WO2021052330A1 - Fine particle size emulsion resin, preparation method therefor and application thereof - Google Patents

Abstract

A fine particle size emulsion resin, a preparation method therefor, and an application thereof in water-based ink for PVC furniture film inkjet printing. The particle size of an emulsion resin prepared using this formulation process reaches a theoretical range of miniemulsion polymerization, and industrial production thereof can be achieved without a high energy consumption process required for the miniemulsion polymerization. The water-based ink for PVC furniture film inkjet printing prepared using the emulsion resin has a fine particle size (less than 100 nm) and narrow diameter distribution (less than 0.1), and does not block the nozzle during an inkjet process, leading to smooth printing. The water ink has low viscosity (less than 10 cp), good storage stability, good plasticizer migration resistance, and high peel strength, and is expected to be used in the field of water-based inkjet printing of PVC furniture films.

Description

A fine particle size emulsion resin and its preparation method and application (1) Technical field

The invention relates to a water-based resin and a preparation method thereof, in particular to a water-based ink resin that can be applied to the inkjet printing of PVC (polyvinyl chloride) furniture film and a preparation method thereof.

(2) Background technology

Water-based inks are inks prepared from water, specific water-based polymer resins, pigments and necessary additives. Since water-based ink uses water as the main dispersion medium, after the ink is transferred to the substrate, it dries into a film as the water volatilizes into the environment or penetrates into the substrate. It has the characteristics of non-toxic, harmless, environmentally friendly and safe.

In water-based ink, water-based polymer resin is the most important component. It mainly acts as a binder in water-based ink, so that the pigment can be evenly dispersed, so that the ink has a certain fluidity, and provides adhesion to the substrate material. , So that the ink can form a uniform ink layer after printing. Therefore, the development of water-based polymer resins that can meet the requirements of water-based inks for inkjet printing of PVC furniture films is the key to the development of water-based inks for inkjet printing of PVC furniture films.

(3) Contents of the invention

The purpose of the present invention is to provide a fine particle size emulsion resin that can be used for ink-jet printing and printing of water-based inks for PVC furniture films and a preparation method thereof.

The technical scheme of the present invention is as follows:

A fine particle size emulsion resin composed of raw materials with the following weight ratios:

3.6-5 parts of main emulsifier, 0.2-1.2 parts of auxiliary stabilizer, 1.1-1.52 parts of alkaline neutralizer, 0.2-0.4 parts of initiator, 0.0004-0.00065 parts of chain transfer reagent, 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 parts of glycidyl methacrylate, 0.04-0.054 parts of tert-butyl hydroperoxide, 0.04-0.054 parts of white powder, purified water 61.3-64.67 copies.

Preferably, the fine particle size emulsion resin is composed of raw materials with the following weight ratios:

Main emulsifier 3.9-4.8 parts, auxiliary stabilizer 0.27-1.2 parts, alkaline neutralizer 1.2-1.5 parts, initiator 0.23-0.35 parts, chain transfer reagent 0.00045-0.00065 parts, vinyl acetate 5.5-10.5 parts , 6.5-11 parts of methyl methacrylate, 12-14 parts of methyl acrylate, 0.25-0.42 parts of glycidyl methacrylate, 0.04-0.052 parts of tert-butyl hydroperoxide, 0.04-0.052 parts of white powder, purified water 62.4-64.23 copies.

More preferably, the fine particle size emulsion resin is composed of raw materials with the following weight ratios:

Main emulsifier 4-4.7 parts, auxiliary stabilizer 0.3-1 parts, alkaline neutralizer 1.335-1.38 parts, initiator 0.24-0.3 parts, chain transfer reagent 0.00045-0.00063 parts, vinyl acetate 5.7-10.2 parts , 6.6-10 parts of methyl methacrylate, 12.6-14 parts of methyl acrylate, 0.3-0.4 parts of glycidyl methacrylate, 0.04-0.05 parts of tert-butyl hydroperoxide, 0.04-0.05 parts of white powder, purified water 63.3-63.35 copies.

In the present invention,

The main emulsifier is lauric acid;

The auxiliary stabilizer is one of palmitic acid and oleic acid or a mixture of two in any ratio;

The alkaline neutralizer is one or a mixture of two of sodium hydroxide and potassium hydroxide in any ratio;

The initiator is dimethyl azobisisobutyrate or azobisisoheptonitrile;

The chain transfer reagent is isooctyl 3-mercaptopropionate or 2-ethylhexyl 3-mercaptopropionate.

A preparation method of fine particle size emulsion resin, the method is:

(1) In the ratio of raw materials, at room temperature (20-30 ℃), the main emulsifier, co-stabilizer, initiator, chain transfer reagent, vinyl acetate, methyl methacrylate, methyl acrylate Mix the ester and glycidyl methacrylate, stir and dissolve at a stirring speed of 200-400 rpm for 30-40 minutes to obtain a dispersed oil phase;

(2) Add alkaline neutralizer to purified water, stir at 200-300rpm until it is completely dissolved, then adjust the stirring speed to 400-600rpm, and start dripping the dispersed oil phase (drops) obtained in step (1) at the same time. The addition time is 4-5h). After the dripping is completed, keep stirring at 400-600rpm and continue stirring for 1-2h, then increase the temperature to 75-80°C, keep the stirring speed for 5-6h and keep the temperature for 5-6h to obtain the polymerization reaction liquid;

(3) Lower the temperature of the polymerization reaction solution in step (2) to 65-70°C, reduce the stirring speed to 300-400rpm, add tert-butyl hydroperoxide (feeding in the form of an aqueous solution), keep stirring for 10-20min, and then add the carving White powder (feeding in the form of aqueous solution), heat preservation and stirring for 10-20min, after the system is cooled to room temperature, pass through a 300 mesh nylon bag, a 2um pore size PP filter membrane, a 1um pore size PP filter membrane, and a 0.45um pore size glass fiber filter membrane. , To obtain the fine particle size emulsion resin.

The fine particle size emulsion resin of the present invention can be applied to water-based ink for inkjet printing of PVC furniture film.

