JPWO2010035579A1 - Method for producing polyurethane resin - Google Patents

Abstract

In the present invention, a polyisocyanate, a polyhydric alcohol and a polycarboxylic acid are used, and in the presence of a solid acid catalyst (A) selected from a metal oxide, zeolite, heteropolyacid acidic salt, etc. that promotes ester reaction. A cured product excellent in moisture and heat resistance retention with little coloration, characterized in that it contains a polyester polyol produced with a polyurethane polyol composition and a polyurethane resin composition capable of controlling the urethanization reaction, and obtained using the same A molded article is provided.

Description

  The present invention relates to a polyurethane resin composition capable of controlling a urethanization reaction, and a molded product thereof, which is capable of obtaining a cured product with little coloration and excellent moisture heat resistance retention.

The polyurethane resin is produced from a polyisocyanate and a polyol, and a polyurethane resin using a polyether polyol or a polyester polyol as the polyol is used in many applications. This polyester polyol is produced using a titanium-based or tin-based homogeneous catalyst. Such a homogeneous catalyst has a problem that it is difficult to control the urethanization reaction by completely mixing in the polyol and also functioning as a catalyst during the urethanization reaction between the polyester polyol and the polyisocyanate. In addition, there is a problem that the urethane resin is colored by the influence of the residual catalyst, resulting in a decrease in quality.

For this reason, polyester polyols for polyurethane resin production are produced by adding polyesters in the presence of a protonic strong acid catalyst in a solvent, adding a basic substance, precipitating and separating the catalyst, and further washing. Attempts have been made to remove (Patent Document 1). In addition, a method of deactivating a catalyst by adding a phosphorus compound has been attempted (Patent Document 2). However, these methods have a problem that there are many work steps and the catalyst remaining in the polyol cannot be sufficiently removed or deactivated.
Japanese Patent Laid-Open No. 06-256461 JP 05-239201 A

  The purpose of the present invention is to produce a catalyst-free type polyester polyol by using a polyester polyol having no residual catalyst, which is excellent in moisture and heat resistance retention (hydrolysis resistance) and easy to control the urethanization reaction. Another object of the present invention is to provide a polyurethane resin composition with very little coloring and a molded product thereof.

As a result of intensive studies on the use of a polyester polyol produced using a separable catalyst as a urethane raw material, the present inventors have completed the present invention.
That is, the present invention includes a polyurethane resin composition comprising a polyisocyanate, a polyester polyol produced using a polyhydric alcohol and a polyvalent carboxylic acid in the presence of a solid acid catalyst (A), and It relates to the molded product.

  In the present invention, by using the polyester polyol produced using the solid acid catalyst (A), the catalyst can be easily removed, and as a result, a catalyst-free polyester polyol is obtained. The use of can facilitate the control of the urethanization reaction, and can provide a polyurethane resin composition and a molded product thereof that can obtain a polyurethane resin that is less colored and excellent in moisture and heat resistance retention.

  The polyisocyanate used in the present invention is usually used for polyurethane resins. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate or a mixture thereof, m- or p-phenylene diisocyanate, p -Xylene diisocyanate, ethylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethyl-diphenylmethane-4,4-biphenylene diisocyanate, 3,3-dichloro-4,4-biphenylene diisocyanate, 4,4-biphenylene diisocyanate or 1,5-naphthalene diisocyanate, tolidine diisocyanate, ifosolone diisocyanate Cyclohexane diisocyanate, toluidine diisocyanate, crude diphenylmethane diisocyanate, and diphenylmethane diisocyanate are triphenylmethane triisocyanate and their various derivatives. Moreover, the urethane prepolymer whose terminal which made the following polyol and one of the said polyisocyanates react is an isocyanate group is also mentioned.

  The polyester polyol produced using the solid acid catalyst (A) used in the present invention is obtained by reacting a commonly used polyvalent carboxylic acid with a polyhydric alcohol in the presence of the solid acid catalyst (A). It is what This catalyst (A) is a solid and can be easily separated by filtration or the like. In order to use the polyester polyol, the solid acid catalyst (A) is preferably removed from the polyester polyol as the reaction product by filtration (suction filtration, ultrafiltration, pressure filtration, etc.) or centrifugation. is there. Thereby, there is no influence on the urethanation reaction of the catalyst, and a urethane resin that can easily control the urethanation reaction can be produced.

  The solid acid catalyst (A) has a function of promoting the esterification reaction, is solid in a temperature range of room temperature to 300 ° C., and has an average particle diameter of 1 μm to 3 cm. May be good.

Examples of the solid acid catalyst (A) that can be used in the present invention include metal oxides, zeolites, and acid salts of heteropolyacids. A metal oxide is preferable.

