CN102977308A - Bi-component cured foam polyurethane resin composition, polyurethane molding body and sole - Google Patents
Bi-component cured foam polyurethane resin composition, polyurethane molding body and sole Download PDFInfo
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- CN102977308A CN102977308A CN201210321422XA CN201210321422A CN102977308A CN 102977308 A CN102977308 A CN 102977308A CN 201210321422X A CN201210321422X A CN 201210321422XA CN 201210321422 A CN201210321422 A CN 201210321422A CN 102977308 A CN102977308 A CN 102977308A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- 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
- C08G2101/00—Manufacture of cellular products
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- 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
- C08G2410/00—Soles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
Abstract
The invention provides a bi-component cured foam polyurethane resin composition, a polyurethane molding body and a sole. Even in a temperature condition of wide range from low temperature to the normal temperature, and in a low humidity condition, differences of resistance values are low, and the bi-component cured foam polyurethane resin composition, the polyurethane molding body and the solehas little temperature dependency and excellent anti-static performance. The invention relates to the bi-component cured foam polyurethane resin composition, characterized by comprising the following components: main agent (i) of polyurethane prepolymer (A) with isocyanate groups, a compound (B) with functional groups which react with the isocyanate groups, water (C) and a curing agent (ii) of a catalyst (D), and an anti-static agent (iii) with alkyl-substituted quaternary ammonium salt (E1) and alkyl-substituted imidazole onium salt (E2). Mass ratio [(E1)/(E2)] of the above ammonium salt (E1) and the imidazole onium salt (E2) is in a range of 95/5-3/70.
Description
Technical field
The present invention relates to excellent electrostatic prevention property two-pack curing foaming polyurethane resin composition, use it and the polyurethane molded body and the sole that obtain.
Background technology
It is continuous that the static of processing the place of such processing hazardous material such as place, Experimental Establishment at comprehensive production, chemical plant, operation site, hazardous material becomes fire and outburst disaster former thereby that cause, and the infringement of people and property is larger, and this is subject to people's worry.
As the countermeasure that prevents such electrostatic hazard, positive active research wear the resin that uses in the footwear, dress material product etc. of usefulness or fiber etc. and is given static electricity resistance and (claim that also system is electrical to human body.), for example, be applied to anti-electrostatic charged with safety shoes, operation footwear, cleaning chamber with various article such as the sole of footwear etc., medical footwear, safety gloves, safety operation clothes, safety helmets.
In the past, as the method for giving static electricity resistance, with comprise the antistatic agent coating of conductive material, ionic substance etc. or be ejected into the surface of synthetic resin method, just adding the antistatic agent inside that comprises conductive material, ionic substance etc. to method in the resin etc.As the example that such method is applied in the urethane resin, be known that such as (1) and add the method for carbon black, conductive filler material etc. or (2) coating or interpolation ionic surfactant's method etc.
Yet, in adding the preceding method (1) of conductive filler material etc., owing to cause the remarkable tackify of resin combination when adding in the urethane resin, thereby the moulding difficult.
In addition, in the preceding method (2) that uses common ionic surfactant, exist to be difficult to improve static electricity resistance until the problem of practical effective level.Therefore, carry out giving the research of better static electricity resistance as purpose.
For example, following scheme has been proposed: an alkali metal salt or the method (for example with reference to patent documentation 1 and 2) of alkaline earth salt or the method (for example with reference to patent documentation 3) of adding alkylsurfuric acid quaternary ammonium, quaternary ammonium perchlorate of adding perchloric acid, thiocyanic acid or nitric acid etc.
Yet in the method for aforementioned patent document 1, patent documentation 2, when the specific compound that uses separately it to put down in writing, early showing anti-static effect to a certain degree, but the performance of polyurethane moldings is still insufficient, in practical existing problems.
In addition, in the method for aforementioned patent document 3, there are the following problems: the just electrical performance of the system after the moulding is excessively slow, and the final performance of polyurethane moldings also is can't fully show static electricity resistance, the practicality extreme difference under the humidity dependence high and low temperature low humidity condition.
Further, following method has been proposed: as ionic anti-electrostatic compound, using substituted sulfonic acid quaternary ammonium etc. nonmetal is that the metals such as anti-electrostatic compound and metal organic sulfonate are the mixture of anti-electrostatic compound, adds the antistatic agent composition that is added with the polar organic solvent of cyclic carbonates such as methane amide or ethylene carbonate, propylene carbonate etc. in the urethane (for example with reference to patent documentation 4).
Yet, in the method for patent documentation 4, because as the necessary polar organic solvent that composition uses methane amide or the cyclic carbonates such as ethylene carbonate, propylene carbonate etc. that contains, thereby be subject to easily the detrimentally affect of residual organic solvent, such as the organic solvent of the oozing out of the reduction of the storage stability of the resin combination that has gained, formed body surface, methane amide etc. cause to human body detrimentally affect etc. aspect secure context, the health, the variety of issue of quality aspect.
In addition, in the situation of patent documentation 4, the cyclic carbonate that in polyvalent alcohol, adds since in the presence of catalyzer heating the time decompose easily, thereby as foaming stock solution and in the situation that premix uses in the polyvalent alcohol, cause in time the foaming dystropy, can't obtain the forming composition of stable physical property, thereby also have online production aspect and qualitative control aspect to produce bad such problem.
Further, proposed following scheme: containing the positively charged ion that is selected from substituted sulfonic acid quaternary ammonium system is that the negatively charged ion that the electrical compound of system and metal-salt are is at least a kind antistatic agent in the electrical compound of system and comprises the urethane resin formed body that lactone is the anti-electrostatic auxiliary agent of monomer (for example with reference to patent documentation 5).
Yet, in the patent documentation 5, there are the following problems: be monomer by adding lactone as the anti-electrostatic auxiliary agent, some static electricity resistances have been obtained, but practical aspect is also insufficient, cementability is also poor in addition, thereby also is difficult to use in the purposes of wide region of safe articles such as the sole of safety shoes etc. or safety gloves etc. etc.
In addition, for the antistatic agent that uses in the patent documentation 5, its static electricity resistance moisture (water) and water large to the dependency of temperature and humidity, under hot and humid degree condition in the absorption atmosphere work as antistatic agent, a part can show good antistatic performance, but with respect to this, exist under low temperature and low humidity degree condition, to show sufficient static electricity resistance and and unpractical problem.
As mentioned above, expect two-pack curing foaming polyurethane resin composition as described below: even under the temperature condition and low humidity condition of the wide region of (20 ± 15 ℃) from low temperature to normal temperature, the two-pack curing foaming polyurethane resin composition of the antistatic performance excellence that the difference of resistance value is also little and temperature dependency is little.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 63-43951 communique
Patent documentation 2: Japanese kokai publication hei 4-298517 communique
Patent documentation 3: Japanese kokai publication hei 4-298518 communique
Patent documentation 4: TOHKEMY 2001-329253 communique
Patent documentation 5: TOHKEMY 2005-60682 communique
Summary of the invention
Invent problem to be solved
Problem to be solved by this invention is, even provide under the temperature condition and low humidity condition of the wide region of (20+15 ℃) from low temperature to normal temperature, the two-pack curing foaming polyurethane resin composition of the excellent electrostatic prevention property that the difference of resistance value is also little and temperature dependency is little, use it and the polyurethane molded body and the sole that obtain.
For the scheme of dealing with problems
The inventor etc. further investigate repeatedly in order to solve above-mentioned problem, found that as antistatic agent, use contains with the amount of specified range in the situation of two-pack curing foaming polyurethane resin composition of specific 2 kinds of salt, even under the temperature condition and low humidity condition of the wide region of (20+15 ℃) from low temperature to normal temperature, the excellent electrostatic prevention property that the difference of resistance value is also little and temperature dependency is little, thus the present invention finished.
