TWI717445B - Spray type cosmetics for hair dyeing or hair bleaching - Google Patents

Spray type cosmetics for hair dyeing or hair bleaching Download PDF

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TWI717445B
TWI717445B TW105143502A TW105143502A TWI717445B TW I717445 B TWI717445 B TW I717445B TW 105143502 A TW105143502 A TW 105143502A TW 105143502 A TW105143502 A TW 105143502A TW I717445 B TWI717445 B TW I717445B
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agent
mass
less
hair
spray
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TW201726028A (en
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野尻昌良
堀江優
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日商花王股份有限公司
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/22Peroxides; Oxygen; Ozone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/342Alcohols having more than seven atoms in an unbroken chain
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41Amines
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/08Preparations for bleaching the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/10Preparations for permanently dyeing the hair

Abstract

本發明之噴霧型染毛用或毛髮脫色用化妝品具備如下外容器,該外容器收納填充有含有鹼劑之第1劑之第1內容器與填充有含有過氧化氫之第2劑之第2內容器,並且 於外容器與各內容器之間之空間中填充內壓0.2~0.8 MPa之噴射劑, 第1及第2內容器係貼合最內層為聚烯烴樹脂層之彎曲剛性0.15~3.0 gf・cm2 /cm之多層片材而形成, (第1內容器之片材之彎曲剛性)/(第2內容器之片材之彎曲剛性)=0.3~5、 (第1劑之黏度)/(第2劑之黏度)=0.5~1.5、 (第2劑之質量)/(第1劑之質量)=0.8以上且未達1.2。The spray type cosmetic for hair dyeing or hair bleaching of the present invention is provided with an outer container which houses a first inner container filled with a first agent containing an alkali agent and a second container filled with a second agent containing hydrogen peroxide Inner container, and the space between the outer container and each inner container is filled with a propellant with an internal pressure of 0.2~0.8 MPa. The first and second inner containers are laminated with the innermost layer of polyolefin resin layer with flexural rigidity of 0.15~ 3.0 gf·cm 2 /cm multi-layered sheet, (bending rigidity of the first inner container sheet)/(bending rigidity of the second inner container sheet) = 0.3~5, (the viscosity of the first agent )/(Viscosity of the second agent)=0.5~1.5, (mass of the second agent)/(mass of the first agent)=0.8 or more and less than 1.2.

Description

噴霧型染毛用或毛髮脫色用化妝品Spray type cosmetics for hair dyeing or hair bleaching

本發明係關於一種噴霧型染毛用或毛髮脫色用化妝品。The present invention relates to a spray type cosmetic for hair dyeing or hair bleaching.

先前,業界提出有如下雙重構造容器(以下,稱為「分離填充、同一加壓噴出型之雙重構造容器」),其具備將毛髮化妝料之第1劑與第2劑分離而填充,並且利用同一加壓噴出系統同時噴出之機構。該分離填充、同一加壓噴出型之雙重構造容器例如揭示於專利文獻1、專利文獻2中。 該等分離填充、同一加壓噴出型之雙重構造容器通常為僅同時噴出相同量之填充至袋狀體中之第1劑與第2劑之設計,係填充於其中之第1劑與第2劑亦以質量比1:1計等量噴出後進行混合而應用於毛髮者。 然而,分離填充、同一加壓噴出型之雙重構造容器由於係利用藉由相同之噴射劑之噴出壓同時噴出第1劑與第2劑之機構者,故而尤其於毛髮化妝料之第1劑與第2劑為相對高黏度之乳霜狀製劑之情形時,若未適當地調整第1劑與第2劑各自之流變特性(由加壓時之流動所產生之噴出性),則實際上無法實現第1劑與第2劑之等量噴出。於等量噴出性受損某程度以上之情形時,無法達成將第1劑與第2劑填充至雙重構造容器中而成之毛髮化妝料之設定之染毛性能。 進而,於毛髮化妝料例如為2劑型之氧化染毛劑或毛髮脫色劑等染毛劑之情形時,於第1劑中至少調配鹼劑(進而氧化染料),於第2劑中調配氧化劑。於此種組成上之制約下,若不自始至終等量噴出第1劑與第2劑,則會因第1劑與第2劑之混合比之變化而使色調發生變化,從而無法達成充分之染毛效果。又,該噴出量比必須隨時間經過而穩定地達成,除第1劑與第2劑之流變特性以外,難以確認進行何種組成設計、容器設計等可實現該等。 專利文獻3中揭示有藉由調整流變特性,而獲得至噴出第2劑之填充量之一半量為止之等量噴出性。然而,現狀為,後半部分之等量噴出性之偏差非常大,未能實現至最終之等量噴出性。如此,於僅針對流變特性之研究中,現狀為未能實現至最終之等量噴出性。 (專利文獻1)日本專利特開2012-229318號公報 (專利文獻2)日本專利特開2013-043659號公報 (專利文獻3)日本專利特開2015-010087號公報Previously, the industry has proposed the following dual structure container (hereinafter referred to as "separate filling, same pressure spray type dual structure container"), which is equipped with the first part and the second part of the hair cosmetics to be filled separately and used The mechanism for simultaneous ejection of the same pressure ejection system. The double-structured container of the separate filling and the same pressure discharge type is disclosed in Patent Document 1 and Patent Document 2, for example. These two-structured containers of separate filling and the same pressurized ejection type are usually designed to eject the same amount of the first agent and the second agent filled into the bag at the same time. The first agent and the second agent are filled in the container. The agent is also sprayed in the same amount at a mass ratio of 1:1 and mixed and applied to the hair. However, the double-structured container of separate filling and the same pressure ejection type utilizes a mechanism that ejects the first agent and the second agent at the same time by the ejection pressure of the same propellant, so it is especially suitable for the first agent and the second agent of hair cosmetics. When the second agent is a relatively high-viscosity cream-like formulation, if the rheological properties of the first and second agents (the ejection properties generated by the flow under pressure) are not properly adjusted, the actual The first dose and the second dose cannot be sprayed in the same amount. In the case where the sprayability of the same amount is impaired to a certain degree or more, it is impossible to achieve the set hair dyeing performance of the hair cosmetics filled with the first agent and the second agent in a double structure container. Furthermore, when the hair cosmetics are hair dyes such as two-part oxidative hair dyes or hair bleaching agents, at least an alkali agent (and further an oxidation dye) is blended in the first agent, and an oxidizing agent is blended in the second agent. Under such compositional constraints, if the first and second parts are not sprayed out in equal amounts from beginning to end, the color tone will change due to the change in the mixing ratio of the first part and the second part, and sufficient dyeing cannot be achieved. Hair effect. In addition, the ejection amount ratio must be achieved stably over time. Except for the rheological properties of the first agent and the second agent, it is difficult to confirm what kind of composition design, container design, etc. can be achieved. Patent Document 3 discloses that by adjusting the rheological properties, an equal ejection property up to half of the filling amount of the second agent is obtained. However, the current situation is that the deviation of the equal-volume ejection performance in the latter half is very large, and the final equal-volume ejection performance cannot be achieved. In this way, in the research on rheological properties only, the current situation is that the final equivalent ejection property has not been achieved. (Patent Document 1) Japanese Patent Laid-Open No. 2012-229318 (Patent Document 2) Japanese Patent Laid-Open No. 2013-043659 (Patent Document 3) Japanese Patent Laid-Open No. 2015-010087

本發明提供一種噴霧型染毛用或毛髮脫色用化妝品,其係具備如下外容器者,該外容器收納填充有含有鹼劑之第1劑之第1內容器、及填充有含有過氧化氫之第2劑之第2內容器之兩者,並且 於該外容器與各內容器之間之空間中,以30℃下之內壓成為0.2 MPa以上且0.8 MPa以下之方式填充有噴射劑, 該第1內容器及第2內容器分別係貼合最內層具有聚烯烴樹脂層之多層構造之片材而形成,該第1內容器之片材之彎曲剛性E(f)及該第2內容器之片材之彎曲剛性E(s)分別為0.15 gf・cm2 /cm以上且3.0 gf・cm2 /cm以下,E(f)與E(s)之比率E(f)/E(s)為0.3以上且5以下, 該第1劑於30℃下之黏度V(f)與該第2劑於30℃下之黏度V(s)之比V(f)/V(s)為0.5以上且1.5以下, 第2內容器內之第2劑之質量M(s)與第1內容器內之第1劑之質量M(f)之比M(s)/M(f)為0.8以上且未達1.2。The present invention provides a spray-type cosmetic for hair dyeing or hair bleaching, which is provided with an outer container that contains a first inner container filled with a first agent containing an alkali agent, and a first inner container filled with hydrogen peroxide Both the second inner container of the second agent and the space between the outer container and each inner container are filled with a propellant so that the internal pressure at 30°C becomes 0.2 MPa or more and 0.8 MPa or less, The first inner container and the second inner container are formed by laminating sheets with a polyolefin resin layer in the innermost layer, respectively. The bending rigidity E(f) of the sheet of the first inner container and the second content The bending rigidity E(s) of the sheet material of the device is 0.15 gf·cm 2 /cm or more and 3.0 gf·cm 2 /cm or less, the ratio of E(f) to E(s) is E(f)/E(s) ) Is 0.3 or more and 5 or less, the ratio V(f)/V(s) of the viscosity V(f) of the first agent at 30°C to the viscosity V(s) of the second agent at 30°C is 0.5 Above and below 1.5, the ratio M(s)/M(f) of the mass M(s) of the second dose in the second inner container to the mass M(f) of the first dose in the first inner container is 0.8 or more And it did not reach 1.2.

