Continuous ventilation sponge and cosmetic puff

Abstract

To provide an open cell-structured sponge that has a moderate liquid absorption rate, and a good skin touch, and a cosmetic puff.SOLUTION: An open cell-structured sponge comprises a mechanical foam of a composition that comprises a polymer polyol comprising dimer acid polyester polyol of 30 mass% or more and 100 mass% or less relative to the total polymer polyol content, diphenyl methane diisocyanate-based isocyanate, a foam stabilizer, and a catalyst. There is also provided a cosmetic puff having the same.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a continuous ventilation sponge and a cosmetic puff. In particular, it relates to an open-cell sponge formed by mechanical foaming and characterized by low water absorption.

Background Art

[0002] The open-cell sponge, which is one application of the present invention, relates to a cosmetic puff that does not allow liquid foundation to soak in excessively. Conventionally, as a method for making it difficult for liquid foundation to soak into a polyurethane sponge used for a cosmetic puff, a method has been proposed in which a non-reactive silicone-based water repellent is kneaded into a polyurethane solution raw material, extruded and molded, and then the solvent is vaporized under reduced pressure by heating to obtain a foam (see Patent Document 1).

[0003] On the other hand, a water-repellent foam has been proposed in which a prepolymer having a terminal isocyanate group obtained by reacting a monool having 8 or more carbon atoms with an isocyanate compound is slab-foamed using a polyol and water as a blowing agent (see Patent Document 2).

[0004] Furthermore, a foam obtained by foaming a polyol made of vegetable oil (castor oil-based) and diphenylmethane diisocyanate-based (MDI-based) isocyanate by a water foaming method has also been proposed (see Patent Document 3). Also, as a mechanically foamed product obtained by mechanical foaming (mechanical froth method), a foam using a polyol having a high terminal primary ratio has been proposed (see Patent Document 4).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0006] Here, the foam obtained by the method of Patent Document 1 has a silicone-based water repellent that does not have a reactive group, so it is easily eluted by washing the cosmetic puff with a detergent, and the water repellency of the foam quickly disappears. Therefore, the liquid absorption rate increases.

[0007] In addition, the foam of Patent Document 2 is water-foamed, so the cells are rough and the texture is not good. In addition, the foam of Patent Document 3 is also water-foamed, so it is likely to form closed cells. Therefore, in order to deliberately roughen the cells to form open cells, fine cells cannot be obtained and the texture is not good.

[0008] And the mechanically foamed body of Patent Document 4 is mechanically foamed, but since it is mainly composed of polypropylene glycol, it is difficult to obtain fine cells and the liquid absorption rate is too high.

[0009] Thus, there is no sponge composed of a conventional foam that has an appropriate liquid absorption rate and a good texture. In particular, a foam having an appropriate liquid absorption rate and a high texture is useful for, for example, a cosmetic puff that suppresses the consumption of liquid foundation and is required to have a good feeling when applying the foundation to the skin, and this is currently in demand.

[0010] Therefore, an object of the present invention is to provide a continuous ventilation type sponge having an appropriate liquid absorption rate and a good texture, and a cosmetic puff.

Means for Solving the Problems

[0011] The above problems are solved by the following means.

[0012] [1] A polymer polyol containing 30% by mass or more and 100% by mass or less of a dimer acid polyester polyol with respect to the all-polymer polyol, a diphenylmethane diisocyanate-based isocyanate, a blowing agent, a catalyst, and a continuous ventilation type sponge composed of a mechanically foamed body of a composition containing the same. [2] The continuous ventilation type sponge according to [1], wherein the polymer polyol contains a polymer polyol other than the dimer acid polyester polyol. [3] The continuous ventilation type sponge according to [2], wherein the polymer polyol other than the dimer acid polyester polyol is at least one selected from an alkylene oxide-added polyether polyol, a polylactone polyol, and a carboxylic acid ester polyol. [4] The continuous ventilation type sponge according to [2] or [3], wherein the mass ratio (dimer acid polyester polyol / polymer polyol other than the dimer acid polyester polyol) of the dimer acid polyester polyol to the polymer polyol other than the dimer acid polyester polyol is 30 / 70 to 80 / 20. [5] The continuous ventilation type sponge according to any one of [1] to [4], having a water absorption rate of 15% or less. [6] The continuous ventilation type sponge according to any one of [1] to [5], wherein the composition contains 5 to 50 parts by mass of an inorganic filler with respect to 100 parts by mass of the polymer polyol. [7] The continuous ventilation type sponge according to any one of [1] to [6], having a self-skin layer. [8] A cosmetic puff having the continuous ventilation type sponge according to any one of [1] to [7]. [Effect of the Invention]

[0013] According to the present invention, it is possible to provide a continuous ventilation type sponge having an appropriate liquid absorption rate and a good skin feel, and a cosmetic puff.

Brief Description of the Drawings

[0014]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0015] Hereinafter, an embodiment which is an example of the present invention will be described.

