JP5061152B2 - Thermoplastic polyurethane resin powder molding material and molded product - Google Patents

Description

  The present invention relates to a thermoplastic polyurethane resin powder molding material. More specifically, the present invention relates to a thermoplastic polyurethane resin powder molding material suitable as a slush molding material for automobile parts, home appliance parts, toys, miscellaneous goods, and the like.

Thermoplastic polyurethane resin powder molding materials are known as slush molding materials for automobile parts, home appliance parts, toys, miscellaneous goods, and the like. The slush molding method is widely used for automobile interior and exterior materials, home appliance parts, toys, miscellaneous goods, and the like because it can easily form a molded body having a complicated shape and the yield of the material is good. As a thermoplastic polyurethane resin powder molding material for slush molding, many improvements have been made in terms of powder fluidity to ensure moldability and performance as a molded product (soft feeling at low temperatures, fogging properties, etc.) Has been made.
For example, an aromatic ring-containing polyester polyurethane resin powder molding material (see Patent Document 1),
A polyester-based polyurethane resin powder molding material (see Patent Document 2) in which a phosphoric ester plasticizer is used as a plasticizer is disclosed.

JP 2000-103957 A JP 2000-17032 A

However, since the polyester-based polyurethane resin has an ester bond that is susceptible to hydrolysis, there is a problem that wet heat aging is not sufficient, and further improvement is required.
The subject of this invention is providing the resin powder molding material which is excellent in powder fluidity | liquidity as a powder molding material, and can obtain the molded object excellent in the soft feeling under low temperature and wet heat aging property.

（式中、Ｒ^１、Ｒ^２は、フェニル基、１〜３個の水素原子が炭素数１〜１０のアルキル基および／またはハロゲン原子で置換されたフェニル基からなる群より選ばれる基であって、同じであっても異なっていてもよい。Ａは炭素数２〜４の直鎖又は分岐アルキレン基、Ａの炭素数が２の場合ｎは３〜５０、Ａの炭素数が３又は４の場合ｎは２〜５０である。） As a result of intensive studies, the present inventors have completed the present invention.
That is, the present invention relates to a resin powder molding material comprising a polyurethane resin powder (A) comprising an aliphatic polyester thermoplastic polyurethane resin (A0) and a plasticizer (B), wherein (A0) comprises an aliphatic diisocyanate. used are those produced by, (B) it is contained diester represented by the following general formula (1), and (A0) and the difference between the solubility parameter of (B) (whose ASP value) 0-1. 5. A resin powder molding material characterized by 5; and a molded product formed by slush molding the resin powder molding material.

(In the formula, R ¹ and R ² are groups selected from the group consisting of a phenyl group, a phenyl group in which 1 to 3 hydrogen atoms are substituted with an alkyl group having 1 to 10 carbon atoms and / or a halogen atom. A is a linear or branched alkylene group having 2 to 4 carbon atoms, and when A has 2 carbon atoms, n is 3 to 50 and A has 3 or 4 carbon atoms. In this case, n is 2 to 50.)

The resin powder molding material of the present invention is excellent in powder flowability as a powder molding material, and can obtain a molded article excellent in soft feeling and wet heat aging at low temperatures.

The aliphatic polyester-based thermoplastic polyurethane resin (A0) in the present invention is a urethane resin obtained by reacting an aliphatic polyester diol and diisocyanate.
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. A thermoplastic polyurethane resin having a Tg of less than -70 ° C is 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 apparatus (for example, Rheogel-E4000; manufactured by UBM Co., Ltd.).
(A0) is a urethane resin obtained by reacting aliphatic polyester diol and diisocyanate as essential components, and a low molecular diol, a low molecular diamine or the like is used as a chain extender as necessary.
The glass transition temperature of (A0) using an aliphatic polyester diol as the main component of the diol is generally about -70 to -30 ° C. An aromatic polyester diol may be used as the diol component, but the use ratio of the aliphatic polyester diol and the aromatic polyester diol is preferably 100: 0 to 60: 40% by weight.

