WO2010101294A1 - Dicyanamide organic salt as antistatic agent in polyurethane resin - Google Patents

Dicyanamide organic salt as antistatic agent in polyurethane resin Download PDF

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Publication number
WO2010101294A1
WO2010101294A1 PCT/JP2010/053930 JP2010053930W WO2010101294A1 WO 2010101294 A1 WO2010101294 A1 WO 2010101294A1 JP 2010053930 W JP2010053930 W JP 2010053930W WO 2010101294 A1 WO2010101294 A1 WO 2010101294A1
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Prior art keywords
polyurethane resin
antistatic agent
antistatic
molding
resin molding
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PCT/JP2010/053930
Other languages
French (fr)
Inventor
Yasuyuki Maeda
Makoto Nishikawa
Kazuhiko Ikebata
Toshihide Tsukatani
Original Assignee
Nicca Chemical Co., Ltd.
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Publication date
Application filed by Nicca Chemical Co., Ltd. filed Critical Nicca Chemical Co., Ltd.
Publication of WO2010101294A1 publication Critical patent/WO2010101294A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/20—Quaternary compounds thereof
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
    • C08K5/3155—Dicyandiamide
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • 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 an antistatic agent comprising, as an effective component, an organic salt in which an anionic component is a dicyanamide anion and a cationic component is a cation having no halogen atom.
  • an antistatic agent used in a polyurethane resin molding such as polyurethane fibers, polyurethane foams and the like; an antistatic polyurethane resin molding and a method of producing an antistatic polyurethane resin molding, using the antistatic agent.
  • the present invention relates to use of the organic salt, as an antistatic agent, in the production of a polyurethane resin or a polyurethane resin molding; and use of the organic salt, as an antistatic agent, in a polyurethane resin or a polyurethane resin molding.
  • a high molecular material represented by a polyurethane resin having a volumetric specific resistance more than 10 13 ⁇ cm the contact surface with other objects easily tends to build up a positive or negative large static charge by friction.
  • electric charges are not leaked to cause various electrostatic troubles and a commercial product using such a high molecular material adsorbs dust from the air by electrostatic suction, thereby decreasing the commercial value.
  • a high molecular material may in some cases cause fire such as dust explosion by discharge spark, ignition of a flammable solvent and the like, depending on their uses and their use conditions, for example, at the time of the processing in a processing factory.
  • the conductive filler when used by blending it to a starting material for a polyurethane resin, it is required to be added in a large amount of the conductive filler in order to obtain the desired antistatic property.
  • the addition of the conductive filler in a large amount causes a drawback that such a method is difficult to use regarding the handling of the starting material because of increase of the viscosity of the starting material.
  • use of the quaternary ammonium salt type antistatic agent causes problems to obtain the antistatic property, i.e., a sufficient effect was not obtained, and a high addition level was required. Further, there is a problem from the viewpoint of environmental load because a quaternary ammonium perchlorate has a halogen.
  • an ionic liquid which is composed of an organic compound and has a melting point of room temperature or less
  • its application as an antistatic agent for a polymer has been found out from the viewpoint of its conductivity and poor volatility (Japanese Patent Laid- Open No. 2003-511505).
  • Japanese Patent Laid- Open No. 2003-511505 Japanese Patent Laid- Open No. 2003-511505
  • most of the anions have a halogen such as fluorine atom and the like, there is a problem from the viewpoint of environmental load.
  • WO 07/090755 discloses 1-ethyl-3-methylimidazolium dicyanamide and 1-butyl-3-methylimidazolium dicyanamide as an antistatic agent for polyurethane resins.
  • An object of the present invention is to provide an antistatic agent for a polyurethane resin comprising, as an effective component, an organic salt having no halogen atom, which exhibits a sufficient antistatic property with a smaller addition amount.
  • a further object of the present invention is to provide an antistatic polyurethane resin molding and a method of producing the antistatic polyurethane resin molding, using the same.
  • Another object of the present invention is to provide the use of the organic salt, as an antistatic agent, in the production of a polyurethane resin or a polyurethane resin molding, as well as the use of the organic salt, as an antistatic agent, in a polyurethane resin or a polyurethane resin molding.
  • the antistatic agent of the present invention is characterized by mainly comprising an organic salt in which an anionic component is a dicyanamide anion and a cationic component is a cation having no halogen atom, and which can impart an antistatic property to a polyurethane resin with a smaller addition amount. Further, since an organic salt having no halogen atom is used as the effective component of the antistatic agent according to the present invention, the entire antistatic agent can be prepared in a form having no halogen atom.
  • the antistatic agent for a polyurethane resin of the present invention comprises, as an effective component, an organic salt composed of a dicyanamide anion represented by the following general formula (1) and a cation represented by the following general formula (2):
  • R 1 represents a linear or branched alkyl group having 1 to 8 carbon atoms, an aryl group or a benzyl group
  • R 2 and R 3 are the same or different and represent H or a linear or branched alkyl group having 1 to 8 carbon atoms.
  • a first aspect of an antistatic polyurethane resin molding according to the present invention is characterized by comprising the above-mentioned antistatic agent.
  • a second aspect of an antistatic polyurethane resin molding according to the present invention is characterized in that the above-mentioned antistatic agent is adhered to at least the surface of a polyurethane resin molding.
  • a polyurethane resin composition according to the present invention is characterized by comprising the above-mentioned antistatic agent and a polyurethane resin.
  • a first aspect of the method of producing an antistatic polyurethane resin molding according to the present invention is characterized in comprising the steps of obtaining a polyurethane resin from a mixture comprising a polyol and a polyisocyanate, and obtaining a polyurethane resin molding, wherein the above-mentioned antistatic agent is added in the step of obtaining the polyurethane resin to provide antistatic property to the polyurethane resin molding.
  • An antistatic polyurethane resin molding can be obtained according to the production method of the first aspect by adding the antistatic agent during the preparation of the polyurethane resin from a mixture comprising a polyol and a polyisocyanate.
  • the preferable production method according to the first aspect includes the following methods:
  • the antistatic property is provided to the polyurethane resin molding by curing a mixture comprising a polyol, a polyisocyanate and the antistatic agent under a condition for molding; and (2) a method, wherein the antistatic property is provided to the polyurethane resin molding by obtaining a polyurethane resin from a mixture comprising a polyol, a polyisocyanate and the antistatic agent; and molding the polyurethane resin thus obtained.
  • a second aspect of a method for producing an antistatic polyurethane resin molding according to the present invention is characterized in that the above-mentioned antistatic agent is blended with a polyurethane resin composition comprising a polyurethane resin, followed by molding the mixture thus obtained.
  • a third aspect of a method for producing an antistatic polyurethane resin molding according to the present invention is characterized in that the above-mentioned antistatic agent is applied to the surface of a polyurethane resin molding or the above-mentioned antistatic agent is impregnated in a polyurethane resin molding.
  • the present invention further includes the use of an organic salt in which an anionic component is a dicyanamide anion represented by the general formula (1) and a cationic component is a cation represented by the general formula (2), as an antistatic agent in the production of a polyurethane resin or a polyurethane resin molding.
  • the effective component of the antistatic agent has poor volatility even at room temperature and at a high temperature
  • the effective component of the antistatic agent has a good compatibility with a polyol and a polyisocyanate
  • the effective component of the antistatic agent has an excellent antistatic property even under a low humidity condition because it is a compound having electric charges.
  • the organic salt in the present invention has no anion component having a halogen atom such as tetrafluoroboric acid anion, bistrifluoromethyl sulfonylimide anion and the like, and a cation having no halogen atom, the organic salt is advantageous in the following points:
  • the organic salt has a low load to environment.