When the solid acid catalyst (A) used in the present invention is a metal oxide, the solid acid catalyst is composed of a composite metal oxide in which the supported metal oxide (A2) is supported on the surface of the metal oxide support (A1). It is preferable that the solid acid catalyst (A) is composed of a metal oxide (A) or a metal oxide carrier (A1) having a nonmetallic compound (A3) supported on the surface thereof. In this case, as the metal oxide support (A1), zirconia (zirconium dioxide, ZrO ₂ ), silica (SiO ₂ ) are used from the viewpoints of easiness of catalyst design / decoration and whether or not the catalyst ability is sufficiently exhibited. ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), silica-alumina (SiO ₂ .Al ₂ O ₃ ), magnesia (MgO), tin oxide (SnO ₂ , SnO), hafnium oxide (HfO ₂ ) At least one selected from iron oxide (Fe ₂ O ₃ , Fe ₃ O ₄ ), diatomaceous earth, cordierite, or zeolite can be used. These uses may be not only one type, but also an oxide carrier obtained by chemically combining two or more types of silica, alumina, titania, zirconia and the like.

Examples of the metal element of the metal oxide (A2) to be supported include molybdenum, tungsten, and tantalum. Examples of the supported metal oxide (A2) include molybdenum oxide (such as MoO ₃ ) and tungsten oxide ( WO ₃ etc.), tantalum oxide (Ta ₂ O ₅ etc.) and the like. The supported metal oxide (A2) may be a composite in which an arbitrary element is further supported in combination with one or more kinds as required. These optional elements that can be combined include silicon, aluminum, phosphorus, tungsten, cesium, niobium, titanium, tin, silver, copper, zinc, chromium, tellurium, antimony, bismuth, selenium, iron, magnesium, calcium, vanadium. , Cerium, manganese, cobalt, iodine, nickel, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and the like. The nonmetallic compound (A3) is either a sulfate group-containing compound or a phosphate group-containing compound, or a combination thereof.

When an acid salt of a heteropolyacid is used as the solid acid catalyst (A) of the present invention, the acid salt of a heteropolyacid is an acid metal salt and an acid onium salt of an acid formed by condensation of two or more inorganic oxygen acids. is there. Examples of the heteroatoms of the heteropolyacid include phosphorus, silicon, boron, aluminum, germanium, titanium, zirconium, cerium, cobalt, chromium and sulfur. Poly atoms include molybdenum, tungsten, vanadium, niobium, and tantalum. These heteropolyacids are conventionally known and can be produced by conventional methods. Examples of the heteropolyacid that can be used in the present invention include known heteropolyacids such as phosphomolybdic acid, phosphotungstic acid, silicon molybdic acid, and silicon tungstic acid. _{H 3 PMo x W 12-x} O 40 or _{H 4 SiMo x W 12-x} O 40 Among these heteropolyacids (wherein x is an integer of 1 ≦ x ≦ 12) represented by a hetero atom phosphorus or The performance of the esterification catalyst when silicon or a heteropolyacid whose polyatom is composed of molybdenum or mixed coordination of molybdenum and tungsten is an acid metal salt or an acid onium salt is particularly preferable.

Examples of acidic metal salts of heteropolyacid include alkali metal salts such as sodium, potassium, rubidium and cesium, alkaline earth metal salts such as beryllium, magnesium, calcium, strontium and barium, transitions such as copper, silver, zinc and mercury Metal salts, and salts of typical elements such as aluminum, thallium, tin and lead can be mentioned. Examples of the acidic onium salt of the heteropoly acid include amine salts, ammonium salts, and phosphonium salts. The number of hydrogen atom substitutions in the acid salt of the heteropolyacid is not particularly limited. There are no particular restrictions on the method of use, and it may be supported on a carrier such as silica, alumina, silica alumina, diatomaceous earth, zeolite, titania, zirconia, silicon carbide, activated carbon and the like.

When zeolite is used as the solid acid catalyst (A), the zeolite is a crystalline aluminosilicate, and its basic structural unit is a tetrahedron of silicon and aluminum cations and oxygen anions. These tetrahedra are bound so that each oxygen anion is shared by other silica or alumina tetrahedra. A crystal lattice formed three-dimensionally becomes a structural unit of the zeolite framework. The skeleton structure obtained by this regular arrangement becomes a pore structure having a large surface area. There are more than 100 types of zeolites depending on the geometric arrangement of the tetrahedron of silica and alumina. Among them, mordenite type, ZSM-5 type, β type, faujasite type, etc., whose counter ion is hydrogen. preferable.

  The polyester polyol used in the present invention is one of the solid acid catalyst (A), heteropolyacid, zeolite obtained from the metal oxide carrier (A1) and the oxide (A2) containing the metal element to be supported, or these Is a polyester polyol produced by using two or more of these together. A solid acid catalyst (A) comprising a metal oxide support (A1) and a supported metal oxide (A2) is preferred.

  The solid acid catalyst (A) is particularly preferably one in which the metal oxide support (A1) of the solid acid catalyst is zirconia and the supported metal oxide (A2) is molybdenum trioxide.

