WO2006022298A1

WO2006022298A1 - Cosmetic puff and process for producing the same

Info

Publication number: WO2006022298A1
Application number: PCT/JP2005/015353
Authority: WO
Inventors: Takuya Okamoto; Junji Terada; Takafumi Kawanaka
Original assignee: Zeon Corporation
Priority date: 2004-08-24
Filing date: 2005-08-24
Publication date: 2006-03-02
Also published as: JPWO2006022298A1

Abstract

A cosmetic puff which feels moist to the touch and does not change in that feeling upon repetitions of washing, etc. The cosmetic puff is characterized by comprising a rubber foam comprising a hydrogenated diene rubber as the main component.

Description

Specification

Cosmetic puff and method for producing the same

Technical field

[0001] The present invention relates to a cosmetic puff having a moist touch and a method for producing the same.

Background art

[0002] Conventionally, as a cosmetic puff, a cosmetic puff having a high hydrophilicity and a soft texture and a smooth tactile sensation has been demanded. Such cosmetic puffs are required to have oil resistance to cosmetics and are in direct contact with the skin. In recent years, consumer demand has been diversified, and cosmetic puffs with various tactile sensations have been demanded.

[0003] Methods for changing the tactile sensation of a cosmetic puff include methods using various additives. For example, Patent Document 1 discloses a cosmetic puff having a sponge physical strength containing a bleedable silicone oil. However, since the cosmetic puff is used after washing, if the additive is simply added, the added additive is eluted by repeated washing. There was a problem when the tactile sensation changed with use.

[0004] Patent Document 1: Japanese Patent Laid-Open No. 6-311909

Disclosure of the invention

Problems to be solved by the invention

[0005] The present invention has a moist feeling and the tactile sensation does not change even after repeated washing or the like! The main object is to provide a cosmetic puff and a method for producing the same.

Means for solving the problem

[0006] As a result of intensive investigations in view of the above circumstances, the present inventors have found that a cosmetic puff having a moist feel unique to the present invention is obtained by using a foam rubber containing hydrogenated rubber as a main component. The inventors have found that the present invention can be obtained and have completed the present invention.

[0007] Forcibly, according to the present invention, the following inventions 1 to 6 are provided. 1. A cosmetic puff characterized by having foam rubber power mainly composed of hydrogenated rubber.

2. The cosmetic according to 1 above, which is a hydride of a copolymer comprising a conjugated diene monomer unit and an ethylenically unsaturated-tolyl monomer unit. For puffs.

3. The cosmetic puff according to 1 or 2 above, wherein the hydrogenation rate of the hydrogenated rubber is 2 to 40%.

4. Foam rubber force The cosmetic puff according to 1 to 3, wherein the hydrogenated rubber latex is foamed and then coagulated.

5. A method for producing a cosmetic puff comprising the steps of foaming and then solidifying a hydrogenated rubber latex having a hydrogenation rate of 2 to 40%.

6. A hydrogenation product of a copolymer obtained by polymerizing a monomer mixture comprising the conjugated hydrogen monomer and the ethylenically unsaturated-tolyl monomer. 6. The method for producing a cosmetic puff according to 5 above.

The invention's effect

[0008] The cosmetic puff of the present invention has a unique moist feel, and is preferably used as one satisfying one aspect of the demands of various consumer cosmetic puffs in recent years. If you can, you will have the effect.

BEST MODE FOR CARRYING OUT THE INVENTION

[0009] The cosmetic puff of the present invention is characterized in that it also has a foam rubber power mainly composed of hydrogenated rubber. Hereinafter, the cosmetic puff of the present invention will be described in detail. The foam rubber used in the present invention contains hydrogenated rubber as a main component. Examples of the gen rubber (hereinafter sometimes simply referred to as “gen rubber”), which is a raw material for the hydrogenated gen rubber, include natural gen rubber and synthetic gen rubber. Of these, synthetic Gen rubber is preferred because various physical properties of foam rubber can be adjusted arbitrarily. Synthetic gen rubbers include conjugated gen monomer units and copolymers comprising ethylenically unsaturated monomer units copolymerizable therewith. Gen rubber, chloroprene rubber, styrene butadiene rubber, and acrylonitrile-butadiene rubber may be mentioned, and the foam rubber is not particularly limited as long as it is a main component. In the present invention, the “main component” means that the total rubber component is contained at least 70% by weight, preferably 90% by weight or more.

[0010] The gen-based rubber used in the present invention contains a conjugated gen monomer unit and an ethylenically unsaturated-tolyl monomer unit from the viewpoint of oil resistance and good tactile sensation of the resulting cosmetic puff. It is preferable to use a copolymer (hereinafter sometimes referred to as an NBR copolymer). In the present invention, a foam rubber obtained by foaming and then solidifying a hydrogenated NBR copolymer is particularly preferably used.

