JP2007070442A - Manufacturing method of powdery thermoplastic polyurethane urea resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a powdery thermoplastic polyurethane urea resin with a readily controllable molecular weight that exhibits excellent melt-molding properties and affords a molded article excellent in mechanical properties, abrasion resistance, crease resistance and the like. <P>SOLUTION: The manufacturing method comprises a step for causing a part of isocyanate groups in an isocyanate group-terminated prepolymer to react with an active hydrogen group in a monofunctional active hydrogen group-containing compound bearing the active hydrogen group and a 4-12C hydrocarbon group while causing the rest of the isocyanate groups in the isocyanate group-terminated prepolymer to react with an active hydrogen group of water in a non-aqueous dispersing medium, where the ratio (x1/x2) of the molar number x1 of the active hydrogen group in the active hydrogen group-containing compound to react with a part of the isocyanate groups to the molar number x2 of the active hydrogen group of water to react with the rest of the isocyanate groups is (5-35)/(95-65). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a powdered thermoplastic polyurethane urea resin suitably used for slush molding or the like.

The slush molding method has a complicated shape and can efficiently form a product having a uniform wall thickness, and is therefore widely used in applications such as automobile interior materials.
Recently, a powdered thermoplastic polyurethane resin excellent in flexibility has been adopted as a slush molding material.

As a method for producing a powder polyurethane resin (polyurethane urea resin) for slush molding, the present applicant can disperse in a non-aqueous dispersion medium. The manufacturing method including the process of making the isocyanate group terminal prepolymer made to react with water and chain-extending is proposed (refer patent document 1).
Patent Document 1 also discloses that a part of the isocyanate group of the isocyanate group-terminated prepolymer is reacted with a low molecular polyol and the like, and then the remainder of the isocyanate group is reacted with water.
JP 2004-161866 A

  However, in the production process of powdered thermoplastic polyurethane urea resin, the isocyanate and water react locally (the urea bond produced by the reaction between isocyanate and water is localized by its strong hydrogen bonding force). In other words, it is said that it has an ultra-high molecular weight in a hardly fusible substance (gel permeation chromatography (hereinafter abbreviated as “GPC”)) having an excessive molecular weight due to the promotion of local urea reaction, etc. There is a problem that a powdered thermoplastic polyurethane urea resin containing such a hardly-fusible substance is extremely inferior in melt moldability.

  In the method of reacting a part of the isocyanate group of the isocyanate group-terminated prepolymer with a low-molecular polyol and the like and then reacting the remainder of the isocyanate group with water, the resin is controlled by controlling the molar ratio of the isocyanate group and the active hydrogen group. There is a problem that it is difficult to control the molecular weight (a molecular weight design method that is frequently used in the past). This is to ensure that a predetermined amount (equivalent to the remainder of the isocyanate group) of the active hydrogen group reacts with the remainder of the isocyanate group by evaporating part of the water during the reaction or subjecting it to a side reaction. It is because it is not possible.

The object of the present invention is a powdered thermoplastic polyurethane urea resin capable of obtaining a molded article having excellent mechanical properties, abrasion resistance and crease resistance, etc., which is easy to control the molecular weight and melted. An object of the present invention is to provide a method capable of reliably producing a powdery thermoplastic polyurethane urea resin excellent in moldability.
Another object of the present invention is to provide a method capable of reliably producing a powdered thermoplastic polyurethane urea resin capable of obtaining a molded article having excellent blooming resistance.
Still another object of the present invention is to provide a method capable of reliably producing a thermoplastic polyurethane urea resin suitable as a powder material for slush molding.

  The production method according to the present invention (the first invention) is a method for producing a powdered thermoplastic polyurethane urea resin, in which a part of the isocyanate group of the isocyanate group-terminated prepolymer is divided into an active hydrogen group and a carbon number. Is reacted with the active hydrogen group of a monofunctional active hydrogen group-containing compound (hereinafter referred to as “specific active hydrogen group-containing compound”) having 4 to 12 hydrocarbon groups, and the isocyanate group-terminated prepolymer. The active hydrogen group possessed by the specific active hydrogen group-containing compound reacting with a part of the isocyanate group, comprising the step of reacting the remainder of the isocyanate group possessed by water with the active hydrogen group possessed by water in a non-aqueous dispersion medium Where x1 is the number of moles and x2 is the number of moles of active hydrogen groups having water which reacts with the remainder of the isocyanate group, the ratio (x1 / x2) Wherein the 5 to 35/95 to 65.

  A production method according to the present invention (second invention) is a method for producing a powdered thermoplastic polyurethane urea resin, which includes the following first to fourth steps, and in the second step, an organic polyisocyanate and The number of moles of active hydrogen groups possessed by the polymer polyol to be reacted is A, and in the third step, the number of moles of active hydrogen groups possessed by the active hydrogen group-containing compound reacting with a part of the isocyanate groups is x1, and the remainder of the isocyanate groups The ratio [(x1 + x2) / A] is 0.3 to 1.5, and the ratio (x1 / x2) is 5 to 35/95 to 65, where x2 is the number of moles of active hydrogen groups in the water to be reacted. It is characterized by being.

First step: A step of preparing a non-aqueous dispersion by dispersing a polymer polyol in an organic solvent that does not substantially dissolve the polymer polyol and the resulting isocyanate group-terminated prepolymer and polyurethane urea resin.
Second step: A step of preparing a dispersion of an isocyanate group-terminated prepolymer by reacting the polymer polyol in the obtained dispersion with an organic polyisocyanate.
Third step: A part of the isocyanate group of the isocyanate group-terminated prepolymer in the obtained dispersion is reacted with the active hydrogen group of the specific active hydrogen group-containing compound, and the isocyanate group-terminated prepolymer has A step of preparing a polyurethane urea resin dispersion by reacting the remaining isocyanate groups with active hydrogen groups in water.
Fourth step: A step of preparing a powdery thermoplastic polyurethane urea resin by separating and drying the polyurethane urea resin from the obtained dispersion.

Further, the ratio [(x1 + x2) / A] is preferably 0.3 to 1.2, and the ratio (x1 / x2) is preferably 5 to 20/95 to 80.
The ratio [(x1 + x2) / A] is preferably 0.75 to 1.5, and the ratio (x1 / x2) is preferably 10 to 35/90 to 65.
Furthermore, it is preferable that the organic polyisocyanate used in the second step is hexamethylene diisocyanate.

(1) By reacting a part of the isocyanate group of the isocyanate group-terminated prepolymer with an active hydrogen group of a specific active hydrogen group-containing compound, the molecular weight can be easily controlled and an excessive molecular weight (for example, Formation of a hardly-fusible substance having a Mn of 500,000 or more in GPC analysis is suppressed. As a result, the melt moldability of the obtained powdered thermoplastic polyurethane urea resin is remarkably improved.
(2) A urea group is introduced into the resulting resin by reacting the remainder of the isocyanate group of the isocyanate group-terminated prepolymer with an active hydrogen group of water, and as a result, a powdered thermoplastic polyurethane urea is obtained. Excellent crease resistance, mechanical properties, and wear resistance are exhibited in a molded article made of resin.
(3) When the carbon number of the hydrocarbon group of the specific active hydrogen group-containing compound is 4 to 12, the molecular weight of the obtained powdered thermoplastic polyurethane urea resin can be reliably controlled, and the powdered thermoplastic A molded article made of polyurethane urea resin has excellent blooming resistance.

The manufacturing method according to the first invention will be described.
<Isocyanate group-terminated prepolymer>
The isocyanate group-terminated prepolymer used in the production method of the present invention can be obtained by reacting a high-molecular polyol with an organic polyisocyanate.

The number average molecular weight of the polymer polyol used for obtaining the isocyanate group-terminated prepolymer is 500 or more, preferably 1,000 to 5,000.
The kind of the polymer polyol is not particularly limited, and examples thereof include polyester polyol, polyester amide polyol, polyether polyol, polyether ester polyol, polycarbonate polyol, polyolefin polyol, and the like. Two or more kinds can be used in combination.

  Examples of the polyester polyol and polyester amide polyol include polycarboxylic acid, polycarboxylic acid derivatives such as polycarboxylic acid, dialkyl esters of polycarboxylic acid, acid anhydrides, and acid halides, low molecular polyols, low molecular weight polyamines having a number average molecular weight of less than 500, It is obtained by a reaction with a low molecular active hydrogen group-containing compound such as a low molecular amino alcohol.

  Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and the like.

  Low molecular polyols include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol (hereinafter 1,4-BD). Abbreviation), 1,5-pentanediol, 1,6-hexanediol (hereinafter abbreviated as 1,6-HD), 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octane Diol, 1,9-nonanediol, 3,3-dimethylolheptane, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-ethyl-1,3-propanediol, 2-normalpropyl- 1,3-propanediol, 2-isopropyl-1,3-propanediol, 2-normalb 1,3-propanediol, 2-isobutyl-1,3-propanediol, 2-tertiarybutyl-1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, 2, 2-diethyl-1,3-propanediol, 2-ethyl-2-normalpropyl-1,3-propanediol, 2-ethyl-2-normalbutyl-1,3-propanediol, 2-ethyl-3-ethyl -1,4-butanediol, 2-methyl-3-ethyl-1,4-butanediol, 2,3-diethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2 , 3,4-triethyl-1,5-pentanediol, trimethylolpropane, dimethylolpropionic acid, dimethylolbutanoic acid, dimer acid diol, Phosphorus, pentaerythritol, alkylene oxide adduct of bisphenol A and the like.

