CN117044719A

CN117044719A - Preservative composition and preparation method and application thereof

Info

Publication number: CN117044719A
Application number: CN202210485909.5A
Authority: CN
Inventors: 杜巧燕; 史国放; 邹冰; 夏斯琴; 曾运生
Original assignee: Hanning Chemical Shanghai Co ltd
Current assignee: Hanning Chemical Shanghai Co ltd
Priority date: 2022-05-06
Filing date: 2022-05-06
Publication date: 2023-11-14

Abstract

The invention provides a preservative composition, a preparation method and application thereof. The preservative composition comprises 50-95% of phenoxyethanol and 1-10% of bronopol by mass percent. The preparation method of the preservative composition comprises the following steps: and mixing phenoxyethanol and bronopol to obtain the preservative composition. The preservative composition provided by the invention can avoid anaphylactic reaction, has excellent preservative effect and yellowing resistance through the compounding of phenoxyethanol and bronopol, and is especially suitable for water-based industrial products.

Description

Preservative composition and preparation method and application thereof

Technical Field

The invention belongs to the technical field of chemical sterilization preservatives, and particularly relates to a preservative composition, a preparation method and application thereof.

Background

The industrial products such as water-based paint, emulsion, building materials and the like contain water and other nutritional ingredients, which is beneficial to the growth of microorganisms. In order to protect the aqueous product from spoilage by microorganisms, ensuring that the product has a sufficient shelf life, preservatives are added. The preservatives commonly used in these industrial products are mainly isothiazolinones.

For example CN111226950a discloses a preservative and a method for preparing the same, the preservative comprising a preservative active, methylisothiazolinone, a stabilizer, the balance being water; the stability of the preservative can be improved by the addition of a preservative active and a stabilizer. However, the amount of the preservative should not be excessive, otherwise sensitization, irritation and the like may occur.

CN113199579a discloses a colorless water-borne multifunctional wood preservative and a preparation and use method thereof, wherein the preservative is prepared by mixing triazole bactericide, iodopropynyl butylcarbamate, isothiazolinone bactericide and pyrethroid serving as active ingredients with an organic solvent, a cosolvent and a surfactant; the preservative can take water as a carrier, the preparation is more stable, the treated wood keeps the original color and good appearance, and can fully infiltrate into the wood, so that the damage of decay fungi, mould, color-changing bacteria, silverfish, termite and the like to the wood can be effectively prevented. CN108294018A discloses a compound preservative comprising isothiazolinone, potassium sorbate, polyoxyethylated castor oil, antioxidant, and the balance water. The composite preservative is economical and practical, has low toxicity and low potential hazard to users and environment. However, due to the presence of isothiazolinones, there may be a risk of sensitization when the preservative is used in too much amount.

A common disadvantage in the prior art is that the european union has concerns about skin irritation and sensitization of isothiazolinone ingredients and requires that products with isothiazolinone ingredient contents exceeding the limits of each ingredient must be labeled with EUH208 (containing the sensitization ingredient, possibly causing allergic reactions) to alert the consumer to the precautions. In order to avoid EUH and 208 labels, each manufacturer can reduce the addition amount of the original isothiazolinone scheme to below the limit value, but when the limit value is very low, the required anti-corrosion effect cannot be achieved.

Therefore, development of a preservative which is free from sensitization reaction and excellent in preservative effect is a problem to be solved in the art.

Disclosure of Invention

Aiming at the defects existing in the prior art, the invention aims to provide a preservative composition, and a preparation method and application thereof. The preservative composition can avoid anaphylactic reaction, has excellent preservative effect and yellowing resistance through the compounding of phenoxyethanol and bronopol, and is particularly suitable for water-based industrial products.

To achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a preservative composition comprising, in mass percent, 50 to 95% phenoxyethanol and 1 to 10% bronopol.

According to the preservative composition provided by the invention, by compounding the phenoxyethanol with the bromonitroalcohol with a specific content, the introduction of isothiazolinone components is avoided, and the sensitization risk is reduced; and the preservative has good preservative effect and yellowing resistance through the synergistic effect among the components.

Preferably, the preservative composition comprises 50 to 95% phenoxyethanol by mass percent, for example, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 74%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, etc.

In the invention, the dosage of the phenoxyethanol is too small to achieve the anti-corrosion effect; the dosage of the anti-corrosion agent is too much, the dosage of other anti-corrosion components is correspondingly reduced, and the overall anti-corrosion effect is poor.

