JP2007217348A - Thickener and cosmetic and cleaner containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To develop a new thickener which is thickened or gelled in a high temperature condition and returns to a sol state in a low temperature condition, and to apply the thickener to cosmetics and cleaners. <P>SOLUTION: This thickener is characterized by comprising a block copolymer in which a polymer portion (A) having LCST in a range of 0 to 50°C and a hydrophilic polymer portion (B) are bound to each other and which has a weight-average mol. wt. of ≤95,000, wherein the aqueous solution of the block copolymer is thickened or gelled, when subjected to the change of temperature in the range of 0 to 50°C. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a thickener that thickens or gels according to temperature changes, and a cosmetic and a cleaning material containing the thickener.

  It is an important requirement for cosmetics to be easy to use and obtain a good feel when used, not to mention the aesthetic effects that make people look beautiful. A thickener and a gelling agent are blended in the cosmetic in order to impart ease of use and good feel to the cosmetic. However, conventional thickeners and gelling agents have been unsatisfactory because the thickening and gelling effects may be impaired under high temperature conditions.

  As a means for solving this problem, a thickener and a gelling agent are often blended in large amounts. However, when the thickening effect or the gelling effect is excessive, it is reflected as an undesirable effect on the cosmetics such as difficulty in use and deterioration in use feeling.

  For this reason, cosmetics that contain thickeners and gelling agents are fully effective without increasing the thickening and gelling effects even under high temperature conditions, and are easy to use and feel to use. Good things are strongly desired.

  On the other hand, cosmetics containing a polymer that thickens or gels according to temperature changes are described in Patent Documents 1 to 5 and the like. However, in any case, the molecular weight of the polymer is very large and is not controlled. When the molecular weight of the polymer constituting the thickener is large, the dispersion stability is lowered, and this is reflected as defects such as water separation in a gel state, deterioration in touch during use, and time required for sol-gel transition. For this reason, there has been a demand for a polymer that controls the molecular weight to be small and exhibits a sufficient thickening and gelling effect even under high temperature conditions.

Japanese Patent No. 3585309 Special table 2004-515570 Special table 2004-522833 Special table 2004-525886 JP-A-2005-314419

The problems to be solved by the present invention are as follows.
(1) To develop a thickener that does not impair the thickening and gelling effects under high temperature conditions.
(2) The cosmetics or cleaning agents containing the thickener are easy to use (easy to apply) and have a good feel to use.
(3) The polymer constituting the thickener is controlled to have a low molecular weight and is excellent in dispersion stability.
(4) To develop a thickening gelling agent that is difficult to separate in a gel state.
(5) A novel low-viscosity sol state at low temperature conditions after application, easy to apply when applied to the skin, and thickening or gelling at high temperature conditions (for example, 15 to 36 ° C.) Develop cosmetics and cleaning materials.
(6) To develop cosmetics and cleaning materials having a new feeling of use.

  As a result of intensive studies in view of the above-mentioned problems, the present inventors have found that the polymer part (A) having LCST in the range of 0 ° C. to 50 ° C. and the hydrophilic polymer part (B) are combined. Surprisingly, the block copolymer having an average molecular weight of 95,000 or less reversibly causes thickening or gelation rapidly depending on the temperature conditions, and the water separation phenomenon and feel of use of the thickener polymer are preferable. It has been found that it has overcome the conventional disadvantage of not. That is, the aqueous composition containing the block copolymer is in a low-viscosity sol state under low temperature conditions, and thickens or gels under high temperature conditions. Furthermore, since the weight average molecular weight of the block copolymer constituting the thickener is controlled to be low, it is excellent in dispersion stability, does not cause water separation, and is excellent in use feeling. As a result, when the thickener composed of the block copolymer is blended in cosmetics and detergents, it can maintain a stable thickening or gelation state even at high temperature conditions, and it reacts sensitively to high temperature conditions. Thus, the present inventors have found that it is thickened or gelled, and that it does not cause water separation and is excellent in use feeling, and has completed the present invention.

  That is, the present invention relates to a block copolymer having a weight average molecular weight of 95,000 or less in which a polymer part (A) having LCST in the range of 0 ° C. to 50 ° C. and a hydrophilic polymer part (B) are bonded. Thus, the present invention provides a thickener characterized by thickening or gelling when the aqueous solution of the block copolymer is subjected to a temperature change in the range of 0 ° C to 50 ° C.

  In the present invention, the polymer moiety (A) is poly-N-acryloylpiperidine, poly-Nn-propylmethacrylamide, poly-N-isopropylacrylamide, poly-N, N-diethylacrylamide, poly- From the group consisting of N-isopropylmethacrylamide, poly-N-cyclopropylacrylamide, poly-N-acryloylpyrrolidine, poly-N, N-ethylmethylacrylamide, poly-N-cyclopropylmethacrylamide, poly-N-ethylacrylamide The present invention provides the above thickener, which is one or two or more selected polymers.

  Furthermore, the present invention provides the above thickening agent, wherein the structure of the block copolymer is (A)-(B)-(A) and / or (A)-(B). To do.

  The present invention also provides the above thickener, wherein the hydrophilic polymer portion (B) has a molecular weight in the range of 4000 to 50000.

  Further, in the present invention, the molecular weight of the polymer part (A) is in the range of 15000 to 75000, and the weight average molecular weight of the entire block copolymer is 95,000 or less, An agent is provided.

  Moreover, this invention provides cosmetics characterized by containing said thickener.

  Furthermore, this invention provides the washing | cleaning material characterized by containing said thickener.

The thickener of the present invention can maintain a stable thickened state at high temperature conditions. In addition, a gel-like substance can be easily applied by rapidly changing to a gel state under a low-temperature condition under a sol state having a low viscosity and under a high temperature condition (body temperature) when applied to the skin. Furthermore, it has the characteristics that it overcomes the conventional drawbacks, does not cause water separation, and is excellent in use feeling.
Cosmetics and detergents containing the thickener of the present invention are sensitive to temperature and can give a unique and excellent feeling of use.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  The polymer constituting the thickener of the present invention has a weight average molecular weight of 95,000 or less in which the polymer part (A) having LCST in the range of 0 ° C. to 50 ° C. and the hydrophilic polymer part (B) are combined. It is characterized by being a block copolymer. In the present invention, LCST (Lower Critical Solution Temperature) means a transition temperature between hydration and dehydration of a polymer compound. The polymers used in the present invention are hydrophilic and soluble in water at temperatures below the LCST, but become hydrophobic and insoluble and precipitate in water at temperatures above the LCST, and this change is reversible. In order to give a reversible change in thickening and gelling, the cosmetic composition containing the thickener of the present invention can quickly respond to the body temperature (skin temperature) when applied. The LCST of A) is preferably about 0 ° C. to 36 ° C. (body temperature), more preferably about 15 ° C. (room temperature) to about 30 ° C. Thereby, the thickening on the skin and the gel effect are exhibited sensitively.

  The polymer portion (A) is composed of poly-N-acryloylpiperidine, poly-Nn-propylmethacrylamide, poly-N-isopropylacrylamide, poly-N, N-diethylacrylamide, poly-N-isopropylmethacrylamide, One or more of poly-N-cyclopropylacrylamide, poly-N-acryloylpyrrolidine, poly-N, N-ethylmethylacrylamide, poly-N-cyclopropylmethacrylamide, and poly-N-ethylacrylamide are preferred. Particularly preferred is poly-N-isopropylacrylamide.

  The polymer portion (B) is not particularly limited as long as it is a polymer that dissolves in water, but polyethylene oxide is preferred. Polyethylene oxide can use a commercial item. The molecular weight of polyethylene oxide is not limited, but PEG 4000, PEG 20000, and the like are preferable. In particular, PEG 20000 is preferable in that the minimum concentration at which sol-gel transition can be performed in an aqueous solution can be lowered.

