An anti-ultraviolet dyeing finishing solution, its preparation method and application

Abstract

The present invention provides an anti-ultraviolet dyeing finishing solution, a preparation method and an application thereof. The anti-ultraviolet dyeing finishing solution comprises a specific content of disperse dye, cerium dioxide, titanium dioxide, lanthanum oxide, crosslinking agent, surfactant and water. By selecting titanium dioxide and cerium dioxide in combination and using lanthanum oxide as a catalyst, the titanium dioxide and cerium dioxide can have a synergistic effect, thereby greatly improving the anti-ultraviolet performance of the anti-ultraviolet dyeing finishing solution. The anti-ultraviolet polyester fabric obtained by tie-dyeing with it also has excellent anti-ultraviolet properties, and the anti-ultraviolet performance will not be significantly reduced after washing, and the washing resistance is very excellent, which is very suitable for preparing sunscreen clothing.

Description

Technical Field

[0001] The present invention belongs to the technical field of textile auxiliaries, and particularly relates to an anti-ultraviolet dyeing finishing solution, a preparation method thereof, and an application thereof. Background Art

[0002] With the continuous development of living standards and the increasing number of outdoor activities, people pay more and more attention to a healthy life. The skin is a vulnerable part of the human body and is easily damaged by various external factors. For example, ultraviolet rays are one of them. Appropriate ultraviolet rays are beneficial to the human body, but excessive ultraviolet rays are very harmful to the human body. It can not only increase human melanin, age the skin, but also cause the skin to blister and form erythema in severe cases, and even cause skin cancer. Therefore, it is particularly important to develop sunscreen clothing with sunscreen and anti-ultraviolet properties.

[0003] At present, in the field of textile fabric technology, polyester has a very wide range of uses. However, most of the existing polyester fabrics with anti-ultraviolet properties are arranged on the surface of the polyester fabric in the form of a coating. Although the polyester fabric has the ability to resist ultraviolet rays, it further reduces the air permeability of the polyester fabric, resulting in certain limitations in the use of the polyester fabric. Moreover, after washing, the anti-ultraviolet coating will be damaged or even fall off, resulting in a reduction or even disappearance of the anti-ultraviolet performance of the polyester fabric.

[0004] Therefore, aiming at the above technical problems, developing an anti-ultraviolet dyeing finishing solution with excellent and lasting anti-ultraviolet performance is still a technical problem urgently to be solved in this field. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide an anti-ultraviolet dyeing finishing solution, a preparation method thereof, and an application thereof. The anti-ultraviolet dyeing finishing solution has excellent and lasting anti-ultraviolet performance. The polyester fabric obtained by impregnation with it also has excellent anti-ultraviolet properties, and the anti-ultraviolet performance will not be significantly reduced after washing, and the washing resistance is very excellent, which is very suitable for preparing sunscreen clothing.

[0006] To achieve this purpose, the present invention adopts the following technical solutions:

[0007] In the first aspect, the present invention provides an anti-ultraviolet dyeing finishing solution. Based on the total weight of the anti-ultraviolet dyeing finishing solution being 100%, the amounts of the respective components are as follows:

[0008]

[0009] The anti-ultraviolet dyeing finishing solution provided by the present invention contains specific contents of disperse dyes, cerium dioxide, titanium dioxide, lanthanum oxide, crosslinking agent and surfactant. By selecting cerium dioxide and titanium dioxide with excellent anti-ultraviolet properties for combination and using lanthanum oxide as a catalyst, a synergistic effect can be achieved between the two, greatly improving the anti-ultraviolet performance of the obtained anti-ultraviolet dyeing finishing solution. At the same time, the anti-ultraviolet polyester fabric obtained by tie-dyeing with it also has excellent anti-ultraviolet properties, and the anti-ultraviolet performance will not decrease significantly after washing, and the washing resistance is very excellent, which is very suitable for preparing sunscreen clothing.

[0010] Among them, the content of the disperse dye can be 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10%, etc.

[0011] The content of the nano-ceria can be 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%, etc.

[0012] The content of the nano-titanium dioxide can be 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10%, etc.

[0013] The content of the lanthanum oxide can be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%, etc.

[0014] The content of the crosslinking agent can be 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8% or 5%, etc.

[0015] The content of the surfactant can be 9%, 9.2%, 9.4%, 9.6%, 9.8%, 10%, 10.2%, 10.4%, 10.6%, 10.8%, 11%, 11.2%, 11.4%, 11.6%, 11.8% or 12%, etc.

