JPH11209258A - Deodorizng and sweat-controlling combination agent - Google Patents
Deodorizng and sweat-controlling combination agentInfo
- Publication number
- JPH11209258A JPH11209258A JP10044189A JP4418998A JPH11209258A JP H11209258 A JPH11209258 A JP H11209258A JP 10044189 A JP10044189 A JP 10044189A JP 4418998 A JP4418998 A JP 4418998A JP H11209258 A JPH11209258 A JP H11209258A
- Authority
- JP
- Japan
- Prior art keywords
- deodorant
- antiperspirant
- sweat
- composite oxide
- following formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Cosmetics (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、酸化亜鉛系複合酸
化物、該複合酸化物を有効成分とする新規な消臭兼制汗
剤、および該複合酸化物の製造方法に関する。The present invention relates to a zinc oxide-based composite oxide, a novel deodorant and antiperspirant containing the composite oxide as an active ingredient, and a method for producing the composite oxide.
【０００２】[0002]
【従来の技術】近年、生活の快適性に対する要求が強く
なってきており、臭もその重要な構成要素である。悪臭
を除去する消臭剤として、活性炭、酸化亜鉛、ケイ酸ア
ルミニウム等が使用されている。特に酸化亜鉛は、白
色、無毒で、消臭機能以外に紫外線吸収機能等もあるこ
とから、ＵＶケア化粧品等にも使用されている。2. Description of the Related Art In recent years, there has been an increasing demand for comfort in life, and odor is also an important component. Activated carbon, zinc oxide, aluminum silicate and the like are used as deodorants for removing malodor. In particular, zinc oxide is used in UV care cosmetics and the like because it is white, non-toxic and has an ultraviolet absorbing function in addition to a deodorizing function.
【０００３】[0003]
【発明が解決しようとする課題】酸化亜鉛の製造方法に
は、乾式法と湿式法がある。乾式法で製造される酸化亜
鉛は、１次及び２次粒子が０．１７〜０．７０μｍの粒
状、もしくは数μｍ以下の針状であり、ＢＥＴ比表面積
は約３〜１０ｍ２／ｇと小さい為、消臭活性が貧弱であ
る。湿式法（活性亜鉛華）の場合は、塩基性炭酸亜鉛を
合成し、それを焼成して製造される為、１次粒子が０．
１μｍ以下で、ＢＥＴ比表面積が約４０〜６０ｍ２／ｇ
と高く、従って消臭効果が高い。しかしながら、活性亜
鉛華は強く凝集している為、平均２次粒子径が約６〜１
０μｍ、最大２次粒子径が約３０〜４０μｍ、と極めて
大きい為に用途が限定される問題がある。例えば、活性
亜鉛華を繊維に練り込もうとすると、紡糸段階で目詰ま
りを起こして、消臭効果が持続する繊維を製造出来な
い。また、デオドラントとかＵＶケアの化粧品に使用す
ると、滑り性、密着性、分散性、透明性等に問題があ
る。The methods for producing zinc oxide include a dry method and a wet method. The zinc oxide produced by the dry method has primary and secondary particles in the form of granules having a particle size of 0.17 to 0.70 μm or needles having a size of several μm or less, and has a BET specific surface area as small as about 3 to 10 m 2 / g. Therefore, the deodorizing activity is poor. In the case of the wet method (activated zinc white), basic zinc carbonate is synthesized and calcined to produce primary particles.
BET specific surface area of about 40 to 60 m 2 / g at 1 μm or less
Therefore, the deodorizing effect is high. However, since active zinc white is strongly agglomerated, the average secondary particle diameter is about 6 to 1
0 μm and the maximum secondary particle diameter is as large as about 30 to 40 μm, which limits the application. For example, if active zinc white is to be kneaded into the fiber, clogging occurs at the spinning stage, and a fiber having a long deodorizing effect cannot be produced. In addition, when used for deodorants or cosmetics for UV care, there are problems in slipperiness, adhesion, dispersibility, transparency and the like.
【０００４】[0004]
【課題を解決するための手段】本発明は、下記式（１）Means for Solving the Problems The present invention provides the following formula (1)
【化１】 Ｍ２＋ １−ｘＭ３＋ ｘ−δＯ （式中、Ｍ２＋はＺｎ又はＺｎを必須成分とする２価金
属を示し、Ｍ３＋はＡｌ，Ｆｅ，Ｃｅ等の３価金属を示
し、ｘは０＜ｘ≦０．５の範囲の数を示し、δはカチオ
ン格子欠陥を示す）で表される複合酸化物を有効成分と
することを特徴とする消臭兼制汗剤を提供する。さらに
本発明は、微粒子、高分散性である、式（１）で表せら
れる新規な複合酸化物およびその製造方法を提供する。## STR1 ## M 2+ 1-x M 3+ x -δ O ( wherein, M 2+ is a divalent metal as an essential component Zn or Zn, M 3+ is Al, Fe, and trivalent metals such as Ce X is a number in the range of 0 <x ≦ 0.5, and δ is a cation lattice defect). provide. Further, the present invention provides a novel composite oxide represented by the formula (1), which has fine particles and high dispersibility, and a method for producing the same.
