Defoaming agent composition applied to gloss oil system and preparation method thereof

Abstract

The invention relates to the technical field of defoaming agents, and particularly discloses a defoaming agent composition applied to a gloss oil system and a preparation method of the defoaming agent composition. The defoaming agent composition applied to the gloss oil system comprises the following raw materials in parts by weight: 60-80 parts of polyether, 5-13 parts of silicon paste, 8-15 parts of an emulsifier, 3-5 parts of a solubilizer, 1-3 parts of a dispersant, 0.5-1 part of a stabilizer, 3-5 parts of a thickener and 0.3-1.5 parts of fat-soluble fatty acid. The silicon paste is hydrosilylation silicon paste; according to the defoaming agent composition prepared by the invention, through the synergistic effect of all the components, the compatibility in a gloss oil system can be considered, and the defoaming agent composition has a relatively good defoaming effect.

Description

Technical Field

[0001] The present application relates to the technical field of defoamers, and particularly relates to a defoamer composition applied to a varnish system and a preparation method thereof. Background Art

[0002] In industries such as printing and painting, varnishes are widely used. The main components of varnishes are resins and additives. During construction, in addition to the emulsifiers added to the varnish, many operations are likely to cause foaming of the varnish. For example, mixing, stirring, spraying, etc. will all cause the generation of a large number of bubbles to varying degrees. These bubbles will not only affect the painting effect, but also cause problems such as uneven coating and decreased adhesion, seriously affecting production efficiency and product quality.

[0003] The main function of a varnish defoamer is to eliminate the bubbles generated during the construction of the varnish. Traditional varnish defoamers are mainly polyether defoamers, which have the problem of unsatisfactory defoaming and foam suppression effects; while silicone defoamers have compatibility problems such as shrinkage holes and pinholes. Summary of the Invention

[0004] In order to improve the deficiencies in defoaming and foam suppression of existing varnish defoamers and their influence on the properties of varnishes, the present application provides a defoamer composition applied to a varnish system and a preparation method thereof.

[0005] In a first aspect, the present application provides a defoamer composition applied to a varnish system, adopting the following technical solution: A defoamer composition applied to a varnish system, comprising the following raw materials in parts by weight: 60 - 80 parts of polyether, 5 - 13 parts of silicone paste, 8 - 15 parts of emulsifier, 3 - 5 parts of solubilizer, 1 - 3 parts of dispersant, 0.5 - 1 part of stabilizer, 3 - 5 parts of thickener, 0.3 - 1.5 parts of fat-soluble fatty acid; the silicone paste is a hydrosilylation silicone paste.

[0006] By adopting the above technical solution, the silicone paste has good defoaming performance and thermal stability, and can utilize its low surface tension to destroy the balance of the foam film, achieving the effects of rapid defoaming and foam suppression. The silicone paste is compounded with polyether compounds, which can enable the prepared defoamer to have good defoaming and foam suppression performance in the varnish system. Compared with other conventional types of silicone paste, the hydrosilylation silicone paste has better compatibility in the varnish system. Adding appropriate amounts of dispersant, solubilizer, and stabilizer to the defoamer raw materials can reduce the aggregation of solid particles or droplets in the defoamer and improve the defoaming stability of the defoamer. In the varnish system, the hydrophobic structure of the fat-soluble fatty acid can be well dispersed in the varnish system, and at the same time, a small amount of hydrophilic structure in the molecular structure can be oriented at the gas-liquid interface to reduce the surface tension, synergistically enhancing the effect with the polyether and silicone paste in the defoamer system, promoting the rupture of bubbles, and achieving the effect of enhancing the defoaming effect of the defoamer.

[0007] Preferably, the solubilizer is one of small molecule fatty alcohols and small molecule hydroxy-containing ether compounds.