Namely, the present invention relates to two-pack curing foaming polyurethane resin composition, the polyurethane molded body that uses it and obtain and sole, described two-pack curing foaming polyurethane resin composition, it is characterized in that, it is the two-pack curing foaming polyurethane resin composition that contains the composition of following (i)～(iii), namely, the host (i) that contains the polyurethane prepolymer (A) with isocyanate group, contain the compound (B) that has with the functional group of isocyanic ester radical reaction, the solidifying agent (ii) of water (C) and catalyzer (D), contain the quaternary ammonium salt (E1) of alkyl replacement and the antistatic agent (iii) of the imidazole salts (E2) that alkyl replaces, the mass ratio [(E1)/(E2)] of aforementioned ammonium salt (E1) and aforementioned imidazole salts (E2) is 95/5～30/70 scope.
The invention effect
Two-pack curing foaming polyurethane resin composition of the present invention is by using the specific antistatic agent of specified quantitative, can obtain under the temperature condition and low humidity condition of the wide region of (20+15 ℃) from low temperature to normal temperature the effect of the excellent electrostatic prevention property that the difference of resistance value is also little and temperature dependency is little.
In addition, polyurethane molded body of the present invention is because can be more in the past than the addition that reduced antistatic agent, thereby when making expanded moldings, the do not foam detrimentally affect of unusual, lower hardness, strength decreased etc. of behavior, and can give static electricity resistance, resistance to bend(ing), with the excellent performance such as other raw-material cementabilities, particularly be suitable for the sole as the typical example of aforementioned polyurethane molded body.。
Embodiment
＜have a polyurethane prepolymer (A) of isocyanate group 〉
Aforementioned polyurethane prepolymer (A) with isocyanate group (below, referred to as polyurethane prepolymer (A).) can polyisocyanates composition and polyhydroxy reactant reaction be obtained according to known method.
In addition, polyisocyanate component refers to, have in the molecule isocyanate group more than 2 (below, be also referred to as the NCO base.) compound.
As polyisocyanate component, can use known aliphatics, aromatic series, reach any in the ester ring type polyisocyanates, for example can list diphenylmethanediisocyanate (MDI; Its 4,4 ' body, 2,4 ' body or 2,2 ' body or their mixture, thick MDI), carbodiimide modified MDI (modification MDI), polymethylene polyphenyl Quito isocyanic ester, carbodiimide ditan polyisocyanates, Xylene Diisocyanate, tolylene diisocyanate (TDI; Its 2,4 bodies, or 2,6 bodies, perhaps their mixture), inferior Xylene Diisocyanate (XDI), 1,5-naphthalene diisocyanate (NDI), tetramethylxylene diisocyanate, the aromatic polyisocyanate of phenylene diisocyanate etc., perhaps hexamethylene diisocyanate (HDI), the dimer acids vulcabond, the norbornylene vulcabond, lysinediisocyanate, the aliphatic polyisocyante of the inferior Xylene Diisocyanate of tetramethyl-etc., perhaps isophorone diisocyanate (IPDI), hydrogenation diphenylmethanediisocyanate (hydrogenation MDI), the inferior Xylene Diisocyanate (hydrogenation XDI) of hydrogenation, cyclohexyl diisocyanate, dicyclohexyl methane diisocyanate, the ester ring type polyisocyanates of isophorone diisocyanate etc., in addition, as commercially available product, for example can list, MILLIONATE MT (trade mark: Nippon Polyurethane Industry Co., Ltd.'s system, 4,4 '-MDI), Cosmonate LL (trade mark: Mitsui Chemical Polyurethane Co., Ltd's system, carbodiimide modified MDI) etc.In the middle of these, from the reactivity of polyhydroxy reactant, with the excellences such as the reactivity of moisture (water) and operability, be preferably MDI, modification MDI, TDI, more preferably make its heating and melting and MDI, modification MDI that steam when using forces down.These can use separately, and also two or more kinds may be used.
As aforementioned polyhydroxy reactant, for example can list polyester polyol, polyether glycol, polycarbonate polyol, low molecular weight diols etc.
The dicarboxylic acid that uses in the manufacturing for aforementioned polyester polyol, as the dicarboxylic acid with aromatic series skeleton, for example can list, terephthalic acid, m-phthalic acid, phthalic acid, naphthalene dicarboxylic acids, diphenyl dicarboxylic acid, 1, two (phenoxy group) ethane-p of 2-, the dicarboxylic acid of p '-dicarboxylic acid etc., perhaps as the dicarboxylic acid that does not have the aromatic series skeleton, for example can list, succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-encircles pentane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, the p-Para Hydroxy Benzoic Acid, p-(2-hydroxyl-oxethyl) M-nitro benzoic acid, trihemellitic acid, pyromellitic acid etc.These can use separately, and also two or more kinds may be used.
The dibasic alcohol that uses in the manufacturing for aforementioned polyester polyol, as the dibasic alcohol with aromatic series skeleton, for example can list, dihydroxy naphthlene, dihydroxyphenyl propane, bisphenol S, bisphenol AF, bisphenol S i2, and the dibasic alcohol of their oxirane affixture etc., perhaps as the dibasic alcohol that does not have the aromatic series skeleton, for example can list, ethylene glycol (EG), Diethylene Glycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1,6-hexylene glycol, neopentyl glycol, tetramethylene ethylene glycol, Diethylene Glycol, triethylene glycol, TEG, dipropylene glycol, tripropylene glycol, the 3-methyl isophthalic acid, the 5-pentanediol, 2-butyl-2-ethyl-1, ammediol, the 2-methyl isophthalic acid, the glycol of ammediol etc.; The dibasic alcohol of the alicyclic di-alcohols of Isosorbide-5-Nitrae-cyclohexanediol, 1,4 cyclohexane dimethanol, hydrogenation dihydroxyphenyl propane etc. etc.These can use separately, and also two or more kinds may be used.
In addition, as the raw material of aforementioned polyester polyol, also can use the alcohols such as glycerine, trimethylolethane, TriMethylolPropane(TMP), sorbyl alcohol, sucrose, equisetic acid (Aconitic) sugar etc.; Perhaps amine etc.
The expectation of the hydroxyl value of aforementioned polyester polyol be considered as host polyurethane prepolymer (A) target viscosities and set.The hydroxyl value of aforementioned polyester polyol is preferably 35～225 scope, more preferably 55～120 scope.In addition, the hydroxyl value of aforementioned polyester polyol (mgKOH/g) expression is based on the value of JISK 1557-1A method mensuration.
The polyester diol that can also contain in the aforementioned polyester polyol and obtain with the carboxylic acid beyond above-mentioned, dibasic alcohol, diamines etc., polymeric amide polyester diol etc.
As aforementioned polyether glycol, for example can list, polyoxyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene propylene glycol (PEPG), polytetramethylene ethylene glycol (PTMG), 2-methyl isophthalic acid, the own diester of 3-propane, 3-methyl isophthalic acid, 5 pentane adipic acid esters, polycarbonate polyol etc., in the middle of these, preferred polytetramethylene ethylene glycol (PTMG, hydroxyl value 35～175).Aforementioned polyether glycol can have any structure in straight chain, branch, the ring-type.
The hydroxyl value of aforementioned polyether glycol can more easily carry out the control of the fragility of polyurethane molded body, from can further improving the viewpoint of high strength and antifriction consumption, is preferably 35～225 scope, 55～115 scope more preferably.In addition, the hydroxyl value of aforementioned polyether glycol (mgKOH/g) expression and the same value that obtains of the hydroxyl value of aforementioned polyester polyol.
Also can use the aforementioned polyether glycol of polytetramethylene ethylene glycol etc. and lactone (such as 6-caprolactone etc.) to carry out ring opening polyaddition and polyvalent alcohol etc.
