JP5465371B2 - Anionic water-based polyurethane resin composition for producing cosmetic puff and method for producing cosmetic puff - Google Patents

Description

  The present invention relates to an anionic water-based polyurethane resin composition for producing a cosmetic puff and a method for producing a cosmetic puff. More specifically, the present invention is excellent in moldability during production, weather resistance, oil resistance, water resistance, and compression. The present invention relates to an anionic water-based polyurethane resin composition for producing a highly functional cosmetic puff having good residual strain and excellent durability, and a method for producing a cosmetic puff.

Conventionally, natural rubber latex has been mainly used as a raw material latex used for cosmetic puffs because the foam feel (soft feeling) obtained is good. However, cosmetic puffs made from natural rubber latex have the following drawbacks.
(1) The weather resistance is poor and it becomes tattered during use.
(2) It is swelled by the oil contained in the foundation.
(3) Due to the proteins and organic substances contained in the natural rubber latex, microorganisms during the use of the puff are propagated and "mold" is generated.

  In order to eliminate these drawbacks, cosmetic puffs using synthetic rubber latex such as NBR have been used, but the effect of improving weather resistance and oil resistance was quite insufficient.

  On the other hand, it is well known to produce a foam from a polyurethane resin. In general, a polyurethane resin is excellent in weather resistance and oil resistance, and has a feature that flexibility can be adjusted by adjusting the degree of crosslinking. Furthermore, it is also known to produce a foam using an aqueous polyurethane resin in which a polyurethane resin is dispersed in water. For example, Patent Document 1 describes that a water-soluble or water-dispersible epoxy resin and its curing agent are added when a polyurethane emulsion is mechanically foamed to form a foam. However, these methods resulted in a non-uniform foam and could not be used as a cosmetic puff.

In addition, it is also proposed to use a polyurethane resin and a synthetic rubber in combination as a raw material for a cosmetic puff. For example, Patent Document 2 discloses an NBR (nitrile-butadiene-rubber) emulsion, a water-soluble urethane emulsion, a crosslinking agent, A method for producing a puff substrate from a composition containing a surfactant and a gelling agent is described. However, in this method, since the solid content of the NBR emulsion is 60% by mass or more based on the total emulsion, the feel is excellent, but sufficient performance is not obtained in terms of weather resistance and elasticity. Furthermore, Patent Literature 3, Patent Literature 4 and the like describe a cosmetic puff by combining foams with different foaming ratios or a combination of a rubber foam and a urethane foam. However, although this cosmetic puff is excellent in softness, softness, and feeling on the skin, it was not satisfactory in terms of weather resistance. Furthermore, the conventional cosmetic puff also has a problem that the water resistance strength is lowered when it comes into contact with an aqueous cosmetic such as an aqueous foundation. As a method for solving all these problems, Patent Document 5 discloses an aqueous urethane resin composition using an anionic emulsifier.
Japanese Patent Laid-Open No. 52-119697 Japanese Patent Publication No. 8-5988 Japanese Utility Model Publication No. 60-33863 JP 62-148608 A JP 2002-146181 A

  However, the water-based urethane resin composition described in Patent Document 5 is not necessarily sufficient in terms of compressive residual strain, which is an index of durability.

  Therefore, the object of the present invention is excellent in moldability when manufacturing a cosmetic puff using a polyurethane resin, weather resistance, oil resistance, water resistance, and good compressive residual strain and durability. An object of the present invention is to provide an excellent anionic water-based polyurethane resin composition for producing a cosmetic puff and a method for producing a cosmetic puff.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by water-dispersing a predetermined aqueous polyurethane resin with an anionic emulsifier, and the present invention It came to be completed.

That is, the cosmetic puff producing anionic aqueous polyurethane resin composition of the present invention, 3 was allowed crosslinked by polyfunctional isocyanate compound, a polyurethane resin having an anionic group, Ri Na is water dispersible by anionic emulsifiers, and, the trifunctional isocyanate compound is characterized in adduct der Rukoto trimers or triol of diisocyanate monomers.

  The method for producing a cosmetic puff of the present invention is characterized in that the anionic water-based polyurethane resin composition is foamed and then cured into a predetermined shape.

