JP2018115257A - Powdery polyurethaneurea resin composition for slash molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powdery polyurethaneurea resin composition for slash molding which achieves both moldability at low temperature and deformation resistance at high temperature of a slash molded article.SOLUTION: A powdery polyurethaneurea resin composition for slash molding (P) contains a thermoplastic polyurethaneurea resin (U), where the thermoplastic polyurethaneurea resin (U) is obtained by reaction of raw materials of polyester diol (A) having a number average molecular weight of 500-3,000, alicyclic diisocyanate (B), aromatic ring-containing diol (C) having a number average molecular weight of 110 or more and less than 500, and aliphatic or alicyclic diamine (D).SELECTED DRAWING: None

Description

  The present invention relates to a powdered polyurethane urea resin composition for slush molding.

The slush molding method has advantages such as the ability to easily form products with complex shapes (undercut and deep drawing, etc.), uniform thickness, and good material yield rate. It is widely used in applications centering on adhesives and the like.
As the slush molding material, soft polyvinyl chloride powder is mainly used, but polyurethane urea resin is also used in recent years (see, for example, Patent Document 1).
In general, molded products made of slush molded urethane urea resin that has a low melt viscosity and can be molded at low temperatures have low heat softening temperatures, and have problems such as deformation in high-temperature usage environments and adhesion between molded products. Arise.
For this reason, when the urea group density | concentration of the polyurethane urea resin used for a slush molding is made high for the purpose of the improvement of the deformation resistance under high temperature, the meltability at the time of shaping | molding is not enough, and the quality of a molded product falls. Further, when the urethane group concentration is increased, there is a problem that the viscosity of the prepolymer is excessively increased and problems such as failure to form particles occur.

JP 2007-204693 A

  An object of the present invention is to provide a powdery polyurethane urea resin composition for slush molding that achieves both low temperature moldability and high temperature deformation resistance of a slush molded product.

  As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention is a powdery polyurethane urea resin composition (P) for slush molding containing a thermoplastic polyurethane urea resin (U), wherein the thermoplastic polyurethane urea resin (U) has a number average molecular weight of 500 to 3000. Reaction of raw material containing polyester diol (A), alicyclic diisocyanate (B), aromatic ring-containing diol (C) having a number average molecular weight of 110 or more and less than 500, and aliphatic or alicyclic diamine (D) It is a powdery polyurethane urea resin composition (P) for slush molding obtained.

  The powdery polyurethane urea resin composition for slush molding of the present invention is excellent in moldability at low temperature and resistance to deformation at high temperature.

<Polyester diol (A) having a number average molecular weight of 500 to 3000>
Examples of the polyester diol (A) in the present invention include polyester diol, polyether ester diol, and a mixture of two or more thereof.
Examples of the polyester diol include (i) a low molecular diol and a dicarboxylic acid or an ester-forming derivative thereof [an acid anhydride, a lower alkyl (1 to 4 carbon atoms) ester, an acid halide, etc.] or a dialkyl carbonate (carbon number of an alkyl group). 1 to 4) by condensation polymerization; (ii) ring-opening polymerization of a lactone monomer using a low molecular diol as an initiator; (iii) a dicarboxylic acid anhydride and an alkylene oxide are reacted using a low molecular diol as an initiator. And mixtures of two or more thereof.

Specific examples of the low molecular diols (i), (ii) and (iii) above include aliphatic diols having 2 to 8 carbon atoms [linear diols (ethylene glycol, diethylene glycol, 1,3-propanediol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc.), branched diols (propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl) -1,3-propanediol, 1,2-, 1,3- or 2,3-butanediol, etc.]]; diols having a cyclic group [C6-C15 alicyclic group-containing diol [1, 4-bis (hydroxymethyl) cyclohexane, hydrogenated bisphenol A, etc.], aromatic ring-containing diol having 8 to 20 carbon atoms (m- or p-xylylene glyco) ), Oxyalkylene ethers of bisphenols (bisphenol A, bisphenol S, bisphenol F, etc.), oxyalkylene ethers of polynuclear phenols (dihydroxynaphthalene, etc.), bis (2-hydroxyethyl) terephthalate, etc.]; these alkylene oxides Examples include adducts (molecular weight less than 500) and mixtures of two or more thereof.
Of these, the diol is preferably an aliphatic diol having 2 to 8 carbon atoms because it is easily available.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-, 1,3-, 1,4- or 2,3-butylene oxide, styrene oxide, and α-olefin having 5 to 10 or more carbon atoms. Examples thereof include funxoxide, epichlorohydrin, and a combination system (block or random addition) of two or more thereof.

