Additives for polyurethane (urea) resins

Abstract

To provide an additive for polyurethane (urea) resin that is superior in plasticity, fogging resistance, and heat-resistant appearance.SOLUTION: An additive for polyurethane (urea) resin includes a compound represented by the general formula (1) in an amount of 94-98 wt.%, and a compound represented by the general formula (2) in an amount of 2-6 wt.%. R1-COO-(EO) n-CO-R2 (1) (in the formula (1), R1 and R2 each represent a benzene ring, EO represents an oxyethylene group, and n represents the average number of moles added, a value that is selected from 4-20). R3-COO-(EO) m-H (2) (in the formula (2), R3 represents a benzene ring, EO represents an oxyethylene group, and m represents the average number of moles added, a value that is selected from 4-20).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to additives for polyurethane (urea) resins. [Background technology]

[0002] Thermoplastic polyurethane resin powder molding materials are known as materials for slush molding of automobile parts, home appliance parts, toys, miscellaneous goods, etc. The slush molding method is widely used for applications such as automobile interior and exterior materials, home appliance parts, toys, miscellaneous goods, etc., because it can easily mold molded objects of complex shapes and has good material yields. To date, many improvements have been made to thermoplastic polyurethane resin powder molding materials for slush molding, such as powder flowability to ensure moldability and performance as molded objects (soft feel at low temperatures, fogging resistance, etc.). For example, a polyurethane resin composition for powder molding using a plasticizer has been disclosed (see Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 4697383 Summary of the Invention [Problem to be solved by the invention]

[0004] However, polyurethane resin compositions for powder molding using the above plasticizers were insufficient in plasticity, fogging resistance and heat-resistant appearance. The present invention provides an additive for polyurethane (urea) resins that is excellent in plasticity, fogging resistance and heat-resistant appearance. [Means for solving the problem]

[0005] The present inventors have conducted intensive research to solve the above problems, and have arrived at the present invention. That is, the present invention is an additive for polyurethane (urea) resins, which contains a compound represented by the following general formula (1) and a compound represented by the following general formula (2), and contains 94 to 98% by weight of the compound represented by the following general formula (1) and 2 to 6% by weight of the compound represented by the following general formula (2), based on the total weight of the compound represented by the following general formula (1) and the compound represented by the following general formula (2). R 1 -COO-(EO)n-CO-R 2 (1) (In formula (1), R 1 and R 2 represents a benzene ring, EO represents an oxyethylene group, and n represents the average number of moles added, which is a number from 4 to 20. R 3 -COO-(EO)mH (2) (In formula (2), R 3 represents a benzene ring, EO represents an oxyethylene group, and m represents the average number of moles added, which is a number from 4 to 20. Effect of the Invention

[0006] By using the additive for polyurethane(urea) resins of the present invention, it is possible to obtain a polyurethane(urea) resin composition having excellent plasticity, fogging resistance and heat-resistant appearance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] In the present invention, the term "urethane (urea) resin" includes both a urethane resin containing only urethane bonds, and a urethane urea resin containing both urethane bonds and urea bonds.

[0008] The present invention is an additive for polyurethane (urea) resins, which comprises a compound represented by the following general formula (1) and a compound represented by the following general formula (2), and contains the compound represented by the following general formula (1) and the compound represented by the following general formula (2) based on the total weight of the compound represented by the following general formula (1) and the compound represented by the following general formula (2). R1 -COO-(EO)n-CO-R 2 (1) In formula (1), R 1 and R 2 represents a benzene ring, and EO represents an oxyethylene group. n represents the average number of moles added, which is a number of 4 to 20, and preferably 4 to 12. R 3 -COO-(EO)mH (2) In formula (2), R 3 represents a benzene ring, and EO represents an oxyethylene group. m represents the average number of moles added, which is a number of 4 to 20, and preferably 4 to 12.

[0009] The additive for polyurethane(urea) resin of the present invention contains 94 to 98% by weight of the compound represented by general formula (1) and 2 to 6% by weight of the compound represented by general formula (2), based on the total weight of the compound represented by general formula (1) and the compound represented by general formula (2), thereby imparting excellent plasticity to the polyurethane(urea) resin composition and enabling it to exhibit excellent fogging resistance and heat-resistant appearance.

[0010] The contents of the compound represented by general formula (1) and the compound represented by general formula (2) contained in the polyurethane (urea) resin additive of the present invention can be confirmed by separating them using high performance liquid chromatography or the like.

