CN109486329B - Fluorescent paint and preparation method and application thereof - Google Patents

Abstract

The invention discloses a fluorescent coating and a preparation method and application thereof, belonging to the technical field of fluorescent coatings. The invention adopts a hydrophobically modified copper particle with low toxicity and good stability as a dispersant, and compared with the traditional dispersant, The hydrophobically modified copper particles are insoluble in water, environmentally friendly and low in toxicity, and can stably exist at the oil/water interface, effectively preventing the aggregation between droplets, thereby stabilizing the luminescent pigment. In addition, it is prepared by pickering emulsion polymerization. When the dispersant is applied to the fluorescent paint, the usage of surfactants, stabilizers and other auxiliary agents in the preparation process of the fluorescent paint can be greatly reduced, which is more environmentally friendly, and the ultraviolet resistance of the fluorescent paint is improved; at the same time, when the fluorescent paint is applied on the fabric The amount of traditional adhesives can be reduced, while the fabric has the advantages of softness and breathability.

Description

A kind of fluorescent paint and its preparation method and application

Technical field:

The invention relates to a novel fluorescent paint, in particular to a low-toxicity, anti-ultraviolet fluorescent paint, a preparation method and its application on textiles.

Background technique:

Fluorescent paint is a functional paint composed of film-forming substances, luminescent pigments and additives. At present, the adjuvants used in fluorescent coatings usually include leveling agents, thickeners, surfactants, dispersants, driers, stabilizers and fillers. Since luminescent pigments are usually insoluble in water and have poor light resistance, in order to prolong their service life and improve the performance of fluorescent coatings on fabrics, it is often necessary to add a large amount of additives such as light stabilizers, dispersants, and emulsifiers to help luminescent pigments. Uniform dispersion and stability in water, such as polyurethane, alkyl phenyl sulfonate, alkyl phosphate. The extensive use of these auxiliaries has a certain negative impact on the environment.

On the other hand, when fluorescent coatings are used on textiles, especially clothing, in order to improve their washing fastness, more adhesives will be used, which will cause the fabric to feel hard and greatly reduce the air permeability and comfort.

Invention content:

The object of the first aspect of the present invention is to provide a fluorescent paint that is environmentally friendly and low in toxicity and can effectively reduce the amount of auxiliary agents used.

The technical scheme adopted by the present invention is as follows:

A kind of fluorescent paint is characterized in that, comprises the following composition by mass percentage:

Further settings are:

The mass ratio of the copper microparticle dispersant and rhodopsin B is 3:1.

The purpose of the second aspect of the present invention is to provide a preparation method of fluorescent paint, which is characterized in that, comprising the following steps:

(1) Preparation of modified copper particle dispersant:

Dehydrated alcohol and water are prepared into a mixed solution, and hexamethyldisilazane is weighed and added to the above mixed solution under stirring, L-ascorbic acid is added, and stirred until completely dissolved; In the three-necked flask that is condensed and refluxed, heating and stirring are started, anhydrous copper sulfate is added into it, heated to reflux, cooled to room temperature, centrifuged, washed with absolute ethanol, and vacuum-dried to obtain a hydrophobically modified copper particle dispersant;

(2) Preparation of fluorescent paint:

Disperse Rhodopsin B in a mixed solution containing 2,2'-azobisisobutyronitrile, butyl acrylate and styrene, then heat the mixed solution, add the modified copper particle dispersant prepared above and an appropriate amount of Distilled water, react under high-speed stirring to obtain suspension dispersion; transfer to a glass reactor protected by nitrogen, and react to obtain fluorescent paint microcapsule latex;

In the fluorescent coating microcapsule latex, add sodium dodecylbenzenesulfonate, ethylene glycol and deionized water, stir well, then place at room temperature, and then transfer to a sand mill for grinding to obtain fluorescent coating.

further:

A preparation method of fluorescent paint, characterized in that:

(1), preparation of modified copper particle dispersant:

50mL mixed solution was prepared with absolute ethanol and water in a ratio of 1:1 by volume, 4.0347g of hexamethyldisilazane was weighed and added to the above mixed solution under stirring, 5.283g of L-ascorbic acid was added, and the mixture was stirred until Completely dissolve; transfer the above-mentioned mixed solution to a three-necked flask equipped with magnetic stirring and condensing reflux, start heating and stirring, slowly add 50 mL of 0.5mol/L copper sulfate pentahydrate solution with a dropping funnel, then stir evenly and the temperature rises to Heating and refluxing for 2.5 hours at 85°C, cooling to room temperature, centrifugation, washing with absolute ethanol 3 times, and vacuum drying for 24 hours to obtain a modified copper particle dispersant;

(2), preparation of fluorescent paint:

