WO2009084175A1 - 粉末状熱可塑性ポリウレタン樹脂組成物、並びにそれを用いた二層構造を有するシート状ポリウレタン樹脂成形物及びその製造方法 - Google Patents
粉末状熱可塑性ポリウレタン樹脂組成物、並びにそれを用いた二層構造を有するシート状ポリウレタン樹脂成形物及びその製造方法 Download PDFInfo
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- WO2009084175A1 WO2009084175A1 PCT/JP2008/003864 JP2008003864W WO2009084175A1 WO 2009084175 A1 WO2009084175 A1 WO 2009084175A1 JP 2008003864 W JP2008003864 W JP 2008003864W WO 2009084175 A1 WO2009084175 A1 WO 2009084175A1
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- polyurethane resin
- thermoplastic polyurethane
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- resin composition
- molded product
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/18—Slush casting, i.e. pouring moulding material into a hollow mould with excess material being poured off
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/584—Scratch resistance
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Definitions
- the present invention relates to a powdery thermoplastic polyurethane resin composition, a sheet-like polyurethane resin molded article having a two-layer structure using the same, and a method for producing the same. More specifically, a sheet-like molded article having a two-layer structure of a foamed layer and a non-foamed layer that has a soft tactile sensation, is excellent in wear resistance, mechanical properties, etc., and realizes weight reduction and cost reduction of the molded product.
- the present invention relates to a powdery thermoplastic polyurethane resin composition capable of obtaining a resin composition, a sheet-like polyurethane resin molded article having a two-layer structure using the same, and a method for producing the same.
- the powder slush molding method has a complicated shape and can be efficiently molded into a product having a uniform thickness, and is therefore widely used for automobile interior materials and the like. Recently, a powdered thermoplastic polyurethane resin excellent in flexibility has been adopted as a powder slush molding material.
- Patent Document 1 Japanese Examined Patent Publication No. 63-27167
- a resin containing a plasticizer has problems of fogging due to volatilization of the plasticizer, loss of softness due to migration of the plasticizer to the surface of the molded article, and deterioration of durability in a long-term use.
- the present invention provides a sheet-like molded article having a two-layer structure of a foamed layer and a non-foamed layer that has a soft tactile feel, is excellent in wear resistance, mechanical properties, etc., and realizes weight reduction and cost reduction of the molded product.
- An object of the present invention is to provide a powdery thermoplastic polyurethane resin composition that can be obtained, a sheet-like polyurethane resin molded article having a two-layer structure using the composition, and a method for producing the same.
- the present invention is as shown in the following (1) to (7).
- a powdery thermoplastic polyurethane resin (A1) having an average particle size of 100 to 350 ⁇ m and a powdery pyrolytic foaming agent (A2) having an average particle size of 20 ⁇ m or less are 0.2 to 1 relative to (A1).
- the foamed layer (a) derived from the powdery thermoplastic polyurethane resin composition (A) of (1) or (2) and the powdery thermoplastic polyurethane resin composition (B) not containing a foaming agent.
- the thickness ratio of the non-foamed layer (b) is 0.08 to 0 with respect to the total thickness of the sheet-like polyurethane resin molded article having a two-layer structure comprising the foamed layer (a) and the non-foamed layer (b).
- the powdery thermoplastic polyurethane resin composition (1) or (2) above After melting the powdery thermoplastic polyurethane resin composition (B) containing no foaming agent on the mold surface, the powdery thermoplastic polyurethane resin composition (1) or (2) above ( The sheet-like polyurethane having the two-layer structure of (3) or (4), wherein A) is laminated, and the non-foamed layer and the foamed layer are integrally formed by melting and foaming the powder resin by heating Manufacturing method of resin molding.
- First step A powdery thermoplastic polyurethane resin composition (B) containing no foaming agent is charged into a mold preheated to 200 ° C. to 300 ° C., and the mold is inverted to remove excess powder material.
- the process of adhering and melting (B) with a uniform thickness on the mold surface Second process: The powdery thermoplastic polyurethane resin composition of the above (1) or (2) with (B) adhered to the mold Step (3): charging the product (A), inverting the mold to remove excess powder material, and depositing (A) on the layer (B) with a predetermined thickness: 200 to 400 ° C.
- the mold with the (B) layer and (A) layer laminated and placed in the heating oven is placed for 30 to 120 seconds to complete the melting and foaming of the powder resin, and then removed from the heating oven to cool the mold. After demolding the molded product
- First step A powdery thermoplastic polyurethane resin composition (B) containing no foaming agent is charged into a mold preheated to 200 ° C. to 300 ° C., and the mold is inverted to remove excess powder material.
- the process of adhering and melting (B) with a uniform thickness on the mold surface Second process: The powdery thermoplastic polyurethane resin composition of the above (1) or (2) with (B) adhered to the mold Step (3): charging the product (A), inverting the mold to remove excess powder material, and depositing (A) with a predetermined thickness on the layer (B); (A) The mold with the laminated layers is self-heated at 200 ° C. to 300 ° C. for 30 to 120 seconds to complete the melting and foaming of the powder resin, and after cooling the mold, the molded product is removed. Molding process
- a sheet-like molded article having a two-layer structure of a foamed layer and a non-foamed layer that has a soft tactile sensation is excellent in wear resistance, mechanical properties, etc., and realizes weight reduction and cost reduction of the molded product. It has become possible to provide a powdery thermoplastic polyurethane resin composition that can be obtained, a sheet-like polyurethane resin molded product having a two-layer structure using the same, and a method for producing the same.
- the powdery thermoplastic polyurethane resin composition (A) of the present invention comprises a powdery thermoplastic polyurethane resin (A1) having an average particle size of 100 to 350 ⁇ m and a powdery pyrolytic foaming agent (A2) having an average particle size of 20 ⁇ m or less. Is compounded at a ratio of 0.2 to 1.0 mass% with respect to (A1).
- the average particle size of the powdered thermoplastic polyurethane resin (A1) used in the present invention is 100 to 350 ⁇ m, preferably 100 to 200 ⁇ m.
- the shape of (A1) is spherical, and the ratio of the minor axis to the major axis (minor axis / major axis) is preferably 0.5 to 1.0, particularly preferably 0.8 to 1.0.
- Examples of the powdered thermoplastic polyurethane resin (A1) used in the present invention include those formed from isocyanate group-terminated prepolymers.
- An isocyanate group-terminated prepolymer obtained by reacting a polymer polyol, an organic polyisocyanate, and a monofunctional active hydrogen group-containing compound hereinafter referred to as “isocyanate group-terminated prepolymer (1)”
- -An isocyanate group-terminated prepolymer obtained by reacting a polymer polyol, an organic polyisocyanate, a monofunctional active hydrogen group-containing compound and a bifunctional active hydrogen group-containing compound hereinafter referred to as "isocyanate group-terminated prepolymer (2)" .
- the number average molecular weight of the polymer polyol used for obtaining the isocyanate group-terminated prepolymer is 500 or more, preferably 1,000 to 5,000.
- the type of polymer polyol is not particularly limited, Examples include polyester polyols, polyester amide polyols, polyether polyols, polyether / ester polyols, polycarbonate polyols, polyolefin polyols and the like, and these are used alone or in combination.
- the polymer polyol in the present invention is preferably a polyester polyol.
- polyester polyol and polyester amide polyol examples include polycarboxylic acids, polycarboxylic acid dialkyl esters, acid anhydrides, acid halides and other polycarboxylic acid derivatives, (number average) a low molecular polyol having a molecular weight of less than 500, a low molecular polyamine, It is obtained by a reaction with a low molecular active hydrogen group-containing compound such as a low molecular amino alcohol.
- polycarboxylic acid examples include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid and the like.
- Low molecular polyols include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-butanediol (hereinafter abbreviated as 1,4-BD), 1,5-pentanediol, 1,6-hexanediol (hereinafter abbreviated as 1,6-HD), 3-methyl-1,5-pentane Diol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-ethyl-1,3-propanediol, 2- Normal propyl-1,3-propanediol, 2-isopropyl-1,3-
- Examples of the low molecular weight polyamine having a number average molecular weight of less than 500 include ethylenediamine, hexamethylenediamine, xylylenediamine, isophoronediamine, and ethylenetriamine.
- Examples of the low molecular amino alcohol having a number average molecular weight of less than 500 include monoethanolamine, diethanolamine, and monopropanolamine.
- polyester polyols such as lactone polyester polyols obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ⁇ -caprolactone, alkyl-substituted ⁇ -caprolactone, ⁇ -valerolactone, and alkyl-substituted ⁇ -valerolactone.
- lactone cyclic ester
- polyether polyol examples include polyethylene glycol, polypropylene ether polyol, polytetramethylene ether polyol, and the like.
- polyether ester polyols examples include polyester polyols produced from the above polyether polyols and the above polycarboxylic acid derivatives.
- the polycarbonate polyol is generally a deethanol condensation reaction of a low molecular polyol and diethyl carbonate, a demethanol condensation reaction of a low molecular polyol and dimethyl carbonate, a dephenol condensation reaction of a low molecular polyol and diphenyl carbonate, or a low molecular polyol.
