CN113480747B - Preparation and application of epoxy acrylate microsphere emulsion - Google Patents
Preparation and application of epoxy acrylate microsphere emulsion Download PDFInfo
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Abstract
The invention discloses preparation and application of epoxy acrylate microsphere emulsion. The preparation method of the epoxy acrylate microsphere emulsion comprises the following steps: (1) mixing allyl diglycol dicarbonate with epoxy acrylate, heating and stirring, and cooling to obtain a mixture A; (2) adding a cross-linking agent into the mixture A prepared in the step (1), and mixing and stirring to obtain a mixture B; (3) and (3) curing the mixture B prepared in the step (2) to obtain the epoxy acrylate microsphere emulsion. The prepared epoxy acrylate microsphere emulsion is used as a light diffusant and directly added into UV resin to prepare the matte film, so that the production is convenient, the environment is protected, and the problem of microsphere agglomeration can be effectively avoided.
Description
Technical Field
The invention relates to the field of preparation of high polymer materials, in particular to preparation and application of an epoxy acrylate microsphere emulsion.
Background
Compared with the traditional incandescent lamp, the LED lighting has the advantages of environmental protection, high conversion efficiency, long service life and the like, however, the white light emitted by the LED as a point light source has relatively high luminous intensity, is easy to generate glare after being directly viewed, and is more easy to cause visual fatigue after being used for a long time. The matte film can convert an LED from a point light source to a surface light source to realize the effect of light uniformization, the blending of the polymer microspheres and the transparent base resin is a traditional method for preparing the matte film, but the problem of polymer microsphere agglomeration in the blending process is difficult to overcome.
The preparation method of the polymer microsphere has been reported at home and abroad, and basically adopts suspension polymerization, dispersion polymerization, emulsion polymerization and seed polymerization. However, the preparation of microspheres by these methods has the disadvantages of multiple steps, complex operation, high production cost, and the like, and a large amount of organic solvent is consumed in the post-treatment process to wash away the dispersing agent, emulsifier, and other auxiliaries on the surfaces of the microspheres, which is not beneficial to industrial production and environmental protection.
The reaction induced phase separation method for preparing the microspheres has the advantages of simple operation, low requirement on equipment and the like, and the prepared microspheres have controllable particle size and good monodispersity. But a large amount of organic solvent is consumed in the post-treatment process, so that the environment is easily polluted. Therefore, it is necessary to provide a simple method for producing microspheres, which can produce microspheres in an optically active solvent and can use the reaction system as a light diffusing agent directly for producing a matte film without washing off the solvent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides preparation and application of epoxy acrylate microsphere emulsion. According to the invention, the optical resin allyl diglycol dicarbonate is used as a solvent phase to prepare the epoxy acrylate microspheres, the conditions in the preparation process are mild, the operation is simple, the particle size of the obtained microspheres is controllable, the monodispersity is good, the emulsion containing the epoxy acrylate microspheres is used as a light diffusant to be directly added into UV resin to prepare the matte film, the production is convenient, the environment is protected, and the problem of microsphere agglomeration can be effectively avoided.
The technical scheme of the invention is as follows:
the preparation method of the epoxy acrylate microsphere emulsion comprises the following steps:
(1) mixing allyl diglycol dicarbonate with epoxy acrylate, heating and stirring, and cooling to obtain a mixture A;
(2) adding a cross-linking agent into the mixture A prepared in the step (1), and mixing and stirring to obtain a mixture B;
(3) and (3) curing the mixture B prepared in the step (2) to obtain the epoxy acrylate microsphere emulsion.
Further, in the step (1), the purity of the allyl diglycol dicarbonate is 95-100%; the purity of the epoxy acrylate is 95-100%; the mass ratio of the allyl diglycol dicarbonate to the epoxy acrylate is 4-10: 1.
Further, in the step (1), the heating temperature is 50-60 ℃; the stirring speed is 1000-1500 r/min, and the time is 30-40 min.
Further, in the step (2), the cross-linking agent is one or more of ethylenediamine, isophoronediamine, diethylenetriamine and triethylenetetramine; the molar ratio of the cross-linking agent to the epoxy acrylate is 1.0-1.2: 1; the stirring speed is 300-500 r/min, and the stirring time is 2-10 min.
