TWI659961B - Organic/inorganic hybrid material including zirconium, method of preparing thereof and fabric production thereof - Google Patents

Abstract

The present invention provides an organic-inorganic hybrid material, the preparation method comprising the steps of: providing a 2-amino-4-methyl-benzothiazole monomer; and 2-amino-4-methyl-benzothiazole monomer and NN Dimethylaniline is subjected to a coupling reaction to obtain a heterocyclic benzothiazole dye; a heterocyclic benzothiazole dye is reacted with vinyltriethoxyoxane to obtain a precursor; and a precursor and a zirconia sol are obtained. The condensation reaction is carried out to obtain an organic-inorganic hybrid material, or the precursor, the zirconia sol, and tetraethoxysilane 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 an organic-inorganic hybrid material capable of improving heat storage and heat retention properties, dyeing fastness, water repellency and the like of a fabric, a method for producing the same, and a method for producing the same Processing fabrics.

Due to advances in technology, people's demands for living standards have increased, and the field of "clothing" in food and clothing has become more and more important. Therefore, Functional Textile or Performance Textile, which can satisfy the characteristics of heat storage, water repellency, fading, and high added value, has emerged. According to the Just-Style market survey, the market potential of global functional textiles is estimated to be approximately $60 billion, representing a significant commercial use of functional textile-related products.

Functional textiles can be obtained using physical and/or chemical processing processes. At present, organic/inorganic hybrid materials can be used in the process of functional textiles because they can simultaneously obtain the advantages of both organic materials and inorganic materials, and can be made into a new material that has the characteristics of the latter. However, after the fabric processing of the current organic/inorganic hybrid material, the heat storage and heat retention properties, dyeing fastness, water repellency and the like of the fabric are still insufficient.

According to an aspect of the invention, there is provided a method for producing an organic-inorganic hybrid material comprising the steps of: providing a 2-amino-4-methyl-benzothiazole monomer represented by the following formula (1); Formula (1); coupling a 2-amino-4-methyl-benzothiazole monomer with NN dimethylaniline to obtain a heterocyclic benzothiazole dye, wherein the heterocyclic benzothiazole dye is as follows Column (2) indicates that Formula (2); reacting a heterocyclic benzothiazole dye 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), Formula (4); or reacting a precursor, a zirconia sol, and tetraethoxy decane 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 heterocyclic benzothiazole dye: vinyl triethoxy decane: zirconium dioxide sol = 1:6: a, and a is between 1 and 15 The molar ratio between the two is obtained by a condensation reaction.

Preferably, the organic-inorganic hybrid material represented by the formula (5) is a heterocyclic benzothiazole dye: vinyl triethoxy decane: zirconium dioxide sol: tetraethoxy decane = 1:6:10:b And a molar ratio of b between 1 and 15 is obtained by a condensation reaction.

Preferably, the organic-inorganic hybrid material represented by the formula (5) is a heterocyclic benzothiazole dye: vinyl triethoxy decane: zirconium dioxide sol: tetraethoxy decane = 1:6:c:10 And a molar ratio of c between 1 and 15 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 production method provided by the present invention.

The present invention provides an organic-inorganic hybrid material, a method for producing the same, and a processed fabric thereof. The benzothiazole structure of the present invention has a relatively large molecular weight, and the two methyl structures of NN dimethylaniline also have a large molecular weight, so the present invention can provide excellent dye fastness, colorability and washing fastness. . At the same time, the zirconium-containing structure of the present invention can provide excellent heat storage and heat retention. Therefore, the organic-inorganic hybrid material of the present invention can simultaneously impart good colorability, leveling property, warmth retention, heat storage property, and water repellency 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 present invention, the drugs used are as follows: 1. Sodium carbonate (Na ₂ CO ₃ ): reagent grade, Shimao Pharmaceutical Co., Ltd. 2. Hydrochloric acid (HCl): reagent grade, NIHON SHIYAKU REAGENT 3. Nitric Acid (69~71%): reagent grade, NIHON SHIYAKU REAGENT 4. Sulfuric acid (H ₂ SO ₄ ): reagent grade, NIHON SHIYAKU REAGENT 5. Sodium nitrite: reagent Grade, (ACROS, Belgium) 6. Ethanol: Linchun Pharmaceutical Industry 7. Acetone: Lin Chun Pharmaceutical Industry 8. Triethoxy-vinylsilane (97%, VTES): Trial Pharmaceutical grade, (ACROS, Belgium) 9. Zirconium n-propoxide (TPOZ, 98%): reagent grade, (ACROS, Belgium) 10. Tetraethyl orthosilicate (TEOS): test Pharmacological grade, (ACROS, Belgium) 11. N,N-dimethylaniline: reagent grade, (ACROS, Belgium) 12. 2-Amino-4-methylbenzothiazole (2 -Amino-4-methylbenzothiazole): Test drug grade (ACROS, Belgium).

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. Stereotype Dryer (Chang Yang R3) 6. Superconducting Nuclear Magnetic Resonance Apparatus 500 NMR (BRUKER AVANCE500 Solution - NMR) 7. Solid-state nuclear magnetic resonance spectrometer (Bruker Advance 400 Solid State NMR) 8. Field emission scanning electron microscope (Fe-SEM) (Philips XL40 FE-SEM) 9. Static contact angle measuring instrument (label: KSV model: CAM100 Finland) System) 10. Color difference meter: (label: NIPPON DENSHOKU, model: ND-300A made in Japan) 11. Halogen thermocouple tester: (TENMARS, TM-747D) 12. Light diffraction analyzer: Rigaku (D/ MAX 2500V)

In one embodiment of the present invention, a 2-amino-4-methyl-benzothiazole monomer represented by the formula (1) is provided as a diazonium salt, and NN dimethylaniline is further provided as a coupling salt, After the coupling reaction, a heterocyclic benzothiazole dye represented by the formula (2) can be obtained. Formula 1) The reaction of formula (2) is shown in the scheme (1): Process (1).

