JP5810767B2 - Two-component curable polyurethane foam resin composition, urethane molded body, shoe sole, and industrial member - Google Patents

Description

The present invention relates to a two-component curable foamed polyurethane resin composition excellent in antistatic properties, a urethane molded article using the same, a shoe sole, and an industrial member.
More specifically, even under a wide range of temperature conditions from low temperature to normal temperature (20 ± 15 ° C.) and low humidity conditions, the temperature dependency is small and the antistatic property is excellent, and the addition amount is the same as that of the conventional antistatic agent. Since it can be greatly reduced compared to the physical properties, for example, various shoe soles such as safety shoes, work shoes, and indoor shoes, bottom materials of various footwear such as indoor slippers and sandals, or safety gloves, safety work clothes, Two-component curable polyurethane foam resin composition useful as various articles such as safety caps, urethane molded articles, shoe soles, and industrial members using the same (for example, packing, hoses, sheets, cushioning materials, vehicle members, packaging members) Etc.).

  Fire and explosion disasters caused by static electricity in places where hazardous materials are handled, such as industrial complexes, chemical factories, work sites, hazardous material handling places, experimental facilities, etc., are constantly increasing, and the magnitude of human and property damage I'm worried.

  As measures to prevent such electrostatic disasters, it has been actively studied to provide antistatic properties (also called antistatic properties) to resins and fibers used in footwear and clothing worn on the human body. For example, it is applied to various articles such as shoe soles such as safety shoes for preventing static electricity, work shoes, and clean room shoes, medical shoes, safety gloves, safety work clothes, and safety caps.

  Conventionally, methods for imparting antistatic properties include a method of applying or spraying an antistatic agent comprising a conductive substance, an ionic substance, or the like onto the surface of a resin molded product, or a method of internally adding the resin into a resin. I have been. Examples of applications of this method to polyurethane resins include (1) a method of adding carbon black, conductive filler, etc., or (2) a method of applying or adding an ionic surfactant. It was.

  However, in the method (1) in which a conductive filler or the like is added, there is a problem that molding becomes difficult because the resin composition significantly increases in viscosity when added to the polyurethane resin. Further, the method (2) using a general ionic surfactant has a problem that it is difficult to improve the antistatic property to a practically effective level. Therefore, studies have been made for the purpose of imparting better antistatic properties.

  For example, a method of adding an alkali metal salt or alkaline earth metal salt such as perchloric acid, thiocyanic acid or nitric acid (see, for example, Patent Documents 1 and 2), or a quaternary ammonium alkylsulfate or a quaternary ammonium perchlorate A method of adding (for example, see Patent Document 3) has been proposed.

  However, in the methods of Patent Document 1 and Patent Document 2, when the specific compound described is used alone, the antistatic effect is manifested to some extent early, but the performance of the urethane molded product is still insufficient and practical. There was a problem.

  Further, in the method of Patent Document 3, the development of antistatic properties immediately after molding is too slow, and the final performance of the urethane molded product is also highly humidity-dependent, and the antistatic property is sufficient under low temperature and low humidity conditions. There was a problem that it was not expressed and was extremely inferior in practicality.

  Furthermore, as a ionic antistatic compound, a mixture of a non-metallic antistatic compound such as a substituted sulfonic acid quaternary ammonium and a metallic antistatic compound such as a sulfonic acid metal salt, formamide, ethylene carbonate, propylene carbonate, etc. There has been proposed a method of adding an antistatic agent composition to which a polar organic solvent such as a cyclic carbonate is added to polyurethane (see, for example, Patent Document 4).

  However, in the method of Patent Document 4, since a polar organic solvent such as cyclic carbonate such as formamide, ethylene carbonate, and propylene carbonate is used as an essential component, it is easily affected by the remaining organic solvent, for example, There were various problems in terms of safety, hygiene, and quality, such as a decrease in storage stability of the obtained resin composition, bleeding out on the surface of the molded product, and adverse effects on the human body due to the generation of organic solvents such as formamide. .

  In addition, in the case of Patent Document 4, the cyclic carbonate added to the polyol is easily decomposed when heated in the presence of a catalyst. An abnormal foaming behavior is caused, and a molded product having stable physical properties cannot be obtained. Therefore, there is a problem that a defect occurs in the line production and quality control aspects.

  Further, an antistatic agent comprising at least one kind selected from a substituted quaternary ammonium-based cationic antistatic compound and a metal salt-based anionic antistatic compound, and a lactone monomer A polyurethane resin molded article containing an auxiliary agent has been proposed (see, for example, Patent Document 5).

  However, in Patent Document 5, by adding a lactone monomer as an antistatic aid, antistatic properties are slightly obtained, but it is still insufficient in practical use and inferior in adhesiveness. There is still a problem that it is still difficult to adopt for a wide range of uses such as shoe soles such as shoes and safety articles such as safety gloves.

  In addition, the antistatic agent used in Patent Document 5 has an antistatic property that is highly dependent on temperature and humidity. Under high temperature and high humidity conditions, moisture (water) in the atmosphere is adsorbed and water acts as an antistatic agent. As a result, there is a problem that, although slightly good antistatic performance can be expressed, sufficient antistatic properties cannot be expressed under low temperature and low humidity conditions, which is impractical.

  As described above, even in a wide range of temperature conditions and low humidity conditions from low temperature to normal temperature (20 ± 15 ° C), the difference in electrical resistance value is small, temperature dependency is small, and antistatic performance is excellent. The amount of additive can be reduced compared to the antistatic agent, so that when producing urethane molded products, there are no harmful effects such as abnormal foaming behavior, reduced hardness, reduced strength, and antistatic properties, flex resistance, and other materials. Development of a two-component curable foamed polyurethane resin composition having excellent performance such as adhesiveness, a urethane molded body using the same, a shoe sole, and an industrial member has been desired.

JP 63-43951 A JP-A-4-298517 JP-A-4-298518 JP 2001-329253 A Japanese Patent Laid-Open No. 2005-60682

  The object of the present invention is that the difference in electrical resistance value is small, the temperature dependence is small, and the antistatic property is excellent even under a wide range of temperature conditions and low humidity conditions from low temperature to normal temperature (20 ± 15 ° C.) Since the amount of addition can be reduced compared with conventional antistatic agents, there are no harmful effects such as abnormal foaming behavior, reduced hardness, reduced strength, etc. when producing urethane molded products, and antistatic properties, flex resistance, other materials It is to provide a two-component curable polyurethane foam resin composition having excellent performance such as adhesiveness, a urethane molded body, a shoe sole, and an industrial member using the same.

  As a result of intensive studies to solve the above problems, the present inventors have used a two-component curable foamed polyurethane resin composition containing two specific types of salts in an amount within a specific range as an antistatic agent. The urethane molded product has a small difference in electrical resistance value, low temperature dependence and excellent antistatic properties even under a wide range of temperature conditions and low humidity conditions from low temperature to normal temperature (20 ± 15 ° C), and Since the amount of addition can be reduced compared with conventional antistatic agents, there are no harmful effects such as abnormal foaming behavior, reduced hardness, reduced strength, etc. when producing urethane molded products, and antistatic properties, flex resistance, other materials The present inventors have found that excellent performance such as adhesiveness can be expressed, and have completed the present invention.

