WO2020230871A1

WO2020230871A1 - Open-cell sponge, and puff for cosmetic

Info

Publication number: WO2020230871A1
Application number: PCT/JP2020/019353
Authority: WO
Inventors: 祐典岩口; 松田　伸也; 剛正杉山; 草川　公一
Original assignee: 日本発條株式会社
Priority date: 2019-05-14
Filing date: 2020-05-14
Publication date: 2020-11-19
Also published as: JP7439370B2; KR20220008270A; CN113811557A; JP2023021161A; JP2020186309A; JP2023021162A; CN113811557B

Abstract

Provided is an open-cell sponge constituted of a mechanical foam of a composition comprising: a high polymer polyol including, with respect to the total high polymer polyol, 30-100 mass% of dimer acid polyester polyol; diphenylmethane diisocyanate-based isocyanate; a foam stabilizer; and a catalyst. In addition, provided is a puff for a cosmetic, the puff having said sponge.

Description

Continuously breathable sponge and cosmetic puff

This disclosure relates to continuously breathable sponges and cosmetic puffs. In particular, the present invention relates to an open-cell sponge which is a foam formed by mechanical foaming and is characterized by a low water absorption rate.

The open-cell sponge, which is one of the uses of this disclosure, relates to a cosmetic puff that does not allow the liquid foundation to penetrate excessively. Conventionally, as a method of making it difficult for the liquid foundation to soak into the polyurethane sponge used for cosmetic puffs, a non-reactive silicone-based water repellent material is kneaded into a polyurethane solution raw material, extruded, and then decompressed under heating to make a solvent. There is a method of obtaining a foam by vaporizing (see Patent Document 1).

On the other hand, a water-repellent foam obtained by slab-foaming a prepolymer having a terminal isocyanate group obtained by reacting a monool having 8 or more carbon atoms with an isocyanate compound using a polyol and water as a foaming agent has been proposed. (See Patent Document 2).

Further, a foam obtained by foaming a polyol composed of vegetable oil (castor oil type) and diphenylmethane diisocyanate type (MDI type) isocyanate by a water foaming method has also been proposed (see Patent Document 3).
Further, as a mechanical foam obtained by mechanical foaming (mechanical floss method), a foam using a polyol having a high terminal primaryization rate has been proposed (see Patent Document 4).

Patent Document 1: Japanese Patent Application Laid-Open No. 6-284923 Patent Document 2: Japanese Patent Application Laid-Open No. 2006-89582 Patent Document 3: Japanese Patent Application Laid-Open No. 2007-54164: Patent Document 4: Patent No. 6106523

Here, in the foam obtained by the method of Patent Document 1, since the silicone-based water-repellent material used does not have a reactive group, it is easily eluted by washing the cosmetic puff with a detergent, so that the foam is water-repellent. Disappears quickly. Therefore, the liquid absorption rate becomes high.

Further, since the foam of Patent Document 2 is water-foamed, the cells are rough and the skin feel is not good.
Further, since the foam of Patent Document 3 is also water-foamed, it tends to become closed cells, and therefore the cells are intentionally roughened to form continuous bubbles, so that fine cells cannot be obtained and the skin feel is not good.

Although the mechanical foam of Patent Document 4 is mechanically foamed, it is mainly composed of polypropylene glycol, so that it is difficult to obtain fine cells and the liquid absorption rate is too high.

As described above, there is no conventional sponge made of foam that has an appropriate liquid absorption rate and a good skin feel. In particular, a foam having an appropriate liquid absorption rate and a high skin feel is useful for, for example, a cosmetic puff that suppresses the consumption of liquid foundation and requires a comfortable feeling when applying the foundation to the skin, and is desired. The current situation is that there is.

Therefore, an object of the present disclosure is to provide a continuously breathable sponge having an appropriate liquid absorption rate and a good skin feel, and a cosmetic puff.

The above problem is solved by the following means.

[1]
Polymer polyols containing 30% by mass or more and 100% by mass or less of polyester dimerate with respect to all polymer polyols,
Diphenylmethane diisocyanate-based isocyanate and
Defoamer and
With the catalyst
A continuously ventilated sponge composed of a mechanical foam of a composition containing.
[2]
The continuously breathable sponge according to [1], wherein the polymer polyol contains a polymer polyol other than the polyester polyol dimerate.
[3]
The continuously ventilated 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 mass ratio (polyester polyol dimerate / polymer polyol other than polyester dimerate) of the polyester polyol dimerate to the polymer polyol other than the polyester dimerate is 30/70 to 80/20 [ 2] or the continuously ventilated sponge according to [3].
[5]
The continuously ventilated sponge according to any one of [1] to [4], which has a water absorption rate of 15% or less.
[6]
The continuously ventilated 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 continuously breathable sponge according to any one of [1] to [6], which has a self-skin layer.
[8]
A cosmetic puff having the continuously breathable sponge according to any one of [1] to [7].

