Film-forming composition and film-coated fabric formed therefrom

Abstract

The present invention provides a film-forming composition and a film-coated fabric formed therefrom that can mitigate the drawbacks of at least one prior art. [Solution] The film-forming composition comprises a copolymerized polyester, a methyl etherified amino resin, a coalescing agent, and an organic solvent. The copolymerized polyester is formed by copolymerizing terephthalic acid, a saturated aliphatic dicarboxylic acid, ethylene glycol, and a saturated aliphatic diol, and has a glass transition temperature in the range of -20°C to 20°C. The coalescing agent is selected from the group consisting of p-toluenesulfonic acid and dodecylbenzenesulfonic acid. A film-coated fabric formed with the above film-forming composition is also provided.

Description

Technical Field

[0001] The present disclosure relates to a film-forming composition, and particularly to a film-forming composition containing a copolymerized polyester, a methyl etherified amino resin, and a core-shell agent, and a film-coated fabric formed therefrom.

Background Art

[0002] Currently, in order to produce recycled fibers from discarded clothing and waste fabrics, it is necessary to use fiber materials containing 100% single component or 97% or more polyester. Only under such conditions can the fiber material be recycled through a physical recycling process (for example, pelletized by injection molding following mechanical cutting or pulverization), and / or a chemical recycling process (for example, alcoholysis following decolorization and then polymerization) or other processes to produce recycled fibers. Furthermore, fabrics made from the aforementioned fiber materials containing 97% or more polyester often do not meet the requirements for resistance to hydrostatic pressure and twist of the fabric.

[0003] U.S. Patent Application Publication No. 2019 / 0300647 discloses a polyester resin that can be produced from terephthalic acid (abbreviated as TPA), sebacic acid, ethylene glycol, and 2,2-dimethyl-1,3-propanediol. By dissolving the polyester resin in ethyl acetate and adding a methylated melamine resin thereto and stirring, a film coating material that can coat a metal can be formed.

[0004] Since the film coating material of U.S. Patent Application Publication No. 2019 / 0300647 does not contain a core-shell agent, fabrics produced from such materials tend to have relatively low resistance to hydrostatic pressure.

[0005] Considering the above, there is still a need to develop materials that can be used to produce fabrics with relatively high resistance to hydrostatic pressure and twist. [Overview of the project] [Problems that the invention aims to solve]

[0006] The object of this disclosure is to provide a film-forming composition and a film-coated fabric formed therefrom that can mitigate at least one drawback of the prior art. [Means for solving the problem]

[0007] According to one aspect of the present disclosure, a film-forming composition comprises a copolymerized polyester, a methyl etherified amino resin, a coalescing agent, and an organic solvent. The copolymerized polyester is formed by copolymerizing terephthalic acid with saturated aliphatic dicarboxylic acid, ethylene glycol, and saturated aliphatic diol, and has a glass transition temperature in the range of -20°C to 20°C. The coalescing agent is selected from the group consisting of p-toluenesulfonic acid and dodecylbenzenesulfonic acid.

[0008] According to other aspects of the present disclosure, a film-coated fabric comprises a base fabric and a film coated on the base fabric. The film is formed by coating the base fabric with the above-mentioned film-forming composition and subsequently performing a crosslinking reaction.

[0009] Other features and advantages of this disclosure will become apparent by referring to the accompanying drawings and describing in detail the embodiments below. [Brief explanation of the drawing]

[0010] [Figure 1] This image shows the surface of the film-coated fabric of Example 1 (EX1) after being bent 1000 times as described in Section B of the "Characteristic Evaluation" below. [Figure 2] This image shows the surface of the film-coated fabric of Example 2 (EX2) after being bent 1000 times as described in Section B of the "Characteristic Evaluation" below. [Figure 3]This image shows the surface of the film-coated fabric of Example 3 (EX3) after being bent 1000 times as described in Section B of the "Characteristic Evaluation" below. [Figure 4] This image shows the surface of the film-coated fabric of Example 4 (EX4) after being bent 1000 times as described in Section B of the "Characteristic Evaluation" below. [Figure 5] This image shows the surface of the film-coated fabric of Example 5 (EX5) after being bent 1000 times as described in Section B of the "Characteristic Evaluation" below. [Figure 6] This image shows the surface of the film-coated fabric of Example 6 (EX6) after being bent 1000 times as described in Section B of the "Characteristic Evaluation" below. [Figure 7] This image shows the surface of the film-coated fabric of Example 7 (EX7) after being bent 1000 times as described in Section B of the "Characteristic Evaluation" below. [Figure 8] This image shows the surface of the film-coated fabric of Example 8 (EX8) after being bent 1000 times as described in Section B of the "Characteristic Evaluation" below. [Figure 9] This image shows the surface of the film-coated fabric of Example 9 (EX9) after being bent 1000 times as described in Section B of the "Characteristic Evaluation" below. [Figure 10] This image shows the surface of the film-coated fabric of Example 10 (EX10) after being bent 1000 times as described in Section B of the "Characteristic Evaluation" below. [Figure 11] This image shows the surface of the film-coated fabric of Comparative Example 4 (CE4) after being bent 1000 times, as described in Section B of the "Characteristic Evaluation" below. [Modes for carrying out the invention]

