CN110437368B - Fine-particle-size emulsion resin and preparation method thereof - Google Patents
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Abstract
A fine particle size emulsion resin is composed of the following raw materials in parts by weight: 3.6-5 parts of main emulsifier, 0.2-1.2 parts of co-stabilizer, 1.1-1.52 parts of alkaline neutralizer, 0.2-0.4 part of initiator, 0.0004-0.00065 part of chain transfer agent, 5.4-10.6 parts of vinyl acetate, 6-12 parts of methyl methacrylate, 11-14.5 parts of methyl acrylate, 0.2-0.44 part of glycidyl methacrylate, 0.04-0.054 part of tert-butyl hydroperoxide, 0.04-0.054 part of rongalite and 61.3-64.67 parts of purified water; the particle size of the emulsion resin prepared by adopting the special formula process reaches the theoretical range of miniemulsion polymerization, but a high-energy-consumption process required by miniemulsion polymerization is not needed, the industrial production can be realized, and the method can be applied to the preparation of PVC furniture film ink-jet printing water-based ink.
Description
(I) technical field
The invention relates to a water-based resin and a preparation method thereof, in particular to a water-based ink resin applied to ink-jet printing of PVC (polyvinyl chloride) furniture films and a preparation method thereof.
(II) background of the invention
The water-based ink is prepared from water, a specific water-based polymer resin, a pigment and necessary auxiliaries. The water-based polymer resin is the most important component, and mainly plays a role of a binder in the ink, so that the pigment can be uniformly dispersed, the ink has certain fluidity, the adhesion with a printing stock material is provided, and the ink can form a uniform ink layer after being printed. Therefore, the development of the water-based polymer resin capable of meeting the requirements of the PVC furniture film ink-jet printing ink is the key point for realizing the development of the PVC furniture film ink-jet printing ink at present. The invention develops a fine-particle-size emulsion resin special for preparing PVC furniture film ink-jet printing water-based ink.
Disclosure of the invention
The invention aims to provide a fine-particle-size emulsion resin for PVC furniture film ink-jet printing water-based ink and a preparation method thereof.
The technical scheme of the invention is as follows:
a fine particle size emulsion resin is composed of the following raw materials in parts by weight:
3.6-5 parts of main emulsifier, 0.2-1.2 parts of co-stabilizer, 1.1-1.52 parts of alkaline neutralizer, 0.2-0.4 part of initiator, 0.0004-0.00065 part of chain transfer agent, 5.4-10.6 parts of vinyl acetate, 6-12 parts of methyl methacrylate, 11-14.5 parts of methyl acrylate, 0.2-0.44 part of glycidyl methacrylate, 0.04-0.054 part of tert-butyl hydroperoxide, 0.04-0.054 part of rongalite and 61.3-64.67 parts of purified water.
Preferably, the fine-particle-size emulsion resin is prepared from the following raw materials in parts by weight:
3.9-4.8 parts of main emulsifier, 0.27-1.2 parts of co-stabilizer, 1.2-1.5 parts of alkaline neutralizer, 0.23-0.35 part of initiator, 0.00045-0.00065 part of chain transfer agent, 5.5-10.5 parts of vinyl acetate, 6.5-11 parts of methyl methacrylate, 12-14 parts of methyl acrylate, 0.25-0.42 part of glycidyl methacrylate, 0.04-0.052 part of tert-butyl hydroperoxide, 0.04-0.052 part of rongalite and 62.4-64.23 parts of purified water.
Further preferably, the fine-particle-size emulsion resin is composed of the following raw materials in parts by weight:
4-4.7 parts of main emulsifier, 0.3-1 part of co-stabilizer, 1.335-1.38 parts of alkaline neutralizer, 0.24-0.3 part of initiator, 0.00045-0.00063 parts of chain transfer agent, 5.7-10.2 parts of vinyl acetate, 6.6-10 parts of methyl methacrylate, 12.6-14 parts of methyl acrylate, 0.3-0.4 part of glycidyl methacrylate, 0.04-0.05 part of tert-butyl hydroperoxide, 0.04-0.05 part of rongalite and 63.3-63.35 parts of purified water.
In the present invention,
the main emulsifier is lauric acid;
the co-stabilizer is one or a mixture of two of palmitic acid and oleic acid in any proportion;
the alkaline neutralizing agent is one or a mixture of two of sodium hydroxide and potassium hydroxide in any proportion;
the initiator is dimethyl azodiisobutyrate or azodiisoheptonitrile;
the chain transfer reagent is isooctyl 3-mercaptopropionate or 2-ethylhexyl 3-mercaptopropionate.
