KR100508655B1 - Thermoplastic polyurethane epidermal material consisting of polyester polyol including ether and method for producing the thermoplastic polyurethane epidermal material, and form utilizing the material - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic polyurethane skin comprising an ether-containing polyester polyol, a method for producing the same, and a molded article using the same, and in particular, an ether-containing poly suitable for an instrument panel of a vehicle requiring high durability, such as high heat resistance and light resistance. To manufacture and apply a thermoplastic polyurethane molded article made of an ester polyol, through this, it is possible to provide a molded article excellent in durability, such as heat aging resistance, light resistance, chemical resistance.

Description

Thermoplastic polyurethane epidermal material consisting of polyester polyol including ether and method for producing the thermoplastic polyurethane epidermal material, and form utilizing the material}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic polyurethane skin comprising an ether-containing polyester polyol, a method for producing the same, and a molded article using the same, and in particular, an ether-containing polyester suitable for an instrument panel of a vehicle requiring high durability, such as high heat aging resistance and light resistance. In order to manufacture and apply a thermoplastic polyurethane molded article made of a polyol, it is possible to provide a molded article excellent in durability, such as heat aging resistance, light resistance, chemical resistance.

In general, the skin material for the instrument panel (instrument panel) is required to be durable, such as heat aging resistance, light resistance, and polyvinyl chloride (PVC) has been widely used for these various performance requirements.

Such a method for forming the skin material for an instrument panel of a vehicle is largely divided into a pad type in which polyurethane foam is attached to the pad material and a non-pad type by injection molding.

First, the pad type is composed of a core material, a pad material and a skin material, and the core material mainly forms a core part of a material having excellent mechanical properties such as a metal plate, and serves to strengthen the mechanical properties of the entire molded product.

In addition, the pad material is mainly cushioning function, such as polyurethane foam, it is wrapped in the skin material to absorb the impact from the outside, and to perform a function that gives a soft feeling.

In addition, the skin member constitutes the outermost part of the molded article as described above, and directly contacts the skin of the user, thereby performing a function of improving aesthetics and feel by the designer.

In particular, the pad type skin material is largely manufactured by a vacuum molding method and a powder slush molding (PSM) method, and the vacuum molding method is performed by heating a resin extruded in a sheet state before molding in a mold by vacuum. Cooling and demolding

On the other hand, the PS method is a method of cooling and solidifying the metal mold and the powder containing the resin powder is shaken and rotated to melt the powder in the mold, and then cooled and solidified.

Therefore, the above-mentioned PS method has the advantage of being able to faithfully transfer the design shape and the embossing as compared to the vacuum molding method, and the situation in which a molded product produced through the PS method is mainly applied to the instrument panel of a high-grade vehicle.

As a result of analysis of 77 types of skin materials for North American vehicle instrument panel as of 2001, the most common type of pad type skin material is polyvinyl chloride molded by PS method and polyvinyl chloride molded by vacuum molding method. to be.

Therefore, there is a demand for development of a skin material which can be recycled in the future, produce a new skin material which is not only superior in sensibility quality but also excellent in heat resistance and durability, and can be applied to a molded article such as an instrument panel of a vehicle.

However, polyvinyl chloride has a weak heat resistance, it is difficult to apply a built-in type airbag, there was a technical problem that the use of dioxin is detected when incineration is expected to be used.

The present invention is to solve the above problems, by applying a thermoplastic polyurethane made of ether-containing polyester polyol with improved durability to the skin material of the vehicle instrument panel, molded articles excellent in durability, such as heat aging resistance, light resistance, chemical resistance To provide a thermoplastic polyurethane skin material consisting of an ether-containing polyester polyol, and a method for producing the same and a molded article using the same.

