JP5513205B2 - Powdery resin composition and molded product - Google Patents

Description

  The present invention relates to a particulate resin composition and a molded article.

  Slush molding is widely used for molding automobile interior parts and the like because it can easily mold a product having a complicated shape and has a good material yield.

  As a slush molding material, for example, a slush obtained by blending a urethane emulsion, a styrene acrylic emulsion, and polydimethyl silicone, obtaining powder by spray drying these, and then mixing a pigment into the powder. A molding powder composition has been proposed (see, for example, Patent Document 1).

JP 2004-91542 A

  However, when the molded product made of the powder composition for slush molding of Patent Document 1 rubs against clothing or the like for a long time, the pigment of the molded product may shift (color transfer) to the clothing.

  Moreover, in the powder composition for slush molding of Patent Document 1, bleed may be seen in the obtained slush molded product.

  However, although the powder composition for slush molding of Patent Document 1 is excellent in powder fluidity, more excellent powder fluidity is required for recent slush molding materials.

  An object of the present invention is to provide a particulate resin composition and a molded product that can prevent color transfer and bleeding, have even more excellent powder flowability, and further have excellent durability. There is.

  The particulate resin composition of the present invention comprises a thermoplastic polyurethane resin and an acrylic modified organopolysiloxane in a proportion of 0.1 to 10 parts by mass of the acrylic modified organopolysiloxane with respect to 100 parts by mass of the thermoplastic polyurethane resin. It is characterized by containing.

  In the particulate resin composition of the present invention, the acrylic-modified organopolysiloxane can be obtained by copolymerizing an organopolysiloxane having a radical polymerizable group at a terminal and a (meth) acrylic acid ester. Is preferred.

  In the particulate resin composition of the present invention, it is preferable that the acrylic-modified organopolysiloxane is particulate.

  In the particulate resin composition of the present invention, it is preferable that the thermoplastic polyurethane resin is synthesized in a non-aqueous dispersion medium.

  In the particulate resin composition of the present invention, it is preferable that the thermoplastic polyurethane resin is synthesized in an aqueous dispersion medium.

  The particulate resin composition of the present invention is preferably used for slush molding.

  The molded article of the present invention is obtained by slush molding the above-mentioned particulate resin composition.

  In addition, the molded product of the present invention is preferably an automobile interior product.

  According to the particulate resin composition of the present invention, since the acrylic modified organopolysiloxane is contained in a specific ratio, when the pigment is contained in the particulate resin composition, color transfer in slush molding is prevented. be able to. Therefore, it is possible to prevent contamination of the molded product of the present invention.

  Moreover, according to the particulate resin composition and the molded product of the present invention, the releasability at the time of slush molding can be improved.

  Moreover, according to the particulate resin composition of the present invention, the occurrence of bleeding of the molded product of the present invention can be prevented.

  Moreover, in the particulate resin composition of this invention, powder fluidity | liquidity is still more excellent. Therefore, the thickness of the molded product of the present invention can be made even more uniform.

  Furthermore, according to the particulate resin composition of the present invention, since the scratch resistance of the molded product of the present invention is excellent, the durability can be improved.

  The particulate resin composition of the present invention contains a thermoplastic polyurethane resin and an acrylic-modified organopolysiloxane.

  The thermoplastic polyurethane resin can be produced by a known synthesis method such as a one-shot method or a prepolymer method.

  In the one-shot method, for example, an isocyanate and a polyol are reacted at a time. Specifically, each component is reacted in a known dispersion medium. Alternatively, the components described above can be melt-kneaded and reacted to obtain a massive thermoplastic polyurethane resin, and then pulverized (for example, freeze pulverized) to obtain a particulate thermoplastic polyurethane resin.

  In the prepolymer method, first, an isocyanate and a polyol are reacted to synthesize an isocyanate group-terminated prepolymer having an isocyanate group at the molecular end. Next, the obtained isocyanate group-terminated prepolymer is reacted with a chain extender.

  Specifically, in order to synthesize a thermoplastic polyurethane resin by a one-shot method in a non-aqueous dispersion medium, for example, isocyanate and polyol are reacted in the non-aqueous dispersion medium.

  To synthesize a thermoplastic polyurethane resin by a prepolymer method in a non-aqueous dispersion medium, for example, first, an isocyanate and a polyol are reacted in the absence of a non-aqueous dispersion medium to synthesize an isocyanate group-terminated prepolymer. To do.

  Thereafter, the obtained isocyanate group-terminated prepolymer, non-aqueous dispersion medium and chain extender are blended, and the isocyanate group-terminated prepolymer and chain extender are reacted in the non-aqueous dispersion medium.

  Moreover, in order to synthesize a thermoplastic polyurethane resin in an aqueous dispersion medium by a one-shot method, for example, an isocyanate and a polyol are reacted in an aqueous dispersion medium.

  In addition, in order to synthesize a thermoplastic polyurethane resin by a prepolymer method in an aqueous dispersion medium, for example, first, an isocyanate and a polyol are reacted in the absence of an aqueous dispersion medium to synthesize an isocyanate group-terminated prepolymer. To do.

  Thereafter, the obtained isocyanate group-terminated prepolymer, aqueous dispersion medium and chain extender are blended, and the isocyanate group-terminated prepolymer and chain extender are reacted in the aqueous dispersion medium.

  Of the above synthesis methods, the thermoplastic polyurethane resin is preferably obtained by a prepolymer method in a non-aqueous dispersion medium or an aqueous dispersion medium. That is, the isocyanate group-terminated prepolymer and the chain extender are reacted in a non-aqueous dispersion medium or an aqueous dispersion medium. Thereby, spherical particles can be obtained, and powder flowability and moldability can be improved.

  Isocyanate-terminated prepolymers are synthesized from isocyanates, polyols, optionally monools and / or monoamines.

  Isocyanate is not particularly limited as long as it is an organic isocyanate used for the production of thermoplastic polyurethane resin, and examples thereof include aliphatic polyisocyanate, alicyclic polyisocyanate, araliphatic polyisocyanate, and aromatic polyisocyanate. It is done. Preferably, aliphatic polyisocyanate, alicyclic polyisocyanate, and araliphatic polyisocyanate are used.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate (TMDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2, Examples include 3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methyl caproate.

  Of the aliphatic polyisocyanates, PDI and HDI are preferable.

Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI). 4,4′-methylenebis (cyclohexyl isocyanate) (H ₁₂ MDI), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane (1,3 -H ₆ XDI) or 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI) and their isomer mixtures, 1,3-bis (isocyanatoethyl) cyclohexane or 1,4-bis (Iso And cyanatoethyl) cyclohexane and mixtures of isomers thereof, bis (isocyanatomethyl) norbornane (NBDI), and the like.

Among the alicyclic polyisocyanates, 1,3-H ₆ XDI, 1,4-H ₆ XDI, and H ₁₂ MDI are preferable.

  Examples of the araliphatic polyisocyanate include 1,3-bis (isocyanatomethyl) benzene or 1,4-bis (isocyanatomethyl) benzene and isomer mixtures thereof.

  Moreover, monoisocyanate can also be used together as an isocyanate in the range which does not impair the long-term heat resistance of a molded article. Examples of the monoisocyanate include methyl isocyanate, ethyl isocyanate, N-hexyl isocyanate, cyclohexyl isocyanate, 2-ethylhexyl isocyanate, phenyl isocyanate, and benzyl isocyanate.

  Isocyanates can be used alone or in combination of two or more. Preferably, combined use of aliphatic polyisocyanate and alicyclic polyisocyanate, or single use of alicyclic polyisocyanate is mentioned.

  When the aliphatic polyisocyanate and the alicyclic polyisocyanate are used in combination, the aliphatic polyisocyanate is contained in an amount of, for example, 60 mol% or more, preferably 70 mol% or more based on the total mol of the isocyanate used in combination.

  Examples of polyols include polyether polyols, polyester polyols, polycarbonate polyols, and polymer polyols obtained by polymerizing vinyl monomers such as styrene, acrylonitrile, and (meth) acrylic acid esters in these polyols. High molecular weight polyol having a hydroxyl value of 10 to 125 mgKOH / g. The number average molecular weight of the high molecular weight polyol is preferably 1400 to 3000, and more preferably 1500 to 2500. On the other hand, when a polymer polyol is used, its hydroxyl value is preferably about 20 to 80 mgKOH / g.

  Examples of the polyether polyol include polypropylene glycol and polytetramethylene ether glycol.

  Examples of the polypropylene glycol include addition polymers of alkylene oxides such as ethylene oxide and propylene oxide (a random and / or block copolymer of two or more alkylene oxides), which are initiated with a low molecular weight polyol or a low molecular weight polyamine. Included).

  The low molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 40 or more and less than 400, such as ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1 , 2-butylene glycol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentane Diol, 1,6-hexanediol, 2,6-dimethyl-1-octene-3,8-diol, alkane (carbon number 7 to 22) diol, cyclohexanedimethanol, hydrogenated bisphenol A, 1,4-dihydroxy- 2-butene, bishydroxyethoxybenzene, xylene glycol, bishi Roxyethylene terephthalate, bisphenol A, diethylene glycol, trioxyethylene glycol, tetraoxyethylene glycol, pentaoxyethylene glycol, hexaoxyethylene glycol, dipropylene glycol, trioxypropylene glycol, tetraoxypropylene glycol, pentaoxypropylene glycol, hexaoxy Dihydric alcohols such as propylene glycol such as glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, tri Such as methylolpropane, 2,2-bis (hydroxymethyl) -3-butanol and other aliphatic triols (8 to 24 carbon atoms) Dihydric alcohols such as tetramethylolmethane (pentaerythritol), tetravalent alcohols such as diglycerin, pentavalent alcohols such as xylitol, such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, dipentaerythritol And the like, for example, 7-valent alcohols such as Perseitol, and 8-valent alcohols such as sucrose.

  Examples of the polytetramethylene ether glycol include a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran, and an amorphous polytetramethylene ether glycol obtained by copolymerizing the above dihydric alcohol such as neopentyl glycol with a repeating unit of tetrahydrofuran. Etc.

  Examples of the polyester polyol include polycondensates obtained by reacting the above dihydric alcohol and polybasic acid under known conditions.

  Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, Azelaic acid, sebacic acid, other aliphatic dicarboxylic acids (11 to 13 carbon atoms), hydrogenated dimer acid, maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, dimer acid, Examples thereof include carboxylic acids such as het acid, and acid anhydrides and acid halides derived from these carboxylic acids.

  Further, as the polyester polyol, for example, polycaprolactone polyol, polyvalerolactone polyol obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone using the above dihydric alcohol as an initiator, Furthermore, the lactone type | system | group polyol which copolymerized said dihydric alcohol to them etc. are mentioned.

