TW460515B - Method for manufacturing the pressure-constant continuing-rolled thermoplastic polyurethane (TPU) foaming product - Google Patents

Abstract

A method for manufacturing the pressure-constant continuing-rolled thermoplastic polyurethane (TPU) foaming product utilizes the pressure-constant foaming method to form continuing-rolled thermoplastic polyurethane(TPU) foaming product, which has good performance and the ability of allowing ventilation and airproof. The method comprises the following steps: passing the composition through the mixture and refined apparatus and the thin-film maker; foaming heat the composition by the foaming apparatus; cooling the composition and rolling out the composition to form the single continuing-rolled foaming product. Furthermore, the method further comprises the step of passing the reenforce material through the paste apparatus, the step of pasting with the glue film made by the reenforce material and thin-film maker, the step of foaming and cooling down and rolling out to form the composite continuing-rolled foaming product.

Description

4605 1 5 Five 'Description of the invention (1) The present invention relates to a method for producing a continuous-pressure continuous-rolled thermoplastic polyurethane foam, which is mainly formed by the normal-pressure foaming method. Continuous TPU foam with excellent air permeability and air permeability. According to the traditional TPU foam manufacturing method, there are roughly five methods, namely (1) Injection Molding (IM), such as the Republic of China Patent Bulletin No. 33926 5 'No. 38258 9 and No. 29382 5. (2) Reaction Injection Molding (RIM), which is commonly known as in-mold foaming, and the foams it produces are classified as semi-rigid foams, such as the United States Patent Nos. 46561 99 and 413 2840. (3) Integral skin Foam ’This method is also a type of RIM, and the foams it produces are also classified as semi-rigid foams. (4) TD I series traditional foaming method (S 1 abst 〇ck F 〇am) 'It can be divided into continuous and batch type' The foams produced by them are classified as flexible foams (Flexible Foam ). (V) Insulation foaming method

Foam). The above five types of TPU foaming system method 'Among them (1) to (3) methods, it is usually necessary to use heating and high pressure sealing method for foam molding', and all are batch production 'with long foaming time , The disadvantage of slow production speed, and when the latter processing industry needs to use the reinforcement material, 're-need to affix the reinforcement material before use. In addition, although the fourth traditional TDI-based foaming method can be continuously produced, TDI is highly toxic 'making it dangerous during processing', and when the subsequent processing industry needs to use reinforcing materials, it also needs to affix reinforcing materials by itself. Before use.

4 605 t 5 V. Description of the invention (2) The raw material used in the present invention is TPU resin pellets, and there is no residual TD I in the pellets, so it has high safety and can be directly bonded to the reinforcing material for consistent operation. As for the fifth conventional foaming system, it is not relevant to the present invention, so it will not be repeated here. Generally speaking, the traditional TPU foaming system method has the disadvantages of low production efficiency, high cost, foam production under high pressure, energy consumption and strong toxicity. That is, in order to solve the shortcomings of the traditional TPU foaming system method, the inventor of this case has conducted a long-term in-depth and systematic exploration and research to find a way to break the bottleneck of the traditional TPU foaming technology, in order to establish a method that can It is a foam system method that manufactures foams with high safety, no joints, continuous continuous rolls, and consistent operation with reinforcing materials. The main object of the present invention is to provide a method for producing a continuous-pressure continuous-type thermoplastic polyurethane foam, which is mainly based on the normal-pressure foaming method. And continuous roll foam with excellent performance. Another object of the present invention is to provide a method for producing a continuous-pressure thermoplastic polyurethane foam at normal pressure, which mainly comprises mixing a composition through a mixing and kneading device, and then a film generating device. The foaming device is heated and foamed under normal pressure, and then cooled and rolled to obtain a "single" continuous roll foamed product. Another object of the present invention is to provide a normal pressure continuous roll thermoplastic polyurethane. For the production method of ester foam, the surface of the product produced can be subjected to various surface treatments through a processing device, a printing device or an embossing device.