As aforementioned polycarbonate polyol, for example can use, make carbonic acid and aliphatic polyol carry out esterification and polyvalent alcohol of obtaining etc.Can list 1 specifically, ammediol, 1,4-butyleneglycol, 1, the reaction product of such dibasic alcohol of 6-hexylene glycol, Diethylene Glycol, polyoxyethylene glycol, polypropylene glycol or polytetramethylene ethylene glycol (PTMG) etc. and methylcarbonate, diphenyl carbonate photoreactive gas etc. etc.These can use separately, and also two or more kinds may be used.
As aforementioned low molecular weight diols, for example can list ethylene glycol (EG), 1,2-PD, 1, ammediol, 1,3-butyleneglycol, BDO, 1,5-PD, 1,6-hexylene glycol, neopentyl glycol, Diethylene Glycol, triethylene glycol, TEG, dipropylene glycol, tripropylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 2-butyl-2-ethyl-1,3-PD, 2-methyl isophthalic acid, the glycol of ammediol etc.; The alicyclic di-alcohols of Isosorbide-5-Nitrae-cyclohexanediol, 1,4 cyclohexane dimethanol, hydrogenation dihydroxyphenyl propane etc.; The hydroxy-containing compounds that the 3 officials energy of glycerine, TriMethylolPropane(TMP), tetramethylolmethane etc. is above etc., preferred Diethylene Glycols (DEG) in the middle of these.Aforementioned low molecular weight diols can have any structure in straight chain, branch, the ring-type.
The molecular weight of aforementioned lower molecular weight glycol can more effectively carry out reactive control, and the viewpoint from formability (yield rate, moulding inequality) becomes better is preferably 50～300 scope, more preferably 50～200 scope.In addition, the molecular weight of aforementioned low molecular weight diols represents the molecular weight by structural formula calculating.
In addition, as polyhydroxy reactant, also for example can use, the polycaprolactone polyol, aromatic polyester polyol, acrylic polyol, polyolefin polyhydric alcohol, the Viscotrol C that are obtained by the ring-opening polymerization of caprolactone monomer are polyvalent alcohol etc.
Further, can also with aforementioned polyhydroxy reactant, in the scope that does not hinder purpose of the present invention, use other polyvalent alcohols.As aforementioned other polyvalent alcohols, can list that oxirane such as the starting raw material with the hydroxyl more than at least 3 that makes glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder etc. and oxyethane, propylene oxide, butylene oxide ring etc. carries out addition polymerization and the polyether glycol of poly-(oxyalkylene) ethylene glycol that obtains, poly-(oxidation tetramethylene) ethylene glycol etc.; Perhaps polycarboxylic acid and the ethylene glycol, 1 of hexanodioic acid, sebacic acid, nonane diacid, succsinic acid, toxilic acid, phthalic acid etc., 2-propylene glycol, 1, ammediol, BDO, 2,3-butanediol, 1,5-pentanediol, 1,6-hexylene glycol, 1,8-ethohexadiol, neopentyl glycol, 2-methyl isophthalic acid, ammediol, 3-methyl isophthalic acid, the polyvalent alcohol of 5-pentanediol, glycerine, TriMethylolPropane(TMP), Diethylene Glycol, triethylene glycol, TEG etc. carry out polycondensation and the polyester polyol that obtains; Perhaps in the presence of poly-lactone polyol, polyester ether polylol, polycarbonate polyol or polybutadiene polyol, polyester ether polylol, make the ethylenically unsaturated monomer of vinyl cyanide, vinylbenzene etc. carry out polymer polyatomic alcohol of polymerization etc.
From can further improving the viewpoint of the operability of utilizing viscosity etc., the isocyanate group equivalent of aforementioned polyurethane prepolymer (A) is (hereinafter referred to as " NCO equivalent ".) be preferably 150～350 scope, more preferably 200～300 scope.
In addition, the present invention's said " isocyanate group equivalent " (unit: g/eq.) refer to, according to JIS K1603-2007 plastics-urethane raw aromatic isocyanate test method First: the value that the computation of the containing ratio of isocyanate group is measured.
The hydroxyl that aforementioned polyurethane prepolymer (A) can have with respect to polyhydroxy reactant according to the NCO base that polyisocyanates becomes branch to have (below, be also referred to as the OH base.) be superfluous add-on, react and make with known method.
As the reaction method that is used for obtaining aforementioned polyurethane prepolymer (A), for example can list, by the polyhydroxy reactant that drips, moisture has been removed in the appropriate means addings such as substep addings, disposable adding, make its reaction until the method that the hydroxyl that polyhydroxy reactant has disappears basically in the polyisocyanates composition in the reaction vessel of packing into.
Make reaction safety in the time of for the stable heat release of controlling in the reaction and normally carry out the adding method that preferably drips or add step by step.
The manufacturing of aforementioned polyurethane prepolymer (A) is carried out under solvent-free usually, but also can make its reaction and manufacturing in organic solvent.In the situation of in organic solvent, reacting, can use the organic solvent that does not hinder reaction, for example can list, vinyl acetic monomer, n-butyl acetate, methylethylketone, toluene etc.The expectation of the organic solvent that uses in the reaction in the reaction or the proper method that heats up in a steamer etc. by decompression heating or film after finishing of reaction remove.
The reaction conditions of aforementioned polyurethane prepolymer (A) (temperature, time, pressure etc.) can be set in the scope that can normally control reflex action, product quality etc.Usually preferably under 50～90 ℃ of temperature of reaction, the condition in 2～24 hours reaction times, carry out.Pressure can be in normal pressure, pressurization, the decompression any.
Reactive mode for example can be selected, in batch, the known reactive mode such as semicontinuous, continuous.
In addition, when making aforementioned polyurethane prepolymer (A), can use as required the polyurethane-reinforcement catalyzer.Aforementioned catalyzer can suitably add in any stage that raw material adds operation, reaction process.In addition, for the addition means of catalyzer, can list disposable interpolation, substep interpolation, continuous adding etc.
As aforementioned polyurethane-reinforcement catalyzer, can use known catalyzer, for example can list the nitrogenous compound of triethylamine, tributylamine, benzyl dibutylamine, Triethylene Diamine, N-methylmorpholine etc.; The perhaps organometallic compound of four butanols titaniums, dibutyl tin oxide, dibutyl tin laurate, 2 ethyl hexanoic acid tin, naphthalene acid zinc, naphthoic acid cobalt, 2 ethyl hexanoic acid zinc, two alkyd molybdenums, Potassium ethanoate, Zinic stearas, stannous octoate, dibutyl tin two lauroleates etc.; Perhaps mineral compound of iron(ic) chloride, zinc chloride etc. etc.
Usually, reaction preferably carries out under the inert gas atmospheres such as nitrogen or argon gas, but also can be under dry air atmosphere or the inferior condition of not sneaking into moisture of air tight condition under carry out.
In aforementioned polyurethane prepolymer (A) synthetic, the NCO equivalent of polyisocyanates composition and the ratio (i.e. [NCO/OH]) of the total of the OH equivalent of aforementioned polyhydroxy reactant can be considered as the physical property, product quality, reflex action of target etc. and set.
The viewpoint of the reactivity when operating from can further improving or the performance balance of polyurethane molded body, aforementioned [NCO/OH] is preferably 2～20 scope, more preferably 3～15 scope.
＜have a compound (B) with the functional group of isocyanic ester radical reaction 〉
As aforementioned have with the compound (B) of the functional group of isocyanic ester radical reaction (below, referred to as reactive compounds (B).), can use the compound that for example has hydroxyl, primary amino or secondary amino group.
