Aqueous one-component epoxy resin dispersions and process for their production

Abstract

The present disclosure relates to the technical field of epoxy resin, and particularly relates to a water-based single-component epoxy resin dispersion and a preparation method thereof. The water-based single-component epoxy resin dispersion comprises the following components in parts by weight: 15-25 parts by weight of a water-based epoxy resin, 5-10 parts by weight of a water-soluble amine compound or a water-soluble acid anhydride compound, 25-35 parts by weight of an oil phase component, 0-1.5 parts by weight of an initiator, 3-8 parts by weight of a surfactant and 95-145 parts by weight of water. The water-based single-component epoxy resin dispersion prepared by the present disclosure has good light resistance.

Description

Technical Field

[0001] This disclosure relates to the field of epoxy resin technology, and in particular to an aqueous one-component epoxy resin dispersion and its preparation method. Background Technology

[0002] Epoxy resins have a wide range of applications, such as coating materials, electrical and electronic insulation materials, and adhesives. In recent years, in particular, there has been a demand for one-component epoxy resin compositions with excellent curing properties and storage stability in order to improve productivity in electronic materials applications.

[0003] Chinese invention patent CN114106757B discloses a low-exudation single-component epoxy adhesive, its preparation method, and its application. The raw materials for preparing the low-exudation single-component epoxy adhesive, by weight, include the following components: 35-50 parts epoxy resin; 4-12 parts modified epoxy resin; 10-30 parts curing agent; 0.1-1 parts stabilizer; 1-5 parts colorant; 1-5 parts coupling agent; and 1-5 parts accelerator. The modified epoxy resin of this invention has a significant inhibitory effect on the exudation of epoxy adhesives, improving the exudation problem of adhesives currently on the market. The low-exudation single-component epoxy adhesive of this invention does not have strict requirements on the external residence time after application, greatly reducing the risk of exudation contaminating lenses and improving product yield.

[0004] Chinese invention patent application CN116004162A discloses a low-modulus epoxy resin adhesive for potting that can be cured by UV heat and its preparation method. The raw material composition, by its total weight, includes 15%-30% epoxy resin, 10%-20% toughening resin, 10%-20% thiol resin, 20%-50% filler, 0.1%-5% thixotropic agent, 0.1%-1% coupling agent, and 0.1%-5% initiator. The adhesive prepared by this invention has low shrinkage, low modulus, strong adhesion to various metal composite materials, good environmental reliability, and can be cured quickly by heat, solving the problem that sealing materials between structural components are prone to material damage and failure under thermal shock.

[0005] Chinese invention patent application CN115785871A discloses a heat-curing flame-retardant epoxy resin one-component adhesive and its preparation method, comprising the following raw materials: 50-200 parts epoxy resin, 10-50 parts epoxy diluent, 80-350 parts flame-retardant filler, 5-25 parts latent curing agent, and 1-5 parts accelerator. This invention involves mixing and dispersing epoxy resin, diluent, and filler evenly, and then mixing them with a modified amine curing agent to allow the amine curing agent to crosslink with the epoxy resin, forming a three-dimensional network structure. The addition of flame-retardant filler to the system further enhances the flame-retardant properties of the cured adhesive.

[0006] However, the epoxy adhesives prepared by the aforementioned patents and existing technologies have poor storage stability at room temperature and still require curing by heating or ultraviolet irradiation. Summary of the Invention

[0007] This disclosure provides an aqueous one-component epoxy resin dispersion to address the shortcomings of related technologies.

[0008] According to a first aspect of the present disclosure, an aqueous one-component epoxy resin dispersion is provided, the aqueous one-component epoxy resin dispersion comprising the following components in parts by weight: 15-25 parts by weight of aqueous epoxy resin, 5-10 parts by weight of water-soluble amine compound or water-soluble acid anhydride compound, 25-35 parts by weight of oil phase component, 0-1.5 parts by weight of initiator, 0-10 parts by weight of surfactant, and 95-145 parts by weight of water.

[0009] In one aspect of the embodiments of this disclosure, preferably, the aqueous one-component epoxy resin dispersion comprises the following components in parts by weight: 15-25 parts by weight of aqueous epoxy resin, 5-10 parts by weight of water-soluble amine compound or water-soluble acid anhydride compound, 25-35 parts by weight of oil phase component, 0.5-1.5 parts by weight of initiator, 0-0.25 parts by weight of catalyst, 3-8 parts by weight of surfactant, 0-8 parts by weight of stabilizer, 110-135 parts by weight of water, and 0-5 parts by weight of cosolvent.

[0010] In one aspect of the embodiments of this disclosure, more preferably, the aqueous one-component epoxy resin dispersion comprises the following components in parts by weight: 15-20 parts by weight of aqueous epoxy resin, 8-10 parts by weight of water-soluble amine compound, 25-30 parts by weight of oil phase component, 0.5-0.8 parts by weight of initiator, 0-0.15 parts by weight of catalyst, 3-8 parts by weight of surfactant, 0-5 parts by weight of stabilizer, 120-135 parts by weight of water, 0-5 parts by weight of cosolvent, 0-1 parts by weight of leveling agent, and 0-1 parts by weight of defoamer.