【０００５】[0005]
【発明の実施の形態】本発明の新規複合酸化物を有効成
分とする消臭兼制汗剤は、従来の酸化亜鉛以上の消臭効
果を示すだけでなく、制汗性（収れん性）にも優れてい
る。さらに、肌への付着性、滑り性、分散性、透明性が
良好で、皮膚刺激性も無いことから化粧品として、クロ
ルヒドロキシアルミニウム等に替わる制汗剤兼デオドラ
ントとして、更にはＵＶケア化粧料としても優れてい
る。この様な特徴は、結晶の外形が六角板状で、しかも
厚みが薄いこと、及び凝集が殆どなく、２次粒子が約
０．２〜１．０μｍと微細であること、（付着性、滑り
性、分散性）、それでいてＢＥＴ比表面積が最大１５０
ｍ２／ｇと極めて高い（透明性、消臭性、収れん性）こ
とに依る。BEST MODE FOR CARRYING OUT THE INVENTION The deodorant and antiperspirant containing the novel composite oxide of the present invention as an active ingredient not only exhibits a deodorant effect than conventional zinc oxide but also has an antiperspirant property (astringency). Is also excellent. In addition, it has good adhesion to the skin, good slipperiness, dispersibility, transparency, and has no skin irritation, so as a cosmetic, as an antiperspirant and deodorant instead of chlorohydroxyaluminum, etc., and as a UV care cosmetic Is also excellent. Such features are that the external shape of the crystal is hexagonal plate-like, and that the thickness is thin, that there is almost no agglomeration, and that the secondary particles are as fine as about 0.2 to 1.0 μm, , Dispersibility), but the BET specific surface area is up to 150
It is extremely high as m 2 / g (transparency, deodorant, astringency).
【０００６】この様な本発明消臭兼制汗剤の特徴は、六
角板状の結晶外形を有する式（２）のハイドロタルサイ
ト類を、好ましくは水熱処理して、六角板状の１次粒子
の成長と、単分散化を行った化合物を、約３００−９０
０℃で焼成して得られる本発明複合酸化物を用いる事に
より、初めて達成された。該複合酸化物は、ハイドロタ
ルサイト類結晶の母塩の形をそのまま残し、母塩中に
０．１μｍ以下の微細な１次粒子が詰まっている。母塩
の形状である六角板状が滑り性を発揮し、母塩が１μｍ
以下で分散していることが優れた付着性を発揮し、１次
粒子が０．１μｍ以下であることが、優れた消臭性、制
汗性、透明性を発揮する原因と考えられる。本発明の消
臭兼制汗剤は、高度の分散性が要求されない繊維とか化
粧品以外の用途については、式（２）のハイドロタルサ
イト類を水熱処理を施す事なく焼成すれば良く、その場
合のＢＥＴ比表面積は、約１０−２００ｍ２／ｇであ
る。[0006] Such a deodorant and antiperspirant of the present invention is characterized in that hydrotalcites of the formula (2) having a hexagonal plate-like crystal outer shape are preferably subjected to a hydrothermal treatment to form a hexagonal plate-like primary. Compounds that have undergone particle growth and monodispersion are applied to about 300-90.
This was achieved for the first time by using the composite oxide of the present invention obtained by firing at 0 ° C. The composite oxide leaves the form of the mother salt of hydrotalcite crystals as it is, and the mother salt is packed with fine primary particles of 0.1 μm or less. Hexagonal plate shape, which is the shape of the mother salt, exhibits slipperiness, and the mother salt is 1 μm
It is considered that the dispersion below shows excellent adhesiveness, and the primary particles having a particle size of 0.1 μm or less is a cause of exhibiting excellent deodorant, antiperspirant, and transparency. The deodorant and antiperspirant of the present invention may be used for fibers other than those requiring a high degree of dispersibility or for uses other than cosmetics, by baking the hydrotalcites of the formula (2) without hydrothermal treatment. Has a BET specific surface area of about 10-200 m 2 / g.
【０００７】酸化亜鉛は、結晶外形が粒状であるために
滑りが悪く、しかも、消臭活性を上げるために、１次粒
子を小さくして、ＢＥＴ比表面積を大きくすると、それ
に伴って２次粒子も大きくなって、付着性、分散性、透
明性の低下という矛盾から抜け出れない。しかし、この
矛盾は、本発明複合酸化物を用いることにより解消出来
た。また、本発明複合酸化物は、酸化亜鉛より遥かに１
次粒子を微細化出来るため、収れん作用が向上し、制汗
剤としても使用出来る。しかも、クロルヒドロキシアル
ミニウム等の制汗剤で時々見られる、肌がかぶれる欠点
が、本発明の消臭兼制汗剤を用いる事により解消でき
た。本発明複合酸化物は、消臭（デオドラント）と制汗
の両機能を持つ以外に、紫外線吸収、抗菌、の機能があ
り、ＵＶケア化粧品、ＵＶカット繊維および樹脂として
も利用できる。[0007] Zinc oxide is poor in slippage due to its granular crystal outer shape. In addition, in order to increase deodorizing activity, the primary particles are made smaller and the BET specific surface area is made larger. Is also increased, and it cannot escape from the contradiction that adhesion, dispersibility and transparency are reduced. However, this contradiction could be resolved by using the composite oxide of the present invention. In addition, the composite oxide of the present invention is much more than zinc oxide.
