TWI866787B - Mixed material of tin dioxide and anthraquinone-containing azo dye and preparation method and use thereof - Google Patents

Abstract

The invention relates to a mixed material of tin dioxide and anthraquinone -containing azo dye and preparation method and use thereof. A mixed material containing anthraquinone azo dye, tetraethoxysilane(TEOS) and tin chloride was prepared using the sol-gel method; when the hybrid material is applied to a fabric, the fabric can have the functions of heat preservation, water repellency and color fixation.

Description

Tin dioxide and anthraquinone-containing azo dye mixed material and preparation method and use thereof

The present invention relates to a mixed material of tin dioxide and anthraquinone-containing azo dye, a preparation method and use thereof, and in particular to a mixed material that can be applied to fabrics to enable them to have the functions of heat storage, heat preservation, water repellency and color fixation, and a preparation method and use thereof.

Due to the lack of natural fiber raw materials, Taiwan has invested in chemical raw materials, weaving, dyeing and finishing, processing and production processes to create a complete artificial fiber industry. In the 1970s, German botanist Wilhelm Barthlot discovered that the surface of lotus leaves has micron-structured hairs and wax particles with low surface energy, which also makes water form spherical water droplets on the surface of lotus leaves, so that the water droplets can roll off the leaves and achieve the effect of cleaning the surface of lotus leaves.

The proposal of the lotus leaf effect opened the prelude to the research of superhydrophobic materials. The superhydrophobic effect of the material surface is determined by the surface geometry and chemical composition of the material. That is, the two necessary elements for the superhydrophobic phenomenon are a micro/nano structure with high roughness and a surface with low surface energy. At present, superhydrophobic materials have been applied to a variety of products such as waterproof and oil-proof clothing, self-cleaning glass, buildings, and marine pollution treatment. With the deepening of research, superhydrophobic film materials, coatings, paints and other products have developed rapidly, and it is common to construct micro/nano superhydrophobic structures with inorganic nanoparticles such as silicon dioxide or titanium dioxide.

Based on the hydrophobic contact angle (θ), wetting behavior can be divided into four types: superhydrophilic (0˚＜θ＜10˚), hydrophilic (10˚＜θ＜90˚), hydrophobic (90˚＜θ＜150˚), and superhydrophobic (150˚＜θ＜180˚) [6]. With considerable industrial and scientific application interests, most researchers use a variety of methods to achieve this goal, including surface modification such as electrochemical, hydrothermal, and chemical deposition, in addition to physical/chemical vapor deposition, sol-gel, and layer-by-layer assembly.

There are many methods for preparing inorganic thin films, such as chemical vapor deposition, spray pyrolysis and sol-gel. Among them, the sol-gel method is one of the most effective methods for preparing crystalline or amorphous oxide coatings. Compared with other preparation methods, it has the following characteristics: (1) simple processing method; (2) low-temperature synthesis can greatly reduce equipment costs; (3) complex shapes can be produced without the use of any special instruments, and its surface properties can be easily controlled; (4) the ratio of organic and inorganic substances can be freely adjusted according to the material requirements; (5) the product is easy to achieve uniformity; (6) it is easy to accurately control the film structure, such as specific surface area and porosity; (7) it is easy to cover substrates with large surface areas, etc. The gel is formed by reacting with an acid catalyst in a solution to form a hydrolysis, thereby generating a network structure such as Si-O-Si.

Tin dioxide (SnO ₂ ) is an inorganic non-metallic material and an excellent transparent conductive material. It is the first transparent conductive material put into commercial use. In order to improve its conductivity and stability, it is often doped, such as SnO ₂ /Sb or SnO ₂ /F. Tin dioxide fiber is a newer variety of inorganic oxide fiber. The conductivity of fibrous tin dioxide is better than that of powdered tin oxide. As long as a small amount of tin dioxide fiber is added to the product, its conductivity can be significantly improved, and its conductivity can be maintained for a long time. In addition, tin dioxide fiber also has excellent wear resistance and softness. In today's era of technological advancement, _SnO2 plays a role in the production of products in many industries. It is now used in the production of ceramic colorants, glass polishes, mordants for printing and dyeing fabrics, and catalysts for organic synthesis.

Studies have shown that after a sol-gel reaction, when applied to fabrics, a wax with a Si-O-Si network structure similar to the surface structure of a lotus leaf will be formed on the surface, making the surface hydrophobic. When applied to special coatings, it can provide excellent anti-fouling and water-resistant effects, and is widely used on a variety of different materials.