  According to the present invention, a polyurethane resin is used to achieve an excellent effect on moldability when producing a cosmetic puff, and weather resistance, oil resistance, water resistance, and further, compression residual strain is good and durability is improved. An excellent anionic water-based polyurethane resin composition for producing a cosmetic puff and a method for producing a cosmetic puff can be provided.

  Hereinafter, the anionic water-based polyurethane resin composition for producing a cosmetic puff of the present invention and the method for producing the cosmetic puff will be described.

  The anionic aqueous polyurethane resin composition according to the present invention is obtained by a method of emulsifying a trifunctional isocyanate compound (A) and a polyurethane resin (B) having an anionic group with an anionic emulsifier (C).

  Specifically, such an anionic water-based polyurethane resin includes a trifunctional isocyanate compound (A), a polyol (b-1) having a carboxyl group or a sulfonic acid group as an anionic group in the molecule, and a polyol component (b-2). And an organic polyisocyanate (b-3) are reacted to form a prepolymer (hereinafter sometimes referred to as polyurethane resin (B)), and then the prepolymer is blended with an anionic emulsifier (C) and a neutralizing agent (D). It is produced by a known method such as a method of dispersing in water in addition to water and increasing the molecular weight with a chain extender (E).

  The trifunctional isocyanate compound (A) is preferably a compound that is a trimer of a diisocyanate monomer or an adduct of a triol.

  Examples of the diisocyanate monomer (a-1) include aliphatic, cycloaliphatic and aromatic polyisocyanates. Specifically, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine. Diisocyanate ester, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, isophorone diisocyanate 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2, '-Diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, polyphenylpolymethylene polyisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 3,3'-dimethoxy-4,4 '-Biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, etc. are mentioned, among them hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate. The polymer is particularly preferred because it is easy to obtain and inexpensive.

  As the triol (a-2) used for obtaining the adduct body, a known trifunctional polyol can be used, and is not particularly limited. Examples thereof include glycerin, trimethylolpropane, ethylene oxide and propylene oxide, and the like. A polyether triol to which an alkylene oxide is added can be used. A polyether triol having a long ether chain lowers the crosslinking density of a polyurethane resin using the polyether triol, and is considered to have an effect on a decrease in physical properties. Therefore, a low molecular weight triol is preferable, and glycerin and trimethylolpropane are particularly preferable.

  Although the usage-amount of a trifunctional isocyanate compound (A) is based also on the kind of polyol and polyisocyanate to be used, it is usually 0.01-0.30 mol with respect to 1.0 mol of a polyol component (b-2), Preferably 0.05 to 0.15 mol is used. When the amount of the trifunctional isocyanate compound (A) used is less than 0.01 mol, the effect such as compression residual strain is small, and when it exceeds 0.30 mol, the workability deteriorates due to the increase in viscosity during prepolymer production. It is not preferable because it adversely affects various properties such as deterioration of water dispersibility of the prepolymer and compression residual strain.

  Examples of the polyol (b-1) having a carboxyl group or a sulfonic acid group in the molecule include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, 1, Examples include 4-butanediol-2-sulfonic acid. The amount of the polyol having a carboxyl group or sulfonic acid group used depends on the type of polyol and polyisocyanate used and the NCO / OH ratio, but is usually 0 with respect to 1.0 mol of the polyol component (b-2). 0.03 to 1.0 mol, preferably 0.1 to 0.7 mol is used. When the amount of the polyol (b-1) having a carboxyl group or a sulfonic acid group is less than 0.03 mol based on 1.0 mol of the polyol component (b-2), the dispersibility of the urethane prepolymer in water and the aqueous polyurethane The storage stability of the resin is inferior, and if it exceeds 1.0 mol, various performances such as compression residual strain may be adversely affected.

