WO2005049731A1

WO2005049731A1 - Thermoplastic polyurethane resin composition for powder shaping and method for producing same

Info

Publication number: WO2005049731A1
Application number: PCT/JP2004/017056
Authority: WO
Inventors: Koichi Yanai; Akihisa Tanaka; Dai Kawanobe
Original assignee: Zeon Corporation
Priority date: 2003-11-20
Filing date: 2004-11-17
Publication date: 2005-06-02

Abstract

Disclosed is a method for producing a thermoplastic polyurethane resin composition for powder shaping which is characterized in that a powder thermoplastic polyurethane (A) and a powder coloring agent (B) containing a powder pigment (b1) and a pigment dispersing agent (b2) are mixed together firstly, and then the resulting is further mixed with a plasticizer (C). Also disclosed is a thermoplastic polyurethane resin composition for powder shaping which mainly contains the product obtained by such a method. With this method, there can be produced a thermoplastic polyurethane resin composition for powder shaping which is excellent in uniform coloring property, mold-releasing property, melting property, and handling of the polyurethane resin powder.

Description

Specification

TECHNICAL FIELD The present invention relates to a thermoplastic polyurethane resin composition for powder molding and a method for producing the same.

[0001] The present invention relates to a resin composition for powder molding, and more particularly, to a thermoplastic polyurethane resin composition for powder molding which gives a molded article having excellent mold release properties without impairing powder fluidity. It relates to the manufacturing method.

Background art

[0002] The powder molding method has recently been used because of its advantages that a product having a complicated shape (undercut, deep drawing, etc.) can be easily molded, the thickness can be made uniform, and the material yield rate is good. It is widely used for applications such as interior materials for automobiles, and is mainly used for soft polychlorinated vinyl resin (hereinafter referred to as PVC) powder. For example, powdered molded products of soft vinyl chloride resin have been mostly used as skin materials for interior parts such as instrument panels, console boxes, door trims and glove boxes of automobiles.

[0003] However, the soft Shii-Dani Buru resin molded product suffers from the disadvantage that the plasticizer contained in the material migrates to the surface due to the effects of heat, light, etc. due to long-term use, and the soft feeling is impaired. Will happen. Furthermore, when the soft vinyl chloride resin molded article is incinerated, there is a problem that the incinerator is corroded by the hydrogen chloride gas generated at that time. Therefore, in order to solve these problems, development of a powder molding material mainly composed of a thermoplastic polyurethane resin as an alternative to the Shiridani bull-based material has been promoted.

[0004] However, thermoplastic polyurethane resins for powder molding have insufficient powder flowability, so that it is difficult to ensure uniform coloring properties, high mold release properties, and uniform wall thickness. There was a problem that there is. Attempts have been made in the past to solve these problems. For example, in Patent Documents 14 to be described later, attempts have been made to obtain uniform coloring properties.

[0005] As an attempt to obtain uniform coloring properties, for example, a method of mixing a paste-like colorant using a plasticizer as a dispersant with powdered polyurethane (see Patent Document 1), powdered polyurethane, pigment, A method in which a plasticizer is added and mixed at once (Patent Document 2, Patent Document 3, Patent Document 4 Reference) has been proposed. However, the methods described in these documents still have problems such as the occurrence of color unevenness and the incorporation of pigment agglomerated particles, and solutions are required.

[0006] Furthermore, when a molded article is manufactured using the thermoplastic polyurethane resin for powder molding, good mold release properties, low mold contamination, low meltability, and the like. (Smoothness of the skin obtained by molding) is also required. To improve the releasability, for example, a method of imparting releasability with a fatty acid metal salt (see Patent Document 5), a fluorine-based release agent, a silicone-based release agent (amino-modified dimethylpolysiloxane, carboxy A method of imparting releasability with a modified dimethylpolysiloxane, dimethylpolysiloxane), a fatty acid ester-based release agent, and an ester phosphate-based release agent (see Patent Document 2 described above) has been proposed.

[0007] However, in the invention described in Patent Document 5, if the metal salt migrates to the mold during slush molding and the mold releasability deteriorates, the problem and the mold contamination deteriorate.ヽぅ Problems remain. The invention described in Patent Document 2 has a problem that adhesion to foamed polyurethane is poor.

[0008] In addition, in order to improve the melting property of thermoplastic polyurethane resin for powder molding, a resin powder which does not soften at 160 ° C or less and has an average particle diameter of 10 m or less is added to improve powder fluidity. (See Patent Document 3 described above) and a method of improving the meltability by mixing fine powdered silica having an average particle diameter of 10 m or less, which has been surface-treated with a coupling agent (see Patent Document 6). Has also been proposed.

[0009] However, in the method described in Patent Document 3, although the powder fluidity is improved, the adhesiveness to the foamed polyurethane (the skin formed by molding the thermoplastic polyurethane resin composition for powder molding and the foaming (Adhesion with polyurethane). In addition, the method described in Patent Document 6 has a problem that the molding temperature during slush molding must be increased. Patent Document 1: JP-A-11 172097

Patent Document 2: JP-A-10-338733

Patent Document 3: JP-A-2000-17033

Patent Document 4: JP 2002-348462 A Patent Document 5: Japanese Patent Application Laid-Open No. 2001-19863

Patent Document 6: Japanese Patent Application Laid-Open No. 2001-11301

Disclosure of the invention

Problems to be solved by the invention

[0010] The present invention has been made in view of such a situation, and an object of the present invention is to provide a fluid having a uniform coloring property and necessary for ensuring excellent demoldability and meltability. An object of the present invention is to provide a thermoplastic polyurethane resin composition for powder molding excellent in mobility and a method for producing the same. Further, the present invention relates to a thermoplastic polyurethane resin composition for powder molding having excellent adhesion to foamed polyurethane, a low metal contamination property, a thermoplastic polyurethane resin composition for powder molding, And a method for producing the same.

Means for solving the problem

[0011] In order to achieve the above object, a method for producing a thermoplastic polyurethane resin composition for powder molding according to the present invention comprises:

Powdery thermoplastic polyurethane (A),

A powder pigment (bl) and a powder colorant (B) containing a pigment dispersant (b2) are mixed with each other, and

It is characterized by adding a plasticizer (C) and subsequently mixing.

[0012] In the production method of the present invention, the step of mixing the powdered thermoplastic polyurethane (A) and the powdered colorant (B) and then adding the plasticizer (C) is employed, whereby the uniformity is obtained. It is possible to obtain a thermoplastic polyurethane resin composition for powder molding having a fluid dynamic property necessary for ensuring excellent coloring properties, excellent demoldability and meltability.

[0013] In the production method of the present invention, preferably,

Said powdery thermoplastic polyurethane (A),

Mixing the powder pigment (bl) and the powder colorant (B) containing the pigment dispersant (b2), and then adding

Said plasticizer (C),

And a silicone oil (D), followed by mixing.

[0014] By containing the silicone oil (D) together with the plasticizer (C), powder composition is obtained. The mold releasability at the time of shaping can be improved.

[0015] In the production method of the present invention, preferably,

Said powdery thermoplastic polyurethane (A),

Said plasticizer (C),

It is characterized in that the hydroxyl-modified silicone oil (D1) and the Z- or (meth) atari-xy-modified silicone oil (D2) are added and then mixed.

[0016] By further reducing the hydroxyl group-modified silicone oil (D1) and the Z- or (meth) atoxy-modified xy group-modified silicone oil (D2), it is possible to improve the adhesion to the foamed polyurethane, and Mold contamination can be reduced. In the present invention, the “(meth) ataryloxy group” means a methacryloxy group and Z or an atarioxy group.

In the production method of the present invention, preferably,

Said powdery thermoplastic polyurethane (A),

After mixing the powder pigment (bl) and the powder colorant (B) containing the pigment dispersant (b2),

The above-mentioned plasticizer (C) is added and further mixed. Thereafter, to the obtained mixture, a hydroxyl group-containing aromatic vinyl copolymer (E) having an average particle diameter of 0.1 to 10 m is added, and then mixed. It is characterized by doing.

[0018] By further containing the hydroxyl group-containing aromatic vinyl copolymer (E) having the average particle diameter in the above-mentioned predetermined range, it becomes possible to improve the adhesiveness to the foamed polyurethane.

In the production method of the present invention,

Along with the plasticizer (C), a silicone oil (D) is added and further mixed, and then the resulting mixture is

It is preferable to add the hydroxyl group-containing aromatic vinyl copolymer (E) and continue mixing.

[0020] In the production method of the present invention, Along with the plasticizer (C), a hydroxyl-modified silicone oil (D1) and a Z- or (meth) acryloxy-group-modified silicone oil (D2) are added and further mixed.

[0021] In the production method of the present invention, the powdery thermoplastic polyurethane (A) has a number average molecular weight force S of 10,000 to 50,000.

[0022] Further, the powdery thermoplastic polyurethane (A) includes an organic polyisocyanate (A1), a polymer polyol (A2), and if necessary, a chain extender (A3) and Z or a terminator (A4). It is preferable that it is composed of

[0023] The organic polyisocyanate (A1) is preferably an aliphatic polyisocyanate and Z or an alicyclic polyisocyanate, more preferably hexamethylene diisocyanate, At least one selected from the group consisting of hydrogenated products of isophorone diisocyanate and 4,4'-diphenylmethane diisocyanate.

[0024] The polymer polyol (A2) is preferably a polyester polyol (A21), more preferably a condensate of an aliphatic diol and a dicarboxylic acid conjugate.

[0025] In the production method of the present invention, the plasticizer (C) is preferably a phthalic acid ester and Z or an aliphatic dibasic acid ester, particularly an aliphatic dibasic acid ester. It is preferred that there be.

[0026] The thermoplastic polyurethane resin composition for powder molding of the present invention comprises:

Powdery thermoplastic polyurethane (A),

The main component is a mixture obtained by adding a plasticizer (C) and subsequently mixing.

[0027] As the thermoplastic polyurethane resin composition for powder molding of the present invention, a powdery thermoplastic polyurethane (A) and a powdery colorant (B) are preliminarily mixed, and then a plasticizer (C) is added. Since the main component is produced by mixing, it has a uniform coloring property and can have a fluid dynamic property necessary to ensure excellent demoldability and meltability. [0028] In the thermoplastic polyurethane resin composition for powder molding of the present invention, preferably, the powdery thermoplastic polyurethane (A)

Said plasticizer (C),

Silicone oil (D) is added, followed by mixing, as a main component.

Alternatively, the thermoplastic polyurethane resin composition for powder molding of the present invention comprises:

Powdery thermoplastic polyurethane (A),

A powder colorant (B) containing a powder pigment (bl) and a pigment dispersant (b2);

A plasticizer (C),

A hydroxyl-modified silicone oil (D1) and a Z- or (meth) atari-xy-modified silicone oil (D2).

[0030] The thermoplastic polyurethane resin composition for powder molding containing the hydroxyl-modified silicone oil (D1) and the Z- or (meth) atari-hydroxyl-modified silicone oil (D2) is preferably

Said powdery thermoplastic polyurethane (A),

Said plasticizer (C),

The main component is a mixture obtained by continuously mixing the hydroxyl-modified silicone oil (D1) and Z or (meth) atari-xy-modified silicone oil (D2).

