TWI659962B - Zirconium-containing organic-inorganic hybrid material, manufacturing method thereof and processed fabric thereof - Google Patents

Abstract

The present invention provides an organic-inorganic hybrid material, the preparation method comprising the steps of: providing a thiazole monomer; coupling a thiazole monomer with NN dimethylaniline to obtain a thiazole dye; and a thiazole dye and a vinyl three The ethoxysilane is reacted to obtain a precursor; and the precursor and the zirconia sol are subjected to a condensation reaction to obtain an organic-inorganic hybrid material, or the precursor, the zirconia sol and the methyltrimethoxydecane are reacted. To obtain an organic-inorganic hybrid material.

Description

Zirconium-containing organic-inorganic hybrid material, manufacturing method thereof and processed fabric thereof

The present invention relates to an organic-inorganic hybrid material, a method for producing the same, and a processed fabric thereof, and more particularly to a property capable of improving heat storage and heat retention, coloring property, leveling property, friction resistance and washing fastness of a processed fabric. Organic-inorganic hybrid material, a method for producing the same, and a processed fabric thereof.

With the development of science and technology, the textile industry has developed accordingly. In order to meet the needs of users in various environments, functional fabrics have gradually become mainstream. The functional mechanism includes water absorption, moisture absorption, hydrophobicity, oleophobic, antifouling, antibacterial, deodorant, antistatic, far infrared heat storage and thermal shielding and ultraviolet shielding. Among them, the functions of water, oil, antifouling and ventilation are large.

Conventionally, the surface of the fabric is often processed by resin coating or by adding an auxiliary agent to produce a desired characteristic of the fabric surface. However, the above method causes an increase in cost, a poor hand feeling of the fabric, and a decrease in moisture permeability of the fabric. Breathable and dye fastness. Moreover, if the residual chemicals are not properly treated, the ecological environment will be polluted as the dyeing and finishing wastewater is discharged. In addition, currently commercially available functional fabrics have only a single function, and for consumers who require multiple functions at the same time, there are still deficiencies in commercially available functional fabrics.

In view of the above problems, according to an object of the present invention, there is provided a method for producing an organic-inorganic hybrid material comprising the steps of: providing a thiazole monomer represented by the following formula (1), Formula (1); coupling a thiazole monomer with NN dimethylaniline to obtain a thiazole dye, wherein the thiazole dye is represented by the following formula (2), Formula (2); reacting a thiazole-based dye with vinyltriethoxyoxane to obtain a precursor, wherein the precursor system is represented by the following formula (3), Formula (3); and subjecting the precursor and the zirconia sol to a condensation reaction to obtain an organic-inorganic hybrid material represented by the following formula (4), Or (4); or reacting a precursor, a zirconia sol, and methyltrimethoxydecane to obtain an organic-inorganic hybrid material represented by the following formula (5), Formula (5).

Preferably, the zirconia sol is obtained by dissolving zirconium n-propanolate in ethanol and then hydrolyzing the reaction to adjust the pH to 3 to 4.

Preferably, the organic-inorganic hybrid material represented by the formula (4) is a thiazole-based dye: vinyltriethoxysilane: zirconium dioxide sol = 1:5:a, and a is between 1 and 12 The ear is prepared by a condensation reaction.

Preferably, the organic-inorganic hybrid material represented by the formula (5) is a thiazole dye: vinyltriethoxysilane: zirconium dioxide sol: methyltrimethoxydecane = 1:5:5:b, and b A molar ratio of between 1 and 12 is obtained by a condensation reaction.

Preferably, the organic-inorganic hybrid material represented by the formula (5) is a thiazole dye: vinyltriethoxysilane: zirconium dioxide sol: methyltrimethoxydecane = 1:5:c:5, and c A molar ratio of between 1 and 10 is obtained by a condensation reaction.

According to another object of the present invention, there is provided an organic-inorganic hybrid material which is produced by the above-described production method.

According to still another object of the present invention, there is provided a processed fabric which is produced by treating a polyester fiber with an organic-inorganic hybrid material produced by the above-described manufacturing method.

The present invention provides an organic-inorganic hybrid material, a method for producing the same, and a processed fabric thereof. Since the present invention adds MTMS having a methyl group, since it is a push electron-based group, its surface energy is low, and a good water-repellent effect can be produced. Among them, the contact angle before washing without water can be as high as 145.9 degrees. Therefore, the present invention can provide a processed fabric having an excellent water repellency effect. Further, since the organic-inorganic hybrid material of the present invention has a large molecular weight, it can produce a good wash fastness. In addition, the mesh structure of the present invention also contributes to fixing color. Further, the present invention has a zirconium-containing structure capable of providing excellent heat storage and heat retention by agglomeration. Therefore, the organic-inorganic hybrid material of the present invention can simultaneously impart various characteristics to the fabric, thereby improving the problems of the prior art.

In order to make the above objects, technical features, and actual implementation benefits more readily understood by those of ordinary skill in the art, the embodiments will be described in more detail below with reference to the drawings.

According to the object of the present invention, a method of producing the organic-inorganic hybrid material of the present invention will be described below.