- This low molecular polyol obtained by deethylene glycol condensation reaction of ethylene carbonate and the like includes the low molecular polyol used to obtain the above-mentioned polyester polyol.
- polyolefin polyol examples include a hydroxyl group-terminated polybutadiene, a hydrogenated product thereof, and a hydroxyl group-containing chlorinated polyolefin.
- Preferred polymer polyols are polyester polyols, polyether polyols, and polycarbonate polyols having an average molecular weight of 1,000 to 5,000 because of the good physical properties and feel of the molded product obtained.
- a polyester polyol having a molecular weight of 1,000 to 5,000 is preferable, and a polyester polyol using 30 mol% or more of an aromatic dicarboxylic acid as an acid component is particularly preferable.
- Organic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, tetramethylxylene diisocyanate, 4,4'-diphenylmethane diisocyanate 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'- Diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate , Aromatic diiso
- the ratio of the polymer polyol used to obtain the isocyanate group-containing prepolymer and the organic polyisocyanate is such that the molar ratio of the latter isocyanate group to the hydroxyl group possessed by the former ([NCO] / [OH]) is 1.
- the ratio is preferably from 0.05 to 5.0, and more preferably from 1.3 to 2.5.
- the monofunctional active hydrogen group-containing compound used for adjusting the molecular weight of the powdered thermoplastic polyurethane resin (A1) is an active hydrogen group-containing compound having an active hydrogen group and a hydrocarbon group having 4 to 12 carbon atoms. is there.
- Examples of the “active hydrogen group” possessed by the monofunctional active hydrogen group-containing compound include a hydroxyl group (—OH), an imino group (> NH), and an amino group (—NH 2 ).
- Examples of the “hydrocarbon group having 4 to 12 carbon atoms” possessed by the monofunctional active hydrogen group-containing compound include an alkyl group and an alkenyl group.
- the carbon number of the “hydrocarbon group” contained in the monofunctional active hydrogen group-containing compound is 4 to 12, preferably 4 to 11, and more preferably 4 to 9.
- an active hydrogen group-containing compound having less than 4 carbon atoms is used, the prepolymerization reaction becomes incomplete because the boiling point is low and the compound tends to evaporate out of the reaction system, and the molecular weight of the resulting resin cannot be controlled.
- an active hydrogen group-containing compound having more than 12 carbon atoms is used, blooming occurs in a molded product of the resulting resin.
- the monofunctional active hydrogen group-containing compound examples include di-n-butylamine, di-isobutylamine, di-t-butylamine, di-n-hexylamine, di-cyclohexylamine, di-n-octylamine, Dialkylamines (secondary amines) such as di-2-ethylhexylamine, di-n-nonylamine, di-dodecylamine; dialkenylamines such as di-allylamine; alkylamines (primary amine) such as dodecylamine; Examples include monools such as n-butanol, isobutanol, n-octanol, 2-ethylhexanol, n-nonanol, n-decanol, lauryl alcohol, and cyclohexanol. These may be used alone or in combination of two or more. Can be used. Of these, dialkylamine is preferred
- the bifunctional active hydrogen group-containing compound used for obtaining the isocyanate group-terminated prepolymer (2) is a bifunctional active hydrogen group-containing compound having a number average molecular weight of less than 500.
- bifunctional active hydrogen group-containing compound examples include compounds exemplified as low molecular polyols used to obtain polyester polyols which are high molecular polyols, and these may be used alone or in combination of two or more. Can be used. Of these, 1,4-BD and 1,6-HD are preferable.
- the water used for obtaining the powdered thermoplastic polyurethane resin (A1) used in the present invention can be used as a chain extender for the isocyanate group-terminated prepolymer and at the same time can serve as a dispersion medium.
- thermoplastic polyurethane resin A1
- Method of obtaining powder of (A1) by freeze-pulverizing TPU pellets (2) Dispersing isocyanate group-terminated prepolymer in a non-aqueous dispersion medium that does not dissolve and reacting with water to extend the chain (3)
- the shape of the obtained resin is spherical and powder
- the methods (2) and (3) are preferred because a good fluidity can be obtained.
- the powdered thermoplastic polyurethane resin (A1) used in the present invention has a number average molecular weight (Mn) of a component related to the main peak having the maximum peak area in a chart obtained by measuring this by gel permeation chromatography (GPC). Is preferably 18,000 to 50,000, more preferably 20,000 to 45,000. When the number average molecular weight (Mn) is too small, sufficient mechanical properties and durability cannot be imparted to the finally obtained molded product. On the other hand, when the number average molecular weight (Mn) is excessive, suitable melt moldability cannot be exhibited.
- Mn number average molecular weight
- An additive can be added to the powdered thermoplastic polyurethane resin (A1) used in the present invention as necessary.
- additives include pigments / dyes, antioxidants, UV absorbers, plasticizers, blocking agents, radical polymerization initiators, coupling agents, flame retardants, inorganic and organic fillers, lubricants, antistatic agents, and crosslinking agents. Etc.
- Suitable examples of powdered pigments include carbon black dispersion pigment “PV-817”, titanium oxide dispersion pigment “PV-7A1301”, and titanium oxide dispersion pigment “PV-346” manufactured by Sumika Color Co., Ltd. It is also possible to use a mixture that has been mixed in advance according to the target color tone.
- the addition amount of the pigment is usually 5% or less, preferably 0.5 to 2.0% with respect to the powdered thermoplastic polyurethane resin.
- an auxiliary agent may be used in combination.
- auxiliary agents include plasticizers, silane coupling agents, silicone oils, etc., preferably plasticizers containing ester groups in the molecule, particularly preferred are ether-based active hydrogen compounds and mono- or di-acids.
- plasticizers particularly preferred are ether-based active hydrogen compounds and mono- or di-acids.
- it is an ether ester plasticizer having an ether group and an ester group in the molecule by an esterification reaction with tricarboxylic acid.
- Examples of the powdered pyrolytic foaming agent (A2) include those shown below.
- Azo compounds azodicarbonamide (hereinafter abbreviated as ADCA), 2,2'-azobisisobutyronitrile, azohexahydrobenzonitrile, diazoaminobenzene, etc.
- Nitroso compounds N, N'-dinitrosopentamethylenetetramine Sulfohydrazine compounds such as N, N'-dinitroso-N, N'-dimethylterephthalamide: benzenesulfonyl hydrazide, benzene-1,3-disulfonyl hydrazide, diphenylsulfone-3,3'-disulfonyl hydrazide, 4, Inorganic compounds such as 4'-oxybis (benzenesulfonylhydrazide) (hereinafter abbreviated as OBSH): sodium bicarbonate These can be used alone or in admixture of two or more.
- OBSH 4'-oxybis (benzenesulfonylhydrazide)
- the preferred pyrolytic foaming agent (A2) in the present invention has a decomposition gas release temperature of 120 to 250 ° C., particularly preferably 130 to 210 ° C. Furthermore, in consideration of the risk of explosion and the environmental impact of the generation of toxic gas at the time of decomposition, those selected from ADCA, OBSH, and sodium bicarbonate are preferable, and ADCA is particularly preferable.
- the average particle size of the pyrolytic foaming agent (A2) used in the present invention is 20 ⁇ m or less, preferably 10 ⁇ m or less, particularly preferably 6 ⁇ m or less.
- the average particle size of (A2) is too large, the expansion ratio is reduced due to non-uniform foaming, the cells are non-uniform, voids are generated, and the touch feeling is deteriorated, and the mechanical properties and durability are low. descend.
- the amount of (A2) in the powdery thermoplastic polyurethane resin composition (A) of the present invention is 0.2 to 1.0% by mass, preferably 0.4 to 1.0% by weight based on (A1).
- the amount is 0.8 mass%, more preferably 0.4 to 0.7 mass%.
- Examples of the method for producing the resin composition (A) include (a) compounding powders, (b) blending (A2) at any stage in the production of (A1), and the like. Since the method (b) may give an extra thermal history to (A2), the method (b) is preferred.
- a powdered thermoplastic polyurethane resin (A1) is charged into a high-speed stirring and mixing apparatus such as a Henschel mixer or a super mixer, and then a powdered pyrolytic foaming agent (A2) is added.
- A) can be produced by stirring and mixing at 1,000 rpm to uniformly adhere (A2) to the particle surface of (A1).
- a high-speed stirring and mixing apparatus such as a Henschel mixer or a super mixer
- A2 powdered pyrolytic foaming agent
- the average particle size of the powdered thermoplastic polyurethane resin (A1) used in the present invention is 100 to 350 ⁇ m, more preferably 100 to 200 ⁇ m. If the average particle size is excessive, pinholes are likely to occur in the undercut portions and corner portions of the obtained molded product. On the other hand, when the average particle size is too small, flowability and powder breakage are deteriorated, and the thickness of the obtained molded product tends to be nonuniform.
- the “average particle diameter” means a value of a cumulative percentage of 50% in a particle diameter distribution (volume distribution) curve measured by a laser diffraction particle size analyzer.
