JP2005146089A - Polyurethane emulsion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a urethane emulsion which has excellent durability (resistance to hydrolysis, heat resistance and lightfastness) when used for artificial leather, can also give the feel and quality, and has superior emulsion stability. <P>SOLUTION: The polyurethane emulsion consists of a polyurethane resin (A) and at least one nonionic and/or anionic surfactant (B) having an HLB of ≥10 and ≤18. The (A) consists of a polycarbonate type diol (A1), an organic polyisocyanate compound (A2), and α,α-dimethylolpropionic acid and/or α,α-dimethylolbutylic acid (A3), and the total content of the carboxy group contained in the (A) is ≥0.01 wt% and ≤1.5 wt% based on the weight of the (A), and the total of the content of the (B) is ≥0.1 wt% and ≤10 wt% based on the weight of the (A). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polyurethane emulsion, a leather-like sheet material that can be produced using the polyurethane emulsion, and a method for producing the leather-like sheet material.

In recent years, as a urethane resin for artificial leather, a shift from a conventional solvent-based polyurethane to a water-based emulsion has been progressed from the viewpoint of strengthening the regulation of VOC reduction. Furthermore, in order to expand to applications that require more durability such as for automobiles and furniture, in addition to apparel, further durability (hydrolysis resistance, heat resistance, light resistance) of polyurethane is desired. Yes. For such high durability, a polyurethane emulsion using a polycarbonate diol has recently been proposed (see, for example, Patent Documents 1 to 3).
JP-A-5-32756 (1 page) JP 7-41539 A (1 page) Japanese Patent No. 3151532 (1 page)

However, the polyurethane emulsions proposed in the above documents 1 to 3 are still insufficient, although the durability is somewhat improved, and it is necessary to further increase the durability in order to expand to the above-mentioned applications. It was. Furthermore, when polycarbonate-based diol is used, there is a drawback that texture (flexibility) and quality are inferior when used for artificial leather.
Further, in the above documents 1 to 3 and the like, in order to improve the emulsion stability of the urethane emulsion, it is dealt with by increasing the hydrophilic group content in the urethane resin. However, durability (particularly hydrolysis resistance) is increased accordingly. ) Is worse.

  An object of the present invention is to solve the above problems. That is, a urethane emulsion that has excellent durability (hydrolysis resistance, heat resistance, light resistance) when made into artificial leather, can give an excellent texture, and has excellent emulsion stability. It is to provide.

As a result of intensive studies to solve this problem, the present inventors have reached the present invention.
That is, the present invention is a polyurethane emulsion comprising the polyurethane resin (a) and at least one nonionic and / or anionic surfactant (A) having a hydrophilic / lipophilic balance (HLB) of 10 to 18. The polyurethane resin (a) is a polymer diol (a1) consisting of at least one polycarbonate diol, an organic polyisocyanate compound (a2) having at least two isocyanate groups in the molecule, and A compound (A3) having at least one group selected from the group consisting of a carboxyl group, a sulfonic acid group, a carboxylate anion group and a sulfonate anion group, and having at least two functional groups which react with an isocyanate group Included in the polyurethane resin (a) The total content of ruboxyl group, sulfonic acid group, carboxylate anion group and sulfonic acid anion group is 0.01% by weight or more and 1.5% by weight or less based on the weight of the polyurethane resin (a). A polyurethane emulsion characterized in that the total content of the agent (A) is 0.1% by weight or more and 10% by weight or less based on the weight of the polyurethane resin (A); the polyurethane emulsion is applied to the fiber material substrate A leather-like sheet material produced by applying the polyurethane emulsion to a fiber material substrate and heat-coagulating it.

  The polyurethane emulsion of the present invention can exhibit excellent durability (hydrolysis resistance, heat resistance, light resistance) and texture when made into artificial leather, and can impart excellent emulsion stability.

The polyurethane resin (a) constituting the polyurethane emulsion of the present invention includes a polymer diol (a1) composed of at least one polycarbonate-based diol, and an organic isocyanate compound (a2) having at least two isocyanate groups in the molecule. ), A compound having at least two functional groups that have at least one group selected from the group consisting of a carboxyl group, a sulfonic acid group, a carboxylate anion group, and a sulfonic acid anion group in the molecule and react with an isocyanate group (A-3) The total content (% by weight) of the carboxyl group, sulfonic acid group, carboxylate anion group and sulfonate anion group (hereinafter abbreviated as carboxyl group) contained in (a) is 0.01 or more of the emulsion based on the weight of (a) From the viewpoint of emulsion stability, it is preferably 0.05 or more, more preferably 0.08 or more, particularly preferably 0.10 or more, most preferably 0.12 or more, 1.5 or less, hydrolysis resistance From the viewpoint, it is preferably 0.75 or less, more preferably 0.50 or less, particularly preferably 0.30 or less, and most preferably 0.20 or less.
If the content (% by weight) of the carboxyl group or the like is less than 0.01, sufficient emulsion stability cannot be obtained, and if it exceeds 1.5, the hydrolysis resistance of the formed resin film is lowered, which is not preferable.
Here, the content (% by weight) of the carboxyl group and the like contained in (a) represents the content when the carboxyl group and / or sulfonic acid group contained in (a) is used. That is, when it is in the form of a carboxylate anion group or a sulfonate anion group, it is calculated as a carboxyl group or a sulfonate group, respectively.

  Examples of the polycarbonate-based diol constituting the high-molecular diol (a1) consisting only of at least one polycarbonate-based diol include, for example, polycarbonate diols obtained by reacting low-molecular diols and carbonic acid diesters, and two or more diols And a mixture of two or more of these polycarbonate diols.

  Examples of the low molecular diol include alkylene diols having 1 to 20 carbon atoms [ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, Neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methylbutane Diol, 2-ethylbutanediol, 2-methylpentanediol, 3-methylpentanediol, 2-ethylpentanediol, 3-ethylpentanediol, 2-methylhexanediol, 3-methylhexanediol, 2-ethylhexanediol, 3-ethyl Xanthdiol, 2-methylheptanediol, 3-methylheptanediol, 4-methylheptanediol, 2-ethylheptanediol, 3-ethylheptanediol, 4-ethylheptanediol, 2-methyloctanediol, 3-methyloctanediol 4-methyloctanediol, 2-ethyloctanediol, 3-ethyloctanediol, 4-ethyloctanediol, 2-methylnonanediol, 3-methylnonanediol, 4-methylnonanediol, 5-methylnonanediol, 2 -Ethylnonanediol, 3-ethylnonanediol, 4-ethylnonanediol, 5-ethylnonanediol, etc.]; low molecular diols having a cyclic group [for example, those described in JP-B No. 45-1474: Bis (hydroxymethyl) Cyclohexane, bis (hydroxyethyl) benzene, ethylene oxide adduct of bisphenol A, etc.], polyalkylene ether diol having a molecular weight of 1,000 or less [polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol], and two or more of these Of the mixture.

  Examples of the carbonic acid diester include dialkyl (carbon number 1 to 12) carbonate (for example, dimethyl carbonate, diethyl carbonate, etc.), alkylene (carbon number 2 to 12) carbonate (for example, ethylene carbonate), diaryl (carbon number 6 to 10). Examples of the carbonate include diphenyl carbonate.