Specifically, 1.64 g (0.001 mole) of 2-amino-4-methyl-benzothiazole monomer was added to 5 mL of concentrated sulfuric acid solution to dissolve the benzothiazole monomer, and then hydrochloric acid was added until completely dissolved, and then added. 0.0724g (0.00105mol) NaNO ₂ NaNO ₂ aqueous solution is prepared, with stirring under ice-cooling for 3 hours. Separately, ₃₀ mL of a 30 mL Na ₂ CO ₃ solution was prepared, and then 0.121 g (0.001 mole) of NN dimethylaniline was added, and finally ethanol was added. The diazonium salt was dropped into the coupling salt in an ice bath to mix the two solutions. After stirring for 2 hours, the pH was adjusted between 5 and 6, and after waiting for 2 hours, finally filtering and drying to obtain the desired heterocyclic benzene. And a thiazole dye.

Following the above, the heterocyclic benzothiazole dye was completely dissolved in an ethanol solvent, and the heterocyclic benzothiazole dye was mixed with vinyl triethoxy decane, placed in a constant temperature water bath, heated under reflux for 5 hours, and placed at room temperature. The solvent is evaporated and dried to obtain a precursor as shown in the formula (3). The reaction of formula (3) is shown in the scheme (2): Process (2).

Further, the zirconium dioxide sol (ZrO ₂ ) of the present invention is prepared by the following steps: zirconium n-propoxide and ethanol are dissolved at a molar ratio of 1:30, and hydrolyzed with water at a molar ratio of 1:4, and heated by reflux. Heat for 30 minutes until completely dissolved, then adjust the pH to about 3 ~ 4 with nitric acid, and finally stir until clarified.

Finally, the precursor and the zirconia sol are subjected to a condensation reaction to obtain an organic-inorganic hybrid material of the present invention. In detail, the organic-inorganic hybrid material of the present invention as shown in the formula (4) is prepared by the reaction scheme 3, and the steps are as follows: the precursor of the formula (3) and the above-mentioned zirconia sol are used. The various ratios in Table 1 were mixed and placed in a constant temperature stirring apparatus, and heated under reflux for 6 hours to carry out a condensation reaction 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 tetraethoxy decane (TEOS) are mixed in different ratios of Table 2 and Table 3, and placed in a constant temperature stirring device, and heated under reflux. After 6 hours, it was subjected to a condensation reaction to obtain an organic-inorganic hybrid material as shown in the formula (5). Among them, tetraethoxy decane is firstly added to 0.01 mole of nitric acid and 10 ml of ethanol to be hydrolyzed first, and then reacted in a reaction flask containing a precursor and a zirconia sol. The reaction is shown in process (3): Process (3).

The organic-inorganic hybrid materials Z ₁ to Z 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 Q ₁ to Q 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. Heterocyclic benzothiazole dye Vinyl triethoxy decane Zirconium oxide sol Z1 1 6 2.5 Z2 1 6 5 Z3 1 6 7.5 Z4 1 6 10

Table 2   No. Heterocyclic benzothiazole dye Vinyl triethoxy decane Zirconia sol Tetraethoxy decane Q1 1 6 10 2.5 Q2 1 6 10 5 Q3 1 6 10 7.5 Q4 1 6 10 10

table 3   No. Heterocyclic benzothiazole dye Vinyl triethoxy decane Zirconia sol Tetraethoxy decane R1 1 6 2.5 10 R2 1 6 5 10 R3 1 6 7.5 10 R4 1 6 10 10

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 fiber is processed by using the organic-inorganic hybrid material of the present invention described above, and the steps are as follows: 15 mL of an organic-inorganic hybrid material is taken, and 50 mL of an ethanol solution is added to dissolve it to be uniformly dispersed, and then a second immersion pressure is taken. The fabric fibers were dyed for 5 minutes, pre-dried at 70 ° C for 2 minutes, and subjected to thermo-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.

In this paper, EZ ₁ ~ EZ ₄ represents the processed fabric obtained by processing PET from Z ₁ ~ Z ₄ respectively; EQ ₁ ~ EQ ₄ represents the processed fabric obtained by processing PET from Q ₁ ~ Q ₄ respectively; ER ₁ ~ ER _{The 4} series represents a processed fabric obtained by processing PET with R ₁ to R ₄ , respectively. The TZ ₁ ~ TZ ₄ series represent the processed fabrics obtained by processing PTT with Z ₁ ~ Z ₄ respectively; the TQ ₁ ~ TQ ₄ series represent the processed fabrics obtained by processing PTT with Q ₁ ~ Q 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 Z ₁ to Z ₄ , Q ₁ to Q ₄ and R ₁ to R _{4 of} the present invention are analyzed by an infrared spectrum analyzer. The parts (A) to (C) of Fig. _{1 are} FT-IR analysis views of the organic-inorganic hybrid materials Z ₁ to Z ₄ , Q ₁ to Q ₄ and R ₁ to R ₄ , respectively.