As the aliphatic polyester diol, a number average molecular weight of 500 to 10,000 is preferable, and examples thereof include (1) condensation polyester diol, (2) polylactone diol, (3) polycarbonate diol, and combinations of two or more of these. It is done.
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, polyhexamethylene succinate diol, polybutylene adipate diol, polytrimethylene sebacate 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 diisocyanate, for example,
C2-C18 aliphatic diisocyanate {1,2-ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 1,12-dodecamethylene diisocyanate, etc.};
C4-C15 alicyclic diisocyanate {isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), 1,4-cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene and the like};
C8-15 aromatic aliphatic diisocyanate {m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), etc.};
Modified products of these diisocyanates (diisocyanate-modified products having a carbodiimide group, a uretdione group, a uretoimine group, a urea group, etc.) can be used.
Of these, aliphatic diisocyanates are preferred, and 1,6-hexamethylene diisocyanate (HDI) is more preferred.

As needed, as a low molecular diol added as a chain extender, for example,
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 diols (1,4-bis (hydroxymethyl) cyclohexane, 1,4-cyclohexanediol, hydrogenated bisphenol A, etc.) and the like can be mentioned.

As a low molecular diamine added as a chain extender as needed, a C2-C18 aliphatic diamine and / or water are mentioned, for example.
Examples of the aliphatic diamine include alicyclic diamines having 4 to 15 carbon atoms {4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexyl. 4,4′-dicyclohexylmethanediamine, cyclohexane-1,4-diamine, isophoronediamine (IPDA), etc.};
C2-C18 aliphatic diamine {1,2-ethylenediamine 1,4-tetramethylenediamine, 1,6-hexamethylenediamine (HDA) 1,8-octamethylenediamine, 1,12-dodecamethylenediamine, etc.} ;
Araliphatic diamines (xylylenediamine, α, α, α ′, α′-tetramethylxylylenediamine, etc.);
C3-C17 carbonate-based diamines such as bis (2-aminoethyl) carbonate, polyoxyethylenediamine (molecular weight of 500 or less), polyoxytetramethylenediamine (molecular weight of 500 or less); and mixtures of two or more thereof. It is done.

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 an aliphatic monoamine having 2 to 18 carbon atoms.
Examples of aliphatic monoamines include monoalkylamines {methylamine, ethylamine, propylamine, butylamine, etc.]; dialkylamines {dimethylamine, diethylamine, dipropylamine, dibutylamine, etc.}; mono- and di-alkanolamines {mono Ethanolamine, diethanolamine, etc.}; and mixtures of two or more thereof.
Examples of the low-molecular monool include aliphatic alcohols {methanol, ethanol, isopropanol, n-butanol, 2-ethylhexanol, 1-octanol and the like}; aliphatic aromatic alcohols {benzyl alcohol and the like}. 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 aliphatic polyester-based thermoplastic polyurethane resin (A0) 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.

Examples of the polyurethane resin powder (A) made of the aliphatic polyester thermoplastic polyurethane resin (A0) include those obtained by the following production method.
(1) First, an isocyanate group-terminated urethane prepolymer is produced from an aliphatic polyester diol and excess diisocyanate by a known method. One produced by reacting an isocyanate group-terminated urethane prepolymer with a blocked chain extender (for example, a ketimine compound) in the presence of water and a dispersion stabilizer. Specifically, for example, those described in JP-A-8-120041 can be used.
(2) A urethane prepolymer similar to (1) is produced by a method of reacting with a chain extender (for example, diamine and / or diol) in the presence of an organic solvent in which the urethane prepolymer does not dissolve and a dispersion stabilizer. thing. Specifically, for example, those described in JP-A-4-202331 can be used.
(3) A mass of a thermoplastic polyurethane resin is obtained by reacting an aliphatic polyester diol, diisocyanate and, if necessary, a chain extender (low molecular diol, low molecular diamine). 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 volume average particle diameter of the polyurethane 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.).

（式中、Ｒ^１、Ｒ^２は、フェニル基、１〜３個の水素原子が炭素数１〜１０のアルキル基および／またはハロゲン原子で置換されたフェニル基からなる群より選ばれる基であって、同じであっても異なっていてもよい。Ａは炭素数２〜４の直鎖又は分岐アルキレン基、Ａの炭素数が２の場合ｎは３〜５０、Ａの炭素数が３又は４の場合ｎは２〜５０である。） Examples of the plasticizer (B) include those represented by the following general formula (1).

