A preservative composition, its preparation method and use

Abstract

The application 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 percentage. The preparation method of the preservative composition comprises: mixing phenoxyethanol and bronopol to obtain the preservative composition. The preservative composition provided by the application can not only avoid allergic reactions, but also has excellent preservative effect and anti-yellowing effect, and is especially suitable for water-based industrial products.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of chemical bactericidal preservatives, and particularly relates to a preservative composition and a preparation method and use thereof. BACKGROUND

[0002] Water-based coatings, emulsions, building materials and other industrial products contain water and other nutrients, which are conducive to the growth of microorganisms. In order to protect water-based products from spoilage caused by microorganisms and ensure that the products have sufficient shelf life, preservatives need to be added. The commonly used preservatives in these industrial products are mainly isothiazolinone products.

[0003] For example, CN111226950A discloses a preservative and a preparation method thereof, the preservative comprising a preservative active substance, methylisothiazolinone, a stabilizer, and the balance being water; by adding the preservative active substance and the stabilizer, the stability of the preservative can be improved. However, the dosage of the preservative should not be too large, otherwise sensitization, irritation and other reactions may occur.

[0004] CN113199579A discloses a colorless water-borne multifunctional wood preservative and a preparation and use method thereof, the preservative being formed by mixing triazole fungicides, iodopropynyl butylcarbamate, isothiazolinone fungicides and pyrethroid as active ingredients, with organic solvents, cosolvents and surfactants; the preservative can use water as a carrier, the preparation is more stable, and the treated wood maintains the original color and good appearance, can fully penetrate into the wood, and effectively prevents and controls the damage of decay fungi, molds, discoloration fungi, borers, termites and the like to the wood. CN108294018A discloses a composite preservative comprising isothiazolinone, potassium sorbate, polyoxyethylene castor oil, an antioxidant, and the balance being water. The composite preservative is economical and practical, has low toxicity, and has little potential danger to users and the environment. However, due to the presence of isothiazolinone, when the dosage of the preservative is too large, there may be a risk of sensitization.

[0005] A common defect in the prior art is that the European Union has concerns about skin irritation and sensitization of isothiazolinone components, and products with isothiazolinone component content exceeding the limit value of each component must be labeled with EUH208 (contains a sensitizing component, which may cause an allergic reaction) to remind consumers to be cautious. In order to avoid the EUH208 label, manufacturers 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 preservative effect cannot be achieved.

[0006] Therefore, it is an urgent problem in the art to develop a preservative that has no sensitization reaction and excellent preservative effect. SUMMARY

[0007] In view of the deficiencies of the prior art, the present application aims to provide a preservative composition, a preparation method and application thereof.The preservative composition is prepared by compounding phenoxyethanol and bronopol, which can not only avoid allergic reactions, but also has excellent preservative effect and anti-yellowing effect, and is particularly suitable for water-based industrial products.

[0008] To achieve the above object, the present application adopts the following technical solutions:

[0009] In a first aspect, the present application provides a preservative composition, which comprises 50-95% phenoxyethanol and 1-10% bronopol by mass percentage.

[0010] The preservative composition provided by the present application is prepared by compounding phenoxyethanol and bronopol in specific amounts, which avoids the introduction of isothiazolinone components and reduces the risk of sensitization; and through the synergistic effect between the components, the preservative has good preservative effect and anti-yellowing effect.

[0011] Preferably, the preservative composition comprises 50-95% phenoxyethanol by mass percentage, for example, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 74%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, etc.

[0012] In the present application, too little phenoxyethanol cannot achieve the preservative effect, and too much phenoxyethanol will reduce the amount of other preservative components, resulting in poor overall preservative effect.

[0013] Preferably, the preservative composition comprises 1-10% bronopol by mass percentage, 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.

[0014] In the present application, too little bronopol cannot achieve the preservative requirement, and too much bronopol can easily cause yellowing of the system.

[0015] Preferably, the preservative composition further comprises 1-30% polyol by mass percentage, 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.

[0016] In the present application, the polyol can assist in synergistic effect, further improve the preservative effect by compounding with phenoxyethanol and bronopol; if the amount of the polyol is too much, the other active ingredients are correspondingly reduced, and the overall preservative effect is poor.

[0017] Preferably, the preservative composition further comprises water.

[0018] In the present application, by controlling the content of water, the viscosity of the preservative can be adjusted, which is more convenient for downstream product addition and use.

[0019] As a preferred technical solution of the present application, the preservative composition comprises 84-95% phenoxyethanol, 3-10% bronopol, 1-5% polyol, and the balance is water.