  • the present invention can impart an excellent antistatic property to a polyurethane resin molding by using the organic salt consisting of a dicyanamide anion of the general formula . (1) and a cation of the general formula (2) as an effective component. Therefore, the present invention can provide an antistatic agent for a polyurethane resin, an antistatic polyurethane resin molding and a method of producing a polyurethane resin molding, using the same.
  • the present invention can provide the use of the organic salt, as an antistatic agent, in the production of a polyurethane resin or a polyurethane resin molding, as well as the use of the organic salt, as an antistatic agent, in a polyurethane resin or a polyurethane resin molding.
  • An antistatic agent for a polyurethane resin of the present invention contains as an effective component an organic salt in which an anionic component is a dicyanamide anion represented by the following general formula (1) and a cationic component is a cation represented by the following general formula (2):
  • R 1 represents a linear or branched alkyl group having 1 to 8 carbon atoms, an aryl group or a benzyl group, and R 2 and R 3 are the same or different and represent H or a linear or branched alkyl group having 1 to 8 carbon atoms.
  • an organic salt is more preferable, in which R 1 is a linear or branched alkyl group having 1 to 8 carbon atoms, and one of R 2 and R 3 is H, while the other is a methyl group, because it has a good compatibility with a polyisocyanate and a polyol. Further, an organic salt is especially preferable, in which R 1 is a linear or branched alkyl group having 2 to 4 carbon atoms, and one of R 2 and R 3 is H, while the other is a methyl group, because it is further excellent in the antistatic properties. In addition, in these cases, the position of the methyl group is preferably at 3- or 4- position.
  • aryl group as each substituent in a quaternary ammonium represented by the general formula (2), there may be mentioned a phenyl group.
  • the present inventors infer that the reason why an organic salt, which is an effective component of the antistatic agent of the present invention, exhibits an excellent effect as an antistatic agent is in the following manner.
  • a dicyanamide anion has a molecular weight of approximately 66.
  • the dicyanamide anion is one of anions having the least molecular weight as an anion as a component of an organic salt having usually a melting point of room temperature or lower. For this reason, the organic salt alone has a high electric conductivity, contributing to the reduction of the leakage resistance value of a polyurethane resin.
  • a polyurethane resin is a resin having a urethane bond which has a high polarity.
  • the dicyanamide anion is an anion only consisting of C and N from C, N and O which are constituent elements of a urethane bond and has a high affinity with a urethane bond.
  • the antistatic agent of the present invention is easily blended into a polyurethane resin.
  • a dicyanamide anion becomes easily compatible with the hard segment region containing urethane bonds from the viewpoint of the constituent elements. That is, the organic salt used in the present invention is not microscopically uniformly distributed in a polyurethane resin and is unevenly distributed in the hard segment region.
  • the organic salt forms a continuous contact structure (percolation structure) and accordingly, a conductive path having a high electric conductivity is efficiently formed, thereby specifically reducing the leakage resistance value and, as a result, enabling to exhibit high antistatic properties.
  • the present inventors infer in the same manner as in the case where the antistatic agent of the present _
  • the present inventors infer that since the affinity between the dicyanamide anion and the urethane bond is high and the wettability of the organic salt to a molded surface is high, a continuous contact structure (percolation structure) is easily formed and a conductive path having a high electric conductivity is efficiently formed.
  • the affinity of the organic salt to polyurethane resins can be further improved by combining the pyridinium cation represented by the general formula (2) with dicyanamide anion.
  • the organic salt of the pyridinium cation is better than that of an imidazolium cation in the affinity to the polyurethane.
  • the organic salt used in the present invention may effectively exhibit the antistatic effect in a polyurethane resin having a urethane bond(s) and the kind of target polyurethane resin is not limited.
  • An antistatic agent of the present invention may be prepared by the above-mentioned organic salt alone or together with a solvent.
  • the solvents for preparing the antistatic agent include alcohols such as ethanol, ethanol, isopropanol and the like; glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and the like; and water.
  • the solvent may be used alone or in combination with two or more solvents, depending on the intended application.
  • An antistatic polyurethane resin molding may be obtained by adding the antistatic agent of the present invention in a polyurethane resin molding.
  • an antistatic polyurethane resin molding may be obtained by applying the antistatic agent of the present invention onto to the surface of a polyurethane resin molding or impregnating the antistatic agent of the present invention in a polyurethane resin molding. Both of the methods can impart excellent antistatic properties to a polyurethane resin molding. Two or more of these methods may be used in combination.
  • the content of the organic salt is preferably from 0.01 to 5 % by mass (wt.%), and more preferably from 0.03 to 3.5 % by mass, based on the mass of a polyurethane resin.
  • the adhered amount of an organic salt is preferably from 0.02 to 1 g/m 2 . In both cases, if the amount of the organic salt is less than the above range, the antistatic property may become insufficient.
  • the moldings include various types of moldings such as polyurethane fibers, films, elastomers, polyurethane foams (soft, hard or semi-hard polyurethane foams, buffer materials) and the like, and surface coating materials such as surface layers of artificial leathers and various paints, and the like.
  • an antistatic polyurethane resin molding may be produced by the following methods, (i) A production method comprising the steps of obtaining a polyurethane resin from a mixture comprising a polyol and a polyisocyanate, and obtaining a polyurethane resin molding, wherein an antistatic agent according to the present invention is added in the step of obtaining the polyurethane resin to provide antistatic property to the polyurethane resin molding.
  • the antistatic polyurethane resin molding is obtained by adding the antistatic agent according to the present invention at any step of the preparation of the polyurethane resin molding from a mixture comprising a polyol and a polyisocyanate to which an additive(s) such as a catalyst, a chain-elongating agent, a foaming agent, a foam-adjusting agent and the like are optionally added.
  • an additive(s) such as a catalyst, a chain-elongating agent, a foaming agent, a foam-adjusting agent and the like are optionally added.
  • the addition amount of the antistatic agent in this case is preferable in the above- mentioned range based on the mass of a polyurethane resin to be produced
  • the amount of the organic salt is preferably from 0.01 to 5 % by mass and more preferably from 0.03 to 3.5 % by mass).
  • the step of obtaining a polyurethane resin and the step of obtaining a polyurethane resin molding can are carried out simultaneously, partially simultaneously or separately.
  • the preferable embodiments of above-mentioned production method (i) include the following methods, (ia) A method, wherein the antistatic property is provided to the polyurethane resin molding by curing a mixture comprising a polyol, a polyisocyanate and the antistatic agent according to the present invention, under a condition for molding.
  • a polyurethane resin is prepared from a mixture comprising a polyol, a polyisocyanate and the antistatic agent of the present invention for molding and, then, the polyurethane resin thus obtained is molded.
  • the addition amount of the antistatic agent in these cases are preferable in the above-mentioned range based on the mass of a polyurethane resin to be produced (that is, the amount of the organic salt is preferably from 0.01 to 5 % by mass and more preferably from 0.03 to 3.5 % by mass).
  • the antistatic agent is added to the reaction system at the stage where the effect as the antistatic agent is effectively obtained.
  • the antistatic agent may be added in advance to at least one of a component containing a polyol and a component containing a polyisocyanate.
  • the antistatic agent may be also added to a reaction system in which a component containing a polyol and a component containing a polyisocyanate are mixed.
  • the antistatic agent of the present invention is preferably mixed in advance with a polyol or a polyisocyanate, especially a polyol.
  • the content of the organic salt is preferably from approximately 0.05 to 5.0 % by mass based on the mass of a polyol.
  • the molding conditions in above-mentioned production method (i) may be provided according to various molding methods.
