method for producing a copolymer of the present invention may be provided with an aging step 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, more preferably 1 to 120 minutes. When the aging time is less than 1 minute, the monomer component may remain due to insufficient aging, causing problems such as toxicity and odor caused by the remaining monomer.
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。 Moreover, the temperature of the preferable polymer solution in an aging process is the same range as the said polymerization temperature. Therefore, the temperature here may also 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 adjusters, anionic surfactants, compatibilizers and stabilizers. .
The antiseptic antibacterial agent of the present invention may further contain a metal salt, a metal oxide, a metal hydroxide, or the like from the viewpoint of improving antibacterial properties. The metal in the metal salt, metal oxide, or metal hydroxide is preferably a heavy metal such as copper, zinc, or silver.
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 antibacterial agent of the present invention is preferably used for cosmetic applications such as skin cosmetics, external preparations for skin, or hair (hair) cosmetics.
Although it does not restrict | limit especially as said skin cosmetics, For example, basic cosmetics, such as a lotion, cream, milky lotion, a cosmetic liquid; Makeup cosmetics, such as a liquid foundation, foundation milky lotion, teak color, eye shadow, mascara, lipstick; Cosmetics for cleansing such as cleansing creams, facial cleansing foams, liquid facial cleansers; cosmetics such as sunscreen cosmetics (including quasi-drugs); bath cosmetics such as bath preparations. Examples of the external preparation for skin include external medicines such as liniments, lotions and ointments.
Although it does not restrict | limit especially as said hair cosmetics, For example, shampoo, rinse, treatment, wax, spray, gel, mist etc. are mentioned.
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 comprising the antiseptic antibacterial agent for cosmetics of the present invention.
The content of the antiseptic antibacterial agent in the cosmetic is not particularly limited, but is 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less with respect to 100% by mass of the cosmetic.
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。 Further, in the cosmetic and skin external preparation of the present invention, water and additive components generally incorporated in the cosmetic and skin external preparation as necessary, for example, an oily base, a moisturizer, a touch improver, a surface activity Agent, polymer, thickening / gelling agent, solvent, propellant, antioxidant, reducing agent, oxidizing agent, antiseptic / antibacterial agent other than the antiseptic antibacterial agent of the present invention, chelating agent, pH adjuster, acid, 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 Agent, squeezing agent, cooling sensation agent, warming sensation agent, wound healing promoter, stimulus relaxation agent, analgesic agent, cell activator, plant / animal / microbe extract, antipruritic agent, exfoliating / dissolving agent, antiperspirant, cooling Agents, astringents, enzymes, nucleic acids, fragrances, pigments, colorants, dyes, pigments, water, etc. Kill.
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; Examples of these additive components include cetanol, myristyl alcohol, oleyl alcohol, lauryl alcohol, cetostearyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, jojoba alcohol, chimyl alcohol, seraalkyl alcohol, batyl. Higher alcohols such as alcohol, hexyldecanol, isostearyl alcohol, 2-octyldodecanol, dimer diol; aralkyl alcohols and derivatives such as benzyl alcohol; lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, undecylen Acid, 12-hydroxystearic acid, palmitooleic acid, oleic acid, linoleic acid, linolenic acid, erucic acid, docosahexaenoic acid, ethyl Higher fatty acids such as cosapentaenoic acid, isohexadecanoic acid, anteisohenicosanoic acid, long-chain branched fatty acid, dimer acid, and hydrogenated dimer acid, and metals such as aluminum salts, calcium salts, magnesium salts, zinc salts, and potassium salts Soaps and nitrogen-containing derivatives such as amides; liquid paraffin (mineral oil), heavy liquid isoparaffin, light liquid isoparaffin, α-olefin oligomer, polyisobutene, hydrogenated polyisobutene, polybutene, squalane, olive-derived squalane, squalene, petrolatum , Solid paraffin, hydrogenated polydecene and other carbides; candelilla wax, carnauba wax, rice wax, wax, beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax Waxes such as cox, petrolatum, Fischer-Tropsch wax, polyethylene wax, ethylene propylene copolymer; palm oil, palm oil, palm kernel oil, safflower oil, olive oil, castor oil, avocado oil, sesame oil, tea oil, evening primrose oil, Wheat germ oil, macadamia nut oil, hazelnut oil, kukui nut oil, rosehip oil, meadow foam oil, persic oil, tea tree oil, mint oil, corn oil, rapeseed oil, sunflower oil, wheat germ oil, linseed oil, cottonseed oil, soybean oil Vegetable oils such as peanut oil, rice bran oil, cacao butter, shea butter, hydrogenated palm oil, hydrogenated castor oil, jojoba oil, hydrogenated jojoba oil; beef tallow, milk fat, horse fat, egg yolk oil, mink oil, turtle Animal fats and oils such as oil; animal nature such as whale wax, lanolin and orange luffy oil C class;
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, adsorptive lanolin, lanolin acetate, lanolin acetate, hydroxy lanolin, polyoxyethylene lanolin, lanolin fatty acid, hard lanolin fatty acid, lanolin alcohol, lanolin alcohol acetate, acetic acid (cetyl lanolyl) ester Phospholipids such as lecithin, phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, sphingomyelin, etc .; phospholipids such as phosphatidic acid, lysolecithin; hydrogenated soybean phospholipid, partially hydrogenated soybean phospholipid, hydrogen Phospholipid derivatives such as added egg yolk phospholipid, partially hydrogenated egg yolk phospholipid; cholesterol, dihydrocholesterol, lanosterol, dihydrora Sterols such as sterol, phytosterol, cholic acid; sapogenins; saponins; cholesteryl acetate, cholesteryl nonanoate, cholesteryl stearate, cholesteryl isostearate, cholesteryl oleate, di-N-lauroyl-L-glutamate (cholesteryl / behenyl / octyl) Dodecyl), N-lauroyl-L-glutamate di (cholesteryl / octyldodecyl), N-lauroyl-L-glutamate di (phytosteryl / behenyl / octyldodecyl), N-lauroyl-L-glutamate di (phytosteryl / octyldodecyl), Acyl sarcosine alkyl esters such as N-lauroyl sarcosine isopropyl, cholesteryl 12-hydroxystearate, macadamia nut oil fatty acid cholesteryl, maca Sterol esters such as peanut 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 Lipid complexes such as the 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 myristate, hexyldecyl myristate, octyldodecyl isostearate, cetyl palmitate, octyldodecyl palmitate, cetyl octanoate, hexyl decyl octanoate, isotridecyl isononanoate, isononyl isononanoate, octyl isononanoate Isodecyl acid, isotridecyl neopentanoate, isostearyl neopentanoate, octyldodecyl neodecanoate, oleyl oleate, octyldodecyl oleate, octyldodecyl ricinoleate, octyldodecyl lanthanate fatty acid, octyldodecyl dimethyloctanoate, octyldodecyl erucate, isostearic acid curing Castor oil, ethyl oleate, avocado oil fatty acid ethyl, myristic acid isop Pill, isopropyl palmitate, octyl palmitate, isopropyl isostearate, lanolin fatty acid isopropyl, diethyl sebacate, diisopropyl sebacate, dioctyl sebacate, diisopropyl adipate, dibutyloctyl sebacate, diisobutyl adipate, dioctyl succinate, triethyl citrate Monoalcohol carboxylic esters such as cetyl lactate, diisostearyl malate, monoisostearic acid hydrogenated castor oil, and the like;
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, glyceryl tri (caprylic acid / capric acid), tri (caprylic acid / capric acid / myristic acid / stearic acid) glyceryl, hydrogenated Rosin triglyceride (hydrogenated ester gum), rosin triglyceride (ester gum), glyceryl behenate, trimethylolpropane trioctanoate, trimethylolpropane triisostearate, neopentyl glycol dioctanoate, neopentyl glycol dicaprate, dioctanoic acid 2-butyl-2-ethyl-1,3-propanediol, propylene glycol dioleate, pentaerythrityl tetraoctanoate, hydrogenated Ginpentaerythrityl, triethylhexanoic acid ditrimethylolpropane, (isostearic acid / sebacic acid) ditrimethylolpropane, triethylhexanoic acid pentaerythrityl, (hydroxystearic acid / stearic acid / rosinic acid) dipentaerythrityl, diisostearate diglyceryl, tetraisostearin Polyglyceryl acid, polyglyceryl nonaisostearate-10, deca (erucic acid / isostearic acid / ricinoleic acid) polyglyceryl-8, (hexyldecanoic acid / sebacic acid) diglyceryl oligoester, glycol distearate (ethylene glycol distearate), etc. Alcohol fatty acid esters;
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。 Dimer dilinoleate diisopropyl, dimer dilinoleate diisostearyl, dimer dilinoleate di (isostearyl / phytosteryl), dimer dilinoleate (phytosteryl / behenyl), dimer dilinoleate (phytosteryl / isostearyl / cetyl / stearyl / Dimer acids or dimers such as behenyl), dimer dilinoleic acid dimer dilinoleyl, diisostearic dimer dilinoleyl, dimer dilinoleic hydrogenated rosin condensate, dimer dilinoleic acid hydrogenated castor oil, hydroxyalkyl dimer dilinoleyl ether Derivatives of diol: 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 (cocamide methyl MEA), etc. Fatty acid alkanolamides: dimethicone (dimethylpolysiloxane), highly polymerized dimethicone (highly polymerized dimethylpolysiloxane), cyclomethicone (cyclic dimethylsiloxane, decamethylcyclopentasiloxane), phenyltrimethicone, diphenyldimethicone, phenyldimethicone, stearoxy Propyldimethylamine, (aminoethylaminopropylmethicone / dimethicone) copolymer, dimethiconol, dimethiconol Ross polymer, silicone resin, silicone rubber, amino-modified silicone such as aminopropyl dimethicone and amodimethicone, polyether-modified silicone such as cation-modified silicone and dimethicone copolyol, polyglycerin-modified silicone, sugar-modified silicone, carboxylic acid-modified silicone, phosphorus Acid-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, cation-modified and polyether-modified silicone, amino-modified and polyether-modified silicone, alkyl Silicones such as modified and polyether-modified silicones and polysiloxane / oxyalkylene copolymers; perfluorodecane, Fluorine-based oils such as -fluorooctane and perfluoropolyether are preferred.