The thermoplastic polyurethane skin material composed of the ether-containing polyester polyol of the present invention comprises diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate or a mixture of two or more thereof. 15 to 60 wt% isocyanate compound selected from the mixtures; 40 to 80% by weight polyfunctional carboxylic acid compound selected from adipic acid, seric acid, abel acid, azelic acid, sebacic acid, dodecanedioic acid, trimeric acid or a mixture consisting of two or more thereof, 1, The hydroxyl value of the polyfunctional alcohol compound selected from diols, such as 4-butylene glycol, ethylene glycol, butanediol, and hexanediol, and triols, such as trimethylol propane, or mixtures of 2 or more of these, is 561.0-56.1 30 to 70 wt% of an ether-containing polyester polyol having a hydroxyl value of 224.11 to 11.22 mgKOH / g by mixing and reacting 20 to 100 wt% of polytetramethylene ether glycol having a mgKOH / g; Selected from diols such as 1,4-butylene glycol, ethylene glycol, diethylene glycol, butanediol and hexanediol, triols such as trimethylolpropane, polytetramethylene ether glycol or a mixture of two or more thereof 5 to 40% by weight of a chain extender; Antioxidants such as p-crasol reaction probes containing dicyclopentadiene and isobutylene, beads sebacate, tetrakis methane, N- (4-isoxylcarbonylphenyl) -N'-phenylformimedine, UV It is achieved by making up from 0.5 to 10% by weight of an additive selected from stabilizers or mixtures of two or more of these.

In addition, the thermoplastic polyurethane skin material manufacturing method of the ether-containing polyester polyol of the present invention is 30 to 70% by weight of the ether-containing polyester polyol and 5 to 40% by weight of the chain extender 1 to 10 at 30 to 100 ℃ A first mixing step of mixing with stirring for a minute; Adding a 15 to 60 wt% isocyanate compound to the mixture obtained in the first mixing step and mixing the mixture at a speed of 300 to 1,000 rpm for 1 to 10 minutes; A aging step of aging the product obtained in the second mixing step for 1 to 48 hours at a temperature range of 60 to 140 ℃; A grinding step of grinding the product obtained in the aging step at a temperature of 0 ° C. or less; A third mixing step of adding an additive consisting of 0.5 to 10 wt% of an antioxidant or a UV stabilizer to the milled product obtained in the milling step; It is achieved by the extrusion step of extruding the product obtained in the third mixing step at a temperature range of 150 to 300 ℃.

An embodiment of the present invention and its operation will be described in detail as follows.

Thermoplastic polyurethane skin materials composed of ether-containing polyester polyols of the present invention include diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate, and dicyclo 15 to 60% by weight isocyanate compound selected from hexyl methane diisocyanate (H12MDI; dicyclohexylmethane diisocyanate), isophorone diisocyanate (IPDI) or a mixture consisting of two or more thereof; Adipic acid, sbelic acid, abelic acid, azelic acid, sebacic acid, dodecandioic acid, trimeric acid Or 40 to 80% by weight of a polyfunctional carboxylic acid compound selected from a mixture consisting of two or more of these, 1,4-butylene glycol, ethylene glycol, butane diol, and hexanediol ( 20 to a hydroxyl value of a polyfunctional alcohol compound selected from a diol such as hexane diol), a triol such as trimethylol propane, or a mixture consisting of two or more thereof, of 561.0 to 56.1 mg KOH / g 30 to 70% by weight of an ether-containing polyester polyol having a hydroxyl value of 224.11 to 11.22 mgKOH / g by mixing and reacting 100% by weight of polytetramethylene ether glycol (PTMG); Selected from diols such as 1,4-butylene glycol, ethylene glycol, diethylene glycol, butanediol and hexanediol, triols such as trimethylolpropane, polytetramethylene ether glycol or a mixture of two or more thereof 5 to 40% by weight of a chain extender; P-cresol reaction prods, with dicyclopentadiene and isobutylene, and biscebacate (bis (1,2,2,6,6-pentamethyl-4-piperinyl), including dicyclopentadiene and isobutylene sebacate), TETRAKIS (METHYLENE (3.5-DI-TERT BUTYL-4-HYDROXY-HYDROCINNAMATE)] METHANE), N- (4-Esoxylcarbonylphenyl) -N'-phenylformimedine (N) The technical basic feature consists of 0.5 to 10% by weight of an additive selected from an antioxidant such as-(4-Ethoxylcarbonylphenyl) -N'-Phenylformamidine), a UV stabilizer or a mixture consisting of two or more thereof.

