Easy-to-wash, continuously breathable sponge, and easy-to-wash cosmetic puff
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- TOKYO QUALITY ONE CORP
- Filing Date
- 2022-09-30
- Publication Date
- 2026-07-07
Smart Images
Figure 0007886239000010 
Figure 0007886239000001 
Figure 0007886239000002
Abstract
Description
[Technical Field]
[0001] The present invention relates to an easily washable, continuously breathable sponge and an easily washable cosmetic puff. [Background technology]
[0002] For example, a so-called "extraction and removal method" is used to produce a porous sponge by dissolving thermoplastic polyurethane in a water-soluble solvent (e.g., dimethylformamide), further mixing in a water-soluble pore-forming agent (e.g., polyvinyl alcohol, methylcellulose), pouring this mixture into a mold, and then extracting the water-soluble solvent and pore-forming agent with water or steam.
[0003] The sponges obtained by this "extraction and removal method" have extremely fine cells and are used in high-end applications, but because they are manufactured using a very complicated method, they have problems such as high cost, a large environmental impact, and the use of large amounts of water (Patent Document 1). An improved version of this "extraction and removal method" is a method for producing a continuously ventilated sponge by mechanically stirring and mixing polyols, isocyanates, foam stabilizers, catalysts, and gases such as nitrogen (the so-called mechanical floss method) (Patent Document 2). However, the mechanical flossing method uses urethane raw materials with polyoxyalkylene polyol as the polyol, resulting in high hydrophilicity and a problem where the foam easily absorbs water and moisture. Furthermore, in the case of cosmetic puffs, this leads to the problem of excessive absorption of liquid foundation. Additionally, a large amount of silicone-based foam stabilizer is used to mix gas with the urethane raw material to create a finer foam and to stabilize the bubbles. As a result, the foam stabilizer remains in the sponge.
[0004] On the other hand, a cosmetic puff has also been proposed that is made from a foam produced by foaming a polyol obtained from vegetable oil and an MDI-based isocyanate using a water foaming method (a common method for foaming polyurethane) (Patent Document 3). Such a foam produced by water foaming is a simple manufacturing method. [Prior art documents] [Patent Documents]
[0005] [Patent Document 1] Japanese Patent Application Publication No. 58-189242 [Patent Document 2] Japanese Patent Publication No. 2014-227426 [Patent Document 3] Japanese Patent Publication No. 2007-54164 [Overview of the project] [Problems that the invention aims to solve]
[0006] However, in the mechanical flossing method, a large amount of silicone-based foam stabilizer is used to mix gas with the urethane raw material to make it finer and to stabilize the foam. As a result, the foam stabilizer remains in the sponge. Therefore, when a sponge gets dirty and is washed, any remaining foaming agent comes out like soap suds. Even if only a small amount of foaming agent remains, it will foam up when it absorbs water, and the foaming agent will not be completely removed.
[0007] Furthermore, foams obtained by foaming polyols derived from vegetable oils and MDI-based isocyanates using the water foaming method (the usual method for foaming polyurethane) tend to form closed cells, so it is necessary to deliberately disrupt the cells to create open cells. As a result, it is difficult to obtain fine cells, and the resulting foam is not very pleasant to the skin when used as a cosmetic puff. In addition, because foam stabilizers remain in the foam, foaming still occurs, and the foam stabilizers are not completely removed.
[0008] Sponges (and processed products) worn on the body, as well as sponges used in close proximity to the human body, are often reused after being washed and cleaned when soiled. Reusing them repeatedly reduces waste and is beneficial from an environmental perspective. For sponges that are used repeatedly for washing and cleaning, it is essential that they are easy to clean.
[0009] Here, "excellent in easy washing property" may include the following contents. (1) It can be kneaded and washed. That is, it can be easily compressed, is difficult to tear during water washing, and water can enter inside the sponge for cleaning. (2) It is easy to remove dirt. That is, dirt is difficult to adhere, and the adhered dirt can be easily removed by washing. (3) It has good foam breakage. That is, it is easy to rinse. Also, there is no foaming additive, the material repels water easily, and water easily penetrates inside the sponge. (4) It is easy to dry. That is, the material itself is difficult to absorb water, and it has high air permeability. It returns to its original dimensions early.
[0010] Thus, a flexible sponge composed of fine cells excellent in easy washing property is desired, but currently there is no sponge made of a flexible polyurethane foam that satisfies this.
[0011] Therefore, an object of the present invention is to provide a continuous ventilation type sponge excellent in easy washing property and a cosmetic puff excellent in easy washing property.
Means for Solving the Problems
[0012] The above problems are solved by the following means.
[0013] <1> Polyether polyol A, Dimer acid polyester polyol B, Diphenylmethane diisocyanate - based isocyanate C, A silicone - based foam stabilizer D having a reactive group that reacts with isocyanate, Water E, Catalyst F, and is composed of a foam of a composition containing them, having an apparent density of 100 - 300 kg / m 3 and an air permeability of 0.05 cm 3 / cm 2A washable, continuously breathable sponge made of flexible polyurethane foam having a hardness of 10 kPa or less, a closed cell ratio of 5%, a 50% compression hardness of 10 kPa or less, and a 50% compression set of 10% or less. <2> Polyether polyol A is an alkylene oxide-added polyol, with a molar ratio of ethylene oxide of 5-30%. <1> An easy-to-clean, continuously breathable sponge made of the flexible polyurethane foam described above. <3> The mass ratio of the polyether polyol A to the dimer acid polyester polyol B (polyether polyol A / dimer acid polyester polyol B) is 1 / 9 to 9 / 1. <1> or <2> An easy-to-clean, continuously breathable sponge made of the flexible polyurethane foam described above. <4> The isocyanate C is two or more isocyanates selected from the group consisting of diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, and polyol-modified diphenylmethane diisocyanate. <1> ~ <3> An easy-to-clean, continuously breathable sponge made of flexible polyurethane foam as described in any one of the items. <5> The composition further comprises an aliphatic isocyanate. <1> ~ <4> An easy-to-clean, continuously breathable sponge made of flexible polyurethane foam as described in any one of the items. <6> The composition further comprises at least one selected from the group consisting of low molecular weight diols having branched chains, diols having an alicyclic structure, and isocyanates having an alicyclic structure. <1> ~ <5> An easy-to-clean, continuously breathable sponge made of flexible polyurethane foam as described in any one of the items. <7> The composition further comprises one or more fillers selected from the group consisting of inorganic fillers and organic fillers. <1> ~ <6> An easy-to-clean, continuously breathable sponge made of flexible polyurethane foam as described in any one of the items. <8> It has a self-skin layer <1> An easy-to-clean, continuously breathable sponge made of the flexible polyurethane foam described above. <9> This sponge is used for applications where easy cleaning is required. <1> ~ <8> An easy-to-clean, continuously breathable sponge made of flexible polyurethane foam as described in any one of the items. <10> These are products that have been heat-welded with other components, ultrasonically fused with other components, or high-frequency welded with other components. <1> ~ <9> An easy-to-clean, continuously breathable sponge made of flexible polyurethane foam as described in any one of the items. <11> <1> ~ <10> An easy-to-clean cosmetic puff having a continuously breathable sponge made of flexible polyurethane foam as described in any one of the items. [Effects of the Invention]
[0014] According to the present invention, it is possible to provide an easy-to-wash, continuously breathable sponge and an easy-to-wash cosmetic puff. [Brief explanation of the drawing]
[0015] [Figure 1] This is a schematic diagram showing an example of an apparatus for carrying out the manufacturing method of an easily washable, continuously breathable sponge according to this embodiment. [Modes for carrying out the invention]
[0016] The following describes an embodiment of the present invention, which is one example of this invention.
