CN103875656A - Solution stabilization additive, isothiazolinone-containing composition solution capable of using by direct dilution and application thereof - Google Patents
Solution stabilization additive, isothiazolinone-containing composition solution capable of using by direct dilution and application thereof Download PDFInfo
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Abstract
The invention discloses a solution stabilization additive, an isothiazolinone-containing composition solution capable of being used by direct dilution and application thereof. The isothiazolinone-containing composition solution capable of being used by direct dilution comprises 0.5 to 20% by weight of an isothiazolone derivative, 5 to 15% by weight of the solution stabilization additive and the balance of a solvent, wherein the isothiazolone derivative is a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, and the solution stabilization additive comprises 2-bromo-2-nitro 1, 3-propylene glycol, a magnesium salt and at least one substance selected from the group consisting of poly epoxy succinate sodium, sodium diacetate, sodium glycinate, sodium tartrate and sodium malate. The isothiazolinone-containing composition solution contains no formaldehyde, methanol and copper ions, is environment friendly, and completely avoids the corrosion of the copper ions on system equipment; the isothiazolinone-containing composition solution as a bactericide is rapid in bactericidal rate, strong in antibacterial ability, long in effect time and better in stability, can be used by direct dilution, and is convenient for users to use and lower in cost.
Description
Technical field
The invention relates to composition solution and the application thereof of a kind of solution-stabilized auxiliary agent, isothiazolone-containing.
Background technology
Use isothiazoline-3-ketone can control the microbial growth in industrial environment (metal fluid, the cooling water in cooling tower, emulsion, plastic foil etc.), by adding system stability agent to make isothiazoline-3-ketone obtain long-term bactericidal activity.Although the chemicals of formaldehyde or release formaldehyde is common system stability agent, its volatility, high temperature degradation, the higher feature such as expense, difficult and potential toxicity, preferably avoid using.Typical system stability agent also has nitrate, and for example, isothiazolinone derivatives---CMIT/MIT mixture is as the Biocidal algae-killing agent of industrial circulating cooling water, and commodity concentration is 1.5%, conventionally in formula, needs to add 2～4 ‰ copper nitrates as stabilizing agent,
US3,870,795 and US4,067,878 explanation adds nitrous acid slaine or nitric acid slaine to stablize the degraded of isothiazolinone with chemically resistant material, but other common slaine, comprise carbonate, sulphate, chlorate, perchlorate and chloride are stablized the solution effect of isothiazolinone not as nitrous acid slaine or nitric acid slaine.Use mantoquita to be as the problem of stabilizing agent existence, (1) copper has potentiality etching problem, can cause the electrochemical corrosion of system metallic recuperator to occur; (2) while use, can cause breakdown of emulsion in the product such as emulsion, cutting fluid; (3) in printing and dyeing, dyeing and finishing technology, use and can produce flaw; (4) while use, can produce " salt bunch " phenomenon in water paint, cause producing defective; (5) copper ion is heavy metal, is discharged in environment and can causes pollution.
Summary of the invention
One of object of the present invention is for the deficiencies in the prior art, and a kind of solution-stabilized auxiliary agent that is different from prior art, does not particularly contain mantoquita and other heavy metal is provided.
Two of object of the present invention is to provide a kind of composition solution of isothiazolone-containing, and said composition solution is longer than the prior art stable existence time due to above-mentioned solution-stabilized auxiliary agent, not copper ions, can directly dilute use.
Three of object of the present invention is to provide and is applied to the method in industrial circle using the composition solution of isothiazolone-containing as bactericide.
Inventor finds through great many of experiments, when with the bromo-2-of 2-nitro-1, ammediol (BNP) and at least one special auxiliary agent, join in the bactericide original liquid product of isothiazolone-containing during with special ratios, needn't add again the inorganic mantoquita of divalence as stabilizing agent, can obtain the composition solution of stable isothiazolone-containing, its effect is better than the effect taking mantoquita as stabilizing agent, and bactericidal effect is good.Based on this, form the present invention.
Therefore, solution-stabilized auxiliary agent provided by the invention, it is characterized in that by 2-bromine 2-nitro-1,3-propylene glycol, magnesium salts and be selected from polyepoxy sodium succinate, sodium Diacetate, Sodium Glycinate, sodium tartrate and natrium malicum at least one form.
