Anti-ultraviolet fabric and treatment method

Abstract

Ultraviolet protective fabrics and methods of making ultraviolet protective fabrics having ferulic acid and / or a ferulic acid derivative, such as ferulic acid ethyl ester, include soaking the fabric in an aqueous solution of ferulic acid and / or a ferulic acid derivative, removing the fabric from the aqueous solution, and drying the soaked fabric. The aqueous solution may optionally comprise one or more surfactants. Ferulic acid and / or ferulic acid derivatives can provide UVA protection, such as UVA transmittance below 5%, and increase UPF, such as 50 or higher, including fabrics that may contain dyes, without changing the color of the fabrics.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Provisional Application 63 / 588,855, filed October 9, 2023, entitled “UV-resistant fabric and treatment method,” the disclosure of which is incorporated herein by reference in its entirety. Background of the Invention

[0004] The harmful effects of solar ultraviolet radiation are well-known. For example, skin cancer is considered the most common type of cancer worldwide. The occurrence of skin cancer is known to be closely related to exposure to ultraviolet radiation.

[0005] Ultraviolet radiation is defined as electromagnetic radiation with wavelengths ranging from 100 to 400 nm. It is arbitrarily divided into three regions: UVA (315-400 nm), UVB (280-315 nm), and UVC (100-280 nm). UVC and approximately 90% of UVB radiation are absorbed by atmospheric components such as ozone, water vapor, oxygen, and carbon dioxide. However, UVA radiation is less affected by the atmosphere. Therefore, ultraviolet radiation reaching the Earth's surface consists primarily of UVA and a small amount of UVB.

[0006] Clothing is considered one of the most effective methods of sun protection. According to the recently implemented European regulations (European Personal Protective Equipment Regulation 2016 / 425), UV-protective clothing is considered Category 1 personal protective equipment (PPE) and must be able to absorb or reflect most of the radiation energy of harmful wavelengths (i.e., the UVB and UVA range). (Cited: Regulation (EU) 2016 / 425 [ec.europa.eu]). Under these regulations, the European standard for sun-protective clothing (EN 13758-1) stipulates that UV-protective clothing must have an ultraviolet protection factor (UPF) greater than 40 (UPF 40+) and UVA transmittance less than 5%. However, achieving such low UVA transmittance is difficult.

[0007] Polyester and its blends are popular fabric choices for sun-protective clothing due to their inherent ability to absorb ultraviolet radiation. Clothing made from these fabrics typically offers UPF 50+ protection, but its UVA transmittance may still be higher than the minimum limit of 5%.

[0008] Some methods to improve the UPF rating of clothing include relying on fabric structure (knitted or woven patterns, fabric density and coverage factor), fabric chemical composition (e.g., synthetic fibers that are naturally able to absorb UVB radiation, such as polyester and blends of polyester fibers with other synthetic fibers (such as spandex), and chemical additives or surface treatments, such as dyes, finishing agents, optical brighteners, etc. that absorb ultraviolet rays.

[0009] Most commercially available UV-absorbing dyes and finishing agents for textiles are based on petroleum-based synthetic aromatic compounds. These compounds are typically derivatives of benzotriazole, phenyltriazine, phenyl salicylate, benzophenone, and diphenylamine oxalate. Most commercially available organic UV absorbers primarily absorb UVB radiation and therefore do not provide the required level of protection, nor do they comply with new regulatory requirements.

[0010] Besides inadequate protection against UVA radiation, textile dyes and finishing products are also significant sources of water pollution. It is estimated that textile dyes and finishing products contribute to approximately one-fifth of global water pollution. With the increasing need to protect natural resources and freshwater supplies, finding sustainable alternatives has become even more crucial. Attached Figure Description

[0011] The following figures are illustrative of embodiments and do not limit the scope of the invention. The figures are not necessarily drawn to scale and are intended for use in conjunction with the following detailed description. Embodiments of the invention will be described with reference to the figures, wherein the same numerals may denote the same elements.

[0012] Figure 1 This is a graph showing the relationship between UPF and cover factor for various fabric types; Figure 2 This is the chemical structure diagram of ferulic acid; Figure 3 This is a chemical structure diagram of cinnamic acid derivatives according to various embodiments; Figure 4 This is the ultraviolet absorption spectrum of ferulic acid in water; Figure 5 This is the ultraviolet absorption spectrum of tannic acid in water; Figure 6 This is the ultraviolet absorption spectrum of ferulic acid and tannic acid in water; Figure 7 This is the ultraviolet absorption spectrum of RAYOSAN C in water; Figure 8 These are photos of a 100% polyester fabric sample before and after treatment with tannic acid and ferulic acid. Figure 9 These are photos of a 93% polyester / 7% spandex fabric sample before and after treatment with tannic acid and ferulic acid. Figure 10 These are photos of a 100% cotton sample before and after treatment with tannic acid and ferulic acid. Figure 11 These are photos of a 100% cotton sample before and after treatment with Rayosan C and ferulic acid; Figure 12 The diffuse transmission spectra were collected from 100% cotton samples before and after treatment with Rayosan C and ferulic acid. Figure 13 These are photos of dyed polyester / spandex fabric samples before and after treatment with ferulic acid. Figure 14 This is a UVA transmittance diagram of dyed polyester / spandex fabrics after ferulic acid treatment and multiple washing cycles. Figure 15 These are photos of multiple fabric samples before and after treatment with ferulic acid; Figure 16 This is a response surface plot of ferulic acid applied at room temperature in a bath. Figure 17 This is the response surface plot of ferulic acid applied in a 70°C bath; Figure 18 This is a graph showing the relationship between the concentration of ferulic acid solubilized and the concentration of surfactant in various emulsifier blends; Figure 19 These are photographs of fabric samples after room temperature treatment in Examples 10 and 11; Figure 20 These are photographs of fabric samples treated at 130°C in Examples 12 and 13; Figure 21 These are UPF graphs of fabrics with various coverage factors before and after treatment with ferulic acid; Figure 22 These are UVA images of fabrics with various coverage coefficients before and after treatment with ferulic acid; and Figure 23 This is a photograph of an undyed polyester / spandex fabric sample treated with commercially available UPF reinforcing agent and ethyl ferulic acid at 130°C. Summary of the Invention

[0013] Various embodiments include methods for treating fabrics to provide UV protection. The methods include immersing the fabric in an aqueous solution of ferulic acid and / or a ferulic acid derivative, removing the fabric from the aqueous solution, and drying the immersed fabric. In some embodiments, the aqueous solution contains ferulic acid, and the temperature of the aqueous solution during the immersion step is between about 25°C and about 90°C. In some such embodiments, the temperature of the aqueous solution during the immersion step is between about 75°C and about 90°C. In other embodiments, the aqueous solution contains ethyl ferulic acid, and the temperature of the aqueous solution during the immersion step is between about 25°C and about 130°C. For example, in some such embodiments, the temperature of the aqueous solution during the immersion step is between about 100°C and about 130°C. In various embodiments, the step of drying the immersed fabric includes heating the immersed fabric at a temperature between about 80°C and about 180°C.

[0014] In some embodiments, the aqueous solution further comprises one or more surfactants, and the total hydrophilic-lipophilic balance (HLB) value of the one or more surfactants is between about 14 and about 20.

[0015] In some embodiments, the aqueous solution contains a ferulic acid derivative, including ethyl ferulic acid, sinapic acid, chlorogenic acid, caffeic acid, rosmarinic acid, p-coumaric acid, and / or ethylhexyl ferulic acid.

[0016] Various embodiments include UV-protective fabrics, which comprise fabrics having fibers having ferulic acid and / or ferulic acid derivatives absorbed by the fabric fibers, wherein the UV-protective fabric has a UVA transmittance of less than 5%. In some embodiments, ferulic acid is absorbed by the fabric fibers. In other embodiments, ethyl ferulic acid is absorbed by the fabric fibers. In some embodiments, the fabric comprises a polyester blend. For example, some such fabrics may be garments. In some embodiments, the fabric has a color, which may include a light color, such as white, that is not altered by the ferulic acid and / or ferulic acid derivatives absorbed by the fabric fibers.

