JP2011231199A - Method for producing thermoplastic urethane resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin powder composition capable of providing a molded body excellent in daily stability of appearance without impairing the appearance or feeling of the molded article.SOLUTION: A method for producing a polyurethane urea resin (A0) includes reacting a prepolymer (UP) having a terminal isocyanate group, which is prepared by reacting a compound (a) containing an active hydrogen group with diisocyanate (e) containing 1,6-hexamethylene diisocyanate and satisfies the following expression (1): 1.0<Y/X≤1.5 (1) when the number of moles of the active hydrogen group in (a) is X and the number of moles of the isocyanate group in (e) is Y, wherein the rate of a peak area equivalent to methanol-blocked 1,6-hexamethylene diisocyanate to the total peak area of the methanol-blocked (UP) by gel permeation chromatography measurement is 0-1.5%, with water and/or low-molecular-weight diamine.

Description

  The present invention relates to a thermoplastic urethane resin suitable as a molding material and a method for producing a thermoplastic urethane resin powder.

Urethane resins are widely used as molding materials, elastomers, foams, coatings, fibers, adhesives, and sealants, and are generally synthesized from diisocyanates and glycols. The urethane resin is composed of a hard segment made of diisocyanate and a soft segment made of glycol, and a urethane resin having various functions can be designed by selecting diisocyanate and glycol.

Conventionally, as a molding material, particularly a slush molding material, for example, it is made of a thermoplastic polyurethane resin (A), and (A) has a diisocyanate having a symmetric structure, a low molecular diamine having a symmetric structure, and an asymmetric structure. A resin powder material for slush molding, which is a polyurethane urea resin having 5 to 50% by weight of a hard segment composed of a low molecular diamine mixture that is a mixture with a low molecular diamine and a soft segment composed of a high molecular diol, is known. (See Patent Document 1).

Urethane resin molded products may cause the appearance or feel of the molded product to be impaired when low molecular oligomers bleed on the surface of the molded product. For example, aliphatic polyester or a composition cleaning method (see Patent Document 2) or lactone A method for producing a polyol and a method for producing a polyurethane resin using the same have been proposed (see Patent Document 3).
On the other hand, 1,6-hexamethylene diisocyanate (hereinafter referred to as HDI) that exhibits high functionality and is non-yellowing diisocyanate is most frequently used industrially.
Even in urethane resin molded products using HDI, low molecular oligomers may bleed on the surface of the molded product, which may impair the appearance or feel of the molded product, and the production of polyurethane resin powder that controls the content of low molecular oligomers A method (see Patent Document 4) has been proposed.

JP 2005-1113010 A JP 7-316276 A JP 2001-261798 A JP 2009-212293 A

However, in general, washing, extraction, and the like with water or a solvent have been proposed as a method for controlling the low-molecular oligomer content of the urethane resin, but none of the fundamental solutions have been known yet.
That is, the problem to be solved by the present invention is a urethane resin molded product using HDI as a diisocyanate component, which does not impair the appearance and feel of the molded product and is excellent in appearance stability over time. Is to provide.

In the present invention, the compound (a) containing an active hydrogen group reacts with the diisocyanate (e) containing 1,6-hexamethylene diisocyanate, and the number of moles of the active hydrogen group in (a) is represented by X, ( When the number of moles of the isocyanate group in e) is Y, the isocyanate group-terminated prepolymer (UP) satisfying the following formula (1), which is obtained by gel permeation chromatography measurement ( UP) The isocyanate group-terminated prepolymer (UP) in which the ratio of the peak area corresponding to the methanol blocked product of 1,6-hexamethylene diisocyanate to the total peak area of the methanol blocked product of Or a polyurethane urea resin (A0) obtained by reacting with a low molecular diamine Manufacturing method of
1.0 <Y / X ≦ 1.5 (1)
It is a manufacturing method of the polyurethane urea resin powder (A) containing this polyurethane urea resin (A0).

A molded product molded from the resin powder composition obtained by the production method of the present invention does not impair the appearance and feel, and is excellent in appearance stability over time.

The polyurethane urea resin (A0) contained in the polyurethane urea resin powder (A) produced by the production method of the present invention has an isocyanate group terminal consisting of diisocyanate (e) whose isocyanate component contains 1,6-hexamethylene diisocyanate. 1,6-hexamethylene in the total peak area of the methanol-blocked product of the isocyanate group-terminated prepolymer (UP) obtained by measurement of gel permeation chromatography (hereinafter referred to as GPC), which is a prepolymer (UP) It is obtained by reacting an isocyanate group-terminated prepolymer (UP) having a peak area corresponding to a methanol blocked product of diisocyanate of 0 to 1.5% with water and / or a low molecular diamine.

The isocyanate group-terminated prepolymer (UP) is obtained by reacting a compound (a) containing an active hydrogen group with a diisocyanate (e) containing 1,6-hexamethylene diisocyanate. When the number of moles is X and the number of moles of the isocyanate group of (e) is Y, the following formula (1), preferably the following formula (2) is satisfied.
1.0 <Y / X ≦ 1.5 (1)
1.1 <Y / X ≦ 1.4 (2)

“Ratio (%) of peak area (h) corresponding to methanol blocked product of 1,6-hexamethylene diisocyanate to total peak area (p) of methanol blocked product of isocyanate group-terminated prepolymer (UP)” (hereinafter referred to as h / p)) is from 0 to 1.5%. h / p is preferably 0.1 to 1.3%, more preferably 0.1 to 1.1%.
When Y / X exceeds 1.5, h / p also exceeds 1.5%.
When h / p exceeds 1.5%, a bleed material appears on the surface of the molded product, and the appearance and feel are impaired, and the stability of appearance over time deteriorates.

h / p is measured as follows.
<Preparation of measurement sample>
1.5 ml of methyl ethyl ketone is added to 0.5 g of isocyanate group-terminated prepolymer (UP) and dissolved at 80 ° C. for 1 hour in a sealed state. Next, 1.5 ml of methanol is added, and the mixture is reacted at 80 ° C. for 1 hour in a sealed state, and then the solvent is removed in an open system for about 2 hours at 80 ° C.
<GPC measurement conditions>
Model name: Alliance (manufactured by Nippon Waters Co., Ltd.), eluent: tetrahydrofuran, column: Guard Column Super HL (TSKgel Super H4000, TSKgel Super H3000, TSKgel Super H2000), detector: RI, standard sample: CTB8405Be (polystyrene, Sanyo Chemical Industries, Ltd.)