  Specific examples of the dicarboxylic acid or ester-forming derivative thereof (i) include aliphatic dicarboxylic acids having 4 to 15 carbon atoms [succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid. Etc.], C8-12 aromatic dicarboxylic acids [terephthalic acid, isophthalic acid, etc.], ester-forming derivatives thereof [acid anhydrides (phthalic anhydride, maleic anhydride, etc.), lower alkyl esters (dimethyl esters, Diethyl ester, etc.), acid halides (acid chloride, etc.) and the like, and mixtures of two or more thereof.

Examples of the lactone monomer (ii) include lactones having 4 to 12 carbon atoms such as γ-butyrolactone, γ-valerolactone, ε-caprolactone, and mixtures of two or more thereof.
Of these, dicarboxylic acids are preferably aliphatic dicarboxylic acids having 4 to 15 carbon atoms and 8 carbon atoms from the viewpoints of availability and chemical resistance of urethane resins and flexibility at low temperatures. -12 aromatic dicarboxylic acid, a combination thereof, and more preferably an aliphatic dicarboxylic acid having 4 to 15 carbon atoms.

As the polyether diol, a polyether diol obtained by dehydration reaction of two hydroxyl group-containing compounds (for example, the low molecular diol, divalent phenols, etc.), and the two hydroxyl group-containing compounds have 2 to 4 carbon atoms. Examples thereof include compounds having a structure to which alkylene oxide [ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO)] is added.
Examples of the divalent phenols include bisphenols [bisphenol A, bisphenol F, bisphenol S, etc.], monocyclic phenols [catechol, hydroquinone, etc.] and the like.
Among these, as polyether diol, since it is easy to obtain, the alkylene oxide adduct having 2 to 3 carbon atoms is preferable, and from the viewpoint of durability of the molded product, 4 carbon atoms are preferable. It is an alkylene oxide adduct.

Examples of the polyether ester diol include those obtained by using the above-mentioned polyether diol in place of the low-molecular diol as a raw material in the polyester diol, for example, one or more of the above-mentioned polyether diols and the dicarboxylic acid exemplified as the raw material for the polyester diol or its Examples thereof include those obtained by condensation polymerization with one or more ester-forming derivatives.
Among these, a polycondensate of a low molecular diol and a dicarboxylic acid is preferable from the viewpoint of easy availability and the viewpoint of chemical resistance of urethane resin and flexibility at low temperature.

The polyester diol (A) has a number average molecular weight (Mn) of 500 to 3000, and preferably 700 to 2500 from the viewpoint of the strength and flexibility of the molded product.
In addition, the number average molecular weight in the present invention is measured by “Waters Alliance 2695” [column: “Guardcolumn Super Super HL” (one), “TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4, and HTS4 Super H4” 1) each of which is manufactured by a company) and is measured by gel permeation chromatography (hereinafter abbreviated as GPC) using tetrahydrofuran (hereinafter abbreviated as THF) as a solvent and polystyrene as a molecular weight standard substance. .

<Alicyclic diisocyanate (B)>
As the alicyclic diisocyanate (B) in the present invention, alicyclic diisocyate having 6 to 18 carbon atoms [isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methyl Cyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene, etc.] and a mixture of two or more thereof.
Of these, IPDI and hydrogenated MDI are preferred from the viewpoint of easy availability and the weather resistance of the molded product.

<Aromatic ring-containing diol (C) having a number average molecular weight of 110 or more and less than 500>
The aromatic ring-containing diol (C) in the present invention has a number average molecular weight (Mn) of 110 or more and less than 500, more preferably 150 to 450, and particularly preferably 180 to 350. The aromatic ring-containing diol (C) is preferably a diol represented by the following general formula (1).

  In general formula (1), a and b each independently represent an integer of 1 to 4. Among these, from the viewpoint of meltability, it is preferable that a and b are each independently 1 to 2.

  In general formula (1), A and B are each independently an alkyleneoxy group having 2 to 8 carbon atoms. Examples of A and B include a propyleneoxy group, an ethyleneoxy group, a butyleneoxy group, and a styreneoxy group, preferably an alkyleneoxy group having 2 to 3 carbon atoms, and more preferably an ethyleneoxy group. It is a group.

In the general formula (1), R ¹ and R ² each independently represents O (C═O) [ester group] or an ether group.