[0017] Various embodiments include UV-protective fabrics prepared by a method comprising immersing the fabric in an aqueous solution of ferulic acid and / or a ferulic acid derivative, removing the fabric from the aqueous solution, and drying the immersed fabric to form a UV-protective fabric, such as a UV-protective fabric with a UPF of about 50 or higher. In some embodiments, the aqueous solution contains ferulic acid or ethyl ferulic acid and one or more surfactants with an HLB of about 13 to about 20. In some embodiments, the aqueous solution may also contain a dye, and the color produced by the dye may be unaffected by ferulic acid or a ferulic acid derivative.

[0018] Other embodiments include methods for treating fabrics to provide UV protection, comprising immersing the fabric in an aqueous solution at a temperature between about 25°C and about 130°C for about 5 minutes to about 30 minutes, said aqueous solution containing ferulic acid and / or ferulic acid derivatives and one or more surfactants with an HLB value between about 10 and about 20, removing the fabric from the aqueous solution, and drying the immersed fabric at a temperature between about 80°C and about 180°C. In some embodiments, the one or more surfactants have an HLB value between about 14 and about 20, and the temperature of the aqueous solution is between about 75°C and about 90°C. In some embodiments, the aqueous solution contains ethyl ferulic acid, and the temperature of the aqueous solution is between about 100°C and about 130°C. Detailed Implementation

[0019] The following detailed description is exemplary in nature and is not intended to limit the scope, applicability, or configuration of the invention. Rather, the following description provides practical guidance for implementing various exemplary embodiments. Those skilled in the art will recognize, using the teachings provided herein, that many examples have suitable alternatives.

[0020] The various embodiments described herein include methods for treating fabrics and treated fabrics with ultraviolet protection properties (including UVA and UVB protection). Fabrics can be treated using ferulic acid or its derivatives (including, but not limited to, ethyl ferulic acid), which can be bio-based, plant-derived molecules, making it a natural, environmentally friendly, and sustainable alternative to other fabric treatments. Furthermore, treatment with ferulic acid and / or ethyl ferulic acid does not alter the color of the fabric. As described herein, fabrics treated with ferulic acid and / or ferulic acid derivatives (such as ethyl ferulic acid) absorb ultraviolet radiation in the desired range from about 280 to about 400 nm. The treated fabric achieves a UPF of at least 50 and a UVA transmittance of less than 5%. The treated fabric blocks 98% or more of ultraviolet transmission.

[0021] Methods and formulations containing ferulic acid can be used as textile finishing agents to improve the UV protection properties of natural and synthetic fibers, textile materials, and fabrics. The active ingredient, ferulic acid and / or its derivatives, can be bio-based, plant-derived molecules (although if ferulic acid is chemically synthesized, it can also be used in the methods and formulations described herein). In some embodiments, the methods and formulations do not alter the color of the fabric after application. The resulting fabric is able to absorb UV radiation, particularly in the 280-400 nm range. This UV protection results in an increased UV protection factor (UPF) and reduced UVA transmittance of the treated fabric.

[0022] The Ultraviolet Protection Factor (UPF) is a calculated value representing the ratio of light transmitted through a fabric to light transmitted through the air. UPF calculations take into account the power of solar irradiance and its erythema effect on the skin, i.e., skin redness caused by exposure to ultraviolet radiation. The equation for calculating UPF is shown below, i.e., Equation 1: Equation 1 Where Eλ is the erythema spectral effectiveness at wavelength λ, Sλ is the solar spectral irradiance at wavelength λ, Tλ is the transmittance value at wavelength λ, and Δλ is the measured wavelength interval (nm).

[0023] Ultraviolet transmittance can be measured at known wavelength intervals using a spectrophotometer equipped with an integrating sphere. The UPF is then calculated using the equation described above via an algorithm integrated into the software. Variables E and S are determined according to the standards followed as part of the test method, such as EN 13758-1, AATCC TM183, or AS / NZS 4399.

[0024] This equation simplifies to UPF = 1 / T, meaning that if UPF = 50, only 2% of the light is transmitted, or if UPF = 20, 5% of all ultraviolet light is transmitted. Table 1 below shows the UPF classification system according to AS / NZS 4399 and ASTM D6603.

[0025] Table 1.

[0026] One of the variables affecting light transmittance through fabric is the fabric's coverage factor, which is the ratio of the area occupied by fibers to the total area covered by the fabric. In other words, the higher the coverage factor, the fewer gaps there are between the fibers that make up the fabric structure (such as the knitted or woven structure), and therefore the less light passes through the fabric. The fabric's coverage factor can be estimated using optical microscopy in light transmission mode, followed by image analysis techniques to calculate the proportion of pixels through which light freely passes out out of the total number of pixels in the image. The coverage factor is then reported as a percentage, where 100% means no light passes through.

[0027] Assuming all other factors (color, fiber material, final finishing chemicals) are the same, UPF can be approximately related to the coverage factor using the following Equation 2: Equation 2

[0028] Where T is the transmittance. For example, a fabric with a coverage factor of 98% will theoretically transmit only 2% of the incident light and should achieve the theoretical value of UPF 50. Figure 1 The correlation between UPF and coverage factor collected from various fabrics is shown. Regardless of fabric type, the measured UPF values ​​follow the theoretical UPF values, with fabrics achieving UPF values ​​above 50 when the coverage factor reaches approximately 98% or higher. Compared to cotton-based fabrics with similar coverage factors, polyester-based fabrics exhibit relatively higher UPFs due to the repeating UV-absorbing units in their polymer structure.

[0029] However, UPF measurements have limitations. UV-protective textiles can be worn in various ways, causing the fabric to stretch or become wet. There is no standardized test to reproduce fabric stretching. The more a fabric stretches, the more light passes through. Therefore, UPF / UVA values ​​will vary depending on the test conditions. Furthermore, UPF calculations are weighted for erythema effectiveness, or skin redness. Skin redness is caused by exposure to UVB radiation, not UVA. Therefore, even if clothing is rated UPF 50+ (i.e., average transmittance less than 2% in the 280-400 nm range), it may still have high UVA transmittance. Therefore, it is useful not only to determine the UPF of protective fabrics but also to determine the absorption spectrum, including both UVA and UVB. Another factor affecting UPF is the fabric's color. Many dyes absorb UV radiation as well as visible light. Dark and / or heavily dyed fabrics with sufficiently high coverage factors tend to achieve UPF 50+. However, in areas where people typically wear light-colored, loosely woven clothing, sun protection measures are often necessary. Existing colorless UV-absorbing molecules have been developed for use as finishing agents and dyes to improve the UPF of textiles without altering their color. However, most of these molecules are synthetic compounds designed to primarily absorb UVB radiation and therefore lack the ability to protect against UVA radiation.

[0030] Various implementations include fabric finishing agents or fabric treatments using ferulic acid and / or ferulic acid derivatives as ultraviolet absorbing components (including protection against UVA radiation). Ferulic acid is an abundant plant polyphenol found in the cell walls of plants, fruits, and vegetables. It is known for its antioxidant properties and is therefore used in therapeutic applications as well as in cosmetics, such as skincare products and sunscreens. Ferulic acid and ferulic acid derivatives have been found to act as ultraviolet absorbers, have an affinity for fibrous materials, and can be applied at application temperatures relevant to the textile industry. In some implementations, ferulic acid and / or ferulic acid derivatives can be applied to the fabric during the dyeing process, for example, together with the dye molecules in the same treatment bath. In other implementations, ferulic acid and / or ferulic acid derivatives can be applied as finishing agents to the dyed fabric as a final step in the fabric manufacturing process after dyeing, for example, after dyeing, before drying the fabric, or after dyeing and drying the fabric. Application temperatures can range from room temperature to 220°C, for example, the choice of temperature depends on, for example, the application step and fabric type, as well as efficiency and cost considerations. For example, at higher temperatures, ferulic acid and / or ferulic acid derivative molecules may diffuse into the fiber more quickly. However, using higher temperatures can be more expensive, and the method can also be used at lower temperatures.

[0031] Fabrics treated with ferulic acid and / or ferulic acid derivative solutions exhibit excellent UPF protection and block UVB and UVA transmission. For example, treated fabrics allow 5% or less UVA transmittance, such as between 0 or 0.1% and 4.5%. The enhanced UV protection provided by treated fabrics is present in both wet and dry fabrics and remains durable after repeated washing. For example, treated fabrics retain a UPF of 50 or higher and less than 5% UVA after at least 50 wash and dry cycles.

