WO2018062803A1 - Capsules comprising pigments, and method for producing same - Google Patents

Capsules comprising pigments, and method for producing same Download PDF

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Publication number
WO2018062803A1
WO2018062803A1 PCT/KR2017/010589 KR2017010589W WO2018062803A1 WO 2018062803 A1 WO2018062803 A1 WO 2018062803A1 KR 2017010589 W KR2017010589 W KR 2017010589W WO 2018062803 A1 WO2018062803 A1 WO 2018062803A1
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WIPO (PCT)
Prior art keywords
pigment
capsule
polymer
solvent
formulation
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PCT/KR2017/010589
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French (fr)
Korean (ko)
Inventor
이연
이현석
최선경
김용진
이존환
김은정
Original Assignee
주식회사 아모레퍼시픽
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Priority claimed from KR1020170123425A external-priority patent/KR102370803B1/en
Application filed by 주식회사 아모레퍼시픽 filed Critical 주식회사 아모레퍼시픽
Priority to US16/338,392 priority Critical patent/US11234910B2/en
Priority to JP2019516999A priority patent/JP7063889B2/en
Priority to CN201780061051.7A priority patent/CN109843247B/en
Priority to EP17856689.9A priority patent/EP3520767A4/en
Publication of WO2018062803A1 publication Critical patent/WO2018062803A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11—Encapsulated compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin

Definitions

  • the present invention relates to a capsule containing a pigment, and a method for manufacturing the same, and more particularly, to include a pigment that may be discolored by an external environment therein, while blocking the pigment from the external environment, while being easily broken and developed when applied to the skin.
  • This relates to capsules that can occur, and methods of making them.
  • Pigments are very important in the field of cosmetics where it may be desirable to alter skin and hair color for aesthetic purposes.
  • the capsules applied to cosmetics should be easily destroyed by pressure when the user is applied to the skin for use, the pigment contained in the capsule should be able to be easily expressed.
  • the pigment can be effectively blocked from the external environment, so it has excellent storage durability and color concealment, and is easily destroyed by pressing, rubbing, wiping or rubbing with a hand or a tool (cotton cloth, sponge, paper, brush, etc.).
  • a capsule that can allow the pigment contained in to sufficiently develop color.
  • the inventors found that the capsule is stable at high temperatures and is not easily broken in the formulation process, so that the pigment remains stable in the formulation before use, but when the formulation is applied to the skin, the capsule is broken and color development occurs.
  • a spherical capsule structure in which silica and pigment were mixed using a polymer was developed.
  • an object of the present invention is to provide a capsule structure containing a pigment, wherein the coloring of the pigment can occur only upon application of the skin while protecting the pigment from the external environment to ensure the stability of the pigment.
  • the present invention is a pigment capsule containing a pigment, the capsule is the inside of the silica, pigments and titanium dioxide pigment is dispersed and the outside covered with a polymer binder having a glass transition temperature of 130 °C or more. It also provides a pigment capsule, characterized in that the C 3 -C 9 trivalent carboxylic acid is contained in the capsule, and a method for producing the same.
  • the capsule of the present invention can completely block the pigment from the external environment, thereby solving the problem of the instability of the pigment to the environment, the capsule is stable in the formulation process, but when applied to the skin to rub or rub with a hand or tool It can be easily broken by the color development.
  • the color of the pigment is blocked by the color in the product does not appear, but after the application to the skin color development occurs may cause interest in the use of the product.
  • FIG. 1 is an image of a capsule (a) containing a pigment prepared according to the present invention and a state in which the capsule is broken by rubbing the capsule with a finger (b) with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • Figure 4 shows the capsule state after the heat treatment for 1 hour in an oven 100 °C capsules prepared by varying the polymer content and pigment (SEM).
  • Figure 5 shows the capsule state after heat-treating the capsule (Examples 1 to 3) prepared by varying the polymer content and the pigment for 24 hours at 100 °C oven (SEM).
  • Figure 6 is to rub the capsules (Examples 1 to 3) prepared by varying the polymer content and pigment by hand 1, 3 or 7 times, and then check whether the capsule is broken (SEM).
  • Figure 7 shows that after the formulation test when the lipstick formulation was made, the capsules remained unbroken (SEM).
  • Figure 10 shows the appearance of the formulation including the pigment capsule according to the citric acid content.
  • Figure 11 shows the degree of color change of the dye according to the citric acid content ((1) ethanol alone; (2) ethanol + citric acid 0.01g; (3) ethanol + citric acid 0.05g; (4) ethanol + citric acid 0.1g; ( 5) ethanol + 1 g).
  • the present invention provides a pigment capsule containing a pigment, wherein the inside of the capsule is dispersed with silica, a dye and a titanium dioxide pigment, and the outside of the capsule is covered with a polymer binder, and a method for producing the same.
  • the pigment capsule of the present invention is characterized in that it retains stability when formulated or stored in the formulated product, but has physical properties that are broken by the pressure applied to the skin.
  • the pigment capsule of the present invention has an average diameter of 10 to 15 ⁇ m, preferably 10 to 12 ⁇ m, especially when pressed, rubbed, wiped or rubbed with a small pressure, that is, generally by hand or a tool (cotton, sponge, brush, etc.). By the pressure applied, the pigment capsule according to the invention can be easily broken, ruptured, dissolved or disintegrated.
  • fumed silica (silica dimethyl silylate) is used as the silica.
  • the present invention uses a polymer binder, the pigment and silica are dispersed therein, Provided is a capsule in which a barrier to the outside is formed.
  • the makeup cosmetic composition is often subjected to a high temperature in the formulation process, especially the lip makeup composition such as lipstick is mainly formulated at a high temperature (for example, 95 °C or more) due to the nature of the raw material mixing process, capsules It is very important to ensure thermal stability. Therefore, in the present invention, a polymer binder having a glass transition temperature (Tg) of 130 ° C or higher is used.
  • Tg glass transition temperature
  • the pigment capsule of the present invention is intended to prevent the discoloration of the pigment in the capsule until the user uses the product, the discoloration of the pigment should not occur by the polymer used.
  • the polymer binder used in the present invention should be such that discoloration of the dye does not occur while the glass transition temperature is high (130 ° C or higher).
  • acrylate copolymers in particular polymethacrylate copolymers, are used in the present invention, preferably acrylic acid and acrylate copolymers, more preferably acrylic acid and methacrylate copolymers, particularly meta Krylic acid and methacrylate copolymers are used.
  • the polymer binder used in the present invention can be used up to 90% by weight based on the total weight of the capsule.
  • the content of silica, titanium dioxide and pigments is relatively low, so that the shape of the capsule is not spherical and is distorted, and also does not break when rubbed by hand. Therefore, in consideration of this point, the content of the polymer binder is preferably 5 to 20% by weight, more preferably 10 to 20% by weight based on the total weight of the capsule.
  • the dyes used in the present invention are not particularly limited in kinds such as water-soluble dyes, oil-soluble dyes, for example, the following pigments may be used:
  • Organic pigments such as azo, anthraquinone, indigo, xanthene, pyrene, quinoline, triphenylmethane and fluorane pigments;
  • Sodium, potassium, calcium, barium, aluminum, zirconium of acid-based dyes such as azo, anthraquinone, indigo, xanthene, pyrene, quinoline, triphenylmethane and fluorane pigments.
  • Insoluble salts of strontium and titanium, these pigments may comprise at least one carboxyl or sulfonic acid group.
  • organic pigments those having the following trade names may be mentioned:
  • the pigment capsule according to the present invention such as the oil-soluble dye Red 27 shows a difference in color expression in the humidity change and alkali conditions can also be used a pigment with low stability.
  • the pigment may be used up to 90% by weight based on the total weight of the capsule.
  • the content of the polymer binder that forms the outer capsules is relatively low, and thus the pigment cannot be completely protected from the external environment, and thus the stability of the pigment may be a problem. Therefore, in consideration of this point, the content of the pigment may be supported in an amount of preferably 0.00001 to 50% by weight, preferably 10 to 50% by weight based on the total weight of the capsule.
  • the pigment capsule of the present invention contains a C 3 -C 9 trivalent carboxylic acid, preferably citric acid, propionic acid, iso-citric acid, aconic acid, tricarvallic acid, and trimesic acid.
  • a C 3 -C 9 trivalent carboxylic acid preferably citric acid, propionic acid, iso-citric acid, aconic acid, tricarvallic acid, and trimesic acid.
  • the trivalent carboxylic acid of C 3 -C 9 does not change the appearance color of the capsule by preventing the discoloration of the pigment, especially if it is an amount that satisfies the pH criteria of the composition when formulated as a lip makeup cosmetic composition It is not limited and may be preferably added in an amount of 1 to 20% by weight, preferably 1 to 5% by weight based on the total weight of the capsule. If less than 1% by weight is insufficient to prevent discoloration phenomenon of the pigment, if it exceeds 20% by weight the difference in effect according to the increase in content.
  • the present invention provides a method of making a pigment capsule comprising a pigment, the method comprising the following steps:
  • the step of dissolving the polymeric binder and the dye is carried out in different solvents so that both the polymeric binder and the dye can be completely dissolved to a sufficient degree, preferably to a degree of 100%, without causing the pigment to develop. Each of them is dissolved and then mixed.
  • polymer binder and the dye used in the present invention those described above may be used.
  • the solvent for dissolving the polymer binder is an organic solvent, preferably one selected from the group consisting of C 1 -C 4 lower alcohols (eg, methanol, ethanol, isopropanol, butanol, etc.), acetone, and mixtures thereof.
  • C 1 -C 4 lower alcohols eg, methanol, ethanol, isopropanol, butanol, etc.
  • acetone and mixtures thereof.
  • the above organic solvent or a mixture of the above organic solvent and water for example methanol, methanol / water 97: 3, ethanol, ethanol / water 6: 4, isopropanol, isopropanol / water 97: 3, isopropanol / water 6: 4, N Butanol, acetone, acetone / water 97: 3, acetone / water 6: 4, acetone / isopropanol 4: 6 may be used, more preferably ethanol or acetone.
  • a chlorine-containing hydrocarbon organic solvent preferably chloroform, dichloromethane (DCM), and more preferably dichloromethane (DCM) may be used as a solvent for dissolving the dye.
  • the ratio of solvent for dissolving the polymeric binder to solvent for dissolving the pigment is about 3: 7.
  • the use ratio of the solvent is less than about 3: 7 (e.g., 1: 9, 2: 8, etc.)
  • the polymer binder precipitates
  • the use ratio of the solvent is greater than about 3: 7 (e.g., , 4: 6, 5: 5, 9: 1, etc.), which may cause discoloration of the pigment, which is not preferable.
  • C 3 -C 9 trivalent carboxylic acid preferably citric acid, propionic acid, or tricarvallic acid
  • the pH inside the capsule can be maintained under acidic conditions to prevent discoloration of the pigment due to contact with the alkaline oil.
  • the trivalent carboxylic acid of C 3 -C 9 is not particularly limited as long as it does not change the appearance color of the capsule to prevent discoloration of the pigment, preferably 1 to 20% by weight relative to the total weight of the capsule Can be added. If less than 1% by weight is insufficient to prevent discoloration phenomenon of the pigment, if more than 5% by weight is the difference in effect according to the increase in content.
  • Spray drying can be carried out under the following conditions: Feed rate—40 L / min air supply to the air nozzle, 100 g / min dispersion supply; Environmental conditions-dispersion (reaction liquid) temperature 25 °C, spray dryer input temperature 80 °C, spray dryer discharge temperature 60 °C. At this time, spray drying may be performed while continuously stirring the polymer mixed solution through a stirrer.