[0031] In addition to the powdery thermoplastic polyurethane (A), the powder colorant (B) and the plasticizer (C), a hydroxyl-modified silicone oil (D1) and a Z- or (meth) atari-hydroxy-modified silicone oil By containing (D2), the adhesion to the foamed polyurethane can be improved and the mold contamination can be reduced.

[0032] Alternatively, the thermoplastic polyurethane resin composition for powder molding of the present invention comprises:

Powdery thermoplastic polyurethane (A), A powder colorant (B) containing a powder pigment (bl) and a pigment dispersant (b2);

A plasticizer (C),

And a hydroxyl group-containing aromatic vinyl copolymer (E) having an average particle size of 0.1-.

In the thermoplastic polyurethane resin composition for powder molding containing the hydroxyl group-containing aromatic vinyl copolymer (E), preferably,

Said powdery thermoplastic polyurethane (A),

The plasticizer (C) is added and mixed continuously, and then the mixture obtained by adding the hydroxyl group-containing aromatic vinyl copolymer (E) to the obtained mixture is mixed as a main component.

[0034] In addition to the powdery thermoplastic polyurethane (A), the powder colorant (B) and the plasticizer (C), a hydroxyl group-containing aromatic vinyl copolymer (E) having an average particle diameter in the above-mentioned predetermined range is further added. By containing it, the adhesiveness to the foamed polyurethane can be improved.

In the thermoplastic polyurethane resin composition for powder molding of the present invention, the silicone oil (D) is used together with the hydroxyl group-containing aromatic vinyl copolymer (E) having an average particle diameter of 0.1 to 10 m. ) Is preferable. The silicone oil (D) is particularly preferably a hydroxyl-modified silicone oil (D1) and a Z- or (meth) atari-oxyl-modified silicone oil (D2)! /.

[0036] In the thermoplastic polyurethane resin composition for powder molding of the present invention, the powdery thermoplastic polyurethane (A) and the plasticizer (C) are the same as those in the production method of the present invention. Prefer to use,.

The invention's effect

According to the present invention, in a thermoplastic polyurethane resin composition for powder molding, a powdery colorant containing a powdery thermoplastic polyurethane (A), a powdery pigment (bl) and a pigment dispersant (b2) ( After mixing with (B), a plasticizer (C) is further added, and the mixture is further mixed, thereby producing the following effects. That is, the instrument panel, headrest, console box Powder molding of skin materials of interior parts of automobiles such as doors, door trims, armrests, etc. is easy, and it has excellent removability during molding and has no color unevenness! ヽ Provides powder molded products with excellent appearance properties A thermoplastic polyurethane resin composition for powder molding is provided.

[0038] Further, according to the present invention, the mold release property during powder molding is improved by further adding a silicone oil (D) to the thermoplastic polyurethane composition for powder molding. Can be done.

Further, according to the present invention, in the thermoplastic polyurethane resin composition for powder molding, as the silicone oil (D), a hydroxyl-modified silicone oil (D1) and Z or (meth) By containing the modified silicone oil (D2), in addition to mold releasability, mold contamination and adhesion to foamed polyurethane can be improved, and a uniform wall thickness can be secured.

Further, according to the present invention, the thermoplastic polyurethane resin composition for powder molding further comprises a hydroxyl group-containing aromatic vinyl copolymer (E) having an average particle diameter of 0.1-. Thereby, the adhesiveness with the foamed polyurethane can be improved.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described based on embodiments.

i implementation

The thermoplastic polyurethane resin composition for powder molding according to the present embodiment (first embodiment) is a powder-colored thermoplastic polyurethane (A), which comprises a powder pigment (bl) and a pigment dispersant (b2). Agent (B) is mixed, and then the resulting mixture is mixed with a plasticizer (C), followed by mixing.

[0042] Powdered thermosetting polyurethane (A)

The powdery thermoplastic polyurethane (A) is composed of an organic polyisocyanate (A1), a polymer polyol (A2), and a chain extender (A3) and Z or a terminator (A4), which are added as necessary. What is configured can be used.

[Organic polyisocyanate (Al)]

Examples of the organic polyisocyanate (A1) include an aliphatic polyisocyanate having 2 to 12 carbon atoms (excluding the carbon in the NCO group; the same applies hereinafter), an alicyclic polyisocyanate having 4 to 15 carbon atoms, Charcoal Examples thereof include an aromatic aliphatic polyisocyanate having a prime number of 8 to 15, an aromatic polyisocyanate having a carbon number of from 6 to 15, and modified products thereof. These can be used in combination of two or more thereof (when the same polyisocyanate is used in combination, for example, when two or more aliphatic polyisocyanates are used in combination). Examples of the above modified products include those containing a carbodiimide group, a pentadione group, a uretoimine group, a urethane group, an urea group, a biuret group, an isocyanurate group, and the like.

As the aliphatic polyisocyanate having 2 to 12 carbon atoms, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2, Examples include 2,4-trimethylhexane-1,6-diisocyanate, lysine diisocyanate, and 2,6-diisocyanatoethyl caproate.

[0045] Examples of the alicyclic polyisocyanate having 415 carbon atoms include isophorone diisocyanate (IPDI), 4,4, dicyclohexynolemethanediisocyanate (hydrogenated MDI), and cyclohexane. Xylene diisocyanate, methylcyclohexylene diisocyanate and the like can be mentioned.

[0046] Examples of the araliphatic polyisocyanate having 8 to 15 carbon atoms include m- and p-xylylene diisocyanate (XDI), a, a, α ', α, -tetramethyl xylylene diisocyanate (ΤΜΧDI ).

[0047] As the aromatic polyisocyanate having 6 to 15 carbon atoms, 2,4- or 2,6-tolylene diisocyanate (TDI), getylbenzene diisocyanate, 2,4 or 4,4 Examples include diphenylmethane diisocyanate (MDI) and naphthylene diisocyanate.

[0048] Among the organic polyisocyanates (A1), aliphatic polyisocyanates and alicyclic polyisocyanates are preferred from the viewpoint of light resistance of the molded product, and in particular, hexamethylene diisocyanate (HHDI). , Isophorone diisocyanate (IPDI) and 4,4, dicyclohexylmethane diisocyanate (hydrogenated MDI) are preferred.

[Polymer polyol (Α2)]

Examples of the polymer polyol (# 2) include a polyester polyol (A21), a polyether polyol (# 22), and a mixture of two or more thereof. The hydroxyl equivalent (number average molecular weight per hydroxyl group based on hydroxyl value measurement; the same applies hereinafter) of the polymer polyol (ポリオール 2) is usually from 250 to 5 from the viewpoint of obtaining a soft feeling and a desired strength of the molded article. , 000, good It is preferably 350-2,500, more preferably 400-1,500. The number of functional groups is usually 214, preferably 2-3, and particularly preferably 2.

The polyester polyol (A21) includes: (1) a low molecular polyol and Z or a product obtained by condensation polymerization of a polyether polyol with a dicarboxylic acid conjugate; (2) a low molecular polyol and Z or a polyether Polyols obtained by ring-opening a rataton monomer and modified dicarboxylic acids; and (3) low-molecular-weight polyols and those obtained by condensation polymerization of Z or polyether polyols with carbonic acid diesters.

These can be used in combination of two or more.

[0051] The low-molecular polyol used in the above (1)-(3) includes a di- or tri- or higher polyol having a hydroxyl equivalent of less than 250. Examples of the dihydric alcohol include aliphatic diols having 2 to 12 carbon atoms and diols having a cyclic group having 6 to 25 carbon atoms. Examples of the trihydric alcohol include glycerin, trimethylolpropane, and the like. Alkylene oxide adduct (hydroxyl equivalent less than 250). These can be used in combination of two or more.

[0052] Specifically, the aliphatic diols having 2 to 12 carbon atoms include ethylene glycol, diethylene glycol, 1,3 propanediol, 1,4 butanediol, 1,5 pentanediol, and 1,6- Linear diols such as xandiol; 1,2-propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-getyl-1,3 propanediol, 1,2-, 1,3 and Examples thereof include diols having a branched chain such as 2,3 butanediol and 1,2 decanediol.

Examples of the diols having a cyclic group having 6 to 25 carbon atoms include those described in Japanese Patent Publication No. 45-1474: alicyclic group-containing diols [1,4 bis (hydroxymethyl) cyclohexane, hydrogenated Bisphenol A, etc.), aromatic ring-containing diols [m and p-xylylene glycol, divalent phenols [monocyclic divalent phenols (hydroquinone, resorcinol, etc.), bisphenols (bisphenol A, bisphenol S, bisphenol F ), Dihydroxynaphthalene, etc.) (hydroxyl equivalent less than 250), bishydroxyalkyl (2-4 carbon atoms) ester of aromatic dicarboxylic acid [bis (2-hydroxyethyl) terephthalate, etc.) ]. As the polyether polyol used in the above (1)-(3), the same ones as the polyester polyol (A22) described later can be used, and preferably those having a hydroxyl equivalent of 500 or less are used.

[0055] Of the above low molecular polyols and Z or polyether polyols, it is preferable to use low molecular polyols, and particularly preferable are low molecular aliphatic diols and low molecular aromatic diol-containing diols.

[0056] In the present invention, the alkylene oxide includes an alkylene oxide having 2 to 10 or more carbon atoms, and a phenyl or halo-substituted product thereof.

Specific examples of the alkylene oxide include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-butylene oxide, 1,3-butylene oxide, 1,4-butylene oxide and 2,4-butylene oxide. , 3-butylene oxide, styrene oxide, hypoolefin having 5 to 10 or more carbon atoms, epino, rohydrin (epichlorohydrin and the like) and the like. These can be used in combination of two or more of them by block and Z or caro with random. Preferred are combinations of EO, PO and these blocks and Z or cascade.

[0057] Specific examples of the dicarboxylic acid conjugate used in the polycondensation of the above (1) include succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, and the like. Aliphatic dicarboxylic acids having 4 to 15 carbon atoms; aromatic dicarboxylic acids having 8 to 15 carbon atoms, such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; ester-forming derivatives thereof, ie, anhydrides and lower alkyls (C1-C4) esters, acid halides (such as acid chloride) and the like. These can be used in combination of two or more.

[0058] Examples of the rataton monomer used in the ring-opened kamut of the above (2) include ratatones having 412 carbon atoms, for example, γ-petit mouth ratatone, ε-force prolatatone, γ-valerolatone, and the like. . These can be used in combination of two or more.

[0059] Examples of the carbonic acid diester used in the polycondensation of the above (3) include dimethyl carbonate and ethylene carbonate.

[0060] Specific examples of the polyester polyol (A21) include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, and polybutyrate. Lenisophthalate diol, polyhexamethylene isophthalate diol, polyneopenthylene adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (diethylene glycol) isophthalate Rate diol, polyproprotatonone diol, adipic acid-modified polyproprotatone diol, terephthalic acid-modified polyproprotatonone diol, isophthalic acid-modified polyproprotatone diol, polyhexamethylene carbonate diol, and the like. These can be used in combination of two or more.

[0061] Examples of the polyether polyol (A22) include compounds having a structure in which the above-mentioned alkylene oxide is added to a low-molecular-weight polyol (for example, those exemplified as the raw materials for the above-mentioned polyester polyol (A21)).