[0011] The hydrogenated gen-based rubber in the present invention is not particularly limited as long as it is a hydrogenated gen-based rubber, but a preferable hydrogenation rate is 2 to 40%, particularly preferably. 5 to 35%. If the hydrogenation rate is too low, the moist feel that is the effect of the present invention may not be obtained. Conversely, if it is too high, it may be difficult to produce foam rubber. Here, the hydrogenation rate is the ratio of hydrogenated carbon-carbon double bonds to the total number of carbon-carbon double bonds present in the gen-based rubber before hydrogenation. The hydrogenation rate of the gen rubber used in

[0012] As the hydrogenated rubber used in the present invention, a hydrogenated rubber latex obtained by hydrogenating a Gen rubber rubber is preferably used because it is easy to handle.

The gen-based rubber latex used in the present invention is mainly composed of a copolymer obtained by polymerizing a monomer mixture comprising a conjugated gen monomer and an ethylenically unsaturated nitrile monomer. A copolymer obtained by emulsion polymerization of a monomer mixture comprising a conjugation monomer, an ethylenically unsaturated-tolyl monomer, and an ethylenically unsaturated monomer copolymerizable therewith. Latex is preferably used.

[0013] Conjugation monomers include, for example, 1,3 butadiene, 2-methyl-1,3 butadiene, 2,3 dimethyl-1,3 butadiene, 2-chloro 1,3 butadiene, 1,3 Examples. Among them, 1, 3 butadiene, 2-methyl 1, 3 butadiene 1,3 Butadiene is more preferred. These can be used alone or in combination of two or more.

The amount of the conjugation monomer used is preferably 50 to 90% by weight, more preferably 60 to 80% by weight in the monomer mixture. If the amount used is too small, when used as a cosmetic puff, the texture becomes hard and the tactile sensation becomes poor. Conversely, if it is too much, the oil resistance becomes insufficient.

[0014] Examples of the ethylenically unsaturated-tolyl monomer include acrylonitrile, methacrylic-tolyl, _a -chloroacrylic acid, a-cyanoethyl acrylate, etc., and particularly preferred are acrylonitrile and methacrylic. Mouth-Trill. These can be used alone or in combination of two or more.

The amount of the ethylenically unsaturated-tolyl monomer used is preferably 10 to 50% by weight, more preferably 20 to 40% by weight in the monomer mixture. If the amount used is too small, the oil resistance becomes insufficient. Conversely, if the amount is too large, the texture becomes hard and the texture tends to deteriorate.

[0015] Ethylene unsaturated monomers copolymerizable with conjugation monomers and ethylenically unsaturated nitrile monomers include, for example, (meth) acrylic acid, (anhydrous) maleic acid, fumaric acid Ethylenically unsaturated carboxylic acids such as itaconic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, lauryl (meth) ate Mono- or dialkyl esters of said ethylenically unsaturated carboxylic acids such as acrylate, mono- or dimethyl maleate, mono- or jetyl fumarate, mono- or di-n-butyl fumarate, mono- or di-n-butyl itaconate; methoxy acrylate, ethoxy acrylate Alkoxylates of the ethylenically unsaturated carboxylic acids such as 2-hydroxyethyl (meth) acrylate, (meth) acrylate having an alkyl group; glycidyl (meth) acrylate; (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl ( (Meth) acrylic amides such as meth) acrylamides and derivatives thereof; acrylates having amino groups such as dimethylaminomethyl acrylate and jetylaminomethyl acrylate; aromatics such as styrene, a-methylstyrene, butyltoluene and chlorostyrene Bull monomer; a-olefin such as ethylene and propylene; non-conjugated monomer such as dicyclopentagen and burnorbornene Etc. When these are used as required, they can be used in the monomer mixture, preferably in the range of 30% by weight or less, within the range where the moist feel of the present invention is not impaired.

[0016] The above-mentioned gen-based rubber latex can be produced by a usual emulsion polymerization technique. As the polymerization agent such as a surfactant, a polymerization initiator, a chelating agent, an oxygen scavenger, and a molecular weight adjusting agent used for emulsion polymerization, each conventionally known agent can be used and is not particularly limited. For example, as the surfactant, an ionic surfactant or an ionic surfactant and a nonionic (nonionic) surfactant are used. The surfactant is usually used in the range of 0.5 to 5% by weight based on the monomer mixture.

Examples of the anionic surfactant include, for example, beef tallow fatty acid potassium, partially hydrogenated beef tallow fatty acid potassium, potassium oleate, sodium oleate, and the like; potassium rosinate, sodium rosinate, and hydrogenated potassium rosinate Succinate such as sodium hydrogenated rosinate; alkylbenzene sulfonate such as sodium dodecylbenzenesulfonate. Examples of non-ionic surfactants include polyethylene glycol ester type, polyethylene glycol ester type, pull nick type surfactants such as block copolymers of ethylene oxide and propylene oxide, and the like. These surfactants may be used alone or in combination of two or more.