It is preferable that the groups having R ¹ and R ² , A and B in the general formula (1) can have structures located at the 1,2-position, the 1,3-position and the 1,4-position, respectively. Among these, 1,3-position and 1,4-position are preferable from the viewpoint of heat resistance.

  As the aromatic ring-containing diol (C), as a specific example, when A is an oxyethylene group as a repeating unit, a = b = 1 (a + b = 2), and 1,4-position 1,4-bis (hydroxyethoxy) benzene having a hydroxyl group, a = b = 1 (a + b = 2), and having a hydroxyl group in the 1,3-position Etc. Of these, bis (hydroxyalkyl) terephthalate, 1,4-bis (hydroxyethoxy) benzene, and 1,3-bis (hydroxyethoxy) benzene having 2 to 6 carbon atoms in alkyl are preferable from the viewpoint of heat resistance.

<Aliphatic or alicyclic diamine (D)>
The diamine (D) in the present invention is an aliphatic or alicyclic diamine (D). As the alicyclic diamine, an alicyclic diamine having 6 to 18 carbon atoms [4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4′-diaminodicyclohexylmethane, diaminocyclohexane, isophoronediamine, etc.] An aliphatic diamine having 2 to 12 carbon atoms [ethylene diamine, propylene diamine, hexamethylene diamine, etc.]; an araliphatic diamine having 8 to 15 carbon atoms [xylylenediamine, α, α, α ′, α′-tetramethylxylylenediamine etc.], and the above compounds can be used as one kind or a mixture of two or more kinds thereof. Of these, isophoronediamine, butylenediamine, and hexamethylenediamine are preferable from the viewpoints of meltability, resin strength, and heat discoloration.

<Powdered polyurethane urea resin composition for slush molding (P)>
The powdered polyurethane urea resin composition (P) for slush molding of the present invention is a powdered polyurethane urea resin composition (P) for slush molding containing a thermoplastic polyurethane urea resin (U), the polyurethane urea resin (U) is a polyester diol (A) having a number average molecular weight of 500 to 3000, the alicyclic diisocyanate (B), an aromatic ring-containing diol (C) having a number average molecular weight of 110 or more and less than 500, and It is obtained by reacting a raw material containing an aliphatic or alicyclic diamine (D).

  The urethane group concentration derived from (B) and (C) in the thermoplastic polyurethane urea resin (U) is preferably 1.0 to from the viewpoint of heat resistance and meltability based on the weight of (U). The urea group concentration derived from (D) and (B) in (U) is preferably 2% from the viewpoint of heat resistance and meltability based on the weight of (U). 0.0 to 6.0% by weight.

In addition to the (U), the slush molding resin particle composition (P) of the present invention may contain an additive (L).
Examples of the additive (L) include inorganic fillers, pigments, plasticizers, mold release agents, organic fillers, stabilizers, and dispersants.
The addition amount (% by weight) of the additive (L) is preferably 1.0 to 40.0% by weight, more preferably 10.0 to 35, based on the weight of the thermoplastic polyurethaneurea resin (U). 0.0% by weight.

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

Examples of the pigment include known organic pigments and / or inorganic pigments. The pigment is preferably 10% by weight or less, more preferably 0.01 to 5% by weight, based on the weight of (U).
Examples of the organic pigment include insoluble or soluble azo pigments, copper phthalocyanine pigments, and quinacridone pigments.
Examples of inorganic pigments include chromates, ferrocyan compounds, metal oxides (titanium oxide, iron oxide, zinc oxide, aluminum oxide, etc.), metal salts [sulfates (barium sulfate, etc.), silicates (calcium silicate, silicate) Magnesium, etc.), carbonate (calcium carbonate, magnesium carbonate, etc.), phosphate (calcium phosphate, magnesium phosphate, etc.)], metal powder (aluminum powder, iron powder, nickel powder, copper powder, etc.), carbon black, etc. It is done.
About the average particle diameter of a pigment, Preferably it is 0.05-5.0 micrometers, More preferably, it is 0.2-1 micrometer.