Referring to the portion of Fig. 1(A), it is understood that the organic-inorganic hybrid materials Z ₁ to Z ₄ have characteristic peaks of Zr-O groups in the vicinity of 477 cm ^-1 , the proportion of zirconium sols increases and the Zr-O absorption peaks gradually increase, near 1033 cm ^-1 . It also has a Si-O absorption peak. 800cm ^-1 -1100cm ^-1 as Zr-O-Si group absorption peak range. However, with the increase in the amount of zirconia sol, Z ₁ from the absorption peak on the weakened, 1256cm ^-1 is near the absorption peak of Si-C, 1630cm ^-1 -1520cm ^-1 is a phenyl group characteristic peaks range, near 3440cm ^-1 The absorption peak of the NH group and the CH group.

Referring to the part of Fig. 1(B), it is understood that the organic-inorganic hybrid materials Q ₁ to Q ₄ have no characteristic change in the characteristic peak of the Zr-O group at 450 cm ^-1 when the amount of the zirconium sol is fixed, in the vicinity of 1054 cm ^-1 . there summit absorption due to Si-O tetraethyl orthosilicate absorption intensity ratio increases significantly, and 800cm ^-1 -1100cm ^-1 is also a Zr-O-Si group absorption peak range, near 1256cm ^-1 Si-C absorption peak, 1630cm ^-1 -1520cm ^-1 is the characteristic peak range of the phenyl group, and there is an absorption peak of the NH group and the CH group near 3430 cm ^-1 , compared with Z _{4 in the} part of Fig. 1 (A), when the zirconium concentration is high, its absorption The peak has increased significantly.

Referring to part (C) of Fig. ¹ , it is understood that the organic-inorganic hybrid materials R ₁ to R ₄ have characteristic peaks of Zr-O groups at 448 cm ^-1 , and the Zr-O absorption peaks gradually increase when the proportion of zirconium sols increases, and 1051 cm ^-1 There is a Si-absorption peak, and 800cm ^-1 -1100cm ^-1 is also a characteristic peak of the Zr-O-Si group, 1630cm ^{-1 -} 1520cm ^-1 is a characteristic peak range of the phenyl group, and there are NH groups and CH near 3440cm ^-1 The absorption peak of the group has an absorption position substantially the same as that of the portion of Fig. 1(A).

¹ H-NMR and ²⁹ Si-NMR analysis

In one example, the heterocyclic benzothiazole dye of the present invention (1), the precursor of the formula (3), and the organic-inorganic hybrid materials Z ₁ to Z ₄ are analyzed by a superconducting nuclear magnetic resonance spectrometer and a solid-state nuclear magnetic resonance spectrometer. Q ₁ to Q ₄ and R ₁ to R ₄ . Fig. 2 (A) to (B) are diagrams showing the ¹ H-NMR analysis of the heterocyclic benzothiazole dye and the precursor, respectively. The parts (A) to (C) of Fig. _{3 are} ²⁹ Si-NMR analysis charts of the organic-inorganic hybrid materials Z ₁ to Z ₄ , Q ₁ to Q ₄ and R ₁ to R ₄ , respectively.

Referring to part (A) of Fig. 2, it is found that a single peak of 6H appears at d = 3.163 ppm, which is the N, N dimethyl group on the phenyl group of the coupling salt of the heterocyclic benzothiazole dye. Methyl absorption; there is also a doublet of 2H at d=7.314–7.338ppm, which is the proton absorption at the 2nd and 6th positions of the phenyl group of the coupling salt of the heterocyclic benzothiazole dye; =6.910-6.931 A double peak of 2H appears at ppm, which is the proton absorption at the 3rd and 5th positions of the phenyl group of the coupling salt of the heterocyclic benzothiazole dye. There is a single peak of 3H at d = 2.683ppm, which is the methyl proton absorption at the 4th position on the benzothiazole ring of the heterocyclic benzothiazole dye; there is a double 1H at d=7.807-7.820 ppm The peak appears, which is the proton absorption at the 5th position on the benzothiazole ring of the heterocyclic benzothiazole dye; there is a double peak of 1H at d=7.862-7.881 ppm, which is a heterocyclic benzothiazole dye. Proton absorption at the 7th position on the benzothiazole ring; a multiplet of 1H at d=7.962-7.883 ppm, which is the sixth on the benzothiazole ring of the heterocyclic benzothiazole dye Proton absorption at the location.

Referring to the part of Fig. 2(B), it is known that a single heavy peak of 6H appears at d = 3.074 ppm, which is the methyl absorption of N, N dimethyl on the phenyl group of the coupling salt of the heterocyclic benzothiazole dye. There is also a double peak of 2H at d=6.743-6.762 ppm, which is the proton absorption at the 2nd and 6th positions of the phenyl group of the heterocyclic benzothiazole dye; at d=6.896- 6.925 ppm The double peak of 2H appears, which is the proton absorption at the 3rd and 5th positions of the phenyl group of the coupling salt of the heterocyclic benzothiazole dye. There is a single peak of 3H at d = 2.400 ppm, which is the methyl proton absorption at the 4th position on the benzothiazole ring of the heterocyclic benzothiazole dye, and 1H at d = 7.317-7.330 ppm. The double peak appears, which is the proton absorption at the 5th position on the benzothiazole ring of the heterocyclic benzothiazole dye. There is a double peak of 1H at d=7.439-7.455 ppm, which is a heterocyclic benzothiazole. Proton absorption at the 7th position on the benzothiazole ring of the dye. In particular, there is a triplet of 2H at d=7.799-7.817 ppm and d=7.858-7.877 ppm, which is the proton absorption of the methylene group of vinyltriethoxydecane, at d= There is a triplet of 9H at 8.028-8.047ppm, which is the methyl absorption on the ethoxy group of vinyltriethoxydecane. There is a quartet of 6H at d=8.195-8.211ppm. This is the methylene absorption on the ethoxy group of vinyltriethoxydecane.

