JP2676031B2 - Method for imparting antistatic properties to polyurethane - Google Patents

Description

The present invention relates to a method for imparting antistatic properties to polyurethane. Polyurethane is used as a foamed body for seat cushions, crash pads for shock absorption, bumpers for automobiles, etc., as well as waterproof coating materials for civil engineering construction,
It is also used in floor coating materials, sealing materials, paints, adhesives, etc. Such a polyurethane is produced by the reaction of a polyisocyanate and a polyol in the presence of a catalyst, or the reaction of a urethane prepolymer having an isocyanate group with a polymian-based or polyol-based curing agent (crosslinking agent). Like molecular substances, they tend to carry an electrostatic charge and have a strong tendency to accumulate them. Therefore, it is required that the polyurethane used for various applications as described above has a property of not charging static charge or quickly erasing charging. The present invention relates to a method of imparting antistatic properties to polyurethane which meets such a demand. <Prior Art and Problems Thereof> Conventionally, a method of reducing electrification has been proposed for polyurethane as well as other polymer substances. A typical example thereof is a method of adding an antistatic agent consisting of a certain cationic surfactant to a mixed system of polyisocyanate and polyol, which is a stock solution for producing polyurethane (US Pat. No. 3933697, JP-A-62-106917). However, before the polyurethane is formed, a cationic surfactant is added to a so-called undiluted solution for producing polyurethane, such as a mixed system of polyisocyanate and polyol, a system of urethane prepolymer, or a mixed system of urethane prepolymer and polyol. Then, the following problems occur. Such a problem similarly occurs when an anionic surfactant is added instead of the cationic surfactant. This is because these surfactants are not stably dissolved in the polyurethane production stock solution, which causes various troubles in the polyurethane production process and induces quality problems in the produced polyurethane. For example, in the case of a cationic surfactant, the above-mentioned JP-A-62-106917 discloses that soybean alkyldimethylethylammonium ethyl sulfate or soybean alkyldimethylethylammonium ethylphosphate is allowed to coexist with a plasticizer to improve the antistatic property. Although it is stated that the synergistic effect and the compatibility are improved, as described above, the quaternary ammonium salt as the cationic surfactant alone is not sufficiently compatible with the stock solution for producing polyurethane, and thus the antistatic property is prevented. Since it is necessary to promote the transfer to the surface due to the effect of the plasticizer in order to develop the sex, such a quaternary ammonium salt is essentially lacking as an antistatic agent. In addition, the quaternary ammonium salt type cationic surfactant is
Since it itself does not have excellent heat resistance, it may cause yellowing and coloration of the obtained polyurethane depending on the production conditions of the polyurethane. Further, anionic surfactants such as organic sulfonic acid alkali metal salts and organic phosphoric acid ester salts having good antistatic properties for various synthetic polymer substances are
Solubility in the undiluted solution for polyurethane production is extremely low, and when these surfactants are added to the undiluted solution for polyurethane production as antistatic agents, precipitation, aggregation and turbidity occur in the reaction system of polyurethane formation, and the resulting polyurethane Excessive migration to the surface, concentration, etc. occur, leading to problems such as surface contamination and contamination of the molding die. When a nonionic surfactant having a polyoxyalkylene chain is added, such a nonionic surfactant is generally more compatible with the undiluted solution for producing polyurethane than when a cationic surfactant or an anionic surfactant is added. Is good,
Although the above-mentioned defects are not recognized so much, there is a basic defect that the target antistatic property is poor. <Problems to be Solved by the Invention and Means for Solving the Problems> The present invention provides a method for imparting antistatic properties to polyurethane, which solves the above-mentioned conventional problems. However, as a result of earnest studies in view of the above circumstances, the inventors of the present invention have found that it is correct and preferable to dissolve a specific sulfonate / phosphonium salt as an antistatic agent in a predetermined ratio in a stock solution for producing polyurethane. I found it. That is, according to the present invention, when a polyurethane-forming stock solution is reacted in the presence of a catalyst or a curing agent to form a polyurethane, the following general formula (I) or (II) is used per 100 parts by weight of the following polyurethane-forming stock solution. The present invention relates to a method for imparting antistatic properties to polyurethane, which comprises dissolving 0.1 to 20 parts by weight of the organic sulfonate / phosphonium salt shown therein. Stock solution for producing polyurethane: 1) a mixture of polyisocyanate and polyol, 2) urethane prepolymer having an isocyanate group obtained by reaction of polyisocyanate and polyol, and 3) 1 selected from a mixture of urethane prepolymer and polyol Stock solution or two or more stock solutions for polyurethane production [However, A is an aliphatic hydrocarbon group having 6 to 18 carbon atoms, an aromatic hydrocarbon group, or an aromatic hydrocarbon group substituted with a hydrocarbon group having 1 to 18 carbon atoms. R ^{1 to} R ⁴ are the same or different, a hydrocarbon group having 1 to 18 carbon atoms, or 1 to 1 carbon atoms having a substituent.