In summary, the sol-gel method can be used to prepare an organic/inorganic hybrid material, and the hybrid material can be applied to various types of fabrics, which is beneficial for obtaining fabrics with functional properties such as heat storage, water repellency, high air permeability, water resistance and/or uniform dyeing.

In order to obtain a functional material that can impart special functional properties such as thermal insulation, water repellency, high air permeability, water-washing fastness and/or dyeing uniformity to various types of fabrics, the main purpose of the present invention is to provide a method for preparing a mixed material of tin dioxide and anthraquinone-containing azo dye, by which a functional mixed material can be obtained, so that the mixed material can be applied to various types of fabrics.

To achieve the above-mentioned object, the present invention provides a tin dioxide and anthraquinone-containing azo dye hybrid material and a preparation method thereof, wherein the anthraquinone-containing azo dye is subjected to a condensation reaction with tin chloride and silicon dioxide, the anthraquinone-containing azo dye is bridged by vinyl triethoxysilane, and then the anthraquinone-containing azo dye is subjected to an addition hydrolysis reaction with tin chloride and tetraethoxysilane, respectively, to form a tin dioxide/silicon dioxide/anthraquinone-containing azo dye hybrid material with a network structure.

The functional hybrid material is obtained, and its structure is analyzed by Energy Dispersive Spectrometer (EDS) and Fourier Transform Infrared Spectrometer (FT-IR). Then, the hybrid material is dyed and finished on polyester fabric. The dyed fabric is subjected to a series of tests on colorability, dyeing levelness, breathability, water repellency, washing fastness and heat storage to explore its various physical properties and evaluate the multifunctional benefits of the hybrid material.

The technical features of the present invention will be described in detail below with specific embodiments and accompanying drawings so that a person skilled in the art can easily understand the purpose, technical features and advantages of the present invention.

In order to clearly express the features, contents, advantages and effects of the present invention, the present invention is described in detail with the help of the attached drawings. The drawings used in the text are only for illustration and auxiliary description, and may not be the actual proportions and precise configurations after the implementation of the present invention. Therefore, the proportions and configurations of the attached drawings should not be used to limit the scope of the patent of the present invention in actual implementation.

In order to make the technical content, purpose of the invention and the effects achieved by the present invention more complete and clear, they are described in detail below, and please refer to the disclosed drawings and figure numbers.

All numbers herein are understood to be modified by "about." As used herein, the term "about" is meant to encompass variations of ±10%.

Example 1 Preparation of mixed materials

1.1 Preparation of Anthraquinone-containing Azo Dyes

Using 1-aminoanthraquinone monomer as the diazonium salt (chemical formula 1) and N-ethyl-N-ethanolaniline as the coupling salt (chemical formula 2), the two can be coupled to produce a heterocyclic anthraquinone-containing azo dye (chemical formula 3).

First, weigh 0.670g (0.003 mole) of 1-aminoanthraquinone monomer and add it to sulfuric acid until the 1-aminoanthraquinone monomer is completely dissolved in the sulfuric acid solution. Then weigh 0.214g (0.003 mole) of sodium nitrite and add an appropriate amount of ionized water. Drop it into the solution of 1-aminoanthraquinone monomer and stir for 1.5 hours until it is evenly dispersed. The reaction is carried out under ice bath. The coupling salt is prepared by adding an appropriate amount of sodium hydroxide aqueous solution to an appropriate amount of ethanol. , weigh 0.496g (0.003 mole) of N-ethyl-N-ethanol aniline liquid and place it in the coupling salt solution, then drop the diazonium salt into the coupling salt to mix the two solutions, and stir for 1 hour under ice bath, and adjust the pH value to between 6 and 7; after stirring for another hour, if the pH value becomes acidic, add sodium carbonate to adjust the acid-base value, then continue stirring for 2 hours, add sodium chloride, continue stirring for another hour, stop, and finally filter and dry to obtain the dye. The synthetic reaction formula of anthraquinone-containing azo dye is shown in Scheme 1.

1.2 Promotor synthesis

The anthraquinone-containing azo dye (chemical formula 3) is completely dissolved in dimethyl sulfoxide solvent, and the dye is mixed with vinyl triethoxysilane (VTES, chemical formula 4) in a certain ratio (1:10), placed in a constant temperature water bath, and heated and refluxed at 95°C for 15 hours to obtain the precursor (chemical formula 5), and the reaction formula is shown in Scheme 2.