Therefore, the present invention also relates to an inkjet printing water-based ink for PVC furniture film, which is composed of raw materials with the following weight ratios:

2-12 parts of main dispersant, 0.5-1.5 parts of auxiliary dispersant, 0.06-0.28 parts of wetting and leveling agent, 3-9 parts of low molecular alcohol, 1-3 parts of co-solvent, 2-12 parts of pigment, 0.6-part filler 2 parts, 8-40 parts of emulsion resin, 0.05-0.18 parts of main defoaming agent, 0.05-0.14 parts of secondary defoaming agent, 36.23-78.45 parts of deionized water.

Preferably, the PVC furniture film inkjet printing water-based ink is composed of raw materials with the following weight ratios:

Main dispersant 3-10 parts, auxiliary dispersant 0.8-1.2 parts, wetting and leveling agent 0.08-0.22 parts, low molecular alcohol 3-8 parts, co-solvent 1-2 parts, pigment 3-10 parts, filler 0.6- 1.5 parts, 10-35 parts of emulsion resin, 0.05-0.12 parts of main defoaming agent, 0.05-0.1 parts of secondary defoaming agent, and 40.23-75.45 parts of deionized water.

Further preferably, the PVC furniture film inkjet printing water-based ink is composed of raw materials with the following weight ratios:

4-10 parts of main dispersant, 0.8-1 part of auxiliary dispersant, 0.1-0.2 part of wetting and leveling agent, 3-7 parts of low molecular alcohol, 1-1.5 parts of cosolvent, 3-8 parts of pigment, 0.6- part of filler 1 part, 10-30 parts of emulsion resin, 0.05-0.1 parts of main defoaming agent, 0.05-0.08 parts of secondary defoaming agent, and 45.27-73.22 parts of deionized water.

Among them, the primary dispersant is preferably a high molecular weight copolymer solution, such as DISPERBYK-190 (BYK company), DISPERBYK-191 (BYK company), DISPERBYK-192 (BYK company), DISPERBYK-194 (BYK company), particularly preferred A high molecular weight block copolymer solution containing pigment affinity groups DISPERBYK-190 (BYK company).

The dispersant is preferably a low molecular weight wetting and dispersing agent, such

Ultra FA 4416 (BASF company),

Ultra FA 4480 (BASF company),

Ultra FA 4437 (BASF company), especially preferred low molecular weight wetting and dispersing agent for modified fatty alcohol ethoxide

Ultra FA 4480 (BASF Corporation).

The wetting and leveling agent is preferably a sulfosuccinate wetting and leveling agent, such as

WE 3475 (BASF company),

WE 3485 (BASF company), especially preferred

WE 3485 (BASF Corporation).

The low-molecular alcohol is one of ethanol and isopropanol or a mixture of the two in any ratio.

The cosolvent is particularly preferably 3-methoxy-3 methyl butyl acetate (Hubei Baidu Chemical Co., Ltd.).

The pigment is preferably any one of anthraquinone fused cyclic ketone organic red, benzimidazolone organic yellow, phthalocyanine organic blue, and carbon black, particularly preferably pigment red 177 (PR177, Zhejiang Baihe Group Co., Ltd. Co., Ltd.), Pigment Yellow 2154C (PY154, Zhejiang Baihe Group Co., Ltd.), 4382 Phthalocyanine Blue BGS (PB15: 3, Zhejiang Baihe Group Co., Ltd.), SPECIAL BLACK 10 (German Degussa Company) Any of them.

The filler is preferably nano-scale silica, especially XT-0806-1-1 nano-silica (average particle size 20nm, Shanghai Gangtian Nanomaterials Co., Ltd.).

The main defoamer is preferably a modified silicone defoamer, such as:

SI 2293 (BASF company),

SI 2213 (BASF company),

SI 2210 (BASF company),

SI 2240 (BASF company),

SI 2250 (BASF company),

SI 2280 (BASF company), especially preferred

SI 2250 (BASF Corporation).

The secondary defoamer is preferably a star-shaped polymer defoamer, such as:

ST 2410 AG (BASF company),

ST 2434 (BASF company),

ST 2438 (BASF company), particularly preferably

ST 2438 (BASF Corporation).

The preparation method of the PVC furniture film inkjet printing water-based ink of the present invention is (the following parts are all parts by weight):

(1) Mixing and dispersion stage:

At room temperature, 36.23-78.45 parts of deionized water, 3-9 parts of low molecular weight alcohol, 2-12 parts of main dispersant, 0.5-1.5 parts of auxiliary dispersant, 0.06-0.28 parts of wetting and leveling agent , 0.05-0.18 parts of main defoamer is added to the dispersion kettle in turn, after stirring and mixing uniformly at a speed of 100-200rpm, then adding 2-12 parts of pigments and 0.6-2 parts of fillers at a speed of 200-300rpm Stir and mix evenly to obtain color paste;

(2) Primary grinding stage:

Transfer the color paste obtained in step (1) to a horizontal sand mill, and grind it for 2-3 passes until the particle size of the color paste reaches 300 nm or less to obtain a first-grade grinding color paste;

(3) Secondary grinding stage:

Transfer the primary grinding color paste to the NMM-30L sand mill, and grind it for 1-2 passes until the particle size of the color paste is below 150nm to obtain the secondary grinding color paste;

(4) Three-stage grinding stage:

Transfer the secondary grinding color paste to the NMM-30L sand mill, and grind it for 3-4 passes until the particle size of the color paste is below 100 nm to obtain a tertiary grinding color paste;

(5) Ink mixing and filtering stage:

After the tertiary grinding color paste is filtered through a 500-mesh nylon bag, it is transferred to the dispersion kettle, and 1-3 parts of cosolvent, 8-40 parts of emulsion resin, and 0.05-0.14 parts of secondary defoamer are added in sequence to Stir and mix at a speed of 100-200rpm to form a complete color ink, and then pass through the secondary 1um pore size PP filter membrane (Cobetter), the tertiary 0.45um pore PP filter membrane (Cobetter), and the fourth stage 0.22um. A pore glass fiber filter membrane (Cobetter Company) is filtered to obtain the PVC furniture membrane inkjet printing water-based ink.