Specific examples of the polycarbonate-based diol include C2-12, preferably C4-10 alkylene carbonate diol {eg, C4-10 linear alkylene carbonate diol (eg, polytetramethylene carbonate diol, polypentamethylene carbonate). Diol, polyhexamethylene carbonate diol, polyheptamethylene carbonate diol, polyoctamethylene carbonate diol, polycarbonate diol of nonane diol, polycarbonate diol of decane diol, polycarbonate diol of dodecane diol), C4-10 branched alkylene carbonate diol ( For example, 2-methylbutanediol polycarbonate diol, 2-ethylbutanediol polycarbonate Diol, polycarbonate diol of neopentyl glycol, polycarbonate diol of 2-methylpentanediol, polycarbonate diol of 3-methylpentanediol, polycarbonate diol of 2-ethylpentanediol, polycarbonate diol of 3-ethylpentanediol, 2-methylhexanediol Polycarbonate diol, 3-methylhexanediol polycarbonate diol, 2-ethylhexanediol polycarbonate diol, 3-ethylhexanediol polycarbonate diol, 2-methylheptanediol polycarbonate diol, 3-methylheptanediol polycarbonate diol, 4 -Methylheptanediol polycarbonate diol, 2-ethyl Polycarbonate diol of butanediol, polycarbonate diol of 3-ethylheptanediol, polycarbonate diol of 4-ethylheptanediol, polycarbonate diol of 2-methyloctanediol, polycarbonate diol of 3-methyloctanediol, polycarbonate diol of 4-methyloctanediol Polycarbonate diol of 2-ethyloctanediol, polycarbonate diol of 3-ethyloctanediol, polycarbonate diol of 4-ethyloctanediol, polycarbonate diol of 2-methylnonanediol, polycarbonate diol of 3-methylnonanediol, 4-methylnonane Polycarbonate diol, Polycarbonate of 5-methylnonanediol Nate diol, polycarbonate diol of 2-ethyl nonane diol, polycarbonate diol of 3-ethyl nonane diol, polycarbonate diol of 4-ethyl nonane diol, polycarbonate diol of 5-ethyl nonane diol, etc.), copolymers thereof, and A mixture is mentioned.
Among these, C4-9 linear alkylene carbonate diols or C4-9 branched chains are preferred because they exhibit flexible resin physical properties and can provide excellent texture and quality when used in artificial leather. Alkylene carbonate diol, copolymer polycarbonate diol of these two or more low molecular diols, and a mixture of two or more, more preferably polytetramethylene carbonate diol, polypentamethylene carbonate diol, polyhexamethylene carbonate diol, poly Heptamethylene carbonate diol, polyoctamethylene carbonate diol, polycarbonate diol of nonanediol, polycarbonate diol of 2-methylpentanediol, polycarbonate diol of 3-methylpentanediol 2-methylhexanediol polycarbonate diol, 3-methylhexanediol polycarbonate diol, 2-methylheptanediol polycarbonate diol, 3-methylheptanediol polycarbonate diol, 4-methylheptanediol polycarbonate diol, 2-methyloctanediol Polycarbonate diols of 3-methyloctanediol, polycarbonate diols of 4-methyloctanediol, copolymer polycarbonate diols of these two or more low molecular diols, and mixtures of two or more, particularly preferably polytetra Methylene carbonate diol, polypentamethylene carbonate diol, polyhexamethylene carbonate diol, nonane Polycarbonate diols of all, polycarbonate diols of 3-methylpentanediol, polycarbonate diols of 2-methyloctanediol, copolymers of two or more low molecular diols, and mixtures of two or more, most preferably tetra A copolymer polycarbonate diol of two or more diols selected from methylene diol, pentamethylene diol, hexamethylene diol, nonane diol, 3-methylpentane diol, and 2-methyloctane diol, and a mixture of two or more.

The copolymerization ratio (mol%) of the diol when used as a copolymerized polycarbonate diol is preferably 5 or more, more preferably 10 or more, particularly preferably 15 or more, and most preferably 20 or more, with the smallest amount of diol. is there.
When used as a mixture of two or more kinds of polycarbonate diols, the mixing ratio (% by weight) is preferably 5 or more, more preferably 10 or more with respect to the weight of the total polycarbonate diol. Particularly preferably, it is 15 or more, most preferably 20 or more.

The number average molecular weight of the polymer diol (A1) is preferably 300 or more, more preferably 500 or more, particularly preferably 1,000 or more, preferably 20,000 or less, more preferably 10,000 or less, Especially preferably, it is 3,000 or less.
The number average molecular weight of (A1) can be determined from the hydroxyl value. The hydroxyl value is measured by a method defined in JIS K0070-1992 (potentiometric titration method).
Further, (A1) may be used as a mixture of two or more having different number average molecular weights.

As the organic polyisocyanate compound (A2) having at least two isocyanate groups in the molecule, those conventionally used for polyurethane production can be used.
Such organic polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), aliphatic polyisocyanates having 2 to 18 carbon atoms, and fats having 4 to 15 carbon atoms. Cyclic polyisocyanates, araliphatic polyisocyanates having 8 to 15 carbon atoms, modified products of these polyisocyanates (carbodiimide-modified products, urethane-modified products, uretdione-modified products, etc.) and mixtures of two or more of these.

  Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI), 2,4 ′. -And / or 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'- Examples include dimethyl-4,4′-diisocyanatodiphenylmethane and 1,5-naphthylene diisocyanate.

  Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanatomethylcaproate. Bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and the like.

  Specific examples of the alicyclic diisocyanate include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2- Examples thereof include dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.

  Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.

  Of these, preferred are aromatic diisocyanates and cycloaliphatic diisocyanates, and particularly preferred are MDI, TDI, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, most preferably isophorone diisocyanate, 4,4'-dicyclohexylmethane. Diisocyanate.

The compound (A3) having a carboxyl group and the like and having at least two functional groups that react with isocyanate groups (hereinafter referred to as active hydrogen groups) is for the purpose of maintaining the emulsion stability of the polyurethane emulsion. It is a component used for anionic hydrophilic group introduction. Among these, from the viewpoint of hydrolysis resistance of the urethane resin, a compound having a carboxyl group and / or a carboxylate anion and having at least two active hydrogen groups is preferable.
Specific examples of the compound (a3) having a carboxyl group and having at least two active hydrogen groups include monohydroxycarboxylic acids such as lactic acid; α, α-dimethylolacetic acid, α, α-dimethylolpropionic acid, α, Examples include dihydroxycarboxylic acids such as α-dimethylolbutyric acid, diaminosulfonic acids such as 3,4-diaminobutanesulfonic acid, and 3,6-diamino-2-toluenesulfonic acid. Of these, preferred are dihydroxycarboxylic acids, and particularly preferred are α, α-dimethylolpropionic acid and α, α-dimethylolbutyric acid.
These (A3) may be used alone or as a mixture of two or more.

The carboxyl group and / or sulfonic acid group in the polyurethane resin (a) is more preferably neutralized with a neutralizing agent from the viewpoint of emulsion stability. Examples of the neutralizing agent include alkali metal (lithium, sodium, potassium, etc.) hydroxide, alkaline earth metal (magnesium, calcium, etc.) hydroxide, and tertiary amine.
Tertiary amines include tertiary monoamines having 3 to 12 or more carbon atoms, such as aliphatic tertiary monoamines (trimethylamine, triethylamine, triethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, etc.); complex Cyclic tertiary monoamines (N-methylpiperidine, N-methylmorpholine, etc.); unsaturated cyclic tertiary monoamines (N-methylpyridine, N-methylquinoline, etc.); aromatic ring-containing aliphatic tertiary monoamines (benzyldimethylamine) , Α-methylbenzyldimethylamine, etc.); aromatic tertiary monoamines (N-dimethylaniline, etc.) and combinations of two or more of these.
Of these, from the viewpoint of hydrolysis resistance, preferred are aliphatic tertiary monoamines, and particularly preferred is triethylamine.

  The addition amount (molar ratio) when the neutralizing agent is used is preferably 0.20 or more, more preferably, relative to the total number of moles of carboxyl groups and sulfonic acid groups contained in the polyurethane resin (a). 0.50 or more, particularly preferably 0.70 or more, particularly preferably 0.80 or more, most preferably 1.00 or more, preferably 2.00 or less, more preferably 1.80 or less, particularly preferably 1 .50 or less, most preferably 1.20 or less.

The HLB of the nonionic and / or anionic surfactant (a) used in the present invention is 10.0 or more, preferably 11.0 or more, more preferably 12.0 or more, particularly preferably 12.5 or more, most Preferably it is 13.0, 18.0 or less, preferably 17.0 or less, more preferably 16.0 or less, particularly preferably 15.0 or less, most preferably 14.5 or less.
When the HLB of (a) is less than 10, problems arise in storage stability such as generation of a coagulum when the emulsion is stored for a long period of time. On the other hand, when the HLB exceeds 18, the affinity of polyurethane for water becomes too large, and therefore, when used for artificial leather, the emulsion is difficult to heat-coagulate, resulting in poor adhesion to fibers.
Further, (i) may be a single or a mixture of two or more as long as the HLB is in the above range.
The HLB value in the present invention is a value calculated by the following Griffin method described in Takehiko Fujimoto, Introduction to New Surfactants, Sanyo Chemical Industries, Ltd. (1992), P128.
HLB = (weight% of hydrophilic group) × (1/5)