Preferably, the preservative composition comprises 1 to 10% by mass of bronopol, which may be, for example, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, etc.

In the invention, the consumption of the bronopol is too small to meet the anti-corrosion requirement, and the system is easy to yellow due to too much consumption.

Preferably, the preservative composition further comprises 1 to 30% by mass of a polyol, which may be, for example, 2%, 3%, 4%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, etc.

In the invention, the polyalcohol can assist synergy, and the anticorrosion effect is further improved by compounding with phenoxyethanol and bronopol; the consumption of the polyol is too much, other active ingredients are correspondingly reduced, and the overall preservative effect is poor.

Preferably, the preservative composition further comprises water.

According to the invention, the viscosity of the preservative can be adjusted by controlling the content of water, so that the downstream product can be more conveniently added and used.

As a preferable technical scheme of the invention, the preservative composition comprises 84-95% of phenoxyethanol, 3-10% of bronopol, 1-5% of polyalcohol and the balance of water in percentage by mass.

Preferably, the mass ratio of phenoxyethanol to bronopol in the preservative composition is (15-35): 1, for example, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, 26:1, 27:1, 28:1, 29:1, 30:1, 31:1, 32:1, 33:1, 34:1, etc. can be used.

Preferably, the number of carbon atoms in the polyol is 5 or more, and for example, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, etc. may be used.

Preferably, the polyols include C5-C10 polyols, which may be C5, C6, C7, C8, C9, C10, etc., for example, and include, but are not limited to, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, etc.

Preferably, the polyol comprises any one or a combination of at least two of 1, 2-pentanediol, 1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 2-octanediol, 1, 8-octanediol, 1, 2-decanediol, or 1, 10-decanediol.

In the invention, when the number of carbon atoms in the polyol is more than 5, the phenoxyethanol and the bronopol have auxiliary synergism, and when the number of carbon atoms is less than 5, the polyol has little corrosion resistance and is only used as a solvent.

Preferably, the polyol comprises any one or a combination of at least two of 1, 2-pentanediol, 1, 2-hexanediol, or 1, 2-octanediol.

In a second aspect, the present invention provides a method of preparing a preservative composition according to the first aspect, the method comprising the steps of:

and mixing phenoxyethanol and bronopol to obtain the preservative composition.

Preferably, the mixed material further comprises a polyol and/or water.

Preferably, the mixing time is 2 to 4 hours, for example, 2 hours, 3 hours, 4 hours, etc.

Preferably, the temperature of the mixing is 30 to 40 ℃, for example, 32 ℃, 34 ℃, 36 ℃, 38 ℃, and the like.

In a third aspect, the present invention provides a preservative comprising a preservative composition according to the first aspect.

In a fourth aspect, the present invention provides a preservative composition according to the first aspect and/or the use of a preservative according to the third aspect in an aqueous industrial product.

The aqueous industrial product comprises any one of an aqueous coating, an aqueous emulsion or an aqueous slurry.

Preferably, the mass percentage of the preservative composition in the aqueous industrial product is 0.2 to 1.5%, for example, may be 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, etc., more preferably 0.5 to 1.0%.

In the invention, the mass percentage of the preservative composition is within 0.2-1.5%, so that the required preservative effect can be achieved. The microbial susceptibility of different products is different, the required shelf life is also different, and the optimal preservative addition amount is also different.

The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.

Compared with the prior art, the invention has the beneficial effects that:

according to the preservative provided by the invention, by compounding phenoxyethanol and bromonitroalcohol, anaphylactic reaction is not easy to occur, the preservative is milder and has excellent preservative effect, after mixed bacterial suspension is inoculated for 7 days for the fourth time, the bacterial content is less than or equal to 9 bacteria/plate, and the antimicrobial pollution capability is strong; and the system did not undergo yellowing.

Detailed Description

The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.

Example 1

The embodiment provides a preservative composition, which comprises 90% phenoxyethanol, 4% bronopol, 5%1, 2-hexanediol and the balance of water in percentage by mass.

The embodiment provides a preparation method of the preservative composition, which comprises the following specific steps:

the preservative composition is obtained by mixing phenoxyethanol, bronopol, 1, 2-hexanediol and water at 40 ℃ for 2 hours.

Example 2

The present example provides a preservative composition comprising, in mass percent, 95% phenoxyethanol, 3% bronitol, 1%1, 2-octanediol, and the balance water.

This example provides a method of preparing the preservative composition, with the specific steps being the same as in example 1.

