WO2005012429A1 - Polyurethane resin formed product and method for production thereof - Google Patents

Abstract

A polyurethane resin formed product, characterized in that it comprises an antistatic agent and an antistatic agent auxiliary comprising a lactone type monomer; and a method for producing the polyurethane resin formed product, which comprises reacting, in a mold for forming, an organic polyisocyanate with a polyol or a urethane prepolymer containing a terminal isocyanate group with a polyamine based curing agent in the presence of an antistatic agent and an antistatic agent auxiliary comprising a lactone type monomer. The use of a combination of an antistatic agent and a lactone type monomer results in the excellent and stable manifestation of the antistatic performance capability of the agent. Further , since a lactone type monomer can be present without decomposition in the co-existence with a urethane formation catalyst, the polyol premix raw material fluid used in the method exhibits satisfactory storage stability, and, in the production of an expanded formed product from the raw material fluid, a product having excellent resistance to bending and excellent antistatic characteristics under low temperature and low moisture conditions ca be produced without an extraordinary behavior in a foaming step and the reduction of physical properties such as hardness, strength and the like.

Description

 Description Polyurethane resin molded article and method for producing the same

 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. Background art

 In recent years, from the viewpoint of preventing static electricity explosion in workplaces and the like, studies have been made to impart antistatic performance to resins and fibers used in shoes, clothes, gloves, etc. worn on the human body. It is applied to shoe soles and the like.

 Conventionally, as a method of imparting antistatic properties to a resin, a method of coating an antistatic agent made of a conductive substance, an ionic substance, or the like on the surface of a resin molded product or adding a part of the resin into the resin has been used. . 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).

However, in the method 1) of adding a conductive filler or the like, a significant increase in viscosity is caused when added to a raw material of polyurethane, which causes a problem in moldability. In addition, sufficient antistatic performance cannot be imparted by the method 2) in which a normal ionic surfactant is added alone. In addition, the perchlorate, thiocyanate, etc. method 3) produces an antistatic effect quickly by using perchlorate, thiocyanate, etc. alone, but the final performance of the molded product is not good. Is enough. In addition, in the method 4) of adding alkyl quaternary ammonium permeate, the antistatic property immediately after molding is slow, and the final performance of the molded product is low. However, it was highly dependent on humidity and could not obtain sufficient antistatic effect under low temperature and low humidity conditions.

 In contrast to these methods, 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).

 However, when formamide and cyclic carbonate are added to the polyurethane resin or polyol as a raw material of the resin, these may bleed out after molding and have poor storage stability. There is a hygiene problem as it affects safety. Cyclic carbonates are easily decomposed when heated in the presence of a catalyst, so when used as a foaming stock solution as a premix for the polyol component, foaming behavior abnormally occurs over time, resulting in a molded product with stable physical properties. Since it could not be obtained, there was a practical problem in line production.

 (Patent Document 1)

Japanese Patent Application Laid-Open No. Sho 63-343995

 (Patent Document 2).

Japanese Patent Application Laid-Open No. Hei 2-1 9 8 5 17

 (Patent Document 3)

Japanese Patent Application Laid-Open No. Hei 4-1 998 518

 (Patent Document 4)

Unexamined Japanese Patent Publication No. JP-A-2001-322953

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. Polyurethane foam by reacting with polyisocyanate 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.

 Furthermore, 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.

In addition, 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. To play. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

 Examples of the polyurethane resin molded article of the present invention 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. Modified diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, trizine diisocyanate, paraphenylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, trihydrogen hydride Examples thereof include range isocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate, and urethane prepolymers having terminal isocyanate groups obtained by reacting these polyisocyanates with polyols. Among these, from the viewpoints of physical properties, reactivity and storage stability, a terminal isocyanate group-containing perethane prepolymer is preferred.

 As the polyol used as a raw material of the urethane prepolymer containing a terminal isocyanate group, a high molecular weight polyol alone or a combination of a high molecular weight polyol and a low molecular weight polyol is preferable. Terminal isocyanate group-containing ゥ Used as a raw material for urethane prepolymer 髙 Examples of 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 of the polyol amount 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

V-call and the like.

 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, diethylene glycol, triethylene glycol, and tetraethylene glycol; and polylatatone polyols, polyetherester polyols, polycarbonate polyols, and polyester polyols. Butadiene polyol and the like. Of these, polyether polyols and polyester polyols are preferred.

 The number average molecular weight of these polyols is preferably from 500 to 100,000, more preferably from 100 to 500.

