JP2012097184A - Resin powder composition for slush molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop a resin powder composition for slush molding, using an aliphatic dicarboxylic acid and an aliphatic diol, originated from biomass and to provide the resin powder composition for thrush molding, responding to the demand of society such as the prevention of global warming, the construction of a circulation type society, etc.SOLUTION: This resin powder composition for slush molding includes (D) a thermoplastic polyurethane resin obtained by reacting (A) a polyester diol obtained by using (J) the aliphatic dicarboxylic acid originated from the biomass and/or (C) the aliphatic diol originated from the biomass as essential monomer components, with (B) a diisocyanate, and (L) an additive.

Description

The present invention relates to a resin powder composition for slush molding mainly composed of thermoplastic resin powder, which is suitable as a molding material for automobile interior parts such as instrument panels and door trims.

Up to now, petroleum-derived raw materials have been mainly used as thermoplastic resin powders for slush molding. Automotive interior parts formed by molding these are incinerated as waste after use. In recent years, global warming caused by carbon dioxide generated at this time has become a problem. In order to solve this problem, there is a demand from society to actively use resin materials using biomass materials derived from organisms such as plants as materials for automobiles. (For example, Patent Documents 1, 2, and 3). The carbon dioxide generated when incinerating parts that use biomass raw materials is absorbed carbon dioxide for photosynthesis in the process of plant growth, and as a whole increases the amount of carbon dioxide in the atmosphere. It is thought that it is not. For this reason, it can contribute to global warming prevention by using biomass raw material actively.
Examples of thermoplastic resin for slush molding include polyvinyl chloride (PVC), thermoplastic polyolefin (TPO), and thermoplastic polyurethane (TPU). Vinyl chloride and olefin, which are raw materials for PVC and TPO, are produced from biomass. Since it cannot be done, the production of carbon dioxide during incineration cannot be suppressed.
On the other hand, TPU, in particular, dicarboxylic acid and diol, which are raw materials for polyester-based TPU, can be produced from biomass. With the recent development of bio-related technologies, attention has been paid to technologies for producing aliphatic dicarboxylic acids and aliphatic diols mainly produced from petroleum so far from biomass. (For example, Patent Documents 4 and 5)

JP 2009-28067 A JP 2008-56779 A JP 2007-314913 A JP 2005-211041 A Special table 2007-502325 gazette

However, there is no known attempt to contribute to the environment by actively using biomass-derived aliphatic dicarboxylic acid or aliphatic diol in the resin powder composition for slush molding. The problem to be solved by the present invention is to develop a resin powder composition for slush molding using an aliphatic dicarboxylic acid derived from biomass and an aliphatic diol, and demands of society such as prevention of global warming and construction of a recycling society To answer.

As a result of intensive studies, the present inventors have completed the present invention.
The present invention is obtained by reacting a polyester diol (A) having a biomass-derived aliphatic dicarboxylic acid (J) and / or a biomass-derived aliphatic diol (C) as an essential monomer component with a diisocyanate (B). It is the resin powder composition for slush molding (S) containing the thermoplastic polyurethane resin (D) and additive (L) which are manufactured.

Since the slush molding resin powder composition (S) of the present invention uses a biomass raw material as a raw material, the use of this product can contribute to the prevention of global warming and the establishment of a recycling society. .

Measurement result of particle size distribution of resin powder (E1) Particle size distribution measurement result of resin powder (E2) Particle size distribution measurement result of resin powder (E3) Result of measurement of particle size distribution of resin powder (E4) Particle size distribution measurement result of resin powder (E5) Result of particle size distribution measurement of resin powder (E6) Particle size distribution measurement result of resin powder (E7) Particle size distribution measurement result of resin powder (E8) Particle size distribution measurement result of resin powder (E9) Particle size distribution measurement result of resin powder (E10) Particle size distribution measurement result of resin powder (E11)

The resin powder composition for slush molding (S) comprises a biomass-derived aliphatic dicarboxylic acid (J) and / or a polyester-diol (A) and diisocyanate containing an aliphatic diol (C) derived from biomass as essential monomer components. A thermoplastic polyurethane resin (D) obtained by reacting (B) is contained.

In the present invention, the polyester diol (A) only needs to contain at least either a biomass-derived aliphatic dicarboxylic acid (J) or a biomass-derived aliphatic diol (C) as a monomer component. Note that. The aliphatic dicarboxylic acid (J) includes its ester-forming derivative (I).
Examples of the ester-forming derivative (I) include acid anhydrides, lower alkyl esters (such as dimethyl esters and diethyl esters), acid halides (such as acid chlorides), and mixtures of two or more thereof.

The aliphatic dicarboxylic acid derived from biomass (J) and the aliphatic diol derived from biomass (C) are not particularly limited as long as they are produced from biomass, but are selected from the group having 2 to 10 carbon atoms. Dicarboxylic acids such as succinic acid, sebacic acid, aliphatic diols selected from the group having 2 to 10 carbon atoms such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1, Examples include 4-butanediol and 1,10-decanediol. Among them, it is preferable to use biomass-derived succinic acid.