  That is, the present invention provides a main agent containing an isocyanate group-terminated urethane prepolymer (A), a curing agent containing an isocyanate group-reactive compound (B), water (C), and a catalyst (D), and an antistatic agent. A two-part curable polyurethane foam resin composition comprising an alkyl-substituted quaternary ammonium salt (E1) and an alkyl-substituted imidazolium salt (E2), wherein the content ratio of the salt (E1) and the salt (E2) is The present invention relates to a two-component curable polyurethane foam resin composition having a mass ratio of 19/1 to 1/1.

  The present invention relates to a urethane molded article obtained by molding using the two-component curable foamed polyurethane resin composition.

The present invention also relates to a shoe sole that is molded using the two-component curable polyurethane foam resin composition and has a density in the range of 0.3 to 1.0 g / cm ³ .

  Furthermore, the present invention relates to an industrial member obtained by molding using the two-component curable foamed polyurethane resin composition.

  The two-component curable foamed polyurethane resin composition of the present invention essentially contains an alkyl-substituted quaternary ammonium salt (E1) and an alkyl-substituted imidazolium salt (E2) as an antistatic agent. Due to the external synergistic effect, the electrical resistance value is reduced even under a wide range of temperature conditions and low humidity conditions from low temperature to normal temperature (20 ± 15 ° C.), compared to the case where the salt (E1) or the salt (E2) is used alone. The difference is small, the temperature dependency is small, and the effect of excellent antistatic properties can be obtained.

  Further, since the urethane molded body of the present invention can reduce the amount of the antistatic agent added than before, when producing the foam molded body, there are no adverse effects such as abnormal foaming behavior, reduced hardness, reduced strength, and the like. Excellent performance such as antistatic property, flex resistance and adhesion to other materials can be imparted. In particular, a shoe sole which is a representative example of the urethane molded product is excellent in terms of production and quality.

<Isocyanate group-terminated urethane prepolymer (A)>
(1) Polyisocyanate Component The two-component curable polyurethane foam resin composition of the present invention comprises an isocyanate group-terminated urethane prepolymer (A) (hereinafter referred to as “urethane prepolymer (A)”) and an isocyanate group. Reactive compound (B) (hereinafter referred to as “reactive compound (B)”), water (C), curing agent containing catalyst (D), and alkyl-substituted quaternary ammonium salt (E1) as an antistatic agent ) And an alkyl-substituted imidazolium salt (E2).

  The urethane prepolymer (A) can be obtained by reacting a polyisocyanate component and a polyol component according to a known method, and the reaction method and reaction conditions are not particularly limited.

  The polyisocyanate component refers to a compound having two or more isocyanate groups (hereinafter also referred to as NCO groups) in the molecule.

  As the polyisocyanate component, any of known aliphatic, aromatic and alicyclic polyisocyanates can be used. For example, diphenylmethane diisocyanate (MDI; 4,4 ′ form thereof, 2,4 'Body or 2,2' body, or a mixture thereof, crude MDI), carbodiimide-modified MDI (modified MDI), polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate, xylene diisocyanate, tolylene diisocyanate (TDI) 2 or 4 or 2, 6 or a mixture thereof), xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate (NDI), aromatic polyisocyanate such as tetramethylxylene diisocyanate, phenylene diisocyanate, etc. Or aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), dimer acid diisocyanate, norbornene diisocyanate, lysine diisocyanate, tetramethylxylylene diisocyanate, or isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate (hydrogenated MDI), Examples include alicyclic polyisocyanates such as hydrogenated xylylene diisocyanate (hydrogenated XDI), cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate. Examples of commercially available products include Millionate MT (trademark: Nippon Polyurethane Industry Co., Ltd.). 4,4'-MDI), Cosmonate LL (Trademark: Mitsui Chemicals Polyurethane Co., Ltd., Carbodiimi Modified MDI) and the like. Among these, MDI and TDI are preferable because they are excellent in reactivity with the polyol component, reactivity with moisture (water), and workability, and more preferably vapor pressure when used by heating and melting. Is a low MDI. These may be used alone or in combination of two or more.

(2) Polyol component Examples of the polyol component include polyester polyol, polyether polyol, polycarbonate polyol, and low molecular weight glycol.

  The dicarboxylic acid used for the production of the polyester polyol is, for example, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane. Examples of dicarboxylic acids such as -p, p'-dicarboxylic acid or dicarboxylic acids having no aromatic skeleton include, for example, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, Examples include 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, trimellitic acid, and pyromellitic acid. These may be used alone or in combination of two or more.

The diol used in the production of the polyester polyol is, for example, a diol having an aromatic skeleton such as dihydroxynaphthalene, bisphenol A, bisphenol S, bisphenol AF, bisphenol Si ₂ , and alkylene oxide adducts thereof, or Examples of the diol having no aromatic skeleton include ethylene glycol (EG), 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, neopentyl glycol, trimethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 3-methyl- Aliphatic diols such as 1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol; 1,4-cyclohexanediol, 1,4- Diols such as cycloaliphatic diols such as cyclohexanedimethanol and hydrogenated bisphenol A can be mentioned. These may be used alone or in combination of two or more.

  In addition, as the raw material of the polyester polyol, for example, alcohols such as glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, and aconite sugar; or amines can be used. These may be used alone or in combination of two or more.

  The hydroxyl value of the polyester polyol is desirably set in consideration of the target viscosity of the urethane prepolymer (A) as the main agent. The hydroxyl value of the polyester polyol is preferably in the range of 35 to 225, more preferably in the range of 55 to 120. If the hydroxyl value of the polyester polyol is within such a range, an extreme increase in viscosity of the urethane prepolymer (A) as the main agent can be suppressed, and a urethane prepolymer having an appropriate viscosity can be obtained.

  Examples of the polyester polyol include polyester diols and polyamide polyester diols obtained by using carboxylic acids, diols, diamines and the like other than those described above in combination.

  Examples of the polyether polyol include polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene propylene glycol (PEPG), polytetramethylene glycol (PTMG), 2-methyl-1,3-propaneadipate, 3 -Methyl-1,5 pentane adipate, polycarbonate polyol, etc. are mentioned, Among these, polytetramethylene glycol (PTMG, hydroxyl value 35-175) is preferable. The polyether polyol may have any structure of linear, branched and cyclic.

  The hydroxyl value of the polyether polyol is preferably in the range of 35 to 225, more preferably 55 to 115. When the hydroxyl value of the polyether polyol is within such a range, the brittleness of the urethane molded product can be easily controlled, and high strength and excellent wear resistance can be obtained.

  A polyol obtained by ring-opening addition polymerization of a lactone (for example, ε-caprolactone or the like) to the polyether polyol such as polytetramethylene glycol can also be used.

  Moreover, as said polycarbonate polyol, what is obtained by esterifying carbonic acid and an aliphatic polyol etc. can be used, for example. Specifically, diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol or polytetramethylene glycol (PTMG), and dimethyl carbonate And reaction products with diphenyl carbonate, phosgene and the like. These may be used alone or in combination of two or more.

  Examples of the low molecular weight glycol include ethylene glycol (EG), 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1, Aliphatic diols such as 3-propanediol and 2-methyl-1,3-propanediol; Alicyclic diols such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; Glycerin , Trimethylolpropane, pen Such trifunctional or more hydroxyl group-containing compound of erythritol and the like, and among these, diethylene glycol (DEG) is preferred. The low molecular weight glycol may have a linear, branched, or cyclic structure.

  The molecular weight of the low molecular weight glycol is preferably in the range of 50 to 300, more preferably in the range of 50 to 200. When the molecular weight of the low molecular weight glycol is in such a range, when used as a polyol component, the reactivity can be controlled more effectively and the moldability (yield and molding unevenness) becomes better.

