阅读说明：本技术 一种高固含耐候型纺织涂饰剂及其制备方法 (High-solid-content weather-resistant textile coating agent and preparation method thereof ) 是由 蒋科 蒋德平 胡月霞 于 2021-09-24 设计创作，主要内容包括：本申请涉及整理剂领域,具体公开了一种高固含耐候型纺织涂饰剂及其制备方法。一种高固含耐候型纺织涂饰剂,包括以下重量份物质：20-30份成膜剂、10-20份乳化剂、30-50份酯类化合物、10-20份耐候剂、3-5份耐候剂、1-2份助剂、0.05-0.2份引发剂以及3-5份乙醇,所述成膜剂包括丙烯酸,所述耐候剂为二氧化硅,所述乳化剂为OP-10；其制备方法为：S1、制备核乳液,S2、制备壳核乳液,S3、制备涂饰剂。本申请的涂饰剂可用于纺织品整理,其具有较为优异的耐候性能以及稳定性的优点。(The application relates to the field of finishing agents, and particularly discloses a high-solid-content weather-resistant textile finishing agent and a preparation method thereof. A high-solid-content weather-resistant textile coating agent comprises the following substances in parts by weight: 20-30 parts of a film forming agent, 10-20 parts of an emulsifier, 30-50 parts of an ester compound, 10-20 parts of a weather resisting agent, 3-5 parts of a weather resisting agent, 1-2 parts of an auxiliary agent, 0.05-0.2 part of an initiator and 3-5 parts of ethanol, wherein the film forming agent comprises acrylic acid, the weather resisting agent is silicon dioxide, and the emulsifier is OP-10; the preparation method comprises the following steps: s1, preparing a core emulsion, S2, preparing a shell-core emulsion, S3 and preparing a coating agent. The coating agent can be used for textile finishing, and has the advantages of excellent weather resistance and stability.)

1. The high-solid-content weather-resistant textile finishing agent is characterized by comprising the following substances in parts by weight: 20-30 parts of a film forming agent, 10-20 parts of an emulsifier, 30-50 parts of an ester compound, 13-25 parts of a weather resistant agent, 1-2 parts of an auxiliary agent, 0.05-0.2 part of an initiator and 3-5 parts of ethanol, wherein the film forming agent comprises acrylic acid, the weather resistant agent comprises silicon dioxide, and the emulsifier comprises OP-10.

2. The high-solid-content weather-resistant textile finishing agent as claimed in claim 1, wherein: the weather resistant agent further comprises graphene oxide.

3. The high-solid-content weather-resistant textile finishing agent as claimed in claim 2, wherein the graphene oxide is sulfonated graphene, and the sulfonated graphene is prepared by the following method:

respectively weighing the following substances in parts by weight: 0.2-1 part of 3-propane-2-acetyl propane-1-sodium sulfonate, 80-100 parts of graphene oxide dispersion liquid, 10-20 parts of sodium hydroxide aqueous solution, 0.2-1 part of sodium borohydride and 0.5-2 parts of ammonia water;

weighing 3-propane-2-acetyl propane-1-sodium sulfonate and graphene oxide dispersion liquid, stirring and mixing to obtain a mixed solution, adjusting the mixed solution to pH =9 by using a sodium hydroxide aqueous solution, reacting for 30min, filtering to retain a filter cake, and washing to be neutral to obtain an intermediate product;

and (3) stirring and mixing the intermediate product, sodium borohydride and ammonia water, reacting at constant temperature for 3-4h, filtering to retain a filter cake, washing the filter cake to be neutral, and drying the filter cake at 50 ℃ for 6-8h to obtain the sulfonated graphene.

4. The high-solid-content weather-resistant textile finishing agent as claimed in claim 3, wherein: the particle size of the sulfonated graphene is 10-50 nm.

5. The high-solid-content weather-resistant textile finishing agent as claimed in claim 1, wherein: the film forming agent also comprises any one of polyacrylic acid and polyacrylate.

6. The high-solid-content weather-resistant textile finishing agent as claimed in claim 1, wherein: the ester compound comprises one or two of polyurethane and epoxy resin.

7. The high-solid-content weather-resistant textile finishing agent as claimed in claim 1, wherein: the silicon dioxide is prepared by reacting tetraethoxysilane with treatment liquid, and the treatment liquid comprises the following substances in parts by weight: 1-2 parts of polyvinylpyrrolidone, 2-3 parts of azobisisobutylamidine hydrochloride, 2-3 parts of styrene, 3-5 parts of deionized water and 0.001-0.003 part of ammonium persulfate.

8. The method for preparing a high-solid-content weather-resistant textile coating agent according to any one of claims 1 to 7, wherein:

s1, preparing a core emulsion: taking half of the emulsifier by weight, stirring and mixing with deionized water, heating to prepare a dispersion, adding an initiator and a film-forming agent into the dispersion under the nitrogen atmosphere, stirring and mixing, and keeping the temperature for 1-2 hours to prepare a core emulsion;

s2, preparing a shell-core emulsion: stirring and mixing the nuclear emulsion, deionized water and a half of the mass of emulsifier to prepare emulsified mixed solution, adding an ester compound and a weather-resistant agent into the mixed solution in a nitrogen atmosphere, and preserving heat for 1-2 hours to prepare a shell-nuclear emulsion;

s3, preparing a coating agent: adding the auxiliary agent, ethanol and weather-resistant agent into the shell-core emulsion, and stirring and mixing to obtain the coating agent.