[0018] Examples of the polymerization initiator include thermal decomposition initiators such as persulfates such as potassium persulfate and ammonium persulfate; t-butyl hydride mouth peroxide, cumene hydride mouth peroxide, diisopropyl benzene hydride mouth. Organic peroxides such as peroxide, otatanyl peroxide, 3,5,5-trimethylhexanoyl peroxide; azobis compounds such as azobisisobutyl-tolyl; these and divalent iron ions And a redox initiator composed of a reducing agent. Of these, redox initiators are preferred. The usage of these initiators is usually in the range of 0.01 to 10% by weight with respect to the monomer mixture.

[0019] Emulsion polymerization can be continuous or batch! Also, the polymerization time, polymerization conversion rate, etc. are not particularly limited. A preferable polymerization conversion rate is 90% or more. The polymerization temperature is preferably 40 ° C or lower, more preferably 0 to 35 ° C. Further, the method for adding the monomer is not particularly limited, and for example, a batch addition method, a division addition method, or the like can be used. Gen system of the present invention A preferred polymerization method for obtaining rubber latex includes, for example, a method in which all monomers are added to a reactor at once and polymerization is carried out at a polymerization temperature of 0 to 35 ° C. using a redox initiator. Further, after polymerization, the particle size can be increased by a known method.

[0020] As a method for increasing the particle size, for example, a method in which the reaction is stopped in the middle of the polymerization and a strong stirring is performed; a conjugation monomer such as butadiene and a solvent such as toluene are added and the mixture is stirred strongly after the polymerization is completed. A method is mentioned. The solid content of the gen rubber latex of the present invention is not particularly limited, but is usually about 30 to 70% by weight. Further, the latex particle diameter is not particularly limited. Usually, it is about 100 to 3, OOOnm, preferably about 200 to 2, OOOrnn.

[0021] According to the present invention, a cosmetic puff characterized by having a foam rubber force obtained by foaming a hydrogenated rubber latex having a hydrogenation rate of 2 to 40% and then coagulating with a foam rubber force is preferable. Appropriately used.

The method for producing the hydrogenated rubber rubber latex of the present invention is not particularly limited, but in order to further improve the feel of the final cosmetic puff, the hydrogen rubber rubber is hydrogenated. A method of hydrogenating to a rate of 2 to 40% is preferably used. Hereinafter, a preferred method for producing such hydrogenated rubber latex will be described.

[0022] In the present invention, as a method for obtaining a hydrogenated rubber latex having a hydrogenation rate within the above range, for example,

(A) A method of adjusting the hydrogenation rate of the gen rubber latex within the above range in the hydrogenation step of hydrogenating the gen rubber latex.

(B) Hydrogenated! / Unusual hydrogenated rubber latex (hereinafter sometimes abbreviated as non-hydrogenated rubber rubber latex) and the hydrogenation rate than the desired hydrogenated rubber rubber latex. A method of mixing with a high hydrogenation rubber rubber latex,

(C) a method of appropriately mixing two or more hydrogenated rubber latexes having different hydrogenation rates, and the like.

Of these, methods (A) and (B) are preferably used because the mixing operation is easy. In method (A), the hydrogenation rate can be adjusted by appropriately selecting the type and amount of the catalyst used for hydrogenation and the hydrogenation reaction conditions such as pH and temperature. it can. In addition, it is preferable that the hydrogenation rate of the hydrogenated rubber latex having a high hydrogenation rate used by mixing with the non-hydrogenated rubber latex in the method) is 30 to 100%. More preferably, it is ˜98%. If the hydrogenation rate is too low, it may not be possible to obtain a feeling of sensation peculiar to the resulting cosmetic puff when mixed with a non-hydrogenated rubber latex.

[0023] In the method (B), the mixing ratio of the non-hydrogenated rubber latex and the hydrogenated rubber latex is such that the hydrogenation rate of the hydrogenated rubber latex used for producing the foam rubber is Although it is not particularly limited as long as it is within the target value, 200 to 2,000 parts by weight of non-hydrogenated rubber latex is mixed with 100 parts by weight of hydrogenated rubber latex. It is particularly preferable to mix 600 to 1500 parts by weight.

As a method for measuring the hydrogenation rate in each hydrogenated rubber latex, either a proton NMR method or an iodine value method (JIS K 6235) can be mentioned. Among these, the iodine value method can indirectly determine the amount of carbon-carbon double bonds in the gen-based rubber from the iodine value. Therefore, the amount of the carbon-carbon double bond is obtained before and after hydrogenation, and the ratio is determined from the ratio “after the hydrogenation relative to the total number of carbon-carbon double bonds present in the gen-based rubber before hydrogenation. The ratio of carbon-carbon double bonds remaining in the gen-based rubber is calculated and the ratio (percentage) obtained is divided from 100 to obtain the `` carbon The ratio of hydrogenated carbon-carbon double bonds to the total number of heavy bonds ”can be calculated.