Referring to the portion (A) of Fig. 3, it is understood that there is an absorption peak at d = -70.6 ppm and d = -79.9 ppm. Referring to part (B) of Figure 3, it is known that there is an absorption peak at d = -70.2 pm and d = -71.0 ppm, and there is an absorption peak at d = -80 pm, which is after hydrolysis of vinyl triethoxy decane. The structure of the absorption peak of Si-O-Si is such that there is an unreacted Si-OH functional group such as R-Si(-OSi≡) _{3 in the} Si tetra-bond, and one of the four bonds of Q ₃ is unreacted. The Si-O functional group is (RO)Si(-OSi≡) type ₃ , and the structure of Q ₄ is that all Si four bonds are completely reacted Si-O functional groups such as Si(-OSi≡) ₄ type presence. Referring to part (C) of Figure 3, it is known that there is an absorption peak at d = -70.5 pm and d = -79.4 ppm, and there is an absorption peak at d = -101.7 pm and d = -100.4 ppm, and d There is an absorption peak at -109.5 pm and d = -110.8 ppm.

Wherein, as shown in part (B) of Fig. 3, when the ratio of the zirconia sol is fixed to the organic-inorganic hybrid materials Q ₁ to Q ₄ and the ratio of tetraethoxy decane is changed, the single fixed amount of the zirconia sol is known. A small amount of tetraethoxy decane is more difficult to form a Zr-O-Si bonded network structure, and when the amount of tetraethoxy decane is gradually increased, the absorption peak intensity is remarkably enhanced, representing a Zr-O-Si bonded network. The structure has gradually formed.

SEM analysis

In one example, the surface of the processed fabric of the present invention is analyzed by a scanning electron microscope. The parts (A) to (B) of Fig. 4 are SEM images of polyester PET raw fabric and polyester PTT original fabric, respectively. Parts (A) to (D) of Fig. _{5 are} SEM analysis views of the processed fabrics EZ ₁ to EZ ₄ , respectively. Fig. 6 (A) to (D) are SEM analysis views of the processed fabrics TZ ₁ to TZ ₄ , respectively. Fig. 7 (A) to (D) are SEM analysis views of the processed fabrics EQ ₁ to EQ ₄ , respectively. Fig. 8 (A) to (D) are SEM analysis views of the processed fabrics TQ ₁ to TQ ₄ , respectively. Fig. 9 (A) to (D) are SEM analysis views of the processed fabrics ER ₁ to ER ₄ , respectively. Fig. 10 (A) to (D) are SEM analysis views of the processed fabrics TR ₁ to TR ₄ , respectively.

Referring to part (A) of Fig. 5, it is understood that the Z-processed fabric EZ ₁ has a film attached to the surface and has a slight amount of fine particles attached to the surface of the fiber. Referring to part (B) of Fig. 5, it can be seen that the surface of the processed fabric EZ ₂ increases with the proportion of the Z-series organic-inorganic hybrid material, the film structure still exists and becomes thick, and there is also a slight microparticle adhesion. Referring to part (C) of Fig. 5, it is understood that the surface of the processed fabric EZ ₃ has agglomerated and it is impossible to form a film covering the surface of the fiber while maintaining the network structure. Referring to part (D) of Fig. 5, it is understood that the surface particles of the fiber of the processed fabric EZ ₄ are significantly enlarged and increased, and the agglomeration phenomenon is more serious and the film structure cannot be maintained. It is represented that when the zirconia sol molar concentration of the mixed materials Z ₁ and Z ₂ can also maintain the sheet structure by the triethoxy decane bond structure of vinyl triethoxy decane, and at the same time exist due to agglomeration The particles produced by the phenomenon show that the zirconia sol has a high agglomeration property, and it is difficult to maintain the sheet structure after exceeding a certain molar concentration. The surface analysis results of the TZ series of processed fabrics processed by Z series organic-inorganic hybrid materials are similar to those of the EZ series. Referring to parts (A) and (B) of Fig. 6, it is also known that the sheet-like structure produces a film covering the surface of the fiber and agglomerates; referring to Fig. 6 (C) and (D), agglomeration is more observed. The phenomenon arises.

Referring to parts (A) to (D) of Fig. 7, it is understood that the surface of the Q series fibers is different from the surface of the Z-series organic-inorganic hybrid material. Referring to part (A) of Fig. 7, it can be seen that there is agglomeration on the surface of the fiber, and a small portion of the surface of the fiber is covered. Referring to parts (A) to (D) of Fig. 7, it can be seen that the fiber surface increases as the molar ratio increases the sheet structure. The more complete the film covers the surface of the fiber, the better. Referring to parts (A) and (D) of Fig. 8, it can be seen that the surface analysis results of the processed fabric TQ series processed by the Q series organic-inorganic hybrid material are similar to those of the EQ series. On the other hand, when the concentration of bismuth in the Q-series organic-inorganic hybrid material increases with the ratio, the processed fabric begins to form a sheet-like structure. It also means that when the concentration of zirconia sol is fixed, and the increase of the molar ratio with the molar ratio will make the network structure more complete fiber coverage, which means that the addition of tetraethoxy decane can help the mixed material in the fiber formation. Integrity, but the ratio of zirconia sol to bismuth oxime is close to solve the agglomeration phenomenon of zirconia sol and stabilize the sheet structure, because the film is cracked when the 矽 molar ratio is increased over the zirconium dioxide zirconia sol The phenomenon of opening, and may have an adverse effect on the processed fabric. Therefore, it is found through the surface of the fiber that the sheet structure is preferably a processed fabric EQ ₃ and a processed fabric TQ ₃ .