[0020] Preferably, the mass ratio of phenoxyethanol to bronopol in the preservative composition is (15-35):1, for example, it can be 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.

[0021] Preferably, the number of carbon atoms in the polyol is ≥5, for example, it can be 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, etc.

[0022] Preferably, the polyol comprises C5-C10 polyol, for example, it can be C5, C6, C7, C8, C9, C10, etc., and exemplarily includes but is not limited to pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, etc.

[0023] 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.

[0024] In the present application, when the number of carbon atoms in the polyol is greater than 5, it has a synergistic effect on phenoxyethanol and bronopol, and when the number of carbon atoms is less than 5, it has little contribution to the preservative and is only used as a solvent.

[0025] Preferably, the polyol comprises any one or a combination of at least two of 1,2-pentanediol, 1,2-hexanediol or 1,2-octanediol.

[0026] In a second aspect, the present application provides a preparation method of the preservative composition according to the first aspect, the preparation method comprising the following steps:

[0027] Mixing phenoxyethanol and bronopol to obtain the preservative composition.

[0028] Preferably, the mixed material further comprises a polyol and / or water.

[0029] Preferably, the mixing time is 2-4h, for example, 2h, 3h, 4h, etc.

[0030] Preferably, the mixing temperature is 30-40℃, for example, 32℃, 34℃, 36℃, 38℃, etc.

[0031] In a third aspect, the present application provides a preservative comprising the preservative composition according to the first aspect.

[0032] In a fourth aspect, the present application provides an application of the preservative composition according to the first aspect and / or the preservative according to the third aspect in an aqueous industrial product.

[0033] The aqueous industrial product comprises any one of an aqueous coating, an aqueous emulsion or an aqueous slurry.

[0034] Preferably, the mass percentage of the preservative composition in the aqueous industrial product is 0.2-1.5%, for example, 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 0.5-1.0%.

[0035] In the present application, the mass percentage of the preservative composition is within 0.2-1.5%, which can achieve the required preservative effect. Different products have different susceptibility to microorganisms, different required shelf life, and different optimal preservative addition amount.

[0036] The numerical range in the present application not only includes the point values listed above, but also includes any point values between the above numerical ranges that are not listed. Due to the limited space and for the sake of simplicity, the present application does not exhaustively list the specific point values included in the range.

[0037] Compared with the prior art, the present application has the following beneficial effects:

[0038] The preservative provided by the present application is compounded by phenoxyethanol and bronopol, so that the preservative is less likely to cause allergic reactions, is more mild, and has excellent preservative effect. After mixing the bacteria suspension for the fourth time for 7 days, the bacterial content is ≤9 / plate, the anti-microbial contamination ability is strong, and the system does not yellow. DETAILED DESCRIPTION

[0039] The technical solutions of the present application are further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations on the present application.

[0040] Embodiment 1

[0041] The present embodiment provides a preservative composition, which comprises 90% phenoxyethanol, 4% bronopol, 5% 1,2-hexanediol, and the balance is water in mass percentage.

[0042] The present embodiment provides a preparation method of the preservative composition, and the specific steps include:

[0043] Phenoxyethanol, bronopol, 1,2-hexanediol and water are mixed at 40°C for 2 hours to obtain the preservative composition.

[0044] Embodiment 2

[0045] The present embodiment provides a preservative composition, which comprises 95% phenoxyethanol, 3% bronopol, 1% 1,2-octanediol, and the balance is water in mass percentage.

[0046] The present embodiment provides a preparation method of the preservative composition, and the specific steps are the same as those in Embodiment 1.

[0047] Embodiment 3

[0048] The present embodiment provides a preservative composition, which comprises 84% phenoxyethanol, 10% bronopol, 1% 1,2-pentanediol, and the balance is water in mass percentage.

[0049] The present embodiment provides a preparation method of the preservative composition, and the specific steps are the same as those in Embodiment 1.

[0050] Embodiment 4

[0051] The present embodiment provides a preservative composition, which comprises 50% phenoxyethanol, 10% bronopol, 20% 1,2-hexanediol, 10% 1,2-octanediol, and the balance is water in mass percentage.

[0052] The present embodiment provides a preparation method of the preservative composition, and the specific steps are the same as those in Embodiment 1.

[0053] Embodiment 5

[0054] The present embodiment provides a preservative composition, which is different from Embodiment 1 only in that the mass percentage of bronopol in the preservative composition is 2%, and the balance is made up with water, and the other components and amounts are the same as those in Embodiment 1.

[0055] The present example provides a preparation method of the preservative composition, and the specific steps are the same as those of Example 1.