In contrast, proton NMR measures the proportion of carbon-carbon single bonds that have been hydrogenated from double bonds to single bonds, among the carbon-carbon single bonds of hydrogenated rubber after hydrogenation. Can do. Thus, the total amount of carbon-carbon double bonds and carbon-carbon double bonds hydrogenated to carbon-carbon single bonds in hydrogenated rubber (i.e., bonds that existed as carbon-carbon double bonds before hydrogenation). The ratio of the carbon-carbon double bond hydrogenated to the carbon-carbon single bond to the total amount) can be determined by the quantity specific force of the hydrogen atom derived from each bond.

Therefore, the hydrogenation rate can be obtained by using only the strength of the hydrogenated gen rubber. [0025] The method for producing the hydrogenated gen-based rubber latex used in the present invention is not particularly limited as long as it is a method capable of hydrogenating the carbon-carbon double bond of the gen-based rubber latex.

Step ( _a ) A step of contacting the gen-based rubber latex with an adsorbent,

Step (b) A step of hydrogenating carbon-carbon double bonds of the polymer by dissolving or dispersing a platinum group element-containing hydrogenation catalyst in the latex,

The method comprising the steps (a) and (b) is preferably used.

The step (a) of bringing the gen-based rubber latex into contact with the adsorbent is performed as follows. The adsorbent used in the step (a) is generally used as an adsorbent. There is no particular limitation as long as it can improve the hydrogenation catalytic activity of the carbon-carbon double bond hydrogenation reaction of the gene rubber when brought into contact with the rubber rubber latex. Examples of adsorbents include activated carbon; kieselguhr, talc, clay, activated clay, silica-containing inorganic compounds such as silica; activated alumina; synthetic zeolite such as radiolite and celite; and ion exchange resin. Among these, activated carbon and ion exchange resin, which have a high effect of improving the hydrogenation catalyst activity, are preferable.

[0026] When activated carbon is used, the specific surface area by the BET adsorption method is preferably 500-2.

500 m ² Zg, more preferably 1,000-1,500 m ² Zg. When the specific surface area of the activated carbon is within the above range, the activity of the hydrogenation catalyst is further improved. Furthermore, the average particle diameter of the activated carbon is preferably 10 to 3,000 μm, more preferably 50 to L, 000 / zm.

In the case of using an ion exchange resin, it is preferable to use an ion exchange resin having a functional group such as sulfonic acid, carboxylic acid, iminoniacetic acid, quaternary ammonium base, and the like. Further, as the resin skeleton structure of the ion exchange resin, it is preferable to use an ion exchange resin having a structure such as a styrene / divinylbenzene copolymer structure or an acrylic acid / divinylbenzene copolymer structure.

[0027] Examples of the ion exchange resin include a strongly acidic cation exchange resin (Amberlyst 15DRY, manufactured by Organo Corporation) having acrylic acid functional group in a styrene'-dibulubenzene copolymer structure, acrylic acid, and the like. 'Dicarboxylic benzene copolymer structure with carboxylic acid Weakly acidic cation exchange resin having functional groups (Amberlite IRC76, manufactured by Organo Co., Ltd.), Chelate ion exchange resin having imino-acetic acid as a functional group in a styrene dibulebenzene copolymer structure (Amberlite IRC748 , Organo Co., Ltd.), the strongest basic anion exchange resin having a quaternary ammonium base as a functional group in a styrene-dibulene benzene copolymer structure (Amberlite IRA900J CL, Organo Co., Ltd.) Among them, a strong acid cation exchange resin and a chelate ion exchange resin are particularly preferred, and a chelate ion exchange resin is most preferred because it has a strong adsorption ability by a chelate bond.

[0028] In the step (a), as a method of bringing the adsorbent into contact with the Gen rubber latex, (1) a method in which the adsorbent is dispersed in the latex and brought into contact by stirring or the like,

(2) A method in which an adsorbent is installed in the reactor as a fixed bed, and the latex is stirred and brought into contact with the fixed bed,

(3) A method of passing latex through a column packed with an adsorbent,

However, it is possible to use the method of (1) above in view of the fact that no apparatus other than the apparatus necessary for the polymerization reaction and hydrogenation reaction is required, and the operation is simple, and the continuous operation is possible. From the viewpoint, the method (3) is preferred.

In the above method, the amount of adsorbent, preferably with respect to diene-based rubber latex 0.01 to 10 weight ^_0/0, more preferably from 0.1 to 1 weight ^_0/0.

[0029] In the present invention, the temperature of the gen-based rubber latex brought into contact with the adsorbent is a temperature excellent in the stability of the latex, the adsorption effect of the hydrogenation reaction inhibitor, etc., that is, preferably 5 to 60 ° C. More preferably, it is 15 to 30 ° C.

Further, the solid content concentration of the gen rubber latex brought into contact with the adsorbent is preferably 5 to 50% by weight, more preferably 15 to 30% by weight.

The adsorbent brought into contact with the latex can be removed from the latex by a known separation operation such as filtration or centrifugation.

[0030] The step (b) of hydrogenating the carbon-carbon double bond of the gen-based rubber by dissolving or dispersing the platinum group element-containing hydrogenation catalyst in the latex brought into contact with the adsorbent is performed. Hydrogenating carbon-carbon double bonds of the above-mentioned Gen-based rubber in Gen-based rubber latex Step (b) is performed as follows.

