TW200925210A - Granular polyurethane resin composition, method for producing the same, and molded article of the same - Google Patents

Abstract

Disclosed is a granular polyurethane resin composition containing a thermoplastic polyurethane resin synthesized in an aqueous dispersion medium, a vinyl monomer polymerized material, a thermally crosslinkable monomer, and 0.1-6 parts by mass of a polymerization inhibitor per 100 parts by mass of the thermally crosslinkable monomer.

Description

200925210 VI. Description of the invention: [Technical field to which the invention pertains] The tree side is in the form of a particulate polyamine-based resin, a method for producing the same, and a molded article, in other words, about a well-suited town (si coffee) The formed particulate form of the polyurethane is a resin composition, a method for producing the same, and a molded article in which the particulate polyurethane resin composition is formed. [Prior Art] The egg material is easily formed into a complex Shaped products, which have a uniform wall thickness and good material yield, are widely used in the forming of automobile shouting parts, etc. For the material for casting and casting, PVC powder of soft f has been used for a long time. Below the freezing point, it will damage the texture, and it will be removed according to the time (4), and the size change will be increased due to the shrinkage of the epidermis, so it is changed to replace the soft gas. Various reviews have been made for the use of polyaminomethyl (tetra) resin powders. ® For example, it is proposed to mix and polymerize an aqueous dispersion of a vinyl monomer in an aqueous dispersion of a thermoplastic polyamine phthalic acid resin. Obtained A powder composition for leaching and casting containing a core layer formed of a thermoplastic resin and a core-shell structure particle formed of a polymer layer of a polymer of a vinyl monomer (for example, refer to the following patent) [1] Patent Document 1. Japanese Patent Laid-Open Publication No. 2005-96432 [Draft of the Invention] (Problems to be Solved by the Invention) 097138844 200925210 However, in addition to the required texture, the mechanical strength is required for the interior parts of the vehicle. In the present invention, it is an object of the present invention to provide a molded article which is excellent in fluidity, moldability, color unevenness, and texture, and which is excellent in mechanical properties, chemical resistance, and long-term heat resistance. A urethane resin composition, a method for producing the same, and a molded article formed of the particulate urethane resin composition. (Means for Solving the Problem) © The particle of the present invention for achieving the above object The polyamino phthalate resin composition comprises: a thermoplastic polyurethane resin synthesized in an aqueous dispersion medium, a vinyl monomer polymer, a thermally crosslinkable monomer, And a polymerization preventive agent in an amount of 0.1 to 6 parts by mass based on 100 parts by mass of the thermally crosslinkable monomer. In the particulate polyaminophthalate resin composition of the present invention, the vinyl monomer polymer is preferably The polymerization reaction is carried out in an amount of 35 to 70% by mass of the aromatic vinyl monomer and 30 to 65% by mass of the α, 10,000-ethylenically unsaturated carboxylic acid alkyl vinegar. 粒子 The particulate polyamino phthalate resin of the present invention In the composition, the vinyl monomer polymerization system preferably contains 5 to 40 parts by mass based on 1 part by mass of the thermoplastic urethane resin. The composition of the particulate polyurethane resin of the present invention The thermally crosslinkable single system preferably contains 2 to 10 parts by mass based on 1 part by mass of the thermoplastic urethane resin. The particulate polyurethane resin composition of the present invention Preferably, the aqueous dispersion of the thermoplastic polyamine phthalate resin and the vinyl monomer polymer is mixed with an aqueous dispersion of 097138844 4 200925210 heat crosslinkable monomer and a polymerization preventive agent, and then reused. Obtained by spray drying. The molded article of the present invention is obtained by leaching and casting the above-mentioned particulate polyurethane carboxylic acid resin composition. • The molded article of the present invention is suitable for use in automotive interior fittings. The method for producing a particulate polyamino phthalate resin composition of the present invention is a water absorbing liquid of a thermoplastic polyamino phthalate resin and a vinyl monomer polymer, and a thermally crosslinkable monomer and After the aqueous dispersion of the polymerization preventive agent was mixed, spray drying was carried out. (Effect of the Invention) The particulate polyamino phthalate resin composition of the present invention contains 1 to 6 parts by mass of a polymerization inhibitor per 1 part by mass of the heat-parent monomer. Control of the hardening reaction of the thermally crosslinkable monomer during the molding process can be performed without impairing the formability of the particulate polyurethane resin composition

