Anti-ultraviolet dyeing finishing liquid as well as preparation method and application thereof

Abstract

The invention provides an anti-ultraviolet dyeing finishing liquid and a preparation method and application thereof.The anti-ultraviolet dyeing finishing liquid is prepared from disperse dye, cerium dioxide, titanium dioxide, lanthanum oxide, a cross-linking agent, a surfactant and water according to the specific content, titanium dioxide and cerium dioxide are selected for matching, lanthanum oxide serves as a catalyst, and the cross-linking agent, the surfactant and the water are mixed, so that the anti-ultraviolet dyeing finishing liquid is obtained. According to the anti-ultraviolet dyeing finishing liquid, titanium dioxide and cerium dioxide can generate a synergistic interaction effect, so that the anti-ultraviolet performance of the anti-ultraviolet dyeing finishing liquid is greatly improved, an anti-ultraviolet polyester fabric subjected to tie-dyeing by adopting the anti-ultraviolet dyeing finishing liquid also has excellent anti-ultraviolet performance, the anti-ultraviolet performance is not obviously reduced after water washing, the water washing resistance is very excellent, and the anti-ultraviolet polyester fabric has good anti-ultraviolet performance. The method is very suitable for preparing sunscreen clothes.

Description

Technical Field

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

[0002] With the continuous improvement of living standards and the increasing number of outdoor activities, people pay more and more attention to healthy living. The skin is a weak link in the human body and is easily damaged by various external factors, such as ultraviolet rays. 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 the melanin in the human body and cause skin aging, but also cause blisters and erythema on the skin in severe cases, and even cause skin cancer. Therefore, it is particularly important to develop sun-proof clothing with sun-proof and anti-ultraviolet properties.

[0003] At present, in the field of textile fabric technology, polyester is widely used, but the existing anti-ultraviolet polyester fabrics are mostly provided in the form of a coating on the surface of the polyester fabric, so that although the polyester fabric has the ability to resist ultraviolet rays, the air permeability of the polyester fabric is further reduced, resulting in certain restrictions on the use of the polyester fabric, and the anti-ultraviolet coating will be destroyed or even fall off after washing, resulting in the reduction or even disappearance of the anti-ultraviolet performance of the polyester fabric.

[0004] Therefore, in view of the above technical problems, developing an anti-ultraviolet dyeing finishing liquid with excellent and durable anti-ultraviolet performance is still a technical problem that needs to be solved urgently in this field. Summary of the invention

[0005] In view of the deficiencies in the prior art, the object of the present invention is to provide an anti-ultraviolet dyeing finishing liquid and a preparation method and application thereof. The anti-ultraviolet dyeing finishing liquid has excellent and lasting anti-ultraviolet performance. The polyester fabric obtained after dyeing with the anti-ultraviolet dyeing finishing liquid also has excellent anti-ultraviolet performance, and the anti-ultraviolet performance will not be significantly reduced after washing. The water washing resistance is very good, and it is very suitable for preparing sun-protective clothing.

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

[0007] In a first aspect, the present invention provides an anti-ultraviolet dyeing finishing liquid. Taking the total weight of the anti-ultraviolet dyeing finishing liquid as 100%, the amounts of the components included are as follows:

[0008]

[0009] The anti-ultraviolet dyeing finishing liquid provided by the present invention contains disperse dyes, cerium dioxide, titanium dioxide, lanthanum oxide, cross-linking agent and surfactant in specific contents. By selecting cerium dioxide and titanium dioxide with excellent ultraviolet resistance for combination and using lanthanum oxide as a catalyst, the two can be made to have a synergistic effect, thereby greatly improving the anti-ultraviolet performance of the obtained anti-ultraviolet dyeing finishing liquid. At the same time, the anti-ultraviolet polyester fabric obtained after tie-dyeing with the anti-ultraviolet dyeing finishing liquid also has excellent ultraviolet resistance, and the anti-ultraviolet performance will not be significantly reduced after washing, and the water washing resistance is very excellent, which is very suitable for preparing sun-proof clothing.