[0008] By adopting the above technical solution, small molecule fatty alcohols and small molecule hydroxy-containing ether compounds as solubilizers can enhance the stability of the defoamer. Small molecule fatty alcohols and small molecule hydroxy-containing ether compounds can utilize their molecular structures to form interactions with solvents and resins in the varnish system, thereby improving the compatibility of the defoamer in the varnish system, improving the uniform distribution of the defoamer components in the varnish, and reducing shrinkage holes, pinholes and other phenomena caused by the incompatibility of the defoamer system components.

[0009] Preferably, the dispersant is alkynol polyether, the stabilizer is an anionic surfactant, and the thickener is a cellulose thickener.

[0010] By adopting the above technical solution, alkynol polyether has amphiphilicity, can significantly reduce the interfacial tension between the defoamer and the varnish system, promote the effective diffusion of the defoamer components on the foam surface, and thus improve the defoaming effect. At the same time, alkynol polyether can utilize steric hindrance and electrostatic stabilization to reduce the sedimentation and aggregation of the defoamer components in the varnish system. Cellulose can improve the suspension and stability of the defoamer in the varnish system by adjusting the viscosity of the defoamer, reduce the sedimentation or aggregation of the defoamer components, and improve the uniform dispersion and stability of the defoamer.

[0011] Preferably, the hydrosilylation silicone paste includes a hydrosilylation silicone paste with a viscosity of 30000-60000 mpa.s and a hydrosilylation silicone paste with a viscosity of 80000-120000 mpa.s; the mass ratio of the hydrosilylation silicone paste with a viscosity of 30000-60000 mpa.s to the hydrosilylation silicone paste with a viscosity of 80000-120000 mpa.s is 2:(8-10).

[0012] By adopting the above technical solution, by compounding hydrosilylation silicone pastes with different viscosities, while taking into account the defoaming and anti-foaming effects of the defoamer in the varnish system, it is also possible to avoid problems such as shrinkage holes and pinholes caused by the incompatibility of the varnish system as much as possible.

[0013] Preferably, the emulsifier comprises the following raw materials in parts by weight: 20-50 parts of hydrogen-containing silicone oil, 10-25 parts of vinyl silicone oil, 25-70 parts of allyl alcohol polyether, and 5-15 ppm of platinum catalyst.

[0014] By adopting the above technical solution, compared with conventional emulsifiers, the emulsifier prepared by reacting hydrogen-containing silicone oil, vinyl silicone oil, allyl alcohol polyether and platinum catalyst has good compatibility with both polyether and silicone paste.

[0015] Preferably, the polyether is one of allyl polyether and PPG polyether.

[0016] By adopting the above technical solution, the PPG polyether is polypropylene glycol polyether, i.e., propylene oxide condensate. In the varnish system, this polyether can significantly reduce the foam height in the varnish system and has better foam suppression effect. Due to the introduction of allyl structure, the allyl polyether can enhance the adsorption ability of polyether molecules on the foam surface, accelerate the rupture of foam, and thus improve the defoaming and foam suppression effects of the defoamer. At the same time, the allyl polyether can also enhance the compatibility between the defoamer components and the varnish system, and promote the uniform dispersion of the defoamer components in the varnish system.

[0017] Preferably, the allyl polyether is capped with butyl, and the specific steps are as follows: After mixing the allyl polyether and sodium hydroxide, stir evenly, heat up to 100 - 110 °C, carry out dehydration reaction under vacuum, cool down to 60 - 70 °C, add bromobutane for reaction, and carry out vacuum distillation and filtration to remove solids to obtain the capped allyl polyether.

[0018] By adopting the above technical solution, using butyl to cap the allyl polyether can improve the problem of shrinkage holes of the defoamer in the varnish system, promote the uniform and stable distribution of the defoamer components in the varnish system, and further improve the defoaming and foam suppression performance of the defoamer in the varnish system.

[0019] Preferably, the mass ratio of the allyl polyether, sodium hydroxide, and bromobutane is 1:(0.1 - 0.15):(0.3 - 0.5).

[0020] In the second aspect, the present application provides a preparation method of a defoamer composition applied to a varnish system, adopting the following technical solution: A preparation method of a defoamer composition applied to a varnish system includes the following specific steps: Preheat and mix the emulsifier and silicone paste in advance, then add polyether, solubilizer, dispersant, stabilizer, thickener, and fat-soluble fatty acid, and stir and disperse to obtain a defoamer composition applied to the varnish system.