In one embodiment of the invention, the drugs used are as follows: 1. Thiourea: ACROS, Belgium, reagent grade. 2. Iodine: Lin Chun Pharmaceutical Industry. 3. Acetophenone: ACROS, Belgium, reagent grade. 4. Sodium carbonate (Na ₂ CO ₃ ): Shimajiu Pharmaceutical Co., Ltd., reagent grade. 5. Hydrochloric acid (HCl): NIHON SHIYAKU REAGENT, reagent grade. 6. Sulfuric acid (97%): reagent grade. 7. Sodium nitric: Lin pure pharmaceutical industry. 8. Nitric Acid (69~71%): NIHON SHIYAKU REAGENT, reagent grade. 9. Ethanol: Linchun Pharmaceutical Industry. 10. Acetone: Lin Chun Pharmaceutical Industry. 11. Zirconium n-propoxide (TPOZ, 98%): ACROS, Belgium, reagent grade. 12. Ethyl ether: ACROS, Belgium, reagent grade. 13. Ammonia water: Lin pure pharmaceutical industry. 14. Methyltrimethoxysilne (MTMS): ACROS, Belgium, reagent grade. 15. Triethoxy-vinylsilane (VTES, 97%): ACROS, Belgium, reagent grade 16. Sodium hydroxide: ACROS, Belgium, reagent grade.

In an embodiment of the invention, the equipment used is as follows: 1. Flat magnet hot stirrer (Whatman, 9970-802NA) 2. Infrared spectrum analyzer (FT-IR, Bio-Red Digilab FTS-40) 3. Microanalytical Scorpio (FA-2000) 4. Constant Temperature Stirrer (Fudata FDO-510) 5. Abrasion Tester (HT-8031) 6. Stereotype Dryer (Chang Yang R3) 7. Superconducting NMR Resonance 500 NMR (BRUKER ADVANCE500 Solution-NMR) 8. Field emission scanning electron microscope (Fe-SEM) (Philips XL40 FE-SEM) 9. Static contact angle measuring instrument (label: KSV, model: CAM100) 10. Color difference meter (label: NIPPON DENSHOKU, model: ND-300A made in Japan) 11. Halogen thermocouple tester (TENMARS, TM-747D)

In an embodiment of the invention, a thiazole monomer of formula (1) is provided. The reaction of formula (1) is shown in the scheme (1): Process (1).

Specifically, thiourea (1.52g; 0.02mole), iodine (1.269g; 0.01mole) and phenethyl hydrazine (1.20g; 0.01mole) were weighed first, placed in a round bottom flask, stirred, and then separated. After heating to reflux for 4 hours, the mixture was filtered and washed with diethyl ether. The solid which was taken out was placed in 300 mL of hot water, and then ammonia water was added dropwise to precipitate a solid.

Following the above, a thiazole monomer having a reactive group as shown in the formula (1) is used as a diazonium salt, and NN dimethylaniline is used as a coupling salt, and the coupling reaction is carried out to obtain a formula (2). ) a thiazole dye as shown. The reaction of formula (2) is shown in the scheme (2): Process (2).

Specifically, 0.176 g (0.001 mole) of thiazole monomer was weighed and 8 mL of hydrochloric acid and 6 mL of sulfuric acid were added until the thiazole monomer was completely dissolved. Then, an appropriate amount of ionized water was added to 0.05 g (0.001 mole) of the sodium sulfite liquid, and a solution containing the thiazole monomer was added dropwise every two minutes, and the mixture was stirred for 1 hour in an ice bath until uniformly dispersed. Another 0.121 g (0.001 mole) of N,N-dimethylaniline liquid was weighed, and an appropriate amount of aqueous sodium carbonate solution and an appropriate amount of alcohol were added. Next, the solution containing the thiazole monomer was dropped into a solution containing N,N-dimethylaniline in an ice bath and mixed, and after stirring for 1 hour, the pH was adjusted to between 4 and 5, and the mixture was stirred for 1 hour. After that, adjust the pH to between 6 and 7. Finally, the thiazole dye is obtained by filtration and drying.

Subsequently, the thiazole dye is completely dissolved in an ethanol solvent, the thiazole dye is mixed with vinyl triethoxy decane, placed in a constant temperature water bath, heated under reflux for 4 hours, and the solvent is evaporated and dried at room temperature. In order to obtain a precursor as shown in the formula (3). The reaction of formula (3) is shown in the scheme (3): Process (3).

In addition, the zirconia sol (ZrO ₂ ) of the present invention is prepared by the following steps: pouring zirconium n-propoxide, ethanol and deionized water into a double-mouth round bottom bottle, and setting it in a reflux device to maintain the temperature at 70 After °C for 30 minutes, nitric acid was added to adjust the pH to between 3 and 4, and the reaction was obtained in one hour.

Finally, the precursor and the zirconia sol are subjected to a condensation reaction to obtain an organic-inorganic hybrid material of the present invention. The reaction scheme of the organic-inorganic hybrid material according to the formula (4) and the formula (5) of the present invention is shown by the scheme (4): Formula (4) Formula (5) Process (4).

Specifically, the precursor shown in the formula (3) and the above-mentioned zirconia sol are mixed in different proportions in Table 1 and placed in a constant temperature stirring device, and the temperature is maintained at 70 ° C and heated under reflux for 6 hours. A condensation reaction is carried out to obtain an organic-inorganic hybrid material as shown in the formula (4).

Alternatively, the precursor as shown in the formula (3) and the above-mentioned zirconia sol and methyltrimethoxydecane (MTMS) are mixed according to the different ratios of Table 2 and Table 3, and placed in a constant temperature stirring device to set the temperature. The mixture was heated under reflux at 70 ° C for 6 hours to carry out a condensation reaction to obtain an organic-inorganic hybrid material as shown in the formula (5).