When the acid strength of the solid acid catalyst (A) is expressed by Hammett acidity function H ₀ , H ₀ is −3 to −9. Hammett's acidity function H ₀ is an index representing the strength of acid / base points on the surface of a solid so that the strength of acid / base of an aqueous solution is represented by pH. Since this function is pH = H ₀ in an aqueous solution, its strength is intuitively understood, and it is widely accepted because the experimental operation is simple. A smaller H ₀ value indicates stronger acidity, and a higher H ₀ value indicates stronger basicity. In the reaction system of the present invention, if H ₀ of the solid acid catalyst (A) of the present invention is larger than −3, the catalytic activity is not exhibited and the reaction is difficult to proceed. On the other hand, if H ₀ of the solid acid catalyst (A) of the present invention is too smaller than −9, a carbon-carbon double bond is generated by intramolecular dehydration of glycol, and further, an etherification reaction by this double bond and glycol, etc. This is because a side reaction may occur, which is not preferable.

The acidity function is a numerical value that quantitatively represents the strength of the acid-base of the solution, and is a function that indicates the ability of the solution to give hydrogen ions or receive hydrogen ions, and the acid is determined by Lewis Hammett. Hammett acidity functions are commonly used to describe the tendency of a solution to transfer protons to a neutral base.
As for Hammett's acidity function, an electrically neutral base B is bonded in an aqueous solution as shown in the following formula.
B + H + Ｂ BH +
Then, assuming that the acid dissociation constant of BH + is pKBH +, the ratio of binding B to H + when it is put in a solution is CBH +, and the ratio of nonbonding is CB, Hammett's acidity function (H ₀ ) is expressed by the following equation. Is done.
H ₀ = −pKBH + + log (CBH + / CB)
The Hammett acidity function (H ₀ ) of the solid acid catalyst (A) used in the present invention is preferably -3 to -9. Hammett's acidity function (H ₀ ) is an index representing the strength of acid / base points on the surface of a solid so that the strength of acid / base of an aqueous solution is represented by pH. Since this function is pH = H ₀ in an aqueous solution, its strength is intuitively understood, and it is widely accepted because the experimental operation is simple. The smaller the H ₀ value, the stronger the acidity, and the larger the H ₀ value, the stronger the basicity.
In the esterification reaction system in the present invention, if the acidity function (H ₀ ) of the solid acid catalyst (A) is more than -3, the catalytic activity is not exhibited, the esterification reaction is difficult to proceed, and it cannot be used as a polyester production catalyst. . On the other hand, if the acidity function (H ₀ ) of the solid acid catalyst (A) of the present invention is too smaller than −9, a carbon-carbon double bond is formed by intramolecular dehydration of glycol, and further an ether by this double bond and glycol. This is because there is a risk of causing a side reaction such as a conversion reaction, which is not preferable as a solid acid catalyst for polyester production.

<Measurement method of Hammett acidity function (H ₀ ) by NH ₃ -TPD measurement>
(Measuring method):
Set 0.1 g of solid acid catalyst as a sample in a quartz cell (inner diameter: 10 mm) of TPD-AT-1 thermal desorption equipment manufactured by Nippon Bell, and helium gas (30 cm ³ min ^-1 , 1 atm) under flow The temperature was raised to 423 K (150 ° C.) at 5 K min ⁻¹ and kept at 423 K for 3 hours. Then, while helium gas was circulated, the temperature was lowered to 7.5 K min ^-1 to 373 K (100 ° C), vacuum degassing, and 100 Torr (1 Torr = 1/760 atm = 133 Pa) NH ₃ was introduced. It was allowed to adsorb for 30 minutes and then degassed for 12 minutes before steaming. As the steam treatment, steam at a pressure of about 25 Torr (about 3 kPa) was introduced at 373 K, kept for 30 minutes, degassed for 30 minutes, again introduced with water vapor for 30 minutes, and again degassed for 30 minutes. Then, helium gas 0.041 mmol s ^-1 (corresponding to 60 cm ³ min ^-1 at 298 K, 25 ° C, 1 atm) was circulated while maintaining a reduced pressure (100 Torr), and kept at 373 K for 30 minutes, Was heated to 983 K (710 ° C.) at 10 K min ⁻¹ and the outlet gas was analyzed with a mass spectrometer (ANELVA M-QA 100F).
In the measurement, all mass spectra of mass numbers (m / e) 2, 4, 14, 15, 16, 17, 18, 26, 27, 28, 29, 30, 31, 32, 44 were recorded. After completion, the 1 mol% -NH ₃ / He standard gas is further diluted with helium to give an ammonia gas concentration of 0, 0.1, 0.2, 0.3, 0.4 mol% and a total flow rate of 0.041 mmol s ^-1 in the detector. The spectrum was recorded, and an ammonia calibration curve was prepared to correct the detector intensity. From the ammonia desorption TPD spectrum of each main mass spectrum measured at the time of temperature-programmed desorption, the average acid strength is determined from the peak area, acid amount, peak position, etc. by a one-point method based on actual measurements. The acid amount and acid strength (ΔH) are calculated, and the acidity function (H ₀ ) is calculated.