[0010] Wherein, 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-cerium dioxide 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 cross-linking 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] According to research, the strength of the anti-ultraviolet performance of cerium dioxide is related to its particle size. When its particle size is large, its anti-ultraviolet ability is mainly based on reflection and scattering, and is effective for ultraviolet rays in the medium-wave region and the long-wave region, but its anti-ultraviolet ability is weak; as its particle size continues to decrease, light can gradually penetrate the surface of the particles, and the reflection and scattering of ultraviolet rays in the long-wave region gradually become less obvious, but the small size effect and quantum size effect of the particles cause the absorption band to have a "blue shift" phenomenon, moving toward 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 nanometer-level. Due to its small particle size and high activity, it can reflect and scatter ultraviolet rays, and absorb ultraviolet rays, so it has a stronger shielding ability against ultraviolet rays. However, the smaller the particles, the better. The smaller the particles, the easier it is to agglomerate into large particles, and the anti-ultraviolet performance will decrease instead; therefore, after the creative labor of the present invention, it is found that the D of the cerium dioxide is further limited to 50 The particle size is 70 to 100 nm (for example, 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.), which can make it have both good ultraviolet shielding performance and excellent particle dispersion effect, and due to the increased dispersion stability, the light quantum efficiency is increased, the absorption rate of ultraviolet rays is increased, the anti-ultraviolet ability is further enhanced, and the visible light transmittance is greatly increased, and it can also play a more excellent synergistic effect with nano antimony dioxide.

[0017] Preferably, the titanium dioxide has a D 50 The particle size is 0.5 to 1 μm, for example, 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.

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

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

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

[0021] Preferably, the anti-ultraviolet dyeing finishing liquid also includes a dispersant.

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

[0023] Preferably, 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.

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

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

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

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

[0028] (1) mixing disperse dye, cerium dioxide, titanium dioxide, lanthanum oxide, a surfactant, a cross-linking agent, optionally a dispersant, and optionally a binder in part of water to obtain a mixed solution;

[0029] (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.

[0030] The preparation method of the anti-ultraviolet dyeing finishing liquid provided by the present invention comprises the steps of mixing disperse dye, cerium dioxide, titanium dioxide, lanthanum oxide, surfactant, cross-linking agent, optional dispersant and optional 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 a proper amount of remaining water according to the grinding situation until the anti-ultraviolet dyeing finishing liquid with uniform dispersion and particle size meeting the requirements is obtained.

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

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

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

[0034] Preferably, the grinding speed in step (2) is 5000-10000 rpm, for example, 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 to 90 min, for example, 40 min, 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 75 min, 80 min, 85 min or 90 min.

[0036] Preferably, the D of the solid particles in the anti-ultraviolet dyeing finishing liquid in step (2) is 50 The particle size is 400 to 600 nm, for example, 400 nm, 420 nm, 440 nm, 460 nm, 480 nm, 500 nm, 520 nm, 540 nm, 560 nm, 580 nm or 600 nm.

[0037] In a third aspect, the present invention provides an anti-ultraviolet polyester fabric, which is obtained by pad-dyeing the polyester fabric with the anti-ultraviolet dyeing finishing liquid 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 can have excellent anti-ultraviolet properties and excellent water resistance.

[0039] Preferably, the antibacterial dyeing finishing liquid needs to be diluted before the tie-dyeing, specifically by mixing 10-25% (for example, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24% or 25%) of the anti-ultraviolet dyeing finishing liquid with 75-90% of water.

[0040] Preferably, the tie-dyeing processing method is two dipping and two padding.

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

[0042] (1) The anti-ultraviolet dyeing finishing liquid provided by the present invention comprises disperse dyes, nano-cerium dioxide, nano-titanium dioxide, lanthanum oxide, cross-linking agent, surfactant and water in specific contents. By selecting two anti-ultraviolet additives, nano-titanium dioxide and nano-cerium dioxide, and using lanthanum oxide as a catalyst, the two can produce a synergistic effect, greatly improving the anti-ultraviolet performance, thereby making the anti-ultraviolet dyeing finishing liquid have excellent and lasting anti-ultraviolet performance, and the anti-ultraviolet polyester fabric after tie-dying with the liquid also has excellent anti-ultraviolet properties.