The composition solution that can directly dilute the isothiazolone-containing of use provided by the invention, it is characterized in that the isothiazolinone derivatives that said composition contains 0.5～20% weight, the solution-stabilized auxiliary agent of 5～15% weight and the solvent of surplus, wherein, said isothiazolinone derivatives is the mixture of CMIT and MIT, said solution-stabilized auxiliary agent is by 2-bromine 2-nitro-1, ammediol, magnesium salts be selected from polyepoxy sodium succinate, sodium Diacetate, Sodium Glycinate, the mixture of at least one composition in sodium tartrate and natrium malicum, said solvent is selected from water, dipropylene glycol or polyethylene glycol.
The above-mentioned composition solution that can directly dilute the isothiazolone-containing of use provided by the invention, can better be applied to the field that the easy breakdown of emulsion such as coating, cosmetics, latex product maybe cannot use heavy metal ion, and color is required to high field, as industries such as weaving, papermaking, cosmetics, brightening agents.The composition solution of said isothiazolone-containing can be used as bactericide for Treatment of Industrial Water, coating, paint, washing agent, ink, textile dyeing and finishing, papermaking, brightening agent, latex product, cosmetic field.When it is for Treatment of Industrial Water, bactericide injected volume is counted 0.2～10 milligram/every liter water for industrial use, preferred 0.5～2 milligram/every liter water for industrial use with isothiazolinone derivatives weight wherein.
Feature of the present invention is:
(1) composition solution that can directly dilute the isothiazolone-containing of use provided by the invention, containing formaldehyde, methyl alcohol,, containing heavy metal, particularly copper ions not, has not thoroughly stopped the corrosion of copper ion to system equipment, environmental protection more.
(2) can avoid demulsifying phenomenon in product emulsion production process to produce, avoid flaw in papermaking, dyeing and finishing process to occur.
(3) product stability is better, and sterilization speed is fast, and bacteriostasis is stronger, and action time is more of a specified duration.
(4) composition solution of isothiazolone-containing can directly dilute use, can directly running water be added stoste just can obtain formulation product, without deionized water, does not also need to add any stabilizing agent, and more convenient user uses, and use cost is lower.
Embodiment
Solution-stabilized auxiliary agent provided by the invention, it is characterized in that by 2-bromine 2-nitro-1,3-propylene glycol, magnesium salts and be selected from polyepoxy sodium succinate, sodium Diacetate, Sodium Glycinate, sodium tartrate and natrium malicum at least one form.Preferably, in the said solution-stabilized auxiliary agent of the present invention, said 2-bromine 2-nitro-1,3-propylene glycol is in 1 part of weight, and at least one parts by weight that are selected from polyepoxy sodium succinate, sodium Diacetate, Sodium Glycinate, sodium tartrate and natrium malicum are 0.2～5 part; More preferably, said 2-bromine 2-nitro-1,3-propylene glycol is 1 with at least one the parts by weight ratio being selected from polyepoxy sodium succinate, sodium Diacetate, Sodium Glycinate, sodium tartrate and natrium malicum: (0.8～2.0); Most preferably, said 2-bromine 2-nitro-1,3-propylene glycol is 1 with at least one the parts by weight ratio being selected from polyepoxy sodium succinate, sodium Diacetate, Sodium Glycinate, sodium tartrate and natrium malicum: (0.95～1.1).Magnesium salts accounts for 40～60 % by weight of said auxiliary agent, and said magnesium salts is generally magnesium chloride and/or magnesium nitrate.
In preferred embodiment of the present invention, said solution-stabilized auxiliary agent contains 2-bromine 2-nitro-1, ammediol, magnesium salts and sodium Diacetate, can be only by 2-bromine 2-nitro-1, ammediol, magnesium salts and sodium Diacetate composition, also can be except 2-bromine 2-nitro-1,3-propylene glycol, magnesium salts and sodium Diacetate, also contain one or more in Sodium Glycinate, sodium tartrate and natrium malicum.
In a preferred embodiment of the present invention, said solution-stabilized auxiliary agent is by 2-bromine 2-nitro-1, ammediol, magnesium salts and sodium Diacetate composition, wherein 2-bromine 2-nitro-1, the parts by weight ratio of ammediol and sodium Diacetate is 0.95～1.05:1, and magnesium salts accounts for 48～52 % by weight of this more preferred auxiliary agent.Said magnesium salts dawn known to those skilled in the art, be conventionally selected from magnesium chloride and/or magnesium nitrate.
Solution-stabilized auxiliary agent provided by the invention, its preparation process there is no special feature, is well known to those skilled in the art, and mixes no longer numerous stating by simple each component according to the proportioning of auxiliary agent.