In producing 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. When the above-mentioned terminal isocyanate group-containing ethane prepolymer is used in producing a polyurethane resin foam molded article, when the terminal isocyanate group-containing phthalate prepolymer is used, it contains an antistatic agent, a ratatone monomer, a foaming agent and a retethane-forming catalyst. Preferably, the urethane prepolymer is reacted with a polyamine-based curing agent.

 Water is mainly used as the blowing agent. Further, as 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.

 Examples of urethanization catalysts include organic acid metal salts such as stannus octoate and dibutyltin dilaurate; triethylenediamine, triethylamine, N-ethylmorpholine, dimethylethanolamine, and pentamethylethylene. Examples include amines such as triamine and panolemicyldimethylamine.

 Examples of polyamine-based curing agents include 4,4'-diamino-3,3, dichlorodiphenylmethane (referred to as MB OCA), trimethylenebis (4-aminobenzoate), and methylenebis (2-ethyl-1-6-methylaniline). And phenylmethane compounds such as methylenebis (2,3-dichloroaniline), polyaminochloromethane, toluenediamine, 4,4′-diaminodiphenylmethane and the like.

 In the production of the polyurethane resin foam molded article, a foam stabilizer, a chain extender, and the like can be used as necessary.

 As the foam stabilizer, 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. .

 As the chain extender, known chain extenders can be used in addition to the low-molecular-weight polyol described above. Among them, ethylene glycol, 1,4-butanediol and diethylene glycol are preferable, and among these, ethylene glycol Is particularly preferred.

As the 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. . The mixing ratio is preferably cationic antistatic compound: anionic antistatic compound = 70 to 99% by weight: 1 to 30% by weight.

 Examples of the substituted quaternary ammonium thiothion-based antistatic compound include quaternary ammonium sulfonic acid substituted with a hydrocarbon group and an oxyhydrocarbon group (hereinafter, quaternary ammonium substituted sulfonic acid). Etc.)

Examples of the substituted sulfonic acid quaternary ammonium include, for example, methyl sulfate, tris-trimethyl-dodecyl ammonium, methyl sulfate, tri-, di-, tri-trimethyl mono-myristyl ammonium, methyl Ν, Ν, Ν-Trimethyl sulfate-palmityl ammonium, methyl sulfate, Ν, Ν, Ν-trimethyl mono-stearyl ammonium, ethyl sulphate, ェ -ethyl Ν, Ν-dimethyl ド -dodecyl ammoniumゥ 硫酸 、 ェ ェ ェ 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Dialkyl sulfate derivatives such as ethyl ethyl, di-dimethyl di-stearial ammonium, ethyl ethyl sulfate, di-ethyl morpholinium, methanesulfonate Methyl-dodecylammonium, methanesulfonic acid Ν, Ν, Ν-trimethinoleate レ ー -myristinoleammonium, methanesnolephonate Ν, Ν, Ν-trimethyl パ ル -palmitylammonium, methanesulfone Acid mono-, di-, tri-methylinoleate, stearyl ammonium, monoethyl methanesulfonate _, dimethinolate _ dodecylammonium, monomethyl methanesulfonate, dimethylinole Ν, dimethinolate Listinoleammonium, methansnolephonate, dimethylsulfonate, palmitylammonium, methanesulfonate, dimethylsulfonate, dimethylsulfonate, stearylammonium Methanesulfonic acid ester derivatives such as methanesulfonic acid Ν, Ν-jetinole morpholinium, ρ-toluenesulfonic acid 一Ν, Ν-trimethyl Ν-dodecylammonium, ρ-toluenesulfonic acid Ν, Ν, Ν-trimethylone-myristyl ammonium, ρ-toluenesulfonic acid Ν, Ν, Ν-trimethylone Ν—Palmityl ammonium, ρ Mono-toluenesulfonic acid-N, N, N-trimethyl-N-stearylammonium, p-tonorenesnolephonate-N-ethyl-N, N-dimethyl-N-dodecylammonium, p-toluenesulfonic acid N-ethyl-N, N-dimethyl-1-N-myristylammonium, p-toluenesulfonic acid-N-ethyl-N, N-dimethinole-1-N-palmitylammonium, p-tonolenesulfonic acid-N-ethyl-N P-toluenesulfonic acid ester derivatives such as N, N-dimethyl-N-stearylammonium, mono-toluenesulfonic acid, N, N-diethylmorpholine, p-toluenesulfonic acid, 1-N-ethynoleic N-methylmonophorinium No. These can be used alone or in combination of two or more.

 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.

 Examples of the organic acid metal salt-based anion-based antistatic compound 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.

 As the metal component of the metal salt, for example, from the viewpoint of solubility in an organic solvent, 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.