因此,本發明係關於一種噴霧型染毛用或毛髮脫色用化妝品,其可將利用分離填充、同一加壓噴出型之雙重構造容器之第1劑與第2劑之噴出量自始至終且隨時間經過維持為等量。 本發明者等人進行努力研究,結果發現,於採用有分離填充、同一加壓噴出型之雙重構造容器的染毛用或毛髮脫色用化妝品中,藉由將噴射劑之壓力、內袋材料之素材、彎曲剛性及彎曲剛性比、以及第1劑與第2劑之黏度比分別調整為特定之範圍,隨時間經過達成自始至終之等量噴出性。 於本說明書中,所謂「於第1劑與第2劑之混合物中之含量」係指於將第1劑與第2劑精確地以質量比1:1進行混合之情形時之混合物中之含量。 [外容器] 本發明之噴霧型染毛用或毛髮脫色用化妝品具備如下外容器,該外容器收納填充有含有鹼劑之第1劑之第1內容器、及填充有含有過氧化氫之第2劑之第2內容器之兩者。 該外容器可使用鋁、鍍錫鐵皮等金屬、或聚對苯二甲酸乙二酯、聚芳酯等合成樹脂。 尤其於使用合成樹脂作為外容器之情形時,較佳為設為具有透光性之合成樹脂材料。此種合成樹脂之外容器可藉由一面沿軸方向延伸一面向內部吹入空氣而使之膨脹之雙軸延伸吹塑成形,使藉由擠出成形而成形之有底筒狀之半成品成形。然而,亦可藉由使筒狀之半成品膨脹,切割下部並進行接著而形成底部之直接吹塑成形進行成形。再者,外容器亦可使碳、氧化鋁、二氧化矽等成為氣體狀,於內表面及/或外面設置蒸鍍膜。 [內容器] 本發明中之內容器係貼合最內層具有聚烯烴樹脂之多層構造之片材而形成。作為該內容器,可列舉將2片之片材重疊,並藉由熱熔接或超音波熔接等將邊緣部貼合而成之袋。作為最內層之聚烯烴樹脂,可列舉聚乙烯樹脂(PE)、聚丙烯樹脂(PP)等,就形成內袋之容易性之觀點、減少第1劑及第2劑於各內容器中之剩餘量之觀點而言,較佳為聚乙烯樹脂。 本發明中之第1內容器之片材之彎曲剛性E(f)及第2內容器之片材之彎曲剛性E(s)為0.15 gf・cm2 /cm以上且3.0 gf・cm2 /cm以下,就自始至終將第1劑與第2劑之噴出量維持為等量之觀點、至最終自各內容器噴出第1劑及第2劑之觀點而言,較佳為0.2 gf・cm2 /cm以上,更佳為0.3 gf・cm2 /cm以上,進而較佳為0.4 gf・cm2 /cm以上,進而較佳為0.5 gf・cm2 /cm以上,進而較佳為0.6 gf・cm2 /cm以上,又,就內容器隨著內容物之噴出操作而追隨變形之觀點而言,較佳為2.8 gf・cm2 /cm以下,更佳為2.5 gf・cm2 /cm以下,進而較佳為2.4 gf・cm2 /cm以下,進而較佳為2.2 gf・cm2 /cm以下,進而較佳為2.0 gf・cm2 /cm以下。 又,E(f)與E(s)之比率E(f)/E(s)為0.3以上且5以下,就自始至終將第1劑與第2劑之噴出量維持為等量之觀點、減少第1劑及第2劑於各內容器中之剩餘量之觀點、初期噴出量優異之觀點而言,較佳為0.4以上,更佳為0.5以上,進而較佳為1.0以上,進而較佳為1.3以上,又,較佳為4.5以下,更佳為4以下,進而較佳為3.33以下,進而較佳為3以下。 片材之彎曲剛性可使用KES(Kawabata Evaluation System,川端評價系統)彎曲試驗機等(例如多功能純彎曲試驗機KES-FB2-S(Kato Tech公司製造))而加以測定。 構成第1內容器之最內層具有聚烯烴樹脂層之多層構造之片材較佳為具有最外層及中間層。 作為最外層,可列舉尼龍(NY)等聚醯胺、聚對苯二甲酸乙二酯(PET)等聚酯等。作為中間層,較佳為使用金屬箔,作為該金屬箔,可列舉鋁箔(Al箔)等輕金屬。 作為第1內容器之片材之最外層、中間層、最內層之組合,可根據內容物而適當選擇,例如根據最外層/中間層/最內層之順序,可列舉:PE/Al箔/PE、PP/Al箔/PE、PET/Al箔/PE、NY/Al箔/PE等。又,第1內容器之片材可為省略最外層之2層構造,亦可為進而設置有中間層之4層以上之構造。 構成第2內容器之最內層具有聚烯烴樹脂層之多層構造之片材就兼顧片材之適度之彎曲剛性與低破損性之觀點而言,較佳為具有最外層及中間層。 作為最外層,與第1內容器之片材同樣地,可列舉尼龍(NY)等聚醯胺、聚對苯二甲酸乙二酯(PET)等聚酯等。作為中間層,可列舉Eval(EVOH)、尼龍(NY)等聚醯胺等具有氣體阻隔性及耐化學品性之合成樹脂層、或於最外層或最內層蒸鍍有二氧化矽(SiOX)等之蒸鍍層等非金屬層。 作為第2內容器之片材之最外層、中間層、最內層之組合,可根據內容物而適當選擇,例如根據最外層/中間層/最內層之順序,可列舉:PE/EVOH/PE、PP/EVOH/PE、PET/EVOH/PE、PE/NY/PE、PP/NY/PE、PET/NY/PE、PE/SiOX/PE、PP/SiOX/PE、PET/SiOX/PE、PE/Al2 O3 /PE等。就兼顧形成之容易性與低破損性之觀點而言,更佳為於中間層使用合成樹脂層。又,第2內容器之片材可為省略最外層之2層構造,亦可為進而任意地設置有合成樹脂層或非金屬氣體阻隔層之4層以上之構造。又,於將外容器設為透光性之情形時,較佳為將第2內容器設為透光性。 [內壓] 向外容器與各內容器之間之空間中,以30℃下之內壓成為0.2 MPa以上且0.8 MPa以下之方式填充噴射劑。關於該內壓,就自始至終將第1劑與第2劑之噴出量維持為等量之觀點、減少第1劑及第2劑於各內容器中之剩餘量之觀點而言,較佳為0.3 MPa以上,更佳為0.4 MPa以上,進而較佳為0.5 MPa以上,又,就自始至終維持第1劑與第2劑之噴出量比之觀點、抑制高溫下之外容器之破裂風險之觀點而言,較佳為0.75 MPa以下,更佳為0.7 MPa以下。 再者,30℃下之內壓例如可使用布爾登管壓力計、應變計式壓力計、快速膜片型壓力計等(具體而言,實施例中所記載之器械)而加以測定。 作為所填充之噴射劑,可列舉:氮氣、壓縮空氣、二氧化碳、一氧化二氮等壓縮氣體、液化石油氣、氫氟烯烴等液化氣體等。 [黏度] 關於第1內容器內之第1劑於30℃下之黏度V(f)、及第2內容器內之第2劑於30℃下之黏度V(s)之各者,就減少第1劑及第2劑於各內容器中之剩餘量之觀點、初期噴出量優異之觀點、自始至終將第1劑與第2劑之噴出量維持為等量之觀點、塗抹於頭髮時防止劑滴垂之觀點而言,較佳為8,000 mPa・s以上,更佳為10,000 mPa・s以上,進而較佳為12,000 mPa・s以上,進而較佳為15,000 mPa・s以上,又,就減少第1劑及第2劑於各內容器中之剩餘量之觀點、初期噴出量優異之觀點、自始至終將第1劑與第2劑之噴出量維持為等量之觀點、於塗抹於頭髮時容易使劑抹勻之觀點而言,較佳為160,000 mPa・s以下,更佳為120,000 mPa・s以下,進而較佳為100,000 mPa・s以下,進而較佳為80,000 mPa・s以下,進而較佳為50,000 mPa・s以下,進而較佳為45,000 mPa・s以下,進而較佳為40,000 mPa・s以下,進而較佳為35,000 mPa・s以下。 又,V(f)與V(s)之比V(f)/V(s)為0.5以上且1.5以下,就自始至終將第1劑與第2劑之噴出量維持為等量之觀點、減少第1劑及第2劑於各內容器中之剩餘量之觀點、初期噴出量優異之觀點而言,較佳為0.55以上,更佳為0.6以上,進而較佳為0.7以上,進而較佳為0.8以上,又,較佳為1.4以下,更佳為1.3以下,進而較佳為1.10以下,進而較佳為1.07以下,進而較佳為1.05以下,進而較佳為1.04以下,進而較佳為1.02以下。 第1劑及第2劑於30℃下之黏度可使用B型黏度計而進行測定,又,第1內容器內之第1劑及第2內容器內之第2劑於30℃下之黏度可自外容器取出各內容器,並自其各內容器取出第1劑及第2劑後,使用B型黏度計進行測定。再者,具體而言,可藉由實施例中所記載之方法進行測定。 [質量比] 關於第2內容器內之第2劑之質量M(s)與第1內容器內之第1劑之質量M(f)之比M(s)/M(f),就自始至終維持第1劑與第2劑之噴出量比之觀點而言,為0.80以上,較佳為0.85以上,更佳為0.90以上,又,未達1.2,較佳為1.15以下,更佳為1.10以下。 [鹼劑] 於第1劑中含有鹼劑。作為鹼劑,可列舉:氨及其鹽(例如碳酸氫銨);單乙醇胺、異丙醇胺、2-胺基-2-甲基丙醇、2-胺基丁醇等烷醇胺及其鹽;1,3-丙二胺等烷烴二胺及其鹽;碳酸胍、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀等碳酸鹽等。該等鹼劑亦可將兩種以上併用。關於第1劑中之鹼劑之含量,就使毛髮充分膨潤而獲得染毛效果之觀點而言,較佳為0.1質量%以上,更佳為0.2質量%以上,進而較佳為0.4質量%以上,又,就減少毛髮損傷或頭皮刺激之觀點而言,較佳為14質量%以下,更佳為12質量%以下,進而較佳為8質量%以下。關於第1劑與第2劑之混合物中之鹼劑之含量,就充分之染毛效果之觀點而言,較佳為0.05質量%以上,更佳為0.1質量%以上,進而較佳為0.2質量%以上,進而較佳為0.5質量%以上,進而較佳為1質量%以上,又,就減少毛髮損傷或頭皮刺激之觀點而言,較佳為7質量%以下,更佳為6質量%以下,進而較佳為5質量%以下,進而較佳為4質量%以下。 [過氧化氫] 於第2劑中含有過氧化氫。關於第2劑中之過氧化氫之含量,就分解毛髮黑色素,並且確保氧化染料之偶合反應而獲得充分之染毛效果之觀點而言,較佳為1質量%以上,更佳為3質量%以上,又,就減少毛髮損傷或頭皮刺激之觀點而言,較佳為9質量%以下,更佳為6質量%以下。關於第1劑與第2劑之混合物中之過氧化氫之含量,較佳為1質量%以上,更佳為2質量%以上,又,較佳為6質量%以下,更佳為5質量%以下。 [界面活性劑] 於第1劑、第2劑中之任一者或兩者中可含有界面活性劑。作為界面活性劑,可列舉:陽離子界面活性劑、非離子界面活性劑、兩性界面活性劑、及陰離子界面活性劑。該等之中,就配方組成之穩定性之觀點而言,較佳為陰離子界面活性劑、非離子界面活性劑。 作為陰離子界面活性劑,可列舉:烷基苯磺酸鹽、烷基醚硫酸鹽、烯基醚硫酸鹽、烷基硫酸鹽、烯基硫酸鹽、烯烴磺酸鹽、烷烴磺酸鹽、飽和或不飽和脂肪酸鹽、烷基醚羧酸鹽、烯基醚羧酸鹽、α-磺基脂肪酸鹽、N-醯基胺基酸鹽、磷酸單或二酯、磺基琥珀酸酯等。作為烷基醚硫酸鹽,可列舉聚氧乙烯烷基醚硫酸鹽。作為該等陰離子界面活性劑之陰離子性基之抗衡離子,可列舉:鈉離子、鉀離子等鹼金屬離子;鈣離子、鎂離子等鹼土金屬離子;銨離子;具有1~3個碳數2或3之烷醇基之烷醇胺鹽(例如單乙醇胺鹽、二乙醇胺鹽、三乙醇胺鹽、三異丙醇胺鹽等)。 作為陽離子界面活性劑,就對染毛後之毛髮賦予優異之觸感之觀點而言,較佳為氯化單烷基三甲基銨、氯化二烷基二甲基銨、溴化單烷基三甲基銨,其中,更佳為氯化硬脂基三甲基銨(Steartrimonium chloride)、氯化鯨蠟基三甲基銨(Cetrimonium chloride)、氯化月桂基三甲基銨(Lauryl Trimonium chloride),亦較佳為將兩種以上混合。 作為非離子界面活性劑,可列舉:聚氧伸烷基烷基醚、聚氧伸烷基烯基醚、高級脂肪酸蔗糖酯、聚甘油脂肪酸酯、高級脂肪酸單或二乙醇醯胺、聚氧乙烯氫化蓖麻油、聚氧乙烯山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇脂肪酸酯、烷基醣、烷基氧化胺、烷基醯胺氧化胺等。該等之中,較佳為聚氧伸烷基烷基醚、聚氧乙烯氫化蓖麻油、烷基醣,更佳為聚氧乙烯烷基(12~14)醚、烷基聚葡糖苷。 作為兩性界面活性劑,可列舉:咪唑啉、羰基甜菜鹼、醯胺甜菜鹼、磺基甜菜鹼、羥基磺基甜菜鹼、醯胺磺基甜菜鹼等,更佳為烷基二甲基胺基乙酸甜菜鹼、脂肪醯胺丙基甜菜鹼等甜菜鹼界面活性劑,進而較佳為脂肪醯胺丙基甜菜鹼。 該等界面活性劑可單獨使用任一種,或將兩種以上組合而使用。關於第1劑與第2劑之混合物中之界面活性劑之含量,就良好之觸感、乳化性能之觀點而言,較佳為0.1質量%以上,更佳為0.2質量%以上,進而較佳為0.5質量%以上,又,就獲得充分之染毛效果之觀點而言,較佳為30質量%以下,更佳為25質量%以下,進而較佳為20質量%以下,進而較佳為10質量%以下,進而較佳為5質量%以下。 [高級醇] 於第1劑、第2劑中之任一者或兩者中可含有高級醇。作為高級醇,可使用下述通式(1)所表示者。 R-OH           (1) [式中,R表示碳數12以上且24以下之直鏈或支鏈之烴基] 作為高級醇,可列舉:月桂醇、肉豆蔻醇、鯨蠟醇、硬脂醇、異硬脂醇、花生醇、山萮醇、二十四烷醇、油醇等。高級醇可單獨使用,或將兩種以上組合而使用。 關於高級醇,就抑制隨時間經過之黏度變化之觀點而言,較佳為(1a)上述通式(1)中之R為碳數12以上且18以下之直鏈烷基者與(1b)上述通式(1)中之R為碳數20以上且24以下之直鏈烷基者之組合,更佳為(1a)上述通式(1)中之R為碳數14以上且18以下之直鏈烷基者與(1b)上述通式(1)中之R為碳數20以上且22以下之直鏈烷基者之組合。關於成分(1a)與成分(1b)之質量比[(1a):(1b)],就抑制隨時間經過之黏度變化之觀點而言,較佳為0.5:9.5~9.5:0.5,更佳為1:9~9:1,進而較佳為1.5:8.5~8.5:1.5,進而較佳為1:4~4:1。 關於第1劑與第2劑之混合物中之高級醇之含量,就將剛製造後之黏度設為作為染毛劑而適當之範圍之觀點、抑制隨時間經過之黏度變化之觀點而言,較佳為3質量%以上,更佳為4質量%以上,進而較佳為5質量%以上,又,就抑制隨時間經過之黏度變化之觀點而言,較佳為12質量%以下,更佳為11質量%以下,進而較佳為10質量%以下,進而較佳為9質量%以下。 [烴] 於第1劑、第2劑中之任一者或兩者中可含有烴。烴可單獨使用,或將兩種以上組合而使用。作為本發明之烴,可列舉:液態石蠟、液態異烷烴、輕質異烷烴、輕質液態異烷烴、重質液態異烷烴、角鯊烷等。該等之中,就抑制隨時間經過之黏度變化之觀點而言,較佳為液態石蠟。 關於第1劑與第2劑之混合物中之烴之含量,就提高染毛或毛髮脫色後之光亮度之觀點而言,較佳為1質量%以上,更佳為2質量%以上,進而較佳為3質量%以上,又,較佳為20質量%以下,更佳為15質量%以下,進而較佳為10質量%以下,進而較佳為8質量%以下。 [酯油] 於第1劑、第2劑中之任一者或兩者中可含有酯油。酯油可單獨使用,或將兩種以上組合而使用。作為本發明之酯油,可列舉:肉豆蔻酸辛基十二烷基酯、肉豆蔻酸異丙酯、異硬脂酸異丙酯、異壬酸異壬酯、異壬酸異十三烷基酯、硬脂酸丁酯、油酸油酯、蓖麻醇酸辛基十二烷基酯、新戊二醇二癸酸酯、蘋果酸二異硬脂酯、羥基硬脂酸辛酯、澳洲胡桃油、橄欖油、蓖麻油、荷荷芭油、鱷梨油、葵花籽油、聚甘油二異硬脂酸酯、聚甘油三異硬脂酸酯、甘油二異硬脂酸酯、甘油三異硬脂酸酯、甘油三(辛酸/癸酸)酯、甘油三(2-乙基己酸酯)、季戊四醇四辛酸酯等。該等之中,就乳化穩定性較高之觀點而言,較佳為作為飽和脂肪酸之支鏈醇酯之肉豆蔻酸異丙酯、異硬脂酸異丙酯、蘋果酸二異硬脂酯、異壬酸異壬酯、異壬酸異十三烷基酯、棕櫚酸2-乙基己酯、肉豆蔻酸辛基十二烷基酯、油酸辛基十二烷基酯、芥子酸辛基十二烷基酯等。 關於第1劑與第2劑之混合物中之酯油之含量,就提高染毛或毛髮脫色後之光亮度之觀點而言,較佳為0.01質量%以上,更佳為0.03質量%以上,又,就混合物於毛髮上之充分之抹勻性之觀點而言,較佳為5質量%以下,更佳為3質量%以下,進而較佳為2質量%以下。 [有機溶劑] 於第1劑、第2劑中之任一者或兩者中可含有有機溶劑。作為有機溶劑,可列舉:乙醇、1-丙醇、2-丙醇等低級烷醇;苄醇、2-苄氧基乙醇、苯氧基乙醇等芳香族醇;丙二醇、1,3-丁二醇、二乙二醇、甘油等多元醇;乙氧基乙醇、乙氧基二乙二醇、甲氧基乙醇等醚醇;N-甲基吡咯啶酮、N-乙基吡咯啶酮等N-烷基吡咯啶酮;碳酸丙二酯等碳酸烷二酯;γ-戊內酯、γ-己內酯等內酯。 該等有機溶劑可單獨使用,或將兩種以上組合而使用,又,關於其於第1劑與第2劑之混合物中之含量,就防止氧化染料自第1劑與第2劑之混合物中析出之觀點而言,較佳為0.1質量%以上,更佳為0.5質量%以上,進而較佳為1質量%以上,又,就防止混合物分離為水系層與油系層之觀點而言,較佳為35質量%以下,更佳為30質量%以下,進而較佳為25質量%以下,進而較佳為20質量%以下,進而較佳為15質量%以下,進而較佳為10質量%以下。 [染料] 於本發明之噴霧型染毛用或毛髮脫色用化妝品為染毛用化妝品之情形時,於第1劑中含有氧化染料中間物或直接染料。 (氧化染料中間物) 作為氧化染料中間物,可使用通常染毛劑中所使用之公知之前驅物及成色劑。作為前驅物,例如可列舉:對苯二胺、甲苯-2,5-二胺、鄰氯對苯二胺、N-苯基對苯二胺、N,N-雙(羥基乙基)對苯二胺、3-甲基-4-胺基苯酚、2-羥基乙基對苯二胺、對胺基苯酚、對甲基胺基苯酚、4-胺基間甲酚、鄰胺基苯酚、及該等之鹽等。 又,作為成色劑,例如可列舉:間苯二酚、2-甲基間苯二酚、1-萘酚、1,5-二羥基萘、5-胺基鄰甲酚、間苯二胺、鄰胺基苯酚、間胺基苯酚、對胺基苯酚、2,4-二胺基苯氧基乙醇、2,6-二胺基吡啶、2-甲基-5-羥基乙基胺基苯酚、2-胺基-3-羥基吡啶、及該等之鹽等。 前驅物與成色劑可分別單獨使用,或將兩種以上組合而使用,第1劑中之前驅物與成色劑各自之含量較佳為0.01質量%以上,更佳為0.1質量%以上,又,較佳為5質量%以下,更佳為4質量%以下。 (直接染料) 作為直接染料,可列舉:酸性染料、硝基染料、分散染料、鹼性染料等。更具體而言,作為酸性染料,可列舉:藍色1號、紫色401號、黑色401號、橙色205號、紅色227號、紅色106號、黃色202號之(1)、黃色202號之(2)、黃色203號、酸性橙3等,作為硝基染料,可列舉:2-硝基對苯二胺、2-胺基-6-氯-4-硝基苯酚、3-硝基對羥基乙基胺基苯酚、4-硝基鄰苯二胺、4-胺基-3-硝基苯酚、4-羥基丙基胺基-3-硝基苯酚、HC藍2、HC橙1、HC紅1、HC黃2、HC黃4、HC黃5、HC紅3、N,N-雙(2-羥基乙基)-2-硝基對苯二胺等,作為分散染料,可列舉:分散紫1、分散藍1、分散黑9等,作為鹼性染料,可列舉:鹼性藍99、鹼性棕16、鹼性棕17、鹼性紅76、鹼性黃76、鹼性橙31、鹼性紅51等。 直接染料可單獨使用,或將兩種以上組合而使用,亦可與氧化染料中間物併用。第1劑中之直接染料之含量較佳為0.001質量%以上,更佳為0.01質量%以上,又,較佳為5質量%以下,更佳為3質量%以下。 [其他任意成分] 於本發明之噴霧型染毛用或毛髮脫色用化妝品之第1劑或第2劑中,除上述成分以外,亦可添加通常用作化妝品原料之其他成分。作為此種任意成分,可列舉:油劑、聚矽氧類、不揮發性親水性溶劑、動植物油脂、天然或合成之高分子、醚類、蛋白質衍生物、水解蛋白質、胺基酸類、防腐劑、螯合劑、穩定劑、抗氧化劑、植物性萃取物、生藥萃取物、維生素類、香料、紫外線吸收劑等。 [pH值] 第1劑之pH值(25℃)較佳為8以上且12以下。就過氧化氫之穩定性之觀點而言,第2劑之pH值(25℃)較佳為2以上且5以下。進而,關於第1劑與第2劑之混合物於使用時之pH值(25℃),就使毛髮膨潤而獲得充分之染毛效果之觀點而言,較佳為8.0以上,更佳為8.5以上,進而較佳為9.0以上,又,就防止頭皮刺激之觀點而言,較佳為11.5以下,更佳為11.0以下,進而較佳為10.5以下。再者,本發明中之pH值係使用堀場製作所公司製造之pH值計F-22,於室溫(25℃)下所測得之值。 [染毛用具] 本發明之噴霧型染毛用或毛髮脫色用化妝品可使用染毛用具而塗抹於毛髮上。作為染毛用具,可使用如日本專利特開平10-71020號公報中所記載之具備梳部及刷毛部之染毛用具、或如日本專利特開2006-326081號公報中所記載之具備梳部及具有用以保持劑之凹部之刷毛部之染毛用具。 [劑型] 第1劑及第2劑之劑型可設為乳霜狀、凝膠狀、糊狀等。 [頭髮染毛或毛髮脫色方法] 本發明之噴霧型染毛用或毛髮脫色用化妝品係向預先準備之混合用托盤中噴出第1劑及第2劑,利用如日本專利特開平10-71020號公報中所記載之染毛用具之刷毛部將第1劑與第2劑混合後,將所獲得之混合物塗抹於頭髮,藉此可將頭髮染色或脫色。 又,本發明之噴霧型染毛用或毛髮脫色用化妝品藉由向如日本專利特開2006-326081號公報中所記載之染毛用具之刷毛部之凹部噴出第1劑及第2劑,並將該刷毛部直接用於頭髮,可一面使第1劑與第2劑於頭髮上混合,一面於頭髮整體上塗抹開,而將頭髮染色或脫色。 關於以上所說明之實施形態,以下進而揭示本發明之較佳之態樣。 <1>一種噴霧型染毛用或毛髮脫色用化妝品,其係具備如下外容器者,該外容器收納填充有含有鹼劑之第1劑之第1內容器、及填充有含有過氧化氫之第2劑之第2內容器之兩者,並且 於該外容器與各內容器之間之空間中,以30℃下之內壓成為0.2 MPa以上且0.8 MPa以下之方式填充有噴射劑, 該第1內容器及第2內容器分別係貼合最內層具有聚烯烴樹脂層之多層構造之片材而形成,該第1內容器之片材之彎曲剛性E(f)及該第2內容器之片材之彎曲剛性E(s)分別為0.15 gf・cm2 /cm以上且3.0 gf・cm2 /cm以下,E(f)與E(s)之比率E(f)/E(s)為0.3以上且5以下, 該第1劑於30℃下之黏度V(f)與該第2劑於30℃下之黏度V(s)之比V(f)/V(s)為0.5以上且1.5以下, 第2內容器內之第2劑之質量M(s)與第1內容器內之第1劑之質量M(f)之比M(s)/M(f)為0.8以上且未達1.2。 <2>如<1>中所記載之噴霧型染毛用或毛髮脫色用化妝品,其中較佳為第1內容器及第2內容器之最內層之聚烯烴樹脂為聚乙烯樹脂或聚丙烯樹脂。 <3>如<1>或<2>中所記載之噴霧型染毛用或毛髮脫色用化妝品,其中E(f)及E(s)較佳為0.2 gf・cm2 /cm以上,更佳為0.3 gf・cm2 /cm以上,進而較佳為0.4 gf・cm2 /cm以上,進而較佳為0.5 gf・cm2 /cm以上,進而較佳為0.6 gf・cm2 /cm以上,又,較佳為2.8 gf・cm2 /cm以下,更佳為2.5 gf・cm2 /cm以下,進而較佳為2.4 gf・cm2 /cm以下,進而較佳為2.2 gf・cm2 /cm以下,進而較佳為2.0 gf・cm2 /cm以下。 <4>如<1>至<3>中任一項所記載之噴霧型染毛用或毛髮脫色用化妝品,其中E(f)/E(s)較佳為0.4以上,更佳為0.5以上,進而較佳為1.0以上,進而較佳為1.3以上,又,較佳為4.5以下,更佳為4以下,進而較佳為3.33以下,進而較佳為3以下。 <5>如<1>至<4>中任一項所記載之噴霧型染毛用或毛髮脫色用化妝品,其中較佳為構成第1內容器之多層構造之片材具有最外層及中間層,最外層為聚醯胺或聚酯,中間層為金屬箔。 <6>如<1>至<5>中任一項所記載之噴霧型染毛用或毛髮脫色用化妝品,其中較佳為構成第2內容器之多層構造之片材具有最外層及中間層,最外層為聚醯胺或聚酯,中間層為具有氣體阻隔性及耐化學品性之合成樹脂層或二氧化矽蒸鍍層。 <7>如<1>至<6>中任一項所記載之噴霧型染毛用或毛髮脫色用化妝品,其中30℃下之內壓較佳為0.3 MPa以上,更佳為0.4 MPa以上,進而較佳為0.5 MPa以上,又,較佳為0.75 MPa以下,更佳為0.7 MPa以下。 <8>如<1>至<7>中任一項所記載之噴霧型染毛用或毛髮脫色用化妝品,其中V(f)及V(s)分別較佳為8,000 mPa・s以上,更佳為10,000 mPa・s以上,進而較佳為12,000 mPa・s以上,進而較佳為15,000 mPa・s 以上,又,較佳為160,000 mPa・s以下,更佳為120,000 mPa・s以下,進而較佳為100,000 mPa・s以下,進而較佳為80,000 mPa・s以下,進而較佳為50,000 mPa・s以下,進而較佳為45,000 mPa・s以下,進而較佳為40,000 mPa・s以下,進而較佳為35,000 mPa・s以下。 <9>如<1>至<8>中任一項所記載之噴霧型染毛用或毛髮脫色用化妝品,其中V(f)/V(s)較佳為0.55以上,更佳為0.6以上,進而較佳為0.7以上,進而較佳為0.8以上,又,較佳為1.4以下,更佳為1.3以下,進而較佳為1.10以下,進而較佳為1.07以下,進而較佳為1.05以下,進而較佳為1.04以下,進而較佳為1.02以下。 <10>如<1>至<9>中任一項所記載之噴霧型染毛用或毛髮脫色用化妝品,其中第2內容器內之第2劑之質量M(s)與第1內容器內之第1劑之質量M(f)之比M(s)/M(f)較佳為0.85以上,更佳為0.90以上,又,較佳為1.15以下,更佳為1.10以下。 <11>如<1>至<10>中任一項所記載之噴霧型染毛用或毛髮脫色用化妝品,其中較佳為於第1劑、第2劑中之任一者或兩者中進而含有界面活性劑。 <12>如<11>中所記載之噴霧型染毛用或毛髮脫色用化妝品,其中第1劑與第2劑之混合物中之界面活性劑之含量較佳為0.1質量%以上,更佳為0.2質量%以上,進而較佳為0.5質量%以上,又,較佳為30質量%以下,更佳為25質量%以下,進而較佳為20質量%以下,進而較佳為10質量%以下,進而較佳為5質量%以下。 <13>如<1>至<12>中任一項所記載之噴霧型染毛用或毛髮脫色用化妝品,其中較佳為於第1劑、第2劑中之任一者或兩者中進而含有高級醇。 <14>如<13>中所記載之噴霧型染毛用或毛髮脫色用化妝品,其中較佳為高級醇為下述通式(1)所表示者。 R-OH           (1) [式中,R表示碳數12以上且24以下之直鏈或支鏈之烴基] <15>如<14>中所記載之噴霧型染毛用或毛髮脫色用化妝品,其中高級醇較佳為(1a)R為碳數12以上且18以下之直鏈烷基之高級醇與(1b)R為碳數20以上且24以下之直鏈烷基之高級醇之組合,更佳為(1a)R為碳數14以上且18以下之直鏈烷基之高級醇與(1b)R為碳數20以上且22以下之直鏈烷基之高級醇之組合。 <16>如<15>中所記載之噴霧型染毛用或毛髮脫色用化妝品,其中成分(1a)與成分(1b)之質量比[(1a):(1b)]較佳為0.5:9.5~9.5:0.5,更佳為1:9~9:1,進而較佳為1.5:8.5~8.5:1.5,進而較佳為1:4~4:1。 <17>如<13>至<16>中任一項所記載之噴霧型染毛用或毛髮脫色用化妝品,其中第1劑與第2劑之混合物中之高級醇之含量較佳為3質量%以上,更佳為4質量%以上,進而較佳為5質量%以上,又,較佳為12質量%以下,更佳為11質量%以下,進而較佳為10質量%以下,進而較佳為9質量%以下。 <18>如<1>至<17>中任一項所記載之噴霧型染毛用或毛髮脫色用化妝品,其中較佳為於第1劑、第2劑中之任一者或兩者中含有烴。 <19>如<18>中所記載之噴霧型染毛用或毛髮脫色用化妝品,其中第1劑與第2劑之混合物中之烴之含量較佳為1質量%以上,更佳為2質量%以上,進而較佳為3質量%以上,又,較佳為20質量%以下,更佳為15質量%以下,進而較佳為10質量%以下,進而較佳為8質量%以下。 <20>如<1>至<19>中任一項所記載之噴霧型染毛用或毛髮脫色用化妝品,其中較佳為於第1劑、第2劑中之任一者或兩者中含有酯油。 <21>如<20>中所記載之噴霧型染毛用或毛髮脫色用化妝品,其中第1劑與第2劑之混合物中之酯油之含量較佳為0.01質量%以上,更佳為0.03質量%以上,又,較佳為5質量%以下,更佳為3質量%以下,進而較佳為2質量%以下。 <22>如<1>至<21>中任一項所記載之噴霧型染毛用或毛髮脫色用化妝品,其中第1劑中之鹼劑之含量較佳為0.1質量%以上,更佳為0.2質量%以上,進而較佳為0.4質量%以上,又,較佳為14質量%以下,更佳為12質量%以下,進而較佳為8質量%以下。 <23>如<1>至<22>中任一項所記載之噴霧型染毛用或毛髮脫色用化妝品,其中第2劑中之過氧化氫之含量較佳為1質量%以上,更佳為3質量%以上,又,較佳為9質量%以下,更佳為6質量%以下。 [實施例] 其次,對本發明之實施例及比較例進行說明。本發明之技術範圍並不受以下之實施例及比較例限定。 實施例1~45、比較例1~14 根據常用方法,而製備於文末之表6中揭示組成之配方1-1~1-11之第1劑與於表7中揭示組成之配方2-1~2-12之第2劑。該等第1劑與第2劑均為乳化後之乳霜狀製劑。於各表中,表示各成分之含量之數值為於第1劑或第2劑中之質量%單位之數值。 將該等第1劑及第2劑以表1~5所示之組合填充至分離填充、同一加壓噴出型之雙重構造容器之第1內容器及第2內容器中,並進行以下之測定及評價。 [第1內容器及第2內容器之片材] 第1內容器係使用根據最外層/中間層/最內層之順序為PET/Al箔/PE者作為片材。又,第2內容器係使用根據最外層/中間層/最內層之順序為PET/NY/PE者作為片材。再者,使用氮氣作為填充之噴射劑。 [黏度測定] 收容於第1內容器內之第1劑及收容於第2內容器內之第2劑於30℃下之黏度係使用附有螺旋支架之B形黏度計(東機產業公司製造、型號TVB-10R、T-BAR STAGE TS-10)。具體而言,利用切割器切斷外容器,繼而利用剪刀切割第1內容器及第2內容器,並取出第1劑及第2劑。於將所獲得之第1劑及第2劑分別放置1天後,若未達50,000 mPa・s,則設為使用主軸No. M4於30℃下以12 rpm使之旋轉1分鐘後之值,若為50,000 mPa・s 以上,則設為使用主軸No. T-C於30℃下以10 rpm旋轉1分鐘後之值。根據主軸No. M4、T-C之順序進行測定,於顯示未超過範圍而測定到之時刻結束測定,其後之測定不再進行。 又,於各表中,所謂「V(f)/V(s)」係表示藉由上述測定法所測得之第1劑之V(f)與第2劑之黏度V(s)之比率「V(f)/V(s)」之值者。 [初期噴出量] 分別將40 g之表6~7中所記載之乳霜狀之第1劑及第2劑填充至分離填充、同一加壓噴出型之雙重構造容器中。其後,於30℃之恆溫槽中浸漬30分鐘,進行同時噴出第1劑與第2劑之操作5秒鐘,而測定各劑之噴出量。 [等量噴出性] 分別將40 g之表6~7中所記載之乳霜狀之第1劑及第2劑填充至分離填充、同一加壓噴出型之雙重構造容器中。其後,於30℃之恆溫槽中浸漬30分鐘,並反覆進行同時噴出第1劑與第2劑之操作,每次噴出填充有第2劑之40 g之25質量%,測定第1劑之噴出量,於噴出所填充之全部量之時刻停止同時噴出操作。並且,將所測得之第1劑之質量基準之噴出量、與所測得之第1劑之質量基準之噴出量相對於第2劑之質量基準之噴出量的比示於各表之「等量噴出性」之欄。 [剩餘量評價試驗] 分別將40 g(噴出前之質量)之表6~7中所記載之乳霜狀之第1劑及第2劑填充至分離填充、同一加壓噴出型之雙重構造容器中。噴出(全量噴出)收容於容器中之第1劑或第2劑直至無法噴出為止,並對全量噴出後之殘留於內容器內之第1劑及第2劑之質量(全量噴出後之質量)進行測定。具體而言,利用切割器切斷外容器,繼而利用剪刀切割第1內容器及第2內容器,並取出殘留於各內容器內之第1劑及第2劑,再測定質量。針對第1劑及第2劑,藉由下述式計算內容器內之剩餘量比率。 剩餘量比率(%)=(全量噴出後之質量)/(噴出前之質量)×100 [內壓測定] 使用作為儀錶用調節器之WGA-710c(共和電業公司製造)、作為小型壓力轉換器之PGM-10KEZ1(共和電業公司製造)對30℃下之內壓進行測定。將小型壓力轉換機之壓力導入部壓抵於分離填充、同一加壓噴出型之雙重構造容器之外容器之壓桿部位特定時間,將成為固定之值設為內壓。 [彎曲剛性測定] 片材之彎曲剛性係於20℃條件下,使用多功能純彎曲試驗機KES-FB2-S(Kato Tech公司製造)而加以測定。具體而言,將內容器中所使用之多層構造之片材切斷為縱2 cm×橫4 cm之形狀。將該切斷之片材夾於試驗機之固定夾頭與移動夾頭之間。繼而,將試驗機之最大曲率設定為2.5 cm-1 ,將循環數設為2次而進行測定。曲率:根據0.5 cm-1 及1.5 cm-1 時之各值求出彎曲力矩-曲率曲線之斜率,並將該值設為彎曲剛性。 [表1]

Figure 105143502-A0304-0001
[表2]
Figure 105143502-A0304-0002
[表3]
Figure 105143502-A0304-0003
[表4]
Figure 105143502-A0304-0004
[表5]
Figure 105143502-A0304-0005
[表6]
Figure 105143502-A0304-0006
[表7]
Figure 105143502-A0304-0007
Therefore, the present invention relates to a spray-type cosmetic for hair dyeing or hair bleaching, which can use separate filling, the same pressure spray type dual structure container of the first agent and the second agent spray amount from the beginning to the end and with the passage of time Maintain the same amount. The inventors of the present invention conducted diligent studies and found that in cosmetics for hair dyeing or hair bleaching using a dual-structured container with separate filling and the same pressure spray type, the pressure of the propellant and the inner bag material The materials, flexural rigidity and flexural rigidity ratio, and the viscosity ratio of the first agent and the second agent are adjusted to specific ranges respectively, and the same ejection property is achieved from beginning to end over time. In this specification, the "content in the mixture of the first agent and the second agent" refers to the content in the mixture when the first agent and the second agent are accurately mixed at a mass ratio of 1:1 . [Outer Container] The spray type cosmetic for hair dyeing or hair bleaching of the present invention is provided with an outer container that houses a first inner container filled with a first agent containing an alkali agent, and a first inner container filled with hydrogen peroxide. Two doses of the second inner container. The outer container can use metals such as aluminum and tin-plated iron, or synthetic resins such as polyethylene terephthalate and polyarylate. Particularly when a synthetic resin is used as the outer container, it is preferably a synthetic resin material having translucency. Such a synthetic resin outer container can be molded by biaxial stretch blow molding in which one side extends in the axial direction and the other side is blown into the inside to expand it, so that a bottomed cylindrical semi-finished product formed by extrusion molding can be molded. However, it can also be formed by direct blow molding that expands the cylindrical semi-finished product, cuts the lower part, and then forms the bottom. Furthermore, the outer container can also make carbon, alumina, silicon dioxide, etc. into a gas state, and provide a vapor deposition film on the inner surface and/or the outer surface. [Inner container] The inner container in the present invention is formed by laminating a sheet with a polyolefin resin in the innermost layer of a multilayer structure. Examples of the inner container include a bag in which two sheets are stacked, and the edges are bonded by heat welding or ultrasonic welding. As the innermost polyolefin resin, polyethylene resin (PE), polypropylene resin (PP), etc. can be cited. From the viewpoint of the ease of forming the inner bag, the amount of the first and second agents in each inner container is reduced. From the viewpoint of the remaining amount, polyethylene resin is preferred. In the present invention, the bending rigidity E(f) of the sheet material of the first inner container and the bending rigidity E(s) of the sheet material of the second inner container are 0.15 gf·cm 2 /cm or more and 3.0 gf·cm 2 /cm Hereinafter, from the viewpoint of maintaining the ejection amount of the first agent and the second agent at the same amount from beginning to end, and the viewpoint of finally ejecting the first agent and the second agent from each inner container, 0.2 gf·cm 2 /cm Above, more preferably 0.3 gf·cm 2 /cm or more, still more preferably 0.4 gf·cm 2 /cm or more, still more preferably 0.5 gf·cm 2 /cm or more, still more preferably 0.6 gf·cm 2 / cm or more, and from the viewpoint that the inner container follows the deformation following the ejection operation of the content, it is preferably 2.8 gf·cm 2 /cm or less, more preferably 2.5 gf·cm 2 /cm or less, and even more preferred It is 2.4 gf·cm 2 /cm or less, more preferably 2.2 gf·cm 2 /cm or less, and still more preferably 2.0 gf·cm 2 /cm or less. Also, if the ratio E(f)/E(s) of E(f) to E(s) is 0.3 or more and 5 or less, the point of view that the discharge amount of the first agent and the second agent is maintained at the same amount is reduced From the viewpoint of the remaining amount of the first agent and the second agent in each inner container and the viewpoint that the initial discharge amount is excellent, it is