Water-resistant, steaming-resistant and sun-proof pale purple lake and preparation method thereof

Abstract

The invention discloses a water-resistant, steaming-resistant and sun-proof pale lotus lake and a preparation method thereof, and belongs to the technical field of pigment preparation. According to the process disclosed by the invention, the sun-proof blue lotus lake is taken as a core material, the composite wall material is prepared from epoxy resin, diisocyanate and polyhedral oligomeric silsesquioxane (POSS), and the composite wall material microcapsule lake is prepared through encapsulation, so that the water resistance and the steaming and boiling resistance of the prepared blue lotus lake are remarkably enhanced. According to the microcapsule lake prepared by the invention, the protection capability of the composite wall material layer on the core material lake is enhanced, and the structural stability and high-temperature tolerance of the microcapsule are greatly improved, so that the microcapsule lake can keep good color stability and structural integrity in the cooking process, and the application range of the sun-proof green lotus lake is expanded.

Description

Technical Field

[0001] The invention belongs to the technical field of pigment preparation, and particularly relates to a water-resistant, boiling-resistant and sun-resistant blue lotus pigment lake and a preparation method thereof. Background Art

[0002] Light-fast Lotus Lake (CI Pigment Violet 3) is a specially treated organic pigment with bright color and strong tinting power. Lotus color is a deep and elegant blue-purple hue, widely used in coatings, inks, plastics, textile printing and dyeing and other industries. Based on the long-term sunlight exposure requirements in outdoor advertising, building exterior wall decoration and automotive painting, Lotus Lake needs to be able to effectively resist color changes caused by ultraviolet rays, keep bright colors and not fade under long-term sunlight exposure, and ensure the service life of the product.

[0003] However, most of the current sun-fast blue lotus color lake products generally have obvious defects such as poor water resistance and poor cooking resistance. They are very easy to transfer colors after water immersion or cooking, which greatly limits their application scope and stability in use. Water resistance and cooking resistance are mainly for some sterile products or products that need to be processed under high temperature and high humidity conditions. This feature requires that the pigment or dye can still maintain color stability after undergoing a high-temperature cooking process. Based on this, it is necessary to develop a water-resistant and cooking-resistant sun-fast blue lotus color lake to expand the application field of blue lotus color lake. Summary of the invention

[0004] In view of the content of the background technology, the present invention provides a water-resistant, boiling-resistant and sun-resistant Qinglian color lake and a preparation method thereof. The process of the present invention uses the sun-resistant Qinglian color lake as the core material, and prepares the microcapsule color lake with epoxy resin, diisocyanate and cage-type polysilsesquioxane (POSS) as the composite wall material, which significantly enhances the water resistance and boiling resistance of the prepared Qinglian color lake.

[0005] To achieve the above purpose, the present invention specifically adopts the following technical solutions: The present invention provides a method for preparing a water-resistant, boiling-resistant and sun-resistant blue lotus lake, comprising the following steps: The sun-fast blue lotus color lake is taken as the core material, and the composite wall material is prepared with epoxy resin, diisocyanate and cage-type polysilsesquioxane. The composite wall material microcapsule color lake is made through encapsulation, which is the water-resistant and boiling-resistant sun-fast blue lotus color lake.

[0006] Preferably, the raw materials for preparing the sun-fast green lotus lake include basic violet 5BN, sodium tungstate, sodium molybdate, pigment additives, and basic dyes, and the specific preparation method is: 1) Mix glacial acetic acid, basic violet 5BN, basic dye, pigment additive and water, heat and stir to dissolve, and obtain a dye mixture for use; 2) Sodium tungstate, sodium molybdate and disodium hydrogen phosphate are mixed with water, heated and stirred to dissolve, and then hydrochloric acid is added to obtain a heteropolyacid mixed solution for use; 3) adding the heteropolyacid mixture obtained in step 2) to the dye mixture obtained in step 1) and stirring for reaction; after the reaction is completed, filtering the material, washing and drying it to obtain a sun-resistant blue lotus color lake.

[0007] Preferably, the pigment auxiliary agent is a higher fatty acid salt or a fatty alcohol polyoxyethylene ether; and the basic dye is at least one of basic fuchsin, basic royal blue or basic royal blue BO.