  • the pigment capsule prepared according to the present invention blocks the pigment from the external environment, prevents the coloring of the pigment from occurring prior to application of the final product such as cosmetics to the skin, and also includes titanium dioxide for the pigment in the pigment capsule. This makes it possible to mask the color inherent in the pigment, making the color of the formulation itself close to colorless. In other words, it is possible to cause fun and interest in make-up by applying a colorless product to the skin when it is applied.
  • Red 27 Lake (20 g, 10%) is dispersed in dichloromethane (DCM, 1580 mL).
  • Citric acid (10 g, 5%) is dissolved in ethanol (402 mL) warmed to 60 ° C. and then the polymer binder, acrylate copolymer (Eudragit® L 100, manufactured by Evonik Co .; 20 g, 10%) is dissolved.
  • the volume ratio of ethanol used to dissolve the polymeric binder excluding the volume of ethanol used to dissolve citric acid
  • dichloromethane used to dissolve the pigment is 3: 7.
  • the mixed dispersion of citric acid and acrylate copolymer is cooled to below 25 ° C. and mixed with Red 27 Lake solution.
  • a pigment capsule was prepared in the same manner as in Example 1, except that 40 g (20%) of the acrylate copolymer was used.
  • a pigment capsule was prepared in the same manner as in Example 1, except that 40 g (20%) of acrylate copolymer was used and 100 g (50%) of Red 27 Lake was used.
  • Red 27 Lake 60 g, 30% is dispersed in dichloromethane (DCM, 1580 mL).
  • Citric acid (10 g, 5%) is dissolved in ethanol (402 mL) warmed to 60 ° C. and then the polymer binder, acrylate copolymer (Eudragit® L 100, manufactured by Evonik Co .; 20 g, 10%) is dissolved.
  • the volume ratio of ethanol used to dissolve the polymeric binder excluding the volume of ethanol used to dissolve citric acid
  • dichloromethane used to dissolve the pigment is 3: 7.
  • the mixed dispersion of citric acid and acrylate copolymer is cooled to below 25 ° C. and mixed with Red 27 Lake solution.
  • Red 27 Lake 60 g, 30% is dispersed in dichloromethane (DCM, 1580 mL).
  • Citric acid (15 g, 7.5%) is dissolved in ethanol (402 mL) warmed to 60 ° C. and then the polymer binder, acrylate copolymer (Eudragit® L 100, manufactured by Evonik Co .; 30 g, 15%) is dissolved.
  • the volume ratio of ethanol used to dissolve the polymeric binder excluding the volume of ethanol used to dissolve citric acid
  • dichloromethane used to dissolve the pigment is 3: 7.
  • the mixed dispersion of citric acid and acrylate copolymer is cooled to below 25 ° C. and mixed with Red 27 Lake solution.
  • Red 27 Lake (40 g, 20%) is dispersed in dichloromethane (DCM, 1580 mL).
  • Citric acid (10 g, 5%) is dissolved in ethanol (402 mL) warmed to 60 ° C. and then the polymer binder, acrylate copolymer (Eudragit® L 100, manufactured by Evonik Co .; 30 g, 15%) is dissolved.
  • the volume ratio of ethanol used to dissolve the polymeric binder excluding the volume of ethanol used to dissolve citric acid
  • dichloromethane used to dissolve the pigment is 3: 7.
  • the mixed dispersion of citric acid and acrylate copolymer is cooled to below 25 ° C. and mixed with Red 27 Lake solution.
  • Silica AEROSIL® R972, manufactured by Evonik Cod; 100g, 50%
  • TiO 2 Purolan® E 171 A, LANXESS; 20g, 10%
  • the dispersion vessel is placed in an ultrasonic disperser bath and dispersed for 30 minutes using a disperser. It is dried and encapsulated using a spray dryer (DJE-FCNM 020R, Dongjin Co., Ltd. product; capacity: 10 kg / hr (based on H 2 O)).
  • Red 27 Lake (40 g, 20%) is dispersed in dichloromethane (DCM, 1580 mL).
  • Citric acid (15 g, 7.5%) is dissolved in ethanol (402 mL) warmed to 60 ° C. and then the polymer binder, acrylate copolymer (Eudragit® L 100, manufactured by Evonik Co .; 30 g, 15%) is dissolved.
  • the volume ratio of ethanol used to dissolve the polymeric binder excluding the volume of ethanol used to dissolve citric acid
  • dichloromethane used to dissolve the pigment is 3: 7.
  • the mixed dispersion of citric acid and acrylate copolymer is cooled to below 25 ° C. and mixed with Red 27 Lake solution.
  • Silica AEROSIL® R972, product of Evonik Co .; 85g, 42.5%) and TiO 2 (Purolan® E 171 A, product of LANXESS; 30g, 15%) are added to the mixed dispersion and dispersed as follows.
  • the dispersion vessel is placed in an ultrasonic disperser bath and dispersed for 30 minutes using a disperser. It is dried and encapsulated using a spray dryer (DJE-FCNM 020R, Dongjin Co., Ltd. product; capacity: 10 kg / hr (based on H 2 O)).
  • the capsules prepared in Examples and Comparative Examples were observed by scanning electron microscopy (SEM) (FIG. 1).
  • Figure 1 (a) is an image of observing the capsule carrying a pigment.
  • spray drying method it was possible to encapsulate the pigment in silica and encapsulate the outside of the pigment in a manner surrounded by the polymer, and it can be confirmed that the polymer is formed of the porous polymer through the SEM image shown in FIG. have.
  • make-up cosmetics in particular lip makeup cosmetics are manufactured at a high temperature, it was confirmed whether the capsule maintains stability at high temperatures.
  • Examples 1 to 3 varying the polymer content and the pigment content (each, 10% polymer content + 10% pigment content, 20% polymer content + 10% pigment content, 20% polymer content + 50% pigment content, respectively) )
  • Capsules were heat-treated in an oven at 100 ° C. for 1 hour or 24 hours, and then the capsules were observed under a scanning electron microscope (SEM). The observation results are presented in Table 1, FIG. 4 (one hour heat treatment) and FIG. 5 (24 hour heat treatment).
  • the pigment capsules prepared according to the present invention are all stable when the polymer is heat-treated at 100 ° C. for 1 hour or 24 hours.
  • the hardness (breakability) of the pigment capsule according to the present invention was confirmed by the following method.
  • Examples 1 to 3 varying the polymer content and the pigment content (each, 10% polymer content + 10% pigment content, 20% polymer content + 10% pigment content, 20% polymer content + 50% pigment content, respectively) ) was rubbed 1, 3 or 7 times by hand, and then the capsule was checked for cracking. At this time, whether it was broken was confirmed by SEM.
  • Ethyl cellulose or iron oxide-supported silica was used as a kind of polymer, and it was confirmed that the capsule was not broken even by rubbing seven times with a hand (see FIG. 8).
  • Lipstick formulations containing pigment capsules according to the invention were prepared in the compositions of Table 3 below.
  • Formulation (a) contains unencapsulated Red 27, and formulations (b) through (d) contain encapsulated Red 27, formulation (b) 10% Red 27 + 5% polymer, formulation (c ) 10% Red 27 + 5% polymer + 1% citric acid, formulation (d) contains 10% Red 27 + 5% polymer + 5% citric acid.
  • Formulation (a) Formulation (b) Formulation (c) Formulation (d) Polyethylene 15.0 15.0 15.0 15.0 Distearyl malate 30.0 30.0 30.0 30.0 vaseline 20.0 20.0 20.0 20.0 20.0 Caprylic / Capric Triglycerides 15.0 15.0 15.0 15.0 Red 27 0.1 - - - capsule - 1.0 1.0 1.0 1.0
  • the appearance color can be adjusted to be almost colorless as shown in FIGS. 9 (c) and 9 (d).
  • the content of citric acid is 5 wt. It can be seen that the optimization condition is set to%.
  • Lipstick formulations containing pigment capsules according to the invention were prepared in the compositions of Table 4 below.
  • Formulation (a) is the capsule of Example 4
  • formulation (b) is the capsule of Example 5
  • formulation (c) is the capsule of Example 6
  • formulation (d) is the capsule of Example 7.
  • Formulation (a) Formulation (b) Formulation (c) Formulation (d) Polyethylene 15.0 15.0 15.0 15.0 Distearyl malate 30.0 30.0 30.0 30.0 vaseline 20.0 20.0 20.0 20.0 20.0 Caprylic / Capric Triglycerides 15.0 15.0 15.0 15.0 Red 27 0.1 - - - capsule - 1.0 1.0 1.0 1.0
  • Formulation 1 Formulation 2
  • Formulation 3 Polyethylene 15.0 15.0 15.0 Distearyl malate 30.0 30.0 30.0 vaseline 20.0 20.0 20.0
  • Caprylic / Capric Triglycerides 15.0 15.0 15.0 RED 7 LAKE (CI 15850: 1) 2.0 2.0 2.0 YELLOW 6 LAKE (CI 15985) 3.5 3.5 3.5 IRON OXIDES (CI 77491) 3.5 3.5 3.5 Red 27 - - 0.1 capsule - 1.0 -
  • the formulation containing the encapsulated pigment according to the present invention (Formulation 2) is the same as the appearance color of the control lipstick (Formulation 1) that does not contain any pigment, while the color development on the skin is not encapsulated Red 27 It can be seen that it is very excellent in the same manner as the formulation containing the pigment (Formulation 3).

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Abstract

The present invention relates to capsules comprising pigments and a method for producing same and, more specifically, to: capsules which comprise therein pigments, which may discolor due to an external environment, and thereby isolate the pigments from the external environment and, when applied to the skin, easily break and allow for color formation; and a method for producing said capsules.

Description

색소를 포함하는 캡슐, 및 이의 제조 방법Capsules containing a pigment, and a method for producing the same
본 발명은 색소를 포함하는 캡슐, 및 이의 제조 방법에 관한 것으로서, 보다 상세하게는 외부 환경에 의해 변색가능성이 있는 색소를 내부에 포함하여 색소를 외부 환경과 차단시키면서, 피부에 도포시 쉽게 깨져 발색이 일어날 수 있는 캡슐, 및 이의 제조 방법에 관한 것이다.The present invention relates to a capsule containing a pigment, and a method for manufacturing the same, and more particularly, to include a pigment that may be discolored by an external environment therein, while blocking the pigment from the external environment, while being easily broken and developed when applied to the skin. This relates to capsules that can occur, and methods of making them.
색소는 미적 목적을 위해 피부 및 모발 색상을 변경하는 것이 바람직할 수 있는 화장품 분야에서 매우 중요하다.Pigments are very important in the field of cosmetics where it may be desirable to alter skin and hair color for aesthetic purposes.
그러나, 화장품에 사용되는 일부 색소는 다양한 환경이 요구되는 화장품에 적용시 염료 자체가 가지는 불안정한 성질로 인하여 제형화 과정에서 이미 변색이 되거나, 빛에 대한 안정성이 약하다는 문제를 가지며, 이러한 문제를 해결하기 위하여, 에멀젼화, 캡슐화 등 여러 가지 방법이 개발되어 왔다.However, some pigments used in cosmetics have a problem that they are already discolored in the formulation process or have poor stability to light due to the unstable properties of the dye itself when applied to cosmetics that require a variety of environments, and solves these problems. To this end, various methods such as emulsification and encapsulation have been developed.
한편, 화장품에 적용되는 캡슐은 그 사용 용도상 사용자가 피부에 도포하면 압력에 의해 쉽게 파괴되어 캡슐 내부에 포함되어 있는 색소가 용이하게 발현이 될 수 있어야 한다.On the other hand, the capsules applied to cosmetics should be easily destroyed by pressure when the user is applied to the skin for use, the pigment contained in the capsule should be able to be easily expressed.
