阅读说明：本技术 一种新型高稳定性透明银离子配合物及其制备方法、应用 (Novel high-stability transparent silver ion complex and preparation method and application thereof ) 是由 宋天龙 刘永龙 陶宏兵 林家洪 杨娟 黄泽彬 于 2020-05-29 设计创作，主要内容包括：本发明公开一种新型高稳定性透明银离子配合物及其制备方法、应用。其中,新型高稳定性透明银离子配合物包含硝酸银、吡咯烷酮类化合物和溶剂。其中,吡咯烷酮类化合物可吸收紫外线,避免银离子吸收紫外光而提高活性产生的变色现象。本发明的银离子配合物的水溶性好、透明度高、稳定性好、配伍性高,其在日化产品中的添加量低,使用安全、温和,可以使日化产品具有良好的抗菌抑菌稳定性。(The invention discloses a novel high-stability transparent silver ion complex and a preparation method and application thereof. The novel high-stability transparent silver ion complex comprises silver nitrate, pyrrolidone compounds and a solvent. Wherein, the pyrrolidone compound can absorb ultraviolet rays, and the phenomenon of discoloration caused by the increase of activity due to the absorption of ultraviolet rays by silver ions is avoided. The silver ion complex has the advantages of good water solubility, high transparency, good stability, high compatibility, low addition amount in daily chemical products, safe and mild use and capability of ensuring that the daily chemical products have good antibacterial and bacteriostatic stability.)

1. A novel high-stability transparent silver ion complex is characterized by comprising silver nitrate, pyrrolidone compounds and a solvent.

2. The novel high-stability transparent silver ion complex according to claim 1, further comprising an amine derivative and a triazole-based substance.

3. The novel high-stability transparent silver ion complex according to claim 2, characterized by comprising the following components in percentage by weight:

4. a novel high-stability transparent silver ion complex according to any one of claims 1 to 3, characterized in that the pyrrolidone-type compound is selected from any one or a mixture of at least two of sodium pyrrolidone carboxylate, zinc pyrrolidone carboxylate, methyl pyrrolidone, ethyl pyrrolidone and octyl pyrrolidone.

5. A novel high stability transparent silver ion complex according to any one of claims 1 to 3, characterized in that the solvent is selected from any one of water, propylene glycol, glycerol, butylene glycol, hexylene glycol or a mixture of at least two thereof.

6. The novel high-stability transparent silver ion complex according to claim 2 or 3, wherein the amine derivative is selected from any one of or a mixture of at least two of acetamidopropyltrimethylammonium chloride, acetyl chitosamine, aminopropyl lauryl glutamine.

7. The novel high-stability transparent silver ion complex according to claim 2 or 3, wherein the triazole-based substance is any one or a mixture of at least two of benzotriazole, bumetazole, methylene bis-benzotriazolyl tetramethylbutylphenol, oxcarbazol, and sodium benzotriazolyl styrene-butadiene-phenol sulfonate.

8. The preparation method of the novel high-stability transparent silver ion complex as claimed in claim 1, wherein the silver nitrate is dispersed in the solvent, and then the pyrrolidone compound is added and stirred uniformly to prepare the novel high-stability transparent silver ion complex;

preferably, the pyrrolidone compound is added and stirred uniformly at the temperature of 20-70 ℃.

9. A method for preparing the novel high-stability transparent silver ion complex according to any one of claims 2 to 7, wherein the silver nitrate is dispersed in the solvent, and then the pyrrolidone compound, the amine derivative and the triazole compound are sequentially added and stirred uniformly to prepare the novel high-stability transparent silver ion complex;

preferably, the pyrrolidone compound, the amine derivative and the triazole substance are added and stirred uniformly at the temperature of 20-70 ℃.

10. Use of the novel high stability transparent silver ion complex according to any one of claims 1 to 7 in daily chemical products including laundry detergents and hand sanitizers.

Technical Field

The invention relates to the technical field of antibacterial disinfection, and particularly relates to a novel high-stability transparent silver ion complex and a preparation method and application thereof.

Background

The antibacterial agent is a compound with sterilization and bacteriostasis functions, and the silver ion antibacterial agent is a metal ion with stronger sterilization and bacteriostasis capability at present, and has the advantages of heat resistance, durability, continuity, safety and the like. However, the silver ion antibacterial products in the current market have some defects, such as poor light stability, easy color change, poor compatibility, poor chloride ion resistance, easy precipitation and the like, and further the application range of the silver ion antibacterial products is greatly reduced. Therefore, the silver ion complex with high stability and good compatibility is of great significance.