- the flow time of the powdered thermoplastic polyurethane resin (A1) used in the present invention is preferably 20 seconds or less. If the flow-down time is too long, flowability and powder breakage will deteriorate, and powdered resin will not get stuck in the undercut and corner parts, resulting in missing parts in the molded product or uneven thickness. It is easy to become.
- the shape of the powdered thermoplastic polyurethane resin (A1) used in the present invention is preferably a spherical shape with good powder flowability (flowability during molding). Moreover, it is preferable that the angle of repose of the said powdery thermoplastic polyurethane resin is 35 degrees or less, More preferably, it is 33 degrees or less. When the angle of repose is excessive, the flowability at the time of molding is deteriorated, and molding defects are likely to occur.
- the sheet-like polyurethane resin molded product having a two-layer structure of the present invention includes a foamed layer (a) derived from the powdered thermoplastic polyurethane resin composition (A) containing the foaming agent and a powder not containing the foaming agent.
- the non-foamed layer (b) derived from the thermoplastic thermoplastic resin composition (B) has a fused structure.
- additives such as pigments, dyes, catalysts, light stabilizers, plasticizers, fillers, antioxidants, flame retardants and the like may be blended.
- the ratio of the thickness of the non-foamed layer (b) to the total thickness of the molded product is 0.08 to 0.6, preferably 0.1 to 0.5, more preferably 0.12 to 0.00. 4.
- the proportion of the non-foamed layer (b) is too large, the weight of the molded product as a whole cannot be reduced, and a soft touch is unlikely to occur. If it is too small, voids appear on the surface and the appearance tends to be poor, the design properties are lowered, and the mechanical properties and durability of the molded product as a whole tend to be insufficient.
- the powdered thermoplastic polyurethane resin (A1) in (A) and the powdered thermoplastic polyurethane resin in (B) may be the same or different.
- the raw material polymer polyol of the powdered thermoplastic polyurethane resin (A1) in (A) and the powdered thermoplastic polyurethane resin in (B) is, for example, It is preferable to use the same type of polyester.
- the method for producing a sheet-like polyurethane resin molded product having a two-layer structure of the present invention is obtained by melting the powdered thermoplastic polyurethane resin composition (B) containing no foaming agent on the mold surface, and then adding the powdery thermoplastic polyurethane resin composition (B) thereon.
- the powdery thermoplastic polyurethane resin composition (A) containing a foaming agent is laminated, and the powder resin is melted and foamed by heating to integrally form the non-foamed layer and the foamed layer.
- Method A A method for indirectly heating a mold, characterized by passing through the following three steps.
- First step A powdery thermoplastic polyurethane resin composition (B) containing no foaming agent is charged into a mold preheated to 200 ° C. to 300 ° C., and the mold is inverted to remove excess powder material.
- Second process The powdery thermoplastic polyurethane resin composition of the above (1) or (2) with (B) adhered to the mold
- Step (3) charging the product (A), inverting the mold to remove excess powder material, and depositing (A) on the layer (B) with a predetermined thickness: 200 to 400 ° C.
- a mold in which the (B) layer and the (A) layer are laminated and attached is placed in a heating oven to complete melting and foaming of the powder resin, and then taken out of the heating oven and cooled to mold. Demolding a product
- Method B A manufacturing method in which the mold self-heats, characterized by passing through the following three steps.
- First step A powdery thermoplastic polyurethane resin composition (B) containing no foaming agent is charged into a mold preheated to 200 ° C. to 300 ° C., and the mold is inverted to remove excess powder material.
- Second process The powdery thermoplastic polyurethane resin composition of the above (1) or (2) with (B) adhered to the mold
- Step (3) charging the product (A), inverting the mold to remove excess powder material, and depositing (A) with a predetermined thickness on the layer (B); (A) A step of self-heating at 200 ° C. to 300 ° C. to complete the melting and foaming of the powdered resin, and then cooling the die and then removing the molded product after self-heating at 200 ° C. to 300 ° C.
- Examples of the mold self-heating system in the method B include a system in which a heating medium flows through a jacket attached to the outer surface of the mold and a system that heats by installing an electric heating wire and energizing it.
- preferred holding times in each step are as follows.
- the sheet-like polyurethane resin molded product having a two-layer structure of the foamed layer and the non-foamed layer thus obtained has a soft tactile sensation, is excellent in abrasion resistance, mechanical properties, etc. Cost reduction is realized.
- the sheet-like polyurethane resin molding obtained by the present invention is optimal for the skin of automobile interior materials (instrument panels, console boxes, armrests, etc.).
- Preparation Example 1 (Preparation of dispersant solution) A reactor having a capacity of 2 L equipped with a stirrer, a thermometer, a distillation column and a nitrogen gas introduction tube was charged with 762 g of adipic acid, 49 g of maleic anhydride and 386 g of ethylene glycol, and at 150 ° C. and normal pressure while flowing nitrogen gas. The esterification reaction was carried out by stirring under the conditions of When condensed water is no longer observed, add 0.1 g of tetrabutyl titanate, gradually reduce the pressure in the reaction system to 0.07 kPa, and gradually raise the temperature to 190 ° C. to continue the reaction. To obtain a polyester.
- the number average molecular weight of the obtained polyester was 2,000, and the iodine value was 12.7 gI / 100 g.
- 74 g of the above polyester and 150 g of butyl acetate were charged into a 500 mL reactor equipped with a stirrer, a thermometer, a distillation column and a nitrogen gas introduction tube, and the temperature was raised to 110 ° C. while flowing nitrogen gas. , Stirred. Thereafter, a dissolved mixture of 75 g of 2-ethylhexyl methacrylate and 1 g of benzoyl peroxide was dropped from the dropping funnel over 1 hour. After completion of the dropwise addition, the temperature was raised to 130 ° C. and the reaction was further continued for 2 hours to obtain a dispersant solution having a solid content of 50%. Hereinafter, this is referred to as “dispersant solution (1)”.
- Preparation Example 2 (Preparation of dispersant solution) A reactor having a capacity of 2 L equipped with a stirrer, a thermometer, a distillation column and a nitrogen gas introduction tube was charged with 565 g of adipic acid and 575 g of 3-methyl-1,5-pentanediol, and 150 ° C. while flowing nitrogen gas.
- the polyester diol having a number average molecular weight of 1,000 was synthesized by an esterification reaction by stirring under normal pressure conditions.
- polyester diol and 150 g of diisononyl adipate were charged into a 1,000 mL reactor equipped with a stirrer, thermometer, distillation column and nitrogen gas inlet tube, and the temperature was raised to 80 ° C. while flowing nitrogen gas. And stirred.
- 42 g of hexamethylene diisocyanate was added and reacted at 80 ° C. for 2 hours to prepare an isocyanate group-containing prepolymer.
- An additional 200 g of polyvinyl alcohol having a number average molecular weight of 1,000 was added thereto and further reacted at 80 ° C. for 2 hours to obtain a dispersion stabilizer solution having a solid content of about 70%.
- dispersant solution (2) this is referred to as “dispersant solution (2)”.
- Synthesis Example 1 Synthesis of powdered thermoplastic polyurethane resin (A1-1)
- a reactor having a capacity of 3 L equipped with a stirrer, thermometer, cooler and nitrogen gas introduction tube 314.6 g of a polyester diol having a number average molecular weight of 2,600 obtained from 1,4-BD, ethylene glycol and adipic acid , 157.3 g of a polyester diol having a number average molecular weight of 2,000 obtained from 1,4-BD and adipic acid, and 314.
- Synthesis Examples 2 to 6 Synthesis of powdered thermoplastic polyurethane resin (A1-2 to 6)
- a powdered thermoplastic polyurethane resin (A1-2-6) was prepared in the same apparatus, raw materials, and steps as in Synthesis Example 1 except that the conditions for dispersing the polymer polyol in isooctane were changed as shown in Table 1. ) was synthesized (see Table 1).
- Synthesis Example 7 (Synthesis of powdered thermoplastic polyurethane resin (B)) A reactor having a capacity of 3 L equipped with a stirrer, a thermometer, a cooler and a nitrogen gas introduction tube was charged with 246.1 g of polyester diol having a number average molecular weight of 2,600 obtained from 1,4-BD, ethylene glycol and adipic acid. 164.1 g of a polyester diol having a number average molecular weight of 2,000 obtained from 1,4-BD and adipic acid, and a polyester diol having a number average molecular weight of 1,500 obtained from 1,6-HD and isophthalic acid. 1 g was mixed at 90 ° C.
- Average particle size A cumulative percent value of 50% in the particle size distribution (volume distribution) curve measured with a laser particle size analyzer “Microtrac HRA” (manufactured by Nikkiso Co., Ltd.) was determined.
- Drop time Using a bulk specific gravity measuring instrument (compliant with JIS-K6720) made by Tsutsui Rika, the time for which 100 cm 3 of the powdered thermoplastic polyurethane resin material flows down the funnel is measured, and the flow rate of ⁇ 20 seconds is passed It was used as an index.
- Formulation Example 1 (Preparation of a powdered thermoplastic polyurethane resin composition (B) containing no foaming agent) Charge 1,500 g of powdered thermoplastic polyurethane resin “B-1” into a 9 L Henschel mixer, then add 1.0% (15 g) of color pigment “C-1” and stir and mix at 1,000 rpm for 30 seconds. Thus, a powdery thermoplastic polyurethane resin (B) containing no foaming agent was prepared and designated as “PU-0” (see Table 2).