[0021] By adopting the above technical solution, through the synergistic effect of each component, the defoamer can be stably and uniformly dispersed in the varnish system, has good defoaming and foam suppression effects, and can take into account the compatibility at the same time.

[0022] Preferably, it includes the following specific steps: Mix the hydrogen-containing silicone oil and vinyl silicone oil, heat to 85 - 95 °C, keep warm for reaction, then add allyl alcohol polyether and platinum catalyst, continue to heat up until the reaction system becomes clear, keep warm for reaction for 20 - 50 min, and cool down to obtain the emulsifier; Preheat the emulsifier and silicone paste by mixing them, then add polyether, solubilizer, dispersant, stabilizer, thickener and fat-soluble fatty acid and mix them, and stir and disperse to obtain an antifoaming agent composition applied to the varnish system.

[0023] In summary, the present application has the following beneficial effects: 1. Since the present application uses a silicone paste obtained by hydrosilylation and polyether in combination, it promotes the antifoaming agent prepared to have good antifoaming performance, foam suppression performance and compatibility in the varnish system. On the other hand, the fat-soluble fatty acid can interact with the polyether and silicone paste in the antifoaming agent system to reduce the surface tension and promote the rupture of the foam.

[0024] 2. In the present application, allyl polyether and PPG polyether are used as polyethers. The PPG polyether is used to improve the foam suppression effect of the antifoaming agent. By using the allyl structure of allyl polyether, the adsorption ability of the polyether molecule on the foam surface is enhanced, thereby improving the antifoaming and foam suppression effects of the antifoaming agent. At the same time, the allyl polyether is butyl-capped to improve the problem of shrinkage holes of the antifoaming agent in the varnish system, and promote the uniform and stable distribution of the antifoaming agent components in the varnish system. Specific Embodiments

[0025] The following further describes the present application in detail with reference to embodiments.

[0026] All raw materials in the embodiments can be obtained commercially. Embodiments

[0027] Example 1 This example provides an antifoaming agent composition applied to the varnish system, including the following raw materials in parts by weight: 70 kg of polyether, 12 kg of silicone paste, 13 kg of emulsifier, 4 kg of solubilizer, 2 kg of dispersant, 0.8 kg of stabilizer, 4 kg of thickener, and 0.9 kg of fat-soluble fatty acid. The polyether is PPG polyether, the number average molecular weight of PPG polyether is 2000, the silicone paste is a silicone paste obtained by hydrosilylation, the viscosity of the silicone paste obtained by hydrosilylation is 50000 cps, the emulsifier is Tween-80, the solubilizer is a small molecule fatty alcohol - isopropanol, the dispersant is an alkynol polyether, and the alkynol polyether is purchased from Tianjin Hepu Feile New Materials Co., Ltd. FS-620, the stabilizer is an anionic surfactant - sodium dodecyl sulfate, the thickener is sodium carboxymethyl cellulose, and the fat-soluble fatty acid is oleic acid.

[0028] The preparation method of the antifoaming agent composition applied to the varnish system includes the following specific steps: Mix the emulsifier and the silicone paste, heat to 60 °C, stir evenly, then add half of the polyether and stir evenly, and then add the remaining polyether, solubilizer, dispersant, stabilizer, thickener and fat-soluble fatty acid and stir evenly to obtain an antifoaming agent composition applied to the varnish system.

[0029] Example 2 The difference between Example 2 and Example 1 is that in the raw materials of the defoaming agent composition, the usage amount of polyether is 60 kg, the usage amount of silicone paste is 13 kg, the usage amount of emulsifier is 8 kg, the usage amount of solubilizer is 3 kg, the usage amount of dispersant is 3 kg, the usage amount of stabilizer is 0.5 kg, the usage amount of thickener is 3 kg, and the usage amount of fat-soluble fatty acid is 0.3 kg.