In this case, the cross-linking structure is imported. Thereby, the long-term heat resistance can be improved while maintaining the original appearance, feel, and formability of the polyaminophthalate resin. Further, by having a thermoplastic polyurethane resin, a vinyl monomer polymer, a heat crosslinkable monomer, and a polymerization preventive agent which are synthesized in an aqueous dispersion medium, the appearance and touch can be improved. , formability and long-term heat resistance. Therefore, the particulate polyamine hydrazine-resin composition of the present invention is excellent in powder flow enthalpy, and the molded article formed from the particulate urethane resin composition is 0 ^ , , '巴Uniformity, shelling, mechanical properties, drug resistance and long-term 097138844 200925210 Excellent heat resistance. Further, the method for producing a particulate polyurethane resin composition of the present invention is based on an aqueous dispersion of a thermoplastic polyamino phthalate resin and a vinyl monomer polymer, and thermal crosslinking property. After mixing the monomer and the aqueous dispersion of the polymerization preventive agent, the particulate polyurethane resin composition in which the components are uniformly dispersed can be easily produced by spray drying. [Embodiment] The particulate polyurethane resin composition of the present invention contains a thermoplastic polyamine phthalate resin, a vinyl monomer polymer, a heat crosslinkable monomer, and a polymerization preventive agent. In the present invention, the 'thermoplastic urethane resin is obtained by reacting an oleic acid terminal prepolymer and a chain extender' in an aqueous dispersion medium. The isocyanate-based terminal prepolymer is synthesized from an isocyanate, a polyhydric alcohol, an optional quinone alcohol and/or a monoamine. The isocyanate vinegar is not particularly limited as long as it belongs to the organic isocyanate used in the production of the polyamino phthalate resin, and is preferably an alicyclic polyisocyanate and/or an aliphatic polyisocyanate. The alicyclic polyisocyanate may, for example, be 1,3-diisocyanate cyclopentaacetic acid, 14-diisocyanate cyclohexanoic acid, 1,3-diisocyanate cyclohexyl ester, isocyanic acid vinegar_3 aza Acid ester methyl-3,5,5-trimethylcyclohexyl ester, 4,4'-methylenebis(cyclohexyl isocyanate), fluorenyl-2,4-diisocyanate cyclohexyl ester, A __26_二异式097138844 6 200925210 Cyclohexyl acrylate, 1,3-bis(isocyanatodecyl)cyclohexane or hydrazine, 4_bis(isocyanatemethyl)cyclohexane and these isomers Mixture, hydrazine, 3_bis(isocyanatoethyl)cyclohexane, or 1,4-bis(isocyanateethyl)cyclohexane, and mixtures of such isomers, and the like. • Among the alicyclic polyisocyanates, for example, 4, 4, _indenyl bis (cyclo) mixed by three isomers such as trans-trans, trans-cis, cis-cis, and the like Hexyl isocyanate), trans-trans isomer relatively high 44,-fluorenylene dioxime (cyclohexyl isocyanate),! , 3_bis(iso-hydroxymethyl)cyclohexane, or U-bis(isocyanatemethyl)cyclohexane, and mixtures of such isomers. Further, examples of the aliphatic polyisocyanate include: trimethylene diisocyanate, tetra-f-butyl diisocyanate, hexamethylene diisocyanate, and pentamethylene diisocyanate; Hexamethylene diisocyanide _, 1 > 2 - diisocyanate propyl vinegar, ^ - diisocyanate butyl 3, 2,3-diisocyanate butyl, 13 - diisocyanate 2'4'4- or 2, 2, 4_trimethylhexamethylene diisocyanate, 2,6-diisocyanurate methylhexanoate, and the like. Further, the sulphuric acid can be used in combination with the monoisocyanate in a range which does not impair the long-term heat resistance of the molded article. Monoisocyanuric acid is intended to be, for example, isoammonic acid methyl vinegar, isocyanide (tetra) ethane, tetrahexyl isocyanate, isocyanate, ethyl 2-ethylhexyl isocyanate, isocyanic acid Phenyl ester, benzyl isocyanate, and the like. The isocyanates may be used singly or in the form of a separate grease. When the materials are used in combination with the total moles of the isocyanate used, the alicyclic polyiso 097138844 200925210 is preferred. It contains 70 mol% or more, more preferably 80 mol% or more. In the present invention, the polyhydric alcohol may, for example, be a polyether polyol, a polyester polyol or a polycarbonate polyol, and a vinyl group such as styrene, acrylonitrile or (meth)acrylate in the polyol. A polymer polyol or the like obtained by polymerization of a monomer, and a high molecular weight polyol having a number average molecular weight of 400 to 5,000 or a hydroxyl group of 10 to 125 mgKOH/g. The number average molecular weight of the high molecular weight polyol is preferably from 1400 to 3,000, more preferably from 1,500 to 2,500. On the other hand, when the polymer polyol is used, the base price is preferably about 20 to 80 mgKOH/g. The polyether polyol may, for example, be polypropylene glycol or polybutylene glycol. The polypropylene glycol may, for example, be an addition polymer of an alkylene oxide such as ethylene oxide or propylene oxide using a low molecular weight polyol or a low molecular weight polyamine as a starting agent (including randomization of two or more kinds of alkylene oxides). / or block copolymer). Further, the low molecular weight polyol is a compound having 2 or more hydroxyl groups and having a number average molecular weight of 60 to 400, and examples thereof include ethylene glycol, propylene glycol, 1,4-butane diol, and 1,3-butylene glycol. 2-butanediol, 1,6-hexanediol, neopentyl glycol, alkane (7-22) diol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3- or 1,4- Cyclohexanediethanol, and mixtures thereof; 1,4-cyclohexanediol, alkane-1,2-diol (C17-20), argon bisphenol A, 1,4-dihydroxy-2 a glycol such as butene, 2,6-dimethyl-1-octene-3, 8-diol or bisphenol A; for example, a trihydric alcohol such as glycerol or trihydroxydecylpropane; for example: A polyhydric alcohol having 4 or more hydroxyl groups, such as tetrahydrononyl decane, pentaerythritol, dipentaerythritol, D-sorbitol, xylitol, D-mannitol, and D-mannitol. 097138844 8 200925210 The polybutylene glycol may, for example, be a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran or a repeating unit of tetrahydrofuran or a non-copolymerization of the above-mentioned diol such as neopentyl glycol. Polybutylene glycol and the like. The polyester polyol is a polycondensate obtained by reacting the above-mentioned diol with a polybasic acid under known conditions. Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, mercapto succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-mercapto-3. -φ ethyl glutaric acid, sebacic acid, sebacic acid, other aliphatic dicarboxylic acids (carbon number 11 to 13), deuterated dimer acid, maleic acid, fumaric acid, clothing Carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, terpene dicarboxylic acid, dimer acid, halo acid, and the like, and anhydrides and acid compounds derived from the carboxylic acids Wait. Further, the polyglycol polyol is, for example, a G-polycaprolactone obtained by subjecting a lactone such as ε-caprolactone or γ-pental vinegar to ring-opening polymerization using the above-mentioned diol as a starting agent. An alcohol or a polyvalerolactone polyol, and a lactone-based polyol which copolymerizes the above-mentioned diol. The polycarbonate polyol is, for example, a vinyl carbonate ring-opening polymer using the above diol as a starting agent, and examples thereof include, for example, 1,4-butanediol, 1,5-pentanediol, 1,6. a diol such as hexanediol, an amorphous polycarbonate polyol copolymerized with a ring-opening polymer, or the like. Further, as the polyol, the above low molecular weight polyol may be used in combination. The monohydric alcohol may, for example, be methanol, ethanol, propanol, butanol, 2-ethylhexanol, 097138844 9 200925210 other alkanols (C5~38), and aliphatically unsaturated alcohols (9-24), enols. 2-propen-1-ol, alkadienol (〇6-8), 3,7-dimercapto-1,6-octadiene-3-ol, and the like. The monoamine may, for example, be diamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-third-butylamine, dihexylamine, 2-ethylhexylamine, 3 - alkoxypropylamine, 3-ethoxypropylamine, 3-(2-ethylhexyloxypropylamine), 3-(dodecyloxy)propylamine, N,N-dimercapto-1,3-propane Diamine, sputum and so on. Further, monohydric alcohol and/or monoamine are used for the molecular weight adjustment of the thermoplastic polyamine phthalate resin, and may be blended as needed. ❹ In the synthesis of the isocyanate-based terminal prepolymer, the isocyanate equivalent ratio (isocyanate) of the isocyanate relative to the active hydrogen group (trans group and amine group) of the polyol and, if desired, the monohydric alcohol and/or the monoamine The base/active hydrogen group is blended in the proportion of Examples 1 to 4, preferably 1.4 to 2.5, and the reaction is carried out. If the above equivalent ratio is less than 1.1, the thermoplastic poly (carbamic acid) tetracarboxylic acid is excessively large and has a reduced formability. On the other hand, if the equivalent ratio is super = condition = the molded article of the raw polyurethane carboxylic acid resin is hard, which is detrimental to the feeling of touch, and the reaction is, for example, in an atmosphere, depending on the reaction. (:, continuous advancement only by the called C, better reaction system Bu time 2 to 7 hours, compared to (four) hours, at the end of _ point ^ the required amount of thief base (such as μ weight is now required 'Addition of an amine or an organometallic compound, etc., the reaction 097138844 200925210 Catalyst. The catalyst is preferably an organometallic compound, for example, tin acetate, tin octylate, tin oleate, Tin laurate, dibutyltin diacetate, diterpene tin dilaurate, dibutyltin dilaurate, dioctyltin dilaurate, dichlorodimidine, lead octoate, lead naphthenate, nickel naphthenate, 001〜5质量份。 0. 01 to 3 parts by mass. ❹ Then, the obtained isocyanate group-terminated prepolymer and the chain extender are subjected to a chain elongation reaction in an aqueous dispersion medium to obtain a thermoplastic polyamine phthalic acid vinegar resin. The chain extender may, for example, be an alicyclic diamine or a fat. a diamine such as an aliphatic diamine or a low molecular weight polyol such as the above diol or the above triol. The alicyclic diamine may, for example, be 1-amino-3-aminoindolyl-3, 5 , 5-trimethyl G, cyclohexane, bis(4-aminocyclohexyl)decane, diaminocyclohexane, 3,9-bis(3-aminopropyl)-2, 4, 8, 10-tetraspiro[5,5]undecane, 1,3- and 1,4-bis(aminomercapto)cyclohexane, and mixtures thereof, etc. Examples of aliphatic diamines are: Diamine, propylenediamine, hexamethylenediamine, hydrazine, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopentane, etc. These chain extenders The diamine is preferably, for example, 1-amino-3-aminoindolyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, 1,3- And 1,4-bis(aminomercapto)cyclohexane, and the like, hexamethylenediamine. Further, 097138844 11 200925210 The low molecular weight polyol preferably has, for example, ethylene glycol or 14-butanediol. , i hexamethylene glycol, l 4 - cyclohexanediol, 1,3-, 1,4-cyclohexanedimethanol, and the special mixture, etc. When the polyisophthalic acid vinegar is used 4, 4 The case of _-indenyl bis(cyclohexyl isocyanate) is preferably 1, a diamine such as bis(aminomethyl)cyclohexane or hexamethylenediamine, and ethylene glycol. The chain extender can be used alone. Use or use two or more kinds in combination ❹ Chain extension (4) is based on (4) Equivalent ratio of active hydrogen group (amine group and warp group) of isocyanate-chain base elongation agent (active hydrogen group / The dissimilar acid vinegar group is formulated such that the ratio of OH is preferably 〇 4 to 1 〇 5. The water dispersion (4) does not substantially dissolve the isocyanate-based end and the thermoplastic water, or the hydrolyzable The aqueous solvent and the aqueous solvent may, for example, be a mixed solution of water and _ (for example, methanol or ethanol). © Chain Stretch Reaction Tray 'Which is first formulated into an aqueous dispersion medium in an isocyanide terminal prepolymer, and the prepolymer aqueous dispersion is prepared by dispersing the isocyanate end prepolymer in an aqueous dispersion medium. . The aqueous knife media was prepolymerized to 16100 parts by mass relative to the isocyanate end. The compounding amount is, for example, 60 to 400 parts by mass, preferably 80 to 120 parts by mass. Further, it is preferred to formulate an emulsifier with an aqueous dispersion medium. The emulsifier may, for example, be a nonionic surfactant such as polyoxyethylene sulphide (IV) or an anionic surfactant such as polyoxyethylene sulphur (IV). The emulsifier may be used alone, 097138844 12 200925210 or two or more types may be used in combination. 5〜5质量份。 The emulsifier is preferably used in an amount of 0.5 parts by mass, preferably 0.5 parts by weight, based on 100 parts by weight of the isocyanate terminal prepolymer. Then, the chain extender is formulated in the aqueous prepolymer dispersion. The chain extender can be added to the isocyanate-based terminal prepolymer in an integrated or batchwise manner. Small, mouth, or drop method. Further, the chain extender is adjusted to be an aqueous solution, and the temperature is adjusted to, for example, 〇 10 to 80 ° C ', preferably 15 to 50 Å', more preferably 15 to 4 Å. On the other hand, the temperature of the prepolymer aqueous dispersion is adjusted to, for example, ι 〇〇 to ι ° ° C. preferably from 15 to 80 ° C, more preferably from 20 to 60 ° C. 5〜5〜5〜5〜5〜5〜5〜5〜5〜5〜5〜5〜5〜5〜5〜5〜5 The reaction may be carried out for 48 hours. Further, the above-mentioned catalyst may be appropriately added as needed. © This can be obtained in the form of an aqueous dispersion (polyurethane dispersion) of the heat-cleavable filament resin. In the present invention, A dilute-based monomer polymerization system such as an aromatic vinyl monomer, and a copolymer of α'ethylenically unsaturated decanoic acid vinegar, by making an aromatic ethylenic monomer and ", point-ethylene is not The saturated acid-based vinegar is obtained by radical copolymerization. The aromatic vinyl single system may, for example, be a styrene monomer