- thermoplastic polyurethane resin composition (A) 2
- Examples 5-7, Comparative Example 4 1,500 g of thermoplastic polyurethane resin “A1-3” was charged into a 9 L Henschel mixer, and azodicarbonamide “ADCA” powder having an average particle size of 3 ⁇ m, 10 ⁇ m, 20 ⁇ m, and 25 ⁇ m as a powdered pyrolytic foaming agent (B) was added by 0.7% (10.5 g). Next, 0.8% (12 g) of the aforementioned color pigment “C-1” was added, and each mixture was stirred and mixed at 1,000 rpm for 40 seconds to prepare a powdered thermoplastic polyurethane resin composition (A). “PU-8” to “PU-11” (see Table 3).
- thermoplastic polyurethane resin composition (A) Part 3-2
- Example 10 1,500 g of thermoplastic polyurethane resin “A1-3” was charged into a Henchel mixer with a capacity of 9 L, and sodium hydrogencarbonate powder “NaHCO 3 ” powder having an average particle diameter of 3 ⁇ m as a powdery pyrolytic foaming agent (B) was 0.95. % (14.25 g) was added. Next, 0.8% (12 g) of the aforementioned color pigment “C-1” was added, and each mixture was stirred and mixed at 1,000 rpm for 40 seconds to prepare a powdery thermoplastic polyurethane resin composition (A). 15 ”(see Table 4).
- Example 14 [Manufacture of a sheet-like polyurethane resin molding having a two-layer structure using a mold heating system with a heating furnace]
- PU-0 as a powdered thermoplastic polyurethane resin composition (B) containing no foaming agent is charged and held for 2 seconds, and the mold is inverted. Excess powder material was removed to form a non-foamed layer.
- PU-3 as a powdered thermoplastic polyurethane resin composition (A) containing a pyrolytic foaming agent (A2) is charged in the same mold with the non-foamed layer adhered, and held for 10 seconds.
- the mold was inverted to remove excess powder material and form a foam layer.
- the mold is put into a heating furnace at 300 ° C. and heated for 30 seconds, and then the mold taken out from the heating furnace is cooled and demolded so that the non-foamed layer (b) and the foamed layer (a) are integrated.
- a two-layered sheet-like polyurethane resin molded product was obtained.
- the thickness of the obtained molded product was 1.2 mm
- the thickness of the non-foamed layer was 0.2 mm
- the characteristic described in Table 6 was confirmed.
- This molded product corresponds to a weight reduction of 36.7% and a decrease in hardness of 23 points as compared with a molded product of only “PU-0” (not foamed) in Comparative Example 18 described later.
- the molded product was soft and had good tactile sensation.
- the reference samples for calculating the weight reduction rate are all referred to as Comparative Example 18 hereinafter.
- Comparative Example 11 In a mold preheated to 250 ° C. in a heating furnace, “PU-3” as a powdered thermoplastic polyurethane resin composition (A) containing a pyrolytic foaming agent (A2) is charged and held for 11 seconds. The mold was inverted to remove excess powder material and form a non-foamed layer. After this mold was placed in a 300 ° C. heating furnace and heated for 30 seconds, the mold taken out from the heating furnace was cooled and removed to obtain a sheet-like polyurethane resin molded product. The thickness of the obtained molded product was 1.2 mm. Moreover, the characteristic described in Table 6 was confirmed.
- Comparative Example 12 A sheet-like polyurethane resin molded product was obtained in the same procedure as Comparative Example 11 except that “PU-6” was used as the powdered thermoplastic polyurethane resin composition (A) containing the pyrolytic foaming agent (A2). . The thickness of the obtained molded product was 1.2 mm. Moreover, the characteristic described in Table 6 was confirmed.
- Comparative Example 18 In a mold preheated to 250 ° C. in a heating furnace, “PU-0” as a powdered thermoplastic polyurethane resin composition (B) was charged and held to a thickness shown in Table 9, The mold was inverted to remove excess powder material. After this mold was placed in a 300 ° C. heating furnace and heated for 30 seconds, the mold taken out from the heating furnace was cooled and removed to obtain a sheet-like polyurethane resin molded product. The thickness of the obtained molded product was 1.2 mm. Moreover, the characteristic described in Table 7 was confirmed.
- Examples 15 to 26, Comparative Examples 8 to 10, 13 to 17 Adjust the holding time of “PU-0” and the holding time of “PU-1 to 4, 6 to 20” so that the non-foamed layer thickness and foamed layer thickness shown in Tables 6 to 9 are obtained, and the rest of the procedure is performed
- a sheet-like polyurethane resin molded article having a two-layer structure in which the non-foamed layer (b) and the foamed layer (a) were integrated was obtained.
- the comparative example 8 did not use the pyrolytic foaming agent (A2), the layer that should originally be the foamed layer (a) was not foamed.
- the molded product itself was not obtained, and hence the subsequent evaluation was not performed (details will be described later).
- the amount of the pyrolytic foaming agent (A2) added is 0.3 to 0.9% by mass.
- the obtained molded product showed the favorable characteristics described in Table 6, was reduced in weight as compared with the molded product having only “PU-0” (Comparative Example 18), and formed into a molded product having a good tactile sensation.
- Comparative Examples 8 to 10 are comparative examples when the amount of the pyrolytic foaming agent (A2) added is outside the range of 0.2 to 1.0% by mass.
- the obtained molded product showed the characteristics shown in Table 6, Comparative Example 8 and Comparative Example 9 were not reduced in weight, and the tactile sensation was insufficient. In Comparative Example 10, a significant decrease in mechanical properties was confirmed. It was.
- the average particle size of the pyrolytic foaming agent OBSH or sodium bicarbonate used is 5 to 20 ⁇ m.
- the obtained molded product exhibited good characteristics described in Table 7, was lighter than the molded product of Comparative Example 18 having no foamed layer, and was a molded product having a good tactile sensation.
- Comparative Example 13 is a comparative example in which the average particle size of the used pyrolytic foaming agent OBSH exceeds 25 ⁇ m, which is the upper limit of the present invention, 20 ⁇ m.
- the obtained molded product exhibited the characteristics described in Table 7, and the cells were non-uniform compared to Example 19 using 20 ⁇ m OBSH, confirming a decrease in mechanical properties.
- the average particle size of the powdered thermoplastic polyurethane resin (A1) used is 100 to 300 ⁇ m.
- the obtained molded product exhibited good characteristics described in Table 8, was reduced in weight as compared with the molded product of Comparative Example 18 described above, and a molded product having a good tactile sensation.
- Comparative Examples 14 and 15 are comparative examples using a powdered thermoplastic polyurethane resin (A1) having an average particle size outside the range of 100 to 350 ⁇ m. In Comparative Example 14 in which “PU-16” was used for the foam layer, the powder flowability was poor because the average particle size of “PU-16” was small, and “PU-16” was formed on the formed non-foam layer.
- the ratio of the thickness of the non-foamed layer (b) to the thickness of the entire molded product is in the range of 0.08 to 0.6.
- the obtained molded product exhibited good characteristics described in Table 9, and was reduced in weight as compared with the molded product of Comparative Example 18 having no foamed layer.
- Comparative Examples 16 and 17 are comparative examples when the ratio of the thickness of the non-foamed layer (b) to the total thickness of the molded product is outside the range of 0.08 to 0.6.
- the obtained molded product showed the characteristics described in Table 9, and in Comparative Example 16 in which the ratio of the thickness of the non-foamed layer (b) was as small as 0.04, it was confirmed that the appearance defect and the mechanical characteristics and the durability were lowered, For the molded product of Comparative Example 17 in which the ratio of the thickness of the non-foamed layer (b) was 0.67, the weight reduction was insufficient and a soft tactile sensation was not obtained.
- Comparative Example 18 is an ordinary single-layered sheet-like polyurethane resin molding formed of only a non-foamed layer and having a thickness of 1.2 mm.
- the obtained molded product exhibited the characteristics described in Table 9. The weight reduction was not achieved and a soft tactile sensation was not obtained.
- Example 27 Circulating oil heated in the jacket so that the surface temperature becomes 250 ° C in a mold equipped with an oil jacket, charging "PU-0” as a powdered thermoplastic polyurethane resin composition (B) and holding for 2 seconds Then, the mold was inverted to remove excess powder material, and a non-foamed layer was formed. Subsequently, “PU-8” as a powdered thermoplastic polyurethane resin composition (A) containing a pyrolytic foaming agent (A2) is charged in the same mold with the non-foamed layer adhered, and held for 10 seconds.
- the mold was inverted to remove excess powder material and form a foam layer.
- the mold was self-heated to 300 ° C. and heated for 30 seconds, and then the mold was cooled and removed, whereby the non-foamed layer (b) and the foamed layer (a) were integrated.
- a sheet-like polyurethane resin molded product having a layer structure was obtained.
- the thickness of the obtained molded product was 1.2 mm
- the thickness of the non-foamed layer was 0.2 mm
- the characteristic described in Table 10 was confirmed.