(I) can use a well-known thing if it is a nonionic and / or anionic surfactant whose HLB is the said range.
Nonionic surfactants include, for example, aliphatic alcohols (8 to 24 carbon atoms) alkylene (2 to 8 carbon atoms) oxide adducts (degree of polymerization 1 to 100), polyvalent (divalent to 10-valent or more). ) Alcohol fatty acid (carbon number 8-24) ester {for example, GL monostearate, sorbitan monolaurate etc.}, fatty acid (carbon number 8-24) alkanolamide {for example, 1: 1 type coconut oil fatty acid diethanolamide, 1 1 type lauric acid diethanolamide, etc.], (poly) oxyalkylene (carbon number 2-8, polymerization degree 1-100) alkyl (carbon number 1-22) phenyl ether, (poly) oxyalkylene (carbon number 2-8) , Polymerization degree 1-100) alkyl (carbon number 8-24) amine, alkyl (carbon number 8-24) dialkyl (carbon number 1-6) amineoxy {E.g., lauryl dimethyl amine oxide}, polyalkylene oxide-modified silicones such as (number 2-8 carbons) and the like.
Examples of the anionic surfactant include ether carboxylic acids having a hydrocarbon group having 8 to 24 carbon atoms or salts thereof (for example, sodium lauryl ether acetate, (poly) oxyethylene (degree of polymerization 1 to 100) lauryl ether acetic acid. Sodium, etc., sulfates or ether sulfates having a hydrocarbon group having 8 to 24 carbon atoms and their salts {for example, sodium lauryl sulfate, (poly) oxyethylene (degree of polymerization 1 to 100) sodium lauryl sulfate, (poly ) Oxyethylene (degree of polymerization 1 to 100) lauryl sulfate triethanolamine, (poly) oxyethylene (degree of polymerization 1 to 100) coconut oil fatty acid monoethanolamide sodium sulfate, etc.}, having a hydrocarbon group having 8 to 24 carbon atoms Sulfonates {e.g. sodium dodecylbenzenesulfonate And the like}, sulfosuccinates having one or two hydrocarbon groups having 8 to 24 carbon atoms, phosphate esters or ether phosphate esters having hydrocarbon groups having 8 to 24 carbon atoms and salts thereof {for example, Sodium lauryl phosphate, (poly) oxyethylene (degree of polymerization 1 to 100) sodium lauryl ether phosphate}, fatty acid salt having a hydrocarbon group having 8 to 24 carbon atoms {for example, sodium laurate, triethanolamine laurate Etc.} and an acylated amino acid salt having a hydrocarbon group having 8 to 24 carbon atoms {for example, coconut oil fatty acid methyl taurine sodium, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, N-coconut oil fatty acid acyl-L -Triethanolamine glutamate, N-coconut oil fatty acid reed -L- glutamate sodium lauroyl methyl -β- alanine sodium and the like}.
Of these, nonionic surfactants are preferred, and nonionic surfactants represented by the following general formula (3) are particularly preferred.
R—O— (CH ₂ —CH ₂ —O—) _X —H (3)
However, R is preferably an alkyl group having 8 to 20 carbon atoms, and may be linear or branched. Specific examples include octyl group, nonyl group, decyl group, lauryl group, cetyl group, oleyl group and the like. Among these, preferred are a lauryl group, a cetyl group and an oleyl group. x represents an integer of 5 to 40, preferably 7 or more and 30 or less.

  Examples of the nonionic surfactant represented by the general formula (3) include polyoxyethylene lauryl ether (x = 9), polyoxyethylene cetyl ether (x = 12), polyoxyethylene stearyl ether (x = 15). ) And higher alcohol ethylene oxide adducts such as polyoxyethylene oleyl ether (x = 20).

The content (% by weight) of (a) is 0.1 or more, preferably 0.3 or more, more preferably 0.5 or more, and particularly preferably 1.0 or more, based on the weight of the polyurethane resin (a). Most preferably, it is 1.5 or more, 10 or less, preferably 8.0 or less, more preferably 7.0 or less, particularly preferably 5.0 or less, and most preferably 3.5 or less.
When the content (% by weight) of (A) is less than 0.1, the emulsion stability is remarkably deteriorated, and when it exceeds 10, the durability (hydrolysis resistance, heat resistance, light resistance) of the urethane resin is deteriorated. It is not preferable.

The method for producing the polyurethane resin (A) in the present invention and the polyurethane emulsion of the present invention may be an ordinary method, and is not particularly limited, but examples thereof include the following methods.
(1) Presence of an organic solvent containing no active hydrogen-containing group in the molecule (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, toluene, xylene, ethyl acetate, butyl acetate, N, N-dimethylformamide, etc.) In the absence or absence of the above-mentioned polymer diol (a), organic polyisocyanate (a 2), a compound containing a carboxyl group and the like and an active hydrogen group (a 3), and optionally a low molecular polyol (a 4) The (NCO / active hydrogen group) equivalent ratio (hereinafter referred to as R value) is usually 1.05 or more, preferably 1.10 or more, more preferably 1.15 or more. Yes, usually in the range of 2.00 or less, preferably 1.75, more preferably 1.50 or less by the one-shot method or multistage method. The nonionic and / or anionic surfactant (A) is added to the terminal NCO group-containing urethane prepolymer, if necessary after neutralizing the prepolymer with the neutralizing agent or while neutralizing the prepolymer. After emulsification, if necessary, it is mixed with water containing a chain extender (A5) and / or a chain terminator (A6) (described later), and a chain extension reaction is carried out until the NCO group disappears. Method to distill off.
(2) In the presence or absence of the organic solvent, the polymer diol (A1), organic polyisocyanate (A2) and a compound containing a carboxyl group and an active hydrogen group (A3), if necessary An active hydrogen component composed of a low molecular polyol (A4) is reacted with an R value in the range of 0.5 to 0.99 by a one-shot method or a multistage method to obtain a urethane polymer containing no terminal NCO group, A method of neutralizing with a neutralizing agent if necessary, or adding and emulsifying the nonionic and / or anionic surfactant (A) while neutralizing, and then distilling off the organic solvent as necessary.
(3) In the presence or absence of the organic solvent, the R value of the high molecular diol (A1), the organic polyisocyanate (A2), and optionally the low molecular polyol (A4) is 2.0 to 1. The reaction is carried out by a one-shot method or a multistage method within the range of .3 to obtain a urethane polymer containing a terminal NCO group, and this is neutralized with a neutralizing agent if necessary (3) containing a carboxyl group and an active hydrogen group. A method in which the R value is reacted in the range of 1.5 to 1.0, the nonionic and / or anionic surfactant (a) is added and emulsified, and then the organic solvent is distilled off if necessary. .
Among the above methods, the method (1) is preferable from an industrial viewpoint.

  The low molecular polyol (A4) includes a polyhydric alcohol having a molecular weight of 50 to 500, divalent to octavalent or higher, and an active hydrogen atom-containing compound (for example, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, etc. Low molecular adducts (e.g., ethylene oxide (EO), propylene oxide (PO), 1,2-, 2,3- and 1,3-butylene oxide, etc.)) The degree of polymerization is 1 to 10), and a polyhydric alcohol is preferable.

The following are mentioned as a polyhydric alcohol.
Dihydric alcohols, such as aliphatic, alicyclic and aromatic dihydric alcohols having 2 to 12 or more carbon atoms [(di) alkylene glycol (represents alkylene glycol and dialkylene glycol; the same expression is used hereinafter) For example, (di) ethylene glycol, (di) propylene glycol, 1,2-, 1,3-, 2,3- and 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,12-dodecanediol and the like;
A low molecular diol having a cyclic group, for example, those described in JP-B No. 45-1474 [bis (hydroxymethyl) cyclohexane, bis (hydroxyethyl) benzene, etc.];
-Trihydric to octahydric or higher polyhydric alcohols such as alkane polyols (triols such as trimethylolpropane, glycerin and hexanetriol;
・ Highly functional polyols such as tetravalent or higher, such as pentaerythritol, sorbitol, xylitol and mannitol, intermolecular or intramolecular dehydrates (diglycerin, dipentaerythritol, sorbitan, etc.), sugars (glucose, fructose, sucrose, etc.) ) And derivatives thereof (glycosides such as α-methyl glucoside).
Among these, from the viewpoint of the physical properties of the resin, preferably a dihydric alcohol, more preferably (di) ethylene glycol, (di) propylene glycol, 1,2-, 1,3-, 2,3- and 1,4. -Butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol.
The low molecular polyol (A4) may be used alone or as a mixture of two or more.

  The amount used (% by weight) when using (A4) is usually 0 or more, preferably 0.1 or more, more preferably 0.5 or more, particularly preferably based on the weight of the polyurethane resin (A). 0.8 or more, usually 10 or less, preferably 5 or less, particularly preferably 2 or less.

Among the above methods (1) to (3), the temperature (° C.) during the production of the terminal NCO group-containing urethane prepolymer is usually 20 ° C. or higher, preferably 60 ° C. or higher, more preferably 80 ° C. or higher, usually 150 ° C. or lower. The temperature is preferably 120 ° C. or lower, more preferably 100 ° C. or lower.
The pressure (kPa, hereinafter referred to as absolute pressure) is not particularly limited, but is usually 101 or more, preferably 108 or more, more preferably 118 or more, and usually 490 or less, preferably 294 or less, more preferably 196 or less. It is.

