JP2010215803A - Method for producing aqueous polyurethane resin, aqueous polyurethane resin and film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a aqueous polyurethane resin without substantially using organic solvents, the aqueous polyurethane resin produced by the method, and a film produced from the aqueous polyurethane resin. <P>SOLUTION: The method for producing the aqueous polyurethane resin comprises: a synthesizing step to react a polyisocyanate with an active hydrogen group-containing compound having multiple active hydrogen groups at an equivalent ratio of the isocyanate group of the polyisocyanate to the active hydrogen group of the active hydrogen group-containing compound of 1.2-4, wherein a nonionic group side chain is introduced to at least one of the polyisocyanate and the active hydrogen group-containing compound, and synthesize a nonionic group-containing prepolymer having a concentration of the nonionic group introduced to the side chain of ≥0.9 mass%; and an emulsification/dissolution step to stir the nonionic group-containing prepolymer and water with a vibration mixer to obtain an emulsion or aqueous solution of the nonionic group-containing prepolymer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing an aqueous polyurethane resin, an aqueous polyurethane resin obtained by the method, and a film obtained from the aqueous polyurethane resin.

In recent years, water-based resins have become widespread from the viewpoints of environmental conservation, resource saving, safety, etc. Especially, water-based polyurethane resins are used for paints and adhesives from the viewpoint of superior durability, chemical resistance, wear resistance, etc. Widely used in the field of adhesives, binders or coating agents.
The aqueous polyurethane resin is usually produced by synthesizing a hydrophilic group-containing urethane prepolymer in an organic solvent, emulsifying it in water, reacting with a chain extender, and then removing the solvent.

In this method, since an organic solvent is used, solvent removal is essential. Therefore, the operation is complicated and uneconomical. Further, it is difficult to completely remove the organic solvent from the obtained aqueous polyurethane resin, and problems such as environmental pollution, safety, and odor caused by the remaining organic solvent are unavoidable.
Therefore, it is desired to produce an aqueous polyurethane without using an organic solvent, and various studies have been made.

For example, urethane prepolymer and water are continuously supplied to a continuous emulsifying machine including stator teeth and rotor teeth, and the rotor teeth are rotated at high speed and dispersed by a shearing force between the rotor teeth and the stator teeth. Thus, a method of continuously emulsifying an aqueous polyurethane resin has been proposed (for example, see Patent Document 1).
In addition, it has been proposed to produce an aqueous dispersion by bringing an isocyanate group-terminated prepolymer and water into contact mixing using a continuous kneader having an operating power of 2 KW / m ³ or more (for example, Patent Documents). 2).

In addition, it has been proposed to obtain an aqueous polyurethane resin by melting and mixing a polyurethane and a polymer having a hydrophilic group together with water using a twin screw extruder (see, for example, Patent Document 3).
On the other hand, it has been proposed to continuously disperse and emulsify an organic solvent solution of urethane prepolymer and water using a vibration stirrer (see, for example, Patent Document 4).

JP 2004-59676 A JP 2003-138021 A JP 2005-232277 A JP-A-8-120091

However, in the method described in Patent Document 1, the viscosity of the urethane prepolymer at the time of dispersion needs to be 10,000 mPa · s or less, and therefore, it is necessary to contain an emulsifier in water. As a result, there exists a malfunction that the water resistance of the coating film obtained from water-based polyurethane resin becomes low.
Moreover, in the method of patent document 2, since the urethane prepolymer which reacted with water adheres to the emulsification part into which water is introduce | transduced in actual manufacture, a malfunction arises in continuous operation and a washability.

Further, in the method described in Patent Document 3, since heat of about 200 ° C. is applied at the time of melt kneading, a part of polyurethane is thermally decomposed, so that the mechanical strength of a film obtained from the aqueous polyurethane resin is insufficient. There is.
The method described in Patent Document 4 is a method for producing an aqueous polyurethane resin using an organic solvent. The viscosity of the urethane prepolymer is low, and it is necessary to remove the solvent after dispersion. In addition, since the aqueous polyurethane resin is intended for a dispersion having a high solid content and a low viscosity, the particle diameter is on the order of microns, and it is not suitable for obtaining a thin and uniform coating film.

  The object of the present invention is that it contains substantially no organic solvent, is environmentally friendly, finely and uniformly emulsified, and does not cause sedimentation, so that an aqueous polyurethane resin excellent in storage stability can be produced. Furthermore, the present invention provides a method for producing a water-based polyurethane resin that is less productive and has excellent productivity, and further provides a water-based polyurethane resin obtained by the method and a film obtained from the water-based polyurethane resin. It is in.

  In order to achieve the above object, the present invention provides a method for producing an aqueous polyurethane resin that does not substantially use an organic solvent, comprising at least one of a polyisocyanate having a nonionic group side chain introduced therein and a plurality of polyisocyanates. The active hydrogen group-containing compound having an active hydrogen group is introduced into the side chain by reacting the equivalent ratio of the isocyanate group of the polyisocyanate to the active hydrogen group of the active hydrogen group-containing compound at a ratio of 1.2 to 4. By synthesizing a nonionic group-containing prepolymer having a nonionic group concentration of 0.9% by mass or more, and stirring the nonionic group-containing prepolymer and water using a vibration stirrer, And an emulsification / dissolution step of obtaining an emulsion or aqueous solution of the nonionic group-containing prepolymer.

In the method for producing an aqueous polyurethane resin of the present invention, the emulsion or aqueous solution of the nonionic group-containing prepolymer and the chain extender are selected from the group consisting of a vibration stirrer, a static mixer, and an in-line mixer. It is preferable that the apparatus further comprises a chain extension step in which the solution is fed to at least one kind of apparatus to be reacted.
The aqueous polyurethane resin of the present invention is obtained by the above-described method for producing an aqueous polyurethane resin.

  Furthermore, the film of the present invention is obtained from the above-mentioned aqueous polyurethane resin.

  According to the method for producing an aqueous polyurethane resin of the present invention, since no organic solvent is used in the synthesis step of synthesizing the nonionic group-containing prepolymer, no solvent removal is required. Therefore, operability can be improved and it is economical. In addition, when emulsifying / dissolving nonionic group-containing prepolymers, nonionic group-containing prepolymers are less likely to adhere to, accumulate on, and are not generated on the vibrating stirrer. Is also excellent. Accordingly, the aqueous polyurethane resin can be produced efficiently and is excellent in economic efficiency.

  The aqueous polyurethane resin of the present invention contains substantially no organic solvent, and is therefore environmentally friendly, finely and uniformly emulsified / dissolved, and does not cause sedimentation / separation. Excellent stability.

It is a schematic explanatory drawing of the manufacturing apparatus employ | adopted in the Example.

The method for producing an aqueous polyurethane resin of the present invention is a method for producing an aqueous polyurethane resin that does not substantially use an organic solvent. First, a side chain of a nonionic group is introduced into at least one of the synthesis steps. A nonionic group-containing prepolymer is synthesized by reacting a polyisocyanate and an active hydrogen group-containing compound.
In the present invention, polyisocyanate is an organic compound having two or more isocyanate groups, and examples thereof include aromatic diisocyanates, araliphatic diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates.