1.3 Preparation of solder paste

Tin chloride, diethanolamine, dimethyl sulfoxide, and nitric acid are poured into a double-necked round-bottomed bottle in a molar ratio of 1:1:10:0.5, and then a magnet is placed in the double-necked round-bottomed bottle. The double-necked round-bottomed bottle is placed on a reflux device, the temperature is maintained at 70°C, and the final time is set to 1 hour to obtain tin dioxide sol (tin gel).

1.4 Synthesis of hybrid materials

The precursor (chemical formula 5), tin dioxide sol and tetraethoxysilane are mixed in different proportions, placed in a constant temperature stirring device, and heated to reflux for 12 hours at a temperature maintained at 95° C. to produce a condensation reaction to obtain a tin dioxide/silicon dioxide/anthraquinone-containing azo dye mixed material. The reaction formula is shown in Scheme 3, and the different mixing ratios of the precursor, tin dioxide sol and tetraethoxysilane in different mixed materials are shown in Tables 1 to 3.

Table 1 Mixed material number Dye/VTES/SnCl ₄ (molar ratio) L ₁ 1/10/1 L ₂ 1/10/2 L ₃ 1/10/3 L ₄ 1/10/4

Table 2 Mixed material number Dye/VTES/SnCl ₄ /TEOS (molar ratio) M ₁ 1/10/3/5 M ₂ 1/10/3/10 M ₃ 1/10/3/15 M ₄ 1/10/3/20

Table 3 Mixed material number Dye/VTES/TEOS/SnCl ₄ (molar ratio) N ₁ 1/10/10/1 N ₂ 1/10/10/2 N ₃ 1/10/10/3 N ₄ 1/10/10/4

1.5 Special functional group analysis (FT-IR analysis)

Figure 1 shows the infrared spectra of the hybrid materials L ₁ ~L _4. The hybrid material without adding tetraethoxysilane but changing the tin dioxide has an absorption peak of OH group at 3395cm ^-1 ~3313cm ^-1 , an absorption peak of CH group at 2950cm ^-1 ~2970cm ^-1 , an absorption peak of carbonyl group near 1632cm ^-1 ~1642cm ^-1 , an absorption peak of phenyl group near 1597cm ^-1 ~1602cm ^-1 , an absorption peak of Si-C at 1382cm ^-1 ~1390cm ^-1 , and an absorption peak of Sn-O at 1064cm ^-1 ~1075cm ^-1 .

Figure 2 is the infrared spectrum of the hybrid material M ₁ ~M _4. There is an absorption peak of OH group at 3420cm ^-1 ~3435cm ^-1 , an absorption peak of CH group at around 2925cm ^-1 , an absorption peak of carbonyl group at around 1650cm ^-1 ~1675cm ^-1 , an absorption peak of phenyl group at around 1595cm ^-1 ~1606cm ^-1 , an absorption peak of Si-C at 1384cm ^-1 ~1390cm ^-1 , an absorption peak of Si-O at 1146cm ^-1 ~1164cm ^-1 , an absorption peak of Si-O at 1050cm ^-1 ~1070cm ^-1 , and an absorption peak of Sn-O at 775cm ^-1 ~785cm ^-1 . The change in the Si-O absorption peak near 1164cm ^-1 is due to the increase in the proportion of tetraethoxysilane, which increases the absorption intensity.

Figure 3 is the infrared spectrum of the hybrid material N ₁ ~N _4. The results show that when tetraethoxysilane is fixed and tin dioxide is changed, there is an absorption peak of OH group at 3408cm ^-1 ~3415cm ^-1 , an absorption peak of CH group at 2922cm ^-1 ~2953cm ^-1 , an absorption peak of carbonyl group near 1670cm ^-1 ~1682cm ^-1 , an absorption peak of phenyl group near 1592cm ^-1 ~1607cm ^-1 , an absorption peak of Si-C at 1276cm ^-1 ~1281cm ^-1 , an absorption peak of Si-O near 1384cm ^-1 , an absorption peak of Si-O-Sn at 1065cm ^-1 ~1069cm ^-1, and an absorption peak of Si-O-Sn at 690cm ^-1 ~770cm -1. ^-1 is the absorption peak of Sn-O. As the proportion of SnO2 increases, the absorption intensity increases significantly.

1.6 Elemental composition analysis (EDS analysis)

The hybrid materials N ₁ ~N ₄ are fixed tetraethoxysilane and changed SnO2. From Table 4, we know that as the SnO2 ratio increases, the content of element C and element Sn increases, and the content of element O and element Si gradually decreases. It can be seen that Si in the Si-O-Si network structure is gradually replaced by SnO2 to form a Si-O-Sn network structure.