  Examples of the low molecular weight polyamine having a number average molecular weight of less than 500 include ethylenediamine, hexamethylenediamine, xylylenediamine, isophoronediamine, and ethylenetriamine.

Examples of the low molecular amino alcohol having a number average molecular weight of less than 500 include monoethanolamine, diethanolamine, and monopropanolamine.
Also suitable are polyester polyols such as lactone polyester polyols obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone, alkyl-substituted ε-caprolactone, δ-valerolactone, and alkyl-substituted δ-valerolactone. Can be used.

  Examples of the polyether polyol include polyethylene glycol, polypropylene ether polyol, and polytetramethylene ether polyol.

  Examples of polyether ester polyols include polyester polyols produced from the above polyether polyols and the above polycarboxylic acid derivatives.

  Polycarbonate polyols include those obtained by deethanol condensation reaction of low molecular polyol and diethyl carbonate; dephenol condensation reaction of low molecular polyol and diphenyl carbonate; deethylene glycol condensation reaction of low molecular polyol and ethylene carbonate, etc. Can be mentioned. Examples of the low molecular polyol used for obtaining the polycarbonate polyol include low molecular polyols exemplified as those for obtaining the polyester polyol.

  Specific examples of the polyolefin polyol include a hydroxyl group-terminated polybutadiene, a hydrogenated product thereof, and a hydroxyl group-containing chlorinated polyolefin.

  Preferred polymer polyols are polyester polyols, polyether polyols, and polycarbonate polyols having a number average molecular weight of 1,000 to 5,000 because of the good physical properties and feel of the resulting molded product. A polyester polyol having an average molecular weight of 1,000 to 5,000 is preferable, and a polyester polyol using 50 mol% or more of an aromatic dicarboxylic acid as an acid component is particularly preferable.

  Examples of the organic polyisocyanate used for obtaining the isocyanate group-terminated prepolymer include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, tetra Methyl xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2, 2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenol Aromatic diisocyanates such as diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3′-dimethoxydiphenyl-4,4′-diisocyanate, tetramethylene diisocyanate, hexamethylene Alicyclics such as diisocyanates (hereinafter abbreviated as HDI), aliphatic diisocyanates such as decamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate In addition to aromatic diisocyanates, their polymers, their polymeric materials, urethane-modified products, and allophanate-modified products , Urea modified products, biuret modified products, carbodiimide-modified products, uretonimine modified product, uretdione modified product, an isocyanurate modified product, and further mixtures of two or more thereof. In the present invention, in consideration of the weather resistance of the molded article, aliphatic and / or alicyclic diisocyanates are preferable, HDI, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate are particularly preferable, and HDI is most preferable.

  As a ratio of the polymer polyol used for obtaining the isocyanate group-terminated prepolymer and the organic polyisocyanate, the molar ratio of the latter isocyanate group to the hydroxyl group possessed by the former ([NCO] / [OH]) is 1. The ratio is preferably from 05 to 5.0, more preferably from 1.3 to 2.5.

  The reaction between the polymer polyol and the organic polyisocyanate is preferably performed in the presence of a non-aqueous dispersion medium (dispersed state), but may be performed in the absence of the dispersion medium.

<Specific active hydrogen group-containing compound>
The specific active hydrogen group-containing compound used in the production method of the present invention is a monofunctional active hydrogen group-containing compound having an active hydrogen group and a hydrocarbon group having 4 to 12 carbon atoms.
In the production method of the present invention, the active hydrogen group of the specific active hydrogen group-containing compound reacts with a part of the isocyanate group of the isocyanate group-terminated prepolymer.

Examples of the “active hydrogen group” possessed by the specific active hydrogen group-containing compound include a hydroxyl group (—OH), an imino group (═NH), and an amino group (—NH ₂ ).

Examples of the “hydrocarbon group having 4 to 12 carbon atoms” possessed by the specific active hydrogen group-containing compound include an alkyl group and an alkenyl group.
The carbon number of the “hydrocarbon group” possessed by the specific active hydrogen group-containing compound is 4 to 12, preferably 4 to 11, and more preferably 4 to 9.
When an active hydrogen group-containing compound having less than 4 carbon atoms is used, the molecular weight of the resulting resin cannot be controlled (see Comparative Example 7). On the other hand, when an active hydrogen group-containing compound having more than 12 carbon atoms is used, blooming is likely to occur in the molded product of the resulting resin (see Comparative Examples 4 to 6).

  Specific examples of the specific active hydrogen group-containing compound include di-n-butylamine, di-isobutylamine, di-t-butylamine, di-n-hexylamine, di-cyclohexylamine, di-n-octylamine, di- Dialkylamines (secondary amines) such as 2-ethylhexylamine, di-n-nonylamine, di-dodecylamine; dialkenylamines such as di-allylamine; alkylamines such as dodecylamine (primary amine); n Examples include monools such as butanol, isobutanol, n-octanol, 2-ethylhexanol, n-nonanol, n-decanol, lauryl alcohol, and cyclohexanol, which are used alone or in combination of two or more. can do. Of these, dialkylamine is preferred.

  The reaction between the isocyanate group-terminated prepolymer (part of the isocyanate group) and the specific active hydrogen group-containing compound (active hydrogen group) is preferably performed in the presence of a non-aqueous dispersion medium (dispersed state). You may carry out in the absence of a dispersion medium.

<Water>
In the production method of the present invention, the active hydrogen group possessed by water reacts with the remainder of the isocyanate group possessed by the isocyanate group-terminated prepolymer.
The reaction between the isocyanate group-terminated prepolymer (the remainder of the isocyanate group) and water (active hydrogen group) is carried out in a non-aqueous dispersion medium.
Here, the “non-aqueous dispersion medium” is composed of a polymer polyol and an organic solvent that does not substantially dissolve the resulting isocyanate group-terminated prepolymer and polyurethane urea resin.

  Organic solvents that can be used as a non-aqueous dispersion medium include pentane, hexane, heptane, and octane in the case where the polymer polyol is a main component that waits for polarity, such as polyester polyol, polyether polyol, and polycarbonate polyol. Non-polar, such as aliphatic organic media such as dodecane, paraffinic solvents, alicyclic organic media such as cyclopentane, cyclohexane, methylcyclohexane, etc., organic media used as plasticizers such as dioctyl phthalate, etc. And / or a low-polar organic medium; when a nonpolar material such as a hydroxyl group-containing polybutadiene or a hydroxyl group-containing hydrogenated polybutadiene is the main component, a polar organic medium such as acetone or methyl ethyl ketone may be used. .

  A dispersant is preferably used from the viewpoint of uniformly dispersing the polymer polyol in the non-aqueous dispersion medium. As the dispersant, for example, a dispersant described in JP-A No. 2004-161866 can be preferably used.

<Specific active hydrogen group-containing compound and water ratio>
The ratio of the specific active hydrogen group-containing compound and water used for the reaction with the isocyanate group-terminated prepolymer (isocyanate group) is the number of moles of active hydrogen groups (reaction moles) of the specific active hydrogen group-containing compound. The ratio (x1 / x2) is 5 to 35/95 to 65, where x1 is x1 and the number of moles of active hydrogen groups having water (number of moles of reaction) is x2.
When this ratio (x1 / x2) is less than 5/95, that is, when the ratio of the specific active hydrogen group-containing compound is too small, formation of an excessively low molecular weight hardly-fusible substance cannot be suppressed. The resulting polyurethane urea resin cannot exhibit suitable melt moldability (particularly leveling properties and pinhole prevention performance) (see Comparative Examples 8 and 10 described later). On the other hand, when the ratio (x1 / x2) exceeds 35/65, that is, when the ratio of the specific active hydrogen group-containing compound is excessive, the molded article made of the polyurethane urea resin has good folding resistance. And wear resistance cannot be imparted (see Comparative Example 9 and Comparative Examples 11 to 13 described later).

  Next, the second invention will be described. This production method includes the first step (preparation of a dispersion of a polymer polyol), the second step (preparation of a dispersion of an isocyanate group-terminated prepolymer), and the third step (preparation of a dispersion of a polyurethane urea resin). And 4th process (preparation of a powdery thermoplastic polyurethane urea resin).

<First step>
In the first step, the polymer polyol is dispersed in an organic solvent (non-aqueous dispersion medium) that does not substantially dissolve the polymer polyol and the resulting isocyanate group-terminated prepolymer and polyurethane urea resin, thereby preparing a dispersion. It is a process.
Here, as the “polymer polyol”, the same polymer polyol as used in the first invention can be used.
Further, as the “organic solvent” constituting the dispersion medium, the organic solvent used in the first invention can be appropriately used according to the type (polarity) of the polymer polyol to be dispersed.
Furthermore, it is preferable to use a dispersant (for example, a dispersant described in JP-A No. 2004-161866) in this step. Here, the amount of the dispersant to be used is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass with respect to the polymer polyol.

  In the dispersion of the polymer polyol obtained in the first step, the mass ratio of the dispersed phase (total amount of raw materials other than the dispersion medium) and the continuous phase (dispersion medium) is determined in consideration of production efficiency and production cost. / Continuous phase = preferably 10/90 to 80/20, more preferably 40/60 to 80/20.