As a method for producing biomass-derived succinic acid, there is a method of producing starch such as corn or wheat by fermentation, and it is preferable to use the succinic acid of the present invention produced by this method. Known succinic acid fermentation methods include Anaerobiospirillus succinici producers (Anaerobiospirillumsuccinic products) (ATCC 35488), anaerobic coryneform bacterium Brevibacterium Examples include a method in which a genetically modified bacterium of Brebacterium flavum is grown and then anaerobically acted on an organic raw material in a carbon dioxide-containing solution (Japanese Patent Laid-Open No. 11-196888). Biomass-derived 1,4-butanediol is obtained by reducing biomass-derived succinic acid.
Biomass-derived sebacic acid has, for example, a method of producing castor oil by alkali melting, and biomass-derived 1,10-decanediol is produced through this method (Japanese Patent Laid-Open No. 2009-7314).
Biomass-derived 1,2-ethanediol and 1,2-propanediol are obtained, for example, by synthesizing and purifying various glycols from starch such as corn and wheat using enzymes and catalysts (Japanese Patent Laid-Open No. 2009-20914). Publication).
Biomass-derived 1,3-propanediol is obtained, for example, by fermenting and purifying starch such as corn (Japanese Patent Laid-Open No. 2007-502325).

  Polyester diol (A) can contain dicarboxylic acid components and diol components other than biomass-derived aliphatic dicarboxylic acid (J) and biomass-derived aliphatic diol (C) as monomer components.

Examples of the dicarboxylic acid component other than the biomass-derived aliphatic dicarboxylic acid (J) include the following compounds.
(I) C4-C15 aliphatic dicarboxylic acid (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.);
(Ii) C8-12 aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, etc.);
(Iii) These ester-forming derivatives (acid anhydrides, lower alkyl esters (dimethyl ester, diethyl ester, etc.), acid halides (acid chloride, etc.) and mixtures of two or more of these.
Of these, aliphatic dicarboxylic acids having 4 to 10 carbon atoms and isophthalic acid are preferred.

Examples of the diol component other than the biomass-derived aliphatic diol (C) include the following.
(I) Aliphatic low molecular diol (ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, etc.);
(Ii) low molecular diol having a ring structure {for example, those described in JP-B No. 45-1474: 1,4-bis (hydroxymethyl) cyclohexane and m- or p-xylylene glycol, etc.};
(Iii) alkylene oxide low molar adducts of bisphenol (number average molecular weight less than 500); and mixtures of two or more thereof.
Among these, an aliphatic low molecular diol is preferable, an aliphatic low molecular diol (C1) having 2 to 10 carbon atoms is more preferable, and 1,6-hexanediol is particularly preferable.

  The content of the biomass-derived aliphatic dicarboxylic acid (J) and / or the biomass-derived aliphatic diol (C) in the polyester diol (A) is usually 10 to 100% by weight from the viewpoint of contribution to the environment. It is preferably 40 to 100% by weight.

The total carbon number of the residue obtained by removing two hydroxyl groups from the aliphatic diol of the polyester diol (A) and the residue obtained by removing two carboxyl groups from the aliphatic dicarboxylic acid of (A) (hereinafter referred to as total C number). ) Is preferably 8-12. When the total C number is 8 or more, the ester group concentration of the polyester diol (A) is lowered and the glass transition point (Tg) is lowered, so that the Tg of the resin molded product (T) for automobile interior materials is lowered and a soft feeling at low temperature. Is preferable because it is excellent. Further, when the total C number is 12 or less, the melting point of the polyester diol (A) is lowered, so that the viscosity of the prepolymer solution is lowered and the application to the particle forming process is facilitated.

In the present invention, together with the polyester diol (A), a polyester diol (A ′) containing no biomass-derived monomer component can be used as a component of the thermoplastic polyurethane resin (D).
Of the polyester diol (A ′), a polyester diol (a ′) composed of an aromatic dicarboxylic acid and an aliphatic low-molecular diol (having 2 to 10 carbon atoms) is preferable, and hexamethylene isophthalate diol is particularly preferable.

In the case where the polyester diol (A) and the polyester diol (A ′) are used in combination, the content of the polyester diol (A) is 30 to 100% by weight based on the total weight of the polyester diol. It is 10 to 95% by weight based on the weight of the resin molded product (T). This range is preferable from the viewpoint of contribution to the environment.
The content of (a ′) is preferably 0 to 30% by weight, more preferably 0 to 10% by weight, based on the weight of the entire polyester diol. When the content of (a ′) is increased, a rigid structure is incorporated into the resin, and durability such as chemical resistance of the resin molded product (T) for automobile interior materials can be increased. When it exceeds 30% by weight, the ratio of the biomass-derived raw material in the resin molded product (T) for automobile interior materials is lowered, and the contribution to the environment is lowered. Moreover, Tg of the resin molded product (T) for automobile interior materials is increased, and the soft feeling at low temperature is inferior.

The polyester diol (A) can be produced, for example, by the following method.
Dicarboxylic acid or an ester-forming derivative thereof and diol are reacted at 200 to 280 ° C. for about 2 to 10 hours under normal pressure and then at 200 to 280 ° C. for about 2 to 10 hours under reduced pressure. When performing the esterification reaction, a known esterification catalyst or polycondensation catalyst may be used. Compounds such as antimony, titanium, germanium, tin, and zinc are preferable, and titanium-based compounds (for example, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, titanium tetra-n-butoxide, titanium tetrahexoxy) , Titanium tetra-2-ethylhexoxide, titanium tetraoctoxide), and titanium tetraisopropoxide is particularly preferable. However, when using a catalyst that affects the production process, performance, etc. of the resin powder composition (S) and the resin molded product for automobile interior materials (T), steps such as deactivation and removal of the catalyst are required. When titanium tetraisopropoxide is used, a catalyst deactivation process is required because it affects the urethanization reaction in the subsequent production process.