  • the molding methods are not particularly limited and a conventionally well-known method can be used.
  • a mixture is prepared by adding a catalyst, water, a foam-adjusting agent and an antistatic agent according to the present invention to a polyol in advance and followed by mixing the mixture well.
  • the mixture and a slightly excessive amount of polyisocyanate are mixed well with a stirrer for a polyurethane preparation, and the resulting mixture is foamed on a belt conveyor or by placing it into a mold for molding.
  • the molding conditions may be provided by a flat surface formed by a belt of a belt conveyor, a surface of a substrate for molding, an extrusion molding vessel, a film-forming roller and the like.
  • the timing of molding and curing of the mixture may be set depending on the curing conditions such as the curing temperature of the mixture and the like.
  • an antistatic agent consisting of the above-mentioned organic salt may be added as it is.
  • the antistatic agent may be added as a solution prepared by dissolving the above-mentioned organic salt in a solvent.
  • the solvent used includes the solvents for preparing the antistatic agent as described above, as well as publicly known solvents or liquid mediums for dissolution or dispersion of polyurethane resins.
  • the antistatic agent of the present invention is blended to a polyurethane resin composition containing a polyurethane resin, followed by molding the mixture.
  • the polyurethane resin composition is not particularly limited as long as it is a resin composition for obtaining a molding which contains a polyurethane resin.
  • the polyurethane resin compositions include liquid polyurethane compositions such as a water-dispersing type and a solvent-solution type.
  • the addition amount of the antistatic agent in this case is preferably in the above- mentioned range based on the mass of a polyurethane rein (that is, the amount of an organic salt is preferably from 0.01 to 5 % by mass and more preferably from 0.03 to 3.5 % by mass).
  • an antistatic agent of the present invention when added to a polyurethane resin composition, an antistatic agent consisting of the above-mentioned organic salt may be added as it is.
  • the antistatic agent may be added as a solution prepared by dissolving the above-mentioned organic salt in a solvent.
  • the solvent used includes the solvents for preparing the antistatic agent as described above.
  • glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and the like are preferably used.
  • a resin(s) other than a polyurethane resin and a various additive(s), in addition to the polyurethane resin and the antistatic agent may be blended to the polyurethane resin composition.
  • the antistatic agent of the present invention is applied to the surface of a polyurethane resin molding or impregnated in a polyurethane resin molding.
  • an antistatic agent consisting of the above-mentioned organic salt may be used as it is.
  • the antistatic agent may be used as a solution prepared by dissolving the above-mentioned organic salt in a solvent.
  • the solvent used includes the solvents for preparing the antistatic agent as described above.
  • the method of application and impregnation is not particularly limited and a method of coating, spraying, dipping or the like can be used.
  • the antistatic agent of the present invention When the antistatic agent of the present invention is impregnated in a polyurethane resin molding, the antistatic agent is preferably imparted at least on the surface of the polyurethane resin molding.
  • the adhered amount in this case may be selected from the above range for application.
  • a molding After the antistatic agent of the present invention is applied or impregnated, a molding may be dried in arbitrarily air or dried by heating.
  • a polyurethane resin to which the antistatic agent of the present invention may be applied contains a polyurethane obtained at least by the reaction of a polyisocyanate with a polyol and may further contain various additives.
  • the polyurethane resin according to the present invention includes a polyurethane resin having other polymer structure such as polyester, polycarbonate and the like.
  • the starting material for a polyurethane resin there can be used a polyol and a polyisocyanate, and a component(s) optionally selected from a catalyst, a chain-elongating agent, a crosslinking agent, water, a foam- adjusting agent and the like.
  • the polyol is not particularly limited and there are used a polyester polyol, polyether polyol, polycarbonate polyol and the like which have a hydroxyl group at the terminus.
  • the polyester polyols includes, for example, ones produced by the ester reaction of a dibasic acid such as adipic acid and the like with a dihydric or trihydric alcohol, and ones produced by the ring-opening polymerization of a lactone.
  • the polyether polyols include, for example, diols which are a homopolymer or copolymer of ethylene oxide, propylene oxide and butylene oxide, and polyols produced by polymerizing a polyhydric alcohol such as glycerin or trimethylolpropane or the like with the ethylene oxide, propylene oxide or butylene oxide, or the like.
  • the polyisocyanate is not particularly limited and there may be used an aromatic, aliphatic and alicyclic polyisocyanate.
  • trilene diisocyanate for example, there may be mentioned trilene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isoholon diisocyanate and the like.
  • a conventionally well-known catalyst for example, chain-elongating agent, crosslinking agent, foam- adjusting agent and the like without any limitation. Examples Hereinafter, the present invention will be explained in more detail based on Examples and Comparative Examples, but the present invention is not limited to these Examples.
  • the leakage resistance value of the molding surface was measured at a voltage of 1000 V. The smaller the value, the better the antistatic values. The measurement was made by using a leakage resistance value measurement equipment: TOA Super Megohmmeter SM-5E (manufactured by DKK-TOA Corporation).
  • step (3) of Production Example 1 concerning a polyurethane foam molding, the volume (a) of the mixture in the frame was measured immediately after the mixture had been poured into the frame. The volume (b) of the mixture in the frame after 1 day maturation was also measured. The ratio of the volume (b) was calculated when the volume (a) was converted into "1". The calculated value was taken as "foaming ratio".
  • Table 1 there are shown the components for the production of a polyurethane foam molding in Examples 1 to 3 and Comparative Examples 1 to 3.
  • a polyurethane foam molding was produced by the following steps. (1) The components of Nos. 1 to 6 were blended, followed by stirring with a disper (2000 rpm x 2 min) to obtain a mixture. (2) Thereafter, to the mixture thus obtained in above step (1) was added the component of No. 7, followed by stirring with a disper (2000 rpm x 10 sec) to obtain a mixture for molding.
  • Example 1 To the polypropylene glycol as a component of No. 1 in Table 1 was added 0.1 part by mass of 1-butyl-3-methylpyridinium dicyanamide having a melting point of 16 °C as an antistatic agent and then a polyurethane foam molding was obtained in the same manner as in Production Example 1.
  • Example 2 To the polypropylene glycol as a component of No. 1 in Table 1 was added 0.3 part by mass of 1-butyl-3-methylpyridinium dicyanamide having a melting point of 16 0 C as an antistatic agent and then a polyurethane foam molding was obtained in the same manner as in Production Example 1.
  • Example 3 An isopropanol solution (1 % by mass) of 1-butyl-3-methylpyridinium dicyanamide having a melting point of 16 0 C was sprayed as an antistatic agent on the surface of a polyurethane foam molding produced in the same manner as in Production Example 1 except for not adding an antistatic agent at a spraying rate of 10 g/m 2 . Thereafter, the polyurethane foam molding was placed still at room temperature (approximately 25 °C) for 24 hours to obtain a polyurethane foam molding.
  • a polyurethane foam molding was obtained in the same manner as in Production Example 1 except for not adding an antistatic agent. (Comparative Example 2)
  • a polyurethane foam molding was obtained in the same manner as in Production Example 1 except for adding 0.1 part by mass of (2- hydroxyethyl)-dimethyl-[3-(lauroylamino)propyl] ammonium perchlorate as an antistatic agent to the polypropylene glycol as a component of No. 1 in Table 1.
  • Evafanol HA-107C (a water-dispersed product of a polycarbonate- based polyurethane resin, non-volatile component: 40 % by mass, produced by Nicca Chemical Co., Ltd.) of 39.2 g was poured into a stainless box (10 cm x 12 cm x 1 cm of length x width x height) and dried at room temperature (approximately 25 0 C) for 3 days to obtain a polyurethane film (10 cm x 12 cm x 1 cm of length x width x thickness).
