WO2005012429A1 - ポリウレタン樹脂成形体及びその製造方法 - Google Patents

ポリウレタン樹脂成形体及びその製造方法 Download PDF

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Publication number
WO2005012429A1
WO2005012429A1 PCT/JP2004/010988 JP2004010988W WO2005012429A1 WO 2005012429 A1 WO2005012429 A1 WO 2005012429A1 JP 2004010988 W JP2004010988 W JP 2004010988W WO 2005012429 A1 WO2005012429 A1 WO 2005012429A1
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Prior art keywords
antistatic
polyurethane resin
agent
molded article
antistatic agent
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PCT/JP2004/010988
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English (en)
French (fr)
Japanese (ja)
Inventor
Masaya Masumoto
Tamotsu Sakamoto
Katsuhide Nishimura
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Dainippon Ink And Chemicals, Inc.
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Application filed by Dainippon Ink And Chemicals, Inc. filed Critical Dainippon Ink And Chemicals, Inc.
Priority to CN2004800161775A priority Critical patent/CN1871304B/zh
Priority to KR1020057023516A priority patent/KR100658111B1/ko
Publication of WO2005012429A1 publication Critical patent/WO2005012429A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0075—Antistatics
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • 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
    • C08J9/16—Making expandable particles
    • C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic

Definitions

  • the present invention relates to a polyurethane resin molded article having excellent antistatic properties and antistatic properties at low temperatures, and a method for producing the same.
  • Examples of applying these methods to polyurethane resins include: 1) a method of adding carbon black, a conductive boiler, etc., 2) a method of applying or adding an ionic surfactant, 3) a perchloric acid, A method of adding an alkali metal salt such as thiocyanic acid or nitric acid (see Patent Documents 1 and 2), 4) A method of adding quaternary ammonium alkyl sulfate / quaternary ammonium park mouthrate (Patent Document 2, Patent Documents 3), 5) Non-metallic antistatic compounds such as substituted quaternary ammonium sulfonic acid, metal antistatic compounds such as sulfonic acid metal salts, and methods of adding polar organic solvents have been proposed. (See Patent Document 4).
  • a mixture of a nonmetallic antistatic compound and a metal antistatic compound is added to a cyclic carbonate such as formamide, ethylene carbonate, or propylene carbonate in order to achieve excellent antistatic performance even at low temperatures.
  • a method has been proposed in which an antistatic agent composition to which a polar organic solvent such as described above is added is added to polyurethane (for example, see Patent Document 4).
  • Patent Document 2 (Patent Document 2).
  • Patent Document 3 Patent Document 3
  • Patent Document 4 Patent Document 4
  • An object of the present invention is to provide a polyurethane resin molded article having excellent antistatic performance and exhibiting an excellent antistatic rate and antistatic property under normal temperature, low temperature and low humidity conditions.
  • Another object of the present invention is to provide a premixed polyol solution prepared by premixing a polyol, an antistatic agent, an antistatic auxiliary agent, a foaming agent, and a catalyst, which is excellent in storage stability even after storage in a heated state, and which is excellent in organic stability.
  • An object of the present invention is to provide a production method capable of producing a polyurethane resin foam molded article excellent in bending resistance and other physical properties without producing an abnormal foaming behavior, a decrease in hardness and a decrease in strength.
  • the present inventors have conducted intensive studies on antistatic aids that improve antistatic performance in order to achieve the above object, and as a result, by adding a lactone-based monomer as an antistatic aid, control at room temperature was achieved.
  • the present inventors have found that it is possible to stably obtain an antistatic property and an excellent antistatic property under low-temperature and low-humidity conditions, and have completed the present invention.
  • the present invention provides a polyurethane resin molded article containing an antistatic agent and an antistatic auxiliary agent comprising a lactone monomer.
  • the present invention provides a method for reacting an organic polyisocyanate with a polyol in a molding die in the presence of an antistatic agent and an antistatic auxiliary agent comprising a rataton-based monomer, or Provided is a method for producing a polyurethane resin molded article by reacting an urethane prepolymer containing an isocyanate group with a polyamine-based curing agent.