A method for preparing a fine particle size emulsion resin, the method comprising:
(1) in the range of the mixture ratio of the raw materials, mixing a main emulsifier, a co-stabilizer, an initiator, a chain transfer reagent, vinyl acetate, methyl methacrylate, methyl acrylate and glycidyl methacrylate at room temperature (20-30 ℃), stirring and dissolving at the stirring speed of 200 plus 400rpm for 30-40min to obtain a dispersed oil phase;
(2) adding an alkaline neutralizing agent into purified water, stirring at a stirring speed of 200-300rpm until the alkaline neutralizing agent is completely dissolved, adjusting the stirring speed to 400-600rpm, simultaneously starting dropwise adding the dispersed oil phase obtained in the step (1) (the dropwise adding time is 4-5h), after dropwise adding, keeping the stirring speed of 400-600rpm, continuously stirring for 1-2h, then heating to 75-80 ℃, maintaining the stirring speed and carrying out heat preservation reaction for 5-6h, and obtaining a polymerization reaction liquid;
(3) and (3) cooling the polymerization reaction liquid in the step (2) to 65-70 ℃, reducing the stirring speed to 300-400rpm, adding tert-butyl hydroperoxide (feeding in the form of an aqueous solution), stirring for 10-20min under heat preservation, then adding rongalite (feeding in the form of an aqueous solution), stirring for 10-20min under heat preservation, cooling the system to room temperature, and sequentially filtering through a 300-mesh nylon bag, a 2 um-aperture PP filter membrane, a 1 um-aperture PP filter membrane and a 0.45 um-aperture glass fiber four-stage filter membrane to obtain the fine-particle-size emulsion resin.
Compared with the prior art, the invention has the beneficial effects that:
1. the particle size of the emulsion resin prepared by adopting the special formula process is far smaller than that of the emulsion resin obtained by conventional emulsion polymerization (the particle size is lower than 45nm and is more than 100nm), and the former is obviously more suitable for the field of ink-jet printing;
2. the particle size of the emulsion reaches the theoretical range (40-100nm) of miniemulsion polymerization, but a high-energy-consumption process (ultrasonic or homogenization) required by miniemulsion polymerization is not needed, and industrial production can be realized;
3. the resin is coated on a PVC furniture film by adopting a KPP gravure proofing machine, the plasticizer mobility per unit area of the furniture film is low, the peeling strength after the furniture film is hot-pressed and pasted with a PVC furniture film wear-resistant sheet is high, and the resin can be applied to PVC furniture film aqueous printing ink;
4. by combining the beneficial effects, the fine-particle-size emulsion resin can be applied to the preparation of water-based ink for PVC furniture film ink-jet printing.
(IV) description of the drawings
FIG. 1 is a graph showing the particle size distribution of the emulsion after one-stage conventional filtration (300 mesh nylon bag) in example 1 of the present invention.
FIG. 2 is a distribution diagram of the particle size of the emulsion after four-stage filtration (300 mesh nylon bag, 2um aperture PP filtration membrane, 1um aperture PP filtration membrane and 0.45um aperture fiberglass filtration membrane) in example 1 of the present invention.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Particle size and particle size distribution testing of the emulsion was performed on a Malvern ZETASIZER 3000HAS particle sizer, at a test temperature of 25 ℃.
The solid content of the emulsion refers to the percentage of the mass of the emulsion after being dried by air blowing at 100 ℃ for 24 hours to the mass of the emulsion before drying.
The storage stability of the emulsion means that the emulsion is allowed to stand at 60 ℃ for 9 days, and the storage stability of the emulsion is represented by no precipitation and no delamination for more than 6 months.
The glass transition temperature measurements of the emulsion resins were performed on a PE DSC7 instrument using a nitrogen atmosphere heated from 40 ℃ to 160 ℃ at a ramp rate of 10 ℃/min, each sample being heated at 160 ℃ for 2min prior to testing to eliminate thermal history.