<Second step>
The second step is a step of preparing a dispersion of the isocyanate group-terminated prepolymer by reacting the organic polyol with the polymer polyol in the dispersion obtained in the first step. Specifically, an organic polyisocyanate is added to the dispersion of the polymer polyol obtained in the first step, and this system is heated to cause a urethanization reaction.
As the “organic polyisocyanate”, the same organic polyisocyanate used in the first invention can be used.

In the second step, the ratio of the polymer polyol used for obtaining the isocyanate group-terminated prepolymer and the organic polyisocyanate is the molar ratio of the latter isocyanate group to the former hydroxyl group ([NCO] / [ OH]) is 1.3 to 2.5.
When the molar ratio ([NCO] / [OH]) is less than 1.3, a sufficient concentration of NCO groups cannot be introduced into the resulting isocyanate group-terminated prepolymer, and this is obtained using this. A sufficient concentration of urea groups cannot be introduced into the polyurethane urea resin to be produced, and excellent crease resistance, mechanical properties, and abrasion resistance cannot be imparted to a molded product of the resin.
On the other hand, when the molar ratio ([NCO] / [OH]) exceeds 2.5, an excess amount of NCO groups is introduced into the resulting isocyanate group-terminated prepolymer, and a polyurethane urea resin obtained by using this is used. The concentration of the urea group in the inside becomes excessive, it is impossible to suppress the formation of a hardly-fusible substance due to side reactions, and the melt moldability is lowered.

In the second step, a conventionally known urethanization catalyst or the like can be used as necessary. Examples of the urethanization catalyst include triethylenediamine, bis-2-dimethylaminoethyl ether, dibutyltin dilaurate, lead naphthenate, iron naphthenate, copper octenoate, and bismuth catalysts.
The reaction conditions in the second step vary depending on the type (boiling point) of the dispersion medium, but are preferably 1 to 4 hours at 40 to 110 ° C, more preferably 2 to 3 hours at 50 to 100 ° C. Is done.

<Third step>
In the third step, a part of the isocyanate group of the isocyanate group-terminated prepolymer in the dispersion obtained in the second step is reacted with the active hydrogen group of the specific active hydrogen group-containing compound, and the isocyanate group This is a step of preparing a polyurethane urea resin dispersion by reacting the remaining isocyanate groups of the terminal prepolymer with active hydrogen groups of water.

  Specifically, a specific active hydrogen group-containing compound is added to the dispersion of the isocyanate group-terminated prepolymer obtained in the second step, and a part of the isocyanate group of the isocyanate group-terminated prepolymer and a specific activity are added. After reacting with the active hydrogen group of the hydrogen group-containing compound, water is added, and the isocyanate group is completely consumed by adding the remainder of the isocyanate group of the isocyanate group-terminated prepolymer and the active hydrogen group of water. Let it react until

  Here, the amount of water added is an isocyanate group (the prepolymer in which the reaction of a part of the isocyanate group is completed) having an isocyanate group terminal after the reaction with the specific active hydrogen group-containing compound ( In view of weight loss due to water evaporation, it is preferably 2 to 100 equivalents, more preferably 3 to 20 equivalents of the remainder of the isocyanate group. Equivalent. If the amount of water to be added is small, the remainder of the isocyanate group cannot be completely consumed (ureaized), and in the molded product of the resulting polyurethane urea resin, mechanical properties may be deteriorated, Due to residual isocyanate groups, deterioration over time may occur.

The reaction temperature in the reaction between a part of the isocyanate groups of the isocyanate group-terminated prepolymer and the active hydrogen groups of the specific active hydrogen group-containing compound is preferably 40 to 85 ° C, more preferably 50 to 80 ° C. ℃.
Moreover, it is preferable that it is 40-85 degreeC as reaction temperature in reaction of the remainder of the isocyanate group which an isocyanate group terminal prepolymer has, and the active hydrogen group which water has, More preferably, it is 50-80 degreeC.
If the reaction temperature is too low, the reaction takes a long time. On the other hand, if the reaction temperature is too high, water and the like evaporate, making it difficult to control the molecular weight.
In this third step, a known surfactant may be used.

<Ratio of polymer polyol, specific active hydrogen group-containing compound and water>
As the ratio (reaction ratio) of the polymer polyol, the specific active hydrogen group-containing compound and water, the number of moles of active hydrogen groups of the polymer polyol that reacts with the organic polyisocyanate in the second step is A, and in the third step. The active hydrogen group-containing compound that reacts with a part of the isocyanate group that the isocyanate group-terminated prepolymer has has x1 the number of moles of active hydrogen groups that the compound has, and the activity that water reacts with the remainder of the isocyanate group that the isocyanate group-terminated prepolymer has When the number of moles of hydrogen groups is x2, the ratio [(x1 + x2) / A] is 0.3 to 1.5, and the ratio (x1 / x2) is 5 to 35/95 to 65.

When the ratio [(x1 + x2) / A] is less than 0.3, a sufficient concentration of urea groups cannot be introduced into the resulting polyurethane urea resin, and the molded product made of the resin has excellent resistance to resistance. It is not possible to impart crease resistance, mechanical properties and wear resistance.
On the other hand, when the ratio [(x1 + x2) / A] exceeds 1.5, the concentration of urea groups in the obtained polyurethaneurea resin becomes excessive, and the production of hardly fusible substances due to side reactions can be suppressed. Therefore, melt moldability is reduced.

When the ratio (x1 / x2) is less than 5/95, that is, when the ratio of the specific active hydrogen group-containing compound is too small, formation of a hardly fusible substance having an excessive molecular weight cannot be suppressed and obtained. The polyurethane urea resin cannot exhibit suitable melt moldability (particularly leveling properties and pinhole prevention performance) (see Comparative Examples 8 and 10 described later).
On the other hand, when the ratio (x1 / x2) exceeds 35/65, that is, when the ratio of the specific active hydrogen group-containing compound is excessive, the molded article made of the polyurethane urea resin has good folding resistance. And wear resistance cannot be imparted (see Comparative Example 9 described later).

In the present invention (second invention)
(1) The ratio [(x1 + x2) / A] is 0.3 to 1.2, and the ratio (x1 / x2) is 5 to 20/95 to 80, and (2) the ratio [(x1 + x2) / A] is particularly preferably 0.75 to 1.5 and the ratio (x1 / x2) is preferably 10 to 35/90 to 65.

<4th process>
The fourth step is a step of preparing a powdery thermoplastic polyurethane urea resin by separating and drying the polyurethane urea resin from the dispersion obtained in the third step.
Specifically, the polyurethane urea resin is separated from the dispersion medium by a filtration method or a decantation method, and then dried under normal pressure or reduced pressure at room temperature or warm.

<Powdered thermoplastic polyurethane urea resin>
The shape of the powdered thermoplastic polyurethane urea resin obtained by the production method of the present invention is a true sphere with good fluidity (flowability during molding). Moreover, it is preferable that the angle of repose of the said powdery thermoplastic polyurethane urea resin is 35 degrees or less, More preferably, it is 20 degrees-33 degrees. When the angle of repose is excessive, the flowability at the time of molding is deteriorated, and molding defects are likely to occur.
In addition, the angle of repose of the powdered thermoplastic polyurethane urea resin produced by freeze-pulverizing the bulk resin exceeds 33 °.

The number average molecular weight (Mn) of the powdered thermoplastic polyurethane urea resin obtained by the production method of the present invention is preferably 18,000 to 50,000, more preferably 20,000 to 45,000.
When the number average molecular weight (Mn) is too small, sufficient mechanical properties and durability cannot be imparted to the finally obtained molded product.
On the other hand, when the number average molecular weight (Mn) is excessive, suitable melt moldability cannot be exhibited (see Comparative Examples 1-2 and Comparative Example 8 described later).
Here, the “number average molecular weight (Mn) of polyurethane urea resin” refers to a value obtained from a peak other than the peak of ultra high molecular weight (Mn is 500,000 or more) by GPC measurement.

The weight average molecular weight (Mw) of the powdered thermoplastic polyurethane urea resin obtained by the production method of the present invention is preferably 43,000-110,000, more preferably 47,000-100,000.
Here, the “weight average molecular weight (Mw) of the polyurethane urea resin” refers to a value obtained from a peak other than the peak of ultrahigh molecular weight by GPC measurement.

The average particle diameter of the powdered thermoplastic polyurethane urea resin obtained by the production method of the present invention is 1,000 μm or less, preferably 10 to 500 μm, more preferably 90 to 200 μm.
If the average particle size is excessive, pinholes are likely to occur in the undercut portions and corner portions of the obtained molded product.
On the other hand, when the average particle size is excessive, flowability and powder breakage are deteriorated, and the thickness of the obtained molded product tends to be nonuniform.
Here, the “average particle size” refers to a cumulative percent value of 50% in a particle size distribution curve measured by a laser particle size analyzer.
The average particle size of the powdered thermoplastic polyurethane urea resin can be adjusted by using a nonpolar and / or low polarity dispersion medium in combination with a polar dispersion medium.

  An additive can be added to the powdered thermoplastic polyurethane urea resin obtained by the production method of the present invention, if necessary. Examples of such additives include pigments / dyes, antioxidants, ultraviolet absorbers, plasticizers, antiblocking agents, radical polymerization initiators, coupling agents, flame retardants, inorganic and organic fillers, lubricants, antistatic agents, and crosslinking. An agent etc. can be mentioned.