[0008] Preferably, the epoxy resin is bisphenol A epoxy resin or bisphenol F epoxy resin; the diisocyanate is isophorone diisocyanate; and the cage-type polysilsesquioxane is trisilanol phenyl-cage-type polysilsesquioxane.

[0009] The present invention uses basic purple 5BN and conventional additives to prepare a sun-fast blue lotus pigment lake, which has good sun-fastness and stable color light, but poor water resistance and boiling resistance. The present invention uses the sun-fast blue lotus pigment lake as a core material, and uses epoxy resin, diisocyanate and cage-type polysilsesquioxane to construct a composite wall material system to prepare microcapsule pigment lake: during the encapsulation process, the epoxy resin cross-linking and curing can form a three-dimensional network structure polymer system, providing basic structural strength and stability; as another main component of the wall material, diisocyanate generates a carbamate bond with polyethylene glycol during the preparation process, and combined with the epoxy resin polymer system, significantly improves the resistance of the microcapsule to water erosion. Cage polysilsesquioxane is a nano-scale silica / siloxane hybrid with high strength, high temperature resistance, good formability, excellent reactivity, porosity and nano-size effect. The present invention incorporates cage polysilsesquioxane into the above system through nano-hybrid composite. The nano-scale molecules can not only restrict the expansion of microcracks and reduce the stress concentration of the matrix, but also strengthen the protection ability of the composite wall material layer to the core material color lake, greatly improve the structural stability and high temperature tolerance of the microcapsule, so that the microcapsule color lake can maintain good color stability and structural integrity during the cooking process.

[0010] Preferably, the raw materials for preparing the composite wall material microcapsule color lake are in the following mass ratio: sun-resistant blue lotus color lake: epoxy resin: diisocyanate: cage-type polysilsesquioxane = 10:(5-12):(3-10):(0.05-0.2).

[0011] Preferably, the method for preparing the composite wall material microcapsule lake specifically comprises the following steps: Step 1: Take epoxy resin, polyethylene glycol, and cage-type polysilsesquioxane and add them to an organic solvent and mix them, then add the sun-fast blue lotus lake and emulsifier, heat and shear them, and obtain an emulsion for use; Step 2: Take another diisocyanate and dissolve it in an organic solvent to obtain a wall material solution, and drop the wall material solution and the curing agent into the emulsion in step 1 at the same time, continue heating and shearing to obtain a cured product, filter the product, wash and dry the filter cake, and obtain a composite wall material microcapsule lake.

[0012] Preferably, the emulsifier in step 1 is Tween-60 or betaine; and the curing agent in step 2 is a polyetheramine curing agent or an aliphatic amine curing agent.

[0013] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention effectively overcomes the defects of traditional sun-resistant blue lotus color lake that it is not resistant to water and boiling. By using it as the core material, a composite wall material system is constructed in combination with epoxy resin, diisocyanate and cage-type polysilsesquioxane to prepare microcapsule color lake. The raw material cost is low and the preparation process is simple, which is suitable for industrial production.

[0014] 2. The composite wall material microcapsule color lake prepared by the present invention significantly enhances the protective ability of the composite wall material layer to the core material color lake, greatly improves the structural stability and high temperature tolerance of the microcapsule, and expands the application scope of the sun-resistant Qinglian color lake. DETAILED DESCRIPTION

[0015] In order to make the purpose, technical scheme and advantages of the present invention clearer, the technical scheme of the present invention will be clearly and completely described below in conjunction with the embodiments. If the specific conditions are not specified in the embodiments, they are carried out according to the conventional conditions or the conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially.

[0016] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0017] Example 1 A method for preparing a water-resistant, boiling-resistant and sun-resistant blue lotus lake, comprising the following steps: 1. Take 25 parts of basic violet 5BN (blue phase), 3 parts of basic fuchsin, 1 part of fatty alcohol polyoxyethylene ether (AEO-7), 1 part of glacial acetic acid, 2 parts of disodium hydrogen phosphate, 32 parts of sodium tungstate, 6 parts of sodium molybdate, and 30 parts of hydrochloric acid (30%) by weight; add glacial acetic acid, basic violet 5BN, basic fuchsin, AEO-7 and 30 times the weight of water to a reactor, heat to 90°C, stir and dissolve to obtain a dye mixture; take another reactor, add sodium tungstate, sodium molybdate, disodium hydrogen phosphate and 10 times the weight of water, heat to 90°C, stir and dissolve, and then continue to add hydrochloric acid to obtain a heteropolyacid mixture after the reaction is completed. Add the heteropolyacid mixture to the dye mixture and stir for reaction for 1 hour. After the reaction is completed, filter the material, wash, dry and crush it to obtain a sun-resistant blue lotus lake.