  The structure of the polymer used in the present invention is a block copolymer in which a polymer part (A) having LCST in the range of 0 ° C. to 50 ° C. and a hydrophilic polymer part (B) are bonded. (A)-(B)-(A), (A)-(B), or a mixture thereof is preferred. It is particularly preferable that the thickener is composed of a block copolymer having only the structure of (A)-(B)-(A).

  In the polymer structure used in the present invention, the molecular weight of the polymer portion (A) having LCST in the range of 0 ° C. to 50 ° C. is preferably 15000 to 75000. This is because the part (A) having LCST aggregates and thickens or gels under high temperature conditions. At this time, if the portion (A) does not have a certain size, a stable structure cannot be formed, and the thickening effect is not exhibited. On the other hand, if the portion (A) is too large, the cohesive force at a high temperature condition is too strong, thereby eliminating water and causing water separation.

  In the polymer structure used in the present invention, the molecular weight of the hydrophilic polymer portion (B) is preferably in the range of 4,000 to 50,000. The hydrophilic polymer part (B) retains water at a high temperature condition and contributes to thickening or gelation. At this time, the (B) portion of a certain size is necessary, and if the (B) portion is too large, the hydrophilicity of the entire polymer is too strong, so that the entire polymer is in a dissolved state, and the viscosity is increased. The effect is not demonstrated.

  Moreover, although the weight average molecular weight of the whole polymer is 95000 or less, it is especially preferable that the weight average molecular weight is 20000-50000. The polymer obtained in this range has a low polydispersity and an Mw / Mn of 1.1 to 1.8, and can provide a thickener that is extremely sensitive to temperature responsiveness. In the present invention, the molecular weight, number average molecular weight (Mn), and weight average molecular weight (Mw) are determined by GPC using a PEG standard.

  The polymer used in the present invention is a known method such as a method of generating radicals from polyethylene oxide and polymerizing N-isopropylacrylamide, or a RAFT polymerization method (see WO 98/01479) which is a kind of living radical polymerization method. Can be manufactured. The RAFT polymerization method is a method in which a reversible addition-fragmentation chain transfer agent (RAFT reagent) is added to the conventional radical polymerization method to control the reactivity of the terminal active radical, and the polymerization proceeds in a pseudo living manner. .

  The polymer used in the present invention is preferably used when the RAFT polymerization method is used because the molecular weight can be controlled to be small. As a particularly preferred polymerization method, for example, a RAFT reagent having a carboxyl group is introduced into the polyethylene oxide of the polymer part (B) via an ester bond, and then N-polyisopropylacrylamide of the polymer part (A) is introduced. The method of polymerizing can be mentioned.

  As the solvent used in the polymerization, any solvent can be used as long as it can dissolve or suspend various monomers. Examples of water and organic solvents include methanol, ethanol, propyl alcohol, and isopropyl. Alcohol solvents such as alcohol and butyl alcohol, hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane and liquid paraffin, ether solvents such as dimethyl ether, diethyl ether and tetrahydrofuran, ketone solvents such as acetone and methyl ethyl ketone, In addition to ester solvents such as methyl acetate, ethyl acetate, and butyl acetate, and chloride solvents such as methylene chloride, chloroform, and carbon tetrachloride, dimethylformamide, diethylformamide, dimethylsulfoxide, dioxane, etc. It is. Two or more of these solvents may be used in combination. Usually, it is suitable to select a solvent having a boiling point higher than the starting temperature of the polymerization initiator to be used.

  The polymerization initiator is not particularly limited as long as it has the ability to initiate radical polymerization. For example, peroxide such as benzoyl peroxide, azobisisobutyronitrile (AIBN), 2,2′-azobis (Isobutyric acid) In addition to azo compounds such as dimethyl, persulfuric acid polymerization initiators such as potassium persulfate and ammonium persulfate may be mentioned. In addition, it can superpose | polymerize also by photochemical reaction, radiation irradiation, etc. irrespective of these polymerization initiators. The polymerization temperature is not less than the polymerization start temperature of each polymerization initiator. For example, in the case of a peroxide-based polymerization initiator, the temperature may usually be about 50 to 70 ° C.

  The polymerization time is not particularly limited, but is usually about 30 minutes to 24 hours. The polymer used in the present invention has a weight average molecular weight of 95,000 or less, and the polymerization time is preferably about 4 to 8 hours. The polymerized polymer is purified by a known method and used as a thickener (or gelling agent). And the aqueous solution (at least 10 mass% aqueous solution) of the thickener (or gelling agent) which consists of this polymer is thickened or gelatinized when it is subject to a temperature change in the range of 0 degreeC-50 degreeC.

  The fundamental difference between the polymer used in the present invention and the conventionally known polymer described in Patent Document 1 is that the polymer described in Patent Document 1 is a crosslinked polymer and a graft copolymer, and has a molecular weight of 100,000 or more. Is collected by fractionation by ultrafiltration. The polymer used in the present invention is a block copolymer that can be easily controlled to a weight average molecular weight of 95,000 or less in the polymerization stage. The polymers described in Patent Documents 2 to 5 are graft copolymers obtained by grafting a polymer portion having LCST to a hydrophilic polymer having an average molecular weight of 400000 or more, a weight average molecular weight of 95000 or less, and a block copolymer. The polymer of the present invention which is a polymer is fundamentally different.

  The cosmetic or cleaning material of the present invention is a temperature-sensitive composition (temperature responsiveness: viscosity changes with temperature change) in which the polymer is blended as a thickener or gelling agent. In addition to the polymer, water, oil, powder, surfactant, fluorine compound, resin, sticking agent, preservative, fragrance, ultraviolet ray absorption, which are usually used in cosmetics and cleaning agents, as long as the effects of the present invention are not impaired. Ingredients such as humectants, humectants, physiologically active ingredients, salts, solvents, antioxidants, chelating agents, neutralizing agents, pH adjusters and the like can be blended and produced by conventional methods according to the dosage form.

  The form of the cosmetic of the present invention is not particularly limited, but skin care cosmetics such as lotion, milky lotion, skin cream, pack and mask, and hair cosmetics such as hair styling, hair conditioner and hair cream are preferred. Also, the form of the cleaning material is not particularly limited, but a hair cleaning material such as shampoo and rinse, and a skin cleaning material such as hand-washing, face-washing, and make-up removal are preferable. These cosmetics and cleaning agents are easy to apply in a low-viscosity sol state when applied, and can give a unique feeling of use that thickens or gels on the skin after application. It is also possible to use cosmetics and cleaning materials in a desired viscosity state in which the containers are immersed in hot water and heated to increase the viscosity or gel.

  Although the comparative example and Example of this invention are given to the following, this invention is not limited to these. First, a method for synthesizing the polymer used in the present invention will be described.