As aforementioned compound with hydroxyl, can use the aforementioned polyhydroxy reactant for the manufacturing of aforementioned polyurethane prepolymer (A).Especially, reach (E2) the deliquescent viewpoint of composition from can further improve polyester polyol and (E1) described later, preferably make spent glycol, Diethylene Glycol, BDO, particularly preferably use polyester polyol and ethylene glycol.
As aforementioned compound with primary amino or secondary amino group, for example can list, quadrol, 1,6-hexamethylene-diamine, piperazine, 2,5-lupetazin, isophorone diamine, 4,4 '-dicyclohexyl methyl hydride diamines, 3,3 '-dimethyl-4,4 '-dicyclohexyl methyl hydride diamines, 1,4-cyclohexane diamine, 1,2-propanediamine, diethylenetriamine, triethylene tetramine, 3,3 '-two chloro-4,4 '-diaminodiphenyl-methane, poly-amino-chloro-benzene methylmethane compound (" BANTEX E-50 ", DIC system) etc.
Viewpoint from the foamed state that can further improve the stirring efficiency that utilizes the low pressure foaming machine, foamed cell, antifriction consumption etc., with respect to aforementioned polyurethane prepolymer (A) 100 mass parts, the amount of being mixed as previous reaction compound (B), be preferably the scope of 40～170 mass parts, more preferably the scope of 75～135 mass parts.
＜water (C) 〉
Among the present invention, water (C) is mixed as the whipping agent in the water foaming.
From can further improving the viewpoint of foamed state, the amount of being mixed of water is preferably the scope of 0.01～1.5 mass parts, more preferably the scope of 0.1～0.6 mass parts with respect to previous reaction compound (B) 100 mass parts.
Among the present invention, make water (C) as whipping agent, but also may be used the known whipping agent that uses in the foaming when polyurethane-reinforcement reacts.
Further, as frothing aid, for example can use 1,1-two chloro-1-fluoroethanes, 1,1,1,3,3-pentafluoropropane, 1,1,1,3, the lower boiling compound of 3-3-pentafluorobutane, methylene dichloride, pentane etc.
When the manufacturing of two-pack curing foaming polyurethane resin composition of the present invention, can use as required the additives such as surfactant.
As aforementioned surfactant, for example can list the tensio-active agent of the oxyethane of the silicone compound of polydimethylsiloxane, polysiloxane-polyalkylene oxide block copolymer etc., metallic soap, alkylphenol, lipid acid and/or propylene oxide adduct etc.
＜catalyzer (D) 〉
As aforementioned catalyzer (D), for example can list, triethylamine, Triethylene Diamine, the palmityl dimethyl amine, the pentamethyl-Diethylenetriamine, N, N-dimethyl aminoethyl ether, dimethylethanolamine, trolamine, N, N, N ', N '-tetramethyl-hexamethylene-diamine, the N-Methylimidazole, N-ethylmorpholine, tolylene diamine, 4, the amine compound of 4 '-diaminodiphenyl-methane etc., perhaps dioctyl tin two lauroleates, stannous octoate, the organometallic compound of dibutyl tin two lauroleates etc., perhaps 4,4 '-diamino-3,3 '-dichloro-diphenyl methane (being called MBOCA), trimethylene two (PABA ester), methylene-bis (2-ethyl-6-monomethylaniline), methylene-bis (2, the 3-dichlorphenamide bulk powder) etc. poly-amino-chloro-benzene methylmethane compound etc., in the middle of these, from the more intense viewpoint of alveolation characteristic, preferred Triethylene Diamine, N, N-dimethyl aminoethyl ether.These can use separately, and also two or more kinds may be used.
From making the more viewpoint of stabilization of foamed state, with respect to previous reaction compound (B) 100 mass parts, the amount of being mixed of aforementioned catalyzer (D) is preferably the scope of 0.15～2 mass parts, the more preferably scope of 0.3～1.5 mass parts.
The imidazole salts (E2) that the quaternary ammonium salt (E1) that＜alkyl replaces and alkyl replace 〉
2 kinds of imidazole salts (E2) that must contain quaternary ammonium salt (E1) that alkyl replaces and alkyl replacement in the two-pack curing foaming polyurethane resin composition of the present invention as antistatic agent.
In addition, in the aforementioned two-pack curing foaming polyurethane resin composition, solving on the problem of the present invention, the quaternary ammonium salt (E1) that aforesaid alkyl replaces is necessary for 95/5～30/70 scope with the mass ratio [(E1)/(E2)] of the imidazole salts (E2) that aforesaid alkyl replaces.Surpassing in the situation of described scope the static electricity resistance that can't obtain to expect.In addition, by in aforementioned range, can further reduce than existing antistatic agent the addition of antistatic agent, thereby when making polyurethane moldings, the evils of unusual, lower hardness, strength decreased etc. of behavior of not foaming, and can obtain static electricity resistance, resistance to bend(ing), with the excellent performance such as other raw-material cementabilities.In addition, as aforementioned [(E1)/(E2)], from can further improving the viewpoint of static electricity resistance, be preferably 90/10～40/60 scope, 90/10～50/50 scope more preferably, more preferably 85/15～60/40 scope is particularly preferably 80/20～70/30 scope.
Quaternary ammonium salt (E1) as the aforesaid alkyl replacement, for example can list, N-ethyl-N, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol, N-ethyl-N, N-dimethyl-N-myristyl QAE quaternary aminoethyl vitriol, N-ethyl-N, N-dimethyl-N-palmityl QAE quaternary aminoethyl vitriol, N-ethyl-N, N-dimethyl-N-stearyl QAE quaternary aminoethyl vitriol etc., these can use separately, and also two or more kinds may be used.In the middle of these, from antistatic performance and with the more excellent aspect of the performance of other raw-material cementabilities etc., preferred N-ethyl-N, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol and/or N-ethyl-N, N-dimethyl-N-myristyl QAE quaternary aminoethyl vitriol, N-ethyl-N particularly preferably, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol.
Imidazole salts (E2) as the aforesaid alkyl replacement, for example can list, 1-ethyl-3-methyl-imidazoles sulfonic acid methyl salt, 1-ethyl-3-methyl-imidazole ethyl vitriol, 1-ethyl-3-methyl-imidazoles thiocyanate-, 1-ethyl-3-methyl-imidazoleacetic acid ester, 1-butyl-3-methyl-imidazoles sulfonic acid methyl salt, 1-butyl-3-methyl-imidazole ethyl vitriol, 1-butyl-3-methyl-imidazoles thiocyanate-, 1-butyl-3-methyl-imidazoleacetic acid salt etc., these can use separately, and also two or more kinds may be used.In the middle of these, from the more excellent aspect of antistatic performance, preferred 1-ethyl-3-methyl-imidazole ethyl vitriol and/or 1-ethyl-3-methyl-imidazoles thiocyanate-, particularly preferably 1-ethyl-3-methyl-imidazole ethyl vitriol.
In the aforementioned two-pack curing foaming polyurethane resin composition, from can further improving the viewpoint of antistatic performance, the total of the mass ratio of aforementioned ammonium salt (E1) and aforementioned imidazole salts (E2) is preferably the scope of 1～10 quality %, the more preferably scope of 1.5～7 quality % in two-pack curing foaming polyurethane resin composition.
In addition, aforementioned salt (E1) and aforementioned salt (E2) are imbued with water-absorbent, thereby mix storage with aforementioned host, have the isocyanate group of polyurethane prepolymer (A) and the possibility that steeping in water for reconstitution is given birth to side reaction, so not preferred.Therefore, aforementioned solidifying agent and the aforementioned host of the dissolving of aforementioned salt (E1) and salt (E2) are referred to, respectively in advance storage mixes necessary amount in use and carries out moulding.Usually, be desirably in the preparation section of the preparation section of solidifying agent rather than host and add in the lump salt (E1) and salt (E2).