The present invention also provides a kind of composition solution that can directly dilute the isothiazolone-containing of use, the isothiazolinone derivatives that said composition solution contains 0.5～20% weight, the solution-stabilized auxiliary agent of 5～15% weight and the solvent of surplus.Wherein, said isothiazolinone derivatives is the mixture of CMIT and MIT; Said solution-stabilized auxiliary agent is 2-bromine 2-nitro-1,3-propylene glycol and at least one and the mixture of magnesium salts that are selected from polyepoxy sodium succinate, sodium Diacetate, Sodium Glycinate, sodium tartrate and natrium malicum; Said magnesium salts is selected from magnesium chloride and/or magnesium nitrate; Said solvent is selected from water, dipropylene glycol or polyethylene glycol.
In the said composition solution of isothiazolone-containing that can directly dilute use, said isothiazolinone derivatives, the preferred weight ratio of its CMIT and MIT is 2～4:1, and preferred part by weight is 3:1.
In the said composition solution of isothiazolone-containing that can directly dilute use, said solution-stabilized auxiliary agent is preferably by 2-bromine 2-nitro-1, ammediol, magnesium salts and sodium Diacetate composition, wherein, said 2-bromine 2-nitro-1, ammediol weight is 1 part of meter, and the weight of sodium Diacetate is 0.2～5 part, and magnesium salts accounts for 40～60 % by weight of said auxiliary agent.
In a preferred embodiment of the composition solution that can directly dilute the isothiazolone-containing of use of the present invention, the isothiazolinone derivatives that contains 1.5～15% weight, the solution-stabilized auxiliary agent of 9～11% weight and the solvent of surplus, wherein, said isothiazolinone derivatives is that ratio is the CMIT of 3:1 and the mixture of MIT, in said solution-stabilized auxiliary agent, 2-bromine 2-nitro-1, ammediol is in 1 part, the weight of sodium Diacetate is 0.95～1.05 part, magnesium salts accounts for 48～52% of solution-stabilized auxiliary agent, said solvent is water.At this moment, the stability of said composition solution and fungicidal effectiveness are more excellent.
In the composition solution of isothiazolone-containing that can directly dilute use provided by the invention, said solvent is selected from water, dipropylene glycol or polyethylene glycol.Wherein the specification of said polyethylene glycol is preferably 400.From cost-effective angle, in the composition solution of isothiazolone-containing provided by the invention, said solvent preferred water.
The most preferred embodiment for the composition solution that can directly dilute the isothiazolone-containing of use provided by the invention, the isothiazolinone derivatives that contains 12% weight, the solution-stabilized auxiliary agent of 10% weight and the solvent of surplus, wherein, said isothiazolinone derivatives is that part by weight is the CMIT of 3:1 and the mixture of MIT, in said solution-stabilized auxiliary agent, the bromo-2-of 2-nitro-1, the part by weight of ammediol and sodium Diacetate is 1:1, magnesium salts is magnesium nitrate and/or magnesium chloride, account for 49～51 % by weight of solution-stabilized auxiliary agent.The number of days that the composition solution of this most preferred embodiment produces precipitation at 55 DEG C is 70 days.
The composition solution that can directly dilute the isothiazolone-containing of use provided by the invention, its preparation process there is no special feature, be well known to those skilled in the art, according to the proportioning of composition, each component of said composition simply mixed under the existence of solvent to no longer numerous stating.
Below by embodiment, the invention will be further described, but not thereby limiting the invention.
In an embodiment, 2-bromine 2-nitro-1,3-propylene glycol is Yan Lin chemical plant, Taicang City, Jiangsu Province product, purity 99%; Polyepoxy sodium succinate (PESA) is Shandong Rui Aite Chemical Co., Ltd. product, solid content 40%; Sodium Glycinate is the special reagent of Chengdu bass Co., Ltd product, purity > 98%; Sodium tartrate is Beijing coupling Science and Technology Ltd. product, purity > 98%; Natrium malicum is lark prestige Science and Technology Ltd. product, purity > 99%; Sodium Diacetate is the abundant Chemical Co., Ltd. in Shanghai, purity > 98%; Polyethylene glycol specification is PEG-400.
Embodiment 1～10
Embodiment 1～10 explanation solution-stabilized auxiliary agent provided by the invention, the proportioning of each auxiliary agent is in table 1.