Table 4 Mixed material number Element composition (%) C O Si Sn N ₁ 49.77 35.82 12.06 12.34 N ₂ 51.94 31.86 11.26 14.94 N ₃ 47.14 38.20 9.39 15.27 N ₄ 45.08 40.13 8.82 15.97

1.7 X-ray diffraction analysis

This analysis is an X-ray diffraction analysis of the N series of hybrid materials. As can be seen from Figure 4, the N series of hybrid materials has two diffraction peaks at room temperature (25°C). Figure 4 shows that the molar ratio of SnCl ₄ is changed for N series N ₁ ~N ₄ , and the molar ratio of tetraethoxysilane (TEOS) is fixed. As the molar ratio of SnCl 4 increases, it is known that N ₁ has a (002) crystal diffraction peak at 2θ=24.78˚, N ₂ has a diffraction peak at 2θ=25.42˚, N ₃ has a diffraction peak at 2θ=25.15˚, and N ₄ has a diffraction peak at 2θ=25.61˚. In addition, as shown in Figure 4, a weaker (101) crystal diffraction peak appears at 2θ=26.59˚ ~26.88˚. Since the hybrid material is not sintered, it presents an amorphous structure and does not have a crystal phase characteristic peak. The aforementioned (002) and (001) are the crystal structure forms measured by XRD scanning of the metal material crystal.

Example 2 Preparation of polyester fabric

The polyester fabric is processed and dyed using the mixed material described in Example 1 to obtain a polyester dyed fabric improved by the mixed material; wherein the polyester fabric is a polyethylene terephthalate (PET) fabric, and the polyester dyed fabrics improved by various types of mixed materials are shown in Tables 5 to 7.

Table 5 Dyed fabric number Hybrid Materials Dye/VTES/SnCl ₄ (molar ratio) EL ₁ 1/10/1 EL ₂ 1/10/2 EL ₃ 1/10/3 EL ₄ 1/10/4

Table 6 Dyed fabric number Hybrid Materials Dye/VTES/SnCl ₄ /TEOS (molar ratio) EM ₁ 1/10/3/5 EM ₂ 1/10/3/10 EM ₃ 1/10/3/15 EM ₄ 1/10/3/20

Table 7 Dyed fabric number Hybrid Materials Dye/VTES/TEOS/SnCl ₄ (molar ratio) EN ₁ 1/10/10/1 EN ₂ 1/10/10/2 EN ₃ 1/10/10/3 EN ₄ 1/10/10/4

Example 3 Analysis of Surface Characteristics of Polyester Dyed Fabrics

The processed polyester dyed fabrics were observed using an XL-40FEG field emission scanning electron microscope to observe the adhesion of various mixed materials on the surface of the polyester dyed fabrics.

FIG. 5 is a SEM surface analysis image of the PET raw fabric, and FIG. 6 to FIG. 9 are SEM surface analysis images of EL ₁ ~EL ₄ dyed fabrics, FIG. 10 to FIG. 13 are SEM surface analysis images of EM ₁ ~EM ₄ dyed fabrics, and FIG. 14 to FIG. 17 are SEM surface analysis images of EN ₁ ~EN ₄ dyed fabrics. The adhesion of each mixed material on the PET fabric can be seen from these SEM images.

As can be seen from Figures 6 to 9, when the molar ratio of tin chloride is the lowest (EL ₁ ), very few particles are attached to the fiber surface. When the molar ratio of tin chloride gradually increases, the particles gradually increase at EL ₂ and EL ₃ , and the attachment is more inclined to a film structure. At EL ₄ , the particles agglomerate into agglomerates, probably due to the agglomeration characteristics of tin dioxide.

Next, it can be seen from Figures 10 to 13 that EM ₂ already has a thin film structure attached to the fiber. Even though some microparticles have been generated due to the agglomeration characteristics of SnO2, as the molar ratio of TEOS increases, the thin film structure covers the entire fiber as shown in EM ₄ in Figure 13, making the network structure more complete, which echoes the Si-O-Si network structure shown by FT-IR. As the molar ratio of TEOS increases, the thin film structure becomes more complete.

Furthermore, it can be seen from FIG. 14 to FIG. 17 that the adhesion of EN ₂ and EN ₃ is closer to a thin film structure. However, as the molar ratio of SnCl2 increases, the particles gradually aggregate, but the thin film still exists on the fiber, forming the structure of EN ₄ as shown in FIG. 17. This indicates that SnO2 has an aggregation property. When SnCl2 is added alone at a molar ratio exceeding a certain value, the thin film structure is difficult to maintain.