Referring to parts (A) to (D) of Fig. 9, it can be seen that the fiber surface-attached film of the processed fabric of the R series of organic-inorganic hybrid materials is agglomerated with a small amount of zirconium, which represents that the proportion of niobium is higher than that of zirconium dioxide. The concentration ratio of the sol is too large, so that the reaction of tetraethoxydecane with vinyltriethoxysilane is more complete than that of the zirconia sol, resulting in a reticular formation of ER ₁ as shown in Fig. 9(A). The film is covered on the fiber, and the agglomerated state of zirconium can be easily observed. Since this phenomenon is also produced in the processed fabric EQ ₄ shown in part (D) of Fig. 7 and the processed fabric TQ ₄ shown in the part (D) of Fig. 8, it is known that when the tetraethoxy decane molar ratio exceeds the oxidation When the zirconium sol Moire ratio, the reaction of tetraethoxy decane with vinyl triethoxy decane is more complete than that of the zirconia sol, and the zirconia sol is not easily involved in the synthesis system, so the agglomeration phenomenon is obvious.

Referring to parts (A) to (D) of Fig. 10, it is understood that the agglomerated state of zirconium is proportionally reduced, and a sheet-like structure is adhered to the fibers. Therefore, it is found through the surface of the fiber that the sheet structure is preferably a processed fabric ER ₃ and a processed fabric TR ₃ . In addition, the zirconia sol molar ratio of the processed fabric ER ₄ processed by the organic-inorganic hybrid material R ₄ and the processed fabric TR ₄ is too large, causing excessive zirconium to take away the position of the ruthenium in the sheet structure, so that the sheet shape The structure is broken and the film cannot be covered on the surface of the fiber, which causes severe agglomeration and adversely affects the physical properties of the fiber.

EDS element analysis

In one example, the organic-inorganic hybrid materials Z ₁ to Z ₄ , Q ₁ to Q ₄ and R ₁ to R _{4 of the} present invention were analyzed by elemental analysis, and the results are shown in Table 4. The parts (A) to (F) of Fig. 11 are EDS analysis charts of the organic-inorganic hybrid materials Z ₁ , Z ₄ , Q ₁ , Q ₄ , R ₁ and R ₄ , respectively.

Table 4   Element composition (%) COS Si Zr Z1 27.11 18.81 0.77 12.34 40.97 Z2 23.68 19.47 0.59 9.00 47.26 Z3 22.29 20.11 0.37 7.73 49.50 Z4 16.94 24.23 0.24 6.54 52.05 Q1 22.51 18.45 0.57 20.31 38.16 Q2 21.40 20.21 0.52 22.35 35.52 Q3 19.34 22.39 0.46 23.70 34.11 Q4 16.05 25.78 0.30 24.23 33.64 R1 20.00 20.88 0.47 35.41 23.24 R2 17.83 20.45 0.32 34.98 26.42 R3 16.40 22.48 0.35 27.82 32.95 R4 14.44 25.87 0.23 24.35 35.11

Referring to Tables 4 and 11 (A) to (B), it is understood that the more the addition of the zirconia sol of the organic-inorganic hybrid materials Z ₁ to Z _{4 ,} the higher the zirconium content, but the added content is increased each time. The element Si decreases, the element C gradually decreases in proportion to the mixed material, and the element O is relatively increased. The zirconium content is gradually increased because ZrO-Zr may be formed when the zirconium oxide film is formed at a high ratio. Referring to Table 4 and Figure 11 (C) to (D), it is understood that the organic-inorganic hybrid materials Q ₁ to Q ₄ fix the molar ratio of the zirconia sol, gradually increase the tetraethoxy decane molar ratio, and Si rises. In other words, when Zr-O-Si is formed in the zirconium oxynitride film bond when the ratio is increased, the position of Zr is gradually replaced by Si, and the proportion of zirconium is gradually decreased. Referring to Table 4 and Figure 11 (E) to (F), it can be seen that under the fixed tetraethoxy decane, the molar ratio of zirconium increases with the molar ratio of zirconium, so that the structural position in the flaky structure of the cerium element The content of the zirconium is relatively decreased, so the Si content in the table is decreased, and the mechanism of action is similar to that of the organic-inorganic hybrid materials Q ₁ to Q ₄ .

Light diffraction analysis

In one example, the zirconia sol powder (unsintered) of the present invention, the organic-inorganic hybrid materials Z ₄ , Q ₄ and the R series were analyzed by light diffraction analysis. Fig. 12(A) is a light diffraction analysis diagram of the zirconium dioxide sol powder and the organic-inorganic hybrid materials Z ₄ , Q ₄ and R ₄ , and Fig. 12 (B) is a light winding of the organic-inorganic hybrid material R series. Shoot the analysis chart.