[0011] The additive for polyurethane (urea) resin of the present invention may contain the compound represented by general formula (1) and the compound represented by general formula (2) in the above-mentioned predetermined ratio, and may be a mixture of the compound represented by general formula (1) and the compound represented by general formula (2) in the above-mentioned predetermined ratio, or may be a composition obtained by purifying an esterification reaction product of an acid and an alcohol so as to obtain a mixture containing the compound represented by general formula (1) and the compound represented by general formula (2) in the above-mentioned predetermined ratio.

[0012] When a mixture of a compound represented by general formula (1) and a compound represented by general formula (2) in a predetermined ratio is used as the additive for the polyurethane (urea) resin of the present invention, the compound represented by general formula (1) and the compound represented by general formula (2) can each be obtained by subjecting a diol (a) and benzoic acid to an esterification reaction by a known method.

[0013] The diol (a) is a diol obtained by adding ethylene oxide to a dihydric alcohol having 2 carbon atoms, and the number of moles of ethylene oxide added (b) is 4 to 20, and is obtained by subjecting the dihydric alcohol having 2 carbon atoms to a ring-opening addition reaction of ethylene oxide by a known method. From the viewpoints of plasticity and viscosity, the dihydric alcohol having 2 carbon atoms is preferably an alkylene glycol having 2 carbon atoms, and a specific example thereof is ethylene glycol. The number of moles of ethylene oxide added (b) is 4-20, and preferably 4-12.

[0014] The method for producing the compound represented by general formula (1) constituting the polyurethane(urea) resin additive of the present invention essentially requires an esterification step in which diol (a) is subjected to an esterification reaction with benzoic acid. Specifically, this is a process in which diol (a), benzoic acid, an esterification catalyst, and, if necessary, a solvent are charged into a reaction apparatus, and while flowing nitrogen through the liquid and heating, the generated water is removed from the system to proceed with the esterification reaction, thereby synthesizing a dibenzoate ester. The amount of benzoic acid used in the compound represented by formula (1) is preferably 2.00 to 2.20 mol, more preferably 2.00 to 2.10 mol, and most preferably 2.00 to 2.05 mol, per mol of the diol (a).

[0015] Examples of the esterification catalyst in the method for producing the compound represented by the general formula (1) include potassium titanium oxalate, sodium titanium oxalate, lithium titanium oxalate, and mixtures thereof. The content of the esterification catalyst in the production method of the compound represented by general formula (1) is preferably 0.000001 to 10 mol %, more preferably 0.000001 to 1 mol %, and most preferably 0.01 to 1.0 mol %, based on the total number of carboxyl groups of benzoic acid, from the viewpoint of low coloration.

[0016] As the solvent, it is more preferable to use a solvent having a boiling point of 90 to 150° C. from the viewpoint of reducing the energy required to distill off the solvent from the reaction apparatus after the esterification step. Examples of solvents having a boiling point of 90 to 150°C include saturated aliphatic hydrocarbons such as 2,2,4-trimethylpentane, n-heptane, n-octane, isooctane, nonane, and decane; alicyclic hydrocarbons such as methylcyclohexane, ethylcyclohexane, cycloheptane, and methylcycloheptane; aromatic hydrocarbons such as toluene, ethylbenzene, propylbenzene, butylbenzene, and xylene; and ketone compounds such as methyl propyl ketone, methyl isopropyl ketone (MIPK), methyl butyl ketone, methyl isobutyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, acetylacetone, and 2-cyclohexen-1-one.

[0017] The temperature range during the heating is preferably 120 to 230°C, and more preferably 180 to 220°C. The reaction time is preferably 6 to 30 hours, more preferably 7 to 25 hours, and most preferably 8 to 20 hours.

[0018] The method for producing the compound represented by general formula (2) constituting the polyurethane(urea) resin additive of the present invention essentially requires an esterification step in which diol (a) is subjected to an esterification reaction with benzoic acid. Specifically, this is a process in which diol (a), benzoic acid, an esterification catalyst, and, if necessary, a solvent are charged into a reaction apparatus, and while flowing nitrogen through the liquid and heating, the generated water is removed from the system to proceed with the esterification reaction, thereby synthesizing a benzoate ester. The amount of benzoic acid used in the compound represented by formula (2) is preferably 0.90 to 1.20 mol, more preferably 1.00 to 1.10 mol, and most preferably 1.00 to 1.05 mol, per mol of the diol (a).