The molded product of polyurethane urea resin powder (A) produced by the above production method bleeds out to the surface and does not impair the appearance and feel.
The bleed-out product on the surface is a low-molecular urea oligomer that is a by-product during the production of the polyurethane urea resin (A0). When (A0) is produced by the above production method, the content of the low-molecular urea oligomer in (A0) is small. Low molecular weight urea oligomers can be quantitatively measured by liquid chromatography.

The diisocyanate (e) may contain another diisocyanate (f) other than 1,6-hexamethylene diisocyanate, and the content of (f) is preferably 0 to 0 based on the weight of (e). 50% by weight, more preferably 0 to 20% by weight.
Examples of the diisocyanate (f) include aliphatic diisocyanates having 2 to 18 carbon atoms (for example, 1,2-ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 1,12-dodeca. Methylene diisocyanate and the like), and alicyclic diisocyanates having 4 to 15 carbon atoms (isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), 1,4-cyclohexylene diisocyanate, methylcyclohexylene diisocyanate ( Hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene, etc.) C8-15 aromatic aliphatic diisocyanate (m- and / or p-xylylene diisocyanate (XDI), α, α, α ', α'-te La methyl xylylene diisocyanate (TMXDI), etc.), modified products of these diisocyanates (carbodiimide, uretdione, urethoimine group, modified diisocyanates having urea group, etc.) and the like.
Among these, aliphatic diisocyanates other than 1,6-hexamethylene diisocyanate (HDI) and alicyclic diisocyanates are preferable.

As a manufacturing method of the polyurethane urea resin powder (A) of this invention, the following manufacturing methods are mentioned, for example.
(1) First, an isocyanate group-terminated urethane prepolymer (UP) is produced from a compound containing an active hydrogen group and excess diisocyanate (e) by the above-described method. One produced by reacting an isocyanate group-terminated urethane prepolymer (UP) with a blocked chain extender (eg, a ketimine compound) in the presence of water and a dispersion stabilizer.
(2) Produced by a method in which a urethane prepolymer (UP) is reacted with a chain extender (for example, diamine and / or water) in the presence of an organic solvent in which the urethane prepolymer (UP) does not dissolve and a dispersion stabilizer. thing.
(3) A mass of a thermoplastic polyurethane resin is obtained by reacting a compound containing an active hydrogen group with diisocyanate and, if necessary, a chain extender (low molecular diamine and / or water). Then, it is manufactured by a method of pulverization (for example, freeze pulverization, a method of cutting through pores in a molten state).
Of the above production methods, (1) is preferred.

The glass transition temperature (hereinafter referred to as Tg) of (A0) is preferably −70 to −30 ° C. Of these, −70 to −40 ° C. is more preferable. When the Tg is −30 ° C. or lower, the soft feeling of the material is obtained when used in a cold region, and the elongation in the tensile test is good. Polyurethane urea resins having a Tg of less than -70 ° C are usually difficult to obtain.
The glass transition temperature here refers to the E ”peak top temperature of the epidermis measured by a dynamic viscoelasticity measuring device (for example, Rheogel-E4000; manufactured by UBM Co., Ltd.). The glass transition temperature of (A0) used for the component is usually about −70 to −30 ° C. Aromatic polyester diol may be used as the diol component, but the ratio of the aliphatic polyester diol to the aromatic polyester diol is used. Is preferably 100: 0 to 60: 40% by weight.

The isocyanate group-terminated prepolymer (UP) is obtained by reacting a compound (a) containing an active hydrogen group with a diisocyanate (e) containing 1,6-hexamethylene diisocyanate. Examples of the compound (a) containing an active hydrogen group include a polymer diol, a polymer diamine, and a polymer dimercaptan, and a polymer diol is preferable. (A) may contain the following low molecular diol.
The polymer diol preferably has a number average molecular weight of 500 to 10,000, and examples thereof include (1) condensed polyester diol, (2) polylactone diol, (3) polycarbonate diol, and a combination of two or more of these. .

The above (1) is, for example, one or more diols (low molecular diols and / or polyether diols) and dicarboxylic acids or ester-forming derivatives thereof [lower alkyl (carbon number 1 to 4) esters, acid anhydrides, halides ( Chloride) and the like], or a reaction of a diol with a dicarboxylic acid anhydride and an alkylene oxide.
The above (2) is obtained by ring-opening polymerization of a lactone using one or more of the above diols as an initiator.
Said (3) can be manufactured by reaction of the said diol and alkylene carbonate (ethylene carbonate).

Among the raw diols for the above (1), (2) and (3), examples of the low molecular diol include aliphatic low molecular diols (ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1 , 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, etc.); low molecular diols having a cyclic group [for example, those described in JP-B No. 45-1474 : 1,4-bis (hydroxymethyl) cyclohexane, and a combination of two or more thereof. Examples of the polyether diol include compounds having two active hydrogen atoms (dihydric alcohol, 1 A compound having a structure in which an alkylene oxide is added to a primary monoamine and the like, and a mixture thereof. The compounds having two active hydrogen atoms are preferably dihydric alcohols, particularly preferably aliphatic low molecular diols (ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1, 6-hexanediol and 1,10-decanediol).

Examples of the raw material dicarboxylic acid for the above (1) include aliphatic dicarboxylic acids having 2 to 10 carbon atoms (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.), these Ester forming derivatives (acid anhydrides, lower alkyl esters (dimethyl ester, diethyl ester, etc.), acid halides (acid chloride, etc.) and the like, and combinations of two or more thereof.

