KR101306611B1 - Thermoplastic polyurethane elastomer composition for vacuum forming and a method for preparing thereof - Google Patents

Abstract

The present invention relates to a polyurethane resin composition for vacuum molding and a method for producing the same, specific configuration of (A) 30 to 70 parts by weight of a polyfunctional carboxylic acid compound, 1,3-propanediol extracted from corn (1,3- PDO; 1.3-Propanediol) ether-containing polyester polyol 30 containing 5 to 30 parts by weight and 20 to 70 parts by weight of polytetramethylene ether glycol (PTMG) and having a hydroxyl value of 11.22 to 224.11 mgKOH / g To 70 parts by weight; (B) 15 to 60 parts by weight of the isocyanate compound; (C) 1 to 10 parts by weight of 2.1 to 12-valent hyperbranched polyol; And (D) 5 to 40 parts by weight of at least one chain extender selected from the group consisting of diols, triols, and polytetramethylene ether glycol; .
According to the present invention, it is excellent in calender formability, T-die extrudability, and blow moldability for Vacuum Forming Molding; Excellent physical properties such as surface feel, sheet formation, and dimensional stability; Excellent wear resistance, scratch resistance, surface precipitation (Blooming), chemical resistance, heat aging, light aging, hydrolysis resistance, etc., air bag deployment performance, anti-fogging, surface precipitation after water deposition, etc. It has excellent physical properties and eco-friendly advantages.

Description

Thermoplastic polyurethane elastomer composition for vacuum forming and a method for preparing Technical}

The present invention relates to a thermoplastic polyurethane resin composition for vacuum molding and a method for manufacturing the same. More particularly, by applying eco-friendly bioglycol, excellent low-temperature characteristics and long-term durability, and generation of volatile organic compounds (VOC) through unpainting The present invention relates to a thermoplastic polyurethane resin composition which ensures T-die molding using thermoplastic characteristics, which is an advantage of thermoplastic polyurethane materials, and imparts vacuum forming.

Vacuum moldable materials include PVC / ABS and thermoplastic polyolefin (TPO). The PVC / ABS contains a plasticizer and is vulnerable to long-term aging, and has a disadvantage in that it is impossible to implement invisible of the passenger seat airbag.

The TPO is made of a compound of ethylene-propylene rubber and polypropylene resin in a chip state, and is currently widely used. However, TPO has problems such as scratching, abrasion resistance, long-term durability during calendering, and it is necessary to apply oily primer on the upper and lower layers and to use a coating agent containing a solvent on the upper layer surface. And disadvantages that cause environmental problems.

Vacuum forming materials for the manufacture of automotive crash pads include calendar formability, T-die extrudability, and Blow moldability for forming sheets; Performances such as embossing power, gloss, and emotional quality as automotive skin coatings; And the absence of an unpleasant odor, anti-fogging, hydrolysis resistance, heat aging resistance, photo aging resistance, air bag deployment performance and the like.

Aliphatic isocyanates and aromatic isocyanate types are generally studied to develop materials that meet the properties required for automotive interior materials and are excellent in sheet molding. However, the aliphatic isocyanate has the disadvantage of satisfying mechanical properties but very poor sheet formability. The aromatic isocyanate type is excellent in vacuum forming but has high physical properties, making it difficult to have an invisible air bag and satisfying physical properties required for long-term durability. There is a disadvantage that can not be.

The present invention is to solve the problems of the prior art as described above, excellent in calender formability, T-die extrudability, and blow moldability for vacuum forming (Vacuum Forming Molding); Excellent physical properties such as surface feel, sheet formability and dimensional stability; It has excellent durability such as abrasion resistance, scratch resistance, surface precipitation resistance (Blooming), chemical resistance, heat aging, light aging and hydrolysis resistance; An object of the present invention is to provide an environmentally friendly vacuum-forming thermoplastic polyurethane and a method of manufacturing the same, having excellent properties such as airbag deployment performance, anti-fogging, and surface precipitation after water deposition.