  Examples of the aromatic diisocyanate include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (hereinafter abbreviated as TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof). ), 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (hereinafter abbreviated as NDI), diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate) Acid or a mixture thereof) (hereinafter abbreviated as MDI), 4,4′-toluidine diisocyanate (hereinafter abbreviated as TODI), 4,4′-diphenyl ether diisocyanate, and the like.

  Examples of the araliphatic diisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (hereinafter abbreviated as XDI), tetramethylxylylene diisocyanate (1,3- or 1). , 4-tetramethylxylylene diisocyanate or a mixture thereof (hereinafter abbreviated as TMXDI), ω, ω′-diisocyanate-1,4-diethylbenzene, and the like.

Examples of the alicyclic diisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5. , 5-trimethylcyclohexyl isocyanate (isophorodiisocyanate, hereinafter abbreviated as IPDI), methylene bis (cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis (cyclohexyl isocyanate, these Trans , Trans- body, Trans, Cis body, Cis, Cis body, or mixtures thereof)) _(hereinafter abbreviated as H 12 MDI), methylcyclohexane diisocyanate Natick (Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (hereinafter abbreviated as NBDI), bis (isocyanenatomethyl) cyclohexane (1,3 -Or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof (hereinafter abbreviated as H ₆ XDI), dimer acid diisocyanate (hereinafter abbreviated as DDI), and the like.

  Examples of the aliphatic diisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene. Examples thereof include diisocyanate (hereinafter abbreviated as HDI), pentamethylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capate and the like.

  Further, as the polyisocyanate, a polymer of the above-mentioned polyisocyanate (for example, dimer, trimer, etc.), for example, a biuret modified product produced by reaction of the above-described polyisocyanate or multimer with water, Allophanate modified product produced by reaction with alcohol or low molecular weight polyol (described later), oxadiazine trione modified product produced by reaction with carbon dioxide gas, or polyol modified product produced by reaction with low molecular weight polyol (described later) Etc.

Polyisocyanates may be used alone or in combination of two or more, and preferably include MDI, TDI, XDI, H ₁₂ MDI, IPDI, H ₆ XDI, HDI, NBDI, or a mixture thereof.
In the present invention, the active hydrogen group-containing compound is an organic compound having a plurality (two or more) active hydrogen groups. The active hydrogen group is an active hydrogen group that reacts with an isocyanate, and examples thereof include a hydroxyl group and an amino group.

Examples of the active hydrogen group-containing compound include polyol. The polyol is an organic compound having two or more hydroxyl groups, and examples thereof include a low molecular weight polyol and a macropolyol.
Examples of the low molecular weight polyol include organic compounds having two or more hydroxyl groups and a number average molecular weight of 60 or more and less than 600, such as low molecular weight diols, low molecular weight triols, and low molecular weight polyols having four or more hydroxyl groups.

  Examples of the low molecular weight diol include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 3-methyl- 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, neopentyl glycol (hereinafter abbreviated as NPG), 1,6-hexanediol, 2,2-diethyl-1,3-propane C2-22 alkanediols such as diol, 3,3-dimethylolheptane, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,18-octadecanediol, for example 2- Butene-1,4-diol, 2,6-dimethyl-1-octene-3,8-dio Aliphatic diols such as alkene diols such as Le, and the like. Examples of the low molecular weight diol include alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, dimer diol, hydrogenated bisphenol A or a C2-4 alkylene oxide adduct thereof. . Examples of the low molecular weight diol include aromatics such as resorcin, xylylene glycol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, bisphenol A, bisphenol S, bisphenol F, and C2-4 alkylene oxide adducts of the above bisphenols. Diols are mentioned. Examples of the low molecular weight diol include ether diols such as diethylene glycol, triethylene glycol, and dipropylene glycol.

  Examples of the low molecular weight triol include glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, and trimethylolethane. , Trimethylolpropane, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3- (hydroxymethyl) pentane, 2,2-bis (hydroxymethyl) -3-butanol and others And aliphatic triols (8 to 24 carbon atoms).

Examples of the low molecular weight polyol having 4 or more hydroxyl groups include tetramethylolmethane, pentaerythritol, dipentaerythritol, D-sorbitol, xylitol, D-mannitol, D-mannitol and the like.
Examples of the macropolyol include polyester polyol, polyether polyol, polycarbonate polyol, acrylic polyol, epoxy polyol, natural oil polyol, silicone polyol, fluorine polyol, and polyolefin polyol.

  The polyether polyol is a polyalkylene oxide, for example, polyethylene glycol, polypropylene glycol obtained by addition reaction of an alkylene oxide such as ethylene oxide and / or propylene oxide using the above low molecular weight polyol as an initiator. Polyethylene polypropylene glycol (random or block copolymer). Examples thereof include polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.

As the polyester polyol, for example, a condensation reaction between a polyhydric alcohol selected from one or more of the above-described low molecular weight polyols, a polybasic acid, an alkyl ester thereof, an acid anhydride thereof, and an acid halide thereof. Or the polyester polyol obtained by transesterification is mentioned.
Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-methyl-3-ethylglutaric acid. , Azelaic acid, sebacic acid, other aliphatic dicarboxylic acids (11 to 13 carbon atoms), hydrogenated dimer acid, maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, dimer acid And het acid.

Examples of the alkyl ester of polybasic acid include methyl ester and ethyl ester of polybasic acid described above.
Examples of the acid anhydride include acid anhydrides derived from the above-mentioned polybasic acids. For example, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl anhydride (carbon number 12-18) ) Succinic acid, tetrahydrophthalic anhydride, trimellitic anhydride and the like.

Examples of the acid halide include acid halides derived from the polybasic acids described above, and examples include oxalic acid dichloride, adipic acid dichloride, and sebacic acid dichloride.
Polyester polyols include, for example, polycaprolactone polyols and polyvalerolactone polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone, for example, using the above-described low molecular weight polyol as an initiator. And polyester polyols.

  Examples of the polycarbonate polyol include polycarbonate polyols obtained by using the above-described low molecular weight polyol as an initiator and carbonates such as ethylene carbonate and dimethyl carbonate. The polycarbonate polyol includes an amorphous polycarbonate diol composed of a copolymer of 1,5-pentanediol and 1,6-hexanediol, and a copolymer of 1,4-butanediol and 1,6-hexanediol. An amorphous polycarbonate diol composed of amorphous polycarbonate diol and 3-methyl-1,5-pentanediol.

Examples of the acrylic polyol include a copolymer obtained by copolymerizing a polymerizable monomer having one or more hydroxyl groups and another monomer copolymerizable therewith.
Examples of the polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, and polyhydroxy. Examples thereof include alkyl maleates and polyhydroxyalkyl fumarate.

  Moreover, as another monomer copolymerizable therewith, for example, (meth) acrylic acid, alkyl (meth) acrylate (C1-12), maleic acid, alkyl maleate, fumaric acid, fumaric acid Alkyl, itaconic acid, alkyl itaconate, styrene, α-methylstyrene, vinyl acetate, (meth) acrylonitrile, 3- (2-isocyanato-2-propyl) -α-methylstyrene, trimethylolpropane tri (meth) acrylate, Examples include pentaerythritol tetra (meth) acrylate.