[0016] It is found by research that the anti-ultraviolet performance of cerium dioxide is related to its particle size. When the particle size is large, its anti-ultraviolet ability is mainly based on reflection and scattering, and it is effective for ultraviolet rays in both the medium-wave region and the long-wave region, but the anti-ultraviolet ability is weak. As the particle size continuously decreases, light can gradually penetrate the particle surface, and the reflection and scattering of ultraviolet rays in the long-wave region gradually become less obvious. However, the small-size effect and quantum-size effect of the particles cause a "blue shift" phenomenon in the absorption band, moving towards the short-wave direction, that is, the absorption of ultraviolet rays in the medium-wave region is significantly enhanced, and the anti-ultraviolet ability is enhanced. The cerium dioxide selected in the present invention is at the nanometer level. Due to its small particle size and large activity, it can not only reflect and scatter ultraviolet rays but also absorb ultraviolet rays, so it has a stronger shielding ability for ultraviolet rays. However, it is not that the smaller the particles, the better. The smaller the particles, the easier they are to agglomerate into large particles, and the anti-ultraviolet performance will instead decline. Therefore, through the creative work of the present invention, it is found that further limiting the D 50 particle size of the cerium dioxide to be 70 - 100 nm (such as 70 nm, 72 nm, 74 nm, 76 nm, 78 nm, 80 nm, 82 nm, 84 nm, 86 nm, 88 nm, 90 nm, 92 nm, 94 nm, 96 nm, 98 nm or 100 nm, etc.) can make it have both good ultraviolet shielding performance and excellent particle dispersion effect. And due to the increased dispersion stability and increased photo-quantum efficiency, the absorption rate of ultraviolet rays increases, the anti-ultraviolet ability is further enhanced, and at the same time, the visible light transmittance is greatly increased, and it can also play a more excellent synergistic effect with nano-antimony oxide.

[0017] Preferably, the D 50 particle size of the titanium dioxide is 0.5 - 1 μm, such as 0.5 μm, 0.55 μm, 0.6 μm, 0.65 μm, 0.7 μm, 0.75 μm, 0.8 μm, 0.85 μm, 0.9 μm or 0.95 μm, etc.

[0018] Preferably, the D50 particle size of the lanthanum oxide is 300 - 600 nm, such as 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm or 600 nm, etc.

[0019] Preferably, the surfactant includes any one or a combination of at least two of carboxylate surfactants, sulfonate surfactants, sulfate ester surfactants or phosphate ester surfactants.

[0020] Preferably, the cross-linking agent includes polysiloxane.

[0021] Preferably, the anti-ultraviolet dyeing and finishing solution further includes a dispersant.

[0022] Preferably, based on the total weight of the anti-ultraviolet dyeing finishing liquid being 100%, the content of the dispersant is 6-14%, such as 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13% or 14%, etc.

[0023] Preferably, the dispersant includes any one or a combination of at least two of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, naphthalene sulfonic acid dispersant or polycarboxylic acid dispersant.

[0024] Preferably, the anti-ultraviolet dyeing finishing liquid further includes an adhesive.

[0025] Preferably, based on the total weight of the anti-ultraviolet dyeing finishing liquid being 100%, the content of the adhesive is 3-6%, such as 3%, 3.5%, 4%, 4.5%, 5%, 5.5% or 6%, etc.

[0026] Preferably, the adhesive includes any one or a combination of at least two of polyurethane adhesives, polyvinyl acetate adhesives, polyacrylate adhesives or butadiene adhesives.

[0027] In a second aspect, the present invention provides a preparation method of the anti-ultraviolet dyeing finishing liquid as described in the first aspect, and the preparation method includes the following steps:

[0028] (1) Mix disperse dyes, cerium dioxide, titanium dioxide, lanthanum oxide, surfactant, crosslinking agent, optionally the dispersant and optionally the adhesive in part of water to obtain a mixed liquid;

[0029] (2) Grind the mixed liquid obtained in step (1), and add the remaining part of water during the grinding process to obtain the anti-ultraviolet dyeing finishing liquid.

[0030] The preparation method of the anti-ultraviolet dyeing finishing liquid provided by the present invention includes mixing disperse dyes, cerium dioxide, titanium dioxide, lanthanum oxide, surfactant, crosslinking agent, optionally the dispersant and optionally the adhesive in part of water to obtain a mixed liquid, and then grinding the obtained mixed liquid. During the grinding process, it is necessary to regularly measure the particle size of the mixed liquid, and add an appropriate amount of the remaining water according to the grinding situation until an anti-ultraviolet dyeing finishing liquid with uniform dispersion and a particle size meeting the requirements is obtained.