[0031] The platinum group element-containing hydrogenation catalyst used in step (b) is a water-soluble or water-dispersible compound containing a platinum group element. Specifically, ruthenium, rhodium, noradium, It is a compound of osmium, iridium and platinum. These hydrogenation catalysts are supported on the carrier or dissolved or dispersed in the latex as it is without being supported, and used for the hydrogenation reaction. The hydrogenation catalyst is particularly preferably a palladium compound, preferably a palladium or rhodium compound. Two or more platinum group element compounds may be used in combination, but in this case as well, it is preferable to use a radium compound as the main catalyst component.

[0032] The palladium compound used in the present invention is not particularly limited as long as it has hydrogenation catalyst activity, but it is more preferably water-soluble, which is preferably water-soluble or water-dispersible. Furthermore, the palladium compound is a compound of palladium having a valence of II or IV, and the form thereof is preferably a salt complex.

Examples of noradium compounds include organic acid salts such as palladium acetate, palladium formate, and propionate; inorganic acid salts such as palladium nitrate and palladium sulfate; and Futzino << radium, palladium chloride, palladium bromide, palladium iodide. Inorganic palladium compounds such as palladium oxide and palladium hydroxide; Organic palladium compounds such as dichloro (cyclootagen) palladium, dichloro (norbornagen) palladium, dichlorobis (triphenylphosphine) palladium; And halogenated salts such as ammonium hexapalladium ammonium; complex salts such as potassium tetracyanopalladium.

[0033] Among these palladium compounds, organic acid salts or inorganic acid salts such as palladium acetate, palladium nitrate, palladium sulfate, etc .; palladium chloride; sodium tetrachloro palladium acid, ammonium hexachloro palladium acid ammonium Palladium acetate, palladium nitrate and palladium chloride are more preferred, such as halogenated salts;

[0034] Examples of rhodium compounds include halides such as rhodium chloride, rhodium bromide and rhodium iodide; inorganic acid salts such as rhodium nitrate and rhodium sulfate; rhodium acetate, rhodium formate, rhodium propionate, rhodium butyrate, Rhodium herbate, rhodium naphthenate, acetylene Organic acid salts such as rhodium cetonate; acid rhodium; rhodium trihydrate;

[0035] The platinum group element compound is commercially available, or can be prepared and used by a known method. In addition, a method of dissolving or dispersing the platinum group compound in the latex is not particularly limited, and examples thereof include a method of directly adding the compound to the latex and a method of adding the compound in a state of being dissolved or dispersed in water. In the latter method, for example, when inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, bromic acid, perchloric acid and phosphoric acid; sodium salts and potassium salts of these inorganic acids; organic acids such as acetic acid; The solubility in water is improved, which may be preferable.

[0036] According to the method for producing hydrogenated hydrogen rubber latex, the activity of the hydrogenation catalyst can be improved by bringing the rubber rubber latex into contact with an adsorbent. Furthermore, the production method of the present invention is characterized in that the hydrogenation catalytic activity can be improved without particularly adjusting the pH or the like of the gen-based rubber latex subjected to the reaction. If the reaction is carried out under basic conditions, the reaction efficiency is further improved and the amount of hydrogenation catalyst used can be further reduced. As basic conditions, the ρΗ of the hydrogenation reaction solution (latex) measured with a pH meter is 7.0 or more, more preferably 8.0 to 12.

[0037] The basic compound for making the hydrogenation reaction liquid basic is not particularly limited. For example, alkali metal compound, alkaline earth metal compound, ammonia, ammonium salt compound, organic amine Compound etc. are mentioned. Preferred are alkali metal compounds and alkaline earth metal compounds.

Alkali metal compounds include hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; lithium bicarbonate, sodium bicarbonate A hydrogen carbonate compound such as potassium hydrogen carbonate is preferably used, and more preferably an alkali metal hydroxide.

[0038] Preferred alkaline earth metal compounds are hydroxides, carbonates and bicarbonates of alkaline earth metals such as magnesium, calcium, strontium and normium. Hydroxide is more preferable.

Ammonium salt compounds include ammonium carbonate and hydrogen carbonate ammonia. I can get lost.

Examples of the organic amine compound include triethylamine, ethanolamine, morpholine, N-methylmorpholine, pyridine, hexamethylenediamine, dodecamethylenediamine, xylylenediamine.

[0039] These basic compounds can be used as they are, or can be used by diluting or dissolving them with an organic solvent such as water or alcohol. The basic compound may be used alone or in combination of two or more, and the amount used may be appropriately selected so that the hydrogenation reaction solution exhibits basicity. Further, the method and timing of adding the basic compound to the hydrogenation reaction liquid are not particularly limited. For example, before adding the hydrogenation catalyst to the hydrogenation reaction liquid, the basic compound is previously added to the latex. And a method in which a basic compound is added after the start of the hydrogenation reaction.