(In the formula, R ¹ and R ² are groups selected from the group consisting of a phenyl group, a phenyl group in which 1 to 3 hydrogen atoms are substituted with an alkyl group having 1 to 10 carbon atoms and / or a halogen atom. A is a linear or branched alkylene group having 2 to 4 carbon atoms, and when A has 2 carbon atoms, n is 3 to 50 and A has 3 or 4 carbon atoms. In this case, n is 2 to 50.)

In the above general formula (1), specific examples of R ¹ and R ² include a phenyl group, a toluyl group, a xylenyl group, a 4-butylphenyl group, a 2,4-dibutylphenyl group, and a 2-methyl-4-chlorophenyl group. And nonylphenyl group.
A is a linear or branched alkylene group having 2 to 4 carbon atoms (ethylene group, propylene group, trimethylene group, isopropylene group, tetramethylene group, isobutylene group, etc.) and halogen-substituted groups thereof (1 -Chloromethylethylene group, 1-bromomethylethylene group, etc.).

Among these, preferred are those in which R ¹ and R ² are phenyl groups, and A is an ethylene group, propylene group, trimethylene group or tetramethylene group. In the general formula (1), when A has 2 carbon atoms, n is 3 to 50, and when A has 3 or 4 carbon atoms, n is 2 to 50. When n exceeds 50, the SP value decreases, the ΔSP with the urethane resin increases, the compatibility with the urethane resin deteriorates, and problems such as stickiness of the resin powder and bleeding out of the plasticizer occur. When the carbon number of A is 2, when n is less than 3, the molecular weight is low and the boiling point is lowered, so that fogging tends to occur. Further, when the carbon number of A is 3 or 4, when n is less than 2, the molecular weight is low and the boiling point is lowered, so that fogging tends to occur.
The plasticizer (B) may be a compound represented by the above general formula (1), and may be a mixture of compounds different in n. In the case of a mixture, n is represented by an average value.

As a manufacturing method of a plasticizer (B), the method (For example, the method of Unexamined-Japanese-Patent No. 2001-64382) which esterifies carboxylic acid and polyoxyalkylene glycol using the titanium catalyst of a specific composition is mentioned.
For a titanium catalyst, for example, O = Ti (OCOQCOOM) ₂
[Wherein, M represents an alkali metal, and Q represents a direct bond or an alkylene group having 1 to 10 carbon atoms] is preferable.

Specific examples of the plasticizer (B) include, for example,
In the general formula (1), (1) R ¹ and R ² are phenyl groups, A is an ethylene group, and n is 6 to 8
(2) R ¹ and R ² are phenyl groups, A is a trimethylene group, and n is 3 to 5
(3) R ¹ and R ² are phenyl groups, A is a tetramethylene group, and n is 2 to 4.
Can be mentioned.

The blending ratio of the plasticizer (B) is preferably 2 to 50 parts by weight, more preferably 2 to 30 parts by weight per 100 parts by weight of the polyurethane 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 (B) is preferably used alone, but can contain a plasticizer other than (B) if necessary. The content of the plasticizer other than (B) is preferably 0 to 50% by weight based on the weight of the plasticizer (B).
The plasticizer other than (B) that can be used is not particularly limited, and examples thereof include an epoxy plasticizer, an ester plasticizer, a phosphate ester plasticizer, and an ether plasticizer.

The difference in solubility parameter (ΔSP value) between the aliphatic polyester-based thermoplastic polyurethane resin (A0) and the plasticizer (B) is 0 to 1.5, preferably 0 to 1.0, and 0 to 0.5. Further preferred. Within this range, the compatibility of both is good, and (B) is well impregnated into the urethane resin powder (A) comprising (A0), so that the performance as a plasticizer can be expressed well, and the particle surface Therefore, the powder has excellent powder flowability. In addition, no bleed out occurs on the surface of the molded skin.

