WO2019163952A1

WO2019163952A1 - Porous polyurethane body and method for producing porous polyurethane body

Info

Publication number: WO2019163952A1
Application number: PCT/JP2019/006817
Authority: WO
Inventors: 朋哉厳本; 啓人芝田
Original assignee: トーヨーポリマー株式会社
Priority date: 2018-02-23
Filing date: 2019-02-22
Publication date: 2019-08-29
Also published as: KR102535128B1; JP2019143096A; CN110650998A; KR20200123375A; JP6596710B2

Abstract

This porous polyurethane body contains an aqueous urethane polymer. The aqueous urethane polymer is a reaction product of components that include (A) a polyol compound which contains a polyether polyol and a polycaprolactone polyol, (B) a polyisocyanate compound, (C) a hydrophilic compound which is reactive with an isocyanate group, and (D) a short-chain diol compound which has two or more hydroxyl groups in each molecule.

Description

Polyurethane porous body and method for producing polyurethane porous body

The present invention relates to a polyurethane porous body and a method for producing a polyurethane porous body. This application claims priority based on Japanese Patent Application No. 2018-30990 filed on Feb. 23, 2018, and incorporates all the description content described in the above Japanese application.

Polyurethane porous body is used for cosmetic sponges. A wet coagulation method is known as one method for producing such a polyurethane porous body (for example, Patent Document 1).

JP2015-116370A

In the above wet coagulation method, for example, a kneaded composition in which a polyurethane resin, a solvent, and an inorganic salt are first kneaded is prepared. Then, the kneaded composition is defoamed to form a molded body. The obtained molded body is solidified in water, and inorganic salts are extracted from the solidified molded body into water and removed. Thereafter, the polyurethane porous body in which a plurality of pores are formed is formed by drying. In the wet solidification method, the pore diameter is controlled by the particle diameter of the inorganic salt.

When the polyurethane porous body as described above is used for a cosmetic sponge, it is preferable to increase flexibility and extensibility in order to improve the texture such as the touch. However, in the wet coagulation method, since the inorganic salt is extracted and removed in water, the shrinkage rate of the polyurethane porous body may increase in the molding step, and the flexibility of the polyurethane porous body may decrease.

Therefore, an object is to provide a polyurethane porous body having high flexibility and extensibility.

The polyurethane porous body according to the first aspect of the present invention includes an aqueous urethane polymer.
The water-based urethane polymer has a polyol compound (A) containing a polyether polyol and a polycaprolactone polyol, a polyisocyanate compound (B), a hydrophilic compound (C) having reactivity with an isocyanate group, and a hydroxyl group in the molecule. It is a reaction product of a component containing two or more short-chain diol compounds (D).

The method for producing a polyurethane porous body according to the second aspect of the present invention includes a polyol compound containing polyether polyol and polycaprolactone polyol, a polyisocyanate compound, a hydrophilic compound having reactivity with an isocyanate group, and a molecule. Preparing a raw material containing a short-chain diol compound having two or more hydroxyl groups therein, a polyol compound, a polyisocyanate compound, a hydrophilic compound having reactivity with an isocyanate group, and a hydroxyl group in the molecule A step of reacting two or more short-chain diol compounds to form a urethane prepolymer, and stirring the urethane prepolymer, water, and a surfactant together to disperse the urethane prepolymer in water to form an O / W (Oil In Water) type emulsion is formed Furthermore, a water-soluble polymer is added to form a urethane prepolymer aqueous dispersion containing water, an O / W emulsion and a water-soluble polymer, and an amine compound is added to the urethane prepolymer aqueous dispersion And a cross-linking reaction to form a water-based urethane polymer, and a step of removing water from the water-based urethane polymer.

According to the present invention, it is possible to provide a polyurethane porous body having high flexibility and extensibility.

It is a flowchart which shows the outline of the manufacturing method of a polyurethane porous body.

[Description of Embodiment of Present Invention]
First, embodiments of the present invention will be listed and described. The polyurethane porous body according to the first aspect of the present application includes an aqueous urethane polymer. The water-based urethane polymer has a polyol compound (A) containing a polyether polyol and a polycaprolactone polyol, a polyisocyanate compound (B), a hydrophilic compound (C) having reactivity with an isocyanate group, and a hydroxyl group in the molecule. It is a reaction product of a component containing two or more short-chain diol compounds (D).

The material constituting the polyurethane porous body of the present application includes an aqueous urethane polymer. The water-based urethane polymer is a urethane obtained by reacting a polyol compound, a polyisocyanate compound, a hydrophilic compound having reactivity with an isocyanate group, and a short-chain diol compound having two or more hydroxyl groups in the molecule. It is obtained by dispersing a prepolymer in water and causing a crosslinking reaction. The hydroxyl group in the polyol compound reacts with the isocyanate group in the polyisocyanate compound to form a urethane polymer. By including a short-chain diol compound having two or more hydroxyl groups in the molecule, the chain length can be extended to increase the molecular weight of the urethane polymer. By including a hydrophilic compound having reactivity with an isocyanate group, the dispersibility of the urethane prepolymer in water is improved, and fine pores can be provided in the porous body.