Preferable examples of the above (1) include, for example, polybutylene adipate diol, polyhexamethylene adipate diol, and combinations thereof.
Preferable examples of the (2) polylactone diol include, for example, γ-butyrolactone, γ-valerolactone, ε-caprolactone, and polylactone diols of a mixture of two or more thereof.
Preferable examples of the (3) polycarbonate diol include polyhexamethylene carbonate diol.

As a low molecular diamine added as a chain extender, a C2-C18 aliphatic diamine and / or water are mentioned, for example. Examples of the aliphatic diamine include aliphatic diamines having 2 to 18 carbon atoms (1,2-ethylenediamine, 1,4-tetramethylenediamine, 1,6-hexamethylenediamine (HDA) 1,8-octamethylenediamine. 1,12-dodecamethylenediamine, etc.), C 4-15 alicyclic diamine (4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4′-diamino-3,3′-) Dimethyldicyclohexyl, 4,4′-dicyclohexylmethanediamine, cyclohexane-1,4-diamine, isophoronediamine (IPDA), etc.), aliphatic aromatic diamine (xylylenediamine, α, α, α ′, α′-tetramethylxylyl) Range amines), carbonate-based diamines having 3 to 17 carbon atoms, such as bis (2-aminoethyl) carbo Over DOO, polyoxyethylene diamine (molecular weight of 500 or less), polyoxytetramethylene diamine (molecular weight of 500 or less), and mixtures of two or more thereof.

Examples of the compound containing an active hydrogen group added as a chain extender in addition to a low molecular diamine as a chain extender include aliphatic diols (ethylene glycol, diethylene glycol, propylene glycol, 1, 3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.), aliphatic cyclic group-containing diol (1,4-bis (hydroxymethyl) cyclohexane, 1, 4-cyclohexanediol, hydrogenated bisphenol A, etc.).

An end-capping agent for adjusting the molecular weight of the thermoplastic polyurethane resin (A0) can be used as necessary. Examples of the end capping agent include a low molecular monool and a low molecular monoamine.
Examples of the low molecular monool include aliphatic alcohols (methanol, ethanol, isopropanol, n-butanol, 2-ethylhexanol, 1-octanol, etc.) fatty aromatic alcohols (benzyl alcohol, etc.).
Low molecular monoamines include, for example, aliphatic monoamines having 2 to 18 carbon atoms (monoalkylamines (methylamine, ethylamine, propylamine, butylamine, etc.), dialkylamines (dimethylamine, diethylamine, dipropylamine, dibutylamine, etc.) Mono- and di-alkanolamines (monoethanolamine, diethanolamine, etc.) and mixtures of two or more thereof.
Of these, preferred are aliphatic alcohols, fatty aromatic alcohols and aliphatic monoamines, and more preferred are 1-octanol, 2-ethylhexanol, benzyl alcohol, dipropylamine and dibutylamine.

The number average molecular weight of the polyurethane urea resin powder (A) is preferably 5,000 to 50,000, more preferably 8,000 to 40,000. 5,000 or more is preferable from the viewpoint of breaking strength of the molded body, and 50,000 or less is preferable from the viewpoint of melt viscosity at the time of heat melting. The number average molecular weight here means the molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography.

The volume average particle diameter of the polyurethane urea resin powder (A) is preferably in the range of 10 to 500 μm, more preferably 70 to 300 μm. The volume average particle diameter is measured by a laser diffraction / scattering method, and can be measured by, for example, a microtrack particle size analyzer (MKIIISRA 7997-10 manufactured by Nikkiso Co., Ltd.).

To the polyurethane urea resin powder composition (S) of the present invention, the additive (C) is added to the polyurethane urea resin powder (A). As additives, plasticizers, fillers, stabilizers, pigments, mold release agents, antiblocking agents, dispersants and the like can be added.
The addition amount of the additive is preferably 0.1 to 50% by weight with respect to the weight of the polyurethane urea resin powder composition (S).

The plasticizer is not particularly limited, and examples thereof include an epoxy plasticizer, an ester plasticizer, a phosphate ester plasticizer, and an ether plasticizer.
The blending ratio of the plasticizer is preferably 2 to 50 parts by weight, more preferably 2 to 30 parts by weight per 100 parts by weight of the polyurethane urea resin powder (A). If it is 2 parts by weight or more, the melt viscosity at the time of molding is low and the moldability is good, and if it is 50 parts by weight or less, it will not bleed out to the surface of the molding skin over time. The plasticizer is preferably used alone, but the above plasticizer can be used in combination as necessary.

Examples of the filler include kaolin, talc, silica, titanium oxide, calcium carbonate, bentonite, mica, sericite, glass flake, glass fiber, graphite, magnesium hydroxide, aluminum hydroxide, antimony trioxide, barium sulfate, and zinc borate. , Inorganic fillers such as alumina, magnesia, wollastonite, zonotlite, whisker, metal powder and the like. Of these, kaolin, talc, silica, titanium oxide, and calcium carbonate are preferred from the viewpoint of promoting crystallization of the thermoplastic resin, and kaolin and talc are more preferred.
The volume average particle size of the inorganic filler is preferably 0.1 to 30 μm, more preferably 1 to 20 μm, and particularly preferably 5 to 10 μm from the viewpoint of dispersibility in the thermoplastic resin.

Examples of the stabilizer include known antioxidants and / or light stabilizers and / or double bonds between carbon atoms in the molecule (an ethylene bond which may have a substituent) (however, two in the aromatic ring). And a triple bond (acetylene bond which may have a substituent).
Examples of the antioxidant include phenolic (2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, etc.) and bisphenol (2,2′-methylenebis (4-methyl-6-t-butylphenol). Etc.), phosphorus-based (triphenyl phosphite, diphenylisodecyl phosphite, etc.) and the like.
Examples of the light stabilizer include ultraviolet absorbers [benzophenone (2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, etc.), benzotriazole (2- (2′-hydroxy-5′-methylphenyl) benzoate. Triazole etc.), quencher [nickel chelate type etc.], salicylic acid type [phenyl salicylate etc.], radical scavenger [hindered amine type ((bis-2,2,6,6-tetramethyl-4-piperidyl) sebacate etc.) Etc.