[0062] Specific examples of the polyether polyol (A22) include polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene (block and Z or random) glycol, polytetramethylene ether glycol, polyoxybutylene polyoxyethylene. (Block and Z or random) glycols, polyoxybutylene polyoxypropylene (block and Z or random) glycols, EO and Z or PO adducts of bisphenol A, and the like. These can be used in combination of two or more.

[0063] Among the polymer polyols (A2), preferred are polyester polyols (A21).

Particularly preferred is a condensate of an aliphatic diol and a dicarboxylic acid conjugate, particularly a condensed polyester diol with an aromatic dicarboxylic acid.

[Chain extender (A3)]

Examples of the chain extender (A3) used if necessary include a low molecular weight polyol (A31) and a polyamine (A32).

The number of functional groups of the chain extender (A3) is 2-3, especially 2, and the hydroxyl (amino) equivalent is less than 250, especially 200 or less.

As the low molecular polyol (A31), the low molecular polyol exemplified as a raw material of the polyester polyol (A21) and a glycol ester of a monohydroxymonocarboxylic acid (such as hydroxyacetic acid and lactic acid) (for example, JP-A No. 61-190717) Publications) I can get lost.

Examples of the polyamine (A32) include aliphatic polyamines having 2 to 12 carbon atoms, alicyclic polyamines having 6 to 15 carbon atoms, araliphatic polyamines having 8 to 15 carbon atoms, aromatic polyamines, and ketimines thereof. And mixtures of two or more of these. The above-mentioned ketimine is one in which a part or all of the amino group is blocked (ketimine) with a ketone (3 to 10 carbon atoms, for example, acetone, methylethylketone, methylisobutylketone).

[0067] Examples of the aliphatic polyamine having 2 to 12 carbon atoms include ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, N-hydroxyethylethylenediamine, and diethylenetriamine. No.

Examples of the alicyclic polyamine having 6 to 15 carbon atoms include 4,4, diaminocyclohexylmethane, 1,4-diaminocyclohexane, 1,3-diaminomethylcyclohexane, and isophorone diamine.

Examples of the araliphatic polyamine having 8 to 15 carbon atoms include m- and p-xylylenediamine.

Examples of the aromatic polyamine include 4,4, diaminodiphenylmethane, tolylenediamine, ethyl tolylenediamine, and phenylenediamine.

These can be used in combination of two or more.

[0068] Among the above polyamines (A32), preferred are aliphatic polyamines, alicyclic polyamines, and ketimines thereof from the viewpoint of light resistance of the molded article. The amount of the chain extender (A3) in the powdery thermoplastic polyurethane (A) is usually from 0 to 30%, preferably from 0.5 to 20%, based on the weight of the polymer polyol (A2). It is.

[Stopper (A4)]

The terminator (A4) includes a monohydric alcohol (A41) and a monoamine (A42).

[0070] Examples of the monohydric alcohol (A41) include aliphatic monohydric alcohols having 1 to 20 carbon atoms, alicyclic monohydric alcohols having 6 to 10 carbon atoms, and aromatic ring-containing monohydric alcohols having 7 to 20 carbon atoms. No.

Specific examples of the monohydric alcohol (A41) include aliphatic monohydric alcohols having 120 carbon atoms (methanol, ethanol, propanol, butanol, octanol, ethinoreserosonolev, Alicyclic monohydric alcohols having 6 to 10 carbon atoms (such as cyclohexanol), and monohydric alcohols having 7 to 20 carbon atoms containing aromatic rings (benzyl alcohol, hydroxyethyl benzene, monohydric alcohols) Examples thereof include (poly) oxyalkylene (ether having 2 to 4 carbon atoms of an alkylene group and a degree of polymerization of 115) ethers of phenols (phenol, tarezol, etc.) and a mixture of two or more of these.

[0071] Specific examples of the monoamine (A42) include mono- or dialkylamines having an alkyl group of 1 to 10 carbon atoms (eg, methylamine, ethylamine, getylamine, n-butylamine, di-n-butylamine), and 6 to 10 carbon atoms. Alicyclic monoamines (such as cyclohexylamine), C6 to C15 aromatic ring-containing monoamines (such as benzylamine and a-phosphorus), C4-10 heterocyclic monoamines (such as morpholine), and carbon atoms of hydroxyalkyl groups Examples include mono- and dialkanolamines represented by Formulas 2 to 4 (monoethanolamine, diethanolamine, diisopropanolamine, and the like), and mixtures of two or more of these.

[0072] The number average molecular weight of the powdery thermoplastic polyurethane (A) is usually from 5,000 to 100,000, preferably from 10,000 to 50,000. The terminal of the powdery thermoplastic polyurethane (A) may be an active hydrogen-containing group (hydroxyl group, amino group, etc.) or may be terminated by a terminator (A4).

[0073] The primary average particle diameter of the powdery thermoplastic polyurethane (A) is usually 50 µm to 500 µm, preferably 100 µm to 300 µm, more preferably 120 µm to 200 µm. It is. If the particle diameter is larger than 500 m, pinholes are likely to occur in the powder-formed skin. On the other hand, when the particle diameter is smaller than 50 m, the powder fluidity becomes poor, the thickness of the skin becomes uneven, and the powder is liable to agglomerate during storage.

[0074] The powdery thermoplastic polyurethane (A) is obtained by subjecting an organic polyisocyanate (A1), a polymer polyol (A2) and, if necessary, a chain extender (A3) to water or non-aqueous emulsion polymerization. By reacting, it is possible to obtain a spherical particle having a target particle diameter and a true spherical shape. Alternatively, a material having a large particle size obtained by suspension polymerization is pulverized using a known pulverizer such as a turbo mill, a hammer mill, or a pulverizer to obtain a product having an intended particle size and an irregular shape. Can be obtained. In the present invention, both the former and the latter can be used.

[0075] Powder colorant (B) The powder colorant (B) contains a powder pigment (b1) and a pigment dispersant (b2).

The powder pigment (bl) alone has insufficient dispersion, and has problems such as poor workability when mixed with thermoplastic polyurethane particles having high scattering properties. Therefore, they are mixed and dispersed in a resin such as low-molecular polyethylene or petroleum resin and pulverized into fine particles, mixed with an inorganic dispersant such as silica or calcium carbonate, or dispersed in a powder pigment (bl. A so-called powder colorant (B), whose surface is treated with a silane coupling agent or the like, is usually used. A series of substances having a pigment dispersing effect, such as the above-mentioned resins such as low molecular polyethylene and petroleum resin; inorganic dispersants such as silica and calcium carbonate; silane coupling agents; b2).

[0076] The ratio of the powder pigment (bl) to the pigment dispersant (b2) in the powder colorant (B) is usually 20 to 80% by weight of the powder pigment (bl) and 80 to 80% by weight of the pigment dispersant (b2). 20% by weight.

[0077] The powder pigment (bl) is not particularly limited, and known organic pigments and Z or inorganic pigments can be used.

Examples of the organic pigment include insoluble azo pigments, copper phthalocyanine pigments, and quinacdrine pigments.

Examples of inorganic pigments include chromates, ferrocyanides, metal oxides (titanium oxide, zinc oxide, etc.), metal salts (sulfates, silicates, carbonates, phosphates, etc.), metal powders, carbon black, etc. Can be

As described above, examples of the pigment dispersant (b2) include resins such as low molecular weight polyethylene and petroleum resin; inorganic dispersants such as silica and calcium carbonate; silane coupling agents; and the like. .

[0079] The content of the powder colorant (B) in the thermoplastic polyurethane resin composition for powder molding is such that the powder pigment in the powder colorant (B) is based on 100 parts by weight of the powdery thermoplastic polyurethane (A). The amount is usually 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, particularly preferably 115 to 5 parts by weight, based on the content of bl).

[0080] Potable agent (C)

Examples of the plasticizer (C) include those described in JP-A-2000-103957, U.S. Application Ser. No. 09/406, 129, for example, polyalkylene glycol (the alkylene group having 2 to 4 carbon atoms; Aromatic monocarboxylic acid (C 7-20: benzoic acid, etc.) diester having a degree of polymerization of 2-25); phthalic acid esters [dibutyl phthalate, dioctyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, etc.]; Dibasic acid esters (such as di-2-ethylhexyl adipate and di-2-ethylhexyl sebacate); trimellitate esters (such as tri-2-ethylhexyl trimellitate and tridecyl trimellitate); fatty acids Esters (such as butyl oleate and isobutyl myristate); Aliphatic phosphates (such as trimethyl phosphate, triethynolephosphate, tributynolephosphate, tri-2-ethynolehexynolephosphate, and tributoxybutyl phosphate); Aromatic phosphates (triphenyl phosphate , Trichloroethane registration Honoré phosphate, tri carboxymethyl Leni Honoré phosphate, Kurejirujifue - Norehosufue over DOO, carboxymethyl Leni Roh registration Hue - Norehosufeto, the 2-Echinore Kishinorejifue - Norehosufeto, tris ^(2, 6-Jimechirufue - Le) phosphate, etc.]; halogen Containing aliphatic phosphate esters [tris (chloroethyl) phosphate, tris (j8-chloropropylpropyl) phosphate, tris (dichloropropylpropyl) phosphate, tris (tribromoneopentyl) phosphate, etc.); and two or more of these And mixtures thereof.

[0081] Among these, preferred are phthalic acid esters (eg, dibutyl phthalate, dioctyl phthalate, dibutylbenzyl phthalate, diisodecyl phthalate) and aliphatic dibasic acid esters (eg, diadipate). Ethylhexyl, di-2-ethylhexyl sebacate, etc.), and particularly preferred are aliphatic dibasic acid esters (di-2-ethylhexyl adipate, di-2-ethylhexyl sebacate). .

[0082] In the present embodiment, it is preferable that a silicone oil (D) is contained in addition to the above-mentioned powdery thermoplastic polyurethane (A), powder colorant (B), and plasticizer (C). ,.

[0083] The silicone oil (D) is not particularly limited, and various silicone oils can be used. The use of silicone oil (D) can improve the releasability during powder molding. The amount of the silicone oil (D) used is usually 0.05-2.0 parts by weight, preferably 0.1-0.5 parts by weight, per 100 parts by weight of the powdery thermoplastic polyurethane (A). is there.

[0084] Method for Producing Thermoplastic Polyurethane Resin Composition for Powder Molding

First, the thermoplastic polyurethane resin composition for powder molding of the present embodiment is a powdery thermoplastic resin. Mix the plastic polyurethane (A) with the powder colorant (B) containing the powder pigment (bl) and the pigment dispersant (b2), add the plasticizer (C) to the resulting mixture, and continue mixing. It is manufactured by

[0085] Powdered thermoplastic polyurethane (A) and powdered colorant (B), and a mixture thereof with a plasticizer

The method of mixing with (C) is not particularly limited, and mixing by any method is possible. Among them, mixing by high-speed stirring is preferable. As the mixing device, any device can be used, but it is preferable to use a high-speed stirring device having a function of stirring at a high speed and mixing powders, such as a Henschel mixer (trade name).

[0086] First, the powdery thermoplastic polyurethane (A) and the powder colorant (B) are mixed with a Henschel mixer or the like.

[0087] The optimum stirring speed may be selected according to the processing capacity (internal volume) of the mixer, but is preferably 100 to 5000 rpm. By mixing at such a stirring speed, the dispersion of the powder colorant (B) becomes uniform as soon as possible, and the melting of the powdery thermoplastic polyurethane (A) due to overheating or the like can be prevented.