According to the present invention,

(A) 30 to 70 parts by weight of the polyfunctional carboxylic acid compound, 5 to 30 parts by weight of 1,3-propanediol (1,3-PDO; 1,3-Propanediol) extracted from corn and polytetramethylene ether glycol (PTMG polytetramethylene ether glycol) comprising 30 to 70 parts by weight of an ether-containing polyester polyol having 20 to 70 parts by weight and having a hydroxyl value of 11.22 to 224.11 mgKOH / g; (B) 15 to 60 parts by weight of the isocyanate compound; (C) 1 to 10 parts by weight of 2.1 to 12-valent hyperbranched polyol; And (D) 5 to 40 parts by weight of at least one chain extender selected from the group consisting of diols, triols and polytetramethylene ether glycol; provides a thermoplastic polyurethane resin composition for vacuum molding.

Further, (A) 30 to 70 parts by weight of the polyfunctional carboxylic acid compound, 5 to 30 parts by weight of 1,3-propanediol extracted from corn and 20 to 70 parts by weight of polytetramethylene ether glycol, and mixed at 140 to room temperature The temperature is raised to 160 ° C. and then maintained for 60 to 120 minutes, followed by the temperature rise to 210 to 230 ° C., followed by 10 to 120 minutes, followed by application to a vacuum of 650 to 760 mmHg, with an acid value of 1 mgKOH / g or less during the vacuum application. 30 to 70 parts by weight of a corn extract propanediol-containing polyester polyol compound obtained by terminating the reaction when the reaction is completed; (B) 15 to 60 parts by weight of the isocyanate compound; (C) 1 to 10 parts by weight of 2.1 to 12-valent hyperbranched polyol; And (D) 5 to 40 parts by weight of at least one chain extender selected from the group consisting of diols, triols, and polytetramethylene ether glycol; It provides a method for producing a urethane resin composition.

Furthermore, the present invention provides a vacuum molding composite sheet made of the thermoplastic polyurethane resin composition for vacuum molding.

The thermoplastic polyurethane resin composition for vacuum molding of the present invention comprises (A) ether-containing polyester polyol, (B) isocyanate compound, (C) 2.1 to 12-valent hyperbranched polyol and (D) chain extender, It explains in detail one by one.

First, the (A) ether-containing polyester polyol occupies 30 to 70 parts by weight in the total composition, because such a problem occurs that the final physical properties of the seat required for automotive applications are not obtained.

The (A) ether-containing polyester polyol has a hydroxyl value of 11.22 to 224.11 mgKOH / g, 30 to 70 parts by weight of a polyfunctional carboxylic acid compound, 1,3-propanediol (1,3-PDO) extracted from corn 1,3-Propanediol) 5 to 30 parts by weight and 20 to 70 parts by weight of polytetramethylene ether glycol (PTMG).

At this time, when the hydroxyl value is less than 11.22 mgKOH / g, the viscosity is too low and the production reactivity is low, the problem of the termination of the reaction occurs, and if it exceeds 224.11 mgKOH / g, the molecular weight is too large and the viscosity is high, the pouring into the mold after the production reaction It is preferable to be within the range of 11.22 to 224.11 mgKOH / g because of a pouring problem.

In addition, the polyfunctional carboxylic acid compound is, for example, adipic acid (sadipic acid), sbelic acid (sbelic acid), abelic acid (abelic acid), azelic acid (azelic acid), sebacic acid (sebacic acid), Dodecandioic acid, trimeric acid and mixtures of two or more thereof may be selected, the content of which is preferably 30 to 70 parts by weight in the synthesis of polyol, if less than 30 parts by weight The viscosity of the polyol is too low, so it is difficult to increase the product viscosity in the future production and the property is too low. If the content exceeds 70 parts by weight, the viscosity is too high. Because there is a high problem.

In addition, the 1,3-propanediol (1,3-PDO; 1,3-Propanediol) extracted from the corn has a problem that the effect is insignificant if less than 5 parts by weight, if it exceeds 30 parts by weight of the molding thermoplastic polyurethane ( TPU) Since the heat resistance of the produced product tends to be lowered, it is preferably 5 to 30 parts by weight in polyol synthesis.

In addition, when the polytetramethylene ether glycol is less than 20 parts by weight, there is a problem of inferior hydrolyzability in the physical properties of the vehicle, and if it exceeds 70 parts by weight, there is a problem of adhesion between the automobile crash pad and the foam layer, and 20 to 70 parts by weight of the polyol synthesis It is preferable to exist in the range. The polytetramethylene ether glycol in the above (A) is characterized in that the hydroxyl value is 56.1 to 561.0 mgKOH / g.