[0016] (Continuous ventilation type sponge) The continuous ventilation type sponge according to the present embodiment (hereinafter, also simply referred to as "sponge") is a polymer polyol containing 30% by mass or more and 100% by mass or less of a dimer acid polyester polyol with respect to the total polymer polyol, an isocyanate of diphenylmethane diisocyanate type (hereinafter, also referred to as "MDI type isocyanate"), a foam stabilizer, a catalyst, and is composed of a mechanically foamed body of a composition containing In addition, the composition for forming the foam (hereinafter also referred to as "urethane raw material liquid") may contain other components in addition to the above components.

[0017] The continuous ventilation type sponge according to the present embodiment becomes a sponge having an appropriate liquid absorption rate and a good touch feeling due to the above configuration. The reason is presumed as follows. Note that there is a correlation between the liquid absorption rate of the liquid foundation and the water absorption rate, and the performance of the liquid absorption rate can be represented by the water absorption rate.

[0018] A mechanically foamed body obtained by mechanically foaming a dimer acid polyester polyol in an amount of 30% by mass or more and 100% by mass or less with respect to a fully polymeric polyol and an MDI-based isocyanate using a foam stabilizer and a catalyst becomes a fine continuous ventilation type foam by using the dimer acid polyester polyol. And the obtained mechanically foamed body has a fine continuous ventilation type, and since the dimer acid polyester polyol has hydrophobicity in its molecular structure, it has the property of not excessively absorbing liquid.

[0019] Therefore, it is presumed that the continuous ventilation type sponge according to the present embodiment becomes a sponge having an appropriate liquid absorption rate and a good touch feeling due to the above configuration. In addition, the continuous ventilation type sponge according to the present embodiment can also ensure mechanical properties such as required strength.

[0020] And, for example, when the continuous ventilation type sponge according to the present embodiment having such characteristics is applied as a cosmetic puff, in addition to a comfortable touch feeling, it becomes a cosmetic puff that does not excessively absorb liquid foundation. Thereby, the consumption amount of the liquid foundation is suppressed, and the feeling of application when applying the foundation to the skin is realized. In addition, since the strength is also ensured, durability is also realized.

[0021] Hereinafter, details of the continuous ventilation type sponge according to the present embodiment will be described.

[0022] (Polymeric polyol)

[0023] Hereinafter, details of the continuous ventilation type sponge according to the present embodiment will be described.

[0024] First, each component of the urethane raw material liquid will be described.

[0025] (Polymeric polyol) As the polymer polyol, dimer acid polyester polyol (hereinafter also referred to as "dimer acid polyester polyol A") is applied. All the polyols may be dimer acid polyester polyol A, but dimer acid polyester polyol A and a polymer polyol other than dimer acid polyester polyol (hereinafter also referred to as "polymer polyol B") may be used in combination. By using polymer polyol B in combination with dimer acid polyester polyol A, it becomes possible to add various functions to the sponge, such as reducing the density of the sponge, controlling the liquid absorption property, and improving the solvent resistance.

[0026] Here, the polymer polyol means a polyol having a hydroxyl value (OHv) of 250 or less. Note that the hydroxyl value OHv of the polyol is a value measured according to JIS K1557-1:2007.

[0027] - Dimer acid polyester polyol A - Examples of the dimer acid polyester polyol A include polyester polyols obtained by condensing dimer acid and glycol. Specifically, for example, as the dimer acid polyester polyol A, there are polyester polyols obtained by condensing dimer acid (b-1) and low molecular weight diol (b-2), and when it is desired to increase the number of functional groups, polyester polyols obtained by further condensing low molecular weight triol (b-3), etc.

[0028] The dimer acid (b-1) is a dibasic acid, which refers to a dibasic acid obtained by bonding two monobasic fatty acids through a carbon-carbon covalent bond, and having a molecular weight twice that of the monobasic fatty acid before bonding. Usually, as the monobasic fatty acid constituting the dimer acid, those having a fatty acid with about 18 carbon atoms are used. Representative compounds of the dimer acid include dibasic acids obtained by heating linoleic acid and oleic acid.

[0029] Generally, in the industrial production method of dimer acid, monomeric acids other than dimer acid, tribasic acids, and polymerized acids are included as by-products. When producing dimer acid polyester polyol A, it is preferable that the purity of dimer acid is high, but they may also be used in a state where these by-products are mixed.

[0030] As the low molecular weight diol (b-2), there is no particular limitation as long as it is a low molecular weight compound having two -OH groups. The low molecular weight diol refers to a compound having two or more carbon atoms in total and having 2 to 10 carbon atoms between the two -OH groups, and more preferably having 4 to 6 carbon atoms. More specifically, examples of the low molecular weight diol (b-2) preferably include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.

[0031] The low molecular weight in the low molecular weight triol (a-3) refers to a compound having 3 to 10 carbon atoms in the hydrocarbon group portion to which three hydroxyl groups are bonded, similar to that shown in the above low molecular weight diol, and more preferably having 3 to 6 carbon atoms. The hydrocarbon group portion may be linear or may have a branched chain. Specific examples of the low molecular weight triol (a-3) include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 2-methylpropanetriol, etc.

[0032] From the viewpoint of obtaining a fine continuous porous foam by mechanical foaming, the dimer acid polyester polyol A is preferably a polyol that is liquid at room temperature (25°C). Specifically, the viscosity of the dimer acid polyester polyol at room temperature (25°C) is preferably 2000 to 10000 mP·s. Note that the viscosity is a value measured by a B-type viscometer.