[0088] The stirring time is preferably 30 seconds to 10 minutes. Preferably, by mixing with stirring time, the dispersion of the powder colorant (B) becomes uniform, and the melting of the powdery thermoplastic polyurethane (A) due to overheating or the like can be prevented. In addition, stirring is usually performed at room temperature, but heat generation due to high shearing occurs somewhat.

Next, a plasticizer (C) is further added to a mixture of the powdery thermoplastic polyurethane (A) and the powder colorant (B), and the mixture is mixed with a Henschel mixer or the like.

[0090] The optimum stirring speed may be selected depending on the processing capacity (internal volume) of the mixer, but is preferably 100 to 5000 rpm. By mixing at this stirring speed, the dispersion of the plasticizer (C) is good, and if the powdered thermoplastic polyurethane (A) melts due to overheating, the volatilization of the plasticizer (C) is prevented. Can be.

[0091] The stirring time is preferably 1 minute to 30 minutes. By mixing during this stirring time, the dispersion of the plasticizer (C) is good, and it also prevents overheating, melting of the powdery thermoplastic polyurethane (A) and volatilization of the plasticizer (C). Can be. The stirring is usually performed at room temperature, but the powdery thermoplastic polyurethane (A) is heated by heating the wall surface of the mixer. Can also promote the absorption of the plasticizer (c). Also, some heat is generated by high shear.

[0092] When the silicone oil (D) is contained, a mixture of the powdered thermoplastic polyurethane (A) and the powdered colorant (B) is added when or after the plasticizer (C) is added. Just put in and mix.

[0093] The thermoplastic polyurethane resin composition for powder molding of the present embodiment preferably has an average particle size of 50 to 500 m, more preferably 100 to 300 m. If the average particle diameter is too small, it will agglomerate during storage of the powder, or if it is too large, the texture of the molded product will be rough, and pinholes will easily occur in the case of thin molded products. Not preferred.

[0094] According to the production method of the present embodiment, a mixture of the powdery thermoplastic polyurethane (A) and the powder colorant (B) containing the powder pigment (b1) and the pigment dispersant (b2) Furthermore, by adding and mixing the plasticizer (C), it has excellent demolding and melting properties, and has no color unevenness or pigment agglomerated particles! \ Production of thermoplastic polyurethane resin composition for powder molding can do.

[0095] Further, preferably, the thermoplastic polyurethane resin composition for powder molding of the present embodiment is a powder comprising the powdery thermoplastic polyurethane (A), the powder pigment (bl) and the pigment dispersant (b2). After mixing with the colorant (B), a plasticizer (C) is further added, and a mixture obtained by continued mixing is a main component.

[0096] The thermoplastic polyurethane resin composition for powder molding of the present embodiment as described above can be applied to powder slush molding and the like, and is particularly used for automobiles such as instrument panels, headrests, console bolts, door trims and armrests. It can be suitably used as a powder molding material for the surface layer of interior parts.

[0097] 2 real 餱

The thermoplastic polyurethane resin composition for powder molding according to the second embodiment of the present invention is a powdery colorant comprising a powdery thermoplastic polyurethane (A), a powder pigment (bl) and a pigment dispersant (b2). It contains, in addition to (B) and the plasticizer (C), a hydroxyl-modified silicone oil (D1) and a Z- or (meth) atoxy-modified silicone oil (D2).

[0098] The powdered thermoplastic polyurethane (A), the powder pigment (bl) and the pigment dispersant (b2) are contained. As the powder colorant (B) and the plasticizer (C), the same ones as in the first embodiment described above can be used, and the addition amounts thereof may be the same as in the first embodiment.

[0099] The present embodiment (second embodiment) is characterized by containing a hydroxyl-modified silicone oil (D1) and a Z- or (meta) atoxy-modified silicone oil (D2). By using these silicone oils (Dl, D2), the releasability can be improved, and by including these in a predetermined amount, compared with the case of using other silicone oils, particularly, The adhesiveness between the skin formed by molding the thermoplastic polyurethane resin composition for powder molding and the foamed polyurethane can be improved. The hydroxyl-modified silicone oil (D1) and the Z- or (meth) atari-xy-modified silicone oil (D2) can be used alone or in combination of two or more. Further, in the present embodiment, the “(meth) ataryloxy group” means a methacryloxy group and Z or an atarioxy group.

[0100] The hydroxyl-modified silicone oil (D1) refers to one in which a hydroxyl group, that is, an OH group is bonded to a silicone oil.

Specifically, “-R— (OH) x”, “1-Z—R— (OH) x” or “1-Z—O—R— (OH) xj (where R is an aromatic ring or an alkylene group) , Z is an alkylene group, X is an integer of 13), or a silyl group or siloxane group having this hydroxyl group is a silicon atom and an oxygen atom of the siloxane skeleton of the silicone oil. It is attached to at least one of the atoms.

[0101] The hydroxyl group-containing group is not particularly limited. For example, C H OH C H OH

6 4 10 6, C H OH C H OH C H — C H OH C H O — C H OH C H O — C H

2 4 3 6 3 6 6 4 2 4 6 4 2 4 6

OH ゝ -C H O-C H OH C H O—C H OH C H O—C H (OH)

As described above, there can be mentioned those containing a hydroxyl group bonded to an aromatic ring or an alkylene group. These may have one type or two or more types.

[0102] A (meth) atalioxy-modified silicone oil (D2) is a (meth) atalyloxy group, that is, -0-CO-CH = CH group and

2 Z or 100-CO-C (CH) = CH group is silicone

3 2

Refers to something connected to a file.

Specifically, “One R- (0—CO-CH = CH) x and

2 Z or R— (0-CO-C (CH) =

Three

CH) x ”,“ -Z—R— (O—CO—CH = CH) and 7 or—2—1 ^ — (0—J0—J = CH) x ”or“ one Z—O—R— (O-CO-CH = CH) x and / or Z—O—R— (O—C

twenty two

O-C (CH) = CH) x ”(where R is an aromatic ring or an alkylene group, Z is an alkylene group, X

3 2

Is an integer of 1 to 3), and the silyl group or the siloxane group having the (meth) atoxy group-containing group or the silyl group or the siloxane group having the (meth) atoxy group is a silicon atom of the siloxane skeleton of the silicone oil. And at least one of oxygen atoms.

[0103] The above-mentioned (meth) atoxy group-containing group is not particularly limited. For example, C H O—CO

6 4

-CH = CH, one CHO—CO—C (CH) = CH, one CHO—CO—CH = CH, one C

2 6 4 3 2 10 6 2 10

H O— CO— C (CH) = CH, one C H O— CO— CH = CH, one C H O— CO— C (CH)

6 3 2 2 4 2 2 4 3

= CH, one CHO-CO-CH = CH, one CHO-CO-C (CH) = CH, one CH-C

2 3 6 2 3 6 3 2 3 6 6

H O-CO-CH = CH, one C H — C H O — CO — C (CH) = CH, -C H O — C H

4 2 3 6 6 4 3 2 2 4 6 4

O-CO-CH = CH, one C H O-C H O— CO— C (CH) = CH, -C H O-C H O

2 2 4 6 4 3 2 2 4 6 4

-CO-CH = CH, one CHO-CHO-CO- C (CH) = CH, one CHO-CHO-

2 2 4 6 4 3 2 3 6 6 4

CO-CH = CH, one CHO-CHO-CO-C (CH) = CH, one CHO-CHO-C

2 3 6 6 4 3 2 3 6 2 4

0-CH = CH, one CHO-CHO-CO-C (CH) = CH, one CHO-CH (O-C

2 3 6 2 4 3 2 3 6 6 11

0-CH = CH)

Aroma, such as 2, 2, —C H O—C H (O—CO—C (CH) = CH)

Examples include those containing a (meth) alicyclic group bonded to an aromatic ring or an alkylene group. These may have one type or two or more types.

[0104] The content of the hydroxyl-modified silicone oil (D1) and the content of the Z- or (meth) atari-hydroxyl-modified silicone oil (D2) are usually 0 parts per 100 parts by weight of the powdery thermoplastic polyurethane (A). 0.5-2.0 parts by weight, preferably 0.1-0.5 parts by weight. If the amount is less than 0.05 part by weight, the effect of improving the releasability is not exhibited, while if the amount is more than 2.0 parts by weight, the adhesiveness to the foamed polyurethane (the thermoplastic polyurethane resin composition for powder molding is molded). Adhesion between the resulting skin and the foamed polyurethane) is inferior.

[0105] The thermoplastic polyurethane resin composition for powder molding of the present embodiment comprises a powdery thermoplastic polyurethane (A) and a powder colorant containing a powder pigment (bl) and a pigment dispersant (b2). (B), and then the resulting mixture is mixed with a plasticizer (C), a hydroxyl-modified silicone oil (D1) and a Z- or (meth) atari-hydroxyl-modified silicone oil (D2). It is manufactured by mixing. [0106] Powdered thermoplastic polyurethane (A) and powdered colorant (B), and mixtures and plasticizers thereof

Mixing with (C) and silicone oil (Dl, D2) is not particularly limited, and the same mixing method and mixing apparatus as in the first embodiment may be employed.

First, the powdery thermoplastic polyurethane (A) and the powder colorant (B) are mixed with a Henschel mixer or the like. The stirring speed and the mixing time at this time may be the same as those in the first embodiment.

[0108] Next, a mixture of the powdery thermoplastic polyurethane (A) and the powder colorant (B) was further mixed with a plasticizer (C) and a hydroxyl-modified silicone oil (D1) and Z or (meth). Add the Atari-Xi group modified silicone oil (D2) and mix with a Henschel mixer. The stirring speed and stirring time at this time were determined by mixing the plasticizer (C) with the mixture of the powdery thermoplastic polyurethane (A) and the powder colorant (B) in the first embodiment described above. The conditions may be the same as in the above. Also in the present embodiment, the heat generation of the powder resin is slightly generated due to the high shear.

[0109] Also in the present embodiment, the average particle diameter of the thermoplastic polyurethane resin composition for powder molding is preferably 50 to 500 µm, more preferably 100 to 300 µm.

[0110] The thermoplastic polyurethane resin composition for powder molding of the present embodiment comprises a powdery thermoplastic polyurethane (A), and a powder colorant (B) containing a powder pigment (bl) and a pigment dispersant (b2). And a plasticizer (C), and further contain a hydroxyl-modified silicone oil (D1) and a Z- or (meth) atoxy-modified silicone oil (D2). Therefore, it is possible to provide a thermoplastic polyurethane resin composition for powder molding which has excellent demoldability and meltability, has excellent adhesiveness to foamed polyurethane, and has low metal contamination.

[0111] In particular, in the present embodiment, after mixing the powdery thermoplastic polyurethane (A) with the powder colorant (B) containing the powder pigment (bl) and the pigment dispersant (b2), the plasticizer ( C) and a hydroxyl-modified silicone oil (D1) and a Z- or (meth) atari-xy-modified silicone oil (D2) are added and mixed to provide uniform coloring. Do what you want.

[0112] The thermoplastic polyurethane resin composition for powder molding of the present embodiment can be applied to powder slush molding and the like, and is particularly useful for instrument panels, headrests, console boxes, and the like. It can be suitably used as a powder molding material for the surface layer of automobile interior parts such as tass, door trims and armrests.