The solubility parameters of (A0) and (B) can be calculated by the method (Fedors method) described in “Polymer Engineering and Science, Vol. 14, No. 2, p 147-154 (1974)”. The SP value can be expressed by the following equation.
SP value (δ) = (ΔH / V) ^1/2
In the formula, ΔH represents the heat of vaporization (cal), and V represents the molar volume (cm ³ ).
Further, as ΔH and V, the total heat of molar evaporation (ΔH) and the total volume (V) of the atomic groups described in pages 151 to 153 of the above-mentioned document can be used.
Those having a close numerical value are easy to mix with each other (high compatibility), and those having a close numerical value are indices that indicate that they are difficult to mix.

The resin powder molding material of the present invention has good compatibility of the plasticizer with the urethane resin by controlling the ΔSP value between the plasticizer and the thermoplastic urethane resin. As a result, the surface of the resin powder does not cause stickiness of the plasticizer, and the powder flowability is good, so that the moldability as a powder molding material is excellent.
In addition, by introducing an aliphatic polyester diol having a low glass transition point into the polyol component of (A0) and further introducing an alkylene group into the plasticizer skeleton, the glass transition point of the plasticizer itself is lowered to reduce softness at low temperatures. The fogging property of the molded product can be maintained by controlling the boiling point of the plasticizer by adjusting the n number shown in the general formula (1) of the plasticizer (B).
Furthermore, when the plasticizer itself is hydrolyzed by wet heat aging, an accelerator such as a strong acid that promotes hydrolysis of the molded body is not generated, so that a molded body excellent in wet heat aging can be provided.

In addition to the polyurethane resin powder (A) and the plasticizer (B), additives can be added to the resin powder molding material of the present invention as necessary. As additives, fillers, stabilizers, pigments, mold release agents, antiblocking agents, dispersants and the like can be added.
The addition amount of the additive is preferably 0 to 50% by weight with respect to the total weight of (A) and (B).

Examples of fillers 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.

The stabilizer is, for example, a known antioxidant and / or light stabilizer and / or a double bond 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.), bisphenol (2,2′-methylenebis (4-methyl-6-t-butylphenol). Etc.), phosphorus-based (triphenyl phosphite, diphenylisodecyl phosphite, etc.) and the like.
Light stabilizers include UV absorbers [benzophenone (2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, etc.), benzotriazole (2- (2′-hydroxy-5′-methylphenyl) benzo 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 thermosetting resins (thermosetting polyurethane resin, guanamine, etc.) having a particle diameter of 10 microns or less. Resin, epoxy resin, etc.), thermoplastic resins having a particle size of 10 microns or less (thermoplastic polyurethane, poly (meth) acrylate resin, etc.), maleimide resin powder, and the like.

A known powder mixing device can be used as a mixing device for adding and mixing the above additives to the polyurethane resin powder (A), and a container rotating type mixer, a fixed container type mixer, a fluid motion type mixing device can be used. 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 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).

In order to form the resin powder composition for slush molding of the present invention by the slush molding method, for example, a box containing the powder composition of the present invention and a mold heated to 200 to 280 ° C. are both vibrated and rotated, It can be suitably carried out by a method of producing a sheet by melting and flowing in a mold and then solidifying after cooling.
The thickness of the sheet molded with the molding material of the present invention is preferably 0.5 to 1.5 mm.
These molded sheets can correspond to various shapes depending on the mold shape, and are suitable as materials for slush molding of automobile interior parts such as instrument panels and door trims, home appliance parts, toys, miscellaneous goods and the like.

  Hereinafter, the present invention will be described in more 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 A polybutylene adipate diol (616.2 parts) having a number average molecular weight (hereinafter referred to as Mn) of 1,000 is oxidized in a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube. An inhibitor (1.2 parts) [manufactured by Ciba Specialty Chemicals; IRGANOX 1010], kaolin (90.7 parts) having a volume average diameter of 9 μm [manufactured by Georgia Engel; ASP400P], charged with nitrogen, and stirred. The mixture was uniformly stirred at 60 ° C. Subsequently, 1-octanol (10.4 parts) and MEK (125.0 parts) were charged, stirred uniformly, cooled to 50 ° C., charged with hexamethylene diisocyanate (155.3 parts), and heated at 90 ° C. for 6 hours. Reacted. 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-1). The NCO content of the obtained (UP-1) was 2.1%.