By using polyether polyol as the polyol compound, a urethane polymer having high flexibility can be obtained. Moreover, a highly strong urethane polymer is obtained by using a polycaprolactone polyol as a polyol compound. By using together polyether polyol and polycaprolactone polyol as the polyol compound, a urethane polymer that is soft and has strength to withstand deformation can be obtained. For this reason, a polyurethane porous body having high flexibility and extensibility can be obtained.

Thus, according to the polyurethane porous body of the present application, a polyurethane porous body having high flexibility and extensibility can be provided.

In the polyurethane porous body, the hydrophilic compound (C) having reactivity with the isocyanate group may contain a polyhydroxy compound having two or more hydroxyl groups in the molecule. By including a polyhydroxy compound having two or more hydroxyl groups in the molecule as described above, the dispersibility of the urethane prepolymer in water can be further improved, and finer pores can be formed in the porous body. .

In the polyurethane porous body, the polyisocyanate compound (B) may contain an aromatic polyisocyanate and an aliphatic polyisocyanate. Thus, by including two types of isocyanate components, the flexibility and extensibility of the polyurethane porous body can be further increased, and a polyurethane porous body in which yellowing is suppressed can be obtained.

In the said polyurethane porous body, content of aromatic polyisocyanate with respect to the total amount of a polyol compound (A), a polyisocyanate compound (B), a hydrophilic compound (C), and a short chain diol compound (D) is 8 mass%. You may make it be 17 mass% or less. By setting the content of the aromatic polyisocyanate to 8% by mass or more, both flexibility and extensibility of the polyurethane porous body can be improved. By setting the content of the aromatic polyisocyanate to 17% by mass or less, yellowing of the polyurethane porous body can be suppressed.

In the polyurethane porous body, the mass ratio (polyether polyol / polycaprolactone polyol) between the blending amount of the polyether polyol and the blending amount of the polycaprolactone polyol may be 1 or more and 4 or less. By setting it as such a range, the softness | flexibility and extendibility of a polyurethane porous body can be improved together.

A method for producing a polyurethane porous body according to the second aspect of the present application includes a polyol compound containing a polyether polyol and a polycaprolactone polyol, a polyisocyanate compound, a hydrophilic compound having reactivity with an isocyanate group, and a molecule. Preparing a raw material containing a short-chain diol compound having two or more hydroxyl groups, a polyol compound, a polyisocyanate compound, a hydrophilic compound having reactivity with an isocyanate group, and two hydroxyl groups in the molecule The step of reacting the short-chain diol compound having the above to form a urethane prepolymer, the urethane prepolymer, water and a surfactant are stirred together, and the urethane prepolymer is dispersed in water to obtain O / W (Oil In Water) type emulsion, Adding a soluble polymer, forming a urethane prepolymer aqueous dispersion containing water, an O / W emulsion, and a water-soluble polymer, adding an amine compound to the urethane prepolymer aqueous dispersion, A step of forming a water-based urethane polymer by crosslinking reaction, and a step of removing water from the water-based urethane polymer.

As one method for increasing the flexibility of the polyurethane porous body, it is conceivable to decrease the density of the polyurethane porous body. The density of the polyurethane porous body can be lowered by increasing the proportion of water in the urethane prepolymer aqueous dispersion to lower the nonvolatile content concentration. However, when the proportion of water is increased, the cohesiveness of the O / W emulsion is lowered, and a three-dimensional network structure may not be formed. Therefore, in the method for producing a porous polyurethane body according to the second aspect of the present application, a water-soluble polymer that dissolves in water and has a viscosity is added to the urethane prepolymer aqueous dispersion, and the urethane prepolymer aqueous dispersion is nonvolatile. By reducing the partial concentration, a low-density polyurethane porous body can be formed.

In the method for producing a porous polyurethane body according to the second aspect of the present application, two specific polyol compounds are included as the polyol compound. Specific two types of polyol compounds are polyether polyol and polycaprolactone polyol. By doing in this way, a polyurethane porous body can be made soft and easily deformed. For this reason, the flexibility and extensibility of the polyurethane porous body are improved.

Thus, according to the method for producing a polyurethane porous body of the present application, a polyurethane porous body having high flexibility and extensibility can be provided.

[Details of the embodiment of the present invention]
Next, an embodiment of the polyurethane porous body of the present invention will be described. The polyurethane porous body according to the present embodiment includes an aqueous urethane polymer. Here, the water-based urethane polymer is obtained by cross-linking a urethane prepolymer aqueous dispersion in which a urethane prepolymer is dispersed in water. Content of the water-based urethane polymer in a polyurethane porous body is 80 to 100 mass%.