[0113] 3 real 餱

The thermoplastic polyurethane resin composition for powder molding according to the third embodiment of the present invention is a powder colorant containing a powdery thermoplastic polyurethane (A), a powder pigment (bl) and a pigment dispersant (b2). In addition to (B) and the plasticizer (C), the composition further contains a hydroxyl group-containing aromatic vinyl copolymer (E).

[0114] The powdery thermoplastic polyurethane (A), the powder colorant (B) containing the powder pigment (bl) and the pigment dispersant (b2), and the plasticizer (C) are the same as those in the first embodiment. Can be used, and the amount of addition may be the same as in the first embodiment.

[0115] The hydroxyl group-containing aromatic vinyl copolymer (E) has an average particle diameter of 0.1-m and is a kind of so-called dusting agent. A dusting agent suppresses agglomeration of powders and improves powder fluidity.

[0116] When the average particle diameter of the hydroxyl group-containing aromatic vinyl copolymer (E) is less than 0: Lm, the handleability becomes extremely poor and the fluidity of the thermoplastic polyurethane resin composition for powder molding is reduced. The effect of improvement and the effect of preventing blocking deteriorate. On the other hand, if it exceeds 10 m, the adhesiveness to the foamed polyurethane (the adhesiveness between the skin obtained by molding the thermoplastic polyurethane resin composition for powder molding and the foamed polyurethane) is deteriorated. The average particle size is preferably 0.5-8 ^ m.

[0117] The hydroxyl group-containing aromatic vinyl copolymer (E) is obtained by introducing a hydroxyl group into a part of an aromatic vinyl copolymer prepared in advance, or converting a hydroxyl group-containing monomer into an aromatic vinyl monomer. It can be obtained by copolymerization. Preferably, an aromatic vinyl monomer, a hydroxyl group-containing vinyl monomer and any other copolymerizable monomer described below are copolymerized. Particularly preferably, it is desirable to obtain the force obtained by emulsion polymerization of the above-mentioned monomer and crushing the obtained polymer to form fine particles, or to obtain the monomer by fine suspension polymerization. .

[0118] The method for introducing a hydroxyl group into a previously produced aromatic vinyl copolymer is not particularly limited. Also, a method of copolymerizing a monomer containing a hydroxyl group with an aromatic vinyl monomer is described. Is as described below.

[0119] First, as the aromatic vinyl monomer, for example, styrene, α-methylstyrene, β-methylstyrene, ρ-methylstyrene, 4t-butylstyrene, 3-chlorostyrene, 4-chlorostyrene, 3,4-dichlorostyrene, 3-methoxystyrene, 4-methoxystyrene, 2-vinylethanol, 3-butyltoluene, 4-butyltoluene, 4-vinylinole-1,2-xylene, 3-ethylenostyrene, 4-ethylstyrene, 1- Vinyl naphthalene, 2-vinyl naphthalene, 5-vinylanthracene, and the like. These can be used alone or in combination of two or more.

[0120] Examples of the hydroxyl group-containing monomer include a hydroxyl group-containing (meth) acrylic ester, a hydroxyl group-containing vinyl ether, a hydroxyl group-containing vinyl monocarboxylic acid ester, a hydroxyl group-containing vinyl dicarboxylic acid ester, a vinyl alcohol, and the aromatic vinyl. Examples include a monomer containing a hydroxyl group. These can be used alone or in combination of two or more.

[0121] Examples of the hydroxyl group-containing (meth) acrylate include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) acrylic acid. -2,3-dihydroxypropyl, 2-hydroxyamyl (meth) acrylate, 2-hydroxyoctyl (meth) acrylate, 2-hydroxydodecyl (meth) acrylate, and the like.

Examples of the hydroxyl group-containing vinyl ether include 2-hydroxypropyl vinyl ether, 2-hydroxybutyl vinyl ether, and 2,4-dihydroxyoctyl ether. Roxypropionate bur and the like.

Examples of hydroxyl group-containing buldicarboxylic acid esters include 2-hydroxypropyl maleate and di (2-hydroxyethyl) fumarate.

[0122] In the copolymerization of the aromatic vinyl monomer and the hydroxyl group-containing vinyl compound, any other copolymerizable monomer is copolymerized to such an extent that the effects of the present invention are not impaired. Obtainable. Examples of such a monomer include the following monomers. (Meth) acrylic acid esters such as ethyl acrylate and methyl methacrylate; (meth) nitrile compounds such as nitrile and bi-lidene cyanide; and mono-carboxylic acid esters such as butyl acetate and butyl propionate; Butyl dicarboxylates such as monobutyl maleate; vinyl ether compounds such as ethyl vinyl ether and methyl vinyl ether; Can be These can be used alone or in combination of two or more.

[0123] The content of the hydroxyl group-containing vinyl compound unit in the hydroxyl group-containing aromatic vinyl copolymer (E) is usually 10 to 60% by weight, preferably 20 to 50% by weight. If it is less than 10% by weight, the adhesiveness to the polyurethane foam will be poor, and if it exceeds 60% by weight, the heat resistance of the molded product will be poor.

[0124] Hydroxyl-containing aromatic vinyl copolymers (E) have various monomer compositions, have various hydroxyl group contents, and have various average particle diameters in the range of 0.1 to 10 m. These can be used alone or in combination of two or more.

[0125] The content of the hydroxyl group-containing aromatic vinyl copolymer (E) in the thermoplastic polyurethane resin composition for powder molding is usually based on 100 parts by weight of the powdery thermoplastic polyurethane (A). 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight. If the amount is less than 0.1 part by weight, powder fluidity may decrease. If the amount exceeds 30 parts by weight, demolding from a mold may become difficult during powder molding.

In the present embodiment, it is preferable to further include the silicone oil (D), and particularly, the hydroxyl-modified silicone oil (D1) and the Z- or (meth) atari-hydroxy-modified silicone oil (D2) Is preferably contained. As such a hydroxyl-modified silicone oil (D1) and a Z- or (meth) atari-hydroxyl-modified silicone oil (D2), it is preferable to use the same one as in the second embodiment described above.

[0127] The thermoplastic polyurethane resin composition for powder molding of the present embodiment comprises a powdery thermoplastic polyurethane (A), a powdery pigment containing a powdery pigment (bl) and a pigment dispersant (b2). (B), and then, a plasticizer (C) is added and mixed, and the resulting mixture is further added with the hydroxyl group-containing aromatic vinyl copolymer (E) and mixed. . In addition, water As the aromatic group copolymer containing an acid group (E), one having an average particle size of 0.1-10 / zm is used.

[0128] First, the powdery thermoplastic polyurethane (A) and the powder colorant (B) are mixed, and then the plasticizer (C) is added and mixed. Note that these mixing may be the same as in the first embodiment.

Next, the hydroxyl group-containing aromatic vinyl copolymer (E) is added to the mixture obtained above and mixed with a Henschel mixer or the like.

The stirring speed at this time may be selected according to the processing capacity (internal volume) of the mixer, but is preferably 100 to 5000 rpm. By mixing at this stirring speed, the dispersion of the hydroxyl group-containing aromatic vinyl copolymer (E) is good, and overheating or melting of the powdery thermoplastic polyurethane (A) or volatilization of the plasticizer (C) is achieved. Can be prevented. The stirring time is preferably 30 seconds to 10 minutes. By mixing during this stirring time, the dispersion of the hydroxyl group-containing aromatic vinyl copolymer (E) is good, and overheating or melting of the powdery thermoplastic polyurethane (A) or plasticizer (C) Volatilization can be prevented.

The stirring is desirably performed at room temperature, but some heat generation due to high shear occurs.

Further, in the present embodiment, when the silicone oil (D), in particular, the hydroxyl-modified silicone oil (D1) and the Z- or (meth) atari-hydroxy-modified silicone oil (D2) are contained, It is preferred that the powdery thermoplastic polyurethane (A) and the powder colorant (B) are mixed and added to the resulting mixture together with the plasticizer (C).

[0131] The thermoplastic polyurethane resin composition for powder molding of the present embodiment comprises a powdery thermoplastic polyurethane (A) and a powder colorant (B) containing a powder pigment (bl) and a pigment dispersant (b2). And a plasticizer (C), and further contain a hydroxyl group-containing aromatic vinyl copolymer (E). Therefore, it is possible to provide a thermoplastic polyurethane resin composition for powder molding having excellent demoldability, excellent adhesiveness to foamed polyurethane, and good meltability.

[0132] In particular, in the present embodiment, the powdery thermoplastic polyurethane (A) and the powdery pigment (bl) And a powder colorant (B) containing a pigment dispersant (b2) and a plasticizer (C) and a hydroxyl group-containing aromatic vinyl copolymer (E), followed by mixing. By doing so, uniform coloring can be imparted.

[0133] The thermoplastic polyurethane resin composition for powder molding of the present embodiment can be applied to powder slush molding and the like, and in particular, for automobiles such as instrument panels, headrests, console bolts, door trims and armrests. It can be suitably used as a powder molding material for the surface layer of interior parts.

[0134] Various additives can be added to or used together with the thermoplastic polyurethane resin composition for powder molding according to each of the first to third embodiments as desired. For example, various known dusting agents, various antiblocking agents, various stabilizers (for example, various antioxidants, various ultraviolet absorbers), various antistatic agents, various flame retardants, etc., impair moldability. It can be added in a range.

Further, in each of the first to third embodiments described above, as long as the gist of the present invention is not impaired, other than the polymer component constituting the thermoplastic polyurethane resin composition for powder molding of the present invention. Can be used in combination.

Example

The present invention is not limited to the following examples and comparative examples, and the present invention is not limited to these examples. In this example, parts and% are based on weight unless otherwise specified. The test method is as follows.

[0137] (1) Average particle size

The average particle size of the powder is a particle size corresponding to a mesh having an integral particle size distribution curve of 50% by weight based on a sieve using a JIS standard sieve.

[0138] (2) Powder flowability

The force specific gravity, the angle of repose at 100 ml of powder, and the falling velocity at 100 ml of powder are measured using a force specific gravity measuring device specified in JIS K6721. It can be said that the smaller the angle of repose and the higher the flow velocity, the better the powder fluidity.

[0139] (3) Meltability

(A) In a 300 ° C oven, an electrically conductive mold (150mm X 180m mX 3mm), and when the mold temperature reaches 280-300 ° C, remove the mold from the oven.

(B) When left in the room, when the mold surface temperature reaches 250 ° C., 500 g of the thermoplastic polyurethane resin composition for powder molding is sprinkled on the mold and left to melt for 10 seconds.

(C) After 10 seconds, after removing excess thermoplastic polyurethane resin composition for powder molding on the mold, the time until the molten resin on the mold becomes smooth (leveling) at room temperature. And this is defined as the melting time. The shorter the melting time, the better the meltability.

[0140] (4) Demoldability

Spray 100 g of the thermoplastic polyurethane resin composition for powder molding on a 120 mm X 70 mm X 3 mm mold (mirror surface) heated to 250 ° C, and let it stand for 10 seconds to melt. Immediately after that, the excess composition is shaken off, and after a lapse of 90 seconds, the mold is cooled with cooling water.When the mold temperature falls to 0 ° C, the molded sheet is removed from the mold by 20 mmZ. Peel off at a pulling speed of seconds and measure the demolding force (unit: NZ70mm).