  Examples of plasticizers include phthalate esters (dibutyl phthalate, dioctyl phthalate, dibutylbenzyl phthalate, diisodecyl phthalate, etc.); aliphatic dibasic acid esters (di-2-ethylhexyl adipate, 2-ethylhexyl sebacate, etc.) ); Trimellitic acid ester (trimellitic acid tri-2-ethylhexyl, trimellitic acid trioctyl, etc.); fatty acid ester (butyl oleate, etc.); benzoic acid esters [polyethylene glycol (degree of polymerization 2-10) dibenzoic acid Ester, polypropylene glycol (degree of polymerization 2-10), etc.]; aliphatic phosphate ester (trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate and tributoxy phosphate) Aromatic phosphates (triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate and tris (2,6-dimethylphenyl) phosphate, etc.) A halogen aliphatic phosphate ester (such as tris (chloroethyl) phosphate, tris (β-chloropropyl) phosphate, tris (dichloropropyl) phosphate and tris (tribromoneopentyl) phosphate); and a mixture of two or more of these Can be mentioned.

  As the mold release agent, known mold release agents can be used, and fluorine compound type mold release agents (triperfluoroalkyl phosphate (8 to 20 carbon atoms) ester such as triperfluorooctyl phosphate and triperfluorododecyl phosphate). Etc.); silicone compound mold release agents (dimethylpolysiloxane, amino-modified dimethylpolysiloxane, carboxyl-modified dimethylpolysiloxane, etc.), fatty acid ester mold release agents (mono- or polyhydric alcohol esters of fatty acids having 10 to 24 carbon atoms, For example, butyl stearate, hydrogenated castor oil, ethylene glycol monostearate, etc.); aliphatic acid amide type mold release agents (mono- or bisamides of fatty acids having 8 to 24 carbon atoms, such as oleic acid amide, palmitic acid amide, stearic acid) Of amide and ethylenediamine Metal soap (such as magnesium stearate and zinc stearate); natural or synthetic wax (such as paraffin wax, microcrystalline wax, polyethylene wax and polypropylene wax); and mixtures of two or more thereof Is mentioned.

As an antiblocking agent, a well-known inorganic type antiblocking agent, an organic type antiblocking agent, etc. can be used.
Examples of the inorganic blocking inhibitor include silica, talc, titanium oxide and calcium carbonate.
Organic blocking inhibitors include thermosetting resins having a particle size of 10 μm or less (thermosetting polyurethane resins, guanamine resins, epoxy resins, etc.) and thermoplastic resins having a particle size of 10 μm or less (thermoplastic polyurethane urea resins and poly (meta)). ) Acrylate resin, etc.).

A stabilizer is a carbon-carbon double bond (such as an ethylene bond which may have a substituent) in the molecule (excluding a double bond in an aromatic ring), a carbon-carbon triple bond (with a substituent). A compound having an acetylene bond which may be present can be used, and an ester (ethylene glycol di (meth) acrylate) of (meth) acrylic acid and a polyhydric alcohol (2 to 10 valent polyhydric alcohol, the same shall apply hereinafter). , Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol tri (meth) acrylate); esters of (meth) allyl alcohol and divalent to hexavalent polycarboxylic acids (diallyl phthalate) And trimellitic acid triallyl ester); poly (meth) allyl ether of polyhydric alcohol (pentaerythritol) Poly (meth) allyl ether, etc.); polyhydric alcohol polyvinyl ether (ethylene glycol divinyl ether, etc.); polyhydric alcohol polypropenyl ether (ethylene glycol dipropenyl ether, etc.); polyvinyl benzene (divinyl benzene, etc.) and their 2 A mixture of seeds or more may be mentioned.
Among these, from the viewpoint of stability (radical polymerization rate), an ester of (meth) acrylic acid and a polyhydric alcohol is preferable, and trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and more preferably Dipentaerythritol penta (meth) acrylate.

The heat softening temperature measured with a flow tester of the powdered polyurethane urea resin composition (P) is preferably 110 ° C. to 140 ° C., more preferably 115 ° C. to 135 ° C., particularly preferably from the viewpoint of heat resistance and meltability. Is 120 ° C to 130 ° C. The thermal softening temperature can be measured by the method described later.
In addition, the melt viscosity at 230 ° C. of the powdery polyurethaneurea resin composition (P) is preferably 500 to 3000 Pa · s, more preferably 700 to 2500 Pa · s from the viewpoints of heat resistance and meltability. The melt viscosity at 230 ° C. can be measured by the method described later.