Compared with the prior art, the present invention has the following beneficial effects:

1. The particle size of the emulsion resin prepared by the special formulation process of the present invention is much smaller than that obtained by conventional emulsion polymerization (below 45nm vs. above 100nm), and the former is obviously more suitable for the field of inkjet printing;

2. The particle size of the emulsion of the present invention reaches the theoretical range of miniemulsion polymerization (40-100nm), but does not require the high energy consumption process (ultrasound or homogenization) required for miniemulsion polymerization, and can realize industrial production;

3. Use the KPP gravure proofing machine to coat the resin of the present invention on the PVC furniture film, the furniture film has a low plasticizer migration rate per unit area, and has high peel strength after hot pressing with the PVC furniture film wear-resistant sheet, which can be applied to PVC In water-based printing ink for furniture film;

4. The water-based ink for inkjet printing and printing of PVC furniture film prepared by the fine particle size emulsion resin of the present invention has a fine particle size (<100nm) and a narrow particle size distribution (<0.1), which can effectively ensure that the printing process does not block the nozzle and stays long. The smoothness of the time-jet printing process; and the viscosity of the ink is low (<10cp), but the storage stability is good, long-term storage does not precipitate, no delamination; at the same time, the ink has good plasticizer migration resistance and high peel strength, which is very beneficial Popularization and application in the field of water-based inkjet printing of PVC furniture film.

(4) Description of the drawings

Figure 1 is the particle size distribution diagram of the emulsion of Example 1 of the present invention after a first-level conventional filtration (300 mesh nylon bag).

Figure 2 is a diagram showing the particle size distribution of the emulsion in Example 1 of the present invention after four-stage filtration (300 mesh nylon bag, 2 um pore size PP filter membrane, 1 um pore size PP filter membrane, and 0.45 um pore size glass fiber filter membrane).

Fig. 3 is a diagram of the particle size distribution of the color paste after the primary grinding stage in the application example 1 of the present invention.

FIG. 4 is a diagram of the particle size distribution of the color paste after the secondary grinding stage of Application Example 1 of the present invention.

Fig. 5 is a particle size distribution diagram of the color paste after the three-stage grinding stage of Application Example 1 of the present invention.

Fig. 6 is a particle size distribution diagram of the color ink after four-stage filtration of the application example 1 of the present invention.

(5) Specific implementation methods

The present invention will be further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited to this.

The particle size and particle size distribution test of the emulsion was carried out on the Malvern ZETASIZER 3000HAS particle size analyzer, and the test temperature was 25°C.

The solid content of the emulsion refers to the percentage of the mass of the residue after the emulsion is air-dried at 100°C 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 for 9 days at 60°C, and the storage stability of the emulsion is >6 months with no precipitation and no stratification.

The glass transition temperature of the emulsion resin was measured on a PE DSC7 instrument, using a nitrogen atmosphere, heated from 40°C to 160°C at a heating rate of 10°C/min, and each sample was heated at 160°C for 2 minutes before testing to eliminate thermal history .

The plasticizer migration resistance of the resin refers to the American standard ASTM D2199-82, the measurement method of plasticizer migration from vinyl fabric to spray paint. Select high-density polyethylene as the contact medium, press the high-density polyethylene into a sheet with a thickness of 1.7mm, press the punch into a disc of the same size as the sample, and weigh the high-density polyethylene disc. The test sample is made into a "sandwich" shape, and a PVC sample piece of the same size is placed between two high-density polyethylene discs (the PVC sample piece uses a KPP gravure proofing machine to coat the emulsion of the present invention on the PVC furniture film It is prepared after drying at 50°C, pressurized at 0.125MPa, placed in an oven at 70°C for 3 days and then taken out, placed in a desiccator at room temperature for 1 hour, and then weighed the weight of the high-density polyethylene sheet. The amount of plasticizer migration loss per unit area is calculated as follows:

The amount of plasticizer migration per unit area = (W ₂ -W ₁ )/S

In the formula, W ₁ refers to the mass of the high-density polyethylene before the experiment, mg; W ₂ refers to the mass of the high-density polyethylene after the experiment, mg; S refers to the sample area, mm ² .

The peel strength test of the resin is as follows: use the KPP gravure proofing machine to coat the emulsion of the present invention on the PVC furniture film and dry it at 50°C, then heat it with the PVC furniture film wear-resistant sheet on a hot press at 160°C for 10s, take it out and cool it down Perform peel strength test according to GB/T2790 to room temperature.

Example 1

At room temperature, 4kg of lauric acid (Nanjing Jiaguan Chemical Co., Ltd.), 1kg of oleic acid (Jinan Rongxin Fine Chemical Co., Ltd.), 0.3kg of azobisisoheptonitrile (Beilingwei Technology Co., Ltd.), 0.0006kg of 3 -Isooctyl mercaptopropionate (Sinopharm Chemical Reagent Co., Ltd.), 5.7 kg of vinyl acetate (Guangzhou Naxin Chemical Co., Ltd.), 10 kg of methyl methacrylate (Guangzhou Zhongye Chemical Co., Ltd.) , 14kg of methyl acrylate (Shanghai Minrell Chemical Technology Co., Ltd.) and 0.3kg of glycidyl methacrylate (Jiangxi Ruixiang Chemical Co., Ltd.) were mixed and stirred and dissolved at 200 rpm for 40 minutes to obtain a dispersed oil phase;

Add 1.3358kg of potassium hydroxide (Hangzhou Xingui Industrial Co., Ltd.) to 61.3kg of purified water, stir at 300rpm until it is completely dissolved, adjust the speed to 400rpm, and start to add the above-mentioned dispersed oil phase dropwise. The time is 4h. After the dripping is completed, keep the speed of 400rpm and continue to stir for 2h, and increase the temperature to 75℃, keep the reaction under this condition for 6h;

The temperature of the polymerization reaction solution was lowered to 65°C, the stirring speed was reduced to 300 rpm, and an aqueous solution of tert-butyl hydroperoxide was added. The aqueous solution of tert-butyl hydroperoxide was composed of 0.04 kg of tert-butyl hydroperoxide (Shanghai Baiyi Chemical Co., Ltd. Company) was dissolved in 1kg of purified water, heated and stirred for 10 minutes, and then added with an aqueous solution of white powder, which was obtained by dissolving 0.04 kg of white powder (Shanghai Fengrui Chemical Co., Ltd.) in 1 kg of purified water, and stirred for 10 minutes. , And then down to room temperature;

The emulsion at the end of the reaction passes through a 300-mesh nylon bag, a 2um pore size PP filter membrane (Cobetter), a 1um pore size PP filter membrane (Cobetter), and a 0.45um pore glass fiber filter membrane (Cobetter). Filter to obtain fine particle size emulsion resin.