  Examples of the polycarbonate polyol include a ring-opening polymer of ethylene carbonate using the above dihydric alcohol as an initiator, and examples thereof include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and the like. Examples thereof include amorphous polycarbonate polyol obtained by copolymerizing a dihydric alcohol and a ring-opening polymer.

  Furthermore, the above-mentioned low molecular weight polyol can be used in combination as the polyol.

  Examples of monools include methanol, ethanol, propanol, butanol, 2-ethylhexyl alcohol, other alkanols (C5-38) and aliphatic unsaturated alcohols (9-24), alkenyl alcohols, 2-propen-1-ols. , Alkadienol (C6-8), 3,7-dimethyl-1,6-octadien-3-ol, and the like. The monool is preferably 2-ethylhexyl alcohol.

  Examples of the monoamine include dimethylamine, diethylamine, di-N-propylamine, diisopropylamine, di-N-butylamine, diisobutylamine, di-t-butylamine, dihexylamine, 2-ethylhexylamine, 3-methoxypropylamine, Examples include 3-ethoxypropylamine, 3- (2-ethylhexyloxypropylamine), 3- (dodecyloxy) propylamine, N, N-dimethyl1,3-propanediamine, morpholine and the like.

  The monool and / or monoamine is blended as necessary to adjust the molecular weight of the thermoplastic polyurethane resin.

  In order to synthesize an isocyanate group-terminated prepolymer, an equivalent ratio of isocyanate groups of isocyanate to active hydrogen groups (hydroxyl group and amino group) of polyol and monool and / or monoamine blended as necessary (isocyanate group / The active hydrogen groups) are mixed and reacted at a ratio of 1.1 to 4.0, preferably 1.4 to 2.5, for example. If the equivalent ratio is less than 1.1, the thermoplastic polyurethane resin may have an excessively high molecular weight, which may reduce moldability. On the other hand, when the equivalent ratio exceeds 4.0, the molded product of the particulate resin composition becomes hard, and the tactile sensation may be impaired.

  This reaction is carried out, for example, under a nitrogen atmosphere at a reaction temperature of 60 to 95 ° C., preferably 70 to 90 ° C., for a reaction time of 1 to 7 hours, preferably 2 to 5 hours. The reaction is terminated when the group content (for example, 2 to 6% by mass) is reached. In the case where an isocyanate is used in combination, the first isocyanate (alicyclic polyisocyanate) and a polyol are blended and reacted to substantially eliminate the isocyanate group in the reaction system. 2 isocyanate (aliphatic polyisocyanate) can be further blended to react the second isocyanate with the remaining polyol to eliminate the hydroxyl group of the reaction system.

  In this reaction, if necessary, a catalyst such as amines or organometallic compounds can be added. Preferred examples of the catalyst include organometallic compounds. Examples of such organometallic compounds include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, and dibutyltin. Examples include dilaurate, dioctyltin dilaurate, dibutyltin dichloride, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, copper octenoate, and bismuth catalysts. A catalyst can be used individually or in combination of 2 or more types, for example, 0.001-5 mass parts with respect to 100 mass parts of polyols, Preferably, 0.01-3 mass parts is added.

  Then, the obtained isocyanate group-terminated prepolymer and the chain extender are subjected to a chain extension reaction in a non-aqueous dispersion medium or an aqueous dispersion medium to obtain a thermoplastic polyurethane resin.

  Examples of the chain extender include diamines such as alicyclic diamines and aliphatic diamines, and low molecular weight polyols such as the above dihydric alcohols and the above trihydric alcohols.

  Examples of the alicyclic diamine include 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis- (4-aminocyclohexyl) methane, diaminocyclohexane, and 3,9-bis (3-aminopropyl). ) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3- and 1,4-bis (aminomethyl) cyclohexane and mixtures thereof.

  Examples of the aliphatic diamine include ethylene diamine, propylene diamine, 1,5-pentane diamine, 1,6-hexamethylene diamine, hydrazine, 1,2-diaminoethane, 1,2-diaminopropane, and 1,3-diaminopentane. Etc. Of these chain extenders, 1,5-pentanediamine and 1,6-hexamethylenediamine are preferably used as the diamine. Moreover, as a low molecular weight polyol, Preferably, 1, 4- butanediol is mentioned.

  Chain extenders can be used alone or in combination of two or more.

  The chain extender has an equivalent ratio (active hydrogen group / isocyanate group) of active hydrogen groups (amino group and hydroxyl group) of the chain extender to isocyanate groups of the isocyanate group-terminated prepolymer, for example, 0.1 to 1.1. Preferably, it is blended at a ratio of 0.4 to 1.05, more preferably 0.7 to 1.05.

  The non-aqueous dispersion medium is a solvent that does not substantially dissolve the isocyanate group-terminated prepolymer and the thermoplastic polyurethane resin, and includes, for example, aliphatic hydrocarbons such as hexane, heptane, octane, pentane, cyclohexane and isomers thereof, and An alicyclic hydrocarbon etc. are mentioned. Preferably, heptane is used.

  Further, as the non-aqueous dispersion medium, for example, esters, ketones, aromatic hydrocarbons and the like can be used in combination.

  Examples of the esters include alkyl esters such as methyl acetate, ethyl acetate, acetic acid-N-butyl, isobutyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-N- And ether esters such as butyl ether acetate and ethyl ethoxypropionate.

  Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone.

  Examples of aromatic hydrocarbons include toluene, xylene, ethylbenzene, and the like.

  The aqueous dispersion medium is water or an aqueous solvent that does not substantially dissolve the isocyanate group-terminated prepolymer and the thermoplastic polyurethane resin, and examples of the aqueous solvent include a mixture of water and alcohols (for example, methanol, ethanol, etc.). Examples include solutions. Preferably, water is used.

  In order to cause the isocyanate group-terminated prepolymer and the chain extender to undergo a chain elongation reaction in a non-aqueous dispersion medium, preferably, in the synthesis of the isocyanate group-terminated prepolymer, a desired isocyanate group content (for example, 2 When the amount reaches ˜6 mass%), a non-aqueous dispersion medium is blended with the isocyanate group-terminated prepolymer, and the isocyanate group-terminated prepolymer is dispersed in the non-aqueous dispersion medium.

The non-aqueous dispersion medium is blended in an amount of, for example, 10 to 150 parts by mass, preferably 25 to 120 parts by mass with respect to 100 parts by mass of the isocyanate group-terminated prepolymer. Thereafter, for example, at 15 to 130 ° C., while confirming the dispersion state of the isocyanate group-terminated prepolymer, the mixture is stirred at a rotational speed of 50 to 3000 min ⁻¹ to disperse the isocyanate group-terminated prepolymer in a non-aqueous dispersion medium. To prepare a prepolymer dispersion.

  The non-aqueous dispersion medium can be added to the isocyanate group-terminated prepolymer all at once or dividedly. In order to make the particle diameter of the isocyanate group-terminated prepolymer uniform, it is preferably added in divided portions. When dividing, the initial addition amount is preferably 5 to 100 parts by mass, more preferably 10 to 70 parts by mass with respect to 100 parts by mass of the isocyanate group-terminated prepolymer. When the desired particle size is reached, for example, 30-500 μm, the remainder is added.

  And a chain extender is mix | blended with a prepolymer dispersion liquid. When diamine is used as a chain extender, the amino group is highly reactive with the isocyanate group of the isocyanate group-terminated prepolymer, and the urea bond formed by the reaction has a very high intermolecular cohesion. Therefore, it is necessary to reduce the local reaction between the chain extender and the isocyanate monomer. Therefore, the chain extender is preferably formulated as an aqueous solution. The concentration of the chain extender in the aqueous solution is preferably at least 20% by mass, more preferably at least 50% by mass. If the chain extender is blended as an aqueous solution, the solubility in the non-aqueous dispersion medium can be reduced, and the reaction with the isocyanate monomer dissolved in the non-aqueous dispersion medium can be reduced. Particle generation can be greatly suppressed.

  Furthermore, if a dispersion stabilizer is added to the non-aqueous dispersion medium, the sedimentation of the dispersed phase can be prevented, and stable chain extension can be achieved in the non-aqueous dispersion medium, whereby suitable particles can be obtained.

  Examples of the dispersion stabilizer include a dispersant described in JP-A No. 2004-169011, for example, a resin obtained by dehydration condensation of an alkenyl succinic anhydride and a polyol or a polyester polyol, such as dicarboxylic acid and pentaerythritol. An alkyd resin obtained by dehydrating and condensing a fatty acid to a part of the residual OH group of the polyester obtained by dehydrating condensation of the polyester, such as a polyol obtained by dehydrating condensation of an unsaturated bond-containing dicarboxylic acid and a polyol or polyester polyol, After graft polymerization of a saturated monomer, after masking the OH group of a resin obtained by masking an OH group, specifically, by dehydration condensation of an unsaturated bond-containing dicarboxylic acid and a polyol or polyester polyol, Ethylenically unsaturated monomer Such resin obtained by RAFT polymerization.

  The compounding quantity of a dispersion stabilizer is 0.05-5 mass parts with respect to 100 mass parts of isocyanate group terminal prepolymers, Preferably, it is 0.1-3 mass parts, More preferably, it is 0.15-1. .5 parts by mass.

  Specifically, for example, a chain extender dispersion containing a chain extender, a non-aqueous dispersion medium and a dispersion stabilizer is first prepared.

  The dispersion of the chain extender is, for example, 10 to 300 parts by mass of the non-aqueous dispersion medium, preferably 20 to 120 parts by mass, and 0.1 to 2 parts by mass of the dispersion stabilizer with respect to 100 parts by mass of the chain extender. Preferably, it prepares by mix | blending them in the ratio of 0.15-1.8 mass part. As described above, the chain extender is preferably prepared in advance in an aqueous solution of at least 20% by mass and blended in the above ratio. If the dispersion of the chain extender is prepared as described above, the aggregation of the particles in the non-aqueous dispersion medium can be suppressed, and the chain extension reaction can be stabilized.

  And in order to mix | blend the dispersion liquid of a chain extender with an isocyanate group terminal prepolymer, you may add collectively or divided | segmenting, or can also be dripped.

  The temperature of the chain extender dispersion is adjusted to, for example, 10 to 80 ° C, preferably 15 to 50 ° C, and more preferably 15 to 40 ° C.

  On the other hand, the temperature of the prepolymer dispersion is adjusted to, for example, 5 to 100 ° C., preferably 10 to 80 ° C., and more preferably 15 to 60 ° C.

  In the chain extension reaction, for example, 20 to 100 ° C., preferably 20 to 40 ° C. after addition of the dispersion of the chain extender, depending on the scale, is allowed to react for 0.5 to 5 hours, The reaction is carried out at 40-60 ° C for 0.5-5 hours, and finally the reaction is completed at 70-100 ° C. If necessary, the above-mentioned catalyst can be added as appropriate.