[0019] The esterification catalyst in the method for producing the compound represented by the general formula (2) includes, for example, organic sulfonic acids, and preferably includes methanesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid, and mixtures thereof. The content of the esterification catalyst in the production method of the compound represented by general formula (2) is preferably 0.000001 to 10 mol %, more preferably 0.000001 to 1 mol %, and most preferably 0.01 to 1.0 mol %, based on the total number of carboxyl groups of benzoic acid, from the viewpoint of low coloration.

[0020] As the solvent, it is more preferable to use a solvent having a boiling point of 90 to 150° C. from the viewpoint of reducing the energy required to distill off the solvent from the reaction apparatus after the esterification step. Examples of solvents having a boiling point of 90 to 150°C include saturated aliphatic hydrocarbons such as 2,2,4-trimethylpentane, n-heptane, n-octane, isooctane, nonane, and decane; alicyclic hydrocarbons such as methylcyclohexane, ethylcyclohexane, cycloheptane, and methylcycloheptane; aromatic hydrocarbons such as toluene, ethylbenzene, propylbenzene, butylbenzene, and xylene; and ketone compounds such as methyl propyl ketone, methyl isopropyl ketone (MIPK), methyl butyl ketone, methyl isobutyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, acetylacetone, and 2-cyclohexen-1-one. The temperature range during the heating is preferably 60 to 160°C, and more preferably 70 to 120°C. The reaction time is preferably 30 minutes to 10 hours, more preferably 50 minutes to 6 hours, and most preferably 1 to 3 hours.

[0021] When the compound represented by general formula (1) and the compound represented by general formula (2) are mixed in a predetermined ratio to prepare the additive for the polyurethane (urea) resin of the present invention, the mixing method may be a conventional method, and examples thereof include a method in which the compound represented by general formula (1) and the compound represented by general formula (2) are stirred using a stirrer or the like.

[0022] When using a composition obtained by purifying and adjusting an esterification reaction product of an acid and an alcohol so as to contain the compound represented by general formula (1) and the compound represented by general formula (2) in the above-mentioned predetermined ratio as the additive for the polyurethane (urea) resin of the present invention, a production method for obtaining a composition containing the compound represented by general formula (1) and the compound represented by general formula (2) in the above-mentioned predetermined ratio can be a production method including an esterification step of esterifying diol (a) and benzoic acid, a neutralization step of adding a neutralizing agent (e), an adsorption step with an adsorbent, and a purification step of filtering the adsorbent.

[0023] In the esterification step for obtaining a composition containing a compound represented by general formula (1) and a compound represented by general formula (2), the amount of raw material used may be appropriately set and is not particularly limited. For example, the amount of benzoic acid used is preferably 2.00 to 2.20 mol, more preferably 2.00 to 2.10 mol, and most preferably 2.00 to 2.05 mol, relative to 1 mol of diol (a).

[0024] By subjecting the reaction product obtained in the esterification reaction process, which contains the compound represented by general formula (1) and the compound represented by general formula (2), to a neutralization process in which a neutralizing agent (e) is added, an adsorption process in which an adsorbent is added, and a purification process in which the adsorbent is filtered, it is possible to produce an additive for polyurethane (urea) resins that contains 94 to 98% by weight of the compound represented by general formula (1) and 2 to 6% by weight of the compound represented by the following general formula (2), based on the total weight of the compound represented by general formula (1) and the compound represented by general formula (2).

[0025] The neutralizing agent (e) added in the neutralization step is not particularly limited as long as it is an alkaline compound that does not inhibit the purification (adsorption step and filtration step), and examples thereof include sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, etc. Among these, sodium hydroxide, sodium carbonate, and sodium bicarbonate are more preferable from the viewpoint of neutralization efficiency.

[0026] From the viewpoint of adjusting the ratio of the compound represented by general formula (1) to the compound represented by general formula (2) to a predetermined ratio, the amount of neutralizing agent (e) added is preferably an amount such that the molar ratio of unreacted benzoic acid (d) to neutralizing agent (e) {(d) / (e)}, calculated based on the acid value of the esterification reaction mixture, is 0.9 to 1.1. The acid value of the esterification reaction mixture can be determined by the acid value measurement method described in JIS K0070.