preferably 0.4 or more, more preferably 0.5 or more, still more preferably 1.0 or more, and still more preferably 1.3 or more, more preferably 4.5 or less, more preferably 4 or less, still more preferably 3.33 or less, and still more preferably 3 or less. The bending rigidity of the sheet can be measured using a KES (Kawabata Evaluation System) bending tester or the like (for example, a multifunctional pure bending tester KES-FB2-S (manufactured by Kato Tech)). It is preferable that the sheet material of the multilayer structure with the polyolefin resin layer in the innermost layer which comprises a 1st inner container has an outermost layer and an intermediate layer. Examples of the outermost layer include polyamides such as nylon (NY) and polyesters such as polyethylene terephthalate (PET). As the intermediate layer, a metal foil is preferably used, and examples of the metal foil include light metals such as aluminum foil (Al foil). The combination of the outermost layer, middle layer, and innermost layer of the sheet of the first inner container can be appropriately selected according to the content. For example, according to the order of outermost layer/middle layer/innermost layer, PE/Al foil can be listed /PE, PP/Al foil/PE, PET/Al foil/PE, NY/Al foil/PE, etc. In addition, the sheet of the first inner container may have a two-layer structure in which the outermost layer is omitted, or a structure in which four or more layers are further provided with an intermediate layer. The sheet of a multilayer structure having a polyolefin resin layer in the innermost layer of the second inner container is preferable to have the outermost layer and the middle layer from the viewpoint of achieving both moderate bending rigidity and low breakage of the sheet. As the outermost layer, similar to the sheet of the first inner container, polyamides such as nylon (NY) and polyesters such as polyethylene terephthalate (PET) can be cited. As the intermediate layer, a synthetic resin layer with gas barrier properties and chemical resistance such as polyamide such as Eval (EVOH), nylon (NY), etc., or a silicon dioxide (SiOX) layer deposited on the outermost or innermost layer ) And other non-metallic layers such as vapor deposition layer. The combination of the outermost layer, the middle layer, and the innermost layer of the sheet of the second inner container can be appropriately selected according to the content. For example, according to the order of the outermost layer/middle layer/innermost layer, the following can be listed: PE/EVOH/ PE, PP/EVOH/PE, PET/EVOH/PE, PE/NY/PE, PP/NY/PE, PET/NY/PE, PE/SiOX/PE, PP/SiOX/PE, PET/SiOX/PE, PE/Al 2 O 3 /PE etc. From the viewpoint of achieving both ease of formation and low breakage, it is more preferable to use a synthetic resin layer for the intermediate layer. In addition, the sheet of the second inner container may have a two-layer structure omitting the outermost layer, or may have a structure in which four or more layers are optionally provided with a synthetic resin layer or a non-metal gas barrier layer. Moreover, when the outer container is made translucent, it is preferable to make the second inner container translucent. [Internal pressure] The space between the outer container and each inner container is filled with propellant so that the internal pressure at 30°C becomes 0.2 MPa or more and 0.8 MPa or less. Regarding the internal pressure, from the viewpoint of maintaining the ejection amounts of the first agent and the second agent at the same amount from beginning to end, and the viewpoint of reducing the remaining amount of the first agent and the second agent in each inner container, it is preferably 0.3 MPa or more, more preferably 0.4 MPa or more, and still more preferably 0.5 MPa or more. In addition, from the viewpoint of maintaining the ratio of the first agent and the second agent from the beginning to the end, and the viewpoint of suppressing the risk of rupture of the outer container at high temperature , Preferably 0.75 MPa or less, more preferably 0.7 MPa or less. Furthermore, the internal pressure at 30°C can be measured using, for example, a Bourdon tube pressure gauge, a strain gauge pressure gauge, a rapid diaphragm pressure gauge, etc. (specifically, the device described in the examples). Examples of the propellant to be filled include compressed gases such as nitrogen, compressed air, carbon dioxide, and nitrous oxide, and liquefied gases such as liquefied petroleum gas and hydrofluoroolefin. [Viscosity] For each of the viscosity V(f) of the first agent in the first inner container at 30°C and the viscosity of the second agent in the second inner container V(s) at 30°C, decrease The point of view of the remaining amount of the first and second agents in each inner container, the point of view that the initial spray volume is excellent, the point of view of maintaining the spray volume of the first and second parts at the same amount from beginning to end, the preventive agent when applied to the hair From the viewpoint of dripping, it is preferably 8,000 mPa·s or more, more preferably 10,000 mPa·s or more, still more preferably 12,000 mPa·s or more, and still more preferably 15,000 mPa·s or more, in order to reduce the The point of view of the remaining amount of the first and second agents in each inner container, the point of view that the initial spray volume is excellent, the point of view of maintaining the spray volume of the first and second parts at the same amount from the beginning to the end, it is easy to apply to the hair From the viewpoint of uniformity of the agent, it is preferably 160,000 mPa·s or less, more preferably 120,000 mPa·s or less, still more preferably 100,000 mPa·s or less, still more preferably 80,000 mPa·s or less, and still more preferably 50,000 mPa·s or less, more preferably 45,000 mPa·s or less, still more preferably 40,000 mPa·s or less, and still more preferably 35,000 mPa·s or less. Also, if the ratio V(f)/V(s) of V(f) to V(s) is 0.5 or more and 1.5 or less, the point of view that the discharge amount of the first and second agents is maintained at the same amount from beginning to end is reduced From the viewpoint of the remaining amount of the first agent and the second agent in each inner container and the viewpoint that the initial discharge amount is excellent, it is preferably 0.55 or more, more preferably 0.6 or more, still more preferably 0.7 or more, and still more preferably 0.8 or more, more preferably 1.4 or less, more preferably 1.3 or less, still more preferably 1.10 or less, still more preferably 1.07 or less, still more preferably 1.05 or less, still more preferably 1.04 or less, and still more preferably 1.02 the following. The viscosity of the first agent and the second agent at 30℃ can be measured with a B-type viscometer, and the viscosity of the first agent in the first inner container and the second agent in the second inner container at 30℃ Each inner container can be taken out from the outer container, and the first and second doses can be taken out from each inner container, and then measured with a B-type viscometer. Furthermore, specifically, it can measure by the method described in an Example. [Mass ratio] The ratio M(s)/M(f) of the mass M(s) of the second dose in the second inner container to the mass M(f) of the first dose in the first inner container, from beginning to end From the viewpoint of maintaining the ratio of the ejection amount of the first agent to the second agent, it is 0.80 or more, preferably 0.85 or more, more preferably 0.90 or more, and less than 1.2, preferably 1.15 or less, and more preferably 1.10 or less . [Alkaline agent] The first agent contains an alkali agent. Examples of alkaline agents include ammonia and its salts (for example, ammonium bicarbonate); alkanolamines such as monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, 2-aminobutanol, and the like Salts; 1,3-propanediamine and other alkane diamines and their salts; carbonates such as guanidine carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. These alkaline agents may be used in combination of two or more kinds. Regarding the content of the alkali agent in the first agent, from the viewpoint of sufficiently swelling the hair to obtain a hair dyeing effect, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.4% by mass or more In addition, from the viewpoint of reducing hair damage or scalp irritation, it is preferably 14% by mass or less, more preferably 12% by mass or less, and still more preferably 8% by mass or less. Regarding the content of the alkali agent in the mixture of the first agent and the second agent, from the viewpoint of sufficient hair dyeing effect, it is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.2% by mass % Or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and from the viewpoint of reducing hair damage or scalp irritation, it is preferably 7% by mass or less, more preferably 6% by mass or less , More preferably, it is 5 mass% or less, More preferably, it is 4 