  • the present invention uses a combined use of an antistatic agent and a lactone-based monomer as an antistatic auxiliary agent to provide a polyurethane resin molded article with excellent antistatic performance under low-temperature and low-humidity conditions. And an effect of imparting stable antistatic performance.
  • the present invention provides a polyol, an antistatic agent, an antistatic agent, since the rataton-based monomer used as an antistatic auxiliary can be stably present without being decomposed in the presence of a urethanization catalyst.
  • the storage stability of the stock solution prepared by premixing the agent and the catalyst in a heated state is greatly improved, and when the stock solution is reacted with an organic polyisocyanate to produce a polyurethane resin foam molded article, the foaming behavior of It is possible to provide a foam molded article with excellent flex resistance and excellent antistatic performance under low-temperature and low-humidity conditions without causing physical property deterioration such as abnormality, hardness reduction and strength reduction.
  • BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.
  • polyurethane resin molded article of the present invention examples include polyurethane resin molded articles such as thermoplastic polyurethane resin, cast polyurethane resin, and foamed polyurethane (polyurethane elastomer foam, rigid and flexible polyurethane foam). Particularly preferred is a polyurethane resin foam molded article.
  • the polyurethane resin molded article of the present invention is obtained by reacting an organic polyisocyanate with a polyol in a molding die in the presence of an antistatic agent and an antistatic auxiliary comprising a lactone monomer, or It can be produced by reacting a polyurethane prepolymer containing a terminal isocyanate group with a polyamine-based curing agent.
  • the organic polyisocyanate used in the present invention includes, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4,1-diphenylmethane diisocyanate, carbodiimidate.
  • Examples thereof include range isocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate, and urethane prepolymers having terminal isocyanate groups obtained by reacting these polyisocyanates with polyols.
  • a terminal isocyanate group-containing perethane prepolymer is preferred.
  • Terminal isocyanate group-containing ⁇ Used as a raw material for urethane prepolymer ⁇
  • molecular weight polyols include poly (oxynorylene) glycol, poly (oxytetramethylene) dalicol, and other polyether polyols, polyester polyols, polylactone polyols, and polyether esters.
  • Polyols, polycarbonate polyols, and high molecular weight polyols such as polybutadiene polyol.
  • Low molecular weight used as a raw material for urethane prepolymers containing terminal isocyanate groups examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene propylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 1,8-octanediol, neopentinole glycol, 2-methinole 1,3-propanediol, 3-methyl-1,5-pentanediol, glycerin, trimethylolpropane, diethylene glycol, triethylene glycol, tetraethylene
  • the polyol amount examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene propylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6- He
  • Examples of the polyol used for the reaction with the organic polyisocyanate include starting materials having at least two hydroxyl groups such as 1,2-propylene glycolone, glycerin, trimethylonolepropane, pentaerythritol, and sorbitol.
  • Polyether polyols such as poly (oxyalkylene) glycol and poly (oxytetramethylene) glycol obtained by addition polymerization of alkylene oxides such as oxide, propylene oxide and butylene oxide; adipic acid, sebacic acid, Polycarboxylic acids such as azelaic acid, succinic acid, maleic acid and phthalic acid and ethylene glycol, 1,2-propylene glycolone, 1,3-propylene glycol, 1,4-butanediol, 2,3-butane Diol, 1, 5-pentane Honole, 1,6-hexanediole, 1,8-octanediol, neopentyl glycol, 2-methinole 1,3-propanediol, 3-methyl-1,5-pentanedionole, glycerin, trimethyi Polyester polyols obtained by polycondensation of polyhydric alcohols such as norepropane, di
  • the number average molecular weight of these polyols is preferably from 500 to 100,000, more preferably from 100 to 500.
  • the foamed polyurethane resin article of the present invention it is preferable to react an organic polyisocynate with a polyol containing an antistatic agent, a lactone-based monomer, a foaming agent, and a urethanizing catalyst.
  • a polyol containing an antistatic agent e.g., a lactone-based monomer, a foaming agent, and a urethanizing catalyst.
  • the terminal isocyanate group-containing ethane prepolymer when used, it contains an antistatic agent, a ratatone monomer, a foaming agent and a retethane-forming catalyst.