  Examples of the “plasticizer” include dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, Phthalic acid esters such as ditridecyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, dibenzyl phthalate, butyl benzyl phthalate and myristyl benzyl phthalate; isophthalic acid esters such as di- (2-ethylhexyl) isophthalate and diisooctyl isophthalate; Tetrahydrophthalic acid esters such as di-2-ethylhexyl tetrahydrophthalate; di- (2-ethylhexyl) adipate, dibutoxy Adipic acid esters such as til adipate and diisononyl adipate; azelaic acid esters such as di-n-hexyl azelate and di- (2-ethylhexyl) azelate; sebacic acid esters such as di-n-butyl sebacate; -Maleic acid esters such as butyl maleate and di- (2-ethylhexyl) maleate; Fumaric acid esters such as di-n-butyl fumarate and di- (2-ethylhexyl) fumarate; Tory (2-ethylhexyl) trimellitate , Trimellitic acid esters such as tri-n-octyl trimellitate, triisooctyl trimellitate; pyromellitic acid esters such as tetra- (2-ethylhexyl) pyromellitate, tetra-n-octyl pyromellitate; -N-butyl citrate, acetyl Citrates such as butyl citrate; itaconates such as dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di- (2-ethylhexyl) itaconate; oleins such as glyceryl monooleate and diethylene glycol monooleate Acid esters; ricinoleic acid derivatives such as glyceryl monoricinoleate and diethylene glycol monoricinoleate; stearic acid esters such as glycerin monostearate and diethylene glycol distearate; other fatty acid esters such as diethylene glycol dipelargonate and pentaerythritol fatty acid esters Tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyldecyl phosphate, diphenyloctyl Phosphate esters such as tilphosphate; glycol derivatives such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di- (2-ethylhexoate), tripropylene glycol dibenzoate, dibutylmethylene bisthioglycolate; Glycerin derivatives such as glycerol monoacetate, glycerol triacetate, glycerol tributyrate; epoxidized soybean oil, epoxybutyl stearate, di-2-ethylhexyl epoxyhexahydrophthalate, diisodecyl epoxyhexahydrophthalate, epoxytriglyceride, epoxidized olein Epoxy derivatives such as octyl acid and epoxidized decyl oleate; other adipic acid polyesters and sebacic acid polyesters Phthalic acid-based polyester, and the like.

  “Pigments” include organic pigments such as insoluble azo pigments, soluble azo pigments, copper phthalocyanine pigments, quinacridone pigments; chromates, ferrocyan compounds, metal oxides, metal salts (sulfates, silicates, carbonates) And inorganic pigments such as metal powder and carbon black. The addition amount of the pigment is usually 5% by mass or less, preferably 1 to 3% by mass with respect to the powdered thermoplastic polyurethane urea resin.

Examples of the “antioxidant” include phenol-based [2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, etc.], bisphenol-based [2,2′-methylenebis (4-methyl-6-t- Butylphenol) and the like] and phosphorus [triphenyl phosphite, diphenylisodecyl phosphite, etc.], and these can be used alone or in combination of two or more.
Examples of “ultraviolet absorbers” include benzophenone [2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, etc.], benzotriazole [2- (2′-hydroxy-5′-methylphenyl) benzotriazole, etc. ], Salicylic acid type [phenyl salicylate, etc.], hindered amine type [bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, etc.], and these may be used alone or in combination of two or more. Can be used.
The addition amount of the antioxidant and the ultraviolet absorber is usually 5% by mass or less, preferably 0.01 to 3% by mass with respect to the powdered thermoplastic polyurethane urea resin.

The “antiblocking agent” is not particularly limited, and examples thereof include known inorganic antiblocking agents and organic antiblocking agents.
Examples of the inorganic anti-blocking agent include silica, talc, titanium oxide, calcium carbonate, and the like. Examples of the organic anti-blocking agent include thermosetting resins having a particle diameter of 10 μm or less (for example, thermosetting polyurethane resin, guanamine type). Resin, epoxy resin, and the like) and thermoplastic resins having a particle diameter of 10 μm or less (for example, thermoplastic polyurethane urea resin, poly (meth) acrylate resin, etc.).
Of these, inorganic blocking inhibitors are preferred, and silica is particularly preferred.
The addition amount of the antiblocking agent is usually less than 3% by mass, preferably 0.1 to 2% by mass with respect to the powdered thermoplastic polyurethane urea resin.

<Slush molding method>
The powdery thermoplastic polyurethane urea resin obtained by the production method of the present invention can be suitably used as a powder material for slush molding.

An example of the slush molding method is as follows.
First, a mold release agent is applied to a mold (mold), and then the mold is heated. Here, the release agent is applied at 60 ° C. or lower. Examples of the method for applying the release agent include an air spray method and a brush coating method. The heating temperature of the mold is usually 150 to 300 ° C, preferably 180 to 280 ° C. Examples of the heating method include a hot sand heating method and an oil heating method.

Next, the powder material (powdered thermoplastic polyurethane urea resin obtained by the production method of the present invention) is charged into a mold and held (powdered) for 15 to 45 seconds to remove excess powder material, and then 200 The mold is placed in a heating oven at ˜400 ° C. and heated for 20 to 300 seconds, preferably 30 to 120 seconds, to complete melting of the powder material.
Then, the metal mold | die taken out from heating oven is cooled by the water cooling method etc., and a slush molding (for example, sheet | seat of 0.7-2 mm thickness) is obtained by removing from a mold.

Moreover, without taking out a slush molding (sheet), by introducing a polyurethane foam-forming material into the same mold, foaming it, and forming a core material made of polyurethane foam, then demolding, A member having a skin layer made of a slush molding (for example, an automobile instrument panel, a console box, an armrest, etc.) can be manufactured. Here, examples of the polyurethane foam include a flexible foam and a semi-rigid foam having a density of 0.02 to 0.5 g / cm ³ .

Examples of the present invention will be described below, but the present invention is not limited thereto.
[Preparation Example 1 (Preparation of Dispersant Solution)]
A reactor having a capacity of 2 L equipped with a stirrer, a thermometer, a distillation column and a nitrogen gas introduction tube was charged with 762 g of adipic acid, 49 g of maleic anhydride and 386 g of ethylene glycol, and at 150 ° C. and normal pressure while flowing nitrogen gas. The esterification reaction was carried out by stirring under the conditions of
When condensed water is no longer observed, add 0.1 g of tetrabutyl titanate, gradually reduce the pressure in the reaction system to 0.07 kPa, and gradually raise the temperature to 190 ° C. to continue the reaction. To obtain a polyester. The number average molecular weight of the obtained polyester was 2,000, and the iodine value was 12.7 gI / 100 g.
Subsequently, 74 g of the above polyester and 150 g of butyl acetate were charged into a 500 mL reactor equipped with a stirrer, a thermometer, a distillation column and a nitrogen gas introduction tube, and the temperature was raised to 110 ° C. while flowing nitrogen gas. , Stirred. Thereafter, a dissolved mixture of 75 g of 2-ethylhexyl methacrylate and 1 g of benzoyl peroxide was dropped from the dropping funnel over 1 hour. After completion of the dropping, the temperature was raised to 130 ° C. and the reaction was further continued for 2 hours to obtain a dispersant solution having a solid content of 50%. Hereinafter, this is referred to as “dispersant solution (1)”.

[Preparation Example 2 (Preparation of Dispersant Solution)]
A dispersant solution having a solid content of 60% was obtained in the same manner as in Preparation Example 1 except that 113 g of diisononyl adipate (DINA) was used instead of butyl acetate and 96 g of lauryl methacrylate was used instead of 2-ethylhexyl methacrylate. Hereinafter, this is referred to as “dispersant solution (2)”.

<Example 1>
(1) First step:
In a reactor having a capacity of 3 L equipped with a stirrer, a thermometer, a cooler, and a nitrogen gas introduction tube, 756.9 g of a polyester diol (EA-2000) having a number average molecular weight of 2,000 obtained from ethylene glycol and adipic acid, 133.6 g of a polyester diol (HoP-1500) having a number average molecular weight of 1,500 obtained from 1,6-HD and orthophthalic acid, 7.4 g of the dispersant solution (1), and isooctane “ Kyowasol C-800 "(manufactured by Kyowa Hakko Chemical Co., Ltd.) 818.2 g and stirring at 90-95 ° C. for 1 hour, polymer polyols (EA-2000 and HoP-1500) in isooctane Dispersion was carried out to prepare a non-aqueous dispersion.

(2) Second step:
To the dispersion obtained in the first step, 102.2 g of hexamethylene diisocyanate (HDI) and 0.050 g of bismuth catalyst “Neostan U-600” (manufactured by Nitto Kasei Co., Ltd.) are added, and 90 to 95 An isocyanate group-terminated prepolymer dispersion was prepared by reacting the polymer polyol with HDI at 3 ° C. for 3 hours.
Here, the use ratio of HDI and polymer polyol is such that the ratio [NCO] / [OH] of the isocyanate group possessed by the former and the polyol group possessed by the latter is 1.30.