According to the present disclosure, it is possible to provide a continuously breathable sponge having an appropriate liquid absorption rate and a good skin feel, and a cosmetic puff.

It is a schematic diagram which shows an example of the apparatus for carrying out the manufacturing method of the continuous ventilation type sponge which concerns on this embodiment. It is a figure which shows the degree of penetration of the liquid foundation of the continuous ventilation type sponge of Example 4. It is a figure which shows the degree of penetration of the kid foundation of the sponge of Comparative Example 7.

Hereinafter, an embodiment which is an example of the present disclosure will be described.

(Continuous ventilation type sponge)
The continuously ventilated sponge (hereinafter, also simply referred to as “sponge”) according to the present embodiment is
Polymer polyols containing 30% by mass or more and 100% by mass or less of polyester dimerate with respect to all polymer polyols,
Diphenylmethane diisocyanate-based isocyanate (hereinafter, also referred to as "MDI-based isocyanate") and
Defoamer and
With the catalyst
It is composed of a mechanical foam having a composition containing.
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.

The continuously ventilated sponge according to the present embodiment has an appropriate liquid absorption rate and a good skin feel due to the above configuration. The reason is presumed as follows. There is a correlation between the liquid absorption rate of the liquid foundation and the water absorption rate of water, and the performance of the liquid absorption rate can be expressed by the water absorption rate.

The mechanical foam obtained by mechanically foaming a polyester polyol dimerate in an amount of 30% by mass or more and 100% by mass or less based on the total polymer polyol and an MDI-based isocyanate using a foam stabilizer and a catalyst is a polyester dimerate. By using a polyol, it becomes a fine continuously ventilated foam. The obtained mechanical foam has a property of not excessively absorbing a liquid because the polyester polyol dimerate is hydrophobic in terms of molecular structure, in addition to being a fine continuous air-permeable type.

Therefore, it is presumed that the continuously ventilated sponge according to the present embodiment will be a sponge having an appropriate liquid absorption rate and a good skin feel due to the above configuration.
Further, the continuously ventilated sponge according to the present embodiment can secure mechanical properties such as required strength.

Then, for example, when the continuously breathable sponge according to the present embodiment having such characteristics is applied as a cosmetic puff, it becomes a cosmetic puff that does not excessively absorb the liquid foundation in addition to a comfortable touch. As a result, the consumption of the liquid foundation is suppressed, and the feeling of applying the foundation to the skin is realized. In addition, since the strength is secured, durability is also realized.

The details of the continuously ventilated sponge according to this embodiment will be described below.

(Polymer polyol)

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

(Polymer polyol)
As the polymer polyol, a polyester polyol dimer acid (hereinafter, also referred to as “polyester polyol dimer acid A”) is applied. All polyols may be polyester polyol A dimer acid, but polyester polyol dimerate A and a polymer polyol other than polyester polyol dimer acid (hereinafter, also referred to as “polymer polyol B”) are used in combination. You may.
By using the polymer polyol B together with the polyester polyol A dimer acid, it is possible to add various functions to the sponge, such as lowering the density of the sponge, controlling the liquid absorption property, and improving the solvent resistance.

Here, the polymer polyol means a polyol having a hydroxyl value (OHv) of 250 or less.
The hydroxyl value OHv of the polyol is a value measured by JIS K1557-1: 2007.

-Polyester polyol dimer acid A-
Examples of the dimer acid polyester polyol A include a polyester polyol obtained by condensing dimer acid and glycol.
Specifically, for example, the dimer acid polyester polyol A is a polyester polyol obtained by condensing dimer acid (b-1) and a low molecular weight diol (b-2), and when the number of functional groups is to be increased, a low molecular weight triol (low molecular weight triol) ( Examples thereof include polyester polyols obtained by further condensing b-3).

Dimeric acid (b-1) is a dibasic acid, which is obtained by binding two monobasic fatty acids in two molecules by a carbon-carbon covalent bond, and has a molecular weight relative to the pre-bonded monobasic fatty acid. Refers to a dibasic acid in which is twice as much. Usually, as the monobasic fatty acid constituting the dimer acid, a fatty acid having a fatty acid having about 18 carbon atoms is used. Typical compounds of dimer acid include linoleic acid and dibasic acid obtained by heating oleic acid.

Normally, in the industrial production method of dimer acid, monomeric acid, tribasic acid and polymerized acid other than dimer acid are contained as by-products. When producing the polyester polyol A dimer acid, it is preferable that the purity of the dimer acid is high, but these by-products may be mixed and used.