[0033] The hydroxyl value OHv of the dimer acid polyester polyol A is preferably 20 to 180 mgKOH / g from the viewpoints of the liquid absorption property of the sponge and cell refinement. When the hydroxyl value is 20 or less, the viscosity becomes high, it is difficult to mix gas by mechanical foaming, and the foaming ratio does not increase, so the density of the foam does not decrease. On the other hand, when the hydroxyl value is 180 or more, the resulting foam becomes hard and the touch becomes poor, which is not preferable. Considering the ease of gas mixing and the softness of the resulting foam, 50 to 150 mgKOH / g is more preferable. The hydroxyl value OHv of the polyol is the value measured according to JIS K1557-1:2007.

[0034] - Polymer polyol B - Examples of the polymer polyol B include alkylene oxide - added polyether polyols, polylactone polyols, carboxylic acid ester polyols, polycarbonate polyols, and the like.

[0035] The alkylene oxide - added polyether polyol is a compound obtained by addition polymerization of an alkylene oxide (ethylene oxide, propylene oxide, copolymer of ethylene oxide and propylene oxide, tetramethylene oxide, etc.) to a low - molecular alcohol (ethylene glycol, glycerin, trimethylolpropane, etc.). Examples of the alkylene oxide - added polyether polyol include polypropylene glycol (PPG), polyethylene glycol (PEG), copolymer of PPG and PEG, polytetramethylene ether glycol (PTMG), copolymer of PTMG and PPG, copolymer of PTMG and PEG, etc. Among them, the polytetramethylene glycol - based is preferable because of its low water absorption rate.

[0036] Examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, polycaprolactone triol, etc. Examples of the carboxylic acid ester polyol include polyols obtained by condensing a carboxylic acid (such as adipic acid, sebacic acid, phthalic acid, etc.) and a glycol (such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 2-methylpropanediol, 3-methylpentanediol, etc.). Examples of the polycarbonate polyol include polyols obtained by reacting a glycol with an alkylene carbonate, polyols obtained by reacting a glycol with a diaryl carbonate, polyols obtained by reacting a glycol with a dialkyl carbonate, and the like.

[0037] Among these, from the viewpoints of high reactivity, improvement in liquid absorption properties and skin feel by cell refinement, and high strength and elongation, as the polymer polyol B, at least one selected from an alkylene oxide-added polyether polyol, a polylactone polyol, and an adipic acid ester polyol is preferable, an alkylene oxide-added polyether polyol is more preferable, polypropylene glycol (PPG) and polytetramethylene ether glycol (PTMG) are further preferable, and polytetramethylene ether glycol (PTMG) is particularly preferable.

[0038] From the viewpoints of foamability during mechanical foaming, strength and elongation of the resulting foam, and resilience, the functional group number f of the polymer polyol B is preferably 1.5 to 3.5, more preferably 2 to 3.

[0039] The hydroxyl value of the polymer polyol B is preferably 30 to 250, more preferably 30 to 220.

[0040] (MDI-based isocyanate) The MDI-based isocyanate (isocyanate C of diphenylmethane diisocyanate type) is an isocyanate having a diphenylmethane diisocyanate skeleton.

[0041] Examples of MDI-based isocyanates include diphenylmethane diisocyanates (pure MDI) such as 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-MDI, and 2,2'-MDI, crude MDI (cr-MDI), carbodiimide-modified MDI, and polyol-modified MDI. In particular, from the perspective of obtaining a fine continuous ventilation type sponge, it is preferable to use an isocyanate selected from the group consisting of diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, and polyol-modified diphenylmethane diisocyanate as the MDI-based isocyanate.

[0042] Examples of polyol-modified isocyanates include polyol-modified isocyanates obtained by modifying MDI-based isocyanates with divalent alcohols having 2 to 18 carbon atoms such as ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 1,10-decanediol; PPG-based glycols; PTGM-based glycols; and polycarbonate-based glycols.

[0043] Together with the MDI-based isocyanate, aromatic isocyanates such as tolylene diisocyanate (TDI) used in the production of polyurethane foam, and aliphatic isocyanates such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), hydrogenated xylylene diphenylmethane diisocyanate (hydrogenated XDI), and cyclohexylene diisocyanate can also be used in combination.

[0044] (Blowing agent) Examples of the foam stabilizer include well-known foam stabilizers such as silicone compounds (e.g., copolymers of polydimethylsiloxane and polyoxyalkylene polyol), fluorine compounds, etc. In particular, (AB)n-type silicone-based foam stabilizers that are preferably sold for mechanical foaming can be preferably used. The foam stabilizer may be used alone or in combination of two or more kinds.