  Examples of the polyol component (b-2) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, and 1,3-butylene glycol. 1,4-butylene glycol, neopentyl glycol, 1,6-hexanediol, hexamethylene glycol, 3-methylpentanediol, trimethylolethane, trimethylolpropane, hexanetriol, glycerin, pentaerythritol, sorbitol, hydrogenated bisphenol A, low molecular weight polyols such as ethylene oxide and / or propylene oxide adducts of bisphenol A; polyethylene glycol, polypropylene glycol, polyethylene and / or pro Polyether polyols such as lenglycol and polytetramethylene ether glycol; low molecular weight polyols or ethylene oxides of low molecular weight amine compounds having two or more active hydrogens such as ammonia and methylamine, ethylamine, aniline, phenylenediamine, isophoronediamine, and / or Or a propylene oxide polyaddition product; a low molecular weight polyol and succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexahydrophthalic acid, etc. Polyester polyol which is a condensate with basic acid or carbonic acid; polycarbonate polyol; polysilicone polyol and polycaprolactone. The amount of the polyol component (b-2) used is preferably 0.25 to 2 times equivalent, more preferably 0.3 to 1 time equivalent to the isocyanate equivalent.

  As the organic polyisocyanate (b-3), well-known general polyisocyanates can be used, and examples thereof include aliphatic, alicyclic and aromatic polyisocyanates. The isocyanate compound etc. which were shown to -1) are mentioned.

  The total use amount of the trifunctional isocyanate (A) and the organic polyisocyanate (b-3) is the sum of active hydrogens of the polyol (b-1) and polyol (b-2) having a carboxyl group or a sulfonic acid group. On the other hand, it is preferably used in an amount of 0.5 to 5 times equivalent, more preferably 1 to 3 times equivalent. If the amount of isocyanate used is less than 0.5 times equivalent, excess polyol or the like will remain, and if it is more than 5 times equivalent, a large amount of urea bonds will be formed when water is added. In either case, there is a risk of deteriorating the characteristics.

  As the anionic emulsifier (C), an anionic surfactant can be used.

  Examples of the anionic surfactant include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate, ammonium dodecyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium sulforicinone; alkali metal salt of sulfonated paraffin, sulfonated paraffin Alkyl sulfonates such as ammonium salts of sodium; sodium laurate, triethanolamine oleate, triethanolamine abietate, sodium laurate, potassium laurate, coconut oil soap, sodium myristate, sodium stearate, sodium palmitate, sodium oleate , Fatty acid salts such as potassium oleate; sodium benzenesulfonate, alkali pheno Alkyl aryl sulfonates such as alkali metal sulfate of hydroxyethyl; High alkyl naphthalene sulfonate; Naphthalene sulfonic acid formalin condensate; Dialkyl sulfosuccinate; Polyoxyethylene alkyl sulfate salt; Polyoxyethylene alkyl aryl sulfate salt .

  The content of the anionic surfactant varies depending on the type of the surfactant and the hydrophobicity of the polymer, but is preferably 0.05 to 10% by mass in the aqueous polyurethane resin composition (emulsion) according to the present invention. More preferably, the content is 0.1 to 5% by mass.

  Examples of the neutralizing agent (D) include organic amines such as ammonia, trimethylamine, triethylamine, tripropylamine, tributylamine, N-methyldiethanolamine, and triethanolamine, and inorganic bases such as sodium hydroxide, potassium hydroxide, and ammonia. These are used in an amount sufficient to neutralize the carboxy or sulfonic acid groups.

  As the chain extender (E), a commonly used chain extender is used, and examples thereof include a low molecular weight polyol compound and a low molecular polyamine compound having an average molecular weight of less than 200, such as ethylene glycol and 1,2-propylene. Glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 3-methylpentanediol, di Polyols such as methylolpropionic acid, trimethylolpropane, pentaerythritol, ethylenediamine, propylenediamine, hexamethylenediamine, tolylenediamine, xylylenediamine, diaminodiphenylamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, Sophoronediamine, melamine, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide, hydrated hydrazine, 1,6-hexamethylenebis (N, N-dimethylsemicarbazide), 1,1,1 ', 1' -Amines such as tetramethyl-4,4 '-(methylene-di-para-phenylene) disemicarbazide and water. These chain extenders can be used alone or in combination of several kinds, and the amount used depends on the molecular weight of the target polyurethane resin, but is usually based on the residual isocyanate equivalent of the prepolymer. 0.1 to 1.5 equivalents are used.