[0011] For the purposes of this specification, the word "includes" means "includes but not limited to," and the word "include" also has a corresponding meaning.

[0012] When prior art documents are referred to in this specification, it should be understood that such references do not admit that the documents form part of the common general knowledge in the art in Taiwan or other countries.

[0013] Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art to which this disclosure belongs. Those skilled in the art can recognize and utilize many methods and materials similar or equivalent to those described herein in the implementation of this disclosure. In fact, this disclosure is not limited to the described methods and materials.

[0014] This disclosure provides a film-forming composition comprising a copolyester, a methyl etherified amino resin, a coreactant, and an organic solvent. The copolyester is formed by copolymerizing terephthalic acid, a saturated aliphatic dicarboxylic acid, ethylene glycol, and a saturated aliphatic diol. The copolyester has a glass transition temperature in the range of -20°C to 20°C. The coreactant is selected from the group consisting of p-toluenesulfonic acid and dodecylbenzenesulfonic acid.

[0015] In some embodiments, the copolyester has a glass transition temperature in the range of -15°C to 15°C.

[0016] In some embodiments, the saturated aliphatic dicarboxylic acid is selected from the group consisting of adipic acid, sebacic acid, and combinations thereof.

[0017] In some embodiments, the saturated aliphatic diol is selected from the group consisting of diethylene glycol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol (abbreviated as "TMPD"), and combinations thereof.

[0018] According to the present disclosure, the methyl etherified amino resin functions as a crosslinking agent. In some embodiments, the methyl etherified amino resin is methyl etherified melamine.

[0019] In some embodiments, the organic solvent is selected from the group consisting of toluene, methyl ethyl ketone (abbreviated "MEK", also called 2-butanone), ethyl acetate (abbreviated "EA"), 1-propanol, N, N-dimethylformamide (abbreviated "DMF"), and dimethyl sulfoxide (abbreviated "DMSO").

[0020] In some embodiments, the film-forming composition further comprises silicon dioxide having a particle size within the range of 1 μm to 15 μm.

[0021] In some embodiments, terephthalic acid is present in an amount of more than 0 mol% and 60 mol% or less, with the total amount of terephthalic acid and saturated aliphatic dicarboxylic acid being 100 mol%. In other embodiments, terephthalic acid is present in an amount of 50 mol% to 60 mol%, with the total amount of terephthalic acid and saturated aliphatic dicarboxylic acid being 100 mol%.

[0022] In some embodiments, ethylene glycol is present in an amount of more than 0 mol% and 50 mol% or less, with the total amount of ethylene glycol and saturated aliphatic diol being 100 mol%. In other embodiments, ethylene glycol is present in an amount of 40 mol% to 50 mol%, with the total amount of ethylene glycol and saturated aliphatic diol being 100 mol%.

[0023] In some embodiments, the weight ratio of the copolyester to the methyl etherified amino resin is within the range of 50:3 to 50:7. In an exemplary embodiment, the weight ratio of the copolyester to the methyl etherified amino resin is 50:5.

[0024] This disclosure also provides a film-coated fabric comprising a base fabric and a film coated on the base fabric. The film is formed by coating the base fabric with the above-mentioned film-forming composition and subsequently performing a crosslinking reaction.

[0025] In some embodiments, the base fabric is a polyester fabric.

