JP2006188669A - Resin powder composition for use in slush molding, and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin powder composition for use in slush moldings, which composition causes little fly of aldehyde compounds such as formaldehyde and acetaldehyde from molded automobile interior components. <P>SOLUTION: The resin powder composition comprises (B) a thermoplastic resin powder as the main body and (AO) a compound, preferably in the form of a fine powder, which has a functional group chemically bonding to an aldehyde compound, preferably at least one kind of a functional group selected from the group consisting of an amino group, a functional group having an urea linkage, and a hydrazino group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is a resin powder composition for slush molding mainly composed of thermoplastic resin powder suitable as a molding material for automobile interior parts such as instrument panels and door trims, and using the resin powder composition The present invention relates to a resin powder composition in which molded automobile interior parts and the like have less scattering of aldehyde compounds such as formaldehyde and acetaldehyde.

As for automobile interior materials, attempts have been made to reduce volatile organic compounds (hereinafter referred to as VOC) as in the case of homes and the like. Among adhesives such as rubber, polyurethane, phenolic resin, and acrylic that are used as adhesives for automobile interiors, some adhesives contain components that generate formaldehyde gas. Formaldehyde can diffuse into the car interior.
In order to solve these problems, a physical adsorbent that takes in and traps formaldehyde gas or a chemical adsorbent that chemically reacts with and binds to aldehyde is effective in deodorization (see, for example, Patent Document 1).

However, in recent years, not only adhesives but also thermoplastic resin powders for slush molding, aldehyde compounds such as formaldehyde and acetaldehyde may be generated and remain in the molded product depending on molding conditions and usage environment during molding. I found out.
JP 2003-96430 A

  An object of the present invention is to provide a resin powder composition for slush molding in which molded automobile interior parts and the like have less scattering of aldehyde compounds such as formaldehyde and acetaldehyde.

  As a result of intensive research, the present inventors have been able to reduce aldehyde scattering by adding a chemical adsorbent having a functional group that forms a chemical bond with an aldehyde compound as an aldehyde catcher agent to the thermoplastic resin powder composition. As a result, the present invention has been completed.

  That is, the present invention comprises a resin powder composition for slush molding characterized by comprising a compound (A0) mainly comprising a thermoplastic resin powder (B) and having a functional group chemically bonded to an aldehyde compound, and the same. It is a resin molded product.

  The resin molded product comprising the resin powder composition for slush molding of the present invention has an effect that the scattering of the aldehyde compound can be reduced.

  Examples of the functional group that forms a chemical bond with the aldehyde compound include a functional group having an —NH— bond.

The functional group having an -NH- bond, such as an amino group _(e.g., -NH 2, -NHR), a functional group having a urea bond (e.g. _{-NHCONH 2, -NRCONH 2, -NHCONHR,} -NRCONHR etc.), amides A functional group having a bond (for example, —CONH ₂ , —CONHR, —NHCOR, etc.), a functional group having a —NHNH— bond [for example, —NHNH ₂ (hydrazino group; in this specification, the term hydrazino group is simply referred to as hydrazide (A compound having a structure in which a hydroxy group of an acid is substituted with a hydrazino group, including a -CONHNH ₂ structure.), -NHNHR, etc.)], a functional group having an imide bond (for example, -CONHCO- and the like. In the above, R represents an organic group. Of these, a hydrazino group is preferred as the functional group having a —NHNH— bond.

  Among these, the functional group having an —NH— bond is preferably an amino group, a functional group having a urea bond, or a functional group having an —NHNH— bond, and an amino group, a functional group having a urea bond, and A hydrazino group is more preferable, and a hydrazino group is still more preferable.

  Examples of the compound having an amino group include aliphatic amines, alicyclic amines, aromatic amines, guanidines, amino acids, derivatives of triazine compounds, hydroxylamines, and melamines.

  Examples of the aliphatic amine include methanolamine, ethanolamine, ethylenediamine, dimethylamine, diethylamine, isopropylamine, butylamine, propylenediamine, and diethylenetriamine.