  • the urethane prepolymer is reacted with a polyamine-based curing agent.
  • Water is mainly used as the blowing agent.
  • foaming aids for example, 1,1-dichloro-1-fluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, methylene Low boiling compounds such as chloride and pentane can be used.
  • urethanization catalysts include organic acid metal salts such as stannus octoate and dibutyltin dilaurate; triethylenediamine, triethylamine, N-ethylmorpholine, dimethylethanolamine, and pentamethylethylene.
  • organic acid metal salts such as stannus octoate and dibutyltin dilaurate
  • triethylenediamine triethylamine, N-ethylmorpholine, dimethylethanolamine, and pentamethylethylene.
  • amines such as triamine and panolemicyldimethylamine.
  • polyamine-based curing agents examples include 4,4'-diamino-3,3, dichlorodiphenylmethane (referred to as MB OCA), trimethylenebis (4-aminobenzoate), and methylenebis (2-ethyl-1-6-methylaniline).
  • MB OCA 4,4'-diamino-3,3, dichlorodiphenylmethane
  • trimethylenebis (4-aminobenzoate)
  • phenylmethane compounds such as methylenebis (2,3-dichloroaniline), polyaminochloromethane, toluenediamine, 4,4′-diaminodiphenylmethane and the like.
  • a foam stabilizer In the production of the polyurethane resin foam molded article, a foam stabilizer, a chain extender, and the like can be used as necessary.
  • any one that is effective for producing a polyurethane resin foam molded article can be used.
  • examples thereof include silicon-based compounds such as polydimethylsiloxane and polysiloxane-polyalkylene oxide block copolymer, and surfactants such as metal oxides, alkylphenols, and ethylene oxide and / or propylene oxide adducts of fatty acids. .
  • chain extender known chain extenders can be used in addition to the low-molecular-weight polyol described above.
  • ethylene glycol, 1,4-butanediol and diethylene glycol are preferable, and among these, ethylene glycol Is particularly preferred.
  • antistatic agent used in the present invention known antistatic agents can be used without particular limitation. However, it is preferable to use at least one kind of a substituted sulfonic acid quaternary ammonium-based cationic antistatic compound and an organic acid metal salt-based anionic antistatic compound, more preferably a mixture of both. .
  • substituted quaternary ammonium thiothion-based antistatic compound examples include quaternary ammonium sulfonic acid substituted with a hydrocarbon group and an oxyhydrocarbon group (hereinafter, quaternary ammonium substituted sulfonic acid). Etc.)
  • substituted sulfonic acid quaternary ammonium examples include, for example, methyl sulfate, tris-trimethyl-dodecyl ammonium, methyl sulfate, tri-, di-, tri-trimethyl mono-myristyl ammonium, methyl ⁇ , ⁇ , ⁇ -Trimethyl sulfate-palmityl ammonium, methyl sulfate, ⁇ , ⁇ , ⁇ -trimethyl mono-stearyl ammonium, ethyl sulphate, ⁇ -ethyl ⁇ , ⁇ -dimethyl ⁇ -dodecyl ammonium ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
  • Substituted sulfonic acid quaternary ammonium is reacted by dropping an equivalent amount of dialkyl sulfuric acid to tertiary amine in one or more solvents such as ethylene glycol, 1,4-butanediol, and diethylene dalicol. Thus, it can be easily prepared.
  • organic acid metal salt-based anion-based antistatic compound examples include metal salts of bis (trifluoromethanesulfonyl) imid, metal salts of tris (trifluoromethanesulfonyl) methane, metal salts of 'alkylsulfonic acid, benzene
  • An organic metal salt such as a metal sulfonic acid salt or a metal alkyl benzene sulfonic acid salt is mentioned, and a metal salt of bis (trifluoromethanesulfonyl) imid and a metal salt of tris (trifluoromethanesulfonyl) methane are particularly preferable.
  • an alkali metal such as lithium, sodium, or potassium, or an alkaline earth metal such as magnesium is preferable, and lithium is particularly preferable. Particularly preferred.