[0018] 2. Take 100 parts of the above-mentioned sun-fast blue lotus lake, 100 parts of bisphenol F epoxy resin, 50 parts of isophorone diisocyanate, 20 parts of PEG-600, 1 part of trisilanol phenyl-cage polysilsesquioxane, and enough xylene by weight. Mix bisphenol F epoxy resin, PEG-600, and trisilanol phenyl-cage polysilsesquioxane and add them to 3 times the total weight of xylene and stir evenly until completely dissolved; then add sun-fast blue lotus lake and 5 parts of Tween-60, and continue high-speed shearing at 2000 rpm for 1 hour under 80°C water bath conditions to obtain an emulsion. Isophorone diisocyanate and 0.1 parts of stannous octoate were dissolved in xylene to obtain a wall material solution. 15 parts of polyetheramine curing agent D230 were dissolved in water. The wall material solution and the curing agent solution were simultaneously dripped into the emulsion. The dropping time was controlled to be 6 h. During the process, a water bath of 80°C and a continuous high-speed shear of 2000 rpm were maintained to obtain a cured product. The product was filtered, and the filter cake was washed and dried to obtain a composite wall material microcapsule lake.

[0019] Example 2 A method for preparing a water-resistant, boiling-resistant and sun-resistant blue lotus lake, comprising the following steps: 1. Take 25 parts of basic violet 5BN (blue phase), 3 parts of basic fuchsin, 1 part of fatty alcohol polyoxyethylene ether (AEO-7), 1 part of glacial acetic acid, 2 parts of disodium hydrogen phosphate, 32 parts of sodium tungstate, 6 parts of sodium molybdate, and 30 parts of hydrochloric acid (30%) by weight; add glacial acetic acid, basic violet 5BN, basic fuchsin, AEO-7 and 30 times the weight of water to a reactor, heat to 85°C, stir and dissolve to obtain a dye mixture; take another reactor, add sodium tungstate, sodium molybdate, disodium hydrogen phosphate and 10 times the weight of water, heat to 85°C, stir and dissolve, and then continue to add hydrochloric acid to obtain a heteropolyacid mixture after the reaction is completed. Add the heteropolyacid mixture to the dye mixture and stir for reaction for 1 hour. After the reaction is completed, filter the material, wash, dry and crush it to obtain a sun-resistant blue lotus lake.

[0020] 2. Take 100 parts of the above-mentioned sun-fast blue lotus lake, 50 parts of bisphenol F epoxy resin, 100 parts of isophorone diisocyanate, 30 parts of PEG-600, 0.5 parts of trisilanol phenyl-cage polysilsesquioxane, and enough xylene by weight for use. Mix bisphenol F epoxy resin, PEG-600, and trisilanol phenyl-cage polysilsesquioxane and add them to 3 times the total weight of xylene and stir evenly until completely dissolved; then add sun-fast blue lotus lake and 5 parts of Tween-60, and continue high-speed shearing at 2000rpm for 1 hour under 80℃ water bath conditions to obtain an emulsion. Isophorone diisocyanate and 0.1 parts of stannous octoate were dissolved in xylene to obtain a wall material solution. 15 parts of polyetheramine curing agent D230 were dissolved in water. The wall material solution and the curing agent solution were simultaneously dripped into the emulsion. The dropping time was controlled to be 6 h. During the process, a water bath of 80°C and a continuous high-speed shear of 2000 rpm were maintained to obtain a cured product. The product was filtered, and the filter cake was washed and dried to obtain a composite wall material microcapsule lake.