The isocyanate compound may be used in the same or similar to those used in the production of a conventional polyurethane, preferably an aromatic isocyanate, aliphatic isocyanate or alicyclic isocyanate.

In this case, the ether-containing polyester polyol is a mixture of the polyfunctional carboxylic acid compound, the polyfunctional alcohol compound and polytetramethylene ether glycol and heated to 140 to 160 ℃ at room temperature, 150 ℃ which is the first elevated temperature At about 60 to 120 minutes, and then again at 150 ° C. to 210 to 230 ° C., at a secondary elevated temperature at 220 ° C. for about 10 to 120 minutes, at 650 to 760 mmHg vacuum at the secondary elevated temperature. After the application, when the acid value is 1 mgKOH / g or less, the reaction is terminated to obtain a hydroxyl value of 224.11 to 11.22 mgKOH / g.

And, the thermoplastic polyurethane skin material manufacturing method consisting of ether-containing polyester polyol, stirring 30 to 70% by weight of ether-containing polyester polyol and 5 to 40% by weight of the chain extender at 30 to 100 ℃ 1 to 10 minutes Primary mixing step of mixing while mixing; Adding a 15 to 60 wt% isocyanate compound to the mixture obtained in the first mixing step and mixing the mixture at a speed of 300 to 1,000 rpm for 1 to 10 minutes; A aging step of aging the product obtained in the second mixing step for 1 to 48 hours at a temperature range of 60 to 140 ℃; A grinding step of grinding the product obtained in the aging step at a temperature of 0 ° C. or less; A third mixing step of adding an additive consisting of 0.5 to 10 wt% of an antioxidant or a UV stabilizer to the milled product obtained in the milling step; It is a technical feature that consists of an extrusion step of extruding the product obtained in the third mixing step at a temperature range of 150 to 300 ℃.

Therefore, the thermoplastic polyurethane skin material manufacturing method of the ether-containing polyester polyol of the present invention configured as described above, firstly mixing the ether-containing polyester polyol and the chain extender evenly in the first mixing step, the second mixing step In the polyurethane is prepared by substantially mixing the isocyanate compound in the mixture produced in the first mixing step.

At this time, the isocyanate compound and the ether-containing polyester polyol were observed to react rapidly in the aging step immediately after mixing, and in particular, the polyurethane molecular weight as a reaction product obtained by aging the polyurethane as a reaction product obtained in the second mixing step. Etc. can be adjusted.

Then, the polyurethane as the reaction product can be adjusted to an appropriate size, etc. through a known third mixing step, grinding and extrusion step, such as pellets that can be processed into products by such a grinding and extrusion process To be molded.

In addition, the molded article using the thermoplastic polyurethane skin material which consists of ether containing polyester polyol is diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, isophorone diisocyanate, or two or more of these. 15 to 60% by weight of isocyanate compound selected from the mixture consisting of a mixture; 40 to 80% by weight polyfunctional carboxylic acid compound selected from adipic acid, seric acid, abel acid, azelic acid, sebacic acid, dodecanedioic acid, trimeric acid or a mixture consisting of two or more thereof, 1, The hydroxyl value of the polyfunctional alcohol compound selected from diols, such as 4-butylene glycol, ethylene glycol, butanediol, and hexanediol, and triols, such as trimethylol propane, or mixtures of 2 or more of these, is 561.0-56.1 30 to 70 wt% of an ether-containing polyester polyol having a hydroxyl value of 224.11 to 11.22 mgKOH / g by mixing and reacting 20 to 100 wt% of polytetramethylene ether glycol having a mgKOH / g; Selected from diols such as 1,4-butylene glycol, ethylene glycol, diethylene glycol, butanediol and hexanediol, triols such as trimethylolpropane, polytetramethylene ether glycol or a mixture of two or more thereof 5 to 40% by weight of a chain extender; Antioxidants such as p-crasol reaction probes containing dicyclopentadiene and isobutylene, beads sebacate, tetrakis methane, N- (4-isoxylcarbonylphenyl) -N'-phenylformimedine, UV A skin material comprising 0.5 to 10% by weight of an additive selected from a stabilizer or a mixture consisting of two or more thereof; A core material made of a material having excellent mechanical properties such as a metal plate to reinforce mechanical properties; It consists of a pad material made of a cushioning material such as polyurethane foam to surround the skin material and absorb shock from the outside is a technical feature of the technology.