The silver element has 18 electrons on the outer layer and one electron on the outermost layer, and mainly forms a + 1 valence compound. Ag + 1 valence⁺There are 4 empty orbitals in total of 5s and 5p, after sp hybridization, a compound with 2-4 coordination numbers can be formed, wherein some chemical substances containing nitrogen and sulfur elements can provide lone-pair electrons, thereby forming a stable complex with silver ions. The silver ion discoloration is mainly affected by organic sulfides, ultraviolet rays, oxidizing agents and the like. Under the conditions of illumination and oxygen, the organic sulfur contacts with silver ions to generate sulfides, so that the silver can be quickly discolored to generate silver sulfide, silver oxide and other substances. Because the forbidden band width of silver is narrow, the ultraviolet part in natural light can lead electrons in the valence bandThe silver ions are excited into a conduction band, so that the activity of the silver ions is improved, and the silver ions are easy to react and discolor. In addition, silver ions exist in an ionic state in an aqueous solution, and are easily combined with chloride ions, sulfate radicals, carbonate radicals and the like in tap water to generate a precipitate insoluble in water, so that the use of the precipitate is limited.

Disclosure of Invention

The invention aims to provide a novel high-stability transparent silver ion complex which is good in water solubility, high in transparency, good in stability and high in compatibility.

The second purpose of the invention is to provide a preparation method of a novel high-stability transparent silver ion complex, and the silver ion complex with good water solubility, high transparency, good stability and high compatibility can be prepared by adopting the preparation method.

The invention also aims to provide the application of the novel high-stability transparent silver ion complex in daily chemical products, so that the daily chemical products have good stability and good antibacterial and bacteriostatic effects.

In order to achieve the purpose, the invention adopts the following technical scheme:

on the one hand, a novel high-stability transparent silver ion complex is provided, which comprises silver nitrate, pyrrolidone compounds and a solvent.

Wherein, the pyrrolidone compound can absorb ultraviolet rays, and the phenomenon of discoloration caused by the increase of activity due to the absorption of ultraviolet rays by silver ions is avoided. When the transparent silver ion complex is added into daily chemical products, the antibacterial and bacteriostatic stability is good, the addition amount is low, and the use is safe and mild.

In the invention, the pyrrolidone compound and the silver nitrate belong to antibacterial agents in the technical field, but the functions of the pyrrolidone compound and the silver nitrate in the application are not antibacterial, but are used for absorbing ultraviolet light, reducing the activity of silver ions and preventing the silver ions from generating a color change phenomenon so as to improve the coordination stability of a silver ion complex.

Further, the novel high-stability transparent silver ion complex further comprises an amine derivative and a triazole substance. The amine derivative, the triazole substance and the pyrrolidone compound generate synergistic effect, so that the ultraviolet absorption and the coordination stability of silver ions are further improved, and the silver ions are prevented from absorbing ultraviolet activity and improving the color change.

Preferably, the novel high-stability transparent silver ion complex comprises the following components in percentage by weight:

0.05-10% silver nitrate, e.g., 0.05%, 0.1%, 0.2%, 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 2%, 2.5%, 3%, 3.4%, 3.8%, 4%, 4.2%, 4.5%, 5%, 5.5%, 6%, 7%, 8%, 9%, or 10%;

0.02 to 40% of a pyrrolidone-based compound, e.g., 0.02%, 0.03%, 0.05%, 0.1%, 0.2%, 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 2%, 2.5%, 3%, 3.4%, 3.8%, 4%, 4.2%, 4.5%, 5%, 5.5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 15%, 18%, 20%, 22%, 25%, 27%, 29%, 30%, 31%, 32%, 34%, 35%, 37%, 39%, or 40%;

0-5% of an amine derivative, such as 0, 0.02%, 0.03%, 0.05%, 0.1%, 0.2%, 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 2%, 2.5%, 3%, 3.4%, 3.8%, 4%, 4.2%, 4.5%, or 5%;

triazoles, for example 0, 0.02%, 0.03%, 0.05%, 0.1%, 0.2%, 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 2%, 2.5%, 3%, 3.4%, 3.8%, 4%, 4.2%, 4.5% or 5%;

the balance of solvent.

The sum of the weight percentages of the components is 100 percent.

Further, the pyrrolidone-based compound is selected from any one of or a mixture of at least two of sodium pyrrolidone carboxylate, zinc pyrrolidone carboxylate, methyl pyrrolidone, ethyl pyrrolidone, and octyl pyrrolidone, for example, a mixture of sodium pyrrolidone carboxylate and zinc pyrrolidone carboxylate, a mixture of sodium pyrrolidone carboxylate and methyl pyrrolidone, a mixture of zinc pyrrolidone carboxylate and octyl pyrrolidone, a mixture of ethyl pyrrolidone and octyl pyrrolidone, a mixture of zinc pyrrolidone carboxylate and ethyl pyrrolidone, a mixture of sodium pyrrolidone carboxylate, zinc pyrrolidone carboxylate, and methyl pyrrolidone, a mixture of methyl pyrrolidone, ethyl pyrrolidone, and octyl pyrrolidone, a mixture of zinc pyrrolidone carboxylate, methyl pyrrolidone, and ethyl pyrrolidone, and the like.