Preferable specific examples of the above 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. these Among them, lithium bis (trifluoromethanesulfonyl) imidium, lithium tris (trifluoromethanesulfonyl) methane, and lithium p-toluenesulfonate are particularly preferred.

Examples of the lactone-based monomer used as the antistatic auxiliary in the present invention include:] lactones such as 3-propiolactone, y-butyrolactone, δ-valerolactone, _ε -force prolacton, and γ-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, γ-butyrolataton and ε-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. By doing so, water acts as an antistatic agent and exhibits more stable antistatic performance, but cannot exhibit sufficient antistatic performance under low temperature and low 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.

 Further, in the present invention, a cyclic ketone, a sorbitan fatty acid ester or the like may be used in combination as an antistatic assistant. Examples of the cyclic ketone include cyclic ketones such as cyclopentanone, cyclohexanone, and cycloheptanone, and derivatives thereof.

 Examples of sorbitan fatty acid esters include sorbitan sesquioleate, sonorebitan monooleate, sorbitan monostearate, sonorebitan 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. In addition, from the viewpoint of maintaining the mechanical properties of the resin molded product, 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.

 From the viewpoint of maintaining sufficient antistatic performance and physical properties of the polyurethane resin molded article, 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.

 Among the above-mentioned polyols, 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. In particular, ethylene glycol is preferred. As the plasticizer, for example, 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 polyurethane resin molded body is composed of an NCO OZ active hydrogen atom (equivalent ratio) of the entire reaction component of an organic polyisocyanate, a polyol, and optionally an active hydrogen atom-containing compound such as a polyamine. (OH group, NH group, etc.) = 0.9 to 1.1.

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. For example, 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. In addition, The material of the mold may be any commonly used material such as iron, aluminum, epoxy resin and the like.

 When producing a polyurethane resin foam molded article, 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. As the foam molding machine, for example, a commonly used low-pressure foam molding machine, injection foam molding machine, or the like can be used.

 Further, as a molding method, a usual method can be adopted. When producing polyurethane resin foam molded products, 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. (4) When a urethane prepolymer containing a terminal isocyanate group is used as the organic polyisocyanate, and this is reacted with a polyamine-based curing agent, an antistatic agent is added to the urethane prepolymer. Addition of a lactone monomer may be employed.

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, In addition, polyurethane is particularly preferable because it can produce a foamed molded article having excellent antistatic performance under low temperature and low humidity conditions.

The density of the polyurethane resin expanded molded article, from the viewpoint of maintaining mechanical properties, durability, 0. 2~1. 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.

Example

 Hereinafter, the present invention will be described specifically with reference to examples. However, the present invention is not limited to the following embodiments. For example, the components of these embodiments may be appropriately combined. “Parts” and “%” in the text are based on weight. Each raw material used in the examples is shown.

Polyol

 Polyol A: Polyester polyol with a hydroxyl value of 66 mgK〇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〇H / g synthesized from diethylene glycol Z trimethylolpropane and adipic acid. Methylene glycol / trimethylolpropane molar ratio 15/1.

Organic Polysocyanate (Rethane Prepolymer Containing Terminal Isocyanate Group) NCO-terminated prepolymer 1: NCO% = 16.8% by weight containing adipic acid, ethylene glycol, polyester obtained from 1,4-butylendalcol A urethane prepolymer obtained by reacting a polyol with 4,4'-diphenylmethane diisocyanate.

NCO-terminated Prepolymer 2: NCO% = 3. 1 wt _^0/0 containing polypropylene grayed recall and tolylene I Société § Natick Bok urethane prepolymer obtained by reacting NCO group-terminated prepolymer 3: NCO% = 4.4% by weight, perethane prevo]) mer obtained by reacting polytetramethylene glycol with tolylene disocyanate. .

Antistatic compound

 · 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.

MB OCA (curing agent): 4,4 'diamino-3,3,1-dichlorodiphenylmethane

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) According to the composition table shown in Tables 1 and 2, 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.

 When the NCO / OH ratio is in the range of 0.9 to 1.1, 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. Set to.

First, after 2.5 minutes, 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. After 5 minutes

 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. .

 A: Form retains its original shape

 B: Form where the high pressure surface of the foam is depressed

Mold density measurement

Sample weight (g) was measured and calculated by dividing the volume of 0.99 cm ^3.

Hardness measurement

 The hardness of the sample was measured with an Asker C hardness tester.