Fluorescent paint formulation, consisting of the following by weight percent:

The preparation method is as follows:

Disperse Rhodopsin B into a mixed solution containing 2,2'-azobisisobutyronitrile, butyl acrylate and styrene, and ultrasonically disperse 20 times in a water bath at 0 to 4 °C for 5 s each time. Then the mixed solution was heated to 40°C, the modified copper particle dispersant prepared above and an appropriate amount of distilled water were added simultaneously, and the suspension was reacted under high-speed stirring for 30min to obtain a suspension dispersion, which was transferred to a glass reactor protected by nitrogen, and heated to 90°C. ℃ of reaction for 30min to obtain fluorescent paint microcapsule latex;

In the fluorescent paint microcapsule latex, add sodium dodecylbenzenesulfonate, ethylene glycol and deionized water, fully stir for 45-60min at 40°C, rotating speed 500 rpm, and then place at room temperature for 4 hour, then transferred to a sand mill for grinding for 2 minutes, and the sand mill rotates at 3000 rpm to obtain fluorescent paint.

The purpose of the third aspect of the present invention is to provide an application of fluorescent paint on pure cotton fabric, which is characterized by comprising the following steps: adding 10% by mass of fluorescent paint, 5% by mass of adhesive and 5% by mass of increasing Thickening agent and appropriate amount of water are mixed into printing paste, and all cotton fabrics are manually scraped and printed.

Further: baking temperature 110 ℃, time 2min.

The beneficial effects of the present invention are as follows:

Compared with the traditional dispersant, the hydrophobically modified copper particles are insoluble in water, environmentally friendly and low in toxicity, and can stably exist in oil/water. The interface can effectively prevent the aggregation between droplets, so as to stabilize the luminescent pigment; the dispersant is prepared by pickering emulsion polymerization and applied to fluorescent coatings, which can greatly reduce the amount of surfactant, stable and stable during the preparation of fluorescent coatings. It is more environmentally friendly, and the UV resistance of fluorescent coatings is improved; at the same time, when the fluorescent coatings are applied to fabrics, the amount of traditional adhesives can be reduced, and the fabrics are soft and breathable.

The present invention will be further described below in conjunction with specific embodiments.

Detailed ways:

Example 1:

1. Preparation of modified copper particle dispersant:

50mL mixed solution was prepared with absolute ethanol and water in a ratio of 1:1 by volume, 4.0347g of hexamethyldisilazane (HMDS) was weighed and added to the above mixed solution under stirring, and 5.283g of L-ascorbic acid was added. , stir until completely dissolved. The above-mentioned mixed solution was transferred to a three-necked flask equipped with magnetic stirring and condensing reflux, and heating and stirring were started, and 50 mL of 0.5mol/L copper sulfate pentahydrate solution was slowly added with a dropping funnel, and then when stirring was uniform and the temperature rose to 85°C Heating under reflux for 2.5h, cooling to room temperature, centrifugation, washing with absolute ethanol for 3 times, and vacuum drying for 24h to obtain a modified copper particle dispersant.

2. Preparation of fluorescent paint:

Fluorescent paint formulation (weight percent):

The preparation method is as follows:

Disperse Rhodopsin B into a mixed solution containing 2,2'-azobisisobutyronitrile, butyl acrylate and styrene, and ultrasonically disperse 20 times in a water bath at 0 to 4 °C for 5 s each time. Then the mixed solution was heated to 40°C, the modified copper particle dispersant prepared above and an appropriate amount of distilled water were added simultaneously, and the suspension was reacted under high-speed stirring for 30min to obtain a suspension dispersion, which was transferred to a glass reactor protected by nitrogen, and heated to 90°C. ℃ of reaction for 30min to obtain fluorescent paint microcapsule latex;

In the fluorescent paint microcapsule latex, add sodium dodecylbenzenesulfonate, ethylene glycol and deionized water, fully stir for 45-60min at 40°C, rotating speed 500 rpm, and then place at room temperature for 4 hour, then transferred to a sand mill for grinding for 2 minutes, and the sand mill rotates at 3000 rpm to obtain fluorescent paint.

3. Application of fluorescent coating on pure cotton fabric:

Mix 10% fluorescent paint, 5% binder, 5% thickener, and an appropriate amount of water into a printing color paste, hand-scratch the cotton fabric, and dry the fabric at 80 °C for 3- 5min, baking temperature 100-150 ℃ time 2-3min. After printing, the cotton fabric has excellent fluorescent properties and washing resistance, and the color fastness to soaping reaches grade 4; and it has a soft hand feel, and the anti-ultraviolet performance of the cotton fabric is improved.