[0027] The temperature range for the neutralization step is preferably 20 to 80°C, and more preferably 55 to 65°C. The reaction time for the neutralization step is preferably 10 minutes to 3 hours, more preferably 30 minutes to 2 hours, and most preferably 1 to 2 hours.

[0028] Examples of the adsorbent to be added in the adsorption step include silicates such as aluminum silicate and magnesium silicate, activated clay, acid clay, silica gel, and the like. Examples of commercially available adsorbents that can be used include silicates such as Kyoward 600 and 700 (trade names: Kyowa Chemical Industry Co., Ltd.), Mizuka Life P-1, P-1S, P-1G, and F-1G (trade names: Mizusawa Chemical Industry Co., Ltd.), and Tomita AD600 and 700 (trade names: Tomita Pharmaceutical Co., Ltd.). Only one of these neutralizing agents may be used, or two or more of them may be used in combination. The amount of the adsorbent added is 0.1 to 1.5 parts by weight, and preferably 0.1 to 1.0 part by weight, relative to 100 parts by weight of benzoic acid used in the esterification reaction, from the viewpoint of adjusting the ratio of the compound represented by general formula (1) to the compound represented by general formula (2) to a predetermined ratio.

[0029] The temperature range for the adsorption step is preferably 20 to 80°C, and more preferably 50 to 60°C. The reaction time for the adsorption step is preferably 10 minutes to 6 hours, more preferably 20 minutes to 5 hours, and most preferably 1 to 3 hours.

[0030] By adding a purification step of filtering the adsorbent to the reaction product obtained in the esterification reaction step, which contains the compound represented by general formula (1) and the compound represented by general formula (2), after the neutralization step and the adsorption step, it is possible to produce an additive for polyurethane (urea) resins that contains 94 to 98% by weight of the compound represented by general formula (1) and 2 to 6% by weight of the compound represented by the following general formula (2), based on the total weight of the compound represented by general formula (1) and the compound represented by general formula (2). The purification step is a step of removing the adsorbent by filtration, and a composition containing the compound represented by general formula (1) and the compound represented by general formula (2) in a predetermined ratio can be obtained.

[0031] The filtration temperature (the temperature of the mixture subjected to filtration) is preferably 40 to 70°C, more preferably 50 to 70°C, and even more preferably 50 to 60°C.

[0032] In the method for obtaining a composition containing a compound represented by general formula (1), a compound represented by general formula (2) diol (a), and a compound represented by general formula (1) and a compound represented by general formula (2), when a solvent is used in the esterification step, a solvent distillation step for distilling off the solvent may be included. The order of the solvent distillation step is not particularly limited, but it can be performed between the esterification step and the adsorption step, between the adsorption step and the filtration step, or after the filtration step. Of these, the solvent distillation step is preferably carried out between the adsorption step and the filtration step from the viewpoint of productivity. The solvent distillation step is preferably carried out under reduced pressure, for example, 5 kPa or less, preferably 4 kPa or less, and more preferably 3 kPa or less. The lower limit of the degree of reduced pressure is, for example, 1 Pa or more, and more preferably 10 Pa or more. The temperature range for the solvent distillation step is preferably 100 to 150°C, and more preferably 120 to 130°C. The reaction time for the solvent distillation step is preferably 5 to 20 hours, more preferably 10 to 20 hours, and most preferably 12 to 20 hours.

[0033] The additive for polyurethane (urea) resin of the present invention is added to and mixed with a polyurethane (urea) resin for use. The polyurethane (urea) resin to which the additive for polyurethane (urea) resin of the present invention is added is not particularly limited as long as it is a polyurethane (urea) resin.

[0034] The polyurethane (urea) resin to which the polyurethane (urea) resin additive of the present invention is added preferably has a urea group concentration of 0 to 10% by weight, a total of the urethane group concentration and the urea group concentration of 4 to 20% by weight, a melting point of 160 to 260°C, and a glass transition temperature of -65 to 0°C. Since the urea group significantly improves the strength, solvent resistance, and abrasion resistance of the urethane resin, the performance of the urethane resin can be greatly improved when the urea group is contained. When the urea group is present, the effect of improving the strength, solvent resistance, and abrasion resistance due to the urea group is significant, and when the urethane resin is molded, the melting point and melt viscosity can be kept low, so that the heat energy required during molding can be reduced. The urea group concentration is preferably 0 to 10% by weight, more preferably 1.0 to 7.0% by weight, and most preferably 1.5 to 5.0% by weight. At the same time, the urethane group, like the urea group, improves the performance of the polyurethane (urea) resin, and the total concentration of the urethane group and the urea group is preferably 4 to 20% by weight, more preferably 6 to 15% by weight, and most preferably 8 to 12% by weight. The urethane group concentration and urea group concentration in the present invention are the concentrations in weight percent of the urethane group and the urea group relative to the urethane resin.