Double bond between carbon atoms (optionally substituted ethylene bond) (excluding double bond in aromatic ring), triple bond (optionally substituted acetylene bond) Specific examples of the compound having) include esters of (meth) acrylic acid and polyhydric alcohols (2 to 10 or more polyhydric alcohols; the same shall apply hereinafter) [for example, ethylene glycol di (meth) acrylate, tri Methylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, etc.]; ester of (meth) allyl alcohol with 2 to 6 or more polyvalent carboxylic acids [ For example, diallyl phthalate, trimellitic acid triallyl ester, etc.]; poly (meth) allylate of polyhydric alcohols [For example, pentaerythritol (meth) allyl ether, etc.]; Polyvinyl ethers of polyhydric alcohols [eg, ethylene glycol divinyl ether, etc.]; Polypropenyl ethers of polyhydric alcohols [eg, ethylene glycol dipropenyl ether, etc.]; For example, divinylbenzene etc.] and a mixture of two or more of these. Among these, preferred are esters of (meth) acrylic acid and polyhydric alcohols in terms of radical polymerization rate, and particularly preferred are trimethylolpropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate. And dipentaerythritol penta (meth) acrylate.

As the pigment, for example, a known organic pigment and / or inorganic pigment can be used. Organic pigments include insoluble azo pigments, soluble azo pigments, copper phthalocyanine pigments, quinacridone pigments, and inorganic pigments include carbon black, chromate, ferrocyanide compounds, metal oxides, selenium sulfide compounds, metal salts ( (Sulfates, oxalates, carbonates, phosphates, etc.) and metal powders.

As the mold release agent, a known mold release agent can be used. For example, a fluorine type mold release agent (such as a fluoroalkyl ester phosphate), a silicon type mold release agent (dimethylpolysiloxane, amino-modified dimethylpolysiloxane, carboxyl-modified dimethyl). Polysiloxane, ether-modified dimethylpolysiloxane, etc.), fatty acid ester release agent (alkane (carbon number 11-24) alkenyl (carbon number 6-24) ester, etc.), phosphate ester release agent (tributyl phosphate) Ester) and the like.

As an antiblocking agent, a well-known inorganic type antiblocking agent and / or an organic type antiblocking agent can be used, for example.
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 thermoplastic resins (thermoplastic polyurethane, thermoplastic polyurethane urea) having a particle diameter of 10 microns or less. , Poly (meth) acrylate resin, etc.), maleimide resin powder, etc., and thermosetting resins (thermosetting polyurethane resin, guanamine resin, epoxy resin, etc.) having a particle size of 10 microns or less.

As a mixing device used when the additive (C) is added to and mixed with the polyurethane urea resin powder (A), a known powder mixing device can be used, and a container rotating mixer, a fixed container mixer, Any of the fluid motion mixers can be used. For example, as a fixed container type mixer, a high-speed flow type mixer, a double-shaft paddle type mixer, a high-speed shear mixing device (Hensiel mixer (registered trademark), etc.), a low-speed mixing device (planetary mixer, etc.), or a conical screw mixer A dry blending method using a machine (Nauta Mixer (registered trademark) or the like) is well known. Among these methods, it is preferable to use a double-shaft paddle type mixer, a low-speed mixing device (planetary mixer or the like), and a conical screw mixer (Nauta mixer (registered trademark, hereinafter omitted) or the like).

Examples of the method for molding the polyurethane urea resin powder composition of the present invention include a slush molding method, an injection molding method, an extrusion molding method, a calendar molding method, and a powder molding method.
For example, for molding by the slush molding method, a box containing the polyurethane urea resin powder composition of the present invention and a mold heated to 200 to 280 ° C. were vibrated and rotated, and the powder was fluidly melted in the mold. It can cool later and can implement suitably by the method of manufacturing a sheet | seat.
The thickness of the sheet molded with the polyurethane urea resin powder composition of the present invention is preferably 0.5 to 1.5 mm. These molded sheets can correspond to various shapes depending on the shape of the mold, and are suitable as, for example, automobile interior parts such as instrument panels and door trims, home appliance parts, toys, and miscellaneous goods.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to production examples and examples, but the present invention is not limited thereto. In the following, “parts” represents parts by weight, and “%” represents% by weight.

Production Example 1
Production of Prepolymer Solution 1 In a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, polybutylene adipate diol (549.3 parts) having a number average molecular weight (hereinafter referred to as Mn) of 1,000, Mn 900 Polyhexamethylene isophthalate diol (61.0 parts) antioxidant (1.2 parts) [manufactured by Ciba Specialty Chemicals; IRGANOX1010], kaolin (91.6 parts) with a volume average diameter of 9 μm [Georgia Engel Made by Asahi; ASP400P] was substituted with nitrogen and stirred uniformly at 60 ° C. with stirring. Subsequently, 2-ethylhexanol (10.3 parts) and MEK (150.0 parts) were charged and stirred uniformly, then cooled to 50 ° C., charged with hexamethylene diisocyanate (134.8 parts), and stirred at 90 ° C. for 6 Reacted for hours. After cooling to 60 ° C., an ultraviolet absorber (1.8 parts) [manufactured by Ciba Specialty Chemicals Co., Ltd .; TINUVIN571] was charged and stirred uniformly to obtain a prepolymer solution (UP-1). Y / X was 1.3.
(UP-1) 1000 parts of colorant (25.5 parts) [Daiichi Seika Kogyo Co., Ltd .; FTR SNY 72 Black], polycarbodiimide (13.2 parts) [Nisshinbo Co., Ltd .; Carbolite V- 09] and stirred uniformly to obtain a colored prepolymer solution (UP-1 ′). (UP-1 ′) has an NCO content of 1.2% and methanol of 1,6-hexamethylene diisocyanate in the total peak area of the methanol blocked product of (UP-1 ′) obtained by gel permeation chromatography measurement. The peak area h / p corresponding to the blocked product was 0.3%.