  Moreover, as a polyol component, the polycaprolactone polyol obtained by the ring-opening polymerization of a caprolactone monomer, an aromatic polyester polyol, an acrylic polyol, a polyolefin polyol, a castor oil type polyol etc. can be used, for example.

  Furthermore, you may use another polyol with the said polyol component in the range which does not inhibit the objective of this invention. Examples of the other polyols are obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide on a starting material having at least three hydroxyl groups such as glycerin, trimethylolpropane, pentaerythritol, and sorbitol. Polyether polyols such as poly (oxyalkylene) glycol and poly (oxytetramethylene) glycol; or polyvalent carboxylic acids such as adipic acid, sebacic acid, azelaic acid, succinic acid, maleic acid, phthalic acid and ethylene glycol, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, ne Polycondensation of polyhydric alcohols such as pentyl glycol, 2, -methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, glycerin, trimethylolpropane, diethylene glycol, triethylene glycol, tetraethylene glycol Polyester polyol obtained by polymerization; or polymer polyol for polymerizing ethylenically unsaturated monomers such as acrylonitrile and styrene in the presence of polylactone polyol, polyether ester polyol, polycarbonate polyol, polybutadiene polyol, polyether ester polyol, etc. Is mentioned.

(3) Urethane prepolymer (A)
The isocyanate group equivalent (hereinafter referred to as “NCO equivalent”) of the urethane prepolymer (A) is preferably in the range of 150 to 350, more preferably in the range of 200 to 300. If the NCO equivalent in the urethane prepolymer (A) is within such a range, a large increase in viscosity can be suppressed, and a urethane prepolymer excellent in workability of viscosity that can be easily used in a low-pressure foaming machine can be obtained.

  The “isocyanate group equivalent” (unit: g / mol) in the present invention is a value measured according to JIS K1603-2007 Plastic-Polyurethane Raw Material Aromatic Isocyanate Test Method Part 1: Determination of Isocyanate Group Content. is there.

  The urethane prepolymer (A) can be produced by reacting the NCO group of the polyisocyanate component in an excess amount relative to the hydroxyl group of the polyol component (hereinafter also referred to as OH group) by a known method. it can.

  Examples of the reaction method for obtaining the urethane prepolymer (A) include, for example, adding a polyol component from which water has been removed to a polyisocyanate component charged in a reaction vessel by an appropriate method such as dropping, dividing, or batching, What is necessary is just to employ | adopt the method made to react until the hydroxyl group which a component has disappears substantially.

  In order to allow the reaction to proceed safely and normally while gently controlling the exotherm during the reaction, a charging method by dropping or dividing is preferred.

  The urethane prepolymer (A) is usually produced in the absence of a solvent, but may be produced by reacting in an organic solvent. When making it react in an organic solvent, what is necessary is just to use the organic solvent which does not inhibit reaction, for example, ethyl acetate, n-butyl acetate, methyl ethyl ketone, toluene etc. are mentioned. The organic solvent used for the reaction is desirably removed by an appropriate method such as heating under reduced pressure or distilling off the thin film during or after the reaction.

  The reaction conditions (temperature, time, pressure, etc.) of the urethane prepolymer (A) are not particularly limited as long as the reaction behavior and product quality can be normally controlled. Usually, it is preferable to carry out the reaction at a reaction temperature of 50 to 90 ° C. under a reaction time of 2 to 24 hours. The pressure may be normal pressure, pressurization, or reduced pressure.

  As the reaction method, for example, a known reaction method such as batch, semi-continuous or continuous can be selected, and is not particularly limited.

  Moreover, when manufacturing the said urethane prepolymer (A), a urethanation catalyst can be used as needed. The said catalyst can be suitably added in the arbitrary steps of a raw material preparation process and a reaction process. Moreover, the addition method of a catalyst is not specifically limited, such as lump, division | segmentation, and continuous.

  As the urethanization catalyst, known catalysts can be used, for example, nitrogen-containing compounds such as triethylamine, tributylamine, benzyldibutylamine, triethylenediamine, N-methylmorpholine; or titanium tetrabutoxide, dibutyltin oxide, dibutyltin dilaurate, Organometallic compounds such as tin 2-ethylcaproate, zinc naphthenate, cobalt naphthenate, zinc 2-ethylcaproate, molybdenum glycolate, potassium acetate, zinc stearate, tin octylate, dibutyltin dilaurate; or iron chloride, Examples include inorganic compounds such as zinc chloride.

  Usually, the reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon, but may be performed in a dry air atmosphere or in a condition where moisture is not mixed, such as a sealed condition.

  In the synthesis of the urethane prepolymer (A), the ratio of the NCO equivalent of the polyisocyanate component to the sum of the OH equivalents of the polyol component (ie, [NCO / OH]) is the target physical property, product quality, and reaction behavior. It may be set in consideration of the above.

  The equivalent ratio of the NCO group of the polyisocyanate component to the OH group of the polyol component (that is, [NCO / OH]) is preferably in the range of 2-20, more preferably in the range of 3-15. is there. If it is the range which requires the said [NCO / OH], the control of reaction at the time of an operation | work can be performed easily and the urethane molded object which has the outstanding performance balance can be obtained, and it is preferable.

<Isocyanate group reactive compound (B)>
Next, the curing agent to be blended and mixed in combination with the main agent will be described below.

  The curing agent used in the two-component curable foamed polyurethane resin composition of the present invention includes an isocyanate group-reactive compound (B) (hereinafter referred to as “reactive compound (B)”) as an essential component and water (C ), Catalyst (D), and alkyl-substituted quaternary ammonium salt (E1) and alkyl-substituted imidazolium salt (E2) as an antistatic agent.

  As the reactive compound (B), active hydrogen atom-containing compounds such as the polyols and polyamines can be used.

  The two-component curable foamed polyurethane resin composition of the present invention comprises an NCO / active hydrogen atom in an equivalent ratio of the entire reaction component of an active hydrogen atom-containing compound such as a polyisocyanate component and a polyol component, and a polyamine added as necessary. It can obtain by making it react in the range of containing group (OH group, NH group, etc.) = 0.7-1.2.

  In addition to the reactive compound (B), other reactive compounds can be used as optional components as long as they do not adversely affect the reaction and performance. The other reactive compound is not particularly limited as long as it has good reactivity with a compound having an isocyanate group. For example, a polyaminochlorophenylmethane compound, a polyaminochlorophenylmethane compound, and a polytetramethylene glycol can be used. Examples thereof include a mixture and 4,4′-diamino-3,3′-dichlorodiphenylmethane (hereinafter referred to as MBOCA) which is a dinuclear polyaminochlorophenylmethane compound. These may be used alone or in combination of two or more.

  The compounding amount of the reactive compound (B) is preferably in the range of 40 to 170 parts by mass, more preferably in the range of 75 to 135 parts by mass with respect to 100 parts by mass of the urethane prepolymer (A). . If the blending amount of the reactive compound (B) is within such a range, it can be efficiently stirred and mixed with a low-pressure foaming machine, foam cells having a uniform and fine shape can be formed, high hardness and wear resistance. It is possible to obtain a two-component curable foamed polyurethane resin composition suitable for articles such as shoe soles that can exhibit excellent performance such as.

<Water (C)>
In the present invention, water (C) is blended in order to serve as a foaming agent in the water foaming method.