Since the secondary particles can be made finer, the astringent action is improved, and it can be used as an antiperspirant. Moreover, the problem of skin irritation sometimes seen with antiperspirants such as chlorohydroxyaluminum could be eliminated by using the deodorant and antiperspirant of the present invention. The composite oxide of the present invention not only has both deodorant and antiperspirant functions, but also has functions of absorbing ultraviolet light and antimicrobial, and can be used as UV care cosmetics, UV cut fibers and resins.
【０００８】本発明の消臭兼制汗剤は、下記式（１）The deodorant and antiperspirant of the present invention has the following formula (1)
【化１】 Ｍ２＋ １−ｘＭ３＋ ｘ−δＯ （式中、Ｍ２＋はＺｎ又はＺｎを必須成分とする２価金
属を示し、Ｍ３＋はＡｌ，Ｆｅ，Ｃｅ等の３価金属、好
ましくはＡｌを示し、ｘは０＜ｘ≦０．５、好ましくは
０．１≦ｘ≦０，４、特に好ましくは０．２≦ｘ＜０．
４の範囲の数を示し、δはカチオン格子欠陥を示す）で
表される酸化亜鉛系複合酸化物を有効成分とすることを
特徴とする。この酸化亜鉛系複合酸化物とは、ＺｎＯに
Ａｌ等のＭ３＋が置換固溶したＺｎＯと同じ結晶構造の
固溶体、或いは該固溶体とスピネル（Ｍ２＋Ｍ３＋ ２Ｏ
４）との混合物を意味する。## STR1 ## M 2+ 1-x M 3+ x -δ O ( wherein, M 2+ is a divalent metal as an essential component Zn or Zn, M 3+ is Al, Fe, 3-valent metals such as Ce, Preferably, it represents Al, and x is 0 <x ≦ 0.5, preferably 0.1 ≦ x ≦ 0.4, particularly preferably 0.2 ≦ x <0.
(4 indicates a number in the range of 4, and δ indicates a cation lattice defect). This zinc oxide-based composite oxide is a solid solution having the same crystal structure as ZnO in which M 3+ such as Al is substituted for ZnO, or a spinel (M 2+ M 3+ 2 O
4 ).
【０００９】本発明の消臭兼制汗剤使用製品の形態とし
ては、粉末、エアゾール、クリーム、ケーキ、直径が約
０．５〜５ｍｍの造粒物、ハニカム状成形体、等を適宜
用途に応じて選択して使用できる。As the form of the product using the deodorant and antiperspirant of the present invention, powders, aerosols, creams, cakes, granules having a diameter of about 0.5 to 5 mm, honeycomb-shaped molded articles, etc. are appropriately used. You can select and use it according to your needs.
【００１０】本発明消臭剤兼制汗剤は、単独で用いるこ
とも、或いは他の消臭剤、例えば下記式（３）The deodorant and antiperspirant of the present invention can be used alone or with another deodorant such as the following formula (3)
【化３】ｍＳｉＯ２，Ａｌ２Ｏ３ｎＨ２Ｏ （但し、式中ｍおよびｎはそれぞれ、１＜ｍ＜２０，０
≦ｎ＜２０，の範囲を満ページ（５）足する）で表され
る合成ケイ酸アルミニウムとか、活性炭と、好ましくは
合成イ酸アルミニウムと、併用して利用することが出来
る。Embedded image mSiO 2 , Al 2 O 3 nH 2 O (where m and n are respectively 1 <m <20,0
≦ n <20, a full page (5) is added). Synthetic aluminum silicate or activated carbon, preferably synthesized aluminum silicate, can be used in combination.
【００１１】化粧品用として利用する場合は、滑り性、
付着性、透明制、分散性の点から、２次粒子径が約１μ
ｍ以下の本発明複合酸化物を用いるのが好ましい。Ｍ
２＋としては、Ｚｎを、Ｍ３＋としては、白色または肌
色に近い色を目的とする場合は、Ａｌ単独、またはΛｌ
とＦｅの併用、ＵＶケアを目的とする場合は、ＡｌとＦ
ｅおよび／またはＣｅとの併用、を用いるとが好まし
い。When used for cosmetics, slipperiness,
The secondary particle size is about 1μ in terms of adhesion, transparency and dispersibility.
It is preferable to use m or less of the composite oxide of the present invention. M
2+ is Zn, and M 3+ is Al alone or Δl when M3 + is intended to be a color close to white or flesh color.