[0032] The treatment formulation described herein may be a solution containing ferulic acid and / or a ferulic acid derivative (such as ethyl ferulic acid). Ferulic acid is commercially available and may be of natural origin or chemically synthesized. Ethyl ferulic acid is an ethyl ester of ferulic acid and is typically obtained through chemical synthesis, either by conventional organic chemistry practices or by enzyme-assisted synthesis. The chemical structure of ferulic acid is as follows: Figure 2 As shown. In various embodiments, the treatment solution comprises an aqueous solution of ferulic acid, wherein the concentration of ferulic acid may be between about 1 and about 4 g / L, although other concentrations may also be used.

[0033] The treatment solution may contain only an aqueous solution of ferulic acid and / or one or more ferulic acid derivatives. The treatment solution may not use or contain any auxiliary chemicals such as salts, binders, pH adjusters, or enzymes. For example, the treatment solution may contain only ferulic acid and / or one or more ferulic acid derivatives (such as ethyl ferulic acid) and optionally one or more surfactants. Alternatively, the treatment solution may also contain other components, such as antioxidants, free radical scavengers, and / or antifouling agents, which can improve the shelf life of the product.

[0034] In some embodiments, the treatment solution may optionally contain one or more surfactants, including but not limited to cetyltrimethylammonium bromide, sodium dodecyl sulfate, polysorbate 20, polysorbate 40, polysorbate 60, polysorbate 80, Tween 20, Tween 40, Tween 60, Tween 80, Span 20, Span 40, Span 60, Span 80, Tergitol 15-S-12, Tergitol 15-S-20, Tergitol 15-S-40, and poloxamer. In some embodiments, the hydrophilic-lipophilic balance (HLB) or combined HLB of the surfactant or surfactant combination used in the treatment solution is 13 or higher, or 14 or higher, or 15 or higher, for example, 13-20, 14-20, or 15-20. In other embodiments, the HLB or combined HLB of the surfactant or surfactant combination used in the treatment solution is 10 or higher, for example, 10-13 or 10-20. For example, HLB values ​​of 10 or higher can be used for alkyl-modified ferulic acid derivatives, such as alkyl ester ferulic acid derivatives.

[0035] Furthermore, the ferulic acid used in various embodiments can be modified ferulic acid, which still imparts UV protection properties. For example, ferulic acid can be functionalized, such as at the acid or hydroxyl end of the molecule. Ferulic acid and its derivatives can be used to treat solutions, including but not limited to salts, such as sodium 3-(4-hydroxy-3-methoxyphenyl)acrylate, ester derivatives, such as ethyl 4-hydroxy-3-methoxycinnamate (also known as ethyl ferulic acid or ethyl ferulic acid), phenyl ether derivatives, such as 3,4-dimethoxycinnamic acid, amide derivatives such as diferoyl putrescine, and combinations of said derivatives.

[0036] Furthermore, ferulic acid is a derivative of a class of chemicals known as cinnamic acid derivatives, which can also impart UV absorption properties in the 280-400 nm range. As described herein, various other cinnamic acid derivatives can be used to impart UV absorption properties. These cinnamic acid derivatives include, but are not limited to, ethyl ferulic acid, sinapic acid, chlorogenic acid, caffeic acid, rosmarinic acid, p-coumaric acid, and ethylhexyl ferulic acid. Figure 3 Examples of cinnamic acid derivatives that can be used in various embodiments are shown, wherein R1 can be -H, -OH or -OCH3, R2 can be -H, -OH or -OCH3, R3 can be -H, -OH, -OCH3, and R4 can be -H, -CH3, -CH2CH3, alkyl (C1-C12), -CH2CH(CH2CH3)(CH2)3CH3, ethylhexyl (-CH2CH(CH2CH3)(CH2)3CH3), or quinic acid.

[0037] Fabrics can be treated by immersing them in a treatment formulation for a sufficient time to fully saturate them. For example, the fabric may be immersed for at least 5 minutes, at least 10 minutes, or at least 15 minutes, such as about 30 minutes. Alternatively, the fabric may be immersed for about 5 minutes to about 60 minutes, or about 10 minutes to about 45 minutes, or about 15 minutes to about 30 minutes. During immersion, the fabric and / or solution may be stirred or agitated, or left to stand. The fabric can then be removed from the treatment formulation. Excess treatment formulation may optionally be removed from the fabric, for example, by rinsing, squeezing, or blotting the fabric. The fabric can then be air-dried at room temperature or dried at a higher temperature, such as between about 80°C and about 180°C, or between about 100°C and about 160°C, or between about 120°C and about 140°C, or about 130°C. The resulting dried fabric is a UVA and UVB protective fabric.

[0038] In some embodiments, the fabric can be immersed in the treatment solution at a temperature above room temperature. For example, for a treatment formulation of ferulic acid, the temperature can be between about room temperature (about 25°C) and about 90°C, for example, about 60°C to about 90°C, or about 75°C to about 90°C, or about 85°C to about 90°C, for example, about 90°C. In some embodiments, for example, for a treatment formulation of ethyl ferulic acid, the temperature can be between about room temperature (about 25°C) and about 130°C, for example, about 80°C to about 130°C, or about 100°C to about 130°C, or about 120°C to 130°C, or about 130°C. In some embodiments, for example, where the treatment solution comprises ferulic acid and another component such as a surfactant, the fabric can be immersed at the above-mentioned temperatures or alternatively at room temperature.

[0039] In some embodiments, the bath pH of the treatment solution can be from about 1 to about 14, preferably from about 4 to about 5, which can be achieved without adjusting the pH.

[0040] In some embodiments, the treated fabric can be air-dried at room temperature. In other embodiments, the fabric can be dried using a dryer, such as a drum dryer or a dryer that blows room temperature or hot air onto the fabric, or other types of heated or room temperature fabric dryers, or a tenter frame and conveyor belt, at the aforementioned temperatures.

[0041] Fabrics that can be used in various embodiments include natural and synthetic fabrics, including synthetic, semi-synthetic, or natural woven or nonwoven textiles, fibers, or microfibers. Examples of textiles that can be used include cotton (such as bleached cotton), polyester (such as spun polyester), polyamide, nylon, spandex, rayon, linen, cashmere, silk, wool (such as worsted wool), acrylic (such as spun acrylic), modified acrylic, olefins, cellulose acetate, viscose (such as spun viscose), polypropylene, polyvinyl chloride, lyocell, latex, and aramid, as well as blends or combinations of one or more of these or other materials or fibers. Thus, textiles can be natural, such as silk (including spun silk), wool, cotton, cellulose fibers, flax, jute, or bamboo; or synthetic, such as nylon, polyester, acrylic, spandex, rayon, polymers such as polypropylene, polyurethane, or combinations of more than one of these. In some embodiments, the material can be a textile comprising blends of the different materials described above.

[0042] While these methods are described for use on fabrics, the same methods can also be used alternatively to treat natural or synthetic fabric precursors, such as yarns, threads, or fibers. These treated fabric precursors can then be used to manufacture UV-protective fabrics, for example, through knitting, weaving, felting, or bonding.

[0043] Fabrics can be treated with a treatment solution before or after being made into clothing or other articles. According to various embodiments, the treated material can be used as UV-protective clothing, such as hats, shirts, trousers, jackets, scarves, and swimwear. In other embodiments, the UV protection of the treated material can reduce or prevent UV damage to the material itself, for example, in products used outdoors and / or exposed to sunlight, UV protection can reduce or prevent fading. In some such embodiments, the treated material can be used in furniture upholstery, automotive or other vehicle upholstery, tents, tarpaulins, umbrellas, towels, blankets, bedding, curtains and other window coverings, and awnings, etc.

[0044] This treatment method provides UV protection without affecting the fabric's color. Therefore, it is particularly useful for white or light-colored fabrics, preserving their whiteness or lightness even after treatment. The color of dyed fabrics is also unaffected by ferulic acid and / or ferulic acid derivative treatment. Thus, ferulic acid and / or ferulic acid derivative treatment provides UV protection without affecting the color of the fabric, whether natural or dyed, including white fabrics.

[0045] The treated fabric (and the treated fabric garment) retains a high level of UV protection, including high UPF and low UVA transmittance, even after washing in a washing machine with detergent on a normal washing cycle. The treated fabric retains UV protection after at least three wash cycles. In some embodiments, the treated fabric retains primary UV protection after at least 10, at least 20, or at least 50 wash cycles. For example, after the aforementioned number of wash cycles, the treated fabric may maintain an improvement in UPF and / or UVA transmittance relative to a control of at least 90%, at least 80%, at least 70%, or at least 50%.