Further, in the step (3), the curing time is 1-2 h, and the temperature is 25-30 ℃; the particle size of the epoxy acrylate microsphere emulsion is 0.5-2.0 μm.
The epoxy acrylate microsphere emulsion is used for preparing a matte film.
Further, the matte film comprises the following components in percentage by mass: 10-30 parts of epoxy acrylate microsphere emulsion, 70-90 parts of polyurethane diacrylate and 3-5 parts of photoinitiator.
Further, the viscosity of the polyurethane diacrylate is 8-10 mPa & s; the initiator is one or more of TPO, 184 and 1173.
Further, the preparation method of the matte film comprises the following steps:
(1) mixing and stirring 10-30 parts of epoxy acrylate microsphere emulsion, 70-90 parts of polyurethane diacrylate and 3-5 parts of photoinitiator to obtain a matt adhesive solution;
(2) and (3) injecting the matte glue solution prepared in the step (1) into a polytetrafluoroethylene mold, and curing to obtain the matte film.
Further, in the step (1), the stirring speed is 300-500 r/min, and the stirring time is 2-10 min; in the step (2), the curing is performed by irradiating for 20-40 s with an ultraviolet lamp with 3000W power; the thickness of the matte film is 0.2-0.5 mm.
The beneficial technical effects of the invention are as follows:
(1) the invention uses a reaction induced phase separation method to prepare the uniform epoxy acrylate microspheres with controllable particle size of 0.5-3.0 mu m by regulating and controlling the proportion of allyl diglycol dicarbonate and epoxy acrylate.
(2) The preparation method of the epoxy acrylate microspheres has the advantages of mild conditions, simple and convenient operation and fast production, and is beneficial to industrial production.
(3) The solvent phase in the epoxy acrylate microsphere emulsion prepared by the invention is allyl diglycol dicarbonate, the two ends of the molecular chain of the epoxy acrylate microsphere emulsion are provided with active double bonds, the microsphere is not required to be eluted in the subsequent use, the emulsion containing the microsphere can be directly added into a photocuring material as extinction mother liquor, no waste liquid is generated in the whole process, and the epoxy acrylate microsphere emulsion has the advantages of environmental protection and no pollution.
(4) The invention effectively avoids the problem of agglomeration of the microspheres in the transparent resin glue solution by using the epoxy acrylate microsphere emulsion.
Drawings
FIG. 1 is a schematic diagram of the reaction of the present invention.
In the figure: (a) is transparent and uniform mixed liquid; (b) is a bicontinuous phase structure; (c) is the initial stage of the formation of the epoxy acrylate microspheres; (d) is epoxy acrylate microsphere emulsion.
FIG. 2 is a digital photograph of mixture B before curing (FIG. a) and an epoxy acrylate microsphere emulsion after curing (FIG. B) in example 1 of the present invention.
FIG. 3 is an infrared spectrum of epoxy acrylate microspheres prepared in example 1 of the present invention and an uncrosslinked epoxy acrylate raw material.
FIG. 4 is a particle size distribution diagram of epoxy acrylate microspheres prepared in example 1 of the present invention.
FIG. 5 is a Scanning Electron Microscope (SEM) image of epoxy acrylate microspheres prepared in example 1 and examples 5-7 of the present invention.
In the figure: a is an SEM picture of the epoxy acrylate microspheres prepared in example 1; b is an SEM picture of the epoxy acrylate microspheres prepared in example 5; c is an SEM image of the epoxy acrylate microspheres prepared in example 6; d is the SEM image of the epoxy acrylate microspheres prepared in example 7.
Fig. 6 is a bar graph of the transmission and haze of matte films prepared in example 2 of the present invention.
Fig. 7 is a digital photograph of the matte film prepared in example 2 of the present invention and the matte film prepared in comparative example 2.
In the figure: a is the matte film prepared in example 2; b is the matte film prepared in comparative example 2.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
The principle brief introduction: mixing allyl diglycol dicarbonate with epoxy acrylate to form a blending system, adding a cross-linking agent, and obtaining the epoxy acrylate microsphere emulsion through a reaction-induced phase separation mechanism.