“Synthesis Example 1: Poly-N-isopropylacrylamide-b-polyethylene oxide-b-poly-N-isopropylacrylamide”

1.20 g (10.6 mmol) of N-isopropylacrylamide, 2.25 g (0.56 mmol) of polyethylene glycol having an average molecular weight of 4000, 0.24 g (2.86 mmol) of sodium hydrogencarbonate, 0.60 g of diammonium cerium (IV) nitrate (1.09 mmol) was dissolved in 360 mL of water. Degassing was performed by bubbling argon for 60 minutes, and the container was capped with a septum and polymerized at room temperature for 24 hours. After completion of the polymerization reaction, the reaction solution was heated in a 45 ° C. warm bath, and the formed white gel was recovered. The obtained white gel was cooled to obtain a transparent solution. (Yield 36.5 g, polymer content 1.53 g). The average molecular weight of the obtained polymer was 340000. (Polymer 1)

“Synthesis Example 2: Poly-N-isopropylacrylamide-b-polyethylene oxide-b-poly-N-isopropylacrylamide”

  6.0 g (53.0 mmol) of N-isopropylacrylamide, 11.3 g (0.56 mmol) of polyethylene glycol having an average molecular weight of 20000, 0.24 g (2.88 mmol) of sodium hydrogen carbonate, 0.60 g of diammonium cerium (IV) nitrate (1.09 mmol) was dissolved in 360 mL of water. Degassing was performed by bubbling argon for 60 minutes, and the container was capped with a septum and polymerized at room temperature for 24 hours. After completion of the polymerization reaction, the reaction solution was heated in a 45 ° C. warm bath, and the formed gel was recovered. The gel was cooled to obtain a clear solution. (Yield 103 g, polymer content 7.18 g). The average molecular weight of the obtained polymer was 930000. (Polymer 2)

“Synthesis Example 3: Poly-N-isopropylacrylamide-b-polyethylene oxide-b-poly-N-isopropylacrylamide”

RAFT reagent 4-cyanopentanoic acid dithiobenzoate (CPD) 6.98 g (25.0 mmol), polyethylene glycol 20.0 g (5.0 mmol) with an average molecular weight of 4000, catalytic amounts of dimethylaminopyridine, dicyclohexylcarbodiimide 5.16 g (25.0 mmol) was dissolved in 180 ml of dichloromethane, deaerated by bubbling argon at 40 ° C. for 60 minutes, and reacted for 20 hours. The white precipitate was removed by filtration under reduced pressure, and the resulting dark red liquid was concentrated by evaporation. The concentrated reaction solution was purified by normal phase column chromatography. Wakogel C-200 (manufactured by Wako Pure Chemical Industries, Ltd.) is used as a filler, chloroform, a mixed solvent of chloroform / methanol with a volume fraction of 95: 5, and a mixed solvent of chloroform / methanol with a volume fraction of 90:10 are sequentially used. It was. Fractions of the target product were collected, concentrated by evaporation, and dried under reduced pressure to obtain RAFT-introduced polyethylene oxide having an average molecular weight of 4000. (Yield 20.2 g, Yield 89.1%).
To 625 g of 1,4-dioxane, 5.0 g of RAFT-introduced polyethylene oxide having an average molecular weight of 4000, 106.1 g (937.5 mmol) of N-isopropylacrylamide, and 51.3 mg (0.31 mmol) of azobisisobutyronitrile were added. It melt | dissolved and deaerated by bubbling argon at 60 degreeC for 60 minute (s), and reaction was advanced. After 22 hours, 12 reaction solutions were cooled with running water to stop the reaction. The mixture was concentrated by evaporation, dropped into a large excess of diethyl ether, and the precipitate was collected by suction filtration. This polymer will be referred to as polymer 3. ¹ H-NMR of polymer 3 in deuterated methanol is shown in FIG.

“Synthesis Example 4: Poly-N-isopropylacrylamide-b-polyethylene oxide-b-poly-N-isopropylacrylamide”

4-cyanopentanoic acid dithiobenzoate (CPD) 1.40 g (5.01 mmol), 20.0 g (1.0 mmol) of polyethylene glycol having an average molecular weight of 20000, catalytic amount of dimethylaminopyridine, 1.03 g (4.99 mmol) of dicyclohexylcarbodiimide Was dissolved in 180 ml of dichloromethane, deaerated by bubbling argon at 40 ° C. for 60 minutes, and reacted for 20 hours. The white precipitate was removed by filtration under reduced pressure, and the resulting dark red liquid was concentrated by evaporation. The concentrated reaction solution was purified by normal phase column chromatography. Wakogel C-200 (manufactured by Wako Pure Chemical Industries, Ltd.) is used as a filler, chloroform, a mixed solvent of chloroform / methanol with a volume fraction of 95: 5, and a mixed solvent of chloroform / methanol with a volume fraction of 90:10 are sequentially used. It was. Fractions of the target product were collected, concentrated by evaporation, and then dried under reduced pressure to obtain RAFT-introduced polyethylene oxide having an average molecular weight of 20000. (Yield 7.64 g, Yield 38.2%).
The obtained RAFT-introduced polyethylene oxide having an average molecular weight of 20000, 5.0 g, 21.2 g (187.5 mmol) of N-isopropylacrylamide, and 10.3 mg (0.063 mmol) of azobisisobutyronitrile were added to 125 g of 1,4-dioxane. It melt | dissolved and deaerated by bubbling argon at 60 degreeC for 60 minute (s), and reaction was advanced. After 4, 6, 8, and 21 hours, 30 g of the reaction solution was collected and cooled with running water to stop the reaction. The mixture was concentrated by evaporation, dropped into a large excess of diethyl ether, and the precipitate was collected by suction filtration. Polymers with reaction times of 4, 6, 8, and 21 hours will be referred to as polymers 4, 5, 6, and 7, respectively. FIG. 2 shows the ¹ H-NMR of polymer 5 in deuterated methanol.

The compositions of Polymers 1 to 7 obtained above are listed in Table 1. The weight average molecular weight is GPC (TOSOH HLC-8220 GPC manufactured by Tosoh Corporation as a device, Shodex Asahipak GF-7M HQ as a column, methanol containing 0.1 mol / L LiClO4 as a mobile phase, and PEG standard as a standard substance. The measurement temperature was 40 ° C.).

"Examples 1 to 15 and Comparative Examples 1 to 6"
The present inventors evaluated whether the above-mentioned aqueous polymer solution exhibited gelation behavior according to temperature. The evaluation items are gelation when placed in a water bath at 45 ° C., or further gelation, the concentration of the polymer required for gelation, the presence or absence of water separation, and the feeling of use. In the present invention, gelation means that no flow occurs when the sample bottle containing the sample is inverted.

"Evaluation of minimum concentration to gel"
The concentration of each aqueous polymer solution was changed and adjusted, and whether or not 2 g of the aqueous solution gelled in a 45 ° C. water bath was determined, and the minimum concentration to be gelled was determined.

  As shown in Tables 1 and 2, it was revealed that all polymer aqueous solutions gelled at 45 ° C.

"Evaluation of water separation during gelation"
Each polymer was adjusted to a minimum concentration aqueous solution required for gelation. 2 g of the aqueous solution was immersed in a 45 ° C. water bath for 15 minutes to sufficiently gel, and the presence or absence of water separation was evaluated.

  As shown in Table 3, while Comparative Example 3 and Comparative Example 4 caused water separation, Examples 6 to 10 did not cause water separation even when immersed in a 45 ° C. water bath for 15 minutes.

"Gel feeling"
Each polymer was adjusted to a minimum concentration aqueous solution required for gelation. 2 g of the aqueous solution was immersed in a 45 ° C. water bath for 15 minutes, sufficiently gelled, and applied on the skin to evaluate the feeling of use.

  As shown in Table 4, Comparative Example 5 and Comparative Example 6 have a rough feel and are uncomfortable, whereas Examples 11 to 15 can be stretched uniformly, and a suitable feel can be obtained.

  From the above evaluations, it has been clarified that by controlling the weight average molecular weight to 95,000 or less, water separation is not caused, and further, it has a characteristic of having a suitable use feeling.

  Examples of the cosmetics and cleaning agents of the present invention will be given below. The present invention is not limited to this. It is a cosmetic and a cleaning material having temperature sensitivity (temperature responsiveness) that responds to temperature and causes a change in viscosity.