  Thereby, a thermoplastic polyurethane resin can be synthesized. The synthesized thermoplastic polyurethane resin is prepared as a dispersion of a non-aqueous dispersion medium (a non-aqueous dispersion of a thermoplastic polyurethane resin).

  Thereafter, the non-aqueous dispersion medium is removed from the non-aqueous dispersion of the thermoplastic polyurethane resin to separate the solid component. In order to remove the non-aqueous dispersion medium, for example, a separation method such as filtration, for example, a vacuum drying method using an evaporator, or the like can be used.

  In filtration, the separated solid content is dried at about 40 to 70 ° C., for example.

  In an evaporator, for example, it is dried at about 40 to 70 ° C. under reduced pressure.

  Thereby, a particulate thermoplastic polyurethane resin can be obtained.

  In order to synthesize a thermoplastic polyurethane resin by subjecting an isocyanate group-terminated prepolymer and a chain extender to chain elongation reaction in an aqueous dispersion medium, it is preferable to first add an aqueous dispersion medium to the isocyanate group-terminated prepolymer. Then, the prepolymer aqueous dispersion is prepared by dispersing the isocyanate group-terminated prepolymer in the aqueous dispersion medium.

  The aqueous dispersion medium is blended in an amount of, for example, 60 to 400 parts by mass, preferably 70 to 120 parts by mass with respect to 100 parts by mass of the isocyanate group-terminated prepolymer.

  Further, preferably, an emulsifier is blended together with the aqueous dispersion medium. Examples of the emulsifier include nonionic surfactants such as polyoxyethylene alkyl ether and anionic surfactants such as sodium polyoxyethylene alkyl ether sulfate. Examples of the emulsifier include reactive emulsifiers such as polyoxyethylene alkenyl ether ammonium sulfate.

  The emulsifiers can be used alone or in combination of two or more. Moreover, an emulsifier is 0.1-10 mass parts with respect to 100 mass parts of isocyanate group terminal prepolymers, Preferably, 0.5-5 mass parts is mix | blended.

  And a chain extender is mix | blended with a prepolymer aqueous dispersion. The chain extender may be added to the isocyanate group-terminated prepolymer in a lump or divided, or may be dropped.

  The chain extender can also be prepared as an aqueous solution, and its temperature is adjusted to, for example, 10 to 80 ° C, preferably 15 to 50 ° C, and more preferably 15 to 40 ° C.

  On the other hand, the temperature of the prepolymer aqueous dispersion is adjusted to, for example, 10 to 100 ° C, preferably 15 to 80 ° C, and more preferably 20 to 60 ° C.

  In the chain extension reaction, for example, 20 to 100 ° C., preferably 20 to 60 ° C. after addition of the aqueous solution of the chain extender, is allowed to react for 0.5 to 48 hours, depending on the scale. If necessary, the above-mentioned catalyst can be added as appropriate.

  Thereby, a thermoplastic polyurethane resin can be synthesized. The synthesized thermoplastic polyurethane resin is prepared as an aqueous dispersion medium dispersion (thermoplastic polyurethane resin aqueous dispersion, polyurethane dispersion).

  Thereafter, the aqueous dispersion liquid of the thermoplastic polyurethane resin is removed by, for example, spray drying at a hot air temperature of 90 to 130 ° C. to obtain a particulate thermoplastic polyurethane resin.

  According to such a production method, it is possible to easily produce a particulate thermoplastic polyurethane resin in which each component is uniformly dispersed, and further a particulate resin composition.

  The volume average particle diameter of the obtained particulate thermoplastic polyurethane resin is, for example, 50 to 300 μm, or preferably 80 to 200 μm. If the volume average particle diameter is less than 50 μm, unevenness may occur during molding due to a decrease in powder fluidity. On the other hand, if the volume average particle diameter exceeds 300 μm, pinholes may occur on the surface of the molded product.

  In the present invention, the acrylic-modified organopolysiloxane can be obtained, for example, by copolymerizing an organopolysiloxane and a (meth) acrylic acid ester.

  Organopolysiloxane has a radical polymerizable group at the terminal, and is specifically a compound represented by the following general formula (1).

(R ¹ , R ² and R ^{3 in} Formula (1) each independently represent a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, and Y represents a monovalent radical polymerizable group. Z ¹ and Z ² each independently represent hydrogen, a lower alkyl group having 1 to 4 carbon atoms, or a group represented by the formula —SiR ⁴ R ⁵ R ^{6. In the} above formula, R ⁴ and R 2 ⁵ independently represents a monovalent hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms exemplified by the above-described R ^{1 to} R ³ , and R ⁶ represents R ^{1 to} R described above. 1 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group or a radical reactive group, as exemplified in ^{3. In} addition, m is a positive integer of 10,000 or less, and n is an integer of 1 or more. .)
In the general formula (1), examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ² and R ³ include alkyl groups such as methyl, ethyl, propyl and butyl, such as phenyl and tolyl. Aryl groups such as xylyl and naphthyl, and aralkyl groups such as benzyl.

As the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ , R ² and R ³ , at least one of hydrogen atoms bonded to the carbon atom of the hydrocarbon group having 1 to 20 carbon atoms described above, For example, a group substituted with a halogen atom such as chlorine or fluorine.

  In the general formula (1), examples of the radical polymerizable group represented by Y include vinyl, allyl, and γ- (meth) acryloxypropyl.

In the general formula (1), examples of the lower alkyl group having 1 to 4 carbon atoms represented by Z ¹ and Z ² include methyl, ethyl, propyl, and butyl.

  m is preferably a positive integer that satisfies the following formula (2).

500 ≦ m ≦ 8000 (2)
n is preferably a positive integer that satisfies the following formula (3).

1 ≦ n ≦ 500 (3)
In the general formula (1), the siloxane chain represented by-(Si (R ¹ ) (R ² ) O) _m- and-(Si (R ³ ) (Y) O) _n- is linear. It may be present or branched.

  The (meth) acrylic acid ester is a methacrylic acid ester (methacrylate) and / or an acrylic acid ester (acrylate), and specifically includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) Alkyl (meth) acrylates such as acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, such as methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, etc. Turkey alkoxyalkyl (meth) acrylates, e.g., cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, for example, an aryl (meth) acrylates such as phenyl (meth) acrylate.

  These (meth) acrylic acid esters can be used alone or in combination of two or more.

  In addition to the above components, a copolymerizable monomer copolymerizable with (meth) acrylic acid ester may be used in combination.

  Examples of the copolymerizable monomer include a polyfunctional ethylenically unsaturated monomer or a monofunctional ethylenically unsaturated monomer.

  Examples of the polyfunctional ethylenically unsaturated monomer include (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-methoxymethyl (meth). Unsaturated amides such as acrylamide and alkylols or alkoxyalkylated products of unsaturated amides, such as oxirane group-containing unsaturated monomers such as glycidyl (meth) acrylate, glycidyl allyl ether, such as 2-hydroxyethyl (meth) acrylate Hydroxyl group-containing unsaturated monomers such as 2-hydroxypropyl (meth) acrylate, for example, carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, maleic anhydride, crotonic acid, itaconic acid, N-dimethylamino Amino group-containing unsaturated monomers such as til (meth) acrylate and N-diethylaminoethyl (meth) acrylate, for example, polyalkylene oxide group-containing unsaturated monomers such as ethylene oxide and propylene oxide adducts of (meth) acrylic acid For example, esters of polyhydric alcohols such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and (meth) acrylic acid, such as allyl (meth) acrylate, divinyl Examples include benzene.

  Examples of the monofunctional ethylenically unsaturated monomer include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate, and vinyl propionate.

  And the compounding ratio in the copolymerization of the organopolysiloxane and the (meth) acrylic acid ester is, for example, 5 to 95% by mass of the organopolysiloxane with respect to the total amount of the organopolysiloxane and the (meth) acrylic acid ester. The (meth) acrylic acid ester is, for example, 5 to 95% by mass.

  The acrylic modified organopolysiloxane can be obtained by a known polymerization method. Specifically, for example, it can be obtained by solution polymerization, emulsion polymerization, suspension polymerization, dispersion polymerization and the like. Preferably, it is obtained by emulsion polymerization.

  In emulsion polymerization, for example, an organopolysiloxane and a (meth) acrylic acid ester are emulsified with a known emulsifier, and then a known radical polymerization initiator is added to the organopolysiloxane to form (meth) acrylic acid. The ester is graft copolymerized.

  In the emulsion polymerization, the organopolysiloxane can be emulsified and / or polymerized with a known emulsifier, and then (meth) acrylic acid ester is graft copolymerized in the emulsion.

  Furthermore, in emulsion polymerization, an organopolysiloxane is emulsified and / or polymerized with a known emulsifier in the presence of seed particles produced by polymerization of a (meth) acrylic monomer, and then a (meth) acrylic acid ester in the emulsion. Can also be obtained by graft copolymerization.

  Alternatively, an acrylic-modified organopolysiloxane having a core-shell structure (multilayer particle structure) can be obtained by performing multistage polymerization so that the organopolysiloxane serves as the core and the polymer of the (meth) acrylic ester serves as the shell. In the core-shell structure, since the shell layer is made of a polymer of (meth) acrylic ester having a high glass transition point (Tg), the powder fluidity of the particulate resin composition can be further improved. Formability can be improved.

  Thereby, acrylic modified organopolysiloxane can be obtained.

  The acrylic-modified organopolysiloxane thus obtained is prepared in the form of particles or an emulsion dispersed in water.

  If the acryl-modified organopolysiloxane is prepared in the form of particles, the acryl-modified organopolysiloxane can be easily blended into the particulate thermoplastic polyurethane resin and can be mixed uniformly with certainty.

  If the acrylic-modified organopolysiloxane is prepared as an emulsion, the acrylic-modified organopolysiloxane can be easily blended into a non-aqueous dispersion or an aqueous dispersion of a thermoplastic polyurethane resin and reliably mixed uniformly. .

  Preferably, the acrylic-modified organopolysiloxane is prepared in the form of particles by spray-drying the emulsion. Thereby, the color transfer property of a particulate resin composition can be prevented reliably, and a mold release property and powder fluidity | liquidity can be improved further.

  The average particle diameter of the acrylic-modified organopolysiloxane prepared as particles is, for example, 3 to 200 μm, preferably 5 to 60 μm, and more preferably 10 to 45 μm.

  The particle diameter of the acrylic-modified organopolysiloxane prepared as an emulsion is, for example, 10 to 1000 nm, preferably 50 to 600 nm, and the viscosity is 20 ° C., for example, 1 to 5000 mPa · s, preferably It is 5-3500 mPa * s, More preferably, it is 5-1000 mPa * s, Solid content concentration is 5-70 mass%, for example, Preferably, it is 20-65 mass%.

  The acrylic-modified organopolysiloxane has a soluble content in the non-aqueous dispersion medium, specifically, a heptane-soluble content, for example, 30% by mass or less, preferably 25% by mass or less, and more preferably. , 20% by mass or less, and usually 0.01% by mass or more.