  Moreover, a solvent can be used as needed to produce the prepolymer (polyurethane resin (B)). Those usually used for the production of polyurethane resins can be used, and a solvent which is inactive to the NCO group or low in activity is preferred. Specifically, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as n-hexane; alcohols such as tertiary butanol Solvents; ether solvents such as dioxane and tetrahydrofuran; ester solvents such as ethyl acetate and cellosolve acetate; amide solvents such as dimethylformamide and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; N-methyl-2-pyrrolidone and the like And other lactam solvents. Among these, ketone solvents such as acetone and methyl ethyl ketone or N-methyl-2-pyrrolidone are particularly preferable from the viewpoints of solubility of the prepolymer during synthesis of the polyurethane resin, dispersibility in water, and the like. These solvents are preferably used in an amount of 3 to 100% by mass based on the total amount of the raw materials used for producing the prepolymer. Among these solvents, a solvent having a boiling point of 100 ° C. or lower is preferably distilled off under reduced pressure after the prepolymer synthesis.

  As described above, it is well known to produce an anionic polyurethane resin from these raw materials, and the order in which these raw materials are charged can be appropriately changed, or can be charged in divided portions.

  The anionic water-based polyurethane resin composition according to the present invention preferably contains a compound capable of reacting with an anionic group (specifically a carboxyl group or a sulfonic acid group) for the purpose of further improving the water resistance. Specific examples of the compound capable of reacting with an anionic group (hereinafter referred to as a sequestering agent) include oxazoline compounds, epoxy compounds, carbodiimide compounds, aziridine compounds, melamine compounds, and zinc complexes. Among these, an oxazoline compound, an epoxy compound, and a carbodiimide compound that can easily react with an anionic group are particularly preferably used.

  Examples of the oxazoline compounds include 2-oxazoline, 2,2′-p-phenylenebis (2-oxazoline), 2,2 ′-(1,3-phenylenebis (2-oxazoline), 4-methyl-2. -Oxazolyl groups obtained by grouting oxazolyl groups on polymers such as oxazoline, 2,2'-bis (2-oxazoline), 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, and styrene or acrylic compounds For example, it is possible to use commercial products such as trade names Epocros K-1010E, Epocros K-1020E, Epocros K-1030E, Epocros K-1050E, and Epocros K-2010E manufactured by Nippon Shokubai Co., Ltd. it can.

  Examples of the epoxy compound include a monoepoxy type having one epoxy group and a polyepoxy type having two or more epoxy groups. Mono-epoxy type epoxy compounds include α-olefin oxides such as ethylene oxide, propylene oxide, butylene oxide, and 1,4-butylene oxide; cyclohexene oxide; epichlorohydrin; glycidol; allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, etc. Glycidyl ether compound of monovalent aliphatic alcohol; Glycidyl ether compound of monovalent phenol compound such as phenol, 4-methylphenol, 4-tert-butylphenol, 2,4-ditert-butylphenol; Aliphatic carboxylic acid or aroma Glycidyl ester compounds of group carboxylic acids and the like, for example, Adekaglycidol ED-501, ED-502, ED-509, ED-518, ED-529 (Corporation A) EKA made, can be used trade name), further EPIOL A, EPIOL B, EPIOL OH, EPIOL P, EPIOL M, EPIOL EH, Blenmer G (manufactured by NOF Corp., a commercially available product trade name) and the like.

  Examples of polyepoxy type epoxy compounds include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcin, pyrocatechol, and phloroglucinol; dihydroxynaphthalene, biphenol, methylene bisphenol (bisphenol F), methylene bis ( Orthocresol), ethylidene bisphenol, isopropylidene bisphenol (bisphenol A), isopropylidene bis (orthocresol), tetrabromobisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4- Hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, Polyglycidyl ether compounds of polynuclear polyhydric phenol compounds such as hobisphenol, oxybisphenol, phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, terpene diphenol; ethylene glycol, propylene glycol, butylene Polyglycidyl ethers of polyhydric alcohols such as glycol, hexanediol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct; maleic acid, fumaric acid, itaconic acid, succinic acid Acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer Aliphatic, aromatic or alicyclic such as acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid Homopolymers or copolymers of glycidyl esters of polybasic acids and glycidyl methacrylate; glycidylamino groups such as N, N-diglycidylaniline and bis (4- (N-methyl-N-glycidylamino) phenyl) methane And epoxy compounds having vinylcyclohexene dioxide. For example, Adekaglycil ED-503, ED-506, ED-513, ED-523, ED-612, ED-505, ED-507, Adeka Resin EP-4000, EP-4005, EP-4085, EP-4000S, Commercial products such as EP-4080S and EP-4085S (trade name, manufactured by ADEKA Corporation) can be used.