  • Evafanol HA-107C (a water-dispersed product of a polycarbonate- based polyurethane resin, non-volatile component: 40 % by mass, produced by Nicca Chemical Co., Ltd.) of 39.2 g was poured into a stainless box (10 cm x 12 cm x 1 cm of length x width x height) and dried at room temperature (approximately 25 0 C) for 3 days to obtain a polyurethane film (10 cm x 12 cm x 1 cm of length x width x thickness). This film was evaluated as a blank.
  • Evafanol HA-107C (a water-dispersed product of a polycarbonate- based polyurethane resin, non-volatile component: 40 % by mass, produced by Nicca Chemical Co., Ltd.) of 39.2 g was poured into a stainless box (10 cm x 12 cm x 1 cm of length x width x height) and dried at room temperature (approximately 25 0 C) for 3 days to obtain a polyurethane film (10 cm x 12 cm x 1 cm of length x width x thickness).
  • a 5% by mass of isopropanol solution of (2-hydroxyethyl)-dimethyl-[3-(lauroylamino)propyl] ammonium was sprayed as an antistatic agent on the film at a spraying rate of 10 g/m 2 , followed by placing it still at room temperature (approximately 25 °C) for 24 hours to obtain an antistatic polyurethane film.
  • a 0.15 part by mass of 1 -butyl-3-methylpyridinium dicyanamide having a melting point of 16 0 C as an antistatic agent was fully mixed with 100 parts by mass of Evafanol HA-107C (a water-dispersed product of a polycarbonate-based polyurethane resin, non-volatile component: 40 % by mass, produced by Nicca Chemical Co., Ltd.).
  • Evafanol HA-107C a water-dispersed product of a polycarbonate-based polyurethane resin, non-volatile component: 40 % by mass, produced by Nicca Chemical Co., Ltd.
  • the mixture thus obtained (12 g) was poured into a stainless box (10 cm x 12 cm x 1 cm of length x width x height) and dried at room temperature (approximately 25°C) for 3 days to obtain a polyurethane film (10 cm x 12 cm x 0.4 cm of length x width x thickness).
  • a 0.15 part by mass of 1-ethyl-3-methylimidazolium dicyanamide having a melting point of -21 0 C was fully mixed with 100 parts by mass of Evafanol HA-107C (a water-dispersed product of a polycarbonate-based polyurethane resin, non-volatile component: 40 % by mass, produced by Nicca Chemical Co., Ltd.).
  • the mixture thus obtained (12 g) was poured into a stainless box (10 cm x 12 cm x 1 cm of length x width x height) and dried at room temperature (approximately 25 °C) for 3 days to obtain a polyurethane film (10 cm x 12 cm x 0.4 cm of length x width x thickness).
  • the results of the measurement of leakage resistance value and fracture strength of each polyurethane film obtained in Example 5 and Comparative Examples 7 and 8 are shown in Table 4.
  • the antistatic agent according to the present invention comprising, as an effective component, an organic salt in which an anionic component is a dicyanamide anion and a pyridinium cationic component is a cation having no halogen atom
  • excellent antistatic properties may be imparted to a polyurethane resin molding, also in a smaller amount.
  • strength decrease of a polyurethane resin molding can be prevented by the antistatic agent according to the present invention in comparison with the conventional ones.
  • the antistatic agent according to the present invention has such an effect in that foaming is not inhibited during the production process so that a good foaming ratio and an excellent antistatic property can be obtained.

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Abstract

There is provided an antistatic agent for a polyurethane resin which exhibits sufficient antistatic properties with a smaller addition amount and in which an effective component has no halogen atom. As the effective component of an antistatic agent for a polyurethane resin, there is used an organic salt composed of a dicyanamide anion represented by the following general formula (1) and a cationic component represented by the following general formula (2): wherein R1 represents a linear or branched alkyl group having 1 to 8 carbon atoms, an aryl group or a benzyl group, and R2 and R3 are the same or different and represent H or a linear or branched alkyl group having 1 to 8 carbon atoms.

Description

DESCRIPTION
DICYANAMIDE ORGANIC SALT AS ANTISTATIC AGENT IN POLYURETHANE RESIN
TECHNICAL FIELD The present invention relates to an antistatic agent comprising, as an effective component, an organic salt in which an anionic component is a dicyanamide anion and a cationic component is a cation having no halogen atom. Specifically, the present invention relates to an antistatic agent used in a polyurethane resin molding such as polyurethane fibers, polyurethane foams and the like; an antistatic polyurethane resin molding and a method of producing an antistatic polyurethane resin molding, using the antistatic agent. Further, the present invention relates to use of the organic salt, as an antistatic agent, in the production of a polyurethane resin or a polyurethane resin molding; and use of the organic salt, as an antistatic agent, in a polyurethane resin or a polyurethane resin molding.
BACKGROUND ART
In a high molecular material represented by a polyurethane resin having a volumetric specific resistance more than 1013 Ωcm, the contact surface with other objects easily tends to build up a positive or negative large static charge by friction. As a result, in such a high molecular material, electric charges are not leaked to cause various electrostatic troubles and a commercial product using such a high molecular material adsorbs dust from the air by electrostatic suction, thereby decreasing the commercial value. Further, such a high molecular material may in some cases cause fire such as dust explosion by discharge spark, ignition of a flammable solvent and the like, depending on their uses and their use conditions, for example, at the time of the processing in a processing factory. For this reason, it is necessary to impart antistatic property to such a high molecular material from the molding step. Conventionally, as a method of imparting antistatic properties to a polyurethane resin, addition of a conductive filler or a quaternary ammonium salt type antistatic agent is known. As the quaternary ammonium salt type antistatic agent, a quaternary ammonium alkyl sulfate (Japanese Patent Laid- Open No. 4-298517), a quaternary ammonium perchlorate (Japanese Patent Laid-Open No. 4-298518) and the like are known. However, when the conductive filler is used by blending it to a starting material for a polyurethane resin, it is required to be added in a large amount of the conductive filler in order to obtain the desired antistatic property. The addition of the conductive filler in a large amount causes a drawback that such a method is difficult to use regarding the handling of the starting material because of increase of the viscosity of the starting material. In addition, use of the quaternary ammonium salt type antistatic agent causes problems to obtain the antistatic property, i.e., a sufficient effect was not obtained, and a high addition level was required. Further, there is a problem from the viewpoint of environmental load because a quaternary ammonium perchlorate has a halogen. Recently, regarding a so-called "an ionic liquid" which is composed of an organic compound and has a melting point of room temperature or less, its application as an antistatic agent for a polymer has been found out from the viewpoint of its conductivity and poor volatility (Japanese Patent Laid- Open No. 2003-511505). However, since most of the anions have a halogen such as fluorine atom and the like, there is a problem from the viewpoint of environmental load.
WO 07/090755 discloses 1-ethyl-3-methylimidazolium dicyanamide and 1-butyl-3-methylimidazolium dicyanamide as an antistatic agent for polyurethane resins.
SUMMARY OF THE INVENTION Technical Problem
The present invention has been made in light of the above problems of the related art. An object of the present invention is to provide an antistatic agent for a polyurethane resin comprising, as an effective component, an organic salt having no halogen atom, which exhibits a sufficient antistatic property with a smaller addition amount. A further object of the present invention is to provide an antistatic polyurethane resin molding and a method of producing the antistatic polyurethane resin molding, using the same. Another object of the present invention is to provide the use of the organic salt, as an antistatic agent, in the production of a polyurethane resin or a polyurethane resin molding, as well as the use of the organic salt, as an antistatic agent, in a polyurethane resin or a polyurethane resin molding. Solution to Problem
The antistatic agent of the present invention is characterized by mainly comprising an organic salt in which an anionic component is a dicyanamide anion and a cationic component is a cation having no halogen atom, and which can impart an antistatic property to a polyurethane resin with a smaller addition amount. Further, since an organic salt having no halogen atom is used as the effective component of the antistatic agent according to the present invention, the entire antistatic agent can be prepared in a form having no halogen atom.