  The heptane-soluble content can be determined as follows.

  Acrylic-modified organopolysiloxane and heptane are weighed and mixed in a container at a ratio of 1: 4, shaken well, and then allowed to stand for 3 days to allow solids to settle. The supernatant collected from here is heated at 40 ° C. for 24 hours to remove heptane and obtain a non-volatile content. The percentage of the non-volatile component mass with respect to the mass of the acrylic-modified organopolysiloxane is calculated as the heptane-soluble component.

  When the heptane-soluble content exceeds the above range, the powder fluidity decreases, and when the molded product is used as an automotive interior product (skin material), the automotive interior product adheres to the urethane foam. May decrease.

  In addition, as the acrylic-modified organopolysiloxane, a general commercially available product can be used, and examples thereof include the Charine series (trade name, manufactured by Nisshin Chemical Co., Ltd.).

  More specifically, for example, particulates such as Charine R-170S (average particle size 30 μm, heptane-soluble content 17% or less, volatile content 1% by mass or less, manufactured by Nisshin Chemical Co., Ltd.) are used. And an emulsion such as Charine R-170EM (viscosity at 20 ° C. of 500 mPa · s or less, solid content concentration of 45 mass%, heptane-soluble content of solid content of 16% or less, particle size of 200 nm, manufactured by Nissin Chemical Co., Ltd.).

  And the particulate resin composition of this invention can be obtained by mix | blending the above-mentioned acrylic modified organopolysiloxane with the above-mentioned thermoplastic polyurethane resin.

  Specifically, a particulate acrylic modified organopolysiloxane is obtained by removing a non-aqueous dispersion of a thermoplastic polyurethane resin, an aqueous dispersion, or a non-aqueous dispersion medium or an aqueous dispersion medium therefrom. The aspect mix | blended with these thermoplastic polyurethane resins is mentioned.

  Alternatively, the emulsion-modified organopolysiloxane in emulsion is a non-aqueous dispersion of a thermoplastic polyurethane resin, an aqueous dispersion, or a particulate thermoplastic polyurethane obtained by removing the non-aqueous dispersion medium or the aqueous dispersion medium therefrom. The aspect mix | blended with resin etc. are mentioned.

  Of the above-described blending modes, preferably, the particulate acrylic modified organopolysiloxane is blended with a non-aqueous dispersion of a thermoplastic polyurethane resin (first embodiment), and the particulate acrylic modified organopolysiloxane is blended. An embodiment (second embodiment) of blending into a particulate thermoplastic polyurethane resin, and an embodiment (third embodiment) of blending an acrylic modified organopolysiloxane in an emulsion with an aqueous dispersion of a thermoplastic polyurethane resin. In the second embodiment, more preferably, the particulate acrylic modified organopolysiloxane is blended with the particulate thermoplastic polyurethane resin obtained by removing the aqueous dispersion medium of the thermoplastic polyurethane resin.

  In the first embodiment, particulate acrylic modified organopolysiloxane is blended and dispersed in a non-aqueous dispersion of thermoplastic polyurethane resin. Thereafter, the non-aqueous dispersion medium is removed from the non-aqueous dispersion of the thermoplastic polyurethane resin, the solid content is separated, and the solid content is dried.

  Specifically, a non-aqueous dispersion of a thermoplastic polyurethane resin at a high temperature (for example, a temperature of 70 to 100 ° C.) immediately after the chain extension reaction is cooled to, for example, 40 ° C. or less, preferably 35 ° C. or less, usually 20 ° C. or more. To do. Thereafter, an acrylic-modified organopolysiloxane is added thereto.

  After cooling the non-aqueous dispersion of the thermoplastic polyurethane resin immediately after the chain extension reaction, the acrylic modified organopolysiloxane is blended with the acrylic modified organopolysiloxane to prevent excessive swelling of the acrylic modified organopolysiloxane in the non-aqueous dispersion medium. Organopolysiloxane can be uniformly mixed and dispersed in a non-aqueous dispersion of thermoplastic polyurethane resin.

  In the second embodiment, the acrylic-modified organopolysiloxane is directly blended into the thermoplastic polyurethane resin from which the aqueous dispersion medium in the aqueous dispersion of the thermoplastic polyurethane resin has been removed, and uniformly stirred.

  In the third embodiment, the acrylic modified organopolysiloxane of the emulsion is mixed and dispersed after blending with the aqueous dispersion of the thermoplastic polyurethane resin. Thereafter, the aqueous dispersion medium is removed from the aqueous dispersion of the thermoplastic polyurethane resin, the solid content is separated, and the solid content is dried.

  Among the above embodiments, the first embodiment and the second embodiment are particularly preferable.

  In the first aspect, the releasability can be further improved as compared with blending with a particulate thermoplastic polyurethane resin obtained by drying a non-aqueous dispersion of a thermoplastic polyurethane resin.

  In the second aspect, color transfer and scratch resistance can be further improved as compared to the third aspect.

  The blending ratio of the acrylic modified organopolysiloxane is 0.1 to 10 parts by weight, preferably 0.2 to 5.0 parts by weight, more preferably 0.4 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic polyurethane resin. 4.0 parts by mass.

  When the blending ratio of the acryl-modified organopolysiloxane exceeds the above range, the powder fluidity is lowered, and the effects such as prevention of bleeding and prevention of color transfer cannot be sufficiently exhibited.

  On the other hand, when the blending ratio of the acrylic-modified organopolysiloxane is less than the above range, effects such as prevention of color transfer, improvement of releasability, and scratch resistance cannot be fully exhibited.

  Moreover, according to the use and the objective, for example, a vinyl monomer polymer, a thermally crosslinkable monomer, and a polymerization inhibitor can be blended in the particulate resin composition of the present invention.

  The vinyl monomer polymer is, for example, a copolymer of an aromatic vinyl monomer and an α, β-ethylenically unsaturated carboxylic acid alkyl ester, and the aromatic vinyl monomer and an α, β-ethylenically unsaturated carboxylic acid alkyl ester. It can be obtained by a radical copolymerization reaction with an ester.

  Examples of the aromatic vinyl monomer include styrene monomers such as styrene and α-methylstyrene, alkyl vinylbenzenes such as vinyltoluene and ethylvinylbenzene, and polycyclic aromatic monovinyl monomers such as vinylnaphthalene. .

  These aromatic vinyl monomers can be used alone or in combination of two or more. Of these, styrene is preferable.

  Examples of the α, β-ethylenically unsaturated carboxylic acid alkyl ester include (meth) acrylate. (Meth) acrylate is acrylate and / or methacrylate, for example, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, isononyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate (methyl methacrylate), butyl methacrylate, cyclohexyl Examples include alkyl (meth) acrylates such as methacrylate and 2-ethylhexyl methacrylate. Examples of the α, β-ethylenically unsaturated carboxylic acid alkyl ester include vinyl cyanide or vinylidene cyanide such as acrylonitrile and methacrylonitrile.

  These α, β-ethylenically unsaturated carboxylic acid alkyl esters can be used alone or in combination of two or more. Of these, methyl methacrylate is preferable.

  And in order to carry out the radical copolymerization reaction of the aromatic vinyl monomer and the α, β-ethylenically unsaturated carboxylic acid alkyl ester, the aromatic vinyl monomer is, for example, 35 to 70% by mass with respect to the total amount of these monomers. Preferably, 45 to 65% by mass, α, β-ethylenically unsaturated carboxylic acid alkyl ester, for example, 30 to 65% by mass, preferably 35 to 55% by mass, and radical polymerization initiator Add.

  Examples of the radical polymerization initiator include persulfates, organic peroxides, azo compounds, and the like.

  Examples of the persulfate include sodium persulfate, potassium persulfate, and ammonium persulfate.

  Examples of the organic peroxide include 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) -2-methylcyclohexane, Peroxyketals such as 1,1-di (t-butylperoxy) cyclohexane, for example, dialkyl peroxides such as di-t-butyl peroxide, such as dilauroyl peroxide, di- (3-methylbenzoyl) Diacyl peroxides such as peroxide, benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide, such as 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5 -Dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hex Luperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, t- And peroxyesters such as butyl peroxy-2-ethylhexyl monocarbonate and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane.

  Examples of the azo compound include azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl 2,2 '-Azobis (2-methylpropionate), 2,2'-azobis (2- (2-imidazolin-2-yl) propane, dimethylmethylpropaneisobutyrate, 2,2,7-azobis [N- (2 -Carboxyl) -2-methylpropionamidine] tetrahydrate, 2,2'-azobis [2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide], 2,2 '-Azobis [N- (2-hydroxyethyl) -2-methylpropanamide], 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) , Like 1,1'-azobis [cyclohexane-1-carbonitrile.

  These radical polymerization initiators can be used alone or in combination of two or more. Of these, preferred are persulfates and azo compounds, and more preferred are sodium persulfate, 2,2′-azobis (2-methylbutyronitrile), dimethyl 2,2′-azobis (2 -Methyl propionate).

  The radical polymerization initiator is added in an amount of, for example, 0.1 to 10 parts by mass, preferably 1 to 7 parts by mass with respect to 100 parts by mass of the total amount of monomers.

  In the radical copolymerization reaction, a chain transfer agent is preferably added to adjust the molecular weight of the vinyl monomer polymer.

  Examples of the chain transfer agent include mercaptans such as t-dodecyl mercaptan and 2-ethylhexyl thioglycolate, and styrene dimers such as α-methylstyrene dimer.

  These chain transfer agents can be used alone or in combination of two or more. Of these, α-methylstyrene dimer is preferable.

  The chain transfer agent is added, for example, 10 parts by mass or less, preferably 0.01 to 5 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of monomers.

  Furthermore, in the radical copolymerization reaction, a known polymerization emulsifier, a known buffering agent, and the like can be added at an appropriate ratio, if necessary.

  In the radical copolymerization reaction, the above-described monomer is reacted, for example, at a reaction temperature of 20 to 130 ° C., preferably 30 to 80 ° C., for a reaction time of 1 to 20 hours, preferably 2 to 15 hours.

  Monomer charging may be performed in a batch, divided, or sequential manner. However, when charging in batches, the reaction temperature is preferably initially set low and then used for the operation in scale-up. In light of the half-life of the radical initiator, the temperature is gradually increased until the target reaction temperature is reached.

  When the thermoplastic polyurethane resin is prepared as a non-aqueous dispersion, the vinyl monomer polymer is synthesized separately from the non-aqueous dispersion of the thermoplastic polyurethane resin under the above-mentioned conditions, and the thermoplastic polyurethane resin is synthesized. It can mix | blend with a non-aqueous dispersion liquid. In addition, the vinyl monomer polymer is a monomer liquid in which a thermoplastic polyurethane resin or a non-aqueous dispersion medium of an isocyanate group-terminated prepolymer is mixed with the above-described monomer, a radical polymerization initiator, and, if necessary, a chain transfer agent. Can be synthesized in the non-aqueous dispersion medium under the above conditions. With the latter method, the manufacturing process can be simplified.