  • bis (trifluoromethanesulfonyl) imid metal salt and tris (trifluoromethanesulfonyl) methane metal salt include bis (trifluoromethanesulfonolino) imidolithium and bis (trifluoromethanesulfonyl) Imidonadium, bis (trifluoromethanesulfonyl) imidium potassium, tris (trifluoronorethosulfonyl) methanelithium, tris (trifluoromethanesulfonyl methanesulfonyl) methane sodium, and tris (trifluoromethanesulfonyl) methane potassium, p- And lithium toluenesulfonate.
  • lithium bis (trifluoromethanesulfonyl) imidium, lithium tris (trifluoromethanesulfonyl) methane, and lithium p-toluenesulfonate are particularly preferred.
  • lactone-based monomer used as the antistatic auxiliary in the present invention examples include:] lactones such as 3-propiolactone, y-butyrolactone, ⁇ -valerolactone, ⁇ -force prolacton, and ⁇ -crotonolactone. Monomers can be used, and each can be used alone or in combination of two or more. From the viewpoint of improving and exhibiting particularly excellent antistatic performance, ⁇ -butyrolataton and ⁇ -force prolataton are preferred. When only the cationic antistatic compound or the metal salt anionic antistatic compound is added to the polyurethane resin, the antistatic effect has a large temperature and humidity dependency, and adsorbs moisture in the atmosphere under high humidity conditions.
  • the present invention can further provide a stable and excellent antistatic expression rate and antistatic property even under low-temperature and low-humidity conditions by using a rataton-based monomer in combination.
  • a cyclic ketone a sorbitan fatty acid ester or the like may be used in combination as an antistatic assistant.
  • the cyclic ketone include cyclic ketones such as cyclopentanone, cyclohexanone, and cycloheptanone, and derivatives thereof.
  • sorbitan fatty acid esters examples include sorbitan sesquioleate, recbitan monooleate, sorbitan monostearate, recbitan monolaurate, polyoxyethylene sonorebitan monodiolate, polyoxyethylene sonorebitan Monostearate, polyoxyethylene sorbitan monooleate, and the like.
  • the content of the antistatic agent in the polyurethane resin molded article is preferably 0.5% by weight or more, and more preferably 1% by weight or more, from the viewpoint of sufficiently exhibiting the antistatic performance. From the viewpoint of maintaining the mechanical properties of the resin, the content is preferably 10% by weight or less, more preferably 7% by weight or less. Therefore, the content of the antistatic agent is preferably from 0 :! to 10% by weight, more preferably from 1 to 7% by weight.
  • the content of the rataton-based monomer in the polyurethane resin molded article is preferably 0.1% by weight or more, more preferably 1% by weight or more, from the viewpoint of sufficiently exhibiting antistatic performance.
  • the content is preferably 6% by weight or less, more preferably 4% by weight or less. Therefore, the content of the rataton-based monomer in the polyurethane resin molded body is preferably 0.1 to 6% by weight, and more preferably 1 to 4% by weight.
  • the content ratio of the rataton-based monomer to the antistatic agent is set to 1 / 2 to 2 OZl are preferred, and 2 to 3 OZl is particularly preferred.
  • the antistatic agent is appropriately used to adjust the flexibility of the polyol or the molded product, as a raw material of the polyurethane resin molded product, so that the antistatic agent is uniformly contained in the polyurethane resin molded product. It is preferable to use it in the state of being dissolved in advance in a plasticizer or the like when producing a polyurethane resin molded article.
  • ethylene glycol, diethylene glycol and 1,4-butanediol have good solubility with an antistatic agent, particularly a cationic antistatic compound and an aion antistatic compound, and thus a concentrated solution is used. It can be made and is preferable from this viewpoint.
  • ethylene glycol is preferred.
  • polyester plasticizers such as azide type and benzoic acid type are preferable.
  • the polyurethane resin molded article of the present invention has a flame retardant, a plasticizer, a filler, a coloring agent, a weather stabilizer, a light stabilizer, and an antioxidant in addition to the components described above, as long as the antistatic property and the moldability are not impaired.
  • An additive such as an agent can be appropriately used.
  • the mold used in the present invention can be used without any particular limitation as long as it is used as a mold for forming a molded body, and may have any shape.