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; As the humectant / feel improver, glycerin, 1,3-butylene glycol, propylene glycol, 3-methyl-1,3-butanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, Polyols such as trimethylolpropane, pentaerythritol, hexylene glycol, diglycerin, polyglycerin, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, ethylene glycol / propylene glycol copolymer and polymers thereof; diethylene glycol monoethyl ether (Ethoxydiglycol), ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dibutyl ether, etc. Sugars such as sorbitol, xylitol, erythritol, mannitol, maltitol; glucose, fructose, galactose, mannose, threose, xylose, arabinose, fucose, ribose, deoxyribose, maltose, trehalose, lactose, raffinose, gluconic acid , Glucuronic acid, cyclodextrins (α-, β-, γ-cyclodextrin and modified cyclodextrins such as maltosylation, hydroxyalkylation, etc.), β-glucan, chitin, chitosan, heparin and derivatives, pectin, arabino Sugars and derivatives thereof such as galactan, dextrin, dextran, glycogen, ethyl glucoside, glucosyl ethyl methacrylate polymer or copolymer; hyaluronic acid, hyal Sodium ronate; sodium chondroitin sulfate; mucoitin sulfate, caroline sulfate, keratosulfate, dermatan sulfate; white jellyfish extract, white jellyfish polysaccharide; fucoidan; tuberose polysaccharide, naturally-occurring polysaccharide; organic acids such as citric acid, tartaric acid, lactic acid and the like Its salts; urea; 2-pyrrolidone-5-carboxylic acid and its salts such as sodium;
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。 Betaine (trimethylglycine), proline, hydroxyproline, arginine, lysine, serine, glycine, alanine, phenylalanine, tyrosine, β-alanine, threonine, glutamic acid, glutamine, asparagine, aspartic acid, cysteine, cystine, methionine, leucine, isoleucine, Amino acids such as valine, tryptophan, histidine, taurine and salts thereof; collagen, collagen derived from fish, 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 and other protein peptides and derivatives thereof; palmitoyl oligopeptide, palmitoyl pentapeptide, palmitoyl tetrapeptide, etc. Acylated peptides; silylated peptides; lactic acid bacteria culture solution, yeast extract, eggshell membrane protein, bovine submandibular mucin, hypotaurine, sesameignan glycoside, glutathione, albumin, whey; choline chloride, phosphorylcholine; placental extract , Aerlastin, collagen, aloe extract, hamamelis water, loofah water, chamomile extract, licorice extract, comfrey extract, silk extract, Izayoi rose extract, yarrow extract, eucalyptus extract, merirotoe Preferred are ceramides such as animal / plant extract components such as kisses, natural ceramides (types 1, 2, 3, 4, 5, 6), hydroxyceramides, pseudoceramides, glycosphingolipids, ceramides and sugar-ceramide-containing extracts As mentioned.
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 an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, and a polymer surfactant. There is no restriction | limiting in particular in HLB of surfactant, It can use from about 1 low thing to about 20 high thing, It is also preferable to combine a low thing and a high thing of HLB.
Examples of preferable surfactants include fatty acid salts such as potassium laurate and potassium myristate; alkyl sulfates such as sodium lauryl sulfate, triethanolamine lauryl sulfate, and ammonium lauryl sulfate; laureth Polyoxyethylene alkyl sulfates such as sodium sulfate and laureth sulfate triethanolamine; cocoyl methyl taurine sodium, cocoyl methyl taurine potassium, lauroyl methyl taurine sodium, myristoyl methyl taurine sodium, lauroyl methyl alanine sodium, lauroyl sarcosine sodium, lauroyl sarcosine triethanol Acyl N-methyl amino acid salts such as amines and sodium methylalanine lauroylglutamate; Cocoyl Glue Acyl amino acid salts such as sodium minate, triethanolamine cocoyl glutamate, sodium lauroyl glutamate, sodium myristoyl glutamate, sodium stearoyl glutamate, ditriethanolamine palmitoyl aspartate, cocoylalanine triethanolamine; polyoxyethylene alkyl ethers such as sodium laureth acetate Acetic acid salt; Succinic acid ester salt such as sodium lauroyl monoethanolamide succinate; Fatty acid alkanolamide ether carboxylate; Acyl lactate; Polyoxyethylene fatty amine sulfate; Fatty acid alkanolamide sulfate; Hardened coconut oil fatty acid sodium glyceryl sulfate Fatty acid glyceride sulfate such as alkylbenzene polyoxyethylene sulfate; α-olefin Olefin sulfonates such as sodium sulfonate; alkylsulfosuccinates such as disodium lauryl sulfosuccinate and dioctyl sodium sulfosuccinate; disodium laureth sulfosuccinate, monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, lauryl polypropylene glycol sulfosuccinic acid Alkyl ether sulfosuccinates such as sodium; alkylbenzene sulfonates such as sodium tetradecylbenzenesulfonate and tetraethanolamine tetraethanol; alkylnaphthalenesulfonates; alkanesulfonates; α-sulfo fatty acid methyl ester salts; Acyl isethionate; alkyl glycidyl ether sulfonate; alkyl sulfoacetate; laurethrin Alkyl ether phosphates such as sodium, sodium dilaureth phosphate, sodium trilaureth phosphate, sodium monooles phosphate; alkyl phosphate salts such as potassium lauryl phosphate; sodium caseinate; alkyl aryl ether phosphate; fatty acid amide ether phosphorus Acid salts; phospholipids such as phosphatidylglycerol, phosphatidylinositol, and phosphatidic acid; silicone-based anionic surfactants such as carboxylic acid-modified silicone, phosphate-modified silicone, and sulfate-modified silicone;