Diisocyanate (B) is
(I) C2-C18 aliphatic diisocyanate [ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethyl] (excluding carbon in NCO group, the same applies hereinafter) Hexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanate Natohexanoate, etc.];
(Ii) C4-C15 alicyclic diisocyate [isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene and the like];
(Iii) C8-15 araliphatic diisocyanate [m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), etc.]; Specific examples of the group polyisocyanates include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and / Or 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4 '-Diisocyanatodiphenylmethane, crude MDI, 1,5-naphthylene diisocyanate, 4,4', 4 "-triphenylmethane triisocyanate Sulfonates, m- and p- isocyanatophenyl sulfonyl isocyanate;
(Iv) Modified products of these diisocyanates (modified diisocyanates having a carbodiimide group, a uretdione group, a uretoimine group, a urea group, etc.);
(V) and a mixture of two or more of these.
Among these, preferred are aliphatic diisocyanates or alicyclic diisocyanates, more preferred are HDI, IPDI, and hydrogenated MDI, with HDI being particularly preferred.

In the present invention, the resin powder (E) containing the thermoplastic polyurethane resin (D) can be obtained, for example, by the following method.
(1) An isocyanate-containing urethane prepolymer (U) obtained from a polyester diol (A) and a diisocyanate (B) is blocked with a low-molecular diamine (F) (for example, ketimine) blocked under stirring in the presence of water and a dispersion stabilizer. Compound (E) is subjected to an elongation reaction to obtain resin powder (E) containing thermoplastic polyurethane resin (D).
(2) The urethane prepolymer (U) is subjected to elongation reaction with a chain extender [low molecular diamine (F), low molecular diol, etc.] under stirring in the presence of a nonpolar organic solvent and a dispersion stabilizer, and is thermoplastic. A resin powder (E) containing the polyurethane resin (D) is obtained.
(3) A lump of thermoplastic polyurethane resin (D) is obtained by reacting polyester diol (A), diisocyanate (B) and low molecular diamine (F) or low molecular diol. Then, the resin powder (E) is obtained by pulverization (for example, freeze pulverization, a method of cutting through pores in a molten state).
The thermoplastic polyurethane resin (D) is obtained by chain-extending an isocyanate group-terminated urethane prepolymer obtained by reacting a polyester diol (A) and a diisocyanate (B) with a low molecular diamine (F) or a low molecular diol. The thing obtained by extending | stretching a chain | strand by low molecular diamine (F) is preferable.
The additive (L) can be appropriately added during the above steps.

Examples of the low molecular diamine (F) include aliphatic diamines having 2 to 18 carbon atoms (F1) (1,4-tetramethylene diamine, 1,6-hexamethylene diamine, 1,8-octamethylene diamine, and 1,10- Decamethylenediamine and the like) and alicyclic diamines (F2) (isophoronediamine and the like) having 6 to 18 carbon atoms are preferable. These (F) may be used independently and may mix and use 2 or more types.

  Examples of the low molecular diol include those described above, and preferred ones are also the same.

In order to improve the low temperature moldability in slush molding of the resin powder composition (S), a mixture of an aliphatic diamine (F1) having 2 to 18 carbon atoms and an alicyclic diamine (F2) as the low molecular diamine (F). Is more preferable, and a mixture of 1,6-hexamethylenediamine and isophoronediamine is particularly preferable. By mixing the alicyclic amine (F2), the cohesive strength of the hard segment is moderately weakened, and the low-temperature meltability of the resin powder composition (S) can be improved.
The mol% of (F1) relative to the total mol of (F1) and (F2) in the amine composition is preferably 70 to 100%, more preferably 80 to 98%, and 85 to 90%. Particularly preferred. When the (F1) ratio is within these ranges, the heat softening temperature does not decrease and the heat distortion resistance in a high temperature environment is good.

  The weight average molecular weight (hereinafter referred to as Mw) of the thermoplastic polyurethane resin (D) by gel permeation chromatography (hereinafter referred to as GPC) is preferably 100,000 to 250,000. If Mw is 100,000 or more, the resin molded product for automobile interior material (T) has good heat distortion resistance under high temperature environment, and if it is 250,000 or less, slush molding of the resin powder composition (S). Good low temperature meltability.

The resin powder composition (S) of the present invention contains a thermoplastic polyurethane resin (D) and an additive (L). Examples of the additive (L) include inorganic fillers, pigments, plasticizers, mold release agents, organic fillers, antiblocking agents (fluidity improvers), stabilizers, and dispersants.
Content of an additive (L) is 0.01 to 45 weight% normally with respect to the weight of a resin powder composition (S), Preferably it is 1 to 25 weight%.
Content of a thermoplastic polyurethane resin (D) is 55-99.99 weight% normally with respect to the weight of a resin powder composition (S), Preferably it is 75-99 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.
Content of an inorganic filler is 0-40 weight% normally with respect to the weight of a thermoplastic polyurethane resin (D), Preferably it is 1-20 weight%.