  Examples of alicyclic amines include cyclohexylamine, isophoronediamine, morpholine, and chitosan.

  Examples of the aromatic amine include aniline, aminobenzoic acid, aminobenzoate, and triaminobenzoic acid.

  Examples of amino acids include glycine, alanine, glutamic acid, melanin and the like.

  Examples of guanidines include guanine, guanidine carbonate, and guanylic acid.

  Examples of the derivatives of the triazine compound include 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine.

  Examples of other compounds having an amino group include hydroxylamines and melamines.

  Furthermore, the compound etc. which have an amino bond in the terminal and / or main chain of a thermoplastic resin are mentioned. Examples of the thermoplastic resin include polyethylene, polypropylene, polycarbonate, polyurethane, polyurea, polyacrylate, polymethacrylate, polyvinyl acetate, polyether, polystyrene, polyester, polyvinyl alcohol, polyamide, polyacrylonitrile, and the like.

Examples of the compound having a functional group having a urea bond include urea, thiourea, ethylene urea, acetyl urea, guanyl urea, azodicarbonamide, and the like.
Furthermore, the compound etc. which have a urea bond in the terminal and / or main chain of a thermoplastic resin are mentioned. As said thermoplastic resin, the same thing as the resin quoted as the compound which has an amino bond in the said terminal and / or principal chain is mentioned.

Examples of the compound having a functional group having an amide bond include phthalimide, succinimide, hydantoin, barbituric acid, and isocyanuric acid.
Furthermore, the compound etc. which have an amide bond in the terminal and / or main chain of a thermoplastic resin are mentioned. As said thermoplastic resin, the same thing as the resin quoted as the compound which has an amino bond in the said terminal and / or principal chain is mentioned.

  Examples of the compound having a functional group having an —NHNH— bond include hydrazide (for example, adipic acid dihydrazide, succinic acid dihydrazide, acetohydrazide, benzhydrazide, phthalic acid dihydrazide), hydrazine and the like.

  Furthermore, the compound etc. which have -NHNH- coupling | bonding in the terminal and / or main chain of a thermoplastic resin are mentioned. As said thermoplastic resin, the same thing as the resin quoted as the compound which has an amino bond in the said terminal and / or principal chain is mentioned.

  More preferable compounds (A0) having a functional group that forms a chemical bond with the aldehyde compound are derivatives of triazine compounds and hydrazide, more preferably hydrazide, and particularly preferably adipic acid dihydrazide.

The said compound (A0) can be added in any process in the manufacturing process of a thermoplastic resin powder (B), and can be contained in (B). (A0) is preferably added in the step after granulating (B).
Further, (A0) is more preferably added as a fine powder (A) by dry blending with the thermoplastic resin powder (B).

  From the viewpoint of blocking resistance and powder flowability as a slush molding material, the volume average particle diameter of the fine powder (A) is preferably 0.01 μm or more, more preferably 0.1 μm or more, preferably 20 μm. Hereinafter, it is more preferably 10 μm or less.

  The compound (A0) is preferably used in an amount of 0.1 to 5% by weight, more preferably 0.3 to 4% by weight, based on the weight of the thermoplastic resin powder (B).

As a form of the fine powder (A),
(1) Form in which compound (A0) is supported on inorganic fine particles (A1),
(2) A form mixed with (A0) and the thermoplastic resin (A2) to form a powder, or
(3) The form which made only (A0) into powder form is mentioned.

(1) Form in which (A0) is supported on inorganic fine particles (A1) As the inorganic fine particles (A1), for example, inorganic fine powders such as silica fine powder (volume average particle size 0.1 to 10 μm), calcium carbonate, Examples include calcium fine powders such as calcium sulfate, barium fine powders such as barium carbonate and barium sulfate, magnesium fine powders such as magnesium silicate and magnesium oxide, and mineral fine powders such as talc and clay. Of these, silica fine powder is preferred. The volume average particle size of the inorganic fine particles is preferably 0.01 μm or more, more preferably 0.1 μm or more, preferably 20 μm or less, from the viewpoint of blocking resistance and powder flowability as a slush molding material. Preferably it is 10 micrometers or less. The method of supporting is not particularly limited, but when (A0) is liquid, it is mixed with (A1) as it is. When (A0) is in a powder form of 0.01 μm or more and 20 μm or less, dry blend with (A1). When (A0) is 20 μm or more, a method in which (A0) is dissolved in a soluble solvent, mixed with (A1), and desolvated can be mentioned.