  • it includes not only the commonly used upper mold and lower mold open molds, flat molds, cylindrical molds and concave molds, but also closed molds used in injection molding.
  • the material of the mold may be any commonly used material such as iron, aluminum, epoxy resin and the like.
  • a foaming agent and a urethanization catalyst are added to the polyol, and, if necessary, a foam stabilizer and a chain extender optionally added to the extent that the antistatic property and moldability are not impaired. It is preferable to use a mixture in which a flame retardant, a plasticizer, a filler, a colorant, a weather stabilizer, a light stabilizer, an antioxidant and the like are premixed in advance.
  • the organic polyisocyanate and such premixed mixture can be mixed and foamed by high-speed stirring in a foam molding machine.
  • the foam molding machine for example, a commonly used low-pressure foam molding machine, injection foam molding machine, or the like can be used.
  • a molding method a usual method can be adopted.
  • a molding method in which the mixed foaming liquid discharged from the molding machine is openly injected into the mold, and an injection in which the mixed foaming liquid is directly injected into a closed mold directly connected to the discharge port of the molding machine.
  • a molding method or the like can be adopted.
  • Examples of a method of adding an antistatic agent and a lactone monomer in producing a polyurethane resin molded article include (1) a method of premixing an antistatic agent and a rataton monomer into a polyol, (2) ) A method in which the antistatic agent and the rataton-based monomer are not premittently added and are independently added from the organic polyisocyanate and the polyol. (3) The anti-static agent is premitted in the polyol and the lactone-based monomer is converted into an organic compound.
  • the lactone monomer used as an antistatic auxiliary in the present invention can be stably stored without decomposition even when stored in a heated state in the presence of a urethanization catalyst.
  • Any of the addition methods 1) to (4) can be adopted.
  • the method (1) is a method in which an antistatic agent and a lactone-based monomer are premixed with a polyol, a foaming agent, and a catalyst, the foaming stock solution is stored in a heated state, and then foamed by a reaction with an organic polyisocyanate. Without foaming behavior abnormality, hardness decrease and strength decrease,
  • polyurethane is particularly preferable because it can produce a foamed molded article having excellent antistatic performance under low temperature and low humidity conditions.
  • L gZcm 3 is preferably, 0. 3 ⁇ 0. 8 gZcm 3 more favorable preferred, 0. 4 ⁇ 0. 7 g / 7 cm 3 being most preferred.
  • the polyurethane resin foam molded article of the present invention is used as a polyurethane elastomer foam to prevent safety explosion in workplaces and the like, and to prevent traces of dust, dust, and static electricity in IC factories. It can be suitably used as shoe soles.
  • Polyol A Polyester polyol with a hydroxyl value of 66 mgK ⁇ H / g synthesized from ethylene glycol / 1,4-butylene glycol and adipic acid. Ethylene glycolone Zl, 4-butyleneglycol mole ratio 5/5.
  • Polyol B Polyester polyol with a hydroxyl value of 6 OmgK ⁇ H / g synthesized from diethylene glycol Z trimethylolpropane and adipic acid. Methylene glycol / trimethylolpropane molar ratio 15/1.
  • Ethylene dalicol containing 90% by weight of antistatic compound A Ethylene glycol solution containing 90% by weight of mono-N-ethyl-N, N-dimethyl-N-dodecylammonium sulfate.
  • Ethylene glycol containing 50% by weight of antistatic compound B Ethylene glycol solution containing 50% by weight of bis (trifluoromethanesulfol) imidolithium.
  • Plasticizer solution containing 20% by weight of antistatic compound C An adipate-based plasticizer solution containing 20% by weight of lithium bis (trifluoromethanesulfonyl) imide.
  • Silicone foam stabilizer SH-193, Toray's Dow Corning Silicone Co., Ltd.
  • Product Foaming agent water
  • Urethane-forming catalyst Triethylenediamine (hereinafter referred to as TED A)
  • Examples 1 to 6 Comparative Examples 1 to 4 (Production of polyurethane elastomer foam)
  • the polyol, foaming agent, catalyst, foam stabilizer, chain extender, antistatic composition And an isocyanate component (hereinafter referred to as Liquid B) comprising the above-mentioned organic polyisocyanate.