  The carbodiimide-based compound is a compound represented by R′—N═C═N—R ″, and an organic diisocyanate is converted into a carbodiimidization compound such as a phospholene compound, a metal carbonyl complex compound, and a phosphate ester. Those obtained by reacting in the presence of a catalyst that promotes the use of dipropylcarbodiimide, dihexylcarbodiimide, dicyclohexylcarbodiimide, di-p-trioylcarbodiimide and triisopropylbenzene poly Carbodiimide etc. are mentioned, For example, Nisshinbo Co., Ltd. brand name carbodilite E-01, carbodilite E-02, etc. can use commercial items.

  Examples of the aziridine compound include diphenylmethane-bis-4-4′-NN′-diethyleneurea, 2,4,6-tris (1′-aziridinyl) -1,3,5-triazine, 2,2- And bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate].

  The said blocking agent is 0.001-10 mass parts as solid content of a blocking agent with respect to 100 mass parts of anionic water-based polyurethane resin composition solid content. In addition, the equivalent ratio of the blocking agent to the anionic group based on the anionic aqueous polyurethane resin composition is 0.1 to 3.0, and more preferably 0.5 to 2.0. If the equivalent ratio of the sequestering agent is less than 0.1, the effect of blending the sequestering agent cannot be obtained, and if it exceeds 3.0, an excess sequestering agent remains, which deteriorates the physical properties of the resulting cosmetic puff. Therefore, it is not preferable.

  The anionic water-based polyurethane resin composition according to the present invention includes a light stabilizer such as a phenol-based antioxidant, an organic phosphorus-based antioxidant, a thioether-based antioxidant, an ultraviolet absorber, or a hindered amine compound as necessary. Fluorine-based or siloxane-based antistatic agents, inorganic colloidal sols such as colloidal silica or colloidal alumina, silane coupling agents, colorants, pigments, wax agents, preservatives, antifoaming agents, plasticizers, solvents, film-forming aids Conventional additives such as dispersants, thickeners, and fragrances can also be added. The additive may be blended during the production of the water-based polyurethane resin or may be blended during the production of the foam described below.

  The resin solid content of the anionic aqueous polyurethane resin in the anionic aqueous polyurethane resin composition according to the present invention is preferably 50% by mass or more, more preferably 50 to 80% by mass, and particularly preferably 55 to 70% by mass. is there. When the resin solid content is less than 50% by mass, foaming of the resulting foam becomes non-uniform, the drying time becomes long, and sufficient mechanical strength cannot be obtained. It becomes high and a uniform foam cannot be obtained.

  Next, the manufacturing method of the cosmetic puff by the anionic water-based polyurethane resin composition for cosmetic puffs of this invention is demonstrated.

  As described above, the cosmetic puff can be obtained by foaming the anionic water-based polyurethane resin composition according to the present invention as shown below and then curing it in a predetermined shape.

  That is, the anionic water-based polyurethane resin composition according to the present invention is mixed with a foaming agent, a foaming aid, a foam stabilizer, a crosslinking agent, and the like as necessary, and then sufficiently bubbled by mixing a gas such as air. The expansion ratio is appropriately adjusted in the range of 2 to 20 times depending on the amount of the foaming agent and foaming aid. The stirring speed at the time of foaming is not particularly limited as long as the gas mixed in the anionic water-based polyurethane resin composition (emulsion composition) according to the present invention is well dispersed, and the stirring time is appropriately adjusted.

  After the anionic water-based polyurethane resin composition is foamed, a curing accelerator is preferably mixed and further mixed. Thereafter, it is poured into a mold and cured by heating. After curing, remove from the mold and wash away excess surfactant and dry to obtain a cosmetic puff.

  The curing accelerator is also called an emulsion breaker or a gelling agent, and specific examples thereof include sodium silicofluoride and potassium silicofluoride. The addition amount of the curing accelerator is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass with respect to the anionic aqueous polyurethane resin in the anionic aqueous polyurethane resin composition according to the present invention. It is. By blending a curing accelerator, the foam bubbles become fine and the curing time is shortened even during curing.