The antistatic agent for a polyurethane resin of the present invention comprises, as an effective component, an organic salt composed of a dicyanamide anion represented by the following general formula (1) and a cation represented by the following general formula (2):
Θ
N≡C— N— C≡N (1)
Figure imgf000005_0001
wherein R1 represents a linear or branched alkyl group having 1 to 8 carbon atoms, an aryl group or a benzyl group, and R2 and R3 are the same or different and represent H or a linear or branched alkyl group having 1 to 8 carbon atoms.
A first aspect of an antistatic polyurethane resin molding according to the present invention is characterized by comprising the above-mentioned antistatic agent.
A second aspect of an antistatic polyurethane resin molding according to the present invention is characterized in that the above-mentioned antistatic agent is adhered to at least the surface of a polyurethane resin molding.
A polyurethane resin composition according to the present invention is characterized by comprising the above-mentioned antistatic agent and a polyurethane resin.
A first aspect of the method of producing an antistatic polyurethane resin molding according to the present invention is characterized in comprising the steps of obtaining a polyurethane resin from a mixture comprising a polyol and a polyisocyanate, and obtaining a polyurethane resin molding, wherein the above-mentioned antistatic agent is added in the step of obtaining the polyurethane resin to provide antistatic property to the polyurethane resin molding.
An antistatic polyurethane resin molding can be obtained according to the production method of the first aspect by adding the antistatic agent during the preparation of the polyurethane resin from a mixture comprising a polyol and a polyisocyanate. The preferable production method according to the first aspect includes the following methods:
(1) a method, wherein the antistatic property is provided to the polyurethane resin molding by curing a mixture comprising a polyol, a polyisocyanate and the antistatic agent under a condition for molding; and (2) a method, wherein the antistatic property is provided to the polyurethane resin molding by obtaining a polyurethane resin from a mixture comprising a polyol, a polyisocyanate and the antistatic agent; and molding the polyurethane resin thus obtained.
A second aspect of a method for producing an antistatic polyurethane resin molding according to the present invention is characterized in that the above-mentioned antistatic agent is blended with a polyurethane resin composition comprising a polyurethane resin, followed by molding the mixture thus obtained.
A third aspect of a method for producing an antistatic polyurethane resin molding according to the present invention is characterized in that the above-mentioned antistatic agent is applied to the surface of a polyurethane resin molding or the above-mentioned antistatic agent is impregnated in a polyurethane resin molding.
The present invention further includes the use of an organic salt in which an anionic component is a dicyanamide anion represented by the general formula (1) and a cationic component is a cation represented by the general formula (2), as an antistatic agent in the production of a polyurethane resin or a polyurethane resin molding. Advantageous Effects of Invention
The antistatic agent for a polyurethane resin according to the present invention has the following advantages based on the organic salt which is an effective component:
- the effective component of the antistatic agent has poor volatility even at room temperature and at a high temperature;
- the effective component of the antistatic agent has a good compatibility with a polyol and a polyisocyanate; and
- the effective component of the antistatic agent has an excellent antistatic property even under a low humidity condition because it is a compound having electric charges.
In addition, since the organic salt in the present invention has no anion component having a halogen atom such as tetrafluoroboric acid anion, bistrifluoromethyl sulfonylimide anion and the like, and a cation having no halogen atom, the organic salt is advantageous in the following points:
- the production cost of the organic salt is low;
- the organic salt is not corrosive; and
- the organic salt has a low load to environment. The present invention can impart an excellent antistatic property to a polyurethane resin molding by using the organic salt consisting of a dicyanamide anion of the general formula. (1) and a cation of the general formula (2) as an effective component. Therefore, the present invention can provide an antistatic agent for a polyurethane resin, an antistatic polyurethane resin molding and a method of producing a polyurethane resin molding, using the same. Further, the present invention can provide the use of the organic salt, as an antistatic agent, in the production of a polyurethane resin or a polyurethane resin molding, as well as the use of the organic salt, as an antistatic agent, in a polyurethane resin or a polyurethane resin molding.
DESCRIPTION OF EMBODIMENTS
Hereinafter, the present invention will be explained with reference to the preferred Embodiments. First, an antistatic agent for a polyurethane resin of the present invention is explained. An antistatic agent for a polyurethane resin of the present invention contains as an effective component an organic salt in which an anionic component is a dicyanamide anion represented by the following general formula (1) and a cationic component is a cation represented by the following general formula (2):
Θ
N≡C— N— C≡N (1)
Figure imgf000009_0001
wherein
R1 represents a linear or branched alkyl group having 1 to 8 carbon atoms, an aryl group or a benzyl group, and R2 and R3 are the same or different and represent H or a linear or branched alkyl group having 1 to 8 carbon atoms.
In the general formula (2), an organic salt is more preferable, in which R1 is a linear or branched alkyl group having 1 to 8 carbon atoms, and one of R2 and R3 is H, while the other is a methyl group, because it has a good compatibility with a polyisocyanate and a polyol. Further, an organic salt is especially preferable, in which R1 is a linear or branched alkyl group having 2 to 4 carbon atoms, and one of R2 and R3 is H, while the other is a methyl group, because it is further excellent in the antistatic properties. In addition, in these cases, the position of the methyl group is preferably at 3- or 4- position.
As an aryl group as each substituent in a quaternary ammonium represented by the general formula (2), there may be mentioned a phenyl group.
The present inventors infer that the reason why an organic salt, which is an effective component of the antistatic agent of the present invention, exhibits an excellent effect as an antistatic agent is in the following manner.
A dicyanamide anion has a molecular weight of approximately 66. The dicyanamide anion is one of anions having the least molecular weight as an anion as a component of an organic salt having usually a melting point of room temperature or lower. For this reason, the organic salt alone has a high electric conductivity, contributing to the reduction of the leakage resistance value of a polyurethane resin. In addition, a polyurethane resin is a resin having a urethane bond which has a high polarity. The dicyanamide anion is an anion only consisting of C and N from C, N and O which are constituent elements of a urethane bond and has a high affinity with a urethane bond. Accordingly, the antistatic agent of the present invention is easily blended into a polyurethane resin. In the blended state, a dicyanamide anion becomes easily compatible with the hard segment region containing urethane bonds from the viewpoint of the constituent elements. That is, the organic salt used in the present invention is not microscopically uniformly distributed in a polyurethane resin and is unevenly distributed in the hard segment region. In this blended state, the organic salt forms a continuous contact structure (percolation structure) and accordingly, a conductive path having a high electric conductivity is efficiently formed, thereby specifically reducing the leakage resistance value and, as a result, enabling to exhibit high antistatic properties. The present inventors infer in the same manner as in the case where the antistatic agent of the present _
invention is applied on the surface of a polyurethane resin molding. That is, the present inventors infer that since the affinity between the dicyanamide anion and the urethane bond is high and the wettability of the organic salt to a molded surface is high, a continuous contact structure (percolation structure) is easily formed and a conductive path having a high electric conductivity is efficiently formed.
The affinity of the organic salt to polyurethane resins can be further improved by combining the pyridinium cation represented by the general formula (2) with dicyanamide anion. In particular, the organic salt of the pyridinium cation is better than that of an imidazolium cation in the affinity to the polyurethane.