즉, 색소를 외부 환경으로부터 효과적으로 차단시킬 수 있어 저장내구성, 색상 은폐력 등이 우수하면서, 손이나 도구(면포, 스폰지, 종이, 브러쉬 등)로 누르기, 비비기, 닦기 또는 문지르기에 의해 용이하게 파괴되어 내부에 포함되어 있는 색소가 충분히 발색할 수 있게 할 수 있는 캡슐에 대한 필요성이 존재한다.In other words, the pigment can be effectively blocked from the external environment, so it has excellent storage durability and color concealment, and is easily destroyed by pressing, rubbing, wiping or rubbing with a hand or a tool (cotton cloth, sponge, paper, brush, etc.). There is a need for a capsule that can allow the pigment contained in to sufficiently develop color.
본 발명자는 상기한 문제점을 해결하기 위하여, 캡슐이 고온에서 안정적이고, 제형화 과정에서 용이하게 깨지지 않아 사용 전의 제형 중에서는 색소가 안정적으로 유지되나, 제형을 피부에 도포시 캡슐이 깨져서 발색이 일어날 수 있게 하기 위하여 고분자를 바인더로 사용하여 실리카와 색소가 혼합된 구형의 캡슐 구조체를 개발하였다.In order to solve the above problems, the inventors found that the capsule is stable at high temperatures and is not easily broken in the formulation process, so that the pigment remains stable in the formulation before use, but when the formulation is applied to the skin, the capsule is broken and color development occurs. In order to make it possible, a spherical capsule structure in which silica and pigment were mixed using a polymer was developed.
따라서, 본 발명은 색소를 외부 환경으로부터 보호하여 색소의 안정성을 확보하면서, 색소의 발색이 피부 도포시에만 일어날 수 있게 하는, 색소를 포함하는 캡슐 구조체를 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide a capsule structure containing a pigment, wherein the coloring of the pigment can occur only upon application of the skin while protecting the pigment from the external environment to ensure the stability of the pigment.
상기한 목적을 달성하기 위하여, 본 발명은 색소를 포함하는 색소 캡슐로서, 상기 캡슐은 실리카, 색소 및 이산화티타늄 안료가 분산되어 있는 내부와, 유리 전이 온도가 130℃ 이상인 고분자 바인더로 덮여 있는 외부를 가지고, 상기 캡슐의 내부에 C3-C9 3가 카르복실산이 포함되어 있는 것을 특징으로 하는 색소 캡슐, 및 이의 제조방법을 제공한다.In order to achieve the above object, the present invention is a pigment capsule containing a pigment, the capsule is the inside of the silica, pigments and titanium dioxide pigment is dispersed and the outside covered with a polymer binder having a glass transition temperature of 130 ℃ or more. It also provides a pigment capsule, characterized in that the C 3 -C 9 trivalent carboxylic acid is contained in the capsule, and a method for producing the same.
본 발명의 캡슐은 색소를 외부 환경으로부터 완벽하게 차단하여, 환경에 대한 색소의 불안정성 문제를 해결할 수 있고, 제형화 과정에서는 캡슐이 안정적이지만, 피부에 도포시에는 손이나 도구로 비비거나 문지르는 힘에 의하여 용이하게 깨져 발색이 쉽게 일어날 수 있다.The capsule of the present invention can completely block the pigment from the external environment, thereby solving the problem of the instability of the pigment to the environment, the capsule is stable in the formulation process, but when applied to the skin to rub or rub with a hand or tool It can be easily broken by the color development.
또한, 색소의 발색을 차단하여 제품 내에서는 색소에 의한 색상이 나타나지 않지만, 피부에 도포가 이루어진 후에 발색이 일어나게 되어 제품의 사용시 흥미를 유발할 수 있다.In addition, the color of the pigment is blocked by the color in the product does not appear, but after the application to the skin color development occurs may cause interest in the use of the product.
도 1은 본 발명에 따라서 제조한 색소를 포함한 캡슐(a) 및 상기 캡슐을 손가락으로 문질러서 캡슐을 깨뜨린 상태(b)를 주사전자현미경(SEM)으로 촬영한 이미지이다.1 is an image of a capsule (a) containing a pigment prepared according to the present invention and a state in which the capsule is broken by rubbing the capsule with a finger (b) with a scanning electron microscope (SEM).
도 2는 EDX 매핑을 통해 고분자 캡슐에 포함된 Si, Ti, O, Br 원소가 고르게 분포되어 있음을 나타내는 것이다.2 shows that the Si, Ti, O, Br elements in the polymer capsule are evenly distributed through EDX mapping.
도 3은 사용한 고분자의 종류 및 용매와의 비율에 따라서 색소의 발색이 일어나는지 여부, 고분자의 침전 여부를 확인한 것이다((1) 에틸셀룰로스 4cps, (2) 에틸셀룰로스 100cps, (3) 에틸셀룰로스 300cps, (4) PVP Mw=55000, (5) PVP Mw=360000, (6) PCL, (7) PLA, (8) 가교된 PMMA).Figure 3 is a check whether the color development of the pigment occurs according to the type of the polymer used and the ratio of the solvent, whether the polymer precipitated ((1) ethyl cellulose 4cps, (2) ethyl cellulose 100cps, (3) ethyl cellulose 300cps, (4) PVP Mw = 55000, (5) PVP Mw = 360000, (6) PCL, (7) PLA, (8) crosslinked PMMA).
도 4는 고분자 함량과 색소를 달리하여 제조한 캡슐(실시예 1 내지 3)을 오븐 100℃에서 1시간 열처리한 다음의 캡슐 상태를 나타내는 것이다(SEM).Figure 4 shows the capsule state after the heat treatment for 1 hour in an oven 100 ℃ capsules prepared by varying the polymer content and pigment (SEM).
도 5는 고분자 함량과 색소를 달리하여 제조한 캡슐(실시예 1 내지 3)을 오븐 100℃에서 24시간 열처리한 다음의 캡슐 상태를 나타내는 것이다(SEM).Figure 5 shows the capsule state after heat-treating the capsule (Examples 1 to 3) prepared by varying the polymer content and the pigment for 24 hours at 100 ℃ oven (SEM).
도 6은 고분자 함량과 색소를 달리하여 제조한 캡슐(실시예 1 내지 3)을 손으로 1번, 3번 또는 7번 문지른 다음, 캡슐이 깨졌는지 여부를 확인한 것이다(SEM).Figure 6 is to rub the capsules (Examples 1 to 3) prepared by varying the polymer content and pigment by hand 1, 3 or 7 times, and then check whether the capsule is broken (SEM).
도 7은 립스틱 제형을 만들었을 때 제형 테스트한 후 캡슐이 깨지지 않고 그대로 유지됨을 확인한 것이다(SEM).Figure 7 shows that after the formulation test when the lipstick formulation was made, the capsules remained unbroken (SEM).
도 8은 고분자 종류를 바꾸거나 캡슐 외곽을 바꾸었을 때 캡슐의 깨짐성을 확인한 것이다(SEM). 여기서, B.의 (a)는 산화철을 담지한 다공성 실리카를 문지르기 전의 이미지이고, (b)는 7번 문지른 후의 이미지이다. 8 is to confirm the breakage of the capsule when changing the polymer type or the capsule outer periphery (SEM). Here, (a) of B. is an image before rubbing porous silica carrying iron oxide, and (b) is an image after rubbing seven times.
도 9는 다양한 조성의 색소 캡슐을 포함한 제형의 외관을 나타내는 것이다.9 shows the appearance of formulations containing pigment capsules of various compositions.
도 10은 시트르산 함량에 따른 색소 캡슐을 포함한 제형의 외관을 나타내는 것이다.Figure 10 shows the appearance of the formulation including the pigment capsule according to the citric acid content.
도 11은 시트르산 함량에 따른 색소의 색상 변화 정도를 나타내는 것이다((1) 에탄올 단독; (2) 에탄올 + 시트르산 0.01g; (3) 에탄올 + 시트르산 0.05g; (4) 에탄올 + 시트르산 0.1g; (5) 에탄올 + 1g).Figure 11 shows the degree of color change of the dye according to the citric acid content ((1) ethanol alone; (2) ethanol + citric acid 0.01g; (3) ethanol + citric acid 0.05g; (4) ethanol + citric acid 0.1g; ( 5) ethanol + 1 g).
도 12는 색소 캡슐 또는 캡슐화하지 않은 색소의 포함에 따른 제형의 외관을 나타내는 것이다.12 shows the appearance of a formulation with the inclusion of a pigment capsule or an unencapsulated pigment.
본 발명은 색소를 포함하는 색소 캡슐로서, 캡슐의 내부는 실리카, 색소 및 이산화티타늄 안료가 분산되어 있고, 캡슐의 외곽은 고분자 바인더로 덮여 있는 색소 캡슐, 및 이의 제조 방법을 제공한다.The present invention provides a pigment capsule containing a pigment, wherein the inside of the capsule is dispersed with silica, a dye and a titanium dioxide pigment, and the outside of the capsule is covered with a polymer binder, and a method for producing the same.
특히, 본 발명의 색소 캡슐은 제형화 시 또는 제형화된 제품의 보관시에는 안정성을 유지하지만, 피부에 도포하는 순간의 압력에 의해 깨지는 물성을 가지는 것을 특징으로 한다.In particular, the pigment capsule of the present invention is characterized in that it retains stability when formulated or stored in the formulated product, but has physical properties that are broken by the pressure applied to the skin.
본 발명의 색소 캡슐은 평균 직경이 10~15μm, 바람직하게는 10~12μm이며, 특히 작은 압력, 즉 일반적으로 손이나 도구(면포, 스폰지, 브러쉬 등)로 누르기, 비비기, 닦기 또는 문지르기를 할 때에 가해지는 압력에 의해 본 발명에 따른 색소 캡슐은 용이하게 파괴, 파열, 용해 또는 붕해될 수 있다.The pigment capsule of the present invention has an average diameter of 10 to 15 µm, preferably 10 to 12 µm, especially when pressed, rubbed, wiped or rubbed with a small pressure, that is, generally by hand or a tool (cotton, sponge, brush, etc.). By the pressure applied, the pigment capsule according to the invention can be easily broken, ruptured, dissolved or disintegrated.
본 발명에서 실리카로는 특히 퓸드 실리카(실리카 디메틸 실릴레이트)가 사용된다. In the present invention, in particular, fumed silica (silica dimethyl silylate) is used as the silica.
또한, 색소를 외부 환경으로부터 보다 완벽하게 차단시키고, 물리적 안정성의 확보를 위해 캡슐의 경도를 증가시키기 위하여, 본 발명은 고분자 바인더를 사용함으로써, 내부에 색소와 실리카가 분산되어 있으며, 고분자 바인더에 의해 외부와의 차단막이 형성되어 있는 캡슐을 제공한다.In addition, in order to more completely block the pigment from the external environment, and to increase the hardness of the capsule to secure physical stability, the present invention uses a polymer binder, the pigment and silica are dispersed therein, Provided is a capsule in which a barrier to the outside is formed.
메이크업 화장료 조성물은 제형화 공정상 고온이 가해지게 되는 경우가 많으며, 특히 립스틱과 같은 립 메이크업용 조성물은 원료 혼합 공정의 특성상 주로 고온(예를 들어, 95℃ 이상)에서 제형화가 이루어지게 되므로, 캡슐의 열적 안정성을 확보하는 것이 매우 중요하다. 따라서, 본 발명에서 고분자 바인더로는 유리 전이 온도(Tg)가 130℃ 이상인 것이 사용된다.The makeup cosmetic composition is often subjected to a high temperature in the formulation process, especially the lip makeup composition such as lipstick is mainly formulated at a high temperature (for example, 95 ℃ or more) due to the nature of the raw material mixing process, capsules It is very important to ensure thermal stability. Therefore, in the present invention, a polymer binder having a glass transition temperature (Tg) of 130 ° C or higher is used.