Table 1
Embodiment 11
The present embodiment illustrates the composition solution of isothiazolone-containing provided by the invention.
The composition solution of the isothiazolone-containing of the present embodiment is by isothiazolinone derivatives (the part by weight 2.55:1 of CMIT and MIT), the solution-stabilized auxiliary agent A of 10% weight and the water of 75.8 % by weight of 14.2% weight.Numbering Y1
Embodiment 12
The present embodiment illustrates the composition solution of isothiazolone-containing provided by the invention.
The composition solution of the isothiazolone-containing of the present embodiment is by isothiazolinone derivatives (the part by weight 3:1 of CMIT and MIT), the solution-stabilized auxiliary agent B of 10% weight and the water of 78 % by weight of 12% weight.Numbering Y2.
Embodiment 13
The present embodiment illustrates the composition solution of isothiazolone-containing provided by the invention.
The composition solution of the isothiazolone-containing of the present embodiment is by the isothiazolinone derivatives (the part by weight 3:1 of CMIT and MIT) of 2.0% weight, the solution-stabilized auxiliary agent C of 10% weight and the water of 88 % by weight.Numbering Y3.
Embodiment 14
The present embodiment illustrates the composition solution of isothiazolone-containing provided by the invention.
The composition solution of the isothiazolone-containing of the present embodiment is by the isothiazolinone derivatives (the part by weight 3:1 of CMIT and MIT) of 8.0% weight, the solution-stabilized auxiliary agent D of 10% weight and the water of 82 % by weight.Numbering Y4.
Embodiment 15
The present embodiment illustrates the composition solution of isothiazolone-containing provided by the invention.
The composition solution of the isothiazolone-containing of the present embodiment is by the isothiazolinone derivatives (the part by weight 3:1 of CMIT and MIT) of 10% weight, the solution-stabilized auxiliary agent E of 10% weight and the water of 80 % by weight.Numbering Y5.
Embodiment 16
The present embodiment illustrates the composition solution of isothiazolone-containing provided by the invention.
The composition solution of the isothiazolone-containing of the present embodiment is by the isothiazolinone derivatives (the part by weight 3:1 of CMIT and MIT) of 11.2% weight, the solution-stabilized auxiliary agent F of 10% weight and the water of 78.8 % by weight.Numbering Y6.
Embodiment 17
The present embodiment illustrates the composition solution of isothiazolone-containing provided by the invention.
The composition solution of the isothiazolone-containing of the present embodiment is by the isothiazolinone derivatives (the part by weight 3:1 of CMIT and MIT) of 12% weight, the solution-stabilized auxiliary agent G of 10% weight and the water of 78 % by weight.Numbering Y7.
Embodiment 18
The present embodiment illustrates the composition solution of isothiazolone-containing provided by the invention.
The composition solution of the isothiazolone-containing of the present embodiment is by the isothiazolinone derivatives (the part by weight 3:1 of CMIT and MIT) of 12% weight, the solution-stabilized auxiliary agent H of 10% weight and the polyethylene glycol of 78 % by weight.Numbering Y8.
Embodiment 19
The present embodiment illustrates the composition solution of isothiazolone-containing provided by the invention.
The composition solution of the isothiazolone-containing of the present embodiment is by the isothiazolinone derivatives (the part by weight 3.5:1 of CMIT and MIT) of 12% weight, the solution-stabilized auxiliary agent I of 10% weight and the water of 78 % by weight.Numbering Y9.
Embodiment 20
The present embodiment illustrates the composition solution of isothiazolone-containing provided by the invention.
The composition solution of the isothiazolone-containing of the present embodiment is by the isothiazolinone derivatives (the part by weight 3:1 of CMIT and MIT) of 12% weight, the solution-stabilized auxiliary agent J of 10% weight and the water of 78 % by weight.Numbering Y10.
Embodiment 21
The present embodiment illustrates the composition solution of isothiazolone-containing provided by the invention.
The composition solution of the isothiazolone-containing of the present embodiment is by isothiazolinone derivatives (the part by weight 3:1 of CMIT and MIT), the solution-stabilized auxiliary agent A of 10% weight and the dipropylene glycol of 75.8 % by weight of 14.2% weight.Numbering Y11.
Test case 1
The present embodiment illustrates the stability of composition solution provided by the invention.
Choose 55 DEG C of temperature as the stability of evaluation solution, by observing the average evaluation stability of the composition solution Precipitation of embodiment 11～21 preparations at 55 DEG C.