such as styrene or α-methylstyrene; or, for example, ethylene. Base benzene, ethyl vinyl benzene, etc. thiol 097138844 13 200925210 olefin benzene; or polycyclic aromatic monovinyl monomer such as vinyl naphthalene. The aromatic vinyl single system can be used alone or in combination 2 In addition, among these, styrene is preferred. • α, ethylene is not Examples of the alkyl carboxylic acid esters include ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, isophthalic acid acrylate, ethyl hexyl acrylate, and f-propyl propyl group. Alkyl acetonate, thioglycolic acid hexanoic acid vinegar, methacrylic acid I ethyl hexyl methacrylate (meth) propylene (4). Further, the ethylenically unsaturated Wei ketone vinegar can be exemplified by: Cyanide or dicyandiamide such as acrylonitrile or methacrylonitrile, etc. These L/3, ethylenically unsaturated butyl ketones may be used singly or in combination of two or more. It is a methyl acetoacetate methyl vinegar or a butyl acrylate. Then, in order to carry out a radical copolymerization reaction of the aromatic ethyl thiol monomer with the α, succinyl-stained unsaturated sulphuric acid vinegar, The total amount of monomers, such as yifang® fragrant vinyl monomer 35~7〇% by mass, preferably 45~65% by mass, α, point-ethylene unsaturated sulphuric acid vinegar 30~65% by mass, Preferably, the ratio of 35 to 55 mass% is carried out, and the radical polymerization initiator is added. The radical polymerization initiator may, for example, be: Sulfate, organic oxide, azo compound, etc. Persulfate may, for example, be sodium persulfate, potassium persulfate or persulfate. The organic peroxide may, for example, be 1, and the second is peroxide. Trihexyl)-3,3'5~trimethylcyclohexene, 1,di(diacetylhexyl peroxide)-2-oxime 097138844 200925210 base ring hexane, 1, bis (peroxide tert-butyl) a peroxy sterol such as cyclohexane; or a dialkyl peroxide such as di-tert-butyl peroxide or, for example, dilauroyl peroxide or bis(3-methylbenzoic acid) a peroxide, a benzamidine (3-methyl benzoyl) peroxide, a dibenzoic peroxide such as a diphenyl benzoate; or, for example, caproic acid-1,1, 3,3-Tetramethyl over & keto-2-ethyl vinegar, 2, 5-dimethyl-2, 5_bis(2-ethylhexyloxyhexyl) hexane, hexanoic acid peroxidation Third hexyl-2-ethyl ester, butyl hexanoate hexanoate, monohexyl isopropyl monoperoxide, dimethyl sulphate peroxidate, succinic acid peroxidized Tributyl isopropyl ester, monocarbonic acid peroxidation A peroxy ester such as a third butyl-2-ethylhexyl ester or a 2, 5-dimethyl-2, 5-di(benzoyl phenyl) hexane. Examples of the azo compound include azobisisobutyronitrile, 2,2, azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(2-methylbutyronitrile). ), dimethyl-2, 2'-azobis(2-mercaptopropionate), 2, 2,-azobis((2-(2-imidazoline)-2-yl)propane, methyl Dimethyl propane isobutyrate, 2, 2, 7-azobis[N-(2-carboxy)-2-methylpropionamidine] tetrahydrate, 2, 2,-azobis[2-methyl -N-[l,l-bis(hydroxyindenyl)-2-hydroxyethyl]propanamide], 2,2,-azobis[N-(2-ethyl)-2-indenyl Indoleamine], 2, 2'-azobis(2,4-dimercapto-4-indolyl valeronitrile), 1, Γ-azobis[cyclohexamethylene-1-carbonitrile], etc. The base polymerization initiator may be used singly or in combination of two or more. In addition, among the 5th, it is preferably dimercapto-2, 2,-azobis(2-mercaptopropionate), 2 2'-azobis(2-mercaptobutyronitrile) 097138844 15 200925210 The radical polymerization initiator is added in an amount of, for example, ο.1 to 2.0 parts by mass, preferably 1 part by mass, based on the total amount of the monomers. In addition, in the free radical copolymerization, in order to carry out the ethylene monomer The chain transfer agent may be added in the middle of the polymer, and a chain transfer agent may be added. The chain transfer agent may, for example, be a mercaptan such as a third (twelve oxime) thiol or a thioglycolic acid-2-ethylhexyl vinegar; Or, for example, a styrene dimer such as a styrene dimer, etc. ❹ These chain transfer agents may be used singly or in combination of two or more. Further, among these, a-methylbenzene is preferred. The ethylene glycol dimer is added in an amount of, for example, 〇1 to 1 part by mass, preferably 〇·5 parts by mass, more preferably 1 to 2 parts by mass, based on 1 part by mass of the total amount of the monomers. Further, in the radical copolymerization reaction, a known additive such as an emulsifier for polymerization or a buffer may be added as needed. Then, in the radical copolymerization reaction, the monomer is, for example, at a reaction temperature of 20 to 9 ( TC, preferably 60 to 90. Under the reaction, the reaction time is 5 〇 2 〇 hours, preferably 1 〜 1 〇 hr. The vinyl monomer polymerization system can be synthesized in a water dispersion medium of thermoplastic polyamine In addition to the phthalic acid ester resin, it is synthesized according to the above conditions and formulated into a thermoplastic polyamine phthalate. In addition, the ethylene monomer polymer can also be added by adding the above monomer in advance in the aqueous dispersion of the thermoplastic polyurethane resin or the isocyanate-based terminal prepolymer. Base polymerization initiator and optional chain transfer agent, emulsification for polymerization 097138844 16 200925210 shot of 'buffer_combined single Zhao emulsion, the method can be more evenly blended with human thermoplastic polyamine μ Acid == ethylene monomer polymer, and can improve the operability in the manufacturing step. The vinyl monomer polymerization system is 1 part by mass relative to the heat & plastic polyurethane resin, for example, 5 ~ 40 parts by mass, preferably 15 to 30 parts by mass. In the present invention, the compound having a plurality of ethylenically unsaturated bonds in the heat-crosslinkable single system can be exemplified by ethylene glycol bis(indenyl) acrylate, propylene glycol bis(methyl decyl) acrylate, butylene glycol. Di(indenyl)acrylate, pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, decanediol di(decyl) An alkanediol bis(indenyl) acrylate such as acrylate or oligoethylene glycol bis(indenyl) acrylate; or, for example, trimethylolpropane tris(mercapto) acrylate or glycerol tris(methyl) Alkenyl poly(poly(decyl) acrylates such as acrylate, pentaerythritol tetrakis (meth) acrylate vinegar, dipentaerythritol jade (meth) acrylate vinegar, and one quarter decyl alcohol hexa(meth) acrylate Or an example of a diallyl ester of an unsaturated carboxylic acid such as diallyl maleate, butylene, diallyl, or propyl allylate; or, for example, amide Ethyl di(meth) acrylate; or for example: polybutadiene > (fluorenyl) acrylate 荨β Among the, preferred is dipentaerythritol penta (meth) acrylate, dipentaerythritol yeast hexa (Yue-yl) acrylate. These thermally crosslinkable monomers may be used alone or in combination of two or more. Further, among these, an alkyl polyol poly(meth)acrylate is preferred. The heat crosslinkable single system is blended with 100 parts by mass of the thermoplastic polyurethane phthalate resin to 097138844 17 200925210, for example, 2 to 10 parts by mass, preferably 4 to 8 parts by mass. : p-benzoquinone, p-methane, naphthalene