Measurement of electrical resistance

Using a battery-type insulation resistance meter (Yokogawa Electric Corporation, type 260401), contact a 300 x 200 x It mm iron plate on the bottom surface of the sample and a 75 x 75 x 31 mm iron plate on the top surface. Then, after the molding, the electric resistance value was measured 1 day and 7 days later. The molded sample was stored in a desiccator, and the electrical resistance was measured under two conditions: normal temperature and low humidity (25 ° C x 15% RH) and low temperature and low humidity (10 ° C x 15% RH). The results are shown in Table 1 and Table 2.

table 1

 Example

 1 2 3 4 5 Polyol A 95 95 95 95 95 Polyol B 5 5 5 5 5 Ethylene gercol 8.5 8.5 8.5 8.5 8.5 Control foaming agent SH-193 0.5 0.5 0.5 0.5 0.5 0.5 Water 0.45 0.45 0.45 0.45 0.45 Liquid TEDA 0.76 0.76 0.76 0.76 0.76 Antistatic compound A 6.33 6.33-6.33 6.33

A Antistatic compound B-I 1.27 3.17-3.17 Liquid Butyrolactone 5.06 5.06 5.06 5.06 ε One-pot prolactone---5.06-

Solution B NCO-end pre-polymer 7.4 117.4 118.2 113.8 117.4 119.2

Solution A 50 ° C storage days (days) 0 4 0 4 0 4 0 4 0 4

High pressure test after 2.5 minutes ¹⁵ AAAAAAAAAA Mold density (g m ³ ) 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 Hardness (AskerG) 69 69 70 70 70 70 69 69 70 70 Electric resistance (ΜΩ)

 10 ° CX15% RHX1 says 75 80 48 50 90 90 80 90 25 27

10 ° C 15% RHX7 65 70 38 40 75 75 70 80 20 22

25 ° CX15% RHX1 14 16 9 8 18 20 17 19 8 8

25 ° CX15% RHX7 12 13 8 7 14 15 14 16 6 5 Tensile strength (MPa) 7.30 7.25 7.10 7.03 7.11 7.09 6.99 7.21 6.98 7.01

100 <½ modulus (MPa) 1.89 1.96 1.80 1.81 1.78 1.88 1.69 1.77 1.88 1.85

300% modulus (MPa) 3.86 3.90 3.60 3.78 3.89 3.91 3.88 3.91 3.71 3.69 Elongation (%) 500 520 480 490 480 480 490 500 470 470 Tear strength (KN / m) 28.9 30.8 27.9 29.0 29.2 28.8 28.2 29.9 27.7 26.6 Flex resistance ²⁾ AAAAAAAAAA Antistatic manifestation (10 ° C) AAAAAAAAAA Antistatic manifestation rate (10 ° C) 87% 88% 79% 80% 83% 83% 88% 89% 80% 81% Antistatic manifestation (25 ° C ) AAAAAAAAAA Antistatic rate (25 ° C) 83% 81% 81% 88% 82% 75% 82% 84% 75% 63% Table 2

 Example Comparison example

 6 1 2 3 4 Polyol A 95 95 95 95 95 Polyol B 5 5 5 5 5 Ethylene glycol 8.5 8.5 8.5 8.5 8.5 Control foam SH-193 0.5 0.5 0.5 0.5 0.5 a Water, 0.45 0.45 0.45 0.45 0.45 Liquid-TEDA 0.76 0.76 0.76 0.76 0.76 Antistatic compound A 6.33 6.33 6.33-6.33

A Antistatic compound B 1.27-1.27 3.17-Liquid 7 "-butyrolactone 2.50---Propylene carbonate--5.06

Solution B NCO end terminal Remar 118.4 117.4 120.0 112.5 117.4

Solution A 50 ° C storage days (days) 0 4 0 4 0 4 0 4 0 4

High pressure test after 2.5 minutes ¹⁾ AAAAAAAAAB Mold density (g m ³ ) 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 0.55 Hardness (Asker C) 70 70 72 72 73 72 73 72 69 63 Electric resistance (ΜΩ)

 10 ° CX15% RHX1 60 66 480 510 200 250 600 650 75 95

10 ° CX15% RHX7 40 40 250 280 150 200 350 400 65 80

25 ° CX15% RHX1 10 9 80 85 35 40 100 200 14 19

25¾x15% RH 7 8 8 40 46 27 30 60 70 12 16 Tensile strength (M Pa) 7.54 7.33 7.19 7.13 7.34 7.55 7.23 7.20 7.28 4.45