Example 2

At room temperature, 4.2kg of lauric acid (Nanjing Jiaguan Chemical Co., Ltd.), 0.8kg of oleic acid (Jinan Rongxin Fine Chemical Co., Ltd.), 0.24kg of azobisisoheptanitrile (Beilingwei Technology Co., Ltd.), 0.00045kg Isooctyl 3-mercaptopropionate (Sinopharm Chemical Reagent Co., Ltd.), 10.2 kg of vinyl acetate (Guangzhou Naxin Chemical Co., Ltd.), 6.6 kg of methyl methacrylate (Guangzhou Zhongye Chemical Co., Ltd.), 12.8 kg of methyl acrylate (Shanghai Minrell Chemical Technology Co., Ltd.) and 0.4 kg of glycidyl methacrylate (Jiangxi Ruixiang Chemical Co., Ltd.) were mixed and stirred and dissolved at 400 rpm for 30 minutes to obtain a dispersed oil phase ；

Add 1.348 kg of potassium hydroxide (Hangzhou Xingui Industrial Co., Ltd.) into 61.35 kg of purified water, stir at 200 rpm until it is completely dissolved, adjust the speed to 600 rpm, and start to add the above-mentioned dispersed oil phase dropwise. The time is 4.5h. After the dripping is completed, keep the rotation speed of 600rpm and continue to stir for 1h, and the temperature is raised to 78℃, and the reaction is maintained for 5.5h under this condition;

The temperature of the polymerization reaction solution was lowered to 70°C, the stirring speed was reduced to 400 rpm, and an aqueous solution of tert-butyl hydroperoxide was added. The aqueous solution of tert-butyl hydroperoxide was composed of 0.042 kg of tert-butyl hydroperoxide (Shanghai Baiyi Chemical Co., Ltd. The company) was dissolved in 1kg of purified water, heated and stirred for 10 minutes, and then added to the aqueous solution of white powder, which was obtained by dissolving 0.042 kg of white powder (Shanghai Fengrui Chemical Co., Ltd.) in 1 kg of purified water, and stirred for 10 minutes. , And then down to room temperature;

The emulsion at the end of the reaction passes through a 300-mesh nylon bag, a 2um pore size PP filter membrane (Cobetter), a 1um pore size PP filter membrane (Cobetter), and a 0.45um pore glass fiber filter membrane (Cobetter). Filter to obtain fine particle size emulsion resin.

Example 3

At room temperature, 4.4kg of lauric acid (Nanjing Jiaguan Chemical Co., Ltd.), 0.6kg of oleic acid (Jinan Rongxin Fine Chemical Co., Ltd.), 0.28kg of azobisisoheptanonitrile (Beilingwei Technology Co., Ltd.), 0.00063kg Isooctyl 3-mercaptopropionate (Sinopharm Chemical Reagent Co., Ltd.), 8.5kg of vinyl acetate (Guangzhou Naxin Chemical Co., Ltd.), 8.5kg of methyl methacrylate (Guangzhou Zhongye Chemical Industry Co., Ltd.) Co., Ltd.), 12.6 kg of methyl acrylate (Shanghai Minrel Chemical Technology Co., Ltd.) and 0.4 kg of glycidyl methacrylate (Jiangxi Ruixiang Chemical Co., Ltd.) were mixed and stirred and dissolved at 300 rpm for 40 minutes to obtain a dispersed oil phase ；

Add 1.361 kg of potassium hydroxide (Hangzhou Xingui Industrial Co., Ltd.) to 60.9 kg of purified water, stir at 200 rpm until it is completely dissolved, adjust the speed to 500 rpm, and start to add the above-mentioned dispersed oil phase dropwise. The time is 5h. After the dripping is completed, keep stirring at 500rpm and continue to stir for 2h, and increase the temperature to 80℃, keep the reaction under this condition for 5h;

The temperature of the polymerization reaction solution was lowered to 65°C, the stirring speed was reduced to 400 rpm, and an aqueous solution of tert-butyl hydroperoxide was added. The aqueous solution of tert-butyl hydroperoxide was composed of 0.05 kg of tert-butyl hydroperoxide (Shanghai Baiyi Chemical Co., Ltd. Company) was obtained by dissolving in 1.2kg of purified water, stirring for 20 minutes, and then adding an aqueous solution of sculpting powder, which was obtained by dissolving 0.05kg of sculpting powder (Shanghai Fengrui Chemical Co., Ltd.) in 1.2kg of purified water. Stir for 20 minutes, then reduce to room temperature;

The emulsion at the end of the reaction passes through a 300-mesh nylon bag, a 2um pore size PP filter membrane (Cobetter), a 1um pore size PP filter membrane (Cobetter), and a 0.45um pore glass fiber filter membrane (Cobetter). Filter to obtain fine particle size emulsion resin.