Al and F are used in combination with Fe and UV care.
It is preferable to use e and / or Ce in combination.
【００１２】本発明消臭兼制汗剤の製造は、下記式
（２）The production of the deodorant and antiperspirant of the present invention is represented by the following formula (2)
【化２】 Ｍ２＋ １−ｘＭ３＋ ｘ（ＯＨ）２Ａｎ ｘ／ｎ
ｍＨ２Ｏ （式中、Ｍ２＋，Ｍ３＋は式（１）と同じ意味、Ａｎ−
は、Ｃｌ−，ＮＯ３ −，ＣＯ３ ２−，等のｎ価のアニオ
ンを示し、ｘ，ｍ及びｎはそれぞれ０＜ｘ≦０．５、好
ましくは０．１≦ｘ≦０，４、さらに好ましくは０．２
≦ｘ＜０．４，０≦ｍ＜４，ｎは１〜６の間の整数、の
範囲を示す）で表されるハイドロタルサイト類を約３０
０〜９００℃、好ましくは約４００〜７００℃で焼成す
ることにより行うことが出来る。式（２）の化合物は、
ＺｎまたはＺｎとＭｇ等のＭ２＋の化合物の水溶液と、
Ａｌ，Ｆｅ，Ｃｅ等のＭ３＋の化合物の水溶液、および
ＮａＯＨ等のアルカリを、ＰＨを約７以上で共沈反応さ
せることにより製造することが出来る。Ｍ２＋の化合物
の例としては、例えばＺｎＣｌ２，Ｚｎ（ＮＯ３）２，
ＺｎＳＯ４，ＭｇＣｌ２等を、Ｍ３＋の化合物の例とし
ては、例えばＡｌＣｌ３，Ａｌ（ＮＯ３）３，Ａｌ
２（ＳＯ４）３，ＮａＡｌ（ＯＨ）４，ＦｅＣｌ３、Ｆ
ｅ２（ＳＯ４）３，ＣｅＣｌ３等を挙げることが出来
る。 Embedded image M 2+ 1-x M 3+ x (OH) 2 An x / n
mH in 2 O (wherein, M 2+, M 3+ is the same meanings as in formula (1), A n-
Represents an n-valent anion such as Cl − , NO 3 − , CO 3 2− , and x, m and n are each 0 <x ≦ 0.5, preferably 0.1 ≦ x ≦ 0, 4, More preferably 0.2
.Ltoreq.x <0.4, 0.ltoreq.m <4, and n is an integer between 1 and 6).
It can be performed by firing at 0 to 900 ° C, preferably about 400 to 700 ° C. The compound of formula (2) is
An aqueous solution of Zn or an M 2+ compound such as Zn and Mg;
An aqueous solution of a compound of M 3+ such as Al, Fe, and Ce, and an alkali such as NaOH can be produced by coprecipitation reaction at a pH of about 7 or more. Examples of the compound of M 2+ include, for example, ZnCl 2 , Zn (NO 3 ) 2 ,
Examples of M 3+ compounds such as ZnSO 4 and MgCl 2 include, for example, AlCl 3 , Al (NO 3 ) 3 , Al
2 (SO 4 ) 3 , NaAl (OH) 4 , FeCl 3 , F
e 2 (SO 4 ) 3 , CeCl 3 and the like.
【００１３】本発明の、平均２次粒子径が１μｍ以下
で、且つ、ＢＥＴ比表面積が１０以上、、好ましくは２
０以上の、式（１）で表される複合酸化物の製造は、前
述の共沈反応後、約１００〜２００℃、好ましくは約１
００〜１５０℃で、約５時間以上、好ましくは約１０時
間以上水熱処理した後、約３００−９００℃、好ましく
は約４００−７００℃で焼成することにより行うことが
出来る。In the present invention, the average secondary particle diameter is 1 μm or less, and the BET specific surface area is 10 or more, preferably 2 or more.
The production of the composite oxide represented by the formula (1) of 0 or more is performed at about 100 to 200 ° C., preferably about 1
Hydrothermal treatment at 00 to 150 ° C. for about 5 hours or more, preferably about 10 hours or more, followed by baking at about 300 to 900 ° C., preferably about 400 to 700 ° C.
【００１４】本発明の消臭兼制汗剤は、撥水性又は保湿
性を付与する為に、表面処理して使用することが出来
る。そのような表面処理剤としては、例えばラウリン
酸、ステアリン酸等の高級脂肪酸、リン酸エステル、シ
ラン系カップリング剤、チタネート系カップリング剤、
アルミニウム系カップリング剤、シリコーンオイル等の
撥水性付与の為の剤、キトサン、コラーゲン、ポリフル
オロアルキルリン酸エステル塩等の保湿性付与の為の剤
を挙げることが出来る。表面処理は、慣用の乾式または
湿式法で行うことが出来る。表面処理剤の量は、本発明
消臭兼制汗剤の重量に基づいて、約０．１〜１０％であ
る。The deodorant and antiperspirant of the present invention can be used after surface treatment in order to impart water repellency or moisture retention. Examples of such surface treatment agents include lauric acid, higher fatty acids such as stearic acid, phosphate esters, silane coupling agents, titanate coupling agents,
Examples thereof include agents for imparting water repellency, such as aluminum-based coupling agents and silicone oils, and agents for imparting moisture retention, such as chitosan, collagen, and polyfluoroalkyl phosphate salts. The surface treatment can be performed by a conventional dry or wet method. The amount of the surface treatment agent is about 0.1 to 10% based on the weight of the deodorant and antiperspirant of the present invention.