The low molecular weight diol (b-2) is not particularly limited as long as it is a low molecular weight compound and has two -OH groups. The low molecular weight diol means a diol having two or more total carbon atoms and 2 to 10 carbon atoms existing between the two -OH groups, and may have 4 to 6 carbon atoms. More preferred.
More specifically, as the low molecular weight diol (b-2), ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol and the like are preferably mentioned.

The low molecule in the low molecular weight triol (a-3) refers to one having 3 to 10 carbon atoms in the hydrocarbon group portion to which the three hydroxyl groups are bonded, as shown in the low molecular weight diol. More preferably, the number is 3-6. 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 and the like.

The polyester polyol A dimer acid is preferably a polyol that is liquid at room temperature (25 ° C.) from the viewpoint of forming a fine continuously ventilated foam by mechanical foaming.
Specifically, the viscosity of the polyester polyol dimerate at room temperature (25 ° C.) is preferably 2000 to 10000 mP · s.
The viscosity is a value measured by a B-type viscometer.

The hydroxyl value OHv of the polyester polyol dimerate A is preferably 20 to 180 mgKOH / g from the viewpoint of liquid absorption of the sponge and cell miniaturization. When the hydroxyl value is 20 or less, the viscosity becomes high, it is difficult for gas to be mixed by mechanical foaming, and the foaming ratio does not increase, so that the density of the foam does not decrease. Further, when the hydroxyl value is 180 or more, the obtained foam becomes hard and the touch is deteriorated, which is not preferable. Considering the ease of mixing with gas and the softness of the obtained foam, 50 to 150 mgKOH / g is more preferable.
The hydroxyl value OHv of the polyol is a value measured by JIS K1557-1: 2007.

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

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

Examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, and polycaprolactone triol.
Examples of the carboxylic acid ester polyol include carboxylic acids (adipic acid, sebacic acid, phthalic acid, etc.) and glycols (ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 2-methylpropanediol, etc.). 3-Methylpentanediol, etc.) and a polyol can be exemplified by condensing with.
Examples of the polycarbonate polyol include a polyol obtained by reacting glycol and alkylene carbonate, a polyol obtained by reacting glycol and diaryl carbonate, and a polyol obtained by reacting glycol and dialkyl carbonate.

Among these, alkylene oxide-added polyether polyols, polylactone polyols, and adipines are examples of high molecular weight polyols B from the viewpoints of high reactivity, liquid absorption, improvement of touch by refining cells, and high strength and elongation. At least one selected from acid ester polyols is preferable, alkylene oxide-added polyether polyols are more preferable, polypropylene glycol (PPG) and polytetramethylene ether glycol (PTMG) are more preferable, and polytetramethylene ether glycol (PTMG) is more preferable. Especially preferable.

The number of functional groups f of the polymer polyol B is preferably 1.5 to 3.5 from the viewpoints of foaming property during mechanical foaming, strength of the obtained foam, enhancement of elongation, and resilience. Is preferably 2 to 3.

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

(MDI-based isocyanate)
The MDI-based isocyanate (diphenylmethane diisocyanate-based isocyanate C) is an isocyanate having a diphenylmethane diisocyanate skeleton.

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, and crude MDI (cr-). MDI), carbodiimide-modified MDI, polyol-modified MDI and the like.
In particular, as the MDI-based isocyanate, it is preferable to use an isocyanate selected from the group consisting of diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, and polyol-modified diphenylmethane diisocyanate from the viewpoint of forming a fine continuously ventilated sponge.

Here, examples of the polyol-modified isocyanate include ethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, and the like having 2 to 2 to carbon atoms. Examples thereof include polyol-modified isocyanate in which MDI-based isocyanate is modified with 18 divalent alcohols; PPG-based glycol; PTGM-based glycol; polycarbonate-based glycol and the like.

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

(Foaming agent)
Examples of the defoaming agent include well-known defoaming agents such as silicone compounds (copolymers of polydimethylsiloxane and polyoxyalkylene polyol) and fluorine-based compounds. In particular, an (AB) n-type silicone-based defoaming agent sold as suitable for mechanical foaming can be preferably used. The foam stabilizer may be used alone or in combination of two or more.

(catalyst)
Examples of the catalyst include an organometallic compound catalyst, an amine catalyst and the like.
Examples of the organometallic compound-based catalyst include tin-based, titanium-based, bismuth-based, copper-based, nickel-based and other organometallic catalysts, and examples thereof include organotin compounds such as stannous octylate and dibutyltin dilaurate. is there.
As the amine-based catalyst, tertiary amines are preferable, and amine-based catalysts such as monoamines, diamines, triamines, cyclic amines, alcohol amines, and ether amines can be mentioned, and examples thereof include triethylenediamine, triethylamine, and n. -Methylmorpholin, n-ethylformolin, N, N, N', N'-tetramethylbutanediamine and the like.
As the catalyst, a temperature sensitive catalyst may be used in order to prevent curing from starting during mechanical stirring of the gas. One type of catalyst may be used alone, or two or more types may be used in combination.