The organic-inorganic hybrid materials D ₁ to D ₄ as shown in the formula (4) can be prepared according to the molar ratio conditions shown in Table 1; the organic-inorganic hybrid materials M ₁ to M ₄ and R ₁ shown in the formula (5) _; ~R ₄ can be prepared according to the molar ratio conditions shown in Table 2 and Table 3, respectively. The present invention relates to the organic-inorganic hybrid materials prepared by the respective molar ratio conditions corresponding to the numbers in Tables 1 to 3, respectively.

Table 1   No. Thiazole dyes Vinyl triethoxy decane Zirconia sol D1 1 5 2.5 D2 1 5 5 D3 1 5 7.5 D4 1 5 10

Table 2   No. Thiazole dyes Vinyl triethoxy decane Zirconia sol Methyl trimethoxy decane Q1 1 5 5 2.5 Q2 1 5 5 5 Q3 1 5 5 7.5 Q4 1 5 5 10

table 3   No. Thiazole dyes Vinyl triethoxy decane Zirconia sol Methyl trimethoxy decane R1 1 5 1 5 R2 1 5 3 5 R3 1 5 5 5 R4 1 5 7 5

In an embodiment, the organic-inorganic hybrid material of the present invention may further comprise Al, Sn, Ti, or a combination thereof.

In one embodiment, the woven fabric fibers are processed using the organic-inorganic hybrid material of the present invention described above, subjected to a two-dip two-pressure method, and subjected to a thermo-penetration treatment. The processed fabric may be polyester PET having a processing condition of 180 ° C for 120 seconds, or may be a polyester PTT having a processing condition of 160 ° C for 120 seconds.

Among them, the molecular formula of polyester PET is as shown in formula (6). Formula (6), and its specifications are .

Among them, the molecular formula of polyester PTT is as shown in formula (7). Equation (7), and its specifications are .

In this paper, ED ₁ ~ ED ₄ represent processed fabrics obtained by processing PET with D ₁ ~ D ₄ respectively; TD ₁ ~ TD ₄ represent processed fabrics obtained by processing PET with D ₁ ~ D ₄ respectively; EM ₁ ~ EM _{The 4} series represents a processed fabric obtained by processing PET with M ₁ to M ₄ , respectively. TM ₁ ~ TM ₄ represent the processed fabrics obtained by processing PTT with M ₁ ~ M ₄ respectively; ER ₁ ~ ER ₄ represent the processed fabrics obtained by processing PET with R ₁ ~ R ₄ respectively; TR ₁ ~ TR ₄ represents The processed fabric obtained by processing PTT with R ₁ to R ₄ respectively.

In the examples of the present invention, the following analysis was carried out to confirm the structure of the organic-inorganic hybrid, and the functionality of the processed polyester fabric was confirmed.

FT-IR analysis

In one example, the functional groups possessed by the organic-inorganic hybrid materials D ₁ to D ₄ and R ₁ to R _{4 of} the present invention are analyzed by an infrared spectrum analyzer. The parts (A) and (B) of Fig. _{1 are} FT-IR analysis views of the organic-inorganic hybrid materials D ₁ to D ₄ and R ₁ to R ₄ , respectively.

As shown in Fig. 1(A), it is understood that the organic-inorganic hybrid materials D ₁ to D ₄ have absorption peaks of NH groups and CH groups at 3438 cm ^-1 and 2932 cm ^-1 , respectively, and 1615 cm ^-1 to 1590 cm ^{-1 .} It is a characteristic peak range of the phenyl group. There is a characteristic peak of Zr-O group near 600cm ^-1 , the proportion of zirconium sol increases and the Zr-O absorption peak increases obviously, and there is also a Si-O absorption peak near 1100 cm ^-1 .

As shown in part (B) of Fig. ¹ , it is understood that the organic-inorganic hybrid materials R ₁ to R ₄ have absorption groups of NH groups and CH groups at 3432 cm ^-1 and 2965 cm ^-1 , respectively, and 1634 cm ^-1 to 1598 cm ^{- 1} is a phenyl group characteristic peaks range, 1243cm ^-1 near the Si-C has an absorption peak at 1054 cm ^-1 when a zirconium sol with a Si-O absorption peak, Zr-O group has characteristic peaks at 560 cm ^-1, The ratio increases and the Zr-O absorption peak slightly increases.

²⁹ Si-NMR analysis

In one example, the organic-inorganic hybrid materials M ₁ to M _{4 of the} present invention are analyzed by a superconducting nuclear magnetic resonance spectrometer. Fig. 2 is a ²⁹ Si-NMR analysis chart of the organic-inorganic hybrid materials M ₁ to M ₄ .

As shown in Fig. 2, it can be seen that the absorption peak T ¹ appears at d: -55.32 ppm, the absorption peak T ² appears at d: -64.16 ppm, and the absorption peak Q ¹ appears at d: -79.08 ppm, which is The structure of the absorption peak of Si-O-Si after hydrolysis of VTES is a structure type of Si-OR such as (OR) ₃ -Si (-OSi≡) having three substituents in the Si tetra bond. When the organic-inorganic hybrid materials M ₁ to M ₄ fix the zirconium dioxide sol ratio and change the MTMS ratio, the higher the MTMS ratio, the weaker the absorption peak intensity of Q ¹ and the T ¹ absorption peak such as R-Si(-OR) ₂ The absorption intensity of the structural form of (-OSi≡) is weakened, and the absorption intensity of the network structure of T ² absorption peak such as R-Si(-OR)(-OSi≡) ₂ is enhanced with the increase of MTMS concentration. trend.