  Further, when the thermoplastic polyurethane resin is prepared as an aqueous dispersion, the vinyl monomer polymer is synthesized separately from the aqueous dispersion of the thermoplastic polyurethane resin under the above conditions, and the thermoplastic polyurethane resin is synthesized. It can mix | blend with the aqueous dispersion of this. The vinyl monomer polymer was prepared by previously mixing the above-described monomer, radical polymerization initiator, and optionally a chain transfer agent, an emulsifier for polymerization, and a buffering agent in an aqueous dispersion of a thermoplastic polyurethane resin or an isocyanate group-terminated prepolymer. By adding it as a monomer emulsion, it can also be synthesized under the above conditions in the aqueous dispersion medium. If it is the latter method, a thermoplastic polyurethane resin and a vinyl monomer polymer can be mix | blended more uniformly, and the handling in a manufacturing process can be improved.

  A vinyl monomer polymer is 5-40 mass parts with respect to 100 mass parts of thermoplastic polyurethane resins, Preferably, 10-35 mass parts, More preferably, 15-30 mass parts is mix | blended.

  Examples of the thermally crosslinkable monomer include compounds having a plurality of ethylenically unsaturated bonds, such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentanediol di ( Alkanediol di (meth) acrylates such as meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, Methylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Alkane polyols poly (meth) acrylates such as lithritol hexa (meth) acrylate, for example, unsaturated carboxylic acid diallyl esters such as diallyl maleate, diallyl fumarate, diallyl itaconate, such as urethane di (meth) acrylate, such as polybutadiene Examples include di (meth) acrylate.

  These thermally crosslinkable monomers can be used alone or in combination of two or more. Of these, alkane polyol poly (meth) acrylate is preferable, and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are more preferable.

  For example, 0.1 to 10 parts by mass, preferably 2 to 10 parts by mass, and more preferably 4 to 8 parts by mass with respect to 100 parts by mass of the thermoplastic polyurethane resin.

  Specifically, the thermally crosslinkable monomer is blended and mixed in a non-aqueous dispersion of a thermoplastic polyurethane resin containing a thermoplastic polyurethane resin and a vinyl monomer polymer or an aqueous dispersion of a thermoplastic polyurethane resin.

  Examples of the polymerization inhibitor include quinones such as p-benzoquinone, p-methoquinone, naphthoquinone, phenanthraquinone, toluquinone, and 2,5-diphenyl-p-benzoquinone, such as hydroquinone, p-t-butylcatechol, Hydroquinones such as 2,5-di-t-butylhydroquinone, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, for example, p-methoxyphenol, di-t-butylparacresol hydroquinone monomethyl And phenols such as ether.

  These polymerization inhibitors can be used alone or in combination of two or more. Of these, phenols are preferable, and p-methoxyphenol is more preferable.

  The polymerization inhibitor is blended in an amount of, for example, 0.1 to 6 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 0.1 to 4 parts by weight with respect to 100 parts by weight of the thermally crosslinkable monomer. . If the number of parts of the polymerization inhibitor is less than 0.1 parts by mass, color unevenness, texture, and long-term heat resistance may decrease. On the other hand, when the blending amount of the polymerization inhibitor exceeds 6 parts by mass, uneven color, mechanical strength, long-term heat resistance, and the like may decrease. If the number of parts of the polymerization inhibitor is within the above range, it is possible to obtain a molded product having excellent color unevenness and texture, and excellent mechanical properties, chemical resistance and long-term heat resistance.

  Specifically, the polymerization inhibitor is blended and mixed together with a thermally crosslinkable monomer in a non-aqueous dispersion or an aqueous dispersion of a thermoplastic polyurethane resin.

  And by mix | blending the above-mentioned vinyl monomer polymer, a heat-crosslinkable monomer, and a polymerization inhibitor, the external appearance of a molded article, a touch feeling, a moldability, and long-term heat resistance can be improved.

  Furthermore, the particulate resin composition of the present invention may contain, as necessary, known additives such as pigments, antioxidants, heat stabilizers, antiblocking agents, plasticizers, light stabilizers, ultraviolet rays. Absorbers, dyes, lubricants, fillers, hydrolysis inhibitors and the like can be added at appropriate ratios.

  Examples of the pigment include carbon black and calcium carbonate.

  These additives may be added at the time of synthesizing each component, or may be added at the time of mixing / dispersing each component, and may also be added after separation / drying of the particulate resin composition.

  The repose angle of the particulate resin composition thus obtained is, for example, 40 degrees or less, preferably 35 degrees or less, and usually 20 degrees or more. The angle of repose can be measured according to JIS R-9301-2.

  When the angle of repose of the particulate resin composition exceeds the above range, a bridge is formed, and the powder fluidity may be reduced and the powder handling property may be reduced.

  And according to the particulate resin composition of the present invention, since the acrylic modified organopolysiloxane is contained in a specific ratio, when the pigment is contained in the particulate resin composition, the color transfer in the slush molding Can be prevented. Moreover, according to the particulate resin composition of the present invention, the releasability at the time of slush molding can be improved.

  When the angle of repose is in the specific range described above, this particulate resin composition can effectively prevent the formation of bridges, ensure even better powder flowability, and improve powder handling properties. be able to.

  Therefore, the particulate resin composition of the present invention can be used as a toner binder and is suitable for slush molding, and is used in various fields such as furniture sheets, sofas and toys where slush molding is performed. The In particular, the particulate resin composition of the present invention can be suitably used for automobile interior parts molded by slush molding (slush molding).

  And, the molded product of the present invention obtained by slush formation of the particulate resin composition of the present invention, especially the automobile interior product, can prevent the occurrence of contamination and bleed around it, and has a uniform thickness Can be secured.

  Moreover, the particulate resin composition of the present invention can be formed into a molded product having a desired shape by a molding method other than slush molding, for example, rotational molding, extrusion molding, injection molding or the like.

  Furthermore, the particulate resin composition of the present invention can be processed and formed into pellets by an extruder.

  Next, although this invention is demonstrated based on a manufacture example, an Example, and a comparative example, this invention is not limited by the following Example.

Production Example 1
(Production of dispersion stabilizer)
After 2000 parts by weight of adipate-based polyester polyol (trade name U-2610, manufactured by Mitsui Chemicals) and 98 parts by weight of maleic anhydride were placed in a three-necked flask equipped with a stirrer, the temperature was gradually raised in a nitrogen stream, Stir at 150 ° C. for 20 hours. Further, while nitrogen bubbling, the temperature was gradually raised to 170 ° C. under a reduced pressure of 2.66 kPa, and the mixture was stirred at the same temperature for 5 hours. As a result, an unsaturated bond-containing polyol containing an unsaturated bond was obtained.

  After raising the temperature to 70 ° C. in a nitrogen atmosphere, 87.4 parts by mass of ethyl isocyanate is gradually added dropwise to 1300 parts by mass of the unsaturated bond-containing polyol, and reacted at 75-80 ° C. for 6 hours. An unsaturated bond-containing compound having a urethane bond at the end was synthesized.

  Next, the unsaturated bond-containing compound was subjected to reduced pressure treatment under conditions of 130 ° C. and 0.66 kPa or less. Furthermore, 14300 parts by mass of butyl acetate was added to 6077 parts by mass of the unsaturated bond-containing compound to prepare a uniform solution, which was then sufficiently purged with nitrogen and heated to 110 ° C.

  In a nitrogen atmosphere at 110 ° C., a monomer liquid in which 21267 parts by mass of lauryl methacrylate and 1100 parts by mass of benzoyl peroxide were mixed in advance was added dropwise in about 1 hour. After reacting at 110 to 120 ° C. for 2 hours, the reaction was further performed at 130 ° C. for 2 hours. As a result, a dispersion stabilizer having a solid concentration of about 65% by mass was obtained.

Production Example 2
(Production of 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ XDI))
Using 1,4-bis (aminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Company) having a trans / cis ratio of 93/7 by ¹³ C-NMR measurement as a raw material, a cold two-stage phosgenation method was carried out under normal pressure.

  That is, a stirring bar, a thermometer, a phosgene introduction tube, a dropping funnel and a cooling tube were attached to the flask, and 400 parts by mass of orthodichlorobenzene was charged into the flask. While cooling the flask with cold water, the temperature in the flask was set to 10 ° C. or less, and 280 parts by mass of phosgene was introduced from the phosgene introduction tube. A dropping funnel was charged with a mixed liquid of 100 parts by mass of 1,4-bis (aminomethyl) cyclohexane and 500 parts by mass of orthodichlorobenzene, and the mixed liquid was added into the flask over 30 minutes. During this time, the temperature in the flask was maintained at 30 ° C. or lower. After completion of the addition, the inside of the flask became a white slurry liquid. Again, the reaction temperature was raised to 150 ° C. while introducing phosgene, and the reaction was continued at 150 ° C. for 5 hours. The reaction liquid in the flask became a light brown clear liquid.

  After completion of the reaction, nitrogen gas was aerated at 100 to 150 ° C. at 10 L / hour for degassing.

  The solvent orthodichlorobenzene was distilled off under reduced pressure, and a fraction having a boiling point of 138 to 140 ° C./0.7 KPa was further collected by distillation under reduced pressure.

The purity of the obtained 1,4-H ₆ XDI as measured by gas chromatography was 99.9%, and the trans / cis ratio as determined by ¹³ C-NMR was 93/7.

Example 1
Takelac U-2024 (trade name, adipate polyester polyol, number average molecular weight 2000, manufactured by Mitsui Chemicals) 81.74 mass as a high molecular weight polyol in a reaction vessel equipped with a nitrogen introduction tube, a thermometer, a cooling tube and a stirring device. Parts, 0.33 parts by mass of 2-ethylhexyl alcohol (manufactured by Wako Pure Chemical Industries) as monool, and 0.50 parts by mass of Irganox 245 (trade name, manufactured by Ciba Specialty Chemicals) as antioxidant The temperature was raised to 80 to 85 ° C. with good stirring.

Next, 3.97 parts by mass of 1,3-bis (isocyanatomethyl) cyclohexane (trade name: Takenate 600, 1,3-H ₆ XDI, manufactured by Mitsui Chemicals, Inc.) was charged as the isocyanate. The reaction solution was measured with an infrared spectrometer, and reacted at 80 to 85 ° C. until the absorption peak derived from the isocyanate group disappeared.

  After confirming the disappearance of the absorption peak derived from the isocyanate group, 10.31 parts by mass of hexamethylene diisocyanate (trade name: Takenate 700, HDI, manufactured by Mitsui Chemicals) was charged again as the isocyanate. After continuing the reaction for 2 hours, it was confirmed that the isocyanate group content had dropped to 3.5% by mass, and an isocyanate group-terminated prepolymer was obtained.