[0011] In one aspect of the embodiments of this disclosure, specifically, the aqueous one-component epoxy resin dispersion comprises the following components in parts by weight: 15-20 parts by weight of aqueous epoxy resin, 8-10 parts by weight of water-soluble amine compound, 25-30 parts by weight of oil phase component, 0.5-0.8 parts by weight of initiator, 0-0.15 parts by weight of catalyst, 3-8 parts by weight of surfactant, 0-5 parts by weight of stabilizer, and 120-135 parts by weight of water.

[0012] In one aspect of the embodiments of this disclosure, more specifically, the aqueous one-component epoxy resin dispersion comprises the following components in parts by weight: 16 parts by weight of aqueous epoxy resin, 8 parts by weight of water-soluble amine compound, 28 parts by weight of oil phase component, 2 parts by weight of phospholipid, 0.6 parts by weight of initiator, 0.05 parts by weight of catalyst, 3 parts by weight of surfactant and 1 part by weight of stabilizer.

[0013] In one aspect of the embodiments of this disclosure, the water-soluble amine compound is selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, or isophoronediamine; the water-soluble acid anhydride compound is selected from maleic anhydride or phthalic anhydride.

[0014] In one aspect of the present disclosure, the waterborne epoxy resin is prepared by hydration modification of epoxy resin. The hydration modification step includes the following: Step 1-a: 1,4-Butanediol diglycidyl ether and polyethylene glycol are added to a reaction vessel, heated to 70°C-80°C and kept stirring to completely melt the reactants.

[0015] Step 2-a: Dissolve K2S2O8 in water to obtain a solution and add it dropwise to the reaction vessel of step 1-a. React for 20-70 minutes, then raise the temperature to 150℃-180℃, and then measure the epoxy value of the system every 30 minutes using the hydrochloric acid-acetic acid method; the product of step 2-a is obtained when the reaction is completed.

[0016] Step 3-a: Provide epoxy resin and aqueous isocyanate emulsion; dissolve the epoxy resin and aqueous isocyanate emulsion in ethyl acetate, heat to 60℃-70℃ while keeping the mixture stirred, then add the product from step 2-a, and react for 3-5 hours to obtain aqueous epoxy resin.

[0017] In one aspect of the embodiments of this disclosure, in step 3-a, the epoxy resin may be selected from E-20, E-44, E-51, NPEL-128, YLE-1300A, etc., and is not limited thereto.

[0018] In one aspect of this disclosure, the aqueous single-component epoxy resin dispersion is a water-in-oil-in-water type multiple emulsion dispersion; in the water-in-oil-in-water type multiple emulsion dispersion, the outer aqueous phase component contains the oil phase component, and the oil phase component further contains the inner aqueous phase component; furthermore, the outer aqueous phase component contains an aqueous epoxy resin; and the inner aqueous phase component contains a water-soluble amine compound or a water-soluble acid anhydride compound.

[0019] In one aspect of the embodiments of this disclosure, preferably, the aqueous single-component epoxy resin dispersion is a water-in-oil-in-water type multiple emulsion dispersion; in the water-in-oil-in-water type multiple emulsion dispersion, the outer aqueous phase component contains the oil phase component, and the oil phase component further contains the inner aqueous phase component; furthermore, the outer aqueous phase component contains an aqueous epoxy resin; the inner aqueous phase component contains a water-soluble amine compound or a water-soluble acid anhydride compound, and a curing agent, wherein the curing agent is selected from water-soluble compounds.

[0020] In one aspect of the embodiments of this disclosure, preferably, the aqueous single-component epoxy resin dispersion is a water-in-oil-in-water type multiple emulsion dispersion; in the water-in-oil-in-water type multiple emulsion dispersion, the outer aqueous phase component contains the oil phase component, and the oil phase component further contains the inner aqueous phase component; furthermore, the outer aqueous phase component contains an aqueous epoxy resin; the inner aqueous phase component contains a water-soluble amine compound or a water-soluble acid anhydride compound; and the oil phase component contains a curing agent, the curing agent being selected from oil-soluble compounds.

[0021] In one aspect of this disclosure, the initiator is selected from photoinitiators, thermal initiators, or cationic initiators.

[0022] In one aspect of the embodiments of this disclosure, the oil phase component is selected from glyceryl tartrate, glyceryl trioleate, glyceryl tripalmitate, glyceryl tristearate, glyceryl dioleate, 1,3-dipalmitoyl-2-oleoylglycerol, glyceryl distearate, glyceryl dilaurate, glyceryl dimyristate, or glyceryl dilinoleate.

[0023] In one aspect of the embodiments of this disclosure, the oil phase component further comprises phospholipids; the phospholipids are selected from lecithin, soybean phospholipids, cephalin, dioleoylphosphatidylcholine, hydrogenated soybean phospholipids, distearylphosphatidylcholine, dipalmitoylphosphatidylcholine, dimyristoylphosphatidylcholine, dioleoylphosphatidylcholine, distearoylphosphatidylglycerol, dipalmitoylphosphatidylglycerol, dimyristoylphosphatidylglycerol, dioleoylphosphatidylglycerol, or phosphatidylethanolamine.

[0024] In one aspect of this disclosure, the mass ratio of the phospholipid to the oil phase component is selected from 1:(10-30).

[0025] In one aspect of this disclosure, the catalyst is selected from dimethylaminophenol or 2-ethyl-4-methylimidazole.