The acrylic polyol can be obtained by copolymerizing these monomers in the presence of an appropriate solvent and a polymerization initiator.
Examples of the epoxy polyol include an epoxy polyol obtained by reacting the above-described low molecular weight polyol with a polyfunctional halohydrin such as epichlorohydrin or β-methylepichlorohydrin.

Examples of the natural oil polyol include hydroxyl group-containing natural oils such as castor oil and coconut oil.
As the silicone polyol, for example, in the copolymerization of the acrylic polyol described above, a vinyl group-containing silicone compound such as γ-methacryloxypropyltrimethoxysilane is used as another copolymerizable monomer. Examples include coalesced and terminal alcohol-modified polydimethylsiloxane.

As the fluorine polyol, for example, in the copolymerization of the above-mentioned acrylic polyol, a copolymer containing a vinyl group-containing fluorine compound, for example, tetrafluoroethylene, chlorotrifluoroethylene, etc., as another copolymerizable monomer Etc.
Examples of the polyolefin polyol include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer.

The macropolyol has a number average molecular weight of, for example, 300 to 10000, preferably 600 to 5000, and a hydroxyl group equivalent of, for example, 100 to 5000, preferably 160 to 2500.
Polyols may be used alone or in combination of two or more. Preferably, a low molecular weight polyol and a macropolyol are used in combination.

In the present invention, a side chain of a nonionic group is introduced into at least one of the polyisocyanate and the active hydrogen group-containing compound.
The nonionic group is a group having an affinity for water, and examples thereof include a polyoxyethylene group.
In order to introduce a nonionic group side chain into a polyisocyanate, for example, a nonionic group-containing polyisocyanate containing two or more isocyanate groups and having a polyoxyethylene group in the side chain (hereinafter referred to as polyoxyethylene side chain containing). Synthesized polyisocyanate).

  In order to synthesize polyoxyethylene side chain-containing polyisocyanate, the following method is exemplified. That is, first, the above-mentioned diisocyanate and one-end-capped polyoxyethylene glycol (polyoxyethylene glycol in which one-end hydroxyl group is sealed with a C1-20 alkyl group) are combined with the hydroxyl group of one-end-capped polyoxyethylene glycol. Then, the polyisocyanate-containing monoisocyanate is obtained by urethanating the diisocyanate at an excess ratio of the isocyanate group and removing the unreacted diisocyanate if necessary. Next, polyoxyethylene side chain-containing polyisocyanate is obtained by subjecting polyoxyethylene chain-containing monoisocyanate and diisocyanate to an allophanatization reaction.

In order to obtain polyoxyethylene side chain-containing polyisocyanate, the diisocyanate is preferably an aliphatic diisocyanate such as HDI, H ₆ XDI, IPDI, H ₁₂ MDI, and NBDI. More preferably, HDI is mentioned.
In order to introduce a side chain of a nonionic group into an active hydrogen group-containing compound, in the synthesis step, for example, as an active hydrogen group-containing compound, an activity having a nonionic group in the side chain alone or together with the above-described polyol. A hydrogen group-containing compound (that is, an active hydrogen group-containing compound having a nonionic group introduced in the side chain) is blended.

  The active hydrogen group-containing compound having a nonionic group in the side chain preferably has a nonionic group in the side chain and has a solid and / or viscosity of 5 Pa · s or more at 40 ° C., preferably 5 to 1000 Pa · s. Active hydrogen group-containing compounds, for example, polyoxyethylene group-containing compounds. The polyoxyethylene group-containing compound is an organic compound containing a polyoxyethylene group in the side chain and having two or more active hydrogen groups.

As a polyoxyethylene group containing compound, a polyoxyethylene side chain containing polyol is mentioned, for example.
The polyoxyethylene side chain-containing polyol is an organic compound having a polyoxyethylene group in the side chain and having two or more active hydrogen groups, and can be synthesized as follows.
That is, first, the above-mentioned diisocyanate and one-end-capped polyoxyethylene glycol (for example, number average molecular weight 200 to 6000, preferably 300 to 3000) are used as the isocyanate of the diisocyanate with respect to the hydroxyl group of the one-end-capped polyoxyethylene glycol. A polyoxyethylene chain-containing monoisocyanate is obtained by urethanation reaction in an excess ratio of groups and removing unreacted diisocyanate if necessary.

Next, polyoxyethylene chain-containing monoisocyanate and dialkanolamine (for example, diethanolamine) are approximately equal in amount of the isocyanate group of polyoxyethylene group-containing monoisocyanate with respect to the secondary amino group of dialkanolamine. The urea reaction is carried out at a rate of
In order to obtain a polyoxyethylene side chain-containing polyol, the diisocyanate is preferably an aliphatic diisocyanate such as HDI, H ₆ XDI, IPDI, H ₁₂ MDI, NBDI. More preferably, HDI is mentioned.

  In addition, when a polyoxyethylene group-containing compound is blended, an aqueous solution of a polyoxyethylene group introduced into a side chain from the viewpoint of improving emulsification / solubility and maintaining the water resistance of a film obtained from an aqueous polyurethane resin. The mass% with respect to the polyurethane resin (solid content) is, for example, 0.9 mass% or more, preferably 0.9 to 30 mass%, more preferably 2 to 20 mass%, still more preferably 2 to 10 mass%. Adjust to be within the range.

The nonionic group may be introduced only into (all or part of) the polyisocyanate, or may be introduced only into (all or part of) the active hydrogen group-containing compound. It can also be introduced into both of the active hydrogen group-containing compounds, and is appropriately selected from its purpose and use.
In the synthesis step, the polyisocyanate and the active hydrogen group-containing compound have an equivalent ratio of the isocyanate group of the polyisocyanate to the active hydrogen group of the active hydrogen group-containing compound (isocyanate group / active hydrogen group) of 1.2 to The reaction is conducted in the range of 4, preferably in the range of 1.2 to 3, more preferably in the range of 1.25 to 2.

When the equivalent ratio (isocyanate group / active hydrogen group) is lower than the lower limit of the above range, the viscosity of the nonionic group-containing prepolymer becomes excessively high and emulsification / dissolution becomes difficult. Moreover, when higher than the upper limit of the said range, foaming or gelation will arise in a chain | stretch elongation process.
In this reaction, the concentration of the nonionic group introduced into the side chain of the obtained nonionic group-containing prepolymer is 0.9 mass% or more, preferably 0.9 to 30 mass%, more preferably, The blending ratio of the polyisocyanate and the active hydrogen group-containing compound is adjusted so as to be in the range of 2 to 20 mass%, more preferably 2 to 10 mass%. If the nonionic group concentration of the nonionic group-containing prepolymer is in the above range, it can be emulsified / dissolved well, and further, a fine aqueous polyurethane resin excellent in storage stability can be obtained.