Example 16
Temperature-sensitive lotion amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Ethanol 8.0
(3) Glycerin 4.0
(4) Dipropylene glycol 5.0
(5) 1,3-butylene glycol 3.0
(6) Hydroxyethyl cellulose 0.13
(7) Citric acid 0.06
(8) Sodium citrate 0.04
(9) EDTA3 sodium 0.1
(10) Phenoxyethanol appropriate amount (11) Fragrance appropriate amount (12) Purified water remainder

  When the temperature-sensitive lotion of Example 16 was applied to the skin, as the lotion was rubbed into the skin, the viscosity increased and a feeling of adhesion to the skin could be obtained, and the feel was good.

Example 17
Temperature-sensitive emulsion Blending amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Dimethylpolysiloxane 3.0
(3) Decamethylcyclopentasiloxane 4.0
(4) Ethanol 5.0
(5) Glycerin 6.0
(6) 1,3-butylene glycol 5.0
(7) Polyoxyethylene methyl glucoside 3.0
(8) Sunflower oil 1.0
(9) Squalane 2.0
(10) Potassium hydroxide 0.1
(11) Sodium hexametaphosphate 0.05
(12) Hydroxypropyl-6-cyclodextrin 0.1
(13) Dipotassium glycyrrhizinate 0.05
(14) Loquat leaf extract 0.1
(15) Sodium L-glutamate 0.05
(16) Fennel extract 0.1
(17) Yeast extract 0.1
(18) Lavender oil 0.1
(19) Giant extract 0.1
(20) Dimorpholinopyridazinone 0.1
(21) Xanthan gum 0.1
(22) Carboxyvinyl polymer 0.1
(23) Acrylic acid / alkyl methacrylate copolymer (Pemulene TR-1)
0.1
(24) Bengala appropriate amount (25) Yellow iron oxide appropriate amount (26) Paraben appropriate amount (27) Purified water residue

Example 18
Temperature-sensitive emulsion Blending amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Dimethylpolysiloxane 2.0
(3) Behenyl alcohol 1.0
(4) Batyl alcohol 0.5
(5) Glycerin 5.0
(6) 1,3-butylene glycol 7.0
(7) Erythritol 2.0
(8) Hardened oil 3.0
(9) Squalane 6.0
(10) Tetra-2-ethylhexanoic acid pentaerythrit 2.0
(11) Polyoxyethylene glyceryl isostearate 1.0
(12) Polystearic acid polyoxyethylene glycerol 1.0
(13) Potassium hydroxide appropriate amount (14) Sodium hexametaphosphate 0.05
(15) Phenoxyethanol appropriate amount (16) Carboxyvinyl polymer 0.1
(17) Purified water residue

Example 19
Temperature-sensitive emulsion Blending amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Liquid paraffin 7.0
(3) Vaseline 3.0
(4) Decamethylcyclopentasiloxane 2.0
(5) Glycerin 5.0
(6) Dipropylene glycol 7.0
(7) Polyethylene glycol 1500 2.0
(8) Jojoba oil 1.0
(9) Isostearic acid 0.5
(10) Stearic acid 0.5
(11) Behenic acid 0.5
(12) Tetra-2-ethylhexanoic acid pentaerythritol 3.0
(13) Cetyl 2-ethylhexanoate 3.0
(14) Glycerol monostearate 1.0
(15) Polystearic acid polyoxyethylene glycerol 1.0
(16) Potassium hydroxide 0.1
(17) Sodium hexametaphosphate 0.05
(18) Stearyl glycyrrhetinate 0.05
(19) L-arginine 0.1
(20) Royal jelly extract 0.1
(21) Yeast extract 0.1
(22) Tocopherol acetate 0.1
(23) Acetylated sodium hyaluronate 0.1
(24) Trisodium edetate 0.05
(25) 4-t-butyl-4′-methoxydibenzoylmethane 0.1
(26) 2-Ethylhexyl paramethoxycinnamate 0.1
(27) Carboxyvinyl polymer 0.15
(28) Paraben appropriate amount (29) Fragrance appropriate amount (30) Purified water remaining

Example 20
Temperature-sensitive emulsion Blending amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Vaseline 5.0
(3) Behenyl alcohol 0.5
(4) Batyl alcohol 0.5
(5) Glycerin 7.0
(6) 1,3-butylene glycol 7.0
(7) 1,2-pentanediol 1.0
(8) Xylit 3.0
(9) Polyethylene glycol 20000 2.0
(10) Hardened oil 2.0
(11) Jojoba oil 2.0
(12) Squalane 5.0
(13) Isostearic acid 0.5
(14) Tetra-2-ethylhexanoic acid pentaerythrit 2.0
(15) Polyoxyethylene hydrogenated castor oil 0.5
(16) Lauryldimethylaminoacetic acid betaine 0.4
(17) Potassium hydroxide appropriate amount (18) Sodium pyrosulfite 0.01
(19) Sodium hexametaphosphate 0.05
(20) Dipotassium glycyrrhizinate 0.05
(21) Trimethylglycine 3.0
(22) Arbutin 3.0
(23) Yeast extract 0.1
(24) Tocopherol acetate 0.1
(25) Thiotaurine 0.1
(26) Clara extract 0.1
(27) Bengala appropriate amount (28) quince seed extract 0.1
(29) Carboxyvinyl polymer 0.2
(30) Appropriate amount of phenoxyethanol (31) Purified water remaining

Example 21
Temperature-sensitive emulsion Blending amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Vaseline 5.0
(3) Dimethylpolysiloxane 2.0
(4) Behenyl alcohol 0.6
(5) Batyl alcohol 0.5
(6) Dipropylene glycol 2.0
(7) 1,3-butylene glycol 4.0
(8) Xylit 1.0
(9) Polyethylene glycol 1500 1.0
(10) Squalane 5.0
(11) Glyceryl tri-2-ethylhexanoate 2.0
(12) Polyoxyethylene hydrogenated castor oil 0.5
(13) Dipotassium glycyrrhizinate 0.1
(14) Yeast extract 0.1
(15) Peonies extract 0.1
(16) EDTA3 sodium 0.05
(17) Xanthan gum 0.1
(18) Carboxyvinyl polymer 0.15
(19) Perfume appropriate amount (20) Purified water remaining

Example 22
Temperature-sensitive emulsion Blending amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Liquid paraffin 35.0
(3) Decamethylcyclopentasiloxane 5.0
(4) Glycerin 2.0
(5) Dipropylene glycol 5.0
(6) 1,3-butylene glycol 1.0
(7) Cetyl 2-ethylhexanoate 8.0
(8) Polyoxyethylene hydrogenated castor oil 2.0
(9) Palm oil fatty acid methyl taurine sodium 1.0
(10) Calcium chloride 0.01
(11) Magnesium chloride 0.01
(12) Phenoxyethanol 0.2
(13) Edetate trisodium 0.01
(14) Carboxyvinyl polymer 0.15
(15) Perfume appropriate amount (16) Purified water residue

Example 23
Temperature-sensitive emulsion Blending amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Liquid paraffin 10.0
(3) Vaseline 5.0
(4) Cetanol 1.0
(5) Diglycerin 0.5
(6) 1,3-butylene glycol 5.0
(7) Polyethylene glycol 1500 3.0
(8) Stearic acid 2.0
(9) Polyoxyethylene sorbitan monolaurate (20E.O.)
0.2
(10) Oleic acid (triethylene glycol / propylene glycol)
2.0
(11) Triethanolamine 1.0
(12) Tocopherol acetate 0.1
(13) Carboxyvinyl polymer 0.03
(14) Appropriate amount of paraben (15) Purified water residue