[0026] In one aspect of the embodiments of this disclosure, the surfactant is selected from Span 20, Span 40, Span 60, Span 80, Tween 20, Tween 40, Tween 60 or Tween 80.

[0027] In one aspect of this disclosure, the stabilizer is selected from gelatin, carrageenan oligosaccharides, or sodium alginate. This disclosure allows for the addition or omission of stabilizers as needed.

[0028] In one aspect of this disclosure, the co-solvent is selected from methanol, ethanol, n-propanol, or isopropanol.

[0029] In one aspect of the embodiments of this disclosure, the defoamer and leveling agent may be any defoamer and leveling agent commonly used in the art, and are not limited thereto.

[0030] According to a second aspect of the present disclosure, a method for preparing the aforementioned aqueous one-component epoxy resin dispersion is provided; the aqueous one-component epoxy resin dispersion is a water-in-oil-in-water type multiple emulsion dispersion; the method includes a process of first preparing an oil-in-water type emulsion dispersion and then preparing a water-in-oil-in-water type multiple emulsion dispersion; the method includes the following steps: when the initiator is selected from water-soluble compounds: step 1-b: dispersing a water-soluble amine compound or a water-soluble acid anhydride compound, and the initiator in water to obtain a first aqueous solution.

[0031] Step 2-b: Provide an oil phase component, add a surfactant to the oil phase component; at a stirring rate of 1500-1800 r / min, add the first aqueous solution dropwise to the oil phase component to obtain a water-in-oil emulsion dispersion.

[0032] Step 3-b: Prepare an aqueous epoxy resin by hydrating and modifying the epoxy resin; disperse the aqueous epoxy resin in water to obtain a second aqueous solution.

[0033] Step 4-b: At a stirring rate of 2500-3000 r / min, the water-in-oil emulsion dispersion prepared in step 2-b is added dropwise to the second aqueous solution to obtain the water-in-oil-in-water multiple emulsion dispersion.

[0034] When the initiator is selected from an oil-soluble compound: Step 1-c: Disperse a water-soluble amine compound or a water-soluble acid anhydride compound in water to obtain a third aqueous solution.

[0035] Step 2-c: Provide an oil phase component, disperse the initiator and surfactant in the oil phase component; add the first aqueous solution dropwise to the oil phase component at a stirring rate of 1500-1800 r / min to obtain a water-in-oil emulsion dispersion.

[0036] Step 3-c: Prepare an aqueous epoxy resin by hydrating and modifying the epoxy resin; disperse the aqueous epoxy resin in water to obtain a fourth aqueous solution.

[0037] Step 4-c: At a stirring rate of 2500-3000 r / min, the water-in-oil emulsion dispersion prepared in step 2-c is added dropwise to the fourth aqueous solution to obtain the water-in-oil-in-water multiple emulsion dispersion.

[0038] In one aspect of this disclosure, when the initiator is selected from oil-soluble compounds, the oil phase component may comprise phospholipids.

[0039] In one aspect of the present disclosure, the method includes the following steps: Step 1-d: dispersing a water-soluble amine compound, a catalyst, and a co-solvent in water to obtain a fifth aqueous solution; wherein the water-soluble amine compound is selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, or diethylaminopropylamine; and the catalyst is selected from dimethylaminophenol or 2-ethyl-4-methylimidazole.

[0040] Step 2-d: Provide an oil phase component, disperse the surfactant and initiator in the oil phase component; add the first aqueous solution dropwise to the oil phase component at a stirring rate of 1500-1800 r / min to obtain a water-in-oil emulsion dispersion; wherein, the oil phase component is selected from glyceryl tartrate, glyceryl trioleate, glyceryl tripalmitate, glyceryl tristearate, glyceryl dioleate, 1,3-dipalmitoyl-2-oleoylglycerol, glyceryl distearate, glyceryl dilaurate, glyceryl dimyristate, or glyceryl dilinoleate; It also contains phospholipids; the phospholipids are selected from lecithin, soybean phospholipids, cephalin, dioleoylphosphatidylcholine, hydrogenated soybean phospholipids, distearylphosphatidylcholine, dipalmitoylphosphatidylcholine, dimyristoylphosphatidylcholine, dioleoylphosphatidylcholine, distearoylphosphatidylglycerol, dipalmitoylphosphatidylglycerol, dimyristoylphosphatidylglycerol, dioleoylphosphatidylglycerol or phosphatidylethanolamine; the surfactant is selected from Span 20, Span 40, Span 60, Span 80, Tween 20, Tween 40, Tween 60 or Tween 80; the initiator is selected from oil-soluble compounds.

[0041] Step 3-d: Prepare an aqueous epoxy resin by hydrating and modifying the epoxy resin; disperse the aqueous epoxy resin in water and add a stabilizer and a defoamer to obtain a sixth aqueous solution.

[0042] Step 4-d: At a stirring rate of 2500-3000 r / min, the water-in-oil emulsion dispersion prepared in step 2-d is added dropwise to the sixth aqueous solution to obtain the water-in-oil-in-water multiple emulsion dispersion.

[0043] In one aspect of this disclosure, the method includes the following steps: Step 1-e: dispersing a water-soluble amine compound, a catalyst, an initiator, and a co-solvent in water to obtain a seventh aqueous solution; wherein the water-soluble amine compound is selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, or diethylaminopropylamine; the catalyst is selected from dimethylaminophenol or 2-ethyl-4-methylimidazole; and the initiator is selected from a water-soluble compound.