【００１５】本発明で用いる繊維または樹脂は、例えば
アクリル繊維、ナイロン繊維、ポリウレタン繊維、ポリ
エステル繊維等の繊維を、ポリエチレン、ポリプロピレ
ン、ポリスチレン、ナイロン、ポリ塩化ビニール、ポリ
ウレタン等の樹脂を、挙げることが出来る。本発明複合
酸化物の繊維または樹脂に対する配合量は、繊維または
樹脂１００重量部に対し、約０．１−１０重量部、好ま
しくは０．５−１０重量部である。The fibers or resins used in the present invention include, for example, fibers such as acrylic fibers, nylon fibers, polyurethane fibers and polyester fibers, and resins such as polyethylene, polypropylene, polystyrene, nylon, polyvinyl chloride and polyurethane. I can do it. The compounding amount of the composite oxide of the present invention with respect to the fiber or the resin is about 0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight based on 100 parts by weight of the fiber or the resin.
【００１６】以下実施例に基ずいて、本発明をより詳細
に説明する。Hereinafter, the present invention will be described in more detail with reference to Examples.
【００１７】[0017]
【実施例１】ＺｎＣｌ２とＡｌＣｌ３の混合水溶液（Ｚ
ｎ２＋＝０．６モル／リットル、Ａｌ３＋＝０．２モル
／リットル）、炭酸ソーダ水溶液（Ｎａ＝０．４モル／
リットル）および水酸化ナトリウム水溶液（Ｎａ＝２モ
ル／リットル）を、それぞれ１００ｍｌ／分、５０ｍｌ
／分および約８０ｍｌ／分の流速で、定量ポンプを用い
て容量２．５リットルの反応槽に攪拌機しながら供給
し、約３０℃、ＰＨを約８．０−８．５に保って反応し
た。得られた白色沈殿を、ろ過、水洗、乾燥、粉砕し
た。粉砕物の粉末Ｘ線回折パターンを測定した結果、ハ
イドロタルサイトと実質的に同じであった。化学分析お
よび熱重量分析の結果、化学組成は次の通りであった。 Ｚｎ６Ａｌ２（ＯＨ）１６ＣＯ３．４Ｈ２Ｏ この物を５００℃で１時間焼成した物のＢＥＴ比表面積
は１２４ｍ２／ｇで、イソプロピルアルコール媒体中で
超音波処理を５分間した後、レーザー回折法で測定した
平均２次粒子径は２．０μｍ，最大２次粒子径は１１．
８μｍであった。粉末Ｘ線パターンは、少し高角度側に
シフトしているが、ＺｎＯと同じであった。このこと
は、ＺｎＯにＡｌが固溶していることを示す。この物の
アンモニア、硫化水素、メチルメルカプタン及びイソ吉
草酸に対する消臭試験を行った結果、それぞれの悪臭成
分に対する除去率は４２％，１００％９５％，１００％
であった。消臭試験は、アンモニア、硫化水素、メチル
メルカプタンの場合、１０００ｍｌの集気瓶に消臭剤
０．１ｇを入れ、真空に排気後、約１０００ｐｐｍの悪
臭ガスを注入し、室温で３０分間保持する。この後、残
存するガス濃度をガス検知管で測定した。イソ吉草酸の
場合は、１０００ｍｌの集気瓶に消臭剤０．０２ｇを入
れ、真空に排気後、イソ吉草酸を１．２マイクロリット
ル注入し、気化後大気圧に戻し、室温で３０分間保持し
た。この後、残存するガス濃度をガスクロマトグラフで
測定した。Embodiment 1 A mixed aqueous solution of ZnCl 2 and AlCl 3 (Z
n 2+ = 0.6 mol / liter, Al 3+ = 0.2 mol / liter), aqueous sodium carbonate solution (Na = 0.4 mol / liter)
Liter) and an aqueous solution of sodium hydroxide (Na = 2 mol / l) at 100 ml / min and 50 ml, respectively.
At a flow rate of about 80 ml / min and at a flow rate of about 80 ml / min, using a metering pump to supply the reaction vessel with a stirrer to a reaction vessel having a capacity of 2.5 liters. . The obtained white precipitate was filtered, washed with water, dried and pulverized. As a result of measuring the powder X-ray diffraction pattern of the pulverized product, it was substantially the same as hydrotalcite. As a result of the chemical analysis and the thermogravimetric analysis, the chemical composition was as follows. Zn 6 Al 2 (OH) 16 CO 3 . 4H 2 O BET specific surface area of this product fired at 500 ° C. for 1 hour is 124 m 2 / g, and after sonication for 5 minutes in an isopropyl alcohol medium, average secondary particle size measured by laser diffraction method Is 2.0 μm and the maximum secondary particle diameter is 11.