18 hydrocarbon groups. Z ¹ is an aliphatic hydrocarbon group having 6 to 18 carbon atoms, an alicyclic hydrocarbon group having 6 to 18 carbon atoms, or a general formula A ¹ O
(R ⁵ _{O) n} - group {wherein, A ¹ represented by the 6 to 18 carbon atoms
An aliphatic hydrocarbon group or an aromatic hydrocarbon group. R ⁵ is an alkylene group having 2 to 4 carbon atoms. n is an integer of 1 to 20. ｝.
Z ² is hydrogen or a general formula A group represented by: (wherein Z ³ is an aliphatic hydrocarbon group having 6 to 18 carbon atoms, an alicyclic hydrocarbon group having 6 to 18 carbon atoms, or a general formula)
_{^{A 2 O (R 7 O)}} m - group represented by (wherein, A ² is 6 carbon atoms
18 aliphatic hydrocarbon groups or aromatic hydrocarbon groups. R ⁷ is
An alkylene group having 2 to 4 carbon atoms. m is an integer of 1 to 20. )｝. The organic sulfonate / phosphonium salt represented by the general formula (I) or (II) (hereinafter referred to as a sulfonate / phosphonium salt) comprises an organic sulfonate anion and an organic phosphonium cation. Specific examples of the organic sulfonate anion corresponding to the general formula (I) include 1) hexyl sulfonate, octyl sulfonate, dodecyl sulfonate, hexadecyl sulfonate, 2-ethylhexyl sulfonate, and other alkyl sulfonates having 6 to 18 carbon atoms, and these. Mixture, 2) aromatic sulfonates such as benzene sulfonate, p-toluene sulfonate, butyl benzene sulfonate, dodecyl benzene sulfonate, dibutyl benzene sulfonate, naphthalene sulfonate, butyl naphthalene sulfonate, diisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate, etc. or alkyl-substituted aromatic sulfonates The kind is mentioned. The organic sulfonate anion corresponding to the general formula (II) includes sulfoacetate when Z ² is hydrogen and sulfosuccinate when it is a group represented by the above general formula. Specific examples thereof include 3) alkyl, alkenyl or cycloalkyl sulfoacetates having 6 to 18 carbon atoms such as octyl sulfoacetate, dodecyl sulfoacetate, oleyl sulfoacetate and cyclohexyl sulfoacetate, 4) POE (3 mol) dodecyl Alkoxylated C6-C18 alkyl, alkenyl or cycloalkyl sulfoacetate such as sulfoacetate, POE (5 mol) oleyl sulfoacetate, polyoxypropylene (3 mol) cyclohexyl sulfoacetate, 5) di-2- Dialkyl, dialkenyl or dicycloalkylsulfo having 6 to 18 carbon atoms such as ethylhexylsulfosuccinate, di-n-dodecylsulfosuccinate, di-oleylsulfosuccinate and di-cyclohexylsulfosuccinate. Kushineto,
6) di-POE (3 mol) dodecyl sulfosuccinate,
Di-POE (5 mol) oleyl sulfosuccinate, di-
Polyoxypropylene (3 mol) cyclohexyl sulfosuccinate and other alkoxylated 6 to 18 carbon atoms
A dialkyl, dialkenyl or dicycloalkylsulfosuccinate having 8 to 18 carbon atoms
Examples thereof include alkoxylated alkylphenyl sulfosuccinate and the like. Specific examples of the organic phosphonium cation include tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, triethylmethylphosphonium, tributylmethylphosphonium, tributylethylphosphonium, trioctylmethylphosphonium, trimethylbutylphosphonium, trimethyloctylphosphonium, trimethyllaurylphosphonium. , Trimethylstearylphosphonium, triethyloctylphosphonium, tributyloctylphosphonium, and other aliphatic phosphonium, tetraphenylphosphonium, triphenylmethylphosphonium, triphenylethylphosphonium, triphenylbenzylphosphonium, tributylbenzylphosphonium, and other aromatic phosphonium. Furthermore, tetramethylolphosphonium, tri (2-cyanoethyl) methylphosphonium, tri (2
-Cyanoethyl) ethylphosphonium, tri (2-cyanoethyl) benzylphosphonium, tri (3-hydroxypropyl) methylphosphonium, tri (3-hydroxypropyl) benzylphosphonium, trimethyl (2-
Phosphonium having a substituent such as hydroxyethyl) phosphonium and tributyl (2-hydroxyethyl) phosphonium can also be used. The sulfonate / phosphonium salt used in the present invention is composed of any combination of these organic sulfonate anions and organic phosphonium cations, but is not limited to these specific examples. Such a sulfonate / phosphonium salt is obtained by mixing a metal salt or ammonium salt of the corresponding organic sulfonate and a quaternary phosphonium salt in a solvent and washing and separating an inorganic salt produced as a by-product, or by using methanol, isopropanol or acetone. It can be produced by extracting phosphonium sulfonate with such an organic solvent. More specifically, for example, in the case of tetrabutylphosphonium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate is used.