The powdery polyurethaneurea resin composition (P) for slush molding of the present invention preferably includes the following steps (1) to (3) from the viewpoint of moldability of the material and strength of the molded product.
Step (1): Step of producing urethane prepolymer (S) by reacting polyester diol (A), diisocyanate (B) and aromatic ring-containing diol (C) Step (2): Urethane prepolymer (S) and Step of producing thermoplastic polyurethane urea resin (U) by reacting with diamine (D) Step (3): Powdered polyurethane urea resin composition (P) for slush molding using thermoplastic polyurethane urea resin (U) Manufacturing process.

Specifically as a manufacturing method of powdery polyurethane urea resin composition (P), as process (1), (1) polyester diol (A) and diisocyanate (B) in the presence or absence of an organic solvent beforehand. A method of obtaining a urethane prepolymer (S) having an isocyanate group at the terminal by reacting a mixture of diol and aromatic diol (C).
As a step (2), the urethane prepolymer (S) is reacted with a diamine (D) in the presence of an organic solvent and a dispersion stabilizer to obtain a thermoplastic polyurethane urea resin (U).
A method of producing a powdery polyurethane urea resin composition (P) for slush molding using a thermoplastic polyurethane urea resin (U) as a step (3).

  Examples of the organic solvent used in the production of the thermoplastic polyurethane urea resin (U) include ketones having 3 to 9 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, and the like), ethers having 4 to 8 carbon atoms (such as tetrahydrofuran), and the like. Examples thereof include esters having 3 to 6 carbon atoms (such as methyl acetate and ethyl acetate). An organic solvent may be used individually by 1 type, or may use 2 or more types together.

  Examples of the dispersion stabilizer used for the production of the thermoplastic polyurethane urea resin (U) include water-soluble polymers (methylcellulose, polyvinyl alcohol, polyethylene glycol, polyacrylates, polyvinylpyrrolidone, and copolymers of diisobutylene and maleic acid. Na salt, etc.), inorganic powders (calcium carbonate powder, calcium phosphate powder, hydroxyapatite powder, silica powder, etc.), surfactants (sodium dodecylbenzenesulfonate, sodium lauryl sulfate, etc.) and the like. A dispersion stabilizer may be used individually by 1 type, or may use 2 or more types together.

  The reaction temperature at the time of producing the urethane prepolymer (S) may be the same as that usually employed for urethanization, and is usually 20 ° C. to 100 ° C. when an organic solvent is used. When not used, it is preferably 20 ° C to 140 ° C, more preferably 80 ° C to 130 ° C.

  In the urethanization reaction, a catalyst usually used for polyurethane can be used as necessary to accelerate the reaction. Examples of the catalyst include amine-based catalysts (such as triethylamine, N-ethylmorpholine, and triethylenediamine), tin-based catalysts (such as trimethyltin laurate, dibutyltin dilaurate, and dibutyltin malate).

  As a method of making the thermoplastic polyurethaneurea resin (U) into a powder form, after obtaining a dispersion in which (U) is dispersed in water or a mixture of water and an organic solvent, a method of removing the dispersion medium, Or the method of obtaining and pulverizing pellet-shaped (U) is mentioned.

  The method for obtaining the thermoplastic polyurethaneurea resin (U) as a dispersion is not particularly limited. For example, the method (1) in the method for producing the polyurethaneurea resin (U), International Publication No. 2011/070784 and International Publication The method of 2013/2013747 is mentioned.

  The emulsifying / dispersing apparatus used for the production of the polyurethane urea resin (U) dispersion is not particularly limited as long as it is generally commercially available as an emulsifying machine or dispersing machine. For example, a homogenizer (manufactured by IKA), Polytron Batch type emulsifiers such as Kinematica (manufactured by Kinematica) and TK auto homomixer (manufactured by Primics), Ebara Milder (manufactured by Ebara Seisakusho), TK Philmix, TK pipeline homomixer (manufactured by Primics), colloid mill ( Shinko Pantech Co., Ltd.), Thrasher, Trigonal Wet Pulverizer (Nihon Coke Kogyo Co., Ltd.), Captron (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Kiko Co., Ltd.) and other continuous emulsifiers, Microfluidizer ( Mizuho Kogyo), Nanomizer (Nanomizer) and APV Gaurin (Gau High-pressure emulsifiers, etc., membrane emulsifiers (made by Chilling Industries Co., Ltd.), vibratory emulsifiers such as Vibro mixer (made by Chilling Industries Co., Ltd.) and ultrasonic homogenizers (Branson) And an ultrasonic emulsifier. Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix and TK pipeline homomixer are preferable from the viewpoint of particle size distribution.