9. The method for preparing the high-solid-content weather-resistant textile coating agent according to claim 8, wherein the method comprises the following steps: the temperature rise temperature is 60-80 ℃.

Technical Field

The application relates to the field of finishing agents, in particular to a high-solid-content weather-resistant textile finishing agent and a preparation method thereof.

Background

The finishing agent generally comprises a film forming agent, a coloring agent, a finishing auxiliary agent, a medium and the like, and can be coated on the surface of the textile by different coating modes, so that a layer of film is formed on the surface of the textile, and the mechanical strength of the textile are improved. The coating agent may be classified according to the use and medium, and is generally classified into a primer coating agent, a middle coating agent, a top coating agent, a water-based coating agent, and a solvent-based coating agent.

In order to make the coating form a film on the textile surface quickly and stably, high-solid coatings are generally used on the market. High solids content generally means a ratio of solid particles to the whole in the finish of greater than or equal to 60%. Compared with the low solid content coating agent, the high solid content coating agent has the advantages of higher production efficiency, high drying speed, lower energy consumption and the like.

In view of the above-mentioned related technologies, the inventors believe that the high solid content in the coating agent tends to result in poor dispersibility of each component in the coating agent, resulting in poor stability of the whole coating agent and poor textile protection effect of the coating agent.

Disclosure of Invention

In order to improve the dispersibility of each component in the coating agent, the application provides a high-solid-content weather-resistant textile coating agent and a preparation method thereof.

In a first aspect, the application provides a high-solid-content weather-resistant textile coating agent, which adopts the following technical scheme:

a high-solid-content weather-resistant textile coating agent comprises the following substances in parts by weight: 20-30 parts of a film forming agent, 10-20 parts of an emulsifier, 30-50 parts of an ester compound, 13-25 parts of a weather resistant agent, 1-2 parts of an auxiliary agent, 0.05-0.2 part of an initiator and 3-5 parts of ethanol, wherein the film forming agent comprises acrylic acid, the weather resistant agent comprises silicon dioxide, and the emulsifier comprises OP-10.

By adopting the technical scheme, the film-forming agent and the ester compound are subjected to the emulsification effect of the emulsifier, so that the film-forming agent and the ester compound are subjected to a crosslinking reaction, the film-forming agent is acrylic acid and has more hydrophilic groups, the dispersion effect of components in a coating agent in a solvent is improved, the stability of the coating agent is improved, the ester compound has better toughness and adhesiveness, the combination effect between the coating agent and a textile is improved, and the coating agent can protect the textile for a long time.

In addition, due to the addition of the weather-resistant agent, the weather-resistant agent and the film-forming agent are crosslinked, so that more hydrophobic groups are generated in the coating agent, the water resistance and solvent resistance of the coating agent are improved, and a thin film formed on the surface of the textile by the coating agent can protect the textile for a long time, so that the coating agent can protect the textile for a long time and prolong the service life of the textile.

Preferably, the weather resistant agent further comprises graphene oxide.

By adopting the technical scheme, the graphene oxide and the acrylic acid react, and a large amount of aerobic polar groups are formed on the surface of the graphene oxide, so that the water dispersion effect of the film forming agent is further improved, and the dispersion effect of each component in the coating agent in a solvent is improved.

In addition, because the graphene oxide has a large specific surface area, a film formed by the coating agent containing the graphene oxide is compact, the corrosion resistance effect of the textile coated with the coating agent is effectively improved, and the service life of the textile is prolonged.

Preferably, the graphene oxide is sulfonated graphene which is subjected to sulfonation treatment, and the sulfonated graphene is prepared by the following method: (1) respectively weighing the following substances in parts by weight: 0.2-1 part of 3-propane-2-acetyl propane-1-sodium sulfonate, 80-100 parts of graphene oxide dispersion liquid, 10-20 parts of sodium hydroxide, 0.2-1 part of sodium borohydride and 0.5-2 parts of ammonia water; (2) weighing 3-propane-2-acetyl propane-1-sodium sulfonate and graphene oxide dispersion liquid, stirring and mixing to obtain a mixed solution, adjusting the mixed solution to pH =9 by using a sodium hydroxide aqueous solution, reacting for 30min, filtering to retain a filter cake, and washing to be neutral to obtain an intermediate product; (3) and (3) stirring and mixing the intermediate product, sodium hydroxide and ammonia water, reacting at constant temperature for 3-4h, filtering to retain a filter cake, washing the filter cake to be neutral, and drying the filter cake at 50 ℃ for 6-8h to obtain the sulfonated graphene.