[0141] (5) Colorability

(A) How to check for uneven skin color

The state of uneven color of the epidermis produced by a predetermined method ((A)-(C) in (3) above) is visually evaluated in the following three stages.

〇: No color unevenness is recognized at all, or only a slight color unevenness is recognized. Δ: Color unevenness that can be slightly confirmed.

X: There is color unevenness that can be clearly seen.

(B) Method for confirming colored particle aggregates on epidermis

The agglomerated particles present on the back surface of the epidermis prepared by the prescribed method are visually evaluated in the following three stages.

〇: A uniform colored state with no or almost no aggregated particles.

Δ: Some agglomerated particles that can be visually confirmed are present.

X: Many agglomerated particles are clearly visible.

[0142] (6) Mold contamination Spread 500g of thermoplastic polyurethane resin composition for powder molding on a 180mm X 150mm X 3mm mold with a grain heated to 250 ° C, and leave it for 10 seconds. Immediately after that, the excess composition was shaken off, and after another 90 seconds, the mold was cooled with cooling water, and when the mold temperature dropped to 40 ° C, the molded sheet was removed from the mold. It was repeated 30 times according to), and the mold contamination at that time was judged by the following index.

〇: Little or no change in hue from initial contamination. Δ: The hue is clearly changed, and the luster is clearly changed.

X: Hue and gloss are remarkably changed, and residues on the epidermis are attached.

(7) Urethane Adhesiveness (Adhesiveness between skin and foamed polyurethane formed by molding thermoplastic polyurethane resin composition for powder molding)

(A) A 180 mm × 25 mm test piece was cut out from the skin having a thickness of about 1 mm obtained from the powder molding material according to the method for forming the skin described in (6) above. The test piece was placed in an aluminum mold with a lid of internal dimensions (length) 800 mm X (width) 150 mm X (depth) 10 mm, and the injection force of the foamed polyurethane resin forming liquid was 600 mm. And the mold surface temperature was kept at 0 ° C.

(B) Next, 94.7 g of the foamed polyurethane forming solution [Polymeric MDI (4,4, diphenylmethanediisocyanate, the number of functional groups: 2.7)] was added to the foamed polyurethane resin forming solution inlet, and Polyol (a mixture of 119.32 g of a trifunctional hydroxyl value containing 50% triethylenediamine and 1.6% water) was poured, and the mold was closed and sealed. After holding the mold for 2 minutes and 30 seconds, open the lid, take out the test piece in which foamed polyurethane resin and skin are laminated, peel off the skin from the foamed polyurethane resin forming liquid inlet side, and cohesive fracture (foam layer fracture ) Was measured. The farther the distance of the cohesive failure (foam layer failure), the better the urethane adhesion. The urethane adhesiveness is indicated as follows.

0: 550—600mm,

△: 450-550mm,

X: 450mm or less.

Next, the raw materials used in this example and comparative examples will be described. [0145] Powdered thermosetting polyurethane (A)

First, in order to synthesize the powdery thermoplastic polyurethane (A), the following polyester 1, polyester 2, polyester 3, and a dispersion medium were prepared.

[0146] [Polyester 1]

1,4 Butanediol and adipic acid force Aromatic ring-free polyester polyol obtained, hydroxyl value = 110 mg KOHZg, average number of functional groups = 2

(Polyesternole 2)

Aromatic ring-containing polyester polyol obtained from isophthalic acid Zazelainic acid = 1/1 (molar ratio), ethylene glycol Z neopentyl glycol = 9Zl (molar ratio), hydroxyl value = 56mgKOHZg, aromatic ring content = 1.97mmol / g, average number of functional groups = 2

[Polyester-3]

3-Methyl-1,5-pentanediol and adipic acid Aromatic ring-free polyester polyol obtained. Hydroxyl value 56mgKOHZg, average number of functional groups 2

(Dispersion medium)

Noraffinic solvent, trade name: Shelsol 71 (manufactured by Sherii Dangaku Co., Ltd.), boiling point 170-2 oo ° c

Next, separately from the above, a dispersion stabilizer was synthesized by the following method, and a powdery thermoplastic polyurethane (A) was synthesized using the obtained dispersion stabilizer and each raw material prepared above.

(1) Synthesis of Polyol Having Unsaturated Bond in Molecule

Into a reaction vessel equipped with a stirrer, thermometer, distillation tower, and nitrogen gas inlet tube, _1,000 parts by weight of the polyester 1 prepared above and 49 parts by weight of maleic anhydride were charged, and nitrogen gas was fed. Heat and mix. In the heating and mixing, first, the reaction is carried out at a temperature of 140 to 160 ° C, the condensed water is taken out of the system, and the reaction is continued while the pressure inside the system is gradually reduced, and finally the reaction is performed at 190 ° C and 30 mmHg. After reacting for 4 hours under the conditions described above, the reaction was terminated to obtain a polyol. The hydroxyl value of the obtained polyol was 53 mgKOHZg, and the acid value was 4.1 mgKOHZg. This polyol had a number average molecular weight of 2,100 and had an average of one double bond in one molecule. (2) Synthesis of dispersion stabilizer

In a reactor equipped with a stirrer, thermometer, dropping funnel and cooler, 44 parts by weight of the polyol synthesized in the above (1) and 99 parts by weight of butyl acetate were weighed. The mixture was heated and mixed while flowing nitrogen gas into the system from above the dropping funnel. Then, when the temperature reached 110 ° C by heating, a dissolved mixture of 102 parts by weight of lauryl methacrylate and 2 parts by weight of benzoyl peroxide was started to be dropped from the dropping funnel. The dropping was completed in one and a half hours, and after that, the mixture was reacted at 130 ° C. for 2 hours, and then the reaction was terminated to obtain a dispersion stabilizer. The resulting dispersion stabilizer had a hydroxyl value of 1 lmgKOH / g.

(3) Synthesis of Powdered Thermoplastic Polyurethane (A)

In a reaction kettle equipped with a high-speed specification stirring motor, 18.2 weight of the dispersion stabilizer obtained above, 51.7 weight% of Polyestenole 2 heated to 100 ^° C and 23. 0 parts by weight, 5.9 parts by weight of 1,4-butanediol and 0.002 parts by weight of dibutyltin dilaurate were charged and uniformly mixed. Then, 100.0 parts by weight of the dispersion medium prepared above was charged, and high-speed stirring was further performed for 10 minutes. After that, 17.4 parts by weight of hexamethylene diisocyanate was charged, the temperature was raised to 80 ° C., and the mixture was reacted for 4 hours. After that, the dispersion medium and the resin were separated by a centrifugal dehydrator to obtain a resin. The resin was dried under reduced pressure to obtain 99.5 parts by weight of a spherical spherical thermoplastic polyurethane (A-1). The obtained powdery thermoplastic polyurethane (A-1) had an average particle diameter of 260 / ζπι and a number average molecular weight of η = 27,000.

[0149] Shy powder

The following powder colorant (II-1) and powder colorant (II-2) were prepared as the powder colorant (II).

Sumika Color Co., Ltd.'s PV-7A1301 (a mixture of titanium oxide (bl-1) as a powder pigment and calcium carbonate (b2-1) as a pigment dispersant at a ratio of 70Z30) was used as a powder colorant ( B-1).

Sumika Color Co., Ltd. PV-817 (a mixture of powdered carbon black (bl-2) and pigment dispersant calcium carbonate (b2-2) at a ratio of 40Z60) was used as a powder colorant ( B-2).

[0150] Potable agent (C) As a plasticizer (C), RS-107 (adipic acid diester type: manufactured by Asahi Denka Kogyo Co., Ltd.) was prepared and used as a plasticizer (C-1).

[0151] Silicone oil (D)

As the silicone oil (D), polydimethylsiloxane (trade name: SH-200, viscosity 300 cps at 25 ° C: manufactured by Shin-Etsu Silicone Co., Ltd.) was prepared and used as silicone oil (D-1).

[0152] Hydrogenated modified silicone oil (D1)

As a hydroxyl-modified silicone oil (D1), FM 0425 [one-end hydroxyl-modified silicone oil (trade name: Silaplane): manufactured by Chisso Co., Ltd.] was prepared, and this was combined with an acid-modified silicone oil (Dl-1). did.

[0153] (Meth) acryloxy certain silicone oil (D2)

FM-0725 [Single-ended meta-tartaric xy group-modified silicone oil (trade name: Cylabrain): manufactured by Chisso Corporation] was prepared as a (meth) atari xy-modified silicone oil (D2). This was a methacryloxy group-modified silicone oil (D2-1).

[0154] 7ki Certain ^^ Bull #: (R)

A hydroxyl group-containing aromatic vinyl copolymer (E) was produced by the following method. First, 200 parts of distilled water was charged into a stainless steel premixing vessel having two-stage blades. Et al of styrene 35 wt ^_0/0, 2-hydroxypropionic Pinot Leme Tak relay HHPMA) 30 weight ^_0/0, and methyl methacrylate (MMA) monomer mixture 40 parts consisting of 35 wt%, linear 18-carbon 1.0 part of a higher chain alcohol, 0.5 part of sodium lauryl sulfate and 0.3 part of peroxyl benzoyl were charged and mixed at 30 ° C for 1 hour. Thereafter, the suspension formed by stirring is passed through a homogenizer, and then transferred into another stainless steel pressure-resistant vessel having two-stage blades, where fine suspension polymerization is performed at 60 ° C, and the hydroxyl group-containing aromatic vinyl A copolymer was produced. The polymerization conversion was 98%. The average particle diameter of the obtained hydroxyl group-containing aromatic vinyl copolymer (E1) was 2.2 m.

[0155] First, Examples 11 to 12 and Comparative Examples 11 to 15 according to the first embodiment of the present invention will be described.

Example 1 1 First, in a Henschel mixer, 100 parts by weight of the powdery thermoplastic polyurethane (A-1) obtained above, 1.8 parts by weight of the powder colorant (B-1), and powder colorant (B-2) 0 18 parts by weight were added and mixed at 100 rpm for 1 minute to obtain a mixture of a powdery thermoplastic polyurethane (A-1) and a powder coloring agent (B-1, B-2).

[0156] Next, in a Henschel mixer, a mixture of the powdery thermoplastic polyurethane (A-1) and the powder colorant (B-1, B-2) was added, and the plasticizer (C1) was further added. 5 parts by weight were added and mixed at 100 O rpm for 5 minutes. Then, 3 parts by weight of Hyprene B409S (manufactured by Nippon Zeon Co., Ltd.) was added as a dusting agent, and the mixture was further mixed at 100 rpm for 1 minute to obtain a thermoplastic polyurethane resin composition for powder molding. With respect to the obtained thermoplastic polyurethane resin composition for powder molding, powder fluidity, meltability, mold release properties, and coloring properties were measured. The results are shown in Table 1.

[0157] Example 1-2

Into a Henschel mixer, 109.98 parts by weight of the thermoplastic polyurethane resin composition for powder molding prepared in Example 1-1 and 0.3 parts by weight of silicone oil (D-1) are mixed and mixed at 100 rpm for 1 minute. Was carried out to produce a thermoplastic polyurethane resin composition for powder molding. Table 1 shows the results.