It was 8 μm. The powder X-ray pattern was slightly shifted to the higher angle side, but was the same as ZnO. This indicates that Al is dissolved in ZnO. As a result of conducting a deodorizing test on ammonia, hydrogen sulfide, methyl mercaptan and isovaleric acid, the removal rates of the respective malodorous components were 42%, 100% 95%, 100%
Met. In the deodorization test, in the case of ammonia, hydrogen sulfide, and methyl mercaptan, 0.1 g of a deodorant is put into a 1000 ml air-collecting bottle, and after evacuation, about 1000 ppm of an odorous gas is injected, and the mixture is kept at room temperature for 30 minutes. . Thereafter, the remaining gas concentration was measured with a gas detection tube. In the case of isovaleric acid, put 0.02 g of a deodorant in a 1000 ml air-collecting bottle, evacuate to vacuum, inject 1.2 microliters of isovaleric acid, return to atmospheric pressure after vaporization, and return to room temperature for 30 minutes. Held. Thereafter, the concentration of the remaining gas was measured by gas chromatography.
【００１８】[0018]
【実施例２】実施例１で得られた消臭剤と、合成ケイ酸
アルミニウム（Ａｌ２Ｏ３，９ＳｉＯ２，８．８Ｈ
２Ｏ）を１００．５０の重量比で粉末同志を混合し、複
合消臭剤を作成した。この消臭剤を用いて消臭試験を実
施例１と同じ要領で行った。アンモニア、硫化水素、メ
チルメルカプタン、イソ吉草酸に対する除去率はそれぞ
れ１００％，１００％，９２％，１００％であった。Example 2 The deodorant obtained in Example 1 and synthetic aluminum silicate (Al 2 O 3 , 9SiO 2 , 8.8H)
The 2 O) were mixed powder each other in a weight ratio of 100.50 were generated composite deodorizing agent. Using this deodorant, a deodorization test was performed in the same manner as in Example 1. The removal rates for ammonia, hydrogen sulfide, methyl mercaptan, and isovaleric acid were 100%, 100%, 92%, and 100%, respectively.
【００１９】
、[0019]
,
【比較例１】市販の活性亜鉛華（ＢＥＴ比表面積が５１
ｍ２／ｇ，平均２次粒子径が７．３μｍ，最大２次粒子
径が３２．８μｍ）を用いて、実施例１と同じ条件で消
臭試験を行った。その結果、アンモニア、硫化水素、メ
チルメルカプタン、及びイソ。吉草酸に対する除去率
は、それぞれ、１６％、８５％、６４％及び９６％であ
った。Comparative Example 1 Commercially available activated zinc white (BET specific surface area: 51
m 2 / g, the average secondary particle diameter was 7.3 μm, and the maximum secondary particle diameter was 32.8 μm), and the deodorizing test was performed under the same conditions as in Example 1. As a result, ammonia, hydrogen sulfide, methyl mercaptan, and iso. The removal rates for valeric acid were 16%, 85%, 64% and 96%, respectively.
【００２０】[0020]
【比較例２】本発明消臭剤の代わりに、活性炭を用いて
実施例１と同じ消臭試験を行った。その結果、アンモニ
ア、硫化水素、メチルメルカプタン、イソ吉草酸に対す
る除去率は、それぞれ、２４％、７８％、７２％、８７
％であった。Comparative Example 2 The same deodorizing test as in Example 1 was carried out using activated carbon instead of the deodorant of the present invention. As a result, the removal rates for ammonia, hydrogen sulfide, methyl mercaptan, and isovaleric acid were 24%, 78%, 72%, and 87%, respectively.
%Met.