[0045] (Catalyst) Examples of the catalyst include organometallic compound-based catalysts, amine-based catalysts, etc. Examples of the organometallic compound-based catalysts include organometallic catalysts such as tin-based, titanium-based, bismuth-based, copper-based, nickel-based, etc., for example, stannous octylate and dibutyltin dilaurate of organotin compounds. As the amine-based catalyst, tertiary amines are preferred, and amine-based catalysts such as monoamines, diamines, triamines, cyclic amines, alcohol amines, ether amines, etc. are included. For example, triethylenediamine, triethylamine, n-methylmorpholine, n-ethylmorpholine, N,N,N’,N’-tetramethylbutanediamine, etc. In order to prevent the curing from starting during mechanical stirring of the gas, a temperature-sensitive catalyst may be used. The catalyst may be used alone or in combination of two or more kinds.

[0046] (Other Components) Examples of the other components include the following additives.

[0047] Examples of the other components include at least one selected from the group consisting of low molecular weight diols (e.g., ethylene glycol, 1,4-butanediol, etc.), polyfunctional low molecular weight alcohols (e.g., glycerin, trimethylolpropane, etc.), low molecular weight diols having a branched chain, polyols having an alicyclic structure, and isocyanates having an alicyclic structure. Here, the low molecular weight diol and the polyfunctional low molecular weight alcohol are polyols having a molecular weight of 300 or less (preferably 60 to 300).

[0048] Examples of other components include fillers. Examples of fillers include one or more selected from the group consisting of inorganic fillers and organic fillers. By adding these fillers, the mechanically agitated bubbles become finer, and since the fine bubbles are less likely to defoam and coalesce, it is easy to obtain a fine sponge. Examples of inorganic fillers include calcium carbonate, aluminum hydroxide, magnesium hydroxide, natural silica, synthetic silica, kaolin, clay, titanium oxide, barium sulfate, zinc carbonate, zinc oxide, glass beads, alumina beads, carbon, etc. In particular, calcium carbonate, aluminum hydroxide, and silicas are effective for microcellular formation. Examples of organic fillers include phenolic beads, styrene beads, acrylic beads, resin balloons, silicone powder, fluorine powder, nylon powder, polyethylene powder, etc. Examples of fillers also include organic-inorganic fillers obtained by adding calcium carbonate to the surface of acrylic balloons, and POP (polymer-dispersed polyol) in which submicron organic polymers (such as acrylonitrile or acrylonitrile / styrene copolymers) are dispersed in polypropylene polyol.

[0049] As other components, gases (such as air and nitrogen) used for mechanical foaming are essential, but as foaming agents, water (such as distilled water, ion-exchanged water, ultrafiltration water, pure water, etc.), low-boiling organic solvents (such as alkyl fluoride compounds, alkyl chloride compounds, etc.), liquefied carbon dioxide gas, etc. can also be used in combination.

[0050] Examples of other components include well-known additives such as flame retardants, antioxidants, colorants, ultraviolet absorbers, antibacterial agents, and antifungal agents, in addition to the above components.

[0051] (Contents of each component of the urethane raw material liquid) - Contents of dimer acid polyester polyol A and high molecular polyol B - The content of dimer acid polyester polyol A is 30% by mass or more and 100% by mass or less, preferably 40% by mass or more and 100% by mass or less, based on the total polymer polyol.

[0052] When polymer polyol B is used in combination, the mass ratio of dimer acid polyester polyol A to polymer polyol B (dimer acid polyester polyol A / polyol B) is preferably 30 / 70 to 90 / 10, more preferably 30 / 70 to 80 / 20, and even more preferably 40 / 60 to 80 / 20.

[0053] When the content of dimer acid polyester polyol A and the mass ratio of dimer acid polyester polyol A to polymer polyol B are controlled within the above ranges and mechanically foamed, a high foaming ratio and a lower hardness mechanical foam can be obtained. Thereby, an appropriate liquid absorption rate and a good touch feeling are achieved. In addition, when the ratio of polymer polyol B increases, the foaming ratio is high, the density becomes low, the touch can be maintained, and it can be preferably used even when the viscosity of the liquid foundation changes. However, since the hydrophobicity decreases, the liquid absorption increases, and there is a tendency to swell and the strength decreases. Therefore, from this viewpoint as well, it is preferable to control the mass ratio of dimer acid polyester polyol A to polymer polyol B within the above ranges.

[0054] - Content of foam stabilizer - The content of the foam stabilizer is preferably 0.4 to 10 parts by mass, more preferably 3 to 5 parts by mass, based on 100 parts by mass of the polymer polyol.

[0055] - Content of filler - From the viewpoint of cell refinement, the content of the filler (especially inorganic filler) is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, based on 100 parts by mass of the polymer polyol.

[0056] (Properties of continuous ventilation type sponge) - Self-skin layer - The continuous ventilation type sponge according to this embodiment may or may not have a self-skin layer. However, when it is desired to suppress the impregnation and water absorption of aqueous liquids such as cosmetic puffs for liquid foundation, it is preferable to have a self-skin layer.

[0057] -Air permeability- Measure the thickness of the sample for measurement with a digital thickness gauge. Set the sample in a frigid type air permeability tester, and adjust with a pressure resistor so that the value of the inclined type manometer shows "5", and read the pressure of the vertical type manometer at that time. Using the conversion table for different types of orifices, obtain the conversion value. Calculate the air permeability according to the following formula. Formula: AP = a × t AP: Air permeability (mL / cm 2 / s) a: Conversion value t: Thickness (cm)

[0058] -Apparent density- The apparent density of the continuous ventilation type sponge according to this embodiment, in addition to appropriate liquid absorption and improved skin feel, from the viewpoints of mechanical strength, prevention of bottom contact during compression use, and operability, is preferably 100 to 400 kg / m 3 and more preferably 150 to 300 kg / m 3 .