The resistance of the resin to plasticizer migration is measured with reference to the U.S. standard ASTM D2199-82 plasticizer migration from vinyl to spray paint. High-density polyethylene is selected as a contact medium, the high-density polyethylene is pressed into a sheet with the thickness of 1.7mm, a round piece with the same size as a sample is pressed by a punch, and the weight of the high-density polyethylene round piece is weighed. The test sample is made into a sandwich shape, a PVC sample piece (the PVC sample piece is prepared by coating the emulsion on a PVC furniture film by a KPP gravure proofing machine and drying at 50 ℃) with the same size is arranged between two high-density polyethylene wafers, the pressure is 0.125MPa, the PVC sample piece is taken out after being placed in a drying oven at 70 ℃ for 3 days, and the high-density polyethylene wafers are weighed after being placed in a drier at room temperature for 1 hour. The plasticizer unit area migration loss amount was calculated as follows:
the amount of plasticizer transferred per unit area is (W)2–W1)/S
In the formula, W1Means the mass of the high density polyethylene before the experiment, mg; w2Means the mass, mg, of the high density polyethylene after the experiment; s is the area of the sample, mm2。
The peel strength of the resin was tested as follows: coating the emulsion on a PVC furniture film by using a KPP gravure proofing machine, drying at 50 ℃, hot-pressing the PVC furniture film and a PVC furniture film wear-resistant sheet on a hot press at 160 ℃ for 10s, taking out, cooling to room temperature, and testing the peel strength according to GB/T2790.
Example 1
4kg of lauric acid (Nanjing Jia Guang chemical Co., Ltd.), 1kg of oleic acid (Jinan Rongxin fine chemical Co., Ltd.), 0.3kg of azobisisoheptonitrile (Bailingwei science and technology Co., Ltd.), 0.0006kg of isooctyl 3-mercaptopropionate (national drug group chemical reagent Co., Ltd.), 5.7kg of vinyl acetate (Naxin chemical Co., Ltd. Guangzhou), 10kg of methyl methacrylate (Naxin chemical Co., Ltd. Guangzhou), 14kg of methyl acrylate (Merrel chemical technology Co., Ltd. Shanghai) and 0.3kg of glycidyl methacrylate (Kyowa Ruixi chemical Co., Ltd.) were mixed and dissolved at a speed of 200rpm for 40 minutes at room temperature to obtain a dispersed oil phase;
adding 1.3358kg of potassium hydroxide (Hangzhou New Gui industry Co., Ltd.) into 61.3kg of purified water, stirring at 300rpm until the potassium hydroxide is completely dissolved, adjusting the rotation speed to 400rpm, simultaneously beginning to dropwise add the dispersed oil phase for 4 hours, after dropwise adding, keeping the rotation speed of 400rpm and continuously stirring for 2 hours, raising the temperature to 75 ℃, and keeping reacting for 6 hours under the condition;
cooling the polymerization reaction liquid to 65 ℃, reducing the stirring speed to 300rpm, adding a tert-butyl hydrogen peroxide aqueous solution, dissolving 0.04kg of tert-butyl hydrogen peroxide (Shanghai Bai chemical Co., Ltd.) in 1kg of purified water, stirring for 10min under heat preservation, adding a rongalite aqueous solution, dissolving 0.04kg of rongalite (Shanghai Feng Rui chemical Co., Ltd.) in 1kg of purified water, stirring for 10min under heat preservation, and cooling to room temperature;
and (3) sequentially carrying out four-stage filtration on the emulsion after the reaction is finished by a 300-mesh nylon bag, a PP filter membrane with the aperture of 2um (Corbter company), a PP filter membrane with the aperture of 1um (Corbter company) and a glass fiber filter membrane with the aperture of 0.45um (Corbter company) to obtain the fine-particle-size emulsion resin.