[0021] Example 3 A method for preparing a water-resistant, boiling-resistant and sun-resistant blue lotus lake, comprising the following steps: 1. Take 30 parts of basic violet 5BN (blue phase), 2 parts of basic fuchsin, 1 part of fatty alcohol polyoxyethylene ether (AEO-7), 1 part of glacial acetic acid, 2 parts of disodium hydrogen phosphate, 32 parts of sodium tungstate, 6 parts of sodium molybdate, and 30 parts of hydrochloric acid (30%) by weight; add glacial acetic acid, basic violet 5BN, basic fuchsin, AEO-7 and 30 times the weight of water to a reactor, heat to 90°C, stir and dissolve to obtain a dye mixture; take another reactor, add sodium tungstate, sodium molybdate, disodium hydrogen phosphate and 10 times the weight of water, heat to 90°C, stir and dissolve, and then continue to add hydrochloric acid to obtain a heteropolyacid mixture after the reaction is completed. Add the heteropolyacid mixture to the dye mixture and stir to react for 1.5 hours. After the reaction is completed, filter the material, wash, dry and crush it to obtain a sun-resistant blue lotus lake.

[0022] 2. Take 100 parts of the above-mentioned sun-fast blue lotus lake, 120 parts of bisphenol F epoxy resin, 30 parts of isophorone diisocyanate, 15 parts of PEG-600, 2 parts of trisilanol phenyl-cage polysilsesquioxane, and enough xylene by weight. Mix bisphenol F epoxy resin, PEG-600, and trisilanol phenyl-cage polysilsesquioxane and add them to 3 times the total weight of xylene and stir evenly until completely dissolved; then add sun-fast blue lotus lake and 5 parts of Tween-60, and continue high-speed shearing at 2000 rpm for 1 hour under 80°C water bath conditions to obtain an emulsion. Isophorone diisocyanate and 0.1 parts of stannous octoate were dissolved in xylene to obtain a wall material solution. 15 parts of polyetheramine curing agent D230 were dissolved in water. The wall material solution and the curing agent solution were simultaneously dripped into the emulsion. The dropping time was controlled to be 6 h. During the process, a water bath of 80°C and a continuous high-speed shear of 2000 rpm were maintained to obtain a cured product. The product was filtered, and the filter cake was washed and dried to obtain a composite wall material microcapsule lake.

[0023] Comparative Example 1 The blank control group was the non-encapsulated sun-fast lotus color lake obtained in step 1 of Example 1.

[0024] Comparative Example 2 The step parameters in Example 1 are referred to, except that in step 2, trisilanol phenyl-cage polysilsesquioxane is not added as a composite wall material raw material to prepare microcapsules.

[0025] Comparative Example 3 The step parameters in Example 1 are referred to, except that bisphenol F epoxy resin is not added in step 2, and the amount of isophorone diisocyanate is changed to 150 parts.

[0026] Test example The pigment samples obtained in the above Examples 1-3 and Comparative Examples 1-3 were tested using a colorimeter (Lab color model), and the results are shown in Table 1.

[0027] Table 1 Pigment sample test results

[0028] Continue to wrap the above pigment samples with filter paper, soak them in water at room temperature for 10 days, put them into test tubes, add water at 100℃ and boil them for 2 hours. After drying, test the treated pigment samples. The results are shown in 2 and 3.

[0029] Table 2 Pigment detection results after immersion

[0030] Table 3 Pigment detection results after cooking

[0031] By comparing the above test results, it can be seen that the composite wall material microcapsule lake prepared in the embodiment of the present invention has excellent water resistance and cooking resistance, and can maintain good color stability after long-term water immersion or 100°C cooking treatment; while the non-encapsulated sun-resistant green lotus lake in comparative example 1 shows obvious discoloration whether it is water immersion or cooking. It can be seen that the present invention gives the core material pigment lake a new protective layer in the form of microcapsules, thereby resisting water erosion or high temperature; the microcapsule lake prepared in comparative example 2 has good water resistance, but also fades significantly after high-temperature cooking. It can be seen that trisilanol phenyl-cage polysilsesquioxane has a key influence on the high temperature resistance of the composite wall material system of the present invention; comparative example 3 only uses isophorone diisocyanate as the main wall material component to prepare microcapsules, and its water resistance and cooking resistance are relatively small. It can be seen that the composite wall material system constructed by combining bisphenol F type epoxy resin with isophorone diisocyanate can further improve the structural stability and high temperature tolerance of the microcapsules. The composite wall material microcapsule color lake of the present invention has a simple preparation process and a low raw material cost, and can be well applied to some products that need to be processed under high temperature and high humidity. The present invention expands the application scope of the sun-resistant blue lotus color lake and has good market competitiveness.