In addition, the density | concentration of the nonionic group introduce | transduced into the side chain of a nonionic group containing prepolymer can be calculated | required by following formula (1).
Nonionic group concentration (mass%) introduced into the side chain = 100 × (charge amount of polyisocyanate and active hydrogen group-containing compound into which the nonionic group is introduced into the side chain (parts by mass)) / [(side chain Charged amount of polyisocyanate and active hydrogen group-containing compound into which nonionic groups are not introduced (mass part)) + (charged amount of polyisocyanate and active hydrogen group-containing compound in which nonionic groups are introduced into the side chain (mass) Part))] (1)
In addition, this reaction is carried out in the presence of an inert gas at a reaction temperature, for example, 50 to 130 ° C., until a predetermined isocyanate group content is reached, for example, for a reaction time, for example, 0.5 minutes to 24 hours. Mix.

In this reaction, when the polyisocyanate is TMXDI or the like and the reactivity with the hydrophilic group is poor, the reaction time is adjusted to, for example, 80 to 130 ° C.
In this reaction, for example, a known urethanization catalyst such as an amine-based, tin-based, or lead-based catalyst can be added as necessary.
Further, in this reaction, the stirring and mixing device for stirring and mixing is not particularly limited as long as the nonionic group-containing prepolymer having high viscosity can be uniformly stirred and mixed, but for example, a planetary type equipped with a planetary moving blade. Examples include a stirring device, a 2 to 4 shaft type stirring device including an anchor blade and a disper blade, various kneaders, a twin screw extruder, and a mill. From the viewpoint of mixing efficiency at the time of synthesizing the nonionic group-containing prepolymer, a planetary type stirring device and a 2 to 4 shaft type stirring device are preferable. In addition, in order to pressure-feed the obtained nonionic group containing prepolymer, press apparatuses, such as a ram press, can also be attached.

  In the nonionic group-containing prepolymer obtained by the above reaction, the isocyanate group content is, for example, 0.1 to 20% by mass, preferably 0.5 to 10% by mass. The nonionic group concentration is as described above. Specifically, the content of the nonionic group introduced into the side chain is 0.9 mass% or more, preferably 0.9 to 30 mass. %, More preferably 2 to 20% by mass. Moreover, the number average molecular weight by GPC measurement obtained by using standard polystyrene as a calibration curve is, for example, 1000 to 50000, preferably 1500 to 20000.

  In addition, as described above, the nonionic group-containing prepolymer contains substantially no organic solvent because it reacts with stirring and mixing the polyisocyanate and the active hydrogen group-containing compound directly in the absence of a solvent. Therefore, the viscosity (40 ° C.) is relatively high, for example, 10 to 2000 Pa · s, preferably 15 to 1800 Pa · s, and more preferably 20 to 1500 Pa · s.

In the method for producing an aqueous polyurethane resin of the present invention, in the emulsification step, the nonionic group-containing prepolymer and water are then mixed and stirred, and the nonionic group-containing prepolymer is emulsified with water, whereby the nonionic group-containing prepolymer is mixed. A polymer emulsion is obtained.
In the emulsification step, for example, a nonionic group-containing prepolymer whose temperature is adjusted to 20 to 65 ° C., preferably 20 to 55 ° C., more preferably 20 to 50 ° C., for example, 5 to 40 ° C., preferably The water whose temperature is adjusted to 5 to 30 ° C. is stirred and mixed with a vibration type stirring device.

Water is not particularly limited, and for example, distilled water or ion exchange water is used. In addition, a chain extender (after-mentioned) can also be contained in water as needed.
If the temperature of the nonionic group-containing prepolymer is lower than the lower limit of the above range, the nonionic group-containing prepolymer that is insufficiently emulsified adheres and deposits in the vibration type stirring device. Moreover, in the obtained water-based urethane resin, the nonionic group containing prepolymer with insufficient emulsification is mixed, which causes a deterioration in quality. On the other hand, if it is higher than the upper limit of the above range, the nonionic group-containing prepolymer and water react in the vibration stirrer, and a hard urethane resin is generated and adhered and deposited in the vibration stirrer. . Moreover, hard urethane resin is also mixed in the obtained water-based urethane resin, the particle diameter increases with time, and the storage stability decreases.

  Similarly, when the temperature of water is lower than the lower limit of the above range, a nonionic group-containing prepolymer with insufficient emulsification adheres and deposits in the vibration type stirring apparatus. Moreover, in the obtained water-based urethane resin, the nonionic group containing prepolymer with insufficient emulsification will be mixed, resulting in quality deterioration. On the other hand, if it is higher than the upper limit of the above range, the nonionic group-containing prepolymer and water react in the vibration agitator, and a hard urethane resin is generated and adheres and accumulates in the vibration agitator. . Moreover, hard urethane resin is also mixed in the obtained water-based urethane resin, the particle diameter increases with time, and the storage stability decreases.

  The temperature of the nonionic group-containing prepolymer is adjusted by, for example, an external temperature controller connected to an adjustment kettle with a jacket for supplying the nonionic group-containing prepolymer to the vibration type stirring device, for example, a constant temperature circulation device. The temperature of the water is adjusted by, for example, an external temperature controller connected to a jacketed water tank for supplying water to the vibration type stirring device, for example, a low temperature constant temperature water tank.

  For example, as shown in FIG. 1, the vibration type agitator is provided in the casing 21 in which the mixing object flows and the casing 21, and is arranged along the longitudinal direction (axial direction) of the casing 21. And a stirring blade 23 spirally provided along the axial direction around the rotation shaft 22, and in the casing 21, the spiral stirring blade 23 is vibrated in the axial direction. This is a continuous vibration type stirring and mixing device that continuously mixes and mixes the objects to be mixed. As a vibration type stirring apparatus, a Vibro mixer (made by a refrigeration industry company) is mentioned, for example.

In the vibration type stirring device, the number of stages of the element part (number of units of the stirring blade 23) is 2 to 8, preferably 4 to 7, and the frequency of the element part is 10 to 35 strokes / Sec, preferably Set to 20 to 35 strokes / Sec. The emulsification time (liquid passing time) is, for example, 0.1 to 10 minutes, preferably 0.1 to 3 minutes.
In the vibration type agitator, if the water supply position is arranged on the upstream side in the supply direction with respect to the supply position of the nonionic group-containing prepolymer, the water is supplied in the vibration type agitator. Since the nonionic group-containing prepolymer can be supplied, it is possible to further prevent the nonionic group-containing prepolymer from adhering and depositing in the vibration type stirring device.

  The nonionic group-containing prepolymer and water are quantitatively supplied to the vibration type stirring device. In order to quantitatively supply the nonionic group-containing prepolymer from the stirring and mixing apparatus to the vibration type stirring apparatus, a liquid feed pump is used, although not particularly limited. The liquid feed pump only needs to be able to quantitatively supply a high-viscosity nonionic group-containing prepolymer, and examples thereof include a Mono pump, a gear pump, a rotor pump, and a piston type linear pump, which are rotary volume type uniaxial eccentric screw pumps. Preferably, a Mono pump, a gear pump, and a rotor pump are mentioned.