By adopting the technical scheme, the sulfonated graphene is formed by the oxidized graphene through an affinity ring-opening reaction, and the sulfonated graphene not only has more polar groups, but also obtains more excellent conductivity, so that the coating agent added with the sulfonated graphene has better antistatic property, and the protective effect of the coating agent on textiles is further improved.

Meanwhile, due to the fact that the sulfonated graphene, the film forming agent and the ester compound are subjected to a cross-linking reaction, the dispersion degree of the film forming agent and the ester compound in the coating agent is improved, the dispersion of the oxidized graphene in the coating agent is uniform, a continuous conductive channel is formed, and the coating agent obtains good anti-corrosion and anti-static effects.

Preferably, the particle size of the sulfonated graphene is 2000-3000 meshes.

By adopting the technical scheme, the micron-sized sulfonated graphene improves the effect of limiting water molecules to pass through by the coating agent, improves the shielding effect of the coating agent on small molecules, further improves the water-resistant effect of the coating agent, prolongs the path of the water molecules and oxygen molecules to the textile through a coating film of the coating agent, and slows down the oxidation and corrosion of the textile coated with the coating agent.

Preferably, the film forming agent further comprises any one of polyacrylic acid and polyacrylate.

By adopting the technical scheme, the film forming agents all have hydrophilic groups, so the dispersing effect of the film forming agents and the solvent is better, the crosslinking degree of the film forming agents and other components in the coating agent is improved by adding the high molecular polymer into the film forming agents, the viscosity of the coating agent is adjusted, the solid content in the coating agent is improved, and the drying speed of the coating agent is improved.

Preferably, the ester compound includes one or both of polyurethane and epoxy resin.

By adopting the technical scheme, the polyurethane and the epoxy resin both have better hydrolysis resistance and high temperature resistance, so that the polyurethane, the epoxy resin and the film forming agent are subjected to crosslinking composite reaction, the coating agent obtains better water resistance and high temperature resistance, and the coating agent prepared by compounding the polyurethane and the epoxy resin not only has better water resistance and high temperature resistance, but also has better toughness and excellent caking property. The textile coated with the finishing agent has better weather resistance and toughness, and the service life of the textile is prolonged.

Preferably, the silicon dioxide is prepared by reacting tetraethoxysilane with a treatment solution, and the treatment solution comprises the following substances in parts by weight: 1-2 parts of polyvinylpyrrolidone, 2-3 parts of azobisisobutylamidine hydrochloride, 2-3 parts of styrene, 3-5 parts of deionized water and 0.001-0.003 part of ammonium persulfate.

By adopting the technical scheme, the silicon dioxide prepared by the reaction of the tetraethoxysilane and the treatment solution has a large number of pores, the coating agent is coated on the textile to form a coating film, and after the porous silicon dioxide reacts with the film forming agent, the number of free radicals in the coating agent is increased, so that the curvature of a channel for water molecules to penetrate through the coating film to reach the textile is reduced, the moisture permeability effect of the coating film is increased, and the wearing comfort of the textile is improved.

In a second aspect, the application provides a preparation method of a high-solid-content weather-resistant textile coating agent, which adopts the following technical scheme:

a preparation method of a high-solid-content weather-resistant textile coating agent comprises the steps of S1, taking half of weight of an emulsifier, stirring and mixing with deionized water, heating to prepare a dispersion liquid, adding an initiator and a film-forming agent into the dispersion liquid under the nitrogen atmosphere, stirring and mixing, and keeping the temperature for 1-2 hours to prepare a core emulsion; s2, mixing the nuclear emulsion with deionized water and half of the deionized water in parts by weight to obtain emulsified mixed solution, adding an ester compound and a weather-resistant agent into the mixed solution in a nitrogen atmosphere, and keeping the temperature for 1-2 hours to obtain a shell-nuclear emulsion; s3, adding the auxiliary agent, ethanol and the weather-resistant agent into the shell-core emulsion, and stirring and mixing to obtain the coating agent.

By adopting the technical scheme, the film-forming agent and the ester compound form a shell-core structure in a shell-core emulsion polymerization mode, the film-forming agent is used as an inner core, and the inner core is softer and has a better cold-resistant effect due to the fact that the film-forming agent has a low glass transition temperature; the ester compound has high glass transition temperature, and the ester compound is used as the outer shell, so that the outer shell is hard and has excellent heat-resistant effect, and a shell-core structure with hard and soft shells is obtained. At higher temperature, the caking property of the coating agent is proper, at lower temperature, the whole coating agent still has better movement capability due to the existence of the soft core, so that a film formed by the coating agent is not easy to crack, and the defect of hot sticking and cold brittleness of the coating agent is improved.

Preferably, the temperature of the temperature rise is 60-80 ℃.

By adopting the technical scheme, the shell-core polymerization effect between the film forming agent and the ester compound is better at a proper temperature, and the reaction degree of shell-core polymerization is improved.