  Thereafter, 0.44 parts by mass of the dispersion stabilizer of Production Example 1 and 68.70 parts by mass of heptane (n-heptane), which had been mixed in advance, were charged all at once into the reaction vessel, and the terminal end of the isocyanate group was taken over 1 hour. The prepolymer was dispersed in heptane.

  Next, 3.65 parts by mass of 1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) was charged as a chain extender.

After completion of the charging, a chain extension reaction was carried out at 80 to 85 ° C. for 5 hours to obtain a heptane dispersion of thermoplastic polyurethane resin. Thereafter, the resulting heptane dispersion of the thermoplastic polyurethane resin was cooled to 30 ° C. or lower.
<Formulation of acrylic modified organopolysiloxane>
After cooling, 0.50 parts by mass of Charine R-170S (trade name, particulate form, average particle diameter of 30 μm, volatile content of 1% by mass or less) as an acrylic-modified organopolysiloxane was charged into a heptane dispersion of a thermoplastic polyurethane resin. And stirred.

Subsequently, this was transferred to an eggplant-shaped flask, and heptane was removed under reduced pressure using a rotary evaporator while heating to 40 ° C., and the solid content was separated to obtain a particulate resin composition. .
<Blend formulation>
100 parts by mass of the obtained particulate resin composition, as a pigment, 0.6 parts by mass of carbon black / calcium carbonate dispersion (trade name: PV-817, manufactured by Sumika Color Co., Ltd.) and 0.4 parts by mass of carbon A black / calcium carbonate dispersion (trade name: PV-801, manufactured by Sumika Color Co., Ltd.) was put into a Henschel mixer and stirred at a rotation speed of 700 min ⁻¹ for 1 minute. Subsequently, the particulate resin composition was colored by passing through a 48-mesh sieve.

Examples 2 and 3
A particulate resin composition was produced and colored in the same manner as in Example 1 except that the composition and blending ratio shown in Table 1 were used.

Example 4
Takelac U-2024 (trade name, adipate polyester polyol, number average molecular weight 2000, manufactured by Mitsui Chemicals, Inc.) 82.36 mass as a high molecular weight polyol in a reaction vessel equipped with a nitrogen introduction tube, a thermometer, a cooling tube and a stirring device. Parts, 0.50 parts by mass of Irganox 245 (trade name, manufactured by Ciba Specialty Chemicals) as an antioxidant, and 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ ) of Production Example 2 as an isocyanate XDI) 14.40 parts by mass was charged and heated to 80-85 ° C. with good stirring.

  Next, 0.33 parts by mass of 2-ethylhexyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) was charged as a monool. Thereafter, it was confirmed that the isocyanate group content had dropped to 2.7% by mass, and an isocyanate group-terminated prepolymer was obtained.

  Thereafter, 0.44 parts by mass of the dispersion stabilizer of Production Example 1 and 68.70 parts by mass of heptane, which were mixed in advance, were charged all at once into the reaction vessel, and the isocyanate group-terminated prepolymer was added in heptane over 1 hour. Dispersed.

  Next, 2.92 parts by mass of 1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) was charged as a chain extender.

After completion of the charging, a chain extension reaction was carried out at 80 to 85 ° C. for 5 hours to obtain a heptane dispersion of thermoplastic polyurethane resin. Thereafter, the resulting heptane dispersion of the thermoplastic polyurethane resin was cooled to 30 ° C. or lower.
<Formulation of acrylic modified organopolysiloxane>
After cooling, 0.50 parts by mass of Charine R-170S (trade name, particulate form, average particle size of 30 μm, volatile content of 1% by mass or less, manufactured by Nissin Chemical Co., Ltd.) as an acrylic-modified organopolysiloxane was added to heptane of a thermoplastic polyurethane resin. The dispersion was charged and stirred.

Subsequently, this was transferred to an eggplant-shaped flask, and heptane was removed under reduced pressure using a rotary evaporator while heating to 40 ° C., and the solid content was separated to obtain a particulate resin composition. .
<Blend formulation>
The obtained particulate resin composition was treated and colored in the same manner as in Example 1.

Example 5
Takelac U-2024 (trade name, adipate polyester polyol, number average molecular weight 2000, manufactured by Mitsui Chemicals) 81.74 mass as a high molecular weight polyol in a reaction vessel equipped with a nitrogen introduction tube, a thermometer, a cooling tube and a stirring device. Parts, 0.33 parts by mass of 2-ethylhexyl alcohol (manufactured by Wako Pure Chemical Industries) as monool, and 0.50 parts by mass of Irganox 245 (trade name, manufactured by Ciba Specialty Chemicals) as antioxidant The temperature was raised to 80 to 85 ° C. with good stirring.

Next, 3.97 parts by mass of 1,3-bis (isocyanatomethyl) cyclohexane (trade name: Takenate 600, 1,3-H ₆ XDI, manufactured by Mitsui Chemicals, Inc.) was charged as the isocyanate. The reaction solution was measured with an infrared spectrometer, and reacted at 80 to 85 ° C. until the absorption peak derived from the isocyanate group disappeared.

  After confirming the disappearance of the absorption peak derived from the isocyanate group, 10.31 parts by mass of hexamethylene diisocyanate (Takenate 700, HDI, manufactured by Mitsui Chemicals, Inc.) was charged again as the isocyanate. After continuing the reaction for 2 hours, it was confirmed that the isocyanate group content had dropped to 3.5% by mass, and an isocyanate group-terminated prepolymer was obtained.

  Thereafter, 0.44 parts by mass of the dispersion stabilizer of Production Example 1 and 68.70 parts by mass of heptane, which had been mixed in advance, were charged all at once into the reaction vessel, and the isocyanate group-terminated prepolymer was dispersed over 1 hour. It was.

  Next, 3.65 parts by mass of 1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) was charged as a chain extender.

After completion of the charging, a chain extension reaction was performed at 80 to 85 ° C. for 2 hours to obtain a heptane dispersion of a thermoplastic polyurethane resin. Thereafter, the resulting heptane dispersion of the thermoplastic polyurethane resin was cooled to 30 ° C. or lower.
<Composition of vinyl monomer polymer>
Separately, a liquid mixture consisting of 5.88 parts by mass of styrene and 3.92 parts by mass of methyl methacrylate was prepared, and V-59 (trade name, 2,2′-azobis (2-methyl) was used as a radical polymerization initiator. Butyronitrile) and Wako Pure Chemical Industries, Ltd.) 0.20 parts by mass were added to prepare a monomer mixture.

  The prepared monomer mixture was charged all at once at a reaction temperature of 30 ° C. into a heptane dispersion of a thermoplastic polyurethane resin. Then, reaction was performed at the temperature of 80 degreeC for 12 hours. As a result, a vinyl monomer polymer was synthesized.

Thereafter, the heptane dispersion of the thermoplastic polyurethane resin synthesized with the vinyl monomer polymer was cooled to 30 ° C. or lower.
<Formulation of acrylic modified organopolysiloxane>
After cooling, 2.00 parts by mass of Charine R-170S (trade name, particulate form, average particle diameter of 30 μm, volatile content of 1% by mass or less, manufactured by Nissin Chemical Co., Ltd.) as an acrylic-modified organopolysiloxane was charged and stirred. did.

Subsequently, this was transferred to an eggplant-shaped flask, and heptane was removed under reduced pressure using a rotary evaporator while heating to 40 ° C., and the solid content was separated to obtain a particulate resin composition. .
<Blend formulation>
The obtained particulate resin composition was treated and colored in the same manner as in Example 1.

Example 6
Takelac U-2024 (trade name, adipate-based polyester polyol, number average molecular weight 2000, manufactured by Mitsui Chemicals, Inc.) 57.56 as a high molecular weight polyol in a reaction vessel equipped with a nitrogen introduction tube, a thermometer, a cooling tube and a stirring device. Parts by mass, Takelac U-2710 (trade name, adipate polyester polyol, number average molecular weight 1000, manufactured by Mitsui Chemicals) 16.83 parts by mass, 1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) 0.31 mass Parts, 0.50 parts by mass of Irganox 245 (manufactured by Ciba Specialty Chemicals) as an antioxidant, and 4,4′-methylenebis (cyclohexyl isocyanate) as an isocyanate (trade names: Desmodur W, H ₁₂ MDI, Sumika Bayer (Made by Urethane Co., Ltd.) The temperature was raised to ~85 ℃.

  Next, 0.69 parts by mass of 2-ethylhexyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) was charged as a monool. After the reaction was continued for about 3.5 hours, it was confirmed that the isocyanate group content had dropped to 2.6% by mass, and an isocyanate group-terminated prepolymer was obtained.

  Thereafter, 0.45 parts by mass of the dispersion stabilizer of Production Example 1 and 29.2 parts by mass of heptane, which were mixed in advance, were charged all at once into the reaction vessel, and the isocyanate group-terminated prepolymer was dispersed over 1 hour. It was.

  Subsequently, after further charging 58.4 parts by mass of heptane at a rate of 30 ml / min, the reaction temperature was lowered to 25 ° C. A preliminarily prepared 70 mass% aqueous solution of 3.27 parts by mass of 1,6-hexamethylenediamine was charged all at once into a heptane dispersion of an isocyanate group-terminated prepolymer.

After completion of the charging, the reaction was carried out at 25 to 35 ° C. for 30 minutes, then the temperature was raised to 45 ° C., then the reaction was continued for 30 minutes at the same temperature, and finally the reaction temperature was raised to 80 to 85 ° C. A heptane dispersion of a thermoplastic polyurethane resin was obtained by a time chain extension reaction.
<Composition of vinyl monomer polymer>
Separately, a liquid mixture consisting of 12.00 parts by mass of styrene and 8.00 parts by mass of methyl methacrylate was prepared, and V-59 (trade name, 2,2′-azobis (2-methyl) was used as a radical polymerization initiator. Butyronitrile) and Wako Pure Chemical Industries, Ltd.) 0.28 parts by mass were added to prepare a monomer mixture.

The prepared monomer mixture was charged all at once at a reaction temperature of 30 ° C. into the resulting heptane dispersion of thermoplastic polyurethane resin. Then, reaction was performed at the temperature of 80 degreeC for 12 hours. As a result, a vinyl monomer polymer was synthesized.
<Composition of thermally crosslinkable monomer and polymerization inhibitor>
Thereafter, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (trade name: Kayrad DPHA, manufactured by Nippon Kayaku Co., Ltd.) 6.33 parts by mass with respect to 100 parts by mass of the thermoplastic polyurethane resin. As a polymerization inhibitor, p-methoxyphenol is added to the thermoplastic polyurethane resin so as to be 1 part by mass with respect to 100 parts by mass of the thermoplastic polyurethane resin (0.20 parts by mass with respect to 100 parts by mass of the thermally crosslinkable monomer). Charged to heptane dispersion and mixed for 30 minutes. Thereafter, the heptane dispersion of the thermoplastic polyurethane resin was cooled to 30 ° C. or lower.
<Formulation of acrylic modified organopolysiloxane>
Subsequently, Charine R-170S (trade name, particulate form, average particle diameter of 30 μm, volatile content of 1% by mass or less, manufactured by Nissin Chemical Co., Ltd.) 0.50 parts by mass was charged as the acrylic-modified organopolysiloxane.