[0059] The apparent density is measured by the following method. First, prepare a sample to be measured (approximate dimensions: length 100 mm × width 100 mm × measured thickness) in an environment of 23 ± 3°C. Next, measure the weight of the sample with a precision balance with an accuracy of 1 / 100 g. Next, using a digital gauge, with a measuring head of diameter Φ10 mm and a load of about 0.6 N, measure the thickness dimension of the sample at 9 points with an accuracy of 1 / 100 mm and obtain the average value. Measure the longitudinal dimension and the transverse dimension of the sample at 3 points each using a digital caliper and obtain the average. Calculate the volume of the sample from the obtained dimensions. Then, obtain the apparent density using the formula: apparent density = weight / volume.

[0060] -Tensile strength · Elongation- The tensile strength of the continuous ventilation sponge according to this embodiment is preferably 0.1 MPa or more from the viewpoints of mechanical strength, prevention of bottom contact during compression use, and operability. The tensile elongation of the continuous ventilation sponge according to this embodiment is preferably 150% or more, more preferably 200% or more, from the viewpoints of mechanical strength and operability.

[0061] The tensile strength and elongation are measured in accordance with JIS K 6400-5(2012). The measurement is carried out by punching out the measurement object into a dumbbell No. 2 shape to obtain a sample and measuring the thickness. For the obtained sample, using the "Tensilon universal material testing machine UCT-500" manufactured by Ori-on Tech Co., Ltd., it is carried out at a speed of 200 mm / min, and the strength and elongation at the time of sample fracture are measured.

[0062] -Tear strength- The tear strength of the continuous ventilation sponge according to this embodiment is preferably 3 N / cm or more, more preferably 5 N / cm, from the viewpoint of mechanical strength.

[0063] The tear strength is a value measured in accordance with JIS6400-5(2012).

[0064] -50% compression hardness- The 50% compression hardness of the continuous ventilation sponge according to this embodiment is preferably 50 kPa or less, more preferably 15 kPa or less, still more preferably 10 kPa or less, from the viewpoints of improving the skin feel, mechanical strength, prevention of bottom contact during compression use, and operability. The 50% compression hardness is measured in accordance with JIS K6400-2(2012). Specifically, a sample is punched out from the measurement object to a size of 50×50 mm. When the thickness is 10 mm or less, it is laminated to be 10 mm or more to obtain a sample. Then, using the "Tensilon universal material testing machine UCT-500" manufactured by Ori-on Tech Co., Ltd., 50% compression is performed on the sample thickness at a compression speed of 50 mm / min, and the 50% compression hardness is measured.

[0065] -Water absorption rate- From the perspective of appropriate liquid absorption, the water absorption rate of the continuous ventilation sponge according to this embodiment is preferably 20% by mass or less, more preferably 15% by mass or less, and most preferably 12% by mass or less. The water absorption rate is measured as follows. Prepare a 10 cm square sample and measure its mass to the nearest 1 / 100 g. Next, put 10 cm of water in a water tank, submerge the sample to a depth of 10 cm, and leave it for 24 hours. After 24 hours, wipe off the water on the surface of the sample and measure the mass of the sample to the nearest 1 / 100 g. Then, measure the liquid absorption rate using the following formula. Liquid absorption rate (%) = (mass after liquid absorption - mass before liquid absorption) / mass before liquid absorption × 100

[0066] -Average cell diameter- From the perspective of appropriate liquid absorption, improved skin feel, and mechanical strength, the average cell diameter of the continuous ventilation sponge according to this embodiment is preferably 270 μm or less, more preferably 250 μm or less, and even more preferably 200 μm or less.

[0067] The average cell diameter is measured by counting the number of cells per 25 mm length in accordance with Appendix 1 of JIS K 6400-1 (2004), and calculated from 25 mm / number of cells. The average cell diameter is measured under magnification using an optical microscope.

[0068] (Manufacturing method of continuous ventilation sponge) The manufacturing method of the continuous ventilation sponge according to this embodiment is not particularly limited. For example, as the manufacturing method of the continuous ventilation sponge according to this embodiment, the following method can be mentioned. A coating step of mechanically foaming a urethane raw material liquid using an oaks mixer or the like and continuously applying the foamed urethane raw material liquid onto a first continuous web (strip) to form a coating film, and a heating step of heating and curing the coating film on the first continuous web to form a foam with a continuous ventilation structure. The manufacturing method of the continuous ventilation sponge includes these steps.