[0056] Example 6

[0057] The present example provides a preservative composition, which is different from Example 1 only in that 1,2-hexanediol is not used, and the rest is made up with water, and the other components and amounts are the same as those of Example 1.

[0058] The present example provides a preparation method of the preservative composition, and the specific steps are the same as those of Example 1.

[0059] Example 7

[0060] The present example provides a preservative composition, which includes 90% phenoxyethanol, 4% bronopol and 6% 1,2-hexanediol by mass percentage.

[0061] The present example provides a preparation method of the preservative composition, and the specific steps are the same as those of Example 1.

[0062] Example 8

[0063] The present example provides a preservative composition, which is different from Example 1 only in that 1,2-hexanediol is replaced with 1,2-propanediol of the same weight, and the other components and amounts are the same as those of Example 1.

[0064] The present example provides a preparation method of the preservative composition, and the specific steps are the same as those of Example 1.

[0065] Comparative Example 1

[0066] The present comparative example provides a preservative composition, which is different from Example 3 only in that the mass percentage of bronopol in the preservative composition is 15%, and there is no water, and the other components and amounts are the same as those of Example 3.

[0067] The present comparative example provides a preparation method of the preservative composition, and the specific steps are the same as those of Example 3.

[0068] Comparative Example 2

[0069] The present comparative example provides a preservative composition, which is Coatpro 679, and the active ingredient is 30% bronopol.

[0070] Comparative Example 3

[0071] The comparative example provides a preservative composition, which is Coatpro 610, the active ingredient is a mixture of 1.5% chloromethylisothiazolinone and methylisothiazolinone, and the mass ratio of the chloromethylisothiazolinone and methylisothiazolinone is 3:1.

[0072] Performance test

[0073] (1) Preservative performance

[0074] The preservative compositions provided by Examples 1-8 and Comparative Examples 1-3 are mixed with water-based polyurethane emulsion, and 28 days of 4-time inoculation challenge is carried out according to GB / T 30792-2014 Test Method for Resistance to Microbial Infestation of Water-borne Coatings in Cans. The mixed bacterial suspension is inoculated on the 0th day, 7th day, 14th day and 21st day of the experiment, respectively, stirred uniformly, and placed at room temperature for a certain period of time. The content of residual bacteria is detected on the 2nd day and 7th day (before inoculation of the mixed bacterial suspension) after each inoculation of the mixed bacterial suspension, respectively;

[0075] Among them, the strains contained in the mixed bacterial suspension include Pseudomonas aeruginosa, Klebsiella pneumoniae, Staphylococcus aureus, Escherichia coli, Pseudomonas putida, Enterobacter aerogenes, and Alcaligenes faecalis;

[0076] Residual bacteria detection method: use a sterile cotton swab to spread the sample to be tested on a tryptic soy agar culture medium, and place it in a constant temperature incubator at 35°C for 3 days. Observe the growth of bacterial colonies and count the score according to Table 1;

[0077] Table 1

[0078] Score Colony count / plate Description of contamination 0 No growth No contamination 1 1-9 Trace contamination 2 10-99 Slight contamination 3 100-300 Moderate contamination 4 >300 Heavy contamination

[0079] Result evaluation: the residual bacteria result score of 0 and 1 is good and passes; the score of 2, 3 and 4 is not good and does not pass. The final result is comprehensively evaluated according to the results of 4-time detection.

[0080] (2) EUH 208 label

[0081] When using, if it is necessary to add the EUH 208 label, mark it as “label”, and if it is not necessary to add the EUH 208 label, mark it as “none”.

[0082] (3) Yellowing resistance performance

[0083] Waterborne polyurethane emulsion: 5 grams of the test sample containing the preservative composition provided in Examples 1-8 and Comparative Examples 1-3 was poured into a disposable plastic flat dish with a diameter of 6 cm, and placed in a 50°C oven for 2 days, and the color of the dry film was observed. The color of the test sample was compared with that of a blank control sample (a blank sample without the preservative composition), and the yellowing grade was evaluated. "-" means consistent with the blank sample, with no visible difference; "+" means slight yellowing; "+" means obvious yellowing; and "++" means severe yellowing.

[0084] The specific test results are shown in Table 2:

[0085] Table 2

[0086]

[0087] As can be seen from Table 2, the preservative composition provided by the present application, by compounding phenoxyethanol, bronopol and polyol in specific amounts, has excellent preservative effect on water-based industrial products, and does not contain allergenic substances, does not need to add the EUH 208 label, and makes the system resistant to yellowing. As can be seen from Examples 1-3, the preservative composition provided by the present application, by compounding phenoxyethanol, bronopol and polyol in specific proportions, the preservative amount is in the range of 0.2-0.5%, the preservative effect test score is 0-1, the challenge test is passed, the preservative effect is good, the EUH 208 label is not needed, and the yellowing resistance is good.