  • Solution A and Solution B each adjusted to 40 ° C are mixed and stirred using a low-pressure foaming machine, and the mixed foaming solution is poured into a mold having an inner dimension of 150 ⁇ 100 ⁇ 1 OHmm, and the mold temperature is 45 ⁇ Samples were molded at 1 ° C with a demold time of 4 minutes.
  • the mixing ratio of Liquid A / B is such that the strength of the free foam becomes the strongest 2.5 minutes after the start of the discharge of the mixed foaming liquid.
  • the sample molded by the above method was subjected to a high pressure test, a mold density, an ASKER C hardness, and an electrical resistance value.
  • the test method and evaluation criteria for each item are described below. 2.
  • the liquid A / liquid B was mixed and stirred at a predetermined mixing ratio with a low-pressure foaming machine, and 150 g of the mixed foaming liquid was poured into a wooden foaming box of 100 ⁇ 100 ⁇ 5 OHmm to cause free foaming. 2.5 minutes after the start of the foaming liquid discharge, the foam was taken out of the foam box, immediately applied a strong pressure to the foam with a fist, bent, and the appearance of foam strength was evaluated based on the degree of collapse of the foam according to the following criteria. .
  • Sample weight (g) was measured and calculated by dividing the volume of 0.99 cm 3.
  • the hardness of the sample was measured with an Asker C hardness tester.
  • a Antistatic compound B-I 1.27 3.17-3.17 Liquid Butyrolactone 5.06 5.06 5.06 5.06 ⁇ One-pot prolactone---5.06-
  • Solution A 50 ° C storage days (days) 0 4 0 4 0 4 0 4 0 4 0 4
  • a Antistatic compound B 1.27-1.27 3.17-Liquid 7 "-butyrolactone 2.50---Propylene carbonate--5.06
  • Solution A 50 ° C storage days (days) 0 4 0 4 0 4 0 4 0 4 0 4
  • a foamed mixed solution was prepared by the above method, and foamed to obtain a sample. After 2.5 minutes, the sample was subjected to a high pressure test, a mold density, an Asker C hardness, an electric resistance value, a tensile strength, a tear strength and a flex resistance. Each item was evaluated in the same manner as described above. 2.After 5 minutes, high pressure test, mold density, ASKER C hardness and electric resistance value are performed in the same manner as above, and tensile strength, tear strength and flex resistance are performed in the following way. Was. The results are shown in Tables 1 and 2.
  • the maximum tear force up to was defined as the tear strength.
  • A The electrical resistance value on the first day at 25 is 30 ⁇ or less and the expression rate is 60% or more
  • B The electrical resistance value on the first day at 25 ° C exceeds 30 ⁇ and the expression rate is less than 60%
  • the temperature of the urethane prepolymer containing terminal isocyanate groups was adjusted to 80 ° C, and the temperature of MBOCA (polyamine curing agent) was adjusted to 120 ° C. C and y-butyrolactone are stirred and mixed at an R value (NH 2 ZNCO ratio) of 0.9 between the prepolymer and the curing agent, and after sufficient defoaming, cast into a mold at a mold temperature of 110 ° C. Then, molding was performed under the curing conditions shown in Tables 3 and 4 to obtain samples.
  • MBOCA polyamine curing agent
  • the hardness, tensile strength, elongation, 100% modulus, 300% modulus, tear strength, rebound resilience, and compression set of the molded products in Tables 3 and 4 were determined using the samples described above and in accordance with JI SK-731 by the following methods. It was measured. Electric resistance value is measured by the above method Hardness test method (molded product hardness)
  • the hardness of the elastomer was measured using a type A durometer (DUROMETER) hardness test.
  • test piece was a 2 mm-thick elastomer molded product, and the shape of the test piece was a dumbbell-shaped No. 3 test piece.
  • the maximum stress (tensile strength) and the elongation at the time of cutting of the elastomer, and the stress (100% modulus, 300% modulus) for a specific elongation were measured. Tear test
  • test piece was a 2 mm-thick elastomer molded product, the shape of which was cut at an angle and the tear strength before cutting was measured. Rebound resilience test
  • the test piece is a 12.5mm thick (height), 29mm diameter, right cylindrical elastomer molded product.