【００２１】[0021]
【実施例３】Ｚｎ（ＮＯ３）２とＡｌ２（ＳＯ４）３の
混合水溶液（Ｚｎ２＋＝２．０モル／リットル、Ａｌ
３＋＝１．０モル／リットル）と、４モル／リットルの
ＮａＯＨ水溶液とを、攪拌下に、ＰＨを約８．５−９．
０に保って反応した。反応物をろ過後、０．４モル／リ
ットルのＮａ２ＣＯ３水溶液で十分に洗浄した。得られ
たケーキを水に再分散させた後、オートクレーブに入
れ、１３０℃で２４時間水熱処理を行った。この処理物
を、ろ過、乾燥、粉砕した。この物の粉末Ｘ線回折パタ
ーンは、ハイドロタルサイトと実質的に同じであった。
この物の化学組成は、化学分析と熱重量分析の結果、下
記の通りであった。 Ｚｎ４Ａｌ２（ＯＨ）１２ＣＯ３３Ｈ２Ｏ この物を７００℃で１時間焼成して、本発明複合酸化物
を得た。この物の粉末Ｘ線回析パターンは、ＺｎＯとＺ
ｎＡｌ２Ｏ４の混合物、但し後者の割合（ピーク強度）
はわずかであった。この物のＢＥＴ比表面積は７４ｍ２
／ｇ、イソプロピルアルコール溶媒中で測定した平均２
次粒子径は０．７５μｍ、最大粒子径は１．８０μｍで
あった。この物を、市販の制汗パウダー（主成分として
クロルヒドロキシアルミニウム、それ以外にメチルポリ
シロキサン、タルク、フェノキトセール、α−ビザボロ
ールを含有）を使用すると、かぶれて継続使用出来ない
女性２人（３２才、４６才）に、使用してもらった。そ
の結果、肌のかぶれは全く発生しなかった。継続して使
用しても、何らの刺激感、副作用も無いと共に、極めて
良好な滑り性及び付着性を示し、１度塗布しただけで２
〜３日間、完全に、臭いと、発汗を抑制出来た。また、
発汗による衣類の黄ばみも生じなかった。Embodiment 3 A mixed aqueous solution of Zn (NO 3 ) 2 and Al 2 (SO 4 ) 3 (Zn 2+ = 2.0 mol / L, Al
3 + = 1.0 mol / l) and a 4 mol / l NaOH aqueous solution while stirring to adjust the pH to about 8.5-9.
The reaction was kept at 0. After filtering the reaction product, it was sufficiently washed with a 0.4 mol / L aqueous solution of Na 2 CO 3 . After the obtained cake was redispersed in water, it was placed in an autoclave and subjected to hydrothermal treatment at 130 ° C. for 24 hours. This treated product was filtered, dried and pulverized. The powder X-ray diffraction pattern of this product was substantially the same as that of hydrotalcite.
The chemical composition of this product was as follows as a result of the chemical analysis and the thermogravimetric analysis. Zn 4 Al 2 (OH) 12 CO 3 3H 2 O This material was calcined at 700 ° C. for 1 hour to obtain a composite oxide of the present invention. The powder X-ray diffraction pattern of this product was ZnO and Z
Mixture of nAl 2 O 4 , but the latter proportion (peak intensity)
Was slight. The BET specific surface area of this product is 74 m 2
/ G, average 2 measured in isopropyl alcohol solvent
The secondary particle size was 0.75 μm, and the maximum particle size was 1.80 μm. When this product is used with a commercially available antiperspirant powder (containing chlorohydroxyaluminum as a main component, methylpolysiloxane, talc, phenoxytosale, and α-visabolol), two women who are rash and cannot use continuously ( (32 years old, 46 years old) used it. As a result, no skin irritation occurred. Even when used continuously, there is no irritation and no side effects, and it shows extremely good slipperiness and adhesiveness.
Smell and sweating could be completely suppressed for ~ 3 days. Also,
There was no yellowing of clothing due to sweating.
【００２２】[0022]
【発明の効果】本発明によれば、悪臭を極めて効率良く
除去出来るとともに、制汗作用にも優れ、且つ従来の制
汗剤の副作用である肌のかぶれを解消し、化粧品として
重要な滑り性、付着性、透明性も付与出来る。According to the present invention, the odor can be removed very efficiently, the antiperspirant effect is excellent, and the skin rash which is a side effect of the conventional antiperspirant is eliminated, and the slipperiness which is important as cosmetics is obtained. , Adhesion and transparency.
Claims (5)
属を示し、Ｍ３＋はＡｌ，Ｆｅ，Ｃｅ等の３価金属を示
し、ｘは０＜ｘ≦０．５の範囲の数を示し、δはカチオ
ン格子欠陥を示す）で表される複合酸化物を有効成分と
することを特徴とする消臭兼制汗剤。1. A following formula (1) ## STR1 ## M 2+ 1-x M 3+ xδ O ( wherein, M 2+ is a divalent metal as an essential component Zn or Zn, M 3+ is Al, Fe , Ce, etc., wherein x is a number in the range of 0 <x ≦ 0.5, and δ is a cation lattice defect), and a complex oxide represented by the following formula: A deodorant and antiperspirant.
２次粒子径が１μｍ以下で、且つ、ＢＥＴ比表面積が１
０以上であることを特徴とする請求項１記載の消臭兼制
汗剤。2. The composite oxide of formula (1) according to claim 1 having an average secondary particle diameter of 1 μm or less and a BET specific surface area of 1
The deodorant and antiperspirant according to claim 1, wherein the amount is 0 or more.
０）で表される合成ケイ酸アルミニウムを併用すること
を特徴とする請求項１記載の消臭兼制汗剤。3. The following formula (3): mSiO 2 Al 2 O 3 nH 2 O (wherein, m and n are 1 <m <20, 0 ≦ n <2, respectively)
The deodorant and antiperspirant according to claim 1, wherein a synthetic aluminum silicate represented by the formula (0) is used in combination.