(2) Form in which (A0) and thermoplastic resin (A2) are mixed and powdered The thermoplastic resin (A2) is, for example, polyethylene, polypropylene, polycarbonate, polyurethane, polyurea, polyacrylate, polymethacrylate, polyacetic acid Examples include vinyl, polyether, polystyrene, polyester, polyvinyl alcohol, polyamide, polyacrylonitrile and the like. The mixing method is not particularly limited, and examples thereof include a method in which (A0) and (A2) are melt-mixed, cooled, pulverized, and powdered.

(3) Form in which only (A0) is powdered (A0), which is solid at normal temperature, can be made into a fine powder (A) by pulverizing the powder as it is, for example.

  Further, in the present invention, as the antiblocking agent (C), for example, silica fine powder, crosslinked cyclohexylmaleimide powder, crosslinked polymethylmethacrylate powder and the like can be used in combination with (A). As (C), from the viewpoint of blocking resistance and powder flowability as a slush molding material, the volume average particle diameter is preferably 0.01 μm or more, more preferably 0.1 μm or more, preferably 20 μm. Hereinafter, it is more preferably 10 μm or less.

  (C) is preferably used in an amount of 0 to 3% by weight, more preferably 0 to 1% by weight, based on the weight of the thermoplastic resin powder (B).

  In the present invention, the thermoplastic resin powder (B) is not particularly limited as long as it is a resin powder that can be used for slush molding. Preferable examples (hereinafter described with the thermoplasticity omitted) polyurethane resin powder, vinyl chloride resin powder, polyolefin resin powder, vinyl aromatic resin powder, acrylate resin powder, conjugated diene resin Examples thereof include a powder and a mixture of two or more thereof, and a polyurethane resin powder is particularly preferable.

  The polyurethane-based resin in the polyurethane-based resin powder is a resin composed of a high-molecular polyol, a polyisocyanate, and a low-molecular diol, a low-molecular diamine, if necessary.

Examples of the polyurethane resin powder include those obtained by the following production method.
(1) It has a urethane bond and a urea bond, and is produced by a method of reacting an isocyanate group-terminated urethane prepolymer with a blocked chain extender (for example, a ketimine compound) in the presence of water and a dispersion stabilizer. Specifically, for example, those described in JP-A-8-120041 can be used.
(2) It is produced by a method in which a urethane prepolymer having a urethane bond and a urea bond is reacted with a chain extender (for example, diamine and / or glycol) in the presence of an organic solvent in which the urethane prepolymer does not dissolve and a dispersion stabilizer. Things. Specifically, for example, those described in JP-A-4-202331 can be used.
(3) A mass of a thermoplastic polyurethane resin is obtained by reacting a diisocyanate, a polymer glycol, and a chain extender (low molecular glycol, low molecular diamine) as necessary. Then, it is manufactured by a method of pulverization (for example, freeze pulverization, a method of cutting through pores in a molten state).

  The vinyl chloride resin powder is, for example, a vinyl chloride homopolymer produced by a suspension polymerization method or a bulk polymerization method, or a copolymer mainly composed of a vinyl chloride monomer such as a vinyl chloride monomer and an ethylene vinyl acetate copolymer. Resin powder is mentioned.

  Any polyolefin resin powder can be used as long as it generally belongs to an olefinic thermoplastic elastomer. Further, for example, polyolefins such as ethylene-propylene-diene-rubber (EPM, EPDM) and a propylene polymer are used. And the like, and olefinic thermoplastic elastomers combined with the above. In addition, an olefin thermoplastic elastomer composed of an α-olefin copolymer and a fine powder of an olefin thermoplastic elastomer composed of an α-olefin copolymer and a propylene resin can also be used.