  In that case, the compounding quantity of water is usually preferably in the range of 0.01 to 1.50 parts by mass, more preferably 0.10 to 0.00 with respect to 100 parts by mass of the reactive compound (B). The range is 60 parts by mass. If the blending amount of water (C) is within such a range, a two-component curable foamed polyurethane resin composition capable of expressing a stable foamed state can be obtained.

  The method of adding water (C) when mixing the main agent and the curing agent is not particularly limited. For example, as the curing agent, reactive compound (B), water (C), catalyst (D), the salt (E1) and the salt (E2), and additives as necessary are mixed in advance. Next, a method of mixing the main agent and the curing agent and injecting, foaming, and curing into the mold may be mentioned.

  In this invention, although water (C) is used as a foaming agent, you may use together the well-known foaming agent used for foaming at the time of a urethanation reaction.

  Furthermore, as a foaming aid, for example, 1,1-dichloro-1-fluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluorobutane, methylene chloride, A low boiling point compound such as pentane can be used.

  In the production of the two-component curable polyurethane foam resin composition of the present invention, additives such as a foam stabilizer can be used as necessary.

  As the foam stabilizer, all those effective for the production of polyurethane resin foam molded articles can be used. Examples thereof include surfactants such as silicon compounds such as polydimethylsiloxane and polysiloxane-polyalkylene oxide block copolymers, metal soaps, alkylphenols and fatty acid ethylene oxide and / or propylene oxide adducts.

<Catalyst (D)>
A catalyst (D) is blended in the two-component curable polyurethane foam resin composition of the present invention.

  The type and addition amount of the catalyst (D) may be selected in consideration of the time from mixing the catalyst to pouring into the mold, the temperature, the final foamed state of the foam, and the like, and is not particularly limited.

  The catalyst (D) is not particularly limited. For example, triethylamine, triethylenediamine, palmityldimethylamine, pentamethyldiethylenetriamine, N, N-dimethylaminoethyl ether, dimethylethanolamine, triethanolamine, N, N, Amine compounds such as N ′, N′-tetramethylhexamethylenediamine, N-methylimidazole, N-ethylmorpholine, toluenediamine, 4,4′-diaminodiphenylmethane, or dioctyltin dilaurate, stannous octoate, dibutyltin Organometallic compounds such as dilaurate, or 4,4′-diamino-3,3′-dichlorodiphenylmethane (referred to as MBOCA), trimethylenebis (4-aminobenzoate), methylenebis (2-ethyl-6) And polyaminochlorophenylmethane compounds such as methylenebis (2,3-dichloroaniline). Among these, triethylenediamine and N, N-dimethylaminoethyl ether are preferred because of their relatively strong foaming properties. Is preferred. These may be used alone or in combination of two or more.

  The blending amount of the catalyst (D) is preferably in the range of 0.15 to 2.00 parts by mass, more preferably 0.30 to 1.0, per 100 parts by mass of the reactive compound (B). The range is 50 parts by mass. If the blending amount of the catalyst (D) is within such a range, a two-component curable foamed polyurethane resin composition capable of expressing a stable foamed state can be obtained.

  A hardening | curing agent can be adjusted by mix | blending and mixing in the range of the said compounding quantity by using water (C), a catalyst (D), etc. as an essential component with the said reactive compound (B) preferably.

  The two-component curable foamed polyurethane resin composition of the present invention can be obtained by blending the main agent and the curing agent prepared as described above according to the formulation and immediately mixing them sufficiently.

  The mixing ratio of the main agent and the curing agent for obtaining the two-component curable foamed polyurethane resin composition of the present invention, that is, [the total number of moles of NCO groups (α) of the urethane prepolymer (A) as the main agent] / [The total number of moles (β) of NCO-reactive groups (that is, OH groups + NH groups) possessed by the curing agent including the reactive compound (B) and water (C)] is preferably α / β = 1/0. The range is from 0.7 to 1 / 1.2, more preferably from 1 / 0.8 to 1 / 1.0. If the blending ratio of the main agent and the curing agent is within such a range, a two-component curable polyurethane foam resin composition capable of exhibiting high strength and excellent wear resistance can be obtained.

<Alkyl-substituted quaternary ammonium salt (E1) and alkyl-substituted imidazolium salt (E2)>
The two-component curable foamed polyurethane resin composition of the present invention essentially contains two kinds of alkyl-substituted quaternary ammonium salt (E1) and alkyl-substituted imidazolium salt (E2) as specific antistatic agents.

  In the two-component curable polyurethane foam resin composition, the ratio of the content of the alkyl-substituted quaternary ammonium salt (E1) and the alkyl-substituted imidazolium salt (E2) is 19/1 to 1/1 mass ratio. The content ratio is preferably 4/1 to 2/1. If the ratio of the contents is within such a range, the amount of use can be reduced when both are used in combination rather than the case where the salt (E1) or the salt (E2) is used alone, and it is much lower even under low temperature conditions. Excellent antistatic performance can be expressed.

  Examples of the alkyl-substituted quaternary ammonium salt (E1) include N-ethyl-N, N-dimethyl-N-dodecyl ammonium ethyl sulfate, N-ethyl-N, N-dimethyl-N-myristyl ammonium ethyl sulfate. Salts, N-ethyl-N, N-dimethyl-N-palmityl ammonium ethyl sulfate, N-ethyl-N, N-dimethyl-N-stearyl ammonium ethyl sulfate, and the like. -Ethyl-N, N-dimethyl-N-dodecylammonium ethyl sulfate is preferred because it is more excellent in performance such as antistatic performance and adhesion to other materials. These may be used alone or in combination of two or more.

  Examples of the alkyl-substituted imidazolium salt (E2) include 1-ethyl-3-methyl-imidazolium sulfonic acid methyl salt, 1-ethyl-3-methyl-imidazolium ethyl sulfate, and 1-ethyl-3-methyl. -Imidazolium thiocyanate, 1-ethyl-3-methyl-imidazolium acetate, 1-butyl-3-methyl-imidazolium sulfonic acid methyl salt, 1-butyl-3-methyl-imidazolium ethyl sulfate, 1-butyl- Examples include 3-methyl-imidazolium thiocyanate and 1-butyl-3-methyl-imidazolium acetate. Among these, 1-ethyl-3-methyl-imidazolium ethyl sulfate, 1-ethyl-3-methyl -Imidazolium thiocyanate is preferred because it has better antistatic performanceThese may be used alone or in combination of two or more.

  In the present invention, as a combination of the alkyl-substituted quaternary ammonium salt (E1) and the alkyl-substituted imidazolium salt (E2), the salt (E1) is N-ethyl-N, N-dimethyl-N-dodecylammonium ethyl. An antistatic agent comprising a combination of 1-ethyl-3-methyl-imidazolium ethyl sulfate and / or 1-ethyl-3-methyl-imidazolium thiocyanate, wherein the salt (E2) is a sulfate, Even under a wide range of temperature conditions and low humidity conditions from room temperature to 20 ± 15 ° C, the difference in electrical resistance is small, the temperature dependence is small, and the antistatic performance is superior. Since the addition amount can be reduced, it is more preferable.

  In the two-component curable polyurethane foam resin composition, the sum of the content of the antistatic agent comprising the alkyl-substituted quaternary ammonium salt (E1) and the alkyl-substituted imidazolium salt (E2) exhibits antistatic performance. From a viewpoint of making it, 0.5 mass% or more is preferable and 1.5 mass% or more is more preferable. Further, from the viewpoint of maintaining the mechanical properties of the resin, it is preferably 10% by mass or less, and more preferably 7% by mass or less. Therefore, the content of the antistatic agent is preferably 1 to 10% by mass, and more preferably the sum of the content is 1.5 to 7% by mass.