Example 3

The present example provides a preservative composition comprising, in mass percent, 84% phenoxyethanol, 10% bronopol, 1%1, 2-pentanediol, and the balance water.

Example 4

The present example provides a preservative composition comprising, in mass percent, 50% phenoxyethanol, 10% bronopol, 20%1, 2-hexanediol, 10%1, 2-octanediol, and the balance water.

Example 5

This example provides a preservative composition which differs from example 1 only in that the mass percent of bronopol in the preservative composition is 2%, the balance being made up with water, and the other components and amounts being the same as in example 1.

Example 6

This example provides a preservative composition which differs from example 1 only in that 1, 2-hexanediol is absent, the balance is made up with water, and the other components and amounts are the same as in example 1.

Example 7

The present example provides a preservative composition comprising 90% phenoxyethanol, 4% bronitol, and 6%1, 2-hexanediol, in mass percent.

Example 8

This example provides a preservative composition which differs from example 1 only in that 1, 2-hexanediol is replaced with an equal weight portion of 1, 2-propanediol, and the other components and amounts are the same as in example 1.

Comparative example 1

This comparative example provides a preservative composition which differs from example 3 in that the mass percent of bronopol in the preservative composition is 15%, no water is present, and the other components and amounts are the same as in example 3.

This comparative example provides a process for preparing the preservative composition, the specific procedure being the same as in example 3.

Comparative example 2

This comparative example provides a preservative composition which is Coatpro 679 with 30% bronopol as the active ingredient.

Comparative example 3

The comparative example provides a preservative composition which is Coatpro 610, and the active ingredient is 1.5% of a mixture of chloromethyl isothiazolinone and methyl isothiazolinone, and the mass ratio of the chloromethyl isothiazolinone to the methyl isothiazolinone is 3:1.

Performance testing

(1) Corrosion resistance

The preservative compositions provided in examples 1 to 8 and comparative examples 1 to 3 were mixed with aqueous polyurethane emulsion and subjected to challenge inoculation for 28 days and 4 times with reference to a test method for antimicrobial infection of aqueous coating materials in a GB/T30792-2014 tank. The mixed bacterial suspension is inoculated on the 0 th day, the 7 th day, the 14 th day and the 21 st day of the experiment respectively, the mixed bacterial suspension is stirred uniformly, the mixed bacterial suspension is placed at room temperature for a certain time, and the content of residual bacteria is detected on the 2 nd day and the 7 th day (before the mixed bacterial suspension is inoculated) after each time of inoculating the mixed bacterial suspension;

wherein the bacterial strains contained in the mixed bacterial suspension comprise: pseudomonas aeruginosa, klebsiella pneumoniae, staphylococcus aureus, escherichia coli, pseudomonas putida, enterobacter aerogenes, and Alcaligenes faecalis;

the residual bacteria detection method comprises the following steps: spreading the sample to be tested on a pancreatic protein soybean agar medium by using a sterile cotton swab, placing the sample into a constant temperature incubator for culturing for 3 days at 35 ℃, observing the growth condition of a bacterial colony and counting scores according to a table 1;

TABLE 1

Score value	Colony count/plate	Description of pollution conditions
			0	No growth	No pollution
1	1-9	Trace contamination
			2	10-99	Slight contamination
3	100-300	Moderate contamination
			4	Greater than 300	Severe contamination

Evaluation of results: the residual bacteria result scores of 0 and 1 are good in effect and pass through; scores of 2, 3 and 4 were poor in effect and failed. And comprehensively evaluating the final result by combining the detection results for 4 times.

(2) EUH208 label

In use, if a EUH208 label needs to be added, it is marked as "label", and if a EUH208 label does not need to be added, it is marked as "none".

(3) Yellowing resistance

Aqueous polyurethane emulsion: 5 g of test specimens containing the preservative compositions provided in examples 1 to 8 and comparative examples 1 to 3 were poured into a disposable plastic plate having a diameter of 6 cm, placed in a 50℃oven for 2 days, and the color of the dry film was observed. The test sample color was compared to a blank control (blank sample without preservative composition) and the yellowing grade was evaluated. "-" means consistent with the blank, with no macroscopic distinction; "±" means slight yellowing; "+" indicates a significant yellowing; "++" indicates severe yellowing.