[0032] The embodiments described above only express several preferred embodiments of the present invention, and the descriptions thereof are relatively specific and detailed, but are not intended to limit the present invention. It should be noted that for those skilled in the art, the present invention may also have various changes and modifications, and any modifications, equivalent substitutions, improvements, etc. made within the concept and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a water-resistant, boiling-resistant and sun-resistant lotus lake, characterized in that: The steps include: The sun-fast blue lotus color lake is taken as the core material, and the composite wall material is prepared with epoxy resin, diisocyanate and cage-type polysilsesquioxane. The composite wall material microcapsule color lake is made through encapsulation, which is the water-resistant and boiling-resistant sun-fast blue lotus color lake.

2. The method for preparing a water-resistant, boiling-resistant and sun-resistant lotus lake according to claim 1, characterized in that: The raw materials for preparing the sun-fast blue lotus lake include basic violet 5BN, sodium tungstate, sodium molybdate, pigment additives, and basic dyes. The specific preparation method is as follows: 1) Mix glacial acetic acid, basic violet 5BN, basic dye, pigment additive and water, heat and stir to dissolve, and obtain a dye mixture for use; 2) Sodium tungstate, sodium molybdate and disodium hydrogen phosphate are mixed with water, heated and stirred to dissolve, and then hydrochloric acid is added to obtain a heteropolyacid mixed solution for use; 3) adding the heteropolyacid mixture obtained in step 2) to the dye mixture obtained in step 1) and stirring for reaction; after the reaction is completed, filtering the material, washing and drying it to obtain a sun-resistant blue lotus color lake.

3. The method for preparing a water-resistant, boiling-resistant and sun-resistant lotus lake according to claim 2, characterized in that: The pigment auxiliary agent is a higher fatty acid salt or a fatty alcohol polyoxyethylene ether; the basic dye is at least one of basic fuchsin, basic fuchsin blue or basic fuchsin blue BO.

4. The method for preparing a water-resistant, boiling-resistant and sun-resistant lotus lake according to claim 1, characterized in that: The epoxy resin is bisphenol A epoxy resin or bisphenol F epoxy resin; the diisocyanate is isophorone diisocyanate; and the cage-type polysilsesquioxane is trisilanol phenyl-cage-type polysilsesquioxane.

5. The method for preparing the water-resistant, boiling-resistant and sun-resistant lotus lake according to claim 1, characterized in that: The raw materials for preparing the composite wall material microcapsule color lake are as follows: light-fast blue lotus color lake: epoxy resin: diisocyanate: cage-type polysilsesquioxane = 10: (5-12): (3-10): (0.05-0.2) in a mass ratio.

6. The method for preparing the water-resistant, boiling-resistant and sun-resistant lotus lake according to claim 1, characterized in that: The preparation method of the composite wall material microcapsule lake specifically comprises the following steps: Step 1: Take epoxy resin, polyethylene glycol, and cage-type polysilsesquioxane and add them to an organic solvent and mix them, then add the sun-fast blue lotus lake and emulsifier, heat and shear them, and obtain an emulsion for use; Step 2: Take another diisocyanate and dissolve it in an organic solvent to obtain a wall material solution, and drop the wall material solution and the curing agent into the emulsion in step 1 at the same time, continue heating and shearing to obtain a cured product, filter the product, wash and dry the filter cake, and obtain a composite wall material microcapsule lake.

7. The method for preparing the water-resistant, boiling-resistant and sun-resistant lotus lake according to claim 6, characterized in that: The emulsifier in step 1 is Tween-60 or betaine; the curing agent in step 2 is a polyetheramine curing agent or an aliphatic amine curing agent.

8. The water-resistant, boiling-resistant and sun-resistant blue lotus lake obtained by the preparation method according to any one of claims 1 to 7.

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