Moreover, in order to supply water quantitatively, for example, a liquid feed pump such as a diaphragm pump, a gear pump, a rotor pump, a plunger pump, a spiral pump, a turbine pump, or a linear pump is used. From the viewpoint of quantitative accuracy, a diaphragm pump, a gear pump, a rotor pump, and a plunger pump are preferably used.
The feed rate of the nonionic group-containing prepolymer and the feed rate of water are such that the dispersion concentration of the nonionic group-containing prepolymer during emulsification is, for example, 9 to 80% by mass, preferably 20 to 70% by mass. If it can adjust, it will not restrict | limit in particular, According to an apparatus scale, it selects suitably.

  Thereby, the dispersion concentration of the nonionic group-containing prepolymer at the time of emulsification is adjusted to, for example, 9 to 80% by mass, preferably 20 to 70% by mass. When the dispersion concentration is lower than the lower limit of the above range, the concentration of the obtained aqueous polyurethane resin becomes excessively low, and it may be necessary to further increase the concentration depending on the application. On the other hand, when the dispersion concentration is higher than the upper limit of the above range, the viscosity of the emulsion of the nonionic group-containing prepolymer becomes excessively high, and aggregation or gelation may occur when the chain extender is added.

As a result, the nonionic group-containing prepolymer is emulsified with water in a vibration type stirring apparatus, and an emulsion of the nonionic group-containing prepolymer is prepared.
The viscosity (25 ° C.) of the emulsion is, for example, 0.01 to 10 Pa · s, preferably 0.02 to 5 Pa · s.
In addition, the above-mentioned emulsification process may be replaced with the melt | dissolution process from which the aqueous solution of aqueous polyurethane resin is obtained.

  More specifically, for example, when a hydrophilic active hydrogen group-containing compound (for example, polyethylene glycol) is used as the active hydrogen group-containing compound in the synthesis step described above, a nonionic group-containing prepolymer and water are used. Are mixed and stirred, the nonionic group-containing prepolymer may be dissolved in water without forming particles, and an aqueous solution of the nonionic group-containing prepolymer may be obtained.

In such a case, the above-described emulsification step of the nonionic group-containing prepolymer is replaced with a dissolution step of the nonionic group-containing prepolymer.
And in the manufacturing method of the aqueous | water-based polyurethane resin of this invention, a nonionic group containing prepolymer and chain extender are made to carry out chain | strand extension reaction in a chain | stretch extension process, and an aqueous | water-based polyurethane resin is obtained.

Examples of chain extenders include polyamines and amino alcohols.
Polyamines include, for example, aromatic polyamines such as 4,4′-diphenylmethanediamine, araliphatic polyamines such as 1,3- or 1,4-xylylenediamine or mixtures thereof, such as 3-aminomethyl- 3,5,5-trimethylcyclohexylamine (common name: isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane, Alicyclic polyamines such as 1,3-bis (aminomethyl) cyclohexane and 1,4-cyclohexanediamine, such as ethylenediamine (EDA), 1,3-propanediamine, 1,4-butanediamine, 1,6-hexa Methylenediamine, hydrazine (including hydrate), diethylenetriamine, triethylene Toramin, and aliphatic polyamines such as tetraethylene pentamine and the like.

  Examples of polyamines include primary amino groups, alkoxysilyl compounds having primary amino groups and secondary amino groups, and polyoxyethylene group-containing polyamines. More specifically, as an alkoxysilyl compound having a primary amino group or a primary amino group and a secondary amino group, for example, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyl Examples include alkoxysilyl group-containing monoamines such as trimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane.

Examples of the polyoxyethylene group-containing polyamine include polyoxyalkylene ether diamines such as polyoxyethylene ether diamine. More specifically, for example, PEG # 1000 diamine of Japanese fats and oils, Jeffamine ED-2003, EDR-148, XTJ-512 of Huntsman, etc. are mentioned.
Examples of amino alcohols include monoalkanol (mono) amines such as monomethanolamine (2-aminomethanol) and monoethanolamine (2-aminoethanol) (MEA), and N- (2-aminoethyl) ethanolamine. Etc.

These chain extenders can be used alone or in combination of two or more.
The chain extender is preferably a combination of a polyamine and an amino alcohol, and more preferably a combination of an aliphatic polyamine and a monoalkanol (mono) amine.
When an aliphatic polyamine and a monoalkanol (mono) amine are used in combination as a chain extender, the equivalent ratio of the amino group in the monoalkanol (mono) amine to the amino group in the aliphatic polyamine (monoalkanol) in (mono) amine NH ₂ / aliphatic polyamine in NH _2, for example, 0.01 to 1, preferably such that the proportion of 0.05 to 0.5 are blended.

When an aliphatic polyamine and a monoalkanol (mono) amine are used in combination as a chain extender, they can be mixed in advance or used separately. In addition, when preparing and using an aliphatic polyamine and monoalkanol (mono) amine separately, multiple chain extension agent tanks mentioned later are installed (addition).
The chain extender has an equivalent ratio (active hydrogen group / isocyanate group) of the active hydrogen group (amino group and hydroxyl group) of the chain extender to the isocyanate group of the nonionic group-containing prepolymer, for example, 0.8 to 1. .2, preferably 0.85 to 1.1, more preferably 0.9 to 1.

The chain extension reaction is not particularly limited as long as a chain extender can be added to the emulsion (aqueous solution) prepared above, but preferably the emulsion (aqueous solution) and the chain extender are mixed into a continuous mixing device. Pump and react.
Examples of the continuous mixing device include a vibration type stirring device, a static mixer, and an in-line mixer.

Examples of the vibration type stirring device include the above-described Vibro mixer (manufactured by Chilling Industries Co., Ltd.).
Examples of the static mixer include a static mixer (manufactured by Noritake Company Limited), Mr. Mix (manufactured by Fujikin), Mr. Disperse (manufactured by Fujikin) and the like.
Examples of in-line mixers include T.I. K. Pipeline homomixer (Primix), T. K. Examples include Fillmix (manufactured by Primics), Milder (manufactured by Taiheiyo Kiko), pipeline mixer (manufactured by Mizuho Kogyo Co., Ltd.) and the like.

Each of these continuous mixing apparatuses can be used as a single apparatus structure or as an apparatus structure appropriately combined.
In the continuous mixing apparatus, the supply rate of the emulsion (aqueous solution) and the supply rate of the chain extender are not particularly limited as long as the equivalent ratio of the nonionic group-containing prepolymer and the chain extender is the above ratio. It is appropriately selected according to the scale. The reaction temperature is set to 0 to 40 ° C., preferably 10 to 35 ° C., and the liquid passing time is set to 0.1 to 10 minutes, preferably 0.1 to 2 minutes.

  The emulsified liquid (aqueous solution) and the chain extender can be fed to the continuous mixer at the above-described supply speed by the above-described liquid feed pump. In this case, both the emulsion liquid (aqueous solution) supply line and the chain extender supply line may be directly connected to the upstream side of the continuous mixing apparatus, or one of them may be directly connected to the upstream side of the continuous mixing apparatus. It is also possible to connect the other and connect the other to the middle of the continuous mixing device in the liquid passing direction. Furthermore, a T-type line is connected to the upstream side of the continuous mixer, and an emulsion (aqueous solution) supply line, a chain extender supply line, and a supply line to the continuous mixer are connected to the T-type line. It can also be connected.