[0031] Preferably, the mixing in step (1) is carried out under the stirring of a stirrer.

[0032] Preferably, the grinding in step (2) is carried out in a vertical grinding machine.

[0033] Preferably, the grinding medium for the grinding in step (2) is zirconium beads.

[0034] Preferably, the rotation speed of the grinding in step (2) is 5000-10000 rpm, such as 5000 rpm, 5500 rpm, 6000 rpm, 6500 rpm, 7000 rpm, 7500 rpm, 8000 rpm, 8500 rpm, 9000 rpm, 9500 rpm or 10000 rpm, etc.

[0035] Preferably, the grinding time in step (2) is 40-90 min, such as 40 min, 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 75 min, 80 min, 85 min or 90 min, etc.

[0036] Preferably, the D 50 particle size of the solid particles in the anti-ultraviolet dyeing and finishing solution in step (2) is 400-600 nm, such as 400 nm, 420 nm, 440 nm, 460 nm, 480 nm, 500 nm, 520 nm, 540 nm, 560 nm, 580 nm or 600 nm, etc.

[0037] In the third aspect, the present invention provides an anti-ultraviolet polyester fabric, which is obtained by padding the polyester fabric with the anti-ultraviolet dyeing and finishing solution as described in the first aspect.

[0038] The preparation process of the anti-ultraviolet polyester fabric provided by the present invention is simple and does not require post-treatment, and it can have excellent anti-ultraviolet properties and very excellent water resistance.

[0039] Preferably, before the padding, the anti-bacterial dyeing and finishing solution needs to be diluted. Specifically, an anti-ultraviolet dyeing and finishing solution with a mass percentage content of 10-25% (such as 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24% or 25%, etc.) and 75-90% of water are mixed.

[0040] Preferably, the processing method of the padding is two-dip two-roll.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] (1) The anti-ultraviolet dyeing and finishing solution provided by the present invention includes a specific content of disperse dye, nano-ceria, nano-titania, lanthanum oxide, cross-linking agent, surfactant and water. By selecting two anti-ultraviolet aids, nano-titania and nano-ceria, and using lanthanum oxide as a catalyst, a synergistic effect can be achieved between the two, greatly improving the anti-ultraviolet performance. Thus, the anti-ultraviolet dyeing and finishing solution has excellent and durable anti-ultraviolet properties. Further, the anti-ultraviolet polyester fabric obtained by padding with this solution also has excellent anti-ultraviolet properties.

[0043] (2) The UPF value of the polyester fabric dyed by tie-dyeing with the anti-ultraviolet dyeing and finishing solution provided by the present invention is as high as 500+, UVA < 0.5%, UVB < 0.5%. After 10 times of household washing and drying, the anti-ultraviolet UPF value is still as high as 500+, UVA < 1.5%, UVB < 0.5%. It also has excellent anti-ultraviolet properties, and the anti-ultraviolet performance will not decrease significantly after washing. The washing resistance is very excellent, and it is suitable for preparing sunscreen clothing. Specific embodiments

[0044] The technical solution of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0045] The detailed information of some raw materials involved in the following specific embodiments is as follows:

[0046] (1) Disperse dyes

[0047] Disperse Blue 79: Industrial grade, purchased from Jiangsu Yabang Dye Co., Ltd.

[0048] Disperse Orange 288: Industrial grade, purchased from Jiangsu Yabang Dye Co., Ltd.

[0049] (2) Cerium dioxide

[0050] Cerium dioxide A: D 50 The particle size is 80 nm, purchased from Hubei Xin Hongli Chemical Co., Ltd., CAS No. 23322-64-7;

[0051] Cerium dioxide B: D 50 The particle size is 0.8 μm, purchased from Shanghai Shiyang Chemical Industry, and the model is 1306-38-3.

[0052] (3) Titanium dioxide: D 50 The particle size is 0.8 μm, purchased from Liangjiang Chemical Industry, and the model is R-223.

[0053] (4) Lanthanum oxide: D 50 The particle size is 500 nm, purchased from Shanghai Shiyang Chemical Industry, and the model is 1312-81-8.

[0054] (5) Surfactant

[0055] Secondary alkyl sulfonate: Purchased from Clariant, model number 68037-49-0;

[0056] Sodium sulfofatty acid methyl ester: Purchased from Hubei Zhonglong Kangsheng, model number 93348-22-2.

[0057] (6) Crosslinking agent

[0058] Epoxy compounds: Purchased from Hubei Xinghengye, model number 110-18-9.