(Other ingredients)
Examples of other components include the following additives.

Other components include low molecular weight diols (ethylene glycol, 1,4-butanediol, etc.), polyfunctional low molecular weight alcohols (glycerin, trimethylolpropane, etc.), low molecular weight diols having branched chains, polyols having an alicyclic structure, etc. And at least one selected from the group consisting of 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).

Examples of other components include fillers.
Examples of the filler include one or more selected from the group consisting of an inorganic filler and an organic filler. By adding these fillers, the mechanically agitated bubbles become finer, and the fine bubbles are difficult to defoam and coalesce, so that a fine sponge can be easily obtained.
Examples of the inorganic filler 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 and the like. In particular, calcium carbonate, aluminum hydroxide, and silica are effective for making fine cells.
Examples of the organic filler include phenol beads, styrene beads, acrylic beads, resin balloons, silicone powder, fluorine powder, nylon powder, polyethylene powder and the like.
Other fillers include an organic-inorganic filler obtained by adding calcium carbonate to the surface of an acrylic balloon, and a POP (polymer-dispersed polyol) in which a submicron organic polymer (acrylonitrile or acrylonitrile / styrene copolymer, etc.) is dispersed in a polypropylene polyol. Can also be mentioned.

As other components, the gas used for mechanical foaming (air, nitrogen, etc.) is indispensable, but as the foaming agent, water (distilled water, ion-exchanged water, ultrafiltered water, pure water, etc.), low boiling point organic A solvent (alkyl fluoride compound, alkyl chloride compound, etc.), liquefied carbon dioxide gas, etc. can also be used in combination.

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.

(Content of each component of urethane raw material liquid)
-Contents of polyester polyol A dimer acid and polymer polyol B-
The content of the polyester dimer acid 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 high molecular weight polyol.

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

When the content of polyester polyol A dimerate and the mass ratio of polyester polyol dimerate A and polymer polyol B are controlled within the above ranges and mechanically foamed, a mechanical foam having a high foaming ratio and a lower hardness can be obtained. .. As a result, the liquid absorption rate is appropriate and the skin feel is improved.
When the ratio of the polymer polyol B is increased, the foaming ratio becomes high, the density becomes low, the feel can be maintained, and even if the viscosity of the liquid foundation changes, it can be suitably used, but the hydrophobicity decreases. Therefore, the liquid absorbency tends to be high, and the liquid tends to swell and decrease in strength. Therefore, from this viewpoint as well, it is preferable to control the mass ratio of the polyester polyol A dimerate and the polymer polyol B within the above range.

-Content of defoamer-
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.

-Filler content-
The content of the filler (particularly, the inorganic filler) is preferably 5 to 50 parts by mass and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the polymer polyol from the viewpoint of cell miniaturization.

(Characteristics of continuous ventilation type sponge)
-Self-skin layer-
The continuously breathable sponge according to this embodiment may or may not have a self-skin layer. However, if it is desired to suppress impregnation and water absorption of water-based liquids such as cosmetic puffs for liquid foundations, it is preferable to have a self-skin layer.

-Ventilation-
Measure the thickness of the measurement sample with a digital thickness gauge. Set the sample in the Frazier type air permeability tester, adjust the value of the inclined barometer so that it shows "5" with a pressurizing resistor, and read the pressure of the vertical barometer at that time. Use the conversion table for each type of orifice to obtain the conversion value. The air permeability is calculated by the following formula.
Formula: AP = a × t
AP: Air permeability (mL / cm ² / s)
a: Converted value t: Thickness (cm)

-Apparent density-
The apparent density of the continuously ventilated sponge according to the present embodiment is 100 to 400 kg / m ³ from the viewpoints of mechanical strength, prevention of bottom contact during compression use, and operability, in addition to appropriate liquid absorption and improvement of skin feel. Is preferable, and 150 to 300 kg / m ³ is more preferable.

The apparent density is measured by the following method.
First, a sample to be measured (approximate size: length 100 mm × width 100 mm × thickness measurement value) is prepared in an environment of 23 ± 3 ° C. Next, the weight of the sample is measured with an accuracy of 1/100 g with a precision balance. Next, using a digital gauge and using a stylus having a diameter of Φ10 mm, the thickness of the sample is measured at 9 points with an accuracy of 1/100 mm under a load of about 0.6 N, and the average value is obtained. The vertical and horizontal dimensions of the sample are measured at three points using a digital caliper, and the average is calculated. The volume of the sample is calculated from each of the obtained dimensions. Then, the apparent density is obtained by the formula: apparent density = weight / volume.