As shown in FIG. 1, since allyl diglycol dicarbonate and epoxyacrylate have good compatibility, a mixture of allyl diglycol dicarbonate and epoxyacrylate is initially transparent and uniform as shown in (a); adding an amine crosslinking agent, heating to 30 ℃, and enabling the compatibility of an epoxy acrylate phase and an allyl diglycol dicarbonate phase to be poor due to the Michael addition reaction of the epoxy acrylate and the amine crosslinking agent in a blending system, wherein the two phases form a bicontinuous phase structure by following a spinodal separation mechanism, as shown in (b); with the deep progress of the crosslinking reaction, under the action of the continuously increased interfacial tension, the continuity of the epoxy acrylate phase is gradually broken, and the prototype of the epoxy acrylate microsphere begins to appear, as shown in (c); at the later stage of the crosslinking reaction, the allyl diglycol dicarbonate phase with high fluidity rapidly disperses the epoxy acrylate microspheres, and finally the crosslinked epoxy acrylate is fixed in the allyl diglycol dicarbonate phase in the form of microspheres, as shown in (d), to obtain the epoxy acrylate microsphere emulsion.
Example 1
The preparation method of the epoxy acrylate microsphere emulsion comprises the following steps:
(1) mixing 4g of allyl diglycol dicarbonate with 1g of epoxy acrylate, the allyl diglycol dicarbonate being purchased from warrior volitant biotechnology limited, wuhan, with a purity of 95%; the purity of the epoxy acrylate is 95 percent, and the epoxy acrylate is purchased from Guangzhou five-element materials Co; stirring at 50 ℃ at 1500r/min for 40min, and naturally cooling to room temperature to obtain a mixture A;
(2) adding 0.09g of cross-linking agent triethylene tetramine (the molar ratio of the cross-linking agent to the epoxy acrylate is 1:1) into the mixture A prepared in the step (1), and stirring at the speed of 500r/min for 10min to obtain a mixture B;
(3) and (3) curing the mixture B prepared in the step (2) at 30 ℃ for 2 hours to obtain epoxy acrylate microsphere emulsion, wherein the particle size of the obtained epoxy acrylate microspheres is 2.0 mu m.
A matte film prepared by using epoxy acrylate microsphere emulsion comprises the following steps:
(1) mixing 10 parts (10-30 parts) of epoxy acrylate microsphere emulsion, 90 parts of polyurethane diacrylate (which is purchased from Guangzhou five-element materials Co., Ltd., and the viscosity is 10mPa & lt/s) and 3 parts of photoinitiator TPO (which is purchased from Shanghai Kaiyin chemical Co., Ltd.), and stirring at the speed of 500r/min for 10min to obtain a matt adhesive solution;
(2) injecting the matt adhesive solution prepared in the step (1) into a polytetrafluoroethylene mold (a circular mold with the diameter of 6cm and the depth of 0.5 mm), and irradiating for 30s by using an ultraviolet lamp with the power of 3000W for curing to obtain a matt film; the thickness of the obtained matte film was 0.3 mm.
And adding the obtained epoxy acrylate microsphere emulsion into absolute ethyl alcohol with the same volume, washing (removing allyl diglycol dicarbonate), and drying at 40 ℃ for 12 hours to obtain the epoxy acrylate microspheres corresponding to the epoxy acrylate microsphere emulsion in the embodiment 1, wherein the epoxy acrylate microspheres are used for testing the performance of the microspheres in the epoxy acrylate microsphere emulsion.