[0044] Step 2-e: Provide an oil phase component, disperse the surfactant in the oil phase component; add the first aqueous solution dropwise to the oil phase component at a stirring rate of 1500-1800 r / min to obtain a water-in-oil emulsion dispersion; wherein the oil phase component is selected from glyceryl tartrate, glyceryl trioleate, glyceryl tripalmitate, glyceryl tristearate, glyceryl dioleate, 1,3-dipalmitoyl-2-oleoylglycerol, glyceryl distearate, glyceryl dilaurate, glyceryl dimyristate, or glyceryl dilinoleate; the surfactant is selected from Span 20, Span 40, Span 60, Span 80, Tween 20, Tween 40, Tween 60, or Tween 80.

[0045] Step 3-e: Prepare an aqueous epoxy resin by hydrating and modifying the epoxy resin; disperse the aqueous epoxy resin in water and add a stabilizer and a defoamer to obtain the eighth aqueous solution.

[0046] Step 4-e: At a stirring rate of 2500-3000 r / min, the water-in-oil emulsion dispersion prepared in step 2-e is added dropwise to the eighth aqueous solution to obtain the water-in-oil-in-water multiple emulsion dispersion.

[0047] In one aspect of the embodiments of this disclosure, the step of preparing waterborne epoxy resin by hydration modification of epoxy resin in steps 3-a, 3-b to 3-e specifically involves: adding 1,4-butanediol diglycidyl ether and polyethylene glycol to a reaction vessel, heating to 70°C-80°C while maintaining stirring, so that the reactants are completely melted; dissolving K2S2O8 in water to obtain a solution and adding it dropwise to the reaction vessel, reacting for 20-70 minutes, then raising the temperature to 150°C-180°C, and then measuring the epoxy value of the system every 30 minutes using the hydrochloric acid-acetic acid method; obtaining the product at the end of the reaction; providing epoxy resin and waterborne isocyanate emulsion; dissolving the epoxy resin and waterborne isocyanate emulsion in ethyl acetate, heating to 60°C-70°C while maintaining stirring, then adding the product, reacting for 3-5 hours to obtain waterborne epoxy resin. The epoxy resin may be selected from E-20, E-44, E-51, NPEL-128, YLE-1300A, etc., and is not limited thereto.

[0048] In this disclosure, the initiator may be selected from methyl ethyl ketone peroxide, tert-butyl peroxide, benzoyl peroxide, tert-butyl peroxyisooctanoate, or diphenoxyethyl peroxydicarbonate.

[0049] The technical solutions provided by the embodiments of this disclosure may include the following beneficial effects: As can be seen from the above embodiments, this disclosure prepares a water-in-oil-in-water type multi-emulsion dispersion, which is relatively stable under normal temperature and pressure; and has the following advantages: (1) In this disclosure, epoxy resin is dispersed in the outer aqueous phase, and water-soluble amine compounds (or water-soluble acid anhydride compounds) of curing agent are dispersed in the inner aqueous phase. When the initiator is a water-soluble compound, the initiator is also dispersed in the inner aqueous phase; the inner aqueous phase is encapsulated by the oil phase component, while the oil The phase components are encapsulated by the outer aqueous phase; therefore, when the structure of the multiple emulsion dispersion is not destroyed, it has good stability. For example, in the prior art, epoxy resin dispersions containing photocuring initiators need to be stored away from light, otherwise they will cure under light. However, when using a water-in-oil-in-water type multiple emulsion dispersion prepared in this disclosure, the photocuring initiator and curing agent are encapsulated in the inner aqueous phase, and the epoxy resin is encapsulated in the outer aqueous phase. The three cannot be mixed, so it is difficult for them to react, thus exhibiting better light resistance.

[0050] (2) Similarly, when the initiator is an oil-soluble compound, the initiator is dispersed in the oil phase, the curing agent is still dispersed in the inner oil phase, and the epoxy resin is still dispersed in the outer oil phase; when the structure of the multiple emulsion dispersion is not destroyed, it has good stability; similarly, for example, in the prior art, epoxy resin dispersions containing photocurable initiators need to be stored away from light, otherwise they will cure under light. However, when using a water-in-oil-in-water type multiple emulsion dispersion prepared in this disclosure, the photocurable initiator is encapsulated in the oil phase, the curing agent is encapsulated in the inner aqueous phase, and the epoxy resin is encapsulated in the outer aqueous phase. Similarly, the three cannot be mixed, so it is difficult to react, thus having good light resistance (and phospholipids can also be added to the oil phase, and phospholipids form a bilayer at the water-oil interface, which can prevent cross-linking between epoxy resin and photocurable initiator).

[0051] (3) In addition, the water-in-oil-in-water type multi-emulsion dispersion prepared in this disclosure is relatively stable at room temperature and pressure. However, when a very small amount of strong acid, strong alkali, salt, osmotic pressure regulator or deemulsifier is added, the emulsion structure can be destroyed. Therefore, it can be applied to some special application scenarios. For example, the water-in-oil-in-water type multi-emulsion dispersion containing a light curing agent prepared in this disclosure can have a certain light resistance and the requirements for light protection storage are not very high. When curing is required, a small amount of salt or osmotic pressure regulator is added, and the emulsion structure can be destroyed. At this time, curing can be completed under light.