4605 1 5 V. Description of Invention (3) ----- to increase product diversity and increase added value. The m❺ of the present invention is to provide a method for manufacturing a continuous atmospheric gas-formed formic acid methyl vinegar foam, which can mount and reinforce a reinforcing material first, and then use the reinforcing material and an adhesive film formed by a film generating device. A person cools and takes it up, and then heats it through a foaming device to obtain a composite continuous roll product. Another type of invention of the present invention is to provide a method for producing a continuous pressure roll polyurethane polymethylaminofoam foam, which is made of "夕 人 ， /; f clothing and compound" Continuous roll-type foamed products can also be subjected to various surface treatments to twist the ancient Ganqian money which still has added value. In order to make your review members have a better understanding and understanding of the structural features of the present invention and the effects achieved, I would like to refer to the preferred embodiment diagrams and detailed descriptions as follows: The formula composition of the present invention contains a thermoplastic polyurethane resin, a foaming agent, a filler and other additives. Among them, the thermoplastic polyamino The methyl formate S can be of two types: Ester type and Ether type; the foaming agent can be ADC (Azodicarbonamide), TSH (p-toluenesulphohydrazide), 0BSH (4, 4-oxybis) (benzenesulphohydrazide) system, THT (2, 4, 6-trihydrazino-1, 3 '5-triazine) system, TSS (p-toluenesulphonylsemicarbazide) system, 5PT (5-phenyl-tetrazole) system, DNPT (dinitrosopentamethylene tetram i ne) Department, Carbonates (NaHC03, NaHC03 / citric acid) series foaming agent, etc.

Page 7 4605 1 5 V. Description of the invention (4); Filler can be heavy calcium carbonate, light calcium carbonate, barium sulfate (BaSO 4), calcium sulfate, micronized silicic acid, silicate, alumina, aluminum powder , Quartz powder, asbestos powder, barytes, Clay, mica powder, Si 1 ica, talc, natural fibers, glass fibers, etc .; other additives can be hard esters Zinc acid, calcium stearate, zinc oxide, antimony oxide (S b 20 3), etc. The proportion (weight ratio) of each component in the formula composition is 100 parts of thermoplastic polyisocyanate resin, 2 to 15 parts of foaming agent, 5 to 100 parts of filler, and 0.05 to 2 of other additives. 0 servings. The present invention can be mainly used to make a single continuous roll foam and a composite continuous roll foam. The process of the manufacturing method will be described separately as follows: 1. A "single" continuous roll foam manufacturing method, which includes the following steps: (a) Raw material composition mixing process: Adding each component to a mixing device, fully Stir to make the composition evenly dispersed; (b) Mixing process: Put the aforementioned mixed and uniformly dispersed composition into a mixing device for refining. During the refining process, the temperature must not exceed the decomposition of the foaming agent and the bridging agent. The temperature and the refining temperature should be controlled to about 90 ~ 180. (C) Thin film process: The rubber material completed through the mixing process is taken out and sent to the thin film production device to form a continuous film, which is coiled by cooling for development. The foam is made into a "single" continuous roll foam, and the operating temperature of the film generating device needs to be controlled below 180 ° C, of which the preferred operating condition is not more than 175 ° C; and (d) Foaming process: The aforementioned film formed by the film generating device is continuously fed into a normal pressure foaming device for heating and foaming, and the temperature of the heating and foaming is

J6〇5i5 Description of the invention (5) The degree needs to be controlled in stages. It should be controlled at about 160 ° C to 26 (TC and stay in the foaming device for 1 to 10 minutes, of which 1 to 90t) to 250. (: Between "and staying in the foaming device for 1.5 to 5 minutes is the preferred operating condition 'after the foaming is completed, it is cooled and coiled to obtain a single continuous roll foam product. &Quot; Composite' 'Continuous roll foam manufacturing method, which includes the following steps: (a) mixing process of raw material composition: adding each component to a mixing device, stirring thoroughly to make the composition uniformly dispersed; (b) / tt * refining process .The aforementioned mixed and dispersed uniform composition is placed in a mixing device for refining. During the refining process, the temperature must not exceed the decomposition temperature of the foaming agent and the bridging agent. The refining temperature is controlled to about 90 ~ 丨 80. ° C; (c) paper-making device, and give ~ 60 seconds (d) the film is prepared and the foam is made into a film, and the production is controlled by not foaming (e), • 1 small and 7 independent publications and pre-production A layer of paste is directly coated on the reinforcing material from the m 珥 elbow thick and strong material as the direct layer, and the drying temperature is 80 ~ 16 (TC 'residence time 10, and the reinforcing material roll will be rolled after coating) Take backup; the continuous win film formed by U15 generator and ζ strong talent η are taken up by cooling In preparation for sending 4 Ν, ... hair / body, in this stage of the process, the operating temperature of the device exceeds 1 75t: A is controlled below 1 80 ° C, and its M 175C 4 is the preferred operating process. The foamed film is heated and foamed in the above-mentioned laminating device, and the compound film of the composite material is continuously fed to a constant control of 16 Ot: to 2 r. The temperature of the thermal foaming needs to be between UC and in the foaming device.