[0017] (Continuously breathable sponge) The easy-to-clean, continuously breathable sponge according to this embodiment (hereinafter also simply referred to as "continuously breathable sponge") is Polyether polyol A and Dimer acid polyester polyol B and Diphenylmethane diisocyanate-based isocyanate C (hereinafter also referred to as "MDI-based isocyanate C"), A silicone-based foam stabilizer D having a reactive group that reacts with isocyanate (hereinafter also referred to as "reactive silicone-based foam stabilizer D"), Water E and Catalyst F and It consists of a foam of a composition containing the following: Apparent density is 100-300 kg / m³ 3 The breathability is 0.05 cm. 3 / cm 2 It consists of a flexible polyurethane foam having a hardness of 10 kPa or less, a cell locking ratio of 5% or less, a 50% compression hardness of 10 kPa or less, and a 50% compression set of 10% or less. Furthermore, the composition for forming the foam (hereinafter also referred to as "urethane raw material liquid") may contain other components in addition to the components mentioned above.
[0018] The continuous-air-ventilated sponge according to this embodiment, with the above configuration, becomes a continuous-cell sponge with excellent ease of washing. The reason for this is presumed to be as follows.
[0019] First, a reactive silicone-based foam stabilizer D is applied as a foam stabilizer, and the foam stabilizer is immobilized in the sponge by the reaction of its reactive groups. The immobilized silicone-based foam stabilizer is unevenly distributed at the inner wall interfaces of the cells that make up the sponge, increasing its hydrophobicity and making it difficult for dirt to adhere. In addition, by achieving a higher apparent density than general polyurethane foam, a fine cell structure is created, and by combining a low cell-locking ratio, high air permeability, and low compression set, the continuously breathable sponge according to this embodiment is easy to wash repeatedly, resistant to deformation, and has excellent washability. Furthermore, applying reactive silicone-based foam stabilizer D yields a foam with extremely fine cells, but this results in closed cells that tend to shrink after foaming. However, by using polyether polyol A and dimer acid polyester polyol B as polyols, and MDI-based isocyanate C as isocyanate, it is possible to achieve fine cells while producing a good foam that does not shrink after foaming. Moreover, because reactive silicone-based foam stabilizer D and dimer acid polyester polyol B are hydrophobic, the resulting foam becomes water-repellent. As a result, it has fine continuous bubbles, is difficult for dirt to adhere to, and even if dirt adheres, it is easy to remove. In addition, even if the sponge gets dirty and is washed, the generation of foaming due to the foam stabilizer is suppressed. In addition, by making the apparent density (100 - 300 kg / m 3 ) higher than that of general flexible polyurethane foam, fine cells are achieved, and it has a low single - cell ratio (5% or less), a high air permeability (0.05 cm 3 / cm 2 ·sec or more), a low 50% compression hardness (10 kPa or less), and a low 50% compression set (10% or less). Combined with the hydrophobic composition of the sponge of this embodiment, it is difficult to lose its shape even after repeated washing and has excellent easy - washability.
[0020] From the above, it is presumed that the continuous - ventilation - type sponge according to this embodiment is a continuous - ventilation - type sponge with excellent easy - washability.
[0021] Hereinafter, the details of the continuous - ventilation - type sponge according to this embodiment will be described.
[0022] First, each component of the urethane raw material liquid will be described.
[0023] (Polyether polyol A) Examples of the polyether polyol A include alkylene oxide - added polyether polyols. Among these, as the polyether polyol A, alkylene oxide - added polyether polyols are preferable.
[0024] Alkylene oxide - added polyether polyols are compounds obtained by addition - polymerizing alkylene oxides (ethylene oxide, propylene oxide, copolymers of ethylene oxide and propylene oxide, tetramethylene oxide (tetrahydrofuran, THF), etc.) to low - molecular - weight alcohols (ethylene glycol, glycerin, trimethylolpropane, etc.). Preferred alkylene oxide-added polyether polyols include polypropylene glycol (PPG), polyethylene glycol (PEG), copolymers of PPG and PEG, and polytetramethylene ether glycol (PTMG).
[0025] In particular, polyether polyol A is preferably an alkylene oxide-added polyol obtained by adding propylene oxide and ethylene oxide to a low molecular weight alcohol, and the molar ratio of ethylene oxide is 5 to 30% (preferably 10 to 30%). If the molar ratio of ethylene oxide is less than 5%, the compatibility with dimer acid polyester polyol B improves, making it difficult for foam-breaking effects to occur, and the sponge may become closed-cell type. Conversely, if the molar ratio of ethylene oxide exceeds 30%, the compatibility with dimer acid polyester polyol B deteriorates excessively, improving the foam-breaking effect, but increasing hydrophilicity, making it difficult to remove dirt, prone to tearing during washing, and difficult to dry. Furthermore, the molar ratio of ethylene oxide may be adjusted to a range of 5-30% by mixing two or more types of polyether polyol A.
[0026] The number of functional groups f of polyether polyol A is preferably 2 to 3 from the viewpoint of low compressive hardness and low compression set.
[0027] The number-average molecular weight Mn of polyether polyol A is preferably 1,000 to 10,000, and more preferably 3,000 to 8,000, from the viewpoint of low compressive hardness. Here, the number-average molecular weight is the molecular weight obtained from the hydroxyl value measured according to JIS K 0070-1992 and the number of functional groups. The number-average molecular weight of other components is measured in the same manner.
[0028] (Dimer acid polyester polyol B) Examples of dimer acid polyester polyol B include polyester polyols obtained by condensing dimer acid and glycol. Specifically, examples of dimer acid polyester polyol B include polyester polyols obtained by condensing a dimer acid (b-1) and a low molecular weight diol (b-2), and polyester polyols obtained by further condensing the polyester polyol with a low molecular weight triol (b-3). A polyester polyol obtained by condensing a dimer acid (b-1) and a low molecular weight diol (b-2), and then further condensing a low molecular weight triol (b-3), is preferably used when it is desired to increase the number of functional groups.
[0029] Dimer acid (b-1) is a dibasic acid obtained by the carbon-carbon covalent bonding of two monobasic fatty acids, resulting in a dibasic acid with twice the molecular weight of the original monobasic fatty acid. Typically, the monobasic fatty acids used to make up dimer acids are those with around 18 carbon atoms. Representative dimer acid compounds include linoleic acid and dibasic acids obtained by heating oleic acid.