Production Example 2
Production of Prepolymer Solution 2 Polybutylene adipate diol (536.2 parts) having a number average molecular weight (hereinafter referred to as Mn) of 1,000 in a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, Mn900 Polyhexamethylene isophthalate diol (59.6 parts) antioxidant (1.2 parts) [manufactured by Ciba Specialty Chemicals; IRGANOX 1010], kaolin (89.4 parts) with a volume average diameter of 9 μm [Georgia Engel Made by Asahi; ASP400P] was substituted with nitrogen and stirred uniformly at 60 ° C. with stirring. Subsequently, 2-ethylhexanol (10.1 parts) and MEK (150.0 parts) were charged and stirred uniformly, then cooled to 50 ° C. and charged with hexamethylene diisocyanate (151.8 parts) at 90 ° C. Reacted for hours. After cooling to 60 ° C., an ultraviolet absorber (1.8 parts) [manufactured by Ciba Specialty Chemicals; TINUVIN571] was charged and stirred uniformly to obtain a prepolymer solution (UP-2). Y / X was 1.5.
(UP-2) 1000 parts of colorant (25.5 parts) [Daiichi Seika Kogyo Co., Ltd .; FTR SNY 72 Black], polycarbodiimide (13.2 parts) [Nisshinbo Co., Ltd .; Carbolite V- 09] and stirred uniformly to obtain a colored prepolymer solution (UP-2 ′). The NCO content of the obtained (UP-2 ′) was 2.2% and 1,6-hexa in the total peak area of the methanol blocked product of (UP-2 ′) obtained by gel permeation chromatography measurement. The peak area h / p corresponding to the methanol blocked product of methylene diisocyanate was 1.5%.

Production Example 3
Production of Prepolymer Solution 3 In a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, polybutylene adipate diol (556.1 parts) having a number average molecular weight (hereinafter referred to as Mn) of 1,000, Mn 900 Polyhexamethylene isophthalate diol (61.8 parts), antioxidant (1.2 parts) [manufactured by Ciba Specialty Chemicals; IRGANOX 1010], kaolin (92.7 parts) with a volume average diameter of 9 μm [Georgia Engel Made by Asahi; ASP400P] was substituted with nitrogen and stirred uniformly at 60 ° C. with stirring. Subsequently, 2-ethylhexanol (10.5 parts) and MEK (150.0 parts) were charged, stirred uniformly, then cooled to 50 ° C., charged with hexamethylene diisocyanate (125.9 parts), and stirred at 90 ° C. for 6 Reacted for hours. After cooling to 60 ° C., an ultraviolet absorber (1.8 parts) [manufactured by Ciba Specialty Chemicals; TINUVIN571] was charged and stirred uniformly to obtain a prepolymer solution (UP-3). Y / X was 1.2.
(UP-3) 1000 parts of a colorant (25.5 parts) [Daiichi Seika Kogyo Co., Ltd .; FTR SNY 72 Black], polycarbodiimide (13.2 parts) [Nisshinbo Co., Ltd .; Carbolite V- 09] and stirred uniformly to obtain a colored prepolymer solution (UP-3 ′). The NCO content of the obtained (UP-3 ′) was 0.7% and 1,6-hexa in the total peak area of the methanol blocked product of (UP-3 ′) obtained by gel permeation chromatography measurement. The peak area h / p corresponding to the methanol blocked product of methylene diisocyanate was 0.1%.

Production Example 4
Production of Prepolymer Solution 4 Polybutylene adipate diol (563.0 parts) having a number average molecular weight (hereinafter referred to as Mn) of 1,000 in a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, Mn900 Polyhexamethylene isophthalate diol (62.6 parts), antioxidant (1.3 parts) [manufactured by Ciba Specialty Chemicals; IRGANOX 1010], kaolin with a volume average diameter of 9 μm (93.8 parts) [Georgia Engel Co., Ltd .; ASP400P] was charged and purged with nitrogen, followed by uniform stirring at 60 ° C. with stirring. Subsequently, 2-ethylhexanol (10.6 parts) and MEK (150.0 parts) were charged and stirred uniformly, then cooled to 50 ° C., charged with hexamethylene diisocyanate (116.9 parts), and stirred at 90 ° C. for 6 Reacted for hours. The mixture was cooled to 60 ° C., charged with an ultraviolet absorber (1.9 parts) [manufactured by Ciba Specialty Chemicals; TINUVIN571], and stirred uniformly to obtain a prepolymer solution (UP-4). Y / X was 1.1.
(UP-4) 1000 parts with a colorant (25.5 parts) [Daisei Seika Kogyo Co., Ltd .; FTR SNY 72 Black], polycarbodiimide (13.2 parts) [Nisshinbo Co., Ltd .; Carbolite V- 09] and stirred uniformly to obtain a colored prepolymer solution (UP-4 ′). The NCO content of the obtained (UP-4 ′) was 0.2% and 1,6-hexa in the total peak area of the methanol blocked product of (UP-4 ′) obtained by gel permeation chromatography measurement. The peak area h / p corresponding to the methanol blocked product of methylene diisocyanate was 0.0%.