In summary, the present application has the following beneficial effects:

1. according to the coating agent, the film forming agent and the ester compound are compounded in a crosslinking mode to serve as main components of the coating agent, and the film forming agent has more hydrophilic groups, so that the dispersion effect of the components in the coating agent is improved, the overall stability of the coating agent is improved, the ester compound has better toughness and adhesiveness, the bonding effect between the coating agent and a textile is better, the textile is protected for a long time by the coating agent, the dispersion effect of the ester compound in the coating agent is improved due to the crosslinking of the ester compound and the film forming agent, and the bonding effect between the coating agent and the textile is further improved.

2. In the application, sulfonated graphene is preferably used as a weather-resistant agent to be added into the coating agent, and because the sulfonated graphene and a cross-linked film-forming agent and an ester compound can perform a cross-linking reaction, the dispersion effect of the sulfonated graphene in the coating agent is improved, and because the sulfonated graphene not only has better conductivity and more polar groups, a coating film formed on a textile by the coating agent obtains a better antistatic effect, the possibility of dust or corrosive substances accumulated on the textile is reduced, and the service life of the textile coated with the coating agent is prolonged.

3. According to the method, the film-forming agent is used as the inner core and the ester compound is used as the outer shell in a shell-core polymerization mode, and the glass transition temperature of the film-forming agent is low and the glass transition temperature of the ester compound is high, so that a soft-core hard-shell structure is obtained, the coating agent is not prone to bonding at high temperature and brittle fracture at low temperature, and the textile coated with the coating agent has an excellent weather-resistant effect.

Detailed Description

The present application will be described in further detail with reference to examples.

In the embodiment of the present application, the selected apparatuses are as follows, but not limited thereto:

the instrument comprises the following steps: WTL-1000 type stirrer of Wangte mechanical equipment, Inc. in Dongguan city, DZF-6020AB type vacuum drying box of Shanghai Kuntan laboratory instrument, STSN-1.4 type horizontal grinder of Shanghai Sungting intelligent equipment, Inc., SDC-100 type water contact angle tester of Chengding precise instrument, Inc. in Dongguan city, ZD-100L type grinder of Guangzhou Reimai mechanical equipment, Inc.

Medicine preparation: the product is prepared from azodiisobutyl amidine hydrochloride LA-3887 from Shandong Liang New Material Co., Ltd, KH-172 vinyltriethoxysilane from Nanjing Roen silicon Material Co., Ltd, PPS from Suzhou Techen Xin International trade Co., Ltd, 1140A6, a defoaming agent DQ-077 from Bainian Macro chemical engineering Co., Ltd, Dongguan, radium general chemical industry Co., Ltd, a leveling agent 301 from Nanjing radium general chemical industry Co., Ltd, and an emulsifier OP-10 from Guanzhou Chengxin chemical industry Co., Ltd, No. 301.

Preparation example

Preparation of silica

Preparation example 1

1kg of polyvinylpyrrolidone, 2kg of azobisisobutylamidine hydrochloride, 3kg of deionized water, 2kg of styrene, 0.001kg of ammonium persulfate, 1.5kg of Tetraethylorthosilicate (TEOS), 0.15kg of Vinyltriethoxysilane (VETS) were weighed in each case. Taking azodiisobutyl amidine hydrochloride, deionized water and 0.5kg of polyvinylpyrrolidone, stirring and mixing to prepare a primary solution, stirring the primary solution at 120r/min, adding styrene into the primary solution during stirring to prepare a secondary solution, placing the secondary solution in an argon atmosphere, heating to 75 ℃, reacting at constant temperature for 24 hours, and cooling to room temperature to prepare a treatment solution. And evaporating and drying the treatment solution to obtain the PS microspheres.

Dispersing 1.5kg of PS microspheres in ethanol, adding 0.5kg of polyvinylpyrrolidone, stirring and mixing to obtain a third solution, heating the third solution to 50 ℃, adding ammonia water, TEOS and VETS at 300r/min to obtain composite microspheres, and dispersing the composite microspheres in tetrahydrofuran to obtain silicon dioxide 1.

Preparation example 2

The difference from preparation example 1 is that: silica 2 was prepared by weighing 1.5kg of polyvinylpyrrolidone, 2.5kg of azobisisobutylamidine hydrochloride, 4kg of deionized water, 2.5kg of styrene, 0.002kg of ammonium persulfate, 2kg of Tetraethylorthosilicate (TEOS), and 0.2kg of Vinyltriethoxysilane (VETS), respectively, and the other preparation conditions and preparation environments were the same as those in preparation example 1.

Preparation example 3

The difference from preparation example 1 is that: silica 3 was prepared by weighing 2kg of polyvinylpyrrolidone, 3kg of azobisisobutylamidine hydrochloride, 5kg of deionized water, 3kg of styrene, 0.003kg of ammonium persulfate, 3kg of Tetraethylorthosilicate (TEOS), and 0.3kg of Vinyltriethoxysilane (VETS), respectively, and the other preparation conditions and preparation environments were the same as in preparation example 1.