SEM analysis

In one example, the surface of the processed fabric of the present invention is analyzed by a scanning electron microscope. Parts (A) to (D) of Fig. _{3 are} SEM analysis views of the processed fabrics ED ₁ to ED ₄ , respectively. Parts (A) to (D) of Fig. _{4 are} SEM analysis views of the processed fabrics EM ₁ to EM ₄ , respectively. Parts (A) to (D) of Fig. _{5 are} SEM analysis views of the processed fabrics ER ₁ to ER ₄ , respectively. Fig. 6 (A) to (D) are SEM analysis views of the processed fabrics TD ₁ to TD ₄ , respectively. Fig. 7 (A) to (D) are SEM analysis views of the processed fabrics TM ₁ to TM ₄ respectively. Fig. 8 (A) to (D) are SEM analysis views of the processed fabrics TR ₁ to TR ₄ , respectively.

As shown in part (A) of Fig. 3, it was found that the processed fabric ED _{1 was} observed on the surface and had a film attached to the surface, and fine small particles adhered to the entire surface of the fiber. As shown in part (B) of Fig. 3, it is understood that as the proportion of the D-series organic-inorganic hybrid material increases, there is still a film structure on the surface of the processed fabric ED ₂ , but fine small particles are increased and the film is thickened. As shown in part (C) of Fig. ₃ , it is known that the surface of the processed fabric ED ₃ has agglomerated and it is impossible to form a film covering the surface of the fiber while maintaining the network structure. As shown in part (D) of Fig. 3, it is understood that the agglomeration phenomenon of the processed fabric ED ₄ is more serious and the film structure cannot be maintained. The reason is that when the concentration of zirconia sol is low, the organic-inorganic hybrid materials D ₁ and D ₂ can maintain the network structure by the triethoxy decane bond structure of vinyl triethoxy decane, but at the same time Small particles produced by the agglomeration phenomenon can still be observed, which shows that the zirconia sol has a high agglomeration property, and when it is unilaterally added to the organic-inorganic hybrid material system, it is difficult to maintain the network structure after exceeding a certain molar ratio. The analysis of the dye adhesion of the same series of organic-inorganic hybrid materials on the TD series of processed fabrics is shown in Figure 6 (A) and (B), which also has a network structure to produce a film covering the fibers. There is agglomeration on the surface, and as shown in Fig. 6 (C) and (D), the agglomeration phenomenon as shown in Fig. 3 can also be observed.

As shown in part (A) of Fig. 4, it can be seen that the surface of the processed fabric EM ₁ adhered to the film and a small amount of zirconium was agglomerated because the concentration ratio of the zirconia melt was too high and the concentration was too large. As shown in parts (B) to (D) of Fig. 4, it is understood that as the proportion of the M-series organic-inorganic hybrid material increases, the surface of the processed fabric EM ₂ to EM ₄ fibers produces more particles and a small amount of film covering the surface of the fiber. The analysis of the dye adhesion of the same series of organic-inorganic hybrid materials on the FabricTM series is shown in Figure 7 (A) to (D), which can also be observed as shown in Figure 4. Fabric surface properties. Therefore, in the M series of organic-inorganic hybrid materials, excessive zirconium takes away the position of the ruthenium in the network structure, causing the network structure to be unmaintained and thus destroyed, resulting in the inability to cover the fiber surface in a mesh shape, and serious agglomeration occurs. And may have an adverse effect on the physical properties of the processed fiber.

As shown in part (A) of Figure 5, it can be seen that a small amount of zirconium agglomerates adhered to the surface of the fiber of the processed fabric ER ₁ because the proportional concentration of cerium is too high, and the concentration of the zirconium sol is too large, resulting in MTMS and vinyl triethoxy. The decane reaction is more complete than that of the zirconia sol, resulting in the processing of the fabric ER _{1 of the} organic-inorganic hybrid material R ₁ after the processing of the polyester PET and the polyester PTT fabric to produce a distinct film covering the fiber but can be easily observed. The phenomenon of agglomerated state of zirconium, and as shown in part (A) of Fig. 8, the same is true for the processed fabric TR1, so that when the MTMS molar ratio exceeds the zirconium sol molar ratio, MTMS and vinyltriethoxy group are known. The decane reaction is more complete than the zirconia sol, and the zirconia sol is not easily involved in the reaction in the synthesis system, so the agglomeration phenomenon is remarkable. As shown in Fig. 5(B) to (D) and Fig. 8(B) to (D), the processed fabric of the R series after the organic-inorganic hybrid material can be found to be in agglomerated state of zirconium. The increase in proportion is due to excessive zirconium robbing the position of the ruthenium in the network structure, resulting in the mesh structure being unsustainable and being destroyed, resulting in the inability to cover the fiber surface in a mesh form, causing severe agglomeration and possibly processing the fiber. The physical properties cause adverse effects.

EDS element analysis

In one example, the organic-inorganic hybrid materials D ₁ to D ₄ , M ₁ to M ₄ and R ₁ to R _{4 of the} present invention were analyzed by elemental analysis, and the results are shown in Table 4 and Figure 9. The parts (A) to (F) of Fig. 9 are EDS analysis charts of the organic-inorganic hybrid materials D ₁ , D ₃ , M ₁ , M ₃ , R ₁ and R ₃ , respectively.