-Tensile strength / elongation-
The tensile strength of the continuously venting sponge according to the present embodiment is preferably 0.1 MPa or more from the viewpoint of mechanical strength, prevention of bottom contact during compression use, and operability.
The tensile elongation of the continuously ventilated sponge according to the present embodiment is preferably 150% or more, more preferably 200% or more, from the viewpoint of mechanical strength and operability.

Tensile strength and elongation are measured in accordance with JIS K 6400-5 (2012). In the measurement, the object to be measured is punched into a dumbbell No. 2 shape, a sample is obtained, and the thickness is measured. The obtained sample is subjected to a speed of 200 mm / min with a "Tensilon universal material tester UCT-500" manufactured by Orion Tech Co., Ltd. Then, the strength and elongation at break of the sample are measured.

-Tear strength-
The tear strength of the continuously venting sponge according to the present embodiment is preferably 3 N / cm or more, more preferably 5 N / cm, from the viewpoint of mechanical strength.

The tear strength is a value measured according to JIS6400-5 (2012).

-50% compression hardness-
The 50% compression hardness of the continuously breathable sponge according to the present embodiment is preferably 50 kPa or less, more preferably 15 kPa or less, from the viewpoints of mechanical strength, prevention of bottom contact during compression use, and operability, in addition to improving the feel on the skin. More preferably, it is 10 kPa or less.
The 50% compressive hardness is measured according to JIS K6400-2 (2012).
Specifically, a sample is punched from the measurement target to a size of 50 × 50 mm. When the thickness is 10 mm or less, the samples are obtained by laminating so as to be 10 mm or more. Then, using the "Tensilon Universal Material Testing Machine UCT-500" manufactured by Orion Tech Co., Ltd., 50% compression is performed on the sample thickness at a compression rate of 50 mm / min, and the 50% compression hardness is measured.

-Water absorption-
The water absorption rate of the continuously ventilated sponge according to the present embodiment is preferably 20% by mass or less, more preferably 15% by mass or less, and most preferably 12% by mass or less from the viewpoint of appropriate liquid absorption. preferable.
The water absorption rate is measured as follows.
Prepare a 10 cm square sample and measure the mass to 1/100 g unit. Next, put 10 cm of water in the water tank, submerge the sample to a depth of 10 cm, and leave it for 24 hours. After 24 hours, the water on the surface of the sample is wiped off, and the mass of the sample is measured to 1/100 g. After that, the liquid absorption rate is measured by the following formula.
Water absorption liquid ratio (%) = (mass after water absorption-mass before liquid absorption) / mass before water absorption x 100

-Average cell diameter-
The average cell diameter of the continuously ventilated sponge according to the present embodiment is preferably 270 μm or less, more preferably 250 μm or less, still more preferably 200 μm or less, from the viewpoint of appropriate liquid absorption and improvement of skin feel, as well as mechanical strength. ..

The average cell diameter is calculated from 25 mm / number of cells by measuring the number of cells for each 25 mm length according to JIS K 6400-1 (2004) Annex 1. The average cell diameter is magnified and measured with an optical microscope.

(Manufacturing method of continuous ventilation type sponge)
The method for producing the continuously ventilated sponge according to the present embodiment is not particularly limited. For example, as a method for producing a continuously ventilated sponge according to the present embodiment, the following method can be mentioned.
A coating process in which the urethane raw material liquid is mechanically foamed using an oak mixer or the like, and the foamed urethane raw material liquid is continuously applied onto the first continuous web (belt-shaped body) to form a coating film, and the first 1. A method for producing a continuously ventilated sponge, which comprises a heating step of heating and curing a coating film on a continuous web to form a foam having a continuously ventilated structure.

On the other hand, after the coating step and before the heating step, the second continuous web (belt) is supplied to the coating film on the first continuous web (belt), and the coating film is sandwiched between the two continuous webs. The step including the second continuous web supply step, in which the heating step heats and cures the coating film in a state of being sandwiched between the two continuous webs, has many merits to form a foam having a continuous ventilation structure.
In particular, when the coating film of the urethane raw material liquid is heat-cured to form a foam having a continuous ventilation structure while being sandwiched between two releasable continuous webs, the foam is sandwiched between the two continuous webs. Since it foams, the foaming agent does not scatter, so the foaming ratio increases (low density). In addition, a thin and smooth skin layer is formed on both surfaces, and it is easy to obtain a foam (that is, sponge) with a continuous ventilation structure that has a high texture and is familiar to fingers (feels moist).

Hereinafter, a method for manufacturing a continuously ventilated sponge of this embodiment will be described with reference to the drawings.