In addition, when comparing the polyester dyed fabrics of the EN series and the EL series, the only difference between the two is that the EN series has TEOS added while the EL series does not. The molar ratio of tin chloride is also gradually increased, so the characteristics presented are also similar. As the molar ratio of tin chloride increases, coagulation begins to occur in the form of a film, and finally a similar agglomerated solid is formed. Although some differences can be seen, and there may be different presentations in physical properties, it also indirectly proves that the N series hybrid materials can be used on PET fabrics.

Example 4 Air Permeability Measurement of Polyester Dyed Fabric

Polyester fabrics processed and dyed with various mixed materials were fixed on a breather according to the ASTM D737-2004 test method. When the air reaches a preset pressure difference and remains stable when passing through the surface of the fabric, the gas flow rate passing through the surface of the fabric is measured. The data at 14 test points are summed up and averaged as the test result (conditions: area ^38cm2 , pressure difference 125Pa). The air permeability is shown in Table 8.

Table 8 Physical properties of dyed fabrics Air permeability (cm ³ /cm ² /s) PET 84.8 EL ₁ 82.8 EL ₂ 82.5 EL ₃ 80.6 EL ₄ 78.7 EM ₁ 83.4 EM ₂ 83.2 EM ₃ 82.6 EM ₄ 81.2 EN ₁ 84.1 EN ₂ 82.5 EN ₃ 80.6 EN ₄ 79.2

As shown in Table 8, the air permeability of each series of dyed fabrics decreases as the molar ratio of the mixed materials increases. The possible reason is the formation of a silica film or agglomeration. From the aforementioned SEM image of the dyed fabric of the M series mixed materials, it can be seen that the formation of a silica film will cover the fibers and make the gaps between the fabrics smaller. As the ratio increases, the agglomeration characteristics will fill the gaps between the fabrics, so the air permeability is worse than the original blank. As for the dyed fabric of the N series mixed materials, the agglomeration characteristics of the silica film will form small particles attached to the gaps. As the silica film increases, the particles increase and fill the gaps between the fabrics, resulting in a decrease in air permeability.

Comparing the dyed fabrics EN ₁ ~EN ₄ in Table 8, it can be found that the air permeability decreases as the molar ratio of tin chloride increases. By comparing the corresponding SEM images, it can be seen that the fiber surface gradually forms agglomerated solids from a relatively incomplete film structure. The agglomerated solids formed block the air flow, causing this phenomenon.

Comparing the difference between EM ₁ and EM ₄ of the dyed fabric, the air permeability decreases as the molar ratio of tin chloride increases. From the corresponding SEM images, it can be seen that the fiber surface will gradually increase from an incomplete film structure to a thick complete film structure, resulting in a decrease in the distance between fibers, making it difficult for gas to enter and exit freely, and the air permeability also decreases.

Therefore, it can be seen from Table 8 that the air permeability of PET dyed fabrics, whether M series or N series, is worse than that of the original fabric. The difference is not significant when observed with the naked eye, but the difference can be seen from this air permeability test.

Example 5: Determination of dyeing levelness and colorability of polyester dyed fabrics

After the polyester dyed fabrics were processed and dyed with various mixed materials, the color difference between the dyed fabrics and the blank fabrics was compared to indicate the shade of the color of the dyed fabrics. The colorimetric ΔE value of the dyed fabrics was obtained using a colorimeter and the data were recorded. The dyeing uniformity of the dyed fabrics was determined by taking the difference between the maximum and minimum values of ΔE measured in the same piece of dyed fabric, and the degree of dyeing uniformity was obtained. The data are shown in Table 9.

Table 9

From the data in Table 9, we can find that the colorability of the EL series of dyes is different from that of the EM and EN series. The colorability of the EM series of dyes decreases with the increase of the molar ratio of tetraethoxysilane. This may be because the film structure disperses the dye, resulting in a lighter color than the EN series of dyes. The colorability of the EN series increases with the increase of the molar ratio of tin chloride. This may be due to the aggregation characteristics of tin dioxide. From the SEM image, we can observe that the film structure attached to the fiber surface aggregates into agglomerates as the molar ratio of tin chloride increases. It is no longer a film form, so its K/S value increases, which means that the colorability can be improved.

In terms of dyeing levelness, the ΔE of the dyed fabric EM series increases with the increase of the molar ratio of tetraethoxysilane, indicating that the dyeing leveling effect decreases. The reason may be that the generated Si-O-Si network film can be effectively and evenly coated on the fabric. The ΔE of the dyed fabric EN series decreases. The reason may be the cohesion of tin dioxide, which makes the dyeing leveling effect of the EN series better than that of the EM series.