[0046] Ferulic acid aqueous solution absorbs ultraviolet radiation. Figure 4 The ultraviolet absorption spectrum of ferulic acid collected from aqueous solution is shown. This chemical exhibits strong absorption of ultraviolet radiation between approximately 260 nm and 360 nm, with maximum absorption at approximately 320 nm. This range covers the UVB (280–315 nm) and UVA (315–400 nm) regions.

[0047] Another bio-based and plant-derived UV absorber is tannic acid. The UV absorption spectrum of tannic acid is as follows: Figure 5As shown, this chemical absorbs ultraviolet radiation in the 250-320 nm range, with a peak at approximately 275 nm. Therefore, this chemical is effective in the UVB range but offers minimal protection against UVA. Furthermore, tannic acid has an associated brown hue and may discolor fabrics after application. Therefore, while tannic acid can be used to provide UV protection for fabrics, ferulic acid offers significant advantages over tannic acid.

[0048] Figure 6 The UV absorption spectra of aqueous solutions of tannic acid and ferulic acid are compared. This figure demonstrates that ferulic acid has superior UVA absorption performance compared to tannic acid.

[0049] Commercially available UV absorbers may also provide little or no UV protection in the UVA spectrum. For example, RAYOSAN C is a commercially available fiber-reactive UV absorber used in cellulosic fibers and polyamide fibers and their blends. The UV absorption spectrum of RAYOSAN C paste (Archroma) is as follows: Figure 7 As shown. Figure 7 The maximum UV absorption of RAYOSAN C is shown to be in the UVB region, with little or no absorption in the UVA region.

[0050] Experimental section: These examples illustrate the application of ferulic acid and ferulic acid derivative formulations on different types of fabrics. Some examples also include comparative data using tannic acid and the commercial formulation RAYOSAN C. Untreated fabrics of the same type were used as control samples. In all examples, unless otherwise stated, the fabric samples were colorless / undyed.

[0051] As described in the following examples, fabric test samples were prepared using various treatment solutions.

[0052] In all embodiments, unless otherwise stated, UV transmittance was measured on a Labsphere UV2000F equipped with an integrating sphere. UPF values ​​and UVA transmittance were determined according to AATCC TM 183 and measured and reported by the UV2000F application software according to the EN13758-1 method.

[0053] In all embodiments, unless otherwise stated, the fabric samples underwent the following washing procedure. A fine cold water wash was performed on an SDL Atlas Vortex M6 washing machine according to the AATCC LP1 protocol, using the 1993 AATCC standard reference detergent WOB. After washing, the fabric samples were dried using an SDL Atlas Vortex M6D with the fabric selector set to "fine" and the drying cycle set to an intermediate indicator between "drier" and "slightly dry" on "Auto Regular / Fine".

[0054] Example 1

[0055] In this embodiment, ferulic acid aqueous solution was used to treat fabric samples, including 100% polyester fabric, 93% polyester / 7% spandex fabric, and 100% cotton fabric. All fabric samples were undyed, except for the 93% polyester / 7% spandex fabric, which was dyed light blue.

[0056] In a 250 mL beaker equipped with a magnetic stirrer, add 100 mL of deionized water and 0.4 g of ferulic acid. Heat the solution to 70°C while stirring at 180 rpm. Monitor the temperature with a temperature probe, and cover the beaker with foil to prevent water evaporation. Once the temperature is reached and the ferulic acid is completely dissolved, immerse 5 g of fabric sample in the solution (liquor ratio 20:1). Reduce the stirrer speed to 60 rpm while maintaining stirring, and treat the fabric sample in the solution for 15–30 minutes. Remove the fabric sample with tweezers, squeezing out excess solution until no more water drips. Dry the fabric sample in a Vastex D-100 infrared curing system at 80°C for 10 minutes or until dry.

[0057] The dried fabric samples were cooled to room temperature before UPF / UVA measurements.

[0058] Example 2

[0059] In this embodiment, fabric samples comprising 93% polyester / 7% spandex and 100% cotton were treated with an aqueous solution of ferulic acid and hexadecyltrimethylammonium bromide. All samples were undyed, except for the 93% polyester / 7% spandex sample, which was dyed a light blue.

[0060] In a 250 mL beaker equipped with a magnetic stirrer, add 100 mL of deionized water, 0.25 g of ferulic acid, and 5.5 g of cetyltrimethylammonium bromide. Stir the solution at 180 rpm at 25°C until a clear solution is formed. Immerse 5 g of a fabric sample in the solution (liquor ratio 20:1). Reduce the stirrer speed to 60 rpm while maintaining stirring, and immerse the fabric sample in the solution for 15–30 minutes. Remove the fabric sample with tweezers, squeezing out excess solution until no more water drips. Dry the fabric sample in a Vastex D-100 infrared curing system at 80°C for 10 minutes or until dry.

[0061] The dried fabric samples were cooled to room temperature before UPF / UVA measurements.

[0062] Example 3

[0063] In this embodiment, tannic acid aqueous solution was used to treat fabric samples, including 100% polyester, 93% polyester / 7% spandex, and 100% cotton. All samples were left undyed, except for the 93% polyester / 7% spandex sample, which was dyed light blue.

[0064] In a 250 mL beaker equipped with a magnetic stirrer, add 100 mL of deionized water and 0.8 g of tannic acid. Stir the solution at 180 rpm at room temperature. Once the tannic acid is completely dissolved, immerse 5 g of fabric sample in the solution (liquor ratio 20:1). Reduce the stirrer speed to 60 rpm while maintaining stirring, and immerse the fabric sample in the solution for 15–30 minutes. Remove the fabric sample with tweezers, squeezing out excess solution until no more water drips. Dry the fabric sample in a Vastex D-100 infrared curing system at 80°C for 10 minutes or until dry.

[0065] The dried fabric samples were cooled to room temperature before UPF / UVA measurements.

[0066] Figures 8 to 10 Photographs are shown of fabric samples before (as shown in the control) and after treatment according to Example 1 (ferulic acid) and Example 3 (tannic acid). Figure 8 It is a photo of a 100% polyester fabric sample. Figure 9 It is a photo of a 93% polyester / 7% spandex fabric sample. Figure 10 These are photographs of 100% cotton fabric samples. In each case, for each material type, the ferulic acid-treated fabric sample (labeled Example 1) showed no color change compared to the control. In contrast, the tannic acid-treated fabric sample (labeled Example 3) showed some discoloration. Undyed fabric ( Figure 8 and Figure 10 After treatment with tannic acid, it exhibits a yellow / brown hue. Figure 9 The 93% polyester / 7% spandex fabric sample shown was light blue before treatment. After treatment with tannic acid, the 93% polyester / 7% spandex fabric sample turned grayish-white or bluish-brown, while the fabric sample treated with ferulic acid had the same color as the control.

[0067] Example 4

[0068] In this embodiment, a 100% cotton sample was treated with RAYOSAN C solution.

[0069] To obtain a 4% RAYOSAN C sizing solution, 30 g of sodium sulfate was dissolved in 500 mL of deionized water while stirring. The solution was heated to 40°C, and 20 g of RAYOSAN C sizing (RAYOSAN C pa) was added. The solution was maintained at 40°C for 10 minutes while the RAYOSAN C sizing dissolved. Then, 30 g of sodium carbonate was added to the solution, followed by 25 g of fabric sample. The fabric sample was treated in the solution for 30 minutes, with periodic stirring and agitation during treatment. After treatment, the fabric sample was removed from the solution and dried at 80°C for 10 minutes in a Vastex D-100 infrared curing system. The fabric sample was first manually rinsed with hot deionized water, then rinsed with cold deionized water, and hung to air dry.

[0070] Figure 11 These are photographs of 100% cotton fabric samples before and after treatment according to Example 1 (ferulic acid) and Example 4 (RAYOSAN C). The colors of the two treated samples appear the same as the untreated control fabric. However, the UV protection data shown below indicate that ferulic acid treatment is superior to RAYOSAN C treatment, especially in the UVA range.

[0071] The data collected from testing the fabric samples of Examples 1-4 and the control are listed in the table below.