또한, 본 발명의 색소 캡슐은 사용자가 제품을 사용하기 전까지 캡슐 내 색소의 변색이 일어나지 않게 하는 것을 목적으로 하므로, 사용되는 고분자에 의해 색소의 변색이 일어나서는 안된다.In addition, since the pigment capsule of the present invention is intended to prevent the discoloration of the pigment in the capsule until the user uses the product, the discoloration of the pigment should not occur by the polymer used.
따라서, 본 발명에서 사용되는 고분자 바인더는 유리 전이 온도가 높으면서(130℃ 이상), 색소의 변색이 일어나지 않게 하는 것이이야 한다. 이러한 조건을 만족시키기 위하여 본 발명에서는 아크릴레이트 코폴리머, 특히 폴리메타크릴레이트계 코폴리머가 사용되며, 바람직하게는 아크릴산과 아크릴레이트 코폴리머, 보다 바람직하게는 아크릴산과 메타크릴레이트 코폴리머, 특히 메타크릴산과 메타크릴레이트 코폴리머가 사용된다. Therefore, the polymer binder used in the present invention should be such that discoloration of the dye does not occur while the glass transition temperature is high (130 ° C or higher). In order to satisfy these conditions, acrylate copolymers, in particular polymethacrylate copolymers, are used in the present invention, preferably acrylic acid and acrylate copolymers, more preferably acrylic acid and methacrylate copolymers, particularly meta Krylic acid and methacrylate copolymers are used.
본 발명에서 사용되는 고분자 바인더는 캡슐 총 중량에 대하여 최대 90중량%까지 사용이 가능하다. 그러나, 고분자 바인더를 다량으로 사용하게 되면, 상대적으로 실리카, 이산화티타늄 및 색소의 함량이 적어지게 되어, 캡슐의 형상이 구형이 되지 못하고 찌그러진 모양이 되며, 또한 손으로 문질렀을 때 깨지지 않게 된다. 따라서, 이러한 점을 고려하였을 때, 고분자 바인더의 함량은 캡슐 총 중량에 대하여 바람직하게는 5~20중량%, 보다 바람직하게는 10~20중량%이다The polymer binder used in the present invention can be used up to 90% by weight based on the total weight of the capsule. However, when the polymer binder is used in a large amount, the content of silica, titanium dioxide and pigments is relatively low, so that the shape of the capsule is not spherical and is distorted, and also does not break when rubbed by hand. Therefore, in consideration of this point, the content of the polymer binder is preferably 5 to 20% by weight, more preferably 10 to 20% by weight based on the total weight of the capsule.
본 발명에서 사용되는 색소로는 수용성 염료, 유용성 염료 등 종류가 특별히 한정되는 것은 아니며, 예를 들어 다음과 같은 색소가 사용될 수 있다:The dyes used in the present invention are not particularly limited in kinds such as water-soluble dyes, oil-soluble dyes, for example, the following pigments may be used:
- 양홍(carmin of cochenille);-Carmin of cochenille;
- 유기안료, 예를 들면 아조계, 안트라퀴논계, 인디고계, 잔텐계, 피렌계, 퀴놀린계, 트리페닐메탄계, 플루오란 색소;Organic pigments such as azo, anthraquinone, indigo, xanthene, pyrene, quinoline, triphenylmethane and fluorane pigments;
- 아조계, 안트라퀴논계, 인디고계, 잔텐계, 피렌계, 퀴놀린계, 트리페닐메탄계, 플루오란 색소와 같은 산계 색소(acid-based dye)의 나트륨, 칼륨, 칼슘, 바륨, 알루미늄, 지르코늄, 스트론튬, 티타늄의 불용성 염류, 이들 색소는 적어도 하나의 카르복실 또는 술폰산기를 포함할 수도 있음.Sodium, potassium, calcium, barium, aluminum, zirconium of acid-based dyes such as azo, anthraquinone, indigo, xanthene, pyrene, quinoline, triphenylmethane and fluorane pigments. Insoluble salts of strontium and titanium, these pigments may comprise at least one carboxyl or sulfonic acid group.
유기 안료의 구체예로서 다음의 상품명을 갖는 것들을 언급할 수 있다:As specific examples of the organic pigments, those having the following trade names may be mentioned:
-D&C Blue No.4, D&C Brown No.1, D&C Green No.5,-D & C Blue No.4, D & C Brown No.1, D & C Green No.5,
-D&C Green No.6, D&C Orange No.4, D&C Orange No.5, D&C Orange No.10,-D & C Green No.6, D & C Orange No.4, D & C Orange No.5, D & C Orange No.10,
-D&C Orange No.11, D&C Red No.6, D&C Red No.7, D&C Red No.17, D&C Red No.21, D&C Red No.22, D&C Red No.27, D&C Red No.28, D&C Red No.30, D&C Red No. 31, D&C Red No.33, D&C Red No.34, D&C Red No.36, D&C Violet No.2, D&C Yellow No.7, D&C Yellow No.8, D&C Yellow No.10, D&C Yellow No.11, FD&C Blue No.1,-D & C Orange No.11, D & C Red No.6, D & C Red No.7, D & C Red No.17, D & C Red No.21, D & C Red No.22, D & C Red No.27, D & C Red No.28, D & C Red No.30, D & C Red No. 31, D & C Red No.33, D & C Red No.34, D & C Red No.36, D & C Violet No.2, D & C Yellow No.7, D & C Yellow No.8, D & C Yellow No.10, D & C Yellow No.11, FD & C Blue No.1,
-FD&C Green No.3, FD&C Red No.40, FD&C Yellow No.5, FD&C Yellow No.6.-FD & C Green No.3, FD & C Red No.40, FD & C Yellow No.5, FD & C Yellow No.6.
특히, 본 발명에 따른 색소 캡슐은 유용성 염료인 Red 27과 같이 습도 변화와 알칼리 조건에서 색상 발현의 차이를 나타내어 안정성이 떨어지는 색소도 사용될 수 있다.In particular, the pigment capsule according to the present invention, such as the oil-soluble dye Red 27 shows a difference in color expression in the humidity change and alkali conditions can also be used a pigment with low stability.
본 발명의 색소 캡슐에서 색소는 캡슐의 총 중량에 대하여 최대 90중량%까지 사용이 가능하다. 그러나, 색소를 다량으로 사용하게 되면, 상대적으로 캡슐 외곽을 형성하는 고분자 바인더의 함량이 적어지게 되어, 색소를 외부 환경으로부터 완벽하게 보호할 수 없게 되므로, 색소의 안정성이 문제될 수 있다. 따라서, 이러한 점을 고려하였을 때, 색소의 함량은 캡슐 총 중량에 대하여 바람직하게는 0.00001~50중량%, 바람직하게는 10~50중량%의 양으로 담지될 수 있다.In the pigment capsule of the present invention, the pigment may be used up to 90% by weight based on the total weight of the capsule. However, when the pigment is used in a large amount, the content of the polymer binder that forms the outer capsules is relatively low, and thus the pigment cannot be completely protected from the external environment, and thus the stability of the pigment may be a problem. Therefore, in consideration of this point, the content of the pigment may be supported in an amount of preferably 0.00001 to 50% by weight, preferably 10 to 50% by weight based on the total weight of the capsule.
또한, 본 발명의 색소 캡슐은 캡슐 내부에 C3-C9의 3가 카르복실산, 바람직하게는 시트르산, 프로피온산, 이소-시트르산, 아코니틱산, 트리카르발릴산, 트리메식산을 함유한다. C3-C9의 3가 카르복실산을 함유함으로써 캡슐 내부의 pH를 산성 조건으로 유지시켜 알칼리 오일과의 접촉에 의한 색소의 변색 현상을 막을 수 있다. 이 때, C3-C9의 3가 카르복실산은 색소의 변색 현상을 막아 캡슐의 외관색을 변하지 않고, 특히 립 메이크업 화장료 조성물로 제형화될 경우 상기 조성물의 pH 기준에 적합하게 하는 양이라면 특별히 제한되지 않으며, 바람직하게는 캡슐 총 중량에 대하여 1~20중량%, 바람직하게는 1~5중량%의 양으로 첨가될 수 있다. 1중량% 미만이면 색소의 변색 현상을 막기에 부족하고, 20중량%를 초과하면 함량 증가에 따른 효과 차이가 미미하다.In addition, the pigment capsule of the present invention contains a C 3 -C 9 trivalent carboxylic acid, preferably citric acid, propionic acid, iso-citric acid, aconic acid, tricarvallic acid, and trimesic acid. By containing the 3-carboxylic acid of the C 3 -C 9 to maintain the pH of the capsule inside the acidic condition it can be prevented from developing color change of the dye by contact with an alkaline oil. At this time, the trivalent carboxylic acid of C 3 -C 9 does not change the appearance color of the capsule by preventing the discoloration of the pigment, especially if it is an amount that satisfies the pH criteria of the composition when formulated as a lip makeup cosmetic composition It is not limited and may be preferably added in an amount of 1 to 20% by weight, preferably 1 to 5% by weight based on the total weight of the capsule. If less than 1% by weight is insufficient to prevent discoloration phenomenon of the pigment, if it exceeds 20% by weight the difference in effect according to the increase in content.
본 발명은 색소를 포함하는 색소 캡슐을 제조하는 방법을 제공하며, 상기 방법은 하기의 단계를 포함한다:The present invention provides a method of making a pigment capsule comprising a pigment, the method comprising the following steps:
1) 고분자 바인더와 C3-C9의 3가 카르복실산을 제1 용매에 용해시키고, 색소를 제2 용매에 각각 용해시킨 다음 이들을 혼합하여 색소를 고분자 바인더 용액에 분산시키는 단계;1) dissolving the polymer binder and C 3 -C 9 trivalent carboxylic acid in the first solvent, dissolving the pigment in the second solvent, respectively, and mixing them to disperse the pigment in the polymer binder solution;
2) 상기 색소가 분산된 고분자 혼합 용액에 실리카와 이산화티타늄을 넣고 분산시키는 단계;2) dispersing silica and titanium dioxide into the polymer mixture solution in which the pigment is dispersed;
3) 상기 2) 단계에서 얻은 용액을 분무 건조하는 단계; 및3) spray drying the solution obtained in step 2); And
4) 분무 건조된 색소/고분자 바인더 복합 분체 입자를 수득하는 단계.4) obtaining spray-dried pigment / polymer binder composite powder particles.
본 발명의 방법에 있어서, 고분자 바인더와 색소를 용해하는 공정은, 색소의 발색이 일어나지 않게 하면서, 고분자 바인더와 색소 모두가 충분히, 바람직하게는 100%의 정도로 완전히 용해될 수 있도록, 상이한 용매에 이들을 각각 용해시킨 다음, 혼합하여 사용함을 특징으로 한다.In the process of the present invention, the step of dissolving the polymeric binder and the dye is carried out in different solvents so that both the polymeric binder and the dye can be completely dissolved to a sufficient degree, preferably to a degree of 100%, without causing the pigment to develop. Each of them is dissolved and then mixed.
본 발명에서 사용되는 고분자 바인더 및 색소로는 상기 기재한 것들이 사용될 수 있다.As the polymer binder and the dye used in the present invention, those described above may be used.