It does not specifically limit as a pigment, A well-known organic pigment and / or an inorganic pigment can be used.
Examples of the organic pigment include insoluble or soluble azo pigments, copper phthalocyanine pigments, quinacridone pigments, and inorganic pigments include chromate, ferrocyan compounds, metal oxides (titanium oxide, iron oxide, Zinc oxide, aluminum oxide, etc.), metal salts [sulfates (barium sulfate, etc.), silicates (calcium silicate, magnesium silicate, etc.), carbonates (calcium carbonate, magnesium carbonate, etc.), phosphates (calcium phosphate, magnesium phosphate, etc.) Etc.], metal powder (aluminum powder, iron powder, nickel powder, copper powder, etc.), carbon black, and the like.
The content of the pigment is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the weight of the thermoplastic polyurethane resin (D).

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 and trimellitic acid trioctyl); fatty acid ester (such as butyl oleate); aliphatic phosphoric acid 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, xyleni Diphenyl phosphate, 2-ethylhexyl diphenyl phosphate and tris (2,6-dimethylphenyl) phosphate, etc.); halogen aliphatic phosphate ester (tris (chloroethyl) phosphate, tris (β-chloropropyl) phosphate, tris (dichloropropyl) phosphate and tris (Tribromoneopentyl) phosphate, etc.); and mixtures of two or more thereof.
Content of a plasticizer is 0-20 weight% normally with respect to the weight of a thermoplastic polyurethane resin (D), Preferably it is 0-15 weight%.

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.
Content of a mold release agent is 0 to 1 weight% normally with respect to the weight of a thermoplastic polyurethane resin (D), Preferably it is 0.1 to 0.5 weight%.

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. Of these, esters of (meth) acrylic acid and polyhydric alcohols are preferable, and trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate are more preferable.
Content of a stabilizer is 0-20 weight% normally with respect to the weight of a thermoplastic polyurethane resin (D), Preferably it is 1-15 weight%.

As the anti-blocking agent (fluidity improver), known inorganic anti-blocking agents and organic anti-blocking agents can be used. Examples of the inorganic blocking inhibitor include silica, talc, titanium oxide and calcium carbonate. Organic blocking inhibitors include thermosetting resins with a particle size of 10 μm or less (thermosetting polyurethane resins, guanamine resins, epoxy resins, etc.) and thermoplastic resins with a particle size of 10 μm or less (thermoplastic polyurethane urea resin and poly ( (Meth) acrylate resin, etc.).
The content of the antiblocking agent (fluidity improver) is usually 0 to 5% by weight, preferably 0.5 to 1% by weight, based on the weight of the thermoplastic polyurethane resin (D).

  As a mixing device used when the resin powder (E) containing the thermoplastic polyurethane resin (D) of the present invention and the additive (L) are mixed to produce a resin powder composition (S), a known mixing device is used. A powder mixing apparatus can be used, and any of a container rotation type mixer, a fixed container type mixer, and a fluid motion type mixer 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.) A method of dry blending using a machine (Nauta-Mixer (registered trademark), etc.) is well known. Among these methods, it is preferable to use a double-shaft paddle type mixer, a low speed mixing device (planetary mixer, etc.), and a conical screw mixer (Nauta mixer (registered trademark, hereinafter omitted), etc.). .

  The volume average particle diameter of the resin powder composition (S) is preferably 10 to 500 μm, more preferably 70 to 300 μm.

Examples of the resin molded product (T) obtained by molding the slush molding resin powder composition (S) of the present invention include, for example, a skin. As the slush molding method, for example, a box containing the powder composition of the present invention and a heated mold are both vibrated and rotated, and the powder is melted and flowed in the mold, and then cooled and solidified to produce a skin. Can be mentioned.
The mold temperature is preferably 200 to 300 ° C, more preferably 210 to 280 ° C. The skin thickness is preferably 0.5 to 1.5 mm.

The molded skin is set so that the surface is in contact with the foaming mold, the urethane foam is poured, and a foamed layer of 5 mm to 15 mm is formed on the back surface to obtain a resin molded product having the skin.
The resin molded product (T) obtained by molding the slush molding resin powder composition (S) of the present invention 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 this. In the following, “parts” represents parts by weight, and “%” represents% by weight.
Production Example 1
Manufacture of polyester diol (A) Biomass-derived succinic acid (manufactured by Bioamber) (690.1 parts), biomass-derived 1,3-propanediol [DuPont Co., Ltd.] in a glass reactor equipped with a Dean-Stark device Sustelra] (520.5 parts) was charged, and the temperature was raised to 170 ° C. while purging with nitrogen. Esterification reaction was performed under reduced pressure (−80 kpa) for 10 hours, titanium tetraisopropoxide (0.02 parts) was added, and the reaction was further performed for 5 hours, and the produced condensed water was removed out of the system. Water (200 parts) was added to the product and heated at 100 ° C. for 3 hours to deactivate titanium tetraisopropoxide. Dehydration was performed under reduced pressure to obtain polytrimethylene succinate diol (A1) (molecular weight 1000).