Comparative production example 1
Polybutylene adipate diol (529.9 parts) having a number average molecular weight (hereinafter referred to as Mn) of 1,000 in a reaction vessel equipped with a production thermometer, a stirrer and a nitrogen blowing tube for prepolymer solution 5, Mn900 Polyhexamethylene isophthalate diol (58.9 parts), antioxidant (1.2 parts) [manufactured by Ciba Specialty Chemicals; IRGANOX 1010], kaolin (88.3 parts) with a volume average diameter of 9 μm [Georgia Engel Co., Ltd .; ASP400P] was charged and purged with nitrogen, followed by uniform stirring at 60 ° C. with stirring. Subsequently, 2-ethylhexanol (10.0 parts) and MEK (150.0 parts) were charged and stirred uniformly, then cooled to 50 ° C., charged with hexamethylene diisocyanate (160.0 parts), and heated at 90 ° C. for 6 Reacted for hours. After cooling to 60 ° C., an ultraviolet absorber (1.8 parts) [manufactured by Ciba Specialty Chemicals; TINUVIN571] was charged and stirred uniformly to obtain a prepolymer solution (UP-4). Y / X was 1.6.
(UP-1 ratio) 1000 parts with colorant (25.5 parts) [Daiichi Seika Kogyo Co., Ltd .; FTR SNY 72 Black], polycarbodiimide (13.2 parts) [Nisshinbo Co., Ltd .; Carbolite V -09] was charged and stirred uniformly to obtain a colored prepolymer solution (UP-1 ratio ′). The NCO content of the obtained (UP-1 ratio ') was 2.7%, which was 1.6% in the total peak area of the methanol blocked product of (UP-1 ratio') obtained by gel permeation chromatography measurement. -The peak area h / p corresponding to the methanol blocked product of hexamethylene diisocyanate was 1.8%.

Comparative production example 2
Production of prepolymer solution 6 A polybutylene adipate diol (523.7 parts) having a number average molecular weight (hereinafter referred to as Mn) of 1,000 in a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, Mn 900 Polyhexamethylene isophthalate diol (58.2 parts), antioxidant (1.2 parts) [manufactured by Ciba Specialty Chemicals; IRGANOX 1010], kaolin with a volume average diameter of 9 μm (87.3 parts) [Georgia Engel Co., Ltd .; ASP400P] was charged and purged with nitrogen, followed by uniform stirring at 60 ° C. with stirring. Subsequently, 2-ethylhexanol (9.9 parts) and MEK (150.0 parts) were charged and stirred uniformly, then cooled to 50 ° C. and charged with hexamethylene diisocyanate (168.0 parts) at 90 ° C. Reacted for hours. After cooling to 60 ° C., an ultraviolet absorber (1.8 parts) [manufactured by Ciba Specialty Chemicals Co., Ltd .; TINUVIN571] was charged and stirred uniformly to obtain a prepolymer solution (UP-2 ratio). Y / X was 1.7.
(UP-2 ratio) 1000 parts colorant (25.5 parts) [manufactured by Dainichi Seika Kogyo Co., Ltd .; FTR SNY 72 Black], polycarbodiimide (13.2 parts) [Nisshinbo Co., Ltd .; Carbolite V -09] and uniformly stirred to obtain a colored prepolymer solution (UP-2 ratio ′). The NCO content of the obtained (UP-2 ratio ′) was 3.1%, which was 1.6% in the total peak area of the methanol blocked product of (UP-2 ratio ′) obtained by gel permeation chromatography measurement. -The peak area h / p corresponding to the methanol blocked product of hexamethylene diisocyanate was 2.3%.

Production Example 5
Preparation of MEK ketimine product of diamine Hexamethylenediamine (116 parts), excess methyl ethyl ketone (hereinafter referred to as MEK, 288 parts, 4 times the molar amount with respect to diamine), n-hexane (29 parts) at 80 ° C. The product water was removed out of the system while refluxing for a period of time. Thereafter, unreacted MEK and n-hexane were removed under reduced pressure to obtain a MEK ketiminate (K-1).

Example 1
In a reaction vessel, the colored prepolymer solution (UP-1 ′) (100.0 parts) obtained in Production Example 1 and the MEK ketimine product (K-1) (3.2 parts) obtained in Production Example 5 were added. The mixture was added, and 300 parts by weight of an aqueous solution in which a dispersant (manufactured by Sanyo Chemical Industries, Ltd .; Sunspear PS-8) (24 parts by weight) was dissolved was added, and JANKE & KUNKEL IKA-Labortechnik; ULTRA-TURRAX T50 was used And mixing at a rotational speed of 5000 rpm for 1 minute. This mixture was transferred to a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen blowing tube, and deMEK was performed for 2 hours under reduced pressure at 60 ° C. while stirring. Filtration and drying were carried out to produce polyurethane urea resin powder (A-1) composed of polyurethane urea resin (A0-1). The glass transition temperature of (A0-1) was −41 ° C., and the urea oligomer content was 18 ppm.

Example 2
In a reaction vessel, the colored prepolymer solution (UP-2 ′) (100.0 parts) obtained in Production Example 2 and the MEK ketimine product (K-1) (5.7 parts) obtained in Production Example 5 were added. The mixture was added, and 300 parts by weight of an aqueous solution in which a dispersant (manufactured by Sanyo Chemical Industries, Ltd .; Sunspear PS-8) (24 parts by weight) was dissolved was added, and JANKE & KUNKEL IKA-Labortechnik; ULTRA-TURRAX T50 was used And mixing at a rotational speed of 5000 rpm for 1 minute. This mixture was transferred to a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen blowing tube, and deMEK was performed for 2 hours under reduced pressure at 60 ° C. while stirring. Filtration and drying were carried out to produce a polyurethane urea resin powder (A-2) comprising a polyurethane urea resin (A0-2). The glass transition temperature of (A0-2) was −41 ° C., and the urea oligomer content was 130 ppm.

Example 3
In a reaction vessel, the colored prepolymer solution (UP-3 ′) (100.0 parts) obtained in Production Example 3 and the MEK ketimine product (K-1) (5.7 parts) obtained in Production Example 5 were added. The mixture was added, and 300 parts by weight of an aqueous solution in which a dispersant (manufactured by Sanyo Chemical Industries, Ltd .; Sunspear PS-8) (24 parts by weight) was dissolved was added, and JANKE & KUNKEL IKA-Labortechnik; ULTRA-TURRAX T50 was used And mixing at a rotational speed of 5000 rpm for 1 minute. This mixture was transferred to a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen blowing tube, and deMEK was performed for 2 hours under reduced pressure at 60 ° C. while stirring. Filtration and drying were carried out to produce polyurethane urea resin powder (A-3) composed of polyurethane urea resin (A0-3). The glass transition temperature of (A0-3) was −41 ° C., and the urea oligomer content was 3 ppm.