  The vinyl aromatic resin powder includes an aromatic vinyl compound homopolymer, a resin powder of a copolymer of an aromatic vinyl compound and a vinyl monomer, and the like. Examples of the aromatic vinyl compound include styrene, t-butyl styrene, α-methyl styrene, p-methyl srene, divinyl benzene, 1,1-diphenyl styrene, bromo styrene, vinyl styrene, vinyl xylene, fluoro styrene, ethyl styrene, and the like. In particular, styrene and α-methylstyrene are preferable.

  Examples of the acrylate resin powder include a (meth) acrylic acid ester homopolymer, a resin powder of a copolymer of a (meth) acrylic acid ester and a vinyl monomer, and the like.

  The conjugated diene resin powder is a copolymer obtained by hydrogenation or partial hydrogenation of a conjugated diene part in a conjugated diene copolymer. For example, an aromatic vinyl compound-conjugated diene compound random copolymer A hydrogenated product of a coalescence, a hydrogenated product of an aromatic vinyl compound-conjugated diene compound block copolymer, and a resin powder of a hydrogenated product of a conjugated diene compound block copolymer are included.

  The volume average particle size of (B) is preferably in the range of 10 to 500 μm, more preferably 70 to 300 μm.

  (B) is preferably 70% by weight or more, more preferably 80% by weight or more, particularly preferably 90% by weight or more, preferably 99% by weight or less, based on the weight of the resin powder composition for slush molding of the present invention. More preferably, it is 98 weight% or less, Most preferably, it contains 97 weight% or less.

  In addition to the above components (A0) and (B), the slush molding resin powder composition of the present invention may contain, as necessary, an additive aid (as long as it can prevent blocking without causing mold contamination). D) is added. As (D), known and commonly used pigments, inorganic fillers, plasticizers, mold release agents, organic fillers, dispersants, ultraviolet absorbers (light stabilizers), antioxidants, and the like can be added.

  The total amount of (D) added is preferably 0 to 60% by weight, more preferably 10 to 50% by weight, based on the weight of the thermoplastic polyurethane resin powder (B).

Examples of the method for producing the slush molding resin powder composition of the present invention include the following methods.
(1) Dry the thermoplastic resin powder (B), the fine powder (A) comprising the compound (A0) having a functional group that forms a chemical bond with the aldehyde compound, and the additive aid (D) added as necessary. How to blend.
(2) A method in which the thermoplastic resin powder (B) is produced in the presence of the additive (D) added as necessary, and then the fine particle powder (A) is dry blended.
(3) The thermoplastic resin powder (B) is produced in the presence of a pigment as necessary, and the obtained additive (B), (A) and, if necessary, an auxiliary additive (D) other than the pigment are added. How to dry blend.
(4) A method in which (A0) is added in any step during the production process of the thermoplastic resin powder (B) and is contained in (B).
Of these, the method (1) is preferred.

  As a mixing apparatus used for the mixing, a known powder mixing apparatus can be used, and any of a container rotating mixer, a fixed container mixer, and a fluid motion mixer can be used. For example, as a fixed container type mixer, a high-speed flow type mixer, a double-shaft paddle type mixer, a high-speed shear mixing device (Hensiel mixer (registered trademark), etc.), a low-speed mixing device (planetary mixer, etc.) A dry blending method using a machine (Nauta Mixer (registered trademark) or the like) is well known. Among these methods, it is preferable to use a double-shaft paddle type mixer, a low-speed mixing device (planetary mixer or the like), and a conical screw mixer (Nauta mixer (registered trademark, hereinafter omitted) or the like).

The resin molded product comprising the slush molding resin powder composition of the present invention can be molded by a slush molding method. For example, the box containing the powder composition of the present invention and a heated mold are both oscillated and rotated, and after the powder is melted and flowed in the mold, it is cooled and solidified to carry out the method suitably. be able to.
The mold temperature is preferably 200 to 300 ° C, more preferably 210 to 280 ° C.