34.8 g and tetrabutylphosphonium bromide 33.9 g and water
Charge 200 ml with a flask and stir at 80 ° C for 1 hour.
The sulfonate / phosphonium salt that separates as an oil layer is separated, washed with 50 ml of warm water, and dehydrated with an evaporator, so that the yield can be about 90%. The undiluted solution for producing polyurethane used in the present invention is 1) a mixture of polyisocyanate and polyol, 2) a urethane prepolymer having an isocyanate group obtained by the reaction of polyisocyanate and polyol, and 3) such a urethane prepolymer and polyol. Mixture, 1 type or 2 or more types selected from the above 1) to 3). In this case, the polyol usually has a molecular weight of 400 to 10,000 and has 2 to 6 hydroxyl groups in the molecule. In addition to polyether polyols, polyester polyols, polyether ester polyols, and modified products thereof, polycarbonate diols, acrylic polyols, polydiene-based polyols, and saponified ethylene-vinyl acetate copolymers may be mentioned. In addition, polyisocyanate has 2
A compound having more than one isocyanate group, specifically, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, or a mixture thereof, 4,4'-
Aromatic isocyanates such as diphenylmethane diisocyanate (MDI), polymeric MDI, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate,
In addition to aliphatic or alicyclic isocyanates such as dicyclohexylmethane diisocyanate, further urethane modified products,
Examples thereof include allophanate modified products, burette modified products, isocyanurate modified products, carbodiimide modified products, and isocyanate dimers. The catalyst or curing agent used when reacting the undiluted solution for producing polyurethane to produce polyurethane, has only the catalytic action of the reaction between the isocyanate group and the hydroxyl group without participating in the reaction with the isocyanate group, or Some of them are directly involved in the reaction with the isocyanate group, and some of them have the functions of both of them. Those having only catalytic action include dibutyltin dilaurate,
Examples include organic tin compounds such as dibutyltin dioctoate, tertiary amines having no active hydroxyl group, and the like. Also, those having a relatively low molecular weight are directly involved in the reaction. Examples of those having both functions include diamines and polyamines having an aliphatic or aromatic primary or secondary amino group, amines having a hydroxyl group, and the like. In the present invention, the above-mentioned sulfonate / phosphonium salt is different in the state at room temperature from liquid to soft-solid to solid depending on the combination of the sulfonate anion and the phosphonium cation. Since the compatibility with the stock solution is extremely good,
It can be used by adding and dissolving it in a stock solution for producing polyurethane. At that time, if the sulfonate / phosphonium salt used is a liquid having a high viscosity or a solid that is somewhat solid, it is preferable to heat and liquefy it to reduce the viscosity and then add and mix it. preferable. These sulfonates
The phosphonium salt may be added and mixed directly to the polyurethane-forming stock solution, or may be added and mixed in advance with the polyol to be dissolved and added to the polyurethane-forming stock solution, and glycerin, propylene glycol, and low molecular weight may be added. Polyurethane glycol, various polyalkanol polyamines, and other polyol-based curing agent (crosslinking agent) components that have been previously added and dissolved may be added to and mixed with the polyurethane-forming stock solution. In the present invention, in order to impart good antistatic properties to the resulting polyurethane, the polyurethane producing stock solution 10 is used.