• Hydrogen g_ such as 2,5-di-p-diylhydrogen; or, for example, p-methoxyphene, * In the present invention, the polymerization inhibitor may, for example, be fluorene, phenanthrenequinone, anthracene, 2, 5-di Phenyl 斟芏 gambling, dibutyl • a pair of hope for nitrogen, early hyperthyroidism and other expectations. These polymerization inhibitors may be used alone or in combination of two or more. In addition, among these, it is difficult to be hydroquinone or p-methoxy. The polymerization inhibitor is formulated in an amount of, for example, 1 to 6 parts by mass, preferably 1 to 5 parts by mass, based on 100 parts by mass of the thermally crosslinkable monomer, more preferably 4 parts by mass. If the number of the polymerization inhibitor is less than 0.1 part by mass, color unevenness, texture, and even long-term heat resistance are lowered. On the other hand, when the number of the polymerization inhibitors exceeds 6 parts by mass, color unevenness, long-term heat resistance, and the like are lowered. When the number of the polymerization inhibitors is within the above range, a molded article excellent in color unevenness and texture, and excellent in mechanical properties, chemical resistance, and long-term heat resistance can be obtained. The hot-parent monomer and the polymerization preventive agent are preferably prepared into an aqueous dispersion together with an emulsifier and an additive described later, and then the aqueous dispersion is formulated to contain a thermoplastic polyurethane resin and a vinyl monomer. The polymer is mixed in an aqueous dispersion medium. Then, the particulate polyaminophthalate resin composition of the present invention can be obtained by subjecting, for example, spray drying to the aqueous dispersion prepared by the above respective components. 097138844 18 200925210 According to this production method, a particulate polyurethane resin composition in which the components are uniformly dispersed can be easily obtained. The volume average particle diameter of the particulate polyaminophthalate resin composition obtained is, for example, 50 to 300 /zm, preferably 80 to 200 μm. If the volume average particle diameter is less than 50, the fluidity of the powder is lowered, resulting in unevenness during molding. On the other hand, when the volume average particle diameter exceeds 300 y in, pinholes may occur on the surface of the molded article. ❹ In the particulate polyamino phthalate resin composition, other known additives may be added as needed, such as: plasticizer, anti-adhesion (anti_M〇cking) agent, heat stabilizer, light stabilizer, release type Agents, as well as antioxidants, ultraviolet absorbers, pigments, dyes, slip agents, fillers, anti-hydrolysis agents, and the like. These additives may be added during the synthesis of the respective components, or may be added during the mixing or dispersion of the components, or may be added after the separation and drying of the particulate polyamino phthalate resin composition. ❹ Then, in the particulate polyamino phthalate resin composition of the present invention, the molding process can be carried out by using a polymerization inhibitor which contains 6 parts by mass of 〇·b relative to the heat-crosslinkable monomer. The curing reaction of the heat crosslinkable monomer is controlled to introduce a crosslinked structure without impairing the formability of the particulate polyurethane resin composition. Thereby, the long-term heat resistance can be improved while maintaining the original appearance, touch, and formability of the polyurethane resin. Further, by containing a thermoplastic polyurethane resin, a vinyl monomer polymer, a heat crosslinkable monomer, and a polymerization preventive agent synthesized in an aqueous dispersion, 097138844 19 200925210 can be used to lift a molded article. Appearance, feel, formability and long-term heat resistance. Therefore, the particulate polyamino phthalate resin composition of the present invention is excellent in powder fluidity and moldability, and the molded article formed from the particulate urethane resin composition is uneven in color. Excellent texture, mechanical properties, drug resistance and long-term heat resistance. Therefore, the "particulate composition of the particulate polyamino phthalic acid g of the present invention can be used as a toner binder in addition to being used as a toner binder", and can be used for the manufacture of furniture such as leaching and casting. Various fields such as sofas and toys. In particular, the particulate polyamine phthalic acid vinegar resin composition of the present invention is most suitable for automotive interior parts formed by transfer molding (leaf casting). Further, the molded article obtained by subjecting the particulate polyurethane resin composition of the present invention to leaching formation, particularly automobile interior parts, has color unevenness, texture, mechanical properties, drug resistance, and long-term heat resistance. Excellent. [Examples] Next, the present invention will be described based on the production examples, examples, and comparative examples, but the present invention is not limited to the following examples. [Example 1] <Synthesis of Thermoplastic Polyuryl Ester Resin Resin> In a polymerization container to which a nitrogen introduction tube and a stirring rod were attached, a product of Takelac® U-2720C, manufactured by Mitsui Chemicals P0LYURETHANES Co., Ltd., 5质量份,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,