$ 9Page V. Description of the invention (6) Retention for 1 to 10 minutes, among which it is better to operate at 190 ° C to 2 5 叱 and stay in the foaming device for 1.5 to 5 minutes. After completion of cooling and winding, 'combined continuous roll type' products can be obtained. Foam-Furthermore, each step of the above process can be carried out separately or continuously ^ and there is no need for a winding action between the steps, and in the final foaming line: coiling is performed. # In addition, the continuous roll-type hair produced by the atmospheric pressure foaming device can be used to package Zhaopin, and the appearance of the products can also be changed through surface treatment, surface printing and embossing to increase product diversity and improve product quality. Additional seat value of the product. Each surface treatment step is described as follows: Valence (f) surface treatment step: continuous rolls of 4 ^ industrial, hair, and white body products obtained in the foaming process are passed through a surface treatment device * to cause various effects. The surface treatment of the treatment agent, and then drying, A, and table V adjacent to pick up, the process conditions are at 80 ° C to 150 ° C drying and G5 5 minutes to 1 minute, of which 8 5 ~ 1 4 Drying at 5 ° C for 15 seconds to 40 seconds is the best, and different surface treatment agents 'can produce a variety of different surface effect strips' such as matte, bright, oil wax, domain wax, color wax …Wait. (g) Surface printing process: The continuous roll-type hair and body products obtained in the foaming process are printed on a single plate or multiple plates with various colors of ink through a surface printing device, and printed into various patterns. The pattern 'is then dried and cooled. The process conditions are: drying at 80 ° C to 150 ° C for about 5 seconds to 1 minute, among which drying at 8 5 ~ 1 4 5 ° C 1 5 Seconds to 40 seconds are better conditions.

Page 10 ί 605 t 5 V. Description of the invention (7) (h) Surface embossing process: The continuous roll foam product obtained in the foaming process is placed in a surface embossing device. After heating, The embossing wheel with various grain patterns is used to press the patterns of various grain patterns, and then it is cooled and taken up. The process conditions are: heating at a temperature of 120 ° C to 200 ° C for 5 seconds to 1 minute, and then pressing. Flowers, where heating at a temperature of 140 ° C to 180 ° C for 10 seconds to 40 minutes, and embossing are preferred conditions. The surface treatment process described above to increase the diversity of continuous roll foam products and increase the added value of the product, each surface treatment step can be overlapped and overlapped, that is, continuous roll foam products can be performed first (f) Step, followed by step (g); or step (g), followed by step (0); or step (h), followed by step (g); (1), followed by step (h), followed by ( f) step, or go through step (h) first, go through step (f), then go through step (g); or go through step (h), go through step (g), then go through step (f), and in the final step After completion, it will be coiled. Therefore, the variety of surface treatment changes of continuous roll foam products is not small! The added value it can produce can not be estimated! Moreover, the method of the present invention is in contrast with the traditional method In comparison, the production method is simple, the production efficiency is high, and the foam can be manufactured under normal pressure, and it can produce a continuous foam with uniform strength without joints. In addition, the surface of this continuous roll foam product can be Increase the product's performance through surface treatment, printing and embossing Improve the added value of the product. The continuous roll foam produced by the method of the present invention has a wide range of applications, such as shoe materials, handbags, suitcases, computer bags, protective cushions, table mats, floor mats. , Linings, furniture, etc.