In particular, the 1,3-propanediol is a glycol extracted from corn and has excellent low temperature properties, low properties, excellent stability and 100% recyclable to serve to make the thermoplastic polyurethane resin have a suitable physical properties for the vacuum molding crash pad. In other words, existing vacuum molding materials contain plasticizers, which are weak in long-term durability, and cannot realize invisibility of airbags.An oily primer is applied to upper / lower layers and a solvent-containing coating agent on the upper layer surface. There is a disadvantage in that cost increases and environmental problems. 1,3-propanediol extracted from corn is used to satisfy the performance of embossing, gloss, and emotional quality as well as the absence of unpleasant odors and anti-fogging.

Therefore, the thermoplastic polyurethane resin composition for vacuum molding of the present invention preferably contains 1,3-propanediol in the amount of 5 to 30 parts by weight in the synthesis of polyol, as described above, when included in less than 5 parts by weight. This is because the effect is inadequate, and when included in excess of 30 parts by weight, the heat resistance of the molding thermoplastic polyurethane product is reduced.

Next, the (B) isocyanate compound occupies 15 to 60 parts by weight of the total composition, but if less than 15 parts by weight, the viscosity is so low that the low reactivity in the production of the final product may cause a problem in the production of difficult products, 60 parts by weight This is because if the molecular weight is too high and the viscosity is high, it may cause a problem that it is difficult to purge the mold after the reaction. Such isocyanate compounds include diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI; hexamethylene diisocyanate), dicyclohexylmethane diisocyanate (H ₁₂ MDI; It is preferably selected from the group consisting of dicyclohexylmethane diisocyanate) and isophorone diisocyanate (IPDI).

Next, the (C) 2.1 to 12-valent hyperbranched polyol occupies 1 to 10 parts by weight of the total composition, but less than 1 part by weight is difficult to form a vacuum due to sagging by heat during the automobile crash pad vacuum molding, 10 parts by weight This is because crosslinking during the extrusion of the product, ie, uneven workability, results in uneven sheet surface.

Next, the (D) chain extender occupies 5 to 40 parts by weight of the total composition, if less than 5 parts by weight is too low physical properties and difficult to terminate the production reaction, if exceeding 40 parts by weight to the car crash pad This is because a problem that is difficult to apply due to higher than desired physical properties occurs. The chain extender is at least one selected from the group consisting of diols, triols, and polytetramethylene ether glycol, and examples of the diols include ethylene glycol, diethylene glycol, Butanediol and hexanediol can be mentioned, The triols include trimethylol propane.

The ether-containing polyester polyol is a mixture of the polyfunctional carboxylic acid compound, 1,3-propanediol and the polytetramethylene ether glycol, and after the temperature is raised to 140 to 160 ℃ at room temperature, the first elevated temperature (preferably Is maintained at 150 ° C.) for about 60 to 120 minutes, and then heated up to 210 to 230 ° C., and then maintained at a secondary elevated temperature (preferably 220 ° C.) for 10 to 120 minutes, and then at the secondary holding temperature. After application to a vacuum of 650 to 760 mmHg, it can be prepared having a hydroxyl value of 11.22 to 224.11 mgKOH / g by terminating the reaction when the acid value is 1 mgKOH / g or less.

If the above temperature rise temperature and holding time are not obtained, polyol synthesis is not achieved and polyol of physical properties necessary for product production cannot be obtained. Especially, since acid value does not fall well, when the product of high acid value is applied, the reactivity is poor during product synthesis. The production of the product is difficult, especially the physical properties of the final product is significantly reduced.

The thermoplastic polyurethane including the glycol-containing polyester polyol extracted from the corn is 30 to 70 parts by weight of the ether-containing polyester polyol, 1 to 10 parts by weight of the 2.1 to 12-valent hyperbranched polyol and 5 to 40 parts by weight of the chain extender. A first mixing step of mixing with stirring at 100 ° C. for 1 to 10 minutes; 15 to 60 isocyanate in the mixture obtained in the first mixing step Adding a part by weight and mixing the mixture at a speed of 300 to 1,000 rpm for 1 to 10 minutes; 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; And an extrusion step of extruding the pulverized product obtained in the crushing step at a temperature range of 150 to 300 ℃.