Referring to part (A) of Fig. 12, it is understood that the organic-inorganic hybrid materials Z ₄ , Q ₄ and R ₄ and the zirconia sol powder exhibit an amorphous structure at room temperature. Referring to part (B) of Figure 12, when the fixed 矽 molar ratio changes the zirconium sol Moire ratio, the R ₁ diffraction peak appears at 2θ = 24 ^o , and the R ₂ diffraction peak appears at 2θ = 25 ^o , R ₃ The peak appears at 2θ=27 ^o , and the R ₄ diffraction peak appears at 2θ=29 ^o . Since the mixed material is not sintered, it exhibits an amorphous structure and no crystal phase characteristic peak appears. In addition, from the comparison of part (A) and (B) of Fig. 12, it can be seen that the zirconium dioxide sol is mixed with the precursor and the ruthenium, and the characteristic peak is shifted to the right, and the zirconium dioxide sol powder is diffracted. Now 2θ=31 ^o , the diffraction peak of the organic-inorganic hybrid material Z _{4 of the} precursor-joined zirconium series appears at 2θ=36 ^o , and the diffraction peak of the organic-inorganic hybrid material Q _{4 in} which the precursor is fixed to the zirconium concentration is changed to 2θ. =38 ^o , the precursor is connected to the zirconium concentration fixed 矽 concentration of the organic-inorganic hybrid material R ₄ diffraction peak appears at 2θ = 38 ^o , due to the organic-inorganic hybrid material Q ₄ and the organic-inorganic hybrid material R ₄ zirconia sol The concentration of cerium is the same, so the angle is the same, and the diffraction peak of the zirconia sol powder is shifted, which is represented by the amorphous phase morphology of vinyl triethoxy decane and tetraethoxy decane. influences.

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 processing fabric PET physical processing fabric PTT Colorability (△E) Dyeing (△E) Coloring (△E) Leveling (△E) EZ1 35.98 0.92 TZ1 35.12 0.58 EZ2 38.79 0.86 TZ2 37.93 0.72 EZ3 43.40 0.98 TZ3 44.85 0.91 EZ4 46.19 0.57 TZ4 43.29 0.57 ER1 29.26 0.59 TR1 30.27 0.44 ER2 30.28 0.93 TR2 34.06 0.56 ER3 33.62 0.29 TR3 28.00 0.28 ER4 28.46 0.36 TR4 26.32 0.40 EQ1 32.12 0.45 TQ1 30.72 0.40 EQ2 39.42 0.42 TQ2 39.23 0.41 EQ3 34.44 0.72 TQ3 38.30 0.22 EQ4 40.42 0.49 TQ4 34.46 0.74

Referring to Table 5, it can be seen that the results of processing different types of fabrics using different organic-inorganic hybrid materials are inconsistent. As shown in Table 5, the colorability of the processed fabrics EZ ₁ -EZ ₄ and the processed fabrics TZ ₁ -TZ ₄ increased as the zirconia sol Moire ratio increased. The SEM analysis showed that the reason was that the EZ ₁ and TZ ₁ fibers formed a network structure attached to the surface, resulting in a decrease in colorability, while the processed fabrics EZ ₂ , EZ ₃ , EZ ₄ , and the processed fabrics TZ ₂ , TZ ₃ , TZ ₄ The reason for the increase in colorability is that the zirconia sol itself has agglomeration characteristics. As the zirconia sol molar ratio increases, the network structure is destroyed, and the agglomerates are attached to the surface of the fiber instead of covering the network structure. Improve the colorability of the processed fabric. Further, based on the above characteristics and in comparison with the SEM image, it was found that the color gradation of the processed fabrics EQ ₃ , EQ ₄ , ER ₃ , ER ₄ , TQ ₃ , TQ ₄ , TR ₃ , and TR ₄ was remarkably low. In addition, the processed fabric has a characteristic of a bright surface due to the structure of the inorganic mesh. The full range of dyeability did not exceed 1, indicating that the level of dyeing ΔE is within the acceptable range. Preferably, finer dye particles are used to achieve better level uniformity.

Wash fastness 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 faded rating is grayed out, and the pollution rating is also grayed out.

Table 6                Physically treated fabric washable fading cloth contaminated cloth EZ1 4 5 EZ2 4 5 EZ3 4-5 4-5 EZ4 4 4-5 ER1 5 5 ER2 4-5 4-5 ER3 5 5 ER4 4-5 5 EQ1 4 5 EQ2 4 -5 4-5 EQ3 4 4-5 EQ4 4-5 5 TZ1 4 4-5 TZ2 4 4-5 TZ3 3-4 5 TZ4 3-4 5 TR1 4-5 4-5 TR2 4 4-5 TR3 4- 5 5 TR4 4-5 5 TQ1 4 5 TQ2 4 4-5 TQ3 5 5 TQ4 4-5 5

Referring to Table 6, it can be seen that the full range of faded ratings is roughly 4-5, and the pollution rating is roughly 4-5, because the bonding force between the azo dye and the polyester is through hydrogen bonding and van der Waals. Bonding, therefore, there is no strong combination of washing fastness. After adding zirconia sol, although the sol has the characteristics of a sheet structure, at the same time, the inorganic zirconium also has agglomerating characteristics, so the processed fabric EZ series and processed fabric TZ series As the proportion increases, the number of grades also decreases, and the processed fabrics TZ ₃ and TZ ₄ fall below level 4. The processed fabrics EZ ₁ , EZ ₂ , TZ ₁ and TZ ₂ can also reach close to 5 because of the low ratio of zirconia sol-mol, and the triethoxy decane bond of vinyl triethoxy decane. The junction structure maintains the network structure to form a film protective fabric. In addition, it can be seen that when the addition amount of zirconium is close to the addition amount of cerium, the more complete the formation of the sheet structure, the processed fabrics EQ ₃ , ER ₃ , TQ ₃ and TR _{3 having the} best fixing effect are observed, and the added content is increased. The higher the number of stages, the better than EQ ₄ , ER ₄ , TQ ₄ and TR ₄ . Therefore, the sheet-like structure formed by adding the cerium/zirconium sol has a better fixing effect than the structure in which only the zirconium sol is added, so that the sheet-like structure contributes to the function of fixing 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 Table 7 and Figure 13 (A) to (F). Fig. 13 (A) to (F) are the contact angle analysis charts of the processed fabric EZ series, TZ series, ER series, TR series, EQ series and TQ 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) EZ1 127 122 EQ1 131 124 EZ3 130 125 EQ2 135 127 EZ3 134 126 EQ3 137 128 EZ4 137 132 EQ4 140 131 ER1 128 123 ER3 134 129 ER2 132 125 ER4 137 131 Physical PTT contact angle (degrees) Physical PTT contact angle (degrees) After washing without washing After washing without washing TZ1 120 115 TQ1 125 116 TZ2 123 117 TQ2 130 122 TZ3 127 122 TQ3 132 125 TZ4 133 125 TQ4 135 130 TR1 125 119 TR3 131 125 TR2 127 122 TR4 133 128