Page 11 V. Description of the invention (8) From the above description, the novelty and uniqueness of the technology of the present invention can be clearly explained. At the same time, the inventor's company has more than 40 years of manufacturing experience in the production of PVC foam rubber. In view of the safety and environmental protection issues of PVC products, the global output is decreasing year by year. Therefore, the inventor's company is actively developing alternative materials. After painstaking research, it finally invented the "manufacturing method of atmospheric pressure continuous roll TPU foam". The new invention has practicality and can replace the existing PVC foam rubber, which has deep industrial economic value. It is a major breakthrough in the manufacturing technology of artificial leather and thermoplastic tape industry. In addition, the manufacturing method of the present invention can save energy, increase continuous production speed, reduce manufacturing costs, and other advantages, and has the patent requirements of the invention. Finally, the inventors made a detailed description of the processing conditions and physical properties of the continuous roll foaming method of the present invention, as described below: Example 1: Production of a single continuous foam body Composition used in this example: thermoplastic polymer 100 parts of urethane (parts by weight, the same applies hereinafter), 6 parts of azodiamidine β. For processing conditions, please refer to the attached table 1 and use a mixing and kneading device to make the film. The manufacturing device is made into a film roll having a thickness of 0.6 mm, and the film roll is foamed under a normal pressure through a foaming device. Then, the foaming ratio and physical properties of the obtained foamed film are measured, such as hardness, tensile strength, elongation, tearing strength, breaking strength, and abrasion loss of the rubber surface. The measurement results are shown in Table 1 above. The foaming ratio and physical properties are tested according to the following methods: (1 1) Foaming ratio (R): R = T / t (times) t: Thickness of the film before foaming (unit: mm)

Page 12 t 4 605 1 § V. Description of the invention (9) T: Thickness of the film after foaming (unit: mm) The state of the foamed airbag: ◦ It means that the diameter of the airbag is 0.3 mm or less, and it is uniform and detailed △ system indicates the uneven distribution of airbag size X system indicates that the airbag is broken (1. 2) Total thickness: measured with a thickness of precision 0. 0 1 X 1 0 mm (1. 3) Hardness: refer to JISK 6 3 Standard test method of 0.1 (1.4) Tensile strength: refer to ASTM D4 1 2 Standard test method (1.5) Elongation: refer to ASTM D41 2 standard test method (1.6) Tear strength: refer to ASTM D6 24 standard test method (1.7) Rupture strength: refer to JIS P8 1 3 1 standard test method (1.8) Rubber abrasion: refer to ASTM D1 044-56 standard test method (1.9) Peel Strength: Refer to JISK 6 7 7 2 standard test method (1. 1 0) Water permeability: Refer to JISK 6 7 7 2 standard test method Example 2-4: Processing conditions as shown in attached table 1, co-composition Same as Example 1 ° Example 5: Production of composite continuous foamed body The processing conditions are shown in the attached table 1. The composition is the same as in Example 1; After the green device is led out, it is laminated with the reinforcing material coated with the adhesive, and then foamed. 5 毫米。 The reinforcing material used in this example is T / R blended fabric, and the thickness of the composite film before foaming is 1. 5 mm. The physical property testing items are shown in Example 1. Examples 6 to 7: The processing conditions, co-compositions and reinforcements shown in Table 1 are the same as in Example 5.

Page 13 4 60515 V. Description of the Invention (Example) 8: The processing conditions shown in Schedule 1 are the same as in Example 5, and the reinforcing material is made of non-woven fabric. Schedule 1 is a comparison table of processing conditions and physical properties of the continuous roll foaming method of the present invention.

Page 14 4605 1 5 Brief description of the drawing Figure 1 is a process flow chart of a single continuous roll foam. Figure 2 is a process flow chart of a composite continuous roll foam.