Example 2
4.2kg of lauric acid (Nanjing Jia Guang chemical Co., Ltd.), 0.8kg of oleic acid (Jinnan Rongxin Fine chemical Co., Ltd.), 0.24kg of azobisisoheptonitrile (Bailingwei science Co., Ltd.), 0.00045kg of isooctyl 3-mercaptopropionate (national drug group chemical reagent Co., Ltd.), 10.2kg of vinyl acetate (Naxin chemical Co., Ltd. Guangzhou), 6.6kg of methyl methacrylate (Naixian chemical Co., Ltd. Guangzhou), 12.8kg of methyl acrylate (Shanghai Mirey chemical technology Co., Ltd.) and 0.4kg of glycidyl methacrylate (Jiangxi Ruixi chemical Co., Ltd.) were mixed and dissolved at a speed of 400rpm at room temperature for 30 minutes to obtain a dispersed oil phase;
adding 1.348kg of potassium hydroxide (Hangzhou New Gui industry Co., Ltd.) into 61.35kg of purified water, stirring at 200rpm until the potassium hydroxide is completely dissolved, adjusting the rotation speed to 600rpm, simultaneously beginning to dropwise add the dispersed oil phase for 4.5h, keeping the rotation speed of 600rpm after dropwise addition, continuing stirring for 1h, heating to 78 ℃, and keeping the reaction for 5.5h under the condition;
cooling the polymerization reaction liquid to 70 ℃, reducing the stirring speed to 400rpm, adding a tert-butyl hydrogen peroxide aqueous solution, dissolving 0.042kg of tert-butyl hydrogen peroxide (Shanghai Bai chemical Co., Ltd.) in 1kg of purified water, stirring for 10min under heat preservation, adding a rongalite aqueous solution, dissolving 0.042kg of rongalite (Shanghai Feng Rui chemical Co., Ltd.) in 1kg of purified water, stirring for 10min under heat preservation, and cooling to room temperature;
and (3) sequentially carrying out four-stage filtration on the emulsion after the reaction is finished by a 300-mesh nylon bag, a PP filter membrane with the aperture of 2um (Corbter company), a PP filter membrane with the aperture of 1um (Corbter company) and a glass fiber filter membrane with the aperture of 0.45um (Corbter company) to obtain the fine-particle-size emulsion resin.
Example 3
4.4kg of lauric acid (Nanjing Jia Guang chemical Co., Ltd.), 0.6kg of oleic acid (Jinnan Rongxin fine chemical Co., Ltd.), 0.28kg of azobisisoheptonitrile (Bailingwei science Co., Ltd.), 0.00063kg of isooctyl 3-mercaptopropionate (national drug group chemical reagent Co., Ltd.), 8.5kg of vinyl acetate (Naxin chemical Co., Ltd. Guangzhou), 8.5kg of methyl methacrylate (Naxin chemical Co., Ltd. Guangzhou), 12.6kg of methyl acrylate (Shanghai Mirey chemical technology Co., Ltd.) and 0.4kg of glycidyl methacrylate (Jiangxi Ruixiang chemical Co., Ltd.) were mixed and dissolved at a speed of 300rpm at room temperature for 40 minutes to obtain a dispersed oil phase;
adding 1.361kg of potassium hydroxide (Hangzhou New Gui industry Co., Ltd.) into 60.9kg of purified water, stirring at 200rpm until the potassium hydroxide is completely dissolved, adjusting the rotation speed to 500rpm, simultaneously starting to dropwise add the dispersed oil phase for 5h, after dropwise addition, keeping the rotation speed of 500rpm, continuously stirring for 2h, heating to 80 ℃, and keeping the reaction for 5h under the condition;
cooling the polymerization reaction liquid to 65 ℃, reducing the stirring speed to 400rpm, adding a tert-butyl hydrogen peroxide aqueous solution, dissolving 0.05kg of tert-butyl hydrogen peroxide (Shanghai Bai chemical Co., Ltd.) in 1.2kg of purified water, stirring for 20min under heat preservation, adding a rongalite aqueous solution, dissolving 0.05kg of rongalite (Shanghai Feng Rui chemical Co., Ltd.) in 1.2kg of purified water, stirring for 20min under heat preservation, and cooling to room temperature;
and (3) sequentially carrying out four-stage filtration on the emulsion after the reaction is finished by a 300-mesh nylon bag, a PP filter membrane with the aperture of 2um (Corbter company), a PP filter membrane with the aperture of 1um (Corbter company) and a glass fiber filter membrane with the aperture of 0.45um (Corbter company) to obtain the fine-particle-size emulsion resin.