[0069] On one hand, after the coating step and before the heating step, a second continuous web (strip) is supplied to the coating film on the first continuous web (strip), and a second continuous web supply step of sandwiching the coating film with two continuous webs is included. The heating step has many merits in heating and curing the coating film while being sandwiched between two continuous webs to form a foam with a continuous ventilation structure. In particular, when the coating film of the urethane raw material liquid is heat-cured while being sandwiched between two release-type continuous webs to form a foam with a continuous ventilation structure, since it foams while being sandwiched between two continuous webs, there is no scattering of the foaming agent, so the foaming ratio increases (the density becomes lower). In addition, thin and smooth skin layers are formed on both surfaces, the feel to the finger is good (the feel is moist), and it is a major feature that it is easy to obtain a foam with a continuous ventilation structure (that is, a sponge) with high texture.

[0070] Hereinafter, a method for manufacturing a continuous ventilation type sponge of this embodiment will be described with reference to the drawings.

[0071] FIG. 1 is a schematic diagram of an example of the apparatus configuration for implementing the method for manufacturing a continuous ventilation type sponge according to the present embodiment. As shown in FIG. 1, the manufacturing apparatus 100 for a continuous ventilation type sponge includes a first web roll 14 that feeds out a first continuous web 14A, a coating device 12 that coats the urethane raw material liquid on the first continuous web 14A, a large-diameter roller 18 that guides the first continuous web 14A fed out from the first web roll 14 directly below the coating device 12, a second web roll 16 that feeds out a second continuous web 16A, a guide roller 20 that guides the second continuous web 16A onto the coating film 10 on the first continuous web 14A, conveyance rollers 28A and 28B that guide the coating film 10 of the urethane raw material liquid sandwiched between the two continuous webs 14A and 16A to a heating device 22 and convey a foam (hereinafter referred to as "foamed urethane sheet") 30 that is heated and cured by the heating device 22, and recovery rollers 24 and 26 that wind up and recover the respective continuous webs 14A and 16A peeled off from the foamed urethane sheet 30.

[0072] - Coating step - First, a urethane raw material liquid obtained by mixing and stirring raw material components is continuously applied onto a first continuous web 14A to form a coating film 10.

[0073] As the first continuous web 14, for example, a resin film or a paper body is preferably used. The resin film is not particularly limited as long as it does not deform by heating in the urethane raw material liquid application and heating processes. However, from the viewpoints of resistance to the urethane raw material liquid, heat resistance, etc., films such as polyester, polypropylene, and polymethylpentene are preferred. If necessary, the surface of the resin film may be subjected to corona discharge treatment, plasma treatment, etc. to improve the adhesiveness with the foamed urethane sheet.

[0074] Also, after manufacturing the foamed urethane sheet, a resin film having releasability on the surface where the coating film of the urethane raw material liquid is formed may be used so that the resin film can be easily peeled off. As the resin film having releasability, there are methods such as applying a silicone release agent to one side of the resin film, using as it is a resin film having releasability such as a polypropylene resin or a polymethylpentene resin, and laminating a resin film having releasability to a polyester film or the like. Also, the surface of the release film or paper release paper can be finished with a matte finish or a embossed pattern to enhance the design and texture.

[0075] When using a paper body as the first continuous web 14A, those obtained by coating the surface of glassine paper or high-quality paper with polypropylene, or those further coated with a silicone release agent, a non-silicone-based release agent, etc. thereon are used. As the first continuous web 14A used in the present invention, a resin film or a release resin film is preferred because the solidification rate of the foam is fast and the thickness accuracy is high.

[0076] As the coating device 12 for applying the urethane raw material liquid onto the first continuous web 14A, it is preferable to use a die coater, a roll coater, a knife coater, a comma coater, or the like. A method of stirring the urethane raw material liquid with a mixing device, discharging it from a discharge nozzle by a traverse (repeated coating) device, and thinly coating it with a roll coater or a knife coater, or a method of introducing the urethane raw material liquid from a discharge nozzle into a die coater and coating it onto the continuous web is also preferable.

[0077] The thickness of the coating film 10 may be determined according to the intended use of the foam (continuous ventilation sponge).

[0078] -Second continuous web supply process- The second continuous web 16A is supplied to the coating film 10 on the first continuous web 14A, and the coating film 10 is sandwiched between the two continuous webs 14A and 16A. As the second continuous web 16A, the resin film or paper body exemplified in the description of the first continuous web 14A can be used. From the viewpoint of facilitating the peeling of at least one-sided continuous web of the foamed urethane sheet 30 after the heating process, it is preferable to use a continuous web having a release property on the surface in contact with the coating film 10 for at least one of the first continuous web 14A and the second continuous web 16A.

[0079] The second continuous web 16A is continuously unwound from the second web roll 16 around which the second continuous web 16A is wound and is placed on the coating film 10 on the first continuous web 14A. As a result, the coating film 10 is sandwiched between the two continuous webs 14A and 16A.

[0080] Although the device shown in FIG. 1 is configured to sandwich the coating film 10 between the two continuous webs 14A and 16A, after forming the coating film on the first continuous web 14A, it may proceed to the next heating process without covering the second continuous web 16A.

[0081] -Heating process- The coating film 10 is conveyed into the heating device 22 while being sandwiched between the two continuous webs 14A and 16A and is cured by heating. The heating temperature for curing is preferably 80 to 120°C, and it is preferably cured at a temperature within this range for 5 to 20 minutes. As the heating device 22, an infrared heater, an electric heater, a gas combustion furnace, etc. can be used.