Preferably, the solvent is selected from any one or a mixture of at least two of water, propylene glycol, glycerol, butylene glycol, hexylene glycol, such as a mixture of water and propylene glycol, a mixture of water and glycerol, a mixture of propylene glycol and glycerol, a mixture of butylene glycol and hexylene glycol, a mixture of water, propylene glycol and glycerol, a mixture of water, glycerol and butylene glycol, and the like.

Further, the amine derivative is selected from any one of or a mixture of at least two of acetamidopropyltrimethylammonium chloride, acetyl chitosamine, aminopropyllauryl glutamine, for example, a mixture of acetamidopropyltrimethylammonium chloride, acetyl chitosamine, a mixture of acetyl chitosamine and aminopropyllauryl glutamine, a mixture of acetamidopropyltrimethylammonium chloride, acetyl chitosamine and aminopropyllauryl glutamine, and the like.

Further, the triazole-based substance is selected from any one of or a mixture of at least two of benzotriazole, bumetazole, methylene bis-benzotriazolyl tetramethylbutylphenol, oxcarbazol, and sodium benzotriazolyl butylphenol sulfonate, for example, a mixture of benzotriazole and bumetazole, a mixture of benzotriazole and methylene bis-benzotriazolyl tetramethylbutylphenol, a mixture of bumetazole and oxcarbazol, a mixture of oxcarbazol and sodium benzotriazolyl butylphenol sulfonate, a mixture of benzotriazole, bumetazole and methylene bis-benzotriazolyl tetramethylbutylphenol, a mixture of benzotriazole, bumetazole and oxcarbazol, and the like.

On the other hand, the invention provides a preparation method of the novel high-stability transparent silver ion complex, which comprises the steps of dispersing the silver nitrate into the solvent, then adding the pyrrolidone compound and uniformly stirring to prepare the novel high-stability transparent silver ion complex.

Under the condition that the pyrrolidone compound exists, the silver nitrate is difficult to dissolve, so the silver nitrate is firstly dissolved in the solvent, and then the pyrrolidone compound is added to be uniformly stirred, and the silver ion complex with good stability can be prepared. The preparation method of the silver ion complex, particularly the adding sequence of the raw materials, is the key for preparing the silver ion complex with good water solubility and stability.

Preferably, the pyrrolidone compound is added and stirred uniformly at 20 to 70 ℃ (e.g., 20 ℃, 22 ℃, 25 ℃, 28 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃). The stirring temperature is preferably 50 to 70 ℃ to accelerate the dissolution.

Further, the invention also provides a preparation method of the novel high-stability transparent silver ion complex, which comprises the steps of dispersing the silver nitrate in the solvent, then sequentially adding the pyrrolidone compound, the amine derivative and the triazole substance, and uniformly stirring to obtain the novel high-stability transparent silver ion complex.

In the invention, the silver ion complex prepared by the preparation method has good water solubility and high transparency, can be conveniently added into a target product and is convenient to use. In addition, the preparation method of the silver ion complex is simple, reduces the energy consumption and the requirements on equipment, and is suitable for large-scale production.

Preferably, the pyrrolidone compound, the amine derivative and the triazole substance are added and stirred uniformly at the temperature of 20-70 ℃.

The invention also provides application of the novel high-stability transparent silver ion complex in daily chemical products, including but not limited to laundry detergents and hand sanitizers. The silver ion complex is added in a small amount in laundry detergent and hand sanitizer, and can enable daily chemical products to have good antibacterial effect and stability.

The silver ion complex of the invention and the traditional silver ion product have the following obvious advantages: good water solubility, high transparency, good stability and high compatibility, which are specifically shown in the following aspects:

the complex can be well compatible with compounds containing chloride ions, the problems of precipitation, flocculation, color change and the like when the traditional silver ion antibacterial agent and the chloride ions exist at the same time can be avoided, and the stability of the silver ions is effectively improved;

the complex can effectively improve the compatibility with alcohol compounds such as ethanol, glycerol and the like, and effectively solves the problems of color change, precipitation and the like when the traditional silver ions and the alcohol compounds coexist;

the complex has good compatibility with disinfection and antibacterial products such as laundry detergent, liquid soap and the like, and effectively solves the problems that the traditional silver ion product added into the products such as the laundry detergent is easy to discolor and precipitate;

(IV) the good stability is mainly reflected in that: the silver ion complex has high stability at high, low and normal temperatures and stable illumination, and effectively solves the problems that the traditional silver ion product is easy to discolor and precipitate when being exposed to light;

the silver ion complex has good water solubility and high transparency, can be conveniently added into a target product, and is convenient to use;

and (VI), the preparation method of the silver ion complex is simple, reduces the energy consumption and the requirements on equipment, and is suitable for large-scale production.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments.

Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.