The specific test results are shown in table 2:

TABLE 2

As can be seen from Table 2, the preservative composition provided by the invention has an excellent preservative effect on aqueous industrial products by compounding the phenoxyethanol, the bronitol and the polyalcohol with specific contents, has no allergic substances, does not need to be added with EUH labels, and enables the system to resist yellowing. From examples 1 to 3, it is known that the preservative composition provided by the invention has the advantages that the using amount of the preservative is within the range of 0.2 to 0.5% in a specific proportion by phenoxyethanol, bronitol and polyalcohol, the test score of the preservative effect is 0 to 1, the challenge test is passed, the preservative effect is good, the EUH label does not need to be added, and the yellowing resistance is good.

As is clear from comparison of examples 1 and 2 with example 3, when the ratio of phenoxyethanol to bronopol is not within the range of (15-35): 1, the preservative is slightly inferior in effect when the amount of the preservative is small; however, when the amount is large, yellowing of the system occurs.

As is clear from comparison of examples 1 to 3 with example 4, when the phenoxyethanol content is lower than the preferred range of the present invention, the overall preservative effect is deteriorated and yellowing occurs. As is evident from a comparison of example 1 with example 5, the preservative performance is poor when the bronopol content is reduced.

As is clear from comparison of examples 1 with examples 6 and 8, the corrosion resistance is slightly inferior without polyol or when the number of carbon atoms of polyol is less than 5; and comparing example 7 with example 1, replacing a small amount of water with polyol, the antiseptic effect is not obviously improved, the viscosity of the product is slightly higher, the production and the addition are inconvenient, and the cost advantage is not generated.

As is clear from the comparison between example 3 and comparative example 1, when the content of bronopol in the preservative composition is too large, the content of preservative in the aqueous polyurethane emulsion is too small, the preservative effect cannot be achieved, and the system is easy to yellow when the usage amount is increased to achieve the preservative effect. Compared with comparative example 2 (0.067% of additive amount), the aqueous polyurethane emulsion of the two schemes has the content of bromonitroalcohol of 200ppm, only bromonitroalcohol in the system has poor anti-corrosion effect and yellowing, and the whole anti-corrosion effect of the embodiment 1 of the invention is good, no yellowing exists, which indicates that other components provide good synergistic effect and are helpful for improving the yellowing.

As is evident from the comparison of examples 1 to 3 with comparative example 3, the active ingredients chloromethylisothiazolinone and methylisothiazolinone mixture were limited to 1.5ppm at EUH 208. When the addition amount is 0.15% of the typical value, the content of the active ingredient in the aqueous polyurethane emulsion is 22.5ppm, the anti-corrosion effect is good, but EUH208 sensitized labels must be added; when the addition amount is 0.01%, the content of the active ingredient in the aqueous polyurethane emulsion is 1.5ppm, a sensitized tag can be omitted, but the anti-corrosion effect is poor, and enough protection cannot be provided for an emulsion system.

In summary, the preservative composition provided by the invention is synergistic by mutually matching phenoxyethanol, bronopol and polyalcohol, so that the preservative can not only meet the preservative requirement without adding EUH label, but also improve the yellowing problem, and has the advantages of simple components and low cost.

While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.

Claims

1. A preservative composition, characterized in that the preservative composition comprises, in mass percent, 50-95% phenoxyethanol and 1-10% bronopol.

2. A preservative composition according to claim 1, characterized in that the preservative composition further comprises, in mass percent, 1-30% of a polyol.

3. A preservative composition according to claim 1 or 2, characterized in that the preservative composition further comprises water;

preferably, the preservative composition comprises 84 to 95% of phenoxyethanol, 3 to 10% of bronopol, 1 to 5% of polyol and the balance of water in percentage by mass.

4. A preservative composition according to any one of claims 1 to 3, wherein the mass ratio of phenoxyethanol to bronopol in the preservative composition is (15 to 35): 1.

5. A preservative composition according to claim 2 or 3, wherein the number of carbon atoms in the polyol is not less than 5;

preferably, the polyol comprises a C5 to C10 polyol;

6. A process for preparing a preservative composition according to any one of claims 1 to 5, characterized in that the process comprises the steps of:

and mixing phenoxyethanol and bronopol to obtain the preservative composition.

7. The method of claim 6, wherein the mixed materials further comprise a polyol and/or water;

preferably, the mixing time is 2-4 hours;

preferably, the temperature of the mixing is 30-40 ℃.

8. A preservative comprising the preservative composition according to any one of claims 1 to 5.

9. Use of a preservative composition according to any one of claims 1 to 5 and/or a preservative according to claim 8 in an aqueous industrial product.

10. The use according to claim 9, characterized in that the preservative composition is present in the aqueous industrial product in a mass percentage of 0.2-1.5%.