[0072] Table 2 shows the UPF and UVA data results for 100% polyester fabrics before and after treatment in Examples 1 and 3. These results indicate that both ferulic acid and tannic acid provide improved UV protection compared to the control. However, the ferulic acid treatment produced the best results, including a higher UPF and lower UVA transmittance compared to tannic acid.

[0073] Table 2. UPF and UVA values ​​are the average values ​​of nine different sites on the same sample. Table 3 shows the UPF and UVA data results for 93% polyester / 7% spandex fabrics before and after treatment in Examples 1, 2, and 3. Both ferulic acid solutions produced excellent results. The fabric treated with ferulic acid alone had a slightly higher UPF and slightly lower UVA transmittance compared to the fabric treated with ferulic acid and surfactant. However, this is believed to be due to the much lower concentration of ferulic acid used in combination with surfactant in this example. In subsequent examples (see Example 5 below), fabrics treated with ferulic acid alone produced similar results to those treated with the same amount of ferulic acid and surfactant combination.

[0074] Table 3.

[0075] Table 4 shows the UPF and UVA data results for 100% cotton fabrics before and after treatment in Examples 1, 2, 3, and 4. Similarly, ferulic acid solution provided the best results in terms of both UPF and UVA transmittance. Although RAYOSAN C provided UPF protection and a reduction in UVA transmittance compared to the control, its effect was far less than that of ferulic acid solution and tannic acid.

[0076] Table 4. UPF and UVA values ​​are averages from nine different locations on the same sample. Transmittance test data of 100% cotton fabric samples produced in Examples 1 and 4 are presented. Figure 12 As shown in the figure, the control fabric sample exhibits significant ultraviolet radiation transmittance, particularly in the UVA spectrum. The RAYOSAN C-treated fabric sample blocks UVB transmission but performs poorly in blocking UVA transmission. In contrast, the ferulic acid-treated fabric sample demonstrates excellent performance in blocking both UVB and UVA transmission.

[0077] Example 5.

[0078] In this embodiment, a fabric sample comprising 93% polyester / 7% spandex is treated with either ferulic acid alone or an aqueous solution of ferulic acid and hexadecyltrimethylammonium bromide.

[0079] In a 250 mL beaker equipped with a magnetic stirrer, add 100 mL of deionized water and 0.25 g or 0.4 g of ferulic acid, alone or together with 5.5 g of cetyltrimethylammonium bromide, as shown in Table 5 below. Stir the solution at 180 rpm at 25°C or 70°C until a clear solution is formed. Immerse 5 g of fabric sample in the solution (liquor ratio 20:1). Reduce the stirrer speed to 60 rpm while maintaining stirring, and immerse the fabric sample in the solution for 15–30 minutes. Remove the fabric sample with tweezers, squeezing out excess solution until no more water drips. Dry the fabric sample in a Vastex D-100 infrared curing system at 80°C for 10 minutes or until dry.

[0080] The dried fabric samples were cooled to room temperature before UPF / UVA measurements.

[0081] The dried fabric sample was then subjected to the following washing procedure. A fine cold water wash was performed on an SDL Atlas Vortex M6 washing machine according to the AATCC LP1 protocol, using the 1993 AATCC standard reference detergent WOB. After washing, the fabric sample was dried using an SDL Atlas Vortex M6D with the fabric selector set to "Fine" and the drying cycle set to an intermediate indicator between "Drier" and "Slightly Dry" on "Auto Regular / Fine". UPF / UVA measurements were obtained after three wash-dry cycles and after five wash-dry cycles.

[0082] The results are shown in Table 5 below, which compares the UPF and UVA transmittance of 93% polyester / 7% spandex fabric samples treated in the treatment solutions at different concentrations and temperatures, with and without surfactant. In this example, the UPF and UVA transmittance were comparable when the amount of ferulic acid in the treatment solution was the same with and without surfactant.

[0083] Table 5.

[0084] Example 6.

[0085] In this embodiment, colored fabric samples, including a blue sample of 93% polyester / 7% spandex and a green sample of 90% polyester / 10% spandex, were treated with an aqueous solution of ferulic acid alone.

[0086] Fabric samples were prepared using 4 g / L ferulic acid according to the method described in Example 1.

[0087] Fabric samples were sent for third-party testing, with tests conducted on both control and treated samples. UPF and UVA values ​​were collected according to AATCC TM 183. Samples were evaluated upon receipt, under dry and wet conditions. Treated samples were also washed according to ISO 6330 / AATCC LP1 using aluminum-free IEC-W liquid wool detergent in normal cycles (cold water wash 27 ± 3°C). Washed samples were then tumble dried at low temperature.

[0088] Tests were conducted at baseline before washing, and after 10, 20, and 50 wash-dry cycles, under wet and dry conditions. The results are shown in Tables 6 and 7 below. Figure 13 and Figure 14 As shown.

[0089] Figure 13Photographs of the fabrics before treatment (control, left column) and after treatment (right column) are shown. The two fabric samples look identical before and after ferulic acid treatment. There was no effect on the visual appearance of the dyed material, neither in terms of color nor texture.

[0090] The results shown in Table 6 are for a blue 93% polyester / 7% spandex fabric sample, and the results shown in Table 7 are for a green 90% polyester / 10% spandex fabric sample. Both dyed fabric samples achieved high levels of UV protection after ferulic acid treatment. Even after 50 wash cycles, they maintained high levels of UV protection under both wet and dry conditions. These results indicate that the UV protection provided by the treatment solution is durable and effective under both wet and dry conditions, including on dyed fabrics. This makes ferulic acid treatment suitable for a variety of applications, including clothing intended for use when wet, such as various types of swimwear, or other casual wear such as fishing or surfing equipment.

[0091] Table 6.

[0092] Table 7.

[0093] The above results are as follows Figure 14 As shown, this figure displays the UVA transmittance results for the two fabrics after treatment and after each washing cycle. The top row is blue (93% polyester / 7% spandex), and the bottom row is green (90% polyester / 10% spandex). The figure shows that ferulic acid treatment resulted in a significant reduction in UVA transmittance, which remained relatively stable even after 50 washing cycles.

[0094] Example 7

[0095] In this embodiment, a multifiber test strip containing various fabric samples is treated with ferulic acid. The test strip includes cellulose acetate, cotton, polyamide, acrylic, silk, viscose, and wool, and is sewn into a single strip.

[0096] Following the method described in Example 1, the test strip (TestFabrics MFF 49) was treated with a 4 g / L aqueous solution of ferulic acid. The test strip was immersed in the treatment solution at 70°C for 15–30 minutes and then dried at 80°C.

[0097] The dried test strips were subjected to UPF and UVA transmittance tests.

[0098] Then, the test strips were washed according to the washing procedure described in Example 5 above. Photos of the control test strips and the treated test strips are shown below. Figure 15 As shown, no color change was observed in any of the fabrics.

[0099] The UPF and UVA transmittance results are shown in Table 8 below. All materials showed significant improvement as UV absorbers, with a significant decrease in UVA transmittance.

[0100] Table 8.

[0101] Example 8.

[0102] In this embodiment, a three-factor central composite design method was used to optimize application parameters with the goal of minimizing UVA (%T). The variables evaluated were bath time, bath temperature, and oven temperature, where the bath time ranged from 10 to 60 minutes, the bath temperature ranged from 25°C to 70°C, and the oven temperature ranged from 70°C to 110°C. The experimental conditions are listed in Table 10. Three 3" x 6" undyed fabric samples were used for each run, consisting of 87% rPET (recycled polyester) and 13% spandex, with a coverage factor of approximately 97%. Each sample was treated in a beaker equipped with a magnetic stirrer containing 4 g / L ferulic acid and 80 g / L Tween 20 solution, with a liquor ratio (liquid to fabric ratio) of 1:10, i.e., 10 grams of water for every 1 gram of fabric. After treatment, the fabric was gently squeezed to remove excess liquid and then cured in an oven. Each fabric sample was measured for UVA (%T) on a 9-point ISO mask using the EN 13758-1:2007 method on a Labsphere 2000F UV spectrophotometer. The dried fabric samples were then subjected to the following washing procedure: a fine cold water wash was performed on an SDL Atlas Vortex M6 washing machine according to the AATCC LP1 protocol using the 1993 AATCC standard reference detergent WOB. After washing, the fabric samples were dried using an SDL Atlas Vortex M6D with the fabric selector set to "fine" and the drying cycle set to an intermediate indicator between "drier" and "slightly dry" on "Auto Regular / Fine". UPF / UVA measurements were obtained after one wash-dry cycle. The results are shown in Table 9.