고분자 바인더를 용해시키기 위한 용매로는, 유기용매, 바람직하게는 C1-C4 저급 알코올(예컨대, 메탄올, 에탄올, 이소프로판올, 부탄올 등), 아세톤, 및 이들의 혼합물로 이루어진 군에서 선택되는 1종 이상의 유기용매, 또는 상기 유기용매와 물의 혼합물, 예를 들어 메탄올, 메탄올/물 97:3, 에탄올, 에탄올/물 6:4, 이소프로판올, 이소프로판올/물 97:3, 이소프로판올/물 6:4, N-부탄올, 아세톤, 아세톤/물 97:3, 아세톤/물 6:4, 아세톤/이소프로판올 4:6이 사용될 수 있으며, 보다 바람직하게는 에탄올 또는 아세톤이 사용될 수 있다.The solvent for dissolving the polymer binder is an organic solvent, preferably one selected from the group consisting of C 1 -C 4 lower alcohols (eg, methanol, ethanol, isopropanol, butanol, etc.), acetone, and mixtures thereof. The above organic solvent or a mixture of the above organic solvent and water, for example methanol, methanol / water 97: 3, ethanol, ethanol / water 6: 4, isopropanol, isopropanol / water 97: 3, isopropanol / water 6: 4, N Butanol, acetone, acetone / water 97: 3, acetone / water 6: 4, acetone / isopropanol 4: 6 may be used, more preferably ethanol or acetone.
또한, 색소를 용해시키기 위한 용매로는 염소함유 탄화수소계 유기용매, 바람직하게는 클로로포름, 디클로로메탄(DCM), 보다 바람직하게는 디클로로메탄(DCM)이 사용될 수 있다.In addition, a chlorine-containing hydrocarbon organic solvent, preferably chloroform, dichloromethane (DCM), and more preferably dichloromethane (DCM) may be used as a solvent for dissolving the dye.
본 발명에 방법에 있어서, 고분자 바인더를 용해시키는 용매 대 색소를 용해시키는 용매의 사용 비율은 약 3:7이다. 용매의 사용 비율이 약 3:7보다 작은 경우(예를 들어, 1:9, 2:8 등)에는, 고분자 바인더가 석출되고, 용매의 사용 비율이 약 3:7보다 큰 경우(예를 들어, 4:6, 5:5, 9:1 등)에는, 색소의 변색이 일어날 수 있어 바람직하지 않다.In the process of the present invention, the ratio of solvent for dissolving the polymeric binder to solvent for dissolving the pigment is about 3: 7. When the use ratio of the solvent is less than about 3: 7 (e.g., 1: 9, 2: 8, etc.), the polymer binder precipitates, and when the use ratio of the solvent is greater than about 3: 7 (e.g., , 4: 6, 5: 5, 9: 1, etc.), which may cause discoloration of the pigment, which is not preferable.
고분자 바인더를 용매에 용해시킬 경우, C3-C9의 3가 카르복실산, 바람직하게는 시트르산, 프로피온산, 또는 트리카르발릴산을 이에 첨가할 수 있다. C3-C9의 3가 카르복실산을 첨가함으로써 캡슐 내부의 pH를 산성 조건으로 유지시켜 알칼리 오일과의 접촉에 의한 색소의 변색 현상을 막을 수 있다. 이 때, C3-C9의 3가 카르복실산은 색소의 변색 현상을 막아 캡슐의 외관색을 변하지 않게 하는 양이라면 특별히 제한되지 않으며, 바람직하게는 캡슐 총 중량에 대하여 1~20중량%의 양으로 첨가될 수 있다. 1중량% 미만이면 색소의 변색 현상을 막기에 부족하고, 5중량%를 초과하면 함량 증가에 따른 효과 차이가 미미하다.When the polymeric binder is dissolved in a solvent, C 3 -C 9 trivalent carboxylic acid, preferably citric acid, propionic acid, or tricarvallic acid can be added thereto. By adding the trivalent carboxylic acid of C 3 -C 9 , the pH inside the capsule can be maintained under acidic conditions to prevent discoloration of the pigment due to contact with the alkaline oil. At this time, the trivalent carboxylic acid of C 3 -C 9 is not particularly limited as long as it does not change the appearance color of the capsule to prevent discoloration of the pigment, preferably 1 to 20% by weight relative to the total weight of the capsule Can be added. If less than 1% by weight is insufficient to prevent discoloration phenomenon of the pigment, if more than 5% by weight is the difference in effect according to the increase in content.
분무 건조는 다음의 조건 하에서 실행될 수 있다: 공급 속도 - 이류체 노즐에 공급되는 공기 공급량 40L/분, 분산액 공급량 100g/분; 환경 조건 - 분산액(반응액) 온도 25℃, 분무건조기 투입 온도 80℃, 분무건조기 배출온도 60℃. 이때, 지속적으로 교반기를 통하여 상기 고분자 혼합 용액을 교반시키면서, 분무 건조를 수행할 수 있다.Spray drying can be carried out under the following conditions: Feed rate—40 L / min air supply to the air nozzle, 100 g / min dispersion supply; Environmental conditions-dispersion (reaction liquid) temperature 25 ℃, spray dryer input temperature 80 ℃, spray dryer discharge temperature 60 ℃. At this time, spray drying may be performed while continuously stirring the polymer mixed solution through a stirrer.
이와 같은 본 발명에 따라서 제조된 색소 캡슐은 색소를 외부 환경으로부터 차단하고, 최종 제품, 예컨대 화장품의 피부에의 도포 이전에 색소의 발색이 일어나지 않게 할 뿐만 아니라, 안료용 이산화티타늄을 색소 캡슐에 포함함으로써 색소 고유의 색을 마스킹하여, 제형 자체의 색이 무색에 가깝게 만들 수 있다. 즉, 무색에 가까운 제품을 피부에 도포시 발색이 일어나게 함으로써, 메이크업시 재미와 흥미를 유발하는 것도 가능하다.The pigment capsule prepared according to the present invention blocks the pigment from the external environment, prevents the coloring of the pigment from occurring prior to application of the final product such as cosmetics to the skin, and also includes titanium dioxide for the pigment in the pigment capsule. This makes it possible to mask the color inherent in the pigment, making the color of the formulation itself close to colorless. In other words, it is possible to cause fun and interest in make-up by applying a colorless product to the skin when it is applied.
이하, 실시예 및 시험예를 들어 본 발명의 구성 및 효과를 보다 구체적으로 설명한다. 그러나 이들 실시예 및 시험예는 본 발명에 대한 이해를 돕기 위해 예시의 목적으로만 제공된 것일 뿐 본 발명의 범주 및 범위가 하기 실시예 및 시험예에 의해 제한되는 것은 아니다.Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to Examples and Test Examples. However, these examples and test examples are provided only for the purpose of illustration in order to facilitate understanding of the present invention, and the scope and scope of the present invention is not limited by the following examples and test examples.
[실시예 1] 색소 캡슐의 제조(1)Example 1 Preparation of Pigment Capsule (1)
Red 27 Lake(20g, 10%)를 디클로로메탄(DCM, 1580mL)에 분산시킨다. 시트르산(10g, 5%)을 60℃로 가온한 에탄올(402mL)에 용해시킨 후 고분자 바인더인 아크릴레이트 코폴리머(Eudragit® L 100, 에보닉대구사 제품; 20g, 10%)을 용해시킨다. 이때, 고분자 바인더를 용해시키는 데 사용되는 에탄올(시트르산을 용해시키는 데 사용되는 에탄올의 부피는 제외함)과 색소를 용해시키는 데 사용되는 디클로로메탄의 부피비는 3:7이다. 시트르산과 아크릴레이트 코폴리머의 혼합 분산액을 25℃ 이하로 냉각시켜 Red 27 Lake 용액과 혼합시킨다. 혼합시킨 분산액에 실리카(AEROSIL® R972, 에보닉대구사 제품; 140g, 70%)와 TiO2(Purolan® E 171 A, LANXESS 제품; 10g, 5%)를 넣고 다음과 같이 분산해준다. 분산액 용기를 초음파분산기 배스에 투입한 후 분산기를 이용하여 30분간 분산해준다. 분무건조기(DJE-FCNM 020R, (주)동진 기연 제품; 용량: 10kg/hr(H2O 기준))를 이용하여 건조화하여 캡슐화시킨다. Red 27 Lake (20 g, 10%) is dispersed in dichloromethane (DCM, 1580 mL). Citric acid (10 g, 5%) is dissolved in ethanol (402 mL) warmed to 60 ° C. and then the polymer binder, acrylate copolymer (Eudragit® L 100, manufactured by Evonik Co .; 20 g, 10%) is dissolved. At this time, the volume ratio of ethanol used to dissolve the polymeric binder (excluding the volume of ethanol used to dissolve citric acid) and dichloromethane used to dissolve the pigment is 3: 7. The mixed dispersion of citric acid and acrylate copolymer is cooled to below 25 ° C. and mixed with Red 27 Lake solution. Add silica (AEROSIL® R972, manufactured by Evonik Daegu; 140g, 70%) and TiO 2 (Purolan® E 171 A, LANXESS; 10g, 5%) to the mixed dispersion and disperse as follows. The dispersion vessel is placed in an ultrasonic disperser bath and dispersed for 30 minutes using a disperser. It is dried and encapsulated using a spray dryer (DJE-FCNM 020R, Dongjin Co., Ltd. product; capacity: 10 kg / hr (based on H 2 O)).
[실시예 2] 색소 캡슐의 제조(2)Example 2 Preparation of Pigment Capsules (2)
아크릴레이트 코폴리머를 40g(20%)을 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 색소 캡슐을 제조하였다.A pigment capsule was prepared in the same manner as in Example 1, except that 40 g (20%) of the acrylate copolymer was used.
[실시예 3] 색소 캡슐의 제조(3)Example 3 Preparation of Pigment Capsules (3)
아크릴레이트 코폴리머를 40g(20%)을 사용하고, Red 27 Lake를 100g(50%) 사용한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 색소 캡슐을 제조하였다.A pigment capsule was prepared in the same manner as in Example 1, except that 40 g (20%) of acrylate copolymer was used and 100 g (50%) of Red 27 Lake was used.
[실시예 4] 색소 캡슐의 제조(4)Example 4 Preparation of Pigment Capsules (4)
Red 27 Lake(60g, 30%)를 디클로로메탄(DCM, 1580mL)에 분산시킨다. 시트르산(10g, 5%)을 60℃로 가온한 에탄올(402mL)에 용해시킨 후 고분자 바인더인 아크릴레이트 코폴리머(Eudragit® L 100, 에보닉대구사 제품; 20g, 10%)을 용해시킨다. 이때, 고분자 바인더를 용해시키는 데 사용되는 에탄올(시트르산을 용해시키는 데 사용되는 에탄올의 부피는 제외함)과 색소를 용해시키는 데 사용되는 디클로로메탄의 부피비는 3:7이다. 시트르산과 아크릴레이트 코폴리머의 혼합 분산액을 25℃ 이하로 냉각시켜 Red 27 Lake 용액과 혼합시킨다. 혼합시킨 분산액에 실리카(AEROSIL® R972, 에보닉대구사 제품; 100g, 50%)와 TiO2(Purolan® E 171 A, LANXESS 제품; 10g, 5%)를 넣고 다음과 같이 분산해준다. 분산액 용기를 초음파분산기 배스에 투입한 후 분산기를 이용하여 30분간 분산해준다. 분무건조기(DJE-FCNM 020R, (주)동진 기연 제품; 용량: 10kg/hr(H2O 기준))를 이용하여 건조화하여 캡슐화시킨다.Red 27 Lake (60 g, 30%) is dispersed in dichloromethane (DCM, 1580 mL). Citric acid (10 g, 5%) is dissolved in ethanol (402 mL) warmed to 60 ° C. and then the polymer binder, acrylate copolymer (Eudragit® L 100, manufactured by Evonik Co .; 20 g, 10%) is dissolved. At this time, the volume ratio of ethanol used to dissolve the polymeric binder (excluding the volume of ethanol used to dissolve citric acid) and dichloromethane used to dissolve the pigment is 3: 7. The mixed dispersion of citric acid and acrylate copolymer is cooled to below 25 ° C. and mixed with Red 27 Lake solution. Add silica (AEROSIL® R972, product of Evonik Co .; 100g, 50%) and TiO 2 (Purolan® E 171 A, product of LANXESS; 10g, 5%) to the mixed dispersion and disperse as follows. The dispersion vessel is placed in an ultrasonic disperser bath and dispersed for 30 minutes using a disperser. It is dried and encapsulated using a spray dryer (DJE-FCNM 020R, Dongjin Co., Ltd. product; capacity: 10 kg / hr (based on H 2 O)).