  In addition, since the salt (E1) and the salt (E2) are rich in water absorption, there is a fear that the isocyanate group of the urethane prepolymer (A) may be side-reacted with water when mixed with the main agent and stored. It is not preferable. Therefore, the curing agent in which the salt (E1) and the salt (E2) are dissolved and the main agent are stored separately, and are molded by mixing necessary amounts at the time of use. Usually, it is desirable to add both the salt (E1) and the salt (E2) in the adjusting step of the curing agent, not in the adjusting step of the main agent.

  In the two-component curable foamed polyurethane resin composition of the present invention, the salt (E1) and the salt (E2) are contained in a specific ratio (that is, a content ratio of 19/1 to 1/1), so that the low temperature to the normal temperature ( Even under a wide range of temperature conditions and low humidity conditions up to 20 ± 15 ° C), the difference in electrical resistance value is small, the temperature dependence is small and the antistatic performance is excellent, and the addition amount is higher than that of conventional antistatic agents. Therefore, when producing urethane molded products, there are no harmful effects such as abnormal foaming behavior, reduced hardness, reduced strength, etc., and excellent performance such as antistatic properties, bending resistance, and adhesion to other materials. Can be obtained.

  In order to uniformly contain the salt (E1) and the salt (E2) in the urethane molded body, the polyol component used as a raw material of the two-component curable polyurethane foam resin composition, or used as necessary. It is preferable to use it at the time of manufacturing a urethane molded article in a state of being previously dissolved, mixed, or dispersed in an additive such as a plasticizer.

  Among the polyol components, for example, low molecular weight glycols such as ethylene glycol, diethylene glycol, and 1,4-butanediol have good solubility with the (E1) and (E2), and can create a solution having a high concentration. From the viewpoint, ethylene glycol is more preferable.

  In the present invention, other known antistatic agents can be used together with the salt (A1) and the salt (A2) that are essential, as long as the object of the present invention is not impaired.

  The other antistatic agent is not particularly limited. For example, a substituted quaternary ammonium cation-based antistatic compound substituted with a hydrocarbon group and an oxyhydrocarbon group, or an organic acid metal salt-based compound. And anionic antistatic compounds.

  Examples of the substituted sulfonic acid quaternary ammonium include dialkylsulfuric acid derivatives, methanesulfonic acid ester derivatives, p-toluenesulfonic acid ester derivatives, and the like. These can be used individually or in mixture of 2 or more types.

  Examples of the organic acid metal salt-based anionic antistatic compound include bis (trifluoromethanesulfonyl) imide metal salt, tris (trifluoromethanesulfonyl) methane metal salt, alkylsulfonic acid metal salt, benzenesulfonic acid metal salt, Alternatively, organic metal salts such as alkylbenzene sulfonic acid metal salts can be used. These can be used individually or in mixture of 2 or more types.

  In addition, a known antistatic aid may be contained as long as the object of the present invention is not impaired, and the content thereof is not particularly limited.

  Examples of the antistatic aid include cyclic ketones, sorbitan fatty acid esters, and lactone monomers. Examples of the cyclic ketones include cyclopentanone, cyclohexanone, cycloheptanone and the like and derivatives thereof. Examples of sorbitan fatty acid esters include sorbitan sesquioleate, sorbitan monooleate, sorbitan monostearate, sorbitan monolaurate. Rate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate and the like, or lactone monomers include, for example, β-propiolactone, γ-butyrolactone, δ- Examples include lactone monomers such as valerolactone, ε-caprolactone, and γ-crotonolactone. These can be used alone or in combination of two or more.

  The antistatic agent and the antistatic auxiliary agent are used as appropriate in order to adjust the flexibility of the polyol component and the molded body so as to be uniformly contained in the polyurethane molded body (for example, It is preferably used in the production of a polyurethane molded product in a state of being previously dissolved in an adipate-based polyester plasticizer, a benzoic acid-based polyester plasticizer, or the like.

<Urethane molded product>
Examples of the urethane molded body of the present invention include a urethane molded body using a polyurethane resin such as a thermoplastic polyurethane resin, a cast polyurethane resin, a polyurethane foam (polyurethane elastomer foam, hard / soft polyurethane foam, etc.), Preferably, it is a urethane foam molded article.

  As a method for producing the urethane (foamed) molded article, a known method can be adopted. Among them, a main agent containing an isocyanate group-terminated urethane prepolymer (A) in which the polyisocyanate component and the polyol component are reacted in advance. And an isocyanate group-reactive compound (B) (for example, a polyamine-based curing agent) in the presence of two types of antistatic agents, the alkyl-substituted quaternary ammonium salt (E1) and the alkyl-substituted imidazolium salt (E2). Etc.), a prepolymer method in which a two-component curable foamed polyurethane resin composition containing a curing agent containing water (C) and a catalyst (D) is reacted is preferable.

  Examples of the method for adding the salt (E1) and the salt (E2) when producing the urethane molded body include (1) a method of premixing (E1) and (E2) together or separately into a polyol component. (2) A method of separately adding each of the above (E1) and (E2) without premixing can be adopted.

  In the present invention, the salt (E1) and the salt (E2) can be stably stored without being decomposed even when stored in a heated state in the presence of a urethanization catalyst.

  The method (1) is capable of producing a stable urethane foam molded article having excellent antistatic performance under low-temperature and low-humidity conditions without causing adverse effects such as abnormal foaming behavior, reduced hardness, and reduced strength. In particular, it is preferable.

  When producing the urethane molded article of the present invention, it is preferable to use a mixture in which, for example, water, a urethanization catalyst, an antistatic agent, or, if necessary, a foaming agent and other additives are premixed in advance in the polyol component. . Such a premixed mixture and the polyisocyanate component can be mixed and foamed by high-speed stirring with a foam molding machine.

  The foam molding machine is not particularly limited, and for example, a low pressure foam molding machine, an injection foam molding machine or the like can be used.

  In addition to the water foaming method as described above, the urethane molded body production method includes, for example, a method of adding hollow beads, a mechanical foaming method, a chemical foaming method, and the like. From the viewpoint of surface and production cost, the water foaming method is more preferable.

  In the urethane molded body of the present invention, for example, a flame retardant, a foam stabilizer, a chain extender, a plasticizer, a filler, a colorant, a weathering stabilizer, in a range that does not impair the performance such as antistatic property and moldability. Known additives such as a light resistance stabilizer and an antioxidant can be appropriately used.

  Moreover, a well-known method is employable as a molding method of the urethane molding of this invention. For example, a mold forming method in which the mixed foaming liquid discharged from the molding machine is open-injected into the mold, an injection molding method in which the mixed foaming liquid is directly injected into a closed mold directly connected to the discharge port of the molding machine, and the like can be employed.

  The mold used in the present invention can be used without particular limitation as long as it is used as a mold for forming a molded body, and any shape may be used. For example, it includes not only a normally used upper mold, lower mold open mold, flat mold, cylindrical mold, and concave mold, but also a closed mold used for injection molding. Further, the material of the mold may be any material as long as it is generally used, such as iron, aluminum, and epoxy resin.

The density of the urethane molded body of the present invention is preferably 0.2 to 1.1 g / cm ^{3 and} more preferably 0.3 to 0.8 g / cm ³ from the viewpoint of maintaining performance such as mechanical characteristics and durability. 0.4 to 0.7 g / cm ³ is most preferable.