[0103] Table 9.

[0104] The results are used to generate Figure 16 and Figure 17 This displays the response surface for predicting UVA values ​​given any combination of factors within the range of studied parameters. A response surface is a statistical method used to show the relationship between variables. In this case, the response surface shows the response of UVA to changes in bath time, bath temperature, and oven temperature. Figure 16 The response surface for a room temperature (25°C) bath application is shown, while Figure 17The response surface for a 70°C bath application is shown.

[0105] Based on these results, oven temperature was found to be the largest contributor to the reduction of UVA (%T) values ​​and their durability during washing cycles. Bath time and bath temperature were also significant factors leading to low UVA (%T) values. The results indicate that using the highest possible oven temperature without degrading UV-active components, depending on the exposure time, still allows for some flexibility in terms of bath time and temperature.

[0106] Based on this study and information gathered from the industry, optimized application conditions for ferulic acid preparations may include a bath temperature of approximately 60°C, a bath time of approximately 30 minutes, and an oven temperature (drying temperature) of approximately 130°C for approximately 6 minutes, although this depends heavily on the type of oven or dryer used, and other optimized conditions may apply to other situations.

[0107] Example 9

[0108] In this embodiment, the solubilization of ferulic acid with surfactants was investigated. Tween 20 and Span 20 were used as model compounds to find the optimal hydrophilic-lipophilic balance (HLB) value for solubilizing ferulic acid. The HLB system is an empirical system that assigns a number from 0 to 20 to describe how the ratio of the hydrophilic and lipophilic portions of a surfactant affects its behavior in an emulsion. In other words, the HLB value indicates the degree of water or oil solubility of a particular surfactant. An HLB value higher than 10 indicates better water solubility, while an HLB value lower than 10 indicates better oil solubility. Span 20 is a lipophilic molecule with an HLB value of 8.6, and Tween 20 is a hydrophilic molecule with an HLB value of 16.7. They have similar chemical structures, with lauric acid forming a hydrophobic tail and sorbitan forming a hydrophilic head; the only difference is that the polyoxyethylene group in Tween 20 gives it higher hydrophilicity. Table 10 shows the surfactant blend compositions used to achieve HLB values ​​in the range of 13–16.7.

[0109] Table 10.

[0110] Ferulic acid was added to different blends of Span 20 and Tween 20 at a surfactant-to-ferulic acid weight ratio of 10:1 (w:w). The mixtures were further diluted to achieve a ferulic acid concentration of 4 g / L. In five solutions, HLB 13 and 14 did not completely dissolve ferulic acid; therefore, only samples with HLB 14 or higher were considered for further evaluation.

[0111] Next, the maximum solubility of ferulic acid in each surfactant blend and its aqueous solutions at concentrations ranging from 5 mM to 300 mM was determined. The results are as follows: Figure 18As shown in the figure, this graph illustrates the correlation between the HLB of each surfactant blend and the solubility of ferulic acid. The amount of solubilized ferulic acid increases with increasing surfactant concentration and HLB, indicating that in this example, the more hydrophilic the surfactant, the better the solubility.

[0112] Example 10

[0113] Examples 10-13 demonstrate the effect of application temperature on UPF / UVA. In some cases, UV-enhancing compounds can be added during the dyeing cycle of the fabric manufacturing process, rather than being applied as finishing agents to the dyed fabric. This can reduce the number of process steps, potentially increasing production costs. Textile finishing agents are typically applied using a treatment bath at room temperature, while the dye bath operates at higher temperatures. Particularly for polyesters, dye bath temperatures can reach up to 130°C, above the fiber's glass transition temperature, to allow small molecules to diffuse into the fibrous material. For the studies shared in Examples 10-13, ferulic acid and ethyl ferulic acid were used as UV-absorbing compounds and applied at room temperature or 130°C. These high application temperatures were achieved using an Ahiba IR dyeing machine. The UPF / UVA results are summarized in Table 11.

[0114] In this embodiment, three undyed fabric samples with a composition of 97% polyester / 3% spandex were treated with an aqueous solution containing ferulic acid and Tween 20.

[0115] A treatment concentrate was prepared by mixing Tween 20 and ferulic acid at a weight ratio of 20:1 and stirring thoroughly at room temperature until no ferulic acid particles were observed. The concentrate was then diluted with water at room temperature to prepare a treatment solution with a ferulic acid concentration of 4 g / L. 100 mL of the treatment solution was then transferred to a 300 mL steel beaker designed for the Ahiba IR dyeing machine. A 10 g fabric sample was immersed in the treatment solution (liquor ratio 10:1). The beaker was then mounted in the Ahiba IR dyeing machine and treated at room temperature for 30 minutes. After treatment, the fabric sample was removed with tweezers and rolled using a manual wringer to remove excess solution. The sample was dried and cured in a Thermo Scientific oven at 130°C for 5–10 minutes. The dried sample was cooled to room temperature before UPF / UVA measurement. An image of the dried sample is shown below. Figure 19 The fabric samples shown (labeled as Example 10), and those of Example 11 below, and the untreated fabric sample as a control. Compared to the control, the color of the treated fabric sample did not change.

[0116] UPF / UVA (%T) of each fabric sample before and after washing was measured on a 9-point ISO mask using the EN 13758-1:2007 method on a Labsphere 2000F UV spectrophotometer. The dried fabric samples were then subjected to the following washing procedure: a fine cold water wash was performed on an SDL Atlas Vortex M6 washing machine according to the AATCC LP1 protocol using the 1993 AATCC standard reference detergent WOB. The washed fabric samples were then dried using an SDL Atlas Vortex M6D with the fabric selector set to "fine" and the drying cycle set to an intermediate indicator between "drier" and "slightly dry" on "Auto Regular / Fine". UPF / UVA measurements were obtained after three wash-dry cycles. The results are shown in Table 11, as well as the results of Examples 11-13.

[0117] Example 11

[0118] In this embodiment, three undyed fabric samples with a composition of 97% polyester / 3% spandex were treated with an aqueous solution containing ethyl ferulic acid and Tween 20.

[0119] A treatment concentrate was prepared by mixing Tween 20 and ethyl ferulic acid at a weight ratio of 20:1 at 70°C until the ethyl ferulic acid was completely dissolved. The concentrate was then diluted with water at room temperature to prepare a treatment solution with a final ethyl ferulic acid concentration of 4 g / L. 100 mL of the treatment solution was then transferred to a 300 mL steel beaker designed for the Ahiba IR dyeing machine. A 10 g fabric sample was immersed in the treatment solution (liquor ratio 10:1). The beaker was then mounted in the Ahiba IR dyeing machine and treated at room temperature for 30 minutes. After treatment, the fabric sample was removed with tweezers and rolled using a manual wringer to remove excess solution. The sample was dried and cured in a Thermo Scientific oven at 130°C for 5–10 minutes. An image of the dried sample is shown below. Figure 19 The image shows (labeled Example 11), along with the fabric sample from Example 11 and an untreated fabric sample as a control. The color of the treated fabric sample did not change compared to the control.

[0120] After drying, the fabric samples were cooled to room temperature before UPF / UVA measurements were performed on a Labsphere 2000F UV spectrophotometer using the EN 13758-1:2007 method on a 9-point ISO mask. The dried fabric samples were then subjected to the following washing procedure: a fine cold water wash was performed on an SDL Atlas Vortex M6 washing machine according to the AATCC LP1 protocol using the 1993 AATCC standard reference detergent WOB. The washed fabric samples were then dried using an SDL Atlas Vortex M6D with the fabric selector set to "fine" and the drying cycle set to an intermediate indicator between "drier" and "slightly dry" on "Auto Regular / Fine". UPF / UVA measurements were obtained after three wash-dry cycles. The results are shown in Table 11, as well as the results for Examples 10, 12, and 13.

[0121] Example 12

[0122] In this embodiment, three undyed fabric samples with a composition of 97% polyester / 3% spandex were treated with an aqueous solution containing ferulic acid and Tween 20.