Example 6 Determination of heat storage and thermal insulation properties of polyester dyed fabrics

After being processed and dyed with various mixed materials, the polyester dyed fabrics were illuminated with a 250-watt halogen lamp for 10 minutes, cooled for 10 minutes, and measured once every minute using a four-point probe thermometer. A total of 20 recorded values were taken, and the results are shown in Figures 18 to 20. The temperatures of the dyed fabrics after heating up for 10 minutes and cooling down for 10 minutes are shown in Table 10.

Table 10 Time Dyed Fabrics Temperature rise 600(sec) Cool down 600(sec) PET 36.7˚C 14.2˚C EL ₁ 56.5˚C 12.4°C EL ₂ 57.1°C 12.4°C EL ₃ 57.9˚C 12.8˚C EL ₄ 58.3˚C 12.9°C EM ₁ 42.1°C 12.4°C EM ₂ 47.8˚C 13.0˚C EM ₃ 48.2˚C 13.6˚C EM ₄ 49.6°C 13.9˚C EN ₁ 54.1°C 11.4°C EN ₂ 55.1°C 11.9°C EN ₃ 56.9˚C 12.0˚C EN ₄ 60.9˚C 12.3˚C

As can be seen from Figures 18 to 20, the temperature of the dyed fabric after the dyeing process is higher than that of the original fabric during the heating and cooling processes compared to the PET fabric. It can be clearly seen that the dyed fabric obtained by dyeing PET fabric with L series, M series mixed materials and N series mixed materials can give PET fabric the characteristic of heat storage.

In addition, Table 10 shows the temperature data of each series of dyed fabrics after heating for ten minutes and cooling for ten minutes. The temperature of the PET raw fabric only reaches 36.7°C after heating for ten minutes. The temperature difference between the raw fabric and the EL ₁ dyed fabric after heating for ten minutes is 19.8°C under the condition that only tin chloride is added without tetraethoxysilane. Therefore, it can be seen that with the increase of tin chloride, the temperature after heating for ten minutes increases significantly.

The temperature of the processed dyed fabrics of the EM series and EN series is above 40°C~60°C after heating for ten minutes. Comparing the EM series and the EN series, it can be found that the heating effect of the EN series dyed fabrics is higher than that of the EM series dyed fabrics as the molar ratio of tin chloride increases. The reason may be that the heat storage effect of tin chloride can be improved; and the temperature of the EN series dyed fabrics also increases significantly after heating for ten minutes as the molar ratio of tin chloride increases.

Example 7 Static contact angle measurement of polyester dyed fabric

The contact angles of polyester dyed fabrics processed and dyed with various mixed materials were measured using a static contact angle meter. The contact angles were measured at five points and then the average of the five-point data was taken. The results are shown in Figures 21 to 23 and Table 11.

Table 11

As can be seen from Figure 21, the EL series only adds tin chloride. As the amount of tin chloride increases, the contact angle also increases. However, when comparing the EM series with the EL series, the EM series has a slightly higher contact angle. The reason may be that the incomplete network structure of the EL series can only provide a hydrophobic effect on the basis of the fabric, while the Si-O-Si network structure formed by the EM series due to the presence of tetraethoxysilane can give the fabric an excellent hydrophobic effect.

Next, as can be seen from Figure 22, the contact angle of the EM series increases with the increase of the tetraethoxysilane ratio, and the contact angle of the EN series also increases with the increase of the tin chloride ratio. From Table 11, it can be seen that the contact angle of the EM series before washing is 125˚~131˚, and the contact angle after washing is 120˚~127˚. The contact angle of the EN series before washing is 124˚~135˚, and after washing it falls to The contact angles of the EM series before and after washing are about 5°~6°, and the contact angles of the EN series before and after washing are about 5°~6°. Because the loose gaps in the polyester PET fabric are larger, it does not have a water-repellent effect by itself, but the addition of tetraethoxysilane and tin chloride increases the surface energy of the fabric, thereby bringing higher wettability and hydrophilicity. Table 11 proves that the mixed material has a better water-repellent effect after dyeing the fabric.

Furthermore, as can be seen from Figure 23, the contact angle of the EN series of dyes has increased due to the gradual increase in SnO2 adhesion, the increase in agglomerates between fabrics, and the increase in surface energy. The same is true for the EM series of dyes, but because the network structure of the fabric surface is more compact as TEOS gradually increases with the molar ratio, the contact angle of the EM series is higher. Therefore, from the static contact angle diagrams of the EM and EN series of dyes before and after washing, it can be seen that the film formed by _SiO2 may bring excellent hydrophobicity to the fabric, and the EN series also has good hydrophobicity before washing, which may be due to the network structure of Si-O-Sn providing the hydrophobic effect of the dye base.