For aforementioned ammonium salt (E1) and aforementioned imidazole salts (E2) are evenly contained in polyurethane molded body, preferably when being used for the manufacturing of polyurethane molded body under the state that makes in advance its dissolving in as the additive of the aforementioned solidifying agent (ii) of the raw material of aforementioned two-pack curing foaming polyurethane resin composition, the fluidizer that uses as required etc., mixing, dispersion etc.
Among the present invention, can also with aforementioned ammonium salt (E1) and the aforementioned imidazole salts (E2) that must use, in the scope of not damaging purpose of the present invention, use known other antistatic agents.
As aforementioned other antistatic agents, for example can list, the electrical compound of positively charged ion system system that the substituted sulfonic acid quaternary ammonium that replaces with alkyl and oxidation alkyl is, the negatively charged ion system of metal salts of organic acids system make electrical compound etc.
As aforementioned substituted sulfonic acid quaternary ammonium, for example can list dialkyl group sulfuric acid derivative, methanesulfonic ester derivative, p-toluenesulphonic acids ester derivative etc.These can use separately or mix more than 2 kinds and use.
The negatively charged ion system that is as aforementioned metal salts of organic acids makes electrical compound; for example can list the organic metal salt of two (trifluoromethane sulfonyl group) imines metal-salt, three (trifluoromethane sulfonyl group) methane metal-salt, alkylsulphonic acid metal-salt, Phenylsulfonic acid metal-salt or benzene sulfonamide acid metal salt etc.These can use separately or mix more than 2 kinds and use.
In addition, in the scope of not damaging purpose of the present invention, can contain known anti-electrostatic auxiliary agent.
As aforementioned anti-electrostatic auxiliary agent, for example can list, cyclic ketone compound, sorbitan fatty acid esters compound, lactone are monomer etc.As aforementioned cyclic ketone compound, can list for example cyclopentanone, pimelinketone, suberone etc. and derivative etc. thereof, perhaps as the sorbitan fatty acid esters compound, can list for example NOFABLE SO-992, dehydrated sorbitol mono-fatty acid ester, sorbitan monostearate, sorbitan monolaurate, Tween 20, the polyoxyethylene sorbitan monostearate, Polysorbate 80 etc., be monomer as lactone perhaps, can list for example beta-propiolactone, gamma-butyrolactone, δ-valerolactone, 6-caprolactone, the internal ester monomer of γ-crotons lactone etc.These can use more than 2 kinds alone or in combination.
For aforementioned other antistatic agents and anti-electrostatic auxiliary agent contain in polyurethane molded body equably, preferably at aforementioned polyhydroxy reactant be suitable for regulating when being used for the manufacturing of polyurethane molded body under the state of in advance dissolving in the fluidizer (for example, own diester-based polyester fluidizer, M-nitro benzoic acid are polyester fluidizer etc.) etc. of flexibility of formed body.
Manufacture method as polyurethane molded body of the present invention, can adopt known method, but in the middle of these, preferably the host that contains aforementioned polyurethane prepolymer (A) (i), contain aforementioned ammonium salt (E1) and aforementioned imidazole salts (E2) antistatic agent (iii) in the presence of, the prepolymer method that the two-pack curing foaming polyurethane resin composition that contains the solidifying agent (ii) that comprises previous reaction compound (B), water (C) and catalyzer (D) is reacted.
Aforementioned ammonium salt (E1) during as the aforementioned polyurethane molded body of manufacturing and the addition means of aforementioned imidazole salts (E2), can adopt for example (1) that aforementioned (E1) and the method, (2) that (E2) are pre-mixed together or respectively aforementioned solidifying agent (ii) with aforementioned (E1) and (E2) are not mixed into aforementioned solidifying agent (ii) in advance, and method that they are added respectively etc.
Among the present invention, even aforementioned ammonium salt (E1) and aforementioned imidazole salts (E2) are preserved with heated condition in the presence of the polyurethane-reinforcement catalyzer, also can stablize and not preservation with decomposing.
Possibility in the evils that do not produce foaming dystropy, lower hardness, strength decreased etc., and, on the viewpoint that can make the stable polyurethane foam formed body with excellent antistatic performance under the low temperature and low humidity degree condition, the method for aforementioned (1) particularly preferably.
Making in the situation of polyurethane molded body of the present invention, the preferred use for example is pre-mixed the mixture that water (C), catalyzer (D) and antistatic agent (iii) or whipping agent as required, other additives form in (B) in the previous reaction compound.Carry out high-speed stirring by mixture and polyisocyanates composition after using foam forming machine to such pre-mixing, can mix and make its foaming.
As foam forming machine, can use such as low pressure foam forming machine, injection-expansion molded machine etc.
Manufacture method as aforementioned polyurethane molded body, except water foaming as described above, also have the foaming such as the method for adding hollow pearl, machinery, the foaming of chemistry etc., from the viewpoint of production efficiency aspect, manufacturing cost etc., more preferably water foaming.
In the scope of not damaging the performances such as static electricity resistance and formability, the known additive of fire retardant, surfactant, chain extension agent, fluidizer, weighting agent, tinting material, weather-proof stablizer, fast light stablizer, antioxidant etc. can also suitably for example be used in the polyurethane molded body of the present invention.
In addition, as the forming method of polyurethane molded body of the present invention, can adopt known method.For example, can adopt the die molding method that will be injected into by the mixed foaming liquid opening of forming machine ejection mould, be injected directly into mixed foaming liquid with the injection moulding method of the direct-connected mold closing of ejiction opening of forming machine etc.
As the shaping mould that uses among the present invention, so long as the mould that uses as the mould that forms formed body just can be not particularly limited use, its shape can be for arbitrarily.For example, be not only normally used open mold, plane mould, cylindrical die, the negative mold that is consisted of by mold, bed die, also be included in mold closing that uses in the injection molding etc.In addition, the material of forming mould is so long as the normally used material of iron, aluminium, Resins, epoxy etc. then can be for arbitrarily.
From keeping the viewpoint of the performances such as mechanical characteristic, weather resistance, the density of polyurethane molded body of the present invention is preferably 0.2～1.1g/cm
3, 0.3～0.8g/cm more preferably
3, most preferably be 0.4～0.7g/cm
3
For polyurethane molded body of the present invention, as the polyurethane elastomer formed body, electrostatic burst from prevent operationlocation, laboratory, hazardous material warehouse, hazardous material treatment facility etc., prevent the viewpoint of dispersing, prevent static generation etc. of micro-dust in IC factory or dust, can be suitable for the safety shoes used such as the static anti-electrostatic or operation footwear, cleaning chamber with various article such as the sole of footwear, safety gloves, safety operation clothes, safety helmets.Polyurethane molded body of the present invention can also utilize in the various fields such as packing, flexible pipe, sheet material, cushioning material, vehicle part, package member with in addition.
Embodiment
Below, enumerate embodiment and comparative example, specify the present invention.
(evaluation of static electricity resistance and judgement)
(1) making of mensuration sample (polyurethane molded body)
Use the two-pack curing foaming polyurethane resin composition that obtains in embodiment and the comparative example, carry out the operation based on a series of water foaming that comprises following (operation 1)～(operation 4), made polyurethane molded body.
The adjustment operation of (operation 1) host
In the reaction unit with nitrogen ingress pipe, condenser, thermometer, cooler, add respectively polyisocyanates composition and polyhydroxy reactant, under 60～90 ℃ of interior temperature, make its reaction when under nitrogen atmosphere, stirring, synthesis of polyurethane prepolymer (A) has obtained containing the host of aforementioned polyurethane prepolymer (A).