Referring to Tables 7 and 13 (A) to (F), it is understood that the Z series is a single addition of a molar ratio of the molar ratio of the zirconia sol, and the contact angle thereof increases with the zirconia sol molar ratio. In addition, it has been found that the effect on the PTT fabric is not as good as that of the PET fabric, and the reason is that the characteristics of the fabric itself, the PET fabric itself has loose fibers and large voids, and when the concentration of the zirconia sol is low, The organic-inorganic hybrid material Z ₁ -Z ₄ can also maintain the sheet structure by the triethoxydecane bond structure of vinyl triethoxy decane, but can observe the small particles generated by the agglomeration phenomenon, and the small particles originally It may be washed away after being washed with water in the gap of the fiber, and the film on the surface of the fiber is left unaffected by the water washing, so the contact angle of about 125 ^o is also retained. However, when the organic-inorganic hybrid materials Z ₃ and Z ₄ are used on the PTT fabric, since the zirconia sol exceeds a certain molar ratio, it is difficult to maintain the sheet by using the triethoxydecane bond structure of vinyl triethoxy decane. The structure is such that the contact angle drops after washing. For the Q series and R series of processed fabrics, due to the agglomeration characteristics of inorganic zirconium, it is necessary to have a molar ratio of zirconium dioxide sol molar ratio and tetraethoxy decane molar ratio to help the zirconia sol form a sheet. The structure covers the surface of the fiber, otherwise the zirconia sol agglomerates to break the sheet structure and lower the contact angle, so the film formation of the zirconia sol is affected when tetraethoxy decane is added. According to Table 7, the interfiber voids of the polyester PET fabric affect the contact angle, and the resulting film and the film have a large void and increase the surface tension. It is possible to agglomerate the fabric to increase the surface tension before washing, but it is agglomerated zirconium. The agglomerates which were not film-formed after washing were washed off, and thus the contact angle was lowered. However, PTT fabrics are more likely to cause agglomeration because of the poor processing properties of the fabric. The contact angles of TZ series processed fabrics TZ ₁ and TZ ₂ are 120 ^o and 123 ^o because they can also be vinyl triethoxydecane. The triethoxydecane bonding structure maintains the sheet structure to form a film, and it is known that the compact structure of the PTT fabric can maintain a good contact angle.

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 8. 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.

Table 8               Physical processing fabric permeability (cm3/cm2/s) Physical processing fabric permeability (cm3/cm2/s) PET original fabric 94.3 PTT original fabric 14.4 EZ1 74.7 TZ1 13.1 EZ2 65.8 TZ2 12.0 EZ3 63.1 TZ3 11.9 EZ4 57.8 TZ4 11.8 ER1 67.3 TR1 13.1 ER2 65.6 TR2 12.1 ER3 65.0 TR3 11.8 ER4 64.6 TR4 11.1 EQ1 59.3 TQ1 12.5 EQ2 56.2 TQ2 11.3 EQ3 56.1 TQ3 10.7 EQ4 55.2 TQ4 10.4

Referring to Table 8, it is understood that the breathability of the processed fabric processed from the PET fabric is better because the breathability of the PET fabric raw fabric is superior to that of the PTT fabric. In addition, the gas permeability of each series of processed fabrics decreases as the molar ratio of the organic-inorganic hybrid material increases, which is due to the relationship between inorganic zirconium and bismuth film formation or inorganic zirconium agglomeration. From the above SEM analysis, it was found that the voids between the woven fabrics became smaller when the zirconia sol was formed into a film. Therefore, as the proportion of zirconium increases, the group formed by zirconium fills the gaps between the woven fabrics, so that the venting is inferior to that of the original woven fabric. Further, since the film is formed between the tetraethoxy decane and the zirconia sol, the voids between the woven fabrics become small, so that the processed fabric is reduced in gas permeability as the ratio increases.