  • An iron bar suspended horizontally by four fishing lines using a rebound resilience tester (a product of Ueshima Seisakusho). (A round bar with a length of 356 mm, a diameter of 12.5 mm, and a mass of 0.35 kg) was suspended from the top at a height of 2000 mm, dropped freely from the horizontal position of the horizontal bar to a height of 100 mm vertically, and dropped onto the molded product. To determine the rebound resilience. Compression set test
  • the test piece is a 12.5 mm thick (height), 29 mm diameter, right cylindrical elastomer molded article. Compressed at 70 ° C for 22 hours, 25% in the thickness direction, and calculated compression set I asked.
  • INDUSTRIAL APPLICABILITY The present invention provides an excellent polyurethane resin molded article under low temperature and low humidity conditions by using an antistatic agent and a rataton-based monomer as an antistatic auxiliary agent in combination. Also imparts antistatic performance and stable antistatic performance.
  • the present invention provides a polyol, an antistatic agent, an antistatic agent, since the lactone monomer used as an antistatic auxiliary can be stably present without being decomposed in the presence of a urethanization catalyst.
  • the storage stability of the stock solution prepared by premixing the agent and the catalyst in a heated state is greatly improved, and when the stock solution is reacted with an organic polyisocyanate to produce a polyurethane resin foam molded article, the foaming behavior of The foamed molded article can be provided with excellent flex resistance and excellent antistatic performance under low-temperature and low-humidity conditions without causing physical properties such as abnormality, hardness reduction, and strength reduction.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2004/010988 2003-07-31 2004-07-26 ポリウレタン樹脂成形体及びその製造方法 WO2005012429A1 (ja)

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CN2004800161775A CN1871304B (zh) 2003-07-31 2004-07-26 聚氨酯树脂模塑体及其制造方法
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EP1630183A1 (de) * 2004-08-31 2006-03-01 Bayer MaterialScience AG Polyurethanelastomere mit verbessertem antistatischen Verhalten
US11008439B2 (en) 2015-10-02 2021-05-18 The Chemours Company Fc, Llc Solid polymeric articles having hydrophobic compounds intermixed therein

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CN101486890B (zh) * 2008-04-30 2012-11-14 上海工程技术大学 一种抗静电剂及其抗静电聚氨酯弹性体材料
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CN102161742A (zh) * 2011-03-24 2011-08-24 上海科华聚氨酯制品有限公司 一种有机高分子聚氨酯弹性体及其制备方法
CN102337020B (zh) * 2011-06-24 2013-03-20 苏州新纶超净技术有限公司 较低湿度条件下使用的防静电聚氨酯弹性体材料及其制备方法
JP5810767B2 (ja) * 2011-09-06 2015-11-11 Dic株式会社 ２液硬化型発泡ポリウレタン樹脂組成物、ウレタン成形体、靴底、及び工業部材
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KR101733081B1 (ko) 2015-03-19 2017-05-08 한국화학연구원 폴리우레탄용 대전방지제 및 이를 이용하여 제조되는 대전방지 기능이 부여된 폴리우레탄 폼 성형체
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CN109796748B (zh) * 2019-02-15 2021-09-17 美瑞新材料股份有限公司 一种阻燃抗静电热塑性聚氨酯弹性体及其制备方法和应用
WO2022219891A1 (ja) 2021-04-13 2022-10-20 Dic株式会社 積層体及び靴底

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EP1630183A1 (de) * 2004-08-31 2006-03-01 Bayer MaterialScience AG Polyurethanelastomere mit verbessertem antistatischen Verhalten
US11008439B2 (en) 2015-10-02 2021-05-18 The Chemours Company Fc, Llc Solid polymeric articles having hydrophobic compounds intermixed therein

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CN1871304A (zh) 2006-11-29
TW200513528A (en) 2005-04-16
TWI327163B (en) 2010-07-11
JP2005060683A (ja) 2005-03-10
JP3772897B2 (ja) 2006-05-10
CN1871304B (zh) 2010-04-21
KR20060016111A (ko) 2006-02-21
KR100658111B1 (ko) 2006-12-14

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