  In addition to the anionic surfactants exemplified as the emulsifier, examples of the foaming aid include higher alcohol sulfate sodium, saponin, gelatin, and casein. The amount of the foaming auxiliary added is preferably 0.05 to 20% by mass, more preferably 0.1 to 5% by mass, based on the anionic aqueous polyurethane resin composition (emulsion) according to the present invention. is there.

  Examples of the foam stabilizer include alkylamine oxides such as lauryldimethylamine oxide; fatty acid alkanolamides such as lauric acid monoethanolamide, lauric acid monoisopropanolamide, lauric acid diethanolamide, and coconut oil fatty acid diethanolamide. The amount of the foam stabilizer added is preferably 0.05 to 20% by mass, more preferably 0.1 to 5% by mass with respect to the anionic aqueous polyurethane resin composition (emulsion) according to the present invention. is there.

  In the cosmetic puff according to the present invention, the anionic water-based polyurethane resin composition is used as a main component as a latex component. If necessary, other water-based urethane emulsions and acrylic-based water can be added to the anionic water-based polyurethane resin composition. Emulsions, epoxy emulsions, rubber emulsions, other aqueous resins, and the like can be blended.

  The cosmetic puff according to the present invention comprises an anionic water-based polyurethane resin composition as a main component, and optionally contains the above other ingredients, but an anionic water-based polyurethane with respect to the total resin solid content of the cosmetic puff. The resin solid content of the resin is preferably 50% by mass or more, more preferably 80% by mass or more. When the content of the anionic water-based polyurethane resin is less than 50% by mass, the shape of the foamed cell may be non-uniform or the weather resistance and oil resistance may be reduced.

  The cosmetic puff according to the present invention is not limited to a cosmetic puff molded as a final product, but also means a cosmetic puff substrate before molding.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples.

<Synthesis of prepolymer>
According to the formulation described in [Table 1-1] to [Table 1-5], (A) a trifunctional isocyanate, (b-1) a polyol having an anionic group, (b-2) a polyol component under a nitrogen stream, (B-3) The isocyanate component was reacted at 100 ° C. for 3 hours to obtain a prepolymer (PP). The numerical values other than the NCO / OH equivalent ratio in [Table 1-1] to [Table 1-5] are all expressed in molar ratios. Here, the NCO / OH equivalent ratio is the sum of the trifunctional isocyanate (A) and the organic polyisocyanate (b-3), and the polyol (b-1) and polyol (b-2) having a carboxyl group or a sulfonic acid group. The equivalent ratio of the total of active hydrogens is shown.

The abbreviations of the raw materials used in Table 1-1 to Table 1-5 are shown below.
[Trifunctional isocyanate]
HDI nurate; trimer of hexamethylene diisocyanate HDI / TMP adduct; adduct of hexamethylene diisocyanate and trimethylolpropane (molar ratio 3: 1); TDI / TMP adduct; tolylene diisocyanate and trimethylolpropane (molar ratio 3: 1) ) Adduct [polyol having a carboxyl group as an anionic group (hereinafter anionic group)]
DMPA; 2,2-dimethylolpropionic acid [polyol component]
Polyol A; polyester diol of 3-methyl-1,5-pentanediol and adipic acid, molecular weight 2000 (made by Kuraray Co., Ltd., trade name Kurapol P-2010)
Polyol B: 1,6-hexanediol, adipic acid, polyester diol of isophthalic acid (molar ratio 1/1), molecular weight 2000 (manufactured by ADEKA, trade name ADEKA NEW ACE YG-215)
Polyol C: Polytetramethylene ether glycol, molecular weight 2000 (manufactured by Hodogaya Chemical Co., Ltd., trade name PTG-2000)
Polyol D: Polypropylene glycol, molecular weight 1000 (manufactured by ADEKA, trade name ADEKA polyether P-1000)
[Isocyanate component]
IPDI; isophorone diisocyanate H-MDI; 4,4′-dicyclohexylmethane diisocyanate [internal crosslinking agent]
TMP; trimethylolpropane