  The skin thickness molded with the slush molding resin powder composition of the present invention is preferably 0.5 to 1.5 mm. The molded skin can be set as a resin molded product by setting the surface to be in contact with the foaming mold, pouring urethane foam, and forming a foamed layer of 5 mm to 15 mm on the back surface.

  The resin molded product of the present invention is suitably used for automobile interior materials such as instrument panels and door trims.

Examples Hereinafter, the present invention will be described in more detail with reference to production examples and examples, but the present invention is not limited thereto.
In the examples, all parts represent parts by weight unless otherwise specified.

Measurement method of volume average particle diameter In the following, measurement of the volume average particle diameter was carried out by Nikkiso Co., Ltd., Microtrac HRA9320-X100. The volume average particle diameter is an average value of two measured values of D50 measured values.

Production Example 1
Production of prepolymer solution In a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, polybutylene adipate (575 parts) having a number average molecular weight (hereinafter referred to as Mn) of 1000 and polyhexamethylene having an Mn of 900 After adding isophthalate (383 parts) and 1-octanol (16.8 parts) and purging with nitrogen, the mixture was heated to 110 ° C. with stirring and melted, and cooled to 60 ° C. Subsequently, hexamethylene diisocyanate (242 parts) was added and reacted at 85 ° C. for 6 hours. Next, after cooling to 60 ° C., tetrahydrofuran (217 parts), stabilizer (2.5 parts) [manufactured by Ciba Specialty Chemicals Co., Ltd., Irganox 1010] and titanium oxide (15.3 parts) [Taipeke R -820, manufactured by Ishihara Sangyo Co., Ltd.] was added and mixed uniformly to obtain a prepolymer solution. The obtained prepolymer solution had an NCO content of 2.2%.

Production Example 2
Production of MEK ketimine product of diamine Hexamethylenediamine and excess MEK (methyl ethyl ketone (hereinafter the same), 4 times molar amount with respect to diamine) were refluxed at 80 ° C. for 24 hours, and the generated water was removed out of the system. Thereafter, unreacted MEK was removed under reduced pressure to obtain a MEK ketiminate.

Production Example 3
Production of Thermoplastic Polyurethane Resin Powder Into a reaction vessel, the prepolymer solution (100 parts) obtained in Production Example 1 and the MEK ketimine compound (5.6 parts) obtained in Production Example 2 are added, and a dispersant [ 340 parts by weight of an aqueous solution in which Sanyo Kasei Kogyo Co., Ltd. Sunspear PS-8] (1.3 parts by weight) is dissolved is added and mixed for 1 minute at a rotation speed of 9000 rpm using an ultradisperser made by Yamato Scientific Co., Ltd. did. This mixture was transferred to a reaction vessel equipped with a thermometer, a stirrer and a nitrogen blowing tube, purged with nitrogen, and then reacted at 50 ° C. for 10 hours with stirring. After completion of the reaction, filtration and drying were performed to produce a thermoplastic polyurethane resin powder (B-1). Mn of (B-1) was 25,000, and the volume average particle size was 151 μm.

Example 1
In a 100 L Nauta mixer, 100 parts of thermoplastic polyurethane resin powder (B-1) and 20 parts of polyethylene glycol dibenzoate [manufactured by Sanyo Chemical Industries, Ltd .; Sunfix EB300] as a plasticizer are added at 70 ° C. For 3 hours. Next, 0.1 part of modified dimethylpolysiloxane [manufactured by Shin-Etsu Chemical Co., Ltd .; KF96] was added as a release agent and mixed for 1 hour, and then cooled to room temperature to obtain a resin powder composition (P-1). . Next, Chemcatch H1100 [hydrazide compound, manufactured by Otsuka Chemical Co., Ltd., volume average particle size 7 μm] (A-1) 0.5 part as a compound having a functional group that forms a chemical bond with an aldehyde compound, crosslinked as an antiblocking agent 0.5 parts of cyclohexylmaleimide powder (volume average particle size 3 μm) was added and mixed to obtain a slush molding resin powder composition (S-1). The volume average particle diameter of (S-1) was 152 μm. The content of the compound (A0) with respect to the thermoplastic resin powder (B) was 0.5% by weight.