  The polymerization concentration and polymerization time during the production of the urethane prepolymer can be appropriately adjusted depending on the monomer composition or the type of polymerization catalyst, polymerization inhibitor, and amount used, if necessary. ) Is usually 10 to 100, preferably 50 to 100, and the polymerization time (hour) is usually 1 to 50, preferably 5 to 30.

As the polymerization catalyst, known urethanization catalysts can be used. For example, amine catalysts such as triethylamine, N-ethylmorpholine, triethylenediamine and cycloamidines described in US Pat. No. 4,524,104 [1,8-diaza -Bicyclo (5,4,0) undecene-7 {manufactured by San Apro Co., Ltd., DBU}, etc.]; tin-based catalysts such as dibutyltin dilaurylate, dioctyltin dilaurate and tin octylate; Examples include titanate. Moreover, as a polymerization inhibitor, a well-known inhibitor can be used, For example, phosphoric acid, sodium hydrogenphosphate, paratoluenesulfonic acid, adipic acid, benzoyl chloride etc. are mentioned.
The amount used (% by weight) when using the polymerization catalyst and the polymerization inhibitor is not particularly limited, and in the case of the polymerization catalyst, the monomer {(1), (2), (3) in the production of the urethane prepolymer. ), If necessary, usually 0 or more, preferably 0.001 or more, more preferably 0.01 or more, usually 5 or less, preferably 1 or less, more preferably 0.2 or less with respect to the total weight of (A4)}. In the case of a polymerization inhibitor, it is usually 0 or more, preferably 0.01 or more, more preferably 0.05 or more, usually 10 or less, preferably 5 or less, more preferably 1 or less.

When neutralizing a carboxyl group and / or a sulfonic acid group using the above-described neutralizing agent, it may be before prepolymer polymerization, after polymerization, before emulsification, or after emulsification.
Moreover, the temperature (degreeC) at the time of neutralizing this prepolymer with the said neutralizing agent does not specifically limit, Usually, it is 10-40.

An emulsifying device for emulsifying by adding the nonionic and / or anionic surfactant (I) is not particularly limited, and examples thereof include an emulsifier of the following method. (A) Vertical stirring system, (b) Rotor-stator system [for example, “Ebara Milder” (manufactured by Ebara Seisakusho)], (c) Line mill system [for example, line flow mixer], (d) Stationary Tube mixing type [for example, static mixer], (e) Vibration type [for example, “VIBRO MIXER” (manufactured by Chilling Industries Co., Ltd.)], (f) Ultrasonic impact type [for example, ultrasonic homogenizer], (g) High pressure impact Formula [e.g., Gaurin homogenizer (Gaulin Inc.)], (h) membrane emulsification type [e.g. membrane emulsification module], and (i) centrifugal thin film contact type [e.g., film mix]. Of these, (b), (e), (h), and (i) are preferred from the viewpoint of easily obtaining a stable emulsion industrially.
The temperature (° C.) at the time of emulsification is not particularly limited, but is usually 10 or more, preferably 20 or more, more preferably 25 or more, and usually 50 or less, preferably 40 or less, more preferably 30 or less.

Examples of the chain extender (A5) and chain terminator (A6) that can be used if necessary include the following.
Chain extenders (A5) include diamines having 2 to 10 carbon atoms (for example, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, toluenediamine, etc.); polyamines (for example, diethylenetriamine, triethylenetetramine, etc.); Hydrazine or derivatives thereof (dibasic acid dihydrazide such as adipic acid dihydrazide); polyhydric alcohols having 2 to 15 carbon atoms [divalent alcohols (for example, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, Diethylene glycol, etc.), trihydric alcohols (eg, glycerin, trimethylolpropane, etc.), alkylene oxides of these polyhydric alcohols (ethylene oxide and / or propylene oxide) ) Low molar adduct (molecular weight less than 500), and the like.
Among these, ethylenediamine and isophoronediamine are preferable from the viewpoint of durability (hydrolysis resistance, heat resistance).

As the chain terminator (A6), monoalcohols having 1 to 8 carbon atoms (methanol, ethanol, isopropanol, butanol, cellosolves, carbitols, etc.), monoamines having 1 to 10 carbon atoms (monomethylamine, monoethylamine, Monobutylamine, dibutylamine, monooctylamine, monoethanolamine, diethanolamine, etc.).
Of these, monoethylamine and monobutylamine are preferable from the viewpoint of durability (hydrolysis resistance, heat resistance).
These chain extenders (A5) and / or chain terminators (A6) can be used alone or as a mixture of two or more.

Amount used when chain extender (A5) and / or chain terminator (A6) is used, that is, molar equivalent ratio {mole of primary or secondary amino group in (A5) or (A6) Number / number of moles of NCO group in the urethane prepolymer} is usually 0.0 or more, preferably 0.1 or more, more preferably 0.3 or more, usually 1. 0 or less, preferably 0.8 or less, more preferably 0.7 or less, and in the case of the chain terminator (A6), usually 0.0 or more, preferably 0.1 or more, more preferably 0.3 or more. Usually 1.0 or less, preferably 0.8 or less, more preferably 0.6 or less.
The reaction temperature (° C.) when reacting with the chain extender (A 5) and / or the chain terminator (A 6) is usually 10 ° C. or higher, preferably 20 or higher, more preferably 25 or higher, and usually 90 or lower. , Preferably 80 or less, more preferably 60 or less.

  The solid content concentration (% by weight) of the polyurethane emulsion of the present invention is not particularly limited, but is usually 10 or more, preferably 20 or more, more preferably 30 or more, from the viewpoint of emulsion stability and industrial productivity. Usually, it is 70 or less, preferably 65 or less, more preferably 50 or less. In addition, the said solid content shows the total content rate of the polyurethane resin (a) in this aqueous dispersion and the other additive (except a volatile substance) added as needed based on the aqueous dispersion.

The average dispersed particle size (μm) of the polyurethane resin (a) in the polyurethane emulsion of the present invention is preferably 0.01 or more, more preferably 0.05 or more, particularly preferably from the viewpoint of migration during the artificial leather processing described later. Is preferably 0.10 or more, most preferably 0.15 or more, and preferably 2.0 or less, more preferably 1.0 or less, particularly preferably 0.50 or less, most preferably from the viewpoint of the emulsion stability of the resin itself. Is 0.35 or less.
The average dispersed particle size (μm) of the present invention can be measured as follows.
Using an ELS-800 electrophoretic light scattering photometer manufactured by Otsuka Electronics Co., Ltd., the average particle diameter is measured using water as the dispersion medium.

   If necessary, the polyurethane resin (a) used in the present invention includes a colorant such as titanium oxide, an ultraviolet absorber (benzophenone series, benzotriazole series, etc.) and an antioxidant [4,4′-butylidene-bis (3-methyl). -6-1-butylphenol), etc .; various stabilizers such as triphenyl phosphite, organic phosphites such as trichloroethyl phosphite, etc.], cross-linking agents (polyepoxy compounds, polyisocyanate compounds, etc.), inorganic filling Agents (calcium carbonate, etc.) and known coagulation regulators [higher alcohols (Japanese Patent Publication No. 42-22719), crystalline organic compounds (Japanese Patent Publication No. 56-41652), hydrophobic nonionic surfactants (Japanese Examined Publication No. 45) -39634 and Japanese Examined Patent Publication No. 45-39635)] and the like It can be. The total amount (% by weight) of these additives is preferably 5 or less with respect to the weight of the polyurethane resin (a). More preferably, it is 0.1 or more and 3 or less.

The elongation at break (A) (%) at a temperature of 25 ° C. and a relative humidity of 65% RH of a dry film having a thickness of 200 μm ± 50 μm obtained from the polyurethane emulsion of the present invention is not particularly limited, but when used for artificial leather From the viewpoint of texture and quality, it is preferably in the range represented by the following general formulas (1) to (2) determined from 100% modulus (B) (MPa) of the dry film under the same conditions.
200 ≦ A ≦ −357 × B + 1714 (1)
0.1 ≦ B ≦ 4.0 (2)
For the polyurethane emulsion of the present invention, when the elongation at break (A) is in the range represented by the formulas (1) and (2) determined from 100% modulus (B), when used for artificial leather, Therefore, it is possible to achieve an unprecedented excellent texture.