- This molded product corresponds to a weight reduction of 42.3% and a hardness reduction of 30 points compared to the molded product of only “PU-0” (not foamed) of Comparative Example 19 described above.
- the molded product was soft and had good tactile sensation.
- Example 28-30 Comparative Example 19
- the holding time of “PU-0” and the holding time of “PU-5, 9 to 11” were adjusted so that the non-foamed layer thickness and the foamed layer thickness shown in Table 10 were obtained, and the remaining procedures were the same as in Example 27.
- a sheet-like polyurethane resin molded article having a two-layer structure in which the non-foamed layer (b) and the foamed layer (a) were integrated was obtained.
- the total thickness of the obtained molded products was 1.2 mm.
- the characteristic described in Table 10 was confirmed.
- Comparative Example 20 In a mold equipped with an oil jacket, oil heated in the jacket was circulated so that the surface temperature was 250 ° C., and “PU-0” was charged as a powdered thermoplastic polyurethane resin composition (B) in Table 10. While maintaining the thickness shown, the mold was inverted to remove excess powder material. The mold was self-heated to 300 ° C. and heated for 30 seconds, and then the mold was cooled and removed to obtain a sheet-like polyurethane resin molded product. The thickness of the obtained molded product was 1.2 mm. Comparative Example 20 is a sheet-like polyurethane resin molded article having a normal single layer structure, which is formed of only a non-foamed layer and has a thickness of 1.2 mm. The obtained molded product exhibited the characteristics described in Table 10, and it was not possible to achieve weight reduction and a soft touch was not obtained.
- B powdered thermoplastic polyurethane resin composition
- the average particle size of the pyrolytic foaming agent ADCA used is 3 to 20 ⁇ m.
- the obtained molded product showed the favorable characteristics described in Table 10, was reduced in weight as compared with the molded product of Comparative Example 20 containing no pyrolyzable foaming agent, and a molded product having a good tactile sensation.
- the comparative example 19 is a comparative example in which the average particle diameter of the used pyrolytic foaming agent ADCA exceeds 25 ⁇ m and 20 ⁇ m which is the upper limit of the present invention.
- the obtained molded product exhibited the characteristics described in Table 7, and the cells became non-uniform compared to Example 30 using 20 ⁇ m ADCA, confirming a decrease in mechanical characteristics.
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Abstract
Description
第一工程:200℃~300℃に予備加熱した金型内に、発泡剤を含有しない粉末状熱可塑性ポリウレタン樹脂組成物(B)を仕込み、金型を反転させて余剰の粉末材料を除去し、金型面に(B)を均一な厚みで付着かつ溶融させる工程
第二工程:(B)を金型に付着させたまま、前記(1)又は(2)の粉末状熱可塑性ポリウレタン樹脂組成物(A)を仕込んで、金型を反転させて余剰の粉末材料を除去し、(B)の層の上に所定の厚みで(A)を付着させる工程
第三工程:200~400℃の加熱オーブン内に、(B)層と(A)層が積層して付着した金型を30~120秒間入れて、粉末樹脂の溶融及び発泡を完結させ、その後加熱オーブンから取り出して金型を冷却した後、成形物を脱型する工程
第一工程:200℃~300℃に予備加熱した金型内に、発泡剤を含有しない粉末状熱可塑性ポリウレタン樹脂組成物(B)を仕込み、金型を反転させて余剰の粉末材料を除去し、金型面に(B)を均一な厚みで付着かつ溶融させる工程
第二工程:(B)を金型に付着させたまま、前記(1)又は(2)の粉末状熱可塑性ポリウレタン樹脂組成物(A)を仕込んで、金型を反転させて余剰の粉末材料を除去し、(B)の層の上に所定の厚みで(A)を付着させる工程
第三工程:(B)層と(A)層が積層して付着した金型を200℃~300℃にて30~120秒間自己加熱して粉末樹脂の溶融及び発泡を完結させ、その後金型を冷却した後、成形物を脱型する工程
・高分子ポリオール、有機ポリイソシアネート、及び一官能活性水素基含有化合物を反応させて得られるイソシアネート基末端プレポリマー(以下,「イソシアネート基末端プレポリマー(1)」という。);
・高分子ポリオール、有機ポリイソシアネート、及び一官能活性水素基含有化合物及び二官能活性水素基含有化合物を反応させて得られるイソシアネート基末端プレポリマー(以下、「イソシアネート基末端プレポリマー(2)」という。)を挙げることができる。
例えばポリエステルポリオール、ポリ
エステルアミドポリオール、ポリエーテルポリオール、ポリエーテル・エステルポリオール、ポリカーボネートポリオール、ポリオレフィンポリオール等の高分子ポリオールが挙げられ、これらは単独又は併用して用いられる。本発明における高分子ポリオールは、ポリエステルポリオールが好ましい。
ル、ビスフェノールAのアルキレンオキサイド付加物等が挙げられる。
ンジイソシアネート、水素添加テトラメチルキシレンジイソシアネート等の脂環族ジイソシアネートの他、その重合体やそのポリメリック体、ウレタン変性体、アロファネート変性体、ウレア変性体、ビウレット変性体、カルボジイミド変性体、ウレトンイミン変性体、ウレトジオン変性体、イソシアヌレート変性体、更にこれらの2種以上の混合物が挙げられる。本発明では、成形物の耐候性等を考慮すると、脂肪族及び/又は脂環族ジイソシアネートが好ましく、特にHDIが好ましい。
(1)TPUペレットを冷凍粉砕して(A1)の粉末を得る方法
(2)イソシアネート基末端プレポリマーを溶解しない非水系の分散媒中に分散させて、水と反応させて鎖延長する工程を経て得られるポリウレタン樹脂を分離・乾燥して粉末状熱可塑性ポリウレタン樹脂(A1)を得る方法
(3)水中に分散させたイソシアネート基末端プレポリマーを、イソシアネート基末端プレポリマーの有するイソシアネート基の残部を水の有する活性水素基と反応させる工程を経て得られるポリウレタン樹脂を分離・乾燥して粉末状熱可塑性ポリウレタン樹脂(A1)を得る方法
これらのうちでは、得られる樹脂の形状が球状となり、粉体流動性が良好なものが得られる(2)及び(3)の方法が好ましい。