  Examples of the shape of the solid acid catalyst (A) include, but are not limited to, powder, spherical particles, irregular granules, cylindrical pellets, extruded shapes, and ring shapes. Further, it may have pores with a size of several angstroms or more, and the reaction field may be in a state where the space is controlled in the pores. The size of the solid acid catalyst (A) is not particularly limited, but a carrier having a relatively large particle size is preferable in consideration of isolating the catalyst after synthesizing the polyester. When using a fixed bed flow reactor for the reaction, if the support is spherical, if the particle diameter is extremely small, a large pressure loss may occur when the reactant is circulated, and the reactant may not be circulated effectively. is there. On the other hand, if the particle size is extremely large, the reaction raw material may not come into efficient contact with the solid acid catalyst (A), and the catalytic reaction may not proceed effectively. Therefore, the size of the solid acid catalyst (A) of the present invention is preferably determined by the size of the column packed with the catalyst and the optimum porosity, and the light scattering method (Microtrack X100 apparatus) of the catalyst of the present invention or The average particle size in the sieving method is preferably 1 μm to 3 cm. More preferably, a metal oxide carrier (A1) having a granular shape of 0.5 mm to 8 mm, in which a metal oxide (A2) is supported in an egg shell type (supporting an outer layer), is preferable.

  The polyester polyol may be any one as long as it has an ester bond by subjecting a polyhydric alcohol and a polyvalent carboxylic acid to a condensation reaction in the presence of a solid acid catalyst. Polyols and the like are also included. The polyester polyol preferably has a number average molecular weight by GPC in terms of polystyrene of 500 to 5000, particularly preferably 1000 to 3000.

  The polyhydric alcohol is preferably a linear glycol having 2 to 15 main chain carbon atoms, specifically ethylene glycol, 1,3-propylene glycol, diethylene glycol, 1,4-butylene glycol, 1,5-pentamethyl. The main chain is a hydrocarbon such as glycol, 1,6-hexamethylene glycol, bishydroxyethoxybenzene or p-xylene glycol. The total number of carbon atoms is preferably 3 to 34, more preferably 3 to 17, such as 1,2-propylene glycol, 2-methyl-1,3-propanediol, di-1,2-propylene glycol, 1, 2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 3-methyl-1,3 , 5-pentanetriol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3 -Hydroxypropanate, neopentyl glycol, 2-normalbutyl-2-ethyl-1,3-propanediol, 3-ethyl-1,5-pen Diol, 3-propyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 3-octyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 3- Myristyl-1,5-pentanediol, 3-stearyl-1,5-pentanediol, 3-phenyl-1,5-pentanediol, 3- (4-nonylphenyl) -1,5-pentanediol, 3,3- Bis (4-nonylphenyl) -1,5-pentanediol, 1,2-bis (hydroxymethyl) cyclopropane, 1,3-bis (hydroxyethyl) cyclobutane, 1,3-bis (hydroxymethyl) cyclopentane, 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) cyclohexane, 1,4-bis Hydroxypropyl) cyclohexane, 1,4-bis (hydroxyethyl) cyclohebutane, 1,4-bis (hydroxymethoxy) cyclohexane, 1,4-bis (hydroxyethoxy) cyclohexane, 2,2-bis (4′-hydroxymethoxycyclohexyl) ) Propane, 2,2-bis (4′-hydroxyedoxycyclohexyl) propane, trimethylolpropane and the like, and these may be used alone or in combination of two or more.

  As the polyhydric alcohol component, a compound having 3 or more hydroxyl groups can be used in combination. The compound that can be used in combination may be any compound that is generally used for polyester polyols, and examples thereof include polyfunctional polyhydroxy compounds such as glycerin, hexanetriol, triethanolamine, pentaerythritol, and ethylenediamine.

  Examples of the polyvalent carboxylic acid include succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, sebacic acid, 1,9-nonamethylenedicarboxylic acid, and 1,10-decamethylenedicarboxylic acid. Acid, 1,11-undecamethylene dicarboxylic acid, 1,12-dodecamethylene dicarboxylic acid, dodecanedicarboxylic acid, and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, hexahydroterephthalic acid, hexa Hydroisophthalic acid or anhydrides thereof can be used alone or in combination of two or more. From an industrial point of view, adipic acid is mainly used. Dimer acid obtained by polymerization of tall oil fatty acid can also be used. The tall oil fatty acid is a mixture of an unsaturated acid such as oleic acid or linoleic acid and palmitic acid or stearic acid.

  The polyurethane resin composition of the present invention can be used in combination with other polyester polyols and other high molecular weight polyols, and if necessary, chain extenders. The high molecular weight polyol has a number average molecular weight of 1000 to 5000, preferably 1200 to 3000 in terms of polystyrene, for example, polyether polyol, acrylic polyol, polybutadiene polyol, polysiloxane polyol, fluorine-based polyol, and polycarbonate polyol. , One or more selected from polycaprolactone polyester polyol, polyether ester polyol, polycarbonate polyester polyol and the like.

  The polyether polyol is a compound having 2 or more, preferably 2-6 active hydrogens, for example, the polyhydric alcohol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, mannitol, ditrimethylolpropane, dipentaerythritol. For example, it is a polyol obtained by addition polymerization of ethylene oxide, propylene oxide, butylene oxide or the like alone or in combination of 2 to 9 moles with respect to alkylene oxide. The number average molecular weight is preferably 1200 to 3000, and the hydroxyl value is preferably 250 to 750.