Production Example 2
Production of prepolymer solution In a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, polytrimethylene succinate diol (A1) (604.13 parts) obtained in Production Example 1 and antioxidant pentaerythritol tetrakis. [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] [manufactured by Ciba Specialty Chemicals Co., Ltd .; Irganox 1010] (1.08 parts), volume average particle size 9.2 μm Of kaolin (18.6 parts) was charged with nitrogen, and the mixture was heated to 120 ° C. with stirring to homogenize and cooled to 60 ° C. Subsequently, 1-octanol (9.45 parts), hexamethylene diisocyanate (B1) (145.11 parts), methyl ethyl ketone (150 parts) were reacted at 90 ° C. for 4 hours. Then, it cools to 65 degreeC and ultraviolet absorber 2- (2H-benzotriazol-2-yl) -6- (straight chain and side chain dodecyl) -4-methylphenol [Ciba Specialty Chemicals Co., Ltd. make; Tinuvin 571] (2.16 parts) and black colorant (28.40 parts) were added and mixed for 1 hour to obtain a prepolymer solution (U1).

Production Example 3
Production of MEK (methyl ethyl ketone) ketimine product of hexamethylenediamine Hexamethylenediamine (F1) and excess MEK (4 times molar amount with respect to the diamine) were refluxed at 80 ° C. for 24 hours, and the generated water was removed from the system. Thereafter, unreacted MEK was removed under reduced pressure to obtain a MEK ketimine product (G1) of hexamethylenediamine.

Production Example 4
Production of Resin Powder Containing Thermoplastic Polyurethane Resin In a reaction vessel, the prepolymer solution (U1) (100 parts) obtained in Production Example 2 and the hexamethylenediamine MEK ketimine compound (G1) (5) obtained in Production Example 3 (5) .20 parts) was added, and a dispersant containing Na salt of a copolymer of diisobutylene and maleic acid (Sansu Pearl PS-8 manufactured by Sanyo Chemical Industries, Ltd.) (1.3 parts) was dissolved therein. Aqueous solution (300 parts) was added and mixed for 1 minute at a rotation speed of 5000 rpm using an ultradisperser manufactured by Yamato Scientific Co., Ltd. The mixture was transferred to a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen blowing tube, purged with nitrogen, and then reacted and deMEKed at 70 ° C. under reduced pressure for 2 hours with stirring. After completion of the reaction, filtration, drying and classification were performed to produce a resin powder (E1) containing a thermoplastic polyurethane resin (D1). Mw of (D1) was 130,000, and the particle diameter corresponding to 50% of the cumulative distribution curve of (E1) (hereinafter referred to as volume average particle diameter) was 152 μm (FIG. 1).

Example 1
Production of Resin Powder Composition In a 3 L planetary mixer, thermoplastic polyurethane resin powder (E1) (100 parts), PEG 330 benzoic acid diester [Sansoft EB-300 manufactured by Sanyo Chemical Industries, Ltd.] (12.0 Part), dipentaerythritol pentaacrylate [Sanyo Chemical Industry Co., Ltd .; DA600] (3.9 parts), UV stabilizer bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1, 2,2,6,6-pentamethyl-4-piperidyl sebacate (mixture) [trade name: TINUVIN 765, manufactured by Ciba] (0.3 parts) was added and impregnated at 70 ° C. for 4 hours. After 4 hours of impregnation, dimethylpolysiloxane (manufactured by Nippon Unicar Co., Ltd .; Kei L45-1000) (0.10 parts), carboxyl-modified silicon [manufactured by Shin-Etsu Chemical Co., Ltd .; X-22-3710] (0.07 parts) was added, mixed for 1 hour, and then cooled to room temperature. Finally, a resin powder composition (S1) was obtained by charging and mixing an antiblocking agent cross-linked polymethyl methacrylate [Gantz Kasei Co., Ltd .; Ganzpearl PM-030S] (0.5 parts).

Example 2
In Production Example 1, instead of biomass-derived succinic acid (manufactured by Bio amber) (690.1 parts), biomass-derived 1,3-propanediol [manufactured by DuPont Co., Ltd .; Sustelra] (520.5 parts) In the same manner as in Production Example 1 except that biomass-derived succinic acid (Bioamber) (520.4 parts) and petroleum-derived 1,6-hexanediol (638.4 parts) are used. Methylene succinate diol (A2) (molecular weight 1000) was obtained.
Subsequently, in Production Example 2, a prepolymer solution (U2) was obtained in the same manner as in Production Example 2 except that (A2) was used instead of (A1).
Subsequently, in Production Example 4, a resin powder (E2) containing a thermoplastic polyurethane resin (D2) was produced in the same manner as in Production Example 4 except that (U2) was used instead of (U1). . The Mw of (D2) was 150,000, and the volume average particle diameter of (E2) was 132 μm (FIG. 2).
Subsequently, in Example 1, a resin powder composition (S2) was produced in the same manner as in Example 1 except that (E2) was used instead of (E1).

Example 3
In Production Example 1, instead of biomass-derived succinic acid (manufactured by Bio amber) (690.1 parts), biomass-derived 1,3-propanediol [manufactured by DuPont Co., Ltd .; Sustelra] (520.5 parts) In addition to using biomass-derived succinic acid (manufactured by Bio amber) (380.7 parts) and biomass-derived 1,10-decanediol (manufactured by Ogura Gosei Kogyo Co., Ltd.) (735.4 parts) Produced polydecamethylene succinatediol (A3) (molecular weight 1000) in the same manner as in Production Example 1.
Subsequently, in Production Example 2, a prepolymer solution (U3) was obtained in the same manner as in Production Example 2 except that (A3) was used instead of (A1).
Subsequently, in Production Example 4, a resin powder (E3) containing a thermoplastic polyurethane resin (D3) was produced in the same manner as in Production Example 4 except that (U3) was used instead of (U1). . The Mw of (D3) was 140,000, and the volume average particle diameter of (E3) was 151 μm (FIG. 3).
Subsequently, in Example 1, a resin powder composition (S3) was produced in the same manner as in Example 1 except that (E3) was used instead of (E1).