[0035] The melting point of the polyurethane (urea) resin to which the additive for polyurethane (urea) resin of the present invention is added is preferably 160 to 260° C., more preferably 210 to 250° C. If the melting point is 160 to 260° C., the particle blocking resistance is excellent in a general storage environment, and the thermal energy during molding can be reduced. The melting point in the present invention is measured by the method described in the Examples.

[0036] The polyurethane (urea) resin to which the additive for polyurethane (urea) resin of the present invention is added preferably has a glass transition temperature of −65 to 0° C., more preferably −50 to −10° C. If the glass transition temperature is −65 to 0° C., the resin can have impact resistance even at a lower temperature. The glass transition temperature in the present invention is measured by the method described in the Examples.

[0037] The additive for polyurethane (urea) resin of the present invention can be suitably used for polyurethane (urea) resin used in slush molding. The polyurethane (urea) resin is preferably in powder form from the viewpoint of use in slush molding.

[0038] The additive for polyurethane (urea) resin of the present invention can be used by mixing with a powdered polyurethane (urea) resin.

[0039] The volume average particle size of the powdered polyurethane (urea) resin is preferably 1 to 700 μm, more preferably 10 to 500 μm, and most preferably 50 to 300 μm. When the volume average particle diameter of the urethane resin particles is 1 μm or more, the powder flowability is good, the moldability during slush molding is good, dust is less likely to be generated, and the working environment is good.When the volume average particle diameter of the urethane resin particles is 700 μm or less, leveling is good during slush molding, and pinholes are less likely to be generated on the mold surface. Here, the volume average particle size is the particle size of 50% undersieve measured by laser light scattering method. An example of the measuring device is Microtrac HRA particle size analyzer 9320-X100 (manufactured by Nikkiso Co., Ltd.).

[0040] The ratio of 90% particle size / 10% particle size of the powdered polyurethane (urea) resin is preferably 2.0 to 3.0. The ratio of 90% particle size / 10% particle size indicates the particle size distribution of the powdered polyurethane (urea) resin, and when it is in the above range, it is suitable for slush molding applications, there are fewer pinholes on the mold surface after slush molding, and the powder flowability is good, making a classification process unnecessary. Here, the 90% particle size / 10% particle size refers to the 90% particle size divided by the 10% particle size. The average particle size, 90% particle size, and 10% particle size can be measured using a laser diffraction particle size distribution measuring device [Microtrac MT3000II manufactured by Nikkiso Co., Ltd.], and the ratio of the 90% particle size / 10% particle size can be calculated.

[0041] The amount of the additive for polyurethane (urea) resin of the present invention added is preferably 3 to 150% by weight, and more preferably 5 to 80% by weight, based on the weight of the polyurethane (urea) resin, from the viewpoints of melting property and powder flowability.

[0042] If necessary, additives other than the additive for polyurethane(urea) resin of the present invention can be added to the polyurethane(urea) resin to which the additive for polyurethane(urea) resin of the present invention is added. As additives other than the additive for polyurethane (urea) resin of the present invention, fillers, antioxidants, pigments, mold release agents, etc. can be added.

[0043] Examples of the filler include inorganic fillers such as kaolin, talc, silica, titanium oxide, calcium carbonate, bentonite, mica, sericite, glass flakes, glass fibers, graphite, magnesium hydroxide, aluminum hydroxide, antimony trioxide, barium sulfate, zinc borate, alumina, magnesia, wollastonite, xonotlite, whiskers, and metal powder.

[0044] Examples of antioxidants include phenol-based (2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, etc.), bisphenol-based (2,2'-methylenebis(4-methyl-6-t-butylphenol) etc.), and phosphorus-based (triphenyl phosphite, diphenyl isodecyl phosphite, etc.).