Preparation of sulfonated graphene

Preparation example 4

0.2kg of 3-propane-2-acetyl propane-1-sodium sulfonate (PPS), 80kg of a 5% graphene oxide dispersion, 10kg of a 10% aqueous sodium hydroxide solution, 0.2kg of sodium borohydride and 0.5kg of 12% aqueous ammonia were weighed out, respectively. Weighing 3-propane-2-acetyl propane-1-sodium sulfonate (PPS) and graphene oxide dispersion, stirring and mixing to obtain a mixed solution, adjusting the pH of the mixed solution to =9 by using a sodium hydroxide aqueous solution, continuing stirring for 30min, filtering to retain a filter cake, and washing the filter cake to be neutral to obtain an intermediate product. And (3) taking the intermediate product, sodium borohydride and ammonia water, stirring and mixing, heating to 90 ℃, stirring and reacting for 3 hours, filtering, retaining a filter cake, washing to be neutral, and drying the filter cake at 50 ℃ for 6-8 hours to obtain the sulfonated graphene 1. And (3) crushing the prepared sulfonated graphene 1, and controlling the particle size of the sulfonated graphene 1 to be 2000 meshes.

Preparation example 5

The difference from preparation example 3 is that: 0.5kg of 3-propane-2-acetyl propane-1-sodium sulfonate, 90kg of a graphene oxide dispersion liquid with a mass fraction of 5%, 15kg of a sodium hydroxide aqueous solution with a mass fraction of 10%, 0.5kg of sodium borohydride and 1kg of ammonia water with a mass fraction of 12% were weighed respectively to prepare sulfonated graphene 2, and the remaining preparation conditions and preparation environment were the same as those in preparation example 3.

Preparation example 6

The difference from preparation example 4 is that: 3-propane-2-acetyl propane-1-sodium sulfonate 1kg, a graphene oxide dispersion liquid 100kg with a mass fraction of 5%, a sodium hydroxide aqueous solution 20kg with a mass fraction of 10%, sodium borohydride 1kg and ammonia water 2kg with a mass fraction of 12% were weighed respectively to prepare sulfonated graphene 3, and the remaining preparation conditions and preparation environment were the same as those in preparation example 3.

Preparation example 7

The difference from preparation example 5 is that: the prepared sulfonated graphene 2 was pulverized, the particle size of the sulfonated graphene 2 was controlled to 2500 mesh, and a sulfonated graphene 4 was prepared, and the other preparation conditions and preparation environment were the same as those in preparation example 5.

Preparation example 8

The difference from preparation example 5 is that: the prepared sulfonated graphene 2 was pulverized, the particle size of the sulfonated graphene 2 was controlled to 3000 mesh, and sulfonated graphene 5 was prepared, and the other preparation conditions and preparation environment were the same as those in preparation example 5.

Examples

Example 1

Respectively weighing 20kg of acrylic acid, 10kg of OP-10, 30kg of polyurethane, 13kg of silicon dioxide, 1kg of auxiliary agent, 0.05kg of initiator, 3kg of ethanol and 5kg of deionized water, wherein the auxiliary agent comprises a leveling agent and a defoaming agent with equal mass, and the initiator is hydrogen peroxide in the embodiment.

Preparing a nuclear emulsion: 5kg of OP-10 and 2.5kg of deionized water are taken, stirred and mixed, the temperature is raised to 60 ℃ to prepare dispersion liquid, hydrogen peroxide and acrylic acid are added into the dispersion liquid under the nitrogen atmosphere, stirred and mixed, and the nuclear emulsion is prepared after heat preservation reaction for 2 hours.

Preparing a shell-core emulsion: stirring and mixing the prepared nuclear emulsion, 2.5kg of deionized water and 5kg of OP-10 to prepare emulsified mixed liquid, adding polyurethane into the mixed liquid in a nitrogen atmosphere, and carrying out heat preservation reaction for 2 hours at the temperature of 60 ℃ to prepare the shell-nuclear emulsion.

Preparing a coating agent: and adding a defoaming agent, a flatting agent, silicon dioxide and ethanol into the shell-core emulsion, and stirring and mixing to obtain the coating agent 1.

Example 2

The difference from example 1 is that: coating agent 2 was prepared by weighing 25kg of acrylic acid, 15kg of OP-10, 40kg of polyurethane, 18kg of silica, 1.5kg of auxiliary, 0.1kg of initiator, 4kg of ethanol and 8kg of deionized water, respectively, and the other preparation conditions and preparation environment were the same as in example 1.

Example 3

The difference from example 1 is that: 30kg of acrylic acid, 20kg of OP-10, 50kg of polyurethane, 25kg of silica, 2kg of an auxiliary, 0.2kg of an initiator, 5kg of ethanol and 10kg of deionized water were weighed, respectively, to prepare a finish 3, and the other preparation conditions and preparation environment were the same as in example 1.

Example 4

The difference from example 3 is that: 30kg of acrylic acid, 20kg of OP-10, 50kg of polyurethane, 2kg of an auxiliary, 0.2kg of an initiator, 5kg of ethanol and 10kg of deionized water were weighed, respectively, to prepare a finish 4, and the remaining preparation conditions and preparation environment were the same as in example 3.