[0043] (2) The UPF value of the polyester fabric after tie-dyeing with the anti-ultraviolet dyeing finishing liquid provided by the present invention is as high as 500+, UVA<0.5%, UVB<0.5%. After 10 times of home washing and drying, the anti-ultraviolet UPF value is still as high as 500+, UVA<1.5%, UVB<0.5%, and it also has excellent anti-ultraviolet properties. The anti-ultraviolet performance will not be significantly reduced after washing, and the washability is very excellent, which is suitable for preparing sun-protective clothing. DETAILED DESCRIPTION

[0044] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

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

[0046] (1) Disperse dyes

[0047] Disperse blue 79: industrial grade, purchased from Jiangsu Yabang Dyestuff Co., Ltd.;

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

[0049] (2) Cerium dioxide

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

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

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

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

[0054] (5) Surfactants

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

[0056] Sulfonic fatty acid methyl ester sodium salt: purchased from Hubei Zhonglong Kangsheng, model number 93348-22-2.

[0057] (6) Cross-linking agent

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

[0059] (7) Dispersant

[0060] Fatty alcohol polyoxyethylene ether: purchased from Roan, model number R128348;

[0061] Fatty acid polyoxyethylene esters: purchased from Wuhan Jixinyibang, model number 106-08-1;

[0062] Polycarboxylic acid dispersant: purchased from Bangpu Chemical, model BP5040.

[0063] (8) Adhesive

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

[0065] Polyvinyl acetate adhesive: purchased from Lianyungang Yinghui Adhesive Industry, model BRJ-5010.

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

[0067] Examples 1 to 6 and Comparative Examples 1 to 6 respectively provide an anti-ultraviolet dyeing finishing liquid, and based on the total mass as 100%, the components and amounts included are shown in Table 1 and Table 2;

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

[0069] Table 1

[0070]

[0071]

[0072] Table 2

[0073]

[0074] The preparation method of the anti-ultraviolet dyeing finishing liquid provided in Examples 1 to 6 and Comparative Examples 1 to 6 comprises the following steps:

[0075] (1) mixing disperse dye, cerium dioxide, titanium dioxide, lanthanum oxide, crosslinking agent, surfactant, crosslinking agent and adhesive in part of water, and stirring the mixture by a stirrer to obtain a mixed solution;

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

[0077] Application Example 1

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

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

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

[0081] A UV-resistant polyester fabric, which differs from Application Example 1 in that the UV-resistant dyeing finishing liquid provided in Examples 2 to 6 and Comparative Examples 1 to 6 are used to replace the UV-resistant dyeing finishing liquid 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 UV Protection of Textiles, the UV resistance of the UV-resistant polyester fabrics provided in Examples 1 to 6 and Comparative Application Examples 1 to 6 and the UV resistance after 10 washes were tested. The test results are shown in Table 3:

[0084] Table 3

[0085]

[0086]

[0087] According to the data in Table 3, we can see that:

[0088] (1) The UPF value of the anti-ultraviolet polyester fabric provided in Application Examples 1 to 3 is 534 to 568, UVA is 0.28 to 0.33%, and UVB is 0.16 to 0.2%, which has excellent anti-ultraviolet performance. Moreover, after 10 times of washing, the UPF value is still as high as 523 to 538, UVA is 0.35 to 0.39%, and UVB is 0.23 to 0.27%, indicating that the water washing resistance is very excellent.

[0089] (2) Compared with Application Example 1, the particle size of cerium dioxide in the anti-ultraviolet dyeing finishing liquid used in Application Example 4 is too large, resulting in insufficient combination of cerium dioxide and lanthanum oxide, thereby reducing the anti-ultraviolet property of the final fabric; no dispersant is added to the anti-ultraviolet dyeing finishing liquid used in Application Example 5, resulting in uneven dispersion, resulting in reduced anti-ultraviolet effect of the final fabric; no adhesive is added to the anti-ultraviolet dyeing finishing liquid used in Application Example 6, resulting in insufficient bonding strength and reduced effective ingredients, which also leads to reduced anti-ultraviolet effect of the final fabric, especially the anti-ultraviolet effect after washing.