[0030] Typically, industrial production of dimer acid includes monomeric acids, tribasic acids, and polymeric acids as by-products. While a higher purity of dimer acid is preferable when producing dimer acid polyester polyol B, it may be used in a mixture containing these by-products. Furthermore, since dimer acid is produced from plant-derived raw materials, it is carbon neutral and environmentally friendly.
[0031] As for the low molecular weight diol (b-2), any compound with a low molecular weight and two -OH groups can be used without particular restrictions. A low molecular weight diol refers to a compound with a total of two or more carbon atoms, and with 2 to 10 carbon atoms between the two -OH groups, with 4 to 6 carbon atoms being more preferable. More specifically, suitable low molecular weight diols (b-2) include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol.
[0032] In low molecular weight triols (b-3), "low molecular weight" refers to a hydrocarbon group to which three hydroxyl groups are bonded, with the number of carbon atoms being 3 to 10, and more preferably 3 to 6. The hydrocarbon group may be linear or branched. Examples of low molecular weight triols (a-3) include, for example, glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, and 2-methylpropanetriol.
[0033] (MDI-based isocyanate C) MDI-type isocyanate C (diphenylmethane diisocyanate-type isocyanate C) is an isocyanate having a diphenylmethane diisocyanate skeleton.
[0034] Examples of MDI-based isocyanates C include 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-MDI, 2.2'-MDI, and other diphenylmethane diisocyanates (pure MDI), crude MDI (cr-MDI), carbodiimide-modified MDI, and polyol-modified MDI. In particular, MDI-based isocyanate C has a good balance of tensile strength and elongation strength, and from the viewpoint of creating a fine, continuously breathable sponge, it is preferable to use two or more isocyanates selected from the group consisting of diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, and polyol-modified diphenylmethane diisocyanate. When used individually, the reaction is either too fast or too slow, making it difficult to control the reaction. Also, when using carbodiimide-modified MDI alone (100%) or pure MDI alone (100%), the resulting sponge has high compression hardness and low elongation.
[0035] Here, examples of polyol-modified isocyanates include 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, in which MDI-based isocyanates are modified. In these polyol-modified isocyanates, the content of MDI-based isocyanates is preferably 30% to 70% by mass (preferably 35% to 60% by mass) from the viewpoint of toughness and rebound elasticity.
[0036] (Reactive silicone-based foam stabilizer D) Reactive silicone foam stabilizer D (silicone foam stabilizer D having a reactive group that reacts with isocyanate) is a silicone compound having a reactive group that reacts with isocyanate and a polysiloxane chain.
[0037] The reactive groups of reactive silicone-based foam stabilizer D include -OH groups, -NHR groups (where R represents a monovalent organic group, such as an alkyl group with 1 to 10 carbon atoms), -NH2 groups, -SH groups, epoxy groups, etc. In particular, from the viewpoint of improving washability, the reactive silicone foam stabilizer D is preferably a silicone foam stabilizer having one or more reactive groups selected from the group consisting of -OH groups, -NHR groups (where R represents a monovalent organic group (for example, an alkyl group having 1 to 10 carbon atoms)), -NH2 groups, and -SH groups.
[0038] Typical examples of reactive silicone-based foam stabilizers D include compounds represented by general formulas (D1) to (D5). However, the examples are not limited to these compounds.
[0039] [ka]
[0040] In general formulas (D1) to (D5), X represents an -OH group, an -NHR group (where R represents a monovalent organic group (e.g., an alkyl group having 1 to 10 carbon atoms)), an -NH2 group, an -SH group, or an epoxy group. R 1 This represents a divalent organic group (for example, an alkylene group or polyalkylene oxide group with 1 to 10 carbon atoms). R 2 , and R 3 Each of these independently represents a monovalent organic group (for example, an alkyl group with 1 to 10 carbon atoms, or a phenyl group). n represents an integer between 2 and 4. n1 and n2 are each independent integers of 0 or greater than or equal to 1 (for example, integers from 0 to 100). p, q, r, and z are each independent integers greater than or equal to 1 (for example, integers between 1 and 100). In general formulas (D1) to (D5), if there are multiple identical signs, these multiple identical signs may represent the same base (or integer) or different bases (or integers).
[0041] (Water E) Water E is used as a foaming agent. Water E is not particularly limited and can include, for example, distilled water, ion-exchanged water, ultrafiltered water, and pure water. Furthermore, a low-boiling point organic solvent (such as alkyl fluoride compounds or alkyl chloride compounds) may be used in combination with water as a blowing agent. Additionally, gases such as nitrogen gas or air may be mixed into the urethane raw material liquid.
[0042] (Catalyst F) Examples of catalyst F include organometallic compound catalysts and amine-based catalysts. Examples of organometallic catalysts include tin-based, titanium-based, bismuth-based, and nickel-based catalysts, such as organotin compounds like stannous octylate and dibutyltin dilaurate. As amine catalysts, tertiary amines are preferred, and examples of amine catalysts include monoamines, diamines, triamines, cyclic amines, alcoholamines, and etheramines. Examples include triethylenediamine, triethylamine, n-methylmorpholine, n-ethylformoline, and N,N,N',N'-tetramethylbutanediamine. The catalyst may be used individually or in combination of two or more types.
[0043] (Other ingredients) Other ingredients include the following additives:
[0044] Other components include at least one selected from the group consisting of low molecular weight diols having branched chains, diols having an alicyclic structure, and isocyanates having an alicyclic structure. Here, a low molecular weight diol is a polyol with a molecular weight of 800 or less (preferably 60 to 300).
[0045] Using low-molecular-weight diols with branched chains improves the flexibility and extensibility of the sponge. Examples of low molecular weight diols with branched chains include aliphatic diols with 3 to 20 carbon atoms, such as 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 3-methyl-1,5-pentanediol (methylpentanediol), 2-ethyl-1,3-hexanediol, 1,2-hexanediol, 1,2-heptanediol, 2,3-heptanediol, 1,2-nonanediol, 1,2-octanediol, 1,2-decanediol, and 1,2-dodecanediol.
[0046] Using diols with an alicyclic structure improves the softness of the sponge when touched. Diols having an alicyclic structure include cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, cycloheptanediol, cyclooctanediol, 1,4-cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo[5,2,1,02,6]decane-dimethanol, bicyclo[4,3,0]-nonanediol, and dicyclohexanol. Examples include xanediol, tricyclo[5,3,1,1]dodecanediol, bicyclo[4,3,0]nonanedimethanol, tricyclo[5,3,1,1]dodecane-diethanol, hydroxypropyltricyclo[5,3,1,1]dodecanol, spiro[3,4]octanediol, butylcyclohexanediol, 1,1′-bicyclohexylidenediol, 2,2-bis-(4-hydroxycyclohexyl)propane, and 1,3-adamantanediol.