[실시예 5] 색소 캡슐의 제조(5)Example 5 Preparation of Pigment Capsules (5)
Red 27 Lake(60g, 30%)를 디클로로메탄(DCM, 1580mL)에 분산시킨다. 시트르산(15g, 7.5%)을 60℃로 가온한 에탄올(402mL)에 용해시킨 후 고분자 바인더인 아크릴레이트 코폴리머(Eudragit® L 100, 에보닉대구사 제품; 30g, 15%)을 용해시킨다. 이때, 고분자 바인더를 용해시키는 데 사용되는 에탄올(시트르산을 용해시키는 데 사용되는 에탄올의 부피는 제외함)과 색소를 용해시키는 데 사용되는 디클로로메탄의 부피비는 3:7이다. 시트르산과 아크릴레이트 코폴리머의 혼합 분산액을 25℃ 이하로 냉각시켜 Red 27 Lake 용액과 혼합시킨다. 혼합시킨 분산액에 실리카(AEROSIL® R972, 에보닉대구사 제품; 70g, 35%)와 TiO2(Purolan® E 171 A, LANXESS 제품; 25g, 12.5%)를 넣고 다음과 같이 분산해준다. 분산액 용기를 초음파분산기 배스에 투입한 후 분산기를 이용하여 30분간 분산해준다. 분무건조기(DJE-FCNM 020R, (주)동진 기연 제품; 용량: 10kg/hr(H2O 기준))를 이용하여 건조화하여 캡슐화시킨다.Red 27 Lake (60 g, 30%) is dispersed in dichloromethane (DCM, 1580 mL). Citric acid (15 g, 7.5%) is dissolved in ethanol (402 mL) warmed to 60 ° C. and then the polymer binder, acrylate copolymer (Eudragit® L 100, manufactured by Evonik Co .; 30 g, 15%) is dissolved. At this time, the volume ratio of ethanol used to dissolve the polymeric binder (excluding the volume of ethanol used to dissolve citric acid) and dichloromethane used to dissolve the pigment is 3: 7. The mixed dispersion of citric acid and acrylate copolymer is cooled to below 25 ° C. and mixed with Red 27 Lake solution. Add silica (AEROSIL® R972, product of Evonik Co .; 70g, 35%) and TiO 2 (Purolan® E 171 A, product of LANXESS; 25g, 12.5%) to the mixed dispersion and disperse as follows. The dispersion vessel is placed in an ultrasonic disperser bath and dispersed for 30 minutes using a disperser. It is dried and encapsulated using a spray dryer (DJE-FCNM 020R, Dongjin Co., Ltd. product; capacity: 10 kg / hr (based on H 2 O)).
[실시예 6] 색소 캡슐의 제조(6)Example 6 Preparation of Pigment Capsules (6)
Red 27 Lake(40g, 20%)를 디클로로메탄(DCM, 1580mL)에 분산시킨다. 시트르산(10g, 5%)을 60℃로 가온한 에탄올(402mL)에 용해시킨 후 고분자 바인더인 아크릴레이트 코폴리머(Eudragit® L 100, 에보닉대구사 제품; 30g, 15%)을 용해시킨다. 이때, 고분자 바인더를 용해시키는 데 사용되는 에탄올(시트르산을 용해시키는 데 사용되는 에탄올의 부피는 제외함)과 색소를 용해시키는 데 사용되는 디클로로메탄의 부피비는 3:7이다. 시트르산과 아크릴레이트 코폴리머의 혼합 분산액을 25℃ 이하로 냉각시켜 Red 27 Lake 용액과 혼합시킨다. 혼합시킨 분산액에 실리카(AEROSIL® R972, 에보닉대구사 제품; 100g, 50%)와 TiO2(Purolan® E 171 A, LANXESS 제품; 20g, 10%)를 넣고 다음과 같이 분산해준다. 분산액 용기를 초음파분산기 배스에 투입한 후 분산기를 이용하여 30분간 분산해준다. 분무건조기(DJE-FCNM 020R, (주)동진 기연 제품; 용량: 10kg/hr(H2O 기준))를 이용하여 건조화하여 캡슐화시킨다.Red 27 Lake (40 g, 20%) is dispersed in dichloromethane (DCM, 1580 mL). Citric acid (10 g, 5%) is dissolved in ethanol (402 mL) warmed to 60 ° C. and then the polymer binder, acrylate copolymer (Eudragit® L 100, manufactured by Evonik Co .; 30 g, 15%) is dissolved. At this time, the volume ratio of ethanol used to dissolve the polymeric binder (excluding the volume of ethanol used to dissolve citric acid) and dichloromethane used to dissolve the pigment is 3: 7. The mixed dispersion of citric acid and acrylate copolymer is cooled to below 25 ° C. and mixed with Red 27 Lake solution. Silica (AEROSIL® R972, manufactured by Evonik Cod; 100g, 50%) and TiO 2 (Purolan® E 171 A, LANXESS; 20g, 10%) are added to the mixed dispersion and dispersed as follows. The dispersion vessel is placed in an ultrasonic disperser bath and dispersed for 30 minutes using a disperser. It is dried and encapsulated using a spray dryer (DJE-FCNM 020R, Dongjin Co., Ltd. product; capacity: 10 kg / hr (based on H 2 O)).
[실시예 7] 색소 캡슐의 제조(7)Example 7 Preparation of Pigment Capsules (7)
Red 27 Lake(40g, 20%)를 디클로로메탄(DCM, 1580mL)에 분산시킨다. 시트르산(15g, 7.5%)을 60℃로 가온한 에탄올(402mL)에 용해시킨 후 고분자 바인더인 아크릴레이트 코폴리머(Eudragit® L 100, 에보닉대구사 제품; 30g, 15%)을 용해시킨다. 이때, 고분자 바인더를 용해시키는 데 사용되는 에탄올(시트르산을 용해시키는 데 사용되는 에탄올의 부피는 제외함)과 색소를 용해시키는 데 사용되는 디클로로메탄의 부피비는 3:7이다. 시트르산과 아크릴레이트 코폴리머의 혼합 분산액을 25℃ 이하로 냉각시켜 Red 27 Lake 용액과 혼합시킨다. 혼합시킨 분산액에 실리카(AEROSIL® R972, 에보닉대구사 제품; 85g, 42.5%)와 TiO2(Purolan® E 171 A, LANXESS 제품; 30g, 15%)를 넣고 다음과 같이 분산해준다. 분산액 용기를 초음파분산기 배스에 투입한 후 분산기를 이용하여 30분간 분산해준다. 분무건조기(DJE-FCNM 020R, (주)동진 기연 제품; 용량: 10kg/hr(H2O 기준))를 이용하여 건조화하여 캡슐화시킨다.Red 27 Lake (40 g, 20%) is dispersed in dichloromethane (DCM, 1580 mL). Citric acid (15 g, 7.5%) is dissolved in ethanol (402 mL) warmed to 60 ° C. and then the polymer binder, acrylate copolymer (Eudragit® L 100, manufactured by Evonik Co .; 30 g, 15%) is dissolved. At this time, the volume ratio of ethanol used to dissolve the polymeric binder (excluding the volume of ethanol used to dissolve citric acid) and dichloromethane used to dissolve the pigment is 3: 7. The mixed dispersion of citric acid and acrylate copolymer is cooled to below 25 ° C. and mixed with Red 27 Lake solution. Silica (AEROSIL® R972, product of Evonik Co .; 85g, 42.5%) and TiO 2 (Purolan® E 171 A, product of LANXESS; 30g, 15%) are added to the mixed dispersion and dispersed as follows. The dispersion vessel is placed in an ultrasonic disperser bath and dispersed for 30 minutes using a disperser. It is dried and encapsulated using a spray dryer (DJE-FCNM 020R, Dongjin Co., Ltd. product; capacity: 10 kg / hr (based on H 2 O)).
[시험예 1] 캡슐에서 색소의 함침 여부 검증Test Example 1 Verification of Impregnation of Pigment in Capsule
상기 실시예 및 비교예에서 제조한 캡슐을 주사전자현미경(SEM)으로 관찰하였다(도 1). The capsules prepared in Examples and Comparative Examples were observed by scanning electron microscopy (SEM) (FIG. 1).
도 1의 (a)는 색소를 담지한 캡슐을 관찰한 이미지이다. 분무건조 방식을 적용함으로써, 색소를 실리카에 담지하고, 이의 외부를 고분자가 둘러싸는 방식으로 캡슐화하는 것이 가능하였으며, 도 1의 (a)에 제시된 SEM 이미지를 통해 다공성 고분자로 형성되어 있음을 확인할 수 있다.Figure 1 (a) is an image of observing the capsule carrying a pigment. By applying the spray drying method, it was possible to encapsulate the pigment in silica and encapsulate the outside of the pigment in a manner surrounded by the polymer, and it can be confirmed that the polymer is formed of the porous polymer through the SEM image shown in FIG. have.
실시예 1의 캡슐을 손가락으로 여러 번 문지렀을 때 캡슐의 상태를 나타낸 도 1의 (b)를 통하여, 캡슐이 깨지면서 색소의 발색이 일어난다는 것을 입증하였다.When the capsule of Example 1 was rubbed several times with a finger through (b) of Figure 1 showing the state of the capsule, it was demonstrated that the color of the pigment occurs as the capsule is broken.
또한, EDX 매핑을 통해 고분자 캡슐에 포함된 Si, Ti, O, Br 원소가 고르게 분포되어 있음을 도 2에서 확인함으로써 색소의 함침 여부를 입증할 수 있다.In addition, it is possible to prove whether the dye is impregnated by confirming in Figure 2 that the Si, Ti, O, Br elements contained in the polymer capsule is evenly distributed through EDX mapping.
[시험예 2] 고분자의 종류 및 용매와의 비율에 따른 색소의 변색 여부 확인[Test Example 2] to determine whether the color of the pigment according to the type of polymer and the ratio with the solvent
고분자로서 에틸셀룰로스, 폴리비닐 피롤리돈(PVP), 폴리카프로락톤(PCL), 폴리락트산(PLA) 또는 폴리(메틸 메타크릴레이트) 0.075g을 5mL의 DCM 용액에 녹인다. Red 27 색소 0.01g을 5ml의 DCM에 녹인다. 두 가지 용액을 각각 따로 제조한 후 혼합하여 색상의 변화를 관찰하였다. 관찰 결과는 도 3에 나타내었다.As a polymer, 0.075 g of ethylcellulose, polyvinyl pyrrolidone (PVP), polycaprolactone (PCL), polylactic acid (PLA) or poly (methyl methacrylate) is dissolved in 5 mL of DCM solution. 0.01 g of Red 27 pigment is dissolved in 5 ml of DCM. The two solutions were prepared separately and then mixed to observe the change in color. The observation result is shown in FIG.