[0158] Comparative Example 1 1

In a Henschel mixer, 100 parts by weight of the powdered thermoplastic polyurethane (A-1) prepared above, 1.8 parts by weight of powder colorant (B-1), 0.18 part by weight of powder colorant (B-2) , And 5 parts by weight of a plasticizer (C1) were added at a time, and mixed at 100,000 rpm for 5 minutes. Thereafter, 3 parts by weight of the dusting agent Hybrene B409S was added, and the mixture was further mixed at 100 rpm for 1 minute to obtain a thermoplastic polyurethane resin composition for powder molding. The results are shown in Table 1.

[0159] Comparative Example 1 2

First, 80 parts by weight of tri (2ethylhexyl) trimellitate as a plasticizer was kneaded and dispersed by a three-roll mill to 20 parts by weight of titanium oxide to prepare a paste colorant (P-1). On the other hand, paste colorant (P-2) was prepared by kneading and dispersing 88.6 parts by weight of tri (2-ethylhexyl) trimellitate with 3 rolls in 11.4 parts by weight of carbon black.

[0160] Next, in the Henschel mixer, the powdery thermoplastic polyurethane (A -1) 100 parts by weight, 6.3 parts by weight of the paste colorant (P 1) and 0.63 parts by weight of the paste colorant (P-2) were added, and mixed at 100 rpm for 2 minutes. Thereafter, the dusting agent Hybrene B409S was added, and the mixture was further mixed at 100,000 rpm for 1 minute to obtain a thermoplastic polyurethane resin composition for powder molding. Table 1 shows the results.

[0161] Comparative Example 13

In a Henschel mixer, 100 parts by weight of the powdered thermoplastic polyurethane (A-1) prepared above, 1.8 parts by weight of powder colorant (B-1), 0.18 part by weight of powder colorant (B-2) , 5 parts by weight of plasticizer (C1) and 0.3 parts by weight of silicone oil (D-1) were added at a time, and mixed at 100,000 rpm for 5 minutes. Thereafter, 3 parts by weight of the dusting agent Hyprene B409S was added, and the mixture was further mixed at 100 rpm for 1 minute to obtain a thermoplastic polyurethane resin composition for powder molding. The results are shown in Table 1.

[0162] Comparative Example 1 4

Powder molding was performed in the same manner as in Example 12 except that 0.3 parts by weight of zinc stearate was used instead of 0.3 parts by weight of polydimethylsiloxane, which is a silicone oil (D-1). A thermoplastic polyurethane resin composition for use was obtained. The results are shown in Table 1.

[0163] Comparative Example 15

The same operation as in Example 11 was carried out except that the plasticizer (C1) was changed from 5 parts by weight to 25 parts by weight, to obtain a thermoplastic polyurethane resin composition for powder molding. The results are shown in Table 1.

[0164] [Table 1]

Example 1-Example 1-2 Ratio 1-5

* 1) Do not fall from the funnel.

* 2] The epidermis was broken without being removed from the mold.

+ 3) Fukutai _c but epidermis was formed, the plasticizer exudes

[0165] In Table 1, AC in the column of the mixing method means the following mixing method.

A: A method in which a powdery thermoplastic polyurethane and a powder colorant are mixed first, and then a plasticizer (and silicone oil) are mixed.

B: A method in which powdery thermoplastic polyurethane, powder colorant, and plasticizer (and silicone oil) are mixed at once.

C: A method in which the powder colorant and the plasticizer are mixed first, and then the powdered thermoplastic polyurethane is mixed.

[0166] From the results in Table 1, the following can be said.

In preparing the thermoplastic polyurethane resin composition for powder molding, a powdery thermoplastic polyurethane (A-1), a powder colorant (B-1), a powder colorant (B-2), and a plasticizer (C In Comparative Example 11 in which 1) was added at once and mixed, a problem occurred in colorability. That is, in Comparative Example 11, there was color unevenness that could be slightly confirmed, and there were many agglomerated particles that could be visually confirmed.

[0167] A paste colorant (PD and paste colorant (P-2)) was used in place of the powder colorant (B-1), the powder colorant (B-2), and the plasticizer (C1). Comparative Example 12 and powdered thermoplastic polyurethane (A-1), powder colorant (B-1), powder colorant (B-2), plasticizer (C1), and silicone oil (D-1) In the case of Comparative Examples 1 to 3 in which was added at a time and mixed, the same problem was also caused in the colorability. The obtained thermoplastic polyurethane resin composition for powder molding was not good, and the funnel force was not dropped.

[0168] In Comparative Examples 1-4, in which zinc stearate was used in place of polydimethylsiloxane, which is a silicone oil (D-1), meltability and mold release were difficult. A pinhole was generated on the surface of the mold, and in the case of the mold release property, the epidermis was broken without being removed from the mold.

[0169] In Comparative Example 15 in which the plasticizer (C1) was increased to 25 parts by weight, the plasticizer was exuded from the thermoplastic polyurethane resin having extremely poor powder flowability. Was.

[0170] In contrast to these comparative examples, the thermoplastic polyurethane resin compositions for powder molding produced in Examples 11 and 12 had good powder flowability, meltability, mold release properties, and coloring properties. Met. Next, Examples 2-1 to 2-2 and Comparative Examples 2-1 to 2-4 according to the second embodiment of the present invention will be described.

Example 2-1

First, in a Henschel mixer, 100 parts by weight of the powdery thermoplastic polyurethane (A-1) prepared above, 1.8 parts by weight of the powder colorant (B-1), and 0.1 part by weight of the powder colorant (B-2). 18 parts by weight were added and mixed at 100 rpm for 1 minute to obtain a mixture of a powdery thermoplastic polyurethane (A-1) and a powder coloring agent (B-1).

[0172] Next, in a Henschel mixer, a mixture of the powdery thermoplastic polyurethane (A-1) and the powdery colorant (B-1, B-2) was added, and the plasticizer (C1) 5 was further added. Parts by weight and 0.3 part by weight of a methacryloxy group-modified silicone oil (D2-1) were added in the order of a plasticizer (Cl) and a methacryloxy group-modified silicone oil (D2-1), and mixed at 100 rpm for 5 minutes. Thereafter, 3 parts by weight of Hyprene B409S (manufactured by Nippon Zeon Co., Ltd.) was added as a dusting agent, and the mixture was further mixed at lOOOr pm for 1 minute to obtain a thermoplastic polyurethane resin composition for powder molding. With respect to the obtained thermoplastic polyurethane resin composition for powder molding, powder fluidity, meltability, mold release, coloring, mold contamination and urethane adhesion were measured. Table 2 shows the results.

[0173] Ornament 12—2

The same operation as in Example 2-1 was carried out except that 0.3 part by weight of the methacryloxy-modified silicone oil (D2-1) was replaced by 0.3 part by weight of the hydroxyl-modified silicone oil (Dl-l) O. Thus, a thermoplastic polyurethane resin composition for powder molding was produced. Table 2 shows the results.

[0174] Comparative Example 2-1

Instead of using 0.3 parts by weight of methacryloxy-modified silicone oil (D2-1), instead of using 0.3 parts by weight of SH-200 (polydimethylsiloxane: manufactured by Shin-Etsu Silicone Co., Ltd.) as polydimethylsiloxane, The same operation as in Example 2-1 was performed to produce a thermoplastic polyurethane resin composition for powder molding. Table 2 shows the results.

[0175] Comparative Example 2-2

In place of using 0.3 parts by weight of methacryloxy group-modified silicone oil (D2-1), 0.3 parts by weight of FZ-3720 (manufactured by Nippon KK) was used as an epoxy group-modified silicone oil. The same operation as in Example 2-1 was performed to obtain a thermoplastic polyurethane resin for powder molding. A composition was made. Table 2 shows the results.

[0176] Comparative Examples 2-3

The procedure was carried out except that 0.3 parts by weight of methacryloxy group-modified silicone oil (D2-1) was replaced by 0.3 parts by weight of amino group-modified silicone oil FZ-3760 (manufactured by Nippon Carker Co., Ltd.) The same operation as in Example 2-1 was performed to produce a thermoplastic polyurethane resin composition for powder molding. Table 2 shows the results.

[0177] Comparative Examples 2 to 4

The methacryloxy group-modified silicone oil (D2-1) was replaced with 0.3 part by weight of zinc stearate (SZ-2000: manufactured by Sakai Danigaku Co., Ltd.). The same operation as in 2-1 was performed to produce a thermoplastic polyurethane resin composition for powder molding. Table 2 shows the results.

[0178] [Table 2]

[0179] From the results in Table 2, the following can be said.

Comparative Example Using Polydimethylsiloxane Instead of Hydroxyl-Modified or (Meth) Attarixyl-Modified Silicone Oil (Dl-1, D2-1) in Making Thermoplastic Polyurethane Resin Composition for Powder Molding In 2-1 and Comparative Example 2-2 using an epoxy group-modified silicone oil, and Comparative Example 2-3 using an amino group-modified silicone oil, the urethane adhesive property (the thermoplastic polyurethane resin composition for powder molding) was used. (Adhesion between the sheet formed from the product and the polyurethane foam) was poor.

[0180] Further, in Comparative Examples 2-4 using zinc stearate instead of the hydroxyl-modified and Z- or (meth) atari-hydroxyl-modified silicone oils (Dl-1, D2-1), the demolding property was reduced. , Mold contamination, and urethane adhesion were all poor. Regarding the demoldability, the epidermis was broken without demolding.

[0181] In comparison, the thermoplastic polyurethane resin compositions for powder molding produced in Examples 2-1 and 2-2 showed powder flowability, demoldability, low mold contamination, and urethane. Adhesion was good. Further, in Examples 2-1 and 2-2, the powdery thermoplastic polyurethane (A-1) and the powder colorant (B-1, B-2) were mixed in advance, and then the plasticizer ( Since the process of adding C-1) and silicone oil (D1-1, D2-1) was adopted, the result was excellent in coloring properties.

Next, Example 3-1-3-2 and Comparative Example 3-1-3-3 according to the third embodiment of the present invention will be described.

Example 3-1

First, in a Henschel mixer, 100 parts by weight of the powdery thermoplastic polyurethane (A-1) prepared above, 1.8 parts by weight of the powder colorant (B-1), and 0.1 part by weight of the powder colorant (B-2). 18 parts by weight were added and mixed at 100 rpm for 1 minute to obtain a mixture of a powdery thermoplastic polyurethane (A-1) and a powder coloring agent (B-1, B-2).

[0183] Next, in a Henschel mixer, a mixture of the powdery thermoplastic polyurethane (A1) and the powdery colorant (B-1, B-2) was added, and the plasticizer (C1) 5 was further added. After mixing at 100 Orpm for 5 minutes, add 3 parts by weight of the hydroxyl group-containing aromatic vinyl copolymer (E-1) having an average particle size of 2.2 m, and mix at lOOOOrpm for another minute. Heatable for powder molding A plastic polyurethane resin composition was obtained. With respect to the obtained thermoplastic polyurethane resin composition for powder molding, powder fluidity, meltability, demoldability, colorability, and urethane adhesiveness were measured. Table 3 shows the results.

Example 3-2

When producing a thermoplastic polyurethane resin composition for powder molding, together with a plasticizer (C 1)

Methacryloxy group-modified silicone oil (D2-1: FM 0725 described above), except that 0.3 parts by weight was mixed and mixed, and the same operation as in Example 3-1 was performed. A urethane resin composition was obtained. Table 3 shows the results.