0.1 parts by weight of sulfonate / phosphonium salt to 0 part by weight
It is used in a proportion of 20 parts by weight, but is preferably used in a proportion of 3 to 15 parts by weight. In the present invention, as described above, a predetermined amount of a specific sulfonate / phosphonium salt is dissolved in the polyurethane-forming stock solution, depending on the purpose, a silicon-based foam stabilizer,
Water, CFC compounds, fillers such as calcium carbonate, glass fiber and tar, pigments, colorants, flame retardants, weather resistance stabilizers, organic solvents and the like may be appropriately contained. Hereinafter, examples and the like will be described in order to make the configuration and effects of the present invention more specific, but the present invention is not limited to these examples. <Examples, etc.> Examples 1-5, Comparative Examples 1-17 80 parts by weight of glycerin / propylene oxide adduct (Sannicks Triol GP-3000, molecular weight 3000, Sanyo Kasei Co., Ltd.) and polypropylene glycol (Sannicks diol) 20 parts by weight of PP-2000, molecular weight 2000, manufactured by Sanyo Kasei Co., Ltd. were mixed, and the additives shown in Table 1 were mixed therein. The mixed solutions of Examples 1 to 5 and Comparative Examples 8 to 16 in Table 1 were all transparent and uniform, but the mixed solutions of Comparative Examples 1 to 7 were markedly cloudy. Next, to the mixed liquid of each example, 50 parts by weight of tolylene diisocyanate, 1.2 parts by weight of dibutyltin dioctoate, 0.2 parts by weight of tetramethylethylenediamine, 0.4 parts by weight of bis-2-dimethylaminoethyl ether, and silicone L-5750 (Japan) as a foam stabilizer. Uniker's or UCC's) 1.5 parts by weight and water 4.0 parts by weight were added to prepare a composition by hand mixing. A soft urethane foam was produced from this composition at a mold temperature of 45 ° C. by a conventional method. A test piece (length 5 cm x width 5 cm x thickness 1 cm) was made from each soft urethane foam and
Leave it in a test room at ℃ × 30% RH and put 50
After a voltage of 00 V was applied, the time (half-life, second) from when the voltage was cut to when the load voltage was halved was measured.