  The urethane molded body of the present invention is a polyurethane elastomer foam, and is used to prevent electrostatic explosions in workplaces, laboratories, dangerous goods warehouses, dangerous goods handling facilities, etc. Therefore, it can be suitably used for various articles such as safety shoes and work shoes for preventing static electricity, shoe soles of clean room shoes, safety gloves, safety work clothes, and safety caps.

  Furthermore, industrial members obtained by molding using the two-component curable polyurethane foam resin composition of the present invention can be used in various fields such as packing, hoses, sheets, cushioning materials, vehicle members, packaging members, and the like. is there.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, “part” and “%” in the text are all based on mass.

[Evaluation and judgment of antistatic properties]
(1) Preparation of measurement sample (urethane molded body) A series of water foaming methods including the following [Step 1] to [Step 4] using the two-component curable foamed polyurethane resin compositions obtained in Examples and Comparative Examples. The urethane molded body was prepared by performing the operation according to.
-[Step 1] Main agent adjustment step A polyisocyanate component and a polyol component are respectively charged into a reactor equipped with a nitrogen introduction tube, a cooling condenser, a thermometer, and a cooler, and the internal temperature is 60 to 90 while stirring in a nitrogen atmosphere. It was made to react at 0 degreeC, the urethane prepolymer (A) was synthesize | combined, and the main ingredient containing the said urethane prepolymer (A) was obtained.
[Step 2] Step of mixing main agent and curing agent Next, the main agent containing the urethane prepolymer (A), and the hardening containing the isocyanate group-reactive compound (B), water (C), and catalyst (D). Agent and antistatic agent, alkyl-substituted quaternary ammonium salt (E1) and alkyl-substituted imidazolium salt (E2), are placed in separate tanks of a two-component mixing low-pressure foaming machine at an appropriate temperature (for example, 40 to 50 ° C. And a foaming reaction liquid is prepared by mixing and stirring a predetermined amount of the main agent and the curing agent at the time of use.
[Step 3] Casting Step The foaming reaction solution is poured into a preheated mold.
[Step 4] Curing step.
The foaming reaction liquid is heated and held in an appropriate temperature range (for example, 40 to 50 ° C.) while being poured into the mold, foamed and cured, and allowed to stand for 3 to 15 minutes in the mold at 40 to 50 ° C. After that, the urethane molded product is taken out. In order to obtain a shoe sole, an appropriate process such as cutting may be performed to adjust the shape of the shoe sole.

(2) Evaluation method of antistatic property Using a battery-type insulation resistance meter (Yokogawa Electric Co., Ltd., Model 260101), an iron plate (75 mm × 75 mm × 10 ^t mm) was prepared on the lower surface of the measurement sample (75 mm × 75 mm × 10 ^t mm) prepared above. 300 mm × 200 mm × 1 ^t mm) and an iron plate (75 mm × 75 mm × 3 ^t mm) were brought into contact with the upper surface, respectively, and the electrical resistance value at the time when 7 days had elapsed after molding was measured to evaluate the antistatic property.
The molded sample is stored in an indoor environment at a temperature of 23 ° C. and a relative humidity of 65%, and then at normal temperature conditions (23 ° C. and relative humidity of 65%) and low temperature and low humidity conditions (0 ° C. and relative humidity of 40%). The electrical resistance value (unit: MΩ) was measured under these two conditions.

(3) Judgment Criteria The antistatic performance was judged according to the overall judgment criteria based on the following two criteria A and B.
<Criteria A>
○: Electrical resistance value under low temperature and low humidity conditions (0 ° C., 40% RH) is 20 MΩ or less.
X: The electrical resistance value under low temperature and low humidity conditions (0 ° C., 40% RH) exceeds 20 MΩ.
<Standard B>
○: The difference in electrical resistance value between the normal temperature condition and the low temperature and low humidity condition is 20 MΩ or less.
X: The difference in electrical resistance value between normal temperature conditions and low temperature and low humidity conditions exceeds 20 MΩ.
<Comprehensive criteria>
Pass: When criteria A and B are both “◯”.
Fail: When only one of criteria A or B or both criteria A and B are “x”.

[Method for measuring density of urethane molded product]
The density (g / cm ³ ) was calculated by dividing the mass of the obtained urethane molded product by the volume.

[Measurement method of hardness of urethane molding]
The hardness of the obtained urethane molded body was evaluated by a spring hardness test (type C) according to Japanese Industrial Standard JIS K 7312-1996 (hardness test).

[Adjustment of main agent (X)]
In a reaction vessel, as an isocyanate component, 543 parts of 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as “4,4′MDI”. Trademark: Millionate MT, manufactured by Nippon Polyurethane Industry Co., Ltd.) and carbodiimide-modified MDI (trademark: Cosmonate LL, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) 28.6 parts were charged and stirring was started.
Next, as a polyol component, a polyester polyol having a hydroxyl value of 56.1 mgKOH / g synthesized from polyol a (ethylene glycol (EG) / 1,4-butylene glycol (1,4BG) and adipic acid (AA). EG / 1 , 4BG = 5/5 molar ratio.) 443.5 parts were charged in portions, mixed, reacted at 60 ° C. for 8 hours under a nitrogen stream, and contained an isocyanate group-terminated urethane prepolymer (A) having an NCO equivalent of 250. The main agent (X) was obtained.

[Adjustment of curing agent (Y)]
91.5 parts of polyol b (polyester polyol having a hydroxyl value of 66 synthesized from EG / 1,4BG and AA. EG / 1,4BG = 5/5 molar ratio) as the isocyanate group-reactive compound (B) 4.8 parts of polyol c (polyethylene polyol having a hydroxyl value of 60 synthesized from diethylene glycol (DEG) / trimethylolpropane (TMP) and AA, DEG / TMP = 15/1 molar ratio), EG 8.8 Part, water (C) 0.37 part as a foaming agent, and triethylenediamine (TEDA) 0.33 part as a catalyst (D) were mixed and stirred sufficiently to prepare a curing agent (Y).

[Example 1]
<< Manufacture of two-component curable polyurethane foam resin composition (P1) >>
In a mixing container, 105.8 parts of the curing agent (Y), 8.75 parts of N-ethyl-N, N-dimethyl-N-dodecylammonium ethyl sulfate (E1) as an antistatic agent and 1-ethyl-3- 1.25 parts of methyl-imidazolium ethyl sulfate (E2) was blended, sufficiently stirred and mixed to obtain a polyol compound (PC1) containing a curing agent (Y) and an antistatic agent.
Next, the main component (X) and the polyol compound (PC1) are blended in a mixing container at a ratio of (X) / (PC1) = 100/96, stirred and mixed, and the two-component curable foamed polyurethane of the present invention. The resin composition (P1) was prepared, 200 g was poured into a mold (290 mm × 120 mm × 10 mm) preheated to 40 ° C., immediately after closing the mold, and left at 40 ° C. for 5 minutes. Thereafter, the finished foam molded product was taken out.
As shown in Table 1, the foam molded article using the two-component curable polyurethane foam resin composition (P1) of the present invention had excellent antistatic performance and characteristics.