アゾ系化合物:アゾジカルボンアミド(以後ADCAと略す)、2,2′-アゾビスイソブチロニトリル、アゾヘキサヒドロベンゾニトリル、ジアゾアミノベンゼン等
ニトロソ系化合物:N,N′-ジニトロソペンタメチレンテトラミン、N,N′-ジニトロソ-N,N′-ジメチルテレフタルアミド等
スルホヒドラジン系化合物:ベンゼンスルホニルヒドラジド、ベンゼン-1,3-ジスルホニルヒドラジド、ジフェニルスルホン-3,3′-ジスルホニルヒドラジド、4,4′-オキシビス(ベンゼンスルホニルヒドラジド)(以後OBSHと略す)等
無機系化合物:炭酸水素ナトリウム
これらは単独あるいは2種以上を混合して用いることができる。本発明において好ましい熱分解型発泡剤(A2)は、スラッシュ成形時の温度を考慮すると、分解ガス放出の温
度が120~250℃であるものであり、特に130~210℃であるものが好ましい。更には爆発の危険性や、分解時の有毒ガスの発生という環境への影響を考慮すると、ADCA、OBSH、炭酸水素ナトリウムから選択されるものが好ましく、特に好ましくはADCAである。
A法:次の3工程を経ることを特徴とする、金型を間接的に加熱する製造方法である。
第一工程:200℃~300℃に予備加熱した金型内に、発泡剤を含有しない粉末状熱可塑性ポリウレタン樹脂組成物(B)を仕込み、金型を反転させて余剰の粉末材料を除去し、金型面に(B)を均一な厚みで付着かつ溶融させる工程
第二工程:(B)を金型に付着させたまま、前記(1)又は(2)の粉末状熱可塑性ポリウレタン樹脂組成物(A)を仕込んで、金型を反転させて余剰の粉末材料を除去し、(B)の層の上に所定の厚みで(A)を付着させる工程
第三工程:200~400℃の加熱オーブン内に、(B)層と(A)層が積層して付着した金型を入れて、粉末樹脂の溶融及び発泡を完結させ、その後加熱オーブンから取り出して金型を冷却した後、成形物を脱型する工程
第一工程:200℃~300℃に予備加熱した金型内に、発泡剤を含有しない粉末状熱可塑性ポリウレタン樹脂組成物(B)を仕込み、金型を反転させて余剰の粉末材料を除去し、金型面に(B)を均一な厚みで付着かつ溶融させる工程
第二工程:(B)を金型に付着させたまま、前記(1)又は(2)の粉末状熱可塑性ポリウレタン樹脂組成物(A)を仕込んで、金型を反転させて余剰の粉末材料を除去し、(B)の層の上に所定の厚みで(A)を付着させる工程
第三工程:(B)層と(A)層が積層して付着した金型を200℃~300℃にて自己発熱させて粉末樹脂の溶融及び発泡を完結させ、その後金型を冷却した後、成形物を脱型する工程
第二工程:4~15秒が好ましい。
第三工程:30~120秒が好ましい。
各保持時間を調節することにより、成形物の厚さ及び各層の厚さ比を調整することができる。
攪拌機、温度計、留出塔及び窒素ガス導入管を備えた容量2Lの反応器に、アジピン酸762gと無水マレイン酸49gとエチレングリコール386gとを仕込み、窒素ガスを流しながら、150℃、常圧の条件で攪拌することによりエステル化反応させた。
縮合水が認められなくなった時点で、テトラブチルチタネート0.1gを添加し、反応系内の圧力を徐々に0.07kPaまで減圧するとともに、190℃まで徐々に昇温して反応を継続することによりポリエステルを得た。得られたポリエステルの数平均分子量は2,000、ヨウ素価は12.7gI/100gであった。
続いて、攪拌機、温度計、留出塔及び窒素ガス導入管を備えた容量500mLの反応器に、上記のポリエステル74gと酢酸ブチル150gとを仕込み、窒素ガスを流しながら110℃まで昇温して、攪拌した。その後、2-エチルヘキシルメタクリレート75gと過酸化ベンゾイル1gとの溶解混合物を滴下ロートから1時間かけて滴下した。滴下終了後、130℃に昇温して更に2時間反応させることにより、固形分50%の分散剤溶液を得た。以下、これを「分散剤溶液(1)」という。
攪拌機、温度計、留出塔及び窒素ガス導入管を備えた容量2Lの反応器に、アジピン酸565gと3-メチル-1,5-ペンタンジオール575gとを仕込み、窒素ガスを流しながら、150℃、常圧の条件で攪拌することによりエステル化反応させ、数平均分子量1,000のポリエステルジオールを合成した。
次に、攪拌機、温度計、留出塔及び窒素ガス導入管を備えた容量1,000mLの反応器に、上記のポリエステルジオール100gとジイソノニルアジペート150gを仕込み、窒素ガスを流しながら80℃まで昇温して攪拌した。ここにヘキサメチレンジイソシアネート42gを追加し、80℃で2時間反応させて、イソシアネート基含有プレポリマーを調整した。ここに数平均分子量1,000のポリビニルアルコールを200g追加で仕込み、更に80℃で2時間反応させて固形分約70%の分散安定剤溶液を得た。以下、これを「分散剤溶液(2)」という。
攪拌機、温度計、冷却器及び窒素ガス導入管を備えた容量3Lの反応器に、1,4-BDとエチレングリコールとアジピン酸とから得られる数平均分子量2,600のポリエステルジオール314.6gと、1,4-BDとアジピン酸とから得られる数平均分子量2,000のポリエステルジオール157.3gと、1,6-HDとイソフタル酸とから得られる数平均分子量1,000のポリエステルジオール314.6gを80~100℃で均一に混合した後に、分散剤溶液(1)15.7gと、非水系の分散媒としてイソオクタン「キョーワゾール C-800」(協和発酵ケミカル(株)製)811.3gとを仕込み、95℃で1.5時間攪拌することにより、高分子ポリオールをイソオクタン中に分散させて、非水系の分散液を調製した。この段階で分散温度や分散時間を適宜調節することで、最終的な粉末状熱可塑性ポリウレタン樹脂の平均粒径を調整することができる(表1参照)。
上記分散液に、HDIを173.0gと、ビスマス系触媒「ネオスタン U-600」(日東化成(株)製)0.05gとを添加し、90~95℃で3時間にわたり、HDIを高分子ポリオールと反応させることにより、イソシアネート基末端プレポリマー(1)の分散液を調製した。前記イソシアネート基末端プレポリマー分散液(1)に、一官能の活性水素基含有化合物であるジ-2-エチルヘキシルアミン24.8gと、二官能の活性水素基含有化合物である1,4-BD9.3gを添加し、イソシアネート基末端プレポリマー(1)と80~90℃にて反応させることにより、イソシアネート基末端プレポリマー(2)の分散液を調製した。
上記のイソシアネート基末端プレポリマー(2)の分散液に、水64.8g〔イソシアネート基末端プレポリマー(2)のイソシアネート基(計算値)の10当量に相当〕を添加し、イソシアネート基末端プレポリマー(2)と水とを、65~70℃にて、イソシアネート基が消費されるまで鎖延長反応させることにより、ポリウレタン樹脂の分散液を調製した。
上記のポリウレタン樹脂の分散液から固形分(ポリウレタン樹脂)を濾別し、これに、下記に示す添加剤(1)~(4)を添加し乾燥した後に、打粉剤「MP1451」(綜研化学(株)製)3.0gを添加することにより、粉末状熱可塑性ポリウレタン樹脂(A1-1)を合成した。得られた樹脂の粒子は真球状(短/長=1.0)であり、平均粒径は70μmであり、流下時間は23秒であり、数平均分子量は30,000であった(表1参照)。
高分子ポリオールをイソオクタンに分散させる際の条件を、表1に示したように変更した以外は、合成例1と同様な装置、原料、工程にて粉末状熱可塑性ポリウレタン樹脂(A1-2~6)を合成した(表1参照)。
(1)酸化防止剤:「イルガノックス245」(チバ・スペシャルティ・ケミカルズ製)、添加量=2.0g。
(2) 紫外線吸収剤:「チヌビン 213」(チバ・スペシャルティ・ケミカルズ製)
、添加量=2.0g。
(3)光安定剤:「チヌビン 765」(チバ・スペシャルティ・ケミカルズ製)、添加量=2.0g。
(4)ブロッキング防止剤:「SH200-300CV」(東レ・ダウコーニング(株)製)、添加量=1.5g。
攪拌機、温度計、冷却器及び窒素ガス導入管を備えた容量3Lの反応器に、1,4-BDとエチレングリコールとアジピン酸とから得られる数平均分子量2,600のポリエステルジオール246.1gと、1,4-BDとアジピン酸とから得られる数平均分子量2,000のポリエステルジオール164.1gと、1,6-HDとイソフタル酸とから得られる数平均分子量1,500のポリエステルジオール410.1gを90℃で混合した。
次に上記混合物を65℃まで冷却し、一官能活性水素基含有化合物であるジ-n-ブチルアミン8.9gと、二官能の活性水素基含有化合物である1,6-HD12.7gを添加後さらに混合し、ヘキサメチレンジイソシアネート(HDI)152.9gと、ビスマス系触媒「ネオスタン U-600」0.05gとを添加し、まず65℃で15分、引き続き80~90℃で3時間にわたり反応させることにより、イソシアネート基末端プレポリマー(3)を得た。
上記のイソシアネート基含有プレポリマー(3)を60℃に冷却した後、MEK199gと分散安定剤(2)42.6gを加えて均一に混合して、イソシアネート基含有プレポリマー/分散剤混合液を調整した。
このMEKの量は、得られたイソシアネート基含有プレポリマーに対して20%に相当する量である。また,分散安定剤溶液(2)の量は,得られたイソシアネート基含有プレポリマーに対して3.0%に相当する量である。
次いで配合物の全量を60℃に調節し、60℃の温水(2353g)中に、プライミクス(株)製ホモミキサー(機械式強制分散機)を用いて8,000rpmの回転数で2分間混合し分散させた。
この混合分散物を温度計,攪拌機及び窒素吹込み管を備えた反応容器に移し,攪拌しながら60℃で10時間反応させた。