Example 4
4.7kg of lauric acid (Nanjing Jia Guang chemical Co., Ltd.), 0.3kg of oleic acid (Jinnan Rongxin fine chemical Co., Ltd.), 0.24kg of azobisisoheptonitrile (Bailingwei science Co., Ltd.), 0.00057kg of isooctyl 3-mercaptopropionate (national medicine group chemical reagent Co., Ltd.), 9.4kg of vinyl acetate (Naxin chemical Co., Ltd. Guangzhou), 7.2kg of methyl methacrylate (Naxin chemical Co., Ltd. Guangzhou), 13kg of methyl acrylate (Shanghai Ruier chemical technology Co., Ltd.) and 0.4kg of glycidyl methacrylate (Jiangxi Ruixiang chemical Co., Ltd.) were mixed and dissolved at a speed of 200rpm for 40 minutes at room temperature to obtain a dispersed oil phase;
adding 1.381kg of potassium hydroxide (Hangzhou New Gui industry Co., Ltd.) into 61.1kg of purified water, stirring at 250rpm until the potassium hydroxide is completely dissolved, adjusting the rotation speed to 500rpm, simultaneously beginning to dropwise add the dispersed oil phase for 5 hours, after dropwise adding, keeping the rotation speed of 500rpm and continuing stirring for 2 hours, raising the temperature to 80 ℃, and keeping reacting for 5 hours under the condition;
cooling the polymerization reaction liquid to 68 ℃, reducing the stirring speed to 300rpm, adding a tert-butyl hydrogen peroxide aqueous solution, dissolving 0.05kg of tert-butyl hydrogen peroxide (Shanghai Bai chemical Co., Ltd.) in 1.1kg of purified water, stirring for 20min under heat preservation, adding a rongalite aqueous solution, dissolving 0.05kg of rongalite (Shanghai Feng Rui chemical Co., Ltd.) in 1.1kg of purified water, stirring for 20min under heat preservation, and cooling to room temperature;
and (3) sequentially carrying out four-stage filtration on the emulsion after the reaction is finished by a 300-mesh nylon bag, a PP filter membrane with the aperture of 2um (Corbter company), a PP filter membrane with the aperture of 1um (Corbter company) and a glass fiber filter membrane with the aperture of 0.45um (Corbter company) to obtain the fine-particle-size emulsion resin.
TABLE 1 Experimental results of examples
Note: comparative example 1 is a product of this company (a PVC furniture film ink resin and a preparation method thereof, a sample prepared in example 4 of ZL 201710612216.7 specification) which can be applied to preparation of gravure printing water-based ink of PVC furniture films; comparative sample 2 was 6120 resin developed by wawa chemical company specifically for attachment to PVC substrate; the blank sample for testing the plasticizer-resistant mobility is a PVC furniture film which is not coated with emulsion, and the blank sample for testing the peel strength is prepared by hot-pressing the PVC furniture film which is not coated with the emulsion and an abrasion-resistant sheet.
The emulsion polymerization process has good stability, and the emulsion has no slag particles after being filtered by a conventional 300-mesh nylon bag after the reaction is finished. The data in figure 1 and table 1 show that the particle size of the emulsion of the invention reaches below 45nm after the first-stage filtration, and the data in figure 2 and table 1 show that the particle size of the emulsion after the subsequent three-stage fine filtration (2um pore diameter PP filter membrane, 1um pore diameter PP filter membrane and 0.45um pore diameter glass fiber filter membrane) is basically unchanged, which proves that the particle size of the emulsion is controlled in the polymerization stage instead of the fine filtration process to obtain the emulsion with fine particle size. In addition, the measured solid content of the emulsion after the four-stage filtration is basically consistent with the designed solid content, which proves the conclusion (if a large amount of emulsion particles with large particle size are filtered, the measured solid content is obviously smaller than the designed solid content). This shows that the particle size of the emulsion can reach the theoretical range of miniemulsion polymerization (40-100nm) by adopting the formula and the process of the invention, and the invention has more industrial production prospect in view of the high energy consumption process (ultrasonic or homogenization) required by miniemulsion polymerization.
As can be seen from the data in Table 1, the emulsion prepared by the invention has a particle size significantly smaller than that of the emulsion prepared by the conventional emulsion polymerization (vs 100nm below 45 nm), and has obvious advantages in the application field of ink jet printing (in the ink jet printing industry, in order to prevent the nozzle from being blocked in the ink jet printing process, the average particle size of the jet printing ink required by a single high-precision industrial nozzle is below 100 nm).
The designed value of the glass transition temperature of the polymer is 46-53 ℃, the actual measurement is 49-52 ℃, and the glass transition temperature is close to that of the PVC furniture film used by the invention (the actual measurement is 49 ℃), thereby achieving the expected design purpose.
As can be seen from the data in Table 1, compared with the commercial products and the PVC furniture film blank samples without emulsion coating, the PVC furniture film coated with the emulsion resin of the invention has very obvious advantages in plasticizer migration resistance and peeling strength improvement of the PVC furniture film and the wear-resistant sheet, and the performance level of the PVC furniture film coated with the emulsion resin is close to that of the proprietary products prepared by the conventional emulsion polymerization of the company.
In conclusion, the emulsion resin is more hopeful to be used as a main film-forming resin in aqueous ink-jet printing of PVC furniture films in the aspects of industrially preparing fine-particle-size emulsion and resisting plasticizer migration and bonding PVC furniture films and wear-resistant sheets.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are within the spirit of the invention and the scope of the claims.