[Example 2]
<< Manufacture of two-component curable foamed polyurethane resin composition (P2) >>
In a mixing container, 105.8 parts of the curing agent (Y), 7.50 parts of N-ethyl-N, N-dimethyl-N-dodecylammonium ethyl sulfate (E1) as an antistatic agent and 1-ethyl-3- 2.50 parts of methyl-imidazolium ethyl sulfate (E2) was blended and sufficiently stirred and mixed to obtain a polyol compound (PC2) containing a curing agent (Y) and an antistatic agent.
Next, the main component (X) and the polyol compound (PC2) are blended in a mixing container at a ratio of (X) / (PC2) = 100/96, stirred and mixed, and the two-component curable foamed polyurethane of the present invention. The resin composition (P2) was adjusted and molded by the same operation as in Example 1, and the foamed molded product was taken out.
As shown in Table 1, the foamed molded article using the two-component curable polyurethane foam resin composition (P2) of the present invention had excellent antistatic performance and characteristics.

Example 3
≪Production of two-component curable polyurethane foam resin composition (P3) ≫
In a mixing container, 105.8 parts of the curing agent (Y), 6.25 parts of N-ethyl-N, N-dimethyl-N-dodecylammonium ethyl sulfate (E1) as an antistatic agent and 1-ethyl-3- 3.75 parts of methyl-imidazolium ethyl sulfate (E2) was blended and sufficiently stirred and mixed to obtain a polyol compound (PC3) containing a curing agent (Y) and an antistatic agent.
Next, the main component (X) and the polyol compound (PC3) are blended in a mixing container at a ratio of (X) / (PC3) = 100/96, stirred and mixed, and the two-component curable foamed polyurethane of the present invention. The resin composition (P3) was adjusted and molded by the same operation as in Example 1, and the foamed molded product was taken out.
As shown in Table 1, the foam molded article using the two-component curable polyurethane foam resin composition (P3) of the present invention had excellent antistatic performance and characteristics.

Example 4
<< Manufacture of two-component curable polyurethane foam resin composition (P4) >>
In a mixing container, 105.8 parts of the curing agent (Y), 5.00 parts of N-ethyl-N, N-dimethyl-N-dodecylammonium ethyl sulfate (E1) as an antistatic agent and 1-ethyl-3- 5.00 parts of methyl-imidazolium ethyl sulfate (E2) was blended, and sufficiently stirred and mixed to obtain a polyol compound (PC4) containing a curing agent (Y) and an antistatic agent.
Next, the main component (X) and the polyol compound (PC4) are blended in a mixing container at a ratio of (X) / (PC4) = 100/96, stirred and mixed, and the two-component curable foamed polyurethane of the present invention. The resin composition (P4) was adjusted and molded by the same operation as in Example 1, and the foamed molded product was taken out.
As shown in Table 1, the foam molded article using the two-component curable foamed polyurethane resin composition (P4) of the present invention had excellent antistatic performance and characteristics.

Example 5
<< Manufacture of two-component curable polyurethane foam resin composition (P5) >>
In Example 5, instead of N-ethyl-N, N-dimethyl-N-dodecylammonium ethyl sulfate as an alkyl-substituted quaternary ammonium salt (E1) as an antistatic agent, N-ethyl-N, N -Dimethyl-N-myristylammonium ethyl sulfate was used.
In a mixing container, 105.8 parts of the curing agent (Y), 7.50 parts of N-ethyl-N, N-dimethyl-N-myristylammonium ethyl sulfate (E1) as an antistatic agent and 1-ethyl-3- 2.50 parts of methyl-imidazolium ethyl sulfate (E2) was blended and sufficiently stirred and mixed to obtain a polyol compound (PC5) containing a curing agent (Y) and an antistatic agent.
Next, the main component (X) and the polyol compound (PC5) are blended in a mixing container at a ratio of (X) / (PC5) = 100/96, stirred and mixed, and the two-component curable foamed polyurethane of the present invention. The resin composition (P5) was adjusted and molded by the same operation as in Example 1, and the foamed molded product was taken out.
As shown in Table 1, the foam molded article using the two-component curable polyurethane foam resin composition (P5) of the present invention had excellent antistatic performance and characteristics.

Example 6
<< Manufacture of two-component curable foamed polyurethane resin composition (P6) >>
In Example 6 and Example 7, instead of 1-ethyl-3-methyl-imidazolium ethyl sulfate as the alkyl-substituted imidazolium salt (E2) as the antistatic agent, 1-ethyl-3-methyl-imidazole Performed with liuthiocyanate.
In a mixing container, 105.8 parts of the curing agent (Y), 7.50 parts of N-ethyl-N, N-dimethyl-N-dodecylammonium ethyl sulfate (E1) as an antistatic agent and 1-ethyl-3- 2.50 parts of methyl-imidazolium thiocyanate (E2) was blended and sufficiently stirred and mixed to obtain a polyol compound (PC6) containing a curing agent (Y) and an antistatic agent.
Next, the main component (X) and the polyol compound (PC6) are blended in a mixing container at a ratio (X) / (PC6) = 100/96 mass ratio, stirred and mixed, and the two-component curable foamed polyurethane of the present invention. The resin composition (P6) was adjusted and molded by the same operation as in Example 1, and the foamed molded product was taken out.
As shown in Table 1, the foam molded article using the two-component curable polyurethane foam resin composition (P6) of the present invention had excellent antistatic performance and characteristics.

Example 7
<< Manufacture of two-component curable foamed polyurethane resin composition (P7) >>
In a mixing container, 105.8 parts of the curing agent (Y), 6.65 parts of N-ethyl-N, N-dimethyl-N-dodecylammonium ethyl sulfate (E1) as an antistatic agent and 1-ethyl-3- 3.35 parts of methyl-imidazolium thiocyanate (E2) was blended and sufficiently stirred and mixed to obtain a polyol compound (PC7) containing a curing agent (Y) and an antistatic agent.
Next, the main component (X) and the polyol compound (PC7) are blended in a mixing container at a ratio of (X) / (PC7) = 100/96, stirred and mixed, and the two-component curable foamed polyurethane of the present invention. The resin composition (P7) was adjusted and molded by the same operation as in Example 1, and the foamed molded product was taken out.
The foamed molded article using the two-component curable foamed polyurethane resin composition (P7) of the present invention had excellent antistatic performance and characteristics as shown in Table 1.

[Comparative Example 1]
<< Manufacture of two-component curable foamed polyurethane resin composition (P8) >>
Comparative Example 1 was performed without using an alkyl-substituted imidazolium salt (E2).
In a mixing container, blend only 105.8 parts of the curing agent (Y) and 10 parts of N-ethyl-N, N-dimethyl-N-dodecylammonium ethyl sulfate (E1) as an antistatic agent. The mixture was stirred and mixed to obtain a polyol compound (PC8) containing a curing agent (Y) and an antistatic agent (E1).
Next, the main component (X) and the polyol compound (PC8) are blended in a mixing container at a ratio of (X) / (PC8) = 100/96, stirred, and mixed to form a two-component curable foamed polyurethane resin composition. (P8) was adjusted, 200 g was poured into a mold (290 mm × 120 mm × 10 mm) preheated to 40 ° C., the mold was immediately covered, and then left at 40 ° C. for 5 minutes. The finished foam molded product was taken out.
As shown in Table 2, the foam molded article using the two-component curable foamed polyurethane resin composition (P8) was inferior in antistatic performance and physical properties.