Table 4   Number element composition (%) COS Si Zr D1 37.48 13.48 2.89 7.25 39.29 D2 36.25 14.77 1.74 5.6 42.05 D3 34.74 16.2 1.22 4.07 44.33 D4 23.63 20.52 1.32 3.11 50.85 M1 24.28 18.07 2.49 14.68 40.52 M2 25.43 19.74 2.14 17.52 35.15 M3 18.22 22.96 1.84 26.75 31.38 M4 14.75 29.23 1.93 29.76 24.74 R1 26.8 24.06 1.43 19.02 28.69 R2 23.16 25.35 1.93 18.32 31.24 R3 22.42 26.31 0.82 17.2 33.26 R4 15.11 28.37 0.69 16.45 39.38

As shown in the parts of Tables 4 and 9 (A) to (B), it is understood that the more the addition of the zirconia sol of the organic-inorganic hybrid materials D ₁ to D _{4 ,} the higher the zirconium content, but the added content per After the increase, the element Si decreases, the element C gradually decreases, and the element O relatively increases. The zirconium content gradually increases because the zirconium oxide film bond Zr-O-Zr may be formed at a high ratio. Referring to Table 4 and Figure 9 (C) to (D), it can be seen that when the organic-inorganic hybrid materials M ₁ to M ₄ fix the molar ratio of the zirconium sol and gradually increase the MTMS molar ratio, the MTMS content from the EDS analysis is more More, Si has a rising condition, which may be due to the formation of zirconium oxynitride film-bonded Zr-O-Si when the ratio is increased, and the position of Zr is gradually replaced by Si. Referring to Tables 4 and 9 (E) to (F), it can be seen that under the fixed MTMS, the molar ratio of zirconium increases with the molar ratio of zirconium, so that the structural position in the network of the yttrium element is reacted by zirconium. The relative decrease, so the Si content in the table will decrease, and its mechanism of action is similar to that of the organic-inorganic hybrid materials M ₁ to M ₄ . In the zirconium-oxygen thin film bonded Zr-O-Si, the position of Si is gradually replaced by Zr.

Dyeing and leveling analysis

In one example, the colorability and leveling property of the processed fabric of the present invention were analyzed, and the results are shown in Table 5. The coloring property is to compare the color difference between the dyed fabric after dyeing and the blank test cloth, and to indicate the shade of the dyed fabric, and to obtain the coloring ΔE value of the dyed fabric by using a color difference meter. The leveling property is the difference between the maximum value and the minimum value of ΔE measured in the same piece of dyed cloth, and the degree of uniformity can be known.

table 5      Physical Fabrics PET Physical Fabrics PTT Colourability (△E) Level Dyeability (△E) Colorability (△E) Level Dyeability (△E) ED1 5.14 0.46 TD1 4.56 0.34 ED2 6.36 0.69 TD2 5.46 0.58 ED3 6.99 0.71 TD3 6.63 0.49 ED4 7.75 0.54 TD4 6.80 0.62 EM1 5.52 0.43 TM1 5.11 0.85 EM2 6.33 0.42 TM2 6.23 0.39 EM3 5.21 0.73 TM3 6.22 0.92 EM4 4.55 0.31 TM4 4.51 0.87 ER1 5.26 0.44 TR1 3.22 0.52 FR2 6.65 0.57 TR2 5.83 0.42 ER3 6.21 0.73 TR3 4.22 0.79 ER4 5.71 0.31 TR4 3.57 0.66

As shown in Table 5, it was found that the results of processing different types of fabrics using different organic-inorganic hybrid materials were inconsistent. The organic-inorganic hybrid material D series of processed fabrics ED ₁ to ED ₄ and the processed fabrics TD ₁ to TD ₄ have improved colorability as the zirconia sol Moire ratio increases, and it can be seen from FIGS. 3 and 6 The reason is that the processed fabric ED ₁ and the TD ₁ fiber surface form a network structure to cause a decrease in colorability, while the processed fabrics ED ₂ , ED ₃ and ED ₄ , and the processed fabrics TD ₂ , TD ₃ and TD _{4 are} colored. The reason for the increase in the probability may be that the zirconia sol itself has agglomeration characteristics, and as the proportion of the zirconium sol increases, the agglomeration will gradually begin to occur, resulting in the destruction of the network structure. Therefore, the agglomerates are attached to the surface of the fiber instead of being covered. The mesh structure, so the colorability rises. At the same time, it can be found that the processed fabrics EM ₃ , EM ₄ , ER ₃ , ER ₄ , TM ₃ , TM ₄ , TR ₃ , TR _{4 ,} etc. are found in the processed fabrics EM series, ER series, TM series and TR series. The tendency to color is reduced.

In addition, the fabric surface of each series of processed fabrics has a bright surface characteristic due to the inorganic mesh structure. In terms of the level of dyeing, the △E values can reach the range acceptable for the rating, and the full range of dyeing properties are not more than 1 in the range standard. Preferably, finer dye particles are used to achieve better level uniformity.

Wash fastness and dyeing abrasion analysis

In one example, the wash fastness of the processed fabric of the present invention was analyzed, and the results are shown in Table 6. The washing resistance test is based on the CNS1494 L48 A3 test method. The test cloth specifications are 1 piece (10 cm × 5 cm) and 1 piece of white cloth (5 cm × 5 cm). The test conditions are soap 5g/L and sodium carbonate 2g. /L, 10 stainless steel balls, 100 ml liquid, and treated at 60 ° C for 30 min. The abrasion resistance of dyed fabrics is determined according to CNS1499 L3032 test method. The test cloth specifications are 1 piece of dyed cloth (22 cm × 3 cm) and 1 piece of white cloth (5 cm × 5 cm). The test conditions are type B (scientific vibration). Type) abrasion tester for 100 times.