FIG. 1 is a schematic view of an example of an apparatus configuration for carrying out the method for manufacturing a continuously ventilated sponge according to the present embodiment.
As shown in FIG. 1, the continuous ventilation type sponge manufacturing apparatus 100 includes a first web roll 14 that feeds out a first continuous web 14A, and a coating apparatus 12 that applies a urethane raw material liquid onto the first continuous web 14A. , A large-diameter roller 18 that guides the first continuous web 14A sent out from the first web roll 14 directly under the coating device 12, a second web roll 16 that sends out the second continuous web 16A, and a second continuous web 16A. The guide roller 20 for guiding the urethane raw material liquid onto the coating film 10 on the first continuous web 14A and the urethane raw material liquid coating film 10 sandwiched between the two

continuous webs

14A and 16A are guided to the heating device 22 and the heating device. Recovery by winding up and collecting the

transport rollers

28A and 28B for transporting the foam (hereinafter referred to as "urethane foam sheet") 30 heated and cured by 22 and the

continuous webs

14A and 16A peeled from the urethane foam sheet 30. It includes

rollers

24 and 26.

-Applying process-
First, the urethane raw material liquid in which the raw material components are mixed and stirred is continuously applied onto the first continuous web 14A to form the coating film 10.

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 is not deformed by coating the urethane raw material liquid and heating in the heating process, but from the viewpoint of resistance to the urethane raw material liquid, heat resistance, etc., a film such as polyester, polypropylene, polymethylpentene, etc. Is preferable.
If necessary, the surface of the resin film may be subjected to a corona discharge treatment, a plasma treatment, or the like to improve the adhesiveness with the urethane foam sheet.

Further, after producing the urethane foam sheet, a resin film having a releasable surface on which 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, a method of applying a silicone releasable agent to one side of the resin film, a method of using a resin film having releasability such as polypropylene resin or polymethylpentene resin as it is, and a releasability property. There is a method such as laminating a resin film on a polyester film or the like. It is also possible to enhance the design and texture by adding a matte finish or a grain pattern to the surface of the release film or the release paper.

When a paper body is used as the first continuous web 14A, the surface of glassine paper or woodfree paper is coated with polypropylene, or a silicone release agent or non-silicone release agent is further applied on the surface of the glassine paper or high-quality paper. Is used.
As the first continuous web 14A used in the present disclosure, a resin film or a releasable resin film is preferable because the solidification rate of the foam is high and the thickness accuracy is high.

As the coating device 12 for coating the urethane raw material liquid on 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 the discharge nozzle with a traverse (repeated coating) device, and applying a thin coat with a roll coater or knife coater, or introducing the urethane raw material liquid from the discharge nozzle to the die coater and continuously webing. The method of coating on top is also preferable.

The thickness of the coating film 10 may be determined according to the intended use of the foam (continuously ventilated sponge).

-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 peeling of the continuous webs on at least one side of the urethane foam sheet 30 after the heating step, at least one continuous web of the first continuous web 14A and the second continuous web 16A is in contact with the coating film 10. It is preferable to use a continuous web having a releasable surface.

The second continuous web 16A is continuously unwound from the second web roll 16 around which the second continuous web 16A is wound and covered with 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.

The apparatus shown in FIG. 1 is configured such that the coating film 10 is sandwiched between two

continuous webs

14A and 16A. However, after forming the coating film on the first continuous web 14A, the second continuous web You may proceed to the next heating step without covering with 16A.

-Heating process-
The coating film 10 is conveyed into the heating device 22 in a state of being sandwiched between two

continuous webs

14A and 16A and cured by heating.
The heating temperature for curing is preferably 80 to 120 ° C., and it is preferable to cure at a temperature in this range in 5 to 20 minutes.
As the heating device 22, an infrared heater, an electric heater, a gas combustion furnace, or the like can be used.

-Peeling process-
The urethane foam sheet 30 foamed and cured by the heating step may be wound while the

continuous webs

14A and 16A are in close contact with the urethane foam sheet 30, and when the

continuous webs

14A and 16A are releasable webs, FIG. As shown in the above, the releasable web is peeled off from the urethane foam sheet 30 and wound around the

recovery rollers

24 and 26 for recovery. The collected

continuous webs

14A and 16A can be reused as supply rolls 14 and 16.

Through the above steps, a continuously ventilated sponge made of a urethane foam sheet (foam having a continuously ventilated structure) can be continuously manufactured.

When the continuous ventilation type sponge according to the present embodiment has a low air permeability, a crushing treatment (a treatment of shearing and compressing the foam to increase the air permeability) may be performed if necessary. If the air permeability is kept low, the restoration speed will be slower, and if the air permeability is increased, the restoration speed will be faster, so the air permeability can be adjusted according to the application.