[0052] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and are not intended to limit this disclosure. Attached Figure Description

[0053] The accompanying drawings, which are incorporated in and form a part of this specification, illustrate embodiments consistent with this disclosure and, together with the description, serve to explain the principles of this disclosure.

[0054] Figure 1 This is a schematic diagram of the structure of a water-in-oil-in-water type multiple emulsion dispersion prepared according to an exemplary embodiment. Detailed Implementation

[0055] To make the objectives, technical solutions, and advantages of this application clearer, the technical solutions of this application will be clearly and completely described below in conjunction with embodiments. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. The embodiments described herein are illustrative in nature and are used to provide a basic understanding of this application. The embodiments of this application should not be construed as limiting this application.

[0056] For the sake of brevity, this article only discloses a few specific numerical ranges. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, just as any upper limit can be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single value can itself serve as a lower or upper limit and be combined with any other point or single value or with other lower or upper limits to form an unspecified range.

[0057] In this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0058] In this description, unless otherwise stated, "above" and "below" include the stated number.

[0059] Unless otherwise stated, the terms used in this disclosure have their common meanings as commonly understood by those skilled in the art. Unless otherwise stated, the values ​​of the parameters mentioned in this disclosure can be measured using various measurement methods commonly used in the art (e.g., they can be tested according to the methods given in the embodiments of this disclosure).

[0060] The term "about" is used to describe and indicate small variations. When used in conjunction with an event or situation, the term may refer to examples in which the event or situation occurred precisely or in examples in which the event or situation occurred very approximately. For example, when used in conjunction with numerical values, the term may refer to a range of variation less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. Additionally, quantities, ratios, and other numerical values ​​are sometimes presented in range format herein. It should be understood that such range format is for convenience and brevity and should be interpreted flexibly to include not only numerical values ​​explicitly specified as range limits but also all individual numerical values ​​or subranges covered within the range, as if each numerical value and subrange were explicitly specified.

[0061] The list of items connected by the terms "at least one of," "at least one of," "at least one of," or other similar terms can mean any combination of the listed items. For example, if items A and B are listed, then the phrase "at least one of A and B" means only A; only B; or A and B. In another instance, if items A, B, and C are listed, then the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A may contain a single component or multiple components. Item B may contain a single component or multiple components. Item C may contain a single component or multiple components.

[0062] The present disclosure is further illustrated below with reference to embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the disclosure.

[0063] Example 1: Example 1 includes the following steps: 1. Preparation of waterborne epoxy resin: 0.25 mol of 1,4-butanediol diglycidyl ether and 0.25 mol of polyethylene glycol are added to a reaction vessel, heated to 80°C and stirred until the reactants are completely melted; 0.6 g of K2S2O8 is dissolved in 200 mL of water to obtain a solution and added dropwise to the reaction vessel, reacted for 60 min, then heated to 170°C, and the epoxy content of the system is measured every 30 minutes using the hydrochloric acid-acetic acid method. Value; the reaction ended after 4 hours, and the product was collected; 0.20 mol of epoxy resin E-51 and aqueous isocyanate emulsion (where the molar amount of isocyanate is 0.12 mol; specifically, it is an aqueous blocked polyisocyanate emulsion with a solid content of 45%, and the blocking agent is 2-butanone oxime, based on isoflurane diisocyanate); the epoxy resin and aqueous isocyanate emulsion were dissolved in ethyl acetate, heated to 70°C and kept stirring, and then the aforementioned product was added. The reaction was carried out for 5 hours, and the aqueous epoxy resin was obtained by rotary evaporation.

[0064] 2. Preparation of the water-in-oil-in-water multiple emulsion dispersion of Example 1: 8 parts by weight of triethylenetetramine and 0.05 parts by weight of the catalyst dimethylaminophenol were dispersed in 15 parts by weight of water to obtain aqueous solution A; 2 parts by weight of phospholipid (lecithin) were dissolved in 28 parts by weight of the oil phase component, and then 3 parts by weight of the surfactant Span 60 and 0.6 parts by weight of the photoinitiator Irgacue 250 were added to obtain the oil phase; aqueous solution A was added dropwise to the oil phase at a stirring rate of 1700 r / min to obtain a water-in-oil emulsion dispersion; 16 parts by weight of the aqueous epoxy resin prepared above were dispersed in 115 parts by weight of water, and 1 part by weight of the stabilizer sodium alginate was added to obtain aqueous solution B; the aforementioned water-in-oil emulsion dispersion was added dropwise to aqueous solution B at a stirring rate of 2800 r / min to obtain the water-in-oil-in-water multiple emulsion dispersion of Example 1; its structure is as follows. Figure 1 As shown.

[0065] Examples 2-4: The steps of Examples 2-4 are the same as those of Example 1, except that: in Example 2, the amount of triethylenetetramine used was changed to 4 parts by weight; in Example 3, the amount of triethylenetetramine used was changed to 12 parts by weight; and in Example 4, the amount of waterborne epoxy resin used was changed to 8 parts by weight. However, none of Examples 2-4 could form a water-in-oil-in-water type multiple emulsion dispersion, and demulsification occurred during the preparation process.