[0045] As the pigment, for example, known organic pigments and / or inorganic pigments can be used. Examples of the organic pigment include insoluble azo pigments, soluble azo pigments, copper phthalocyanine pigments, quinacridone pigments, etc., and examples of the inorganic pigment include carbon black, chromates, ferrocyanide compounds, metal oxides, selenium sulfide compounds, metal salts (sulfates, silicates, carbonates, phosphates, etc.), metal powders, etc.

[0046] As the release agent, known release agents can be used, and examples thereof include fluorine-based release agents (fluoroalkyl ester phosphoric acid, etc.), silicon-based release agents (dimethylpolysiloxane, amino-modified dimethylpolysiloxane, carboxyl-modified dimethylpolysiloxane, ether-modified dimethylpolysiloxane, etc.), fatty acid ester-based release agents (alkane (having 11 to 24 carbon atoms) acid alkenyl (having 6 to 24 carbon atoms) esters, etc.), and phosphate-based release agents (tributyl ester phosphoric acid, etc.).

[0047] The amount of additives other than the additive for polyurethane (urea) resin of the present invention added is preferably 0 to 50% by weight, more preferably 0 to 35% by weight, based on the weight of the polyurethane (urea) resin.

[0048] As a mixing device used when adding and mixing the polyurethane (urea) resin additive of the present invention and additives other than the polyurethane (urea) resin additive of the present invention to a powdered polyurethane (urea) resin, a known powder mixing device can be used, and any of a container rotation type mixer, a fixed container type mixer, and a fluid motion type mixer can be used. For example, as a fixed container type mixer, a method of dry blending using a high-speed fluid type mixer, a double-shaft paddle type mixer, a high-speed shear mixer (HENSIEL MIXER (registered trademark), etc.), a low-speed mixer (planetary mixer, etc.), or a conical screw mixer (NAUTA MIXER (registered trademark), etc.) is well known. Among these methods, it is preferable to use a double-shaft paddle type mixer, a low-speed mixer (planetary mixer, etc.), and a conical screw mixer (NAUTA MIXER (registered trademark, omitted below), etc.).

[0049] The powdered polyurethane(urea) resin composition obtained by mixing the additive for polyurethane(urea) resin of the present invention with a powdered polyurethane(urea) resin can be molded, for example, by a slush molding method, to produce, for example, automotive interior parts such as instrument panels and door trims, home appliance parts, toys, miscellaneous goods, and the like. EXAMPLES

[0050] The present invention will be further described below with reference to examples, but the present invention is not limited to these. In the examples, parts represent parts by weight, and % represents % by weight.

[0051] <Production Example 1> (1) <Production of polycondensation product (B) of 1,4-butanediol and adipic acid> In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 65.6 parts by weight of adipic acid and 49.7 parts by weight of 1,4-butanediol were placed and reacted for 5 hours under a nitrogen stream at 210°C while distilling off the water generated, and then reacted under a reduced pressure of 5 to 20 mmHg to take out a polycondensate (B) of 1,4-butanediol and adipic acid. The hydroxyl value of the resulting (B) was measured, and the number average molecular weight was calculated to be 950. The hydroxyl value was measured by the method specified in JIS K 0070 (1995 edition).

[0052] (2) <Production of prepolymer solution (S)> A reaction vessel equipped with a thermometer, a stirrer, and a nitrogen inlet tube was charged with 54.8 parts by weight of polyester diol (B), 1.6 parts by weight of 1,6-hexanediol, 1.1 parts by weight of benzyl alcohol, 1.6 parts by weight of kaolin, 3.8 parts by weight of a heat stabilizer ("Irganox 1010" manufactured by BASF Japan Ltd.), and 19.9 parts by weight of MEK (methyl ethyl ketone). After replacing with nitrogen, the mixture was heated to 90°C with stirring to melt, and then cooled to 60°C. Subsequently, 18.7 parts by weight of hexamethylene diisocyanate was added and reacted at 85° C. for 6 hours to obtain 90.0 parts by weight of urethane prepolymer (S).