Comparative Example 1: Printing on cotton fabric with commercially available fluorescent red paint

The mass fraction: 10% commercial fluorescent red paint, 20% mass fraction of binder, 5% mass fraction of thickener and water were mixed into printing color paste, and the cotton fabric was hand-scratched, and the fabric was dried at 80 °C. Dry for 5 minutes, and bake at 110°C for 2 minutes.

Comparative Example 2: The commercial fluorescent red paint with a mass fraction of 15%, a binder with a mass fraction of 20%, a thickener with a mass fraction of 5% and water were mixed into a printing color paste, and the cotton fabric was manually scratched and printed. Dry at 80°C for 5 minutes, and bake at 110°C for 2 minutes.

In the above-mentioned embodiment, the binder is selected from the commercially available paint printing adhesive YH-50B, and the thickener is selected from the commercially available paint printing thickener HR-1411.

The fabrics after printing in the embodiment of the present invention and the comparative example were tested respectively, and the K/S value, fluorescence performance, color fastness to washing, color fastness to rubbing and UV protection performance of the printed fabrics were tested. The specific detection methods are as follows: The test results are shown in Table 2:

The K/S value was measured using a DataColor 600 computerized color matching instrument, using D ₆₅ light source and 10o field of view conditions, the fabric was folded 4 layers, and four different points were measured and the average value was taken.

The fluorescence properties of fabrics shall be evaluated according to the method of GB 20653-2006 "High Visibility Warning Clothing for Occupation".

Table 1. Base material requirements:

Among them, the x, y and β values were determined by a Datacolor 600 computer colorimeter and color matching instrument using a D ₆₅ light source and a 2o field of view.

Color fastness to washing: Test according to the No. 1 instructions of GB/T3920-2008 "Color fastness to soaping of textiles".

Test of color fastness to rubbing: Test according to GB/T3920-2008 "Color fastness to rubbing test of textiles".

Ultraviolet resistance performance refers to AS/NZS 4399:1996 "Evaluation and Classification of Anti-UV Fabrics" to test the UVA transmittance of fabrics. The smaller the UVA transmittance, the better the UV protection performance.

Table 2, the performance comparison of fluorescent red paint of the present invention and conventional fluorescent red paint

As shown in Table 2, the fluorescent paint prepared by the present invention is applied to pure cotton fabric, and compared with commercially available fluorescent red paint, the K/S value, fluorescence performance (brightness coefficient), color fastness to washing, color fastness to rubbing , hand feel and anti-ultraviolet performance (UVA transmittance) have been significantly improved, and the reasons are analyzed: the dispersant containing copper particles has a good dispersing effect in the fluorescent coating, and the fluorescent coating is more uniformly distributed, so the fluorescent character of the fabric is better. Excellent, the modified copper dispersant also has good film-forming properties on the surface of the fabric, so the fabric is resistant to washing, the color fastness to rubbing is improved, and the anti-ultraviolet performance is improved.

The effect of the ratio of rose essence B and dispersant on the properties of fluorescent coatings:

Based on Example 1, the difference is: adjust the mass ratio of rose essence B and modified copper particle dispersant in the fluorescent paint, and detect the performance of the fabric fluorescent paint after paint printing, as shown in Table 3:

table 3

As shown in Table 3: Adjust the mass ratio of rose essence B and modified copper dispersant to prepare fluorescent paint, and test the coating stability and particle size. The fluorescent paint prepared at 30% has the best stability and smaller particle size. When the amount of modified copper dispersant is low and the amount of rose essence is too high, the paint stabilizer will be poor, and delamination and precipitation will occur after a long standing time, which will affect the use of the paint.

The influence of the paint printing process on the properties of the paint:

Based on Example 1, the difference is: adjust the paint printing process conditions of cotton fabric, and detect the fluorescent paint performance respectively, as shown in Table 4:

Table 4

As shown in Table 4: The baking temperature and baking time have a significant impact on the properties of the cotton fabric after printing. (brightness coefficient) and UV protection performance (UVA transmittance) increased slightly, but the hand feeling of the fabric decreased significantly, which may be because the long-term high temperature treatment will make the adhesive hard and the fabric hand feel worse.

Claims (6)

1. The fluorescent paint is characterized by comprising the following components in percentage by mass:

20-40% of modified copper particle dispersant

5-15 parts of rose essence B

2, 2' -azobisisobutyronitrile 1-3

3-8 parts of butyl acrylate

3-8% of styrene

5-10 parts of sodium dodecyl benzene sulfonate

5-10% of ethylene glycol

The balance of deionized water;

the modified copper particle dispersant is prepared by the following method:

preparing mixed solution from absolute ethyl alcohol and water, weighing hexamethyldisilazane, adding the hexamethyldisilazane into the mixed solution under stirring, adding L-ascorbic acid, stirring until the hexamethyldisilazane is completely dissolved, transferring the mixed solution into a three-neck flask with magnetic stirring and condensation reflux, starting heating and stirring, adding anhydrous copper sulfate, heating and refluxing, cooling to room temperature, centrifugally separating, washing with absolute ethyl alcohol, and drying in vacuum to obtain the hydrophobic modified copper particle dispersing agent.