[0030] Example 3 The difference between Example 3 and Example 1 is that in the raw materials of the defoaming agent composition, the usage amount of polyether is 80 kg, the usage amount of silicone paste is 5 kg, the usage amount of emulsifier is 15 kg, the usage amount of solubilizer is 5 kg, the usage amount of dispersant is 1 kg, the usage amount of stabilizer is 1 kg, the usage amount of thickener is 5 kg, and the usage amount of fat-soluble fatty acid is 1.5 kg.

[0031] Example 4 The difference between Example 4 and Example 1 is that in the raw materials of the defoaming agent composition, the silicone paste is a hydrosilylation silicone paste with a viscosity of 100000 mPa·s.

[0032] Example 5 The difference between Example 5 and Example 1 is that in the raw materials of the defoaming agent composition, the silicone paste is a mixture of hydrosilylation silicone pastes with viscosities of 50000 mPa·s and 100000 mPa·s, and the mass ratio of the hydrosilylation silicone paste with a viscosity of 50000 mPa·s to the hydrosilylation silicone paste with a viscosity of 100000 mPa·s is 2:9.

[0033] Example 6 The difference between Example 6 and Example 5 is that in the raw materials of the defoaming agent composition, the emulsifier includes the following raw materials in parts by weight: 25 kg of hydrogen-containing silicone oil, 18 kg of vinyl silicone oil, 47 kg of allyl alcohol polyether, and 10 ppm of platinum catalyst. The hydrogen-containing silicone oil is a hydrogen-containing silicone oil with a hydrogen content of 0.1%, the vinyl content in the vinyl silicone oil is 0.18%, the viscosity is 1000 mPa·s, the allyl alcohol polyether is allyl polyoxyethylene polyoxypropylene ether, purchased from Zhejiang Huangma 767R, and the platinum catalyst is chloroplatinic acid.

[0034] The preparation method of the defoaming agent composition applied to the varnish system includes the following specific steps: S1: Mix the hydrogen-containing silicone oil and vinyl silicone oil, heat to 90°C, hold the reaction for 30 min, then add allyl alcohol polyether and platinum catalyst, continue to heat up until the reaction system becomes clear, hold the reaction for 30 min, and cool down to obtain the emulsifier.

[0035] S2: Mix the emulsifier with the silicone paste, heat to 60 °C, stir evenly, then add one - half of the polyether and stir evenly, then add the remaining polyether, solubilizer, dispersant, stabilizer, thickener and fat - soluble fatty acid and stir evenly to obtain the defoamer composition applied to the varnish system.

[0036] Example 7 The difference between Example 7 and Example 6 is that in the raw materials of the defoamer composition, the emulsifier includes the following raw materials in parts by weight: 48.8 kg of hydrogen - containing silicone oil, 24.4 kg of vinyl silicone oil, 26.8 kg of allyl alcohol polyether, and 5 ppm of platinum catalyst.

[0037] Example 8 The difference between Example 8 and Example 6 is that in the raw materials of the defoamer composition, the emulsifier includes the following raw materials in parts by weight: 21.3 kg of hydrogen - containing silicone oil, 10.6 kg of vinyl silicone oil, 68.1 kg of allyl alcohol polyether, and 15 ppm of platinum catalyst.

[0038] Example 9 The difference between Example 9 and Example 6 is that in the emulsifier raw materials of the defoamer composition, the hydrogen - containing silicone oil is a hydrogen - containing silicone oil with a hydrogen content of 0.18%, and the allyl alcohol polyether is allyl alcohol polyether APEG - 500.

[0039] Example 10 The difference between Example 10 and Example 6 is that the allyl polyether in the raw materials of the defoamer composition is end - capped with butyl.

[0040] The preparation method of the defoamer composition applied to the varnish system includes the following specific steps: S1: Mix allyl polyether and sodium hydroxide, stir evenly, heat to 105 °C, carry out dehydration reaction under vacuum for 3 h, cool to 65 °C and add bromobutane to react for 5 h. The mass ratio of allyl polyether, sodium hydroxide and bromobutane is 1:0.12:0.4. Remove the excess bromobutane by vacuum distillation, and then filter to remove the solid to obtain the end - capped allyl polyether.