Production Example 5
Production of polyester diol Glass reactor equipped with Dean-Stark equipment was charged with isophthalic acid (580.9 parts) and petroleum-derived 1,6-hexanediol (598.7 parts), and up to 230 ° C. with nitrogen substitution. The temperature rose. Esterification was performed at 230 ° C. under pressure (50 kpa) for 4 hours and at 210 ° C. under reduced pressure (−80 kpa) for 8 hours to obtain polyhexamethylene isophthalate diol (A′1) (molecular weight 900). .

Example 4
In Production Example 2, polyhexamethylene succinate diol (A2) (422.89 parts) and polyhexamethylene isophthalate diol (A′1) (181.2 parts) were used in place of (A1). Obtained a prepolymer solution (U4) in the same manner as in Production Example 2.
Subsequently, in Production Example 4, a resin powder (E4) containing a thermoplastic polyurethane resin (D4) was produced in the same manner as in Production Example 4 except that (U4) was used instead of (U1). . The Mw of (D4) was 150,000, and the volume average particle diameter of (E4) was 140 μm (FIG. 4).
Subsequently, in Example 1, a resin powder composition (S4) was produced in the same manner as in Example 1 except that (E4) was used instead of (E1).

Production Example 6
Production of MEK (methyl ethyl ketone) ketimine product of isophorone diamine The product water was removed from the system while refluxing isophorone diamine (F2) and excess MEK (4 times molar amount with respect to the diamine) at 80 ° C. for 24 hours. Thereafter, unreacted MEK was removed under reduced pressure to obtain a MEK ketimine product (G2) of isophoronediamine.

Example 5
In Production Example 4, instead of the prepolymer solution (U1) (100 parts), the prepolymer solution (U4) (100 parts) was used, and instead of the MEK ketimine compound (G1) (5.20 parts) of hexamethylenediamine. A thermoplastic polyurethane in the same manner as in Production Example 4 except that the MEK ketimine compound (G1) (4.66 parts) of hexamethylenediamine and the MEK ketimine compound (G2) (0.12 parts) of isophoronediamine were used. Resin powder (E5) containing resin (D5) was produced. The Mw of (D5) was 120,000, and the volume average particle size of (E5) was 148 μm (FIG. 5). In the same manner as in Example 1, a resin powder composition (S5) was produced.

Example 6
In Production Example 1, instead of biomass-derived succinic acid (manufactured by Bio amber) (690.1 parts), biomass-derived 1,3-propanediol [manufactured by DuPont Co., Ltd .; Sustelra] (520.5 parts) And using biomass-derived sebacic acid [manufactured by Ogura Gosei Co., Ltd.] (831.0 parts) and biomass-derived 1,2-ethanediol [manufactured by Changchun Taisei Group] (317.1 parts) In the same manner as in Production Example 1, polydimethylene sebacate diol (A4) (molecular weight 1000) was obtained.
Subsequently, in Production Example 2, a prepolymer solution (U5) was obtained in the same manner as in Production Example 2 except that (A4) was used instead of (A1).
Subsequently, in Production Example 4, a resin powder (E6) containing a thermoplastic polyurethane resin (D6) was produced in the same manner as in Production Example 4 except that (U5) was used instead of (U1). . Mw of (D6) was 150,000, and the volume average particle diameter of (E6) was 155 μm (FIG. 6).
Subsequently, in Example 1, a resin powder composition (S6) was produced in the same manner as in Production Example 5 except that (E6) was used instead of (E1).

Example 7
In Production Example 1, instead of biomass-derived succinic acid (manufactured by Bio amber) (690.1 parts), biomass-derived 1,3-propanediol [manufactured by DuPont Co., Ltd .; Sustelra] (520.5 parts) In addition, biomass-derived sebacic acid [manufactured by Ogura Gosei Co., Ltd.] (771.2 parts) and biomass-derived 1,3-propanediol [manufactured by DuPont Co., Ltd .; Sustelra] (366.2 parts) are used. Except that, polytrimethylene sebacate diol (A5) (molecular weight 1000) was obtained in the same manner as in Production Example 1.
Subsequently, in Production Example 2, a prepolymer solution (U6) was obtained in the same manner as in Production Example 2 except that (A5) was used instead of (A1).
Subsequently, in Production Example 4, a resin powder (E7) containing a thermoplastic polyurethane resin (D7) was produced in the same manner as in Production Example 4 except that (U6) was used instead of (U1). . The Mw of (D7) was 130,000, and the volume average particle diameter of (E7) was 154 μm (FIG. 7).
Subsequently, in Example 1, a resin powder composition (S7) was produced in the same manner as in Example 1 except that (E7) was used instead of (E1).