The polyurethane porous body in the present embodiment has an open cell structure. More specifically, it has a structure in which pores are formed inside the polyurethane porous body, and small pores are formed on the wall surface defining the pores, and communicated with each other. By doing in this way, a polyurethane porous body can be made lightweight. Moreover, a liquid can be absorbed and a liquid can be hold | maintained inside a polyurethane porous body.

The water-based urethane polymer has a polyol compound (A) containing a polyether polyol and a polycaprolactone polyol, a polyisocyanate compound (B), a hydrophilic compound (C) having reactivity with an isocyanate group, and a hydroxyl group in the molecule. It is a reaction product of a component containing two or more short-chain diol compounds (D). That is, the water-based urethane polymer in the present embodiment is derived from the structural unit derived from the polyol compound (A), the structural unit derived from the polyisocyanate compound (B), and the hydrophilic compound (C) having reactivity with the isocyanate group. And a structural unit derived from a short-chain diol compound (D) having two or more hydroxyl groups in the molecule.

The polyol compound in the present embodiment includes at least a polyether polyol and a polycaprolactone polyol. Thus, by including two types of polyol components, the polyurethane porous body can be made soft and easily deformed. The content of the polyether polyol and the polycaprolactone polyol with respect to the total amount of the polyol compound (A), the polyisocyanate compound (B), the hydrophilic compound (C) and the short-chain diol compound (D) is preferably 50% by mass or more and 70% by mass. % Or less, more preferably 50% by mass or more and 65% by mass or less, and further preferably 50% by mass or more and 60% by mass or less.

The mass ratio of the blending amount of the polyether polyol and the blending amount of the polycaprolactone polyol (polyether polyol / polycaprolactone polyol) is preferably 1 or more and 4 or less. By setting it as such a range, the softness | flexibility and extendibility of a polyurethane porous body can be improved together. A preferable range of the mass ratio (polyether polyol / polycaprolactone polyol) is 1 or more and 3.8 or less, and more preferably 1 or more and 3.5 or less.

As the polyether polyol, those obtained by polymerizing alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) can be used. More specifically, polyethylene glycol, polypropylene glycol, polyethylene-polypropylene (block or random) glycol, polyethylene-tetramethylene glycol (block or random), polytetramethylene glycol, poly-2-methyltetramethylene glycol, polyhexamethylene Glycol and the like. Among these, polytetramethylene glycol can be preferably used.

As the polycaprolactone polyol, polycaprolactone diol, polycaprolactone triol, or the like can be used. Among these, polycaprolactone diol can be preferably used.

As the polyol compound, in addition to the polyether polyol and polycaprolactone polyol, it may be used in the production of ordinary polyurethane and may contain a polyol having two or more hydroxyl groups in the molecule. Examples of such polyols include polycarbonate polyols, polyolefin polyols, acrylic polyols, castor oil-based polyols, and silicone-based polyols. These can be used alone or in admixture of two or more.

The number average molecular weight of the polyol compound is preferably 500 to 5000, more preferably 500 to 4000, and particularly preferably 500 to 3000. The number average molecular weight is obtained from a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene. The hydroxyl value of the polyol compound is preferably 22 mgKOH / g to 340 mgKOH / g, more preferably 28 mgKOH / g to 340 mgKOH / g, particularly preferably 37 mgKOH / g to 340 mgKOH / g.

The polyisocyanate compound (B) has two or more isocyanate groups at the terminals in the molecule. As a polyisocyanate compound (B) in this Embodiment, aromatic polyisocyanate and its hydrogenated substance, alicyclic polyisocyanate, aliphatic polyisocyanate etc. can be used, for example, These are individual or 2 types. The above can be mixed and used. Among these, it is preferable to include an aromatic polyisocyanate and an aliphatic polyisocyanate. Thus, by including two specific polyisocyanate compounds, the flexibility and extensibility of the polyurethane porous body can be further increased, and yellowing of the polyurethane porous body can be suppressed.

In the case of containing an aromatic polyisocyanate and an aliphatic polyisocyanate as the polyisocyanate compound (B), the polyol compound (A), the polyisocyanate compound (B), the hydrophilic compound (C), and the short-chain diol compound (D) The content of the aromatic polyisocyanate with respect to the total amount is preferably 8% by mass to 17% by mass, more preferably 9% by mass to 15% by mass, and further preferably 10% by mass to 15% by mass. . By setting the content of the aromatic polyisocyanate to 8% by mass or more, both flexibility and extensibility of the polyurethane porous body can be improved. Moreover, yellowing of a polyurethane porous body can be suppressed by content of aromatic polyisocyanate being 17 mass% or less.