This was transferred to an eggplant-shaped flask, heptane was removed under reduced pressure using a rotary evaporator while heating to 40 ° C., and the solid content was separated to obtain a particulate resin composition.
<Blend formulation>
The obtained particulate resin composition was treated and colored in the same manner as in Example 1.

Example 7
PTG2000 (trade name, polytetramethylene ether glycol, number average molecular weight 2000, manufactured by Hodogaya Chemical Co., Ltd.) 43.47 parts by mass as a high molecular weight polyol in a reaction vessel equipped with a nitrogen introduction tube, a thermometer, a cooling tube and a stirring device And 26.74 parts by mass of PTG1000 (trade name, polytetramethylene ether glycol, number average molecular weight 1000, manufactured by Hodogaya Chemical Co., Ltd.), 0.65 parts by mass of ethylene glycol as a low molecular weight polyol, and 2-ethylhexyl as a monool 0.74 parts by mass of alcohol was added and stirred and mixed at 80 ° C. for 1 hour. To this mixed solution, 25.51 parts by mass of 4,4′-methylenebis (cyclohexyl isocyanate) (trade name: Desmodur W, H ₁₂ MDI, manufactured by Sumika Bayer Urethane Co., Ltd.) was added, and the mixture was further stirred at 80 ° C. for 2 hours. Mixed. Then, 0.003 part by mass of stanoct (trade name, tin octylate, manufactured by API Corporation) was further added to this mixed solution, and stirring and mixing were continued at a temperature of 90 ° C. or lower for 2 hours. Then, after confirming that the isocyanate group content had dropped to 3.07% by mass, the system was cooled to obtain an isocyanate group-terminated prepolymer.

  97.12 parts by mass of the resulting isocyanate group-terminated prepolymer was put into a stainless steel beaker, and the temperature was adjusted to 60 ° C. to obtain Latemul PD-104 (trade name, reactive emulsifier, polyoxyethylene alkenyl ether ammonium sulfate, 20 5.00 parts by mass (mass% aqueous solution, manufactured by Kao Corporation) was added, and the mixture was stirred for 10 minutes using a TK homodisper (trade name, high-speed stirrer, manufactured by Tokushu Kika Kogyo). After adding 11.53 parts by mass of deionized water to this mixture, the mixture was stirred and mixed for 30 minutes. Furthermore, 59.55 parts by mass of deionized water was added to obtain an aqueous dispersion of an isocyanate group-terminated prepolymer. And after adding 2.88 mass parts 1, 6-hexamethylenediamine 20 mass% aqueous solution (14.4 mass parts as aqueous solution), it heated up at 50 degreeC and was made to carry out chain extension reaction.

Thereafter, the mixture was aged overnight to obtain an aqueous dispersion (solid content: 50% by mass) of a thermoplastic polyurethane resin.
<Polymerization of vinyl monomer polymer>
Separately, a liquid mixture consisting of 11.94 parts by mass of styrene and 7.96 parts by mass of methyl methacrylate was prepared, and 0.10 parts by mass of α-methylstyrene dimer (0.5 parts per 100 parts by mass of the total amount of monomers) was prepared. 25 parts by mass Aqualon HS-1025 aqueous solution (trade name, reactive emulsifier, polyoxyalkylene alkenyl ether ammonium sulfate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.48 parts by mass, 2% by mass hydrogen carbonate A monomer emulsion was prepared by adding 1.0 part by weight of an aqueous sodium solution and 11.12 parts by weight of deionized water and mixing uniformly.

  Then, in a reaction vessel equipped with a nitrogen introduction tube, a thermometer, a cooling tube, and a stirring device, 200 parts by mass of the aqueous dispersion of the thermoplastic polyurethane resin obtained above (100 parts by mass as a solid content) was charged, The temperature was raised to 80 ° C. After raising the temperature to 80 ° C., 8.0 parts by mass of a 2% by mass aqueous sodium persulfate solution was added and stirred for 10 minutes.

  Then, the monomer emulsion prepared as described above is continuously fed over 3 hours to the aqueous dispersion of the thermoplastic polyurethane resin so that the total monomer amount becomes 20 parts by mass with respect to 100 parts by mass of the thermoplastic polyurethane resin. did.

After the feed was completed, the feed line was washed with 1.6 parts by mass of deionized water and further aged at 80 ° C. for 2 hours. As a result, a vinyl monomer polymer was synthesized. The solid content concentration of the aqueous dispersion of the thermoplastic polyurethane resin containing the vinyl monomer polymer was 50% by mass.
<Composition of thermally crosslinkable monomer and polymerization inhibitor>
Kayrad DPHA (trade name, dipentaerythritol hexaacrylate and dipentalysitol pentaacrylate) with respect to 100 parts by mass of the solid content of the aqueous dispersion of the thermoplastic polyurethane resin (that is, thermoplastic polyurethane resin and vinyl monomer polymer). Mixture, manufactured by Nippon Kayaku Co., Ltd.) 6.00 parts by mass, 0.06 parts by mass of p-methoxyphenol (that is, 1.00 parts by mass with respect to 100 parts by mass of the thermally crosslinkable monomer), Irganox 245 (trade name, Heat-resistant stabilizer, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.00 parts by mass, Sunnol TD-3130 (alkyl ether sulfate ester salt) 0.19 parts by mass, deionized water 5.75 parts by mass, and thermally crosslinkable An aqueous dispersion of monomer and polymerization inhibitor was prepared.

Then, the prepared aqueous dispersion of the thermally crosslinkable monomer and the polymerization inhibitor was blended in an aqueous dispersion of a thermoplastic polyurethane resin (including a vinyl monomer polymer) and stirred for 10 minutes. After stirring, particles were obtained by spray drying with a spray dryer (L-12, manufactured by Okawara Chemical Co., Ltd.) at an atomizer rotational speed of 5000 min ⁻¹ and a hot air temperature of 100 ° C.
<Formulation of acrylic modified organopolysiloxane>
The obtained particles were put into a Henschel mixer, and furthermore, for 100 parts by mass of the thermoplastic polyurethane resin, Charine R-170S (trade name, particulate, average particle size 30 μm, volatile content 1% by mass or less, Nisshin Chemical Co., Ltd. (Product made) After adding 0.5 mass part, the particulate resin composition was obtained by stirring for 1 minute with the rotational speed of 700min- ¹ .
<Blend formulation>
The obtained particulate resin composition was treated and colored in the same manner as in Example 1.

Example 8
<Combination of thermally crosslinkable monomer, polymerization inhibitor and acrylic modified organopolysiloxane>
Kayrad DPHA (trade name: Dipentaerythritol hexaacrylate and dipentalysitol pentaacrylate mixture, Nippon Kayaku Co., Ltd.) 6.00 parts by mass, p-methoxyphenol 0.06 parts by mass (that is, 100 parts by mass of thermally crosslinkable monomer) 1 part by weight), Irganox 245 (trade name, heat stabilizer, manufactured by Ciba Specialty Chemicals) 1.00 part by weight, Sannol TD-3130 (alkyl ether sulfate ester salt) 0.19 part by weight, desorption An aqueous dispersion of a thermally crosslinkable monomer and a polymerization inhibitor was prepared by blending 5.75 parts by mass of ionic water.

Then, 12.94 parts by mass of an aqueous dispersion of the prepared heat-crosslinkable monomer and polymerization inhibitor, and Charine R-170EM (emulsion, viscosity at 20 ° C. of 500 mPa · s or less, particle size 200 nm, solid content concentration 45% by mass) , Manufactured by Nissin Chemical Co., Ltd.) 1.10 parts by mass (0.495 parts by mass in solid content) of an aqueous dispersion of a thermoplastic polyurethane resin prepared in the same manner as in Example 7 <Polymerization of vinyl monomer polymer> It mix | blended with 200 mass parts (100 mass parts as solid content), and stirred for 10 minutes. After stirring, the mixture was spray-dried with a spray dryer (trade name: L-12, manufactured by Okawahara Chemical Co., Ltd.) at an atomizer rotational speed of 5000 min ⁻¹ and a hot air temperature of 100 ° C. to obtain a particulate resin composition.
<Blend formulation>
The obtained particulate resin composition was treated and colored in the same manner as in Example 1.

Comparative Examples 1 and 2
A particulate resin composition was produced and colored in the same manner as in Example 1 except that the composition and blending ratio shown in Table 3 were used.

Comparative Example 3
Instead of 0.50 parts by mass of Charine R-170S (trade name, particulate form, average particle size of 30 μm, volatile content of 1% by mass or less) in <Formulation of acrylic modified organopolysiloxane> in Example 1 As TSF4450 (dimethyl silicone, manufactured by Momentive Performance Materials Japan) 0.50 parts by mass, the same treatment as in Example 1 (with TSF4450 inserted at the same timing as Example 1) Thus, a particulate resin composition was obtained and colored.

Comparative Example 4
In a reaction vessel equipped with a nitrogen introduction tube, a thermometer, a cooling tube, and a stirring device, Takelac U-2024 (trade name, adipate polyester polyol, number average molecular weight 2000, manufactured by Mitsui Chemicals) as a polyol is 75.2 parts by mass. Irganox 245 (manufactured by Ciba Specialty Chemicals) as an antioxidant, 0.05 part by mass, 4,4′-methylenebis (cyclohexyl isocyanate) as an isocyanate (trade name: Desmodur W, H ₁₂ MDI, Sumika Bayer Urethane 21.6 parts by mass) was charged, and the temperature was raised to 80 to 85 ° C. while stirring well.

  Next, 0.49 parts by mass of 2-ethylhexyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) was charged as a monool. After continuing the reaction for about 3.5 hours, it was confirmed that the isocyanate mass% had decreased to 3.6 mass%, and an isocyanate group-terminated prepolymer was obtained.

  Thereafter, 0.45 parts by mass of the dispersion stabilizer of Production Example 1 and 29.2 parts by mass of heptane, which were mixed in advance, were charged all at once into the reaction vessel, and the isocyanate group-terminated prepolymer was dispersed over 1 hour. It was.

  Subsequently, after further charging 58.4 parts by mass of heptane at a rate of 30 ml / min, the reaction temperature was lowered to 25 ° C. In advance, 2.7 parts by mass of a 70% by mass aqueous solution of 1,6-hexamethylenediamine and 0.31 part by mass of 1,4-butanediol (manufactured by Wako Pure Chemical Industries, Ltd.) A chain extender dispersion prepared by dispersing in 06 parts by mass and 3.86 parts by mass of heptane was charged all at once.