Example 4
In a reaction vessel, the colored prepolymer solution (UP-4 ′) (100.0 parts) obtained in Production Example 4 and the MEK ketimine product (K-1) (1.6 parts) obtained in Production Example 5 were added. The mixture was added, and 300 parts by weight of an aqueous solution in which a dispersant (manufactured by Sanyo Chemical Industries, Ltd .; Sunspear PS-8) (24 parts by weight) was dissolved was added, and JANKE & KUNKEL IKA-Labortechnik; ULTRA-TURRAX T50 was used And mixing at a rotational speed of 5000 rpm for 1 minute. This mixture was transferred to a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen blowing tube, and deMEK was performed for 2 hours under reduced pressure at 60 ° C. while stirring. Filtration and drying were carried out to produce a polyurethane urea resin powder (A-4) composed of a polyurethane urea resin (A0-4). The glass transition temperature of (A0-4) was −41 ° C., and the urea oligomer content was 0 ppm.

Comparative Example 1
In a reaction vessel, the colored prepolymer solution (UP-5 ′) (100.0 parts) obtained in Comparative Production Example 1 and the MEK ketimine product (K-1) obtained in Production Example 5 (7.0 parts) Was added thereto, and 300 parts by weight of an aqueous solution in which a dispersant (Sanyo Kasei Kogyo Co., Ltd .; Sunspear PS-8) (24 parts by weight) was dissolved was added, and JANKE & KUNKEL IKA-Labortechnik; ULTRA-TURRAX T50 was added. And mixed for 1 minute at a rotational speed of 5000 rpm. This mixture was transferred to a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen blowing tube, and deMEK was performed for 2 hours under reduced pressure at 60 ° C. while stirring. Filtration and drying were performed to produce a polyurethane urea resin powder (A-1 ratio) made of a polyurethane urea resin (A0-1 ratio). The glass transition temperature of (A0-1 ratio) was −41 ° C., and the urea oligomer content was 167 ppm.

Comparative Example 2
In a reaction vessel, the colored prepolymer solution (UP-6 ′) (100.0 parts) obtained in Comparative Production Example 2 and the MEK ketimine product (K-1) obtained in Production Example 5 (8.0 parts) Was added thereto, and 300 parts by weight of an aqueous solution in which a dispersant (Sanyo Kasei Kogyo Co., Ltd .; Sunspear PS-8) (24 parts by weight) was dissolved was added, and JANKE & KUNKEL IKA-Labortechnik; ULTRA-TURRAX T50 was added. And mixed for 1 minute at a rotational speed of 5000 rpm. This mixture was transferred to a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen blowing tube, and deMEK was performed for 2 hours under reduced pressure at 60 ° C. while stirring. Filtration and drying were performed to produce a polyurethane urea resin powder (A-2 ratio) composed of a polyurethane urea resin (A0-2 ratio). The glass transition temperature of (A0-2 ratio) was −41 ° C., and the urea oligomer content was 201 ppm.

Examples 5-8
Polyurethane urea resin powders (A-1) to (A-4) (103.0 parts) obtained in Examples 1 to 4, plasticizer (polyethylene glycol dibenzoate [manufactured by Sanyo Chemical Industries, Ltd .; Sun Soft EB300] 11.5 parts, Stabilizer [manufactured by Sanyo Chemical Industries; Neomer DA600] 4.0 parts, Light Stabilizer [Ciba Specialty Chemicals Co., Ltd .; Sanol LS765] 0.3 parts , 0.1 part of dimethylpolysiloxane [Toray Dow Corning Co., Ltd .; SH200 (10000)] and 0.1 part of modified dimethylpolysiloxane [Shin-Etsu Chemical Co., Ltd .; X-22-3710ST] were added. And mixing at 70 ° C. for 4 hours.
Next, after cooling to room temperature, 0.3 parts of polymethyl methacrylate fine powder [manufactured by Ganz Kasei Co., Ltd .; Gantz Pearl PM-030S], 0.3 part of silica fine powder [manufactured by Grace Devison Chemical; silo block S200] The mixture was charged and mixed to obtain resin powder compositions for molding (S-1) to (S-4). The volume average particle size of (S-1) is 148 μm, the volume average particle size of (S-2) is 151 μm, the volume average particle size of (S-3) is 150 μm, and the volume average particle size of (S-4) is It was 155 μm.

Comparative Examples 3 and 4
Polyurethane urea resin powders obtained in Comparative Production Examples 3 and 4 (A-1 ratio), (A-2 ratio) (103.0 parts), plasticizer (polyethylene glycol dibenzoate [Sanyo Chemical Industries, Ltd.) Sunsoft EB300] 11.5 parts, Stabilizer [manufactured by Sanyo Chemical Industries; Neomer DA600] 4.0 parts, Light stabilizer [Ciba Specialty Chemicals Co., Ltd .; Sanol LS765] 0 .3 parts, 0.1 part of dimethylpolysiloxane [manufactured by Dow Corning Toray; SH200 (10000)], 0.1 part of modified dimethylpolysiloxane [manufactured by Shin-Etsu Chemical Co., Ltd .; X-22-3710ST] And mixed at 70 ° C. for 4 hours.

  Next, after cooling to room temperature, 0.3 parts of polymethyl methacrylate fine powder [manufactured by Ganz Kasei Co., Ltd .; Gantz Pearl PM-030S], 0.3 part of silica fine powder [manufactured by Grace Devison Chemical; silo block S200] The mixture was charged and mixed to obtain a molding resin powder composition (S-1 ratio) and (S-2 ratio). The volume average particle diameter of (S-1 ratio) was 150 μm, and the volume average particle diameter of (S-2 ratio) was 151 μm.