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), steareth (polyoxyethylene stearyl ether), behenes (polyoxyethylene behenyl ether), isosteares (poly Polyoxyethylene alkyl ethers with various polyoxyethylene addition numbers such as oxyethylene isostearyl ether), octyldecesses (polyoxyethylene octyldodecyl ether); polyoxyethylene alkylphenyl ether; polyoxyethylene hydrogenated castor oil, poly Oxyethylene castor oil, polyoxyethylene hydrogenated castor oil monoisostearate, polyoxyethylene hydrogenated castor oil triisostearate, polyoxyethylene hydrogenated castor oil mono Polyglutamic acid monoisostearic acid diester, castor oil and hardened castor oil derivatives such as polyoxyethylene hydrogenated castor oil maleic acid; polyoxyethylene phytosterol; polyoxyethylene cholesterol; polyoxyethylene cholestanol; polyoxyethylene lanolin; polyoxyethylene lanolin; Lanolin; polyoxyethylene / polyoxypropylene cetyl ether, polyoxyethylene / polyoxypropylene 2-decyltetradecyl ether, polyoxyethylene / polyoxypropylene monobutyl ether, polyoxyethylene / polyoxypropylene hydrogenated lanolin, polyoxyethylene・ Polyoxyethylene such as polyoxypropylene glycerin ether ・ Polyoxypropylene alkyl ether; Polyoxyethylene Polyoxypropylene glycol; (poly) glycerin polyoxypropylene glycol such as PPG-9 diglyceryl; glyceryl stearate, glyceryl isostearate, glyceryl palmitate, glyceryl myristate, glyceryl oleate, glyceryl palm oil fatty acid, mono cottonseed oil fatty acid Glycerin fatty acid partial esters such as glycerin, glyceryl monoerucate, glyceryl sesquioleate, glycerin α, α'-oleic acid pyroglutamate, glyceryl monostearate, malic acid monostearate; polyglyceryl-2 stearate, 3, 4, 4 , 6, 8, 10, polyglyceryl distearate-6, 10, polyglyceryl tristearate, polyglyceryl decastearate-10, polyglyceryl isostearate -2, 3, 4, 5, 6, 8, 10, diglycostyl diisostearate (diglyceryl diisostearate), 3, 10, polyglyceryl-2 triisostearate, tetraisostearic acid Polyglyceryl-2, polyglyceryl-10 decaisostearate, polyglyceryl-2 oleate, 3, 4, 5, 6, 8, 10, dioleate polyglyceryl-6, trioleate polyglyceryl-2, dekaoleic acid Polyglyceryl fatty acid esters such as polyglyceryl-10; ethylene glycol monofatty acid esters such as ethylene glycol monostearate; propylene glycol monofatty acid esters such as propylene glycol monostearate; pentaerythritol partial fatty acid esters; sorbitol Partial fatty acid ester; maltitol partial 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; Maltitol ether; sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, tetra Sorbitan fatty acid esters such as diglycerol sorbitan-2-ethylhexylate; sugar derivative partial esters such as sucrose fatty acid ester, methyl glucoside fatty acid ester, and undecylenic acid trehalose; alkyl glucoside such as caprylyl glucoside; alkyl polyglycoside; lanolin alcohol; Lanolin; polyoxyethylene distearate, polyethylene glycol diisostearate, polyoxyethylene monooleate Polyoxyethylene fatty acid mono- and diesters such as polyoxyethylene dioleate; polyoxyethylene propylene glycol fatty acid ester; polyoxyethylene glycerin monostearate, polyoxyethylene glycerin monoisostearate, polyoxyethylene glycerin triisostearate Polyoxyethylene glycerin fatty acid ester such as polyoxyethylene monooleate; polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tetraoleate, etc. Oxyethylene sorbitan fatty acid ester; polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol Polyoxyethylene sorbitol fatty acid esters such as oleate, polyoxyethylene sorbitol pentaoleate, polyoxyethylene sorbitol monostearate; polyoxyethylene methyl glucoside fatty acid ester; polyoxyethylene alkyl ether fatty acid ester; polyoxyethylene sorbitol beeswax Oxyethylene animal and vegetable fats and oils; alkyl glyceryl ethers such as isostearyl glyceryl ether, chimyl alcohol, ceralkyl alcohol, and batyl alcohol; polyhydric alcohol alkyl ether; polyoxyethylene alkylamine; tetrapolyoxyethylene tetrapolyoxypropylene Ethylenediamine condensates; natural surfactants such as saponins and sophorolipids; 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), fatty acid alkanolamides such as palmitic acid monoethanolamide (partamide MEA), palmitic acid diethanolamide (partamide DEA), coconut oil fatty acid methylethanolamide (cocamidomethyl MEA);
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 oxide; polyoxyethylene alkyl mercaptan; polyether-modified silicone such as dimethicone copolyol; polysiloxane oxyalkylene Silicone nonionic surfactants such as copolymers, polyglycerin-modified silicones, sugar-modified silicones, etc .; for cationic surfactants, behentrimonium chloride, steartrimonium chloride, cetrimonium chloride, lauryltrimonium chloride Alkyltrimethylammonium chloride such as stearyltrimonium bromide; alkyltrimethylammonium bromide such as stearyltrimonium bromide; distearyldimonium chloride, dico Dialkyldimethylammonium chlorides such as dimonium chloride; fatty acid amidoamines such as stearamidepropyldimethylamine and stearamideethyldiethylamine and salts thereof; alkyl ether amines such as stearoxypropyldimethylamine and salts or quaternary salts thereof; ethyl sulfate long chain Fatty acid amide type quaternary ammonium salts such as branched fatty acid (12-31) aminopropylethyldimethylammonium and ethyl lanolin sulfate fatty acid aminopropylethyldimethylammonium; polyoxyethylene alkylamine and salts or quaternary salts thereof; alkylamine salt; fatty acid Amidoguanidinium salt; alkyl ether amine ammonium salt; alkyltrialkylene glycol ammonium salt; benzalkonium salt; benzethonium salt; Pyridinium salts such as dinium; imidazolinium salts; alkylisoquinolinium salts; dialkyl morpholinium salts; polyamine fatty acid derivatives; amino-modified silicones such as aminopropyl dimethicone and amodimethicone, cation-modified silicones, cation-modified and polyether-modified Silicone-based cationic surfactants such as silicone, amino-modified and polyether-modified silicones; in amphoteric surfactants, N-alkyl-N, N-dimethylamino acid betaines such as laurylbetaine (lauryldimethylaminoacetic acid betaine); Fatty acid amide alkyl-N, N-dimethylamino acid betaines such as cocamidopropyl betaine and lauramidopropyl betaine; imidazoline type betaines such as sodium cocoamphoacetate and sodium lauroamphoacetate; Alkylsulfobetaines such as rudimethyltaurine; sulfate-type betaines such as alkyldimethylaminoethanol sulfate; phosphate-type betaines such as alkyldimethylaminoethanol phosphate; sphingolines such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, and sphingomyelin Lipids such as lipid, lysolecithin, hydrogenated soybean phospholipid, partially hydrogenated soybean phospholipid, hydrogenated egg yolk phospholipid, partially hydrogenated egg yolk phospholipid, hydroxylated lecithin; silicone-based amphoteric surfactant, etc .; polymer interface Preferred examples of the activator include polyvinyl alcohol, sodium alginate, starch derivative, tragacanth gum, acrylic acid / alkyl methacrylate copolymer, and various silicone surfactants.