(3) Third step:
Part of the isocyanate group possessed by the isocyanate group-terminated prepolymer is obtained by adding 5.0 g of di-dodecylamine, which is a specific active hydrogen group-containing compound, to the dispersion of the isocyanate group-terminated prepolymer obtained in the second step. And an active hydrogen group possessed by di-dodecylamine were reacted at 65 to 70 ° C. Next, 24 g of water (corresponding to 10 equivalents of the remainder of the isocyanate group (calculated value = 0.133 mol)) was added to this system, and the remainder of the isocyanate group of the isocyanate group-terminated prepolymer and the active hydrogen of water A polyurethane urea resin dispersion was prepared by reacting the group at 65 to 70 ° C. until the isocyanate group was consumed.
In this example, the ratio [(x1 + x2) / A] is 0.30 and the ratio (x1 / x2) is 5/95.

(4) Fourth step:
After the solid content (polyurethane urea resin) is filtered off from the polyurethane urea resin dispersion obtained in the third step, the following additives (i) to (v) are added thereto, and dried. A powdery thermoplastic polyurethane urea resin was prepared by adding 0.30 g of a dusting agent “MP1451” (manufactured by Soken Chemical Co., Ltd.). The obtained resin had a spherical shape and an angle of repose of 26 °.

〔Additive〕
(I) Black pigment: Mixture (mixing ratio) of carbon black dispersion pigment “PV-817” (manufactured by Sumika Color Co., Ltd.) and titanium oxide dispersion pigment “PV-7A1301” (manufactured by Sumika Color Co., Ltd.) = 70/30), addition amount = 1.5% by mass relative to the resin.
(Ii) Antioxidant: “Irganox 245” (manufactured by Ciba Specialty Chemicals), addition amount = 0.25 g.
(iii) UV absorber: “Tinubin 213” (manufactured by Ciba Specialty Chemicals), added amount = 0.15 g.
(Iv) Light stabilizer: “Tinuvin 765” (manufactured by Ciba Specialty Chemicals), added amount = 0.15 g.
(V) Internal mold release agent: “SH200-100,000 cs” (manufactured by Toray Dow Corning Co., Ltd.), addition amount = 0.20 g.

<Examples 2 to 12>
Through the following first to fourth steps, powdery thermoplastic polyurethane urea resins were prepared.

(1) First step:
According to the formulation shown in Table 1 below, a non-aqueous system was prepared in the same manner as in the first step of Example 1 except that a polymer polyol, a dispersant solution, and a non-aqueous dispersion medium (isooctane) were charged into the reactor. A dispersion was prepared.
In Example 2, 75.0 g of a plasticizer “PEG400 dibenzoate” obtained from polyethylene glycol 400 (1 mol) and benzoic anhydride (2 mol) was used; in Example 5, the plasticizer “PEG400 dibenzoate” was used. 50.0 g of benzoate ”and 50.0 g of the plasticizer“ PEG200 dibenzoate ”obtained from polyethylene glycol 200 (1 mol) and benzoic anhydride (2 mol); in Example 11, the plasticizer“ PEG200 "Dibenzoate" 50.0 g was used.

(2) Second step:
Dispersion of the isocyanate group-terminated prepolymer in the same manner as in the second step of Example 1 except that HDI and a catalyst were added to the dispersion obtained in the first step of each example according to the formulation shown in Table 1 below. A liquid was prepared.
Here, the value of the ratio [NCO] / [OH] between the isocyanate group in the used HDI and the polyol group in the used polymer polyol is also shown in Table 1 below.

(3) Third step:
In accordance with the formulation shown in Table 1 below, a specific active hydrogen group-containing compound is added to the dispersion of the isocyanate group-terminated prepolymer obtained in the second step, and a part of the isocyanate group that the isocyanate group-terminated prepolymer has, The active hydrogen group which the specific active hydrogen group containing compound has was made to react at 65-70 degreeC.
Next, water (corresponding to 10 equivalents of the remainder of the isocyanate group) is added to this system, and the remainder of the isocyanate group that the isocyanate group-terminated prepolymer has and the active hydrogen group that the water has are at 65 to 70 ° C. A polyurethane urea resin dispersion was prepared by reacting until the isocyanate groups were consumed.
Here, the values of the ratio [(x1 + x2) / A] and the ratio (x1 / x2) are also shown in Table 1 below.

(4) Fourth step:
The solid content (polyurethane urea resin) was filtered off from the polyurethane urea resin dispersion obtained in the third step, and the additives (i) to (v) used in Example 1 were added thereto (respectively). The amount added was also the same as in Example 1.) After drying this, 0.30 g of the dusting agent “MP1451” was added to prepare a powdered thermoplastic polyurethane urea resin.
The obtained resins were all spherical and the repose angle was 26 °.

In Table 1 and Table 2 below, the substances indicated by abbreviations are as follows.
* "BA-1000":
A polyester diol having a number average molecular weight of 1,000, obtained from 1,4-BD and adipic acid.
* “BA-2000”:
A polyester diol having a number average molecular weight of 2,000, obtained from 1,4-BD and adipic acid.
* “BA-2500”:
A polyester diol having a number average molecular weight of 2,500 obtained from 1,4-BD and adipic acid.
* “BEA-2600”:
A polyester diol having a number average molecular weight of 2,600 obtained from 1,4-BD, ethylene glycol and adipic acid.
* "EA-1000":
A polyester diol having a number average molecular weight of 1,000, obtained from ethylene glycol and adipic acid.
* “EA-2000”:
A polyester diol having a number average molecular weight of 2,000, obtained from ethylene glycol and adipic acid.
* “HiP-1000”:
A polyester diol having a number average molecular weight of 1,000, obtained from 1,6-HD and isophthalic acid.
* “HoP-1500”:
A polyester diol having a number average molecular weight of 1,500 obtained from 1,6-HD and orthophthalic acid.

* "Isooctane (dispersion medium)":
“Kyowasol C-800” (manufactured by Kyowa Hakko Chemical Co., Ltd.).
* "U-600 (catalyst)":
Bismuth-based catalyst “Neostan U-600” (manufactured by Nitto Kasei Co., Ltd.).

<Comparative Example 1>
According to the formulation shown in Table 2 below, 341.2 g of polyester diol (EBA-2600), 511.8 g of polyester diol (HiP-1000), 14.2 g of dispersant solution (2), and isooctane “Kyowasol C-800 A non-aqueous dispersion was prepared in the same manner as in the first step of Example 1 except that 666.7 g was charged into the reactor.
Next, the dispersion of the isocyanate group-terminated prepolymer was performed in the same manner as in the second step of Example 1, except that 143.3 g of HDI and 0.050 g of the catalyst “Neostan U-600” were added to the obtained dispersion. A liquid was prepared. Here, the ratio of use of HDI and polymer polyol is such that the ratio [NCO] / [OH] of the isocyanate group possessed by the former and the polyol group possessed by the latter is 1.33.
Next, 38 g of water (corresponding to 10 equivalents of the isocyanate group) was added to the resulting dispersion of the isocyanate group-terminated prepolymer, and the isocyanate group possessed by the isocyanate group-terminated prepolymer and the active hydrogen group possessed by water were A polyurethane urea resin dispersion was prepared by reacting at 65 to 70 ° C. until the isocyanate groups were consumed. In this comparative example, the ratio [(x1 + x2) / A] is 0.33, and the ratio (x1 / x2) is 0.
Next, using the obtained polyurethane urea resin dispersion, a powdery thermoplastic polyurethane urea resin was prepared in the same manner as in the fourth step of Example 1.
Comparative Example 1 is a comparative example in which no specific active hydrogen group-containing compound is used.

<Comparative example 2>
In accordance with the formulation shown in Table 2 below, 612.0 g of polyester diol (BA-2000), 262.3 g of polyester diol (HoP-1500), 29.1 g of dispersant solution (1), and isooctane “Kyowasol C-800 A non-aqueous dispersion was prepared in the same manner as in the first step of Example 1, except that 818.2 g was charged into the reactor.
Next, the dispersion of the isocyanate group-terminated prepolymer was performed in the same manner as in the second step of Example 1, except that 121.3 g of HDI and 0.050 g of the catalyst “Neostan U-600” were added to the obtained dispersion. A liquid was prepared. Here, the ratio of HDI and polymer polyol used is such that the ratio [NCO] / [OH] of the former isocyanate group and the latter polyol group is 1.50.
Next, 43 g of water (corresponding to 10 equivalents of the isocyanate group) was added to the resulting dispersion of the isocyanate group-terminated prepolymer, and the isocyanate group possessed by the isocyanate group-terminated prepolymer and the active hydrogen group possessed by water were A polyurethane urea resin dispersion was prepared by reacting at 65 to 70 ° C. until the isocyanate groups were consumed. In this comparative example, the ratio [(x1 + x2) / A] is 0.50, and the ratio (x1 / x2) is 0.
Next, using the obtained polyurethane urea resin dispersion, a powdery thermoplastic polyurethane urea resin was prepared in the same manner as in the fourth step of Example 1.
Comparative Example 2 is a comparative example in which no specific active hydrogen group-containing compound is used.