Examples of aromatic polyisocyanates and hydrogenated products thereof include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, and 3,3′-dichloro-4,4′-diphenylmethane diisocyanate. 2,2′-diphenylmethane diisocyanate, xylylene diisocyanate, phenylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, and the like. Among these, 4,4'-diphenylmethane diisocyanate can be preferably used.

Examples of the alicyclic polyisocyanate include 1,4-cyclohexane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, and the like. Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, and the like. Among these, 1,6-hexamethylene diisocyanate can be preferably used.

As the hydrophilic compound (C) having reactivity with the isocyanate group in the present embodiment, for example, an anionic chain length agent, a nonionic chain length agent, a cationic chain length agent and the like can be used. Or a mixture of two or more. Among these, an anionic chain extender can be preferably used. As the anionic chain extender, a polyhydroxy compound having two or more hydroxyl groups in the molecule can be used, for example, a polyhydroxy compound having one or more hydrophilic groups (carboxyl group or sulfone group) in the molecule, etc. Is mentioned. More specifically, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, 1,4- Examples include butanediol-2-sulfonic acid. Among these, 2,2-dimethylolbutanoic acid can be preferably used. As a nonionic chain length agent, an ethylene oxide compound etc. are mentioned, for example. Examples of the cationic chain extender include N-methyldiethanolamine.

The content of the hydrophilic compound (C) having reactivity with the isocyanate group with respect to the total amount of the polyol compound (A), polyisocyanate compound (B), hydrophilic compound (C) and short-chain diol compound (D) is preferably It is 1 mass% or more and 2 mass% or less, More preferably, it is 1.3 mass% or more and 1.9 mass% or less, More preferably, it is 1.4 mass% or more and 1.8 mass% or less. By setting it as such content, the dispersibility in water of a urethane prepolymer can be improved more, and the porous body in which the fine void | hole was formed can be obtained. Further, when the hydrophilic compound (C) having reactivity with the isocyanate group contains a hydroxyl group, the hydroxyl group of the hydrophilic compound (C) having reactivity with the isocyanate group with respect to the isocyanate group of the polyisocyanate compound (B) The molar ratio is preferably 5 mol% to 8 mol%, more preferably 5.5 mol% to 7.5 mol%.

The short chain diol compound (D) having two or more hydroxyl groups in the molecule is a chain extender and can be used without particular limitation as long as it is used for the production of ordinary polyurethane. The short-chain diol compound (D) having two or more hydroxyl groups in the molecule is a compound other than the hydrophilic compound (C) having reactivity with the isocyanate group. More specifically, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, Examples include 3-methyl-1,5-pentanediol, nonanediol, octanediol, dimethylolheptane, and the like. These can be used alone or in admixture of two or more. Among these, 3-methyl-1,5-pentanediol can be preferably used. The number average molecular weight of the short-chain diol compound (D) is preferably 500 or less, more preferably 50 to 400, and further preferably 50 to 200. The number average molecular weight is obtained from a value measured by GPC and calculated by polystyrene conversion.

Here, the material constituting the polyurethane porous body in the present embodiment includes an aqueous urethane polymer. The water-based urethane polymer is a urethane obtained by reacting a polyol compound, a polyisocyanate compound, a hydrophilic compound having reactivity with an isocyanate group, and a short-chain diol compound having two or more hydroxyl groups in the molecule. It is obtained by dispersing a prepolymer in water and causing a crosslinking reaction. The hydroxyl group in the polyol compound reacts with the isocyanate group in the polyisocyanate compound to form a urethane polymer. By including a short-chain diol compound having two or more hydroxyl groups in the molecule in the above component, the chain length can be extended to increase the molecular weight of the urethane polymer. By including a hydrophilic compound having reactivity with an isocyanate group in the above component, the dispersibility of the urethane prepolymer in water can be improved, and fine pores can be provided in the porous body.

Thus, according to the polyurethane porous body in the present embodiment, a polyurethane porous body having high flexibility and extensibility can be provided.

The polyurethane porous body in the present embodiment includes a water absorbent roll, a roll for OA equipment, a water absorbent member, a seal member, a mat for bed, a beauty or cosmetic tool, an abrasive sheet, an air cleaning equipment filter, artificial leather, and agricultural materials. It can be suitably used for various products such as electronic equipment manufacturing-related materials and health and welfare products. In particular, when used in a beauty or cosmetic tool (especially a puff for beauty or cosmetics), since it has high flexibility and extensibility, the tactile sensation when touching human skin can be improved.

Next, a method for producing a polyurethane porous body in the embodiment will be described. FIG. 1 is a flowchart showing an outline of a method for producing a polyurethane porous body. Referring to FIG. 1, first, as a step (S10), a polyol compound, a polyisocyanate compound, a hydrophilic compound having reactivity with an isocyanate group, and a short-chain diol compound having two or more hydroxyl groups in the molecule, A step of preparing a raw material containing is performed. The polyol compound is prepared so as to contain at least a polyether polyol and a polycaprolactone polyol. Specifically, a predetermined amount of the raw material is blended in a flask or the like.