As a result, the nonionic group-containing prepolymer and the chain extender undergo a chain extension reaction to produce an aqueous polyurethane resin. When the aqueous polyurethane resin is produced in an emulsion, it is prepared as an aqueous dispersion that is dispersed in water. When the aqueous polyurethane resin is produced in an aqueous solution of a nonionic group-containing prepolymer, the aqueous polyurethane resin is prepared as an aqueous polyurethane resin aqueous solution. Prepared.
The solid concentration of the prepared aqueous dispersion (aqueous solution) is usually adjusted to, for example, 9 to 80% by mass, and preferably 20 to 70% by mass.

  In the prepared aqueous polyurethane resin, the nonionic group concentration introduced into the side chain per solid content is such that the content of the nonionic group introduced into the side chain is, for example, 0.9 mass as described above. % Or more, preferably 0.9 to 30% by mass, more preferably 2 to 20% by mass, and still more preferably 2 to 10% by mass. Moreover, the number average molecular weight by GPC measurement obtained by using standard polystyrene as a calibration curve is, for example, 2000 to 200000, preferably 3000 to 150,000.

  In addition, as described above, the aqueous polyurethane resin is obtained by directly stirring and mixing the polyisocyanate and the active hydrogen group-containing compound in the absence of a solvent to obtain a nonionic group-containing prepolymer. Specifically, by reacting the group-containing prepolymer with the chain extender, the content of the organic solvent per aqueous dispersion (aqueous solution) is, as a mass standard, substantially free of organic solvent. For example, it is prepared to be 100 ppm or less, preferably 50 ppm or less, and more preferably 10 ppm or less.

  Furthermore, the average particle diameter of the aqueous polyurethane resin in the dispersion is, for example, 2 to 700 nm, preferably 5 to 500 nm. When the average particle size is smaller than the lower limit of the above range, the viscosity of the aqueous polyurethane resin may be increased. On the other hand, when the average particle size is larger than the upper limit of the above range, the storage stability may be lowered, for example, precipitation occurs. And if the average particle diameter of water-based polyurethane resin is the said range (average particle diameter of a nanometer order), a thin and uniform coating film can be obtained.

  And according to the manufacturing method of the above-mentioned water-based urethane resin, since an organic solvent is not used, a desolvation process is unnecessary, it is excellent in the ease of operation and economical efficiency, and productivity can be improved. Further, even when the viscosity of the nonionic group-containing prepolymer at the time of emulsification / dissolution is relatively high, it can be well emulsified / dispersed without blending an emulsifier and the like, and a vibration type stirring device It is possible to continuously emulsify and disperse / dissolve the nonionic group-containing prepolymer without adhering and volume. Furthermore, it can be emulsified and dispersed / dissolved at a relatively low temperature without melt kneading.

  Therefore, the obtained aqueous polyurethane resin is environmentally friendly, that is, it can eliminate problems such as environmental pollution, safety, and odor caused by a small amount of organic solvent. In addition, since the obtained water-based polyurethane resin is fine and uniformly emulsified / dissolved without causing precipitation / separation, it has excellent storage stability, and further improves water resistance and mechanical strength. You can plan.

  In particular, when an active hydrogen group-containing compound having a nonionic group and having a nonionic group and having a solid and / or viscosity of 5 Pa · s or higher is used as the active hydrogen group-containing compound having a nonionic group, Since the active hydrogen group-containing compound has low solubility in polyol, the viscosity of the nonionic group-containing prepolymer becomes extremely high when an organic solvent is not used (for example, the viscosity at 40 ° C. is 10 to 2000 Pa · s). ). For this reason, the nonionic group-containing prepolymer cannot be synthesized by a normal method, and even if it can, it is emulsified / dissolved as non-uniform particles having a large average particle size.

However, according to the above method, even when a solid and / or an active hydrogen group-containing compound having a viscosity of 5 Pa · s or higher is used at 40 ° C., as described above, it is fine and uniform without causing precipitation / separation. Can be emulsified / dissolved.
Therefore, the obtained water-based polyurethane resin can form a coating film (film) that adheres satisfactorily when it is applied to an adherend (object to be coated). Therefore, it can be effectively used in various fields such as paints, adhesives, binders or coating agents.

In addition, when producing a film, aqueous polyurethane resin is apply | coated on a base material using an applicator etc., and is dried.
In addition, the aqueous urethane resin or aqueous dispersion / aqueous solution of the present invention includes, for example, an antifoaming agent, a leveling agent, a filler, a pigment, a dye, a silicon compound, a rosin, and a silane depending on the purpose and application. Various additives such as a coupling agent, an antioxidant, an ultraviolet absorber, a colorant, a whitening agent, a thickening agent, and a stabilizer can be appropriately added.

Next, although this invention is demonstrated based on a synthesis example, an Example, and a comparative example, this invention is not limited by the following Example. In the following description, “part” and “%” are based on mass unless otherwise specified. In addition, manufacturing apparatuses, analysis methods, and measurement methods used in Examples and the like are shown below.
(Manufacturing equipment)
The apparatus shown in FIG. 1 was adopted. In FIG. 1, a planetary mixer 1 (equipped with a thermometer, a nitrogen introduction tube, a planetary stirring blade, PLM-15, manufactured by Inoue Seisakusho), and a ram press 2 (PH-15, manufactured by Inoue Seisakusho) In addition, a MONO pump 3 (3NELS10PL type Heisin MONO pump, manufactured by Hyojin Equipment Co., Ltd.) was connected to the downstream side of the ram press 2 (“downstream side” or “upstream side” is based on the liquid feeding direction). On the other hand, a plunger pump 5 (double plunger pump, manufactured by Nippon Seimitsu Kagaku) was connected to the downstream side of the water tank 4. The downstream side of the Mono pump 3 and the downstream side of the plunger pump 5 were connected to the upstream side (lower part) of the Vibro mixer 6 (the housing inner diameter of the vibration element was 35 mmφ, the number of elements was 6 stages, manufactured by Kyo Kogyo Co., Ltd.).

On the upstream side of the vibro mixer 6, they were connected to the connection position of the Mono pump 3 so that the connection position of the plunger pump 5 was on the upstream side (lower part).
A vessel 7 with a stirrer (equipped with a nitrogen introduction pipe, with an extraction opening opened at the bottom) is connected to the downstream side (top) of the vibro mixer 6, and a plunger pump is connected to the downstream side of the vessel 7 with a stirrer 8 (double plunger pump, manufactured by Japan Precision Science Co., Ltd.) was connected. On the other hand, a plunger pump 10 (double plunger pump, manufactured by Japan Precision Science Co., Ltd.) was connected to the downstream side of the chain extender tank 9. The downstream side of the plunger pump 8 and the downstream side of the plunger pump 10 were connected to the upstream side of the injection T line 11.