As described above, the organic salt used in the present invention may effectively exhibit the antistatic effect in a polyurethane resin having a urethane bond(s) and the kind of target polyurethane resin is not limited. An antistatic agent of the present invention may be prepared by the above-mentioned organic salt alone or together with a solvent. The solvents for preparing the antistatic agent include alcohols such as ethanol, ethanol, isopropanol and the like; glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and the like; and water. The solvent may be used alone or in combination with two or more solvents, depending on the intended application.
An antistatic polyurethane resin molding may be obtained by adding the antistatic agent of the present invention in a polyurethane resin molding. Alternatively, an antistatic polyurethane resin molding may be obtained by applying the antistatic agent of the present invention onto to the surface of a polyurethane resin molding or impregnating the antistatic agent of the present invention in a polyurethane resin molding. Both of the methods can impart excellent antistatic properties to a polyurethane resin molding. Two or more of these methods may be used in combination.
In the case of a polyurethane resin molding in which the antistatic agent of the present invention is contained or impregnated, the content of the organic salt is preferably from 0.01 to 5 % by mass (wt.%), and more preferably from 0.03 to 3.5 % by mass, based on the mass of a polyurethane resin. Further, in the case of a polyurethane resin molding on which surface the antistatic agent of the present invention is adhered, the adhered amount of an organic salt is preferably from 0.02 to 1 g/m2. In both cases, if the amount of the organic salt is less than the above range, the antistatic property may become insufficient. On the other hand, even if the amount of the organic salt exceeds the above range, the improvement of the antistatic property compatible with the amount of an organic salt is not only obtained but the physical properties of the polyurethane resin and the quality of the molding may be deteriorated in some cases. The moldings include various types of moldings such as polyurethane fibers, films, elastomers, polyurethane foams (soft, hard or semi-hard polyurethane foams, buffer materials) and the like, and surface coating materials such as surface layers of artificial leathers and various paints, and the like.
Specifically, an antistatic polyurethane resin molding may be produced by the following methods, (i) A production method comprising the steps of obtaining a polyurethane resin from a mixture comprising a polyol and a polyisocyanate, and obtaining a polyurethane resin molding, wherein an antistatic agent according to the present invention is added in the step of obtaining the polyurethane resin to provide antistatic property to the polyurethane resin molding.
(ii) A production method, in which the antistatic agent according to the present invention is blended with a polyurethane resin composition comprising a polyurethane resin, followed by molding the mixture thus obtained.
(iii) A production method, in which the antistatic agent according to the present invention is applied to the surface of a polyurethane resin molding, or in which the antistatic agent according to the present invention is impregnated in a polyurethane resin molding.
These methods may be employed in combination where necessary.
In above-mentioned production method (i), the antistatic polyurethane resin molding is obtained by adding the antistatic agent according to the present invention at any step of the preparation of the polyurethane resin molding from a mixture comprising a polyol and a polyisocyanate to which an additive(s) such as a catalyst, a chain-elongating agent, a foaming agent, a foam-adjusting agent and the like are optionally added. The addition amount of the antistatic agent in this case is preferable in the above- mentioned range based on the mass of a polyurethane resin to be produced
(that is, the amount of the organic salt is preferably from 0.01 to 5 % by mass and more preferably from 0.03 to 3.5 % by mass).
In above-mentioned production method (i), the step of obtaining a polyurethane resin and the step of obtaining a polyurethane resin molding can are carried out simultaneously, partially simultaneously or separately.
Therefore, the preferable embodiments of above-mentioned production method (i) include the following methods, (ia) A method, wherein the antistatic property is provided to the polyurethane resin molding by curing a mixture comprising a polyol, a polyisocyanate and the antistatic agent according to the present invention, under a condition for molding.
(ib) A method, wherein the antistatic property is provided to the polyurethane resin molding by obtaining a polyurethane resin from a mixture comprising a polyol, a polyisocyanate and the antistatic agent according to the present invention; and molding the polyurethane resin thus obtained. In above-mentioned production method (ia), when a polyol and a polyisocyanate are reacted by optionally adding an additive such as a catalyst, a chain-elongating agent, a foaming agent, a foam-adjusting agent and the like, the antistatic agent of the present invention is added and these materials are reacted, followed by molding the reaction mixture. In above- mentioned production method (ib), a polyurethane resin is prepared from a mixture comprising a polyol, a polyisocyanate and the antistatic agent of the present invention for molding and, then, the polyurethane resin thus obtained is molded.
The addition amount of the antistatic agent in these cases are preferable in the above-mentioned range based on the mass of a polyurethane resin to be produced (that is, the amount of the organic salt is preferably from 0.01 to 5 % by mass and more preferably from 0.03 to 3.5 % by mass).
In consideration of the curing conditions such as a curing rate of the reaction mixture and the like, the antistatic agent is added to the reaction system at the stage where the effect as the antistatic agent is effectively obtained. The antistatic agent may be added in advance to at least one of a component containing a polyol and a component containing a polyisocyanate. Alternatively, the antistatic agent may be also added to a reaction system in which a component containing a polyol and a component containing a polyisocyanate are mixed. Since the organic salt, which is an effective component of the antistatic agent, has a good compatibility with a polyol and a polyisocyanate, the antistatic agent of the present invention is preferably mixed in advance with a polyol or a polyisocyanate, especially a polyol. In this case, the content of the organic salt is preferably from approximately 0.05 to 5.0 % by mass based on the mass of a polyol.
The molding conditions in above-mentioned production method (i) may be provided according to various molding methods. The molding methods are not particularly limited and a conventionally well-known method can be used. For example, when polyurethane foams are molded, a mixture is prepared by adding a catalyst, water, a foam-adjusting agent and an antistatic agent according to the present invention to a polyol in advance and followed by mixing the mixture well. The mixture and a slightly excessive amount of polyisocyanate are mixed well with a stirrer for a polyurethane preparation, and the resulting mixture is foamed on a belt conveyor or by placing it into a mold for molding. Further, the molding conditions may be provided by a flat surface formed by a belt of a belt conveyor, a surface of a substrate for molding, an extrusion molding vessel, a film-forming roller and the like. The timing of molding and curing of the mixture may be set depending on the curing conditions such as the curing temperature of the mixture and the like.
In above-mentioned production method (i), when the antistatic agent of the present invention is added to the reaction system, an antistatic agent consisting of the above-mentioned organic salt may be added as it is. Alternatively, the antistatic agent may be added as a solution prepared by dissolving the above-mentioned organic salt in a solvent. The solvent used includes the solvents for preparing the antistatic agent as described above, as well as publicly known solvents or liquid mediums for dissolution or dispersion of polyurethane resins.
In above-mentioned production method (ii), the antistatic agent of the present invention is blended to a polyurethane resin composition containing a polyurethane resin, followed by molding the mixture. The polyurethane resin composition is not particularly limited as long as it is a resin composition for obtaining a molding which contains a polyurethane resin. The polyurethane resin compositions include liquid polyurethane compositions such as a water-dispersing type and a solvent-solution type. The addition amount of the antistatic agent in this case is preferably in the above- mentioned range based on the mass of a polyurethane rein (that is, the amount of an organic salt is preferably from 0.01 to 5 % by mass and more preferably from 0.03 to 3.5 % by mass). In this production method, when an antistatic agent of the present invention is added to a polyurethane resin composition, an antistatic agent consisting of the above-mentioned organic salt may be added as it is. Alternatively, the antistatic agent may be added as a solution prepared by dissolving the above-mentioned organic salt in a solvent. The solvent used includes the solvents for preparing the antistatic agent as described above. In particular, glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and the like are preferably used. In addition, a resin(s) other than a polyurethane resin and a various additive(s), in addition to the polyurethane resin and the antistatic agent, may be blended to the polyurethane resin composition.