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; Polymers, thickeners and gelling agents include guar gum, locust bean gum, queens seed, carrageenan, galactan, arabic gum, tara gum, tamarind, far selelain, karaya gum, troarooi, cara gum, tragacanth gum, pectin, pectic acid and sodium Salt such as salt, salt such as alginic acid and sodium salt, mannan; starch such as rice, corn, potato, wheat; xanthan gum, dextran, succinoglucan, curdlan, hyaluronic acid and its salt, xanthan gum, pullulan, gellan gum, chitin , Chitosan, agar, gypsum extract, chondroitin sulfate, casein, collagen, gelatin, albumin; methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropi Cellulose, carboxymethylcellulose and its salts such as sodium, methylhydroxypropylcellulose, sodium cellulose sulfate, cellulose dialkyldimethylammonium sulfate, crystalline cellulose, cellulose powder such as cellulose powder; soluble starch, carboxymethyl starch, methylhydroxypropyl starch, Starch-based polymers such as methyl starch, starch derivatives such as hydroxypropyltrimonium chloride, octenyl succinate corn starch and aluminum; alginic acid derivatives such as sodium alginate and propylene glycol alginate; polyvinylpyridone (PVP), polyvinyl alcohol (PVA), Vinyl pydridone-vinyl alcohol copolymer, polyvinyl methyl ether Polyethylene glycol, polypropylene glycol, polyoxyethylene / polyoxypropylene copolymer; amphoteric methacrylic acid such as (methacryloyloxyethylcarboxybetaine / alkyl methacrylate) copolymer, (acrylates / stearyl acrylate / ethylamine methacrylate oxide) copolymer, etc. Ester copolymer; (Dimethicone / vinyl dimethicone) crosspolymer, (alkyl acrylate / diacetone acrylamide) copolymer, (alkyl acrylate / diacetone acrylamide) copolymer AMP; Polyvinyl acetate partial saponification product, maleic acid copolymer; Vinylpyrrolidone / dialkylaminoalkyl methacrylate copolymer; acrylic resin alkanolamine; polyester, water-dispersible polyester; Kurylamide; Polyacrylic acid ester copolymer such as polyethyl acrylate, carboxyvinyl polymer, polyacrylic acid and its sodium salt, 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 / methacrylic acid alkyl copolymer; cationic cellulose such as polyquaternium-10, diallyldimethylammonium chloride / acrylamide copolymer such as polyquaternium-7, acrylic acid / diallyldimethylammonium chloride copolymer such as polyquaternium-22 Acrylic acid / diallyldimethylammonium chloride / acrylamide copolymer such as polyquaternium-39, acrylic acid / cationized methacrylic acid ester copolymer, acrylic acid / cationized methacrylic acid amide copolymer, polyquaternium-47, etc. Acrylic acid / methyl acrylate / methacrylamidopropyltrimethylammonium chloride copolymer, methacrylic acid choline ester polymer; cationized oligosaccharide, cationized dextran, Cationic polysaccharides such as arhydroxypropyltrimonium chloride; polyethyleneimine; cationic polymers; copolymers of 2-methacryloyloxyethyl phosphorylcholine such as polyquaternium-51 and copolymers of butyl methacrylate; acrylic resin emulsions , Polymer emulsions such as polyethyl acrylate emulsion, polyacryl alkyl ester emulsion, polyvinyl acetate resin emulsion, natural rubber latex, synthetic latex; nitrocellulose; polyurethanes and various copolymers; various silicones; acrylic-silicone grafts Various silicone-based copolymers such as copolymers; various fluorine-based polymers; 12-hydroxystearic acid and its salts; dextrin palmitate, dextrin myristate Dextrin fatty acid esters; silicic anhydride, fumed silica (ultrafine silica), magnesium aluminum silicate, magnesium magnesium silicate, metal soap, metal dialkyl phosphate, bentonite, hectorite, organically modified clay mineral, Preferred examples include sugar fatty acid esters and fructooligosaccharide fatty acid esters.
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。 Solvents and propellants include ethanol, 2-propanol (isopropyl alcohol), butanol, isobutyl alcohol and other lower alcohols; propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, isopentyl diol and other glycols 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 ethylene glycol monoethyl ether Glycol ether esters such as acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate; Glycol esters such as diethoxyethyl succinate, ethylene glycol disuccinate; benzyl alcohol, benzyloxyethanol, propylene carbonate, dialkyl carbonate , Acetone, ethyl acetate, N-methylpyrrolidone; toluene; fluorocarbon, next-generation flon; propellants such as LPG, dimethyl ether, carbon dioxide, and the like are preferable.
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; gallic acid derivatives such as propyl gallate; vitamin C (ascorbic acid) and / or derivatives thereof; erythorbic acid and derivatives thereof; Preferred are sulfites such as sodium sulfite; bisulfites such as sodium bisulfite; thiosulfates such as sodium thiosulfate; metabisulfites; thiotaurine, hypotaurine; thioglycerol, thiourea, thioglycolic acid, cysteine hydrochloride As mentioned.
Preferred examples of the reducing agent include thioglycolic acid, cysteine, cysteamine and the like.
Preferred examples of the oxidizing agent include aqueous hydrogen peroxide, ammonium persulfate, sodium bromate, and percarbonate.
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 acid such as methylparaben, ethylparaben, propylparaben and butylparaben and salts or esters thereof; salicylic acid; sodium benzoate; phenoxyethanol; 1,2-diols such as pentanediol and 1,2-hexanediol; isothiazolinone derivatives such as methylchloroisothiazolinone and methylisothiazolinone; imidazolinium urea; dehydroacetic acid and its salts; phenols; Halogenated bisphenols, acid amides, quaternary ammonium salts; trichlorocarbanide, zinc pyrithione, benzalkonium chloride, benzethonium chloride, sorbic acid, chlorhexidine, chlorhexidine gluconate, halocarban Hexachlorophene, hinokitiol; other phenols such as phenol, isopropylphenol, cresol, thymol, parachlorophenol, phenylphenol, sodium phenylphenol; phenylethyl alcohol, photosensitizers, antibacterial zeolite, silver ion are preferred. .
Examples of chelating agents include edetate (ethylenediaminetetraacetate) such as EDTA, EDTA2Na, EDTA3Na, and EDTA4Na; hydroxyethylethylenediaminetriacetate such as HEDTA3Na; pentetate (diethylenetriaminepentaacetate); phytic acid; Phosphonic acid and its sodium salt; sodium oxalate; polypolyamino acids such as polyaspartic acid and polyglutamic acid; sodium polyphosphate, sodium metaphosphate, phosphoric acid; sodium citrate, citric acid, alanine, dihydroxyethylglycine Gluconic acid, ascorbic acid, succinic acid, and tartaric acid are preferable.
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, hydroxylation Sodium, potassium hydroxide, aqueous ammonia, guanidine carbonate, and ammonium carbonate are preferable.
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。
Examples of powders include mica, talc, kaolin, sericite, montmorillonite, kaolinite, mica, muscovite, phlogopite, synthetic mica, red mica, biotite, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, silica Barium acid, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, zeolite, barium sulfate, calcined calcium sulfate, calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder, bentonite, smectite, clay, mud, Metal soap (eg, zinc myristate, calcium palmitate, aluminum stearate), calcium carbonate, bengara, yellow iron oxide, black iron oxide, ultramarine, bitumen, carbon black, titanium oxide, fine particles and super Titanium oxide, zinc oxide, fine and ultrafine zinc oxide, alumina, silica, fumed silica (ultrafine silica), mica titanium, fish scale foil, boron nitride, photochromic pigment, synthetic fluorophlogopite, fine particle composite powder Body, gold, aluminum, etc., various sizes and shapes of inorganic powders, and these are treated with various surface treatment agents such as hydrogen silicone, cyclic hydrogen silicone, or other silane or titanium coupling agents Inorganic powders such as hydrophobized or hydrophilized powders; starch, cellulose, nylon powder, polyethylene powder, polymethyl methacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, polyester powder, Benzoguanamine resin powder, polyethylene terephthalate polymer Organic powders and surface-treated powders of various sizes and shapes, such as polyurethane powder, polyethylene terephthalate / aluminum / epoxy powder, urethane powder, silicone powder, Teflon (registered trademark) powder, organic-inorganic composite powder The body is preferred.