<Preparation of polyurethane emulsion (anionic aqueous polyurethane resin composition)>
Deionized water in which an emulsifier and a neutralizing agent blended as shown in the following [Table 2] and [Table 3] are dissolved is heated to 40 ° C. while maintaining this temperature, the above [Table 1-1] to [Table 1 5] was added dropwise, followed by addition of a chain extender to increase the molecular weight, thereby obtaining an aqueous polyurethane emulsion (anionic aqueous polyurethane resin composition). However, the neutralizing agent used was triethylamine in an amount of 1: 1 equivalent to the anionic group of the anionic group of the urethane prepolymer. In addition, the numerical value of the amount of the emulsifier in [Table 2] and [Table 3] is shown in parts by mass of the active component of the emulsifier with respect to 100 parts by mass of the polyurethane resin. −5] is represented by an equivalent ratio of the urethane prepolymer to the residual isocyanate group, and the polyurethane resin solid content is represented by mass% of the solid content excluding the emulsifier.

〔乳化剤〕
乳化剤ＳＡ−１；（アニオン性乳化剤）ヤシ油アルコールポリオキシエチレン硫酸ナトリウム 濃度２５質量％（（株）ＡＤＥＫＡ製、商品名アデカホープＹＥＳ−２５）
乳化剤ＳＡ−２；（アニオン性乳化剤）ポリオキシエチレンノニルフェニルエーテル硫酸アンモニウム 濃度３０質量％（（株）ＡＤＥＫＡ製、商品名アデカホープＮＥＳ−６０Ｎ）
乳化剤ＳＡ−３；（アニオン性乳化剤）ヒマシ油脂肪酸カリウム 濃度３３質量％
〔鎖伸長剤〕
ＥＤＡ；エチレンジアミン
ＡＤＨ；アジピン酸ジヒドラジド

〔emulsifier〕
Emulsifier SA-1; (anionic emulsifier) coconut oil alcohol polyoxyethylene sodium sulfate concentration 25% by mass (manufactured by ADEKA, trade name Adeka Hope YES-25)
Emulsifier SA-2; (anionic emulsifier) Polyoxyethylene nonylphenyl ether ammonium sulfate concentration 30% by mass (manufactured by ADEKA, trade name Adeka Hope NES-60N)
Emulsifier SA-3; (anionic emulsifier) Castor oil fatty acid potassium concentration 33% by mass
[Chain extender]
EDA; ethylenediamine ADH; adipic acid dihydrazide

乳化剤ＳＮ−１；（ノニオン性乳化剤）ノニルフェノールエトキシレート 分子量８００ 濃度１００質量％

Emulsifier SN-1; (nonionic emulsifier) nonylphenol ethoxylate molecular weight 800 concentration 100% by mass

[Examples 1-1 to 1-19 and Comparative Examples 1-1 to 1-12] <Production of foam (decorative puff)>
The polyurethane emulsion and NBR emulsion obtained in [Table 2] and [Table 3] (trade name NBR531B manufactured by Nippon Zeon Co., Ltd .; high acrylonitrile product of acrylonitrile butadiene rubber, resin solid content 65% by mass) [Table 4] And 0.5 parts by mass of tetrakis (3,5-ditert-butyl-4-hydroxyphenylpropionyloxymethyl) methane as a phenol-based antioxidant, and potassium oleate as a foaming aid in an amount of 0. 25 parts by mass was mixed, and air was mixed to sufficiently foam. As a hardening accelerator, 4 parts by mass of sodium silicofluoride was mixed and further stirred. Thereafter, it was poured into a mold, heated at 110 ° C. for 7 minutes, cured and dehydrated, removed from the mold, and excess surfactant and the like were removed. Further drying gave a product. The moldability, weather resistance, oil resistance, and repeated compressive residual strain rate of the resulting cosmetic puff were measured.

<Evaluation>
(Formability)
○: Good formability
X: Bubbles are roughened and molding is poor.
(Weatherability)
The tensile strength after irradiation with ultraviolet rays at a black panel of 63 ° C. for 100 hours with a sunshine weather meter (without rain) was measured according to JIS K 6301, and the rate of change (%) from the initial tensile strength was calculated.
(Oil resistance)
After the foam was immersed in mineral oil at room temperature for 100 hours, the tensile strength was measured and the rate of change (%) from the initial tensile strength was calculated.
(Repeated compression residual strain)
In accordance with JIS K 6400-4 (Method B), the compression residual strain rate (%) was measured repeatedly.