Comparative production example 2
Production of Prepolymer Solution 2 In a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, polyhexamethylene isophthalate diol (616.2 parts) of Mn 1,000, antioxidant (1.2 parts) [ Ciba Specialty Chemicals Co., Ltd .; IRGANOX 1010] Kaolin (90.7 parts) having a volume average diameter of 9 μm [Georgia Engel; ASP400P] was charged, purged with nitrogen, and stirred uniformly at 60 ° C. with stirring. Subsequently, 1-octanol (10.4 parts) and MEK (125.0 parts) were charged, stirred uniformly, then cooled to 50 ° C., charged with isophorone diisocyanate (205.2 parts), and reacted at 90 ° C. for 6 hours. I let you. The mixture was cooled to 60 ° C., and an ultraviolet absorber (1.9 parts) [manufactured by Ciba Specialty Chemicals Co., Ltd .; TINUVIN571] was charged and stirred uniformly to obtain a prepolymer solution (UP-2 ′). The NCO content of the obtained (UP-2 ′) was 2.1%.

Production Example 3
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 an hour. Thereafter, unreacted MEK and n-hexane were removed under reduced pressure to obtain a MEK ketiminate (K-1).

Production Example 4
Into the reaction vessel, the prepolymer solution (UP-1) (100.0 parts) obtained in Production Example 1 and the MEK ketimine product (K-1) (5.4 parts) obtained in Production Example 3 were mixed and charged. 300 parts by weight of an aqueous solution in which a dispersant (manufactured by Sanyo Chemical Industries, Ltd .; Sunspar PS-8) (24 parts by weight) was dissolved was added, and the rotation speed was 5000 rpm using JANKE & KUNKEL IKA-Labortechnik; ULTRA-TURRAX T50. 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. The polyurethane resin powder (A-1) which consists of a thermoplastic polyurethane resin (A0-1) was manufactured by filtering and drying. The glass transition temperature of (A0-1) was −46 ° C.

Comparative Production Example 5
Into the reaction vessel, the prepolymer solution (UP-2 ′) (100.0 parts) obtained in Comparative Production Example 2 and the MEK ketimine product (K-1) (5.4 parts) obtained in Production Example 3 were mixed and charged. Then, 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 rotated using JANKE & KUNKEL IKA-Labortechnik; ULTRA-TURRAX T50 Mixing was performed at several 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 performed to produce a polyurethane resin powder (A-2 ′) composed of a thermoplastic polyurethane resin (A0-2 ′). The glass transition temperature of (A0-2 ′) was −29 ° C.

Production Example 6
A glass reactor equipped with a Dean-Stark apparatus was charged with 244 g of benzoic acid, 330 g of polyethylene glycol (molecular weight 330), 0.51 g of potassium titanium oxalate, and 70 g of xylene, and while performing a nitrogen pass in the liquid (flow rate 30 ml / min), 200 The temperature was raised to ° C. Esterification reaction was performed for 8 hours, and condensed water generated during the reaction was removed out of the system. The product was washed with a 5% by weight aqueous solution of sodium carbonate, and then xylene was distilled off under reduced pressure to obtain 540 g of polyethylene glycol dibenzoic acid ester (PEG benzoic acid) (B-1). In the general formula (1), n (average value) is 7.1.

Production Example 7
A glass reactor equipped with a Dean-Stark apparatus was charged with 244 g of benzoic acid, 250 g of polytrimethylene glycol (molecular weight 250) (manufactured by Plant Dupont; Cerenol H250), 0.51 g of potassium titanium oxalate, and 70 g of xylene. The temperature was raised to 200 ° C. while performing a nitrogen pass (flow rate 30 ml / min). Esterification reaction was performed for 8 hours, and condensed water generated during the reaction was removed out of the system. The product was washed with a 5% by weight aqueous solution of sodium carbonate, and then xylene was distilled off under reduced pressure to obtain 450 g of polytrimethylene glycol dibenzoate (P3MG250benzoic acid) (B-2). In the general formula (1), n (average value) is 4.