[0059] (7) Dispersant

[0060] Fatty alcohol polyoxyethylene ether: Purchased from Ron, model number R128348;

[0061] Fatty acid polyoxyethylene ester: Purchased from Wuhan Jixin Yibang, model number 106-08-1;

[0062] Polycarboxylic acid dispersant: Purchased from Bump Chemical, model number BP5040.

[0063] (8) Adhesive

[0064] Polyurethane adhesive: Purchased from Xinhui Chemical, model number Xh-fw201;

[0065] Polyvinyl acetate adhesive: Purchased from Lianyungang Yinghui Rubber Industry, model number BRJ-5010.

[0066] Examples 1-6 and Comparative Examples 1-6

[0067] Examples 1-6 and Comparative Examples 1-6 respectively provide an anti-ultraviolet dyeing finishing solution. Calculated based on the total mass of 100%, the respective components and dosages are shown in Tables 1 and 2;

[0068] In Tables 1 and 2, the dosage unit of each component is "%";

[0069] Table 1

[0070]

[0071]

[0072] Table 2

[0073]

[0074] The preparation methods of the anti-ultraviolet dyeing finishing solutions provided by Examples 1-6 and Comparative Examples 1-6 include the following steps:

[0075] (1) Mix disperse dyes, cerium dioxide, titanium dioxide, lanthanum oxide, crosslinking agent, surfactant, crosslinking agent and adhesive in part of water, and stir them evenly with a stirrer to obtain a mixed solution;

[0076] (2) Add the mixed solution described in step (1) to a vertical grinding machine, use zirconium beads as the grinding medium, grind at a speed of 8000 rpm for 50 min, and test the particle size of the mixed solution every 15 min during the grinding process to control the D of the solid particles in the mixed solution50 The particle size is 500 nm, and the remaining part of water is added during the grinding process according to the grinding condition to obtain the anti-ultraviolet dyeing finishing solution.

[0077] Application Example 1

[0078] An anti-ultraviolet polyester fabric is obtained by one-bath pad dyeing finishing using a two-dip two-roll processing method;

[0079] Among them, the finishing solution used for pad dyeing finishing includes 20% by mass of the antibacterial dyeing finishing solution provided in Example 1 and 80% of deionized water, the padding rate is 90%, and the process of pad dyeing finishing is as follows: dip → pad → dip → pad → drying → baking → washing → drying; among them, the drying temperature is 80 °C and the time is 5 min; the baking temperature is 180 °C and the time is 10 min, and the washing temperature is 85 °C and the time is 15 min.

[0080] Application Examples 2-6 and Comparative Application Examples 1-6

[0081] An anti-ultraviolet polyester fabric, which is different from Application Example 1 in that the anti-ultraviolet dyeing finishing solutions provided in Examples 2-6 and Comparative Examples 1-6 are respectively used to replace the anti-ultraviolet dyeing finishing solution provided in Example 1, and other conditions and parameters are the same as those in Application Example 1.

[0082] Performance test:

[0083] Referring to the test method provided in "GB / T18830-2009 Evaluation of Ultraviolet Resistance of Textiles", the anti-ultraviolet properties of the anti-ultraviolet polyester fabrics provided in Application Examples 1-6 and Comparative Application Examples 1-6 and the anti-ultraviolet properties after 10 times of washing are tested, and the test results are shown in Table 3:

[0084] Table 3

[0085]

[0086]

[0087] It can be seen from the data in Table 3 that:

[0088] (1) The UPF values of the anti-ultraviolet polyester fabrics provided in Application Examples 1-3 are 534-568, the UVA is 0.28-0.33%, and the UVB is 0.16-0.2%, having excellent anti-ultraviolet properties, and the UPF values after 10 times of washing are still as high as 523-538, the UVA is 0.35-0.39%, and the UVB is 0.23-0.27%, indicating that the wash resistance is very excellent.

[0089] (2) Compared with Application Example 1, the particle size of cerium dioxide in the anti-ultraviolet dyeing finishing solution used in Application Example 4 is relatively large, resulting in insufficient combination with lanthanum oxide, and further reducing the anti-ultraviolet property of the finally obtained fabric; the anti-ultraviolet dyeing finishing solution used in Application Example 5 does not contain a dispersant, and thus its dispersion is uneven, resulting in a reduction in the anti-ultraviolet effect of the finally obtained fabric; the anti-ultraviolet dyeing finishing solution used in Application Example 6 does not contain an adhesive, and thus its adhesion fastness is insufficient and the effective components are reduced, also resulting in a reduction in the anti-ultraviolet effect of the finally obtained fabric, especially the anti-ultraviolet effect after washing.