  As a method for producing the block-shaped or pellet-shaped thermoplastic polyurethane urea resin (U), for example, a batch type kneader such as a kneader and a screw type extruder with a side feeder attached can be used. Next, the thermoplastic polyurethane urea resin (U) can be obtained by cooling with liquid nitrogen or the like and pulverizing with an impact pulverizer such as a turbo mill.

The additive (L) is a step (1) or (2) for producing the polythermoplastic urethane urea resin (U), or a step for producing the powdery thermoplastic urethane urea resin composition (P) for slush molding (3). ).
When the additive (L) is a plasticizer, a release agent, a fluidity modifier, or an anti-blocking agent, it is added in the step (3) for producing the powdery urethane urea resin composition (P) for slush molding ( The method of impregnation or mixing) is preferred.

  A known powder mixing device can be used as a mixing device in the case of mixing with additives after obtaining the thermoplastic polyurethane urea resin (U), and is a container rotating type mixer, a fixed container type mixer, and a fluid motion type mixing device. Any machine 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 mixer [Hensiel mixer (registered trademark), etc.], a low-speed mixer (planetary mixer, etc.), and a conical screw mixer [Nauta mixer (registered trademark, omitted below), etc.] are preferable, and among these, a double-shaft paddle type mixer, a low speed mixing device (planetary mixer, etc.) and a conical screw mixer (Nauta mixer, etc.) are preferable. It is.

<Molded product>
The molded article of the present invention is formed by molding a powdery polyurethaneurea resin composition (P) for slush molding.
The molded product molded with the powdered polyurethane urea resin composition (P) for slush molding is suitably used for automobile interior materials such as instrument panels and door trims.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In the following, parts and% represent parts by weight and% by weight, respectively.

Production Example 1
<Production of polycondensate (A-1) of 1,4-butanediol and adipic acid>
507 parts of adipic acid and 493 parts of 1,4-butanediol are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and the generated water is distilled off at 210 ° C. under a nitrogen stream for 5 hours. After making it react, it was made to react under the reduced pressure of 5-20 mmHg, and 1,4-butanediol and the polycondensate (A-1) of adipic acid were taken out. It was 530 as a result of measuring the hydroxyl value of obtained (A-1), and calculating Mn.

Production Example 2
<Production of polycondensate (A-2) of 1,4-butanediol and adipic acid>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 591 parts of adipic acid and 409 parts of 1,4-butanediol were placed for 5 hours while distilling off the water produced at 210 ° C. under a nitrogen stream. After making it react, it was made to react under the reduced pressure of 5-20 mmHg, and 1, 4- butanediol and the polycondensate (A-2) of adipic acid were taken out. It was 1950 as a result of measuring the hydroxyl value of obtained (A-2), and calculating Mn.

Production Example 3
<Production of polycondensate (A-3) of 1,4-butanediol and adipic acid>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 600 parts of adipic acid and 400 parts of 1,4-butanediol were placed for 5 hours while distilling off the water produced at 210 ° C. under a nitrogen stream. After making it react, it was made to react under the reduced pressure of 5-20 mmHg, and 1,4-butanediol and the polycondensate (A-3) of adipic acid were taken out. It was 3020 as a result of measuring the hydroxyl value of obtained (A-3), and calculating Mn.

<Example 1>
In a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, the polyester diol (A), aromatic ring-containing diol (C) described in Table 1, monofunctional alcohol, inorganic filler, stabilizer and solvent are listed in Table 1. The amount described in the above was charged and purged with nitrogen, then heated to 90 ° C. with melting and melted, and cooled to 60 ° C.
Subsequently, the amount of diisocyanate (B) shown in Table 1 was added and reacted at 85 ° C. for 6 hours to obtain the yield of urethane prepolymer (S) shown in Table 1.

  To the reaction vessel was added 1421.1 parts of an aqueous solution in which 53.1 parts of a dispersant (“Sunspear PS-8” manufactured by Sanyo Chemical Industries Ltd.) were dissolved in 1368 parts of water and 333.9 parts of MEK at 20 ° C. After uniformly mixing, the amount of diamine (D) described in Table 1 was added under stirring at a peripheral speed of 23 m / s (rotation speed: 10,000 rpm) using an ultradisperser manufactured by Yamato Scientific Co., Ltd. Mixed for minutes. While continuing the stirring, 900 parts of the urethane prepolymer solution (S) produced as described above, which was temperature-controlled at 75 ° C., was added and mixed, and the mixture was also mixed at a peripheral speed of 23 m / s for 2 minutes. The obtained mixture was transferred to a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, purged with nitrogen, and reacted at 50 ° C. for 10 hours with stirring. After completion of the reaction, the product was separated by filtration and dried to obtain the polyurethane urea resin (U) as shown in Table 1.