Examples of the thermoplastic polyurethane skin material consisting of the ether-containing polyester polyol of the present invention as described above and a manufacturing method thereof and the comparative examples produced in the prior art will be described separately by describing experimental results through experimental examples. same.

Example

49.6 kg of adipic acid, which is a polyfunctional carboxylic acid compound, 22.0 kg of 1,4-butylene glycol, which is a polyfunctional alcohol compound, and 40.7 kg of polytetramethylene ether glycol having a hydroxy value of 448.8 mgKOH / g are mixed, and at room temperature. After the temperature was raised to 150 ° C., the temperature was maintained at 150 ° C., which is the primary temperature riser, for about 90 minutes. After application to a vacuum of 720 mmHg at an elevated temperature, when the acid value is 1 mgKOH / g or less, the reaction is terminated to prepare an ether-containing polyester polyol having a hydroxyl value of 12.2% of condensation and a hydroxyl value of 74.8 mgKOH / g. It was.

In the first mixing step, 6 kg of 1,4-butylene glycol as a chain extender was stirred at 60 ° C. for 3 minutes to 61 kg of the ether-containing polyester polyol, and 43 kg of hexamethylene diisocyanate, an isocyanate compound, was added in the second mixing step. After mixing for 3 minutes at a speed of 500rpm to obtain a polymer, in the aging step, the polymer was aged at 80 ℃ for 8 hours.

Subsequently, in the crushing step, the polymer is pulverized at a temperature of 0 ° C. or less to form flakes, and in the third mixing step, p-crack containing dicyclopentadiene and isobutylene as additives to 100 kg of the crushed chips. 1 kg of Razole reaction probes, beads sebacate, tetrakis methane, and N- (4-isoxylcarbonylphenyl) -N'-phenylformimidine were added and mixed, and then extruded at 180 ° C in an extrusion step. Molded into pellets in ground form.

Subsequently, a molded article composed of a core material, a pad material and a skin material was prepared according to the known PSM method using the pellet-type thermoplastic polyurethane obtained above, and a part thereof was taken as a sample.

Comparative Examples 1 to 4

In Comparative Examples 1 to 4, a part of the currently available instrument panel was taken as a sample.

In Comparative Example 1, a part of a molded article manufactured according to the known PS method was taken as a sample using polyvinyl chloride of Hanwha Co., Ltd. as a skin material, and as Comparative Example 2, polyvinyl chloride / ABS of LG Chem. A part of the molded article manufactured by the well-known vacuum molding method was taken as a sample using resin (acrylonitrile-butadiene-styrene copolymer) as a skin material.

In Comparative Example 3, a part of the molded article manufactured according to a known vacuum molding method using thermoplastic olefin of LG Chemical Co., Ltd. as a skin material was taken as a sample. A part of the molded article manufactured by the well-known PSM method was taken as a sample using the well-known thermoplastic polyurethane which consists of ester as a skin material.

Experimental Example 1

Measurement of specific gravity

Specific gravity was measured by the underwater substitution method according to the method specified in ASTM D 792, the results are shown in Table 1 below.

Experimental Example 2

Tensile Strength Measurement

Tensile strength was measured using the MTS 1 ton universal testing machine according to the method specified in Clause 3 of JIS K 6301, and the results are shown in Table 1 below, wherein the specimen is a dumbbell No. 1 type, tensile The speed was 200 m / min.

Experimental Example 3

Measurement of surface hardness

Surface hardness was measured by using the Shore hardness tester Form A according to the method specified in ASTM D 2240, the hardness in the initial compression state, the results are shown in Table 1 below.