<Comparative Example 3>
In accordance with the formulation shown in Table 2 below, 384.4 g of polyester diol (BA-1000), 192.2 g of polyester diol (HiP-1000), 192.2 g of polyester diol (HoP-1500), and dispersant solution (2) A non-aqueous dispersion was prepared in the same manner as in the first step of Example 1 except that 25.6 g and 600.0 g of isooctane “Kyowasol C-800” were charged into the reactor.
Next, the dispersion of the isocyanate group-terminated prepolymer was performed in the same manner as in the second step of Example 1, except that 197.5 g of HDI and 0.050 g of the catalyst “Neostan U-600” were added to the obtained dispersion. A liquid was prepared. Here, the ratio of use of HDI and polymer polyol is such that the ratio [NCO] / [OH] of the former isocyanate group and the latter polyol group is 1.67.
Next, 29.2 g of 1,6-HD was added to the resulting dispersion of the isocyanate group-terminated prepolymer, and a part of the isocyanate group of the isocyanate group-terminated prepolymer and the activity of 1,6-HD were possessed. A hydrogen group (hydroxyl group) was reacted. Next, 4.4 g of water (equivalent to the remainder of the isocyanate group) was added to this system, and the remainder of the isocyanate group contained in the isocyanate group-terminated prepolymer and the active hydrogen group contained in water at 65 to 70 ° C. A polyurethane urea resin dispersion was prepared by reacting. In this comparative example, the ratio [(x1 + x2) / A] is 0.35 and the ratio (x1 / x2) is 0.
Next, using the obtained polyurethane urea resin dispersion, a powdery thermoplastic polyurethane urea resin was prepared in the same manner as in the fourth step of Example 1.
This Comparative Example 3 is a comparative example in which a low molecular polyol is used in place of the specific active hydrogen group-containing compound.

<Comparative example 4>
According to the formulation shown in Table 2 below, 401.0 g of polyester diol (BA-2500), 200.5 g of polyester diol (HiP-1000), 200.5 g of polyester diol (HoP-1500), and dispersant solution (1) A non-aqueous dispersion was prepared in the same manner as in the first step of Example 1, except that 33.4 g and 818.2 g of isooctane “Kyowasol C-800” were charged into the reactor.
Next, the dispersion of the isocyanate group-terminated prepolymer was carried out in the same manner as in the second step of Example 1, except that 158.1 g of HDI and 0.050 g of the catalyst “Neostan U-600” were added to the obtained dispersion. A liquid was prepared. Here, the ratio of use of HDI and polymer polyol is such that the ratio [NCO] / [OH] between the isocyanate group possessed by the former and the polyol group possessed by the latter is 1.90.
Next, 50.8 g of di-tridecylamine (an active hydrogen group-containing compound having an alkyl group having 13 carbon atoms) was added to the resulting dispersion of the isocyanate group-terminated prepolymer, A part of the isocyanate group possessed was reacted with an active hydrogen group possessed by di-ditridecylamine. Next, 68 g of water (corresponding to 10 equivalents of the remainder of the isocyanate group) is added to this system, and the remainder of the isocyanate group of the isocyanate group-terminated prepolymer and the active hydrogen group of water are brought to 65 to 70 ° C. Then, a polyurethane urea resin dispersion was prepared by reacting until the isocyanate groups were consumed.
Next, using the obtained polyurethane urea resin dispersion, a powdery thermoplastic polyurethane urea resin was prepared in the same manner as in the fourth step of Example 1.
Comparative Example 4 is a comparative example using an active hydrogen group-containing compound having a long-chain alkyl group having more than 12 carbon atoms in place of the specific active hydrogen group-containing compound.

<Comparative Example 5>
In accordance with the formulation shown in Table 2 below, 272.8 g of polyester diol (BA-2000), 506.6 g of polyester diol (HoP-1500), 3.9 g of dispersant solution (2), and isooctane “Kyowasol C-800 A non-aqueous dispersion was prepared in the same manner as in the first step of Example 1 except that 666.7 g was charged into the reactor.
Next, the dispersion of the isocyanate group-terminated prepolymer was performed in the same manner as in the second step of Example 1 except that 175.5 g of HDI and 0.050 g of the catalyst “Neostan U-600” were added to the obtained dispersion. A liquid was prepared. Here, the ratio of use of HDI and polymer polyol is such that the ratio [NCO] / [OH] of the isocyanate group possessed by the former and the polyol group possessed by the latter is 2.20.
Next, 36.4 g of tetradecanol (an active hydrogen group-containing compound having an alkyl group having 14 carbon atoms) is added to the resulting isocyanate group-terminated prepolymer dispersion, and the isocyanate group-terminated prepolymer has an isocyanate. A part of the group was reacted with an active hydrogen group possessed by tetradecanol. Next, 87 g of water (corresponding to 10 equivalents of the remainder of the isocyanate group) is added to this system, and the remainder of the isocyanate group of the isocyanate group-terminated prepolymer and the active hydrogen group of water are brought to 65 to 70 ° C. Then, a polyurethane urea resin dispersion was prepared by reacting until the isocyanate groups were consumed.
Next, using the obtained polyurethane urea resin dispersion, a powdery thermoplastic polyurethane urea resin was prepared in the same manner as in the fourth step of Example 1.
This Comparative Example 5 is a comparative example using an active hydrogen group-containing compound having a long-chain alkyl group having more than 12 carbon atoms in place of the specific active hydrogen group-containing compound.

<Comparative Example 6>
According to the formulation shown in Table 2 below, 403.4 g of polyester diol (BA-2500), 201.7 g of polyester diol (HiP-1000), 201.7 g of polyester diol (HoP-1500), and dispersant solution (2) A non-aqueous dispersion was prepared in the same manner as in the first step of Example 1, except that 33.6 g and 666.7 g of isooctane “Kyowasol C-800” were charged into the reactor.
Next, the dispersion of the isocyanate group-terminated prepolymer was performed in the same manner as in the second step of Example 1 except that 159.0 g of HDI and 0.050 g of the catalyst “Neostan U-600” were added to the obtained dispersion. A liquid was prepared. Here, the ratio of use of HDI and polymer polyol is such that the ratio [NCO] / [OH] between the isocyanate group possessed by the former and the polyol group possessed by the latter is 1.90.
Next, 28.8 g of tetradecanol (an active hydrogen group-containing compound having an alkyl group having 14 carbon atoms) is added to the resulting dispersion of the isocyanate group-terminated prepolymer, so that the isocyanate group-terminated prepolymer has an isocyanate. A part of the group was reacted with an active hydrogen group possessed by tetradecanol. Next, 69 g of water (corresponding to 10 equivalents of the remainder of the isocyanate group) is added to this system, and the remainder of the isocyanate group of the isocyanate group-terminated prepolymer and the active hydrogen group of water are brought to 65 to 70 ° C. Then, a polyurethane urea resin dispersion was prepared by reacting until the isocyanate groups were consumed.
Next, using the obtained polyurethane urea resin dispersion, a powdery thermoplastic polyurethane urea resin was prepared in the same manner as in the fourth step of Example 1.
This Comparative Example 6 is a comparative example using an active hydrogen group-containing compound having a long-chain alkyl group having more than 12 carbon atoms in place of the specific active hydrogen group-containing compound.

<Comparative Example 7>
According to the formulation shown in Table 2 below, 238.7 g of polyester diol (BA-1000), 159.2 g of polyester diol (BA-2500), 397.9 g of polyester diol (HiP-1000), and dispersant solution (1) Non-aqueous system as in the first step of Example 1 except that 39.8 g, 39.8 g of the dispersant solution (2) and 1500.0 g of isooctane “Kyowasol C-800” were charged into the reactor. A dispersion was prepared.
Next, the dispersion of the isocyanate group-terminated prepolymer was carried out in the same manner as in the second step of Example 1, except that 194.3 g of HDI and 0.050 g of the catalyst “Neostan U-600” were added to the obtained dispersion. A liquid was prepared. Here, the ratio of use of HDI and polymer polyol is such that the ratio [NCO] / [OH] of the former isocyanate group and the latter polyol group is 1.65.
Next, 2.1 g of ethanol was added to the obtained dispersion liquid of isocyanate group-terminated prepolymer, and a part of the isocyanate group possessed by the isocyanate group-terminated prepolymer was reacted with the active hydrogen group possessed by ethanol. Next, 78 g of water (corresponding to 10 equivalents of the remainder of the isocyanate group) is added to this system, and the remainder of the isocyanate group of the isocyanate group-terminated prepolymer and the active hydrogen group of water are brought to 65 to 70 ° C. Then, a polyurethane urea resin dispersion was prepared by reacting until the isocyanate groups were consumed.
Next, using the obtained polyurethane urea resin dispersion, a powdery thermoplastic polyurethane urea resin was prepared in the same manner as in the fourth step of Example 1.
This Comparative Example 7 is a comparative example using an active hydrogen group-containing compound having an alkyl group having less than 4 carbon atoms in place of the specific active hydrogen group-containing compound.