[0047] Using isocyanates with an alicyclic structure improves the softness of the sponge when touched. Examples of isocyanates having an alicyclic structure include isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, and hydrogenated xylylene diisocyanate (H6XDI).
[0048] Other components include aliphatic isocyanates. Adding a small amount of aliphatic isocyanate can reduce the degree of foam closure in the sponge and also has the effect of reducing its compressive hardness. Examples of aliphatic isocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.
[0049] Other ingredients include fillers. The filler can be one or more selected from the group consisting of inorganic fillers and organic fillers. By adding these fillers, a high average cell count can be achieved. Examples of inorganic fillers include calcium carbonate, aluminum hydroxide, magnesium hydroxide, natural silica, synthetic silica, kaolin, clay, titanium dioxide, barium sulfate, zinc carbonate, zinc oxide, glass beads, alumina beads, and carbon. Examples of organic fillers include phenol beads, styrene beads, acrylic beads, resin balloons, silicone powder, fluorine powder, nylon powder, and polyethylene powder. Other fillers include organic-inorganic fillers obtained by adding calcium carbonate to the surface of acrylic balloons, and POP (polymer-dispersed polyols) in which submicron organic polymers (such as acrylonitrile or acrylonitrile / styrene copolymers) are dispersed in polypropylene polyol.
[0050] Other ingredients include well-known additives such as flame retardants, antioxidants, colorants, UV absorbers, antibacterial agents, and antifungal agents, in addition to the ingredients mentioned above.
[0051] (Content of each component in the urethane raw material liquid) -Content of polyether polyol A and dimer acid polyester polyol B- The mass ratio of polyether polyol A to dimer acid polyester polyol B (polyether polyol A / dimer acid polyester polyol B) is preferably 1 / 9 to 9 / 1, and more preferably 3 / 7 to 7 / 3. When the mass ratio of polyether polyol A to dimer acid polyester polyol B is within the above range, the moderately low compatibility of the polyols makes it difficult for the sponge to form a closed-cell structure, and fine cells can be achieved, making it easier to obtain a sponge with a continuous breathable structure. If this mass ratio is lower than the above range, the sponge is more likely to form a closed-cell structure, while if it is higher than the above range, the sponge may easily attract dirt, tear easily when washed, and be difficult to dry.
[0052] -Content of reactive silicone-based foam stabilizer D- The content of the reactive silicone-based foam stabilizer D is preferably 0.5 to 3 parts by mass, and more preferably 1 to 2 parts by mass, based on 100 parts by mass of the total of polyether polyol A and dimer acid polyester polyol B.
[0053] -Water content- The water content is appropriately selected depending on the foaming ratio, but is preferably 0.3 to 1.4 parts by mass, and more preferably 0.5 to 1.2 parts by mass, per 100 parts by mass of the total of polyether polyol A and dimer acid polyester polyol B.
[0054] -Content of low molecular weight diols with branched chains- The content of branched low molecular weight diols is preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 3 parts by mass, per 100 parts by mass of the total of polyether polyol A and dimer acid polyester polyol B.
[0055] -Content of diols having an alicyclic structure- The content of the diol having an alicyclic structure is preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 3 parts by mass, per 100 parts by mass of the total of polyether polyol A and dimer acid polyester polyol B.
[0056] -Content of isocyanates having an alicyclic structure- The content of isocyanates having an alicyclic structure is preferably 0.1 to 5% by mass, and more preferably 0.2 to 3% by mass, relative to the total weight of isocyanates.
[0057] -Aliphatic isocyanate content- The aliphatic isocyanate content is preferably 0.1 to 5% by mass, and more preferably 0.2 to 3% by mass, relative to the total weight of isocyanates.
[0058] -Filler content- The filler content is preferably 5 to 40 parts by mass, and more preferably 10 to 30 parts by mass, based on 100 parts by mass of the total of polyether polyol A and dimer acid polyester polyol B.
[0059] (Characteristics of a continuously ventilated sponge) -Self-skin layer- The continuously ventilated sponge according to this embodiment may or may not have a self-skin layer. However, if it is desired to suppress the impregnation and absorption of water-based liquids, such as in a makeup puff for liquid foundation, it is preferable to have a self-skin layer.
[0060] -Apparent Density- The apparent density of the continuously ventilated sponge according to this embodiment is 100 to 300 kg / m², from the viewpoint of mechanical strength, particularly tear strength during use and washing, prevention of bottom contact during compressed use, and ease of handling during cosmetic application. 3 The apparent density is preferably 100-200 kg / m³. 3 Comfortable, 100-150 kg / m 3 That is the case.
[0061] The apparent density is measured by the following method. First, prepare the sample to be measured (approximate dimensions: 100mm length x 100mm width x measured thickness) in an environment of 23±3℃. Next, measure the weight of the sample with an accuracy of 1 / 100g using a precision balance. Then, using a digital gauge, measure the thickness of the sample at 9 points with an accuracy of 1 / 100mm using a measuring probe with a diameter of Φ10mm and a load of approximately 0.6N, and calculate the average value. Measure the length and width of the sample at 3 points each using a digital caliper and calculate the average. Calculate the volume of the sample from the obtained dimensions. Finally, calculate the apparent density using the formula: apparent density = weight / volume.
[0062] -Ventilation- The air permeability of the continuously breathable sponge according to this embodiment is set to 0.05 cm, from the viewpoint of easy washing, good rinsing, and easy drying. 3 / cm 2 • 1.0m or longer 3 / cm 2 • sec or more is preferable. The air permeability is more preferably 1 cm 3 / cm 2 It is 2 seconds or longer.
[0063] The air permeability is measured using a sponge approximately 10 mm thick, according to the Franjour method of woven fabric air permeability testing in accordance with JIS L 1004 (1972). The measured value is converted to the air permeability value for a 10 mm thickness. As for the apparatus, for example, the measurement is performed using the air permeability tester No. 8-6-9 manufactured by Toyo Seiki Co., Ltd.
[0064] -Closed foam rate- The continuously ventilated sponge according to this embodiment is a sponge with a cell-locking ratio of 5% or less. More preferably, the cell-locking ratio is 1% or less. The percentage of closed cells is measured by the Remington method (according to ASTM D 1940-62T). Specifically, the sample chamber volume R1 is measured using a mercury manometer. Next, the sample, whose volume V and weight W have been measured, is placed in the sample chamber and sealed. In this state, the sample chamber volume R2 is measured using a mercury manometer. The percentage of closed cells (%) is calculated using the following formula. (R1-R2-W / d) / (VW / d)×100 R1; Sample chamber volume (blank) (ml) R2; Sample chamber volume (with sample) (ml) W; Sample weight (g) d; True specific gravity (g / cm3) V; Sample volume (apparent volume) (cm³) 3 )
[0065] -50% Compression Hardness- The 50% compression hardness of the continuously ventilated sponge according to this embodiment is 10 kPa or less from the viewpoint of low hardness and ease of washing. Preferably, the 50% compression hardness is 5 kPa or less. The 50% compression hardness is measured in accordance with JIS K6400-2 (2012). Specifically, a sample measuring 50 x 50 mm is punched out from the object to be measured. If the thickness is 10 mm or less, the sample is obtained by stacking the samples until the thickness is 10 mm or more. Then, using the "Tensilon Universal Material Testing Machine UCT-500" manufactured by Orion Tech Co., Ltd., the sample is compressed to 50% of its thickness at a compression speed of 50 mm / min, and the 50% compression hardness is measured.