  As the polycaprolactone polyester polyol, for example, lactone polyester diols obtained by ring-opening polymerization of lactones such as ε-caprolactone can also be used. Examples of the lactone polyester diols include those obtained by addition polymerization of one or more of ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone and the like to the polyhydric alcohol described above. Can be used.

  As said polycarbonate polyol, for example, a low molecular polyol and a dialkyl carbonate can be obtained by a condensation reaction. Examples of the low molecular polyol include 1,6-hexanediol and 1,5-pentanediol. Examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, and ethylene carbonate.

  Examples of the polycarbonate polyol include a lactone-modified polycarbonate polyol obtained by further ring-opening addition polymerization of a lactone to a polycarbonate polyol, and a co-condensed polycarbonate polyol obtained by co-condensing a polycarbonate polyol with another polyester polyol or polyether polyol. Is mentioned.

  When the polyurethane resin composition of the present invention is a thermoplastic polyurethane elastomer, a chain extender can be used. Preferably, a low molecular weight linear diol having 2 to 10 carbon atoms is used. Typical examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 2,2′-dimethyl-1,3-propanediol. , Diethylene glycol, 1,5 pentamethylene glycol, 1,6-hexamethylene glycol, cyclohexane 1,4-diol, cyclohexane-1,4 diol, cyclohexane-1,4 dimethanol and the like. 1,4-butanediol is particularly preferable.

The polyurethane resin composition of the present invention can be not only a urethane elastomer but also an aqueous polyurethane resin or a water-based polyurethane resin. This polyurethane resin composition introduces one or more types such as an anionic group, a cationic group, and a nonionic group as a hydrophilic group in order to disperse in water. At this time, a chain extender having a hydrophilic group may be used for the polyester polyol produced using the solid acid catalyst, or a glycol containing a hydrophilic group as a raw material for the polyester polyol produced using the solid acid catalyst. In addition, a polyester polyol hydrophilized by partially using a dibasic acid containing a hydrophilic group can be produced and used, and a water-based or aqueous polyurethane resin composition can be obtained using a known technique.

As a production method thereof, for example, (i) a polyester polyol produced using a solid acid catalyst and containing no hydrophilic group is used, and at least one hydroxyl group or amine group capable of reacting with an isocyanate group is present in one molecule. A method for producing an aqueous or aqueous polyurethane resin using a compound containing one or more hydrophilic groups selected from anionic groups, cationic groups, and nonionic groups in one molecule,

(Ii) An anionic group, a cationic group, a nonionic group, a polyol containing a hydrophilic group represented by a neutralized salt thereof, and / or a polycarboxylic acid containing the hydrophilic group or an ester derivative thereof is essential. A method for producing a polyester polyol containing a hydrophilic group using a solid acid catalyst using a polyol and a dicarboxylic acid as components, and producing an aqueous or aqueous polyurethane resin using the polyester polyol can be employed. .

  Preferred examples of the anionic group as the hydrophilic group include a carboxyl group, a carboxylate group, a sulfonic acid group, and a sulfonate group. The cationic group is a tertiary amino group, part or all of which is an acidic compound. Preferred are those that are summed or quaternized with a known quaternizing agent, and the nonionic group is preferably polyethylene glycol or a copolymer thereof.

  The anionic group and the cationic group may be partially or wholly neutralized with a known basic compound or acidic compound, and a tertiary amino group as a cationic group is converted into a quaternizing agent. The quaternized product may be used.

  Examples of the polyester polyol containing an anionic group include a carboxyl group-containing polyester polyol and a sulfonic acid group-containing polyester polyol.

  The polyurethane resin of the present invention includes a polyester polyol produced by using a solid acid catalyst and a polyisocyanate, and a terminal isocyanate group reacted with hydroxy (meth) acrylate, that is, a urethane acrylate resin. Such resins can be cured using radical polymerization initiators, such as organic peroxides, electron beam polymerization initiators such as light and UV, photosensitizers, polymerization inhibitors, and curing accelerators. it can.

  The urethane resin composition of the present invention can be produced by a conventionally known polyurethane production method, for example, a one-shot method, a prepolymer method or a quasi-prepolymer method, and further, bulk polymerization, solution polymerization, emulsion polymerization, emulsion polymerization, etc. Can be used. The production method may be a conventionally known method, such as a slab method, a double conveyor method, a hot cure method, a cold cure method, a RIM method, molding by an open mold, an integral molding with a composite material, an on-site construction method, a spray method, a casting method. Methods such as injection, coating, and impregnation can be used. In the production, the polyisocyanate and the polyol are preferably reacted at a molar ratio (NCO / OH) of 0.8 to 1.1, more preferably 1.0 to 1.05. Moreover, a well-known urethanization catalyst, surfactant, another adjuvant, etc. can be used in the addition amount generally used when manufacturing urethane.

  Furthermore, the urethane composition of the present invention may contain an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, a filler, a colorant, a reinforcing agent, a release agent, a flame retardant, and the like as necessary. Furthermore, other thermoplastic polyurethane elastomers and other general-purpose thermoplastic resins such as ABS resin, AS resin, vinyl chloride resin, polyamide and the like can be added within a range not impairing the effect of the urethane resin composition according to the present invention. . The composition of the present invention may contain various additives selected from surfactants, catalysts, stabilizers, and pigments.