[0185] Comparative Example 3-1

Instead of the hydroxyl group-containing aromatic vinyl copolymer (E-1), the hydroxyl group-containing aromatic vinyl copolymer having an average particle diameter of 50 μm and the same monomer unit composition as E-1 Except for using 3 parts by weight, the same operation as in Example 3-1 was performed to produce a thermoplastic polyurethane resin composition for powder molding. Table 3 shows the results.

[0186] Comparative Example 3-2

The same procedure as in Example 3-1 was carried out except that 3 parts by weight of acrylic resin powder No. 3 and iprene B409S (manufactured by Nippon Zeon Co., Ltd.) were used instead of the hydroxyl group-containing aromatic vinyl copolymer (E-1). The operation was performed to prepare a thermoplastic polyurethane resin composition for powder molding. Table 3 shows the results.

[0187] Comparative Example 3-3

The same operation as in Example 3-1 was carried out except that 3 parts by weight of Aerosil A200 (fine-particle silica; manufactured by Nippon Aerosil Co., Ltd.) was used instead of the hydroxyl group-containing aromatic vinyl copolymer (E-1). A thermoplastic polyurethane resin composition for body molding was produced. Table 3 shows the results.

[0188] [Table 3] Powdered thermoplastic polyurethane A— 1 100 100 100 100 100 (parts by weight)

Powder colorant B- 1 P V-7 A 1 301 1.8 1.8 1.8 1.8 1.8

B-2 P V-81 7 0.18 0.1 0.18 0.18 0.18 0.18 Plasticizer (parts by weight) C- 1 RS-1 07 5 5 5 5 5 Methacryloxy-modified silicone

D 2-1 FM-0725 0.3

Nineile (SM

Hydroxyl-containing aromatic pinyl copolymer

(Particle size 2.Zum) E- 1 ― 3 3

(Overlapping part)

Hydroxyl-containing aromatic vinyl copolymer

(Particle diameter 50 m) ― ― 3

(Mass part)

Other dusting agents-Hybrene B409S 3

(Parts by weight)-Aerosil A 200 3

109.98 110.28 109.98 109.98 109.98 Average particle size Average particle size (Wm) 1 86 1 89 1 87 1 89 1 87

Or specific gravity ^{(fi / cm 3 0. 68 0.} 69 0. 70 0. 67 0. 70 powder fluidity angle of repose (degree) 25 25 23 26 24

Flow rate (sec) 1 0 10 9 10 9 Meltability Surface pinhole No No No No No Yes Demolding Demolding force (NZ70mm) 5.9.2.0 5.7.5.5.60

Color shading 〇

Colorability O 〇 O O

Aggregated particles O 〇 O 〇 o Urethane adhesiveness O O Δ 厶 X

[0189] From the results in Table 3, the following can be said.

In preparing a thermoplastic polyurethane resin composition for powder molding, the average particle diameter was 50 μm instead of the hydroxyl group-containing aromatic vinyl copolymer (E-1) having an average particle diameter of 2.2 μm. In Comparative Example 3-1 using a hydroxyl group-containing aromatic vinyl copolymer having a particle size of μm and Comparative Example 2-2 using an acrylic resin powder NO and Ibrene B409S, urethane adhesion was poor.

[0190] In Comparative Example 3-3 using fine-particle silica aerosil A200 instead of the hydroxyl group-containing aromatic vinyl copolymer (E-1), the meltability and urethane adhesion were poor.

[0191] In comparison, the thermoplastic polyurethane resin composition for powder molding produced in Example 3-1 had good powder flowability, meltability, and urethane adhesiveness. Further, in Example 3-2 in which a metallized xy group-modified silicone oil (D2-1) was added, the demolding property was further improved. Furthermore, in Examples 3-1, 3-2, the powdery thermoplastic polyurethane (A1) and the powder colorant (B-1, B-2) were mixed, and then the plasticizer (C1 ), And then the step of adding a hydroxyl group-containing aromatic vinyl copolymer (E-1) resulted in excellent colorability.

Claims

The scope of the claims

[1] a powdery thermoplastic polyurethane (A),

A method for producing a thermoplastic polyurethane resin composition for powder molding, comprising adding a plasticizer (C) and subsequently mixing.

[2] The powdery thermoplastic polyurethane (A),

Said plasticizer (C),

2. The method for producing a thermoplastic polyurethane resin composition for powder molding according to claim 1, wherein the silicone oil (D) and the silicone oil (D) are added and subsequently mixed.

[3] The powdery thermoplastic polyurethane (A),

Said plasticizer (C),

The heat for powder molding according to claim 1 or 2, wherein the hydroxyl-modified silicone oil (D1) and Z or (meth) atoxy-modified xy-group modified silicone oil (D2) are added and subsequently mixed. A method for producing a plastic polyurethane resin composition.

[4] The powdery thermoplastic polyurethane (A),

The above-mentioned plasticizer (C) is added and further mixed. Thereafter, to the obtained mixture, a hydroxyl group-containing aromatic vinyl copolymer (E) having an average particle diameter of 0.1 to 10 m is added, and then mixed. 2. The method for producing a thermoplastic polyurethane resin composition for powder molding according to claim 1, wherein:

[5] Along with the plasticizer (C), a silicone oil (D) is added and further mixed, and then the resulting mixture is The method for producing a thermoplastic polyurethane resin composition for powder molding according to claim 4, wherein the hydroxyl group-containing aromatic vinyl copolymer (E) is added and then mixed.

[6] The hydroxyl group-modified silicone oil (D1) and the Z or (meth) acryloxy group-modified silicone oil (D2) are added together with the plasticizer (C), and further mixed.

6. The method for producing a thermoplastic polyurethane resin composition for powder molding according to claim 4, wherein the hydroxyl group-containing aromatic vinyl copolymer (E) is added and subsequently mixed.

[7] The thermoplastic polyurethane resin composition for powder molding according to any one of [16] to [16], wherein the number average molecular weight of the powdery thermoplastic polyurethane (A) is 10,000 to 50,000. Production method.

[8] The powdery thermoplastic polyurethane (A) is composed of an organic polyisocyanate (A1), a polymer polyol (A2), and, if necessary, a chain extender (A3) and Z or a terminator (A4). The method for producing a thermoplastic polyurethane resin composition for powder molding according to any one of claims 17 to 17, which is to be performed.

9. The thermoplastic polyurethane resin composition for powder molding according to claim 8, wherein the organic polyisocyanate (A1) is an aliphatic polyisocyanate and Z or an alicyclic polyisocyanate. Manufacturing method.

[10] The organic polyisocyanate (A1) power: a group consisting of hexamethylene diisocyanate, isophorone diisocyanate, and a hydrogenated kamite of 4,4′-diphenylmethane diisocyanate. 10. The method for producing a thermoplastic polyurethane resin composition for powder molding according to claim 8, which is one kind.

[11] The method for producing a thermoplastic polyurethane resin composition for powder molding according to any one of claims 8 to 10, wherein the polymer polyol (A2) is a polyester polyol (A21).

12. The thermoplastic polyurethane resin composition for powder molding according to claim 8, wherein the polymer polyol (A2) is a condensate of an aliphatic diol and a dicarboxylic acid conjugate. Method of manufacturing a product.

13. The method for producing a thermoplastic polyurethane resin composition for powder molding according to claim 11, wherein the plasticizer (C) is a phthalic acid ester and a Z or aliphatic dibasic acid ester. .

14. The process for producing a thermoplastic polyurethane resin composition for powder molding according to claim 11, wherein the plasticizer (C) is an aliphatic dibasic acid ester.

[15] a powdery thermoplastic polyurethane (A),

A thermoplastic polyurethane resin composition for powder molding mainly comprising a mixture obtained by adding a plasticizer (C) and then mixing.

[16] The thermoplastic polyurethane resin composition,

Said powdery thermoplastic polyurethane (A),

Said plasticizer (C),

16. The thermoplastic polyurethane resin composition for powder molding according to claim 15, wherein a main component is obtained by adding and subsequently mixing a silicone oil (D).

[17] a powdery thermoplastic polyurethane (A),

A plasticizer (C),

A thermoplastic polyurethane resin composition for powder molding, comprising: a hydroxyl group-modified silicone oil (D1) and a Z or (meth) atoxy group-modified silicone oil (D2).

[18] The thermoplastic polyurethane resin composition,

Said powdery thermoplastic polyurethane (A),

Said plasticizer (C),

Said hydroxyl-modified silicone oil (D1) and Z- or (meth) atari-xy-modified silicone 18. The thermoplastic polyurethane resin composition for molding powder according to claim 17, wherein the thermoplastic polyurethane resin composition is mainly composed of a mixture obtained by successively mixing a wax oil (D2).

[19] a powdery thermoplastic polyurethane (A),

A plasticizer (C),

A thermoplastic polyurethane resin composition for powder molding, comprising: a hydroxyl group-containing aromatic vinyl copolymer (E) having an average particle diameter of 0.1-.

[20] The thermoplastic polyurethane resin composition,

Said powdery thermoplastic polyurethane (A),

The method according to claim 19, wherein the plasticizer (C) is added and subsequently mixed, and then the mixture obtained by adding the hydroxyl group-containing aromatic vinyl copolymer (E) to the obtained mixture is used as a main component. Thermoplastic polyurethane resin composition for powder molding.

21. The thermoplastic polyurethane resin composition for powder molding according to claim 19, wherein the thermoplastic polyurethane resin composition further comprises a silicone oil (D).

[22] The thermoplastic polyurethane for powder molding according to claim 21, wherein the silicone oil (D) is a hydroxyl-modified silicone oil (D1) and a Z- or (meth) atari-hydroxyl-modified silicone oil (D2).榭 Fat composition.

23. The thermoplastic polyurethane resin composition for powder molding according to any one of claims 15 to 22, wherein the number average molecular weight of the powdery thermoplastic polyurethane (A) is 10,000 to 50,000.

[24] The powdery thermoplastic polyurethane (A) is composed of an organic polyisocyanate (A1), a polymer polyol (A2) and, if necessary, a chain extender (A3) and Z or a terminator (A4). 24. The thermoplastic polyurethane resin composition for powder molding according to any one of claims 15 to 23, wherein the composition is prepared.

25. The thermoplastic polyurethane resin set for powder molding according to claim 24, wherein the organic polyisocyanate (A1) is an aliphatic polyisocyanate and Z or an alicyclic polyisocyanate. Adult.

[26] The organic polyisocyanate (A1) power is at least selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, and a hydrogenated product of 4,4′-diphenylmethane diisocyanate. 26. The thermoplastic polyurethane resin composition for powder molding according to claim 24, which is one kind.

[27] The thermoplastic polyurethane resin composition for powder molding according to any one of claims 24-26, wherein the polymer polyol (A2) is a polyester polyol (A21).

[28] The thermoplastic polyurethane resin composition for powder molding according to any one of claims 24-27, wherein the polymer polyol (A2) is a condensate of an aliphatic diol and a dicarboxylic acid conjugate. object.

[29] The thermoplastic polyurethane resin composition for powder molding according to any one of claims 15 to 28, wherein the plasticizer (C) is a phthalate ester and a dibasic or aliphatic dibasic ester.

[30] The thermoplastic polyurethane resin composition for powder molding according to any one of claims 15 to 29, wherein the plasticizer (C) is an aliphatic dibasic acid ester.