[0066] -50% compression set- The 50% compression set of the continuously ventilated sponge according to this embodiment is 10% or less, from the viewpoint of suppressing deformation after repeated washing. Preferably, the 50% compression set is 1% or less.
[0067] The 50% compression set is measured according to JIS K6400-4 Method A (2004). Specifically, a sample is punched out from the object to be measured to a size of 50 x 50 mm. If the thickness is 10 mm or less, the sample is obtained by stacking the pieces until the thickness reaches 10 mm or more. Next, the sample is sandwiched and fixed between metal plates via a spacer 50% thicker than the sample thickness t0 (mm). This is then maintained at room temperature for 22 hours. Next, after releasing the sample from the metal plate and letting it stand for 30 minutes, the sample thickness t1 (mm) is measured. Then, the compression set (%) is calculated using the following formula. Compression set (%) = (t0 - t1) / t0 × 100
[0068] -Average number of cells- The average number of cells in the continuously ventilated sponge according to this embodiment is preferably 75 or more, and more preferably 150 or more. The average cell count was calculated by measuring the number of cells at 10 mm intervals in accordance with JIS K 6400-1 (2004) Annex 1, and then multiplying that number by 2.5 to obtain the cell count (cells / 25 mm). The average cell count was measured under magnification using an optical microscope. In the case of test specimens with skin layers on both sides, the bottom skin layer at the time of manufacture was measured. In the case of specimens with a skin layer on one side after halving, the halved surface was measured.
[0069] - Volume water absorption rate (volume %) - The volumetric water absorption rate of the continuously breathable sponge according to this embodiment is preferably 1% by volume or more and 10% by volume or less, from the viewpoint of cosmetic retention and ease of washing. The method for measuring volumetric water absorption rate (volume %) is as follows: First, prepare a sample (approximate dimensions: 100mm x 100mm x mm) to be measured in an environment of 23±3℃. Next, measure the weight of the sample with an accuracy of 1 / 1000g using a precision balance. This weight will be defined as the initial weight w0 (g). Then, using a digital gauge, measure the thickness dimension t (mm) of the sample at 9 locations with an accuracy of 1 / 100mm using a measuring probe with a diameter of Φ10mm and a load of approximately 0.6N, and calculate the average value. Measure the length dimension a (mm) and width dimension b (mm) of the sample at 3 locations each using a digital caliper and calculate the average value. Submerge the sample in water at 23±3℃. Ensure the top surface of the sample is submerged in 100mm of water using a wire mesh or similar device. After 24 hours, carefully remove the sample (with minimal external pressure) and wipe off any adhering water from the surface with a Kimwipe or similar. The weight of the wiped sample is measured to an accuracy of 1 / 1000g using a precision balance. This weight is designated as the post-test weight w1(g). The water absorption rate (by volume %) is calculated using the following formula. Water absorption rate (volume %) = (w1 - w0) / (t × a × b / 1000) × 100
[0070] -Tensile strength and elongation- The tensile strength of the continuously ventilated sponge according to this embodiment is preferably 100 kPa or more, from the viewpoint of handling, processing, and ease of washing. More preferably, it is 180 kPa or more. The elongation of the continuously ventilated sponge according to this embodiment is preferably 100% or more from the viewpoint of handling, processing, and ease of washing. More preferably, it is 180% or more. Tensile strength and elongation will be measured in accordance with JIS K 6400-5 (2012). Specifically, a dumbbell-shaped test specimen (No. 2) will be pulled at a tensile speed of 200 mm / min, and the maximum stress and maximum elongation at the time of specimen fracture will be determined.
[0071] -Easy to wash- The continuously ventilated sponge according to this embodiment offers excellent ease of cleaning. The ease of cleaning of the continuously ventilated sponge according to this embodiment will be evaluated according to the following criteria. First, prepare a sample of the object to be measured (approximate dimensions: 100mm length x 100mm width x measured thickness) in an environment of 23±3℃. Prepare a tank containing water at a depth of 20cm or more, maintained at the same temperature for at least half a day. Only if all of the following items are passed will the sample be considered easy to wash (indicated as "〇" in the table). On the other hand, if even one item is failed, the sample will be considered easy to wash but failed (indicated as "×" in the table). (1) It can be compressed with light force underwater. (2) When (1) is true, no significant air remains inside the sponge. (3) When released underwater from the state in (2), it should return to its original shape within 10 seconds. (4) When steps (1) to (3) are repeated five times, there should be no foaming or foaming additives. (5) After repeating (1) to (3) five times, the water can be drained by compressing it lightly in the air. (6) In all of the above items, there should be no tears in the sponge.
[0072] -Form appearance (moldability)- The continuously ventilated sponge according to this embodiment also exhibits excellent foam appearance (moldability). The foam appearance (moldability) of the continuously ventilated sponge according to this embodiment shall be evaluated according to the following criteria. Only if all of the following items are passed shall the foam appearance be considered acceptable (indicated as "〇" in the table). On the other hand, if even one item is not passed, the foam appearance shall be considered unacceptable (indicated as "×" in the table). (1) No shrinkage of the form. (2) The form must be free from cracks inside and outside. (3) The foam surface and interior should not become sticky due to insufficient curing. (4) The entire form does not lack significant uniformity (for example, it does not have two or three layers). (5) If the foam has a skin layer, there must be no defects beneath the skin layer (i.e., it must not be in a so-called loose state).
[0073] (Method for manufacturing a continuous-air sponge) The method for manufacturing the continuously ventilated sponge according to this embodiment is not particularly limited. For example, the following method can be used to manufacture the continuously ventilated sponge according to this embodiment. A method for manufacturing a continuously ventilated sponge, comprising: a coating step of continuously applying a urethane raw material liquid onto a first continuous web (strip-shaped body) 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 continuously ventilated structure.
[0074] On the other hand, a process that includes a second continuous web supply step, in which a second continuous web (strip-shaped body) is supplied to the coated film on the first continuous web (strip-shaped body) after the coating step and before the heating step, sandwiching the coated film between the two continuous webs, and then heating and curing the coated film while it is sandwiched between the two continuous webs to form a foam with a continuous ventilation structure, has numerous advantages. In particular, when a coating film of urethane raw material liquid is heat-cured while sandwiched between two continuous release webs to form a foam with a continuous breathable structure, the foaming occurs while sandwiched between the two continuous webs, so there is no scattering of the foaming agent, resulting in a higher foaming ratio (lower density). This allows for the production of a foam with a high continuous breathable structure (i.e., a sponge) with a small amount of water, resulting in good stain resistance. Furthermore, the reduced urea bonding gives it a moist feel to the touch. A thin, smooth skin layer is formed on both surfaces, making it easy to obtain a foam with a high texture that conforms well to the fingers (a moist feel) and has a continuous breathable structure (i.e., a sponge).