[0066] Examples 5-7: Examples 5-7 used water-soluble epoxy resin prepared by the method for preparing water-soluble epoxy resin provided in Example 2 of CN201410503428.8 to replace the water-soluble epoxy resin prepared in Example 1; wherein Example 5 used 16 parts by weight of the water-soluble epoxy resin prepared in Example 2 of CN201410503428.8; Example 6 used 10 parts by weight of the water-soluble epoxy resin prepared in Example 2 of CN201410503428.8; Example 7 used 20 parts by weight of the water-soluble epoxy resin prepared in Example 2 of CN201410503428.8; however, Examples 5-7 could not form a water-in-oil-in-water type multiple emulsion dispersion, and demulsification occurred during the preparation process.

[0067] Examples 8-10: Examples 8-10 use the following steps to prepare a water-soluble epoxy resin instead of the water-soluble epoxy resin prepared in Example 1: Take 0.20 mol of phenolic epoxy resin and prepare a 30% dioxane solution; under ice water protection and at a temperature not exceeding 10°C, add a 15% ethanol solution containing 0.15 mol of dimethylamine dropwise using a peristaltic pump; the dropwise addition time is controlled at 1 h. Then add a small amount of 3g citric acid, dissolve it completely, and slowly add 25 mL of 30% hydrogen peroxide dropwise. Finally, raise the temperature to 60°C, keep it at that temperature for 2 h, cool it, and collect the product to obtain the water-soluble epoxy resin.

[0068] Example 8 used 16 parts by weight of the water-soluble epoxy resin prepared by the aforementioned method; Example 9 used 10 parts by weight of the water-soluble epoxy resin prepared by the aforementioned method; Example 10 used 20 parts by weight of the water-soluble epoxy resin prepared by the aforementioned method; however, none of Examples 8-10 could form a water-in-oil-in-water multi-emulsion dispersion, and demulsification occurred during the preparation process.

[0069] Comparative Example 1: Comparative Example 1 includes the following steps: 1. Preparation of waterborne epoxy resin: 0.25 mol of 1,4-butanediol diglycidyl ether and 0.25 mol of polyethylene glycol are added to a reaction vessel, heated to 80°C and stirred until the reactants are completely melted; 0.6 g of K2S2O8 is dissolved in 200 mL of water to obtain a solution and added dropwise to the reaction vessel. The reaction is carried out for 60 min, then the temperature is raised to 170°C, and the epoxy content of the system is measured every 30 minutes using the hydrochloric acid-acetic acid method. Value; the reaction ended after 4 hours, and the product was collected; 0.20 mol of epoxy resin E-51 and aqueous isocyanate emulsion (where the molar amount of isocyanate is 0.12 mol; specifically, it is an aqueous blocked polyisocyanate emulsion with a solid content of 45%, and the blocking agent is 2-butanone oxime, based on isoflurane diisocyanate); the epoxy resin and aqueous isocyanate emulsion were dissolved in ethyl acetate, heated to 70°C and kept stirring, and then the aforementioned product was added. The reaction was carried out for 5 hours, and the aqueous epoxy resin was obtained by rotary evaporation.

[0070] 2. Preparation of oil-in-water emulsion dispersion of Comparative Example 1: 16 parts by weight of the aqueous epoxy resin prepared above, 1 part by weight of the stabilizer sodium alginate, 8 parts by weight of triethylenetetramine, and 0.05 parts by weight of the catalyst dimethylaminophenol were dispersed in 130 parts by weight of water to obtain aqueous solution C.

[0071] Two parts by weight of phospholipid (lecithin) were dissolved in 28 parts by weight of oil phase component, and then three parts by weight of surfactant Span 60 and 0.6 parts by weight of photoinitiator Irgacue 250 were added to obtain the oil phase.

[0072] At a stirring rate of 1700 r / min, the oil phase was added dropwise to aqueous solution C to obtain the oil-in-water emulsion dispersion of Comparative Example 1.

[0073] Comparative Example 2: The steps for Comparative Example 2 are the same as those for Comparative Example 1, except that phospholipids are not added in Comparative Example 2.

[0074] Lightfastness test of Example 1 and Comparative Examples 1-2: At room temperature and pressure, Example 1 and Comparative Examples 1-2 were irradiated with 365nm ultraviolet light. After irradiation for 1 hour, the sample of Comparative Example 1 showed partial curing; the sample of Comparative Example 2 was completely cured; the sample of Example 1 was stable. After irradiation for 3 hours, the sample of Comparative Example 1 showed obvious curing; the sample of Example 1 remained stable.

[0075] When 1 part by weight of saturated sodium chloride solution was added to the sample of Example 1, the sample of Example 1 immediately demulsified and then showed obvious solidification within 2 minutes.

[0076] The reason why the properties of Example 1 are significantly better than those of Comparative Example 1 is that the photocuring initiator is encapsulated in the oil phase, the curing agent is encapsulated in the inner aqueous phase, and the epoxy resin is encapsulated in the outer aqueous phase; these three are separated from each other, and a phospholipid bilayer exists at the water / oil interface, thus exhibiting excellent lightfastness. In Comparative Example 1, the curing agent and photocuring initiator are encapsulated in the oil phase, and the epoxy resin is encapsulated in the outer aqueous phase. Although a phospholipid bilayer exists at the water / oil interface, there is still a probability of curing through the phospholipid bilayer. Furthermore, the crosslinking products generated after curing can damage the phospholipid bilayer, resulting in lightfastness far inferior to that of Example 1.