Inorganic salts include sodium chloride-containing salts such as salt, common salt, rock salt, sea salt, natural salt; potassium chloride, aluminum chloride, calcium chloride, magnesium chloride, bittern, zinc chloride, ammonium chloride; sodium sulfate, aluminum sulfate, Aluminum sulfate / potassium sulfate (alum), aluminum sulfate / ammonium sulfate, barium sulfate, calcium sulfate, potassium sulfate, magnesium sulfate, zinc sulfate, iron sulfate, copper sulfate; sodium phosphates such as 1Na, 2Na and 3Na phosphates, phosphoric acid Potassium, 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 ultraviolet absorbers 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 ester. Benzoic acid-based ultraviolet absorbers such as esters, N, N-dimethylparaaminobenzoic acid butyl ester, N, N-dimethylparaaminobenzoic acid ethyl ester; Anthranilic acid-based ultraviolet absorbers such as homomenthyl-N-acetylanthranilate; Salicylic acid And salicylic acid-based purple such as sodium salt, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate Line absorber: Octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p- Methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, 2-ethylhexyl p-methoxycinnamate (octyl paramethoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate (sinoxate), Cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl α-cyano-β-phenylcinnamate (octocrine), glyceryl mono-2-ethylhexanoyl-diparamethoxy Cinnamic acid UV absorbers such as cinnamate, ferulic acid and derivatives thereof; 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone (oxybenzone-3), 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone -5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, etc. Benzophenone UV absorber; 3- (4′-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor; 2-phenyl-5-methylbenzoxazole; 2,2′-hydroxy-5 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole; 2- (2′-hydroxy-5′-methylphenylbenzotriazole; dibenzalazine; dianisoylmethane; 5- (3 , 3-dimethyl-2-norbornylidene) -3-pentan-2-one; dibenzoylmethane derivatives such as 4-t-butylmethoxydibenzoylmethane; octyl triazone; urocanic acid derivatives such as urocanic acid and ethyl urocanate; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 1 Hydantoin derivatives such as (3,4-dimethoxyphenyl) -4,4-dimethyl-1,3-pentanedione, dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl, phenylbenzimidazolazolesulfonic acid, terephthalylidene diene Preference is given to camphorsulfonic acid, drometrizole trisiloxane, methyl anthranilate, rutin and its derivatives, oryzanol 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 whitening agents include hydroquinone glycosides such as arbutin and α-arbutin and esters thereof; ascorbic acid phosphate salts such as ascorbic acid, sodium ascorbate phosphate and magnesium ascorbate phosphate, ascorbic acid Ascorbic acid fatty acid esters such as tetraisopalmitic acid ester, ascorbic acid alkyl ethers such as ascorbic acid ethyl ether, ascorbic acid glucosides such as ascorbic acid-2-glucoside and fatty acid esters thereof, ascorbic acid sulfate ester, tocopheryl ascorbyl phosphate Ascorbic acid derivatives such as kojic acid, ellagic acid, tranexamic acid and its derivatives, ferulic acid and its derivatives, placenta extract, glutathione, oryzanol, butylreso Shinoru, oil-soluble Kamomiraekisu, oil-soluble licorice extract, Nishikawa willow extract, be mentioned as saxifrage extract, and the like 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。 Vitamins and their derivatives include vitamin A such as retinol, retinol acetate, retinol palmitate; thiamine hydrochloride, thiamine sulfate, riboflavin, riboflavin acetate, pyridoxine hydrochloride, pyridoxine dioctanoate, pyridoxine dipalmitate, Flavin adenine dinucleotide, cyanocobalamin, folic acid, nicotinic acid such as nicotinic acid amide / benzyl nicotinate, vitamin B group such as choline; vitamin C such as ascorbic acid and its sodium salt; vitamin D; α, Vitamin Es such as β, γ, δ-tocopherol; other vitamins such as pantothenic acid and biotin; ascorbic acid phosphates such as ascorbic acid phosphate sodium salt and ascorbic acid phosphate magnesium salt; Ascorbic acid fatty acid esters such as corobic acid tetraisopalmitic acid ester, ascorbyl stearate, ascorbyl palmitate and ascorbyl dipalmitate, ascorbic acid alkyl ether such as ascorbic acid ethyl ether, ascorbic acid glucoside such as ascorbic acid-2-glucoside and Ascorbic acid derivatives such as fatty acid esters and tocopheryl phosphate ascorbyl; vitamin derivatives such as tocopherol nicotinate, tocopherol acetate, tocopherol acetate, tocopherol linoleate, tocopherol phosphate, tocopherol phosphate etc., tocotrienol, and other various vitamin derivatives Is preferable.
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 glycyrrhizic acid and its derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, guaiazulene, allantoin, indomethacin, zinc oxide, hydrocortisone acetate, prednisone, diphedramine hydrochloride, chlorpheniramine maleate; peach leaf extract A plant extract such as a koji leaf extract is preferable.
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。
Plant growth and tinctures such as assembly extract, red pepper tincture, ginger tincture, ginger extract, cantalis tincture; capsaicin, nonyl acid valenylamide, gingeron, ictamol, tannic acid Borneol, cyclandelate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin, γ-oryzanol, cephalanthin, vitamin E and nicotinic acid tocopherol, acetic acid tocopherol and other derivatives, γ-oryzanol, nicotinic acid, nicotinic acid amide, nicotinic acid benzyl Derivatives such as ester, inositol hexanicotinate, nicotine alcohol, allantoin, photosensitizer 301, photosensitizer 401, capronium chloride, pentadecanoic acid monoglyceride, Preferable examples include flavonol derivatives, stigmasterol or stigmasteranol, its glycosides, and minoxidil.
Preferred hormones include estradiol, estrone, ethinyl estradiol, cortisone, hydrocortisone, prednisone and the like.
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 remedies such as anti-wrinkle agents, anti-aging agents, squeeze agents, cooling sensations, warming sensation agents, wound healing promoters, irritation relievers, analgesics, cell activators include retinols, retinoic acids, retinoin Acid tocopheryl; derivatives such as lactic acid, glycolic acid, gluconic acid, fruit acid, salicylic acid and glycosides / esterified products thereof, α- or such as hydroxycapric acid, long chain α-hydroxy fatty acid, long chain α-hydroxy fatty acid cholesteryl β-hydroxy acids and derivatives thereof; γ-aminobutyric acid, γ-amino-β-hydroxybutyric acid; carnitine; creatine; ceramides, sphingosines; caffeine, xanthine and the like; and coenzyme Q10, carotene, lycopene, astaxanthin Antioxidant / active oxygen scavengers such as α-lipoic acid; catechins; flavins such as quercetin Bonnes; isoflavones; gallic acid and ester sugar derivatives; polyphenols such as tannin, sesamin, protoanthocyanidins, chlorogenic acid and apple polyphenol; derivatives such as rutin and glycosides; derivatives such as hesperidin and glycosides; Sugar bodies; licorice extract-related substances such as grabrizine, glabrene, liquiritin, and isoliquiritin; lactoferrin; gingerol; fragrance substances such as menthol, camphor, cedrol, and derivatives thereof; capsaicin, vanillin, and derivatives; insects such as diethyltoluamide A repellent; a complex of a physiologically active substance and cyclodextrins is preferable.
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。 As plant / animal / microbe extracts, Iris extract, Ashitaba extract, Asunaro extract, Asparagus extract, Avocado extract, Achacha extract, Almond extract, Altea extract, Arnica extract, Aloe extract, Apricot extract, Ginkgo biloba extract, Ginkgo biloba extract , Incheon extract, Fennel extract, Turmeric extract, Oolong tea extract, Peony extract, Ages extract, Echinacea leaf extract, Enmeo extract, Ogon extract, Oat extract, Auren extract, Barley extract, Panax ginseng extract, Hypericum extract, Odori extract , Dutch mustard extract, orange extract, dried sea water, seaweed extract, oyster leaf extract, oyster extract, hydrolyzed elastin, hydrolyzed wheat powder, hydrolysis Luc, Cascon extract, Chamomile extract, Oil-soluble chamomile extract, Carrot extract, Kawara mugi extract, Oat extract, Calcade extract, Licorice extract, Oil-soluble Licorice extract, Kiwi extract, Kiou extract, Cyprid extract, Quina extract, Cucumber extract, Kiri leaf extract, Guanosine, guava extract, cucumber extract, gardenia extract, kumazasa extract, clara extract, walnut extract, chestnut extract, grapefruit extract, clematis extract, black rice extract, brown sugar extract, black vinegar, chlorella extract, mulberry extract, gentian extract, Gentian pepper extract, tea Extract, yeast extract, kokuboku extract, coffee extract, burdock extract, rice extract, rice fermented extract, rice bran fermented extract, rice germ oil, comfrey extract, Lagen, Cowberry extract, Saishin extract, Psycho extract, Saitai extract, Saffron extract, Salvia extract, Salmon extract, Sasa extract, Hawthorn extract, Sansha extract, Salamander extract, Shiitake extract, Giant extract, Shikon extract, Perilla extract, Linden extract, Shimosukeso Extract, jatoba extract, peonies extract, ginger cucumber extract, ginger root extract, white birch extract, white jellyfish extract, horsetail extract, stevia extract, stevia fermented product, west river willow extract, horse chestnut extract, hawthorn extract, elderberry extract, yarrow extract , Mint extract, sage extract, mallow extract, nematode extract, essence extract, Sakuhakuhi extract, Diou extract, Dai Extract, peanut extract, thyme extract, dandelion extract, lichen extract, tea extract, clove extract, chigaya extract, chimpi extract, tea tree oil, tea tea extract, red pepper extract, red snapper extract, red snapper extract, red spruce extract, red spruce extract, tomato Extract, natto extract, carrot extract, garlic extract, wild rose extract, hibiscus extract, bacmond extract, lotus extract, parsley extract, birch extract, honey, hamamelis extract, parietalia extract, hyacinth extract, bisabolol, cypress extract, bifidobacteria extract, Loquat extract, dandelion extract, burdock extract, bukkuri extract, butcher bloom extract, grape extract, grape seed extract, propolis, loofah extract, Safflower extract, peppermint extract, body extract, button extract, hop extract, squid extract, pine extract, maroonnier extract, mizubasho extract, mukuroji extract, melissa extract, mozuku extract, peach extract, cornflower extract, eucalyptus extract, yukinoshita extract, yuzu extract, lily extract, Yokuinin extract, mugwort extract, lavender extract, green tea extract, eggshell membrane extract, apple extract, rooibos tea extract, litchi extract, lettuce extract, lemon extract, forsythia extract, forsythia extract, rose extract, rosemary extract, roman chamomile extract, royal jelly Extracts such as an extract and a bitumen extract are preferred.