도 3에서 (1) 내지 (3)은 에틸셀룰로스를 각각 4cps, 100cps, 300cps를 사용한 것을 나타내는데, 분자량이 커질수록 색상이 더 진한 것으로 나타났다.In Figure 3 (1) to (3) indicates that ethyl cellulose is used 4cps, 100cps, 300cps, respectively, the higher the molecular weight was found to be darker in color.
한편, 도 3에서 (4) 및 (5)는 폴리비닐 피롤리돈의 분자량이 각각 55,000, 360,000인 것을 사용한 것을 나타내는데, 폴리비닐 피롤리돈의 분자량이 커질수록 색상이 연한 것으로 나타났다.On the other hand, (4) and (5) in Figure 3 shows that the molecular weight of the polyvinyl pyrrolidone is 55,000, 360,000, respectively, the higher the molecular weight of the polyvinyl pyrrolidone, the color was lighter.
따라서, 색상의 차이가 조금 있기는 하지만, 결론적으로 고분자의 분자량에 상관없이 변색이 있음이 관찰되었다.Therefore, although there is little difference in color, in conclusion, it was observed that there is discoloration regardless of the molecular weight of the polymer.
다른 종류의 고분자 바인더인 PCL, PLA, 가교된 PMMA를 사용할 경우 Red 27 Lake의 변색은 없지만 유리 전이 온도(Tg)가 105℃ 이하이어서, 일반적으로 메이크업 화장품, 특히 립 메이크업용 화장품의 제조 온도인 95℃ 이상에서 안정성이 확보되지 않으므로, 본 발명의 색소 캡슐에 적용하기에 적합하지 않다(도 3의 (6) 내지 (8) 참조).When using other types of polymer binders, PCL, PLA, and crosslinked PMMA, there is no discoloration of Red 27 Lake, but the glass transition temperature (Tg) is 105 ° C or lower, so it is generally 95 Since stability is not ensured at or above the 占 폚, it is not suitable for application to the dye capsule of the present invention (see Figs.
[시험예 3] 색소 캡슐의 고온 안정성 평가Test Example 3 High Temperature Stability Evaluation of Pigment Capsule
일반적으로 메이크업 화장품, 특히 립메이크업 화장품은 고온에서 제조되므로, 캡슐이 고온에서 안정성을 유지하는지 여부를 확인하였다.In general, make-up cosmetics, in particular lip makeup cosmetics are manufactured at a high temperature, it was confirmed whether the capsule maintains stability at high temperatures.
구체적으로, 고분자 함량과 색소의 함량을 달리한 상기 실시예 1 내지 3(각각, 고분자 함량 10% + 색소 함량 10%, 고분자 함량 20% + 색소 함량 10%, 고분자 함량 20% + 색소 함량 50%)의 캡슐을 오븐 100℃에서 1시간 또는 24시간 열처리한 다음, 주사전자현미경으로 캡슐 상태를 관찰하였다(SEM). 관찰 결과는 하기 표 1, 도 4(1시간 열처리) 및 도 5(24시간 열처리)에 제시되어 있다.Specifically, Examples 1 to 3 varying the polymer content and the pigment content (each, 10% polymer content + 10% pigment content, 20% polymer content + 10% pigment content, 20% polymer content + 50% pigment content, respectively) ) Capsules were heat-treated in an oven at 100 ° C. for 1 hour or 24 hours, and then the capsules were observed under a scanning electron microscope (SEM). The observation results are presented in Table 1, FIG. 4 (one hour heat treatment) and FIG. 5 (24 hour heat treatment).
고분자 함량 10%+색소 함량 10%10% of polymer content + 10% of pigment content 고분자 함량 20%+색소 함량 10%Polymer content 20% + pigment content 10% 고분자 함량 20%+색소 함량 50%Polymer content 20% + pigment content 50%
오븐 100도에서 1시간 열처리 1 hour heat treatment at 100 degrees oven SEM 분석 결과 모두 안정함All SEM results are stable
오븐 100도에서 24시간 열처리 24-hour heat treatment at 100 degrees oven
상기 표 1에 나타낸 바와 같이, 본 발명에 따라 제조한 색소 캡슐은 고온인 100℃에서 고분자를 1시간 또는 24시간 열처리하였을 때, 모두 안정성을 유지한다는 것을 확인할 수 있다.As shown in Table 1, it can be seen that the pigment capsules prepared according to the present invention are all stable when the polymer is heat-treated at 100 ° C. for 1 hour or 24 hours.
[시험예 4] 색소 캡슐의 경도(깨짐성) 평가Test Example 4 Evaluation of Hardness (Fragility) of Pigment Capsule
본 발명에 따른 색소 캡슐의 경도(깨짐성)을 다음과 같은 방법으로 확인하였다.The hardness (breakability) of the pigment capsule according to the present invention was confirmed by the following method.
구체적으로, 고분자 함량과 색소의 함량을 달리한 상기 실시예 1 내지 3(각각, 고분자 함량 10% + 색소 함량 10%, 고분자 함량 20% + 색소 함량 10%, 고분자 함량 20% + 색소 함량 50%)의 캡슐을 손으로 1번, 3번 또는 7번 문지른 다음, 캡슐이 깨졌는지 여부를 확인하였다. 이때 깨졌는지 여부는 SEM을 통하여 확인하였다.Specifically, Examples 1 to 3 varying the polymer content and the pigment content (each, 10% polymer content + 10% pigment content, 20% polymer content + 10% pigment content, 20% polymer content + 50% pigment content, respectively) ) Was rubbed 1, 3 or 7 times by hand, and then the capsule was checked for cracking. At this time, whether it was broken was confirmed by SEM.
평가 결과는 하기 표 2 및 도 6에 나타내어져 있다.The evaluation results are shown in Table 2 below and FIG. 6.
고분자 함량 10%+색소 함량 10%10% of polymer content + 10% of pigment content 고분자 함량 20%+색소 함량 10%Polymer content 20% + pigment content 10% 고분자 함량 20%+색소 함량 50%Polymer content 20% + pigment content 50%
손으로 1번 문질렀을 때When rubbed once by hand 안 깨짐Not broken 안 깨짐Not broken 안 깨짐Not broken
손으로 3번 문질렀을 때When you rub your hand three times 깨짐fracture 깨짐fracture 안 깨짐Not broken
손으로 7번 문질렀을 때When you rub seven times with your hands 깨짐fracture 깨짐fracture 깨짐fracture
상기 표 2 및 도 6의 결과를 보면, 고분자 바인더의 함량이 높아질수록 경도가 높아져서 쉽게 깨지지 않으며, 손으로 7번 정도 문질렀을 때에는 캡슐이 모두 깨져 발색이 일어났으므로, 특별한 도구나 장치 없이 사용자가 메이크업시 용이하게 피부에서 발색이 일어나게 할 수 있음을 확인할 수 있다.In the results of Table 2 and Figure 6, the higher the content of the polymer binder, the higher the hardness is not easy to break, and when rubbed about 7 times by hand, the capsules are all broken color development occurs, the user without special tools or devices It can be seen that the makeup can easily cause color development on the skin.
[시험예 5] 립스틱 제형 테스트 전과 후의 캡슐의 깨짐성 평가[Test Example 5] Evaluation of the fragility of the capsule before and after the lipstick formulation test
립스틱 제형을 만들었을 때 제형 테스트한 후 캡슐이 깨지지 않고 그대로 유지됨을 확인하였다(도 7 참조).When the lipstick formulation was made, it was confirmed that the capsule remained unbroken after the formulation test (see FIG. 7).
[시험예 6] 고분자 종류를 바꾸거나 캡슐 외곽을 바꾸었을 때 캡슐의 깨짐성 평가[Test Example 6] Evaluation of the fragility of the capsule when changing the polymer type or the outside of the capsule
고분자의 종류로서 에틸셀룰로스를 사용하거나 산화철을 담지한 실리카를 사용하면 손으로 7번 문질러도 캡슐이 깨지지 않음을 확인하였다(도 8 참조). Ethyl cellulose or iron oxide-supported silica was used as a kind of polymer, and it was confirmed that the capsule was not broken even by rubbing seven times with a hand (see FIG. 8).
[시험예 7] 캡슐의 외관 색 발현과 피부 착색력 관찰[Test Example 7] appearance color appearance and skin pigmentation observation of the capsule
본 발명에 따른 색소 캡슐을 함유하는 립스틱 제형을 하기 표 3의 조성으로 제조하였다. 제형 (a)는 캡슐화하지 않은 Red 27을 함유하는 것이고, 제형 (b) 내지 (d)는 캡슐화한 Red 27을 함유하는 것인데, 제형 (b)는 Red 27 10% + 고분자 5%, 제형 (c)는 Red 27 10% + 고분자 5% + 시트르산 1%, 제형 (d)는 Red 27 10% + 고분자 5% + 시트르산 5%를 함유하는 것이다. Lipstick formulations containing pigment capsules according to the invention were prepared in the compositions of Table 3 below. Formulation (a) contains unencapsulated Red 27, and formulations (b) through (d) contain encapsulated Red 27, formulation (b) 10% Red 27 + 5% polymer, formulation (c ) 10% Red 27 + 5% polymer + 1% citric acid, formulation (d) contains 10% Red 27 + 5% polymer + 5% citric acid.
이와 같은 조성으로 제조한 립스틱 제형을 손등 피부에 도포한 후 발색 정도를 관찰하고, 고분자 캡슐의 외관 색 발현과 피부 착색력 결과를 도 9에 나타내었다.After applying the lipstick formulation prepared in such a composition on the skin of the back of the hand, the degree of color development was observed, and the appearance color expression and skin coloration results of the polymer capsule are shown in FIG. 9.
(단위: 중량%)(Unit: weight%)
제형 (a)Formulation (a) 제형 (b)Formulation (b) 제형 (c)Formulation (c) 제형 (d)Formulation (d)
폴리에틸렌Polyethylene 15.015.0 15.015.0 15.015.0 15.015.0
디스테아릴 말레이트Distearyl malate 30.030.0 30.030.0 30.030.0 30.030.0
바셀린vaseline 20.020.0 20.020.0 20.020.0 20.020.0
카프릴릭/카프릭 트리글리세라이드Caprylic / Capric Triglycerides 15.015.0 15.015.0 15.015.0 15.015.0
Red 27Red 27 0.10.1 -- -- --
캡슐capsule -- 1.01.0 1.01.0 1.01.0
캡슐화하지 않은 색소를 함유하는 제형 (a)와 캡슐화한 색소를 함유하는 제형 (b)를 나타낸 도 9의 (a) 및 (b)를 비교하면, 색소를 캡슐화하는 것만으로도 립스틱의 외관 색 발현을 억제할 수 있음을 알 수 있다. Comparing the formulation (a) containing the unencapsulated pigment and the formulation (b) containing the encapsulated pigment (a) and FIG. 9 (a) and (b), the appearance of the color appearance of the lipstick only by encapsulating the pigment It can be seen that can be suppressed.
또한 시트르산을 첨가하여 캡슐 내부의 pH를 산성으로 조절하면 도 9의 (c)와 (d)와 같이 외관 색을 무색에 가깝게 조절할 수 있으며, 특히 도 9(d)를 통해 시트르산의 함량을 5중량%로 하는 것이 최적화 조건임을 확인할 수 있다.In addition, when the pH inside the capsule is adjusted to acid by adding citric acid, the appearance color can be adjusted to be almost colorless as shown in FIGS. 9 (c) and 9 (d). In particular, the content of citric acid is 5 wt. It can be seen that the optimization condition is set to%.