Example 24
Temperature-sensitive emulsion Blending amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Vaseline 1.0
(3) Dimethylpolysiloxane 3.0
(4) Methylphenylpolysiloxane 3.0
(5) Stearyl alcohol 0.5
(6) Glycerin 7.0
(7) Dipropylene glycol 3.0
(8) 1,3-butylene glycol 7.0
(9) Xylitol 3.0
(10) Squalane 1.0
(11) Isostearic acid 0.5
(12) Stearic acid 0.5
(13) Polystearic acid polyoxyethylene glycerol 1.0
(14) Glycerol monostearate 2.0
(15) Potassium hydroxide 0.05
(16) L-ascorbyl magnesium phosphate 0.1
(17) Tocopherol acetate 0.1
(18) Acetylated sodium hyaluronate 0.1
(19) EDTA3 sodium 0.05
(20) 4-t-butyl-4'-methoxydibenzoylmethane 2.0
(21) 2-Ethylhexyl paramethoxycinnamate 5.0
(22) Carboxyvinyl polymer 0.1
(23) Phenoxyethanol appropriate amount (24) perfume appropriate amount (25) purified water remainder

Example 25
Temperature-sensitive emulsion Blending amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Decamethylcyclopentasiloxane 3.0
(3) Methylphenylpolysiloxane 3.0
(4) Behenyl alcohol 1.0
(5) 1,3-butylene glycol 5.0
(6) Polyoxyethylene glyceryl isostearate 1.5
(7) Polystearic acid polyoxyethylene glycerol 1.0
(8) Dipotassium glycyrrhizinate 0.05
(9) Trimethylglycine 1.0
(10) L-ascorbic acid 2-glucoside 2.0
(11) edetate trisodium 0.1
(12) 2-Ethylhexyl paramethoxycinnamate 7.0
(13) Xanthan gum 0.1
(14) Carboxyvinyl polymer 0.3
(15) Appropriate amount of phenoxyethanol (16) Appropriate amount of perfume (17) Purified water remaining

Example 26
Temperature-sensitive emulsion Blending amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Dimethylpolysiloxane 3.0
(3) Methylphenylpolysiloxane 3.0
(4) Ethanol 5.0
(5) Glycerin 4.0
(6) Dipropylene glycol 5.0
(7) Di-2-ethylhexyl succinate 3.5
(8) Potassium hydroxide 0.1
(9) Sodium hexametaphosphate 0.1
(10) Thiotaurine 0.1
(11) Trisodium edetate 0.1
(12) 4-t-butyl-4'-methoxydibenzoylmethane 3.0
(13) 2-Ethylhexyl paramethoxycinnamate 3.0
(14) Iron oxide 0.01
(15) Acrylic acid / alkyl methacrylate copolymer (Pemulene TR-2)
0.1
(16) Carboxyvinyl polymer 0.2
(17) Paraben appropriate amount (18) Fragrance appropriate amount (19) Purified water remaining

Example 27
Temperature-sensitive emulsion Blending amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Cetanol 1.0
(3) Glycerin 5.0
(4) 1,3-butylene glycol 5.0
(5) Polyethylene glycol 20000 2.0
(6) Tetra (2-ethylhexanoic acid / paramethoxycinnamic acid) pentaerythritol
3.0
(7) Di-2-ethylhexyl succinate 3.0
(8) Potassium hydroxide 0.1
(9) edetate trisodium 0.1
(10) Methylbis (trimethylsiloxy) silylisopentyl trimethoxycinnamate
2.0
(11) 4-t-butyl-4′-methoxydibenzoylmethane 2.0
(12) 2-Ethylhexyl paramethoxycinnamate 2.0
(13) Diparamethoxycinnamic acid mono-2-ethylhexanoic acid glyceryl
2.0
(14) Carboxyvinyl polymer 0.15
(15) Acrylic acid / alkyl methacrylate copolymer (Pemulene TR-1)
0.1
(16) Paraben appropriate amount (17) Phenoxyethanol Appropriate amount (18) Fragrance Appropriate amount (19) Purified water remaining

Example 28
Temperature-sensitive lotion amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Ethyl alcohol 5.0
(3) Glycerin 1.0
(4) 1,3-butylene glycol 5.0
(5) Polyoxyethylene polyoxypropylene decyl tetradecyl ether
0.2
(6) Sodium hexametaphosphate 0.03
(7) Trimethylglycine 1.0
(8) Sodium polyaspartate 0.1
(9) α-Tocopherol 2-L-ascorbic acid phosphate diester potassium
0.1
(10) Thiotaurine 0.1
(11) Green tea extract 0.1
(12) Western mint extract 0.1
(13) Iris root extract 0.1
(14) EDTA3 sodium 0.1
(15) Carboxyvinyl polymer 0.05
(16) Potassium hydroxide 0.02
(17) Phenoxyethanol appropriate amount (18) perfume appropriate amount (19) purified water remainder

Example 29
Temperature-sensitive lotion amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Glycerin 2.0
(3) 1,3-butylene glycol 4.0
(4) Erythritol 1.0
(5) Polyoxyethylene methyl glucoside 1.0
(6) Polyoxyethylene hydrogenated castor oil 0.5
(7) Citric acid 0.02
(8) Sodium citrate 0.08
(9) Phenoxyethanol appropriate amount (10) N-coconut oil fatty acid acyl L-arginine ethyl DL-pyrrolidone carboxylic acid
0.1
(11) Purified water residue

Example 30
Temperature-sensitive lotion amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Ethanol 5.0
(3) Glycerin 0.5
(4) Dipropylene glycol 2.0
(5) 1,3-butylene glycol 6.0
(6) Rosemary oil 0.01
(7) Sage oil 0.01
(8) Citric acid 0.02
(9) Sodium citrate 0.08
(10) Sodium hexametaphosphate 0.03
(11) Hydroxypropyl-β-cyclodextrin 0.1
(12) Mukuroji extract 0.1
(13) Ages extract 0.1
(14) Lily extract 0.1
(15) Oat extract 0.1
(16) Capsicum extract 0.1
(17) Kiso extract 0.1
(18) Lavender oil 0.1
(19) Tonin extract 0.1
(20) Sodium alginate 0.001
(21) Purified water residue

Example 31
Temperature-sensitive lotion amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Ethanol 10.0
(3) Glycerin 2.0
(4) Dipropylene glycol 1.0
(5) Isostearic acid 0.1
(6) Poly (oxyethylene / oxypropylene) / methylpolysiloxane copolymer
1.0
(7) Lauryldimethylaminoacetic acid betaine 0.1
(8) Citric acid 0.02
(9) Sodium citrate 0.08
(10) Sodium hexametaphosphate 0.01
(11) Hipotaurine 0.1
(12) Chamomile extract 0.1
(13) Lavender oil 0.001
(14) Appropriate amount of phenoxyethanol (15) Active hydrogen water 1.0
(16) Purified water residue

Example 32
Temperature-sensitive lotion amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Ethanol 10.0
(3) Dipropylene glycol 1.0
(4) Polyethylene glycol 1000 1.0
(5) Polyoxyethylene methyl glucoside 1.0
(6) Jojoba oil 0.01
(7) Glyceryl tri-2-ethylhexanoate 0.1
(8) Polyoxyethylene hydrogenated castor oil 0.2
(9) Polyglyceryl diisostearate 0.15
(10) Sodium N-stearoyl-L-glutamate 0.1
(11) Citric acid 0.05
(12) Sodium citrate 0.2
(13) Potassium hydroxide 0.4
(14) Dipotassium glycyrrhizinate 0.1
(15) Arginine hydrochloride 0.1
(16) L-ascorbic acid 2-glucoside 2.0
(17) Ogon Extract 0.1
(18) Yukinoshita extract 0.1
(19) Nettle extract 0.1
(20) Tranexamic acid 1.0
(21) Trisodium edetate 0.05
(22) 2-ethylhexyl paramethoxycinnamate 0.01
(23) Dibutylhydroxytoluene Appropriate amount (24) Paraben Appropriate amount (25) Deep sea water 3.0
(26) Perfume appropriate amount (27) Purified water residue