2-mmolhexanol 0.5 parts by mass, stirred and mixed at 80 ° C for 1 hour. To the mixed liquid, 4,4'-methylene bis(cyclohexyl isocyanate) (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Desmodur W) was added in an amount of 21.6 parts by mass, and then carried out at 80 ° C. 2 Mix and mix for an hour. Then, add Stanoct® (trade name, API) to the mixture.

Manufactured by Corporation, tin-based catalyst 〇. 〇〇 3 parts by mass, and stirred at a temperature of 90t: for 2 hours. Then, it was confirmed that the NC0 mass ❹ % was lowered to 2.83 mass%, and after cooling, an isocyanate group terminal prepolymer was obtained. The amount of the isocyanate group-terminated prepolymer was 97.28 parts by mass, and the mixture was placed in a stainless steel beaker, and the temperature was adjusted to 60° C., and a total of 13.56 parts by mass of SUNN0L® TD3130 (product name, manufactured by LION Corporation, emulsifier 31% by mass aqueous solution) was added. Stirring was carried out for 10 minutes using TK HOMO DISPER (trade name, manufactured by Kosei Kogyo Co., Ltd., high speed mixer). Add deionized water to the mixture. 6. After the mass fraction, carry out mixing for 30 minutes. Further, a part by mass of deionized water was added to obtain an aqueous dispersion of an isocyanate-terminated prepolymer. Then, after adding a 2.7 mass% aqueous solution of hexamethylenediamine (1,6-hexanediamine in terms of an aqueous solution), the temperature was raised to 50 C, and the mixture was aged overnight to obtain a thermoplastic polyamine group. An aqueous dispersion of a formate resin (solid content: 5% by mass). &lt;Synthesis of Vinyl Monomer Polymer&gt; After mixing styrene and methacrylic acid methyl ketone to 6 〇 mass% and 4 〇 mass%, respectively, the 魏(10) mass relative to the material 097 138 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 2 mass% sodium hydrogencarbonate aqueous solution 1. 〇 mass part, deionized water 9.50 parts by mass, and uniformly mixed to prepare a monomer emulsion. 200 parts by mass of an aqueous dispersion of the thermoplastic polyamine phthalate resin obtained as described above in a polymerization vessel equipped with a reflux condenser, a nitrogen introduction tube, and a mixing rod (based on the solid content) Parts), heating up to 8 〇χ:. The temperature is raised to 80. (: After that, a 2% by mass aqueous sodium persulfate solution &amp; 〇 mass part was added and stirred for 10 minutes. Then, with respect to 1 part by weight of the thermoplastic polyaulate phthalate resin, 20 parts by weight based on the total amount of the monomers. In a portion, the monomer emulsion is continuously fed to the aqueous dispersion of the thermoplastic polyamine phthalate resin for 3 hours. After the end of the feed, the feed line is 1.62 parts by mass of deionized water. The "cleaning" was further carried out at 80 ° C for 2 hours to obtain an aqueous medium (solid content: 50% by mass) containing a thermoplastic polyamine-based phthalic acid vinegar resin and a vinyl monomer polymer. &lt;Heat crosslinkability Preparation of monomer and polymerization inhibitor&gt; Relative to aqueous medium solids containing thermoplastic polyamine phthalate resin and vinyl monomer polymer (ie, thermoplastic polyurethane resin and vinyl monomer) The mass of the methoxy phenol is 0. 06 mass. 097138844 22 20 0925210 (that is, 1 part by mass based on 100 parts by mass of the thermally crosslinkable monomer), SUNN0L® TD-3130 〇. 19 parts by mass, Irganox 245 (trade name, Ciba Super Chemical Co., Ltd., heat stabilizer)〇 1 part by mass, TINUVIN® 765 (trade name, Ciba Super Chemical Co., Ltd., light stabilizer) 质量. 5 parts by mass, TINUVIN® 213 (trade name, Ciba Super Chemical Co., Ltd., UV absorber) 〇.5 Parts by mass, Silicon TSF-451-3000 (Momentive Performance Materials, manufactured by Nippon Co., Ltd., release agent) 5. 5 parts by mass, and deionized water © 5.15 parts by mass, prepared aqueous dispersion (additive aqueous dispersion) Then, the aqueous dispersion was formulated into an aqueous medium containing a thermoplastic urethane resin and a vinyl monomer polymer, and stirred for 10 minutes. After stirring, 'using a spray dryer (Okawakawa Chemical Co., Ltd.) Company system, L-12), according to the atomizer rotation number 5000min_1, hot air temperature 1〇〇. (: spray drying, to obtain a particulate polyamino phthalate resin composition. &lt;Pigment blending &gt; Ο The obtained particle shape Base phthalate resin composition: 1 part by mass, 0.6 parts by mass of pigment, carbon black/calcium carbonate dispersion (manufactured by SUMIKA COLOR, trade name: PV-817), and 0.4 parts by mass of carbon black/calcium carbonate dispersion (manufactured by SUMIKA COLOR Co., Ltd., trade name: pv-801), it was put into a Hansu blender, and stirred at a rotation speed of γΟΟπάιΤ1 for 1 minute to color the particulate polyurethane resin composition. [Examples 2 to 20, Comparative Examples 1 to 5] In the same manner as in Example 1, except that the composition and the mixing ratio shown in Tables 1 to 3 were set, the same procedure as in Example 1 was carried out to produce a particulate polyamine group. The formate resin composition is colored. (Evaluation of physical properties) The powdery properties of the particulate polyamine phthalic acid-ester resin composition (hereinafter referred to as "each powder") obtained in each of the examples and the comparative examples, that is, adhesion and powder fluidity ( The angle of repose was measured by the following method. Further, a cast embossing mold having a size of 150 mm x 150 mm x 3 mm was heated to 240 C, and 300 g of each powder was sprinkled on the mold and allowed to stand for 8 seconds, and then the unmelted excess powder was dropped. Subsequently, it was allowed to stand at 250X: for 6 seconds, and then formed into a sheet by water cooling. Then, the physical properties of the molded article were measured in accordance with the following method. The results are shown in Tables 1 to 3. Further, the average particle diameter of each powder is about 100 to 13 Å/zm. The average particle diameter of each powder was a particle size analyzer (manufactured by Nikkiso Co., Ltd., model: 'MicroTRAC HRA). ' ❹ &lt; Adhesion> 100 g of each powder was allowed to stand at 40 ° C? 4 J 祛 , 罝 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 &lt;Powder fluidity (resting angle)&gt; The measurement of the angle of reciprocation of the yoke lamp powder using the injection of a & t &quot; according to JIS R-9301-2. &lt;Fusibility (backside gloss)&gt; The gloss of the back surface of the sheet (one side of the non-compressed cast) was measured using a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., model os os &quot; coffee 097138844 24 200925210 VG2000). When the gloss is higher, it is judged that the higher the meltability of the powder, the lower the gloss, and it is judged that the powder is not melted. &lt;Color unevenness (visual)&gt; The color unevenness on the surface of the sheet was evaluated in accordance with the following criteria. (Evaluation criteria) "〇": colorless unevenness and uniformity. 「 “△”: Only some uneven color is found. "χ": I noticed uneven color. <Texture (wrinkle)&gt; After the sheet was held in a 180-fold state for 2 seconds, it was returned to its original state and left to stand overnight. Observe the bent place according to the visual observation and perform the evaluation according to the following criteria. (Evaluation Criteria) © "〇": No folds were found. "△": Only a few wrinkles were found. ^ χ": I found a significant fold of the enemy. &lt;Crosslinkability (gel fraction)&gt; The sheet was pulverized and weighed to about 4 g. This was immersed in 500 ml of tetrahydrofuran (hereinafter referred to as "THF") at 23 ° C for 24 hours. Then, decompression filtration was performed using an aspirator. The undissolved material which was not dissolved in THF, which was deposited on the filter paper, was washed with acetone, and nitrogen was blown off to sufficiently evaporate the acetone, and then allowed to stand in a 40 C oven for 20 hours under the environment of nitrogen 097138844 25 200925210. Then, the undissolved matter which was not dissolved in THF was weighed. The mass of the undissolved matter was divided by the mass of the sheet before immersion in THF, and multiplied by 100 to obtain a gel fraction (〇/〇). &lt;Tensile Strength (Elastic Modulus) and Tensile Stretching&gt; The tensile test of the sheet was carried out, and the modulus of elasticity (MPa) at the time of occurrence of the fracture and the stretching between the marks at the time of the fracture were measured (%) ). Specifically, the test piece was pressed by a jIS_4 dumbbell according to the method described in JIS K-6251, and a tensile tester (manufactured by ORIENTEC Co., Ltd., trade name: universal tensile test device RTA-500 type) was used. 'Measurement was carried out under the conditions of a tensile speed of 300 mm/min. In addition, the "%" of the stretched tensile system is expressed by a numerical value. &lt;Drug resistance (alcohol resistance)&gt; A few drops of ethanol were dropped on a surface of a sheet by a pipette of 0.1 ml capacity, and after holding at 25 C for 1 hour, followed by holding at 80 ° C for 1 hour, The surface of the Φ sheet was subjected to wiping, and the state of the surface was evaluated as "5 grade" according to the visual observation of the surface I, and the state in which the surface was completely dissolved was rated as "grade 1", and The status between the two is evaluated according to each level. &lt;Fluidity (strength retention and appearance change)&gt; After the skin of the silk was allowed to stand in a 12 (rc hot air circulation oven) for 5Q0 hours, the tensile strength of the skin before and after the heat treatment was determined according to the above tensile strength and The measurement method of the tensile elongation was measured, and the tensile strength of the heat-treated skin was divided by the tensile strength before heat treatment, and multiplied by 1 GG to obtain a strength of 097138844 26 200925210 (%). The measurement of the gloss of the die-cast surface of the skin after heat treatment was carried out (the product of Sakamoto Electric Co., Ltd., model: Gloss Meter VG2000). The higher the gloss, the change in appearance was judged. In addition, the skin before heat treatment The gloss is all 1.1.