The temperature in the first mixing step is 30 to 100 ℃, because it is difficult to synthesize the polyurethane and the desired physical properties out of this temperature range. It is preferable to stir at this temperature for 1 to 10 minutes, but if the stirring time is too small, the synthesis is not well achieved and the desired physical properties are difficult to obtain, and if stirring for too long, the polyol temperature is lowered and thus it is difficult to synthesize the product. do.

The secondary mixing step is to prepare a polyurethane by mixing isocyanate compounds and glycol-containing polyester polyols extracted from corn, which are mixed at a speed of 300 to 1,000 rpm for 1 to 10 minutes. This is because too low a rate may delay the reaction, while a too fast rate may cause an instant reaction so that the polymer is not sufficiently arranged and the reaction is terminated.

The aging step is aged for 1 to 48 hours in the temperature range of 60 to 140 ℃, because the physical properties of the polymerized product at the temperature and time within this range shows the best results.

The grinding step is carried out at a temperature of 0 ° C or less, because at the temperature of 0 ° C or more, the polymerization products stick together.

The extrusion step is carried out at 150 to 300 ° C, because it shows the best workability, the product visual state and the physical properties of the final product within the above range, too low temperature does not melt during extrusion, there is work difficulties, too This is because the product flows and carbonizes when it is high.

It was observed that the isocyanate compound and the glycol-containing polyester polyol extracted from the corn reacted rapidly immediately after mixing. In particular, the molecular weight of the polyurethane as a reaction product obtained by aging the polyurethane as a reaction product obtained in the second mixing step can be adjusted. Then, the polyurethane as the reaction product can be adjusted to an appropriate size and the like through known grinding and extrusion processes. It is also molded into pellets that can be processed into products by grinding and extrusion processes.

The thermoplastic polyurethane resin composition of the present invention may further include 5 to 10 parts by weight of the external lubricant and 1 to 5 parts by weight of the internal lubricant in order to improve blocking resistance and smoothness during calender and T-die extrusion. Although not limited thereto, it is preferable to use a reactive silicone having a bi-functional hydroxy group as used in the following examples as the internal lubricant, and partially saponified montan ester wax type lubricant as the external lubricant. It is preferable to use saponified montanic ester wax. In addition, it is not preferable because an additive appears on the surface during the water immersion blooming test when the application exceeds the content range.

The present invention also relates to a vacuum molding sheet manufactured from the above-mentioned vacuum molding thermoplastic polyurethane resin composition. The thermoplastic polyurethane resin composition for vacuum molding of the present invention can be processed into a calendar and a T-die molding method to produce a vacuum molding sheet.

The conditions of the T-die sheet molding machine used in the present invention are as follows:

i) Extruder type: single screw extruder, L / D-36 / 1, compression ratio ◎ 3/1, screw diameter -120 mm, motor capacity ◎ DC 200 HP, T-die width: 47 inches

ii) Dry form:

-UNWINDING: 2 shafts (Shaft stand type)

-Forming Part: Consists of cold forming roller, forming rubber roller, cooling smooth roller, and touch rubber roller

-Take up device: guide roller, smoothing device, take up steel roller, rubber pressure roll

-Winding device: 2 shaft turret type, winding width 1500 mm

-Additional facilities: dehumidifying dryer, quenching machine

iii) Cylinder temperature: 150 ~ 180 ℃

iv) head, screen changer, melt pump: 150 ~ 170 ℃

v) Tee-dice heaters 1 to 8: consist of 160 to 180 ° C.

The sheet that can be vacuum formed is divided into the first layer and the second layer. The first layer is for interior design of automobiles, and the second layer is made of thermoplastic polyurethane. Consists of composite resin The resin constituting the second layer together with the sheet for vacuum forming of the present invention is selected from the group consisting of ABS, polycarbonate, polyacetal (POM), PVC, PBT (PBT), polyester elastomer, polyester ether elastomer and the like. One or more types selected can be mentioned. When the content of approximately 30 to 40% is applied to the polyurethane resin, the moldability shows the best result, and a slight difference is seen depending on the type of the composite resin.

The vacuum forming sheet and the two-layer vacuum forming composite sheet manufactured as described above have excellent product performance such as surface feel, sheet forming, dimensional stability, and the like; It has excellent durability such as wear resistance, scratch resistance, surface precipitation resistance (Blooming), chemical resistance, heat aging, light aging and hydrolysis resistance; It is suitable for use as an environmentally friendly automobile crash pad skin material such as airbag deployment performance, anti-fogging and surface precipitation after water deposition.