[0026] The following describes embodiments of this disclosure. These embodiments are illustrative and explanatory, and should not be construed as limiting the disclosure. [Examples]

[0027] Example 1 (EX1) First, 83.065 kg (i.e., 500 mol) of terephthalic acid, 73.07 kg (i.e., 500 mol) of adipic acid (functioning as a saturated aliphatic dicarboxylic acid), 31.035 kg (i.e., 500 mol) of ethylene glycol, 31.836 kg (i.e., 300 mol) of diethylene glycol (functioning as a saturated aliphatic diol), 29.246 kg (i.e., 200 mol) of 2,2,4-trimethyl-1,3-pentanediol (abbreviated as "TMPD", functioning as a saturated aliphatic diol), and 0.36 mol of tetrabutoxytitanium(IV) (functioning as a catalyst) were placed in a reactor and mixed. The resulting mixture was then subjected to an esterification reaction under a nitrogen atmosphere at 240°C for 2 hours to obtain a prepolymer. Then, 0.36 moles of tetrabutoxytitanium(IV) (acting as a catalyst) were added to the prepolymer, and the copolymerization reaction was carried out for 6 hours at a pressure in the range of 1 torr to 10 torr (i.e., close to vacuum) and a temperature of 260°C to obtain the copolymerized polyester EX1. Subsequently, the glass transition temperature of the copolymerized polyester EX1 was measured using a differential scanning calorimeter, the acid value was measured using an automatic titrator, and the number-average molecular weight was measured using techniques well known to those skilled in the art. According to the measurement results, the copolymerized polyester EX1 has a glass transition temperature of -10°C, an acid value of 2.0 mg KOH / g, and a number-average molecular weight of 26000 ± 2000.

[0028] Subsequently, the copolymer polyester of EX1 was cooled to 80°C, and 239 kg of methyl ethyl ketone (abbreviated as "MEK," also called 2-butanone) was gradually added to the copolymer polyester of EX1 to obtain a copolymer polyester solution of EX1. Then, the solid content and viscosity of the copolymer polyester solution of EX1 were measured using techniques well known to those skilled in the art. According to the measurement results, the copolymer polyester solution of EX1 has a solid content of approximately 50% and a viscosity of 5000 mPa·s ± 500 mPa·s.

[0029] Subsequently, 100 g of the copolymer polyester solution of EX1, 5 g of methyl etherified amino resin (functioning as a crosslinking agent; manufacturer: Allnex, model number: CYMEL® 303 LF), 0.4 g of p-toluenesulfonic acid (functioning as a coalescing agent), 15 g of toluene (functioning as an organic solvent), 5 g of silicon dioxide, and 0.05 g of polyether-modified polydimethylsiloxane (functioning as a leveling agent) were stirred and mixed for 15 minutes, and then filtered using a sieve with a mesh count of 150 to obtain the EX1 film-forming composition. For silicon dioxide, the particle size was measured using a laser scattering particle size analyzer, and the specific surface area was measured using the Brunauer-Emmett Teller (abbreviated as "BET") method with nitrogen gas as the adsorbing gas. According to the measurement results, silicon dioxide had a particle size of 4 μm to 8 μm and a specific surface area of ​​approximately 130 m 2 It has a specific surface area of ​​ / g. The viscosity of the film-forming composition EX1 was measured using techniques well known to those skilled in the art. According to the measurement results, the film-forming composition EX1 has a viscosity of 3500 mPa·s ± 500 mPa·s.

[0030] Polyethylene terephthalate (abbreviated as "PET") plain weave fabric (functions as a base fabric, fiber denier: 75D x 75D, basis weight: 102g / m²) 2The fabric was then calendered at a pressure of 100 kgf, a temperature of 150°C, and a speed of 25 m / min to obtain a calendered PET plain weave fabric. Subsequently, the film-forming composition EX1 was float-coated onto the calendered PET plain weave fabric at a speed of 10 m / min. During the float-coating period of the film-forming composition EX1, the calendered PET plain weave fabric was pressed down to 0.8 mm below the moving surface using a coating blade to form a coated film on the surface of the calendered PET plain weave fabric (abbreviated as "pre-coated fabric"). The pre-coated fabric was then heated in an oven at a speed of 10 m / min to cause a crosslinking reaction, resulting in a basis weight of 25.6 g / m². 2 A film-coated fabric of EX1 having a dry film was obtained. Specifically, a temperature gradient was set in a 20-meter-long oven as follows: 90°C from 0m to 4m, 120°C from 4m to 8m, 130°C from 8m to 12m, 150°C from 12m to 16m, and 160°C from 16m to 20m.