mass% or less. [Hydrogen peroxide] The second agent contains hydrogen peroxide. Regarding the content of hydrogen peroxide in the second agent, from the viewpoint of decomposing melanin in hair and ensuring the coupling reaction of oxidation dyes to obtain sufficient hair dyeing effect, it is preferably 1% by mass or more, more preferably 3% by mass Above, from the viewpoint of reducing hair damage or scalp irritation, it is preferably 9% by mass or less, and more preferably 6% by mass or less. Regarding the content of hydrogen peroxide in the mixture of the first agent and the second agent, it is preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 6% by mass or less, more preferably 5% by mass the following. [Surfactant] A surfactant may be contained in either or both of the first agent and the second agent. Examples of the surfactant include cationic surfactants, nonionic surfactants, amphoteric surfactants, and anionic surfactants. Among them, from the viewpoint of the stability of the formulation composition, anionic surfactants and nonionic surfactants are preferred. Examples of anionic surfactants include alkylbenzene sulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or Unsaturated fatty acid salts, alkyl ether carboxylates, alkenyl ether carboxylates, α-sulfo fatty acid salts, N-amino acid salts, phosphoric acid mono- or diesters, sulfosuccinates, etc. Examples of alkyl ether sulfates include polyoxyethylene alkyl ether sulfates. The counter ions of the anionic groups of the anionic surfactants include: alkali metal ions such as sodium ions and potassium ions; alkaline earth metal ions such as calcium ions and magnesium ions; ammonium ions; Alkanolamine salt of 3-alkanol group (for example, monoethanolamine salt, diethanolamine salt, triethanolamine salt, triisopropanolamine salt, etc.). As a cationic surfactant, from the viewpoint of imparting excellent touch to the hair after dyeing, monoalkyltrimethylammonium chloride, dialkyldimethylammonium chloride, and monoalkyl bromide are preferred. Trimethylammonium chloride, among them, more preferred are Steartrimonium chloride, Cetrimonium chloride, Lauryl Trimonium chloride (Lauryl Trimonium chloride) chloride), it is also preferable to mix two or more kinds. Examples of nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, higher fatty acid sucrose esters, polyglycerin fatty acid esters, higher fatty acid mono- or diethanolamides, and polyoxyalkylene ethers. Ethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, alkyl sugar, alkyl amine oxide, alkyl amine amine oxide, etc. Among these, polyoxyalkylene alkyl ether, polyoxyethylene hydrogenated castor oil, and alkyl sugar are preferred, and polyoxyethylene alkyl (12-14) ether and alkyl polyglucoside are more preferred. Examples of the amphoteric surfactant include imidazoline, carbonyl betaine, amide betaine, sultaine, hydroxy sultaine, amide sultaine, etc., more preferably alkyl dimethyl amine group Betaine surfactants such as betaine acetate and fatty amidopropyl betaine are more preferably fatty amidopropyl betaine. These surfactants can be used alone or in combination of two or more. Regarding the content of the surfactant in the mixture of the first agent and the second agent, from the viewpoint of good touch and emulsification performance, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and more preferably It is 0.5% by mass or more, and from the viewpoint of obtaining a sufficient hair dyeing effect, it is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, and still more preferably 10 Mass% or less, more preferably 5 mass% or less. [Higher alcohol] A higher alcohol may be contained in either or both of the first agent and the second agent. As the higher alcohol, those represented by the following general formula (1) can be used. R-OH (1) [In the formula, R represents a linear or branched hydrocarbon group with a carbon number of 12 or more and 24 or less] As higher alcohols, there may be exemplified: lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, Isostearyl alcohol, arachidyl alcohol, behenyl alcohol, tetracosanol, oleyl alcohol, etc. Higher alcohols can be used alone or in combination of two or more kinds. Regarding higher alcohols, from the viewpoint of suppressing the change in viscosity with the passage of time, (1a) those in which R in the above general formula (1) is a linear alkyl group having 12 or more and 18 or less carbon atoms and (1b) R in the above general formula (1) is a combination of linear alkyl groups having 20 or more and 24 carbon atoms, more preferably (1a) R in the above general formula (1) is a combination of 14 or more and 18 carbon atoms A combination of a linear alkyl group and (1b) a combination of a linear alkyl group having a carbon number of 20 or more and 22 or less as R in the general formula (1). Regarding the mass ratio of component (1a) to component (1b) [(1a): (1b)], from the viewpoint of suppressing the change in viscosity over time, it is preferably 0.5:9.5 to 9.5:0.5, more preferably 1:9-9:1, more preferably 1.5:8.5-8.5:1.5, still more preferably 1:4-4:1. Regarding the content of the higher alcohol in the mixture of the first agent and the second agent, the viscosity immediately after production is set to an appropriate range as a hair dye, and the viscosity change over time is suppressed. It is preferably 3% by mass or more, more preferably 4% by mass or more, and still more preferably 5% by mass or more, and from the viewpoint of suppressing the change in viscosity over time, it is preferably 12% by mass or less, and more preferably 11% by mass or less, more preferably 10% by mass or less, and still more preferably 9% by mass or less. [Hydrocarbon] A hydrocarbon may be contained in either or both of the first agent and the second agent. Hydrocarbons can be used alone or in combination of two or more kinds. Examples of the hydrocarbon of the present invention include liquid paraffin, liquid isoalkane, light isoalkane, light liquid isoalkane, heavy liquid isoalkane, squalane, and the like. Among them, from the viewpoint of suppressing the change in viscosity with the passage of time, liquid paraffin is preferred. Regarding the content of hydrocarbons in the mixture of the first agent and the second agent, from the viewpoint of improving the brightness after dyeing or hair bleaching, it is preferably 1% by mass or more, more preferably 2% by mass or more, and more It is preferably 3% by mass or more, more preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and still more preferably 8% by mass or less. [Ester oil] Ester oil may be contained in either or both of the first agent and the second agent. Ester oil can be used alone or in combination of two or more kinds. Examples of the ester oil of the present invention include octyl dodecyl myristate, isopropyl myristate, isopropyl isostearate, isononyl isononanoate, and isononyl isononanoate. Esters, butyl stearate, oleyl oleate, octyl dodecyl ricinoleate, neopentyl glycol dicaprate, diisostearyl malate, octyl hydroxystearate, Australian walnut oil , Olive oil, castor oil, jojoba oil, avocado oil, sunflower oil, polyglyceryl diisostearate, polyglyceryl triisostearate, glyceryl diisostearate, glyceryl triisostearate Fatty acid esters, triglycerides (caprylic acid/capric acid), triglycerides (2-ethylhexanoate), pentaerythritol tetracaprylate, etc. Among them, from the viewpoint of higher emulsification stability, isopropyl myristate, isopropyl isostearate, and diisostearyl malate, which are branched alcohol esters of saturated fatty acids, are preferred. , Isononyl isononanoate, isotridecanyl isononanoate, 2-ethylhexyl palmitate, octyl dodecyl myristate, octyl dodecyl oleate, octyl ten erucic acid Dialkyl esters and so on. Regarding the content of the ester oil in the mixture of the first agent and the second agent, from the viewpoint of improving the brightness after dyeing or hair bleaching, it is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and From the viewpoint of sufficient spreading properties of the mixture on the hair, it is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 2% by mass or less. [Organic solvent] An organic solvent may be contained in either or both of the first agent and the second agent. Examples of organic solvents include lower alkanols such as ethanol, 1-propanol, and 2-propanol; aromatic alcohols such as benzyl alcohol, 2-benzyloxyethanol, and phenoxyethanol; propylene glycol, 1,3-butane Alcohol, diethylene glycol, glycerin and other polyols; ethoxyethanol, ethoxydiethylene glycol, methoxyethanol and other ether alcohols; N-methylpyrrolidone, N-ethylpyrrolidone, etc. N -Alkylpyrrolidone; alkyl diesters such as propylene carbonate; lactones such as γ-valerolactone and γ-caprolactone. These organic solvents can be used singly or in combination of two or more, and their content in the mixture of the first agent and the second agent prevents oxidation dyes from the mixture of the first agent and the second agent From the standpoint of