From the same viewpoint as described above, more preferably, the range satisfies the following formulas (1-1) and (2-1),
300 ≦ A ≦ −357 × B + 1714 (1-1)
0.1 ≦ B ≦ 3.8 (2-1)
More preferably, it is a range satisfying the following formulas (1-2) and (2-2),
400 ≦ A ≦ −357 × B + 1714 (1-2)
0.5 ≦ B ≦ 3.5 (2-2)
Particularly preferably, the range satisfies the following formulas (1-3) and (2-3),
450 ≦ A ≦ −357 × B + 1714 (1-3)
0.8 ≦ B ≦ 3.5 (2-3)
Most preferably, it is a range satisfying the following formulas (1-4) and (2-4),
500 ≦ A ≦ −357 × B + 1714 (1-4)
1.0 ≦ B ≦ 3.0 (2-4)
Most preferably, it is a range satisfying the following formulas (1-5) and (2-5).
600 ≦ A ≦ −357 × B + 1714 (1-5)
1.2 ≦ B ≦ 2.8 (2-5)
In order to make (A) and (B) within the above range, the R value described above is preferably 1.10 or more, more preferably 1.15 or more, during the production of the prepolymer of the urethane emulsion of the present invention. And preferably 1.75, more preferably 1.50 or less. Further, as the polymer diol (a), a copolymer polycarbonate diol of two or more kinds of diols described above and two kinds It is more preferable to use the above mixture.

From the polyurethane emulsion of the present invention, the dry film can be prepared by the following method.
An outer frame made of cardboard having a width of 1 cm and a thickness of 0.1 cm is attached to a periphery of a glass plate having a smooth surface of 20 cm × 25 cm with a double-sided tape or the like, and a concave portion (18 cm × 23 cm, depth 0. 1 cm and a volume of about 41 cm 3), gently pouring a dispersion of 100 parts of the polyurethane emulsion prepared in advance to a solid content concentration of 40% and 30 parts of N-methylpyrrolidone as a film-forming aid so that the whole becomes uniform. spread. The plate is allowed to stand horizontally, naturally dried at room temperature (about 20 ° C.) for 24 hours, and further dried for 1 hour in a smooth air dryer adjusted to 105 ° C. After drying, it is allowed to stand at room temperature (about 20 ° C.) for 24 hours, and then gently peeled off from the glass plate to obtain a resin film having a thickness of 200 μm ± 50 μm.

As a measuring method of breaking elongation (A) (MPa) and 100% modulus (B) (MPa), it can measure with the following method.
The film obtained with a No. 3 dumbbell cutter was cut into a test piece, which was then used as an autograph {AGS-500D, manufactured by Shimadzu Corp.}, at a tensile rate of 300 mm / min. , 100% modulus, tensile strength at break (hereinafter referred to as tensile strength)}. This test is carried out under conditions of a temperature of 25 ° C. and a relative humidity of 65% RH, and it is necessary to adjust the temperature of the test sample under the same conditions for 2 hours or more before the measurement.

Since the polyurethane emulsion of the present invention has unprecedented durability and moderate flexibility, it can be suitably used for fiber impregnation agents, adhesives, coating agents, water-based paints, and the like.
Among these, since a soft texture and high quality can be achieved, it is preferably used as an impregnating agent for fibers, and more preferably used as a binder for artificial leather.

As a method for producing artificial leather using the polyurethane emulsion of the present invention, a known method (for example, JP-A-6-316877) can be used. Specifically, it can be produced by impregnating or applying the emulsion of the present invention inside the fiber material base, applying the urethane resin to the inside of the fiber base by solidification and drying, and grinding the surface of the base if necessary.
Examples of a method for applying a polyurethane emulsion to a fiber substrate by impregnation or coating include, for example, a method of preparing a pickup by squeezing with a mangle after impregnation, a method of directly applying by knife coating, air knife coating, roll coating, spray coating, etc. Is mentioned.
The fiber material substrate to which the emulsion is applied is subjected to treatments such as washing with water, dyeing, finishing (for example, softening, water repellent treatment, etc.) as necessary.

As a method for coagulating the urethane emulsion applied to the fiber substrate, for example, water, and if necessary, at least one nonionic and / or anionic surfactant (c) and an inorganic salt (d) are added to the urethane emulsion. Impregnating or applying a mixed solution (hereinafter referred to as a coagulation bath) to a fiber material substrate,
(1) A method of solidifying by spraying heated steam,
(2) A method of coagulating in an acid bath (for example, acetic acid aqueous solution),
(3) The method of introducing into a drying apparatus as it is, heating and solidifying, and drying is mentioned.
Among these, the method (1) is more preferable because the polyurethane emulsion of the present invention can effectively exhibit excellent fiber adhesion.
Here, the excellent fiber adhesion of the polyurethane emulsion of the present invention means that the coagulation rate is fast, so that the migration of the urethane resin to the surface of the fiber material base following the movement of water during subsequent drying is prevented. The urethane resin can be uniformly applied to the inside of the fiber material base. If this performance is insufficient, the urethane resin moves to the surface of the fiber material substrate during drying, and the urethane resin is not uniformly attached to the fiber material substrate, so the texture is hard and the resulting leather-like sheet The strength of the material is weakened.

The nonionic and / or anionic surfactant (c) used in the coagulation bath is not particularly limited, but preferably has a polyether unit which does not ionically dissociate in water as a hydrophilic group from the viewpoint of coagulation rate. It is a surfactant, and those described as the surfactant (A) are preferable, and nonionic surfactants represented by the general formula (3) are particularly preferable. (C) may be the same as the nonionic and / or anionic surfactant (A) used in the present invention, or may be of a different type. It can also be used as a mixture of two or more.
The HLB of (c) is not particularly limited, but from the same viewpoint, it is usually 10.0 or more, preferably 10.5 or more, more preferably 11.0 or more, and usually 18.0 or less, preferably 14. 0 or less, more preferably 13.0 or less.
The addition amount (% by weight) of (c) is not particularly limited, but is preferably 0.5% by weight or more, more preferably 1% by weight or more based on the weight of the polyurethane resin (a), preferably 20% by weight. % Or less, more preferably 15% by weight or less.

Examples of the inorganic salt (d) made of an alkali metal salt or an alkaline earth metal salt include the following.
Examples of the alkali metal salt include sodium carbonate, sodium sulfate, sodium hydroxide, sodium nitrate, potassium chloride, and potassium carbonate, and examples of the alkaline earth metal salt include calcium chloride and calcium sulfate.

  The amount of (d) added is preferably 0.5% by weight or more, more preferably 1% by weight or more based on the weight of the polyurethane resin (a), from the viewpoint of storage stability of the coagulation bath, preferably 5% or more. % By weight or less, more preferably 4% by weight or less.

The order of addition of water to the polyurethane emulsion of the present invention in the preparation of the coagulation bath and, if necessary, (c) and (d) is not particularly limited, but preferably water, (c) and (d) are premixed. What is necessary is just to mix | blend slowly with (a), stirring aqueous solution.
The temperature (° C.) for preparing the coagulation bath is not particularly limited, but is usually 10 to 40, preferably 20 to 30 from the stability of the coagulation bath.
The concentration (% by weight) of the polyurethane resin (a) in the coagulation bath is usually 1 or more, preferably 5 or more, more preferably 10 or more, and usually 40 or less, preferably 30 or less, particularly preferably 20 or less. is there.

The temperature (° C.) at which the polyurethane emulsion of the present invention is coagulated is usually 40 or more, preferably 50 or more, more preferably 60 from the viewpoint of preventing the migration by quickly coagulating the coagulation bath and coagulating the polyurethane resin. Above, especially preferably 70 or more, usually 180 or less, preferably 150 or less, more preferably 140 or less, particularly preferably 120 or less.
The thermal coagulation temperature is measured as follows.
10 g of an aqueous dispersion diluted to a solid content of 20% was weighed in a test tube (inner diameter 18 mm) and heated at a rate of 10 ° C./min in a 90 ° C. hot water bath without stirring. The temperature of the aqueous dispersion when the aqueous dispersion loses fluidity and becomes a gel-like material is defined as a thermal coagulation temperature.

In addition, it is preferable to remove moisture contained in the leather-like sheet by applying the polyurethane emulsion of the present invention to the fiber substrate by heat coagulation and then performing heat drying or air drying.
The weight of the urethane resin (a) attached to the fiber material substrate after drying is preferably 3 parts by weight or more, more preferably 10 parts by weight or more, and particularly preferably 20 parts by weight or more with respect to 100 parts by weight of the fiber material substrate. The amount is preferably 150 parts by weight or less, more preferably 100 parts by weight or less, and particularly preferably 50 parts by weight or less.