Example 33
Temperature-sensitive lotion amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Dimethylpolysiloxane 1.0
(3) Ethanol 3.0
(4) Behenyl alcohol 0.3
(5) Glycerin 5.0
(6) Dipropylene glycol 5.0
(7) Erythritol 1.0
(8) Polyethylene glycol 4000 1.0
(9) Squalane 0.4
(10) Cetyl 2-ethylhexanoate 0.1
(11) Sodium N-stearoyl-L-glutamate 0.2
(12) Magnesium chloride 0.1
(13) Arginine chloride 0.1
(14) Hipotaurine 0.1
(15) Trisodium edetate 0.1
(16) Paraben appropriate amount (17) Fragrance appropriate amount (18) Purified water remaining

Example 34
Temperature-sensitive lotion amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Ethanol 40.0
(3) Dipropylene glycol 1.0
(4) Polyoxyethylene polyoxypropylene decyl tetradecyl ether
0.1
(5) Silicic anhydride 1.0
(6) Salicylic acid 0.1
(7) Sodium citrate 0.2
(8) Zinc paraphenol sulfonate 0.2
(9) Dipotassium glycyrrhizinate 0.1
(10) Pyridoxine hydrochloride 0.1
(11) L-menthol 0.05
(12) EDTA3 sodium 0.05
(13) Cellulose powder 1.0
(14) Bentonite 0.8
(15) Purified water residue

Example 35
Temperature-sensitive lotion amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Glycerin 1.0
(3) Dipropylene glycol 12.0
(4) Ethanol 8.0
(5) POE methyl glucoside 3.0
(6) POE (24) POP (13) Decyl tetradecyl ether 0.5
(7) Citric acid 0.02
(8) Sodium citrate 0.08
(9) Hydroxypropyl-6-cyclodextrin 0.5
(10) Thiotaurine 0.1
(11) Adenosine triphosphate-2 sodium 0.1
(12) Sodium hyaluronate 0.01
(13) EDTA3 sodium 0.01
(14) Hydroxyethyl cellulose 0.1
(15) Paraben appropriate amount (16) Fragrance appropriate amount (17) Purified water remaining

Example 36
Temperature-sensitive lotion amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Ethyl alcohol 5.0
(3) Glycerin 1.0
(4) 1,3-butylene glycol 5.0
(5) Polyoxyethylene (30) phytosterol 0.1
(6) Sorbitan sesquiisostearate 0.033
(7) Squalane 0.25
(8) Isostearic acid 0.25
(9) Sodium hexametaphosphate 0.03
(10) Trimethylglycine 1.0
(11) Sodium polyaspartate 0.1
(12) α-Tocopherol 2-L-ascorbic acid phosphate diester potassium
0.1
(13) Thiotaurine 0.1
(14) Green tea extract 0.1
(15) Western mint extract 0.1
(16) Iris root extract 0.1
(17) EDTA3 sodium 0.1
(18) Citric acid 0.2
(19) Sodium citrate 0.8
(20) Phenoxyethanol appropriate amount (21) perfume appropriate amount (22) purified water remainder

Example 37
Temperature sensitive pack, amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Ethanol 10.0
(3) 1,3-butylene glycol 6.0
(4) Polyethylene glycol 4000 2.0
(5) Olive oil 1.0
(6) Macadamia nut oil 1.0
(7) Phytosteryl hydroxystearate 0.05
(8) Lactic acid 0.05
(9) Sodium lactate 0.1
(10) L-ascorbic acid sulfate disodium 0.1
(11) α-Tocopherol 2-L-ascorbic acid phosphate diester potassium
0.1
(12) Vitamin E acetate 0.1
(13) Fish collagen 0.1
(14) Chondroitin thorium sulfate 0.1
(15) Carboxymethylcellulose sodium 0.2
(16) Polyvinyl alcohol 12.0
(17) paraoxybenzoic acid ester appropriate amount (18) perfume appropriate amount (19) purified water remainder

Example 38
Temperature sensitive pack, amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Glycerin 1.0
(3) 1,3-butylene glycol 8.0
(4) Xylit 2.0
(5) Polyethylene glycol 1500 2.0
(6) Rosemary oil 0.01
(7) Sage oil 0.1
(8) Citric acid 0.02
(9) Sodium citrate 0.08
(10) Sodium hexametaphosphate 0.01
(11) Hydroxypropyl-6-cyclodextrin 0.1
(12) Aloe extract 0.1
(13) Birch extract 0.1
(14) Lavender oil 0.01
(15) Xanthan gum 0.05
(16) Carboxyvinyl polymer 0.15
(17) Paraoxybenzoic acid ester (18) Purified water remaining

Example 39
Temperature sensitive pack, amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Ethanol 3.0
(3) Glycerin 5.0
(4) 1,3-butylene glycol 6.0
(5) Polyethylene glycol 1500 5.0
(6) Polyoxyethylene methyl glucoside 2.0
(7) Glyceryl tri-2-ethylhexanoate 1.0
(8) Sodium hexametaphosphate 0.05
(9) Hydroxypropyl-6-cyclodextrin 0.1
(10) Dipotassium glycyrrhizinate 0.1
(11) Loquat leaf extract 0.1
(12) Sodium L-glutamate 0.1
(13) Fennel extract 0.1
(14) Hammamel extract 0.1
(15) Oat extract 0.1
(16) Giant extract 0.1
(17) Eucalyptus oil 0.05
(18) Dimorpholinopyridazinone 0.1
(19) Xanthan gum 0.05
(20) Carboxyvinyl polymer 0.5
(21) Acrylic acid / alkyl methacrylate copolymer (Pemulene TR-1)
0.05
(22) Potassium hydroxide 0.05
(23) Phenoxyethanol appropriate amount (24) Purified water residue

Example 40
Temperature sensitive pack, amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Vaseline 6.0
(3) Behenyl alcohol 2.5
(4) Glycerin 10.0
(5) Maltitol solution 2.0
(6) Polyethylene glycol 1500 12.0
(7) Squalane 10.0
(8) Potassium behenate 2.0
(9) Cholesteryl hydroxystearate 0.1
(10) N-alkylene (20-30) glycol monoisostearate
3.0
(11) Cetyl 2-ethylhexanoate 4.0
(12) Polyoxyethylene hydrogenated castor oil 0.3
(13) Glycerol monostearate 2.0
(14) Titanium oxide 1.0
(15) Sodium hexametaphosphate 0.1
(16) L-arginine 0.1
(17) Vitamin E acetate 0.1
(18) Carrot extract 0.1
(19) Bentonite 0.5
(20) paraoxybenzoic acid ester appropriate amount (21) perfume appropriate amount (22) purified water remainder

Example 41
Temperature-sensitive shampoo Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Glycerin 3.0
(3) Polyoxyethylene lauryl ether (12E.O.) 1.0
(4) Palm oil fatty acid diethanolamide 3.0
(5) Polyoxyethylene alkyl (12,13) ether triethanolamine sulfate
15.0
(6) Lauryldimethylaminoacetic acid betaine 4.0
(7) Polymer JR-400 (Union Carbide) 0.6
(8) Citric acid 0.25
(9) Sodium monohydrogen phosphate 0.1
(10) Iris root extract 0.02
(11) Sodium benzoate appropriate amount (12) Edetate disodium appropriate amount (13) Fragrance appropriate amount (14) Purified water remainder

Example 42
Temperature-sensitive shampoo Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Sodium polyoxyethylene lauryl ether sulfate 4.0
(3) Polyoxyethylene lauryl ether sulfate triethanolamine
1.0
(4) Palm oil fatty acid amidopropyl betaine 5.0
(5) Polymer JR-400 (Union Carbide) 0.6
(6) Citric acid 0.05
(7) Sodium chloride 0.5
(8) Sodium benzoate appropriate amount (9) Fragrance appropriate amount (10) Purified water remaining