The downstream side of the injection T line 11 was connected to the upstream side of the static mixer 12 (T4-21R-S type, manufactured by Noritake Co.), and the container 13 with a stirrer was connected to the downstream side of the static mixer 12.
(Isocyanate group content (NCO%))
The isocyanate group content (% by mass) of the nonionic group-containing prepolymer was measured by a back titration method using hydrochloric acid of dibutylamine (based on JIS K 1556: polyurethane raw material-toluene diisocyanate test method (Appendix 1)).
(With or without sedimentation / separation)
The aqueous polyurethane resin was taken in a sample bottle and left in a constant temperature and humidity room at 23 ° C. and 55% RH, and after one month, it was visually determined whether or not a sediment / separate was observed at the bottom of the sample bottle.

“Yes” indicates that sedimentation / separation was confirmed, and “No” indicates that sedimentation was not confirmed.
(Internal or non-contaminated equipment)
After carrying out the continuous emulsification / dissolution test for 2 hours, the vibration type stirring device was disassembled, and the contamination of the element part (stirring blade) was visually confirmed. The evaluation criteria are shown below.
×: Nonionic group-containing prepolymer is not emulsified / dissolved, and is adhered and deposited in the element ×: Hard urethane resin in which water and the nonionic group-containing prepolymer reacted is adhered and deposited on the element State Δ: Adhered matter can be confirmed, but the amount is not so large as to obstruct the flow of the emulsion liquid. ○: There is almost no adhering material. Raw material production example 1 (synthesis of polyoxyethylene side chain-containing polyol (PEGOH-1)) )
In a reactor equipped with a thermometer, a nitrogen gas inlet tube and a stirrer, 627.1 parts of hexamethylene diisocyanate (trade name: Takenate 700, HDI, manufactured by Mitsui Chemicals Polyurethanes), number average molecular weight 1000 heated to 50 ° C. Of methoxypolyethylene glycol (trade name: methoxy PEG-1000, manufactured by Toho Chemical Industry Co., Ltd.) was charged, and the mixture was reacted at 80 ° C. for 6 hours while introducing nitrogen gas. After reaching a predetermined isocyanate group content, unreacted hexamethylene diisocyanate was removed with a Smith type thin film distiller to obtain polyoxyethylene chain-containing monoisocyanate (PEGNCO-1).

  Next, 99.2 parts of diethanolamine was charged at room temperature in a reactor equipped with a thermometer, a nitrogen gas inlet tube and a stirrer. While introducing nitrogen gas and cooling, 900.8 parts of polyoxyethylene chain-containing monoisocyanate (PEGNCO-1) was added and reacted at 60 ° C. for 3 hours. Formation of urea bonds was confirmed by infrared absorption spectrum, and a polyoxyethylene side chain-containing polyol (PEGOH-1) was obtained. The calculated number average molecular weight of this polyoxyethylene side chain-containing polyol (PEGOH-1) was 1060.

Synthesis Example 1 (Synthesis Step: Synthesis of Nonionic Group-Containing Prepolymer (A))
1,3-bis (isocyanatomethyl) cyclohexane (trade name: Takenate 600, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) 657.7 parts, polyethylene glycol (PEG 1000) (trade name: Toho Polyethylene Glycol 1000, manufactured by Toho Chemical Industries, Ltd., hydroxyl group (Value: 118.1 mgKOH / g) 1915.0 parts and polyoxyethylene side chain-containing polyol (PEGOH-1) 427.4 parts were charged into planetary mixer 1 and heated to 75 ° C. in a nitrogen atmosphere. After the temperature rise, stannous octylate (trade name: Stanocto, manufactured by API Corporation) was added in a small amount, and the reaction was continued at 75 ° C. until a predetermined isocyanate group content (%) was reached. Subsequently, it cooled to 30 degreeC and the nonionic group containing prepolymer (A) was obtained.

The details of the synthesis conditions and the properties of the nonionic group-containing prepolymer (A) are shown in Table 1.
Synthesis Example 2 (Synthesis Step: Synthesis of Nonionic Group-Containing Prepolymer (B))
A nonionic group-containing prepolymer (B) was obtained in the same manner as in Synthesis Example 1, except that the raw materials shown in Table 1 were used. The details of the synthesis conditions of the obtained nonionic group-containing prepolymer (B) and the properties of the nonionic group-containing prepolymer (B) are shown in Table 1.

Synthesis Example 3 (Synthesis Step: Synthesis of Nonionic Group-Containing Prepolymer (C))
A nonionic group-containing prepolymer (C) was obtained in the same manner as in Synthesis Example 1 except that the raw materials shown in Table 1 were used. The details of the synthesis conditions of the obtained nonionic group-containing prepolymer (C) and the properties of the nonionic group-containing prepolymer (C) are shown in Table 1.
Synthesis Example 4 (Synthesis Step: Synthesis of Nonionic Group-Containing Prepolymer (D))
A nonionic group-containing prepolymer (D) was obtained in the same manner as in Synthesis Example 1, except that the raw materials shown in Table 1 were used. The details of the synthesis conditions of the obtained nonionic group-containing prepolymer (D) and the properties of the nonionic group-containing prepolymer (D) are shown in Table 1.

The nonionic group-containing prepolymer (D) was separated (non-uniformized) at 25 ° C., and the emulsification / dissolution process could not be performed.
Synthesis Example 5 (Synthesis Step: Synthesis of Nonionic Group-Containing Prepolymer (E))
A nonionic group-containing prepolymer (E) was obtained in the same manner as in Synthesis Example 1, except that the raw materials shown in Table 1 were used. The details of the synthesis conditions of the obtained nonionic group-containing prepolymer (E) and the properties of the nonionic group-containing prepolymer (E) are shown in Table 1.

Synthesis Example 6 (Synthesis Step: Synthesis of Nonionic Group-Containing Prepolymer (F))
A nonionic group-containing prepolymer (F) was obtained in the same manner as in Synthesis Example 1 except that the raw materials shown in Table 1 were used. The details of the synthesis conditions of the obtained nonionic group-containing prepolymer (F) and the properties of the nonionic group-containing prepolymer (F) are shown in Table 1.
The nonionic group-containing prepolymer (F) gelled at 25 ° C., and the emulsification / dissolution process could not be performed.

Example 1 (Synthesis of aqueous polyurethane resin (A))
(Emulsification (dispersion) / dissolution process)
The nonionic group-containing prepolymer (A) was moved from the planetary mixer 1 to the ram press 2 together with the container. The ram press 2 applied a hydraulic pressure of 0.4 MPa (gauge pressure), and the nonionic group-containing prepolymer (A) was fed to the MONO pump 3 from the outlet at the bottom of the kettle.

The Mono pump 3 was operated simultaneously with the liquid feeding, and the nonionic group-containing prepolymer (A) at 24 ° C. was quantitatively fed to the lower part of the Vibro mixer 6 at a feeding rate of 112.6 g / min.
On the other hand, before supplying the nonionic group-containing prepolymer (A) to the Vibro mixer 6, distilled water at 24 ° C. was supplied from the water tank 4 at a supply rate of 259.0 g / min by the plunger pump 5. The liquid was quantitatively fed to the lower part of 6 (below the connection position of the Mono pump 3). Vibro mixer 6 internal residence time (emulsification (dispersion) / dissolution time) was 26 seconds. The vibration frequency of the element part of the vibromixer 6 was 30 strokes / second.