[0041] S2: Mix hydrogen - containing silicone oil and vinyl silicone oil, heat to 90 °C, keep warm and react for 30 min, then add allyl alcohol polyether and platinum catalyst, continue to heat until the reaction system becomes clear and transparent, keep warm and react for 30 min, and then cool to obtain the emulsifier.

[0042] S3: Mix the emulsifier with the silicone paste, dissolve it at 60 °C, stir evenly, then add one - half of the modified allyl polyether and stir evenly, then add the remaining modified allyl polyether, solubilizer, dispersant, stabilizer, thickener and fat - soluble fatty acid and stir evenly to obtain the defoamer composition applied to the varnish system.

[0043] Comparative Example Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that fat-soluble fatty acids are not used in the raw materials of the defoaming agent composition.

[0044] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the silicone paste in the raw materials of the defoaming agent composition is a condensation-type silicone paste with a viscosity of 100000 cps.

[0045] Performance detection test For the defoaming agent compositions applied to the varnish system provided in Examples 1-10 and Comparative Examples 1-2 of the present application, the following performance detections were carried out, and the specific detection results are shown in Table 1.

[0046] Detection method Defoaming effect and compatibility Put 100 g of varnish, 2 g of foaming liquid and 0.3 g of the defoaming agent composition prepared in the present application into a high-speed dispersion container. The rotation speed is 2000 r / min. After high-speed dispersion for 1 h, immediately weigh 70 g of the high-speed dispersion liquid and pour it into a 100 ml graduated cylinder to observe the foam height at that time, after standing for 15 min, and after standing for 30 min; finally, use a color spreading wheel to scrape a film on the hiding power measurement plate to see if there are shrinkage holes and how many shrinkage holes there are. The film scraping grades are as follows: Grade 1, there are almost no shrinkage holes or pinholes, or there are very few individual ones; Grade 2, there are a small number of shrinkage holes or pinholes, accounting for ≤5% of the area; Grade 3, there are more shrinkage holes or pinholes, accounting for 5-30% of the area; Grade 4, there are a large number of shrinkage holes or pinholes, accounting for 30-50% of the area; Grade 5, all are shrinkage holes or pinholes, accounting for 50-100% of the area; Table 1: Data table of performance detection results It can be seen from the performance detection results that the defoaming agent composition prepared in the present application has good defoaming and foam suppression effects, and at the same time has good compatibility in the varnish system. In Examples 1-3, the usage amounts of the components in the raw materials of the defoaming agent composition are different, and among them, the comprehensive performance of Example 1 is better.

[0047] By comparing Examples 4-5 with Example 1, it can be seen that in Example 5, a mixture of two silicone hydrosilylation silicone pastes with different viscosities is used. It can be seen from the performance detection results that the defoaming agent prepared in Example 5 can significantly reduce the foam height. It further shows that the defoaming agent prepared by compounding silicone hydrosilylation silicone pastes with high and low viscosities has a better defoaming effect in the varnish system.

[0048] Comparing Examples 6 - 9 with Example 1, it can be seen that the emulsifiers used in Examples 6 - 9 have better effects, can better disperse the silicone paste and polyether in the varnish system, and promote the defoaming agent to have better defoaming and foam suppression effects.

[0049] In Example 10, the allyl polyether is end - capped with butyl. From the performance test results, it can be seen that the defoaming and foam suppression performance of the defoaming agent is improved. This may be because the allyl polyether end - capped with butyl can promote the uniform dispersion of the defoaming agent composition in the varnish system.

[0050] Comparing Comparative Examples 1 - 2 with Example 1, it can be seen that changing any component in this application will affect the prepared defoaming agent. In Comparative Example 2, a conventional condensation - type silicone paste is used. From the performance test results, it can be seen that the compatibility of the condensation - type silicone paste used in Comparative Example 2 in the varnish system is poor, which further leads to shrinkage holes and pinholes in the defoaming agent in the varnish system. This further illustrates that through the synergistic effect of each component in this application, the aggregation of solid particles or droplets in the defoaming agent is reduced, and the stability, defoaming, and foam suppression effects of the defoaming agent in the varnish system are improved.