Example 5

The difference from example 3 is that: 30kg of acrylic acid, 20kg of OP-10, 50kg of polyurethane, 20kg of silica, 5kg of graphene oxide, 2kg of an auxiliary, 0.2kg of an initiator, 5kg of ethanol and 10kg of deionized water were weighed, respectively, to prepare a finish 5, and the remaining preparation conditions and preparation environment were the same as in example 3.

Example 6

The difference from example 5 is that: 30kg of acrylic acid, 20kg of OP-10, 50kg of polyurethane, 20kg of silica, 5kg of sulfonated graphene 1, 2kg of an auxiliary agent, 0.2kg of an initiator, 5kg of ethanol and 10kg of deionized water were weighed, respectively, to prepare a coating agent 6, and the remaining preparation conditions and preparation environment were the same as in example 5.

Examples 7 to 10

The difference from example 6 is that: sulfonated graphenes 2 to 5 were respectively used instead of the sulfonated grapheme 1 in example 6 to prepare coating agents 6 to 9, and the preparation conditions and the preparation environment were the same as those in example 6.

Examples 11 to 13

The difference from example 9 is that: coating agents 11 to 13 were prepared by using silica 1 to 3, respectively, in place of the silica in example 9, and the preparation conditions and preparation environment were the same as those in example 9.

Example 14

The difference from example 12 is that: 15kg of acrylic acid and 15kg of polyacrylic acid were weighed to prepare a finish 14 in place of 30kg of acrylic acid in example 12, and the preparation conditions and preparation environment were the same as in example 12.

Example 15

The difference from example 12 is that: 15kg of acrylic acid and 15kg of polyacrylate were weighed out in place of 30kg of acrylic acid in example 12 to prepare a finish 15, and the other preparation conditions and preparation environment were the same as those in example 12.

Example 16

The difference from example 15 is that: 50kg of an epoxy resin was weighed to prepare a finishing agent 16 in place of 50kg of the polyurethane in example 15, and the other preparation conditions and preparation environment were the same as in example 15.

Example 17

The difference from example 15 is that: a finishing agent 17 was prepared by weighing 25kg of an epoxy resin and 25kg of polyurethane in place of 50kg of the polyurethane in example 15, and the other preparation conditions and preparation environments were the same as in example 15.

Example 18

The difference from example 17 is that: the temperature was raised to 70 ℃ to prepare a coating agent 18, and the other preparation conditions and preparation environment were the same as in example 17.

Example 19

The difference from example 17 is that: the temperature was raised to 80 ℃ to prepare a coating agent 19, and the other preparation conditions and preparation environment were the same as those in example 17.

Performance test

(1) Solid content determination: according to GB 1725-79(89) determination of coating solids content, 1-2g of a sample (to the nearest 0.0002 g) is weighed into a weighing bottle which is dried at 105 + -2 ℃ in advance and has a constant weight, the weighing bottle is placed in an oven and dried at 105 + -2 ℃ for 4h, the weighing bottle is taken out and covered, the weighing bottle is placed in a drying oven and cooled for 30min to room temperature and weighed, and the solid content w of the coating agent is recorded.

(2) And (3) cold resistance detection: the textile coated with the coating agent is folded in the front plane by 180 degrees and placed in a test box for testing, the temperature is adjusted to be 0 ℃, 20 ℃ and 40 ℃, and whether the coating film of the coating agent is cracked or not is observed.

(3) And (3) detecting heat resistance: preparing 3 sample plates on tinplate according to GB1727-79 general paint film preparation method, after the paint film is dried, measuring under the conditions of constant temperature and constant humidity, placing a dried paper sheet on the paint film, placing the paint film with the paper sheet in a test box, adjusting the temperature to be 20 ℃, 40 ℃ and 60 ℃, carrying out constant temperature treatment for 2 hours, taking out, shaking the paint film, and observing the bonding condition between the paper sheet and the paint film.

(4) And (3) detecting the corrosion resistance: the salt spray resistance of the anticorrosive coating is tested by using an HJ-YW60 salt water spray tester (Hengjun instruments and equipment Co., Ltd., Dongguan city) according to the GB/T1771-2007 color paint and varnish neutral salt spray resistance test method, and the salt spray resistance of the paint film is rated according to the GB/T1740-2007 paint film damp and heat resistance test method.

(5) And (3) detecting the waterproof performance: and testing the water contact angle E of the sample by using a water contact angle tester.

(6) And (3) detecting the water vapor permeability: measuring by using a water vapor permeability tester; 30mL of distilled water is measured and placed in a tester, a rubber gasket and a sample are sequentially placed on the tester, then an aluminum screw cap is tightened without air leakage, and then the tester is weighed on a balance. The sample dish was then placed in a desiccator containing concentrated sulfuric acid having a relative density of 1.84 (the desiccator diameter was 25 cm), and the desiccator was placed in an air at 20 ℃ C, and after standing, it was weighed, and the difference P between the weights was recorded.

(7) Testing the adhesive force of the coating film: the adhesion of the coating was tested according to the paint adhesion test GB/T1720-1979 (1989).