Example 2
In the same manner as in Example 1, in a 100 L Nauta mixer, 120.1 parts of resin powder composition (P-1) and Chemcatch N1180 (made by Otsuka Chemical Co., Ltd., volume average particle size 5 μm) as (A0) (A -2) and 1 part of a cross-linked cyclohexylmaleimide powder (volume average particle size 3 μm) 0.5 parts were charged and mixed to obtain a slush molding resin powder composition (S-2). The volume average particle diameter of (S-2) was 152 μm. The content of the compound (A0) with respect to the thermoplastic resin powder (B) was 1% by weight.

Example 3
In the same manner as in Example 1, in a 100 L Nauta mixer, 120.1 parts of the resin powder composition (P-1) and 2,4-diamino-6- [2′-methylimidazolyl which is a triazine compound as (A0) -(1 ')]-ethyl-s-triazine [trade name Curesol 2MZ-A (manufactured by Shikoku Kasei Kogyo Co., Ltd.), volume average particle size 4 μm] (A-3) 0.5 part, crosslinked cyclohexylmaleimide powder ( 0.5 parts of a volume average particle diameter of 3 μm) was charged and mixed to obtain a slush molding resin powder composition (S-3). The volume average particle diameter of (S-3) was 152 μm. The content of the compound (A0) with respect to the thermoplastic resin powder (B) was 0.5% by weight.

Example 4
In the same manner as in Example 1, in a 100 L Nauta mixer, 120.1 parts of resin powder composition (P-1), 0.5 part of (A-1), crosslinked polymethylmethacrylate powder (volume average) as an antiblocking agent 0.5 parts of a particle size of 10 μm) was added and mixed to obtain a slush molding resin powder composition (S-4). The volume average particle diameter of (S-4) was 153 μm. The content of the compound (A0) with respect to the thermoplastic resin powder (B) was 0.5% by weight.

Example 5
In the same manner as in Example 1, in a 100 L Nauta mixer, 120.1 parts of resin powder composition (P-1), 0.5 part of (A-1), silica fine powder [manufactured by GRACE DAVISON, Silo block S200 (volume average particle size 5 μm)] 0.3 part was added and mixed to obtain a resin powder composition for slush molding (S-5). The volume average particle diameter of (S-5) was 151 μm. The content of the compound (A0) with respect to the thermoplastic resin powder (B) was 0.5% by weight.

Example 6
As in Example 1, in a 100 L Nauta mixer, 120.1 parts of the resin powder composition (P-1), 1 part of adipic acid dihydrazide [volume average particle size 4 μm], silica fine powder [GRACE as an antiblocking agent] DAVISON made silo block S200] 0.3 parts was added and mixed to obtain a slush molding resin powder composition (S-6). The volume average particle diameter of (S-6) was 150 μm. The content of the compound (A0) with respect to the thermoplastic resin powder (B) was 1% by weight.

Example 7
As in Example 1, in a 100 L Nauta mixer, 120.1 parts of resin powder composition (P-1), 3 parts of adipic acid dihydrazide [volume average particle size 4 μm], silica fine powder [GRACE as an antiblocking agent] DAVISON made silo block S200] 0.3 parts was charged and mixed to obtain a slush molding resin powder composition (S-7). The volume average particle diameter of (S-7) was 150 μm. The content of the compound (A0) with respect to the thermoplastic resin powder (B) was 3% by weight.

Example 8
In the same manner as in Example 1, in a 100 L Nauta mixer, 120.1 parts of resin powder composition (P-1), 2 parts of benzhydrazide [volume average particle diameter 2 μm], silica fine powder [GRACE DAVISON as an antiblocking agent] Manufactured, silo block S200] 0.3 parts was added and mixed to obtain a slush molding resin powder composition (S-8). The volume average particle diameter of (S-8) was 151 μm. The content of the compound (A0) with respect to the thermoplastic resin powder (B) was 2% by weight.