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, and zinc paraphenol sulfonate.
Examples of the refreshing agent include menthol and methyl salicylate.
Examples of the astringent include citric acid, tartaric acid, lactic acid, aluminum sulfate / potassium sulfate, and tannic acid.
Examples of enzymes include superoxide dismutase, catalase, lysozyme chloride, lipase, papain, pancreatin, protease, and the like.
Preferred nucleic acids include ribonucleic acid and salts thereof, deoxyribonucleic acid and salts thereof, and adenosine triphosphate disodium.
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 perfumes, acetyl cedrene, amylcinnamaldehyde, allyl amyl glycolate, β-ionone, iso-Esuper, isobutyl quinoline, Iris oil, Iron, indole, ylang ylang oil, undecanal, undecenal, γ-undecalactone, Estragole, eugenol, oak moss, opoponax resinoid, orange oil, eugenol, auranthiol, galac solid, carvacrol, L-carvone, camphor, cannon, carrot seed oil, clove oil, methyl cinnamate, geraniol, geranyl nitrile , Isobornyl acetate, geranyl acetate, dimethylbenzyl carvinyl acetate, styrylyl acetate, cedolyl acetate, terpinel acetate, pt-butylcyclohexyl acetate, vetiberyl acetate, benzyl acetate Linalyl acetate, isopentyl salicylate, benzyl salicylate, sandalwood oil, santalol, cyclamenaldehyde, cyclopentadecanolide, methyl dihydrojasmonate, dihydromyrsenol, jasmine absolute, jasmine lactone, cis-jasmon, citral, citronenol, Citronellal, cinnamon bark oil, 1,8-cineole, cinnamaldehyde, stylax resinoid, cedarwood oil, cedrene, cedrol, celery seed oil, thyme oil, damascon, damassenone, thymol, tuberose absolute, decanal, decalactone, terpineol, γ- Terpinene, triplar, nerol, nonanal, 2,6-nonadienol, nonalactone, patchouli alcohol, vanilla Solute, vanillin, basil oil, patchouli oil, hydroxycitronellal, α-pinene, piperitone, phenethyl alcohol, phenylacetaldehyde, petitglen oil, hexylcinnamaldehyde, cis-3-hexenol, perubalsum, vetiver oil, vetiverol, peppermint oil , Pepper oil, heliotropin, bergamot oil, benzyl benzoate, borneol, milresinoid, musk ketone, methyl nonyl acetaldehyde, γ-methyl ionone, menthol, L-menthol, L-menthol, eucalyptus oil, β-ionone, lime oil, lavender oil Synthetic and natural fragrances such as D-limonene, linalool, linal, rillial, lemon oil, rose absolute, rose oxide, rose oil, rosemary oil, and various essential oils In addition, various kinds of blended fragrances are preferable.
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; As pigments / colorants / dyes / pigments, brown 201, black 401, purple 201, purple 401, blue 1, blue 2, blue 201, blue 202, blue 203, 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 No. 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- No. 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 Legal pigments such as Yellow 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。 Base dyes such as Aryanor Sienna Brown, Aryanor Madder Red, Aryanor Steel Blue, Aryanor Straw Yellow, etc .; HC Yellow 2, HC Yellow 5, HC Red 3, 4-hydroxypropylamino 3-nitro-ol 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 low-order titanium oxide; Inorganic purple pigments such as Ngo violet and cobalt violet; inorganic green pigments such as chromium oxide, chromium hydroxide and cobalt titanate; inorganic blue pigments such as ultramarine and bitumen; titanium oxide coated mica and titanium oxide coated bismuth oxychloride Pearl pigments such as titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil; metal powder pigments such as aluminum powder, copper powder and gold; surface treatment inorganic and metal powder pigments; red 201, red 202 No., Red No. 204, Red No. 205, Red No. 220, 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 104, Red 106, Red 227, Red 230, Red 40 No., Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Green No. 3, Blue No. 1, etc., organic pigments such as zirconium, barium or aluminum lakes; surface treated organic pigments Anthraquinones such as astaxanthin and alizarin, anthocyanidin, β-carotene, catenal, capsanthin, chalcone, calsamine, quercetin, naphthoquinones such as crocin, chlorophyll, curcumin, cochineal, shikonin, bixin, flavones, betacyanidine, henna, hemoglobin Natural pigments and dyes such as lycopene, riboflavin, rutin; p-phenylenediamine, toluene-2,5-diamine, o-, m-, or p-aminophenol, m-phenylenediamine, 5-amino-2-methyl Phenol, resorci Preferred examples include oxidative dye intermediates and couplers such as chloroquine, 1-naphthol, 2,6-diaminopyridine, and salts thereof; autooxidative dyes such as indoline; and dihydroxyacetone.
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。
Preferred examples of water include normal water, purified water, hard water, soft water, natural water, deep sea water, electrolytic alkaline ionized water, electrolytic acidic ionized water, ionic water, and clustered water.
In addition to these, cosmetic raw material standards, blending ingredient standard by cosmetic varieties, Japan Cosmetic Industry Association ingredient display name list, INCI dictionary (The International Cosmetic Ingredient and Handbook), quasi-drug raw material standards, Japanese pharmacopoeia, pharmaceutical additives Standards, ingredients listed in the Food Additives, etc., and international patent classification IPC described in Japan and foreign patent gazettes and patent publications (including publications and republications) belonging 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 skin external preparations of the present invention will be described in more detail. Basic cosmetics include soft lotions, astringent lotions, cleansing lotions, multi-layer lotions, etc .; emollient lotions, moisture Lotion, Milky Lotion, Nourishing Lotion, Nourishing Milk, Skin Moisture, Moisturizer Emulsion, Massage Lotion, Cleansing Lotion, Protect Emulsion, Sun Protect, Sun Protector, UV Care Milk, Sun Screen, Makeup Lotion, Horny Smoother, Elbow Milky lotion, hand lotion, body lotion, etc .; emollient cream, nourishing cream, nourishing cream, burnishing cream, moisture cream, night cream, massage cream Cleansing cream, makeup cream, base cream, pre-makeup cream, sunscreen cream, suntan cream, hair removal cream, deodorant cream, shaving cream, keratin softening cream, etc .; Moisture gel, etc .; Moisturizing essence, whitening essence, UV Essences such as prevention essences; Liposome cosmetics such as liposome cosmetics and liposome lotions; Packs and masks such as peel-off packs, powder packs, washing packs, oil packs, cleansing masks; cleansing foams, cleansing creams, cleansing milks, cleansings Facial cleansers such as lotions, cleansing gels, cleansing oils, cleansing masks, washing powders, face washing powders, cosmetic soaps, Akira soap, medicated soap, liquid soap, shaving soap, be mentioned as soaps and synthetic toilet soaps are preferred.