  The present invention can be used as thermoplastic elastomer (TPU), thermosetting elastomer (TSU), aqueous polyurethane resin, radical curable urethane resin, molding material, adhesive, adhesive, paint, foam, sealing agent, light It can be used for polyurethane products in all fields such as curable resins. Specifically, three-dimensional molded products such as yarns, films, sheets, belts, hoses, rolls, tires, anti-vibration materials, packings, and shoe soles, as well as artificial leather, synthetic leather, soft / hard foams, textile materials It can be used in many fields such as industrial materials, electrical and electronic materials, optical materials, medical materials, and civil engineering materials.

EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to this. The parts in Examples and Comparative Examples represent parts by weight unless otherwise specified.
Polyester synthesis

Preparation Example 1 <Preparation of Solid Acid Catalyst (MoO ₃ / ZrO ₂ ) (a1)>
As for MoO ₃ / ZrO ₂ , 50 g of zirconium hydroxide (Zr (OH) ₄ , manufactured by Nippon Light Metal Industry) dried overnight at 100 ° C. was added to ammonium molybdate [(NH ₄ ) ₆ Mo ₇ O _24. 4H ₂ O (manufactured by Kishida Chemical Co., Ltd.)] is added in an aqueous solution (0.04 mol · dm ⁻³ ), and the ammonium molybdate aqueous solution corresponding to the pore volume of zirconium hydroxide is added little by little. Obtained in a uniformly wet state (Incipient Wetness method). The amount of molybdenum trioxide (MoO ₃ ) supported was adjusted by the solution concentration so that the weight ratio was Mo / Zr = 0.1. As a pretreatment for the reaction, firing was performed for 3 hours at a firing temperature of 1073 K in an oxygen atmosphere. It was allowed to cool naturally and brought to room temperature to obtain a solid acid catalyst (a1).

Preparation Example 2 <Preparation of Solid Acid Catalyst (MoO ₃ / ZrO ₂ ) (a2)>
A solid acid catalyst (a2) was obtained in the same manner as in Preparation Example 1 except that the calcination temperature was changed to 673K.

<Measurement method of H ₀ function by NH ₃ -TPD measurement>
Measuring method:
About 0.1 g of the solid acid catalyst (a1) and (a2) was set in a quartz cell (inner diameter: 10 mm) of a TPD-AT-1 type thermal desorption apparatus manufactured by Bell Japan, and helium gas (30 cm ³ min ⁻¹ , 1 atm), and the temperature was raised to 423 K (150 ° C.) at 5 K min ⁻¹ and maintained at 423 K for 3 hours. Thereafter, the temperature is lowered to 373 K (100 ° C.) at 7.5 K min ⁻¹ while the helium gas is circulated, and then vacuum degassing is performed. Then, 100 Torr (1 Torr = 1/760 atm = 133 Pa) of NH ₃ is introduced. For 30 minutes and then degassed for 12 minutes before steaming. As the water vapor treatment, water vapor of about 25 Torr (about 3 kPa) was introduced at 373 K, kept for 30 minutes, degassed for 30 minutes, again introduced with water vapor for 30 minutes, and again degassed for 30 minutes. Thereafter, helium gas 0.041 mmol s ⁻¹ (298 K, corresponding to 60 cm ³ min ⁻¹ at 25 ° C. and 1 atm) was allowed to flow while maintaining a reduced pressure (100 Torr) and maintained at 373 K for 30 minutes. The sample bed was heated to 983 K (710 ° C.) at 10 K min ⁻¹ , and the outlet gas was analyzed with a mass spectrometer (ANELVA M-QA 100F).

In the measurement, all mass spectra of mass numbers (m / e) 2, 4, 14, 15, 16, 17, 18, 26, 27, 28, 29, 30, 31, 32, 44 were recorded. After completion, the 1 mol% -NH ₃ / He standard gas is further diluted with helium to give an ammonia gas concentration of 0, 0.1, 0.2, 0.3, 0.4 mol% and a total flow rate of 0.041 mmol s ^-1 in the detector. The spectrum was recorded, and an ammonia calibration curve was prepared to correct the detector intensity.

1 and 2 show main mass spectra measured during temperature programmed desorption. The other mass number (m / e) signals were almost on the baseline and showed no peaks.
Both samples show a peak of m / e = 16 indicating ammonia desorption near 500 K, and more than 900 K for the solid acid catalyst (a1) and small at around 780 K for the solid acid catalyst (a2). A shoulder with m / e = 16 can be seen. However, at the same time as the appearance of these high-temperature shoulders, a large peak at m / e = 44 (CO ₂ fragment) and m / e = 28 (CO ₂ fragment + N ₂ ) are also seen, The shoulder is probably due to CO ₂ fragments, not ammonia. Therefore, this portion was excluded in the determination of ammonia described later.
FIG. 3 shows an ammonia TPD spectrum calculated from m / e = 16. The acid amount and acid strength (ΔH) were calculated from these spectra and shown in Table-1.
In the one-point method based on actual measurement, the average acid strength can be determined from the peak area, acid amount, peak position, and the like. According to this method, it seems that the acid amount of the solid acid catalyst (a1) per mass is about 0.03 mol kg ⁻¹ , and the acid amount of the solid acid catalyst B is about 0.2 mol kg ^−1. The (acid amount / surface area) of the solid acid catalysts (a1) and (a2) was about 0.4 to 0.7 nm ⁻² . The average acid strength is ΔH = 133 kJ mol ^-1 , converted to H ₀ for solid acid catalyst (a1), and -7.4, while that for solid acid catalyst (a2) is converted to ΔH = 116 kJ mol ^-1 , H ₀ And it was slightly weak at -4.4.