[0090] (3) Compared with Application Example 1, the anti-ultraviolet dyeing finishing liquid used in Comparative Application Examples 1 to 3 does not contain cerium dioxide and / or titanium dioxide, resulting in the lack of effective anti-ultraviolet functional components, and the anti-ultraviolet performance of the fabric obtained is significantly reduced.

[0091] (4) Compared with Application Example 1, lanthanum oxide was not added to the anti-ultraviolet dyeing finishing liquid used in Comparative Application Example 4, resulting in no promotion of cerium dioxide and / or titanium dioxide, and the anti-ultraviolet performance of the resulting fabric was reduced.

[0092] (5) Compared with Application Example 1, the total amount of titanium dioxide and cerium dioxide added in the anti-ultraviolet dyeing finishing liquid 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 fabric finally obtained.

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

[0094] The applicant declares that the present invention illustrates an anti-ultraviolet dyeing finishing liquid and 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, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An anti-ultraviolet dyeing finishing liquid, characterized in that: Taking the total weight of the anti-ultraviolet dyeing finishing liquid as 100%, the amounts of the various components included are as follows:

2. The anti-ultraviolet dyeing finishing liquid according to claim 1 or 2, characterized in that: The D of the cerium dioxide 50 Particle size is 70-100nm; Preferably, the titanium dioxide has a D 50 Particle size is 0.5-1 μm; Preferably, the D of the lanthanum oxide 50 The particle size is 300~600nm.

3. The anti-ultraviolet dyeing finishing liquid according to claim 1 or 2, characterized in that: The surfactant includes any one or a combination of at least two of a carboxylate surfactant, a sulfonate surfactant, a sulfate ester surfactant or a phosphate ester surfactant; Preferably, the cross-linking agent comprises polysiloxane.

4. The UV-resistant dyeing finishing liquid according to any one of claims 1 to 3, characterized in that: The anti-ultraviolet dyeing finishing liquid also includes a dispersant; Preferably, based on the total weight of the anti-ultraviolet dyeing finishing liquid being 100%, the content of the dispersant is 6 to 14%; Preferably, 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 UV-resistant dyeing finishing liquid according to any one of claims 1 to 4, characterized in that: The anti-ultraviolet dyeing finishing liquid also includes an adhesive; Preferably, the content of the adhesive is 3-6% based on the total weight of the anti-ultraviolet dyeing finishing liquid as 100%; Preferably, the adhesive includes any one of a polyurethane adhesive, a polyvinyl acetate adhesive, a polyacrylate adhesive or a butadiene adhesive, or a combination of at least two of them.

6. A method for preparing the anti-ultraviolet dyeing finishing liquid according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: (1) mixing disperse dye, cerium dioxide, titanium dioxide, lanthanum oxide, a surfactant, a cross-linking agent, optionally a dispersant, and optionally a 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 preparation method according to claim 6, characterized in that: The grinding in step (2) is carried out in a vertical grinding machine; Preferably, the grinding medium used in the grinding in step (2) is zirconium beads; Preferably, the grinding speed in step (2) is 5000-10000 rpm; Preferably, the grinding time in step (2) is 40 to 90 minutes; Preferably, the D of the solid particles in the anti-ultraviolet dyeing finishing liquid in step (2) is 50 The particle size is 400~600nm.

8. An anti-ultraviolet polyester fabric, characterized in that: The anti-ultraviolet polyester fabric is obtained by pad-dyeing the polyester fabric with the anti-ultraviolet dyeing finishing liquid as described in any one of claims 1 to 5.

9. The anti-ultraviolet polyester fabric according to claim 8, characterized in that: The processing method of tie-dyeing is two dipping and two rolling.

10. A sun-protective clothing, characterized in that: The sun-protective clothing comprises the anti-ultraviolet polyester fabric as described in claim 8 or 9.

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