한편, 제형 (a) 내지 (d) 각각을 피부에 도포한 결과는 하단의 (1) 내지 (4)에 나타내었는데, 이로부터 제형의 외관 색이 억제되어도 피부에 대한 착색력은 그대로 유지함을 확인할 수 있다.On the other hand, the results of applying each of the formulations (a) to (d) on the skin is shown in (1) to (4) at the bottom, from which it can be seen that the coloring power to the skin is maintained even if the appearance color of the formulation is suppressed. have.
[시험예 8] 시트르산 함량에 따른 캡슐의 외관 색 발현 관찰Test Example 8 Observation of Appearance Color of Capsules According to Citric Acid Content
본 발명에 따른 색소 캡슐을 함유하는 립스틱 제형을 하기 표 4의 조성으로 제조하였다. 제형 (a)는 실시예 4의 캡슐, 제형 (b)는 실시예 5의 캡슐, 제형 (c)는 실시예 6의 캡슐, 제형 (d)는 실시예 7의 캡슐을 함유하는 것이다.Lipstick formulations containing pigment capsules according to the invention were prepared in the compositions of Table 4 below. Formulation (a) is the capsule of Example 4, formulation (b) is the capsule of Example 5, formulation (c) is the capsule of Example 6, and formulation (d) is the capsule of Example 7.
(단위: 중량%)(Unit: weight%)
제형 (a)Formulation (a) 제형 (b)Formulation (b) 제형 (c)Formulation (c) 제형 (d)Formulation (d)
폴리에틸렌Polyethylene 15.015.0 15.015.0 15.015.0 15.015.0
디스테아릴 말레이트Distearyl malate 30.030.0 30.030.0 30.030.0 30.030.0
바셀린vaseline 20.020.0 20.020.0 20.020.0 20.020.0
카프릴릭/카프릭 트리글리세라이드Caprylic / Capric Triglycerides 15.015.0 15.015.0 15.015.0 15.015.0
Red 27Red 27 0.10.1 -- -- --
캡슐capsule -- 1.01.0 1.01.0 1.01.0
이와 같은 조성으로 제조한 립스틱 제형의 외관을 관찰하여, 시트르산 함량에 따른 외관 색 변화 정도를 관찰하였다. 결과는 도 10에 나타내었다.Observation of the appearance of the lipstick formulation prepared in such a composition, the degree of appearance color change according to the citric acid content was observed. The results are shown in FIG.
도 10을 보면, Red 27 Lake의 함량이 일정할 때 시트르산의 함량을 증가시켜도 제형의 외관 색은 크게 변하지 않는다는 것을 확인할 수 있다.Referring to FIG. 10, when the content of Red 27 Lake is constant, the appearance color of the formulation does not change significantly even when the content of citric acid is increased.
이를 통해, 시트르산의 함량이 일정 농도 이상이 되면, 색상 변화에 있어서 시트르산의 역할이 크지 않다는 것을 알 수 있다.Through this, when the content of citric acid is more than a certain concentration, it can be seen that the role of citric acid in the color change is not large.
한편, 캡슐화 하지 않은 색소의 시트르산에 의한 색상 변화 정도를 확인하기 위하여, Red 27 Lake 0.01g을 EtOH 10mL에 녹인 후 시트르산을 0g, 0.01g, 0.05g, 0.1g 및 1g을 첨가하여(각각 도 11의 (1) 내지 (5)에 해당함), Red 27 Lake의 색상 변화를 관찰하였다. 결과는 도 11에 나타내었다.On the other hand, to confirm the degree of color change due to citric acid of the unencapsulated pigment, 0.01 g of Red 27 Lake was dissolved in 10 mL of EtOH, and then 0 g, 0.01 g, 0.05 g, 0.1 g and 1 g of citric acid were added (each of FIG. 11). Corresponds to (1) to (5)), the color change of Red 27 Lake was observed. The results are shown in FIG.
도 11을 보면, 동량의 Red 27 Lake에 대하여 시트르산을 0.01g, 0.05g 및 0.1g을 각각 첨가한 경우, Red 27 Lake의 색상이 거의 동일하게 나타난다는 것을 확인할 수 있다.Referring to FIG. 11, when 0.01 g, 0.05 g, and 0.1 g of citric acid were added to the same amount of Red 27 Lake, the colors of Red 27 Lake appeared almost the same.
[시험예 9] 제형 중 Red 27의 유무에 따른 외관 색 발현과 피부 착색력 관찰[Test Example 9] Observation of the appearance color appearance and skin pigmentation according to the presence or absence of Red 27 in the formulation
색소를 전혀 함유하지 않는 립스틱 제형(제형 1), 본 발명에 따른 색소(Red 27 Lake) 캡슐을 함유하는 립스틱 제형(제형 2), 및 캡슐화하지 않은 Red 27 Lake를 함유하는 립스틱 제형(제형 3)을 표 5의 조성으로 제조하였다.Lipstick formulations containing no pigment (Formulation 1), lipstick formulations containing pigment (Red 27 Lake) capsules according to the invention (Formulation 2), and lipstick formulations containing unencapsulated Red 27 Lake (Formulation 3) To was prepared in the composition of Table 5.
(단위: 중량%)(Unit: weight%)
제형 1 Formulation 1 제형 2 Formulation 2 제형 3 Formulation 3
폴리에틸렌Polyethylene 15.0 15.0 15.0 15.0 15.0 15.0
디스테아릴 말레이트Distearyl malate 30.0 30.0 30.0 30.0 30.0 30.0
바셀린vaseline 20.0 20.0 20.0 20.0 20.0 20.0
카프릴릭/카프릭 트리글리세라이드Caprylic / Capric Triglycerides 15.0 15.0 15.0 15.0 15.0 15.0
RED 7 LAKE (CI 15850:1) RED 7 LAKE (CI 15850: 1) 2.0 2.0 2.0 2.0 2.0 2.0
YELLOW 6 LAKE (CI 15985) YELLOW 6 LAKE (CI 15985) 3.5 3.5 3.5 3.5 3.5 3.5
IRON OXIDES (CI 77491)IRON OXIDES (CI 77491) 3.5 3.5 3.5 3.5 3.5 3.5
Red 27Red 27 -- -- 0.1 0.1
캡슐capsule -- 1.0 1.0 --
이와 같은 조성으로 제조한 립스틱 제형을 손등 피부에 도포한 후 발색 정도를 관찰하고, 고분자 캡슐의 외관 색 발현과 피부 착색력 결과를 도 12에 나타내었다.After applying the lipstick formulation prepared in such a composition to the skin on the back of the hand, the degree of color development was observed, and the appearance color expression and skin coloration results of the polymer capsule are shown in FIG. 12.
도 12를 보면, 본원발명에 따른 캡슐화한 색소를 함유하는 제형(제형 2)은 색소가 전혀 들어가지 않은 대조군 립스틱(제형 1)의 외관색과 동일하면서, 피부에서의 발색력은 캡슐화하지 않은 Red 27 색소를 함유하는 제형(제형 3)과 동일하게 매우 뛰어나다는 것을 확인할 수 있다.12, the formulation containing the encapsulated pigment according to the present invention (Formulation 2) is the same as the appearance color of the control lipstick (Formulation 1) that does not contain any pigment, while the color development on the skin is not encapsulated Red 27 It can be seen that it is very excellent in the same manner as the formulation containing the pigment (Formulation 3).

Claims (9)

  1. 색소를 포함하는 색소 캡슐로서,As a pigment capsule containing a pigment,
    상기 캡슐은 실리카, 색소 및 이산화티타늄 안료가 분산되어 있는 내부와, 유리 전이 온도가 130℃ 이상인 고분자 바인더로 덮여 있는 외부를 가지고,The capsule has an inside in which silica, a dye and a titanium dioxide pigment are dispersed, and an outside covered with a polymer binder having a glass transition temperature of 130 ° C. or more,
    상기 캡슐의 내부에 C3-C9 3가 카르복실산이 포함되어 있는 것을 특징으로 하는, 색소 캡슐.C3-C9 trivalent carboxylic acid is contained in the interior of the capsule, pigment capsule.
  2. 제1항에 있어서, 상기 고분자 바인더는 아크릴레이트 코폴리머임을 특징으로 하는, 색소 캡슐.The pigment capsule of claim 1, wherein the polymer binder is an acrylate copolymer.
  3. 제1항에 있어서, 상기 고분자 바인더의 함량은 캡슐 총 중량에 대하여 5~20중량%임을 특징으로 하는, 색소 캡슐.According to claim 1, wherein the content of the polymeric binder is a pigment capsule, characterized in that 5 to 20% by weight based on the total weight of the capsule.
  4. 제1항에 있어서, 상기 색소의 함량은 캡슐 총 중량에 대하여 0.00001~50중량%임을 특징으로 하는, 색소 캡슐.According to claim 1, wherein the content of the pigment, characterized in that 0.00001 to 50% by weight relative to the total weight of the capsule, the pigment capsule.
  5. 제1항에 있어서, 상기 캡슐의 평균 직경은 15~25μm임을 특징으로 하는, 색소 캡슐.According to claim 1, wherein the average diameter of the capsule is characterized in that the pigment capsule, 15 ~ 25μm.
  6. 1) 고분자 바인더와 C3-C9 3가 카르복실산을 제1 용매에 용해시키고, 색소를 제2 용매에 각각 용해시킨 다음 이들을 혼합하여 색소를 고분자 바인더 용액에 분산시키는 단계;1) dissolving the polymer binder and C 3 -C 9 trivalent carboxylic acid in the first solvent, dissolving the pigment in the second solvent, respectively, and mixing them to disperse the pigment in the polymer binder solution;
    2) 상기 색소가 분산된 고분자 혼합 용액에 실리카와 이산화티타늄을 넣고 분산시키는 단계;2) dispersing silica and titanium dioxide into the polymer mixture solution in which the pigment is dispersed;
    3) 상기 2) 단계에서 얻은 용액을 분무 건조하는 단계; 및3) spray drying the solution obtained in step 2); And
    4) 분무 건조된 색소/고분자 바인더 복합 분체 입자를 수득하는 단계4) obtaining spray dried pigment / polymer binder composite powder particles
    를 포함하는, 색소 캡슐을 제조하는 방법.Including, a method for producing a pigment capsule.
  7. 제6항에 있어서, 상기 제1 용매는 C1-C4 저급 알코올, 아세톤, 및 이들의 혼합물로 이루어진 군에서 선택되는 1종 이상의 유기용매, 또는 상기 유기용매와 물의 혼합물임을 특징으로 하는, 색소 캡슐을 제조하는 방법.The dye according to claim 6, wherein the first solvent is at least one organic solvent selected from the group consisting of C 1 -C 4 lower alcohols, acetone, and mixtures thereof, or a mixture of the organic solvent and water. How to make a capsule.
  8. 제6항에 있어서, 상기 제2 용매는 염소함유 탄화수소계 용매임을 특징으로 하는, 색소 캡슐을 제조하는 방법.The method of claim 6, wherein the second solvent is a chlorine-containing hydrocarbon solvent.
  9. 제6항에 있어서, 상기 고분자를 용해시키는 데 사용되는 제1 용매와 상기 색소를 용해시키는 데 사용되는 제2 용매의 사용 비율은 3:7임을 특징으로 하는, 색소 캡슐을 제조하는 방법.The method of claim 6, wherein the ratio of the first solvent used to dissolve the polymer and the second solvent used to dissolve the pigment is 3: 7.
PCT/KR2017/010589 2016-09-30 2017-09-26 Capsules comprising pigments, and method for producing same WO2018062803A1 (en)

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Cited By (2)

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WO2021020352A1 (en) * 2019-07-29 2021-02-04 株式会社 資生堂 Solid cosmetic
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