上記のポリウレタン樹脂の分散液から固形分(ポリウレタン樹脂)を濾別し,これに,以下に示した添加剤(1)~(4)を添加し乾燥した後に,打粉剤「MP1451」(綜研化学(株)製)3.0gを添加することにより,粉末状熱可塑性ポリウレタン樹脂(B-1)を調製した。得られた樹脂の粒子は真球状(短/長=0.9)であり、平均粒径は150μmであり、流下時間は18秒であり、数平均分子量は34,000であった。
〔添加剤〕
(1)酸化防止剤:「イルガノックス245」(チバ・スペシャルティ・ケミカルズ社製),添加量=2.0g。
(2) 紫外線吸収剤:「チヌビン 213」(チバ・スペシャルティ・ケミカルズ社製
),添加量=2.0g。
(3)光安定剤:「チヌビン 765」(チバ・スペシャルティ・ケミカルズ社製),添加量=2.0g。
(4)内部離型剤:「SH200-100,000cs」(東レ・ダウコーニング(株)
製),添加量=2.0g。
レーザー式粒度分析計「マイクロトラック HRA」(日機装(株)製)にて測定した粒径分布(体積分布)カーブにおける50%の累積パーセントの値を求めた。
(2)落下時間:
筒井理化製のかさ比重測定器(JIS-K6720準拠)を用いて、100cm3の粉末状熱可塑性ポリウレタン樹脂材料が漏斗を流下する時間を測定し、流下時間≦20秒のものを流動性合格の指標とした。
(3)分子量測定:
GPC測定により、測定したチャートにおいて、ピーク面積が最大である主ピークに係る成分の数平均分子量(Mn)及び重量平均分子量(Mw)を求めた。測定条件は下記のとおりである。
・測定器:「HLC-8120」(東ソー(株)製)
・カラム:「TSKgel MultiporeHXL-M 」(東ソー(株)製)
平均粒径=5μm、サイズ=7.8mmID×30cm×4本
・キャリア:テトラヒドロフラン(THF)
・検出器:視差屈折
・サンプル:THF/n-メチルピロリドン=2/1(質量比)を溶媒とした1%溶液
・検量線:標準ポリスチレン
実施例1~4、比較例1~3
粉末状熱可塑性ポリウレタン樹脂「A1-3」1,500gを容量9Lのヘンシェルミキサーに仕込み、粉末状熱分解型発泡剤(B)として平均粒径5μmのアゾジカルボンアミド「ADCA」粉末を0%(0g)~1.2%(18g)の範囲で添加量を変更して追加した。次いで、以下の着色顔料「C-1」を0.8%(12g)添加し、それぞれ1,000rpmで40秒間撹拌混合して粉末状熱可塑性ポリウレタン樹脂組成物(A)を調製し、夫々を樹脂「PU-1」~「PU-7」とした(表2参照)。
住化カラー製カーボンブラック分散顔料「PV-817」667gと,同社製酸化チタン分散顔料「PV-7A1301」333gを,粉体専用リボンミキサーを用いて均一になるまで混合した。
粉末状熱可塑性ポリウレタン樹脂「B-1」1,500gを容量9Lのヘンシェルミキサーに仕込み、次いで着色顔料「C-1」を1.0%(15g)添加し,1,000rpmで30秒間撹拌混合して発泡剤を含有しない粉末状熱可塑性ポリウレタン樹脂(B)を調製し、「PU-0」とした(表2参照)。
実施例5~7、比較例4
熱可塑性ポリウレタン樹脂「A1-3」1,500gを容量9Lのヘンシェルミキサーに仕込み、粉末状熱分解型発泡剤(B)として平均粒径3μm、10μm、20μm、25μmのアゾジカルボンアミド「ADCA」粉末をそれぞれ0.7%(10.5g)追加した。次いで前述の着色顔料「C-1」を0.8%(12g)添加し、各々1,000rpmで40秒間撹拌混合して粉末状熱可塑性ポリウレタン樹脂組成物(A)を調製し、夫々を樹脂「PU-8」~「PU-11」とした(表3参照)。
実施例8~9、比較例5
熱可塑性ポリウレタン樹脂「A1-3」1,500gを容量9Lのヘンシェルミキサーに仕込み、粉末状熱分解型発泡剤(B)として平均粒径5μm、20μm、25μmの4,4′-オキシビス(ベンゼンスルホニルヒドラジド)「OBSH」粉末をそれぞれ0.95%(14.25g)追加した。次いで前述の着色顔料「C-1」を0.8%(12g)添加し、各々1,000rpmで40秒間撹拌混合して粉末状熱可塑性ポリウレタン樹脂組成物(A)を調製し、夫々を樹脂「PU-12」~「PU-14」とした(表4参照)。
実施例10
熱可塑性ポリウレタン樹脂「A1-3」1,500gを容量9Lのヘンシェルミキサーに仕込み、粉末状熱分解型発泡剤(B)として平均粒径3μmの炭酸水素ナトリウム粉末「NaHCO3 」粉末を0.95%(14.25g)追加した。次いで前述の着色顔料「C-1」を0.8%(12g)添加し、各々1,000rpmで40秒間撹拌混合して
粉末状熱可塑性ポリウレタン樹脂組成物(A)を調製し、「PU-15」とした(表4参照)。
実施例11~13、比較例6、7
平均粒径の異なる粉末状熱可塑性ポリウレタン樹脂「A1-1」~「A1-6」を、容量9Lのヘンシェルミキサーにそれぞれ1,500g仕込み,粉末状熱分解型発泡剤(B)として平均粒径5μmのアゾジカルボンアミド「ADCA」粉末を0.7%(10.5g)追加した。次いで前述の着色顔料「C-1」を0.8%(12g)添加し、各々1,000rpmで40秒間撹拌混合して粉末状熱可塑性ポリウレタン樹脂組成物(A)を調製し、夫々を樹脂「PU-16」~「PU-20」とした(表5参照)。
実施例14
加熱炉にて250℃に予備加熱した金型内に、発泡剤を含有しない粉末状熱可塑性ポリウレタン樹脂組成物(B)として「PU-0」を仕込んで2秒間保持し、金型を反転させて過剰の粉末材料を除去し、非発泡層を形成した。続いて非発泡層が付着したままの同じ金型内に、熱分解型発泡剤(A2)を含有する粉末状熱可塑性ポリウレタン樹脂組成物(A)として「PU-3」を仕込んで10秒間保持し、金型を反転させて過剰の粉末材料を除去し発泡層を形成した。この金型を300℃の加熱炉に入れて30秒間にわたり加熱した後で、加熱炉から取り出した金型を冷却し脱型することで、非発泡層(b)と発泡層(a)が一体となった2層構造のシート状ポリウレタン樹脂成形物を得た。
得られた成形物の厚みは1.2mmで、非発泡層の厚みは0.2mm、発泡層の厚みは1.0mmであった(非発泡層/全層=0.17)。また、表6に記載した特性を確認した。成形物の真比重は0.75、硬度はHA=57度であった。この成形物は後述する比較例18の、「PU-0」のみの成形品(発泡していない)に比較して、36.7%の軽量化と23ポイントの硬度低下に相当し、非常に柔軟で良好な触感の成形物となった。なお、軽量化率を計算するための基準サンプルは以後全て比較例18とする。
加熱炉にて250℃に予備加熱した金型内に、熱分解型発泡剤(A2)を含有する粉末状熱可塑性ポリウレタン樹脂組成物(A)として「PU-3」を仕込んで11秒間保持し、金型を反転させて過剰の粉末材料を除去し非発泡層を形成した。この金型を300℃の加熱炉に入れて30秒間にわたり加熱した後で、加熱炉から取り出した金型を冷却し脱型することで、シート状ポリウレタン樹脂成形物を得た。
得られた成形物の厚みは1.2mmであった。また、表6に記載した特性を確認した。
熱分解型発泡剤(A2)を含有する粉末状熱可塑性ポリウレタン樹脂組成物(A)として「PU-6」を用いる以外は比較例11と同手順にて、シート状ポリウレタン樹脂成形物を得た。
得られた成形物の厚みは1.2mmであった。また、表6に記載した特性を確認した。
加熱炉にて250℃に予備加熱した金型内に、粉末状熱可塑性ポリウレタン樹脂組成物(B)として「PU-0」を仕込んで表9に示す厚さになるように保持して、金型を反転させて過剰の粉末材料を除去した。この金型を300℃の加熱炉に入れて30秒間にわたり加熱した後で、加熱炉から取り出した金型を冷却し脱型することで、シート状ポリウレタン樹脂成形物を得た。
得られた成形物の厚みは1.2mmであった。また、表7に記載した特性を確認した。
表6~9に示す非発泡層厚、発泡層厚になるように「PU-0」の保持時間及び「PU-1~4、6~20」の保持時間を調整し、残りの手順は実施例14と同様にして非発泡層(b)と発泡層(a)が一体となった2層構造のシート状ポリウレタン樹脂成形物を得た。
なお、比較例8は熱分解型発泡剤(A2)を用いていないため、本来発泡層(a)であるべき層が発泡していなかった。また、比較例14は成形物そのものが得られなかったため、以後の評価は行わなかった(詳細は後述)。
比較例8~10は、熱分解型発泡剤(A2)の添加量が0.2~1.0質量%の範囲外である場合の比較例である。得られた成形物は表6に記載した特性を示し、比較例8及び比較例9は軽量化が達成されず触感も不十分であり、比較例10については機械的特性の著しい低下が確認された。
比較例11、12は、得られた成形物に非発泡層が存在しない。これらの成形物は表6に記載した特性を示し、ピンホールによる製品面の外観不良や機械的特性や耐久性の著しい低下が確認された。
層を有しない比較例18の成形物と比較して軽量化され、良好な触感の成形物となった。比較例13は,使用した熱分解型発泡剤OBSHの平均粒径が25μmと,本発明の上限である20μmを超える比較例である。得られた成形物は表7に記載した特性を示し、20μmのOBSHを使用した実施例19に比較してセルが不均一となり機械的特性の低下が確認された。
比較例14、15は、粉末状熱可塑性ポリウレタン樹脂(A1)の平均粒径が100~350μmの範囲外のものを使用した比較例である。発泡層に「PU-16」を使用した比較例14は、「PU-16」の平均粒径が小さいために粉体流動性が悪く、形成された非発泡層の上に「PU-16」を均一な厚みで積層させることが困難であり、成形物を得ることが困難であった。一方、平均粒径が400μmと大きい「PU-20」を使用した比較例15については、二層構造を有するシート状ポリウレタン樹脂成形物が得られたが、溶融不良による機械的特性や耐久性の低下が確認された。得られた成形物の特性を表8に記載した。