Example 8
In Production Example 1, instead of biomass-derived succinic acid (manufactured by Bio amber) (690.1 parts), biomass-derived 1,3-propanediol [manufactured by DuPont Co., Ltd .; Sustelra] (520.5 parts) The same as in Production Example 1 except that sebacic acid derived from biomass [manufactured by Ogura Gosei Co., Ltd.] (627.3 parts) and 1,6-hexanediol derived from petroleum (484.4 parts) are used. Thus, polyhexamethylene sebacate diol (A6) (molecular weight 1000) was obtained.
Subsequently, in Production Example 2, a prepolymer solution (U7) was obtained in the same manner as in Production Example 2 except that (A6) was used instead of (A1).
Subsequently, in Production Example 4, a resin powder (E8) containing a thermoplastic polyurethane resin (D8) was produced in the same manner as in Production Example 4 except that (U7) was used instead of (U1). . The Mw of (D8) was 120,000, and the volume average particle diameter of (E8) was 166 μm (FIG. 8).
Subsequently, in Example 1, a resin powder composition (S8) was produced in the same manner as in Example 1 except that (E8) was used instead of (E1).

Example 9
In Production Example 1, instead of biomass-derived succinic acid (manufactured by Bio amber) (690.1 parts), biomass-derived 1,3-propanediol [manufactured by DuPont Co., Ltd .; Sustelra] (520.5 parts) And Example 1 except that petroleum-derived succinic acid (690.1 parts) and biomass-derived 1,3-propanediol [manufactured by DuPont Co., Ltd .; Susterra] (520.5 parts) are used. Similarly, polytrimethylene succinate diol (A7) (molecular weight 1000) was obtained.
Subsequently, in Production Example 2, a prepolymer solution (U8) was obtained in the same manner as in Production Example 2 except that (A7) was used instead of (A1).
Subsequently, in Production Example 4, a resin powder (E9) containing a thermoplastic polyurethane resin (D9) was produced in the same manner as in Production Example 4 except that (U8) was used instead of (U1). . The Mw of (D9) was 120,000, and the volume average particle diameter of (E9) was 159 μm (FIG. 9).
Subsequently, in Example 1, a resin powder composition (S9) was produced in the same manner as in Example 1 except that (E9) was used instead of (E1).

Comparative Example 1
In Production Example 1, instead of biomass-derived succinic acid (manufactured by Bio amber) (690.1 parts), biomass-derived 1,3-propanediol [manufactured by DuPont Co., Ltd .; Sustelra] (520.5 parts) Polyhexamethylene succinate diol in the same manner as in Production Example 1 except that petroleum succinic acid (520.4 parts) and petroleum-derived 1,6-hexanediol (638.4 parts) are used. (A′2) (molecular weight 1000) was obtained.
Subsequently, in Production Example 2, a prepolymer solution (U9) was obtained in the same manner as in Production Example 2 except that (A′2) was used instead of (A1).
Subsequently, in Production Example 4, the prepolymer solution (U9) (100 parts) was used instead of the prepolymer solution (U1) (100 parts), and the MEK ketimine compound (G1) (5.20 parts) of hexamethylenediamine was used. ) In place of hexamethylenediamine MEK ketimine compound (G1) (4.66 parts) and isophoronediamine MEK ketimine compound (G2) (0.12 parts). Resin powder (E10) containing a thermoplastic polyurethane resin (D10) was produced. The Mw of (D10) was 120,000, and the volume average particle diameter of (E10) was 163 μm (FIG. 10).
Subsequently, in Example 1, a resin powder composition (S10) was produced in the same manner as in Example 1 except that (E10) was used instead of (E1).

Comparative Example 2
In Production Example 1, instead of biomass-derived succinic acid (manufactured by Bio amber) (690.1 parts), biomass-derived 1,3-propanediol [manufactured by DuPont Co., Ltd .; Sustelra] (520.5 parts) And polyhexamethylene succinate diol in the same manner as in Production Example 1 except that petroleum-derived adipic acid (664.3 parts) and petroleum-derived 1,6-hexanediol (499.5 parts) are used. (A'3) (molecular weight 1000) was obtained.
Subsequently, in Production Example 2, a prepolymer solution (U10) was obtained in the same manner as in Production Example 2 except that (A′3) was used instead of (A1).
Subsequently, in Production Example 4, a resin powder (E11) containing a thermoplastic polyurethane resin (D11) was produced in the same manner as in Production Example 4 except that (U10) was used instead of (U1). . The Mw of (D11) was 120,000, and the volume average particle diameter of (E11) was 144 μm (FIG. 11).
Subsequently, in Example 1, a resin powder composition (S11) was produced in the same manner as in Example 1 except that (E11) was used instead of (E1).

Production of resin molded product Slush molding was performed as follows. The slush molding resin powders of Examples 1 to 9 and Comparative Examples 1 and 2 were previously applied to Ni electromolds having a wrinkle pattern heated to 230 ° C. in Example 5 and Comparative Example 1 in advance, and to 270 ° C. otherwise. The compositions (S1) to (S11) are filled, and after 10 seconds, the excess resin powder composition is discharged. After allowing to cool for 60 seconds, the product was cooled with water and demolded from the Ni electric mold to obtain resin molded products (T1) to (T11) having a thickness of 1 mm.