Next, as a step (S20), a step of forming a urethane prepolymer is performed. More specifically, an organic solvent is added to a flask containing the above raw materials, and stirred at a temperature of about 80 ° C. for about 3 hours to form a urethane prepolymer. By adding the organic solvent in this way, the viscosity can be lowered during the formation of the urethane prepolymer. In addition, various well-known methods can be used as a method of adding an organic solvent and forming a urethane prepolymer.

Examples of the organic solvent include acetone, methyl ethyl ketone, N-methylpyrrolidone, toluene, tetrahydrofuran, dioxane, N, N′-dimethylformamide, N, N′-diethylformamide, N, N′-dimethylacetamide and the like. Among these, N, N′-dimethylformamide can be preferably used from the viewpoint of solubility of the urethane prepolymer. From the viewpoint of environmental friendliness, N, N′-diethylformamide having low volatility can be preferably used.

Next, as a step (S30), a step of forming a urethane prepolymer aqueous dispersion is performed. More specifically, the obtained urethane prepolymer is cooled to a temperature of 70 ° C. to 80 ° C., triethylamine or the like is added as a neutralizing agent, and the mixture is stirred for about 15 minutes. Then, an urethane prepolymer is added to an aqueous solution containing a surfactant and an antifoaming agent, and stirred for about 10 minutes with a dispersing device such as a disper mixer, a homomixer, or a homogenizer, and contains an urethane prepolymer dispersed in water. A / W type emulsion is formed. In addition, you may make it form by the method of adding water to a urethane prepolymer, and carrying out transfer emulsification. Then, a water-soluble polymer is added. As a result, a urethane prepolymer aqueous dispersion containing water, a water-soluble polymer, and an O / W emulsion containing a urethane prepolymer is formed. In addition, a colorant, an antibacterial agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a pH adjuster, and the like may be further added. You may add these individually or in mixture of 2 or more types. The non-volatile content of the urethane prepolymer component in the urethane prepolymer aqueous dispersion is preferably 10% by mass to 25% by mass, more preferably 12% by mass to 20% by mass, and even more preferably 13% by mass to 17% by mass. It is. By setting it as such a range, the density of a polyurethane porous body can be made low. Here, the non-volatile content concentration of the urethane prepolymer component of the urethane prepolymer aqueous dispersion is the ratio (mass%) of the solid content of the urethane prepolymer to the urethane prepolymer aqueous dispersion. The solid content of the urethane prepolymer is a residue obtained by removing volatile components from the urethane prepolymer.

As the surfactant, for example, an anionic surfactant, a nonionic surfactant, a cationic surfactant and the like can be used. Examples of the anionic surfactant include alkyl ether sulfate ester salt, alkylbenzene sulfonate salt, sulfosuccinic acid dialkyl ester salt and the like. Nonionic surfactants include higher alcohol alkylene oxide adducts (polyoxyalkylene alkyl ethers), higher alcohol ethylene oxide adducts (polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl. Ether), higher alcohol propylene oxide adduct, higher alcohol (ethylene oxide-propylene oxide) adduct, alkylphenol ethylene oxide adduct (polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, etc.), arylphenol ethylene oxide addition , Fatty acid ethylene oxide adduct, fatty acid polyethylene glycol ester, fatty acid amide Tylene oxide adduct, long chain alkylamine ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, ethylene oxide adduct of fats and oils, glycerin fatty acid ester, polyglyceride, pentaerythritol fatty acid ester, sorbitol fatty acid ester (sorbitan ester) Sorbitan ester ethylene oxide adduct, sucrose fatty acid ester, alkyl ether of polyhydric alcohol, fatty acid amide of alkanolamines and the like. Among these, higher alcohol alkylene oxide adducts can be preferably used. From the viewpoint of improving the water dispersibility of the urethane prepolymer, the HLB value of the surfactant in the present embodiment is preferably 10 to 15, more preferably 10 to 14, and further preferably 11 to 13. is there.

As the water-soluble polymer, for example, cellulose ethers such as methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and hydroxypropyl methyl cellulose can be used. Of these, hydroxypropylmethylcellulose can be preferably used. The amount of the water-soluble polymer is preferably 1.8 parts by mass or more and 3.4 parts by mass or less with respect to 100 parts by mass of the solid content of the urethane prepolymer. By setting it as such a compounding quantity, the aggregation state of the O / W type emulsion in water can be kept favorable.