[0082] - Peeling process - The foamed urethane sheet 30 that has been foamed and cured by the heating process may be wound up with the continuous webs 14A and 16A remaining in close contact with the foamed urethane sheet 30. When the continuous webs 14A and 16A are release webs, as shown in FIG. 1, the release webs are peeled off from the foamed urethane sheet 30 and wound up on the respective recovery rollers 24 and 26 for recovery. Note that the recovered continuous webs 14A and 16A can be reused as supply rolls 14 and 16.

[0083] Through the above process, a continuous ventilation type sponge made of a foamed urethane sheet (foam with a continuous ventilation structure) can be continuously manufactured.

[0084] In addition, when the continuous ventilation type sponge according to this embodiment has a low air permeability, if necessary, a crashing process (a process of shearing and compressing the foam to increase air permeability) may be performed. If the air permeability is kept low, the restoration speed will be slow, and if the air permeability is increased, the restoration will be fast, so the air permeability can be adjusted according to the application.

[0085] In addition to the above, known methods such as the slab stock method and the mold method of molding in a mold can be applied to the manufacturing method of the continuous ventilation type sponge according to this embodiment.

[0086] In this specification, the term "process" includes not only independent processes but also cases where it cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

[0087] (Applications of the continuous ventilation type sponge) The continuous ventilation type sponge according to this embodiment can be applied to uses such as cosmetic puffs, bra pads, sports clothing pads, body protection pads (such as pads for the head, knees or elbows), medical pads (such as for fish eyes), insoles, supporters, water stop sealants, liquid (drugs, lotions, etc.) impregnated sheets, masks, and handbags.

[0088] (Cosmetic puff) The cosmetic puff according to this embodiment has the continuous ventilation type sponge according to this embodiment. Thereby, the cosmetic puff according to this embodiment can suppress the excessive penetration of liquid foundation. Thereby, the consumption amount of liquid foundation is reduced. In addition, the liquid foundation also has a good feel.

[0089] The cosmetic puff according to this embodiment may be a single-layer puff of the continuous ventilation type sponge according to this embodiment, or may be a multi-layer puff in which the continuous ventilation type sponge according to this embodiment and another skin material are integrated.

Example

[0090] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following, "parts" are based on mass unless otherwise specified.

[0091] <Example 1> · 100 parts of polymer polyol A (a polyester polyol obtained from dimer acid and diethylene glycol, manufactured by Hitachi Chemical Co., Ltd., OHv = 85, viscosity 5500 mPa·s) · 5 parts of foam stabilizer SZ1923 (a silicone-based foam stabilizer manufactured by Toray Dow Corning Co., Ltd.) · 0.1 part of catalyst SO (stannous octoate manufactured by Mitsubishi Chemical Corporation) A mixture containing the above polyol component other than isocyanate is continuously supplied to an oximixer, and nitrogen gas is supplied to cause mechanical foaming. While doing so, 22.4 parts of isocyanate (manufactured by Tosoh Corporation, carbodiimide-modified diphenylmethane diisocyanate (carbodiimide-modified MDI), NCO% = 29) is added to the oximixer, and it is discharged while reacting the polyol component with the isocyanate. The total discharge amount of the raw materials at that time is 250 g / min, and the discharge amount of nitrogen gas is 800 cc / min. The discharged reaction solution is applied onto a release film, cured at 70 °C for 5 minutes and then at 100 °C for 10 minutes to obtain a continuous ventilation type sponge with a thickness of about 8 mm.

[0092] <Examples 2 to 15, Comparative Examples 1 to 7> According to the compositions in Tables 1 to 8, continuous ventilation type sponges were obtained in the same manner as in Example 1, except that the types and amounts of the materials (the values in the tables are parts) were changed. However, in Examples 13 and 14, under the same mechanical foaming conditions as in Example 1, a block-shaped sponge with a thickness of 50 × length 200 × width 200 mm was produced, and then sliced to a thickness of 8 mm to obtain a continuous ventilation type sponge without a self-skin layer. Also, in Comparative Examples 4 to 6 (water foaming), continuous ventilation type sponges were obtained as follows. The stirred urethane raw material liquid was applied onto a release film that had been release-treated using a die coater so that the cured thickness would be about 8.0 mm, and another release film that had been release-treated on the top was covered on the coating film such that the release-treated surface was in contact with the coating film of the urethane raw material liquid. Next, the coating film of the urethane raw material liquid sandwiched between the two release films was heat-cured in an oven under the conditions of 80 °C for 3 minutes and 100 °C for 5 minutes. After that, the films on both sides were peeled off to obtain a continuous ventilation type sponge with a thickness of about 8.0 mm. Also, in Comparative Examples 7 and 8, commercially available products were used.