Comparative Example 1
In the same manner as in Example 1, 120.1 parts of the resin powder composition (P-1) and 0.5 part of the cross-linked cyclohexylmaleimide powder (volume average particle size 3 μm) were added and mixed in a 100 L Nauta mixer, and slush molding was performed. Resin powder composition (S-6 ′) was obtained. The volume average particle diameter of (S-6 ′) was 153 μm.

Comparative Example 2
In the same manner as in Example 1, in a 100 L Nauta mixer, 120.1 parts of the resin powder composition (P-1) and the deodorant composition 0 listed in Example 2 of JP-A-2003-70887 as an aldehyde catcher agent 0 0.5 part, 0.5 part of a cross-linked cyclohexylmaleimide powder (volume average particle size 3 μm) as an antiblocking agent was added and mixed to obtain a slush molding resin powder composition (S-7 ′). The deodorant composition is 0.12 part of Bincho charcoal (cooperative latest production) having a volume average particle size of about 5 μm, which is carbonized and fired at 700 ° C. or higher, and volume average particles which are carbonized and fired in the range of 300 to 500 ° C. Black coal with a diameter of about 4 μm (cooperative latest manufacture) 0.30 parts, zeolite powder (manufactured by Nitto Flour Industry) 0.06 parts, copper phthalocyanine with a volume average particle diameter of 10 nm (manufactured by Ciba) 0.01 parts, iron phthalocyanine (Sanyo dye production) 0.01 parts were mixed and prepared. The volume average particle diameter of (S-7 ′) was 153 μm.

  Slush molding resin powder compositions (S-1) to (S-8) of Examples 1 to 8 and Slush molding resin powder compositions (S-6 ′) to (S-7) of Comparative Examples 1 and 2 ') Was used to measure the angle of repose, meltability, and aldehyde volatilization by the methods shown below, and the results are shown in Tables 1 and 2.

<Evaluation method>
-Angle of repose In order to evaluate the powder fluidity of the resin powder composition for slush molding, the angle of repose was measured with a powder tester (PT-R type manufactured by Hosokawa Micron Corporation). The measurement was carried out in a temperature-controlled room adjusted to a temperature of 23 ± 0.5 ° C. and a humidity of 50 ± 2%. The smaller the angle of repose, the better the powder flowability.

-Meltability A Ni electric mold having a grain pattern preheated to 270 ° C was filled with a resin powder composition for slush molding, and after 10 seconds, an excess powder resin powder composition was discharged. After heating at 270 ° C. for another 90 seconds, it was cooled with water to prepare a skin (thickness 1 mm).
The state of the back surface of the obtained skin was visually confirmed. Evaluation was made according to the following criteria.
○: Melted uniformly and glossy.
(Triangle | delta): Although there exists some unmelted powder | flour, it has gloss.
X: The back surface is not glossy.