As the fiber material substrate used in the production of the leather-like sheet material of the present invention, any nonwoven fabric and woven fabric conventionally used in the production of fiber material substrates can be used without any particular limitation. The nonwoven fabric may be one in which a woven fabric or the like is laminated inside or on the surface for the purpose of reinforcement or the like.
The constituent fiber may be either natural fiber or chemical fiber, natural fiber is cotton, wool, silk, asbestos, etc., chemical fiber is regenerated fiber such as rayon and tencel, semi-synthetic fiber such as acetate and triacetate, polyamide , Synthetic fibers such as polyester, polyolefin, and acrylic. Moreover, it is also possible to use appropriately a fiber using a mixture of these.

The leather-like sheet material of the present invention is extremely useful as a sheet material because it has a moderate texture and a good texture similar to that of natural leather.
The leather-like sheet material of the present invention can be suitably used in various applications, for example, mattresses, lining materials, clothing, shoe core materials, cushioning materials, automobile interior materials, wall materials, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In the examples, “parts” represents parts by weight, and “%” represents% by weight.

Example 1
In a closed reaction vessel equipped with a thermometer and a stirrer, 547 parts of polyhexamethylene carbonate diol (hereinafter referred to as C6-PCDL) having a number average molecular weight of 2,000, α, α-dimethylolpropionic acid (hereinafter referred to as DMPA) ) 6.3 parts, 4,4'-dicyclohexylmethane diisocyanate (hereinafter referred to as HMDI) 147 parts and acetone 300 parts (polymerization concentration 70%), after replacing the reaction system with nitrogen gas, under stirring It was made to react at 90 degreeC for 12 hours, and the NCO terminal urethane prepolymer (a1) was obtained. The obtained acetone solution was cooled to 40 ° C., 4.7 parts of triethylamine was added, and after sufficiently neutralizing with stirring, polyoxyethylene (degree of polymerization 10) lauryl ether {Sanyo Kasei) was added to the acetone solution as an emulsifier. “Emalmine NL-100” manufactured by Kogyo Co., Ltd., 21.0 parts of HLB = 14.2} and 763 parts of water were added and emulsified by stirring for 5 minutes with a homomixer. A solution composed of 6.0 parts of diethylenetriamine, 10.5 parts of isophoronediamine and 312 parts of water was dropped into the obtained emulsion solution over about 10 minutes, and a chain elongation reaction was performed at room temperature (about 20 ° C.) for 30 minutes. Then, it heated at 60 degreeC and made it react for 2 hours. Acetone was distilled off under reduced pressure, and the concentration was adjusted with water to obtain 1,700 parts of the polyurethane emulsion (1) of the present invention having a urethane resin solid content of 40%. In the polyurethane emulsion (1) of the present invention, the content of carboxyl groups and the like contained in the polyurethane resin (a) was 0.30%, and the content of the surfactant (A) relative to the polyurethane resin was 3.0%. It was. Moreover, the breaking elongation measured by the above-mentioned method was 600%, and the 100% modulus was 3.0 MPa.

Example 2
Instead of C6-PCDL having a number average molecular weight of 2,000, C4, C6-PCDL having a number average molecular weight of 2,000: 1,4-butanediol / 1,6-hexanediol copolymer polycarbonate having a number average molecular weight of 2,000 Diol (hereinafter referred to as C4, C6-PCDL) {Asahi Kasei Co., Ltd., "PCDL T4672", copolymerization molar ratio 7/3} 598 parts, DMPA 3.5 parts, HMDI 98 parts Example 1 In the same manner as above, an NCO-terminated urethane prepolymer (a2) was obtained.
Subsequently, emulsification was carried out in the same manner as in Example 1 using 2.7 parts of triethylamine, 21.0 parts of polyoxyethylene (degree of polymerization 10) lauryl ether and 991 parts of water, and further 1.2 parts of diethylenetriamine and 2. part of isophoronediamine. 1 part of the polyurethane emulsion (2) of the present invention having a urethane resin solid content of 40% was obtained in the same manner as in Example 1 by using a dissolving liquid consisting of 1 part and 64 parts of water. In the polyurethane emulsion (2) of the present invention, the content of carboxyl groups and the like contained in the polyurethane resin (a) was 0.17%, and the content of the surfactant (A) relative to the polyurethane resin was 3.0%. It was. The elongation at break was 850%, and the 100% modulus was 2.3 MPa.

Example 3
Instead of C6-PCDL having a number average molecular weight of 2,000, 3-methyl-1,5-pentanediol / 1,6-hexanediol copolymer polycarbonate diol having a number average molecular weight of 2,000 (hereinafter referred to as 3-MeC6, C6) -Described as PCDL.) {NCO, manufactured by Daicel Chemical Industries, Ltd., "PLACCEL CD220PL", copolymerization molar ratio 9/1}, 571 parts, DMPA 5.2 parts, HMDI 123 parts A terminal urethane prepolymer (a3) was obtained.
Subsequently, emulsification was carried out in the same manner as in Example 1 using 3.9 parts of triethylamine, 21.0 parts of polyoxyethylene (degree of polymerization 10) lauryl ether and 982 parts of water, and further 2.6 parts of diethylenetriamine and 1.3 parts of ethylenediamine. 1,700 parts of the polyurethane emulsion (3) of the present invention having a urethane resin solid content of 40% was obtained in the same manner as in Example 1 by using a dissolving solution consisting of 74 parts of water and 74 parts of water. In the polyurethane emulsion (3) of the present invention, the content of carboxyl groups and the like contained in the polyurethane resin (a) was 0.25%, and the content of the surfactant (I) relative to the polyurethane resin was 3.0%. It was. The elongation at break was 730% and the 100% modulus was 2.5 MPa.

Example 4
Instead of C6-PCDL having a number average molecular weight of 2,000, C4, C6-PCDL having a number average molecular weight of 2,000 (manufactured by Asahi Kasei Co., Ltd., “PCDL T4672”, copolymerization molar ratio 7/3} 590 parts, Instead, an NCO-terminated urethane prepolymer (a4) was obtained in the same manner as in Example 1 except that 6.9 parts of α, α-dimethylolbutyric acid (hereinafter referred to as DMBA) and 103 parts of HMDI were used.
Subsequently, 4.7 parts of triethylamine, polyoxyethylene (polymerization degree 7) lauryl ether {“Emalmine NL-70” manufactured by Sanyo Chemical Industries, Ltd., HLB = 12.4}, 21.0 parts, and 1021 parts of water were used. The emulsification was carried out in the same manner as in Example 1, and further using a solution comprising 1.5 parts of diethylenetriamine, 0.19 part of ethylenediamine and 31 parts of water, as in Example 1, and having a urethane resin solid content of 40%. 1,700 parts of polyurethane emulsion (4) were obtained. In the polyurethane emulsion (4) of the present invention, the content of carboxyl groups and the like contained in the polyurethane resin (a) was 0.30%, and the content of the surfactant (A) relative to the polyurethane resin was 3.0%. It was. The elongation at break was 750%, and the 100% modulus was 2.2 MPa.

Example 5
Example except that 579 parts of C6-PCDL having a number average molecular weight of 2,000, 7.4 parts of 1,4-butanediol, 6.3 parts of DMPA, and 107 parts of isophorone diisocyanate (hereinafter referred to as IPDI) are used instead of HMDI. In the same manner as in Example 1, an NCO-terminated urethane prepolymer (a5) was obtained.
Subsequently, emulsification was carried out in the same manner as in Example 1 using 4.7 parts of triethylamine, 21.0 parts of polyoxyethylene (degree of polymerization 10) lauryl ether and 1015 parts of water, and further 1.8 parts of diethylenetriamine and 0.23 of ethylenediamine. 1,700 parts of the polyurethane emulsion (5) of the present invention having a urethane resin solid content of 40% was obtained in the same manner as in Example 1 by using a dissolving solution consisting of 38 parts of water and 38 parts of water. In the polyurethane emulsion (5) of the present invention, the content of carboxyl groups and the like contained in the polyurethane resin (a) was 0.30%, and the content of the surfactant (A) relative to the polyurethane resin was 3.0%. It was. The elongation at break was 780%, and the 100% modulus was 1.5 MPa.

Example 6
Instead of C6-PCDL having a number average molecular weight of 2,000, C4, C6-PCDL having a number average molecular weight of 2,000 (manufactured by Asahi Kasei Co., Ltd., “PCDL T4672”, copolymerization molar ratio 7/3} 595 parts, DMPA1. An NCO-terminated urethane prepolymer (a6) was obtained in the same manner as in Example 1 except that 0 part and 101 parts of HMDI were used.
Subsequently, emulsification was carried out in the same manner as in Example 1 using 0.8 parts of triethylamine, 56.0 parts of polyoxyethylene (degree of polymerization 10) lauryl ether and 1022 parts of water, and further 1.4 parts of diethylenetriamine and 0.18 of ethylenediamine. 1 part of a polyurethane emulsion (6) of the present invention having a urethane resin solid content of 40% was obtained in the same manner as in Example 1 using a solution composed of parts and water 31 parts. In the polyurethane emulsion (6) of the present invention, the content of carboxyl groups and the like contained in the polyurethane resin (a) was 0.05%, and the content of the surfactant (A) relative to the polyurethane resin was 8.0%. It was. The elongation at break was 900% and the 100% modulus was 1.8 MPa.