In addition to the above, known methods such as a slab stock method and a molding method for molding in a mold can be applied to the method for producing a continuously ventilated sponge according to the present embodiment.

In addition, in this specification, the term "process" is not limited to an independent process, as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. Included in this term.

(Use of continuous ventilation type sponge)
The continuously breathable sponge according to the present embodiment includes cosmetic puffs, brassiere pads, sports clothing pads, body protection pads (head, knee or elbow pads, etc.), medical (fish eyes, etc.) pads, insoles, etc. It can be applied to supporters, waterproof sealants, liquid (chemicals, lotions, etc.) impregnated sheets, masks, packaging bags, etc.

(Cosmetic puff)
The cosmetic puff according to the present embodiment has the continuously breathable sponge according to the present embodiment. As a result, the cosmetic puff according to the present embodiment is prevented from being excessively infiltrated with the liquid foundation. As a result, the consumption of liquid foundation is reduced. In addition, the liquid foundation is comfortable to wear.

The decorative puff according to the present embodiment may be a puff having a single layer structure of the continuously breathable sponge according to the present embodiment, or may be a multi-layer in which the continuously breathable sponge according to the present embodiment and another skin material are integrated. It may be a structural puff.

The present disclosure will be specifically described with reference to Examples below, but the present disclosure is not limited to these Examples. In the following, "part" is based on mass unless otherwise specified.

<Example 1>
・ High molecular weight polyol A (polyester polyol obtained from dimer acid and diethylene glycol, manufactured by Hitachi Kasei Co., Ltd., OHv = 85, viscosity 5500 mPa · s) 100 parts ・ Foaming agent SZ1923 (silicone-based foaming agent manufactured by Toray Dau) 5 parts ,
-Catalyst SO (manufactured by Mitsubishi Chemical Co., Ltd., Stanasoctate) 0.1 part While continuously supplying a mixture containing the above polyol component other than isocyanate to the oak mixer, and supplying nitrogen gas to mechanically foam it. 22.4 parts of isocyanate (Carbodiimide-modified diphenylmethane diisocyanate (carbodiimide-modified MDI), NCO% = 29) manufactured by Tosoh Corporation is added to an oak mixer, and the polyol component is discharged while reacting with isocyanate. At that time, the total discharge amount of the raw material was 250 g / min, the discharge amount of nitrogen gas was 800 cc / min, the discharged reaction solution was applied on a release film, and cured at 70 ° C. × 5 minutes and then at 100 ° C. for 10 minutes. , A continuously ventilated sponge having a thickness of about 8 mm was obtained.

<Examples 2 to 15, Comparative Examples 1 to 7>
A continuously ventilated sponge was obtained in the same manner as in Example 1 except that the type and amount of the material (the numerical values in the table are the number of copies) were changed according to the compositions of Tables 1 to 3.
However, in Examples 13 and 14, under the same mechanical foaming conditions as in Example 1, a block-shaped sponge having a thickness of 50 × length 200 × width 200 mm was prepared and then sliced to a thickness of 8 mm without a self-skin layer. A continuously ventilated sponge was obtained.
Further, in Comparative Examples 4 to 6 (water foaming), a continuously ventilated sponge was obtained as follows. A surface obtained by applying the stirred urethane raw material liquid on a release film that has been released from the mold so that the thickness after curing is about 8.0 mm using a die coater, and then another release film is released from above. Was put on the coating film so as to be in contact with the coating film of the urethane raw material liquid. Next, the coating film of the urethane raw material liquid was heat-cured in an oven under the conditions of a temperature of 80 ° C. × 3 minutes and 100 ° C. × 5 minutes while being sandwiched between two release films. Then, the films on both sides were peeled off to obtain a continuously breathable sponge having a thickness of about 8.0 mm.
Further, as Comparative Examples 7 and 8, commercially available products were used.

<Measurement of physical properties>
The following physical properties of the continuously ventilated sponge obtained in each example were measured according to the method described above.
・ Apparent density ・ Tensile strength ・ Tensile elongation ・ Tear strength ・ 50% compression hardness ・ Water absorption rate ・ Average cell diameter ・ Air permeability

<Evaluation>
The following evaluations were carried out on the continuously ventilated sponges obtained in each example.
-Skin feel-
Regarding the skin feel, we confirmed the skin feel when makeup was applied by five women, and monitored and evaluated it according to the following criteria. As for the evaluation, the most frequently evaluated among the five people is shown in the table.
A: Very good skin feel B: Good skin feel C: Not good with a slightly rough or rough feeling D: Poor skin feel

-Tactile index-
The tactile index was quantified by multiplying the 50% compression hardness by the cell diameter. When the multiplied value is lower than 2, the feel is very good, when it is 2 to 3, it feels good, and when it is 3 to 4, it feels a little rough or stiff, and when it is 4 or more, it feels bad. There was a correlation with the evaluation.