[0123] A treatment concentrate was prepared by mixing Tween 20 and ferulic acid at a weight ratio of 20:1 and stirring thoroughly at room temperature until no ferulic acid particles were observed. The concentrate was then diluted with water at room temperature to prepare a treatment solution with a ferulic acid concentration of 4 g / L. 100 mL of the treatment solution was then transferred to a 300 mL steel beaker designed for an Ahiba IR dyeing machine. A 10 g fabric sample was immersed in the treatment solution (liquor ratio 10:1). The beaker was then mounted in the Ahiba IR dyeing machine and treated at 130°C for 30 minutes. After treatment, the fabric sample was removed with tweezers and rolled using a manual wringer to remove excess solution. The sample was dried and cured in a Thermo Scientific oven at 130°C for 5–10 minutes. The dried sample was cooled to room temperature before UPF / UVA measurement. An image of the dried sample is shown below. Figure 20 The fabric samples shown (labeled as Example 12), and those of Example 13 below, and the untreated fabric sample as a control. Compared to the control, the treated fabric sample exhibits a yellowish hue.

[0124] UPF / UVA measurements of the treated fabric samples were collected on a 9-point ISO mask using the EN 13758-1:2007 method on a Labsphere 2000F UV spectrophotometer. The fabric samples were then subjected to the following washing procedure: a fine cold water wash was performed on an SDL Atlas Vortex M6 washing machine according to the AATCC LP1 protocol using the 1993 AATCC standard reference detergent WOB. After washing, the fabric samples were dried using an SDL Atlas Vortex M6D with the fabric selector set to "fine" and the drying cycle set to an intermediate indicator between "drier" and "slightly dry" on "Auto Regular / Fine". UPF / UVA measurements were obtained after three wash-dry cycles. The results are shown in Table 11, as well as the results of Examples 10-11 and 13.

[0125] Example 13

[0126] In this embodiment, three undyed fabric samples with a composition of 97% polyester / 3% spandex were treated with an aqueous solution containing ethyl ferulic acid and Tween 20.

[0127] A treatment concentrate was prepared by mixing Tween 20 and ethyl ferulic acid at a weight ratio of 20:1 at 70°C until the ethyl ferulic acid was completely dissolved. The concentrate was then diluted with water at room temperature to prepare a treatment solution with an ethyl ferulic acid concentration of 4 g / L. 100 mL of the treatment solution was then transferred to a 300 mL steel beaker designed for the Ahiba IR dyeing machine. A 10 g fabric sample was immersed in the treatment solution (liquor ratio 10:1). The beaker was then mounted in the Ahiba IR dyeing machine and treated at 130°C for 30 minutes. After treatment, the fabric sample was removed with tweezers and rolled using a manual wringer to remove excess solution. The sample was dried and cured in a Thermo Scientific oven at 130°C for 5–10 minutes. The dried sample was cooled to room temperature before UPF / UVA measurement. An image of the dried sample is shown below. Figure 20 The fabric sample shown (labeled as Example 13), as well as the fabric sample from Example 12 described above, and the untreated fabric sample as a control. Compared to the control, the color of the treated fabric sample did not change.

[0128] UPF / UVA measurements of the treated fabric samples were collected using the EN 13758-1:2007 method on a 9-point ISO mask on a Labsphere 2000F UV spectrophotometer. The treated fabric samples were then subjected to the following washing procedure: a fine cold water wash was performed on an SDL Atlas Vortex M6 washing machine according to the AATCC LP1 protocol using the 1993 AATCC standard reference detergent WOB. The washed fabric samples were then dried using an SDL Atlas Vortex M6D with the fabric selector set to "fine" and the drying cycle set to an intermediate indicator between "drier" and "slightly dry" on "Auto Regular / Fine". UPF / UVA measurements were obtained after three wash-dry cycles. The results are shown in Table 11 below, as well as the results of Examples 10-12.

[0129] Table 11.

[0130] The results of Examples 10-13 showed that both formulations improved UPF and UVA values. The improvement was more significant with increasing bath temperature, likely due to the more efficient diffusion of the UV-absorbing compounds into the fibrous material. It was observed that the fabric color remained unchanged in both cases when the treatment was applied at room temperature. When applied at 130°C, the fabric treated with ethyl ferulic acid retained its color, while the fabric treated with ferulic acid turned yellow. This color change indicates a change in the chemical structure of ferulic acid, most likely due to hydrolytic degradation or condensation caused by high temperature.

[0131] Example 14

[0132] In this embodiment, a fabric sample composed of 87% recycled polyester / 13% spandex was treated with an aqueous solution of caffeic acid.

[0133] In a 200 mL beaker equipped with a magnetic stirrer, add 100 mL of deionized water and 0.4 g of caffeic acid to achieve a caffeic acid concentration of 4 g / L. Heat the solution to 70°C while stirring at 180 rpm. Monitor the temperature with a temperature probe, and cover the beaker with foil to prevent water evaporation. Once the temperature is reached and the ferulic acid is completely dissolved, immerse a 5 g fabric sample in the solution (liquor ratio 20:1). Reduce the stirrer speed to 60 rpm while maintaining stirring, and treat the fabric sample in the solution for 15–30 minutes. Remove the fabric sample with tweezers, squeezing out excess solution until no more water drips. Dry the fabric sample in a Vastex D-100 infrared curing system at 80°C for 10 minutes or until dry.

[0134] The dried fabric samples were cooled to room temperature before UPF / UVA measurements.

[0135] The dried fabric sample was then subjected to the following washing procedure. A fine cold water wash was performed on an SDL Atlas Vortex M6 washing machine according to the AATCC LP1 protocol, using the 1993 AATCC standard reference detergent WOB. After washing, the fabric sample was dried using an SDL Atlas Vortex M6D with the fabric selector set to "Fine" and the drying cycle set to an intermediate indicator between "Drier" and "Slightly Dry" on "Auto Regular / Fine". UPF / UVA measurements were obtained after three wash-dry cycles. The results are shown in the table below.

[0136] Table 12.

[0137] Example 15

[0138] In this embodiment, a fabric sample composed of 87% recycled polyester / 13% spandex was treated with an aqueous chlorogenic acid solution.

[0139] In a 200 mL beaker equipped with a magnetic stirrer, add 100 mL of deionized water and 0.2 g of chlorogenic acid to achieve a chlorogenic acid concentration of 2 g / L. Heat the solution to 70°C while stirring at 180 rpm. Monitor the temperature with a temperature probe, and cover the beaker with foil to prevent water evaporation. Once the temperature is reached and the ferulic acid is completely dissolved, immerse a 5 g fabric sample in the solution (liquor ratio 20:1). Reduce the stirrer speed to 60 rpm while maintaining stirring, and treat the fabric sample in the solution for 15–30 minutes. Remove the fabric sample with tweezers, squeezing out excess solution until no more water drips. Dry the fabric sample in a Vastex D-100 infrared curing system at 80°C for 10 minutes or until dry.

[0140] The dried fabric samples were cooled to room temperature before UPF / UVA measurements.

[0141] The dried fabric sample was then subjected to the following washing procedure. A fine cold water wash was performed on an SDL Atlas Vortex M6 washing machine according to the AATCC LP1 protocol, using the 1993 AATCC standard reference detergent WOB. After washing, the fabric sample was dried using an SDL Atlas Vortex M6D with the fabric selector set to "Fine" and the drying cycle set to an intermediate indicator between "Drier" and "Slightly Dry" on "Auto Regular / Fine". UPF / UVA measurements were obtained after three wash-dry cycles. The results are shown in the table below.

[0142] Table 13.

[0143] Example 16

[0144] In this embodiment, an aqueous solution of ferulic acid and chlorogenic acid was used to treat a fabric sample composed of 87% recycled polyester / 13% spandex.

[0145] In a 200 mL beaker equipped with a magnetic stirrer, add 100 mL of deionized water, 0.2 g of ferulic acid, and 0.1 g of p-coumaric acid. Heat the solution to 70°C while stirring at 180 rpm. Monitor the temperature with a temperature probe, and cover the beaker with foil to prevent water evaporation. Once the temperature is reached and the ferulic acid is completely dissolved, immerse a 5 g fabric sample in the solution (liquor ratio 20:1). Reduce the stirrer speed to 60 rpm while maintaining stirring, and treat the fabric sample in the solution for 15–30 minutes. Remove the fabric sample with tweezers, squeezing out excess solution until no more water drips. Dry the fabric sample in a Vastex D-100 infrared curing system at 80°C for 10 minutes or until dry.