The melt flow rate was measured by the method shown below about the resin powder compositions (E1) to (E9) of Examples 1 to 9 and Comparative Examples 1 and 2. In addition, the glass transition temperature (Tg), the thermal softening temperature (° C.), and the skin physical properties were measured by the methods described below for the resin molded products (T1) to (T11) of Examples 1 to 9 and Comparative Examples 1 and 2. Went. The results are shown in Tables 1 and 2.
Moreover, the particle size distribution was measured by the following particle size distribution measuring method about resin powder (E1)-(E11), and the result was shown to FIGS.

<MFR measurement method>
Equipment: Melt flow indexer (manufactured by Yasuda Seiki Seisakusho)
Load: 2.16kgf
Temperature: 215 ° C
Sample amount: 50 g
The higher the MFR value (g / 10 min) under the above conditions, the better the low-temperature moldability during slush molding of the slush molding resin powder composition (S).

<Glass transition temperature measurement method>
A test piece having a width of about 5 mm and a length of about 45 mm was cut out and attached to a dynamic viscoelasticity measuring apparatus (Rheogel-E4000, manufactured by UBM), and the tensile temperature dependency was measured from −80 ° C. to 30 ° C. at a frequency of 10 Hz. . The obtained E ″ peak top temperature is defined as the glass transition temperature (Tg) (° C.) of the resin. The lower the glass transition temperature, the better the soft feeling of the resin molded product (T) under low temperature conditions.

<Method for measuring thermal softening temperature>
Equipment: Thermomechanical analyzer TMA / SS6100
Data processing device EXSTAR6000 [made by SII Nanotechnology Co., Ltd.]
Measurement conditions: Measurement temperature range 25-250 ° C., heating rate 5 ° C./min, load 5 g, needle diameter 0.5 mm.
Analysis method: In the TMA chart, the intersection of the tangents of the TMA curve is obtained according to the method of “JIS K7121-1987, p.
The higher the heat softening temperature, the better the deformation resistance of the resin molded product (T) under the high temperature condition, which is preferable.
<Tensile strength measurement method>
A JISK6251 tensile test specimen dumbbell No. 1 was prepared from the resin molded product (T). The measurement was performed according to JISK6251 “Tensile test”.
<Method for measuring particle size distribution>
Instrument: Microtrac HRA particle size analyzer 9320-X100 (manufactured by Nikkiso Co., Ltd.) Laser light scattering method measurement sample preparation method: 5 g of sample and 50 g of dispersant aqueous solution (4 g of Sanspar PS-8 manufactured by Sanyo Kasei Kogyo Co., Ltd.) Put in the exchange water 46g). A stirrer piece is added and stirred at 200 rpm for 5 minutes, and about 1 ml of the dispersion is collected with a dropper or the like while maintaining the state in which the sample is dispersed in water, and used as a measurement sample.

As shown in the Examples and Comparative Examples, even when an aliphatic dicarboxylic acid derived from biomass and / or an aliphatic diol derived from biomass is used as a raw material, an aliphatic dicarboxylic acid derived from petroleum and an aliphatic diol derived from petroleum It was found that the same physical properties as when using was used.
In comparison with Examples 1-8 using biomass-derived aliphatic dicarboxylic acids, in particular, Examples 2-8, in which the total C number of the polyester diol (A) is 8 or more, have a low Tg. Since it is excellent in the soft feeling in the low temperature condition of (T), it is preferable. Examples 1 to 7 having a total C number of 12 or less are preferable because the viscosity of the prepolymer is low and application to the particle formation process becomes easy. As in Example 4, a polyester diol (A) and a polyester (A ′) composed of an aromatic dicarboxylic acid may be used in combination for the purpose of improving chemical resistance and the like. In comparison with Examples 2 and 5, when a mixture of 1,6-hexamethylenediamine and isophoronediamine is used as the diamine (F), the value of MFR can be increased as in Example 5, and the slush molding This is particularly preferable because of excellent low-temperature formability.
Since the slush molding resin powder composition (S) described in this example uses biomass raw materials, it can contribute to the prevention of global warming and the establishment of a recycling society by using this product. it can.

The resin molded product (T) obtained by slush molding the slush molding resin powder composition (S) of the present invention is suitably used as an automobile interior material such as an instrument panel and a door trim.

Claims (5)

Thermoplastic polyurethane obtained by reacting biomass-derived aliphatic dicarboxylic acid (J) and / or polyester diol (A) containing aliphatic diol (C) derived from biomass as essential monomer components and diisocyanate (B) A slush molding resin powder composition (S) containing a resin (D) and an additive (L). The total carbon number of the residue obtained by removing two hydroxyl groups from the aliphatic diol (C) of the monomer component and the residue obtained by removing two carboxyl groups from the aliphatic dicarboxylic acid (J) is 8 to 12. Item 2. A slush molding resin powder composition (S) according to Item 1. The slush molding resin powder composition (S) according to claim 1 or 2, wherein the biomass-derived aliphatic dicarboxylic acid (J) is succinic acid and / or sebacic acid. The biomass-derived aliphatic diol (C) is at least one selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, and 1,10-decanediol. Item 4. The slush molding resin powder composition (S) according to any one of Items 1 to 3. The thermoplastic polyurethane resin (D) is obtained by chain-extending an isocyanate group-terminated urethane prepolymer obtained by reacting a polyester diol (A) and a diisocyanate (B) with a low molecular diamine (F). The resin powder composition (S) for slush molding according to any one of the above.

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