Page 15 4605 1 5 Schedule 1 Production of single continuous foam and production of composite continuous foam 1 2 3 4 5 6 7 8 Mixing temperature of this hair ΓΟ / a 25 (60) 28/60 27 / 60 28/60 25/60 30/60 28/60 27/60 Ming mixing temperature (° C) / hour (sec) 130 140 150 155 150/12 0 140/12 0 130/12 0 155/12 0 Process temperature of film making device (° C) 150 155 160 165 140 150 150 160 Processing foaming temperature rc) 220 220 240 240 220 220 240 240 Conditioning foaming time (sec) 80 120 80 120 80 120 80 120 foaming Magnification (times) 2.5 3 3 5 2.5 3 3 5 State of gas inspection 〇 〇〇〇〇〇〇〇 Hardness (shore-A) 56 50 50 60 Tensile strength (Note 1) (kg! / 3cm) After 10 8 8 5 68 57 65 54 Weft 8 7 6. 5 3.8 52 51 58 54 Physical properties of foam ^ Application rate (%) Warp 500 550 550 650 31 30 25 63 Weft 400 430 435 550 40 47 40 72 t Crack strength (kg / cm2) Warp 0.5 0.4 0.4 0.3 3.3 2.5 3.5 5.0 Weft 0.4 0.2 0.3 0.2 3.2 2.4 2.9 5.7 Rupture strength (Note 2) (kgf / cm2)-1 —-14.6 14.2 25 20.2 Peel strength (Note 3) (kgf / 3cm ) Warp-- -N (Note 4) NNN latitude---NNNN Permeability _ (g / m2. 24hrs)----280.1 452.1 449.9 696.0 One surface wear (g / 1000 revolutions) 0.0125 0.0132 0.0148 0.0136 0.0125 0.0156 0.0197 0.0129 Note ϊ : Reinforcing material: T / C blended fabric was used in Examples 5 to 7, and non-woven fabric was used in Example 8. Note 2: The single continuous film does not measure the breaking strength. Note 3: Adhesive strength between cloth and glue. Note 4: N means it cannot be peeled off.

Claims (1)