Table 1 examples 1-19 performance testing

TABLE 2 EXAMPLES 1-19 Cold and Heat resistance tests

Referring to the comparison of the performance tests of tables 1 and 2, it can be found that:

(1) the coating agent prepared by adjusting the proportion of the components in the examples 1-3 has a coating film with higher solid content, better water resistance effect and more excellent cold and heat resistance effects, which shows that the shell-core structure with a soft core and a hard shell is prepared by adopting a shell-core emulsion polymerization mode, the weather resistance of the coating agent is improved, the coating film formed by the coating agent can protect textiles for a long time, the performance of the coating agent prepared in the example 3 is optimal, and the components of the coating agent prepared in the example 3 are more suitable.

(2) Comparing examples 1-3 with example 4, it can be seen that the water resistance of the coating agent prepared in examples 1-3 is improved, which indicates that the water resistance and water resistance of the coating film formed by the coating agent are improved by adding silicon dioxide into the coating agent, so that the textile is not easily soaked by water under the protection of the coating film, and the service life of the textile is prolonged.

(3) Comparing example 5 with example 3, it can be found that: the corrosion resistance, water resistance and water vapor permeability of the coating agent prepared in example 5 are improved, which shows that the corrosion resistance effect of the coating agent formed coating film is improved by adding graphene oxide into the coating agent, because the graphene oxide has a large specific surface area, the formed coating film is dense, and the water resistance and corrosion resistance effect of the coating agent formed coating film are improved.

(4) Comparing examples 6-8 with example 3, it can be seen that: the corrosion resistance of the coating agents prepared in examples 6 to 8 was improved, which indicates that the corrosion resistance of the coating agents was improved by adding sulfonated graphene to the coating agents, because sulfonated graphene has a good antistatic effect, and thus corrosive substances and the like are not easily attached to the surface of the coating film, thereby improving the corrosion resistance of the coating agents.

(5) Comparison of examples 9-10 with example 6 shows that: the corrosion resistance and adhesion of the coating agents prepared in examples 9 to 10 are improved, which shows that the corrosion resistance of the coating agent formed by the coating agent is improved by filling the coating agent with micron-sized sulfonated graphene, because the micron-sized sulfonated graphene is uniformly dispersed in the coating agent, the compactness of the coating film is further enhanced, and the corrosion resistance of the coating film is improved, and because the dispersion effect of the components in the coating agent is improved, the bonding effect between the coating agent and the textile is improved, the corrosion resistance of example 9 is better, which shows that the particle size of the sulfonated graphene is more suitable at this time.

(6) Comparison of examples 11 to 13 with example 9 shows that: the coating films formed by the coating agents prepared in examples 11 to 13 have significantly improved water vapor permeability, which indicates that the silica prepared by reacting tetraethoxysilane with the treatment solution improves the water vapor permeability of the coating film, because the silica prepared has a porous structure, the number of free radicals in the coating agent is increased, the water vapor permeability of the coating film is improved, the wearing comfort of the textile is improved, and the water vapor permeability of the coating film in example 12 is the best, which indicates that the ratio of the components in the treatment solution is proper.

(7) Comparison of examples 14-15 with example 12 shows that: examples 14-15, which show that the adhesion of the coating agent is improved by using polyacrylic acid and acrylic acid, polyacrylate and acrylic acid instead of acrylic acid alone, show that the adhesion of the coating agent is improved by using a polymeric material to crosslink the polyurethane, thereby increasing the degree of crosslinking of the coating agent, i.e., increasing the bonding effect between the coating film and the textile, and the polyacrylate reacts not only with the polyurethane but also with other components of the coating agent, thereby increasing the solid content of the coating agent, increasing the compatibility between the components of the coating agent, and increasing the bonding effect between the coating agent and the textile, and the solid content of the coating agent prepared in example 15 is the highest when the proportions of the components of the coating agent are more suitable when tables 1 and 2 are combined.

(8) Comparison of examples 16-17 with example 15 shows that: the adhesion effect and cold and heat resistant effect of the coating agent prepared in example 17 are improved, which means that the coating agent prepared in this application has improved heat and cold resistant effect because the polyurethane and the epoxy resin are compounded to form the ester compound shell, and the polyurethane and the epoxy resin are crosslinked to give better adhesiveness and toughness to the core-shell structure.

(9) Comparison of examples 18 to 19 with example 17 shows that: the water resistance of the coatings prepared in examples 18 to 19 was improved, which indicates that the core emulsion and the shell-core emulsion were prepared at appropriate temperatures, so that the degree of crosslinking between the components in the coating and the dispersion effect in the coating were improved, the solid content of the coating was increased, the water resistance of the coating was improved, the water resistance of the coating prepared in example 18 was better, and the temperature rise in example 18 was more appropriate.

Comparative example

Comparative example 1

The difference from example 18 is that: the coating agent 20 was prepared without adding an emulsifier, and the other preparation conditions and preparation environments were the same as in example 18.

Comparative example 2

The difference from example 18 is that: the finishing agent 21 was prepared using polycarbonate instead of acrylic acid and polyacrylate, and the other preparation conditions and preparation environments were the same as in example 18.