  Table 4 shows the composition of the foam and the physical property evaluation results. However, “total puff base resin solids” in [Table 4] is the total of the polyurethane resin solids in the polyurethane emulsion and the resin solids in the NBR emulsion.

[Examples 2-1 to 2-15 and Comparative Examples 2-1 to 2-7]
With respect to 100 parts by mass of the polyurethane emulsion obtained in [Table 2] and [Table 3], a blocking agent was blended in the proportions shown in [Table 5], and the rest of the foam (decorative puff) was prepared in the same manner as in the examples. ) Was manufactured. The resulting cosmetic puff was measured for weather resistance, oil resistance, water resistance and repeated compressive residual strain rate. However, with respect to 100 parts by mass of polyurethane emulsion, 0.25 part by mass of foaming agent (potassium oleate), 4.0 parts by mass of curing accelerator (sodium silicofluoride), phenolic antioxidant (tetrakis (3, 3, 0.5 parts by mass of 5-di-tert-butyl-4-hydroxyphenylpropionyloxymethyl) methane) was blended. Moreover, the ratio% of the polyurethane resin solid content to the total resin solid content of the decorative puff substrate is 100%.
(Water resistance test)
The tensile strength after immersion for 1 hour in water at 40 ° C. was measured, and the rate of change (%) from the initial tensile strength was calculated.

〔封鎖剤＊〕添加量：ポリウレタンエマルジョン１００質量部に対する質量部数、
当量比：ポリウレタンエマルジョン中のＣＯＯＨ基１個に対する封鎖剤の当量比
封鎖剤ＣＡ−１；オキサゾリン系化合物（日本触媒（株）製、商品名エポクロスＫ−２０１０Ｅ）
封鎖剤ＣＡ−２；エポキシ系化合物：ＢＰＡ型エポキシ樹脂エマルジョン固形分６５％
封鎖剤ＣＡ−３；エポキシ系化合物：ブチルグリシジルエーテル
封鎖剤ＣＡ−４；カルボジイミド系化合物：日清紡績（株）製、商品名カルボジライトＥ−０２

[Sequestration agent *] addition amount: parts by mass with respect to 100 parts by mass of polyurethane emulsion,
Equivalent ratio: Equivalent ratio of sequestering agent for one COOH group in polyurethane emulsion CA-1; Oxazoline compound (trade name Epocross K-2010E, manufactured by Nippon Shokubai Co., Ltd.)
Blocking agent CA-2; epoxy compound: BPA type epoxy resin emulsion solid content 65%
Blocking agent CA-3; epoxy compound: butyl glycidyl ether blocking agent CA-4; carbodiimide compound: Nisshinbo Co., Ltd., trade name Carbodilite E-02

  As described above, by using the anionic water-based polyurethane resin composition for producing a cosmetic puff according to the present invention, the moldability during production is excellent, and the weather resistance, oil resistance, water resistance and compressive residual strain are good and durable. Can produce high quality cosmetic puffs.

Claims (6)

Was allowed crosslinked trifunctional isocyanate compound, a polyurethane resin having an anionic group, Ri Na is water dispersible by anionic emulsifiers, and the trifunctional isocyanate compound, a trimer or an adduct of triol diisocyanate monomer cosmetic puff producing anionic aqueous polyurethane resin composition characterized der Rukoto. The solid content of the anionic water-based polyurethane resin, according to claim 1 cosmetic puff for producing anionic aqueous polyurethane resin composition wherein at least 50 wt%. The anionic aqueous polyurethane resin composition for producing cosmetic puffs according to claim 1 or 2, further comprising a compound capable of reacting with an anionic group of the anionic aqueous polyurethane resin. The anionic aqueous polyurethane resin composition for producing a cosmetic puff according to claim 3, wherein the compound capable of reacting with the anionic group is one or more compounds selected from the group consisting of oxazoline compounds, epoxy compounds and carbodiimide compounds. object. A method for producing a cosmetic puff, wherein the anionic water-based polyurethane resin composition according to any one of claims 1 to 4 is foamed and then cured into a predetermined shape. The method for producing a cosmetic puff according to claim 5, wherein the resin solid content of the anionic water-based polyurethane resin composition is 50% by mass or more based on the total resin solid content of the resulting cosmetic puff.