<Comparative Example 8>
According to the formulation shown in Table 2 below, 413.2 g of polyester diol (BA-2500), 206.6 g of polyester diol (HiP-1000), 206.6 g of polyester diol (HoP-1500), and dispersant solution (2) A non-aqueous dispersion was prepared in the same manner as in the first step of Example 1 except that 34.4 g and 1500.0 g of isooctane “Kyowasol C-800” were charged into the reactor.
Next, the dispersion of the isocyanate group-terminated prepolymer was performed in the same manner as in the second step of Example 1 except that 162.9 g of HDI and 0.050 g of the catalyst “Neostan U-600” were added to the obtained dispersion. A liquid was prepared. Here, the ratio of use of HDI and polymer polyol is such that the ratio [NCO] / [OH] between the isocyanate group possessed by the former and the polyol group possessed by the latter is 1.90.
Next, 2.7 g of a specific active hydrogen group-containing compound, di-allylamine, is added to the resulting isocyanate group-terminated prepolymer dispersion, and a portion of the isocyanate groups possessed by the isocyanate group-terminated prepolymer and di- -Reacted with an active hydrogen group of allylamine. Next, 80 g of water (corresponding to 10 equivalents of the remainder of the isocyanate group) is added to this system, and the remainder of the isocyanate group of the isocyanate group-terminated prepolymer and the active hydrogen group of water are brought to 65 to 70 ° C. Then, a polyurethane urea resin dispersion was prepared by reacting until the isocyanate groups were consumed.
In this comparative example, the ratio [(x1 + x2) / A] is 0.90, and the ratio (x1 / x2) is 3/97.
Next, using the obtained polyurethane urea resin dispersion, a powdery thermoplastic polyurethane urea resin was prepared in the same manner as in the fourth step of Example 1.
The comparative example 8 is a comparative example in which the ratio (x1 / x2) is less than 5/95 (the ratio of the specific active hydrogen group-containing compound is too small).

<Comparative Example 9>
According to the formulation shown in Table 2 below, 138.5 g of polyester diol (BA-1000), 138.5 g of polyester diol (EA-1000), 277.0 g of polyester diol (HiP-1000), and polyester diol (HoP-1500) ) 138.5 g, 28.9 g of the dispersant solution (2), and 1000.0 g of isooctane “Kyowasol C-800” were charged to the reactor in the same manner as in the first step of Example 1, except that An aqueous dispersion was prepared.
Next, the dispersion of the isocyanate group-terminated prepolymer was performed in the same manner as in the second step of Example 1, except that 194.1 g of HDI and 0.050 g of the catalyst “Neostan U-600” were added to the obtained dispersion. A liquid was prepared. Here, the use ratio of HDI and polymer polyol is such that the ratio [NCO] / [OH] of the isocyanate group possessed by the former and the polyol group possessed by the latter is 1.79.
Next, 83.6 g of di-2-ethylhexylamine, which is a specific active hydrogen group-containing compound, and 25.7 g of n-butanol, which is a specific active hydrogen group-containing compound, are added to the obtained isocyanate group-terminated prepolymer dispersion. Was added to react part of the isocyanate groups of the isocyanate group-terminated prepolymer with the active hydrogen groups of di-2-ethylhexylamine and n-butanol. Next, 42 g of water (corresponding to 10 equivalents of the remainder of the isocyanate group) was added to this system, and the remainder of the isocyanate group of the isocyanate group-terminated prepolymer and the active hydrogen group of water were brought to 65 to 70 ° C. Then, a polyurethane urea resin dispersion was prepared by reacting until the isocyanate groups were consumed.
In this comparative example, the ratio [(x1 + x2) / A] is 0.89, and the ratio (x1 / x2) is 60/40.
Next, using the obtained polyurethane urea resin dispersion, a powdery thermoplastic polyurethane urea resin was prepared in the same manner as in the fourth step of Example 1.
The comparative example 9 is a comparative example in which the ratio (x1 / x2) exceeds 35/65 (the ratio of the specific active hydrogen group-containing compound is excessive).

<Comparative Example 10>
According to the formulation shown in Table 2 below, 226.6 g of polyester diol (BA-2000), 188.8 g of polyester diol (EBA-2600), 399.8 g of polyester diol (HiP-1000), and dispersant solution (1) A non-aqueous dispersion was prepared in the same manner as in the first step of Example 1, except that 62.9 g and 538.5 g of isooctane “Kyowasol C-800” were charged into the reactor.
Next, the dispersion of the isocyanate group-terminated prepolymer was carried out in the same manner as in the second step of Example 1 except that 221.1 g of HDI and 0.050 g of the catalyst “Neostan U-600” were added to the obtained dispersion. A liquid was prepared. Here, the use ratio of HDI and polymer polyol is such that the ratio [NCO] / [OH] of the isocyanate group possessed by the former and the polyol group possessed by the latter is 2.50.
Subsequently, 8.2 g of n-octanol which is a specific active hydrogen group-containing compound is added to the obtained isocyanate group-terminated prepolymer dispersion, and a part of the isocyanate groups possessed by the isocyanate group-terminated prepolymer; The active hydrogen group which n-octanol has was made to react. Next, 135 g of water (corresponding to 10 equivalents of the remainder of the isocyanate group) is added to this system, and the remainder of the isocyanate group of the isocyanate group-terminated prepolymer and the active hydrogen group of water are brought to 65 to 70 ° C. Then, a polyurethane urea resin dispersion was prepared by reacting until the isocyanate groups were consumed.
In this comparative example, the ratio [(x1 + x2) / A] is 1.50, and the ratio (x1 / x2) is 4/96.
Next, using the obtained polyurethane urea resin dispersion, a powdery thermoplastic polyurethane urea resin was prepared in the same manner as in the fourth step of Example 1.
The comparative example 10 is a comparative example in which the ratio (x1 / x2) is less than 5/95 (the ratio of the specific active hydrogen group-containing compound is too small).

<Comparative Example 11>
In accordance with the formulation shown in Table 2 below, 435.9 g of polyester diol (BA-2500), 435.9 g of polyester diol (HoP-1500), 7.2 g of dispersant solution (1), and isooctane “Kyowazol C-800 A non-aqueous dispersion was prepared in the same manner as in the first step of Example 1 except that 666.7 g was charged into the reactor.
Next, the dispersion of the isocyanate group-terminated prepolymer was performed in the same manner as in the second step of Example 1, except that 101.7 g of HDI and 0.050 g of the catalyst “Neostan U-600” were added to the obtained dispersion. A liquid was prepared. Here, the use ratio of HDI and polymer polyol is such that the ratio [NCO] / [OH] of the isocyanate group possessed by the former and the polyol group possessed by the latter is 1.30.
Next, 24.9 g of di-2-ethylhexylamine, which is a specific active hydrogen group-containing compound, is added to the resulting dispersion of the isocyanate group-terminated prepolymer, and a part of the isocyanate groups of the isocyanate group-terminated prepolymer is added. And an active hydrogen group of di-2-ethylhexylamine were reacted. Next, 16 g of water (corresponding to 10 equivalents of the remainder of the isocyanate group) is added to this system, and the remainder of the isocyanate group of the isocyanate group-terminated prepolymer and the active hydrogen group of water are brought to 65 to 70 ° C. Then, a polyurethane urea resin dispersion was prepared by reacting until the isocyanate groups were consumed.
In this comparative example, the ratio [(x1 + x2) / A] is 0.30, and the ratio (x1 / x2) is 37/63.
Next, using the obtained polyurethane urea resin dispersion, a powdery thermoplastic polyurethane urea resin was prepared in the same manner as in the fourth step of Example 1.
The comparative example 11 is a comparative example in which the ratio (x1 / x2) exceeds 35/65 (the ratio of the specific active hydrogen group-containing compound is excessive).

<Comparative Example 12>
According to the formulation shown in Table 2 below, 234.0 g of polyester diol (BA-1000), 156.0 g of polyester diol (BA-2500), 390.0 g of polyester diol (HiP-1000), and dispersant solution (1) A non-aqueous dispersion was prepared in the same manner as in the first step of Example 1 except that 39.0 g and 1000.0 g of isooctane “Kyowasol C-800” were charged into the reactor.
Next, the dispersion of the isocyanate group-terminated prepolymer was performed in the same manner as in the second step of Example 1, except that 190.5 g of HDI and 0.050 g of the catalyst “Neostan U-600” were added to the obtained dispersion. A liquid was prepared. Here, the ratio of use of HDI and polymer polyol is such that the ratio [NCO] / [OH] of the former isocyanate group and the latter polyol group is 1.65.
Then, 24.5 g of n-butanol, which is a specific active hydrogen group-containing compound, is added to the resulting dispersion of the isocyanate group-terminated prepolymer, and a part of the isocyanate group possessed by the isocyanate group-terminated prepolymer, The active hydrogen group which n-butanol has was made to react. Next, 51 g of water (corresponding to 10 equivalents of the remainder of the isocyanate group) is added to this system, and the remainder of the isocyanate group of the isocyanate group-terminated prepolymer and the active hydrogen group of water are brought to 65 to 70 ° C. Then, a polyurethane urea resin dispersion was prepared by reacting until the isocyanate groups were consumed.
In this comparative example, the ratio [(x1 + x2) / A] is 0.65, and the ratio (x1 / x2) is 37/63.
Next, using the obtained polyurethane urea resin dispersion, a powdery thermoplastic polyurethane urea resin was prepared in the same manner as in the fourth step of Example 1.
The comparative example 12 is a comparative example in which the ratio (x1 / x2) exceeds 35/65 (the ratio of the specific active hydrogen group-containing compound is excessive).