[Comparative Example 2]
<< Manufacture of two-component curable foamed polyurethane resin composition (P9) >>
Comparative Example 2 was carried out without using an alkyl-substituted quaternary ammonium salt (E1).
In a mixing container, blend 105.8 parts of the curing agent (Y) and 10 parts of 1-ethyl-3-methyl-imidazolium ethyl sulfate (E2) as an antistatic agent, and stir and mix thoroughly. A polyol compound (PC9) containing a curing agent (Y) and an antistatic agent (E2) was obtained.
Next, the main component (X) and the polyol compound (PC9) are blended in a mixing container at a ratio (X) / (PC9) = 100/96 mass ratio, stirred, and mixed to form a two-component curable foamed polyurethane resin composition. (P9) was adjusted and molded by the same operation as in Example 1, and a foam molded product was taken out.
As shown in Table 2, the foamed molded product using the two-component curable foamed polyurethane resin composition (P9) was inferior in antistatic performance and physical properties.

[Comparative Example 3]
<< Manufacture of two-component curable foamed polyurethane resin composition (P10) >>
In a mixing container, 105.8 parts of the curing agent (Y), 9.6 parts of N-ethyl-N, N-dimethyl-N-dodecylammonium ethyl sulfate (E1) as an antistatic agent and 1-ethyl-3- 0.40 part of methyl-imidazolium ethyl sulfate (E2) was blended and sufficiently stirred and mixed to obtain a polyol compound (PC10) containing a curing agent (Y) and an antistatic agent.
Next, the main component (X) and the polyol compound (PC10) are blended in a mixing container at a ratio (X) / (PC10) = 100/96 mass ratio, stirred and mixed, and a two-component curable foamed polyurethane resin composition. (P10) was adjusted, molded by the same operation as in Example 1, and a foam molded product was taken out.
As shown in Table 2, the foamed molded article using the two-component curable foamed polyurethane resin composition (P10) was inferior in antistatic performance and physical properties.

[Comparative Example 4]
<< Manufacture of two-component curable foamed polyurethane resin composition (P11) >>
In a mixing container, 105.8 parts of the curing agent (Y), 2.50 parts of N-ethyl-N, N-dimethyl-N-dodecylammonium ethyl sulfate (E1) as an antistatic agent and 1-ethyl-3- 7.50 parts of methyl-imidazolium ethyl sulfate (E2) was blended, and sufficiently stirred and mixed to obtain a polyol compound (PC11) containing a curing agent (Y) and an antistatic agent.
Next, the main component (X) and the polyol compound (PC11) are mixed in a mixing container at a ratio of (X) / (PC11) = 100/96, stirred, mixed, and mixed into a two-component curable foamed polyurethane resin composition. (P11) was adjusted, molded by the same operation as in Example 1, and a foam molded product was taken out.
As shown in Table 2, the foamed molded article using the two-component curable foamed polyurethane resin composition (P11) was inferior in antistatic performance and physical properties.

[Comparative Example 5]
<< Manufacture of two-component curable polyurethane foam resin composition (P12) >>
In a mixing container, 105.8 parts of the curing agent (Y), 9.0 parts of N-ethyl-N, N-dimethyl-N-dodecylammonium ethyl sulfate (E1) as an antistatic agent, and bis (trifluoromethylsulfonyl) ) 1.0 part of imidolithium salt was mixed, and sufficiently stirred and mixed to obtain a polyol compound (PC12) containing a curing agent (Y) and an antistatic agent.
Next, the main component (X) and the polyol compound (PC12) are blended in a mixing container at a ratio of (X) / (PC12) = 100/96, and stirred and mixed to form a two-component curable foamed polyurethane resin composition. (P12) was adjusted and molded by the same operation as in Example 1, and a foam molded product was taken out.
As shown in Table 2, the foamed molded article using the two-component curable foamed polyurethane resin composition (P12) was inferior in antistatic performance and physical properties.

In addition, the symbol and name as described in an Example and a comparative example are as follows.
4,4 ′ MDI: 4,4′-diphenylmethane diisocyanate EG: ethylene glycol 1,4BG: 1,4-butylene glycol AA: adipic acid DEG: diethylene glycol TMP: trimethylolpropane TEDA: triethylenediamine ammonium salt (E1): alkyl Substituted quaternary ammonium salt imidazolium salt (E2): alkyl substituted imidazolium salt AM1 salt: N-ethyl-N, N-dimethyl-N-dodecylammonium ethyl sulfate AM2 salt: N-ethyl-N, N-dimethyl -N-myristyl ammonium ethyl sulfate IM1 salt: 1-ethyl-3-methyl-imidazolium ethyl sulfate IM2 salt: 1-ethyl-3-methyl-imidazolium thiocyanate Li salt; bis (trifluoromethylsulfonyl) imidolithium Salt

  The two-part curable polyurethane foam resin composition of the present invention essentially contains an alkyl-substituted quaternary ammonium salt (E1) and an alkyl-substituted imidazolium salt (E2) as an antistatic agent, and the synergistic effect of these two salts. Thus, the difference in electrical resistance value is smaller even in a wide range of temperature conditions and low humidity conditions from low temperature to normal temperature (20 ± 15 ° C.), compared with the case where the salt (E1) or the salt (E2) is used alone. The temperature dependence is small and the antistatic performance is excellent, and the amount added can be reduced compared to conventional antistatic agents. Therefore, when manufacturing urethane molded products, there are problems such as abnormal foaming behavior, reduced hardness, and reduced strength. And exhibit excellent performance such as antistatic properties, bending resistance, and adhesion to other materials. In addition, since the amount of the antistatic agent added to the polyurethane molded product of the present invention can be reduced as compared with the conventional one, there is no adverse effect such as abnormal foaming behavior, reduced hardness, reduced strength, etc. when producing the foamed molded product. Excellent performance such as prevention, bending resistance and adhesion to other materials can be imparted. In particular, a shoe sole, which is a typical example of the polyurethane molded product, is excellent in production and quality.

Claims (7)

Alkyl-substituted quaternary as main agent containing isocyanate group-terminated urethane prepolymer (A), curing agent containing isocyanate group-reactive compound (B), water (C), catalyst (D), and antistatic agent A two-component curable foamed polyurethane resin composition comprising an ammonium salt (E1) and an alkyl-substituted imidazolium salt (E2), wherein the alkyl-substituted quaternary ammonium salt (E1) is N-ethyl-N, N- Dimethyl-N-dodecylammonium ethyl sulfate, wherein the alkyl-substituted imidazolium salt (E2) is 1-ethyl-3-methyl-imidazolium ethyl sulfate and / or 1-ethyl-3-methyl-imidazolium thiocyanate Yes, wherein the content ratio of the salt of the resin composition (E1) and salt (E2) is 19 / 1-1 / 1 mass ratio Two-part curable polyurethane foam resin composition. The sum of the content ratios of the alkyl-substituted quaternary ammonium salt (E1) and the alkyl-substituted imidazolium salt (E2) in the two-component curable polyurethane foam resin composition is 1 to 10% by mass. The two-component curable foamed polyurethane resin composition described. The two-component curable polyurethane foam resin composition according to claim 1, wherein an isocyanate group equivalent in the isocyanate group-terminated urethane prepolymer (A) is 150 to 350. With respect to 100 parts by mass of the isocyanate group-reactive compound (B), the amount of water (C) is 0.01 to 1.50 parts by mass, and the amount of catalyst (D) is 0.15 to 2. The two-component curable foamed polyurethane resin composition according to claim 1, which is 00 parts by mass. A urethane molded body obtained by molding using the two-component curable polyurethane foam resin composition according to any one of claims 1 to 4 . A shoe sole formed using the two-component curable polyurethane foam resin composition according to any one of claims 1 to 4 , and having a density in the range of 0.3 to 1.0 g / cm3. . An industrial member obtained by molding using the two-component curable polyurethane foam resin composition according to any one of claims 1 to 4 .