The mixed processes of (operation 2) host and solidifying agent
Then, to contain the host of aforementioned polyurethane prepolymer (A) and contain isocyanate group reactive compounds (B), water (C), and the imidazole salts (E2) that replaces of the solidifying agent of catalyzer (D), the quaternary ammonium salt (E1) that replaces as the alkyl of antistatic agent and alkyl put into two-pack and mix each tank of using the low pressure foaming machine, be adjusted to suitable temperature (for example 40～50 ℃), in use the specified amount of aforementioned host and solidifying agent carried out mix and blend, preparation foamable reaction liquid.
(operation 3) notes type operation
Aforementioned foamable reaction liquid is injected in the pre-heated mould.
(operation 4) curing process
Under the state in injecting mould the heating of foamable reaction liquid is remained on suitable temperature range (for example 40～50 ℃), make its foaming, curing, it was placed after 3～15 minutes, take out polyurethane moldings.Obtaining in the situation of sole, can implement the suitable processing of machining etc., be adjusted into the shape of sole.
(2) evaluation method of static electricity resistance
Use battery type insulating-resistance meter (Yokogawa Electric Corporation's system, 260401 types), respectively with mensuration sample (75mm * 75mm * 10 of above-mentioned making
tMm) following and iron plate (300mm * 200mm * 1
tMm) contact, with above it with iron plate (75mm * 75mm * 3
tMm) contact, 7 Nikkeis are crossed resistance value constantly after the mensuration moulding, have estimated static electricity resistance.
In addition, sample after the moulding is preserved under the indoor environment of 23 ℃ of temperature, relative humidity 65%, then normal temperature condition (23 ℃, relative humidity 65%), and 2 conditions of low temperature and low humidity degree condition (0 ℃, relative humidity 40%) under measured resistance value (unit: M Ω).
(3) determinating reference
The judgment basis of antistatic performance is the synthetic determination benchmark of benchmark based on following benchmark A and B 2.
＜benchmark A 〉
Zero: the resistance value of low temperature and low humidity degree condition (0 ℃, 40%RH) is below the 20M Ω.
*: the resistance value of low temperature and low humidity degree condition (0 ℃, 40%RH) surpasses 20M Ω.
＜benchmark B 〉
Zero: the difference of the resistance value of normal temperature condition and low temperature and low humidity degree condition is below the 20M Ω.
*: the difference of the resistance value of normal temperature condition and low temperature and low humidity degree condition is for surpassing 20M Ω.
＜synthetic determination benchmark 〉
Qualified: benchmark A and B are the situation of " zero ".
Defective: both are the situation of " * " to only have the side of benchmark A or B or benchmark A and B.
(measuring method of the density of polyurethane molded body)
By with the quality of the polyurethane molded body of gained divided by volume, thereby the density of calculating (g/cm
3).
(the determination of hardness method of polyurethane molded body)
Based on the JIS K 7312-1996 of Japanese Industrial Standards (hardness test), use spring hardness test (Type C) to estimate the hardness of the polyurethane molded body of gained.
(preparation of host (i-1))
In reaction vessel, as isocyanate prepolymer composition, add 4,4 '-diphenylmethanediisocyanate (is designated hereinafter simply as " 4,4 ' MDI ".Trade mark: MILLIONATE MT, Nippon Polyurethane Industry Co., Ltd.'s system.) 543 mass parts and carbodiimide modified MDI (trade mark: Cosmonate LL, Mitsui Chemical Polyurethane Co., Ltd's system.) 28.6 mass parts, begun stirring.
Then, as polyhydroxy reactant, substep adds polyvalent alcohol a (by the polyester polyol of the synthetic hydroxyl value 56.1mgKOH/g of ethylene glycol (EG)/BDO (Isosorbide-5-Nitrae BG) and hexanodioic acid (AA).EG/1, the 4BG=5/5 mol ratio.) 443.5 mass parts and mix, under nitrogen gas stream, carry out reaction in 8 hours at 60 ℃, obtained the host (i-1) of the polyurethane prepolymer (A) that containing of NCO equivalent 250 have isocyanate group.
(preparation of solidifying agent (ii-1))
Be mixed as have with the polyvalent alcohol b of the compound (B) of the functional group of isocyanic ester radical reaction (by EG/1, the polyester polyol of the hydroxyl value 66 that 4BG and AA are synthetic.EG/1, the 4BG=5/5 mol ratio.) 91.5 mass parts, polyvalent alcohol c are (by the polyester polyol of the synthetic hydroxyl value 60 of Diethylene Glycol (DEG)/TriMethylolPropane(TMP) (TMP) and AA.The DEG/TMP=15/1 mol ratio.) 4.8 mass parts, EG8.8 mass parts, as 0.37 part in the water (C) of whipping agent, as Triethylene Diamine (TEDA) 0.33 mass parts of catalyzer (D), fully stir, mix, prepared solidifying agent (ii-1).
(embodiment 1)
" manufacturing of two-pack curing foaming polyurethane resin composition (P1) "
Be mixed in the mixing vessel aforementioned solidifying agent (ii-1) 105.8 mass parts, as the N-ethyl-N of antistatic agent, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol (E1) 8.75 mass parts と 1-ethyl-3-methyl-imidazole ethyl vitriol (E2) 1.25 mass parts, fully stir, mix, obtained containing the polyol blends (PC1) of solidifying agent (ii-1) and antistatic agent.
Then, in the mixing vessel with (i-1)/(PC1)=100/96 mass ratio be mixed aforementioned host (i-1) and aforementioned polyol blends (PC1), and stir, mix, prepare two-pack curing foaming polyurethane resin composition of the present invention (P1), to be heated in advance 40 ℃ mould (inject 200g among 290mm * 120mm * 10mm), cover mould lid immediately after, 40 ℃ of lower placements 5 minutes, then, take out the foam molded product of finishing.
The foam molded product that uses two-pack curing foaming polyurethane resin composition of the present invention (P1) to form is as shown in table 1, has excellent antistatic performance and characteristic.
(embodiment 2)
" manufacturing of two-pack curing foaming polyurethane resin composition (P2) "
Be mixed in the mixing vessel aforementioned solidifying agent (ii-1) 105.8 mass parts, as the N-ethyl-N of antistatic agent, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol (E1) 7.50 mass parts and 1-ethyl-3-methyl-imidazole ethyl vitriol (E2) 2.50 mass parts, fully stir, mix, obtained containing the polyol blends (PC2) of solidifying agent (ii-1) and antistatic agent.
Then, in the mixing vessel with (i-1)/(PC2)=100/96 mass ratio be mixed aforementioned host (i-1) and aforementioned polyol blends (PC2), and stir, mix, prepare two-pack curing foaming polyurethane resin composition of the present invention (P2), carry out moulding by operating similarly to Example 1, take out foam molded product.
The foam molded product that uses two-pack curing foaming polyurethane resin composition of the present invention (P2) to form is as shown in table 1, has excellent antistatic performance and characteristic.
(embodiment 3)
" manufacturing of two-pack curing foaming polyurethane resin composition (P3) "
Be mixed in the mixing vessel aforementioned solidifying agent (ii-1) 105.8 mass parts, as the N-ethyl-N of antistatic agent, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol (E1) 6.25 mass parts and 1-ethyl-3-methyl-imidazole ethyl vitriol (E2) 3.75 mass parts, fully stir, mix, obtained containing the polyol blends (PC3) of solidifying agent (ii-1) and antistatic agent.
Then, in the mixing vessel with (i-1)/(PC3)=100/96 mass ratio be mixed aforementioned host (i-1) and aforementioned polyol blends (PC3), and stir, mix, prepare two-pack curing foaming polyurethane resin composition of the present invention (P3), carry out moulding by operating similarly to Example 1, take out foam molded product.
The foam molded product that uses two-pack curing foaming polyurethane resin composition of the present invention (P3) to form is as shown in table 1, has excellent antistatic performance and characteristic.