Next, as a step (S40), a step of forming a water-based urethane polymer is performed. More specifically, an amine compound is added to the urethane prepolymer aqueous dispersion and stirred for about 10 seconds. And it casts into a type | mold etc. in order to shape | mold, and it is left still at about 40 degreeC for about 12 hours, and is made to crosslink, and the molded object containing an aqueous urethane polymer is obtained. And as a process (S50), the process of removing a water | moisture content from a water-based urethane polymer is implemented. More specifically, the obtained molded body is washed with water and dried with hot air at a temperature of about 90 ° C. to obtain a urethane porous body.

The amine compound is not particularly limited as long as it has two or more active hydrogen atoms in the molecule (contains two or more primary and / or secondary amino groups in one molecule). Examples of the amine compound include ethylene diamine, propylene diamine, 1,3-diaminopentane, 1,5-diaminopentane, tetramethylene diamine, hexamethylene diamine, 1,7-diaminoheptane, and 1,5-diamino-2-methyl. Pentane, 3,3'-diaminodipropylamine, 3,3'-methyliminobispropylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethylenediamine, N, N'-bisaminopropyl- 1,3-propylenediamine, N, N′-bisaminopropyl-1,4-butylenediamine, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis (3-aminopropoxy) ethane, , 4-Bis (3-aminopropoxy) Tan, 2-hydroxylamino-propylamine, bis - (3-aminopropyl) ether, 1,3-bis - (3-amino-propoxy) -2,2-aliphatic polyamides such as dimethyl propane. Among these, ethylenediamine can be preferably used.

Here, as one method of increasing the flexibility of the polyurethane porous body, it is conceivable to decrease the density of the polyurethane porous body. The density of the polyurethane porous body can be lowered by increasing the proportion of water in the urethane prepolymer aqueous dispersion to lower the nonvolatile content concentration. However, when the proportion of water is increased, the cohesiveness of the O / W emulsion is lowered, and a three-dimensional network structure may not be formed. Therefore, in the method for producing a porous polyurethane body according to the second aspect of the present application, a water-soluble polymer that dissolves in water and has a viscosity is added to the urethane prepolymer aqueous dispersion, and the urethane prepolymer aqueous dispersion is nonvolatile. By reducing the partial concentration, a low-density polyurethane porous body can be formed.

Further, in the method for producing a polyurethane porous body in the present embodiment, two specific polyol compounds are included as the polyol compound. Specific two types of polyol compounds are polyether polyol and polycaprolactone polyol. By doing in this way, a polyurethane porous body can be made soft and easily deformed. For this reason, the flexibility and extensibility of the polyurethane porous body are improved. Thus, according to the method for producing a polyurethane porous body in the present embodiment, it is possible to provide a polyurethane porous body having high flexibility and extensibility.

Hereinafter, the present invention will be described more specifically with reference to examples. Note that the scope of the present invention is not construed as being limited by the description of these examples. In the examples, unless otherwise specified, “parts” and “%” are based on mass.

(Example 1 to Example 3)
Each component was mix | blended based on the compounding quantity shown in Table 1, and the urethane prepolymer was obtained. In addition, below the compounding quantity of the component of Table 1, content (mass%) of each component with respect to the total amount of the component which comprises a urethane prepolymer is shown. More specifically, as the polyol compound (A), polytetramethylene glycol (trade name “PTMG1500”, manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 1500), and polycaprolactone diol (trade name “Placcel L220AL”, Inc. 3-methyl-1,5-pentanediol (trade name “MPD”, manufactured by Kuraray Co., Ltd.) as a short-chain diol compound (D) having a number average molecular weight of 2000 and a hydroxyl group in the molecule. ), 2,2-dimethylolbutanoic acid (trade name “DMBA”, manufactured by Nippon Kasei Co., Ltd.) as the hydrophilic compound (C) having reactivity with the isocyanate group, and 1,6 as the polyisocyanate compound (B). -Hexamethylene diisocyanate (trade name "HDI", manufactured by Tosoh Corporation) and 4,4'- Diphenylmethane diisocyanate (trade name “Millionate MT”, manufactured by Tosoh Corporation) and dimethylformamide as a solvent were blended and prepared in a three-necked round bottom flask in the proportions shown in Table 1. Next, it stirred at 80 degreeC for 3 hours, and obtained the urethane prepolymer.

Next, based on the blending amounts shown in Table 1 with respect to the urethane prepolymer obtained above, urethane prepolymer water is blended with triethylamine, surfactant, antifoaming agent, water-soluble cellulose ether and distilled water. A dispersion was obtained. More specifically, the urethane prepolymer obtained above was cooled to a temperature of 70 ° C. to 80 ° C., triethylamine was added as a neutralizing agent, and the mixture was stirred for 15 minutes. Next, the urethane prepolymer obtained above was mixed with a nonionic surfactant (trade name “Naroacty CL-70”, manufactured by Sanyo Chemical Industries, HLB: 11.7) and a silicone-based antifoaming agent (trade name “ KS-538 ”(manufactured by Shin-Etsu Chemical Co., Ltd.) was added to a 30 ° C. aqueous solution previously dissolved, and the mixture was stirred with a homomixer for 10 minutes. Thereafter, an aqueous solution in which water-soluble cellulose ether (trade name “hi-Metrouse 65SH4000”, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in advance was added to obtain an aqueous urethane prepolymer dispersion.