precipitation, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more, and from the standpoint of preventing separation of the mixture into water-based and oil-based layers, it is more Preferably it is 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably 10% by mass or less . [Dyes] When the spray-type hair dyeing or hair bleaching cosmetics of the present invention are hair dyeing cosmetics, the first agent contains an oxidation dye intermediate or a direct dye. (Oxidation Dye Intermediate) As the oxidation dye intermediate, known precursors and couplers commonly used in hair dyeing agents can be used. Examples of precursors include p-phenylenediamine, toluene-2,5-diamine, o-chlorop-phenylenediamine, N-phenylp-phenylenediamine, N,N-bis(hydroxyethyl)p-benzene Diamine, 3-methyl-4-aminophenol, 2-hydroxyethyl p-phenylenediamine, p-aminophenol, p-methylaminophenol, 4-amino m-cresol, o-aminophenol, and Such salt, etc. Furthermore, as the coupler, for example, resorcinol, 2-methylresorcinol, 1-naphthol, 1,5-dihydroxynaphthalene, 5-amino o-cresol, m-phenylenediamine, O-aminophenol, m-aminophenol, p-aminophenol, 2,4-diaminophenoxyethanol, 2,6-diaminopyridine, 2-methyl-5-hydroxyethylaminophenol, 2-amino-3-hydroxypyridine, and their salts, etc. The precursor and the coupler can be used individually or in combination of two or more. The content of the precursor and coupler in the first agent is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and, It is preferably 5% by mass or less, and more preferably 4% by mass or less. (Direct Dyes) Examples of direct dyes include acid dyes, nitro dyes, disperse dyes, and basic dyes. More specifically, examples of acid dyes include: Blue No. 1, Purple No. 401, Black No. 401, Orange No. 205, Red No. 227, Red No. 106, Yellow No. 202 (1), Yellow No. 202 ( 2) Yellow No. 203, Acid Orange 3, etc., as nitro dyes, include: 2-nitro-p-phenylenediamine, 2-amino-6-chloro-4-nitrophenol, 3-nitro-p-hydroxy Ethylaminophenol, 4-nitro o-phenylenediamine, 4-amino-3-nitrophenol, 4-hydroxypropylamino-3-nitrophenol, HC blue 2, HC orange 1, HC red 1. HC yellow 2, HC yellow 4, HC yellow 5, HC red 3, N,N-bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine, etc. As disperse dyes, examples include: disperse violet 1. Disperse Blue 1, Disperse Black 9, etc. Basic dyes include: Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Red 76, Basic Yellow 76, Basic Orange 31, Alkali Sex red 51 and so on. The direct dye may be used alone, or in combination of two or more kinds, or may be used in combination with an oxidation dye intermediate. The content of the direct dye in the first agent is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, more preferably 5% by mass or less, and more preferably 3% by mass or less. [Other optional ingredients] In addition to the above-mentioned ingredients, other ingredients commonly used as raw materials for cosmetics may be added to the first or second agent of the spray-type hair dyeing or hair bleaching cosmetics of the present invention. Examples of such optional ingredients include oils, silicones, non-volatile hydrophilic solvents, animal and vegetable fats and oils, natural or synthetic polymers, ethers, protein derivatives, hydrolyzed proteins, amino acids, preservatives , Chelating agents, stabilizers, antioxidants, plant extracts, crude drug extracts, vitamins, fragrances, UV absorbers, etc. [pH value] The pH value (25°C) of the first agent is preferably 8 or more and 12 or less. From the viewpoint of the stability of hydrogen peroxide, the pH value (25°C) of the second agent is preferably 2 or more and 5 or less. Furthermore, regarding the pH value (25°C) of the mixture of the first agent and the second agent during use, from the viewpoint of swelling the hair and obtaining a sufficient hair dyeing effect, it is preferably 8.0 or more, more preferably 8.5 or more It is more preferably 9.0 or more, and from the viewpoint of preventing scalp irritation, it is preferably 11.5 or less, more preferably 11.0 or less, and still more preferably 10.5 or less. Furthermore, the pH value in the present invention is a value measured at room temperature (25°C) using a pH meter F-22 manufactured by Horiba Manufacturing Co., Ltd. [Hair dyeing tool] The spray-type hair dyeing or hair bleaching cosmetics of the present invention can be applied to hair using a hair dyeing tool. As the hair dyeing tool, a hair dyeing tool provided with a comb and a bristle part as described in Japanese Patent Laid-Open No. 10-71020, or a hair dyeing tool provided with a comb as described in Japanese Patent Laid-Open No. 2006-326081 can be used And the hair dyeing tool with the bristles part of the concave part for the retaining agent. [Dosage Form] The dosage forms of the first and second agents can be cream, gel, paste, or the like. [Method for hair dyeing or hair bleaching] The spray-type hair dyeing or hair bleaching cosmetic of the present invention sprays the first and second agents into a pre-prepared mixing tray, using, for example, Japanese Patent Laid-Open No. 10-71020 After mixing the first agent and the second agent in the bristles part of the hair dyeing tool described in the bulletin, the obtained mixture is applied to the hair to dye or decolor the hair. In addition, the spray-type cosmetic for hair dyeing or hair bleaching of the present invention sprays the first agent and the second agent into the recesses of the hair portion of the hair dyeing tool as described in Japanese Patent Laid-Open No. 2006-326081, and The bristles can be directly applied to the hair, and the first agent and the second agent can be mixed on the hair while being spread on the whole hair to dye or bleach the hair. Regarding the embodiments described above, the following further discloses the preferred aspects of the present invention. <1> A spray-type cosmetic for hair dyeing or hair bleaching, which is provided with an outer container that contains a first inner container filled with a first agent containing an alkali agent, and a first inner container filled with hydrogen peroxide Both the second inner container of the second agent and the space between the outer container and each inner container are filled with a propellant so that the internal pressure at 30°C becomes 0.2 MPa or more and 0.8 MPa or less, The first inner container and the second inner container are formed by laminating sheets with a polyolefin resin layer in the innermost layer, respectively. The bending rigidity E(f) of the sheet of the first inner container and the second content The bending rigidity E(s) of the sheet material of the device is 0.15 gf·cm 2 /cm or more and 3.0 gf·cm 2 /cm or less, the ratio of E(f) to E(s) is E(f)/E(s) ) Is 0.3 or more and 5 or less, the ratio V(f)/V(s) of the viscosity V(f) of the first agent at 30°C to the viscosity V(s) of the second agent at 30°C is 0.5 Above and below 1.5, the ratio M(s)/M(f) of the mass M(s) of the second dose in the second inner container to the mass M(f) of the first dose in the first inner container is 0.8 or more And it did not reach 1.2. <2> The spray-type hair dyeing or hair bleaching cosmetics as described in <1>, in which it is preferable that the innermost polyolefin resin of the first inner container and the second inner container is polyethylene resin or polypropylene Resin. <3> The spray type hair dyeing or hair bleaching cosmetics as described in <1> or <2>, wherein E(f) and E(s) are preferably 0.2 gf·cm 2 /cm or more, more preferably 0.3 gf·cm 2 /cm or more, more preferably 0.4 gf·cm 2 /cm or more, still more preferably 0.5 gf·cm 2 /cm or more, still more preferably 0.6 gf·cm 2 /cm or more, and , Preferably 2.8 gf·cm 2 /cm or less, more preferably 2.5 gf·cm 2 /cm or less, still more preferably 2.4 gf·cm 2 /cm or less, still more preferably 2.2 gf·cm 2 /cm or less , And more preferably 2.0 gf·cm 2 /cm or less. <4> The spray-type hair dyeing or hair bleaching cosmetics as described in any one of <1> to <3>, wherein E(f)/E(s) is preferably 0.4 or more, more preferably 0.5 or more , More preferably 1.0 or more, still more preferably 1.3 or more, more preferably 4.5 or less, more preferably 4 or less, still more preferably 3.33 or less, and still more preferably 3 or less. <5> The spray-type cosmetics for hair dyeing or hair bleaching as described in any one of <1> to <4>, wherein it is preferable that the sheet of the multilayer structure constituting the first inner container has an outermost layer and an intermediate layer , The outermost layer is polyamide or polyester, and the middle layer is metal foil. <6> The spray type cosmetics for hair dyeing or hair bleaching as described in any one of <1> to <5>, wherein it is preferable that the sheet of the multilayer structure constituting the second inner container has an outermost layer and an intermediate layer , The outermost layer is polyamide or polyester, and the middle layer is a synthetic resin layer or silicon dioxide vapor deposition layer with gas barrier and chemical resistance. <7> The spray-type hair dyeing or hair bleaching