Example 8 Analysis of the abrasion and washing fastness of polyester dyed fabrics

The polyester dyed fabrics processed and dyed with various mixed materials were tested according to the CNS1499 L3032 test method, and the abrasion resistance was observed by rubbing 100 times with a B-type (Xuezhen type) abrasion tester; and the washing fastness was observed according to the CNS1494 L48 A3 test method, with 5g/L soap, 2g/L sodium carbonate, 10 stainless steel balls and 100ml liquid, at 60˚C for 30 minutes. The results are shown in Table 12.

Table 12 Physical properties of dyed fabrics Washable Abrasion resistance Faded cloth Contaminated cloth Wet Dry Faded cloth Contaminated cloth Faded cloth Contaminated cloth EM ₁ 4 3-4 3 3-4 3 3 EM ₂ 4 3-4 3 3-4 3-4 3-4 EM ₃ 4 4 4 4 3 4 EM ₄ 4 4 4 4 3-4 4 EN ₁ 3-4 3 3-4 3 3 3 EN ₂ 4 3-4 3-4 4 3 3 EN ₃ 4 4 4 4 3-4 3-4 EN ₄ 4 4 4 4 4 4

It can be seen from Table 12 that the washing fastness rating of each series of mixed materials on PET fabrics is that EM ₁ ~EM ₄ are PET dyed fabrics with fixed tin chloride and changed TEOS mixing ratio. The EM series has a faded fabric rating of about 4 and a contaminated fabric rating of about 4. EN ₁ ~EN ₄ are PET dyed fabrics with fixed TEOS and changed tin chloride. The EN series has a faded fabric rating of about 4 and a contaminated fabric rating of about 3~4.

In addition, it can be seen from Table 12 that the abrasion fastness ratings of the EM series and EN series of dyed fabrics are generally around level 3~4 in terms of dry and wet abrasion fastness. The wet abrasion fastness is slightly worse than the dry abrasion fastness. Since the mixed material is attached to the fabric fiber in sheet form, the friction force is greater during the test, resulting in a decrease in abrasion resistance, which in turn contaminates the dyed fabric being tested for abrasion resistance, resulting in a slightly lower rating for the dyed fabric.

In summary, the present invention synthesizes a series of hybrid materials containing anthraquinone-based azo dyes, uses a sol-gel method to prepare organic/inorganic hybrid materials, and uses the prepared hybrid dyeing materials to dye polyester fabrics and analyze their physical properties. The experimental results obtained in the above embodiments can provide the following conclusions:

1. FT-IR analysis confirmed that in the hybrid material, the absorption peak of the Sn-O group appeared near 750cm ^-1 , the absorption peak of the Si-O group appeared near 1650cm ^-1 , and the characteristic peak of the Si-O-Sn group appeared near 1060cm ^-1 , confirming the existence of Si-O-Sn functional groups in the hybrid material.

2. X-ray diffraction analysis shows that the hybrid material has a (002) characteristic peak, while N ₄ with the highest Sn concentration has a (101) characteristic peak.

3. EDS analysis shows that in the mixed materials N ₁ ~N ₄ , the more Sn chloride is added, the higher the Sn content is, and as the Sn addition amount increases, the C content gradually decreases.

4. The adhesion of the mixed materials on the surface of the dye was observed by SEM. In the EN series, when the single addition of tin chloride exceeded a certain molar ratio, it was difficult to maintain the network structure.

5. The air permeability of each series of dyed fabrics decreases as the molar ratio of the mixed materials increases. The possible reason is that tin dioxide and silicon form a thin film, as well as the coagulation of tin dioxide. Therefore, the air permeability is worse than that of the original grey fabric.

6. The dyeing properties of PET fabrics processed with various series of mixed materials gradually increase with the increase of the molar ratio of tin chloride; and the ΔE values of dyeing uniformity can reach the acceptable range standard.

7. The influence of heat storage and thermal insulation. After 10 minutes of heating, the temperature difference between EL ₁ ~EL ₄ and the original grey fabric is 19.8˚C~21.6˚C; EM ₁ ~EM ₄ series is 5.4˚C~12.9˚C; EN ₁ ~EN ₄ series is 17.4˚C~24.2˚C. All three are higher than the original grey fabric, which means that the dyed fabric has a heat storage effect due to the enhanced heat absorption of the mixed material.