[0031] Example 2 (EX2) The procedure and materials for manufacturing the film-coated fabric of EX2 are the same as those for EX1, except that EX2 does not contain silicon dioxide, which was used in EX1.

[0032] Examples 3-5 (EX3-EX5) The procedure and materials for manufacturing the film-coated fabrics EX3 to EX5 are the same as those for EX1, except that the silicon dioxide used is changed as follows: In EX3, silicon dioxide has a particle size of 2 μm to 4 μm and approximately 100 m 2 It has a specific surface area of ​​ / g. In EX4, silicon dioxide has a particle size of 9μm to 11μm and approximately 190m 2 It has a specific surface area of ​​ / g. In EX5, silicon dioxide has a particle size of 13 μm to 15 μm and approximately 500 m 2 It has a specific surface area of ​​ / g.

[0033] Examples 6-10 (EX6-EX10) The procedure and materials for preparing the film-coated fabrics EX6 to EX10 are the same as in EX1, except that toluene (which functions as an organic solvent) used in EX1 is replaced with MEK (in the case of EX6), ethyl acetate (abbreviated as "EA" in the case of EX7), 1-propanol (in the case of EX8), N,N-dimethylformamide (abbreviated as "DMF" in the case of EX9), or dimethyl sulfoxide (abbreviated as "DMSO" in the case of EX10).

[0034] Comparative example 1 (CE1) The procedure and materials for manufacturing the CE1 film-coated fabric are the same as those used in EX1, except that the methyl etherified melamine used in EX1 is replaced with poly(hexamethylene diisocyanate) (abbreviated as "polyHDI", which functions as an isocyanate crosslinking agent, manufacturer: Tai Chin Chemical Industry Co., LTD., model number: X-100).

[0035] Comparative Example 2 (CE2) The procedure and materials for manufacturing the CE2 film-coated fabric are the same as those used in EX1, except that the methyl etherified melamine used in EX1 is replaced with a bisphenol A (BPA)-based liquid epoxy resin (manufacturer: Chang Chun Plastics Co., Ltd., model number: BE-188).

[0036] Comparative Example 3 (CE3) The procedure and materials for manufacturing the CE3 film-coated fabric are the same as those used in EX1, except that the methyl etherified melamine used in EX1 is replaced with a polycarbodiimide crosslinking agent (manufacturer: Nisshinbo Microdevices, model number: CARBODILITE™® V-02B).

[0037] Comparative Example 4 (CE4) The procedure and materials for manufacturing the CE4 film-coated fabric are the same as those used in EX1, except that the copolymer polyester used in EX1 is replaced with amorphous saturated copolymer polyester (manufacturer: Mitsubishi Chemical, model number: TP-217, glass transition temperature: 40°C).

[0038] Comparative Example 5 (CE5) The procedure and materials for manufacturing the CE5 film-coated fabric are the same as those for EX1, except that CE5 does not contain p-toluenesulfonic acid (which functions as a coalescing agent), which was used in EX1.

[0039] Characteristic evaluation A. Measurement of resistance to hydrostatic pressure For each of the film-coated fabrics EX1-EX10, CE1-CE3, and CE5, resistance to hydrostatic pressure was measured according to the standard hydrostatic pressure test method, i.e., the procedure specified in ISO 811 (published in 2018). The results are shown in Table 1 below.

[0040] [Table 1]

[0041] Referring to Table 1, the hydrostatic pressure resistance of each film-coated fabric from EX1 to EX10 ranges from 5100 mmH2O to 5600 mmH2O, while the hydrostatic pressure resistance of each film-coated fabric from CE1 to CE3 and CE5 is 1000 mmH2O or less.

[0042] These results demonstrate that the film-coated fabrics of this disclosure, including films formed from each of the film-forming compositions EX1 to EX10, can exhibit relatively high resistance to hydrostatic pressure.

[0043] B. Measurement of resistance to torsion The film-coated fabrics EX1-EX10 and CE4 were subjected to torsional resistance by bending them 1000 times according to the procedure specified in ISO 7854 Method C (published in 2019), followed by photography to obtain 11 images, as shown in Figures 1-11.