[0075] The method for manufacturing a continuously ventilated sponge according to this embodiment will be described below with reference to the drawings.
[0076] Figure 1 is a schematic diagram showing an example of an apparatus configuration for carrying out the manufacturing method of a continuously ventilated sponge according to this embodiment. As shown in Figure 1, the continuous ventilation sponge manufacturing apparatus 100 includes a first web roll 14 for feeding out the first continuous web 14A, a coating apparatus 12 for applying urethane raw material liquid onto the first continuous web 14A, a large-diameter roller 18 for guiding the first continuous web 14A fed out from the first web roll 14 directly below the coating apparatus 12, a second web roll 16 for feeding out the second continuous web 16A, and a gas for guiding the second continuous web 16A onto the coating film 10 on the first continuous web 14A. The system includes a guide roller 20, a second conveyor roller 28A and a first conveyor roller 28B that guide the coated film 10 of urethane raw material liquid sandwiched between two continuous webs 14A and 16A to the heating device 22 and convey the continuously breathable foam (hereinafter referred to as "foamed urethane sheet") 30 heated and hardened by the heating device 22, and a first recovery roller 24 and a second recovery roller 26 that wind up and recover each of the continuous webs 14A and 16A that have been peeled off from the foamed urethane sheet 30.
[0077] -Coating process- First, the urethane raw material liquid, which is a mixture of raw material components, is continuously applied onto the first continuous web 14A to form a coating film 10.
[0078] For the first continuous web 14, a resin film or paper material is preferably used. The resin film is not particularly limited as long as it does not deform when heated during the application and heating process of the urethane raw material liquid. However, from the viewpoint of resistance to the urethane raw material liquid and heat resistance, films such as polyester, polypropylene, and polymethylpentene are preferred. If necessary, the resin film surface may be treated with corona discharge, plasma treatment, or other methods to improve its adhesion to the foamed urethane sheet.
[0079] Furthermore, after manufacturing the foamed urethane sheet, a resin film with release properties may be used on the surface where the urethane raw material liquid coating is formed, in order to make it easier to peel off the resin film. Methods for producing release-type resin films include applying a silicone release agent to one side of the resin film, using a release-type resin film such as polypropylene resin or polymethylpentene resin as is, or laminating a release-type resin film onto a polyester film or the like. When using paper, paper bodies coated with polyethylene or polypropylene on the surface of glassine paper or fine paper, or paper bodies further coated with a silicone release agent are used. Furthermore, the surface of the release film or paper release paper can be given a matte finish or a textured pattern to enhance its design and texture.
[0080] In the present invention, the first continuous web 14A is preferably a resin film coated with a silicone release agent on one side or a resin film having release properties, because it allows for a fast solidification rate of the foam and high thickness accuracy.
[0081] For coating the urethane raw material liquid onto the first continuous web 14A, it is preferable to use a die coater, roll coater, knife coater, comma coater, etc. as the coating device 12. It is also preferable to use a method in which the urethane raw material liquid is stirred with a mixing device and discharged from a discharge nozzle with a traverse (repeated coating) device and thinly coated with a roll coater or knife coater, or a method in which the urethane raw material liquid is introduced from a discharge nozzle into a die coater and coated onto the continuous web.
[0082] The thickness of the coating film 10 can be determined according to the intended use of the foam (continuously ventilated sponge), but from the viewpoint of the foaming ratio of the polyurethane foam sheet and the desired thickness, it is preferably 0.5 to 5 mm.
[0083] -Second continuous web supply process- The second continuous web 16A is supplied to the coated film 10 on the first continuous web 14A, so that the coated film 10 is sandwiched between the two continuous webs 14A and 16A. As the second continuous web 16A, a resin film or paper material as exemplified in the description of the first continuous web 14A can be used. Furthermore, from the viewpoint of making it easier to peel off the continuous web on at least one side of the foamed urethane sheet 30 after the heating process, it is preferable that at least one of the continuous webs of the first continuous web 14A and the second continuous web 16A has a release property on the surface that comes into contact with the coating film 10.
[0084] The second continuous web 16A is continuously unwound from the second web roll 16 on which it is wound, and placed over 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.
[0085] Although the apparatus shown in Figure 1 is configured to sandwich the coating film 10 between two continuous webs 14A and 16A, the process may proceed to the next heating step after forming the coating film on the first continuous web 14A without covering it with the second continuous web 16A.
[0086] -Heating process- The coated film 10 is transported into the heating device 22 while sandwiched between two continuous webs 14A and 16A, and is cured by heating. The heating temperature for curing is preferably 80 to 120°C, and curing is preferably achieved within 5 to 20 minutes at this temperature range. As the heating device 22, an infrared heater, an electric heater, a gas combustion furnace, etc., can be used.
[0087] -Peeling process- The foamed urethane sheet 30, which has been foamed and hardened by the heating process, is conveyed by the second conveyor roller 28A and the first conveyor roller 28B, and the continuous webs 14A and 16A may be wound up while remaining in close contact with the foamed urethane sheet 30. Alternatively, if the continuous webs 14A and 16A are release webs, as shown in Figure 1, the foamed urethane sheet 30 is conveyed by the second conveyor roller 28A and the first conveyor roller 28B while the release webs are peeled off from the foamed urethane sheet 30 and wound up onto the respective recovery rollers 24 and 26 for recovery. The first recovery roll 24 and the second recovery roll 26, from which the continuous webs 14A and 16A have been recovered, can be reused as the supply rolls, the first web roll 14 and the second web roll 16.
[0088] Through the above process, a continuously ventilated sponge made of foamed urethane sheet (a foam with a continuously ventilated structure) can be continuously manufactured.
[0089] In addition to the methods described above, known methods such as the slab stock method and the mold method, which involves molding in a mold, can be applied to the manufacturing method of the continuously ventilated sponge according to this embodiment.
[0090] In this specification, the term "process" includes not only independent processes but also any process that cannot be clearly distinguished from other processes, as long as its intended purpose is achieved.
[0091] (Applications of continuous ventilation sponges) The continuously breathable sponge according to this embodiment can be used for applications such as cosmetic puffs, bra pads, sportswear pads, knee or elbow pads, medical pads for corns, insoles, supporters, waterproof sealing materials, and liquid-impregnated sheet masks such as those containing lotions. In particular, the continuously ventilated sponge according to this embodiment is suitable for applications where the sponge is washed and reused.