The thermoplastic polyurethane for vacuum molding of the present invention is excellent in calendar moldability, T-die extrudability and blow moldability for vacuum molding; Excellent product performance such as surface feel, sheet formability and dimensional stability; It has excellent durability such as wear resistance, scratch resistance, surface precipitation resistance, chemical resistance, heat aging, light aging, hydrolysis resistance, and the like; It has excellent properties such as airbag deployment performance, soaking, surface deposition after water deposition. Therefore, it is possible to provide an environmentally friendly automobile crash pad skin having excellent performance.

The following examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by the following examples. The following examples may be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Example

(Invention Example 1 and Invention Example 2)

49.6 kg adipic acid, 1,3-propaneglycol extracted from corn (trade name: Susterra ^TM Propanediol, DuPont, molecular formula: C ₃ H ₈ O ₂ , molecular weight: 76.1, specific gravity (20/20 ° C): 1.055, viscosity (cP ): 52, Flash Point (℃): 131, Boiling Point (℃): 214, Freezing Point (℃):-24, Excellent low temperature property, low toxicity, excellent stability, 100% eco-friendly) 22.0 kg, hydroxy value 40.7 kg of polytetramethylene ether glycol of 448.8 mgKOH / g are mixed, and then heated to 150 ° C. at room temperature, and then maintained at 150 ° C., which is the first elevated temperature, for about 90 minutes, and then heated up to 220 ° C., followed by a second temperature increase. After maintaining at a temperature of 220 ° C. for about 30 minutes and applying to a vacuum of 720 mmHg at the second elevated temperature, when the acid value is 1 mgKOH / g or less, the reaction is terminated to obtain 12.2% of condensed water and a hydroxyl value. Ether containing polyester polyols having a hydroxyl value of 74.8 mgKOH / g were prepared.

65 kg of the prepared ether-containing polyester polyol, 3 kg of hyperbranched polyol (12-valent hyperbranched polyol) and 1,4-BG 7 kg were stirred at 60 ° C. for 3 minutes, and 45 kg of hexamethylene diisocyanate was added thereto. Mixing was carried out at 400 rpm for 3 minutes to obtain a polymer, which was aged at 90 ° C. for 8 hours. Subsequently, the polymer was pulverized at a temperature below 0 ° C. to form chips (flakes), which were extruded at 190 ° C. to form pellets in the pulverized form.

Subsequently, the thermoplastic polyurethane in pellet form obtained above is calendered or T-die-molded to obtain a sheet for vacuum molding, and a molded article composed of a core material, a pad material and a skin material is manufactured according to the vacuum molding method, and a part thereof is sampled. Was taken.

Among test specimens containing 1,3-propanediol extracted from corn, the sample is classified into Inventive Example 1 (high flowable product) and Inventive Example 2 according to the flowability (Melt Index) among the test products having the best processability. Low-Temperature) T-die extrusion molding the cylinder temperature of 170 ~ 200 ℃ to a thickness of 1.3 ~ 1.4 mm to prepare a molded article of the skin material by vacuum molding method and the manufactured sheet was tested by vacuum molding equipment of Duckyang industry.

(Comparative Example 1 and Comparative Example 2)

Comparative Examples 1 and 2 sampled some of the currently available crash pad skins. In Comparative Example 1, a part of the molded article manufactured by vacuum molding method was taken as a sample using a thermoplastic polyolefin of Hanwha General Chemical as a skin material. In Comparative Example 2, a part of the molded article manufactured by the vacuum molding method using the thermoplastic polyolefin of LG Chem as a skin material was sampled.

(Comparative Example 3 and Comparative Example 4)

Comparative Example 3 is the same test product as Example 1 except that 1,3-butanediol is not used instead of 1,3-propanediol extracted from corn, and Comparative Example 4 is 1,3-propanediol extracted from corn Except for using 40 Kg excessively, the same specimen as in Inventive Example 1 was taken, and the sheet was molded in the same manner as Inventive Examples 1 and 2, and the vacuum molding test was performed.