Example 7
Instead of C6-PCDL having a number average molecular weight of 2,000, C4, C6-PCDL having a number average molecular weight of 2,000 (manufactured by Asahi Kasei Co., Ltd., “PCDL T4672”, copolymerization molar ratio 7/3} 564 parts, DMPA 15. An NCO-terminated urethane prepolymer (a7) was obtained in the same manner as in Example 1 except that 6 parts and 120 parts of HMDI were used.
Subsequently, 11.8 parts of triethylamine, 0.70 part of polyoxyethylene (degree of polymerization 10) lauryl ether and 1017 parts of water were emulsified in the same manner as in Example 1, and further 1.7 parts of diethylenetriamine and 0.22 of ethylenediamine. 1,700 parts of the polyurethane emulsion (7) of the present invention having a solid content of urethane resin of 40% was obtained in the same manner as in Example 1 using a dissolving solution consisting of 36 parts of water and 36 parts of water. In the polyurethane emulsion (7) of the present invention, the content of carboxyl groups and the like contained in the polyurethane resin (a) was 0.75%, and the content of the surfactant (A) relative to the polyurethane resin was 0.1%. It was. The elongation at break was 700% and the 100% modulus was 2.8 MPa.

Comparative Example 1
An NCO-terminated urethane prepolymer (b1) was obtained in the same manner as in Example 1 except that 502 parts of C6-PCDL having a number average molecular weight of 2,000, 37.5 parts of DMPA, and 160 parts of HMDI were used.
Subsequently, emulsification was carried out in the same manner as in Example 1 using 28.3 parts of triethylamine and 955 parts of water, and further using a solution consisting of 2.0 parts of diethylenetriamine, 3.5 parts of isophoronediamine and 103 parts of water. 1, 700 parts of polyurethane emulsion (ratio 1) having a solid content of urethane resin of 40% was obtained. The content of carboxyl groups and the like contained in the polyurethane resin (a) in the polyurethane emulsion (ratio 1) was 1.80%, and the content of the surfactant (A) relative to the polyurethane resin was 0.0%. The elongation at break was 510%, and the 100% modulus was 4.0 MPa.

Comparative Example 2
An NCO-terminated urethane prepolymer (b2) was obtained in the same manner as in Example 1 except that 608 parts of C6-PCDL having a number average molecular weight of 2,000 and 92 parts of HMDI were used.
Subsequently, emulsification was carried out in the same manner as in Example 1 using 105 parts of polyoxyethylene (degree of polymerization 10) lauryl ether and 1024 parts of water, and further dissolving 1.3 parts of diethylenetriamine, 0.17 parts of ethylenediamine and 28 parts of water. Using the solution, 1,700 parts of a polyurethane emulsion (ratio 2) having a urethane resin solid content of 40% was obtained in the same manner as in Example 1. The content of the carboxyl group and the like contained in the polyurethane resin (a) in the polyurethane emulsion (ratio 2) was 0.00%, and the content of the surfactant (i) relative to the polyurethane resin was 15.0%. The elongation at break was 710%, and the 100% modulus was 2.4 MPa.

Comparative Example 3
In place of C6-PCDL having a number average molecular weight of 2,000, C4, C6-PCDL having a number average molecular weight of 2,000 (manufactured by Asahi Kasei Corporation, “PCDL T4672”, copolymerization molar ratio 7/3} 591 parts, DMPA6. An NCO-terminated urethane prepolymer (b3) was obtained in the same manner as in Example 1 except that 3 parts and 103 parts of HMDI were used.
Subsequently, 4.7 parts of triethylamine, polyoxyethylene (degree of polymerization 5) oleyl cetyl ether {“Emalmin 50” manufactured by Sanyo Chemical Industries, Ltd., HLB = 9.0}, 21.0 parts, and 989 parts of water were used. Emulsified in the same manner as in Example 1, and a polyurethane emulsion having a urethane resin solid content of 40% in the same manner as in Example 1 using a solution composed of 1.3 parts of diethylenetriamine, 2.2 parts of isophoronediamine and 67 parts of water. Ratio 3) 1,700 parts were obtained. The content of carboxyl groups and the like contained in the polyurethane resin (a) in the polyurethane emulsion (ratio 3) was 0.30%, and the content of the surfactant (A) relative to the polyurethane resin was 3.0%. The elongation at break was 750%, and the 100% modulus was 2.5 MPa.

Comparative Example 4
Using 1,000 parts of urethane prepolymer (b3) obtained in the same manner as in Comparative Example 3, polyoxyethylene (degree of polymerization 70) nonylphenol ether {“Nonipol 700” manufactured by Sanyo Chemical Industries, Ltd., HLB = 18 7} 21.0 parts, 4.7 parts of triethylamine, and 989 parts of water were emulsified in the same manner as in Example 1, and further dissolved in 1.3 parts of diethylenetriamine, 2.2 parts of isophoronediamine, and 67 parts of water. Using the liquid, 1,700 parts of a polyurethane emulsion (ratio 4) having a urethane resin solid content of 40% was obtained in the same manner as in Example 1. The content of carboxyl groups and the like contained in the polyurethane resin (a) in the polyurethane emulsion (ratio 4) was 0.30%, and the content of the surfactant (I) relative to the polyurethane resin was 3.0%. The elongation at break was 730%, and the 100% modulus was 2.2 MPa.

Comparative Example 5
Example 6 except that 419 parts of C6-PCDL having a number average molecular weight of 2,000, 179 parts of polytetramethylene glycol (hereinafter referred to as PTMG) having a number average molecular weight of 2,000, 3.5 parts of DMPA, and 98 parts of HMDI are used. Thus, an NCO-terminated urethane prepolymer (b5) was obtained.
Subsequently, emulsification was carried out in the same manner as in Example 1 using 4.7 parts of triethylamine, 21.0 parts of polyoxyethylene (degree of polymerization 10) lauryl ether and 1023 parts of water, and further 1.4 parts of diethylenetriamine and 0.18 of ethylenediamine. 1,700 parts of a polyurethane emulsion (ratio 5) having a urethane resin solid content of 40% was obtained in the same manner as in Example 1 by using a solution composed of 30 parts of water and 30 parts of water. The content of the carboxyl group and the like contained in the polyurethane resin (a) in the polyurethane emulsion (ratio 5) was 0.30%, and the content of the surfactant (A) relative to the polyurethane resin was 3.0%. The elongation at break was 800% and the 100% modulus was 3.5 MPa.

Comparative Example 6
Example 6 except that 413 parts of C6-PCDL having a number average molecular weight of 2,000, 177 parts of polyhexamethylene adipate (hereinafter referred to as PHA) having a number average molecular weight of 2,000, 6.3 parts of DMPA, and 103 parts of HMDI are used. As a result, an NCO-terminated urethane prepolymer (b6) was obtained.
Subsequently, emulsification was carried out in the same manner as in Example 1 using 4.7 parts of triethylamine, 21.0 parts of polyoxyethylene (degree of polymerization 10) lauryl ether and 1023 parts of water, and further 1.3 parts of diethylenetriamine and 0.28 of ethylenediamine. 1,700 parts of a polyurethane emulsion (ratio 6) having a urethane resin solid content of 40% was obtained in the same manner as in Example 1 by using a solution composed of 30 parts of water and 30 parts of water. The content of the carboxyl group and the like contained in the polyurethane resin (a) in the polyurethane emulsion (ratio 6) was 0.17%, and the content of the surfactant (A) relative to the polyurethane resin was 3.0%. The elongation at break was 610%, and the 100% modulus was 3.2 MPa.

  Table 1 shows the results of the obtained polyurethane emulsions (1) to (7) of the present invention and the conventional polyurethane emulsions (ratio 1) to (ratio 6) prepared for comparison. The average particle size of the emulsion was measured by the method described above. About emulsification stability, it left still at room temperature (about 20 degreeC), and observed the number of days required until isolate | separated.