Comparative example 3

The difference from example 18 is that: a coating agent 22 was prepared without adding an ester compound, and the other preparation conditions and preparation environments were the same as those of example 18.

Comparative example 4

The difference from example 18 is that: the coating agent 23 was prepared using graphene instead of sulfonated graphene, and the preparation conditions and preparation environment were the same as those in example 18.

Comparative example 5

The difference from example 18 is that: the finishing agent 24 was prepared without adding a weather resistant agent, and the other preparation conditions and preparation environments were the same as in example 18.

Performance test

(1) Solid content determination: according to GB 1725-79(89) determination of coating solids content, 1-2g of a sample (to the accuracy of 0.0002 g) is weighed into a weighing bottle which is dried at 105 + -2 ℃ in advance and has a constant weight, the weighing bottle is placed in an oven and dried at 105 + -2 ℃ for 4h, the weighing bottle is taken out and covered, the weighing bottle is placed in a drying oven and cooled for 30min to room temperature and weighed, and the solid content w of the coating agent is recorded.

(2) And (3) cold resistance detection: the textile coated with the coating agent is folded in the front plane by 180 degrees and placed in a test box for testing, the temperature is adjusted to be 0 ℃, 20 ℃ and 40 ℃, and whether the coating film of the coating agent is cracked or not is observed.

(3) And (3) detecting heat resistance: preparing 3 sample plates on tinplate according to GB1727-79 general paint film preparation method, after the paint film is dried, measuring under the conditions of constant temperature and constant humidity, placing a dried paper sheet on the paint film, placing the paint film with the paper sheet in a test box, adjusting the temperature to be 20 ℃, 40 ℃ and 60 ℃, carrying out constant temperature treatment for 2 hours, taking out, shaking the paint film, and observing the bonding condition between the paper sheet and the paint film.

(4) And (3) detecting the corrosion resistance: the salt spray resistance of the anticorrosive coating is tested by using an HJ-YW60 salt water spray tester (Hengjun instruments and equipment Co., Ltd., Dongguan city) according to the GB/T1771-2007 color paint and varnish neutral salt spray resistance test method, and the salt spray resistance of the paint film is rated according to the GB/T1740-2007 paint film damp and heat resistance test method.

(5) And (3) detecting the waterproof performance: and testing the water contact angle E of the sample by using a water contact angle tester.

(6) And (3) detecting the water vapor permeability: measuring by using a water vapor permeability tester; 30mL of distilled water is measured and placed in a tester, a rubber gasket and a sample are sequentially placed on the tester, then an aluminum screw cap is tightened without air leakage, and then the tester is weighed on a balance. The sample dish was then placed in a desiccator containing concentrated sulfuric acid having a relative density of 1.84 (the desiccator diameter was 25 cm), and the desiccator was placed in an air at 20 ℃ C, and after standing, it was weighed, and the difference P between the weights was recorded.

(7) Testing the adhesive force of the coating film: the adhesion of the coating was tested according to the paint adhesion test GB/T1720-1979 (1989).

TABLE 3 comparative examples 1-5 Performance test

TABLE 4 comparative examples 1-5 Cold and Heat resistance test

Combining the performance tests in table 3 and table 4, it can be found that:

(1) comparing comparative examples 1, 3 with example 18, it can be found that: the water resistance, corrosion resistance, adhesion and cold and heat resistance of the coating agent prepared in example 18 are significantly improved, which indicates that the coating agent adopts a film forming agent and an ester compound to form a shell-core structure through shell-core emulsion polymerization, so that a soft-core and hard-shell structure is formed, the heat and cold resistance effects of the coating agent are improved, meanwhile, the hydrophilic group in the film forming agent is wrapped in the shell of the ester compound, the water resistance effect of the coating agent is improved, and meanwhile, corrosive substances are not easily attached to a coating film, so that the corrosion resistance effect of the coating film formed by the coating agent is improved.

(2) Comparing comparative example 2 with example 18, it can be found that: the coating agent obtained in example 18 was excellent in adhesion and corrosion resistance, because the acrylic acid and polyacrylate were compounded to exhibit a good crosslinking effect between the soft core and the outer shell, so that the dispersion effect in the coating agent was good, and the adhesion property between the coating film of the coating agent and the textile was improved.

(3) Comparing comparative example 4 with example 18, it can be found that: the corrosion resistance of the coating agent prepared in example 18 is improved, which shows that the corrosion resistance effect of the coating agent can be effectively improved by using sulfonated graphene, because the sulfonated graphene not only has a better specific surface area, but also has a certain antistatic effect, so the corrosion resistance effect of the coating agent is improved.

(4) Comparing comparative example 5 with example 18, it can be found that: the water resistance and water vapor permeability of the finish prepared in example 18 were improved, which indicates that the water resistance and water vapor permeability of the finish were improved by adding a weather resistant agent to the finish, since silica in the weather resistant agent was dispersed in the finish, the water resistance of the finish was improved, and since the silica had a porous structure inside, the path of the moisture contacting the textile was reduced, and the water vapor permeability of the coating film formed from the finish was improved.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.