, 1.3 parts by mass of an aqueous solution containing 10% ethylenediamine was added to 100 parts by mass of the urethane prepolymer aqueous dispersion obtained above, and the mixture was stirred and mixed for 10 seconds in an environment of room temperature 20 ± 5 ° C. Then, in order to shape | mold the obtained mixture, it poured into the type | mold, and left still at 40 degreeC for 12 hours, and was made to react, and the molded object which consists of water-system urethane polymer was obtained. Next, the obtained molded body was washed with water and dried at 90 ° C. to obtain a urethane porous body.

(Examples 4 to 5)
A urethane porous body was obtained in the same manner as in Example 2 except that the blending amount of water-soluble cellulose ether (trade name “himetrouse 65SH4000”, manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to the blending amount shown in Table 2.

(Example 6)
A urethane porous body was obtained in the same manner as in Example 2 except that the solvent was changed from dimethylformamide to diethylformamide.

(Comparative Example 1)
Polycarbonate diol (trade name “T-4671”, manufactured by Asahi Kasei Corporation, number average molecular weight: 1000), ethylene glycol (trade name “EG”, manufactured by Nippon Shokubai Co., Ltd.), 2,2-dimethylolpropionic acid as polyol compounds (Trade name “DMPA”, manufactured by Perstorp), 1,6-hexamethylene diisocyanate (trade name “HDI”, manufactured by Tosoh Corporation) as the polyisocyanate compound, and dimethylformamide as the solvent in the proportions shown in Table 2 Prepared by blending into bottom flask. Next, it stirred at 80 degreeC for 3 hours, and obtained the urethane prepolymer.

The urethane prepolymer obtained above was heated to 80 ° C., triethylamine was added as a neutralizing agent, and the mixture was stirred for 15 minutes. Next, the urethane polymer obtained above was added to a 27 ° C. aqueous solution in which a nonionic surfactant (trade name “Adecatol TN-100”, manufactured by Asahi Denka Kogyo Co., Ltd., HLB: 13.8) was previously dissolved. The mixture was further stirred for 2 minutes. Next, the urethane prepolymer to which the neutralizing agent and the surfactant were added was added to distilled water, and the mixture was stirred with a homomixer for 5 minutes to obtain a urethane prepolymer aqueous dispersion.

To 100 parts by weight of the urethane polymer aqueous dispersion obtained above, 1.5 parts by mass of ethylenediamine was added, and the mixture was stirred for 10 seconds in an environment of room temperature 20 ± 5 ° C. and mixed. Then, in order to shape | mold the obtained mixture, it poured into the type | mold, and left still for 12 hours and made it react in the environment of room temperature 20 +/- 5 degreeC, and the molded object which consists of a water-based urethane polymer was obtained. Next, the obtained molded body was washed with water and dried at 80 ° C. to obtain a urethane porous body.

The density, tensile strength, 100% modulus, and elongation rate of the porous urethane material obtained in Examples and Comparative Examples were measured by the following methods.

(1) Density A test piece having a size of 50 mm × 50 mm × 3 mm was cut out from the obtained urethane porous body, and the mass of the test piece was measured. The density (g / cm3) of the urethane porous body was calculated from the mass of the test piece.

(2) Tensile strength The tensile strength was measured according to JIS K6301. More specifically, a test piece having a size of 60 mm in length, 10 mm in width, and 2 mm in thickness was cut out from the obtained urethane porous body, and an autograph (manufactured by Shimadzu Corporation, model number: AGS-50D) was used. It was measured. Measurement was performed so that the tensile direction was the longitudinal direction of the test piece, and the tensile strength (N / mm ² ) was calculated based on the following formula using the strength when the test piece was broken. [Tensile strength (N / mm ² )] = [Break strength (N)] / [Cross sectional area of test piece (mm ² )]

(3) 100% modulus The 100% modulus was measured according to JIS K 6301. More specifically, a test piece having a size of 60 mm in length, 10 mm in width, and 2 mm in thickness was cut out from the obtained urethane porous body, and an autograph (manufactured by Shimadzu Corporation, model number: AGS-50D) was used. It was measured. Measurement was performed so that the tensile direction was the longitudinal direction of the test piece, and the 100% modulus (N / mm ² ) was calculated based on the following formula using the strength when the test piece was stretched 100%. [100% modulus (N / mm ² )] = [strength when the test piece is stretched 100% (N)] / [cross-sectional area of the test piece (mm ² )]