Production Example 8
A glass reactor equipped with a Dean-Stark device was charged with 244 g of benzoic acid, 234 g of polytetramethylene glycol (molecular weight 234), 0.51 g of potassium titanium oxalate, and 70 g of xylene, and a nitrogen pass in the liquid (flow rate 30 ml / min) was performed. The temperature was raised to 200 ° C. Esterification reaction was performed for 8 hours, and condensed water generated during the reaction was removed out of the system. The product was washed with a 5% by weight aqueous solution of sodium carbonate, and then xylene was distilled off under reduced pressure to obtain 400 g of polytetramethylene glycol dibenzoate (P4MG benzoic acid) (B-3). In the general formula (1), n (average value) is 3.

Production Example 9
A glass reactor equipped with a Dean-Stark apparatus was charged with 244 g of benzoic acid, 650 g of polytrimethylene glycol (molecular weight 650) (manufactured by Dupont, Cerenol H650), 0.51 g of potassium titanium oxalate, and 70 g of xylene. The temperature was raised to 200 ° C. while performing a nitrogen pass (flow rate 30 ml / min). Esterification reaction was performed for 8 hours, and condensed water generated during the reaction was removed out of the system. The product was washed with a 5% by weight aqueous solution of sodium carbonate, and then xylene was distilled off under reduced pressure to obtain 850 g of polytrimethylene glycol dibenzoate (P3MG650benzoic acid) (B-4). In the general formula (1), n (average value) is 10.9.

Comparative production example 10
A glass reactor equipped with a Dean-Stark apparatus was charged with 244 g of benzoic acid, 1503 g of polypropylene glycol (molecular weight 1503), 0.51 g of potassium titanium oxalate, and 70 g of xylene, and while performing a nitrogen pass (flow rate 30 ml / min) in the liquid 200 The temperature was raised to ° C. Esterification reaction was performed for 8 hours, and condensed water generated during the reaction was removed out of the system. The product was washed with a 5% by weight aqueous solution of sodium carbonate, and then xylene was distilled off under reduced pressure to obtain 1700 g of polypropylene glycol dibenzoic acid ester (PPG benzoic acid) (B-5 ′). In the general formula (1), n (average value) is 25.6.

Example 1
Polyurethane resin powder (A-1) (103.0 parts) obtained in Production Example 4, plasticizer polyethylene glycol dibenzoate (PEG benzoic acid) (B-1) 11.5 obtained in Production Example 6 Part, stabilizer [manufactured by Sanyo Chemical Industries; Neomer DA600] 4.0 parts, light stabilizer [manufactured by Ciba Specialty Chemicals Co., Ltd .; 0.3 parts Sanol LS765], dimethylpolysiloxane [Toray -Dow Corning Co., Ltd .; SH200 (10000)] 0.1 part, modified dimethylpolysiloxane [Shin-Etsu Chemical Co., Ltd .; X-22-3710ST] 0.1 part was charged, and 70 ° C. for 4 hours. Mixed.
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 slush molding resin powder composition (S-1). The volume average particle diameter of (S-1) was 148 μm.

Example 2
Polyurethane resin powder (A-1) (103.0 parts), plasticizer polytrimethylene glycol dibenzoate (P3MG250benzoic acid) (B-2) 11.5 parts obtained in Production Example 7, stabilizer [ Sanyo Chemical Industries, Ltd .; Neomer DA600] 4.0 parts, Light stabilizer [Ciba Specialty Chemicals Co., Ltd .; Sanol LS765] 0.3 parts, Dimethylpolysiloxane [Toray Dow Corning Co., Ltd. ); SH200 (10000)] 0.1 part and modified dimethylpolysiloxane [Shin-Etsu Chemical Co., Ltd .; X-22-3710ST] 0.1 part were added 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 slush molding resin powder composition (S-2). The volume average particle diameter of (S-2) was 151 μm.

Example 3
Polyurethane resin powder (A-1) (103.0 parts), plasticizer polytetramethylene glycol dibenzoate (P4MG benzoic acid) (B-3) 11.5 parts obtained in Production Example 8, stabilizer [ Sanyo Chemical Industries, Ltd .; Neomer DA600] 4.0 parts, Light stabilizer [Ciba Specialty Chemicals Co., Ltd .; Sanol LS765] 0.3 parts, Dimethylpolysiloxane [Toray Dow Corning Co., Ltd. ); SH200 (10000)] 0.1 part and modified dimethylpolysiloxane [Shin-Etsu Chemical Co., Ltd .; X-22-3710ST] 0.1 part were added 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 resin powder composition for slush molding (S-3). The volume average particle diameter of (S-3) was 152 μm.