After completion of the charging, the reaction is carried out at 25 to 35 ° C. for 30 minutes, and then the temperature is raised to 45 ° C., then the chain extension reaction is continued at the same temperature for 30 minutes, and finally the reaction temperature is raised to 80 to 85 ° C. A chain extension reaction was further performed for 3 hours to obtain a heptane dispersion of a thermoplastic polyurethane resin.
<Composition of vinyl monomer polymer>
12.00 parts by mass of styrene, 8.00 parts by mass of methyl methacrylate, 0.10 parts by mass of α-methylstyrene dimer (0.5 parts by mass with respect to 100 parts by mass of monomer), V-601 as a radical polymerization initiator (Product name, dimethyl 2,2′-azobis (2-methylpropionate), manufactured by Wako Pure Chemical Industries, Ltd.) A monomer mixed solution consisting of 0.80 parts by mass was reacted with a heptane dispersion of a thermoplastic polyurethane resin. The batch was charged at a temperature of 30 ° C. Then, reaction was performed at the temperature of 80 degreeC for 12 hours. As a result, a vinyl monomer polymer was synthesized.
<Composition of thermally crosslinkable monomer and polymerization inhibitor>
Thereafter, 0.5 parts by mass of Tinuvin 213 (benzotriazole-based, manufactured by Ciba Specialty Chemicals) as an ultraviolet absorber, and Tinuvin 765 (hindered amine-based, Ciba Specialty) as a light-resistant stabilizer, relative to 100 parts by mass of the thermoplastic polyurethane resin. Chemicals) 0.5 parts by weight, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as a thermally crosslinkable monomer (trade name: Kayarad DPHA, Nippon Kayaku Co., Ltd.) 6.0 parts by weight, polymerization inhibitor P-methoxyphenol as a dispersion liquid of thermoplastic polyurethane resin so as to be 1 part by mass with respect to 100 parts by mass of thermoplastic polyurethane resin (0.20 parts by mass with respect to 100 parts by mass of thermally crosslinkable monomer). Charged and mixed for 30 minutes. Thereafter, the resulting heptane dispersion of the thermoplastic polyurethane resin was cooled to 30 ° C. or lower.

Thereafter, the heptane dispersion of the thermoplastic polyurethane resin was filtered to collect a solid (cake-like product).
<Combination of mold release material>
Thereafter, in a dryer (Nauter mixer type), 100 parts by mass of the collected solid, TSF-451-3000 (trade name, dimethyl silicone, viscosity 3000 mm ² / s (25 ° C.), Momentive Performance 0.5 parts by mass of Materials Japan Co., Ltd.) and 0.3 part by mass of an anti-blocking agent (trade name: PM030S, composition: polymethyl methacrylate, average particle size 27 μm, acrylic fine particles, manufactured by Ganz Kasei Co., Ltd.) The mixture was dried at 40 ° C. for 3 hours with stirring under reduced pressure.

Then, after cooling the content to 25 degrees C or less, the particulate resin composition was obtained by taking out particles from a dryer.
<Blend formulation>
The obtained particulate resin composition was treated and colored in the same manner as in Example 1.

Comparative Example 5
Instead of 0.50 parts by mass of Charine R-170S (trade name, particulate form, average particle size of 30 μm, volatile content of 1% by mass or less) in <Formulation of acrylic modified organopolysiloxane> in Example 1 As in Example 1 except that 0.50 parts by mass of PM030S was used (PM030S was charged at the same timing as Example 1) to obtain a particulate resin composition. Colored.

(Evaluation)
The powder properties (angle of repose) of the particulate resin compositions (hereinafter abbreviated as “powder”) obtained in the respective Examples and Comparative Examples were measured by the following method.

  Further, slush molding described below was performed to evaluate the releasability during molding, scratch resistance of the molded product, and bleed of the molded product.

The results are shown in Tables 1 to 3.
<Powder fluidity (rest angle)>
The angle of repose (degree) of the powder was measured by an injection method based on JIS R-9301-2.
<Slush molding>
After heating the mold with wrinkles to 240 ° C., 300 g of each powder was sprinkled on the mold placed horizontally and allowed to stand for 8 seconds, then the mold was placed vertically and excess powder that did not melt I have paid off. Next, the mold was allowed to stand at 250 ° C. for 60 seconds and then cooled with water to form a sheet having a thickness of about 1 mm.

  In addition, the volume average particle diameter of each powder was about 120-150 micrometers. The volume average particle diameter of each powder was determined by measuring the volume average particle diameter of the powder using a particle size analyzer (model: MICROTRAC HRA, manufactured by Nikkiso Co., Ltd.). The volume average particle size was a value of 50% cumulative percentage in the particle size distribution curve of the volume fraction.

<Releasability>
After water cooling in slush molding, before the sheet was released from the mold (released), a 1-inch wide cut was made in the sheet, and the resistance at the time of releasing was measured with a push-pull gauge.

<Color transfer>
The color transfer of the obtained sheet was evaluated according to JIS L0849.

  That is, a 25 × 170 mm test piece was sampled from the sheet and set on a friction tester (trade name, Gakuden-shaped dyeing friction fastness tester, manufactured by Yasuda Seiki Seisakusho Co., Ltd.) with the embossed surface facing up. A white cotton cloth of about 50 × 50 mm was placed on the friction element and fixed, and a reciprocating friction was performed 100 times at a speed of 30 times / minute between two points of 100 mm with a load of 5N.

  After the test, the degree of contamination of the white cotton cloth was observed from a maximum of 5 points to evaluate the color transfer. The evaluation criteria for the degree of contamination (color transfer) are shown below.

5 points No change 3 points Slightly colored 1 point Clearly colored In addition, after the above friction test, the appearance change of the sheet was visually observed to evaluate the scratch resistance. The evaluation criteria for scratch resistance are shown below.

○ No change △ Slightly fading or no scratch × Scratch occurrence <bleed>
After the obtained sheet was allowed to stand at 10 ° C., the degree of contamination on the textured surface side of the sheet was visually observed to evaluate bleeding. The evaluation criteria for bleed are shown below.

○ No change × Bleed

  In Tables 1 to 3, composition abbreviations are shown below.

Takenate 700: isocyanate (composition: hexamethylene diisocyanate, HDI, manufactured by Mitsui Chemicals)
Takenate 600: Isocyanate (composition: 1,3-bis (isocyanatomethyl) cyclohexane, 1,3-H ₆ XDI, manufactured by Mitsui Chemicals, Inc.)
1,4-H ₆ XDI: 1,4-bis (isocyanatomethyl) cyclohexane (trans / cis ratio = 93/7)
Death module W: isocyanate (composition: 4,4′-methylenebis (cyclohexyl isocyanate), H ₁₂ MDI, manufactured by Sumika Bayer Urethane Co., Ltd.)
Takelac U-2024: Polyester polyol (Composition: 1,4-butanediol / 1,6-hexanediol / adipic acid, number average molecular weight 2000, manufactured by Mitsui Chemicals, Inc.)
Takelac U-2710: Polyester polyol (composition: ethylene glycol / 1,4-butanediol / adipic acid, number average molecular weight 1000, manufactured by Mitsui Chemicals, Inc.)
PTG2000: polytetramethylene ether glycol (number average molecular weight 2000, manufactured by Hodogaya Chemical Co., Ltd.)
PTG1000: polytetramethylene ether glycol (number average molecular weight 1000, manufactured by Hodogaya Chemical Co., Ltd.)
Irganox 245: Antioxidant / heat stabilizer (triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals)
Latemul PD-104: Reactive emulsifier (polyoxyethylene alkenyl ether ammonium sulfate, 20% by mass aqueous solution, manufactured by Kao Corporation)
MMA: methyl methacrylate MSD: α-methylstyrene dimer V-59: radical polymerization initiator (2,2′-azobis (2-methylbutyronitrile), manufactured by Wako Pure Chemical Industries, Ltd.)
V-601: radical polymerization initiator (dimethyl 2,2′-azobis (2-methylpropionate), manufactured by Wako Pure Chemical Industries, Ltd.)
Aqualon HS-1025 (trade name, reactive emulsifier, polyoxyalkylene alkenyl ether ammonium sulfate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
DPHA: Kayalad DPHA (trade name, mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.)
SANNOL TD-3130: emulsifier (alkyl ether sulfate ester, manufactured by Lion Corporation)
MQ: p-methoxyphenol Charine R-170S: acrylic modified organopolysiloxane (average particle size 30 μm, volatile content 1% by mass or less, heptane soluble content 17% or less, manufactured by Nisshin Chemical Co., Ltd.)
Charine R-170EM: Acrylic-modified organopolysiloxane (emulsion, viscosity at 20 ° C. of 500 mPa · s or less, particle size 200 nm, solid content concentration 45 mass%, heptane soluble content 16% or less in solid content, manufactured by Nissin Chemical)
TSF4450: mold release agent (dimethylsilicone, manufactured by Momentive Performance Materials Japan)
TSF-451-3000: mold release agent (dimethylsilicone, viscosity 3000 mm ² / s (25 ° C.), manufactured by Momentive Performance Materials Japan)
PM030S: acrylic fine particles (composition: polymethyl methacrylate, average particle size 27 μm, manufactured by Ganz Kasei Co., Ltd.)
PV-817: Pigment (trade name, carbon black / calcium carbonate dispersion, manufactured by Sumika Color Co., Ltd. PV-801: Pigment (trade name, carbon black / calcium carbonate dispersion, manufactured by Sumika Color Co., Ltd.)

Claims (4)

A powdery resin composition containing a thermoplastic polyurethane resin and an acrylic modified organopolysiloxane in a proportion of 0.1 to 10 parts by mass of the acrylic modified organopolysiloxane with respect to 100 parts by mass of the thermoplastic polyurethane resin . And
The acrylic-modified organopolysiloxane is obtained by copolymerizing an organopolysiloxane having a radical polymerizable group at a terminal and a (meth) acrylic acid ester,
The acrylic modified organopolysiloxane is prepared as particles having an average particle size of 3 to 200 μm, or the powdery resin composition is prepared by adding an emulsion of acrylic modified organopolysiloxane having an average particle size of 10 to 1000 nm to the heat After blending into the aqueous dispersion of the plastic polyurethane resin, they are mixed and dispersed, and then the aqueous dispersion medium is removed from the aqueous dispersion of the thermoplastic polyurethane resin and the emulsion to separate the solid component. Prepared by drying ,
A powdery resin composition, wherein the powdery resin composition is used for slush molding.   The powdery resin composition according to claim 1, wherein the acrylic-modified organopolysiloxane is in the form of particles. A molded product obtained by slush molding the powdery resin composition according to claim 1 or 2 . The molded product according to claim 3 , wherein the molded product is an automobile interior product.