097138844 27 200925210 Ο

Hr 9.0 L'l TT VI Lrt.o hr w

SI 09 0 inch s 9ICO.0

SIC-.Q

SI

l.Q 9.0 s s 6Γ0 grILTa

IV zoo 09 b. s

(NII 019

SI L.l hrLn.o hrQ.o

Lo.o oco 09

Lo.o ζι ΖΓΟ 9·Ι 89·9Ι Γ0 s

Ln.o 9.0 6Γ0 srILn I&gt;

IS 〇 09

SI hr w ZL· s 09 0 inch

Lo.o looro ΖΓΙΙ β 09 0 inch

Ln.o 8Γ.0 ΖΙΊΙ r.z -r.l

l.Q lrQ

G.o lr.Q

ILO.O _ g.Q g.o i s

looO.Q 11.1

go.Q 65 Γ.Ζ lo.o i.l rl llo.0 g·0

IV 63 s s

6.ZI § 91 1&gt; oco s 3⁄4

SI 03⁄4 oo s s

OCVI οι 06

Lo.o 8r.0 ΖΙ.ΙΙ Γ0 s

Loo s.o 6Γ0

srILO l&gt;

OS

9S b, Bu Ln

6.ZI s win

OOJ 06 01 s ιοοκο ΖΓΙΙ Γ0 s 9.0 ΙΛ.0 6ΙΌ

glILO I&gt; s 3⁄4

V UO9

SI 6.1 01 oco

Lo.o oos ΖΙ.1Ι Γ0

Ln.o s

Lno 6ΙΌ

Lnrs l&gt;

Lns Γ.ΖΙ g. inch inch

OO.I 09

Lo.o 09 09 0 inch I 0 inch

G.o _ILO.O 91 ΙΟΙ 1100 r.Q a ΙΡ.Ι a 莽·0

S ICNi ζζ ·ζ Igr.lcozurll

VO s 9Ό 6ΙΌ grs coco 09

OS Z.Q1 sln s ε

VO 9.0 1Λ.0

LTJ.O

6I.D srs I&gt; 003 s inch

V m

SI i 9 inch τι

OO.I Γ0 9.0

Lo.o s.o 6ΙΌ 9110

IV Φ 39 9.31 s inch LO oo ·»—η

OOIN o (#¥i!w)m .51 (#s)Discussion In .·¥ you)181i¥w)ss —sg—rjl $SIi (—sg—rjll

i£00E ilsgy

isvqH-91 (gas i) l-1 (NII ds β a

$, is)il^lio Forge Stupid Itgl 1

_S0 _ISlgL νε

Isll^揉 _I1CT 彦好一 oi—IgTJSIi —on lai— ϊ$ (l^g)l^llK-le

SI (I want elf (said taste) (lail> last name 11rl) l±il ffi inch sooroi 200925210

t 霊g CO » ^ 03 inch CO L〇0〇oo 1 丨i 1 1 i uO os 5 Λ =〇〇r—t !N1 — f 1 &lt; C^J 1 a-γ F—♦ 1 1 r —H o L〇o LO 〇=&gt; Si =&gt; ?3 V &lt;] Λ JO 3〇&lt; o! Λ S LO Γ-Η § CO 〇3 but CO LTD oo 〇〇1 1 1 1 1 1 io C3 卜 c&lt;is 3 LD 〇oo 0.48 1 t cD — in f—* o LO o LO C3 〇〇Λ V 〇〇[〇s 2 m inch S οά ΐκ 9C I § CO ?3 呀CO m oo Oo li 1 i 1 1 LO &lt;=&gt; Bu CO s S ΙΛ 〇〇〇〇CO 1 I —— — 1 o LD 〇LO 〇in C=5 2 O ?5 lt5 V CO 〇〇OO ^ i ο LO § οα C—j S c^ 1 Ο ο s CO 〇3 CO inch CD UT&gt; 呀CD L〇oo oo oo oc 1 1 1 1 1 i 1 1 1 1 1 L〇o LO Gi 卜t&gt;a c^is § s 〇ΙΛ &lt;=} oo oo 〇' ο ?-&lt;1112 11.12 CO CD I co 1 *—H 0 1 C5 to a&gt; : o in C3 : o ΙΛ o : o CD oo Call LT5 ί LC r—&lt; V : V ?5 : CO : 〇ό 〇ό g ιχ5 3 ; s inch LO οα 1 inch 03⁄4 τ—&lt; ψί UJ I ο 2 21.6 1 1 1 1 1 1 56.4 18.8 mo 卜 CNl g LO C&gt; oo 0.48 11.12 CO 1 LO CD ΙΛ o LO o' 0.19 5.75 V 83 5§ 0 〇s 11.5 g ΙΓ. ο 卜 r-; ψ ^ά* 1 £=) Ξ CD 1 1 1 1 to Pan 05 &lt;=&gt; 1 1 inch a £ § LT3 Ο* oo 0.48 11.12 CD 1 1 *—1 c> lT5 〇ID 〇in o 2 in IT. V 8S 0 〇〇s LD CO ο 吞 LO § 00 S r»H 1 ο 2 22.6 1 1 LT5 Cd 卜 CT&gt;C&gt; 1 1 1 1 CD οο s LO C5 oo 0.48 11.12 CO I f—^ 1 r— o L〇o LjO o in o 0.19 iT. IT: V 0 s 笃CC 1 ΙΛ 勹q· t, 1 C CO ύ CO to oo 〇c 1 I 1 1 1 1 L〇oo* 03 s § in c&gt; oo 0.48 1—^ 11.12 CO 1 ΙΛ &lt;=3 1 Τ Ο mom c&gt; m c&gt; Ξ o ^- ιή V Another 0 0 t—1 1 〇OO 1*H and τ—Η § CO d cd LC oo C3C ) ] 1 1 1 1 L〇oc— (ΝΪ § LO o oo 〇— 11.12 1 1 r —t (=&gt; LO C&gt; LO C3 Lrt 〇2 O* 03⁄4 cc r·^ VC 0 23⁄4 CN1 CO »—H 1 〇〇03 Η £ rate 遛tO ¢ - 1 mib 1 &lt;7) 7 / —s N c3 1 N m 05 Rarely $ pH ! 1 p «ΊΝ ! •w 1« g P | W g &lt;z&gt; i M SK s 屮OJ 1 _ CO i «Η 1 φι Φκ $ Φ ^QK &gt ;H gi 1 want I ! 1 I ί ig 1 i s » ♦ s [IMP-3A L〇兮C&lt;1 I m eg Ϊ i CO %. i 1—H g 2 fo CO Ψ '&lt; p 1 Call 6 'oil 1 ς ς~\ /^\ tffl : 1 bUL 电 S 寒απ Κ- «3 1 8 i I ¥赛赛 9 1 想i 8 1 办 i $ 株1 鮏¥ m 8 1 Exchange: 1 雔% ζ^&gt; «rl Tea Ιΐφλ sst- Love tO difficult to sam sac « silkworm I t 1 溜 ο s sS| , 琢 % I 蚌 3 φ φ | m Si dysentery • W g U 〇 nose # I &lt; 〇 S 铋 5 g 狴 〇 〇 〇 ® - i 宝1 Ιι 5 I % 露1 - ii 〇Γ^Λ--------- _ If# --- 里—--- 6Z 200925210 Composition Comparative Example 1 Comparative Example 2 Comparative Example 2 Comparative Example 4 Comparative Example 5 Heat 1 g of urethane resin (parts by mass) 100 100 100 100 100 Isocyanate Desmodur W (parts by mass) 21.6 21.6 21.6 21.6 21.6 Polyol U-2720C parts by mass) 56.4 56.4 56.4 56.4 56.4 U -2710C parts by mass) 18.8 18.8 18.8 18.8 18.8 C-2090C parts by mass) — — — — — 1,4-BD (parts by mass) — — — — —ΙΌ—249 (parts by mass) — 一 — — — 1,4-Η ) (mass parts) — — — — — PTG2000 (mass parts) — 一— — — PTG1000 (parts by mass) — — — — — Monol 2-EtHA (parts by mass) 0.5 0.5 0.5 0.5 0.5 Chain extender 1, 6-HDA (parts by mass) 2.7 2.7 2.7 2.7 2.7 Ethylene; 1 k Monomer polymer (parts by mass) 20 0 20 20 20 Aromatic vinyl monomer St (% by mass) 60 — 60 60 60 Acrylate MMA (mass 90 40 — 40 40 40 chain transfer agent MSD (relative to monomer 100) Parts by mass of the mass part) 0.5 - 0.5 0.5 0.5 Monomer emulsion (parts by mass relative to 100 parts by mass of the thermoplastic urethane resin) 2% persulfate aqueous solution 8 - 8 8 8 25% Aqualon HS-1025 Aqueous solution 0.48 — 0.48 0.48 0.48 2%* aqueous solution of sodium hydrogencarbonate 1 — 1 1 1 Deionized water 11.12 — 11.12 11.12 11.12 Thermally crosslinkable monomer (parts by mass) DPHA 6 6 — 6 6 ΤΜΡ-3Α — — — — — The polymerization preventive agent (parts by mass relative to 100 parts by mass of the thermally crosslinkable monomer) m 0. 0025 1 - 0.05 7 HQ — — — — — aqueous dispersion (100 parts by mass relative to the thermoplastic urethane resin) Parts by mass) Irganox 245 0.1 0.1 0.1 0.1 0.1 UNWIN® 765 0.5 0 .5 0.5 0.5 0.5 TINUVIP 213 0.5 0.5 0.5 0.5 0.5 rSF-451-3000 0.5 0.5 0.5 0.5 0.5 TD3130 0.19 0.19 0.00 0.19 0.19 Deionized water 5.11 5.15 1.07 5.11 5.39 Evaluation of ship-based adhesion (%) &lt;1 45 &lt; 1 &lt;1 &lt;1 Powder fluidity (resting angle X〇) 30 51 30 32 32 Formability meltability (back gloss) 4 65 62 11 65 Color unevenness (visual) XX 〇X Δ Texture (wrinkle grade) X 〇〇〇〇 crosslinkability (gel fraction) (%) 25 38 15 39 45 Mechanical properties Tensile strength (modulus of elasticity) (MPa) 8.9 7.9 8.5 9.1 9.3 Tensile at break (%) 320 700 620 400 520 Resistance (Alcohol resistance X grade) 4 3 3 4 3.5 Heat resistance strength retention (%) 52 60 42 55 58 Appearance change (gloss) 3.2 4.2 25 3.1 3.5 097138844 30 200925210 In addition, Table 1 to Table 3 The composition code is as follows: U-2720: Adipate polyester polyol (quantitative average molecular weight 2000, manufactured by Mitsui Chemicals POLYURETHANES Co., Ltd.) U-2710: Adipate polyester polyol (quantitative average Molecular weight 1〇〇〇, manufactured by Mitsui Chemicals POLYURETHANES Co., Ltd.) C-2090: Polycarbonate diol (quantity Molecular Weight 2000, manufactured by Kuraray Co., Ltd.) ❿ TONE0249: Polycaprolactone diol (quantitative molecular weight: 2000, manufactured by Dow Chemical Co., Ltd.) PTG2000: polybutylene glycol (quantitative molecular weight: 2000, manufactured by Hodogaya Chemical Co., Ltd.) PTG1000: polybutylene ether Glycol (quantitative average molecular weight: 1000, manufactured by Hodogaya Chemical Co., Ltd.) 1,4-BD: 1,4-butanediol ❹ 2-EtHA: 2-ethylhexanol 1,6-HDA: 1,6-hexanediamine St :styrene MMA: methyl methacrylate MSD: α-mercaptostyrene dimer DPHA : KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacetic acid vinegar, manufactured by Nippon Kayaku Co., Ltd.) ΤΜΡ- 3Α: Trihydroxydecylpropane triacrylate 097138844 31 200925210 MQ: p-methoxyphenol HQ: hydroquinone In addition, the above description is provided as an exemplified embodiment of the present invention, which is merely illustrative and not to be construed as limiting. Modifications of the present invention which are readily apparent to those skilled in the art are covered by the scope of the appended claims. (Industrial Applicability) 3 The particulate polyamino phthalate resin composition of the present invention is suitable for use in leaching and casting. 097 097138844 32