Example 4
Polyurethane resin powder (A-1) (103.0 parts), plasticizer polytrimethylene glycol dibenzoate (P3MG650 benzoate) (B-4) 11.5 parts obtained in Production Example 9, stabilizer [Sanyo] Manufactured by Kasei Kogyo Co., Ltd .; Neomer DA600] 4.0 parts, light stabilizer [Ciba Specialty Chemicals Co., Ltd .; Sanol LS765] 0.3 parts, dimethylpolysiloxane [Toray Dow Corning Co., Ltd.] Made; SH200 (10000)] 0.1 part and modified dimethylpolysiloxane [Shin-Etsu Chemical Co., Ltd .; X-22-3710ST] 0.1 part were charged and mixed at 70 ° C. for 4 hours.
Next, after cooling to room temperature, 1.0 part of polymethyl methacrylate fine powder [manufactured by Ganz Kasei Co., Ltd .; Ganz Pearl PM-030S], 1.0 part of silica fine powder [manufactured by Grace Devison Chemical; silo block S200] The mixture was charged and mixed to obtain a resin powder composition for slush molding (S-4). The volume average particle size of (S-4) was 150 μm.

Comparative Example 1
Polyurethane resin powder (A-1) (103.0 parts), 11.5 parts of plasticizer polypropylene glycol dibenzoate (PPG benzoic acid) (B-5 ′) obtained in Comparative Production Example 10, stabilizer [ Sanyo Chemical Industries, Ltd .; Neomer DA600] 4.0 parts, Light stabilizer [Ciba Specialty Chemicals Co., Ltd .; Sanol LS765] 0.3 parts, Dimethylpolysiloxane [Toray Dow Corning Co., Ltd. ); SH200 (10000)] 0.1 part and modified dimethylpolysiloxane [Shin-Etsu Chemical Co., Ltd .; X-22-3710ST] 0.1 part were added 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 slush molding resin powder composition (S-5 ′). The volume average particle diameter of (S-5 ′) was 151 μm.

Comparative Example 2
Polyurethane resin powder (A-1) (103.0 parts), phosphate ester plasticizer (B-6 ′) (11.5 parts) [manufactured by Daihachi Chemical Co., Ltd .; CR741], stabilizer [Sanyo Kasei Kogyo Co., Ltd .; Neomer DA600] 4.0 parts, Light stabilizer [Ciba Specialty Chemicals Co., Ltd .; Sanol LS765] 0.3 parts, Dimethylpolysiloxane [Toray Dow Corning Co., Ltd.] ; 0.1 part of SH200 (10000)] and 0.1 part of modified dimethylpolysiloxane [manufactured by Shin-Etsu Chemical Co., Ltd .; X-22-3710ST] were added 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 resin powder composition for slush molding (S-6 ′). The volume average particle diameter of (S-6 ′) was 150 μm.

Comparative Example 3
Polyurethane resin powder (A-2 ′) (103.0 parts) obtained in Comparative Production Example 5, plasticizer polyethylene glycol dibenzoate (B-1) 11.5 parts, stabilizer [Sanyo Chemical Industries, Ltd. Neomer DA600] 4.0 parts, light stabilizer [Ciba Specialty Chemicals Co., Ltd .; Sanol LS765] 0.3 parts, dimethylpolysiloxane [Toray Dow Corning Co., Ltd .; SH200 ( 10000)] 0.1 part, modified dimethylpolysiloxane [manufactured by Shin-Etsu Chemical Co., Ltd .; X-22-3710ST] 0.1 part was added 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 resin powder composition for slush molding (S-7 ′). The volume average particle diameter of (S-7 ′) was 149 μm.

Slush molding resin powder compositions (S-1) to (S-4) of Examples 1 to 4 and slush molding resin powder compositions (S-5 ′) to (S-7) of Comparative Examples 1 to 3. ') Was used to measure powder flowability, tensile strength, glass transition temperature, fogging, and wet heat aging by the methods shown below, and the results are shown in Table 1.