At 55 DEG C produce precipitation number of days and 55 DEG C, 37 days after precipitation capacity (ppm) in table 2.
Table 2
Test case 2
The present embodiment illustrates the bactericidal property of composition solution provided by the invention.
Composition solution Y1～the Y11 that chooses isothiazolone-containing prepared by embodiment 11～embodiment 21, evaluates its bactericidal property.
Assessment method is with reference to the assay method of standard GB/T/T 14643.1-1993 heterotroph.Bacterial classification is running water enrichment culture, and starter bacteria number is 1.3 × 10
7individual/ml.
Table 3
Claims (10)
1. a solution-stabilized auxiliary agent, it is characterized in that by 2-bromine 2-nitro-1,3-propylene glycol, magnesium salts and be selected from polyepoxy sodium succinate, sodium Diacetate, Sodium Glycinate, sodium tartrate and natrium malicum at least one form.
2. according to the solution-stabilized auxiliary agent of claim 1, wherein, said 2-bromine 2-nitro-1,3-propylene glycol weight is 1 part of meter, the weight that is selected from polyepoxy sodium succinate, sodium Diacetate, Sodium Glycinate, sodium tartrate and natrium malicum is 0.2～5 part, and magnesium salts accounts for 40～60 % by weight of said auxiliary agent.
3. according to the solution-stabilized auxiliary agent of claim 1 or 2, it is characterized in that this auxiliary agent is made up of 2-bromine 2-nitro-1,3-propylene glycol, sodium Diacetate and magnesium salts.
4. one kind can directly be diluted the composition solution of the isothiazolone-containing of use, it is characterized in that the isothiazolinone derivatives that said composition contains 0.5～20% weight, the solution-stabilized auxiliary agent of 5～15% weight and the solvent of surplus, wherein, said isothiazolinone derivatives is the mixture of CMIT and MIT, said solution-stabilized auxiliary agent is by 2-bromine 2-nitro-1, ammediol be selected from polyepoxy sodium succinate, sodium Diacetate, Sodium Glycinate, at least one in sodium tartrate and natrium malicum and magnesium salts composition, said solvent is selected from water, dipropylene glycol or polyethylene glycol.
5. according to the composition solution of claim 4, wherein, in said isothiazolinone derivatives, the part by weight of CMIT and MIT is 2～4:1.
6. according to the composition solution of claim 4, wherein, said solution-stabilized auxiliary agent is by 2-bromine 2-nitro-1, ammediol, magnesium salts and sodium Diacetate composition, wherein, said 2-bromine 2-nitro-1,3-propylene glycol weight is 1 part of meter, the weight that is selected from polyepoxy sodium succinate, sodium Diacetate, Sodium Glycinate, sodium tartrate and natrium malicum is 0.2～5 part, and magnesium salts accounts for 40～60 % by weight of said auxiliary agent.
7. according to the composition solution of claim 4, it is characterized in that the isothiazolinone derivatives that said composition contains 1.5～15% weight, the solution-stabilized auxiliary agent of 9～11% weight and the solvent of surplus, wherein, said isothiazolinone derivatives is that part by weight is the CMIT of 3:1 and the mixture of MIT, in said solution-stabilized auxiliary agent, 2-bromine 2-nitro-1, ammediol is in 1 part, the weight of sodium Diacetate is 0.95～1.05 part, magnesium salts accounts for 48～52% of solution-stabilized auxiliary agent, said solvent is water.
8. according to the composition solution of claim 7, wherein, the isothiazolinone derivatives that contains 12% weight, the solution-stabilized auxiliary agent of 10% weight and the solvent of surplus, wherein, said isothiazolinone derivatives is that part by weight is the CMIT of 3:1 and the mixture of MIT, said solution-stabilized auxiliary agent is that part by weight is the bromo-2-of 2-nitro-1 of 1:1, the mixture of ammediol and sodium Diacetate, magnesium salts is magnesium nitrate and/or magnesium chloride, accounts for 49～51 % by weight of solution-stabilized auxiliary agent.
9. the composition solution of the isothiazolone-containing that can directly dilute use of one of claim 4～8 is applied in Treatment of Industrial Water, coating, paint, washing agent, ink, textile dyeing and finishing, papermaking, brightening agent, latex product, cosmetic field as bactericide.
10. according to the application of claim 9, it is characterized in that for Treatment of Industrial Water, bactericide injected volume is counted 0.2～10 milligram/every liter water for industrial use with isothiazolinone derivatives weight wherein
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