Table 6   Washable, abrasion resistant, fading, cloth, cloth, wet, dry, fading cloth, contaminated cloth, fading cloth, pollution cloth, ED1 4 4 4 3-4 3-4 4 ED2 4 4 4-5 4 4-5 4 ED3 4 5 4-5 4 4- 5 5 ED4 4-5 5 4-5 4-5 4-5 5 EM1 3-4 3-4 4 4 4 4 EM2 4 4 4 4 4 4 EM3 4 5 4-5 4-5 4 4 EM4 4-5 5 4-5 4 4 4-5 ER1 4 4 4 3-4 4-5 4 ER2 4-5 4-5 4 3-4 4-5 4 ER3 4 4-5 4 5 4-5 4 ER4 4-5 4-5 4-5 5 4-5 4-5 TD1 3-4 3-4 3-4 3-4 4-5 4 TD2 4 4-5 4 3-4 4-5 4 TD3 4 4-5 4 4 4-5 4 TD4 4-5 4-5 4 4 4-5 4 TM1 3-4 4 4-5 3-4 4 3-4 TM2 4 4-5 4-5 3-4 4-5 4-5 TM3 4-5 4-5 4-5 3-4 4-5 4-5 TM4 4-5 4-5 4-5 4 4-5 4-5 TR1 4 4-5 3-4 3-4 4-5 3 -4 TR2 4 4-5 5 3-4 4-5 4-5 TR3 4 4-5 5 4 4-5 4 TR4 4-5 4-5 5 5 4-5 4

As shown in Table 6, it can be seen that the full range of processed fabrics has a fast rub resistance rating, dry rubbing is roughly 4-5 grades, wet rub fastness is roughly 4-5 grades, and each dyed fabric is known to have a wash fastness rating. The fading rating is roughly 4, and the pollution rating is roughly 4-5. Due to the bonding force between the azo dye and the polyester fiber, it is a combination of hydrogen bonding and van der Waals. Therefore, the washing fastness is not very good. Strong combination, after the addition of zirconium dioxide sol, the zirconia sol has the characteristics of forming a network, but at the same time, the inorganic zirconium also has agglomeration characteristics, and has the effect of protecting and fixing the color. The network structure formed by adding the cerium/zirconium sol has a better fixing effect than the addition of the zirconia sol, and it can be known that the reticular network structure contributes to the function of fixing the color.

Contact angle analysis

In one example, the contact angle of the processed fabric of the present invention was analyzed, and the results are shown in Tables 7 and 10 (A) to (F). Fig. 10 (A) to (F) are the contact angle analysis charts of the processed fabric ED series, TD series, EM series, TM series, ER series and TR series, respectively. The contact angle of the processed fabric of the present invention was measured by a static contact angle measuring instrument, and the contact angle angle measured at five points was taken and the average value was calculated.

Table 7          Physical PET contact angle (degrees) Physical PET contact angle (degrees) ED1 after washing without washing and washing with water ED1 133.4 126.9 EM3 141.8 135.6 ED2 135.9 128.4 EM4 145.9 138.2 ED3 137.1 131.2 ER1 134.9 127.4 ED4 139.9 132.1 ER2 136.3 128.3 EM1 138.9 130.4 ER3 139.1 130.4 EM2 139.8 132.2 ER4 141.4 133.9 Physical PTT Contact angle (degrees) Physical PTT contact angle (degrees) Not washed after washing without washing After washing TD1 123.6 116.5 TM3 139.9 131.6 TD2 126.2 118.2 TM4 141.5 134.9 TD3 128.9 124.1 TR1 124.8 117.6 TD4 131.8 127.3 TR2 130.1 121.6 TM1 134.1 125.9 TR3 132.4 124.9 TM2 136.6 128.6 TR4 134.7 126.5

As shown in Tables 7 and 10 (A) to (B), the D series of organic-inorganic hybrid materials is a single addition of a molar ratio of molar ratio of zirconia sol, and the contact angle is related to the zirconia sol. The proportion increased and the contact angle increased. At the same time, it was found that the effect of polyester PTT processing was not as good as that of polyester PET, but the performance on polyester fabrics had the same regular physical properties. As shown in Table 7 and Figure 10 (C) to (F), the organic-inorganic hybrid material M series is fixed with a fixed zirconia sol molar ratio and a modified MTMS molar ratio, and the organic-inorganic hybrid material R series is fixed. The MTMS molar ratio and the changed zirconia sol Moire ratio show that the effect of adding the fixed zirconia sol molar ratio to the change of the molar ratio is better, and the higher the contact angle is, the higher the contact angle is. The effect of polyester PTT processing is not as good as polyester PET. According to the results of the above observations, it is found that the polyester fiber has a large interfiber void, which affects the contact angle property. When polyester PET is processed by various series of organic-inorganic hybrid materials, the resulting fiber-to-film is compared with the film. Large enough but not sufficient to support the water droplets, the agglomerated zirconium is used to help the fabric support the water droplets before the water washing, but after the water washing, the agglomerates which are not formed into a film are washed away, and thus the contact angle is lowered.