Example 4

At room temperature, 4.7kg of lauric acid (Nanjing Jiaguan Chemical Co., Ltd.), 0.3kg of oleic acid (Jinan Rongxin Fine Chemical Co., Ltd.), 0.24kg of azobisisoheptanonitrile (Beilingwei Technology Co., Ltd.), 0.00057kg Isooctyl 3-mercaptopropionate (China National Pharmaceutical Group Chemical Reagent Co., Ltd.), 9.4 kg of vinyl acetate (Guangzhou Naxin Chemical Co., Ltd.), 7.2 kg of methyl methacrylate (Guangzhou Zhongye Chemical Co., Ltd.), 13 kg of methyl acrylate (Shanghai Minrell Chemical Technology Co., Ltd.) and 0.4 kg of glycidyl methacrylate (Jiangxi Ruixiang Chemical Co., Ltd.) were mixed and stirred and dissolved at 200 rpm for 40 minutes to obtain a dispersed oil phase;

Add 1.381 kg of potassium hydroxide (Hangzhou Xingui Industrial Co., Ltd.) into 61.1 kg of purified water, stir at 250 rpm until it is completely dissolved, adjust the speed to 500 rpm, and start dripping the above-mentioned dispersed oil phase at the same time. The time is 5h. After the dripping is completed, keep stirring at 500rpm and continue to stir for 2h, and increase the temperature to 80℃, keep the reaction under this condition for 5h;

The temperature of the polymerization reaction solution was lowered to 68°C, the stirring speed was reduced to 300 rpm, and an aqueous solution of tert-butyl hydroperoxide was added. The aqueous solution of tert-butyl hydroperoxide was composed of 0.05 kg of tert-butyl hydroperoxide (Shanghai Baiyi Chemical Co., Ltd. Company) was obtained by dissolving in 1.1kg of purified water, stirring for 20 minutes, and then adding an aqueous solution of sculpting powder, which was obtained by dissolving 0.05kg of sculpting powder (Shanghai Fengrui Chemical Co., Ltd.) in 1.1kg of purified water. Stir for 20 minutes, then reduce to room temperature;

The emulsion at the end of the reaction passes through a 300-mesh nylon bag, a 2um pore size PP filter membrane (Cobetter), a 1um pore size PP filter membrane (Cobetter), and a 0.45um pore glass fiber filter membrane (Cobetter). Filter to obtain fine particle size emulsion resin.

Table 1. Experimental results of the examples

Note: Comparative sample 1 is the company's patented product ("A PVC Furniture Film Ink Resin and Its Preparation Method", patent authorization number: ZL 201710612216.7 The sample prepared in Example 4 in the specification), this product can be applied to PVC Preparation of water-based ink for gravure printing on furniture film; Comparative sample 2 is the 6120 resin specially developed by Wanhua Chemical Company for attaching to PVC substrate; the blank sample used for plasticizer migration resistance test sample is uncoated with emulsion PVC furniture film, the blank sample of the peel strength test sample is prepared by hot pressing the PVC furniture film and the wear-resistant sheet without emulsion coating.

The emulsion polymerization process of the invention has good stability, and the emulsion has no slag particles after being filtered through a conventional 300-mesh nylon bag after the reaction is completed. From the data in Figure 1 and Table 1, it can be seen that the particle size of the emulsion of the present invention has reached 45nm or less after the first-stage filtration, and from the data in Figure 2 and Table 1, it can be seen that after three subsequent fine filtrations (2um pore size PP filter membrane, 1um pore size PP The particle size of the filter membrane and the 0.45um pore glass fiber filter membrane has basically no change, which proves that the present invention has controlled the particle size of the emulsion in the polymerization stage, instead of relying on the fine filtration process to obtain a fine particle size emulsion. In addition, the measured solid content of the emulsion after four-stage filtration is basically the same as the designed solid content, which also proves the above conclusion (if a large number of large-diameter latex particles are filtered out, the measured solid content will be significantly less than the designed solid content). This shows that with the formulation and process of the present invention, the particle size of the emulsion can reach the theoretical range of miniemulsion polymerization (40-100nm). In view of the high energy consumption process (ultrasonic or homogenization) required for miniemulsion polymerization, the present invention is more industrialized. Production prospects.

From the data in Table 1, it can be seen that the particle size of the emulsion prepared by the present invention is significantly smaller than the particle size of the emulsion prepared by ordinary emulsion polymerization (below 45nm vs. above 100nm), and its application in the field of inkjet printing is obviously more advantageous (in the inkjet printing industry) , In order to prevent nozzle blockage during inkjet printing, individual high-precision industrial-grade nozzles require the average particle size of inkjet printing ink to be below 100nm).

The design value of the glass transition temperature of the polymer of the present invention is 46-53°C, and the measured value is 49-52°C, which is close to the PVC furniture film used in the present invention (measured value: 49°C), and achieves the expected design purpose.

It can be seen from the data in Table 1 that compared with the blank samples of commercially available products and uncoated PVC furniture film, the PVC furniture film coated with the emulsion resin of the present invention is effective in resisting plasticizer migration and improving the PVC furniture film The wear-resistant sheet has obvious advantages in peel strength, which is close to the performance level of the company's patented products prepared by conventional emulsion polymerization.

In summary, the emulsion resin of the present invention is more promising as the main film-forming resin, whether it is in the industrial preparation of fine particle size emulsions, or in anti-plasticizer migration and bonding of PVC furniture films and wear-resistant sheets. Used in water-based inkjet printing of PVC furniture film.

The following is the application of the fine particle size emulsion resin of the present invention in the water-based ink for ink-jet printing of PVC furniture film. The fine particle size emulsion resin is prepared according to the method of Example 2 above.

The particle size and particle size distribution test of the color paste and color ink are carried out on the Malvern ZETASIZER 3000 HAS particle size analyzer, and the test temperature is 25°C.

The viscosity of ink is tested on NDJ-5S viscometer (Shanghai Fangrui Instrument Co., Ltd.), using 0# rotor, 30rpm speed, and the test temperature is 25℃.

The storage stability of ink and wash means that the emulsion is allowed to stand for 9 days at 60°C, and the storage stability of ink and wash is >6 months with no precipitation and no layering.

The peel strength test of the ink is as follows: water-based monochromatic ink (red, yellow, blue, black) is printed on the PVC furniture film with an inkjet printer, dried at 50℃, and the PVC furniture film wear-resistant sheet is placed on a hot press 160 Hot press at ℃ for 10s, take it out and cool to room temperature to test the peel strength according to GB/T2790.