[0077] Other embodiments of this disclosure will readily occur to those skilled in the art upon consideration of the specification and practice of the disclosure herein. This disclosure is intended to cover any variations, uses, or adaptations of this disclosure that follow the general principles of this disclosure and include common knowledge or customary techniques in the art not disclosed herein.

Claims

1. An aqueous one-component epoxy resin dispersion, characterized in that, The aqueous one-component epoxy resin dispersion comprises the following components in parts by weight: 15-25 parts by weight of waterborne epoxy resin, 5-10 parts by weight of water-soluble amine compound or water-soluble acid anhydride compound, 25-35 parts by weight of oil phase component, 0-1.5 parts by weight of initiator, 0-10 parts by weight of surfactant and 95-145 parts by weight of water. The oil phase component is selected from glyceryl tartrate, glyceryl trioleate, glyceryl tripalmitate, glyceryl tristearate, glyceryl dioleate, 1,3-dipalmitoyl-2-oleoylglycerol, glyceryl distearate, glyceryl dilaurate, glyceryl dimyristate, or glyceryl dilinoleate. The oil phase component further comprises phospholipids; the phospholipids are selected from lecithin, cephalin, dioleoylphosphatidylcholine, distearylphosphatidylcholine, dipalmitoylphosphatidylcholine, dimyristoylphosphatidylcholine, distearylphosphatidylglycerol, dipalmitoylphosphatidylglycerol, dimyristoylphosphatidylglycerol or dioleoylphosphatidylglycerol; The aqueous single-component epoxy resin dispersion is a water-in-oil-in-water type multiple emulsion dispersion; in the water-in-oil-in-water type multiple emulsion dispersion, the outer aqueous phase component contains the oil phase component, and the oil phase component further contains the inner aqueous phase component; and the outer aqueous phase component contains aqueous epoxy resin. The inner aqueous phase component contains water-soluble amine compounds or water-soluble acid anhydride compounds; The waterborne epoxy resin is prepared by hydrating and modifying epoxy resin, and the hydration and modification steps include the following: Step 1-a: Add 1,4-butanediol diglycidyl ether and polyethylene glycol to a reaction vessel, heat to 70℃-80℃ and keep stirring to completely melt the reactants; wherein, the molar ratio of the 1,4-butanediol diglycidyl ether and polyethylene glycol is selected as 1:1; Step 2-a: Dissolve K2S2O8 in water to obtain a solution and add it dropwise to the reaction vessel of step 1-a. React for 20-70 min, then heat to 150℃-180℃, and then measure the epoxy value of the system every 30 minutes using the hydrochloric acid-acetic acid method; when the reaction is completed, the product of step 2-a is obtained. Step 3-a: Provide epoxy resin and aqueous isocyanate emulsion; dissolve the epoxy resin and aqueous isocyanate emulsion in ethyl acetate, heat to 60℃-70℃ while keeping the mixture stirred, then add the product from step 2-a, and react for 3-5 hours to obtain aqueous epoxy resin.

2. The aqueous single-component epoxy resin dispersion according to claim 1, characterized in that, The aqueous one-component epoxy resin dispersion comprises the following components in parts by weight: 15-25 parts by weight of waterborne epoxy resin, 5-10 parts by weight of water-soluble amine compound or water-soluble acid anhydride compound, 25-35 parts by weight of oil phase component, 0.5-1.5 parts by weight of initiator, 0-0.25 parts by weight of catalyst, 3-8 parts by weight of surfactant, 0-8 parts by weight of stabilizer, 110-135 parts by weight of water and 0-5 parts by weight of cosolvent.

3. The aqueous single-component epoxy resin dispersion according to claim 1, characterized in that, The aqueous one-component epoxy resin dispersion comprises the following components in parts by weight: 15-20 parts by weight of waterborne epoxy resin, 8-10 parts by weight of water-soluble amine compound, 25-30 parts by weight of oil phase component, 0.5-0.8 parts by weight of initiator, 0-0.15 parts by weight of catalyst, 3-8 parts by weight of surfactant, 0-5 parts by weight of stabilizer, 120-135 parts by weight of water, 0-5 parts by weight of cosolvent, 0-1 parts by weight of leveling agent and 0-1 parts by weight of defoamer.

4. The aqueous single-component epoxy resin dispersion according to claim 1, characterized in that, The water-soluble amine compound is selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine, or isophoronediamine; the water-soluble acid anhydride compound is selected from maleic anhydride or phthalic anhydride.

5. The aqueous one-component epoxy resin dispersion according to any one of claims 2 or 3, characterized in that, The aqueous one-component epoxy resin dispersion satisfies at least one of the following conditions: (1) The initiator is selected from photoinitiators, thermal initiators or cationic initiators; (2) The catalyst is selected from dimethylaminophenol or 2-ethyl-4-methylimidazole; (3) The surfactant is selected from Span 20, Span 40, Span 60, Span 80, Tween 20, Tween 40, Tween 60 or Tween 80; (4) The stabilizer is selected from gelatin, carrageenan oligosaccharide or sodium alginate; (5) The cosolvent is selected from methanol, ethanol, n-propanol or isopropanol.