Experimental Example 4

Measurement of heat aging resistance

The heat aging resistance was measured by using a well-known Miniscan XE plus color difference meter after aging at 120 ° C. for 500 hours using a thermo-hygrostat of Denshoku Co., Ltd., Japan. Shown in

Experimental Example 5

Measurement of light resistance

Light resistance is achieved using an accelerated light resistance tester, the Atlas Ci 65 Xenon Arc Weather-O-meter and the Q-UV Weather-O-meter. The color difference of the sample was measured, and the results are shown in Table 1 below.

At this time, the test conditions of the xenon arc weather-o-meter was a phase wavelength of 340nm, the light intensity 53W / ㎡, the temperature of the blackboard was tested for 100 hours under the condition of 89 ℃, Q-WEB weather-o-meter is F- Light by 40 (FS-40) fluorescent solar lamp is 280 ~ 350nm of ultraviolet energy, and the lamp capacity is 40W × 8, 102V (0.43A), and the distance from the sample is fixed at 50mm. The temperature of was tested 250 hours on 60 degreeC conditions.

division Example Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 importance 1.10 1.20 1.28 0.92 1.08 Tensile strength (kgf / cm ² ) 135 122 148 100 70 Surface Hardness (Shore A) 77 78 94 76 78 Heat aging resistance (ΔE) Skin 0.62 0.4 0.4 1.2 2.8 Skin + Pad 0.82 1.0 1.3 1.1 3.1 Light resistance (ΔE) Skin 0.3 0.8 0.3 0.4 2.08 Skin + Pad 0.6 1.2 0.3 1.1 1.5

As shown in Table 1, in the case of heat aging resistance, in general, the solar irradiation amount in the instrument panel of the vehicle is very large compared to other parts, resulting in a rapid increase in the vehicle interior temperature, resulting in a change in the polymer structure and deterioration ( As degradation occurs, heat resistance in the instrument cluster is one of the most important durability performances directly related to merchandise.

The general standard in the automobile company for the color difference is ΔE value of 3 or less, Comparative Example 1 to Comparative Example 3 and the embodiment according to the present invention was confirmed that the value of 3 or less, only, Comparative Example 4 In the case of, it was confirmed that only 3 values were satisfied.

In the case of the skin material with a polyurethane pad, the aspect is different. The polyvinyl chloride-based material rapidly increases yellowing by reaction with an amine group migrated in the polyurethane pad in a high temperature atmosphere, whereas Comparative Example 3 and the present invention In the example according to the present invention, only a slight change was observed, and it was confirmed that yellowing due to migration or the like hardly occurred.

In the case of light resistance, similar results were confirmed.

As described above, the molded article using the thermoplastic polyurethane skin material consisting of the ether-containing polyester polyol according to the present invention in terms of heat resistance and light aging resistance is improved for heat, light aging resistance, chemical resistance, etc., which is optimal for instrument panels of vehicles. I could confirm that.

The present invention as described above is to apply a thermoplastic polyurethane made of ether-containing polyester polyol with improved durability to the skin material of the vehicle instrument panel, to provide a molded article excellent in durability, such as heat aging resistance, light resistance, chemical resistance will be.

Claims (4)