[0146] The dried fabric samples were cooled to room temperature before UPF / UVA measurements.

[0147] The dried fabric sample was then subjected to the following washing procedure. A fine cold water wash was performed on an SDL Atlas Vortex M6 washing machine according to the AATCC LP1 protocol, using the 1993 AATCC standard reference detergent WOB. After washing, the fabric sample was dried using an SDL Atlas Vortex M6D with the fabric selector set to "Fine" and the drying cycle set to an intermediate indicator between "Drier" and "Slightly Dry" on "Auto Regular / Fine". UPF / UVA measurements were obtained after three wash-dry cycles. The results are shown in the table below.

[0148] Table 14.

[0149] Example 17

[0150] In this embodiment, fabrics with different coverage factors were treated with ferulic acid at room temperature and applied according to the methods described in Example 1 or Example 10. Fabrics were selected from a range of materials and coverage factors. Fabric materials were grouped according to the composition of the major components. The polyester group included fabrics composed of 100% polyester, or 93% / 7%, 90% / 10%, or 87% / 13% polyester / spandex (by weight), or 76% recycled polyester, 19% Tencel Lyocell, and 5% elastane, or 94% polyester, 4% nylon, and 2% spandex. Nylon fabrics were composed of 100% nylon. Cotton fabrics were composed of 100% cotton or 96% modal and 4% spandex (by weight). The fabric colors were light shades, such as white, light blue, or light green. The UPF and UVA data presented were collected from fabric samples before and after treatment. The fabrics were not washed before measurement.

[0151] The results are as follows Figure 21 and Figure 22 As shown, UPF and UVA were improved in all fabric types after treatment. Figure 21 The UPF of fabrics with different coverage factors is shown before and after application. Figure 22 The UVA transmittance of fabrics with different coverage factors before and after application is shown. Once treated with a finishing agent containing ferulic acid, the UPF of the fabrics increases to above 50 for a wide range of coverage factors (50-100%). Similarly, the UVA transmittance of the fabrics decreases significantly. For fabrics with a coverage factor of 94% or higher, UVA transmittance below 5% is achieved, meeting the requirements of EU regulations.

[0152] Example 18

[0153] In this embodiment, undyed fabric samples composed of 97% polyester / 3% spandex were treated with commercially available UPF reinforcing agents Rayosan PES (Archroma), Jintex TUV (Jintex), and Fadex F (Archroma). Solutions were prepared according to the technical data sheets of each product. To prepare a 3% solution, 0.6 g of Rayosan PES was dissolved in 200 mL of deionized water. Similarly, 0.8 g of Jintex TUV or Fadex F was added to 200 mL of deionized water to prepare a 4% solution. Each solution was stirred at room temperature for 10 minutes until completely mixed. Then, 100 mL of the treatment solution was transferred to a 300 mL steel beaker designed for the Ahiba IR dyeing machine. Two fabric samples were prepared for each treatment condition. 10 g of the fabric sample was immersed in the treatment solution (liquor ratio 10:1). The beaker was then mounted in the Ahiba IR dyeing machine and treated at 130°C for 30 minutes. After the treatment, the fabric sample was removed with tweezers and gently squeezed by hand to remove excess solution. The sample was then rinsed by hand under cold running water, and excess water was squeezed out again. It was then cured in a Thermo Scientific oven at 130°C for 20 minutes until dry. The dried sample was cooled to room temperature before UPF / UVA measurement.

[0154] UPF / UVA measurements of the treated fabric samples were collected on a 9-point ISO mask using the EN 13758-1:2007 method on a Labsphere 2000F UV spectrophotometer. The treated fabric samples were then subjected to the following washing procedure: a fine cold water wash was performed on an SDL Atlas Vortex M6 washing machine according to the AATCC LP1 protocol using the 1993 AATCC standard reference detergent WOB. The washed fabric samples were then dried using an SDL Atlas Vortex M6D with the fabric selector set to "fine" and the drying cycle set to an intermediate indicator between "drier" and "slightly dry" on "auto regular / fine". UPF / UVA measurements were obtained after three wash-dry cycles. The results are shown in the table below and compared with ethyl ferulic acid and Tween 20 treatments performed at the same temperature on the same fabric composition (Example 13).

[0155] Table 15.

[0156] The processed fabric sample is as follows Figure 23 As shown. The fabric samples, from left to right, include: control, Rayosan PES, Jintex TUV, Fadex F, and ethyl ferulic acid and Tween 20 treatments. These results indicate that ethyl ferulic acid and Tween 20 treatments produced results comparable to commercial products without altering the fabric color.

[0157] In the foregoing description, the present invention has been described with reference to specific embodiments. However, it should be understood that various modifications and changes can be made without departing from the scope of the present invention.

Claims

1. A method of treating a fabric to provide ultraviolet protection, the method comprising: The fabric is soaked in an aqueous solution of ferulic acid and / or ferulic acid derivatives; Remove the fabric from the aqueous solution; as well as Dry the soaked fabric.

2. The method according to claim 1, wherein, The aqueous solution contains ferulic acid, and the temperature of the aqueous solution during the soaking step is between about 25°C and about 90°C.

3. The method according to claim 2, wherein, The temperature of the aqueous solution during the soaking step is between about 75°C and about 90°C.

4. The method of claim 1, wherein the aqueous solution comprises ethyl ferulic acid, and the temperature of the aqueous solution during the soaking step is between about 25°C and about 130°C.

5. The method according to claim 4, wherein, The temperature of the aqueous solution during the soaking step is between about 100°C and about 130°C.

6. The method according to claim 1, wherein, The aqueous solution also contains one or more surfactants, the total of which has a hydrophilic-lipophilic balance (HLB) value between about 14 and about 20.

7. The method according to claim 1, wherein, The aqueous solution contains ferulic acid derivatives, including sinapic acid, chlorogenic acid, caffeic acid, rosmarinic acid, p-coumaric acid and / or ethylhexyl ferulic acid.

8. The method according to claim 1, wherein, Drying the soaked fabric involves heating the soaked fabric at a temperature between about 80°C and about 180°C.

9. An ultraviolet-protective fabric comprising a fabric having fibers having ferulic acid and / or ferulic acid derivatives absorbed by the fabric fibers, wherein the UVA transmittance of the ultraviolet-protective fabric is less than 5%.

10. The ultraviolet-protective fabric according to claim 9, wherein the ultraviolet-protective fabric is prepared by a method comprising the following steps: The fabric is soaked in an aqueous solution of ferulic acid and / or ferulic acid derivatives; Remove the fabric from the aqueous solution; and Dry the soaked fabric; The UV protection fabric described therein has a UPF of approximately 50 or higher.

11. The fabric according to claim 10, wherein, The aqueous solution contains ferulic acid or ethyl ferulic acid and one or more surfactants with HLB between about 13 and about 20.

12. The fabric according to claim 10, wherein, The aqueous solution also contains a dye, and the UV-protective fabric has a color produced by the dye, wherein the color is not affected by ferulic acid or a ferulic acid derivative.

13. The fabric according to claim 9, wherein, The fabric contains ferulic acid that is absorbed by the fabric fibers.

14. The fabric according to claim 9, wherein, The fabric contains ethyl ferulic acid that is absorbed by the fabric fibers.

15. The fabric according to claim 9, wherein, The fabric comprises a polyester blend.

16. The fabric according to claim 9, wherein, The fabric includes clothing.

17. The fabric according to claim 9, wherein, The fabric has a color, and the color is not altered by ferulic acid and / or ferulic acid derivatives absorbed by the fabric fibers.

18. A method of treating a fabric to provide ultraviolet protection, the method comprising: The fabric is immersed in an aqueous solution at a temperature between about 25°C and about 130°C for about 5 minutes to about 30 minutes, the aqueous solution containing ferulic acid and / or ferulic acid derivatives and one or more surfactants with HLB between about 10 and about 20. Remove the fabric from the aqueous solution; and The soaked fabric is dried at a temperature between approximately 80°C and approximately 180°C.

19. The method according to claim 18, wherein, The aqueous solution contains ferulic acid, wherein the HLB of one or more surfactants is between about 14 and about 20, and wherein the temperature of the aqueous solution is between about 75°C and about 90°C.

20. The method according to claim 18, wherein, The aqueous solution contains ethyl ferulic acid, and the temperature of the aqueous solution is between about 100°C and about 130°C.

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