属を示し、Ｍ３＋はＡｌ，Ｆｅ，Ｃｅ等の３価金属を示
し、ｘは０＜ｘ＜０．５の範囲の数を示し、δはカチオ
ン格子欠陥を示す）で表され、平均２次粒子径が１μｍ
以下で、且つ、ＢＥＴ比表面積が１０以上であることを
特徴とする複合酸化物。4. The following formula (1): M 2+ 1−x M 3+ xδ O (wherein, M 2+ represents Zn or a divalent metal containing Zn as an essential component, and M 3+ represents Al, Fe , Ce, etc., x is a number in the range of 0 <x <0.5, δ is a cation lattice defect), and the average secondary particle diameter is 1 μm
A composite oxide having a BET specific surface area of 10 or less;
ｘ／ｎｍＨ２Ｏ （式中、Ｍ２＋．Ｍ３＋は式（１）と同じ意味を示し、
Ａｎ−はｎ価のアニオンを示し、ｘ，ｍ及びｎはそれぞ
れ０＜ｘ≦０．５，０≦ｍ＜４，ｎは１〜６の間の整
数、の範囲を示す）で表されるハイドロタルサイト類
を，１００−２００℃で、５時間以上水熱処理後、３０
０〜９００℃で焼成することを特徴とする、請求項４記
載の複合酸化物の製造方法。5. The following formula (2): ## STR2 ## M 2 + 1 -x M 3+ x (OH) 2 An-
x / n mH 2 O (wherein, M 2+ .M 3+ has the same meaning as in formula (1);
An- represents an n-valent anion, and x, m, and n each represent a range of 0 <x ≦ 0.5, 0 ≦ m <4, and n represents an integer of 1 to 6). Hydrotalcites at 100-200 ° C for more than 5 hours after hydrothermal treatment
The method for producing a composite oxide according to claim 4, wherein the method is calcined at 0 to 900 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10044189A JPH11209258A (en) | 1998-01-20 | 1998-01-20 | Deodorizng and sweat-controlling combination agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10044189A JPH11209258A (en) | 1998-01-20 | 1998-01-20 | Deodorizng and sweat-controlling combination agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11209258A true JPH11209258A (en) | 1999-08-03 |
Family
ID=12684634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10044189A Pending JPH11209258A (en) | 1998-01-20 | 1998-01-20 | Deodorizng and sweat-controlling combination agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11209258A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005330641A (en) * | 2004-04-23 | 2005-12-02 | Chisso Corp | Deodorant fiber, fiber molded article using the same, and fiber product |
| JP2007107144A (en) * | 2005-10-14 | 2007-04-26 | Chisso Corp | Hydrophilic antimicrobial/deodorant fiber, fiber formed product and textile product |
| JP2009191030A (en) * | 2008-02-15 | 2009-08-27 | Nivea Kao Kk | Method of preventing clogging of powdered aerosol |
| JP2017119015A (en) * | 2015-12-28 | 2017-07-06 | 日本国土開発株式会社 | Deodorant using layered double hydroxide and method for producing the same, and deodorant resin, deodorant fiber, deodorant garment, deodorant filter, and deodorant mask using layered double hydroxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58214338A (en) * | 1982-06-04 | 1983-12-13 | Kyowa Chem Ind Co Ltd | Composite adsorbent |
| JPH0614981A (en) * | 1992-06-29 | 1994-01-25 | Fuji Kagaku Kogyo Kk | Deodorizing composition |
| JPH08337768A (en) * | 1995-04-10 | 1996-12-24 | Kyowa Chem Ind Co Ltd | Ultraviolet light shielding agent and its utilization |
-
1998
- 1998-01-20 JP JP10044189A patent/JPH11209258A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58214338A (en) * | 1982-06-04 | 1983-12-13 | Kyowa Chem Ind Co Ltd | Composite adsorbent |
| JPH0614981A (en) * | 1992-06-29 | 1994-01-25 | Fuji Kagaku Kogyo Kk | Deodorizing composition |
| JPH08337768A (en) * | 1995-04-10 | 1996-12-24 | Kyowa Chem Ind Co Ltd | Ultraviolet light shielding agent and its utilization |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005330641A (en) * | 2004-04-23 | 2005-12-02 | Chisso Corp | Deodorant fiber, fiber molded article using the same, and fiber product |
| JP2007107144A (en) * | 2005-10-14 | 2007-04-26 | Chisso Corp | Hydrophilic antimicrobial/deodorant fiber, fiber formed product and textile product |
| JP2009191030A (en) * | 2008-02-15 | 2009-08-27 | Nivea Kao Kk | Method of preventing clogging of powdered aerosol |
| JP2017119015A (en) * | 2015-12-28 | 2017-07-06 | 日本国土開発株式会社 | Deodorant using layered double hydroxide and method for producing the same, and deodorant resin, deodorant fiber, deodorant garment, deodorant filter, and deodorant mask using layered double hydroxide |
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