Water dialing analysis

In one example, the water repellency of the processed fabric of the present invention was analyzed, and the results are shown in Table 8. The dyed fabrics were placed in a 6-inch circular frame and sprayed onto the dyed fabric via a 250 mL funnel. After about 20-25 seconds, the water droplets on the surface of the fabric were dropped, thereby determining the water level. . According to the CNS AATCC JIS score and ISO rating, the test cloth size is 20 cm × 20 cm. ISO rating 1 indicates that the surface is all wet, CNS AATCC JIS score is 50; ISO rating 2, representing the majority of the surface is wet, CNS AATCC JIS score is 70; ISO rating 3, representing the surface of the dispersion of wet The CNS AATCC JIS score is 80; the ISO rating is 4, which means the surface is slightly wet, the CNS AATCC JIS score is 90; the ISO rating is 5, which means the surface is not wet, and the CNS AATCC JIS score is 100.

Table 8   Fabrics for processing PET water-repellent PTT water-repellent ED1 3-4 TD1 3 ED2 3-4 TD2 3 ED3 4 TD3 3-4 ED4 3-4 TD4 3 EM1 4 TM1 4 EM2 4-5 TM2 4 EM3 4-5 TM3 4-5 EM4 5 TM4 4-5 ER1 4 TR1 3-4 ER2 4 TR2 4 ER3 4-5 TR3 4 ER4 4-5 TR4 4-5

As shown in Table 8, the number of processed fabric grades of polyester PTT is generally worse than that of polyester PET, which is gradually reduced by the processed fabrics ED ₁ to ED ₄ and TD ₁ to TD ₄ to which the zirconium dioxide zirconia sol is attached, wherein The ED ₁ in the processed fabric ED series is up to 3-4 grades. The organic-inorganic hybrid material R series of processed fabrics ER ₁ to ER ₄ and TR ₁ to TR _{4 are} also gradually lowered, but ER ₁ can reach level 4. Organic-inorganic hybrid material M series of processed fabrics EM ₁ to EM ₄ and TM ₁ to TM ₄ gradually increase the number of stages, EM ₄ is closer to 5, which proves that MTMS and zirconia sol have film-forming properties, which can cover the surface of the fabric. Water transfer effect.

Gas permeability analysis

In one example, the gas permeability of the processed fabric of the present invention was analyzed, and the results are shown in Table 9. According to the ASTM D737-2004 test method, the test sample is fixed on the ventilator, and when the air passes through the surface of the fabric to a predetermined pressure difference and remains stable, the gas flow rate through the sample is measured, and the data at the 14-point position is tested. The average is the result of the test. Among them, the test cloth specifications are 1 yard of dyed cloth and a pressure difference of 125Pa.

Table 9               Physical processing fabric permeability (cm3/cm2/s) Physical processing fabric permeability (cm3/cm2/s) PET original fabric 90.4 PTT original fabric 15 ED1 82.9 TD1 12.9 ED2 81.6 TD2 12.5 ED3 80.9 TD3 12.2 ED4 79.1 TD4 11.2 EM1 79.1 TM1 14.9 EM2 78.5 TM2 14.8 EM3 78.1 TM3 14.2 EM4 75.0 TM4 13.5 ER1 84.5 TR1 13.1 ER2 80.8 TR2 12.6 ER3 76.1 TR3 11.9 ER4 75.5 TR4 11

As shown in Table 9, it is understood that the breathability of the original embryo is higher than that of the PTT fabric because the PET fabric is looser than the PTT fabric fiber, and therefore the gas permeability is better. The gas permeability of the processed fabrics of various series of organic-inorganic hybrid materials decreases with the increase of the molar ratio of the organic-inorganic hybrid materials, which may be due to the relationship between inorganic zirconium and bismuth film formation or inorganic zirconium agglomeration. In contrast to the above SEM, in the ED series and the TD series of processed fabrics of D series processing of organic-inorganic hybrid materials, the gap between the fabrics becomes smaller when the processed fabric ED ₁ and the TD ₁ zirconia sol form a film, and as the zirconium ratio increases, The inorganic zirconium agglomeration characteristics produced by the processed fabrics ED ₂ to ED ₄ and TD ₂ to TD ₄ fill the voids between the fabrics, and thus the gas permeability is inferior to that of the original embryo. In the EM series, ER series, TM series and TR series of organic-inorganic hybrid materials M series and R series processing, when the film is formed by MTMS and zirconia sol, the gap between the fabrics becomes smaller, so the ventilation is reduced as the ratio increases. Sex.

Thermal storage analysis

In one example, the heat storage and heat retention properties of the processed fabric of the present invention were analyzed, and the results are shown in Table 10 and Figure 11 (A) to (D). Figure 11 (A) to (D) are the thermal insulation analysis of the processed fabric ED series, TD series, ER series and TR series. Among them, the four-point probe temperature difference meter is used for detection and comparison. The test cloth specification is 10 cm × 10 cm, and the 250-watt halogen lamp is used for 10 minutes and the temperature is lowered for 10 minutes. It is recorded once every minute and 20 data is taken as result.