Example 2
The preparation method of the epoxy acrylate microsphere emulsion comprises the following steps:
(1) mixing 4g of allyl diglycol dicarbonate, which is commercially available from Wuhan Huaxiang Biotech, Inc. and has a purity of 95%, with 1g of epoxy acrylate; the purity of the epoxy acrylate is 95 percent, and the epoxy acrylate is purchased from Guangzhou Wuxing materials Co., Ltd; stirring at 50 ℃ at 1500r/min for 40min, and naturally cooling to room temperature to obtain a mixture A;
(2) adding 0.08g of cross-linking agent diethylenetriamine (the dosage of the cross-linking agent is determined according to the molar ratio of the cross-linking agent to the epoxy acrylate of 1:1) into the mixture A prepared in the step (1), and stirring at the speed of 500r/min for 10min to obtain a mixture B;
(3) and (3) curing the mixture B prepared in the step (2) at 30 ℃ for 2 hours to obtain epoxy acrylate microsphere emulsion, wherein the particle size of the obtained epoxy acrylate microspheres is 1.5 mu m.
A matte film prepared by epoxy acrylate microsphere emulsion comprises the following steps:
(1) mixing 20 parts of epoxy acrylate microsphere emulsion, 80 parts of polyurethane diacrylate (which is purchased from Guangzhou five-element materials Co., Ltd., and has the viscosity of 10mPa & lt/s) and 3 parts of photoinitiator 184 (which is purchased from Shanghai Kayin chemical Co., Ltd.), and stirring at the speed of 500r/min for 10min to obtain a matte glue solution;
(2) injecting the matt adhesive solution prepared in the step (1) into a polytetrafluoroethylene mold (a circular mold with the diameter of 6cm and the depth of 0.5 mm), and irradiating for 30s by using an ultraviolet lamp with the power of 3000W for curing to obtain a matt film; the thickness of the obtained matte film was 0.2 mm.
Example 3
The preparation method of the epoxy acrylate microsphere emulsion comprises the following steps:
(1) mixing 4g of allyl diglycol dicarbonate, which is purchased from Wuhan Huaxiang Biotech limited and has a purity of 100%, with 1g of epoxy acrylate; the purity of the epoxy acrylate is 100 percent, and the epoxy acrylate is purchased from Guangzhou Wuxing materials Co., Ltd; stirring at 60 ℃ at the speed of 1000r/min for 30min, and naturally cooling to room temperature to obtain a mixture A;
(2) adding 0.06g of cross-linking agent ethylenediamine into the mixture A prepared in the step (1) (the dosage of the cross-linking agent is determined according to the molar ratio of the cross-linking agent to the epoxy acrylate of 1.1: 1), and stirring at the speed of 300r/min for 2min to obtain a mixture B;
(3) and (3) curing the mixture B prepared in the step (2) at 25 ℃ for 1h to obtain epoxy acrylate microsphere emulsion, wherein the particle size of the obtained epoxy acrylate microsphere is 1.6 mu m.
A matte film prepared by epoxy acrylate microsphere emulsion comprises the following steps:
(1) mixing 30 parts of epoxy acrylate microsphere emulsion, 70 parts of polyurethane diacrylate (purchased from Guangzhou five-element materials Co., Ltd., viscosity of 8mPa · s) and 4 parts of photoinitiator 1173 (purchased from Shanghai Kai-Yin chemical Co., Ltd.), and stirring at the speed of 300r/min for 2min to obtain a matte glue solution;
(2) injecting the matt adhesive solution prepared in the step (1) into a polytetrafluoroethylene mold (a circular mold with the diameter of 6cm and the depth of 0.5 mm), and irradiating for 20 seconds by using an ultraviolet lamp with the power of 3000W to obtain a matt film; the thickness of the obtained matte film was 0.4 mm.
Example 4
The preparation method of the epoxy acrylate microsphere emulsion comprises the following steps:
(1) mixing 4g of allyl diglycol dicarbonate, which is purchased from Wuhan Huaxiang Biotech limited and has a purity of 97%, with 1g of epoxy acrylate; the purity of the epoxy acrylate is 97 percent, and the epoxy acrylate is purchased from Guangzhou five-element materials Co; stirring at 55 ℃ at a speed of 1200r/min for 35min, and naturally cooling to room temperature to obtain a mixture A;
(2) adding 0.2g of cross-linking agent isophorone diamine (the amount of the cross-linking agent is determined according to the molar ratio of the cross-linking agent to the epoxy acrylate of 1.2: 1) into the mixture A prepared in the step (1), and stirring at the speed of 400r/min for 5min to obtain a mixture B;
(3) and (3) curing the mixture B prepared in the step (2) at 28 ℃ for 1.5h to obtain epoxy acrylate microsphere emulsion, wherein the particle size of the obtained epoxy acrylate microsphere is 1.8 mu m.