Furthermore, a catalyst stabilizer can be used for the purpose of maintaining the stability of the platinum group element compound in the latex. Specific examples of the catalyst stabilizer include polybulurpyrrolidone, polybulol alcohol, polybulucaltal, sodium polyacrylate, sodium polyphosphate, gelatin, albumin, protalbic acid, lysalbic acid and the like. Of these, polybulurpyrrolidone, polybulal alcohol, and sodium polyacrylate are particularly preferred.

[0040] The temperature of the hydrogenation reaction is usually 0 ° C to 200 ° C, preferably 10 to 100 ° C. If the reaction temperature is too high, side reactions such as hydrogenation of nitrile groups may occur, which is undesirable. On the other hand, if it is too low, the reaction rate decreases, which is not practical.

The hydrogen pressure is preferably 0.1 MPa to 20 MPa, more preferably 0.1 MPa to 1 OMPa. The reaction time is not particularly limited, but is usually 30 minutes to 50 hours.

[0041] According to the method for producing the hydrogenated rubber latex, particularly the hydrogenation reaction under basic conditions, the hydrogenation reaction proceeds rapidly despite the reaction in the latex state. The hydrogenation rate of the obtained hydrogenated latex can be arbitrarily controlled in the range of 1 to 100% by appropriately changing the various reaction conditions described above.

In such a method for producing hydrogenated rubber latex, a platinum group element used for the hydrogenation reaction is complexed with a complexing agent to form a water-insoluble complex, which is filtered and centrifuged. The latex force is preferably separated by adsorption or the like. In that case, it is preferable to carry out the oxidation treatment by bringing the reduced catalyst in the system after completion of the hydrogenation reaction into contact with an oxidizing agent. By performing the oxidation treatment, a complex is more easily generated.

[0042] The complexing agent is added to the latex after completion of the hydrogenation reaction in the form of powder or solution. In order to form a complex by bringing a complexing agent and a platinum group element into contact with each other and to precipitate this in a latex and to grow or agglomerate it to a particle size larger than the polymer particles, stirring in a heated state followed by static It is preferable to take the steps of placing and cooling. The latex pH at the time of complex formation is preferably adjusted to about 8 to 10.5.

[0043] The complexing agent is not particularly limited as long as it forms a water-insoluble complex with the platinum group element, but a water-insoluble complex having a strong self-aggregation property is preferable. Specific examples include oxime compounds, and OC and β-alkanedione dioximes such as dimethyl daroxime and cyclohexanedione dioxime, which are preferred as dioxime compounds because of their strong complexing ability, are more preferred. Of these, dimethyldarioxime is most preferable. The amount of the complexing agent used is preferably 1 to 50 times mol, more preferably 2 to 30 times mol, with respect to the platinum group element of the catalyst used.

[0044] By adding a complexing agent, precipitates precipitated in the latex and having a particle size larger than the polymer particles are removed from the latex by a known simple separation operation such as filtration or centrifugation. To be recovered. For example, when the precipitate is filtered, the filtering device and the filtering method are not limited except that a filter cloth that passes only latex is used. Both vacuum filtration and pressure filtration can be used. In order to perform filtration efficiently, it is preferable to coat the filter cloth with a filter aid such as diatomaceous earth. The catalyst recovered as a precipitate in this way can be used for the hydrogenation reaction after regenerating as necessary.

The method for producing a cosmetic puff of the present invention is characterized in that a hydrogenated rubber latex having a hydrogenation rate of 2 to 40% is foamed and then coagulated.

A method for producing foam rubber from the above-described gen-based rubber latex having a hydrogenation rate will be described.

In the present invention, the foam rubber production method itself is not particularly limited. For example, conventional methods such as a method of foaming a Gen rubber latex with a foaming agent or a foaming machine, etc. Any known method can be used. When producing foam rubber, first add vulcanizing agent, vulcanization aid, other compounding agents, and if necessary coagulant to hydrogenated rubber latex, and mix and disperse to form rubber. A hydrogenated rubber latex composition for production is prepared.

[0046] The vulcanizing agent and the vulcanizing aid can be used as long as they are used in the production of ordinary foam rubber using a gen-based rubber latex, and are not particularly limited. Examples of the vulcanizing agent include sulfur, particularly colloidal sulfur, and examples of the vulcanizing aid include acid oxide and vulcanization accelerator. Examples of vulcanization accelerators include 2-mercaptobenzozothiazole and its zinc salt, thiazole accelerators such as dibenzothiazyl disulfide, and dithiocarbamate vulcanization accelerators such as zinc jetyldithiocarbamate. Medicines. The amount of these vulcanizing agents and vulcanizing auxiliaries is not particularly limited, but sulfur 0.1 to: LO parts by weight, zinc oxide 0.5 to 0.5 parts per 100 parts by weight of the solid content of the Gen rubber latex. 10 parts by weight, vulcanization accelerator 0.1 to 5 parts by weight. The amount used is determined to meet the required performance of cosmetic puffs.