6. A method for preparing the aqueous one-component epoxy resin dispersion of claim 5, characterized in that, The aqueous one-component epoxy resin dispersion is a water-in-oil-in-water type multiple emulsion dispersion; the method includes the process of first preparing a water-in-oil type emulsion dispersion and then preparing a water-in-oil-in-water type multiple emulsion dispersion; the method includes the following steps: When the initiator is selected from water-soluble compounds: Step 1-b: Disperse the water-soluble amine compound or water-soluble acid anhydride compound, and the initiator in water to obtain a first aqueous solution; Step 2-b: Provide an oil phase component, add a surfactant to the oil phase component; at a stirring rate of 1500-1800 r / min, add the first aqueous solution dropwise to the oil phase component to obtain a water-in-oil emulsion dispersion; Step 3-b: Prepare an aqueous epoxy resin by hydration modification of the epoxy resin; disperse the aqueous epoxy resin in water to obtain a second aqueous solution; Step 4-b: At a stirring rate of 2500-3000 r / min, the water-in-oil emulsion dispersion prepared in step 2-b is added dropwise to the second aqueous solution to obtain the water-in-oil-in-water multiple emulsion dispersion; When the initiator is selected from oil-soluble compounds: Step 1-c: Disperse the water-soluble amine compound or water-soluble acid anhydride compound in water to obtain a third aqueous solution; Step 2-c: Provide an oil phase component, disperse the initiator and surfactant in the oil phase component; add the first aqueous solution dropwise to the oil phase component at a stirring rate of 1500-1800 r / min to obtain a water-in-oil emulsion dispersion; Step 3-c: Prepare an aqueous epoxy resin by hydration modification of the epoxy resin; disperse the aqueous epoxy resin in water to obtain a fourth aqueous solution; Step 4-c: At a stirring rate of 2500-3000 r / min, the water-in-oil emulsion dispersion prepared in step 2-c is added dropwise to the fourth aqueous solution to obtain the water-in-oil-in-water multiple emulsion dispersion.

7. The method according to claim 6, characterized in that, The method includes the following steps: Step 1-d: Disperse the water-soluble amine compound, catalyst, and co-solvent in water to obtain the fifth aqueous solution; The water-soluble amine compound is selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, or diethylaminopropylamine; the catalyst is selected from dimethylaminophenol or 2-ethyl-4-methylimidazole. Step 2-d: Provide an oil phase component, disperse the surfactant and initiator in the oil phase component; add the first aqueous solution dropwise to the oil phase component at a stirring rate of 1500-1800 r / min to obtain a water-in-oil emulsion dispersion; The oil phase component is selected from glyceryl tartrate, glyceryl trioleate, glyceryl tripalmitate, glyceryl tristearate, glyceryl dioleate, 1,3-dipalmitoyl-2-oleoylglycerol, glyceryl distearate, glyceryl dilaurate, glyceryl dimyristate, or glyceryl dilinoleate. The oil phase component further comprises phospholipids; the phospholipids are selected from lecithin, cephalin, dioleoylphosphatidylcholine, distearylphosphatidylcholine, dipalmitoylphosphatidylcholine, dimyristoylphosphatidylcholine, distearylphosphatidylglycerol, dipalmitoylphosphatidylglycerol, dimyristoylphosphatidylglycerol or dioleoylphosphatidylglycerol; The surfactant is selected from Span 20, Span 40, Span 60, Span 80, Tween 20, Tween 40, Tween 60 or Tween 80; The initiator is selected from oil-soluble compounds; Step 3-d: Prepare an aqueous epoxy resin by hydration modification of the epoxy resin; disperse the aqueous epoxy resin in water and add a stabilizer and a defoamer to obtain a sixth aqueous solution; Step 4-d: At a stirring rate of 2500-3000 r / min, the water-in-oil emulsion dispersion prepared in step 2-d is added dropwise to the sixth aqueous solution to obtain the water-in-oil-in-water multiple emulsion dispersion.

8. The method according to claim 6, characterized in that, The method includes the following steps: Step 1-e: Disperse the water-soluble amine compound, catalyst, initiator, and co-solvent in water to obtain the seventh aqueous solution; Wherein, the water-soluble amine compound is selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, or diethylaminopropylamine; the catalyst is selected from dimethylaminophenol or 2-ethyl-4-methylimidazole; and the initiator is selected from water-soluble compounds. Step 2-e: Provide an oil phase component, disperse the surfactant in the oil phase component; add the first aqueous solution dropwise to the oil phase component at a stirring rate of 1500-1800 r / min to obtain a water-in-oil emulsion dispersion; The oil phase component is selected from glyceryl tartrate, glyceryl trioleate, glyceryl tripalmitate, glyceryl tristearate, glyceryl dioleate, 1,3-dipalmitoyl-2-oleoylglycerol, glyceryl distearate, glyceryl dilaurate, glyceryl dimyristate, or glyceryl dilinoleate. The surfactant is selected from Span 20, Span 40, Span 60, Span 80, Tween 20, Tween 40, Tween 60 or Tween 80; Step 3-e: Prepare an aqueous epoxy resin by hydrating and modifying the epoxy resin; disperse the aqueous epoxy resin in water and add a stabilizer and a defoamer to obtain the eighth aqueous solution; Step 4-e: At a stirring rate of 2500-3000 r / min, the water-in-oil emulsion dispersion prepared in step 2-e is added dropwise to the eighth aqueous solution to obtain the water-in-oil-in-water multiple emulsion dispersion.

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