[0051] This specific embodiment is only an interpretation of this application, and it is not a limitation of this application. After reading this specification, those skilled in the art can make modifications without creative contributions to this embodiment as needed, but as long as it is within the scope of the claims of this application, it is protected by the patent law.

Claims

1. A defoamer composition used in a varnish system, characterized in that: The invention comprises the following raw materials in parts by weight: 60-80 parts of polyether, 5-13 parts of silicone paste, 8-15 parts of emulsifier, 3-5 parts of solubilizer, 1-3 parts of dispersant, 0.5-1 parts of stabilizer, 3-5 parts of thickener and 0.3-1.5 parts of fat-soluble fatty acid; the silicone paste is hydrosilylation silicone paste.

2. The defoamer composition used in a varnish system according to claim 1, characterized in that: The solubilizer is one of a small molecular fatty alcohol and a small molecular hydroxyl-containing ether compound.

3. The defoamer composition used in a varnish system according to claim 1, characterized in that: The dispersant is acetylene alcohol polyether, the stabilizer is an anionic surfactant, and the thickener is a cellulose thickener.

4. The defoamer composition used in a varnish system according to claim 1, characterized in that: The hydrosilylation silicone paste includes a hydrosilylation silicone paste having a viscosity of 30000-60000 mpa.s and a hydrosilylation silicone paste having a viscosity of 80000-120000 mpa.s; The mass ratio of the hydrosilicone addition silicone paste with a viscosity of 30000-60000 mpa.s to the hydrosilicone addition silicone paste with a viscosity of 80000-120000 mpa.s is 2:(8-10).

5. The defoamer composition used in a varnish system according to claim 1, characterized in that: The emulsifier comprises the following raw materials in parts by weight: 20-50 parts of hydrogen-containing silicone oil, 10-25 parts of vinyl silicone oil, 25-70 parts of allyl alcohol polyether, and 5-15 ppm of platinum catalyst.

6. The defoamer composition used in a varnish system according to claim 1, characterized in that: The polyether is one of allyl polyether and PPG polyether.

7. The defoamer composition used in a varnish system according to claim 6, characterized in that: The allyl polyether is capped with butyl, comprising the following specific steps: mixing the allyl polyether and sodium hydroxide, stirring evenly, heating to 100-110° C., performing dehydration reaction under vacuum, cooling to 60-70° C., adding bromobutyl to react, performing reduced pressure distillation, filtering to remove solids to obtain the capped allyl polyether.

8. The defoamer composition used in a varnish system according to claim 6, characterized in that: The mass ratio of the allyl polyether, sodium hydroxide and butyl bromide is 1:(0.1-0.15):(0.3-0.5).

9. A method for preparing the defoamer composition used in a varnish system according to any one of claims 1 to 8, characterized in that: The specific steps include: The emulsifier and the silicone paste are mixed and heated in advance, and then polyether, a solubilizer, a dispersant, a stabilizer, a thickener and a fat-soluble fatty acid are added, mixed, stirred and dispersed to prepare a defoamer composition used in a varnish system.

10. The method for preparing the defoamer composition used in a varnish system according to any one of claims 1 to 8, characterized in that: The specific steps include: Mix hydrogenated silicone oil and vinyl silicone oil, heat to 85-95°C, keep warm for reaction, then add allyl alcohol polyether and platinum catalyst, continue to heat until the reaction system becomes clear, keep warm for reaction for 20-50 minutes, and cool down to obtain an emulsifier; The emulsifier and the silicone paste are mixed and heated in advance, and then polyether, a solubilizer, a dispersant, a stabilizer, a thickener and a fat-soluble fatty acid are added, mixed, stirred and dispersed to prepare a defoamer composition used in a varnish system.

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