・ Measurement of aldehyde volatilization Test environment The test was conducted in a room of 23 ± 2 ° C. and a relative humidity of 50 ± 5% in principle.
2. Preparation of test piece By the above molding, the obtained skin was cut into 8 × 10 cm test pieces.
3. Heating method of test piece The following procedure was followed.
(1) 10L tedlar with a one-sleeve (registered trademark; hereinafter omitted) Back (sleeve outer diameter φ7) (GL Science AA-10) is connected to a silicon tube (inner diameter φ6.5) and a stop valve is attached. .
(2) Fill the Tedlar bag with pure nitrogen gas.
(3) The filled pure nitrogen gas is extracted with an aspirator.
(4) Repeat operations (2) and (3) twice.
(5) Cut one end of the tedlar bag with scissors.
(6) 2. After weighing the test piece prepared in step (1), a protective tape (Nakajima Kasei Kogyo Flow Adhesive Tape: ASF-110) for preventing diffusion is applied to the cut surface, and then placed in a tedlar bag.
(7) Double-fold one end of the Tedlar bag and seal with a wide range of tape.
(8) Put an appropriate amount of pure nitrogen gas into the tedlar bag.
(9) The nitrogen gas is removed with an aspirator.
(10) Thereafter, 4 L of pure nitrogen gas is filled into the Tedlar bag using a flow meter, and the stop valve attached to the silicon tube is closed.
(11) A Teflon (registered trademark) tube (outer diameter φ6) of about 20 cm is attached to the tip of the silicon tube.
(12) Put the Tedlar bag in the circulating dryer, take out the Teflon (registered trademark) tube from the hole of the circulating dryer upper thermometer, and fasten the Teflon (registered trademark) tube with a clip.
(13) A silicon tube (inner diameter φ6) of about 3 cm is attached to the tip of the Teflon (registered trademark) tube.
(14) Heat in this state at 65 ° C. for 2 hours.
4). Method for collecting aldehydes The following procedure was followed.
(1) As a method for collecting aldehydes, a DNPH cartridge (Sep-Pak (registered trademark) Long manufactured by Water) is used.
(2) The DNPH cartridge is connected via a silicon tube, and the downstream side is connected to a pump (Shibata Kagaku MP-Σ300) and a rotary flow meter (Shinagawa DC-1C).
(3) The entire amount of gas in the tedlar bag is sampled at a sampling rate of 0.1 L / min.
(4) After completion of air sampling, tighten the plug of the DNPH cartridge.
(5) Store in the refrigerator until analysis.
5. Quantification of aldehyde content by high performance liquid chromatography The DNPH cartridge after collection was analyzed by the following procedure.
(1) Take acetonitrile into a 6 mL syringe, connect to one end of a DNPH cartridge and slowly extract. The receiver uses a 10 mL test tube or the like.
(2) Further, after the solvent is discharged, a small amount of air is taken into the syringe and all the solvent remaining in the DNPH cartridge is distilled off.
(3) Since acetonitrile is highly volatile, it should be sealed immediately.
(4) The acetonitrile solution of (3) is analyzed using a high performance liquid chromatograph.
Analysis condition analyzer: Shimadzu HPLC VP
Detector: UV360nm
Column: GL Sciences INTERSIL ODS-80
Developing solution: acetonitrile 55%-water 45%
Column temperature: 40 ° C
6). Calculation of aldehyde volatilization amount The aldehyde volatilization amount from the test piece was calculated by the following formula. However, the case where the said operation was implemented without the skin was made into the blank value.
(Aldehyde volatilization amount μg / piece)
= (Analysis value by liquid chromatography)-(blank value)

The skin formed from the resin powder composition for slush molding of the present invention is suitably used as a skin for automobile interior materials such as instrument panels and door trims.

Claims (12)

  A slush molding resin powder composition comprising a thermoplastic resin powder (B) as a main component and a compound (A0) having a functional group that forms a chemical bond with an aldehyde compound.   The resin powder composition according to claim 1, wherein the compound (A0) is a fine powder (A).   The resin powder composition according to claim 1 or 2, wherein the compound (A0) is a compound having at least one functional group selected from the group consisting of an amino group, a functional group having a urea bond, and a hydrazino group.   The resin powder composition according to claim 3, wherein the compound (A0) is a derivative of a triazine compound.   The resin powder composition according to claim 4, wherein the compound (A0) is 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine.   The resin powder composition according to claim 3, wherein the compound (A0) is hydrazide.   The fine powder (A) is a form in which the compound (A0) is supported on the inorganic fine particles (A1), the form obtained by mixing the (A0) and the thermoplastic resin (A2), and the form (A0) The resin powder composition according to any one of claims 2 to 6, wherein the resin powder composition is in a powder form only.   The resin powder composition according to any one of claims 2 to 7, wherein the fine powder (A) has a volume average particle size of 0.01 µm or more and 20 µm or less.   The resin powder composition according to any one of claims 1 to 8, wherein the compound (A0) is contained in an amount of 0.1 wt% or more and 5 wt% or less with respect to the thermoplastic resin powder (B).   The resin powder composition according to any one of claims 1 to 9, wherein the thermoplastic resin powder (B) is a thermoplastic polyurethane resin powder.   The resin molded product which consists of a resin powder composition in any one of Claims 1-10. The resin molded product according to claim 11, which is an automobile interior material.