[0092] The continuously ventilated sponge according to this embodiment does not bleed out because the foam stabilizer is reactive. As a result, it is suitable for heat fusion, ultrasonic fusion, and high-frequency fusion, and has the advantage of being easy to shape, bond with other components, and attach ribbons to. Therefore, in particular, the continuously ventilated sponge according to this embodiment may be a sponge that has been bonded to other components by heat welding, ultrasonic welding, or high-frequency welding. In other words, the continuously ventilated sponge according to this embodiment may be a product that has been heat-welded to other components, an ultrasonically fused product that has been bonded to other components, or a high-frequency welded product that has been bonded to other components. Other materials include latex rubber foam, other polyurethane foams, sheets made of thermoplastic resins such as polyester, polyurethane, and nylon, fabrics made of synthetic fibers, and resin sheets such as nonwoven fabrics, warif, and nets.
[0093] (Makeup puff) The makeup puff according to this embodiment has a continuously breathable sponge according to this embodiment. As a result, the makeup puff according to this embodiment is prevented from being excessively soaked with liquid foundation. This reduces the amount of liquid foundation consumed. In addition, even if the makeup puff becomes dirty and is washed repeatedly, the generation of foam caused by foam stabilizers is suppressed, and it is easy to wash.
[0094] The cosmetic puff according to this embodiment may be a single-layer puff with a continuous breathable sponge structure according to this embodiment, or it may be a multi-layer puff having the continuous breathable sponge according to this embodiment as the outer layer material. [Examples]
[0095] 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" refers to mass unless otherwise specified.
[0096] <Example 1> • Polyether polyol A: Actcol EP-240 (manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd., Mn=6,000, f=3, EO / PO=15 / 85, hydroxyl value OHv=23.7) 50 parts • Dimer acid polyester polyol B: Teslac 2458 (manufactured by Showa Denko Materials Co., Ltd., Mn=2,500, OHv=73.6) 50 parts • Foaming agent (water) E: 0.9 parts deionized water • Foam stabilizer D: 1.0 part of F-342 (hydroxyl group-containing side-chain type silicone modified product) manufactured by Shin-Etsu Chemical Co., Ltd. • Catalyst F1: 0.1 parts of Stanoct (bis(2-ethylhexanoate)tin(II)) manufactured by Mitsubishi Chemical Corporation (indicated as "SO" in the table). • Catalyst F2: 0.1 parts of DABCO(R)33LV (triethylenediamine (1 / 3), dipropylene glycol (2 / 3)) manufactured by Evonik Japan Co., Ltd. (indicated as "33lv" in the table). The above materials were stirred and mixed to obtain a polyol-based solution, and this solution was heated to 50°C.
[0097] Meanwhile, as isocyanates C1 and C2, carbodiimide-modified MDI (NCO%=28.1, Cosmonate LK, manufactured by Mitsui Chemicals, Inc.) and prepolymer A (polyol-modified MDI, NCO%=13.3) were stirred and mixed in a mass ratio of 50 / 50 to obtain an isocyanate mixture, which was then heated to 50°C. Here, prepolymer A is a prepolymer obtained by mixing pure diphenylmethane diisocyanate (Pure MDI, Myrionate MT, manufactured by Tosoh Corporation) and polyoxypropylene glycol (Mw=700, f=2, Uniol D-700, manufactured by NOF Corporation) in a molar ratio of 3.4 / 1, and reacting them at approximately 80°C in a reaction vessel with a stirrer under atmospheric pressure while passing nitrogen gas through it.
[0098] Next, an isocyanate mixture (39.04 parts) with an isocyanate index equivalent to 103 was stirred and mixed with the polyol-based solution to obtain a urethane mixture.
[0099] Next, the resulting mixture was uniformly applied to a PET film (100 μm thick) whose surface had been treated with a mold release agent. Then, another PET film (100 μm thick) with the same surface treatment was placed on top, sandwiching the urethane mixture between the two PET films. In this state, it was heated in an 80°C oven for 5 minutes, and then immediately afterwards heated in a 120°C oven for another 10 minutes. After heating was complete, the foam was removed from the oven, the PET film was removed, and an 8mm thick polyurethane foam with a self-skinning surface was prepared.
[0100] <Examples 2-7, Comparative Examples 1-2> Polyurethane foam was obtained in the same manner as in Example 1, by changing the amount of blowing agent (water) E (the values in Table 1 indicate the amount of parts). However, the amounts of isocyanates C1 to C2 were changed in order to achieve an isocyanate index of 103. In addition, the amount of catalyst F1 was adjusted as necessary.
[0101] <Examples 8-12, Comparative Example 3> Polyurethane foam was obtained in the same manner as in Example 1, by changing the foam stabilizer D to a reactive type other than F-342. However, the foam stabilizer D used was as follows: Example 8; KF6106 (polyglycerin-modified (terminal OH group), manufactured by Shin-Etsu Chemical Co., Ltd.) Comparative Example 3: KF6001 (OH groups at both ends, manufactured by Shin-Etsu Chemical Co., Ltd.) Example 9; X-22-170BX (one-ended OH group, manufactured by Shin-Etsu Chemical Co., Ltd.) Example 10; X-22-176F (two OH groups at one end, manufactured by Shin-Etsu Chemical Co., Ltd.) Example 11; KF6000 (OH groups at both ends, manufactured by Shin-Etsu Chemical Co., Ltd.) Example 12; X-22-1660B-3 (Terminal amino group, manufactured by Shin-Etsu Chemical Co., Ltd.)
[0102] <Comparative Examples 4-8> Polyurethane foam was obtained in the same manner as in Example 1, by changing the foam stabilizer D to a non-reactive type. However, the foam stabilizer D used was as follows: Comparative Example 4: SZ1642 (Terminal OR type, manufactured by Dow Toray Ltd.) Comparative Example 5: SH193 (Terminal OR type, manufactured by Dow Toray Ltd.) Comparative example 6; F-242T (terminal OR type, manufactured by Shin-Etsu Chemical Co., Ltd.) Comparative Example 7; L5614 (Non-reactive (AB)n type, manufactured by Momentive Performance Materials Japan LLC) Comparative Example 8: SZ1952 (Non-reactive (AB) n-type, manufactured by Dow Toray Ltd.)
[0103] <Examples 13-18, Comparative Examples 9-10> Polyurethane foam was obtained in the same manner as in Example 1 by changing the ratio of polyether polyol A and dimer acid polyester polyol B.
[0104] <Examples 19-22> Polyurethane foam was obtained in the same manner as in Example 1, by changing the types and ratios of isocyanates C1 to C2. Additionally, the amounts of catalysts F1 to F2 were adjusted as needed.
[0105] <Examples 23-28> Polyurethane foam was obtained in the same manner as in Example 1, by changing the type and ratio of polyether polyol A. However, the polyether polyol A used was as follows: Example 23; Excenol 4030 (manufactured by AGC Inc., Mn=4,000, f=3, PO=100%, hydroxyl value OHv=42.0) Example 24; Actcol EP-505S (manufactured by Mitsui Chemicals SKC Polyurethane Co., Ltd., Mn=3,300, f=3, EO / PO=70 / 30, hydroxyl value OHv=51.2) Example 25; A polyol with a molar ratio of ethylene oxide of 5.2% was obtained by blending Actcol EP-240 and Exenol 4030. Example 26: A polyol with a molar ratio of ethylene oxide of 10.0% was obtained by blending Actcol EP-240 and Exenol 4030. Example 27: A polyol with a molar ratio of ethylene oxide of 29.7% obtained by blending Actcol EP-505S and Exenol 4030. Example 28: A polyol with a molar ratio of ethylene oxide of 37.9% obtained by blending Actcol EP-505S and Exenol 4030.