<Powder fluidity (spatula angle / repose angle)>
In order to evaluate the powder fluidity, a spatula angle and an angle of repose were measured with a powder tester (PT-R type manufactured by Hosokawa Micron Corporation). The measurement was carried out in a temperature-controlled room adjusted to a temperature of 23 ± 0.5 ° C. and a humidity of 50 ± 2%. The smaller the value of the spatula angle / repose angle, the better the powder flowability.

<Method for creating molded sheet>
Resin powder compositions (S-1) to (S-4), (S-5 ′) to (S-7 ′), polyurethane resin powder (A-1) on a Ni electric mold with a grain heated to 270 ° C. in advance. , (A-2 ′) is poured, 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 skin having a thickness of about 1 mm was obtained.

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.

The glass transition temperature, fogging test, and moist heat aging resistance test were used after the sheet was prepared and stored for 24 hours at 23 ° C. and 50% RH.
-A test piece 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)
Put a test piece 5.0g in a bottomed cylindrical tube with an inner diameter of 50mm and a length of 150mm, cover it with a transparent glass plate with a thickness of 4mm, then immerse it in a 100 ° C oil bath to a position 50mm from the bottom and let it 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.
・ After storing the heat and heat aging resistance test specimen for 400 hours in a constant temperature and humidity machine set at 80 ° C. and 95% RH, use it for measurement for 24 hours under conditions of 25 ° C. and 50% RH, The tear strength was measured according to JIS K6252-2004. The rate of change (%) was determined from the initial tear strength and the tear strength after the test and evaluated. The smaller the change rate, the better the heat and heat aging resistance.
Rate of change (%) = 100 × (Initial tear strength−Tear strength after 400 hours) / (Initial tear strength)

As can be seen from Table 1, the resin powder compositions for slush molding of Examples 1 to 4 of the present invention are excellent in powder flowability as a powder molding material. On the other hand, the resin powder composition of Comparative Example 1 was inferior in powder fluidity, poor in moldability, and sticky, so that a good skin could not be obtained.
The skins of Examples 1 to 4 have low Tg and excellent softness at low temperatures. On the other hand, the skin of Comparative Example 3 has a high Tg and is inferior in softness at low temperatures.
Although the skin of Examples 1-4 is excellent in wet heat aging property, the skin of Comparative Example 2 is inferior in wet heat aging property.
In the skins of Examples 1 to 4, the generation of fogging components is small, and the tensile strength and tear strength are sufficient.
The skin formed from the resin powder molding material of the present invention is suitably used as a slush molding material for automobile parts, home appliance parts, toys, miscellaneous goods, etc., for example, as a slush molding material for instrument panels, door trims, etc. The
Furthermore, since biomass raw materials are used as raw materials, using this product can contribute to the prevention of global warming and the establishment of a recycling-oriented society.

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

Claims (6)

In a resin powder molding material comprising a polyurethane resin powder (A) comprising an aliphatic polyester thermoplastic polyurethane resin (A0) and a plasticizer (B), (A0) is produced using an aliphatic diisocyanate. are those, that (B) is a difference in the solubility parameter of the containing diester represented by the following general formula (1), and the (A0) (B) (whose ASP value) 0 - 1.5 Characteristic resin powder molding material.

(In the formula, R ¹ and R ² are groups selected from the group consisting of a phenyl group, a phenyl group in which 1 to 3 hydrogen atoms are substituted with an alkyl group having 1 to 10 carbon atoms and / or a halogen atom. A is a linear or branched alkylene group having 2 to 4 carbon atoms, and when A has 2 carbon atoms, n is 3 to 50 and A has 3 or 4 carbon atoms. In this case, n is 2 to 50.) The resin powder molding material according to claim 1, wherein the aliphatic polyester thermoplastic polyurethane resin (A0) has a glass transition temperature of -70 to -30 ° C. The resin powder molding material according to claim 1 or 2, wherein the plasticizer (B) is contained in an amount of 2 to 50% by weight based on the weight of the polyurethane resin powder (A). The resin powder molding material according to any one of claims 1 to 3, which is used for slush molding. A molded product formed by slush molding the resin powder molding material according to any one of claims 1 to 4. The molded article according to claim 5, which is an automobile interior part.