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。
Examples of makeup cosmetics that may be preferably used include white powder, dusts, foundations, lipsticks, lip gloss, blushers, eyeliner, mascara, eye shadow, eyebrow, eyebrow, nail enamel, enamel remover, and nail treatment.
Preferred examples of the aromatic cosmetics include perfume, perfume, parfum, eau de parfum, eau de toilette, eau de cologne, perfumes, fragrance powder, perfume soap, body lotion and bath oil.
Body cosmetics such as body shampoos; deodorant lotions, deodorant powders, deodorant sprays, deodorant sticks and other deodorant cosmetics; decoloring agents, hair removal / hair removal agents; bathing agents; insect repellents A repeller is 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。 Cosmetics for hair include oil shampoo, cream shampoo, conditioning shampoo, dandruff shampoo, hair color shampoo, shampoo with integrated rinse, shampoo for rinse, treatment, hair pack, color lotion, split coat, permanent wave Preference is given to agents, straight perm agents, oxidative hair dyes, hair bleaches, hair color pre-treatments, hair color after treatments, perm pre-treatments, perm after treatments, hair manicures, hair tonics and hair restorers.
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 an external preparation for skin, it can 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 external preparation for skin of the present invention, emulsification such as oil-in-water (O / W) type, water-in-oil (W / O) type, W / O / W type, O / W / O type, etc. Type cosmetics, oily cosmetics, solid cosmetics, liquid cosmetics, paste cosmetics, stick cosmetics, volatile oil cosmetics, powder cosmetics, jelly cosmetics, gel cosmetics, pastes Preferred examples include cosmetics, emulsified polymer cosmetics, sheet cosmetics, mist cosmetics, and spray cosmetics.
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 antibacterial agent of the present invention has the above-described configuration and can exhibit a higher antiseptic antibacterial effect than conventional antiseptic antibacterial agents. Therefore, basic cosmetics, makeup cosmetics, aromatic cosmetics, body cosmetics, ointments It can be suitably used for external preparations for skin, 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。 The present invention will be described in more detail with reference to the following examples. However, 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 and apparatus are as follows.
Equipment: EcoSEC HLC-8320GPC manufactured by Tosoh Corporation
Detector: Differential refractometer (RI) detector Column: TSKgel α-M, α-2500 manufactured by Tosoh Corporation
Column temperature: 40 ° C
Flow rate: 0.4 mL / min
Injection volume: 20 μL (eluent preparation solution with sample concentration of 0.4 wt%)
Calibration curve: GL Sciences polyethylene glycol GPC software: Tosoh EcoSEC-WS
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 growth inhibitory concentration (MIC)>
The aqueous solution containing the antiseptic antibacterial agent was sequentially diluted two-fold in the Mueller Hinton medium to prepare a dilution series of the antiseptic antibacterial agent-containing medium. Thereafter, 50 μL of a medium containing antiseptic antibacterial agent at each concentration was added to a 96-well plate made of polystyrene. Next, E. coli (Escherichia coli, NBRC-15034, NBRC-3972), Staphylococcus aureus (NBRC-15035, NBRC-13276) and Pseudomonas aeruginus (Pseudomonas aerugin) grown on Mueller Hinton agar medium for 18 hours. , NBRC-13275) colonies were suspended in a butterfield buffer solution to prepare about 10 × 10 8 cells / mL bacterial solution. The prepared bacterial solution was diluted to about 10 × 10 6 cells / mL in Mueller Hinton medium, and 50 μL was added to the dilution series prepared above. After standing at 35 ° C. for 20 hours, the minimum antibacterial and antibacterial agent concentration (ppm) in the medium in which the bacteria did not grow was determined as the minimum growth inhibitory concentration (MIC). The presence or absence of the growth of the fungus was judged based on whether the turbidity was increased visually.
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。
<Preservation test 1>
A potato dextrose agar (PDA) medium containing 2000 ppm of the copolymer (preservative antibacterial agent) synthesized in Synthesis Examples 1 to 5 below was prepared.
A pre-cultured culture solution prepared by diluting Aspergillus brasiliensis ATCC 16404 (Agaricus mildew) to about 10 7 cells / mL is prepared as a bacterial suspension, and the suspension is added to 15 ml of the 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 cultured PDA medium 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。
<Preservation test 2: (Challenge test using O / W cream sample and lotion sample (preservation efficacy test))>
The copolymer (antiseptic antibacterial agent) 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 lotion.
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 lotion.
About the said cream and lotion, the challenge test by the following method was done and antiseptic power was evaluated.
For the following bacterial species, a pre-cultured culture solution diluted to about 10 8 cells / mL for bacteria and Candida and about 10 7 cells / mL for Aspergillus was used as a cell suspension. The number of bacteria in the suspension was confirmed by the colony count method.
Bacteria: Escherichia coli (NBRC-3972), Staphylococcus aureus (NBRC-13276), Pseudomonas aeruginosa (NBRC-13275)
Yeast: Candida (Candia albicans ATCC 10231)
Mold: Aspergillus brasiliensis ATCC 16404
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 cultured at 25 ° C. After 2, 7, 14, and 21 days, 1 g of each sample was withdrawn, and the sample diluted with physiological saline was mixed in an agar medium. Bacteria and Candida were cultured for 48 hours, and Aspergillus niger were cultured for 7 days. Thus, the number of remaining 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>
A glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 90.0 g of pure water and heated to 90 ° C. with stirring. Subsequently, 2- (dimethylamino) ethyl methacrylate (N, N-dimethylaminoethyl methacrylate) (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter referred to as DAM) 51 was placed in a polymerization reaction system at a constant temperature of 90 ° C. with stirring. Monomer solution 1 consisting of .3 g, acetic acid 18.6 g and ethyl methacrylate (hereinafter referred to as EMA) 8.56 g; 2,2′-azobis (2-methylpropionamidine) dihydrochloride (Wako Pure Chemical Industries, Ltd.) ), And hereinafter referred to as V-50) An aqueous initiator solution composed of 29.3 g of a 2.5% aqueous solution; a monomer solution 2 composed of 25.7 g of DAM and 9.32 g of acetic acid were dropped from separate dropping nozzles.
Regarding the dropping start time, the monomer solution 1 and the aqueous initiator solution started to be dropped simultaneously, and the monomer solution 1 was dropped for 120 minutes and the aqueous initiator solution was dropped for 210 minutes. The monomer solution 2 was dropped over 60 minutes after the completion of dropping of the monomer solution 1. After completion of the dropwise addition, the reaction solution was further aged at 90 ° C. for 30 minutes to complete the polymerization, and copolymer 1 was obtained.
The obtained copolymer had a solid content of 36.8%, a pH of 6.41, and a weight average molecular weight of 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>
A copolymer 2 was obtained by polymerization in the same manner as in Synthesis Example 1 except that EMA was changed to butyl acrylate (hereinafter referred to as BA).
The obtained copolymer 2 had a solid content of 35.7%, a pH of 6.41, and a weight average molecular weight of 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>
A glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 50 g of pure water and 22 g of propylene glycol, and heated to 90 ° C. with stirring. Next, in a polymerization reaction system at a constant temperature of 90 ° C. with stirring, 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 5% aqueous solution of V-50; 18% acrylic A monomer solution 2 composed of 25.6 g of an acid (hereinafter also referred to as AA) aqueous solution was dropped from separate dropping nozzles. Regarding the dropping start time, the monomer solution 1 was dropped for 180 minutes, and the aqueous initiator solution and the monomer solution 2 were dropped for 210 minutes.
After completion of the dropwise addition, the reaction solution was further aged at 90 ° C. for 30 minutes to complete the polymerization, whereby a copolymer 3 was obtained.
The obtained copolymer 3 had a solid content of 34.9%, a pH of 6.15, and a weight average molecular weight of 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>
A glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 70 g of 1,3-butanediol and heated to 90 ° C. with stirring. Next, under stirring, in a polymerization reaction system at a constant temperature of 90 ° C., a monomer solution consisting of 73.8 g of DAM and 13.5 g of EMA, an initiator aqueous solution consisting of 21.9 g of a 7% aqueous solution of V-50, 18.3% acrylic acid Monomer solution 2 composed of 14.7 g of aqueous solution was dropped from separate dropping nozzles.