[0044] Referring to Figures 1-11, the surfaces of the film-coated fabrics EX1-EX10, after being bent 1000 times, were relatively smooth (see Figures 1-10, respectively), whereas the surface of the film-coated fabric CE4, after being bent 1000 times, clearly showed numerous creases (see Figure 11). These results indicate that the film-coated fabrics of this disclosure, comprising a base fabric and a film formed from the film-forming compositions in each of EX1-EX10 and coated onto the base fabric, exhibit relatively high resistance to twisting, and therefore, a low likelihood of the film delaminating from the base fabric.

[0045] In summary, the test results described above clearly demonstrate that, due to the effects of the materials used to manufacture the film-forming composition (including copolymerized polyester, methyl etherified amino resin, coalescing agent, and organic solvent), film-coated fabrics containing films formed from the film-forming composition of this disclosure can exhibit relatively high resistance to hydrostatic pressure and torsion. Furthermore, since the film-coated fabrics of this disclosure are mainly made from polyester, such film-coated fabrics can be easily recycled by physical and / or chemical recycling processes or other processes to produce recycled fibers.

[0046] In the above, many specific details have been provided to facilitate a complete understanding of the embodiments for illustrative purposes. However, it will be apparent to those skilled in the art that one or more other embodiments can be implemented without specific details. Furthermore, in descriptions of "one embodiment" or "one example" in this specification, it should be understood that all descriptions accompanied by ordinal numbers or other designations may be included in specific implementations of the present invention having a particular aspect, structure, or feature. Moreover, in this description, multiple variations are sometimes incorporated into a single embodiment, drawing, or description thereof, for the purpose of streamlining this description and to illustrate the multifaceted nature of the present invention. Additionally, one or more features or specific examples in one embodiment may, where appropriate, be implemented in conjunction with one or more features or specific examples in other embodiments of this disclosure.

[0047] While this disclosure is described in relation to exemplary embodiments, it should be understood that this disclosure is not limited to the disclosed embodiments and is intended to encompass a wide range of configurations that fall within the spirit and scope of the broadest interpretation, and to include all such modifications and equivalent configurations.

Claims

1. A copolymerized polyester formed by copolymerizing terephthalic acid, saturated aliphatic dicarboxylic acid, ethylene glycol, and saturated aliphatic diol, having a glass transition temperature in the range of -20°C to 20°C, Methyl etherified amino resin and A coalescing agent selected from the group consisting of p-toluenesulfonic acid and dodecylbenzenesulfonic acid, A film-forming composition comprising an organic solvent.

2. The film-forming composition according to claim 1, wherein the copolymerized polyester has a glass transition temperature in the range of -15°C to 15°C.

3. The film-forming composition according to claim 1, wherein the saturated aliphatic dicarboxylic acid is selected from the group consisting of adipic acid, sebacic acid, and combinations thereof.

4. The film-forming composition according to claim 1, wherein the saturated aliphatic diol is selected from the group consisting of diethylene glycol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol (TMPD), and combinations thereof.

5. The film-forming composition according to claim 1, wherein the methyl etherified amino resin is methyl etherified melamine.

6. The film-forming composition according to claim 1, wherein the organic solvent is selected from the group consisting of toluene, methyl ethyl ketone (MEK), ethyl acetate (EA), 1-propanol, N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO).

7. A film-forming composition according to any one of claims 1 to 6, further comprising silicon dioxide having a particle size in the range of 1 μm to 15 μm.

8. The film-forming composition according to any one of claims 1 to 6, wherein the terephthalic acid is present in an amount greater than 0 mol% and less than or equal to 60 mol%, with the total amount of the terephthalic acid and the saturated aliphatic dicarboxylic acid being 100 mol%.

9. The film-forming composition according to any one of claims 1 to 6, wherein the ethylene glycol is present in an amount greater than 0 mol% and less than or equal to 50 mol%, with the total amount of the ethylene glycol and the saturated aliphatic diol being 100 mol%.

10. The film-forming composition according to any one of claims 1 to 6, wherein the weight ratio of the copolymerized polyester to the methyl etherified amino resin is in the range of 50:3 to 50:

7.

11. A film-coated fabric comprising a base fabric and a film coated on the base fabric, wherein the film is formed by coating the base fabric with a film-forming composition according to any one of claims 1 to 6, and then performing a crosslinking reaction.

12. The film-coated fabric according to claim 11, wherein the base fabric is a polyester fabric.

Images