[0088] As can be seen by comparing Examples 1 and 2 with Example 3, when the ratio of phenoxyethanol to bronopol is not in the range of (15-35):1, the preservative effect is slightly worse when the amount of the preservative is small; but when the amount is large, the system will yellow.

[0089] As can be seen by comparing Examples 1-3 with Example 4, when the content of phenoxyethanol is lower than the preferred range of the present application, the overall preservative effect is poor and yellowing occurs. As can be seen by comparing Example 1 with Example 5, when the content of bronopol is reduced, the preservative performance is poor.

[0090] As can be seen by comparing Example 1 with Examples 6 and 8, when there is no polyol or the number of carbon atoms of the polyol is less than 5, the preservative performance is slightly poor; and by comparing Example 7 with Example 1, a small amount of water is replaced by polyol, the preservative effect is not significantly improved, the viscosity of the product is slightly high, production is not convenient, and there is no cost advantage.

[0091] It can be seen from the comparison of Example 3 and Comparative Example 1 that when the content of bronopol in the preservative composition is too much, the content of the preservative in the waterborne polyurethane emulsion is too little, the preservative effect cannot be achieved, the use amount is increased to achieve the preservative effect, and the system is prone to yellowing. By comparing Example 1 and Comparative Example 2 (0.067% addition amount), the content of bronopol in the waterborne polyurethane emulsion of the two schemes is 200 ppm, there is only bronopol in the system, the preservative effect is poor, and yellowing occurs. The overall preservative effect of Example 1 of the present application is good, and there is no yellowing, which indicates that the other ingredients provide good synergistic effect, and help to improve yellowing.

[0092] It can be seen from the comparison of Examples 1-3 and Comparative Example 3 that the active ingredient chloromethylisothiazolinone and the mixture of methylisothiazolinone in EUH208 is limited to 1.5 ppm. When the addition amount is a typical value of 0.15%, the content of the active ingredient in the waterborne polyurethane emulsion is 22.5 ppm, the preservative effect is good, but a sensitization label of EUH208 must be added; when the addition amount is 0.01%, the content of the active ingredient in the waterborne polyurethane emulsion is the limit value of 1.5 ppm, and no sensitization label is required, but the preservative effect is poor and cannot provide sufficient protection for the emulsion system.

[0093] In summary, the preservative composition provided by the present application, through the mutual cooperation of phenoxyethanol, bronopol and polyol, synergistic effect, so that the preservative does not need to add EUH208 label, and can meet the preservative requirements, improve the yellowing problem, and the components are simple and the cost is low.

[0094] The above specific embodiments further illustrate the purpose, technical solutions and beneficial effects of the present application. It should be understood that the above description is only a specific embodiment of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A preservative composition, characterized by, The preservative composition comprises 50-95% of phenoxyethanol and 1-10% of bronopol by mass percentage; The mass ratio of phenoxyethanol to bronopol in the preservative composition is (15-35):

1.

2. The preservative composition according to claim 1, characterized in that, The preservative composition further comprises 1-30% of polyol by mass percentage.

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

4. The preservative composition according to claim 1 or 2, characterized in that, The preservative composition comprises 84-95% of phenoxyethanol, 3-10% of bronopol, 1-5% of polyol by mass percentage, and the balance is water.

5. The preservative composition according to claim 1 or 2, characterized in that, The polyol has a carbon number ≥5.

6. The preservative composition according to claim 1 or 2, characterized in that, The polyol comprises C5-C10 polyol.

7. The preservative composition according to claim 1 or 2, characterized in that, 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.

8. A method for the preparation of a preservative composition according to any one of claims 1 to 7, characterized in that, The preparation method comprises the following steps: Mixing phenoxyethanol and bronopol to obtain the preservative composition.

9. The production method according to claim 8, characterized by, The mixed material further comprises polyol and / or water.

10. The preparation method according to claim 8, characterized in that, The mixing time is 2-4h.

11. The preparation method according to claim 8, characterized in that, The mixing temperature is 30-40℃.

12. A preservative characterized in that, The preservative comprises the preservative composition according to any one of claims 1-5.

13. Use of the preservative composition according to any one of claims 1-7 and / or the preservative according to claim 12 in an aqueous industrial product.

14. Use according to claim 13, characterized in that, The mass percentage of the preservative composition in the aqueous industrial product is 0.2-1.5%.

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