C6-PCDL: polyhexamethylene carbonate diol having a number average molecular weight of 2,000 C4, C6-PCDL: copolymerization of 1,4-butanediol / 1,6-hexanediol having a number average molecular weight of 2,000 (copolymerization) (Molar ratio 7/3)
3-MeC6, C6-PCDL: Copolymerized polycarbonate diol of 3-methyl-1,5-pentanediol / 1,6-hexanediol having a number average molecular weight of 2,000 (copolymerization molar ratio 9/1)
PTMG: Polytetramethylene glycol having a number average molecular weight of 2,000 PHA: Polyhexamethylene adipate having a number average molecular weight of 2,000 HMDI: 4,4′-dicyclohexylmethane diisocyanate IPDI: Isophorone diisocyanate DMPA: α, α-dimethylolpropionic acid DMBA: α, α-dimethylolbutyric acid 1,4-BG: 1,4-butanediol

Examples 8-14, Comparative Examples 7-12
The polyurethane emulsions (1) to (7) of the present invention obtained in Examples 1 to 7 and the conventional polyurethane emulsions (Ratio 1) to (Ratio 6) obtained in Comparative Examples 1 to 6, respectively, were used as described above. A dry film was prepared by the method described above, and the tensile strength (MPa) was measured. Further, hydrolysis resistance, heat resistance, and light resistance were measured by the following methods. The results are shown in Table 2.
<Hydrolysis resistance test>
The dry film obtained above was left in a thermo-hygrostat adjusted to a temperature of 75 ° C. and a relative humidity of 90% for 10 weeks, then removed from the thermo-hygrostat and allowed to stand at room temperature (about 20 ° C.) for 24 hours. . In the same manner as described above, the tensile strength (MPa) was measured, and the tensile strength (MPa) retention before and after this test was calculated from the following equation. It means that it is excellent in hydrolysis resistance, so that a retention rate is high.
Retention rate (%) = [Tensile strength after test (MPa) / Tensile strength before test (MPa)] × 100
<Heat resistance test>
A part of the dry film thus obtained was cut out, and the thermal softening point was measured using a TMA measuring apparatus (manufactured by Rigaku Corporation, TMA8140) (heating rate 5 ° C./min). The higher the heat softening point, the better the heat resistance.
<Light resistance test>
The obtained dry film was left in a fade meter (STANDARD UV LONG LIFE FADE METER, temperature 63 ° C., manufactured by Suga Test Instruments Co., Ltd.) for 200 hours, then taken out from the fade meter and kept at room temperature (about 20 ° C.). For 24 hours. In the same manner as described above, the tensile strength (MPa) was measured, and the tensile strength (MPa) retention before and after this test was calculated. Higher retention means better light resistance.

  From the results in Table 2, the polyurethane emulsions (1) to (7) of the present invention have superior durability (hydrolysis resistance, heat resistance, light resistance) compared to conventional polyurethane emulsions (ratio 1) to (ratio 6). ).

<Manufacture of non-woven fabric>
A laminated sheet is made from polyethylene terephthalate short fibers, this sheet is needle punched so that the number of shots is 280 / cm ² , and then dried, and a nonwoven fabric having a weight of 380 g / m ² and an apparent density of 0.18 g / cm ² . Got.

Examples 15-21, Comparative Examples 13-18
Using the polyurethane emulsions (1) to (7) of the present invention obtained in Examples 1 to 7 and the conventional polyurethane emulsions (Ratio 1) to (Ratio 6) obtained in Comparative Examples 1 to 6, respectively, An aqueous solution composed of 0.80 parts of calcium chloride and 185 parts of water was slowly added to 100 parts of the urethane emulsion while stirring to prepare a coagulation bath solution having a polyurethane resin concentration of 14%.
Each of the above non-woven fabrics is impregnated with the prepared coagulation bath solution, squeezed with mangles so that the resin adhesion rate is about 50% by weight with respect to the non-woven fabric weight, and then thermally coagulated in saturated steam at 100 ° C. for 2 minutes. Furthermore, the sheet was obtained by drying with a hot air dryer at 120 ° C. for 10 minutes, washing with water, and again drying with a hot air dryer at 100 ° C. for 10 minutes.

<Performance test>
About the leather-like sheet | seat manufactured in Examples 15-21 and Comparative Examples 13-18, the presence or absence of migration and the texture were evaluated by the following test method. These results are shown in Table 3.

[Resin adhesion rate]
It calculated by following Formula in the leather-like sheet | seat after drying.
100 × [(weight of leather-like sheet) − (weight of fiber material substrate)] / (weight of fiber material substrate) (unit weight%)
[Migration status]
The cross section of the sheet is observed with an electron microscope (S-800, manufactured by Hitachi, Ltd.), and the adhesion state of the surface portion and the central portion of the polyurethane resin to the substrate is examined. The polyurethane resin is uniformly distributed in the fiber material substrate. The case where migration did not occur was determined as “◯”, and the polyurethane resin was unevenly distributed on the surface portion of the fiber material base, and the case where migration occurred was determined as “X”.
[Texture]
When the sheet has a natural leather-like texture, it is judged as “○”, and when the sheet is slightly inferior in comparison with natural leather, “△”, the sheet has a natural leather-like texture due to insufficient flexibility. The case where it did not present was determined as “×”. Judgment was made by a sensory test based on the hand touch.
[Breathability]
Using a Gurley densometer, the time (seconds) required for 50 ml of air to pass was measured according to the method of JIS P8117.

  From the results shown in Table 3, when the polyurethane emulsion of the present invention is used, the urethane resin can be uniformly attached to the fiber material substrate without occurrence of migration. Therefore, even when the fiber material substrate surface is subsequently ground, Can be uniformly adjusted, and high quality can be provided. It was also found that the obtained leather-like sheet had an excellent texture.

The polyurethane emulsion of the present invention can be used for artificial leather (for example, mattresses, lining materials, clothing, shoe core materials, cushions, automobile interior materials, wall materials, etc.), paints, adhesives, and adhesives (dry Laminate adhesives, etc.), coating agents, binders for antibacterial agents, and textile processing agents (synthetic leather, binders for pigment printing, etc.) other than the above artificial leather.

Claims (9)

  A polyurethane emulsion comprising at least one nonionic and / or anionic surfactant (A) having a hydrophilic / lipophilic balance (HLB) of 10 to 18 inclusive, wherein the polyurethane resin (a) A) a polymeric diol (a1) comprising only at least one polycarbonate-based diol, an organic polyisocyanate compound (a2) having at least two isocyanate groups in the molecule, and a carboxyl group or a sulfonic acid group in the molecule And a compound (A3) having at least one group selected from the group consisting of a carboxylate anion group and a sulfonate anion group and having at least two functional groups that react with an isocyanate group. ) Carboxyl group, The total content of acid groups, carboxylate anion groups, and sulfonate anion groups is 0.01% by weight or more and 1.5% by weight or less based on the weight of the polyurethane resin (a). ), The total content of which is 0.1 wt% or more and 10 wt% or less based on the weight of the polyurethane resin (a).   The polyurethane emulsion according to claim 1, wherein the polycarbonate diol (A1) is a copolymerized polycarbonate diol composed of two or more diols.   The polyurethane emulsion according to claim 1 or 2, wherein the compound (a3) is a compound having at least two functional groups having at least one carboxyl group and / or carboxylate anion group in the molecule and reacting with an isocyanate group. .   The polyurethane emulsion according to any one of claims 1 to 3, wherein the compound (A3) is α, α-dimethylolpropionic acid and / or α, α-dimethylolbutyric acid.   The polyurethane emulsion according to any one of claims 1 to 4, wherein the surfactant (I) is a nonionic surfactant. The following general formulas (1) and (2) in which the breaking elongation (A) (%) at a temperature of 25 ° C. and a relative humidity of 65% RH of a dry film having a thickness of 200 μm ± 50 μm is obtained from 100% modulus (B) (MPa) It is in the range shown by 2), The polyurethane emulsion in any one of Claims 1-5.
200 ≦ A ≦ −357 × B + 1714 (1)
0.1 ≦ B ≦ 4.0 (2)   The polyurethane emulsion according to any one of claims 1 to 6, which is used for artificial leather.   8. The polyurethane emulsion according to any one of claims 1 to 7, optionally at least one nonionic and / or anionic surfactant (U) having a hydrophilic / lipophilic balance (HLB) of 10 to 18, and an alkali metal A leather-like sheet material obtained by applying a polyurethane resin composition comprising an inorganic salt (e) comprising a salt or an alkaline earth metal salt to a fiber material substrate. 8. The polyurethane emulsion according to any one of claims 1 to 7, optionally at least one nonionic and / or anionic surfactant (U) having a hydrophilic / lipophilic balance (HLB) of 10 to 18, and an alkali metal A method for producing a leather-like sheet material, which comprises applying a mixed solution comprising an inorganic salt (e) comprising a salt or an alkaline earth metal salt to a fiber material substrate and heat-coagulating the mixture.