Claims (7)
1. The fine-particle-size emulsion resin is characterized by comprising the following raw materials in parts by weight:
3.6-5 parts of main emulsifier, 0.2-1.2 parts of co-stabilizer, 1.1-1.52 parts of alkaline neutralizer, 0.2-0.4 part of initiator, 0.0004-0.00065 part of chain transfer agent, 5.4-10.6 parts of vinyl acetate, 6-12 parts of methyl methacrylate, 11-14.5 parts of methyl acrylate, 0.2-0.44 part of glycidyl methacrylate, 0.04-0.054 part of tert-butyl hydroperoxide, 0.04-0.054 part of rongalite and 61.3-64.67 parts of purified water;
the main emulsifier is lauric acid;
the preparation method of the fine-particle-size emulsion resin comprises the following steps:
(1) in the range of the mixture ratio of the raw materials, mixing a main emulsifier, a co-stabilizer, an initiator, a chain transfer reagent, vinyl acetate, methyl methacrylate, methyl acrylate and glycidyl methacrylate at room temperature, stirring and dissolving at the stirring speed of 200 plus 400rpm for 30-40min to obtain a dispersed oil phase;
(2) adding an alkaline neutralizing agent into purified water, stirring at a stirring speed of 200-300rpm until the alkaline neutralizing agent is completely dissolved, adjusting the stirring speed to 400-600rpm, simultaneously starting dropwise adding the dispersed oil phase obtained in the step (1), keeping the stirring speed of 400-600rpm and continuing stirring for 1-2h after dropwise adding is finished, then heating to 75-80 ℃, maintaining the stirring speed and keeping the temperature for reaction for 5-6h to obtain a polymerization reaction liquid;
(3) and (3) cooling the polymerization reaction liquid in the step (2) to 65-70 ℃, reducing the stirring speed to 300-400rpm, adding tert-butyl hydroperoxide, keeping the temperature and stirring for 10-20min, then adding rongalite, keeping the temperature and stirring for 10-20min, and then carrying out four-stage filtration on the system to room temperature through a 300-mesh nylon bag, a 2-um-aperture PP filter membrane, a 1-um-aperture PP filter membrane and a 0.45-um-aperture glass fiber filter membrane in sequence to obtain the fine-particle-size emulsion resin.
2. The fine particle size emulsion resin as claimed in claim 1, which is prepared from the following raw materials in parts by weight:
3.9-4.8 parts of main emulsifier, 0.27-1.2 parts of co-stabilizer, 1.2-1.5 parts of alkaline neutralizer, 0.23-0.35 part of initiator, 0.00045-0.00065 part of chain transfer agent, 5.5-10.5 parts of vinyl acetate, 6.5-11 parts of methyl methacrylate, 12-14 parts of methyl acrylate, 0.25-0.42 part of glycidyl methacrylate, 0.04-0.052 part of tert-butyl hydroperoxide, 0.04-0.052 part of rongalite and 62.4-64.23 parts of purified water.
3. The fine particle size emulsion resin as claimed in claim 1, which is prepared from the following raw materials in parts by weight:
4-4.7 parts of main emulsifier, 0.3-1 part of co-stabilizer, 1.335-1.38 parts of alkaline neutralizer, 0.24-0.3 part of initiator, 0.00045-0.00063 parts of chain transfer agent, 5.7-10.2 parts of vinyl acetate, 6.6-10 parts of methyl methacrylate, 12.6-14 parts of methyl acrylate, 0.3-0.4 part of glycidyl methacrylate, 0.04-0.05 part of tert-butyl hydroperoxide, 0.04-0.05 part of rongalite and 63.3-63.35 parts of purified water.
4. A fine particle size emulsion resin according to any of claims 1 to 3 wherein the co-stabilizer is one or a mixture of two of palmitic acid and oleic acid in any proportion.
5. A fine particle size emulsion resin according to any of claims 1 to 3 wherein the alkali neutralizing agent is one or a mixture of two of sodium hydroxide and potassium hydroxide in any proportion.
6. A fine particle size emulsion resin according to any of claims 1 to 3 wherein the initiator is dimethyl azobisisobutyrate or azobisisoheptonitrile.
7. A fine particle size emulsion resin according to any of claims 1 to 3 wherein the chain transfer agent is isooctyl 3-mercaptopropionate or 2-ethylhexyl 3-mercaptopropionate.
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