8. The contact angle test analysis shows that the contact angle of the EN series increases due to the gradual increase in the adhesion of tin dioxide. The same is true for the EM series. As the molar ratio of TEOS gradually increases, the network structure on the surface of the fabric becomes denser. The contact angle of all dyed fabrics before washing is between 128˚~136˚, and after washing is between 125˚~132˚.

9. The water resistance test shows that the network structure of Si-O-Sn helps its color fixing properties, so it has a good rating in fading and staining ratings.

The embodiments of the invention covered by this patent are defined by the scope of the patent application, not the content of this invention. This invention content is a high-level summary of various aspects of the invention and introduces some concepts further described in the following detailed description. This invention content is not intended to identify the key or essential features of the claimed subject matter, nor is it intended to be used alone to define the scope of the claimed subject matter. The subject matter should be understood by reference to the entire specification, any or all drawings, and the appropriate parts of each invention patent application scope.

without

Exemplary embodiments of the present invention will be more fully understood from the following detailed description and the accompanying drawings of various embodiments of the present invention, however, these embodiments should not be construed as limiting the present invention to specific embodiments, but are only used for description and understanding.

FIG. 1 is an infrared spectrum of the mixed materials L ₁ ~L ₄ ; FIG. 2 is an infrared spectrum of the mixed materials M ₁ ~M ₄ ; FIG. 3 is an infrared spectrum of the mixed materials N ₁ ~N ₄ ; FIG. 4 is an XRD analysis diagram of the mixed materials N ₁ ~N ₄ ; FIG. 5 is a SEM surface analysis diagram of the PET raw embryo fabric; FIG. 6 to FIG. 9 are SEM surface analysis diagrams of the EL ₁ ~EL ₄ dyeing fabrics in sequence; FIG. 10 to FIG. 13 are SEM surface analysis diagrams of the EM ₁ ~EM ₄ dyeing fabrics in sequence; FIG. 14 to FIG. 17 are SEM surface analysis diagrams of the EN ₁ ~EN ₄ dyeing fabrics in sequence; FIG. 18 to FIG. 20 are heat storage and heat preservation analysis diagrams of the EL series, EM series and EN series dyeing fabrics in sequence; Figures 21 to 23 are respectively the static contact angle analysis diagrams of EL series, EM series and EN series dyed fabrics before and after washing.

Claims (8)

A method for preparing a mixed material of tin dioxide and anthraquinone-containing azo dye, the preparation method is as follows: 1-aminoanthraquinone and N-ethyl-N-ethanolaniline are coupled to obtain a heterocyclic anthraquinone-containing azo dye; The heterocyclic anthraquinone-containing azo dye is reacted with vinyl triethoxysilane to obtain a precursor; and The precursor is reacted with tin dioxide sol and tetraethoxysilane to obtain the mixed material of tin dioxide and anthraquinone-containing azo dye, wherein the molar ratio of the heterocyclic anthraquinone-containing azo dye to the vinyl triethoxysilane is 1:10; and The molar ratio of the precursor, the tin dioxide sol and the tetraethoxysilane ranges from 1:1:10 to 1:4:10. The preparation method as described in claim 1, wherein the tin dioxide sol is obtained by mixing tin chloride, diethanolamine, dimethyl sulfoxide and nitric acid, and the molar ratio of the tin chloride, the diethanolamine, the dimethyl sulfoxide and the nitric acid is 1:1:10:0.5. The preparation method as described in claim 1, wherein the mixed material of tin dioxide and anthraquinone-containing azo dye has a Sn-O group absorption peak near 750 cm ^-1 , a Si-O group absorption peak near 1650 cm ^-1 , and a Si-O-Sn group characteristic peak near 1060 cm ^-1 when analyzed by Fourier transform infrared spectrometer (FT-IR). The preparation method as described in claim 1, wherein the mixed material of tin dioxide and anthraquinone-containing azo dye has a (002) characteristic peak when analyzed by X-ray diffraction. A mixed material of tin dioxide and anthraquinone-containing azo dye is produced by the preparation method described in any one of claims 1 to 4. A use of a mixed material of tin dioxide and anthraquinone-containing azo dye as described in claim 5, wherein the mixed material of tin dioxide and anthraquinone-containing azo dye is used as a dye for fabric, so that the fabric has the effects of heat storage, heat preservation, water repellency and color fixation. The use as described in claim 6, wherein the fabric is a polyester fabric. The use as described in claim 7, wherein the polyester fabric is a polyethylene terephthalate (PET) fabric.