[0106] <Examples 29-32> Polyurethane foam was obtained in the same manner as in Example 1 using an aliphatic isocyanate, a low molecular weight diol having a branched chain, a diol having an alicyclic structure, or an isocyanate having an alicyclic structure. However, the materials used were as follows: Example 29; Hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd., Mn=168, NCO%=50.0, hexamethylene diisocyanate used at 2% of the total isocyanates) Example 30; 2-Ethyl-1,3-Hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd., Mn = 767.3, f = 2, hydroxyl value OHv = 767.3) Example 31; 1,4-Cyclohexanedimethanol (manufactured by Tokyo Chemical Industry Co., Ltd., Mn = 144, f = 2, hydroxyl value OHv = 778.6) Example 32; Isophorone diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd., Mn=222.29, NCO%=37.8, isophorone diisocyanate used at 2% of the total isocyanates)
[0107] <Examples 33-34> Polyurethane foam was obtained in the same manner as in Example 1 by adding an inorganic or organic filler. However, the fillers used were as follows: Example 33; MC Coat S-1 (manufactured by Maruo Calcium Co., Ltd., inorganic filler, surface treatment calcium bicarbonate) Example 34; MZ-10HN(S) (manufactured by Soken Chemical Co., Ltd., organic filler, methacrylate ester copolymer)
[0108] <Examples 35-37> Examples 1, 2, and 6 were cut in half lengthwise, and their physical properties were measured. The average cell count was measured on the halved surface, not the skin layer surface.
[0109] <Physical property measurement> The following physical properties of the polyurethane foam obtained in each example were measured according to the method described above. • Apparent density • Ventilation ·Closed foam rate 50% compression hardness 50% compression set ·Easy to wash • Form appearance (moldability) • Average number of cells • Volumetric water absorption rate • Tensile strength ·stretch
[0110] <Rating> The results of the physical property measurements of the polyurethane foam obtained in each example are shown in the table. The overall evaluation was based on the following criteria. ◎: Passes all criteria including ease of washing, foam appearance (moldability), apparent density, air permeability, cell-lock ratio, 50% compression hardness, and 50% compression set, and also meets the following suitable ranges: average cell count of 150 cells / 25 mm or more, volumetric water absorption of 1-10% by volume, tensile strength of 180 kPa or more, and elongation of 180% or more. ○: If the product meets all criteria regarding ease of washing, foam appearance (moldability), apparent density, air permeability, cell-lock ratio, 50% compression hardness, and 50% compression set, and one or more of the following criteria are not within the suitable range: average cell count of 150 cells / 25 mm or more, volumetric water absorption of 1 to 10% by volume, tensile strength of 180 kPa or more, or elongation of 180% or more. △: Passes all items in terms of ease of washing, foam appearance (moldability), apparent density, air permeability, cell lock ratio, 50% compression hardness, and 50% compression set, and also meets one or more of the following criteria: average cell count less than 75 cells / 25 mm, volumetric water absorption rate outside of 1-10% by volume, tensile strength less than 100 kPa, and elongation less than 100%. ×: Failure to meet any of the following criteria: ease of cleaning, foam appearance (moldability), apparent density, air permeability, cell lock ratio, 50% compression hardness, or 50% compression set.
[0111] [Table 1]
[0112] [Table 2]
[0113] [Table 3]
[0114] [Table 4]
[0115] [Table 5]
[0116] [Table 6]
[0117] [Table 7]
[0118] [Table 8]
[0119] From the above results, it can be seen that the urethane foam of the example is superior to the urethane foam of the comparative example in terms of ease of cleaning and foam appearance (moldability). [Explanation of Symbols]
[0120] 10 Coating film 12 Coating device 14. First Web Roll 14A First Consecutive Web 16. Second Web Roll 16A Second consecutive web 18 Large diameter rollers 20 Guide rollers 22 Heating device 24 First Recovery Roll 26 Second Recovery Roll 28A Second conveyor roller 28B First conveyor roller 30. Foam with continuous ventilation structure (foamed urethane sheet) 100 Continuous ventilation type sponge manufacturing equipment
Claims
1. Polyether polyol A and Dimer acid polyester polyol B and Diphenylmethane diisocyanate-based isocyanate C, A silicone-based foam stabilizer D having a reactive group that reacts with isocyanate, Water E and Catalyst F and It consists of a foam of a composition containing the following: The foam stabilizer is the silicone-based foam stabilizer D alone. Apparent density is 100-300 kg / m³ ３ The breathability is 0.05 cm. ３ / cm ２ A washable, continuously breathable sponge made of flexible polyurethane foam having a hardness of sec or higher, a cell density of 5% or less, a 50% compression hardness of 10 kPa or less, and a 50% compression set of 10% or less.
2. An easy-to-clean, continuously breathable sponge made of flexible polyurethane foam according to claim 1, wherein polyether polyol A is an alkylene oxide-added polyol and the molar ratio of ethylene oxide is 5 to 30%.
3. An easy-to-wash, continuously breathable sponge made of flexible polyurethane foam according to claim 1, wherein the mass ratio of the polyether polyol A to the dimer acid polyester polyol B (polyether polyol A / dimer acid polyester polyol B) is 1 / 9 to 9 / 1.
4. The easy-to-clean, continuous-breathable sponge made of flexible polyurethane foam according to claim 1, wherein the isocyanate C is two or more isocyanates selected from the group consisting of diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, and polyol-modified diphenylmethane diisocyanate.
5. An easy-to-clean, continuously breathable sponge made of a flexible polyurethane foam according to claim 1, wherein the composition further comprises an aliphatic isocyanate.
6. The easy-to-clean, continuous-breathable sponge made of a flexible polyurethane foam according to claim 1, further comprising at least one selected from the group consisting of a low molecular weight diol having a branched chain, a diol having an alicyclic structure, and an isocyanate having an alicyclic structure.
7. The easy-to-clean, continuously breathable sponge made of flexible polyurethane foam according to claim 1, wherein the composition further comprises one or more fillers selected from the group consisting of inorganic fillers and organic fillers.
8. An easy-to-clean, continuously breathable sponge made of flexible polyurethane foam according to claim 1, having a self-skin layer.
9. An easy-to-clean, continuously breathable sponge made of flexible polyurethane foam according to claim 1, which is used for applications where easy cleaning is required.
10. An easy-to-clean, continuously breathable sponge made of flexible polyurethane foam according to claim 1, which is a product that has been heat-welded with other components, ultrasonically fused with other components, or high-frequency fused with other components.
11. An easy-to-clean cosmetic puff having an easy-to-clean, continuously breathable sponge made of the flexible polyurethane foam described in any one of claims 1 to 10.