(Synthesis Example 1) <Synthesis of Aliphatic Polyester Polyol>
Into a 5 L 4-necked flask, 2050 parts of 1,4-butanediol (BG), 2950 parts of adipic acid (AA) and 50 parts of a solid acid catalyst (a1) were charged, and a condenser tube, an aggregating tube and a nitrogen introducing tube were set. The temperature was raised to 210 ° C. while blowing nitrogen, followed by dehydration condensation to obtain a polyester polyol. The catalyst was removed by suction filtration with a 1 micron filter. The obtained polyester polyol had a hydroxyl value of 56.4, an acid value of 0.18, and a color tone (APHA) of 30.

(Synthesis Example 2) <Synthesis of aromatic polyester polyol>
A 5 L 4-necked flask was charged with 2185 parts of diethylene glycol, 1318 parts of adipic acid, and 1498 parts of isophthalic acid, and 50 parts of a solid acid catalyst (a1) was further added. Next, a cooling tube, an aggregating tube, and a nitrogen introducing tube were set, the temperature was raised to 230 ° C. while blowing nitrogen, and dehydration condensation was performed to obtain a polyester polyol. The catalyst was removed by suction filtration with a 1 micron filter. The obtained polyester polyol had a hydroxyl value of 55.8, an acid value of 0.22, and a color tone (APHA) of 60.

(Comparative Synthesis Example 1) <Synthesis of Aliphatic Polyester Polyol>
Into a 5 L four-necked flask, 2050 parts of 1,4 butanediol, 2950 parts of adipic acid, and 0.5 part of tetrabutyl titanate (TBT) are charged, and a condenser tube, a condensation tube, and a nitrogen introduction tube are set. Next, the temperature was raised to 210 ° C. while blowing nitrogen, followed by dehydration condensation to obtain a polyester polyol. The obtained polyester polyol had a hydroxyl value of 56.1, an acid value of 0.31, and a color tone (APHA) of 40.

(Comparative Synthesis Example 2) <Synthesis of aromatic polyester polyol>
A 5 L 4-necked flask was charged with 2185 parts of diethylene glycol, 1318 parts of adipic acid and 1498 parts of isophthalic acid, and 0.50 part of tetrabutyl titanate (hereinafter abbreviated as TBT) was added. Next, a cooling tube, an aggregating tube, and a nitrogen introducing tube were set, the temperature was raised to 230 ° C. while blowing nitrogen, and dehydration condensation was performed to obtain a polyester polyol. The obtained polyester polyol had a hydroxyl value of 56.0, an acid value of 0.12, and a color tone (APHA) of 90.

色調（ＡＰＨＡ）：ＡＳＴＭ Ｄ ４８９０−９８

Color tone (APHA): ASTM D 4890-98

<Measurement of catalyst residue of polyester polyol>
In order to quantify the residual catalyst component in the polyester polyol by separating the catalyst, a fluorescent X-ray analysis of the polyester polyol after filtration was performed. While the comparative example using the homogenized catalyst detected 100% of the metal content of the catalyst used, it was confirmed that the polyester polyol of the example was below the detection limit of the measuring instrument (detection limit 5 ppm) or below. .

<Creation of polyurethane sheet>
(Example 1) <Preparation of polyurethane sheet using aliphatic polyester polyol>
After weighing 500 parts by weight of the aliphatic polyester polyol synthesized in Example 1 adjusted to 80 ° C. and 63 parts by weight of diphenylmethane diisocyanate (hereinafter abbreviated as MDI) adjusted to 60 ° C. into a cup, they were mixed thoroughly. The sheet was put into a rotary molding machine at 140 ° C. to prepare a 2 mm pressure sheet. After 2 hours, it was taken out from the molding machine and further aftercured at 110 ° C. for 12 hours to obtain a measurement polyurethane sheet.

(Example 2) <Production of polyurethane sheet using aromatic polyester polyol>
500 parts by weight of the aromatic polyester polyol synthesized in Example 2 adjusted to 80 ° C. and 43.8 parts by weight of trilene diisocyanate (abbreviated as TDI) adjusted to 60 ° C. were weighed and mixed thoroughly. Thereafter, the sheet was put into a rotary molding machine at 140 ° C. to prepare a 2 mm pressure sheet. After 2 hours, it was taken out from the molding machine and further aftercured at 110 ° C. for 12 hours to obtain a measurement polyurethane sheet.