The resistance to plasticizer migration of the ink is based on the American Standard ASTM D2199-82, the measurement method of plasticizer migration from vinyl fabric to spray paint. Select high-density polyethylene as the contact medium, press the high-density polyethylene into a sheet with a thickness of 1.7mm, press the punch into a disc of the same size as the sample, and weigh the high-density polyethylene disc. The test sample is made into a "sandwich" shape, and a PVC sample piece of the same size is placed between two high-density polyethylene discs (monochrome ink PVC sample piece is made of water-based monochrome ink (red, yellow, blue, black) ) Printed on PVC furniture film with inkjet printer and dried at 50℃), pressurize 0.125MPa, put it in an oven at 70℃ for 3d and then take it out, put it in a dryer at room temperature for 1h, weigh the high density Weight of polyethylene sheet. The amount of plasticizer migration loss per unit area is calculated as follows:

The amount of plasticizer migration per unit area = (W ₂ -W ₁ )/S

In the formula, W ₁ refers to the mass of the high-density polyethylene before the experiment, mg; W ₂ refers to the mass of the high-density polyethylene after the experiment, mg; S refers to the sample area, mm ² .

Application Example 1

1) Mixing and dispersion stage:

At room temperature, 73.22kg of deionized water, 7kg of ethanol (Suzhou Outer Chemical Co., Ltd.), 4kg of DISPERBYK-190 (BYK company), 0.8kg of

Ultra FA 4480 (BASF company), 0.2kg

WE 3485 (BASF company) and 0.1kg

SI 2250 (BASF company) was added to the dispersing kettle one by one, stirred and mixed at a speed of 200 rpm, and then 3 kg of Pigment Red 177 (PR177, Zhejiang Lily Group Co., Ltd.) and 0.6 kg of XT-0806-1-1 were added. Nano-silica (average particle size 20nm, Shanghai Gangtian Nano Material Co., Ltd.), stir and mix uniformly at a speed of 200 rpm.

2) Primary grinding stage:

Transfer the above-mentioned color paste to a horizontal sand mill (TBM-50, 0.2mm zirconium beads, Taiyi (Shanghai) Industrial Co., Ltd.), and grind 2 passes until the particle size of the color paste reaches below 300 nm.

3) Secondary grinding stage:

Transfer the first grade grinding color paste to the NMM-30L sand mill (filled with 0.08mm zirconium beads and 0.1mm zirconium beads at a mass ratio of 2:1, Boyi (Shenzhen) Industrial Technology Co., Ltd.), and grind 2 passes until the color The particle size of the slurry is below 150nm.

4) Three-stage grinding stage:

Transfer the secondary grinding color paste to a NMM-30L sand mill (0.06mm zirconium beads, Boyi (Shenzhen) Industrial Technology Co., Ltd.), and grind 3 passes until the particle size of the color paste is below 100nm.

5) Ink mixing and filtering stage:

The three-stage grinding color paste is filtered through a first-class 500 mesh nylon bag and transferred to the dispersion kettle, and 1kg of 3-methoxy-3 methyl butyl acetate (Hubei Baidu Chemical Co., Ltd.) and 10kg of emulsion resin ( Homemade) and 0.08kg

ST 2438 (BASF company), stir and mix at a speed of 100rpm to form a complete color ink; then pass through a secondary 1um pore size PP filter membrane (Cobetter company) and a third level 0.45um pore PP filter membrane (Cobetter company) And four-stage 0.22um pore glass fiber filter membrane (Cobetter) to obtain PVC furniture membrane water-based printing red ink.

Application Example 2

1) Mixing and dispersion stage:

Put 55.54kg of deionized water, 6kg of ethanol (Suzhou Outer Chemical Co., Ltd.), 9kg of DISPERBYK-190 (BYK company), 1kg of

Ultra FA 4480 (BASF company), 0.1kg

WE 3485 (BASF company) and 0.08kg

SI 2250 (BASF company) was added to the dispersing kettle one by one, stirred and mixed uniformly at a speed of 100 rpm, and then added 6 kg of pigment yellow Yellow 2154C (PY154, Zhejiang Baihe Group Co., Ltd.), 1 kg of XT-0806-1-1 nanometer Silica (average particle size 20nm, Shanghai Gangtian Nano Material Co., Ltd.), stir and mix uniformly at a speed of 200 rpm.

2) Primary grinding stage:

Transfer the above-mentioned color paste to a horizontal sand mill (TBM-50, 0.2mm zirconium beads, Taiyi (Shanghai) Industrial Co., Ltd.), and grind 3 passes until the particle size of the color paste reaches below 300 nm.

3) Secondary grinding stage:

Transfer the first-level grinding color paste to the NMM-30L sand mill (filled with 0.08mm zirconium beads and 0.1mm zirconium beads at a mass ratio of 2:1, Boyi (Shenzhen) Industrial Technology Co., Ltd.), and grind 1 pass to the color The particle size of the slurry is below 150nm.

4) Three-stage grinding stage:

Transfer the secondary grinding color paste to a NMM-30L sand mill (0.06mm zirconium beads, Boyi (Shenzhen) Industrial Technology Co., Ltd.), and grind 4 passes until the color paste particle size reaches 100nm or less.

5) Ink mixing and filtering stage:

The tertiary grinding color paste is filtered through a 500-mesh nylon bag and transferred to the dispersing kettle, and then 1.2 kg of 3-methoxy-3 methyl butyl acetate (Hubei Baidu Chemical Co., Ltd.) and 20 kg of emulsion resin are added in sequence (Homemade) and 0.08kg

ST 2438 (BASF company), stir and mix at a speed of 200rpm to form a complete color ink; then pass through a secondary 1um pore size PP filter membrane (Cobetter company) and a third level 0.45um pore size PP filter membrane (Cobetter company) And four-stage 0.22um pore glass fiber filter membrane (Cobetter) to obtain PVC furniture membrane water-based inkjet printing yellow ink.