(embodiment 4)
" manufacturing of two-pack curing foaming polyurethane resin composition (P4) "
Be mixed in the mixing vessel aforementioned solidifying agent (ii-1) 105.8 mass parts, as the N-ethyl-N of antistatic agent, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol (E1) 5.00 mass parts and 1-ethyl-3-methyl-imidazole ethyl vitriol (E2) 5.00 mass parts, fully stir, mix, obtained containing the polyol blends (PC4) of solidifying agent (ii-1) and antistatic agent.
Then, in the mixing vessel with (i-1)/(PC4)=100/96 mass ratio be mixed aforementioned host (i-1) and aforementioned polyol blends (PC4), and stir, mix, prepare two-pack curing foaming polyurethane resin composition of the present invention (P4), carry out moulding by operating similarly to Example 1, take out foam molded product.
The foam molded product that uses two-pack curing foaming polyurethane resin composition of the present invention (P4) to form is as shown in table 1, has excellent antistatic performance and characteristic.
(embodiment 5)
" manufacturing of two-pack curing foaming polyurethane resin composition (P5) "
Among the embodiment 5, the quaternary ammonium salt (E1) as the alkyl of antistatic agent replaces uses N-ethyl-N, and N-dimethyl-N-myristyl QAE quaternary aminoethyl vitriol is replaced N-ethyl-N, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol.
Be mixed in the mixing vessel aforementioned solidifying agent (ii-1) 105.8 mass parts, as the N-ethyl-N of antistatic agent, N-dimethyl-N-myristyl QAE quaternary aminoethyl vitriol (E1) 7.50 mass parts and 1-ethyl-3-methyl-imidazole ethyl vitriol (E2) 2.50 mass parts, fully stir, mix, obtained containing the polyol blends (PC5) of solidifying agent (ii-1) and antistatic agent.
Then, in the mixing vessel with (i-1)/(PC5)=100/96 mass ratio be mixed aforementioned host (i-1) and aforementioned polyol blends (PC5), and stir, mix, prepare two-pack curing foaming polyurethane resin composition of the present invention (P5), carry out moulding by operating similarly to Example 1, take out foam molded product.
The foam molded product that uses two-pack curing foaming polyurethane resin composition of the present invention (P5) to form is as shown in table 1, has excellent antistatic performance and characteristic.
(embodiment 6)
" manufacturing of two-pack curing foaming polyurethane resin composition (P6) "
Among embodiment 6 and the embodiment 7, as the imidazole salts (E2) that the alkyl of antistatic agent replaces, use 1-ethyl-3-methyl-imidazoles thiocyanate-, replace 1-ethyl-3-methyl-imidazole ethyl vitriol.
Be mixed in the mixing vessel aforementioned solidifying agent (ii-1) 105.8 mass parts, as the N-ethyl-N of antistatic agent, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol (E1) 7.50 mass parts and 1-ethyl-3-methyl-imidazoles thiocyanate-(E2) 2.50 mass parts, fully stir, mix, obtained containing the polyol blends (PC6) of solidifying agent (ii-1) and antistatic agent.
Then, in the mixing vessel with (i-1)/(PC6)=100/96 mass ratio be mixed aforementioned host (i-1) and aforementioned polyol blends (PC6), and stir, mix, prepare two-pack curing foaming polyurethane resin composition of the present invention (P6), carry out moulding by operating similarly to Example 1, take out foam molded product.
The foam molded product that uses two-pack curing foaming polyurethane resin composition of the present invention (P6) to form is as shown in table 1, has excellent antistatic performance and characteristic.
(embodiment 7)
" manufacturing of two-pack curing foaming polyurethane resin composition (P7) "
Be mixed in the mixing vessel aforementioned solidifying agent (ii-1) 105.8 mass parts, as the N-ethyl-N of antistatic agent, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol (E1) 6.65 mass parts and 1-ethyl-3-methyl-imidazoles thiocyanate-(E2) 3.35 mass parts, fully stir, mix, obtained containing the polyol blends (PC7) of solidifying agent (ii-1) and antistatic agent.
Then, in the mixing vessel with (i-1)/(PC7)=100/96 mass ratio be mixed aforementioned host (i-1) and aforementioned polyol blends (PC7), and stir, mix, prepare two-pack curing foaming polyurethane resin composition of the present invention (P7), carry out moulding by operating similarly to Example 1, take out foam molded product.
The foam molded product that uses two-pack curing foaming polyurethane resin composition of the present invention (P7) to form is as shown in table 1, has excellent antistatic performance and characteristic.
(comparative example 1)
" manufacturing of two-pack curing foaming polyurethane resin composition (P8) "
The imidazole salts (E2) that comparative example 1 does not use alkyl to replace is carried out.
Only be mixed in the mixing vessel aforementioned solidifying agent (ii-1) 105.8 mass parts, and as the N-ethyl-N of antistatic agent, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol (E1) 10 mass parts, fully stir, mix, obtained containing the polyol blends (PC8) of solidifying agent (ii-1) and antistatic agent (E1).
Then, in the mixing vessel with (i-1)/(PC8)=100/96 mass ratio be mixed aforementioned host (i-1) and aforementioned polyol blends (PC8), and stir, mix, preparation two-pack curing foaming polyurethane resin composition (P8), to be heated in advance 40 ℃ mould (inject 200g among 290mm * 120mm * 10mm), cover mould lid immediately after, 40 ℃ of lower placements 5 minutes, then, take out the foam molded product of finishing.
The foam molded product that uses aforementioned two-pack curing foaming polyurethane resin composition (P8) to form is as shown in table 2, antistatic performance transitivity variation.
(comparative example 2)
" manufacturing of two-pack curing foaming polyurethane resin composition (P9) "
The quaternary ammonium salt (E1) that comparative example 2 does not use alkyl to replace carries out.
Only be mixed in the mixing vessel aforementioned solidifying agent (ii-1) 105.8 mass parts, and as the 1-ethyl of antistatic agent-3-methyl-imidazole ethyl vitriol (E2) 10 mass parts, fully stir, mix, obtained containing the polyol blends (PC9) of solidifying agent (ii-1) and antistatic agent (E2).
Then, in the mixing vessel with (i-1)/(PC9)=100/96 mass ratio be mixed aforementioned host (i-1) and aforementioned polyol blends (PC9), and stir, mix, preparation two-pack curing foaming polyurethane resin composition (P9), carry out moulding by operating similarly to Example 1, take out foam molded product.
The foam molded product that uses aforementioned two-pack curing foaming polyurethane resin composition (P9) to form is as shown in table 2, antistatic performance transitivity variation.
(comparative example 3)
" manufacturing of two-pack curing foaming polyurethane resin composition (P10) "
Be mixed in the mixing vessel 105.8 parts in aforementioned solidifying agent (ii-1), as the N-ethyl-N of antistatic agent, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol (E1) 9.6 mass parts and 1-ethyl-3-methyl-imidazole ethyl vitriol (E2) 0.40 mass parts, fully stir, mix, obtained containing the polyol blends (PC10) of solidifying agent (ii-1) and antistatic agent.
Then, in the mixing vessel with (i-1)/(PC10)=100/96 mass ratio be mixed aforementioned host (i-1) and aforementioned polyol blends (PC10), and stir, mix, preparation two-pack curing foaming polyurethane resin composition (P10), carry out moulding by operating similarly to Example 1, take out foam molded product.
The foam molded product that uses aforementioned two-pack curing foaming polyurethane resin composition (P10) to form is as shown in table 2, antistatic performance transitivity variation.