(Comparative Example 1) <Preparation of polyurethane sheet using aliphatic polyester polyol>
In the same manner as in the examples, 500 parts by weight of the aliphatic polyester polyol synthesized in Comparative Example 1 adjusted to 80 ° C. and 62.8 parts by weight of MDI adjusted to 60 ° C. were weighed into a cup and thoroughly mixed. Was put into a rotary molding machine and a sheet with a pressure of 2 mm was prepared. After 2 hours, it was taken out from the molding machine and further aftercured at 110 ° C. for 12 hours to obtain a measurement polyurethane sheet.

(Comparative Example 2) <Preparation of polyurethane sheet using aromatic polyester polyol>
500 parts by weight of the aromatic polyester polyol synthesized in Comparative Example 2 adjusted to 80 ° C. and 43.6 parts by weight of TDI adjusted to 60 ° C. were weighed into a cup and thoroughly mixed. A sheet with a pressure of 2 mm was prepared. After 2 hours, it was taken out from the molding machine and further aftercured at 110 ° C. for 12 hours to obtain a measurement polyurethane sheet.

<Reactivity evaluation of polyester polyol>
300 parts by weight of polyester polyols of Examples 1 and 2 and Comparative Examples 1 and 2 adjusted to 80 ° C. were weighed into a cup, and MDI adjusted to 60 ° C. was 1.05 in molar ratio to the polyester polyol. The amount to become was weighed in and mixed with a stirring motor for 1 minute, and the time for 20 Pas was measured with a BM type rotational viscometer. The mixture (polyurethane resin) was measured in a thermostatic oil bath adjusted to 80 ° C. so that the temperature did not decrease. The results are shown in Table-3. Compared with the polyester polyol synthesized by TBT, the polyester polyol synthesized by the solid acid catalyst was confirmed to have a slow reactivity with isocyanate (does not affect the urethane reaction).

<Color tone evaluation of polyurethane sheet>
The degree of coloring of the polyurethane sheets of Examples and Comparative Examples was confirmed visually. The polyurethane sheet using the polyester polyol using the solid acid catalyst of the example was confirmed to be less colored than the polyurethane sheet using the TBT of the comparative example. The results are shown in Table-3.

<Evaluation of wet heat resistance retention rate (hydrolysis resistance)>
The hydrolysis resistance of the polyurethane sheet was evaluated by the strength retention under wet heat conditions. The polyurethane sheet was allowed to stand in a constant temperature and humidity chamber at 80 ° C. × 95% RH for 1 week, and the moisture heat resistance retention rate with respect to the tensile strength of the polyurethane sheet before treatment was confirmed. The polyurethane sheet using the polyester polyol using the solid acid catalyst of the example was confirmed to have higher strength retention than the polyurethane sheet using the TBT of the comparative example. The results are shown in Table-3.

Main mass spectrum measured during temperature programmed desorption of solid acid catalyst a1 by mass spectrometer Main mass spectrum measured during temperature programmed desorption of solid acid catalyst a2 by mass spectrometer Ammonia TPD spectrum of solid acid catalysts a1 and a2 by TPD-AT-1 temperature programmed desorption device

A: Solid acid catalyst a1
B: Solid acid catalyst a2

As a result of intensive studies on the use of a polyester polyol produced using a separable catalyst as a urethane raw material, the present inventors have completed the present invention.
That is, the present invention includes a polyisocyanate, a polyester polyol produced using a polyhydric alcohol and a polycarboxylic acid in the presence of a solid acid catalyst (A), and the solid acid catalyst (A ) Is a composite metal oxide composed of a metal oxide support (A1) and a supported metal oxide (A2), or a metal oxide composed of a metal oxide support (A1) and a supported nonmetallic compound (A3). The Hammett acidity function H _{0 of the} solid acid catalyst (A) is H ₀ = −3 to −9, and relates to a polyurethane resin composition and a molded product thereof.

Claims (8)

A polyurethane resin composition comprising: a polyisocyanate; and a polyester polyol produced using a polyhydric alcohol and a polycarboxylic acid in the presence of a solid acid catalyst (A). The polyurethane resin composition according to claim 1, wherein the polyester polyol is obtained by removing the solid acid catalyst (A) from the polyester polyol after production. The solid acid catalyst (A) is a composite metal oxide composed of a metal oxide support (A1) and a supported metal oxide (A2), or a non-metallic compound (A3) supported on a metal oxide support (A1). The polyurethane resin composition according to claim 1, wherein the polyurethane resin composition is a metal oxide. The polyurethane resin composition according to claim 1, wherein the Hammett acidity function H _{0 of the} solid acid catalyst (A) is H ₀ = −3 to −9. The polyurethane resin composition according to claim 3, wherein the metal oxide support (A1) is any one of silica, alumina, titania, zirconia, or a solid acid catalyst using a support using these. . 4. The polyurethane resin composition according to claim 3, wherein the metal oxide (A2) to be supported is one of tungsten oxide and molybdenum oxide, or a solid acid catalyst using these in combination. The polyurethane resin composition according to claim 3, wherein the metal oxide support (A1) of the solid acid catalyst is zirconia, and the oxide (A2) to be supported is molybdenum trioxide. A molded article using the polyurethane resin composition according to any one of claims 1 to 7.

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