100 parts of the polyurethane urea resin (U) prepared above and 2.6 parts of carbon black as a colorant are dibenzoate esters of polyethylene glycol (polymerization degree 2 to 10) (“Sansoft” manufactured by Sanyo Chemical Industries, Ltd.) EB300 ") 10.6 parts of a pigment dispersion dispersed in 8.0 parts was put into a Henschel mixer and stirred for 1 minute at a rotation speed of 700 rpm.
Next, the mixture was transferred to a Nauter mixer, and 0.3 part of an ultraviolet absorber (“TINUBIN 765” manufactured by BASF Japan Ltd.) was added and mixed at 70 ° C. with stirring for 4 hours, and Sunsoft EB300 and Tinuvin 765 were mixed (P ).
Next, 0.06 part of dimethylpolysiloxane as an internal release agent (“Kay L45-10000” manufactured by Nippon Unicar Co., Ltd.) was added, mixed for 1 hour, and then cooled to room temperature. Finally, 0.5 parts of anti-blocking agent (“Gantz Pearl PM-030S” manufactured by Ganz Kasei Co., Ltd.) is added and mixed, and after passing through a 48 mesh sieve, except those passing through a 200 mesh sieve A powdery polyurethane urea resin composition (P) for slush molding was obtained.

<Examples 2 to 7, Comparative Example 1>
In Example 1, each urethane prepolymer (S) was obtained in the same manner as in Example 1 except that each raw material was in accordance with Table 1.
Moreover, in Example 1, except having followed each raw material according to Table 1, it carried out similarly to Example 1, and obtained each polyurethane urea resin (U).
Further, each powdery polyurethaneurea resin composition (P) was obtained in the same manner as in Example 1 except that each raw material was in accordance with Table 1.
Each powdery polyurethane urea resin composition (P) obtained was evaluated according to the evaluation method described later. The results are shown in Table 1.

In addition, the composition of the brand name which used the following symbols for the symbols in Table 1 is as follows.
(C-1): Bis (hydroxyethyl) terephthalate [manufactured by Tokyo Chemical Industry Co., Ltd.]
(C-2): 1,4-bis (hydroxyethoxy) benzene [manufactured by Tokyo Chemical Industry Co., Ltd.]
(C-3): 1,3-bis (hydroxyethoxy) benzene [manufactured by Tokyo Chemical Industry Co., Ltd.]

<Measurement method of urea group concentration>
Instrument: AVANCEIII400 type digital NMR [manufactured by Bruker Biospin Co., Ltd.]
Measurement condition:
(1) 100 mg of the resin composition (P) and 4 mL of dimethyl sulfoxide are added to an NMR test tube and dissolved in an oil bath at 100 ° C.
(2) A 0.4 mL of the solution is subjected to ¹ HNMR measurement at 80 ° C.
(3) Analysis method: The urea group concentration is calculated from the area ratio of the urea group peak near 5.6 ppm and the peak area ratio derived from the polyester diol near 2.3 ppm whose molar amount is known.

<Measurement method of urethane group concentration>
Instrument: AVANCEIII400 type digital NMR [manufactured by Bruker Biospin Co., Ltd.]
Measurement condition:
(1) 100 mg of the resin composition (P) and 4 mL of dimethyl sulfoxide are added to an NMR test tube and dissolved in an oil bath at 100 ° C.
(2) A 0.4 mL of the solution is subjected to ¹ HNMR measurement at 80 ° C.
(3) Analytical method: The urethane group concentration is calculated from the area ratio of the aromatic peak near 6.8 ppm and the peak area ratio derived from the polyester diol near 2.3 ppm whose molar amount is known.

<Thermal softening temperature>
Using a flow tester CFT-500 manufactured by Shimadzu Corporation, the temperature was raised at a constant speed under the following conditions, and the temperature at which the resin started to soften was defined as the heat softening temperature.
・ Load: 5kg
-Die: hole diameter 0.5mm, length 1.0mm
-Temperature rising rate: 5 ° C./min.

<230 degreeC melt viscosity measuring method>
Using a flow tester CFT-500 manufactured by Shimadzu Corporation, the temperature was raised at a constant speed under the following conditions, and the melt viscosity at 190 ° C. was measured.
・ Load: 5kg
-Die: hole diameter 0.5mm, length 1.0mm
-Temperature rising rate: 5 ° C./min.