The residence time was calculated by the following formula (2), where the specific gravity of the nonionic group-containing prepolymer was 1 (density was 1 (g / ml)). (The volume in the Vibro mixer was 160.8 ml.)
Residence time (seconds) = [160.8 (ml) × 1 (g / ml)] / [(feed rate of nonionic group-containing prepolymer) (g / min) + (water feed rate) (g / min )] X 60 (seconds / minute) (2)
The aqueous solution of the nonionic group-containing prepolymer (A) is continuously discharged from the top of the vibromixer 6 and continuously charged into the container 7 with a stirrer. Removal and concentration uniformity were attempted.

In the obtained aqueous solution, no settling / separation was observed, and the dissolved state was good.
Moreover, although the deposit | attachment with respect to the element part of the vibro mixer 6 after continuous melt | dissolution was confirmed, the deposit | attachment was hardly recognized.
(Chain extension process)
An aqueous solution of a nonionic group-containing prepolymer was fed from the container 7 with a stirrer to the injection T line 11 by a plunger pump 8 at a supply rate of 100.0 g / min.

  On the other hand, 0.83 part of 20% monoethanolamine (MEA, 2-aminoethanol) aqueous solution and 20% ethylenediamine (EDA) at a feed rate of 3.15 g / min. A liquid obtained by mixing 2.32 parts of the aqueous solution was sent to the injection T line 11. Thereafter, a mixed solution of an aqueous solution, a 20% monoethanolamine (MEA, 2-aminoethanol) aqueous solution, and a 20% ethylenediamine (EDA) aqueous solution is fed to the static mixer 12, mixed uniformly, and subjected to chain extension reaction. Thus, an aqueous solution of the aqueous polyurethane resin (A) was obtained.

The obtained aqueous solution was continuously fed to the container 13 with a stirrer, and the chain extension reaction was completed under gentle stirring.
In the obtained aqueous solution, no sedimentation / separation was observed even after 1 month.
Table 2 shows the properties of the aqueous polyurethane resin (A) obtained.
Example 2 (Synthesis of aqueous polyurethane resin (B))
An aqueous polyurethane resin (B) was obtained in the same manner as in Example 1 except that the synthesis was performed under the conditions shown in Table 2. Table 2 shows the details of the synthesis conditions of the obtained aqueous polyurethane resin (B) and the properties of the aqueous polyurethane resin (B).

Example 3 (Synthesis of aqueous polyurethane resin (C))
An aqueous polyurethane resin (C) was obtained under the same conditions as in Example 1 except that the nonionic group-containing prepolymer (B) was used. Table 2 shows details of the synthesis conditions of the obtained aqueous polyurethane resin (C) and the properties of the aqueous polyurethane resin (C).
Example 4 (Synthesis of aqueous polyurethane resin (D))
An aqueous polyurethane resin (D) was obtained under the same conditions as in Example 1 except that the nonionic group-containing prepolymer (C) was used. Table 2 shows the details of the synthesis conditions of the obtained aqueous polyurethane resin (D) and the properties of the aqueous polyurethane resin (D).

Example 5 (Synthesis of aqueous polyurethane resin (E))
An aqueous polyurethane resin (E) was obtained under the same conditions as in Example 1 except that the temperature of the nonionic group-containing prepolymer (A) was 10 ° C. Details of the synthesis conditions of the obtained aqueous polyurethane resin (E) and the properties of the aqueous polyurethane resin (E) are shown in Table 2. A white urethane resin was adhered in the apparatus after dissolution, but the amount was not so large as to hinder the flow of the emulsion.

Example 6 (Synthesis of aqueous polyurethane resin (F))
An aqueous polyurethane resin (F) was obtained under the same conditions as in Example 1 except that the temperature of the nonionic group-containing prepolymer (A) was 70 ° C. Table 3 shows the details of the synthesis conditions of the obtained aqueous polyurethane resin (F) and the properties of the aqueous polyurethane resin (F). A white urethane resin was adhered in the apparatus after dissolution, but the amount was not so large as to hinder the flow of the emulsion.

Example 7 (Synthesis of aqueous polyurethane resin (G))
An aqueous polyurethane resin (G) was obtained under the same conditions as in Example 1 except that the temperature of water was 2 ° C. Details of the synthesis conditions of the obtained aqueous polyurethane resin (G) and the properties of the aqueous polyurethane resin (G) are shown in Table 3. A white urethane resin was adhered in the apparatus after dissolution, but the amount was not so large as to hinder the flow of the emulsion.

Example 8 (Synthesis of aqueous polyurethane resin (H))
An aqueous polyurethane resin (H) was obtained under the same conditions as in Example 1 except that the temperature of water was 60 ° C. Table 3 shows the details of the synthesis conditions of the obtained aqueous polyurethane resin (H) and the properties of the aqueous polyurethane resin (H). A white urethane resin was adhered in the apparatus after dissolution, but the amount was not so large as to hinder the flow of the emulsion.

Comparative Example 1
It melt | dissolved on the conditions similar to Example 2 except the frequency of the element part of the vibro mixer 6 having been 0 stroke / second. Details of the conditions are shown in Table 3. However, immediately after dissolution, the nonionic group-containing prepolymer (A) settled / separated, and an aqueous polyurethane resin could not be obtained.

Comparative Example 2
It melt | dissolved on the conditions similar to Example 1 except having used nonionic group containing prepolymer (E). Details of the conditions are shown in Table 3. However, foaming is observed in the aqueous solution of the nonionic group-containing prepolymer (E) discharged from the vibromixer 6, and clogging occurs in the static mixer 12 when 20% MEA aqueous solution and 20% EDA aqueous solution are continuously added. However, the chain extension reaction could not be continued.

Claims (4)

A method for producing an aqueous polyurethane resin substantially using no organic solvent,
The equivalent ratio of the isocyanate group of the polyisocyanate to the active hydrogen group-containing compound of the active hydrogen group-containing compound, the polyisocyanate having a nonionic side chain introduced into at least one of them and the active hydrogen group-containing compound having a plurality of active hydrogen groups Is synthesized at a ratio of 1.2 to 4 to synthesize a nonionic group-containing prepolymer having a nonionic group concentration of 0.9% by mass or more introduced into the side chain;
It comprises an emulsification / dissolution step of obtaining an emulsion or aqueous solution of a nonionic group-containing prepolymer by stirring the nonionic group-containing prepolymer and water using a vibration type stirring device. A method for producing an aqueous polyurethane resin. The nonionic group-containing prepolymer emulsion or aqueous solution and the chain extender are fed to at least one device selected from the group consisting of a vibration stirrer, a static mixer, and an in-line mixer, and reacted. The method for producing an aqueous polyurethane resin according to claim 1, further comprising a chain extending step.   An aqueous polyurethane resin obtained by the method for producing an aqueous polyurethane resin according to claim 1.   A film obtained from the aqueous polyurethane resin according to claim 3.

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