比較例16、17は、成形物全体の厚さに対する非発泡層(b)の厚みの割合が、0.08~0.6の範囲外である場合の比較例である。得られた成形物は表9に記載した特性を示し、非発泡層(b)の厚みの割合が0.04と小さい比較例16では外観不良及び機械的特性や耐久性の低下が確認され、非発泡層(b)の厚みの割合が0.67と過大な比較例17の成形物については軽量化が不十分でありソフトな触感が得られなかった。
実施例27
オイルジャケットを備えた金型に、表面温度が250℃になるようにジャケットに熱したオイルを循環させ、粉末状熱可塑性ポリウレタン樹脂組成物(B)として「PU-0」を仕込んで2秒間保持し,金型を反転させて過剰の粉末材料を除去し,非発泡層を形成した。続いて非発泡層が付着したままの同じ金型内に、熱分解型発泡剤(A2)を含有する粉末状熱可塑性ポリウレタン樹脂組成物(A)として「PU-8」を仕込んで10秒間保持し、金型を反転させて過剰の粉末材料を除去し発泡層を形成した。この金型を300℃になるように自己加熱して30秒間にわたり加熱した後、金型を冷却し脱型することで、非発泡層(b)と発泡層(a)が一体となった2層構造のシート状ポリウレタン樹脂成形物を得た。
得られた成形物の厚みは1.2mmで、非発泡層の厚みは0.2mm、発泡層の厚みは1.0mmであった(非発泡層/全層=0.17)。また、表10に記載した特性を確認した。成形物の真比重は0.68、硬度はHA=50度であった。この成形物は先述の比較例19の、「PU-0」のみの成形品(発泡していない)に比較して、42.3%の軽量化と30ポイントの硬度低下に相当し、非常に柔軟で良好な触感の成形物となった。
表10に示す非発泡層厚、発泡層厚になるように「PU-0」の保持時間及び「PU-5、9~11」の保持時間を調整し、残りの手順は実施例27と同様にして非発泡層(b)と発泡層(a)が一体となった2層構造のシート状ポリウレタン樹脂成形物を得た。
得られた成形物の全厚みは全て1.2mmであった。また、表10に記載した特性を確認した。
オイルジャケットを備えた金型に、表面温度が250℃になるようにジャケットに熱したオイルを循環させ、粉末状熱可塑性ポリウレタン樹脂組成物(B)として「PU-0」を仕込んで表10に示す厚さになるように保持して、金型を反転させて過剰の粉末材料を除去した。この金型を300℃になるように自己加熱して30秒間にわたり加熱した後、金型を冷却し脱型することで、シート状ポリウレタン樹脂成形物を得た。
得られた成形物の厚みは1.2mmであった。比較例20は非発泡層のみで形成され、その厚さは1.2mmである通常の一層構造のシート状ポリウレタン樹脂成形物である。得られた成形物は表10に記載した特性を示し、軽量化が達成されずソフトな触感が得られなかった。
比較例19は、使用した熱分解型発泡剤ADCAの平均粒径が25μmと、本発明の上限である20μmを超える比較例である。得られた成形物は表7に記載した特性を示し、20μmのADCAを使用した実施例30に比較してセルが不均一となり機械的特性の低下が確認された。
Claims (7)
- 平均粒径100~350μmの粉末状熱可塑性ポリウレタン樹脂(A1)と、平均粒径20μm以下の粉末状熱分解型発泡剤(A2)を、(A1)に対して0.2~1.0質量%の割合でコンパウンドした粉末状熱可塑性ポリウレタン樹脂組成物(A)。
- (A1)が、粒子形状が球状である粉末状熱可塑性ポリウレタン樹脂であることを特徴とする、請求項1記載の粉末状熱可塑性ポリウレタン樹脂組成物(A)。
- 請求項1又は2に記載の粉末状熱可塑性ポリウレタン樹脂組成物(A)に由来する発泡層(a)、及び発泡剤を含有しない粉末状熱可塑性ポリウレタン樹脂組成物(B)に由来する非発泡層(b)の二層構造を有するシート状ポリウレタン樹脂成形物。
- 発泡層(a)と非発泡層(b)からなる二層構造を有するシート状ポリウレタン樹脂成形物における非発泡層(b)の厚み比が、二層構造を有するシート状ポリウレタン樹脂成形物全体の厚みに対して0.08~0.6であることを特徴とする、請求項3記載の二層構造を有するシート状ポリウレタン樹脂成形物。
- 金型表面で発泡剤を含有しない粉末状熱可塑性ポリウレタン樹脂組成物(B)を溶融させた後に、その上に請求項1又は2に記載の粉末状熱可塑性ポリウレタン樹脂組成物(A)を積層し、加熱により粉末樹脂を溶融及び発泡させて非発泡層と発泡層とを一体成形することを特徴とする、請求項3又は4に記載の二層構造を有するシート状ポリウレタン樹脂成形物の製造方法。
- 次の3工程を経ることを特徴とする、請求項5記載の二層構造を有するシート状ポリウレタン樹脂成形物の製造方法。
第一工程:200℃~300℃に予備加熱した金型内に、発泡剤を含有しない粉末状熱可塑性ポリウレタン樹脂組成物(B)を仕込み、金型を反転させて余剰の粉末材料を除去し、金型面に(B)を均一な厚みで付着かつ溶融させる工程
第二工程:(B)を金型に付着させたまま、請求項1又は2に記載の粉末状熱可塑性ポリウレタン樹脂組成物(A)を仕込んで、金型を反転させて余剰の粉末材料を除去し、(B)の層の上に所定の厚みで(A)を付着させる工程
第三工程:200~400℃の加熱オーブン内に、(B)層と(A)層が積層して付着した金型を30~120秒間入れて、粉末樹脂の溶融及び発泡を完結させ、その後加熱オーブンから取り出して金型を冷却した後、成形物を脱型する工程 - 次の3工程を経ることを特徴とする、請求項5記載の二層構造を有するシート状ポリウレタン樹脂成形物の製造方法。
第一工程:200℃~300℃に予備加熱した金型内に、発泡剤を含有しない粉末状熱可塑性ポリウレタン樹脂組成物(B)を仕込み、金型を反転させて余剰の粉末材料を除去し、金型面に(B)を均一な厚みで付着かつ溶融させる工程
第二工程:(B)を金型に付着させたまま、請求項1又は2に記載の粉末状熱可塑性ポリウレタン樹脂組成物(A)を仕込んで、金型を反転させて余剰の粉末材料を除去し、(B)の層の上に所定の厚みで(A)を付着させる工程
第三工程:(B)層と(A)層が積層して付着した金型を200℃~300℃にて30~120秒間自己加熱して粉末樹脂の溶融及び発泡を完結させ、その後金型を冷却した後、成形物を脱型する工程
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WO2010027058A1 (ja) * | 2008-09-04 | 2010-03-11 | 日本ポリウレタン工業株式会社 | 発泡性粉末状熱可塑性ポリウレタン樹脂組成物及び非発泡性粉末状熱可塑性ポリウレタン樹脂組成物、並びにシート状ポリウレタン樹脂成形物及びその製造方法 |
JP2010058388A (ja) * | 2008-09-04 | 2010-03-18 | Nippon Polyurethane Ind Co Ltd | 非発泡性粉末状熱可塑性ポリウレタン樹脂組成物、並びにそれを用いた二層構造を有するシート状ポリウレタン樹脂成形物及びその製造方法 |
JP2010059314A (ja) * | 2008-09-04 | 2010-03-18 | Nippon Polyurethane Ind Co Ltd | 発泡性粉末状熱可塑性ポリウレタン樹脂組成物、並びにそれを用いた二層構造を有するシート状ポリウレタン樹脂成形物及びその製造方法 |
WO2021170803A1 (en) * | 2020-02-28 | 2021-09-02 | Basf Se | Non-primary hydroxyl group based foams |
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JPH04218540A (ja) * | 1990-03-03 | 1992-08-10 | Basf Ag | 焼結による発泡ポリウレタン−成形物の製造法 |
JP2007253782A (ja) * | 2006-03-23 | 2007-10-04 | Mitsuboshi Kaseihin Kk | 自動車用内装品及びその製造方法 |
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WO2010027058A1 (ja) * | 2008-09-04 | 2010-03-11 | 日本ポリウレタン工業株式会社 | 発泡性粉末状熱可塑性ポリウレタン樹脂組成物及び非発泡性粉末状熱可塑性ポリウレタン樹脂組成物、並びにシート状ポリウレタン樹脂成形物及びその製造方法 |
JP2010058388A (ja) * | 2008-09-04 | 2010-03-18 | Nippon Polyurethane Ind Co Ltd | 非発泡性粉末状熱可塑性ポリウレタン樹脂組成物、並びにそれを用いた二層構造を有するシート状ポリウレタン樹脂成形物及びその製造方法 |
JP2010059314A (ja) * | 2008-09-04 | 2010-03-18 | Nippon Polyurethane Ind Co Ltd | 発泡性粉末状熱可塑性ポリウレタン樹脂組成物、並びにそれを用いた二層構造を有するシート状ポリウレタン樹脂成形物及びその製造方法 |
WO2021170803A1 (en) * | 2020-02-28 | 2021-09-02 | Basf Se | Non-primary hydroxyl group based foams |
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