15 to 60% by weight isocyanate compound selected from diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate or a mixture consisting of two or more thereof; 40 to 80% by weight polyfunctional carboxylic acid compound selected from adipic acid, seric acid, abel acid, azelic acid, sebacic acid, dodecanedioic acid, trimeric acid or a mixture consisting of two or more thereof, 1, The hydroxyl value of the polyfunctional alcohol compound selected from diols, such as 4-butylene glycol, ethylene glycol, butanediol, and hexanediol, and triols, such as trimethylol propane, or mixtures of 2 or more of these, is 561.0-56.1 30 to 70 wt% of an ether-containing polyester polyol having a hydroxyl value of 224.11 to 11.22 mgKOH / g by mixing and reacting 20 to 100 wt% of polytetramethylene ether glycol having a mgKOH / g; Selected from diols such as 1,4-butylene glycol, ethylene glycol, diethylene glycol, butanediol and hexanediol, triols such as trimethylolpropane, polytetramethylene ether glycol or a mixture of two or more thereof 5 to 40% by weight of a chain extender; Antioxidants such as p-crasol reaction probes containing dicyclopentadiene and isobutylene, beads sebacate, tetrakis methane, N- (4-isoxylcarbonylphenyl) -N'-phenylformimedine, UV A thermoplastic polyurethane skin comprising an ether containing polyester polyol, characterized in that it comprises 0.5 to 10% by weight of an additive selected from stabilizers or mixtures of two or more thereof. The method of claim 1 wherein the ether containing polyester polyol is After mixing the polyfunctional carboxylic acid compound, the polyfunctional alcohol compound, and polytetramethylene ether glycol, the temperature is raised to 140 to 160 ° C. at room temperature, and then maintained at 150 ° C., which is the first elevated temperature, for about 60 to 120 minutes. Further, the temperature was raised to 210 to 230 ° C. at 150 ° C., and maintained at 220 ° C., which is the secondary temperature, for about 10 to 120 minutes. When the reaction is terminated, a thermoplastic polyurethane skin material comprising an ether-containing polyester polyol, characterized in that a hydroxyl value of 224.11 to 11.22 mgKOH / g is obtained. A first mixing step of mixing 30 to 70 wt% of the ether containing polyester polyol and 5 to 40 wt% of the chain extender while stirring for 1 to 10 minutes at 30 to 100 ° C .; Adding a 15 to 60 wt% isocyanate compound to the mixture obtained in the first mixing step and mixing the mixture at a speed of 300 to 1,000 rpm for 1 to 10 minutes; A aging step of aging the product obtained in the second mixing step for 1 to 48 hours at a temperature range of 60 to 140 ℃; A grinding step of grinding the product obtained in the aging step at a temperature of 0 ° C. or less; A third mixing step of adding an additive consisting of 0.5 to 10 wt% of an antioxidant or a UV stabilizer to the milled product obtained in the milling step; Method for producing a thermoplastic polyurethane skin material consisting of an ether-containing polyester polyol, characterized in that the extrusion step of extruding the product obtained in the third mixing step at a temperature range of 150 to 300 ℃. 15 to 60% by weight isocyanate compound selected from diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate or a mixture consisting of two or more thereof; 40 to 80% by weight polyfunctional carboxylic acid compound selected from adipic acid, seric acid, abel acid, azelic acid, sebacic acid, dodecanedioic acid, trimeric acid or a mixture consisting of two or more thereof, 1, The hydroxyl value of the polyfunctional alcohol compound selected from diols, such as 4-butylene glycol, ethylene glycol, butanediol, and hexanediol, and triols, such as trimethylol propane, or mixtures of 2 or more of these, is 561.0-56.1 30 to 70 wt% of an ether-containing polyester polyol having a hydroxyl value of 224.11 to 11.22 mgKOH / g by mixing and reacting 20 to 100 wt% of polytetramethylene ether glycol having a mgKOH / g; Selected from diols such as 1,4-butylene glycol, ethylene glycol, diethylene glycol, butanediol and hexanediol, triols such as trimethylolpropane, polytetramethylene ether glycol or a mixture of two or more thereof 5 to 40% by weight of a chain extender; Antioxidants such as p-crasol reaction probes containing dicyclopentadiene and isobutylene, beads sebacate, tetrakis methane, N- (4-isoxylcarbonylphenyl) -N'-phenylformimedine, UV A skin material comprising 0.5 to 10% by weight of an additive selected from a stabilizer or a mixture consisting of two or more thereof; A core material made of a material having excellent mechanical properties such as a metal plate to reinforce mechanical properties; Molded article using a thermoplastic polyurethane skin material consisting of an ether-containing polyester polyol, characterized in that the pad material is made of a cushioning material such as polyurethane foam to surround the skin material to absorb the impact from the outside.