-Comprehensive evaluation-
The continuously ventilated sponges of each example were comprehensively evaluated according to the following criteria.
A: Puff sponge with very good skin feel and low water absorption rate B: Puff sponge with excellent skin feel and low water absorption rate C: Puff sponge with poor skin feel and high water absorption rate D: Poor skin feel Highly absorbent puff sponge

From the above results, it can be seen that the continuously ventilated sponge of the example has an appropriate liquid absorption rate and a better skin feel than the sponge of the comparative example.
Here, the degree of penetration of the liquid foundation of the continuously ventilated sponge of Example 4 and the sponge of Comparative Example 7 is shown in FIGS. 2 and 3.
As shown in FIG. 2, the continuously breathable sponge of Example 4 is moderately impregnated with the liquid foundation, whereas the sponge of Comparative Example 7 is excessively impregnated with the liquid foundation as shown in FIG. You can see that it is embedded.

The details of the components shown in the table are as follows.
-Polymer polyol A-
-Polyester polyol dimer acid A1: Polyester dimer acid 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
-Polyester polyol dimer acid A2: Polyester dimer acid 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
Polyester polyol dimer acid A3: Polyester dimer acid polyol obtained from dimer acid and diethylene glycol, manufactured by Hitachi Kasei Co., Ltd., hydroxyl value OHv = 70 mgKOH / g, viscosity (25 ° C.) = 10000 mPa · s

-Polycarbonate B-
-PTMG: Polytetramethylene ether glycol, hydroxyl value OHv = 133 mgKOH / g, number of functional groups f = 2
-PCL: Polycaprolactone diol, hydroxyl value OHv = 210.8 mgKOH / g, number of functional groups f = 2
Adipate: Adipate ester polyol (polyoxide obtained by condensing adipic acid and 1,3 butanediol, hydroxyl value OHv = 117 mgKOH / g, number of functional groups f = 2
-PPG: Polypropylene glycol, hydroxyl value OHv = 112 mgKOH / g, number of functional groups f = 2, molar ratio of ethylene oxide EO = 0%, 30%

-Filler-
・ CaCO3: General-purpose calcium carbonate first grade manufactured by Sankyo Seiko Co., Ltd. ・ Al (OH) 3: Aluminum hydroxide: Heidilite H10 manufactured by Showa Denko Co., Ltd.

-Foaming agent-
SZ1923: SZ-1923, manufactured by Toray Dow, silicone-based defoaming agent

-catalyst-
・ Stanas octate: Metal catalyst, SO (manufactured by Mitsubishi Chemical Corporation, Stanas octate)
-Dabco 33Lv: Amine catalyst, Dabco 33Lv (manufactured by Air Products Japan Co., Ltd.)

-Isocyanate-
-Carbodiimide-modified MDI: Tosoh, carbodiimide-modified diphenylmethane diisocyanate, NCO% = 29

-Commercial goods-
・ Commercially available NBR puff: NBR sponge manufactured by Yukigaya Chemical Co., Ltd. ・ Commercially available pore agent extraction method PU based puff: Ruby cell manufactured by Toyo Chemical Co., Ltd.

The description of the reference numerals is as follows.
10 Coating film 12 Coating device 14 1st web roll 14A 1st continuous web 16 2nd web roll 16A 2nd continuous web 18 Large diameter roller 22 Heating device 24 1st recovery roll 26 2nd recovery roll 30 Continuous ventilation structure Foam (urethane foam sheet)
100 Continuous ventilation type sponge manufacturing equipment

The entire disclosure of Japanese Patent Application No. 2019-091336 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

Claims

Polymer polyols containing 30% by mass or more and 100% by mass or less of polyester dimerate with respect to all polymer polyols,
Diphenylmethane diisocyanate-based isocyanate and
Defoamer and
With the catalyst
A continuously ventilated sponge composed of a mechanical foam of a composition containing.
The continuously breathable sponge according to claim 1, wherein the polymer polyol contains a polymer polyol other than the polyester polyol dimerate.
The continuously ventilated sponge according to claim 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.
A claim that the mass ratio (polyester polyol dimerate / polymer polyol other than polyester dimerate) of the polyester polyol dimerate to a polymer polyol other than the polyester dimerate is 30/70 to 80/20. The continuously ventilated sponge according to claim 2 or 3.
The continuously ventilated sponge according to any one of claims 1 to 4, wherein the water absorption rate is 15% or less.
The continuously breathable sponge according to any one of claims 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.
The continuously ventilated sponge according to any one of claims 1 to 6, which has a self-skin layer.
A cosmetic puff having the continuously breathable sponge according to any one of claims 1 to 7.