(comparative example 4)
" manufacturing of two-pack curing foaming polyurethane resin composition (P11) "
Be mixed in the mixing vessel 105.8 parts in aforementioned solidifying agent (ii-1), as the N-ethyl-N of antistatic agent, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol (E1) 2.50 mass parts and 1-ethyl-3-methyl-imidazole ethyl vitriol (E2) 7.50 mass parts, fully stir, mix, obtained containing the polyol blends (PC11) of solidifying agent (ii-1) and antistatic agent.
Then, in the mixing vessel with (i-1)/(PC11)=100/96 mass ratio be mixed aforementioned host (i-1) and aforementioned polyol blends (PC11), and stir, mix, preparation two-pack curing foaming polyurethane resin composition (P11), carry out moulding by operating similarly to Example 1, take out foam molded product.
The foam molded product that uses aforementioned two-pack curing foaming polyurethane resin composition (P11) to form is as shown in table 2, antistatic performance transitivity variation.
(comparative example 5)
" manufacturing of two-pack curing foaming polyurethane resin composition (P12) "
Be mixed in the mixing vessel 105.8 parts in aforementioned solidifying agent (ii-1), as the N-ethyl-N of antistatic agent, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol (E1) 9.0 mass parts and two (trimethyl fluoride sulfonyl) imines lithium salts 1.0 mass parts, fully stir, mix, obtained containing the polyol blends (PC12) of solidifying agent (ii-1) and antistatic agent.
Then, in the mixing vessel with (i-1)/(PC12)=100/96 mass ratio be mixed aforementioned host (i-1) and aforementioned polyol blends (PC12), and stir, mix, preparation two-pack curing foaming polyurethane resin composition (P12), carry out moulding by operating similarly to Example 1, take out foam molded product.
The foam molded product that uses aforementioned two-pack curing foaming polyurethane resin composition (P12) to form is as shown in table 2, antistatic performance transitivity variation.
In addition, abbreviation and the title put down in writing in embodiment and the comparative example are as described below.
4,4 ' MDI:4,4 '-diphenylmethanediisocyanate
EG: ethylene glycol
Isosorbide-5-Nitrae BG:1, the 4-butyleneglycol
AA: hexanodioic acid
DEG: Diethylene Glycol
TMP: TriMethylolPropane(TMP)
TEDA: Triethylene Diamine
Ammonium salt (E1): the quaternary ammonium salt that alkyl replaces
Imidazole salts (E2): the imidazole salts that alkyl replaces
AM1 salt: N-ethyl-N, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol
AM2 salt: N-ethyl-N, N-dimethyl-N-myristyl QAE quaternary aminoethyl vitriol
IM1 salt: 1-ethyl-3-methyl-imidazole ethyl vitriol
IM2 salt: 1-ethyl-3-methyl-imidazoles thiocyanate-
Li salt; Two (trifluoromethyl sulfonyl) imines lithium salts
[table 1]
[table 2]
[table 3]
[table 4]
As can be known, even two-pack curing foaming polyurethane resin composition of the present invention be embodiment 1～7 under the temperature condition and low humidity condition of the wide region of (20 ± 15 ℃) from low temperature to normal temperature, the difference of resistance value is also little and temperature dependency is little, excellent electrostatic prevention property.
On the other hand, as can be known, comparative example 1, the 2nd does not contain the form of the imidazole salts that quaternary ammonium salt that alkyl replaces or alkyl replace, but all is that the difference of the resistance value under low temperature and the normal temperature is large, particularly the resistance value under the low temperature is large in addition, static electricity resistance is bad.
In addition, as can be known, the mass ratio of the imidazole salts that the quaternary ammonium salt that comparative example 3, the 4th, alkyl replace and alkyl replace is above the form of the scope of stipulating among the present invention, all be the difference of the resistance value under low temperature and the normal temperature greatly, in addition, particularly the resistance value under the low temperature is large, static electricity resistance is bad.
In addition, as can be known, comparative example 5 is to use two (trifluoromethyl sulfonyl) imines lithium salts to replace the form of the imidazole salts that alkyl replace, the difference of the resistance value under low temperature and the normal temperature greatly, in addition, particularly the resistance value under the low temperature is large, static electricity resistance is bad.
Claims (6)
1. a two-pack curing foaming polyurethane resin composition is characterized in that, it is the two-pack curing foaming polyurethane resin composition that contains following (i)～(iii) composition,
Contain the polyurethane prepolymer (A) with isocyanate group host (i),
Contain have with the solidifying agent (ii) of compound (B), water (C) and the catalyzer (D) of the functional group of isocyanic ester radical reaction,
And the antistatic agent (iii) that contains the imidazole salts (E2) that quaternary ammonium salt (E1) that alkyl replaces and alkyl replace,
Described ammonium salt (E1) is that (E1)/(E2) is 95/5～30/70 scope with the mass ratio of described imidazole salts (E2).
2. two-pack curing foaming polyurethane resin composition according to claim 1, wherein,
The quaternary ammonium salt (E1) that described alkyl replaces is N-ethyl-N, N-dimethyl-N-dodecyl QAE quaternary aminoethyl vitriol and/or N-ethyl-N, N-dimethyl-N-myristyl QAE quaternary aminoethyl vitriol.
3. two-pack curing foaming polyurethane resin composition according to claim 1, wherein,
The imidazole salts (E2) that described alkyl replaces is 1-ethyl-3-methyl-imidazole ethyl vitriol and/or 1-ethyl-3-methyl-imidazoles thiocyanate-.
4. two-pack curing foaming polyurethane resin composition according to claim 1, wherein,
The total of the mass ratio of described ammonium salt (E1) and described imidazole salts (E2) is the scope of 1～10 quality % in two-pack curing foaming polyurethane resin composition.
5. a polyurethane molded body is characterized in that, it is that right to use requires in 1～4 the described two-pack curing of any one foaming polyurethane resin composition and obtains.
6. a sole is characterized in that, it is that right to use requires in 1～4 the described two-pack curing of any one foaming polyurethane resin composition and obtains.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2011193806A JP5810767B2 (en) | 2011-09-06 | 2011-09-06 | Two-component curable polyurethane foam resin composition, urethane molded body, shoe sole, and industrial member |
| JP2011-193806 | 2011-09-06 |
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| CN103265807A (en) * | 2013-05-31 | 2013-08-28 | 苏州市景荣科技有限公司 | PU (Poly Urethane) sole antistatic agent |
| CN110876508A (en) * | 2019-12-10 | 2020-03-13 | 耐乐途(广东)皮鞋制造有限公司 | Preparation method of far infrared health-care insole |
| CN115926101A (en) * | 2023-02-14 | 2023-04-07 | 旭川化学（苏州）有限公司 | Low-temperature-resistant polyurethane sole resin and preparation method and application thereof |
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| KR101351556B1 (en) * | 2013-07-25 | 2014-02-17 | 에스케이씨 주식회사 | A flame retardant composition of polyurethane-urea hybrid coating agent comprising exfoliated graphite and a method for preparing thereof |
| JP2016535127A (en) * | 2013-10-15 | 2016-11-10 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Conductive thermoplastic polyurethane |
| KR102000105B1 (en) * | 2017-12-19 | 2019-07-15 | 주식회사 아트캠 | Eco-friendly polyurethane composition and its preparing method |
| KR102034733B1 (en) * | 2018-08-23 | 2019-10-21 | 주식회사 에이로 | Safety boots using polyurethane composition |
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| JP7232149B2 (en) * | 2019-08-02 | 2023-03-02 | 花王株式会社 | Polyurethane composition |
| KR102145163B1 (en) | 2020-05-06 | 2020-08-18 | 에스켐텍(주) | Fast-curing polyurethane resin composition for rotary casting |
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| JP2013053265A (en) | 2013-03-21 |
| KR20130027419A (en) | 2013-03-15 |
| JP5810767B2 (en) | 2015-11-11 |
| KR101838580B1 (en) | 2018-03-15 |
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