The results are shown in Table 1. Note) In Table-1, SP-1: C _{14 to} C ₁₅ alkyl sulfonic acid / tetrabutylphosphonium SP-2: di-n-octylsulfosuccinate / tetrabutylphosphonium SP-3: POE (3 mol) octylsulfone Acetate Tetraphenylphosphonium SP-4: Dodecylbenzenesulfonic acid tetrabutylphosphonium A-1: C _{14 to} C ₁₅ sodium alkylsulfonate A-2: POE (3 mol) potassium lauryl phosphate C-1: Lauryl dimethyl Ethyl ammonium / ethyl sulfate C-2: Tetramethylphosphonium chloride C-3: Tetramethylphosphonium phosphate C-4: Tetramethylphosphonium sulphite C-5: Tetrakis (chloromethyl) phosphonium acetate CR-1: Methyl sulfonate Tetramethylphosphonium CR-2: eicosyl sulfonate Tetraethylphosphonium CR-3: methylsulfoacetate / tetraethylphosphonium CR-4: eicosylsulfoacetate / tetramethylphosphonium CR-5: POE (3 mol) methylsulfoacetate / tetramethylphosphonium CR-6: POE (3 mol) eicosyl sulfoacetate tetraethylphosphonium CR-7: di-methyl sulfosuccinate tetramethylphosphonium CR-8: di-eicosyl sulfosuccinate tetraethylphosphonium CR-9: di-POE (3 Mol) Methyl sulfosuccinate / tetramethylphosphonium / Example 6, Comparative Examples 18 to 32 The additives shown in Table 2 were added to dipropylene glycol to prepare an additive liquid containing 50% by weight of the additive. 10 parts by weight of this additive liquid, urethane prepolymer (Samprene FL
R-18, manufactured by Sanyo Kasei Co., Ltd.) 100 parts by weight, curing agent (Cuamine ML-100, manufactured by Ihara Chemical Industry Co., Ltd.) 50 parts by weight, calcium carbonate 40 parts by weight, and white pigment 5 parts by weight are mixed, stirred and applied. A flooring formulation was produced. The above-mentioned formulation was applied at a rate of 0.3 kg / m ² as a top coat agent for a concrete floor provided with a primer layer and a urethane intermediate coating layer. The electrical resistance value of the coated surface after curing for 1 week at room temperature was measured according to JIS-K6911, and the results are shown in Table 2. In Example 6, an excellent coated surface was exhibited during and after the coating operation, but in Comparative Examples 18 to 22, the oily phase-separated product which was already seen as an additive during the coating operation was applied on the coated surface. Was observed everywhere, and after the coating, the coated surface was slightly soiled, and the appearance was remarkably poor. <Effects of the Invention> As is apparent from the results of each table, the present invention described above has an effect that excellent antistatic properties can be imparted to the polyurethane produced without impairing its surface characteristics. .

Claims (1)

(57) [Claims] When a polyurethane-forming stock solution is reacted in the presence of a catalyst or a curing agent to form a polyurethane, an organic sulfonate represented by the following general formula (I) or (II) per 100 parts by weight of the following polyurethane-forming stock solution is previously prepared.・
A method for imparting antistatic properties to polyurethane, which comprises dissolving 0.1 to 20 parts by weight of a phosphonium salt. Stock solution for producing polyurethane: 1) a mixture of polyisocyanate and polyol, 2) urethane prepolymer having an isocyanate group obtained by reaction of polyisocyanate and polyol, and 3) 1 selected from a mixture of urethane prepolymer and polyol Stock solution or two or more stock solutions for polyurethane production [However, A is an aliphatic hydrocarbon group having 6 to 18 carbon atoms, an aromatic hydrocarbon group, or an aromatic hydrocarbon group substituted with a hydrocarbon group having 1 to 18 carbon atoms. R ^{1 to} R ⁴ are the same or different, a hydrocarbon group having 1 to 18 carbon atoms, or 1 to 1 carbon atoms having a substituent.
18 hydrocarbon groups. Z ¹ is an aliphatic hydrocarbon group having 6 to 18 carbon atoms, an alicyclic hydrocarbon group having 6 to 18 carbon atoms, or a general formula A ¹ O
(R ⁵ _{O) n} - group {wherein, A ¹ represented by the 6 to 18 carbon atoms
An aliphatic hydrocarbon group or an aromatic hydrocarbon group. R ⁵ is an alkylene group having 2 to 4 carbon atoms. n is an integer of 1 to 20. ｝.
Z ² is hydrogen or a general formula A group represented by: (wherein Z ³ is an aliphatic hydrocarbon group having 6 to 18 carbon atoms, an alicyclic hydrocarbon group having 6 to 18 carbon atoms, or a general formula)
_{^{A 2 O (R 7 O)}} m - group represented by (wherein, A ² is 6 carbon atoms
18 aliphatic hydrocarbon groups or aromatic hydrocarbon groups. R ⁷ is
An alkylene group having 2 to 4 carbon atoms. m is an integer of 1 to 20. )｝. ]