Method for Analyzing Bleed Material Content The main component of the low molecular weight oligomer that becomes the bleed material is a low molecular weight urea oligomer, and the content of the low molecular weight urea oligomer (B) can be quantitatively measured by chromatography.

<LC-UV measurement>
(1) Urea oligomer extraction in urethane urea resin powder Polyurethane urea resin powders (A-1) to (A-6) 100 g of ultrapure water is used for about 1.0 g and the temperature is stirred at 60 ° C. Extract urea oligomers.
(2) Measurement of urea oligomer amount The supernatant of the extraction solution obtained in (1) is filtered with a microfilter, and measurement is performed under the following conditions using LC-UV (Prominence UFLC manufactured by Shimadzu Corporation). A calibration curve is prepared using N, N dimethylacetamide as a standard substance.
The urea oligomer amount is calculated from the peak area ratio of the urea oligomer to the peak area of tetraethylene glycol.

<HPLC conditions>
Mobile phase A solution 100 mM NaH ₂ PO ₄ · 2H ₂ O · 1 mM Na ₂ PO ₄ / 12H ₂ O aqueous solution B solution methanol / column Shinwa Kako Shimpak ODS-II length 150 mm inner diameter 2 mm particle size 5 μm temperature 40 ° C.
・ Detector Measurement wavelength 200nm Slit width 1.2nm Cell semi-micro flow cell ・ Sample injection volume 10μm

Molding resin powder compositions (S-1), (S-2), (S-3), (S-4) of Examples 5 to 8 and molding resin powder compositions of Comparative Examples 3 and 4 (S -1 ratio) and (S-2 ratio) are used to create a molded sheet, and the appearance and tactile sensation of the molded sheet are evaluated over time, and the tensile strength and glass transition temperature are measured by the methods described below. The results are shown in Table 1.

<Method for creating molded sheet>
The polyurethane urea resin powder compositions (S-1) to (S-6) are poured into a Ni electric mold with a grain heated to 270 ° C. in advance, and after 10 seconds, excess resin powder is discharged. After standing at room temperature for 60 seconds and then cooling with water and demolding, a uniform molded sheet having a thickness of about 1 mm was obtained.

<Bleedability>
The molded sheet is put in a bag of polyethylene or the like and stored at room temperature, and the change with time is visually and tactilely determined by the following series.
<Judgment criteria>
Grade 0: Bleed material is not observed Grade 1: Slightly bleed material is seen only on the back of the molded product.
Second grade: Slightly bleed material is seen on both side and back of molded product. (There is no change in tactile sensation in 0-2 grade.)
3rd grade: Bleed material is clearly seen in part. Slight slime and dampness can be felt in the bleed part.

Grade 4: Bleed material is clearly seen on the entire surface. Slight slime and dampness can be felt in the bleed part.
Grade 5: Bleed materials can be seen to the extent that the color and texture of the molded product are difficult to judge. The bleed part clearly feels slime and moist.

The molded sheet prepared by the above method was measured for tensile strength and tear strength by the following method.
-Tensile strength was measured according to JIS K6251-2004.
-Tear strength was measured according to JIS K6252-2004.

Further, the glass transition temperature and fogging test were used after preparing a molded sheet and storing it for 24 hours under conditions of 23 ° C. and 50% RH.
-A molded sheet having a glass transition temperature width of about 5 mm and a length of about 45 mm is cut out and attached to a dynamic viscoelasticity measuring device (Rheogel-E4000, manufactured by UBM), and the tensile temperature dependence from −80 ° C. to 30 ° C. at a frequency of 10 Hz. Measurements were made. The obtained E ″ peak top temperature was estimated as the glass transition temperature of the resin.
・ Foging test (glass sag)
After putting 5.0 g of a molded sheet into a cylindrical tube with a bottom of an inner diameter of 50 mm and a length of 150 mm, and covering with a transparent glass plate with a thickness of 4 mm, it is immersed in a 100 ° C. oil bath to a position of 50 mm from the bottom and allowed to stand for 24 hours. It was heated. After the test, the transmittance of the glass plate was measured. The higher the transmittance of the glass plate, the less fogging components are generated.

As can be seen from Table 1, the molded sheets obtained from the resin powder compositions for slush molding of Examples 1 to 4 of the present invention are excellent in the stability of the appearance and feel over time. Moreover, Tg is low and it is excellent in the soft feeling under low temperature.
The skin formed from the resin powder composition of the present invention is suitably used as a slush composition for automobile parts, home appliance parts, toys, miscellaneous goods, etc., for example, as a slush composition for instrument panels, door trims, and the like.

  The skin formed from the resin powder composition of the present invention is suitably used as a slush composition for automobile parts, home appliance parts, toys, miscellaneous goods, etc., for example, as a slush composition for instrument panels, door trims, and the like.

Claims (4)

The compound (a) containing an active hydrogen group reacts with a diisocyanate (e) containing 1,6-hexamethylene diisocyanate, and the number of active hydrogen groups in (a) is X, and the isocyanate in (e). Isocyanate group-terminated prepolymer (UP) satisfying the following formula (1) when the number of moles of the group is Y, and methanol of the isocyanate group-terminated prepolymer (UP) obtained by gel permeation chromatography measurement Isocyanate group-terminated prepolymer (UP) in which the ratio of the peak area corresponding to the methanol blocked product of 1,6-hexamethylene diisocyanate to the total peak area of the blocked product is 0 to 1.5%, water and / or low molecular diamine A process for producing a polyurethaneurea resin (A0) obtained by reacting with .
1.0 <Y / X ≦ 1.5 (1) The production method according to claim 1, wherein the diisocyanate (e) is 1,6-hexamethylene diisocyanate. The manufacturing method of the polyurethane urea resin powder (A) whose polyurethane urea resin (A0) obtained by the manufacturing method of the polyurethane urea resin (A0) of Claim 1 or 2 is a powder. A method for producing a polyurethane urea resin powder composition (S), wherein an additive (C) is added to the polyurethane urea resin powder (A) obtained by the production method according to claim 3.