<Comparative Example 13>
According to the formulation shown in Table 2 below, 148.1 g of polyester diol (BA-1000), 148.1 g of polyester diol (EA-2000), 74.1 g of polyester diol (HiP-1000), and polyester diol (HoP-1500) ) 370.3 g, 18.5 g of the dispersant solution (1), and 818.2 g of isooctane “Kyowasol C-800” were charged into the reactor in the same manner as in the first step of Example 1, except that An aqueous dispersion was prepared.
Next, the dispersion of the isocyanate group-terminated prepolymer was performed in the same manner as in the second step of Example 1, except that 182.7 g of HDI and 0.050 g of the catalyst “Neostan U-600” were added to the obtained dispersion. A liquid was prepared. Here, the ratio of use of HDI and polymer polyol is such that the ratio [NCO] / [OH] between the isocyanate group possessed by the former and the polyol group possessed by the latter is 2.00.
Next, 57.7 g of di-2-ethylhexylamine, which is a specific active hydrogen group-containing compound, and 12.9 g of n-butanol, which is a specific active hydrogen group-containing compound, are added to the resulting isocyanate group-terminated prepolymer dispersion. Was added to react part of the isocyanate groups of the isocyanate group-terminated prepolymer with the active hydrogen groups of di-2-ethylhexylamine and n-butanol. Next, 61 g of water (corresponding to 10 equivalents of the remainder of the isocyanate group) is added to this system, and the remainder of the isocyanate group of the isocyanate group-terminated prepolymer and the active hydrogen group of water are brought to 65 to 70 ° C. Then, a polyurethane urea resin dispersion was prepared by reacting until the isocyanate groups were consumed.
In this comparative example, the ratio [(x1 + x2) / A] is 1.00, and the ratio (x1 / x2) is 38/62.
Next, using the obtained polyurethane urea resin dispersion, a powdery thermoplastic polyurethane urea resin was prepared in the same manner as in the fourth step of Example 1.
This comparative example 13 is a comparative example in which the ratio (x1 / x2) exceeds 35/65 (the ratio of the specific active hydrogen group-containing compound is excessive).

<Evaluation of powdered thermoplastic polyurethane urea resin>
For each of the powdery thermoplastic polyurethane urea resins obtained in Examples 1 to 15 and Comparative Examples 1 to 13, the following items were measured and evaluated. The results are shown in Table 3 and Table 4 below.
In Comparative Example 3 and Comparative Example 7, measurement and evaluation related to some items were not performed.

(1) Molecular weight measurement:
According to GPC measurement, the ratio (peak area ratio in the measurement chart) of the hardly fusible substance (component with Mn of 500,000 or more), the number average molecular weight (Mn) and the weight average molecular weight (Mw) in the component excluding the hardly fusible substance Asked. The measurement conditions are as follows.
-Measuring instrument: "HLC-8120" (manufactured by Tosoh Corporation)
Column: “TSKgel Multipore _{H XL-M} ” (manufactured by Tosoh Corporation)
Particle size = 5 μm, size = 7.8 mm ID × 30 cm × 4 carriers ・ Carrier: Tetrahydrofuran (THF)
Detector: Parallax refraction Sample: 1% solution of THF / n-methylpyrrolidone = 2/1 Calibration curve: standard polystyrene

(2) Average particle size:
A cumulative percent value of 50% in a particle size distribution curve measured with a laser particle size analyzer “Microtrac HRA” (manufactured by Nikkiso Co., Ltd.) was determined.

(3) Melt formability (leveling property):
Molded polyurethane resin is heated for 10 seconds in a mold heated to 230 ° C, unmelted powder is removed, left in an oven at 300 ° C for 45 seconds, and then cooled with water to form a 1mm thick molded sheet Was made. The molten state of the sheet thus obtained was visually observed and evaluated according to the following criteria.

(Evaluation criteria)
“◎”: No melting failure is observed.
“◯”: Some unsatisfactory melting failure is recognized.
“×”: Melting failure is considerably recognized.

(4) Melt formability (pinhole state):
The presence and extent of pinholes on the surface of the sheet obtained by (3) above were visually observed and evaluated according to the following criteria.

(Evaluation criteria)
“◎”: Pinholes are not allowed.
“◯”: Some pinholes are inconspicuous.
“X”: Pinholes are considerably recognized.

(5) Melt moldability (green strength expression at the time of demolding):
The presence / absence and degree of deformation of the sheet obtained by (3) above at the time of demolding were visually observed and evaluated according to the following criteria.

(Evaluation criteria)
“◎”: Deformation is not recognized.
“◯”: Slight deformation is observed.
"X": Deformation is clearly recognized.

(6) Folding resistance of the molded product:
The sheet obtained by the above (3) is left for 30 seconds after demolding, held for 30 seconds in a state where it is bent 180 °, spread and left to stand for 24 hours, and then the bent portion is visually observed. Observed and evaluated according to the following criteria.

(Evaluation criteria)
“◎”: No creases are allowed.
“O”: Some creases are inconspicuous.
“×”: creases are clearly recognized.

(7) Abrasion resistance of molding surface:
About the sheet | seat obtained by said (3), 100 reciprocation tests were done on the following conditions using the reciprocating motion plane abrasion tester, the state of the sheet | seat surface was observed visually, and it evaluated according to the following reference | standard.

(conditions)
・ Reciprocating speed = 40 times / min ・ Friction: 30 mm × 12 mm
・ Load = 29.4N
・ Wear material: Stack of 5 white cotton kanakin No.3

“◎”: No damage was observed.
“◯”: Some damage is inconspicuous.
"X": Damage is noticeable.

(8) Mechanical properties of the molded product:
About the sheet | seat obtained by said (3), the tension test and the tear test were done according to JISK6251-6252, and the tensile strength, the breaking, and the tear strength were measured.

(9) Blooming resistance of the molded product:
The sheet obtained by the above (3) was immersed in water at 50 ° C. for 48 hours, and then dried, and the presence / absence and degree of blooming on the surface were visually observed and evaluated according to the following criteria.

(Evaluation criteria)
“◎”: Blooming is not allowed.
“◯”: Blooming is slightly observed.
“X”: Blooming is noticeable.

* 1) The molecular weight fluctuated from lot to lot. This is an attempt to control the reaction between the remainder of the isocyanate group and the active hydrogen group of the water with R = 0.98, but a part of the added water evaporates, and a predetermined amount (with the remainder of the isocyanate group and This is because the equivalent hydrogen) active hydrogen group could not be reliably reacted with the remainder of the isocyanate group.

* 2) The molecular weight fluctuated greatly from lot to lot. This is thought to be due to the evaporation of ethanol.

The powdery thermoplastic polyurethane urea resin obtained by the production method of the present invention is suitable as a powder material for slush molding. The slush molding made of the polyurethane urea resin is particularly suitable as an interior material for automobiles, and is also useful as a material for indoor furniture such as a sofa.

Claims (6)

A method for producing a powdered thermoplastic polyurethane urea resin,
While reacting a part of the isocyanate group of the isocyanate group-terminated prepolymer with the active hydrogen group of a monofunctional active hydrogen group-containing compound having an active hydrogen group and a hydrocarbon group having 4 to 12 carbon atoms,
A step of reacting the remaining isocyanate group of the isocyanate group-terminated prepolymer with an active hydrogen group of water in a non-aqueous dispersion medium,
When the number of moles of active hydrogen groups in the active hydrogen group-containing compound that reacts with a part of the isocyanate groups is x1, and the number of moles of active hydrogen groups in water that react with the remainder of the isocyanate groups is x2, the ratio ( x1 / x2) is 5-35 / 95-65, The manufacturing method of the powdery thermoplastic polyurethane urea resin characterized by the above-mentioned. A method for producing a powdered thermoplastic polyurethane urea resin,
Including the following first to fourth steps,
The number of moles of active hydrogen groups possessed by the polymer polyol that reacts with the organic polyisocyanate in the second step is A, and the number of moles of active hydrogen groups possessed by the active hydrogen group-containing compound that reacts with a part of the isocyanate groups in the third step. Is x1, and the number of moles of active hydrogen groups having water that reacts with the remainder of the isocyanate group is x2, the ratio [(x1 + x2) / A] is 0.3 to 1.5, and the ratio (x1 / x2) Is 5 to 35/95 to 65, A method for producing a powdered thermoplastic polyurethaneurea resin
First step: A step of preparing a non-aqueous dispersion by dispersing a polymer polyol in an organic solvent that does not substantially dissolve the polymer polyol and the resulting isocyanate group-terminated prepolymer and polyurethane urea resin.
Second step: A step of preparing a dispersion of an isocyanate group-terminated prepolymer by reacting the polymer polyol in the obtained dispersion with an organic polyisocyanate.
Third step: a monofunctional active hydrogen group-containing compound having an active hydrogen group and a hydrocarbon group having 4 to 12 carbon atoms as a part of the isocyanate group of the isocyanate group-terminated prepolymer in the obtained dispersion And reacting the remaining isocyanate group of the isocyanate group-terminated prepolymer with the active hydrogen group of water to prepare a polyurethane urea resin dispersion.
Fourth step: A step of preparing a powdery thermoplastic polyurethane urea resin by separating and drying the polyurethane urea resin from the obtained dispersion.   The powdery heat according to claim 2, wherein the ratio [(x1 + x2) / A] is 0.3 to 1.2, and the ratio (x1 / x2) is 5 to 20/95 to 80. A method for producing a plastic polyurethane urea resin.   The powdery heat according to claim 2, wherein the ratio [(x1 + x2) / A] is 0.75 to 1.5, and the ratio (x1 / x2) is 10 to 35/90 to 65. A method for producing a plastic polyurethane urea resin.   The method for producing a powdered thermoplastic polyurethane urea resin according to any one of claims 2 to 4, wherein the organic polyisocyanate used in the second step is hexamethylene diisocyanate. The method for producing a powdered thermoplastic polyurethane urea resin according to any one of claims 1 to 5, wherein a powdery thermoplastic polyurethane urea resin for slush molding is produced.