Application Example 3

1) Mixing and dispersion stage:

At room temperature, mix 49.75kg of deionized water, 6kg of ethanol (Suzhou Outer Chemical Co., Ltd.), 9kg of DISPERBYK-190 (BYK), 1kg of

Ultra FA 4480 (BASF company), 0.1kg

WE 3485 (BASF company) and 0.1kg

SI 2250 (BASF company) was added to the dispersing kettle one by one, stirred and mixed evenly at a speed of 200 rpm, and then added 7 kg of 4382 Phthalocyanine Blue BGS (PB15: 3, Zhejiang Lily Group Co., Ltd.), 1 kg of XT-0806- 1-1 Nano-silica (average particle size 20nm, Shanghai Gangtian Nano Material Co., Ltd.), stir and mix uniformly at a speed of 300 rpm.

2) Primary grinding stage:

Transfer the above-mentioned color paste to a horizontal sand mill (TBM-50, 0.2mm zirconium beads, Taiyi (Shanghai) Industrial Co., Ltd.), and grind 3 passes until the particle size of the color paste reaches below 300 nm.

3) Secondary grinding stage:

Transfer the first grade grinding color paste to the NMM-30L sand mill (filled with 0.08mm zirconium beads and 0.1mm zirconium beads at a mass ratio of 2:1, Boyi (Shenzhen) Industrial Technology Co., Ltd.), and grind 2 passes until the color The particle size of the slurry is below 150nm.

4) Three-stage grinding stage:

Transfer the secondary grinding color paste to a NMM-30L sand mill (0.06mm zirconium beads, Boyi (Shenzhen) Industrial Technology Co., Ltd.), and grind 3 passes until the particle size of the color paste is below 100nm.

5) Ink mixing and filtering stage:

The tertiary grinding color paste is filtered through a first-level 500 mesh nylon bag and transferred to the dispersing kettle, and 1 kg of 3-methoxy-3 methyl butyl acetate (Hubei Baidu Chemical Co., Ltd.) and 25 kg of emulsion resin ( Homemade) and 0.05kg

ST 2438 (BASF company), stir and mix at a speed of 100rpm to form a complete color ink; then pass through a secondary 1um pore size PP filter membrane (Cobetter company) and a third level 0.45um pore PP filter membrane (Cobetter company) And four-stage 0.22um pore glass fiber filter membrane (Cobetter) to obtain PVC furniture membrane water-based inkjet printing blue ink.

Application Example 4

1) Mixing and dispersion stage:

Put 45.27kg of deionized water, 3kg of ethanol (Suzhou Outer Chemical Co., Ltd.), 10kg of DISPERBYK-190 (BYK company), 1kg of

Ultra FA 4480 (BASF company), 0.1kg

WE 3485 (BASF company) and 0.05kg

SI 2250 (BASF company) was added to the dispersing kettle one by one, stirred and mixed evenly at a speed of 200 rpm, and then added 8 kg of pigment black SPECIAL BLACK 10 (Germany Degussa company), 1 kg of XT-0806-1-1 nano dioxide Silicon (average particle size 20nm, Shanghai Gangtian Nanomaterials Co., Ltd.) was stirred and mixed uniformly at a speed of 300 rpm.

2) Primary grinding stage:

Transfer the above-mentioned color paste to a horizontal sand mill (TBM-50, 0.2mm zirconium beads, Taiyi (Shanghai) Industrial Co., Ltd.), and grind 2 passes until the particle size of the color paste reaches below 300 nm.

3) Secondary grinding stage:

Transfer the first-level grinding color paste to the NMM-30L sand mill (filled with 0.08mm zirconium beads and 0.1mm zirconium beads at a mass ratio of 2:1, Boyi (Shenzhen) Industrial Technology Co., Ltd.), and grind 1 pass to the color The particle size of the slurry is below 150nm.

4) Three-stage grinding stage:

Transfer the secondary grinding color paste to a NMM-30L sand mill (0.06mm zirconium beads, Boyi (Shenzhen) Industrial Technology Co., Ltd.), and grind 3 passes until the particle size of the color paste is below 100nm.

5) Ink mixing and filtering stage:

The three-stage grinding color paste is filtered through a first-class 500 mesh nylon bag and transferred to the dispersing kettle, and 1.5kg of 3-methoxy-3-methyl butyl acetate (Hubei Baidu Chemical Co., Ltd.) and 30kg of emulsion resin are sequentially added. (Homemade) and 0.08kg

ST 2438 (BASF company), stir and mix at a speed of 100rpm to form a complete color ink; then pass through a secondary 1um pore size PP filter membrane (Cobetter company) and a third level 0.45um pore PP filter membrane (Cobetter company) And four-stage 0.22um pore glass fiber filter membrane (Cobetter) to obtain PVC furniture membrane water-based printing black ink.

Table 2. Experimental results of application examples

Note: The plasticizer resistance migration test sample of the blank sample uses unprinted PVC furniture film, and the peel strength test sample of the blank sample is made by hot pressing the unprinted PVC furniture film and wear-resistant sheet. .

It can be seen from the data in Table 2 that the particle size of the four single-color inks is reduced to less than 300nm after the first grinding process. After the secondary grinding process, the particle size is reduced to less than 150nm. After the third level grinding, the particle size It is reduced to below 100nm, and the particle size distribution is significantly narrowed; compared to the three-stage grinding, the color ink particle size and particle size distribution change little after four-stage filtration.

The particle size monitoring data of each process shows that the "three-stage grinding + four-stage filtration" process of the present invention can effectively prepare nano-scale water-based color paste/ink, which ensures the fluency of the ink-jet printing process of the present invention. The ink of the invention has low viscosity but good storage stability. In terms of resistance to plasticizer migration and peel strength, the sample printed with the ink of the present invention is significantly better than the blank sample. It can be seen that the water-based inkjet printing ink for PVC furniture film of the present invention is expected to be applied to the field of water-based inkjet printing of PVC furniture film.

The above-mentioned embodiments are used to explain the present invention, not to limit the present invention. Any modification and change made to the present invention within the spirit of the present invention and the protection scope of the claims shall fall into the protection scope of the present invention.