Example 43
Temperature-sensitive shampoo Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Polyoxyethylene / methylpolysiloxane copolymer 0.2
(3) Glycerin 1.0
(4) Macadamia nut oil 0.01
(5) Cetyl 2-ethylhexanoate 0.5
(6) Polyoxyethylene lauryl ether (20E.O.) 3.5
(7) Palm oil fatty acid diethanolamide 6.5
(8) Polyoxyethylene beef tallow alkyl hydroxymyristyl ether
0.5
(9) Lauroylmethyl-β-alanine sodium 1.0
(10) 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine 10.0
(11) Lauryldimethylaminoacetic acid betaine 8.0
(12) Stearyltrimethylammonium chloride 2.0
(13) Polycoat NH 1.5
(14) Citric acid 0.8
(15) Sodium citrate 2.0
(16) Hydrolyzed fish collagen solution 0.1
(17) Disodium edetate Appropriate amount (18) Fragrance Appropriate amount (19) Purified water remainder

Example 44
Temperature-sensitive shampoo Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Ethanol 10.0
(3) Glycerin 3.0
(4) Glyceryl tri-2-ethylhexanoate 0.15
(5) Palm oil fatty acid methyl taurine sodium 4.5
(6) 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine 1.5
(7) Polymer JR-400 (Union Carbide) 0.5
(8) Citric acid 0.1
(9) Ethylenediamine hydroxyethyl triacetate trisodium 0.05
(10) Xanthan gum 0.3
(11) Purified water residue

Example 45
Temperature-sensitive shampoo Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Ethylene glycol distearate 1.5
(3) Palm oil fatty acid ethanolamide 5.5
(4) Palm oil fatty acid methyl taurine sodium 8.0
(5) Palm oil fatty acid amidopropyl betaine 5.0
(6) Polymer JR-400 (Union Carbide) 0.5
(7) Citric acid 0.5
(8) Sodium chloride 1.2
(9) Loquat leaf extract 0.1
(10) Phenoxyethanol 0.1
(11) Sodium benzoate appropriate amount (12) Edetate disodium appropriate amount (13) Fragrance appropriate amount (14) Purified water remainder

Example 46
Temperature-sensitive shampoo Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Dimethylpolysiloxane 1.5
(3) Dipropylene glycol 3.0
(4) Ethylene glycol distearate 2.0
(5) Palm oil fatty acid monoethanolamide 2.0
(6) Lauroylmethyl taurine sodium 0.1
(7) Sodium polyoxyethylene lauryl ether sulfate 7.5
(8) Polyoxyethylene lauryl ether sulfate triethanolamine
3.5
(9) Palm oil fatty acid amidopropyl betaine 3.5
(10) Marcoat 550 (Calgon) 7.5
(11) Citric acid 0.01
(12) L-glutamic acid 0.2
(13) Sodium chloride 1.0
(14) Sodium benzoate appropriate amount (15) Disodium edetate appropriate amount (16) Sodium hydroxide 0.01
(17) Perfume appropriate amount (18) Purified water remaining

Example 47
Temperature-sensitive shampoo Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Dimethylpolysiloxane 2.0
(3) Polyoxyethylene / methylpolysiloxane copolymer 2.0
(4) Cetanol 0.5
(5) Polyoxyethylene hydrogenated castor oil 4.0
(6) Ethylene glycol distearate 2.0
(7) Palm oil fatty acid diethanolamide 7.0
(8) Sodium polyoxyethylene lauryl ether sulfate 5.0
(9) Polyoxyethylene lauryl ether sulfate triethanolamine
2.5
(10) Lauroylmethyl-β-alanine sodium 1.0
(11) Palm oil fatty acid methyl taurine sodium 4.0
(12) Lauryldimethylaminoacetic acid betaine 5.0
(13) Polymer JR-400 (Union Carbide) 0.4
(14) Stearyltrimethylammonium chloride (25%) 0.1
(15) Citric acid 0.4
(16) Sodium benzoate appropriate amount (17) Disodium edetate appropriate amount (18) Fragrance appropriate amount (19) Purified water remainder

Example 48
Temperature-sensitive shampoo Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Glycerin 5.0
(3) Polyethylene glycol 1500 3.0
(4) Polyoxyethylene lauryl ether (12E.O.) 2.0
(5) Polyoxyethylene (25) Polyoxypropylene glycol (30)
0.5
(6) Ethylene glycol distearate 2.8
(7) Palm oil fatty acid diethanolamide 7.0
(8) Palm oil fatty acid methyl taurine sodium 5.0
(9) Palm oil fatty acid amidopropyl betaine 5.0
(10) Polymer JR-400 (Union Carbide) 0.5
(11) Citric acid 0.5
(12) Sodium lactate 0.05
(13) Tocopherol acetate 0.1
(14) Lily extract 0.01
(15) Sodium benzoate appropriate amount (16) Trichlorocarbanilide 0.3
(17) Disodium edetate Appropriate amount (18) Fragrance Appropriate amount (19) Purified water remainder

Example 49
Temperature-sensitive shampoo Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Dimethylpolysiloxane 0.2
(3) Highly polymerized dimethylpolysiloxane 0.15
(4) Ethylene glycol distearate 2.5
(5) Palm oil fatty acid diethanolamide 6.0
(6) Sodium dodecane-1,2-diol ether ether 1.5
(7) Palm oil fatty acid methyl taurine sodium 7.5
(8) Palm oil fatty acid amidopropyl betaine 5.0
(9) Polymer JR-400 (Union Carbide) 0.1
(10) Dimethyldiallylammonium chloride / acrylamide copolymer
1.0
(11) Citric acid 0.7
(12) Sodium chloride 0.7
(13) Phenoxyethanol appropriate amount (14) sodium benzoate appropriate amount (15) edetate disodium appropriate amount (16) perfume appropriate amount (17) purified water residue

Example 50
Temperature-sensitive shampoo Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Dimethylpolysiloxane 0.5
(3) Dipropylene glycol 2.0
(4) Ethylene glycol distearate 2.0
(5) Palm oil fatty acid monoethanolamide 2.0
(6) Sodium dodecane-1,2-diol acetate ether 3.5
(7) Polyoxyethylene lauryl ether sodium sulfate 35.0
(8) Lauroylmethyl taurine sodium 0.5
(9) Palm oil fatty acid amidopropyl betaine 5.0
(10) Hydroxypropyltrimonium chloride starch 0.5
(11) Polymer JR-400 (Union Carbide) 0.5
(12) Citric acid 0.2
(13) L-glutamic acid 0.1
(14) Lecithin 0.1
(15) Sodium chloride 0.3
(16) Sodium benzoate appropriate amount (17) Disodium edetate appropriate amount (18) Sodium hydroxide appropriate amount (19) Fragrance appropriate amount (20) Purified water remainder

Example 51
Temperature-sensitive shampoo Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Ethanol 7.0
(3) Glycerin 1.0
(4) Erythritol 1.0
(5) Stearic acid 0.1
(6) Polyoxyethylene (25) Polyoxypropylene glycol (30)
10.0
(7) Ethylene glycol distearate 1.0
(8) Palm oil fatty acid methyl taurine sodium 2.0
(9) Myristoyl methyl taurine sodium 1.0
(10) 2-Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine 8.0
(11) Dimethylaminopropylamide stearate 0.5
(12) Polymer JR-400 (Union Carbide) 0.8
(13) Citric acid 0.8
(14) Dipotassium glycyrrhizinate 0.1
(15) Ethylenediamine hydroxyethyl triacetic acid trisodium appropriate amount (16) Rosemary oil appropriate amount (17) Artemisia extract 0.1
(18) Orange oil appropriate amount (19) Purified water residue