<Production of epidermis>
A powdery polyurethane urea resin composition was filled in a Ni electric mold having a grain pattern that had been heated to 230 ° C. in advance, and after 10 seconds, the excess powdery polyurethane urea resin composition was discharged. After 60 seconds, it was cooled with water to prepare a skin (thickness 1 mm).

<Melability> (Evaluation of formability at low temperature)
The central part of the back surface of the molded skin was visually observed, and the meltability was evaluated in five stages according to the following criteria.
<Criteria>
5: Uniform and glossy.
4: There is a partially unmelted powder, but it is glossy.
3: There are irregularities on the entire back surface and there is no gloss. There are no pinholes penetrating the surface.
2: There are irregularities in the form of powder on the entire back surface, and there are pinholes penetrating the surface.
1: The powder does not melt and does not become a molded product.
X: It melt | dissolves too much and a molding skin cannot be created.

<Heat adhesion test> (Evaluation of deformation resistance at high temperature)
Cut out two 7 cm × 3 cm skins from the molded skin, and use a cutter to make a 0.4 ± 0.2 mm depth cut at 1.5 cm from the top and bottom of the short side.
Thereafter, the sample is allowed to stand for 100 hours in a thermostatic bath at 130 ° C., and the sample taken out is evaluated.
The result is obtained from the following formula.
Non-thermal fusion rate (%) = (length of non-thermal fusion part) × 100 / (total length)

  From the results of Table 1, the powdery polyurethaneurea resin composition (P) for slush molding of the present invention is superior in moldability at low temperature and deformation resistance at high temperature compared to the comparative one. I understand.

  The powdered polyurethane urea resin composition for slush molding of the present invention is suitably used as a skin of a molded product, for example, a skin such as an automobile interior material (instrument panel, door trim, etc.).

Claims (7)

  A slush-molding powdery polyurethaneurea resin composition (P) containing a thermoplastic polyurethaneurea resin (U), wherein the thermoplastic polyurethaneurea resin (U) is a polyester diol (A) having a number average molecular weight of 500 to 3000 And a slash obtained by reacting a raw material containing an alicyclic diisocyanate (B), an aromatic ring-containing diol (C) having a number average molecular weight of 110 or more and less than 500, and an aliphatic or alicyclic diamine (D) Powdery polyurethane urea resin composition (P) for molding. The powdery polyurethane urea resin composition according to claim 1, wherein the aromatic ring-containing diol (C) is a compound represented by the following general formula (1).

[Wherein, a and b are each independently an integer of 1 to 4; A and B are each independently an alkyleneoxy group having 2 to 8 carbon atoms; R ¹ and R ² are each independently O ( C = O) or an ether group. ]   The urethane group concentration derived from the (B) and (C) in the polyurethane urea resin (U) is 1.0 to 5.0% by weight based on the weight of (U), The powdery polyurethane urea resin composition according to claim 1 or 2, wherein the concentration of urea groups derived from (D) and (B) is 2.0 to 6.0 wt% based on the weight of (U).   The aromatic ring-containing diol (C) is composed of bis (hydroxyalkyl) terephthalate, 1,4-bis (hydroxyethoxy) benzene, and 1,3-bis (hydroxyethoxy) benzene, wherein the alkyl has 2 to 6 carbon atoms. The powdery polyurethane urea resin composition according to any one of claims 1 to 3, which is at least one selected from the group consisting of:   The powdered polyurethane urea resin composition according to any one of claims 1 to 4, wherein a heat softening temperature measured by a flow tester is 110 ° C to 140 ° C, and a melt viscosity at 230 ° C is 500 to 3000 Pa · s.   The molded product which shape | molded the powdery polyurethane urea resin composition (P) for slush molding in any one of Claims 1-5. The manufacturing method of the powdery polyurethane urea resin composition (P) for slush molding in any one of Claims 1-5 including the process of the following (1)-(3).
Step (1): Step of producing urethane prepolymer (S) by reacting polyester diol (A), diisocyanate (B) and aromatic ring-containing diol (C) Step (2): Urethane prepolymer (S) and Step of producing thermoplastic polyurethane urea resin (U) by reacting with diamine (D) Step (3): Powdered polyurethane urea resin composition (P) for slush molding using thermoplastic polyurethane urea resin (U) Manufacturing process.