A matte film prepared by using epoxy acrylate microsphere emulsion comprises the following steps:
(1) mixing 10 parts of epoxy acrylate microsphere emulsion, 90 parts of polyurethane diacrylate (which is purchased from Guangzhou five-element materials Co., Ltd., the viscosity is 9mPa · s) and 5 parts of photoinitiator TPO (which is purchased from Shanghai Kayya chemical Co., Ltd.), stirring at the speed of 400r/min for 5min to obtain a matte glue solution;
(2) injecting the matt adhesive solution prepared in the step (1) into a polytetrafluoroethylene mold (a circular mold with the diameter of 6cm and the depth of 0.5 mm), and irradiating for 40 seconds by using an ultraviolet lamp with the power of 3000W to obtain a matt film; the thickness of the obtained matte film was 0.5 mm.
Examples 5 to 7
Examples 5 to 7 were the same as in example 1 except that in step (1) of preparing the epoxy acrylate microsphere emulsion, the mass ratio of allyl diglycol dicarbonate to epoxy acrylate was different (the other parameters were also the same), and the mass ratios of allyl diglycol dicarbonate to epoxy acrylate used in examples 5, 6 and 7 were 6:1, 8:1 and 10:1, respectively.
The obtained epoxy acrylate microsphere emulsion was washed with the same volume of absolute ethanol (to remove allyl diglycol dicarbonate), and dried at 40 ℃ for 12 hours to obtain epoxy acrylate microspheres corresponding to the epoxy acrylate microsphere emulsions of examples 5 to 7, for testing the performance of the microspheres in the epoxy acrylate microsphere emulsions, when the mass ratios of allyl diglycol dicarbonate to epoxy acrylate were 4:1, 6:1, 8:1, and 10:1, respectively, the average particle diameters of the epoxy acrylate microspheres were 2.0 μm, 1.5 μm, 0.8 μm, and 0.5 μm, respectively.
Comparative example 1
A transparent film without epoxy acrylic acid microsphere emulsion is prepared by the following steps:
80 parts of urethane diacrylate (obtained from Guangzhou five elements materials Co., Ltd., viscosity: 10 mPas) and 3 parts of photoinitiator 184 (obtained from Shanghai Kay chemical Co., Ltd.) were mixed, stirred at a speed of 500r/min for 10min, and then a transparent film was obtained by the method described in the step (2) of preparing a matte film in example 2.
Comparative example 2
A matte film prepared by epoxy acrylate microspheres comprises the following steps:
(1) mixing 4 parts of the washed and dried epoxy acrylate microspheres obtained in example 1, 80 parts of polyurethane diacrylate (obtained from Guangzhou Wuxing materials Co., Ltd., viscosity of 10mPa · s) and 3 parts of photoinitiator 184 (obtained from Shanghai Kaiyin chemical Co., Ltd.), and stirring at a speed of 500r/min for 10min to obtain a matt adhesive solution;
(2) injecting the matt adhesive solution prepared in the step (1) into a polytetrafluoroethylene mold (a circular mold with the diameter of 6cm and the depth of 0.5 mm), and irradiating for 30s by using an ultraviolet lamp with the power of 3000W for curing to obtain a matt film; the thickness of the resulting matte film was 0.2 mm.
Test example:
FIG. 2 is a digital photograph of mixture B before curing (FIG. a) and an epoxy acrylate microsphere emulsion after curing (FIG. B) in example 1 of the present invention. As shown in the figure, before the curing reaction occurs, the compatibility of the allyl diglycol dicarbonate and the epoxy acrylate is better, and the system is in a transparent and uniform state; as the curing reaction proceeds, the compatibility of the epoxy acrylate with allyl diglycol gradually deteriorates, phase separation occurs, and finally the epoxy acrylate exists in the allyl diglycol dicarbonate in the form of microspheres (FIG. b).