[0047] Examples of the compounding agent used as necessary include an anti-aging agent, a coloring agent, and a foam stabilizer. Examples of the dispersant for stably dispersing the various compounding agents in latex include NASF (a sodium salt of naphthalenesulfonic acid formalin condensate). Examples of the thickener include polyacrylic acid and its sodium salt, sodium alginate, and polyvinyl alcohol. As the foam stabilizer, a surfactant, for example, an aliphatic alkali soap such as potassium oleate or a higher alcohol sulfate such as sodium dodecyl sulfate is added to the hydrogenated rubber latex in the required amount. This comes out.

[0048] The foam rubber used in the present invention can be obtained by adding the above-mentioned additive to the hydrogenated rubber latex, foaming it, and then coagulating and vulcanizing it. As a gas for foaming the hydrogenated latex composition obtained by adding the above-mentioned various additives, usually, air is used. Carbonate such as ammonium carbonate and sodium bicarbonate; azodicarboxylic acid Azo compounds such as amide, azobisisobutyoritol-tolyl, etc .; from blowing agents that are gas generating substances such as benzenesulfonyl hydrazide The gas generated can also be used. In the case of using air, a method of stirring the hydrogenated rubber latex composition and entraining air is used for foaming. For example, an oak foaming machine or an ultrasonic foaming machine can be used. it can.

[0049] The hydrogenated latex composition is foamed at a predetermined foaming ratio by the above-described method or the like, and the foamed latex is coagulated in order to fix it in the foamed state. The coagulation method is not particularly limited as long as the latex can be gelled and solidified, and any conventionally known method can be used. For example, sodium hexafluorosilicate sodium coagulant as a coagulant (sodium fluorosilicate, potassium), titanium fluoride sodium compound such as titanium fluoride is added to the foamed latex (normal temperature) A coagulation method); a thermal coagulation method in which a thermal coagulant such as an organopolysiloxane, polybutymethyl ether, or zinc sulfate ammonium complex is added to the foamed latex; a freeze coagulation method or the like is used. The amount of the coagulant used is not particularly limited, but is usually about 0.5 to about LO parts by weight with respect to 100 parts by weight of the latex (solid content).

[0050] The foamed latex composition to which the coagulant is added and still having fluidity is transferred to a mold having a predetermined shape and coagulated, and then vulcanized at a temperature of about 100 to 160 ° C for about 15 to 60 minutes, for example. By doing so, foam rubber can be obtained. Mold strength Take out the foam rubber and wash it with water at about 20-70 ° C for about 5-15 minutes with stirring. After washing, drain the water and dry at a temperature of about 30-90 ° C so that the texture of the foam rubber is not impaired!

A cosmetic puff can be produced by molding the foam rubber obtained by the above method. In the production of such a cosmetic puff, usually, the obtained foam rubber is sliced to a predetermined thickness, cut into a predetermined shape, and then the side surface is polished with a rotating turret to make the cosmetic puff. Is manufactured.

[0051] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and the embodiment has substantially the same configuration as the technical idea described in the claims of the present invention. Are also included in the technical scope of the present invention.

Example [0052] The present invention will be specifically described below with reference to Examples and Comparative Examples. Unless otherwise stated, “%” related to parts or formulation is based on weight.

[0053] Preparation of NMR measurement sample

Dissolve hydrogenated rubber latex in acetone, then re-precipitate with methanol and dissolve 40 mg of purified sample in 1 ml of heavy chloroform. After the sample was completely dissolved, the sample solution was transferred to an NMR sample tube with a diameter of 5 mm to prepare an NMR measurement sample.

[0054] (2) Preparation of NBR latex

(Production Example 1)

A pressure-resistant reactor was charged with 140 parts of ion exchange water, 25 parts of acrylonitrile, 0.3 part of t-dodecyl mercaptan, 3 parts of potassium oleate and 0.05 part of sodium ethylenediaminetetraacetate, and the atmosphere was replaced with nitrogen. After adding 75 parts of butadiene, the temperature of the contents was set at 5 ° C. while stirring, and 0.05 part of cumene hydride peroxide and 0.001 part of ferrous sulfate were added to initiate the polymerization reaction. After 20 hours, N, N-jetylhydroxylamine was added to terminate the polymerization reaction at a conversion rate of 95% to obtain an NBR latex.

Add the same amount of butadiene to the NBR latex as the solid weight of the NBR latex, stir at a temperature of 15 ° C with a paddle type stirring blade at a rotation speed of 1, OOOrpm for 5 hours, and enlarge the particle size To obtain NBR latex (LX-1).

[0055] (Production Example 2)

The total solid concentration of the latex was adjusted to 15%, and 1 part of an iminoacetic acid-based chelate ion-exchanged resin (trade name: Amberlite IRC748, manufactured by Organo Corporation) was added to 100 parts of the NBR latex. After stirring for 3 hours at a temperature of 25 ° C., the chelate resin was removed by filtration.