cosmetics as described in any one of <1> to <6>, wherein the internal pressure at 30°C is preferably 0.3 MPa or more, more preferably 0.4 MPa or more, It is more preferably 0.5 MPa or more, more preferably 0.75 MPa or less, and more preferably 0.7 MPa or less. <8> The spray-type hair dyeing or hair bleaching cosmetics as described in any one of <1> to <7>, wherein V(f) and V(s) are each preferably 8,000 mPa·s or more, and more It is preferably 10,000 mPa·s or more, more preferably 12,000 mPa·s or more, still more preferably 15,000 mPa·s or more, more preferably 160,000 mPa·s or less, more preferably 120,000 mPa·s or less, and more It is preferably 100,000 mPa·s or less, more preferably 80,000 mPa·s or less, still more preferably 50,000 mPa·s or less, still more preferably 45,000 mPa·s or less, still more preferably 40,000 mPa·s or less, and more Preferably, it is 35,000 mPa·s or less. <9> The spray-type hair dyeing or hair bleaching cosmetics as described in any one of <1> to <8>, wherein V(f)/V(s) is preferably 0.55 or more, more preferably 0.6 or more , More preferably 0.7 or more, still more preferably 0.8 or more, more preferably 1.4 or less, more preferably 1.3 or less, still more preferably 1.10 or less, still more preferably 1.07 or less, and still more preferably 1.05 or less, It is more preferably 1.04 or less, and still more preferably 1.02 or less. <10> The spray-type hair dyeing or hair bleaching cosmetics described in any one of <1> to <9>, wherein the mass M(s) of the second agent in the second inner container and the first inner container The ratio M(s)/M(f) of the mass M(f) of the first agent in the inside is preferably 0.85 or more, more preferably 0.90 or more, more preferably 1.15 or less, and more preferably 1.10 or less. <11> The spray-type hair dyeing or hair bleaching cosmetics as described in any one of <1> to <10>, wherein it is preferably used in either or both of the first agent and the second agent It also contains a surfactant. <12> The spray type cosmetics for hair dyeing or hair bleaching as described in <11>, wherein the content of the surfactant in the mixture of the first agent and the second agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, more preferably 0.5% by mass or more, more preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, and still more preferably 10% by mass or less, More preferably, it is 5 mass% or less. <13> The spray-type hair dyeing or hair bleaching cosmetics as described in any one of <1> to <12>, wherein it is preferably in one or both of the first and second agents It also contains higher alcohols. <14> The spray type cosmetics for hair dyeing or hair bleaching as described in <13>, in which the higher alcohol is preferably represented by the following general formula (1). R-OH (1) [In the formula, R represents a linear or branched hydrocarbon group with a carbon number of 12 or more and 24 or less] <15> The spray-type hair dyeing or hair bleaching cosmetics as described in <14>, Among them, the higher alcohol is preferably a combination of (1a) a higher alcohol in which R is a linear alkyl group with a carbon number of 12 or more and 18 or less and (1b) a higher alcohol in which R is a linear alkyl group with a carbon number of 20 or more and 24 or less, More preferably, it is a combination of (1a) a higher alcohol in which R is a linear alkyl group having a carbon number of 14 or more and 18 or less, and (1b) a higher alcohol in which R is a linear alkyl group having a carbon number of 20 or more and 22 or less. <16> The spray type cosmetics for hair dyeing or hair bleaching as described in <15>, wherein the mass ratio of ingredient (1a) to ingredient (1b) [(1a):(1b)] is preferably 0.5:9.5 ~9.5:0.5, more preferably 1:9-9:1, still more preferably 1.5:8.5-8.5:1.5, still more preferably 1:4-4:1. <17> The spray-type hair dyeing or hair bleaching cosmetics as described in any one of <13> to <16>, wherein the content of higher alcohol in the mixture of the first agent and the second agent is preferably 3 mass % Or more, more preferably 4% by mass or more, still more preferably 5% by mass or more, more preferably 12% by mass or less, more preferably 11% by mass or less, still more preferably 10% by mass or less, and still more preferably It is 9% by mass or less. <18> The spray-type hair dyeing or hair bleaching cosmetics as described in any one of <1> to <17>, wherein it is preferably in either or both of the first and second agents Contains hydrocarbons. <19> The spray-type cosmetics for hair dyeing or hair bleaching as described in <18>, wherein the hydrocarbon content in the mixture of the first agent and the second agent is preferably 1% by mass or more, more preferably 2% by mass % Or more, more preferably 3% by mass or more, more preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and still more preferably 8% by mass or less. <20> The spray-type hair dyeing or hair bleaching cosmetics as described in any one of <1> to <19>, wherein it is preferably used in either or both of the first agent and the second agent Contains ester oil. <21> The spray type cosmetics for hair dyeing or hair bleaching as described in <20>, wherein the content of the ester oil in the mixture of the first agent and the second agent is preferably 0.01% by mass or more, more preferably 0.03 Mass% or more, more preferably 5 mass% or less, more preferably 3 mass% or less, and still more preferably 2 mass% or less. <22> The spray-type hair dyeing or hair bleaching cosmetics as described in any one of <1> to <21>, wherein the content of the alkali agent in the first agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, more preferably 0.4% by mass or more, more preferably 14% by mass or less, more preferably 12% by mass or less, and still more preferably 8% by mass or less. <23> The spray-type hair dyeing or hair bleaching cosmetics as described in any one of <1> to <22>, wherein the content of hydrogen peroxide in the second agent is preferably 1% by mass or more, more preferably It is 3% by mass or more, more preferably 9% by mass or less, and more preferably 6% by mass or less. [Examples] Next, examples and comparative examples of the present invention will be described. The technical scope of the present invention is not limited by the following Examples and Comparative Examples. Examples 1 to 45, Comparative Examples 1 to 14 According to common methods, the first agent of the formula 1-1 to 1-11 with the composition disclosed in Table 6 at the end of the article and the formula 2-1 with the composition disclosed in Table 7 were prepared ~ The second dose of 2-12. The first and second agents are both emulsified cream preparations. In each table, the value indicating the content of each ingredient is the value in units of mass% in the first or second agent. The first and second agents were filled with the combinations shown in Tables 1 to 5 into the first and second inner containers of a separate-filled, double-structured container of the same pressure ejection type, and the following measurements were made And evaluation. [Sheets of the first inner container and the second inner container] The first inner container uses PET/Al foil/PE according to the order of the outermost layer/middle layer/innermost layer as the sheet material. In addition, the second inner container uses PET/NY/PE in the order of the outermost layer/middle layer/innermost layer as a sheet. Furthermore, nitrogen is used as the propellant for filling. [Viscosity measurement] The viscosity of the first agent contained in the first inner container and the second agent contained in the second inner container at 30°C was measured using a B-shaped viscometer with a screw holder (manufactured by Toki Sangyo Co., Ltd.) , Model TVB-10R, T-BAR STAGE TS-10). Specifically, the outer container is cut with a cutter, and then the first inner container and the second inner container are cut with scissors, and the first dose and the second dose are taken out. After leaving the obtained first and second doses for 1 day, if it does not reach 50,000 mPa·s, set it as the value after rotating it with spindle No. M4 at 30°C and 12 rpm for 1 minute. If it is 50,000 mPa·s or more, set the value after using the spindle No. TC to rotate at 30°C and 10 rpm for 1 minute. The measurement is performed in the order of spindle No. M4, TC, and the measurement is ended when the display does not exceed the range and the measurement is completed, and subsequent measurements will not be performed. In addition, in each table, the so-called "V(f)/V(s)" means the ratio of the V(f) of the first agent and the viscosity of the second agent V(s) measured by the above-mentioned measurement method The value of "V(f)/V(s)". [Initial discharge amount] Each of 40 g of the cream-like first agent and the second agent described in Tables 6 to 7 was filled into a separate-filled, double-structured container of the same pressure discharge type. After that, it was immersed in a thermostat at 30°C for 30 minutes, and the operation of simultaneously spraying the