[0053] (3) <Production of polyurethane urea resin composition (P)> A reaction vessel was charged with 142.1 parts by weight of an aqueous solution prepared by dissolving 5.3 parts by weight of a dispersant ("Sunspearl PS-8" manufactured by Sanyo Chemical Industries, Ltd.) in 136.8 parts by weight of water, and 33.4 parts by weight of MEK, and mixed uniformly at 20°C. After that, 3.0 parts by weight of isophoronediamine was added while stirring at a peripheral speed of 23 m / s (rotation speed: 10,000 rpm) using an Ultra Disperser manufactured by Yamato Scientific Co., Ltd., and mixed for 1 minute. While continuing the stirring, 90 parts by weight of the urethane prepolymer solution (S) produced above, which had been adjusted to a temperature of 75°C, was then added and mixed, and similarly mixed for 2 minutes at a peripheral speed of 23 m / s. The resulting mixture was transferred to a reaction vessel equipped with a thermometer, a stirrer, and a nitrogen inlet tube, and after replacing with nitrogen, the mixture was reacted at 50°C for 10 hours while stirring. After completion of the reaction, the mixture was filtered and dried to obtain 66.5 parts by weight of a powdered polyurethane urea resin composition (P). The resulting powdered polyurethane The urea resin composition (P) had a urea group concentration of 2.6% by weight, a sum of the urethane group concentration and the urea group concentration of 11.5% by weight, a melting point of 190°C, a glass transition temperature of -35°C, a volume average particle diameter of 210 μm, and a ratio of 90% particle diameter / 10% particle diameter of 2.7.

[0054] <Melt point measurement> Using a Shimadzu CFT-500 flow tester, the temperature was raised at a constant rate under the following conditions, and the melting point was determined as the temperature at which the outflow amount was reduced to half. Load capacity: 5kg Die: 0.5mmΦ-1mm Heating rate: 5℃ / min.

[0055] <Measurement of glass transition temperature (Tg)> Measurements were performed using a differential scanning calorimeter (Seiko Instruments Inc., "RDC220 Robot DSC") under the following conditions. Measurement conditions: Sample amount 5 mg. (1) The temperature is increased from -100°C to 100°C at a rate of 20°C / min, and then held at 100°C for 10 minutes. (2) Cool from 100°C to -100°C at a rate of -90°C / min, then hold at -100°C for 10 minutes. (3) Heat the sample from -100°C to 100°C at a rate of 20°C / min. Analysis method: Calculate Tg from the DSC curve during the second heating.

[0056] <Examples 1 to 2, Comparative Examples 1 to 3> In a reaction vessel equipped with stirring and a Dean / Stark apparatus, the diol (a), benzoic acid, potassium titanium oxalate, and xylene in the weight parts shown in Table 1 were placed, and the temperature was raised to 200° C. while flowing nitrogen into the liquid in the reaction vessel. Thereafter, the esterification reaction step was carried out by reacting at 200° C. for 20 hours while removing the generated water from the system. The acid value of the resulting reaction product was measured, and sodium hydroxide in the weight parts shown in Table 1 was added as a neutralizing agent, followed by stirring at 60° C. for 1 hour to carry out a neutralization step. Next, an acid adsorbent [Kyoward 600, manufactured by Kyowa Chemical Industry Co., Ltd.] was added and the mixture was stirred at 60°C for 2 hours to carry out the adsorption process, followed by filtration and a purification process. Furthermore, a solvent distillation process was carried out to distill off xylene under a reduced pressure of 3 kPa at 125°C for 12 hours. After distilling off the xylene, the solution was cooled to 60 degrees and then filtered to obtain additives for polyurethane (urea) resins (X-1) to (X-2) and (Comparative X-1) to (Comparative X-3) according to Examples 1 to 2 and Comparative Examples 1 to 3. The obtained polyurethane (urea) resin additives (X-1) to (X-2) and (Comparative X-1) to (Comparative X-3) were analyzed by high performance liquid chromatography, and it was found that the compounds represented by formula (1) and formula (2) were contained in the ratios shown in Table 1.

[0057] <High performance liquid chromatography measurement conditions> Hitachi High-Technologies Corporation LaChrom7000 Developing solvent: methanol / water / sodium perchlorate = 87 / 10 / 3 (weight ratio) Column: GL Sciences Inertsil Ph-3 Column temperature: 40℃ Flow rate: 1.0mL / min Detector: UV detector (254 nm)