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 Tables 9 and 14 (A) to (F). Figure 14 (A) to (F) are the heat storage and heat insulation analysis drawings of processed fabrics EZ series, TZ series, ER series, TR series, EQ series and TQ 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 9          Time PET heating 600 (sec) cooling 1200 (sec) time PTT heating 600 (sec) cooling 1200 (sec) raw fabric 54.87 ° C 0.22 ° C raw fabric 53.75 ° C 0.17 ° C EZ1 58.77 ° C 2.02 ° C TZ1 56.52 ° C 1.65 ° C EZ2 59.97 °C 2.22°C TZ2 56.75°C 2.30°C EZ3 61.35°C 2.65°C TZ3 57.02°C 2.60°C EZ4 61.50°C 3.48°C TZ4 57.22°C 3.45°C ER1 59.00°C 1.47°C TR1 59.27°C 2.18°C ER2 62.20°C 2.50°C TR2 59.97°C 2.25°C ER3 60.35 °C 3.12°C TR3 62.00°C 2.55°C ER4 62.87°C 3.42°C TR4 62.50°C 2.82°C EQ1 55.15°C 2.98°C TQ1 59.00°C 1.47°C EQ2 57.87°C 3.22°C TQ2 62.12°C 2.50°C EQ3 61.60°C 3.32°C TQ3 62.42°C 3.12°C EQ4 62.02 °C 3.52°C TQ4 62.87°C 3.42°C

Referring to Table 8 and Figure 14 (A) to (F), the maximum and minimum values of the temperature difference of the polyester raw fabric after 1200 seconds of irradiation with a halogen lamp are known, wherein the maximum value is 600 seconds and the minimum value is 1200. The temperature of seconds. The temperature difference between the processed fabrics TZ ₄ and EZ ₄ with the highest zirconia sol content is about 4 ° C to 7 ° C, which means that the temperature difference is larger as the content of zirconia sol increases. The heat absorption of the organic-inorganic hybrid material is enhanced to impart a heat storage effect to the processed fabric. Referring to parts (C) to (D) of Fig. 14, it can be seen that the more the ratio of zirconia sol is, the better the heat retaining property is, and the heat retention of the processed fabric ER ₄ and the processed fabric TR ₄ is compared with that of the original fabric PET and PTT. The temperature differences were 3.42 ° C and 2.82 ° C, respectively. Referring to parts (E) to (F) of Fig. 14, it can be seen that when processing with modified tetraethoxy decane and fixed zirconium sol Q series, compared with raw fabric PET and PTT, processed fabric EQ ₄ and processed fabric TQ The thermal insulation temperature difference of ₄ is 3.52 ° C and 3.42 ° C. From the processing fabric EZ and TZ series processing fabric temperature difference is 3 ° C, the processing fabric ER and TR series and processed fabric EQ and TQ series close, the reason is due to the formation of agglomeration of inorganic zirconium due to zirconia sol, When the concentration is higher, the agglomeration phenomenon becomes more serious, and the particles will gradually increase. The particles will make the gap between the fabrics become smaller, so that the air will not easily run away through the fabric air in the fabric, so that the air content in the fabric is increased, and zirconium is increased. The inorganic zirconium properties of itself and agglomeration are better in heat insulation because they are not easy to cool down.

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 appended claims.

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

Fig. 2 (A) to (B) are diagrams showing the ¹ H-NMR analysis of the heterocyclic benzothiazole dye and the precursor, respectively.

The parts (A) to (C) of Fig. _{3 are} ²⁹ Si-NMR analysis charts of the organic-inorganic hybrid materials Z ₁ to Z ₄ , Q ₁ to Q ₄ and R ₁ to R ₄ , respectively.

The parts (A) to (B) of Fig. 4 are SEM images of polyester PET raw fabric and polyester PTT original fabric, respectively.

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

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

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

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

Fig. 9 (A) to (D) are SEM analysis views of the processed fabrics ER ₁ to ER ₄ , respectively.

Fig. 10 (A) to (D) are SEM analysis views of the processed fabrics TR ₁ to TR ₄ , respectively.

The parts (A) to (F) of Fig. 11 are EDS analysis charts of the organic-inorganic hybrid materials Z ₁ , Z ₄ , Q ₁ , Q ₄ , R ₁ and R ₄ , respectively.

Fig. 12(A) is a light diffraction analysis diagram of the zirconium dioxide sol powder and the organic-inorganic hybrid materials Z ₄ , Q ₄ and R ₄ , and Fig. 12 (B) is a light winding of the organic-inorganic hybrid material R series. Shoot the analysis chart.

Fig. 13 (A) to (F) are the contact angle analysis charts of the processed fabric EZ series, TZ series, ER series, TR series, EQ series and TQ series, respectively.

Figure 14 (A) to (F) are the heat storage and heat insulation analysis drawings of processed fabrics EZ series, TZ series, ER series, TR series, EQ series and TQ series.

Claims (7)

A method for producing an organic-inorganic hybrid material, comprising the steps of: providing a 2-amino-4-methyl-benzothiazole monomer represented by the following formula (1), Formula (1); coupling a 2-amino-4-methyl-benzothiazole monomer with NN dimethylaniline to obtain a heterocyclic benzothiazole dye, wherein the heterocyclic benzothiazole dye It is expressed by the following formula (2). The heterocyclic benzothiazole dye is reacted with vinyl triethoxyoxane 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 the tetraethoxy decane 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 a heterocyclic benzothiazole dye: vinyltriethoxysilane: zirconium dioxide sol = 1: 6: a, and a molar ratio of between 1 and 15 is obtained by a condensation reaction. The manufacturing method according to the first aspect of the invention, wherein the organic-inorganic hybrid material represented by the formula (5) is the heterocyclic benzothiazole dye: vinyl triethoxy decane: zirconium dioxide sol: tetraethyl Oxydecane = 1:6:10:b, and a molar ratio of b between 1 and 15 is obtained by a condensation reaction. The manufacturing method according to the first aspect of the invention, wherein the organic-inorganic hybrid material represented by the formula (5) is the heterocyclic benzothiazole dye: vinyl triethoxy decane: zirconium dioxide sol: tetraethyl Oxydecane = 1:6:c:10, and a molar ratio of c between 1 and 15 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.