Table 10          Time PET heating 600 (sec) cooling 1200 (sec) time PTT heating 600 (sec) cooling 1200 (sec) raw fabric 28.43 0.27 original fabric 29.27 0.17 ED1 45.14 2.15 TD1 43.93 1.98 ED2 48.17 2.27 TD2 44.81 2.07 ED3 49.36 2.47 TD3 44.99 2.19 ED4 50.65 2.77 TD4 50.49 2.55 ER1 30.82 2.07 TR1 40.27 1.62 ER2 28.65 4.22 TR2 40.48 2.15 ER3 36.73 4.17 TR3 40.52 2.69 ER4 33.42 4.89 TR4 41.37 3.04

As shown in Tables 10 and 11 (A) to (D), it can be seen that the temperature difference of the polyester raw fabric after being irradiated by the halogen lamp for 600 seconds is the smallest, and the value of the temperature difference is increased as the content of the zirconia sol increases. Large, representing that the processed fabric is heated by the endothermic action of the organic-inorganic hybrid material, so that the processed fabric has a heat storage effect, so the more insulation of the MTMS/zirconia sol is better. Among them, in terms of thermal insulation, ED series and TD series of processed fabrics with zirconia sol alone, and ER series and TR series of processed fabrics with MTMS and zirconia sol, processed fabric ED series and TD series performance Preferably, the reason is that the zirconia sol alone causes the agglomeration of the inorganic zirconium, and the voids of the processed fabric become smaller to cover the air, and the characteristics of the zirconium itself and the agglomerated inorganic zirconium make it difficult to cool down. Produces better insulation properties.

In summary, the organic-inorganic hybrid material of the present invention can process the fabric to make the fabric have good coloring property, leveling property, heat storage property, heat preservation property and water repellency, and can adjust the inorganic mixing of the machine according to the use requirement. An organic-inorganic hybrid material having a molar ratio of materials.

While the present invention specifically describes the organic-inorganic hybrid material of the present invention, the method for producing the same, and the processed fabric thereof by way of examples and examples, it should be understood by those of ordinary skill in the art that the present invention does not deviate from the technical principles of the present invention. Modifications and changes to the examples are made under the spirit. Therefore, the scope of protection of the present invention should be as described in the patent application.

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The parts (A) and (B) of Fig. _{1 are} FT-IR analysis views of the organic-inorganic hybrid materials D ₁ to D ₄ and R ₁ to R ₄ , respectively.

Fig. 2 is a ²⁹ Si-NMR analysis chart of the organic-inorganic hybrid materials M ₁ to M ₄ .

Parts (A) to (D) of Fig. _{3 are} SEM analysis views of the processed fabrics ED ₁ to ED ₄ , respectively.

Parts (A) to (D) of Fig. _{4 are} SEM analysis views of the processed fabrics EM ₁ to EM ₄ , respectively.

Parts (A) to (D) of Fig. _{5 are} SEM analysis views of the processed fabrics ER ₁ to ER ₄ , respectively.

Fig. 6 (A) to (D) are SEM analysis views of the processed fabrics TD ₁ to TD ₄ , respectively.

Fig. 7 (A) to (D) are SEM analysis views of the processed fabrics TM ₁ to TM ₄ respectively.

Fig. 8 (A) to (D) are SEM analysis views of the processed fabrics TR ₁ to TR ₄ , respectively.

The parts (A) to (F) of Fig. 9 are EDS analysis charts of the organic-inorganic hybrid materials D ₁ , D ₃ , M ₁ , M ₃ , R ₁ and R ₃ , respectively.

Fig. 10 (A) to (F) are the contact angle analysis charts of the processed fabric ED series, TD series, EM series, TM series, ER series and TR series, respectively.

Figure 11 (A) to (D) are the thermal insulation analysis of the processed fabric ED series, TD series, ER series and TR series.

Claims (7)

A method for producing an organic-inorganic hybrid material, comprising the steps of: providing a thiazole monomer represented by the following formula (1), Formula (1); coupling a thiazole monomer with NN dimethylaniline to obtain a thiazole dye, wherein the thiazole dye is represented by the following formula (2), The thiazole dye is reacted with vinyl triethoxy decane to obtain a precursor, wherein the precursor system is represented by the following formula (3), Formula (3); and subjecting the precursor and the zirconia sol to a condensation reaction to obtain an organic-inorganic hybrid material represented by the following formula (4), (4); or reacting the precursor, the zirconia sol, and methyltrimethoxydecane to obtain an organic-inorganic hybrid material represented by the following formula (5), Formula (5). The production method according to claim 1, wherein the zirconium dioxide sol is obtained by dissolving zirconium n-propoxide in ethanol and hydrolyzing the reaction to adjust the pH to 3 to 4. The production method according to claim 1, wherein the organic-inorganic hybrid material represented by the formula (4) is the thiazole dye: vinyltriethoxysilane: zirconia sol = 1:5:a, And a molar ratio of between 1 and 12 is obtained by a condensation reaction. The manufacturing method according to claim 1, wherein the organic-inorganic hybrid material represented by the formula (5) is the thiazole dye: vinyl triethoxy decane: zirconium dioxide sol: methyl trimethoxy decane = 1:5:5:b, and a molar ratio of b between 1 and 12 is obtained by condensation reaction. The manufacturing method according to claim 1, wherein the organic-inorganic hybrid material represented by the formula (5) is the thiazole dye: vinyl triethoxy decane: zirconium dioxide sol: methyl trimethoxy decane = 1:5: c: 5, and a molar ratio of c between 1 and 10 is obtained by a condensation reaction. An organic-inorganic hybrid material produced by the method according to any one of claims 1 to 5. A processed fabric produced by treating a polyester fiber with an organic-inorganic hybrid material as described in claim 6 of the patent application.