[0056] To 300 mL of palladium catalyst acidic aqueous solution obtained by adding nitric acid of 5 times molar equivalent of palladium to palladium chloride (the amount used is Pd metal Z and the ratio of NBR is 250 ppm), the weight average molecular weight is 5, 000 polyburrpyrrolidone was added in an amount 5 times that of palladium. Further, an aqueous solution of potassium hydroxide and potassium was added to prepare an aqueous catalyst solution having a pH of 6.5.

[0057] 100 parts of NBR latex contacted with a chelate ion exchange resin as described above, and the catalyst 37.5 parts of the aqueous solution was put into an autoclave equipped with a stirrer, and nitrogen gas was allowed to flow for 10 minutes to remove dissolved oxygen in the rattus. The inside of the system was replaced twice with hydrogen gas and then pressurized with hydrogen to bring the inside of the system to 5 MPa. The contents were heated to 55 ° C and reacted for 4 hours to obtain hydrogenated NBR latus status.

Next, the pH of the hydrogenated NBR latex was adjusted to 9.5, and dimethyldarioxime corresponding to 5 times the molar amount of noradium was added as a powder. When heated to 80 ° C and stirred for 5 hours, insolubles were precipitated in the latex. The entire amount of the latex was suction filtered to separate the precipitate. The obtained white filtrate was concentrated under reduced pressure using a rotary evaporator to obtain a hydrogenated NBR latex (LX-2) having a solid concentration of 66%. As a result of conducting proton NMR measurement of the obtained LX-2, the hydrogenation rate of LX-2 was 30%.

[0058] (Production Example 3)

A pressure-resistant reactor was charged with 180 parts of ion-exchanged water, 37 parts of acrylonitrile, 0.5 part of t-dodecyl mercaptan and 2 parts of potassium oleate and purged with nitrogen. After adding 63 parts of butadiene, the temperature of the contents was changed to 10 ° C. while stirring, and 0.01 part of tamenoid oxide and 0.01 part of ferrous sulfate were added to initiate the polymerization reaction. . After 16 hours, a 10% hydroquinone aqueous solution was added to stop the polymerization reaction at a conversion rate of 90%, and unreacted monomers were removed. The NBR latex obtained here was hydrogenated in the same manner as in Production Example 2 except that the amount of palladium chloride used as the catalyst was changed to 700 ppm in terms of the ratio of Pd metal ZNBR, and the hydrogenation rate was 90%. NBR latex (LX-3) was obtained.

[0059] (3) Method for producing cosmetic puff

(Examples 1 to 3)

A latex containing 65% solid content LX-1 and 40% solid content LX-3 with the formulation shown in Table 1 is mixed with 5 parts colloidal sulfur dispersion (solid content 50%), zinc white dispersion. (Solid content 50%) 3 parts and trimene base aqueous solution (solid content 50%) 1 part were added and stirred with a hand mixer and mechanically foamed. Next, 3 parts of sodium silicofluoride (solid content 20%) was added and stirred, then poured into a rectangular parallelepiped mold (200 mm X 150 mm X 10 mm) and allowed to stand for 10 minutes. After that, it was vulcanized at 110 ° C for 40 minutes. The foam rubber taken out from the mold was punched with a circular cylinder with a diameter of 38 mm. Next, it is thoroughly washed in running water and then dried to make it cosmetic. I got a puff.

[Example 4]

A cosmetic puff was prepared in the same manner as in Example 1 except that 100 parts of LX-2 was used as latex.

(Comparative Example 1)

A cosmetic puff was prepared in the same manner as in Example 1 except that 100 parts of LX-1 was used as latex.

[0061] A sensory test was conducted on the moist feeling of these cosmetic puffs.

The cosmetic puffs of Examples 1 to 4 and Comparative Example 1 were evaluated according to the following evaluation criteria by 8 female panelists, and the evaluation results having the largest number of evaluators were used. The results are shown in Table 1.

[0062] A: Moist feeling is very good

○: Moist feeling is good

X: Moist feeling is not good

[0063] [Table 1]

As is apparent from Table 1, the cosmetic puffs of the examples within the scope of the present invention had a specific moist feeling as compared with the comparative examples.

Claims

The scope of the claims

[1] A cosmetic puff characterized by having a foam rubber power mainly composed of hydrogenated rubber.

[2] The hydrogenated rubber-based rubber force is a hydride of a copolymer comprising a conjugated diene monomer unit and an ethylenically unsaturated-tolyl monomer unit. The cosmetic puff according to Item.

[3] The cosmetic puff according to claim 1 or 2, wherein the hydrogenation rate of the hydrogenated rubber is 2 to 40%.

[4] The cosmetic puff according to any one of claims 1 to 3, wherein the foam rubber force is obtained by foaming and then coagulating the hydrogenated rubber latex.

[5] A method for producing a cosmetic puff comprising the steps of foaming and then coagulating a hydrogenated rubber latex having a hydrogenation rate of 2 to 40%.

[6] A hydrogenated product of a copolymer obtained by polymerizing a monomer mixture comprising a conjugated diene monomer and an ethylenically unsaturated-tolyl monomer. The method for producing a cosmetic puff according to claim 5.