2. A fluorescent paint according to claim 1, characterized in that: the mass ratio of the modified copper particle dispersant to the rose essence B is 3:1.

3. The preparation method of the fluorescent paint is characterized by comprising the following steps:

(1) preparing a modified copper particle dispersant:

preparing mixed solution from absolute ethyl alcohol and water, weighing hexamethyldisilazane, adding the hexamethyldisilazane into the mixed solution under stirring, adding L-ascorbic acid, stirring until the hexamethyldisilazane is completely dissolved, transferring the mixed solution into a three-neck flask with magnetic stirring and condensation reflux, starting heating and stirring, adding anhydrous copper sulfate, heating and refluxing, cooling to room temperature, performing centrifugal separation, washing with absolute ethyl alcohol, and performing vacuum drying to obtain the hydrophobic modified copper particle dispersing agent;

(2) preparing a fluorescent paint:

dispersing rose essence B into a mixed solution containing 2, 2' -azobisisobutyronitrile, butyl acrylate and styrene, heating the mixed solution, adding the prepared modified copper particle dispersing agent and a proper amount of distilled water, and reacting under high-speed stirring to obtain a suspension dispersion liquid; transferring the mixture into a glass reaction kettle protected by nitrogen to react to obtain fluorescent paint microcapsule latex;

adding sodium dodecyl benzene sulfonate, glycol and deionized water into the fluorescent paint microcapsule latex, fully stirring, then placing at room temperature, and transferring to a sand mill for grinding to obtain the fluorescent paint.

4. The method for preparing a fluorescent paint according to claim 3, characterized in that:

(1) preparing a modified copper particle dispersing agent:

preparing 50m L mixed solution by absolute ethyl alcohol and water according to the volume ratio of 1:1, weighing 4.0347g of hexamethyldisilazane, adding the hexamethyldisilazane into the mixed solution under stirring, adding 5.283g of L-ascorbic acid, stirring until the hexamethyldisilazane is completely dissolved, transferring the mixed solution into a three-neck flask with magnetic stirring and condensation reflux, starting heating and stirring, slowly adding 0.5 mol/L of blue vitriol solution 50m L by using a dropping funnel, heating and refluxing for 2.5h when the temperature is raised to 85 ℃ after the stirring is uniform, cooling to room temperature, performing centrifugal separation, washing for 3 times by absolute ethyl alcohol, and performing vacuum drying for 24h to obtain the modified copper particle dispersing agent;

(2) and preparing the fluorescent paint:

the fluorescent paint formula comprises the following components in percentage by weight:

modified copper particulate dispersant 30

Rose essence B10

2, 2' -azobisisobutyronitrile 2

Butyl acrylate 5

Styrene 5

Sodium dodecyl benzene sulfonate 5

Ethylene glycol 5

The balance of deionized water;

the preparation method comprises the following steps:

dispersing the rose essence B into a mixed solution containing 2, 2' -azobisisobutyronitrile, butyl acrylate and styrene, ultrasonically dispersing for 20 times in a water bath at 0-4 ℃ for 5s each time, then heating the mixed solution to 40 ℃, simultaneously adding the prepared modified copper particle dispersing agent and a proper amount of distilled water, reacting for 30min under high-speed stirring to obtain a suspension dispersion, transferring the suspension dispersion into a nitrogen-protected glass reaction kettle, and heating to 90 ℃ for reacting for 30min to obtain fluorescent coating microcapsule latex;

adding sodium dodecyl benzene sulfonate, glycol and deionized water into the fluorescent paint microcapsule latex, fully stirring for 45-60 min at 40 ℃ and the rotating speed of 500 r/min, standing for 4 hours at room temperature, transferring into a sand mill, and grinding for 2 minutes at the rotating speed of 3000 r/min to obtain the fluorescent paint.

5. The use of the fluorescent coating of claim 1 on a pure cotton fabric, comprising the steps of: mixing 10% of fluorescent paint, 5% of adhesive, 5% of thickening agent and a proper amount of water into printing paste, manually scraping and printing the all-cotton fabric, drying the fabric at 80 ℃ for 3-5min, and baking at 100 ℃ for 150 ℃ for 2-3 min.

6. The use of a fluorescent coating according to claim 5 on pure cotton fabric, wherein: the baking temperature is 110 ℃, and the baking time is 2 min.