(4) Elongation rate The elongation rate was measured according to JIS K6301. More specifically, a test piece having a size of 60 mm in length, 10 mm in width, and 2 mm in thickness was cut out from the obtained urethane porous body, and an autograph (manufactured by Shimadzu Corporation, model number: AGS-50D) was used. It was measured. Measurement was performed at a marked line of 20 mm so that the tensile direction was the longitudinal direction of the test piece, and the elongation (%) was calculated based on the following formula using the elongation when the test piece was broken. [Elongation rate (%)] = ([length between marked lines at break (mm)] − [marked distance (mm)]) / [marked distance (mm)] × 100

Tables 1 to 3 show the compositions of Examples (Examples 1 to 5) and Comparative Examples. Table 4 shows the evaluation results of the respective evaluation items.

As can be seen from the evaluation results in Table 4, in Examples 1 to 6 containing polyether polyol and polycaprolactone polyol as the polyol compound, the urethane porous body was compared with Comparative Example 1 containing polyol compounds other than those described above. The 100% modulus, which is an index indicating the hardness of the film, is low and soft. Similarly, it can be seen that the density and the tensile strength are low in Examples 1 to 6. In Examples 1 to 6, as compared with Comparative Example 1, the elongation rate, which is an index indicating the ease of deformation of the urethane porous body, is improved and is easily deformed. From the above results, it can be said that the urethane porous bodies of Examples 1 to 6 are urethane porous bodies excellent in flexibility and extensibility that are both soft and easy to deform.

In Examples 1 to 3 in which the content of the aromatic polyisocyanate in the urethane prepolymer is 9% by mass to 15% by mass, the modulus becomes lower by 100% compared to Comparative Example 1, Elongation rate increases. Further, in Example 2, Example 4 and Example 5 in which the blending amount of the water-soluble cellulose ether was changed, 100% modulus was lowered and the elongation ratio was increased as compared with Comparative Example 1. Also in Example 6 in which diethylformamide was used as the organic solvent used for forming the urethane prepolymer, the modulus was reduced 100% and the elongation ratio was increased as compared with Comparative Example 1.

Thus, according to the urethane porous body of the present application, a polyurethane porous body having high flexibility and extensibility can be provided.

It should be understood that the embodiment disclosed herein is illustrative in all respects and is not restrictive in any way. The scope of the present invention is defined by the scope of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the scope of the claims.

The polyurethane porous body of the present application can be applied particularly advantageously in a field where it is required to provide a polyurethane porous body having high flexibility and extensibility.

Claims

A polyurethane porous body containing an aqueous urethane polymer,
The water-based urethane polymer is
A polyol compound (A) comprising a polyether polyol and a polycaprolactone polyol;
A polyisocyanate compound (B);
A hydrophilic compound (C) having reactivity with an isocyanate group;
A polyurethane porous body, which is a reaction product of a component comprising a short-chain diol compound (D) having two or more hydroxyl groups in the molecule.
The polyurethane porous body according to claim 1, wherein the hydrophilic compound (C) having reactivity with the isocyanate group includes a polyhydroxy compound having two or more hydroxyl groups in a molecule.
The polyurethane porous body according to claim 1 or 2, wherein the polyisocyanate compound (B) contains an aromatic polyisocyanate and an aliphatic polyisocyanate.
The content of the aromatic polyisocyanate with respect to the total amount of the polyol compound (A), the polyisocyanate compound (B), the hydrophilic compound (C), and the short-chain diol compound (D) is 8% by mass or more and 17% by mass. The polyurethane porous body according to claim 3, which is not more than%.
The mass ratio (polyether polyol / polycaprolactone polyol) between the blending amount of the polyether polyol and the blending amount of the polycaprolactone polyol is 1 or more and 4 or less. The polyurethane porous body described in 1.
Preparation of a raw material containing a polyol compound containing polyether polyol and polycaprolactone polyol, a polyisocyanate compound, a hydrophilic compound having reactivity with an isocyanate group, and a short-chain diol compound having two or more hydroxyl groups in the molecule And a process of
Urethane prepolymer by reacting the polyol compound, the polyisocyanate compound, the hydrophilic compound having reactivity with the isocyanate group, and the short-chain diol compound having two or more hydroxyl groups in the molecule. Forming a step;
Stir together the urethane prepolymer, water and surfactant, disperse the urethane prepolymer in water to form an O / W (Oil In Water) type emulsion, and further add a water-soluble polymer, Forming a urethane prepolymer aqueous dispersion comprising water, the O / W emulsion, and the water-soluble polymer;
Adding an amine compound to the urethane prepolymer aqueous dispersion and causing a crosslinking reaction to form an aqueous urethane polymer;
Removing the water from the water-based urethane polymer. A method for producing a polyurethane porous body.