And (4) SEM test:
examples 1 and 5 to 7 epoxy acrylate microsphere emulsions having different particle sizes were prepared by changing the mass ratio of allyl diglycol dicarbonate to epoxy acrylate used in the step (1) of preparing epoxy acrylate microsphere emulsions, and the obtained epoxy acrylate microsphere emulsions were washed (to remove allyl diglycol dicarbonate) and dried to obtain epoxy acrylate microspheres corresponding to the epoxy acrylate microsphere emulsions of examples 1 and 5 to 7.
Fig. 5 is a Scanning Electron Microscope (SEM) image of epoxy acrylate microspheres prepared in example 1 and examples 5-7, wherein an epoxy acrylate microsphere sample is dispersed with ethanol, subjected to ultrasonic treatment for 30min, dropped on a silicon wafer, the silicon wafer is fixed on a sample stage, and after ethanol is completely volatilized, the sample is sprayed with gold for 25s for SEM observation. In the figure, a, b, c and d respectively correspond to the mass ratio of allyl diglycol dicarbonate to epoxy acrylate being 4: 1. 6: 1. 8: 1. 10, 1 time epoxy acrylate microsphere in emulsion. As can be seen from fig. 5, the particle size of the epoxy acrylate microspheres in the emulsion gradually decreased with increasing allyl diglycol dicarbonate content.
And (3) infrared testing:
the epoxy acrylate microspheres prepared in the example 1 are tested and analyzed by an infrared spectrometer, and the scanning range is 4000-500 cm-1Resolution of 16 scans was 4cm-1. FIG. 3 is an infrared spectrum of epoxy acrylate microspheres and epoxy acrylate raw material prepared in example 1, and it can be seen from FIG. 3 that 1650 cm after crosslinking-1The characteristic absorption peak of the double bond disappears, and the double bond in the epoxy acrylate is concluded to have reacted completely. In addition, the characteristic absorption peaks before and after crosslinking have no other obvious difference, which shows that the epoxy acrylate microspheres and the epoxy acrylate raw materials have no structural difference, and the prepared microsphere product is pure.
And (3) particle size testing:
the data were statistically significant by analyzing the particle size of at least 300 microsphere particles in the SEM Image of the epoxy acrylate microspheres prepared using example 1 using the software Image J. As shown in fig. 4, the particle size distribution of the epoxy acrylate microspheres is narrow, and the average particle size is 2.0 μm, which is consistent with the result observed by the SEM picture (fig. 5 a).
And (3) testing mechanical properties:
the mechanical properties of the matte film were tested by a universal tensile tester. Tensile properties were tested with reference to GB/T1040.2-2006. Table 1 shows tensile test data of the matte film prepared in example 2 and the transparent film prepared in comparative example 1. As can be seen from Table 1, after the epoxy acrylate microsphere emulsion is added, the tensile strength is obviously increased, and the elongation at break is basically unchanged. Generally, the tensile strength can be improved but the elongation at break is reduced when the light diffusion film is prepared by directly mixing inorganic light diffusion particles, and experimental results show that the tensile strength can be well improved by adding the epoxy acrylate microsphere emulsion, and the matt film has proper elongation at break.
TABLE 1
| Sample(s) | Tensile Strength (MPa) | Elongation at Break (%) |
| Example 2 | 8.92±0.60 | 558±11.7 |
| Comparative example 2 | 4.08±0.31 | 562±12.2 |
Transmittance and haze test:
the matte film was tested for transmission and haze in the visible wavelength range by UV-3600 PLUS. Fig. 6 is a bar graph of the transmittance and haze of the matte film prepared in example 2 and the transparent film prepared in comparative example 1, and it can be seen from fig. 6 that the haze of the film is significantly improved and the transmittance is reduced but still maintained at 90% or more after the epoxy acrylate microsphere emulsion is added. Therefore, the matte film prepared in the embodiment 2 of the invention has excellent light diffusion effect while maintaining high transmittance.