Claims (16)

1. A fine particle size emulsion resin, which is characterized in that it is composed of raw materials with the following weight ratios:

   3.6-5 parts of main emulsifier, 0.2-1.2 parts of auxiliary stabilizer, 1.1-1.52 parts of alkaline neutralizer, 0.2-0.4 parts of initiator, 0.0004-0.00065 parts of chain transfer reagent, 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 parts of glycidyl methacrylate, 0.04-0.054 parts of tert-butyl hydroperoxide, 0.04-0.054 parts of white powder, purified water 61.3-64.67 copies.
2. The fine particle size emulsion resin of claim 1, wherein the main emulsifier is lauric acid.
3. The fine particle size emulsion resin of claim 1, wherein the co-stabilizer is one of palmitic acid and oleic acid or a mixture of two in any ratio.
4. The fine particle size emulsion resin according to claim 1, wherein the alkaline neutralizer is one of sodium hydroxide and potassium hydroxide or a mixture of two in any ratio.
5. The fine particle size emulsion resin of claim 1, wherein the initiator is dimethyl azobisisobutyrate or azobisisoheptonitrile.
6. The fine particle size emulsion resin of claim 1, wherein the chain transfer agent is isooctyl 3-mercaptopropionate or 2-ethylhexyl 3-mercaptopropionate.
7. The method for preparing fine particle size emulsion resin according to claim 1, wherein the method is:

   (1) Shrink the main emulsifier, co-stabilizer, initiator, chain transfer agent, vinyl acetate, methyl methacrylate, methyl acrylate, and methacrylic acid within the ratio of raw materials at room temperature. Mix the glycerides, stir and dissolve at a stirring speed of 200-400 rpm for 30-40 minutes to obtain a dispersed oil phase;

   (2) Add alkaline neutralizer to purified water, stir at 200-300 rpm until it is completely dissolved, then adjust the stirring speed to 400-600 rpm, and start dripping the dispersed oil phase obtained in step (1) at the same time. After the addition is completed, keep stirring at 400-600rpm and continue stirring for 1-2h, then increase the temperature to 75-80°C, keep the stirring speed for 5-6h and keep the temperature for 5-6h to obtain the polymerization reaction solution;

   (3) Lower the temperature of the polymerization reaction solution in step (2) to 65-70°C, reduce the stirring speed to 300-400rpm, add tert-butyl hydroperoxide, keep stirring for 10-20min, then add white powder, keep stirring for 10- After 20 minutes, after the system is cooled to room temperature, it is filtered through a 300-mesh nylon bag, a 2um pore size PP filter membrane, a 1um pore size PP filter membrane, and a 0.45um pore size glass fiber filter membrane to obtain the fine particle size emulsion resin.
8. The application of the fine particle size emulsion resin of claim 1 in the water-based ink for inkjet printing of PVC furniture film.
9. The application according to claim 8, wherein the water-based ink for inkjet printing of the PVC furniture film is composed of raw materials with the following weight ratios:

   2-12 parts of main dispersant, 0.5-1.5 parts of auxiliary dispersant, 0.06-0.28 parts of wetting and leveling agent, 3-9 parts of low molecular alcohol, 1-3 parts of co-solvent, 2-12 parts of pigment, 0.6-part filler 2 parts, 8-40 parts of emulsion resin, 0.05-0.18 parts of main defoaming agent, 0.05-0.14 parts of secondary defoaming agent, 36.23-78.45 parts of deionized water.
10. The application according to claim 9, wherein the main dispersant is a high molecular weight copolymer solution; and the auxiliary dispersant is a low molecular weight wetting and dispersing agent.
11. The application according to claim 9, wherein the wetting and leveling agent is a sulfosuccinate type wetting and leveling agent.
12. The application according to claim 9, wherein the co-solvent is 3-methoxy-3 methyl butyl acetate.
13. The application according to claim 9, wherein the pigment is any one of anthraquinone fused ring ketone organic red, benzimidazolone organic yellow, phthalocyanine organic blue, and carbon black.
14. The application according to claim 9, wherein the filler is nano-sized silica.
15. The application according to claim 9, wherein the primary defoamer is a modified silicone defoamer; and the secondary defoamer is a star-shaped polymer defoamer.
16. The application according to claim 9, wherein the preparation method of the water-based ink for inkjet printing of the PVC furniture film is:

    (1) Mixing and dispersion stage:

    At room temperature, 36.23-78.45 parts of deionized water, 3-9 parts of low molecular weight alcohol, 2-12 parts of main dispersant, 0.5-1.5 parts of auxiliary dispersant, 0.06-0.28 parts of wetting and leveling agent , 0.05-0.18 parts of main defoamer is added to the dispersion kettle in turn, after stirring and mixing uniformly at a speed of 100-200rpm, then adding 2-12 parts of pigments and 0.6-2 parts of fillers at a speed of 200-300rpm Stir and mix evenly to obtain color paste;

    (2) Primary grinding stage:

    Transfer the color paste obtained in step (1) to a horizontal sand mill, and grind it for 2-3 passes until the particle size of the color paste reaches 300 nm or less to obtain a first-grade grinding color paste;

    (3) Secondary grinding stage:

    Transfer the primary grinding color paste to the NMM-30L sand mill, and grind it for 1-2 passes until the particle size of the color paste is below 150nm to obtain the secondary grinding color paste;

    (4) Three-stage grinding stage:

    Transfer the secondary grinding color paste to the NMM-30L sand mill, and grind it for 3-4 passes until the particle size of the color paste is below 100 nm to obtain a tertiary grinding color paste;

    (5) Ink mixing and filtering stage:

    After the tertiary grinding color paste is filtered through a 500-mesh nylon bag, it is transferred to the dispersion kettle, and 1-3 parts of cosolvent, 8-40 parts of emulsion resin, and 0.05-0.14 parts of secondary defoamer are added in sequence. Stir and mix at a speed of 100-200rpm to form a complete color ink, and then pass through the second-stage 1um pore size PP filter membrane, the third-stage 0.45um pore size PP filter membrane, and the fourth-stage 0.22um pore size glass fiber filter membrane to obtain the PVC Inkjet printing water-based ink for furniture film.

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