(Invention Example 3 and Invention Example 4)

Inventive Example 3 is a test article containing 5 parts by weight of 1,3-propanediol extracted from corn when synthesizing polyol, and Inventive Example 4 is a test article containing 10 parts by weight of a molded article of sheet sheathing material as in Examples 1 and 2 above. Prepared.

The vacuum forming test was conducted using the sheets prepared in each of the inventive examples and comparative examples, and the results of the inventive examples 1, 2 and comparative examples 1, 2 are shown in Table 1, inventive examples 3, 4, and Comparative Examples 3 and 4 are shown in Table 2 below. The value for each property test is an average of five times.

-Vacuum forming process conditions

i) Process temperature: based on sheet heating temperature just before molding

ii) Heating time: the time required to heat the sheet on the hot plate

iii) Vacuum forming time: time required for vacuum forming the heated sheet into the mold

iv) Cycle time: Total time taken to go through the process steps of preheating, forming, cooling and demolding a single mold

Molding property measurement conditions and specifications

i) Hardness: ASTM D 2240

ii) tensile strength and elongation: ASTM D 412

iii) tear strength: ASTM D 624

iv) MI (Melt Index): ASTM D 1238 (165 ℃ / 2.16kg)

v) Blooming: Visual observation of the specimen surface after 30 days * 70% relative humidity at 120 days

vi) Heat aging resistance: Measurement of physical properties after temperature 120 ℃ and 500 hrs

vii) Resistance to light aging: Temperature 89 ℃, Humidity 50% WEATHER OMETER 530 hrs

Item Inventive Example 1 Inventive Example 2 Comparative Example 1 Comparative Example 2 Vacuum forming process Process temperature (℃) 230 220 240 240 Heating time (sec) 40 35 40 40 Vacuum forming time (seconds) 5 5 5 5 Cycle time (seconds) 80 70 90 90 Formability Good demoulding Good demoulding Good demoulding Good demoulding Molded article
Properties Hardness 84 84 74 74 Tensile strength (shore A) 155 145 133 134 Tear strength (kgf / cm) 90 85 74 74 Elongation (%) 780 775 789 798 MI (kgf / cm) 20 15 12 14 Immersion Blooming none none none none Heat aging resistance clear clear clear clear Photo-aging property clear clear clear clear

Item Inventive Example 3 Inventive Example 4 Comparative Example 3 Comparative Example 4 Vacuum forming process Process temperature (℃) 230 220 240 240 Heating time (sec) 40 35 40 40 Vacuum forming time (seconds) 5 5 5 5 Cycle time (seconds) 80 70 90 90 Formability Good demoulding Good demoulding Good demoulding Demold falling Molded article
Properties Hardness 84 84 84 84 Tensile strength (shore A) 160 140 225 110 Tear strength (kgf / cm) 85 80 95 70 Elongation (%) 755 780 741 851 MI (kgf / cm) 15 25 9 30 Immersion Blooming none none none none Heat aging resistance clear clear clear Deterioration Photo-aging property clear clear clear Deterioration

As shown in Tables 1 and 2, Inventive Examples 1 to 4 according to the present invention contain 5 to 30 parts by weight of 1,3-propanediol extracted from corn, which are good for long-term durability properties and demolding during vacuum molding. The results could be confirmed.

On the other hand, Comparative Example 1-2 is a product used in the existing vacuum molding, and the physical properties and vacuum forming can be compared with the invention Examples 1 to 4 to some extent, 1,3-propanediol extracted from corn was not used In Comparative Example 3, the physical properties were too high to be applied to the vacuum forming in the automobile. In Comparative Example 4, which was manufactured out of the values given in the appropriate range in the present invention, the long-term durability was lowered and the flowability was too high, resulting in vacuum The molding sagging and demolding showed difficult results.