In above-mentioned production method (iii), the antistatic agent of the present invention is applied to the surface of a polyurethane resin molding or impregnated in a polyurethane resin molding. Even in this production method, an antistatic agent consisting of the above-mentioned organic salt may be used as it is. Alternatively, the antistatic agent may be used as a solution prepared by dissolving the above-mentioned organic salt in a solvent. The solvent used includes the solvents for preparing the antistatic agent as described above. The method of application and impregnation is not particularly limited and a method of coating, spraying, dipping or the like can be used. When the antistatic agent of the present invention is impregnated in a polyurethane resin molding, the antistatic agent is preferably imparted at least on the surface of the polyurethane resin molding. The adhered amount in this case may be selected from the above range for application. After the antistatic agent of the present invention is applied or impregnated, a molding may be dried in arbitrarily air or dried by heating.
A polyurethane resin to which the antistatic agent of the present invention may be applied contains a polyurethane obtained at least by the reaction of a polyisocyanate with a polyol and may further contain various additives. Further, the polyurethane resin according to the present invention includes a polyurethane resin having other polymer structure such as polyester, polycarbonate and the like. As the starting material for a polyurethane resin, there can be used a polyol and a polyisocyanate, and a component(s) optionally selected from a catalyst, a chain-elongating agent, a crosslinking agent, water, a foam- adjusting agent and the like. The polyol is not particularly limited and there are used a polyester polyol, polyether polyol, polycarbonate polyol and the like which have a hydroxyl group at the terminus. The polyester polyols includes, for example, ones produced by the ester reaction of a dibasic acid such as adipic acid and the like with a dihydric or trihydric alcohol, and ones produced by the ring-opening polymerization of a lactone. The polyether polyols include, for example, diols which are a homopolymer or copolymer of ethylene oxide, propylene oxide and butylene oxide, and polyols produced by polymerizing a polyhydric alcohol such as glycerin or trimethylolpropane or the like with the ethylene oxide, propylene oxide or butylene oxide, or the like. The polyisocyanate is not particularly limited and there may be used an aromatic, aliphatic and alicyclic polyisocyanate. For example, there may be mentioned trilene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isoholon diisocyanate and the like. There may be used a conventionally well-known catalyst, chain-elongating agent, crosslinking agent, foam- adjusting agent and the like without any limitation. Examples Hereinafter, the present invention will be explained in more detail based on Examples and Comparative Examples, but the present invention is not limited to these Examples.
In addition, the evaluation of the antistatic properties and the measurements of foaming ratio and fracture strength for the polyurethane resin moldings obtained in Examples and Comparative Examples were performed in the following manners. (Evaluation of Antistatic Properties)
After a polyurethane resin molding was placed still under constant temperature and humidity conditions of 20 °C and 40 % for 3 hours, the leakage resistance value of the molding surface was measured at a voltage of 1000 V. The smaller the value, the better the antistatic values. The measurement was made by using a leakage resistance value measurement equipment: TOA Super Megohmmeter SM-5E (manufactured by DKK-TOA Corporation).
(Measurement of Foaming Ratio) In step (3) of Production Example 1 concerning a polyurethane foam molding, the volume (a) of the mixture in the frame was measured immediately after the mixture had been poured into the frame. The volume (b) of the mixture in the frame after 1 day maturation was also measured. The ratio of the volume (b) was calculated when the volume (a) was converted into "1". The calculated value was taken as "foaming ratio".
(Measurement of Fracture Strength)
A polyurethane film was placed still under constant temperature and humidity conditions of 200C and 65% for 3 hours. According to Japanese Industrial Standard (JIS) K 6251 (2004), test specimens were punched from the film with the punching blade having No. 3 shape like a dumbbell and fracture strength of each test specimen thus obtained was measured. For the measurement, an autograph (AG-1S, Shimadzu) was used. The tensile strength was 300mm/min. (1) Polyurethane Foam Molding (Production Example 1)
In Table 1 , there are shown the components for the production of a polyurethane foam molding in Examples 1 to 3 and Comparative Examples 1 to 3.
Table 1 : Formula of Polyurethane Foamed Product
Figure imgf000020_0001
In Table 1 , "Adeka Polyether P-3000" (produced by ADEKA Corporation) was used as polypropylene glycol and "SH-190" (produced by Dow Corning Corporation) as a foam-adjusting agent.
A polyurethane foam molding was produced by the following steps. (1) The components of Nos. 1 to 6 were blended, followed by stirring with a disper (2000 rpm x 2 min) to obtain a mixture. (2) Thereafter, to the mixture thus obtained in above step (1) was added the component of No. 7, followed by stirring with a disper (2000 rpm x 10 sec) to obtain a mixture for molding.
(3) The mixture for molding thus obtained was immediately poured into a frame, followed by ageing at room temperature (approximately at 25 °C) for 1 day to obtain a polyurethane foam molding. (Example 1) To the polypropylene glycol as a component of No. 1 in Table 1 was added 0.1 part by mass of 1-butyl-3-methylpyridinium dicyanamide having a melting point of 16 °C as an antistatic agent and then a polyurethane foam molding was obtained in the same manner as in Production Example 1.
(Example 2) To the polypropylene glycol as a component of No. 1 in Table 1 was added 0.3 part by mass of 1-butyl-3-methylpyridinium dicyanamide having a melting point of 16 0C as an antistatic agent and then a polyurethane foam molding was obtained in the same manner as in Production Example 1.
(Example 3) An isopropanol solution (1 % by mass) of 1-butyl-3-methylpyridinium dicyanamide having a melting point of 16 0C was sprayed as an antistatic agent on the surface of a polyurethane foam molding produced in the same manner as in Production Example 1 except for not adding an antistatic agent at a spraying rate of 10 g/m2. Thereafter, the polyurethane foam molding was placed still at room temperature (approximately 25 °C) for 24 hours to obtain a polyurethane foam molding.
(Comparative Example 1)
A polyurethane foam molding was obtained in the same manner as in Production Example 1 except for not adding an antistatic agent. (Comparative Example 2)
To the polypropylene glycol as a component of No. 1 in Table 1 was added 0.3 part by mass of 1-ethyl-3-methylimidazolium dicyanamide having a melting point of -21 0C as an antistatic agent and then a polyurethane foam molding was obtained in the same manner as in Production Example 1. (Comparative Example 3)
A polyurethane foam molding was obtained in the same manner as in Production Example 1 except for adding 0.1 part by mass of (2- hydroxyethyl)-dimethyl-[3-(lauroylamino)propyl] ammonium perchlorate as an antistatic agent to the polypropylene glycol as a component of No. 1 in Table 1.
The results of the measurement of leakage resistance value and foaming ratio of each polyurethane foam molding obtained in Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 2.