first agent and the second agent was performed for 5 seconds, and the spray amount of each agent was measured. [Equivalent sprayability] Each of 40 g of the cream-like first agent and the second agent described in Tables 6 to 7 was filled into a separate filling, double-structured container of the same pressure spray type. After that, it was immersed in a constant temperature bath at 30°C for 30 minutes, and the operation of simultaneously spraying the first and second agents was repeated, each spraying 25% by mass filled with 40 g of the second agent, and measuring the first agent The ejection amount, the simultaneous ejection operation is stopped at the moment when all the filled amount is ejected. In addition, the ratio of the measured ejection amount on the mass basis of the first dose and the measured ejection amount on the mass basis of the first dose to the ejection amount of the second dose on the mass basis is shown in each table " Equal sprayability" column. [Remaining amount evaluation test] Each of 40 g (mass before spraying) of the cream-like first part and second part described in Tables 6 to 7 was filled into a separate filling, double-structured container of the same pressure spray type in. Spray (full volume spray) the first or second dose contained in the container until it cannot be sprayed, and the mass of the first and second dose remaining in the inner container after the full volume is sprayed (the mass after full spray) Perform the measurement. Specifically, the outer container is cut with a cutter, and then the first inner container and the second inner container are cut with scissors, and the first and second agents remaining in each inner container are taken out, and the mass is measured. For the first dose and the second dose, the ratio of the remaining amount in the inner container was calculated by the following formula. Remaining amount ratio (%) = (mass after full volume ejection)/(mass before ejection) × 100 [Internal pressure measurement] Use WGA-710c (manufactured by Kyowa Electric Co., Ltd.) as a meter regulator, as a small pressure conversion PGM-10KEZ1 (manufactured by Kyowa Electric Co., Ltd.) was used to measure the internal pressure at 30°C. The pressure introduction part of the small pressure conversion machine is pressed against the pressure rod part of the container outside the double structure container of separate filling and the same pressure ejection type for a specific time, and the internal pressure is set to a fixed value. [Measurement of Flexural Rigidity] The flexural rigidity of the sheet was measured at 20°C using a multifunctional pure bending tester KES-FB2-S (manufactured by Kato Tech). Specifically, the multilayer structure sheet used in the inner container was cut into a shape of 2 cm in length × 4 cm in width. Clamp the cut sheet between the fixed chuck and the moving chuck of the testing machine. Then, the maximum curvature of the testing machine was set to 2.5 cm -1 , and the number of cycles was set to 2 for measurement. Curvature: Calculate the slope of the bending moment-curvature curve based on the values at 0.5 cm -1 and 1.5 cm -1 , and set this value as the bending rigidity. [Table 1]
Figure 105143502-A0304-0001
[Table 2]
Figure 105143502-A0304-0002
[table 3]
Figure 105143502-A0304-0003
[Table 4]
Figure 105143502-A0304-0004
[table 5]
Figure 105143502-A0304-0005
[Table 6]
Figure 105143502-A0304-0006
[Table 7]
Figure 105143502-A0304-0007

Claims (17)

一種噴霧型染毛用或毛髮脫色用化妝品,其具備如下外容器,該外容器收納填充有含有鹼劑之第1劑之第1內容器、及填充有含有過氧化氫之第2劑之第2內容器之兩者,並且於該外容器與各內容器之間之空間中,以30℃下之內壓成為0.2MPa以上且0.8MPa以下之方式填充有噴射劑,該第1內容器及第2內容器分別係貼合最內層具有聚烯烴樹脂層之多層構造之片材而形成,該第1內容器之片材之彎曲剛性E(f)及該第2內容器之片材之彎曲剛性E(s)分別為0.15gf‧cm2/cm以上且3.0gf‧cm2/cm以下,E(f)與E(s)之比率E(f)/E(s)為0.4以上且4以下,該第1劑於30℃下之黏度V(f)與該第2劑於30℃下之黏度V(s)之比V(f)/V(s)為0.55以上且1.4以下,第2內容器內之第2劑之質量M(s)與第1內容器內之第1劑之質量M(f)之比M(s)/M(f)為0.8以上且未達1.2。 A spray-type cosmetic for hair dyeing or hair bleaching, comprising an outer container containing a first inner container filled with a first agent containing an alkaline agent and a second agent filled with a second agent containing hydrogen peroxide 2 Two of the inner containers, and the space between the outer container and each inner container is filled with propellant so that the internal pressure at 30° C. becomes 0.2 MPa or more and 0.8 MPa or less, the first inner container and The second inner container is formed by laminating sheets with a multi-layer structure with a polyolefin resin layer in the innermost layer. The bending rigidity E(f) of the sheet of the first inner container and the thickness of the sheet of the second inner container are Bending rigidity E(s) is 0.15gf‧cm 2 /cm or more and 3.0gf‧cm 2 /cm or less, the ratio of E(f) to E(s) E(f)/E(s) is 0.4 or more and 4 or less, the ratio V(f)/V(s) of the viscosity V(f) of the first agent at 30°C to the viscosity V(s) of the second agent at 30°C is 0.55 or more and 1.4 or less, The ratio M(s)/M(f) of the mass M(s) of the second dose in the second inner container to the mass M(f) of the first dose in the first inner container is 0.8 or more and less than 1.2. 如請求項1之噴霧型染毛用或毛髮脫色用化妝品,其中第1內容器及第2內容器之最內層之聚烯烴樹脂為聚乙烯樹脂。 Such as the spray-type cosmetics for hair dyeing or hair bleaching of claim 1, wherein the innermost polyolefin resin of the first inner container and the second inner container is polyethylene resin. 如請求項1或2之噴霧型染毛用或毛髮脫色用化妝品,其中上述V(f)及上述黏度V(s)分別為8,000mpa‧s以上且160,000mpa‧s以下。 Such as the spray-type hair dyeing or hair bleaching cosmetics of claim 1 or 2, wherein the above-mentioned V(f) and the above-mentioned viscosity V(s) are respectively 8,000mpa‧s or more and 160,000mpa‧s or less. 如請求項1或2之噴霧型染毛用或毛髮脫色用化妝品,其中進而於第1 劑及/或第2劑中含有界面活性劑。 Such as the spray-type hair dyeing or hair bleaching cosmetics of claim 1 or 2, in which the first The agent and/or the second agent contains a surfactant. 如請求項4之噴霧型染毛用或毛髮脫色用化妝品,其中第1劑與第2劑之混合物中之界面活性劑之含量為0.1質量%以上且30質量%以下。 The spray-type cosmetics for hair dyeing or hair bleaching according to claim 4, wherein the content of the surfactant in the mixture of the first agent and the second agent is 0.1% by mass to 30% by mass. 如請求項1或2之噴霧型染毛用或毛髮脫色用化妝品,其中進而於第1劑及/或第2劑中含有高級醇。 The spray-type hair dyeing or hair bleaching cosmetic of claim 1 or 2, which further contains a higher alcohol in the first agent and/or the second agent. 如請求項6之噴霧型染毛用或毛髮脫色用化妝品,其中高級醇為下述通式(1)所表示者,R-OH (1)[式中,R表示碳數12以上且24以下之直鏈或支鏈之烴基]。 The spray type cosmetics for hair dyeing or hair bleaching according to claim 6, wherein the higher alcohol is represented by the following general formula (1), R-OH (1) [where, R represents a carbon number of 12 or more and 24 or less The straight or branched chain hydrocarbon group]. 如請求項6之噴霧型染毛用或毛髮脫色用化妝品,其中第1劑與第2劑之混合物中之高級醇之含量為3質量%以上且12質量%以下。 The spray-type cosmetic for hair dyeing or hair bleaching according to claim 6, wherein the content of the higher alcohol in the mixture of the first agent and the second agent is 3% by mass or more and 12% by mass or less. 如請求項1或2之噴霧型染毛用或毛髮脫色用化妝品,其中E(f)及E(s)為0.6gf‧cm2/cm以上且2.0gf‧cm2/cm以下。 For the spray-type hair dyeing or hair bleaching cosmetics of claim 1 or 2, where E(f) and E(s) are 0.6gf‧cm 2 /cm or more and 2.0gf‧cm 2 /cm or less. 如請求項1或2之噴霧型染毛用或毛髮脫色用化妝品,其中E(f)/E(s)為0.5以上且3以下。 The spray type cosmetics for hair dyeing or hair bleaching according to claim 1 or 2, wherein E(f)/E(s) is 0.5 or more and 3 or less. 如請求項1或2之噴霧型染毛用或毛髮脫色用化妝品,其中V(f)/V(s) 為0.6以上且1.4以下。 The spray-type hair dyeing or hair bleaching cosmetics of claim 1 or 2, where V(f)/V(s) It is 0.6 or more and 1.4 or less. 如請求項1或2之噴霧型染毛用或毛髮脫色用化妝品,其中於第1劑、第2劑中之任一者或兩者中進而含有烴。 According to claim 1 or 2, the spray-type cosmetic for hair dyeing or hair bleaching, which further contains a hydrocarbon in either or both of the first agent and the second agent. 如請求項12之噴霧型染毛用或毛髮脫色用化妝品,其中第1劑與第2劑之混合物中之烴之含量為1質量%以上且20質量%以下。 The spray type cosmetics for hair dyeing or hair bleaching according to claim 12, wherein the hydrocarbon content in the mixture of the first agent and the second agent is 1% by mass or more and 20% by mass or less. 如請求項1或2之噴霧型染毛用或毛髮脫色用化妝品,其中進而於第1劑、第2劑中之任一者或兩者中含有酯油。 According to claim 1 or 2, the spray-type cosmetic for hair dyeing or hair bleaching, which further contains ester oil in either or both of the first agent and the second agent. 如請求項14之噴霧型染毛用或毛髮脫色用化妝品,其中第1劑與第2劑之混合物中之酯油之含量為0.01質量%以上且5質量%以下。 The spray type cosmetics for hair dyeing or hair bleaching according to claim 14, wherein the content of the ester oil in the mixture of the first agent and the second agent is 0.01% by mass to 5% by mass. 如請求項1或2之噴霧型染毛用或毛髮脫色用化妝品,其中第1劑中之鹼劑之含量為0.1質量%以上且14質量%以下。 The spray-type cosmetic for hair dyeing or hair bleaching of claim 1 or 2, wherein the content of the alkali agent in the first agent is 0.1% by mass or more and 14% by mass or less. 如請求項1或2之噴霧型染毛用或毛髮脫色用化妝品,其中第2劑中之過氧化氫之含量為1質量%以上且9質量%以下。Such as the spray type cosmetics for hair dyeing or hair bleaching of claim 1 or 2, wherein the content of hydrogen peroxide in the second agent is 1% by mass or more and 9% by mass or less.
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