Example 52
Temperature-sensitive rinse Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Polyoxyethylene / methylpolysiloxane copolymer 6.0
(3) Ethanol 10.0
(4) Octyldodecanol 0.15
(5) Glycerin 5.0
(6) 1,3-butylene glycol 2.0
(7) Squalane 0.1
(8) Pyroglutamate glyceryl oleate 0.05
(9) Stearyltrimethylammonium chloride (80%) 1.15
(10) Hydrolyzed keratin solution 0.1
(11) N- (2-hydroxy-3- (trimethylammonio) propyl) chloride collagen hydrolyzed 0.5
(12) p-hydroxybenzoic acid ester appropriate amount (13) hydroxyethyl cellulose 1.0
(14) Appropriate amount of perfume (15) Purified water remaining

Example 53
Temperature-sensitive rinse Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Dimethylpolysiloxane 2.0
(3) Stearyl alcohol 2.0
(4) Behenyl alcohol 1.0
(5) Glycerin 1.5
(6) Octyl palmitate 1.0
(7) Polyoxyethylene stearyl ether 0.2
(8) Citric acid 0.05
(9) Paraoxybenzoic acid ester appropriate amount (10) Phenoxyethanol appropriate amount (11) Hydroxyethyl cellulose 0.1
(12) Stearyltrimethylammonium chloride 1.0
(13) Highly polymerized methylpolysiloxane 1.5
(14) Appropriate amount of perfume (15) Purified water remaining

Example 54
Temperature-sensitive rinse Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Dimethylpolysiloxane 20.0
(3) Highly polymerized dimethylpolysiloxane 1.0
(4) Cetanol 4.5
(5) Glycerin 10.0
(6) Cetyl 2-ethylhexanoate 2.0
(7) Alkyltrimethylammonium chloride 1.5
(8) Distearyldimethylammonium chloride 0.3
(9) Citric acid 0.01
(10) Tocopherol acetate 0.05
(11) p-hydroxybenzoic acid ester appropriate amount (12) phenoxyethanol appropriate amount (13) hydroxyethyl cellulose 0.05
(14) Appropriate amount of perfume (15) Purified water remaining

Example 55
Temperature-sensitive rinse Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Dimethylpolysiloxane 2.0
(3) Cetanol 0.5
(4) Behenyl alcohol 3.0
(5) Glycerin 3.0
(6) Cetyl 2-ethylhexanoate 1.0
(7) Polyoxyethylene stearyl ether 0.1
(8) Stearyltrimethylammonium chloride 0.7
(9) Citric acid 0.05
(10) Sodium lactate solution 0.01
(11) Dipotassium glycyrrhizinate 0.1
(12) Lily extract 0.1
(13) Hydroxyethyl cellulose 0.1
(14) paraoxybenzoic acid ester appropriate amount (15) perfume appropriate amount (16) purified water remainder

Example 56
Temperature-sensitive rinse Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Cetanol 1.0
(3) Behenyl alcohol 5.0
(4) Glycerin 2.5
(5) Glycerin fatty acid ester eicosannic acid condensate 0.5
(6) Cetyl 2-ethylhexanoate 2.0
(7) Self-emulsifying glyceryl monostearate 1.0
(8) Amisafe LMA-60 (Ajinomoto Co., Inc.) 0.5
(9) Dimethylaminopropylamide stearate 0.5
(10) Citric acid 0.4
(11) Phenoxyethanol appropriate amount (12) Sodium benzoate appropriate amount (13) Fragrance appropriate amount (14) Purified water remainder

Example 57
Temperature-sensitive rinse Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Highly polymerized dimethylsiloxane / methyl (aminopropyl) siloxane copolymer
0.2
(3) Hardened rapeseed oil alcohol 3.0
(4) Glycerin 3.5
(5) 3-methyl-1,3-butanediol 5.0
(6) Hydroxystearic acid 0.5
(7) Cetyl 2-ethylhexanoate 1.0
(8) Isononyl isononanoate 0.5
(9) Sensormer CI-50 (Nalco) 0.2
(10) Dimethylaminopropylamide stearate 1.0
(11) Marcote 550 (Calgon) 1.0
(12) L-glutamic acid 0.5
(13) Phenoxyethanol 0.5
(14) Lecithin 0.1
(15) Perfume appropriate amount (16) Dye appropriate amount (17) Purified water remaining

Example 58
Temperature-sensitive rinse Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Highly polymerized dimethylsiloxane / methyl (aminopropyl) siloxane copolymer
3.0
(3) Behenyl alcohol 10.0
(4) 1,3-butylene glycol 2.0
(5) Stearyltrimethylammonium chloride (80%) 1.2
(6) Citric acid 0.07
(7) paraoxybenzoic acid ester appropriate amount (8) pigment appropriate amount (9) purified water remainder

Example 59
Temperature-sensitive rinse Formulation amount (% by mass)
(1) Polymer 5 described in Synthesis Example 4 10.0
(2) Dimethylpolysiloxane 0.5
(3) Benzyl alcohol 5.0
(4) Cetostearyl alcohol 7.0
(5) Behenyl alcohol 3.0
(6) Self-emulsifying glyceryl monostearate 1.0
(7) N-stearoyl-N-methyltaurine sodium 1.0
(8) Citric acid 0.2
(9) Phenoxyethanol appropriate amount (10) Fragrance appropriate amount (11) Purified water remaining

  The thickener of the present invention can exhibit a stable thickening effect under high temperature conditions. Moreover, since it becomes a sol state with low viscosity under low temperature conditions, and changes rapidly into a gel state under high temperature conditions (body temperature) after application to the skin, easy application of gel-like substances is possible. Furthermore, it has the characteristics that it overcomes the drawbacks of thickeners made of polymers, does not cause water separation, and is excellent in use feeling, so it is extremely useful for cosmetics and cleaning agents.

It is a ¹ H-NMR of the polymer (Polymer 3 of Synthesis Example 3) constituting the thickener of the present invention. Polymer constituting the thickener of the present invention is a ¹ H-NMR of the (polymer 5 in Synthesis Example 4).

Claims (7)

  A block copolymer having a weight average molecular weight of 95,000 or less in which a polymer part (A) having LCST in the range of 0 ° C. to 50 ° C. and a hydrophilic polymer part (B) are bonded, A thickener characterized by thickening or gelling when a combined aqueous solution is subjected to a temperature change in the range of 0 ° C to 50 ° C.   The polymer portion (A) is poly-N-acryloylpiperidine, poly-Nn-propylmethacrylamide, poly-N-isopropylacrylamide, poly-N, N-diethylacrylamide, poly-N-isopropylmethacrylamide, One selected from the group consisting of poly-N-cyclopropylacrylamide, poly-N-acryloylpyrrolidine, poly-N, N-ethylmethylacrylamide, poly-N-cyclopropylmethacrylamide, poly-N-ethylacrylamide or The thickener according to claim 1, wherein the thickener is two or more kinds of polymers.   The thickener according to claim 1 or 2, wherein the structure of the block copolymer is (A)-(B)-(A) and / or (A)-(B).   The thickener according to claim 1, 2 or 3, wherein the hydrophilic polymer portion (B) has a molecular weight in the range of 4000 to 50000.   The molecular weight of the polymer part (A) is in the range of 15000 to 75000, and the weight average molecular weight of the whole block copolymer is 95,000 or less, 5 or 5, Thickener.   A cosmetic comprising the thickener according to claim 1, 2, 3, 4 or 5. A cleaning material comprising the thickener according to claim 1, 2, 3, 4 or 5.

Images