Table 2
Figure imgf000022_0001
(2) Polyurethane Film (Spray Treatment) (Example 4)
Evafanol HA-107C (a water-dispersed product of a polycarbonate- based polyurethane resin, non-volatile component: 40 % by mass, produced by Nicca Chemical Co., Ltd.) of 39.2 g was poured into a stainless box (10 cm x 12 cm x 1 cm of length x width x height) and dried at room temperature (approximately 25 0C) for 3 days to obtain a polyurethane film (10 cm x 12 cm x 1 cm of length x width x thickness). A 1 % by mass of isopropanol solution of 1-butyl-3-methylpyridinium dicyanamide having a melting point of 16 0C was sprayed as an antistatic agent on the film at a spraying rate of 10 g/m2, followed by placing it still at room temperature (approximately 25 0C) for 24 hours to obtain an antistatic polyurethane film. (Comparative Example 4)
Evafanol HA-107C (a water-dispersed product of a polycarbonate- based polyurethane resin, non-volatile component: 40 % by mass, produced by Nicca Chemical Co., Ltd.) of 39.2 g was poured into a stainless box (10 cm x 12 cm x 1 cm of length x width x height) and dried at room temperature (approximately 25 0C) for 3 days to obtain a polyurethane film (10 cm x 12 cm x 1 cm of length x width x thickness). This film was evaluated as a blank. (Comparative Example 5) Evafanol HA-107C (a water-dispersed product of a polycarbonate- based polyurethane resin, non-volatile component: 40 % by mass, produced by Nicca Chemical Co., Ltd.) of 39.2 g was poured into a stainless box (10 cm x 12 cm x 1 cm of length x width x height) and dried at room temperature (approximately 25 0C) for 3 days to obtain a polyurethane film (10 cm x 12 cm x 1 cm of length x width x thickness). A 1% by mass of isopropanol solution of 1-ethyl-3-methylimidazolium dicyanamide having a melting point of -21 °C was sprayed as an antistatic agent on the film at a spraying rate of 10 g/m2, followed by placing it still at room temperature (approximately 25 0C) for 24 hours to obtain an antistatic polyurethane film. (Comparative Example 6)
Evafanol HA-107C (a water-dispersed product of a polycarbonate- based polyurethane resin, non-volatile component: 40 % by mass, produced by Nicca Chemical Co., Ltd.) of 39.2 g was poured into a stainless box (10 cm x 12 cm x 1 cm of length x width x height) and dried at room temperature (approximately 25 0C) for 3 days to obtain a polyurethane film (10 cm x 12 cm x 1 cm of length x width x thickness). A 5% by mass of isopropanol solution of (2-hydroxyethyl)-dimethyl-[3-(lauroylamino)propyl] ammonium was sprayed as an antistatic agent on the film at a spraying rate of 10 g/m2, followed by placing it still at room temperature (approximately 25 °C) for 24 hours to obtain an antistatic polyurethane film.
The results of the measurement of leakage resistance value of each polyurethane film obtained in Example 4 and Comparative Examples 4 to 6 are shown in Table 3.
Table 3
Figure imgf000024_0001
(3) Polyurethane Film (Mixing into Polyurethane Composition) (Example 5)
A 0.15 part by mass of 1 -butyl-3-methylpyridinium dicyanamide having a melting point of 16 0C as an antistatic agent was fully mixed with 100 parts by mass of Evafanol HA-107C (a water-dispersed product of a polycarbonate-based polyurethane resin, non-volatile component: 40 % by mass, produced by Nicca Chemical Co., Ltd.). The mixture thus obtained (12 g) was poured into a stainless box (10 cm x 12 cm x 1 cm of length x width x height) and dried at room temperature (approximately 25°C) for 3 days to obtain a polyurethane film (10 cm x 12 cm x 0.4 cm of length x width x thickness).
(Comparative Example 7) Evafanol HA-107C (a water-dispersed product of a polycarbonate- based polyurethane resin, non-volatile component: 40 % by mass, produced by Nicca Chemical Co., Ltd.) of 12 g was poured into a stainless box (10 cm x 12 cm x 1 cm of length x width x height) and dried at room temperature (approximately 25 °C) for 3 days to obtain a polyurethane film (10 cm x 12 cm x 0.4 cm of length x width x thickness). (Comparative Example 8)
A 0.15 part by mass of 1-ethyl-3-methylimidazolium dicyanamide having a melting point of -21 0C was fully mixed with 100 parts by mass of Evafanol HA-107C (a water-dispersed product of a polycarbonate-based polyurethane resin, non-volatile component: 40 % by mass, produced by Nicca Chemical Co., Ltd.). The mixture thus obtained (12 g) was poured into a stainless box (10 cm x 12 cm x 1 cm of length x width x height) and dried at room temperature (approximately 25 °C) for 3 days to obtain a polyurethane film (10 cm x 12 cm x 0.4 cm of length x width x thickness). The results of the measurement of leakage resistance value and fracture strength of each polyurethane film obtained in Example 5 and Comparative Examples 7 and 8 are shown in Table 4.
Table 4
Figure imgf000026_0001
As mentioned above, with the antistatic agent according to the present invention comprising, as an effective component, an organic salt in which an anionic component is a dicyanamide anion and a pyridinium cationic component is a cation having no halogen atom, excellent antistatic properties may be imparted to a polyurethane resin molding, also in a smaller amount. In addition, strength decrease of a polyurethane resin molding can be prevented by the antistatic agent according to the present invention in comparison with the conventional ones. When the polyurethane resin molding is polyurethane foam, the antistatic agent according to the present invention has such an effect in that foaming is not inhibited during the production process so that a good foaming ratio and an excellent antistatic property can be obtained.

Claims

1. An antistatic agent for a polyurethane resin characterized by comprising, as an effective component, an organic salt composed of a dicyanamide anion represented by the following general formula (1) and a cation represented by the following general formula (2):
Θ N≡C— N— C≡N (1)
Figure imgf000027_0001
wherein R1 represents a linear or branched alkyl group having 1 to 8 carbon atoms, an aryl group or a benzyl group, and R2 and R3 are the same or different and represent H or a linear or branched alkyl group having 1 to 8 carbon atoms.
2. An antistatic polyurethane resin molding characterized by comprising the antistatic agent according to claim 1.
3. A method of producing an antistatic polyurethane resin molding characterized in comprising the steps of obtaining a polyurethane resin from a mixture comprising a polyol and a polyisocyanate, and obtaining a polyurethane resin molding, wherein the antistatic agent according to claim 1 is added in the step of obtaining the polyurethane resin to provide antistatic property to the polyurethane resin molding.
4. A method according to claim 3, wherein the antistatic property is provided to the polyurethane resin molding by curing a mixture comprising a polyol, a polyisocyanate and the antistatic agent under a condition for molding.
5. A method according to claim 3, wherein the antistatic property is provided to the polyurethane resin molding by obtaining a polyurethane resin from a mixture comprising a polyol, a polyisocyanate and the antistatic agent; and molding the polyurethane resin thus obtained.
6. A method of producing an antistatic polyurethane resin molding characterized in that the antistatic agent according to claim 1 is blended with a polyurethane resin composition comprising a polyurethane resin, followed by molding the mixture thus obtained.
7. An antistatic polyurethane resin composition characterized by comprising the antistatic agent according to claim 1 and a polyurethane resin.
8. An antistatic polyurethane resin molding characterized in that the antistatic agent according to claim 1 is adhered to at least the surface of a polyurethane resin molding.
9. A method for producing an antistatic polyurethane resin molding characterized in that the antistatic agent according to claim 1 is applied to the surface of a polyurethane resin molding or the antistatic agent according to claim 1 is impregnated in a polyurethane resin molding.
10. Use of an organic salt composed of a dicyanamide anion represented by the following general formula (1) and a cation represented by the following general formula (2) , as an antistatic agent in the production of a polyurethane resin or a polyurethane resin molding:
Θ
N≡C-N-C≡N (1)
Figure imgf000029_0001
wherein
R1 represents a linear or branched alkyl group having 1 to 8 carbon atoms, an aryl group or a benzyl group, and R2 and R3 are the same or different and represent H or a linear or branched alkyl group having 1 to 8 carbon atoms.
PCT/JP2010/053930 2009-03-03 2010-03-03 Dicyanamide organic salt as antistatic agent in polyurethane resin WO2010101294A1 (en)

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