Solvent resistance test:
the matte film prepared in example 2 was immersed in water, ethanol, acetone and sodium hydroxide (5 wt%) solutions for 24h, and then taken out, and the change of haze and transparency was measured. Table 2 is a table of transmittance and haze data of the matte film prepared in example 2 of the present invention after being soaked in different solvents for 24 hours. It can be seen that the optical performance of the matte film is not affected basically after the matte film is soaked in different solvents for 24 hours, because the solvent phase in the added epoxy acrylate microsphere emulsion is allyl diglycol dicarbonate, which can well endow the matte film with solvent resistance as a solvent-resistant optical resin with excellent performance.
TABLE 2
| Water (W) | Ethanol | Acetone (II) | Sodium hydroxide (5 wt%) | |
| Transmittance (%) | 92.35 | 91.82 | 91.70 | 92.07 |
| Haze (%) | 88.01 | 87.92 | 87.86 | 87.91 |
Fig. 7 is a digital photograph of the matte film prepared in example 2 of the present invention (fig. a) and the matte film prepared in comparative example 2 (fig. b). Obviously, compared with the film prepared by directly blending the microspheres in the comparative example 2, the method in the example 2 can obviously improve the dispersion effect of the microspheres in the matte film and effectively avoid the agglomeration phenomenon of the microspheres.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by one skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The epoxy acrylate microsphere emulsion is characterized in that the preparation method of the epoxy acrylate microsphere emulsion comprises the following steps:
(1) mixing allyl diglycol dicarbonate with epoxy acrylate, heating and stirring, and cooling to obtain a mixture A;
(2) adding a cross-linking agent into the mixture A prepared in the step (1), and mixing and stirring to obtain a mixture B;
(3) curing the mixture B prepared in the step (2) to obtain epoxy acrylate microsphere emulsion;
the mass ratio of the allyl diglycol dicarbonate to the epoxy acrylate is (4-10): 1.
2. the epoxy acrylate microsphere emulsion of claim 1, wherein in step (1), the allyl diglycol dicarbonate has a purity of 95-100%; the purity of the epoxy acrylate is 95-100%.
3. The epoxy acrylate microsphere emulsion according to claim 1, wherein in the step (1), the heating temperature is 50-60 ℃; the stirring speed is 1000-1500 r/min, and the stirring time is 30-40 min.
4. The epoxy acrylate microsphere emulsion according to claim 1, wherein in the step (2), the cross-linking agent is one or more of ethylenediamine, isophoronediamine, diethylenetriamine and triethylenetetramine; the molar ratio of the cross-linking agent to the epoxy acrylate is 1.0-1.2: 1; the stirring speed is 300-500 r/min, and the stirring time is 2-10 min.
5. The epoxy acrylate microsphere emulsion according to claim 1, wherein in the step (3), the curing time is 1-2 h, and the temperature is 25-30 ℃; the particle size of the epoxy acrylate microsphere emulsion is 0.5-2.0 μm.
6. The use of the epoxy acrylate microsphere emulsion according to any one of claims 1 to 5, wherein the epoxy acrylate microsphere emulsion is used for preparing a matte film.
7. The use according to claim 6, wherein the matte film comprises the following components in parts by mass: 10-30 parts of epoxy acrylate microsphere emulsion, 70-90 parts of polyurethane diacrylate and 3-5 parts of photoinitiator.
8. Use according to claim 7, wherein the polyurethane diacrylate has a viscosity of 8 to 10 mPa-s; the initiator is one or more of TPO, 184 and 1173.
9. The use according to any one of claims 6 to 7, wherein the matte film is prepared by a method comprising the steps of:
(1) mixing and stirring 10-30 parts of epoxy acrylate microsphere emulsion, 70-90 parts of polyurethane diacrylate and 3-5 parts of photoinitiator to obtain a matt adhesive solution;
(2) and (3) injecting the matte glue solution prepared in the step (1) into a polytetrafluoroethylene mold, and curing to obtain the matte film.
10. The use according to claim 9, wherein in the step (1), the stirring speed is 300-500 r/min, and the stirring time is 2-10 min; in the step (2), the curing is carried out by irradiating for 20-40 s with an ultraviolet lamp with 3000W power; the thickness of the matte film is 0.2-0.5 mm.
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