Claims (14)

(A) 30 to 70 parts by weight of a polyfunctional carboxylic acid compound, 5 to 30 parts by weight of 1,3-propanediol extracted from corn and 20 to 70 parts by weight of polytetramethylene ether glycol, and a hydroxyl value of 11.22 to 30 to 70 parts by weight of an ether containing polyester polyol of 224.11 mgKOH / g;
(B) 15 to 60 parts by weight of the isocyanate compound;
(C) 1 to 10 parts by weight of 2.1 to 12-valent hyperbranched polyol; And
(D) 5 to 40 parts by weight of at least one chain extender selected from the group consisting of diols, triols, and polytetramethylene ether glycol;
The polyfunctional carboxylic acid compound is selected from the group consisting of adipic acid, seric acid, abelic acid, azelic acid, sebacic acid, dodecanedioic acid, trimeric acid and mixtures of two or more thereof.
Thermoplastic polyurethane resin composition for vacuum molding. The method according to claim 1,
Polytetramethylene ether glycol in the above (A) has a hydroxyl value of 56.1 to 561.0 mgKOH / g, characterized in that
Thermoplastic polyurethane resin composition for vacuum molding. The method according to claim 1,
The ether-containing polyester polyol is characterized in that the acid value is 1 mgKOH / g or less
Thermoplastic polyurethane resin composition for vacuum molding. delete The method according to claim 1,
The isocyanate compound (B) is at least one selected from the group consisting of diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate
Thermoplastic polyurethane resin composition for vacuum molding. The method according to claim 1,
Diols in the (D) is selected from the group consisting of ethylene glycol, diethylene glycol, butanediol and hexanediol, the triol is characterized in that trimethylolpropane
Thermoplastic polyurethane resin composition for vacuum molding. The method according to claim 1,
Further characterized in that it further comprises 5 to 10 parts by weight of the outer lubricant and 1 to 5 parts by weight of the inner lubricant
Thermoplastic polyurethane resin composition for vacuum molding. The method of claim 7,
The external lubricant is a partially saponified montanic ester wax.
Thermoplastic polyurethane resin composition for vacuum molding. The method of claim 7,
The internal lubricant is a reactive silicone having a bifunctional hydroxy group
Thermoplastic polyurethane resin composition for vacuum molding. (A) 30 to 70 parts by weight of a polyfunctional carboxylic acid compound selected from the group consisting of adipic acid, seric acid, abelic acid, azelic acid, sebacic acid, dodecanedioic acid, trimeric acid and mixtures of two or more thereof; 5 to 30 parts by weight of 1,3-propanediol extracted from corn and 20 to 70 parts by weight of polytetramethylene ether glycol were mixed and heated to 140 to 160 ° C. at room temperature, and then maintained for 60 to 120 minutes,
Then heated to 210-230 ° C. and held for 10-120 minutes and then subjected to a vacuum of 650-760 mmHg,
30 to 70 parts by weight of a corn extract propanediol-containing polyester polyol compound obtained by terminating the reaction when the acid value is 1 mgKOH / g or less during vacuum application; (B) 15 to 60 parts by weight of the isocyanate compound; (C) 1 to 10 parts by weight of 2.1 to 12-valent hyperbranched polyol; And (D) 5 to 40 parts by weight of at least one chain extender selected from the group consisting of diols, triols, and polytetramethylene ether glycol.
Method for producing a thermoplastic polyurethane resin composition for vacuum molding. The method of claim 10,
30 to 70 parts by weight of the (A) ether-containing polyester polyol, (C) 2.1 to 12 parts by weight of the divalent hyperbranched polyol, and (D) 5 to 40 parts by weight of the chain extender at 1 to 10 at 30 to 100 ° C. A first mixing step of mixing with stirring for a minute;
A second mixing step of adding 15 to 60 parts by weight of the (B) isocyanate to the mixture obtained in the first mixing step and mixing at a speed of 30 to 1000 rpm for 1 to 10 minutes;
Aging step of aging the product obtained in the second mixing step for 1 to 48 hours at 60 to 140 ℃;
A grinding step of grinding the product obtained in the aging step at 0 ° C. or less; And
An extrusion step of extruding the milled product obtained in the milling step at a temperature of 150 to 300 ° C; And wherein the step
Method for producing a thermoplastic polyurethane resin composition for vacuum molding. The thermoplastic polyurethane resin composition for vacuum molding according to any one of claims 1 to 3 and 5 to 9 is produced by a calender or T-die method.
Vacuum forming sheet. The method of claim 12,
The vacuum forming sheet is from the group consisting of ABS (ABS), polycarbonate (PC), polyacetal (POM), FVC (PVC), PBT (PBT), polyester elastomer, polyester ether elastomer, and the like At least one selected is made of 2Layer together, characterized in that used as the skin material of the car crash pad
Vacuum forming sheet. Manufactured by including the vacuum forming sheet of claim 13,
Car Crash Pad.