Claims (1)

200925210 VII. Patent Application Range: 1. A particulate polyurethane resin composition containing a thermoplastic polyamine phthalate resin or a vinyl monomer polymer synthesized in a water dispersion medium. 1〜6质量份的聚合剂剂。 The heat-crosslinkable monomer, and the amount of the heat-crosslinkable monomer is 0. 1~6 parts by mass of the polymerization inhibitor. 2. The particulate polyaminophthalate wax composition according to claim 1, wherein the vinyl monomer polymerization system is composed of an aromatic vinyl monomer ❹ 35 to 70% by mass, and α, It is obtained by a polymerization reaction of an alkyl group of an ethylenically unsaturated carboxylic acid of from 3 65 to 65% by mass. 3. The particulate polyurethane resin composition according to claim 1, wherein the vinyl monomer polymerization system contains 5 to 40 masses per 100 parts by mass of the thermoplastic polyamine phthalic acid resin. Share. 4. The particulate polyamino phthalate resin composition of claim 1, wherein the thermally crosslinkable single system contains 1 part by mass of the thermoplastic polyurethane phthalate resin. 2 to 10 parts by mass. 5. The particulate polyamino phthalate resin composition as claimed in claim 1 is an aqueous dispersion of a thermoplastic polyurethane resin and a vinyl monomer polymer, and thermal crosslinkability. The aqueous dispersion of the monomer and the polymerization preventive agent is mixed and obtained by spray drying. 6. A molded article comprising a thermoplastic polyurethane resin synthesized in an aqueous dispersion medium, a vinyl monomer polymer, a heat crosslinkable monomer, and a heat crosslinkable monomer 100 The mass fraction is 097138844 33 200925210 of a polymerization preventive agent of 0.02 parts by mass. The particulate polyurethane resin composition is obtained by leaching and casting. 7. For the molded article of the sixth application patent, it is an automotive interior fitting. 8. A method for producing a particulate polyamino phthalate resin composition, comprising: an aqueous dispersion of a thermoplastic polyamino phthalate resin and a vinyl monomer polymer, and a thermally crosslinkable monomer; After the aqueous dispersion of the polymerization preventive agent was mixed, spray drying was carried out. 097138844 34 200925210 IV. Designation of representative drawings: (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative figure is simple: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: beneficial 097138844 2