100% modulus (MPa) 1.88 1.77 1.86 1.89 1.78 1.91 1.90 1.85 1.86 0.95

3000 Modulus (M Pa) 3.66 3.45 3.88 3.78 3.92 3.86 3.88 3.80 3.78 1.99 Elongation (%) 460 450 480 480 470 480 490 460 500 360 Tear strength (KNZm) 26.7 35.8 30.4 29.9 28.9 29.6 29.8 28.8 29.6 18.9 Flexibility ^{2 )} AAAAAAAAAB Antistatic manifestation (10 ° C) AABBBBBBAB Antistatic manifestation rate (10 ° C) 67% 61% 52% 55% 75% 80% 58% 62% 87% 84% Antistatic manifestation (25 ° C) AABBBBBBAA Antistatic rate (25 ° C) 80% 89% 50% 54% 77% 75% 60% 35% 86% 84% Solution A was stored in a 50 ° C dryer for 4 days immediately after the blend. With respect to the solution A having been stored at 50 ° C for 4 days, 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.

Tensile strength

JISK using 6252-93 in accordance with the test apparatus AUTOGRAPH AG- I (Shimadzu works plant products), by sampling test pieces in the shape of a dumbbell shape No. 3 shape, tested at tensile speed = 500 mm / mi _n. The maximum tensile force until the piece was cut was defined as the tensile strength, and the distance between the marked lines at the time of cutting was measured to determine the breaking elongation. In the tensile strength test, 100% modulus, 300% modulus, and elongation at break were also measured.

Tear strength

 Using a test device AUTOGRAPH AG-I (manufactured by Shimadzu Corporation) in accordance with JISK 625 1 -93, the test specimen is sampled into an angled shape without cutting, and the test specimen is cut at a tearing rate = 500 nim / min. The maximum tear force up to was defined as the tear strength.

Flex resistance

 Using a testing device DE MATTIA FLEX CRACK I NG TESTER (TOYO SEIKI products) in accordance with JISK 6260-93, sample the specimen into a 150 x 25 x 6 mm strip shape, A 2 mm notch was made in the bend, and the bend speed was 300 rpm at room temperature. The degree of crack growth was measured with a vernier caliper every 20,000 bending cycles, and the growth width was recorded. The test was performed up to 100,000 times. The growth of the crack when it reached 100,000 times was examined and evaluated according to the following criteria.

 A: No crack growth.

B: There is crack growth. Antistatic manifestation

Hanging ¾nL

 A: The electrical resistance value on the first day at 25 is 30ΜΩ or less and the expression rate is 60% or more B: The electrical resistance value on the first day at 25 ° C exceeds 30ΜΩ and the expression rate is less than 60%

Low temperature

 A: On the first day at 10 ° C, the electrical resistance is 9 9Ω or less, and the onset rate is 60% or more. B: On the first day at 10 ° C, the electrical resistance exceeds 90 MΩ. Rate is 60% Yf¾

Antistatic rate

 The value of [(electric resistance on day 7 / electric resistance on day 1) X 100] at 25 ° C (%)

 The value of [(electric resistance value on day 7 Z electric resistance value on day 1) X 100] at 10 ° C (%)

 Examples 7-8, Comparative Examples 5-6

According to the recipes shown in Tables 3 and 4, 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.

Table 3

Table 4

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. Tensile test

 Using a test device AUTOGRAPH AG-I (manufactured by Shimadzu Corporation), the 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

 Using a test device AUTOGRAPH AG-I (manufactured by Shimadzu Corporation), the 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.

 In addition, 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.

Claims

The scope of the claims

1. A polyurethane resin molded article characterized by containing an antistatic agent and an antistatic auxiliary agent comprising a lactone monomer.

2. The polyurethane resin molded article according to claim 1, wherein the rataton-based monomer is at least one selected from γ-butyrolataton and ε-force prolactone.

3. The antistatic agent is at least one selected from quaternary ammonium cation-based antistatic compounds and metal salt-based anionic antistatic compounds, and the lactone monomer 2. The polyurethane resin molded article according to claim 1, wherein the body is at least one member selected from 0-butyrolataton and ε-force prolataton.

4. The polyurethane resin molded article according to claim 1, wherein the polyurethane resin molded article is a polyurethane resin foam molded article.

5. Production of a polyurethane resin molded article characterized by reacting (1) an organic polyisocyanate with (2) a polyol containing the antistatic agent and a lactone-based monomer in a molding die. Method.

6. The method for producing a polyurethane resin molded article according to claim 5, wherein the polyol further contains a foaming agent.

7. Polyurethane characterized in that (1) a urethane prepolymer containing terminal isocyanate group containing the antistatic agent and a lactone monomer and (2) a polyamine curing agent in a molding die. A method for producing a resin molded article.