[0058] 100 parts by weight of powdered polyurethane urea resin (P) and 12.5 parts by weight of a colorant dispersion obtained by dispersing 2.5 parts by weight of carbon black as a colorant in 10 parts by weight of the obtained polyurethane (urea) resin additives (X-1) to (X-2) and (Comparative X-1) to (Comparative X-3) were added to a Henschel mixer and stirred at 700 rpm for 1 minute. The mixture was then transferred to a Nauta mixer and mixed at 70° C. with stirring for 4 hours. Furthermore, 0.06 parts by weight of dimethylpolysiloxane ("Kei L45-10000" manufactured by Nippon Unicar Co., Ltd.) was added as a release agent, mixed for 1 hour, and then cooled to room temperature to obtain powdered polyurethane urea resin compositions (P-1) to (P-2) and (Comparative P-1) to (Comparative P-3). The obtained polyurethane urea resin compositions (P-1) to (P-2) and (Comparative P-1) to (Comparative P-3) were evaluated according to the following evaluation methods. The results are shown in Table 2.

[0059] <Creating the epidermis> The powdered polyurethane urea resin composition was filled into a Ni electroforming mold with a grained pattern that had been preheated to 230°C, and after 10 seconds, the excess powdered polyurethane urea resin composition was discharged. After 60 seconds, the molded skin (thickness 1 mm) was prepared by cooling with water. The molded skin was evaluated for fogging resistance, heat resistance appearance, and melting property.

[0060] <Evaluation of fogging resistance> Using equipment conforming to the ISO6452 standard, a test sample of the molded product (a circle with a diameter of 8 cm cut out from a molded skin with a thickness of 1 mm) was placed in a glass container heated to 100°C, and a glass plate with a temperature controlled at 40°C was placed in the upper opening, and a fogging test was carried out for 20 hours. Next, the glass haze (HAZE) of the glass plate after the test was measured using NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd.

[0061] <Evaluation of heat resistance appearance> The obtained epidermis was cut into a piece measuring 15 cm length x 15 cm length, and the gloss was measured (K1). Next, the skin was kept in a circulating air dryer at 90° C. for 24 hours. The gloss of the skin was measured (K2). The gloss was measured using a gloss meter (Portable Gloss Meter GMX-202: manufactured by Murakami Color Research Laboratory). The smaller the change in gloss calculated by the following formula (1), the more excellent the heat resistant appearance. (Heat-resistant appearance) = Gloss value (K2) - Gloss value (K1)

[0062] <Melting property> (Evaluation of plasticity at low temperatures) The center of the back surface of the molded skin was visually observed, and the melting property was evaluated on a 5-point scale according to the following criteria. <Judgment criteria> 5: Uniform and shiny. 4: There is some unmelted powder, but it is glossy. 3: The entire back surface is uneven and has no gloss. There are no pinholes penetrating the surface. 2: There are powder-shaped bumps all over the back surface, and there are pinholes that penetrate to the surface. 1: The powder does not melt and a molded product is not formed. ×: Excessive melting prevents formation of a molded skin.

[0063] [Table 1]

[0064] [Table 2]

[0065] The results in Table 2 show that the molded articles of the polyurethane urea resin compositions (P) of Examples 1 and 2 are excellent in plasticity, fogging resistance and heat-resistant appearance. [Industrial Applicability]

[0066] A polyurethane (urea) resin molded product using the polyurethane (urea) resin additive obtained by the present invention has excellent plasticity, fogging resistance, and heat-resistant appearance, and can therefore be suitably used in the production of, for example, automobile interior parts such as instrument panels and door trims, home appliance parts, toys, miscellaneous goods, etc.

Claims

[Claim 1] The present invention includes a compound represented by the following general formula (1) and a compound represented by the following general formula (2), A method for producing an additive for a polyurethane(urea) resin, which contains 94 to 98% by weight of a compound represented by the following general formula (1) and 2 to 6% by weight of a compound represented by the following general formula (2), based on the total weight of a compound represented by the following general formula (1) and a compound represented by the following general formula (2), the method comprising an esterification step of subjecting a diol (a) and a benzoic acid to an esterification reaction, wherein the content of an esterification catalyst in the step is 0.22 to 0.28 mol % relative to the total number of carboxyl groups in the benzoic acid. R １ -COO-(EO)n-CO-R ２ (1) (In formula (1), R １ and R ２ represents a benzene ring, EO represents an oxyethylene group, and n represents the average number of moles added, which is a number from 4 to 20. ( ３ ________________________________ (In formula (2), R ３ represents a benzene ring, EO represents an oxyethylene group, and m represents the average number of moles added, which is a number from 4 to 20.

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