Shen Yili Fan Shu 4605 1 5 ~ [wx A method for producing a continuous pressure thermoplastic polyurethane foam at normal pressure, which mainly includes the following steps: (a) Mixing process of raw material composition: adding all ingredients In the mixing device, fully stir to make the composition uniformly dispersed, and the mixing temperature is from normal temperature to 100 ° C, and the time is 10 seconds to 5 minutes; (b) mixing process: the aforementioned mixed and dispersed composition is uniform , Placed in a mixing device for refining, during the refining process, the temperature must not exceed the decomposition temperature of the blowing agent and bridging agent, the refining temperature is controlled at 90 ~ 180 ° C; (c) film process: The rubber material completed through the mixing process is taken out and sent to the film production device to form a continuous film, which is taken up by cooling for foaming. The operating temperature of the film production device needs to be controlled below 180 ° C; and (d) Foaming process: the aforementioned film formed by the film generating device is continuously fed into a normal pressure foaming device for heating and foaming, and the temperature of the heating and foaming needs to be controlled in stages, which is controlled at 18.5 ° C ~ 2 6 0 ° C, residence time 1 ~ 5 minutes, foaming finished After completion, it is cooled and taken up to obtain a continuous rolled foam. 2 The method for manufacturing a continuous-pressure thermoplastic polymethylurethane foam at atmospheric pressure as described in item 1 of the scope of the patent application, which can be separately processed through a surface treatment process, a surface printing process, or a surface embossing process to increase the product. Changes in appearance enhance the added value of the product. The method for manufacturing an atmospheric continuous roll-type thermoplastic polyurethane foam as described in item 2 of the scope of patent application, wherein the surface treatment process is Page 16 4605 1 i VI. Patent application scope The continuous roll foam product obtained in the foaming process is surface-treated with a surface treatment agent that can cause various surface effects through a surface treatment device, and then dried, Cool off. 4. The method for manufacturing an atmospheric continuous roll thermoplastic polyurethane foam as described in item 2 of the scope of the patent application, wherein the surface printing process is a continuous roll foam obtained in a foaming process through Surface printing device, using single and multi-plate printing with various colors of ink, printing various patterns of different patterns, and then drying, cooling and taking up 0 5, atmospheric pressure as described in item 2 of the scope of patent application Production method of continuous roll thermoplastic polyurethane foam, wherein the surface embossing process is to place the continuous roll foam product obtained in the foaming process in a surface embossing device, and then heat it first With various embossing wheels with different grain patterns, the patterns of various grain patterns are pressed, and then cooled and rolled up, as is the normal pressure continuous roll type thermoplastic polyurethane foam as described in item 1 of the scope of patent application. The manufacturing method also includes a papermaking process, in which the reinforcing material is directly coated on the reinforcing material as a direct layer through a papermaking device and dried at a drying temperature of 80. 1 6 0 ° C, the residence time 0 seconds 1 0~6. 7. The manufacturing method of the continuous pressure thermoplastic polyurethane foam as described in item 6 of the scope of the patent application, wherein the reinforcing material can also be directly used by the user without going through the mounting process. 8. Atmospheric continuous roll thermoplastic polymer as described in item 6 of the scope of patent application Page 17 4 β0515 VI. Scope of Patent Application For the production method of urethane foam, the τ die extruder can also be used to apply the paste on the reinforcing material. 9. The method for manufacturing a continuous-pressure thermoplastic polyurethane foam as described in item 6 of the scope of the patent application, wherein the reinforcing material is selected from the group consisting of fiber products, paper products, rubber and plastic films, and metal foils. 10. The method for producing a continuous pressure thermoplastic polyurethane foam as described in item 6 of the scope of the patent application, wherein when the adhesive film obtained in the foaming process is to be bonded to a reinforcing material, it will form The adhesive film is laminated with the prepared reinforcing material, and is taken up by cooling and is ready to be foamed. 11. The method for manufacturing a continuous pressure thermoplastic polyurethane foam as described in item 6 of the scope of the patent application, wherein when the reinforcing material is bonded, the composite film with the reinforcing material is foamed. Foaming in the device, its heating temperature needs to be controlled in sections, and its foaming temperature conditions are 190 ~ 250 ° C, and the residence time is 1. 5 ~ 4 minutes. After the foaming is completed, the composite continuous roll is cooled and coiled. Foam. 1 2. The production method of the continuous pressure thermoplastic polyurethane urethane foam as described in item 1 of the scope of patent application, wherein the temperature of the film generating device is controlled below 175 ° C. 1 3. The production method of the continuous pressure thermoplastic polyurethane foam as described in item 1 of the scope of the patent application, wherein the film generating device is a calender, a T-die extruder, a coating machine or a blower. Film machine. 14. The method for producing a normal pressure continuous roll-type thermoplastic polymethylurethane foam as described in item 1 of the scope of patent application, wherein the temperature of the foaming device is controlled at 190 ~ 250 ° C. Retention time 1. 5 ~ 4 minutes. P.18 4 5 1 5 VI. Application for Patent Scope 1 5. The method for producing atmospheric pressure continuous roll thermoplastic polyurethane foam as described in item 1 of the scope of patent application, which is applicable to thermoplastic polyurethane In the production of foams, the thermoplastic polyurethane is selected from two types: Ester type and Ether type. 16. The method for manufacturing a continuous pressure thermoplastic polyurethane foam as described in item 3 of the scope of patent application, wherein the drying temperature of the surface treatment process is controlled at 8 5 ~ 1 4 5 ° C The drying time is controlled in the range of 15 to 40 seconds. 0 1 7. The production method of the continuous pressure thermoplastic polyurethane foam as described in item 3 of the scope of patent application, wherein the surface treatment device is Rotary surface treatment machine. 18. The method for producing a normal pressure continuous roll thermoplastic polyurethane foam as described in item 3 of the scope of patent application, wherein the surface treatment agent is selected from the group consisting of PVC, PU and acrylic surface treatment agents. . 19. The method for manufacturing a normal pressure continuous roll thermoplastic polyurethane foam as described in item 4 of the scope of patent application, wherein the drying temperature of the surface printing device is controlled at 8 5 ~ 1 4 5 ° C The time is controlled between 15 and 40 seconds. 20. The method for producing a normal pressure continuous roll thermoplastic polyurethane foam as described in item 4 of the scope of the patent application, wherein the surface printing device is a letterpress or gravure single-plate or multi-plate rotary printing machine or Single and multi-screen screen printing machines. 2 1. Atmospheric continuous roll thermoplastic polymer as described in item 4 of the scope of patent application Page 19 ^ 0515 6. Scope of patent application The method for producing urethane foam, in which the surface printing ink is selected from PVC, acrylic and PU inks. 2 2. The manufacturing method of the continuous pressure thermoplastic polyurethane foam as described in item 5 of the scope of the patent application, wherein the heating temperature of the embossing process is controlled at 140 to 180 ° C. The heating time is controlled between 10 and 40 seconds. 2 3. The production method of the continuous pressure thermoplastic polyurethane f-ester foam according to item 3 of the scope of the patent application, wherein the surface treatment process, the surface printing process or the surface embossing process may overlap each other. Proceeder. Page 20