[0090] (3) Compared with Application Example 1, cerium dioxide and / or titanium dioxide are not added to the anti-ultraviolet dyeing finishing solutions used in Comparative Application Examples 1 to 3, resulting in the lack of anti-ultraviolet effective functional components and a significant reduction in the anti-ultraviolet performance of the finally obtained fabric.

[0091] (4) Compared with Application Example 1, lanthanum oxide is not added to the anti-ultraviolet dyeing finishing solution used in Comparative Application Example 4, resulting in the lack of promotion effect on cerium dioxide and / or titanium dioxide, and a decrease in the anti-ultraviolet performance of the finally obtained fabric.

[0092] (5) Compared with Application Example 1, the total addition amount of titanium dioxide and cerium dioxide in the anti-ultraviolet dyeing finishing solution used in Comparative Application Example 5 is too low, resulting in a reduction in effective functional components and a decrease in the anti-ultraviolet performance of the finally obtained fabric.

[0093] (6) Compared with Application Example 1, the total addition amount of titanium dioxide and cerium dioxide in the anti-ultraviolet dyeing finishing solution used in Comparative Application Example 6 is too high, resulting in the inhibition of the promotion effect of lanthanum oxide and a decrease in the anti-ultraviolet performance of the finally obtained fabric.

[0094] The applicant declares that the present invention illustrates an anti-ultraviolet dyeing finishing solution, its preparation method and application through the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc. all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. An anti-ultraviolet polyester fabric, characterized in that: The anti-ultraviolet polyester fabric is obtained by pad-dyeing the polyester fabric with an anti-ultraviolet dyeing finishing liquid; Taking the total weight of the anti-ultraviolet dyeing finishing liquid as 100%, the dosage of each component is as follows: Disperse dyes 5~10%; Cerium dioxide 6~15%; Titanium dioxide 5~10%; Lanthanum oxide 1~5%; Cross-linking agent 3~5%; Surfactant 9~12%; Dispersant 6~14%; Adhesive 3~6%; Water balance; The D of the cerium dioxide 50 Particle size is 70~100 nm; The D of titanium dioxide 50 Particle size is 0.55~1 μm; The D of the lanthanum oxide 50 The particle size is 300~600 nm.

2. The anti-ultraviolet polyester fabric according to claim 1, characterized in that: The surfactant includes any one of a carboxylate surfactant, a sulfonate surfactant, a sulfate surfactant or a phosphate surfactant, or a combination of at least two of them.

3. The anti-ultraviolet polyester fabric according to claim 1, characterized in that: The crosslinking agent includes polysiloxane.

4. The anti-ultraviolet polyester fabric according to claim 1, characterized in that: The dispersant includes any one of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, naphthalene sulfonic acid dispersant or polycarboxylic acid dispersant or a combination of at least two thereof.

5. The anti-ultraviolet polyester fabric according to claim 1, characterized in that: The adhesive includes any one of polyurethane adhesive, polyvinyl acetate adhesive, polyacrylate adhesive or butadiene adhesive, or a combination of at least two of them.

6. The anti-ultraviolet polyester fabric according to claim 1, characterized in that: The preparation method of the anti-ultraviolet dyeing finishing liquid comprises the following steps: (1) mixing disperse dye, cerium dioxide, titanium dioxide, lanthanum oxide, surfactant, crosslinking agent, dispersant and binder in part of water to obtain a mixed solution; (2) Grinding the mixed solution of step (1), and adding the remaining water during the grinding process to obtain the anti-ultraviolet dyeing finishing solution.

7. The anti-ultraviolet polyester fabric according to claim 6, characterized in that: The grinding in step (2) is carried out in a vertical grinding machine.

8. The anti-ultraviolet polyester fabric according to claim 6, characterized in that: The grinding medium used in the grinding in step (2) is zirconium beads.

9. The anti-ultraviolet polyester fabric according to claim 6, characterized in that: The grinding speed in step (2) is 5000-10000 rpm.

10. The anti-ultraviolet polyester fabric according to claim 6, characterized in that: The grinding time in step (2) is 40 to 90 min.

11. The anti-ultraviolet polyester fabric according to claim 6, characterized in that: D of solid particles in the anti-ultraviolet dyeing finishing liquid in step (2) 50 The particle size is 400~600 nm.

12. The anti-ultraviolet polyester fabric according to claim 1, characterized in that: The pad dyeing process is two-dipping and two-padding.

13. A sun-protective clothing, characterized in that: The sun-protective clothing comprises the anti-ultraviolet polyester fabric as described in any one of claims 1 to 12.

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