[0093] <Physical Property Measurement> The following physical properties of the continuous ventilation type sponges obtained in each example were measured according to the methods described above. · Apparent density · Tensile strength · Tensile elongation · Tear strength · 50% Compression Hardness · Water Absorption Rate · Average Cell Diameter · Air Permeability

[0094] <Evaluation> The following evaluations were performed on the continuous ventilation type sponges obtained in each example. - Skin Feel Regarding the skin feel, the skin feel when 5 women put on makeup was confirmed and monitored and evaluated according to the following criteria. The most common evaluation among the 5 people was shown in the table. ◎: The skin feel is very good 〇: The skin feel is good △: A slightly rough or stiff feeling, not a good skin feel ×: The skin feel is bad

[0095] - Touch Index As the touch index, it was quantified by multiplying the 50% compression hardness and the cell diameter. There was a correlation with the above monitoring evaluation of the skin feel that when the multiplied value was less than 2, the touch was very good; when it was between 2 and 3, the touch was good; when it was between 3 and 4, a slightly rough or stiff feeling was felt and the touch was not good; and when it was 4 or more, the touch was bad.

[0096] - Comprehensive Evaluation The continuous ventilation type sponges of each example were comprehensively evaluated according to the following criteria. ◎: A puff sponge with very excellent skin feel and low water absorption rate 〇: A puff sponge with excellent skin feel and low water absorption rate △: A puff sponge with not very good skin feel and high water absorption rate ×: A puff sponge with bad skin feel and high liquid absorption

[0097]

Table 1

[0098]

Table 2

[0099]

Table 3

[0100] From the above results, it can be seen that the continuous ventilation type sponge of the example has an appropriate liquid absorption rate and a good touch feeling compared with the sponge of the comparative example. Here, the penetration degrees of the liquid foundation into the continuous ventilation type sponge of Example 4 and the sponge of Comparative Example 7 are shown in FIGS. 2 and 3. As shown in FIG. 2, it can be seen that the continuous ventilation type sponge of Example 4 is moderately penetrated with the liquid foundation, while as shown in FIG. 3, the sponge of Comparative Example 7 is excessively penetrated with the liquid foundation.

[0101] The details of the components shown in the table are as follows. - Polyol A- · Dimer acid polyester polyol A1: A dimer acid polyester polyol obtained from dimer acid and diethylene glycol, manufactured by Hitachi Chemical Co., Ltd., hydroxyl value OHv = 85 mgKOH / g, viscosity (25 °C) = 5500 mPa·s · Dimer acid polyester polyol A2: A dimer acid polyester polyol obtained from dimer acid and diethylene glycol, manufactured by Hitachi Chemical Co., Ltd., hydroxyl value OHv = 150 mgKOH / g, viscosity (25 °C) = 2000 mPa·s · Dimer acid polyester polyol A3: A dimer acid polyester polyol obtained from dimer acid and diethylene glycol, manufactured by Hitachi Chemical Co., Ltd., hydroxyl value OHv = 70 mgKOH / g, viscosity (25 °C) = 10000 mPa·s

[0102] - Polyol B- · PTMG: Polytetramethylene ether glycol, hydroxyl value OHv = 133 mgKOH / g, functionality f = 2 · PCL: Polycaprolactone diol, hydroxyl value OHv = 210.8 mgKOH / g, functionality f = 2 · Adipate: Adipic acid ester polyol (condensed from adipic acid and 1,3 - butanediol), polyol, hydroxyl value OHv = 117mgKOH / g, functionality f = 2 · PPG: Polypropylene glycol, hydroxyl value OHv = 112mgKOH / g, functionality f = 2, molar ratio of ethylene oxide EO = 0%, 30%

[0103] - Filler - · CaCO3: General - purpose calcium carbonate grade 1, manufactured by Sankyo Seifun Co., Ltd. · Al(OH)3: Aluminum hydroxide: High - light H10 manufactured by Showa Denko K.K.

[0104] - Foam stabilizer - SZ1923: SZ - 1923, a silicone - based foam stabilizer manufactured by Toray Dow Corning Co., Ltd.

[0105] - Catalyst - · Stannous octoate: Metal catalyst, SO (manufactured by Mitsubishi Chemical Corporation, stannous octoate) · Dabco 33Lv: Amine catalyst, Dabco 33Lv (manufactured by Air Products Japan Co., Ltd.)

[0106] - Isocyanate - · Carbodiimide - modified MDI: Carbodiimide - modified diphenylmethane diisocyanate, manufactured by Tosoh Corporation, NCO% = 29

[0107] - Commercially available product - · Commercially available NBR - based puff: NBR sponge manufactured by Yukigaya Chemical Co., Ltd. · Commercially available pore - forming agent - extracted PU - based puff: Ruby Cell manufactured by Toyo Chemical Co., Ltd.

[0108] 10 Coating film 12 Coating device 14 First web roll 14A First continuous web 16 Second web roll 16A Second continuous web 18 Large - diameter roller 22 Heating device 24 First recovery roll 26 Second recovery roll 30 Foam with continuous ventilation structure (urethane foam sheet) 100 Manufacturing apparatus for continuously ventilated sponge

Claims

【Claim 1】 A polymeric polyol having a hydroxyl value (OHv) of 250 mg KOH / g or less, the polymeric polyol containing 30% by mass or more and 100% by mass or less of a dimer acid polyester polyol based on the total polymeric polyol, a diphenylmethane diisocyanate-based isocyanate, a foam stabilizer, a catalyst, A cosmetic puff having a continuous ventilation type sponge composed of a mechanically foamed body of a composition containing

Images