Regarding the dropping start time, the monomer solutions 1 and 2 were dropped for 180 minutes, and the aqueous initiator solution and the monomer solution 2 were dropped for 210 minutes.
After completion of the dropwise addition, the reaction solution was kept at 90 ° C. for aging for 90 minutes to complete the polymerization. 50 g of pure water was added to obtain a copolymer 4.
The obtained copolymer 4 had a solid content of 35.2%, a pH of 9.0, and a weight average molecular weight of 30,500.
<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>
A glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 60 g of 1,3-butanediol and heated to 90 ° C. with stirring. Next, in a polymerization reaction system at a constant temperature of 90 ° C. with stirring, a monomer solution consisting of 81 g of DEAM 1: an initiator aqueous solution consisting of 28.1 g of 5% aqueous solution of V-50, and 21.3 g of 42.4% aqueous acrylic acid solution The resulting 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 aqueous initiator solution and the monomer solution 2 were dropped for 210 minutes.
After completion of the dropwise addition, the reaction solution was kept at 90 ° C. for aging for 90 minutes to complete the polymerization. 50 g of pure water was added to obtain a copolymer 5.
The obtained copolymer 5 had a solid content of 32.9%, a pH of 8.8, and a weight average molecular weight of 22,000.
<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>
A glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 24.0 g of pure water and 72 g of propylene glycol (hereinafter also referred to as PG), and heated to 90 ° C. with stirring. Next, in a polymerization reaction system at a constant temperature of 90 ° C. with stirring, 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 separate dropping nozzles. Regarding the dropping time, the monomer solutions 1 and 2 and the aqueous initiator solution started dropping simultaneously, the monomer solutions 1 and 2 were dropped for 180 minutes, and the aqueous initiator solution was dropped for 210 minutes. After completion of the dropwise addition, the reaction solution was further aged at 90 ° C. for 90 minutes to complete the polymerization, whereby a copolymer 6 was obtained.
The obtained copolymer 6 had a solid content of 35.2% and a weight average molecular weight of 22,100.
<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 BA in the monomer solution 2 of Synthesis Example 6 was changed to 2-ethylhexyl acrylate (2EHA) to obtain a copolymer 7. The obtained copolymer 7 had a solid content of 36.4% and a weight average molecular weight of 70700.
<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. Next, under stirring, a monomer solution composed of 72 g of DAM, 27.52 g of acetic acid and 18 g of butyl acrylate; an aqueous initiator solution composed of 29.9 g of a 5% aqueous solution of V-50 were separately added dropwise to a polymerization reaction system at a constant temperature of 90 ° C. It dripped from the nozzle. The monomer solutions 1 and 2 were dropped for 180 minutes and the initiator aqueous solution was dropped for 210 minutes. After completion of the dropwise addition, the reaction solution was further aged at 90 ° C. for 90 minutes, and 50 g of pure water was added to complete the polymerization, thereby obtaining a copolymer 8. The obtained copolymer 8 had a solid content of 31.2% and a weight average molecular weight of 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>
A glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 42.0 g of pure water and 28 g of 1,3-BG, and heated to 90 ° C. with stirring. Next, a monomer solution consisting of 67.5 g of DAM, 25.8 g of acetic acid and 18 g of ethyl methacrylate, and an initiator aqueous solution consisting of 22.6 g of a 7% aqueous solution of V-50; A monomer solution 2 composed of 16.5 g of a 3% AA aqueous solution was dropped from separate dropping nozzles. Regarding the dropping time, the monomer solutions 1 and 2 and the aqueous initiator solution started to be dropped simultaneously, the monomer solutions 1 and 2 were dropped for 120 minutes, and the aqueous initiator solution was dropped for 150 minutes. After the completion of the dropwise addition, the reaction solution was further aged at 90 ° C. for 90 minutes, and 50 g of pure water was added to complete the polymerization, whereby a copolymer 9 was obtained.
The obtained copolymer 9 had a solid content of 32% and a weight average molecular weight of 30,200.
<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>
MIC was evaluated about the copolymers 1-9 obtained by the synthesis examples 1-9 and the methylparaben and phenoxyethanol as a comparative example, and the evaluation result was shown to Table 1 and 2. FIG.
<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: Preservation Test 1>
Preservation 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 performed without using the antiseptic 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: Preservation Test 2>
Preservation test 2 was performed on the creams 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: Preservation Test 2>
The antiseptic test 2 was conducted on the lotions 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: Preservation Test 2>
The antiseptic test 2 was performed on the lotions 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 copolymer 2 obtained in Synthesis Example 2 were added, and the mixture was emulsified by stirring with a homomixer at 8000 rpm for 10 minutes. It was 210 nm when the particle diameter of the emulsified liquid was measured by a particle diameter measuring device (concentrated analyzer FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.).
(Comparative Example 9)
An emulsion performance test was conducted in the same manner as in Example 16 except that 0.66 g of copolymer 2 was changed to 0.25 g of nonionic surfactant NC2305 (manufactured by Nippon Emulsifier). 450 nm.
Further, when the emulsions of Example 23 and Comparative Example 9 were allowed to stand at room temperature for 1 week, Comparative Example 9 was separated and the emulsified state was broken, whereas Example 23 was emulsified. The state was maintained. From the above, it has been clarified that the material of the present invention can be finely dispersed as compared with existing surfactants and further has excellent 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 describe formulation examples of the cosmetics of the present invention. In addition, when the antiseptic test 2 was implemented to the cosmetics composition of this invention in these prescription examples, in any prescription example, antibacterial activity value (antibacterial activity value = log (viable cell count at the time of inoculation) -log (after 7 days) The number of viable bacteria, however, was 14 or more after 14 days), and the evaluation was “good”.
処方例1〜3 美白ローション Formulation Examples 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。 (Manufacturing method) The raw material which belongs to A was heated at 70 degreeC, and it melt | dissolved completely, Then, it cooled to room temperature. Then, the raw material which belongs to B was mixed, and the whitening lotion was obtained.
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。 (Manufacturing method) The raw material of the oil phase part belonging to A and the raw material of the water phase part belonging to B were heated to 70 ° C. and completely dissolved, and then the oil phase part was mixed with the aqueous phase part 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 Formulation Examples 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。 (Manufacturing method) The raw material of the oil phase part belonging to A and the raw material of the water phase part belonging to B were heated to 70 ° C. and completely dissolved, and then the oil phase part was mixed with the aqueous phase part 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 Formulation Examples 10 to 12
(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 part belonging to A and the raw material of the water phase part belonging to B are heated to 75 ° C. and dissolved, and then the aqueous phase part is mixed with the oil phase part and then stirred until 30 ° C. It cooled and the face-wash cream was obtained.
処方例13〜15 サンスクリーンクリーム Formulation Examples 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。 (Manufacturing method) The raw material of the oil phase part belonging to A and the raw material of the water phase part belonging to B were heated to 75 ° C. and completely dissolved, and then the oil phase part was mixed with the aqueous phase part and emulsified with a homomixer. The emulsion was cooled to 30 ° C. to obtain 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) Formulation Examples 16-18 Liquid Foundation (Shake Well 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 part which belongs to A is heated to 60 degreeC, and it cools to room temperature after that. The raw material of the oil phase part belonging to A and the raw material of the water phase part belonging to B were mixed at room temperature and emulsified with a homomixer to obtain a shake well type liquid foundation.
処方例19〜21 シャンプー Formulation Examples 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。 (Manufacturing method) The oil phase part which belongs to A was heated to 80 degreeC, and it cooled to room temperature after that, and obtained the shampoo.
処方例22〜24 コンディショナー Formulation Examples 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。 (Manufacturing method) The oil phase part which belongs to A and B was heated to 80 degreeC, C heated to 80 degreeC was mixed at 80 degreeC, and it emulsified with the 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)〜(6);
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 to 200,000,
The amino group-containing monomer (A) is represented by the following formulas (4) to (6);
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