CN107987214B

CN107987214B - Diffusion particles suitable for aqueous adhesive system and preparation method thereof

Info

Publication number: CN107987214B
Application number: CN201610951544.5A
Authority: CN
Inventors: 任远飞; 李刚; 崔钧; 唐海江; 张彦
Original assignee: Ningbo Exciton Technology Co Ltd
Current assignee: Ningbo Exciton Technology Co Ltd
Priority date: 2016-10-26
Filing date: 2016-10-26
Publication date: 2020-11-27
Anticipated expiration: 2036-10-26
Also published as: CN107987214A

Abstract

The invention relates to the field of optical films, in particular to a diffusion particle suitable for a water-based adhesive system and a preparation method thereof. The invention provides a diffusion particle suitable for an aqueous adhesive system and a preparation method thereof, aiming at solving the problem that the existing diffusion particle cannot be well dispersed in the aqueous adhesive system. The raw material of the diffusion particles comprises mixed monomers; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and an oily monomer; the oily monomer is selected from one of methyl methacrylate, butyl methacrylate or styrene; the mass portion ratio of the N-vinyl pyrrolidone to the oily monomer is 50: 50-4: 96, and the total mass portion of the mixed monomer is 100. The diffusion particles have hydrophilic groups and lipophilic groups, and have better water-oil balance. The preparation method provided by the invention is simple in process and easy to operate.

Description

Diffusion particles suitable for aqueous adhesive system and preparation method thereof

Technical Field

The invention relates to the field of optical films, in particular to a diffusion particle suitable for a water-based adhesive system and a preparation method thereof.

Background

The optical film is a film with optical function for converting point and line light sources into line and plane light sources. When light passes through the optical film, the light can generate a plurality of refraction, reflection and scattering phenomena, so that a corresponding optical effect is generated, and the optical film belongs to the field of optical display. The optical film is widely applied to a backlight module of a flat panel display and a novel illumination light source, such as televisions, computer monitors, notebook computers, mobile phones, digital cameras, MP4 players, GPS navigators, various daily and industrial illumination light sources and the like.

As flat panel displays are increasingly used in daily life, the demand of optical films in the market is increasing. The existing production of optical films in the industry adopts solvent-based glue production, the solvent-based glue has the function of uniformly dispersing and adhering diffusion particles on the surface of a substrate to form an optical functional layer, but a large amount of organic solvent generated in the production process of the solvent-based glue is harmful to the health of operators on line, flammable and explosive potential safety hazards exist, the treatment of the large amount of organic solvent brings huge cost pressure to enterprises, and meanwhile, the discharge of VOC can cause serious pollution to the air environment.

Therefore, the production of optical films by replacing solvent-based glue with the water-based glue system is a trend of industry development, and the problems of potential safety hazards in production, environmental pollution and the like do not exist because the solvent used by the water-based glue system is water. However, the diffusion particles used for producing the optical film at present are all in an organic solvent dispersion form, cannot be well dispersed in water, and are not suitable for an aqueous adhesive system.

In summary, the development of the diffusing particles suitable for the aqueous adhesive system is a great problem to be solved urgently in the technical field.

Disclosure of Invention

The invention provides a diffusion particle suitable for an aqueous adhesive system and a preparation method thereof, aiming at solving the problem that the existing diffusion particle cannot be well dispersed in the aqueous adhesive system. The diffusion particles have hydrophilic groups and lipophilic groups, and have better water-oil balance. The preparation method provided by the invention is simple in process and easy to operate.

In order to solve the technical problems, the invention adopts the following technical scheme:

the invention provides a diffusion particle, wherein the raw material of the diffusion particle comprises a mixed monomer; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is selected from one of methyl methacrylate, butyl methacrylate or styrene; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 50: 50-4: 96, and the total mass portion of the mixed monomer is 100 parts.

The diffusion particles are water-oil equilibrium diffusion particles.

The diffusing particles are prepared by an aqueous emulsion polymerization process.

Furthermore, the raw material of the diffusion particles also comprises a coupling agent, and the addition amount of the coupling agent is 1-20% of the weight of the mixed monomer.

Furthermore, the raw material of the diffusion particles also comprises an initiator, and the addition amount of the initiator is 2-10% of the weight of the mixed monomer.

The initiator is a free radical initiator.

Furthermore, the raw material of the diffusion particles also comprises a surfactant and deionized water, and the addition amount of the deionized water is 1-5 times of the weight of the mixed solvent; the addition amount of the surfactant is 1-10% of the weight of the mixed monomer.

Further, the surfactant is selected from one or a combination of at least two of nonionic surfactant and/or anionic surfactant.

Further, the non-ionic surfactant is selected from one or a combination of at least two of Tween 20, Tween 80, AEO9, AEO12, Triton X-100, Triton X-165 or OP-10; the anionic surfactant is selected from one or the combination of at least two of ammonium dodecyl sulfate, sodium dodecyl sulfonate or sodium dodecyl benzene sulfonate.

The surfactant acts to form latex strands, providing a site for polymerization. The size of the emulsion micelle can be effectively controlled by controlling the concentration of the surfactant, so that the particle size of the diffusion particles prepared by synthesis is regulated and controlled.

Further, the coupling agent is selected from one of ethylene glycol dimethacrylate, tripropylene glycol diacrylate or dipropylene glycol diacrylate.

Further, the initiator is selected from one of azo type or peroxy type initiators or a combination of at least two of the azo type or the peroxy type initiators.

Further, the azo initiator is selected from one or a combination of at least two of azodiisobutyl amidine hydrochloride, azodiisobutyl imidazoline hydrochloride or azodiisopropyl imidazoline.

Further, the peroxy initiator is selected from one or a combination of at least two of ammonium persulfate, potassium persulfate and sodium persulfate.

Further, the mass part ratio of NVP to another oily monomer is 15: 85-4: 96, and the total mass part of the mixed monomers is 100 parts; the addition amount of the initiator is 4-7.5% of the weight of the mixed monomer; the addition amount of the coupling agent is 4-20% of the weight of the mixed monomer.

Further, the diffusion fine particles have an average particle diameter of 1 to 35 μm. Further, the diffusion fine particles have an average particle diameter of 5 to 25 μm.

Further, the mass part ratio of NVP to the other oily monomer is 15: 85-5: 95.

The mass ratio of NVP to the oily monomer may be 40:60, 30:70, 25:75, 20:80, or 10:90, etc.

Further, the addition amount of the initiator is 4-6% of the weight of the mixed monomer. The amount of initiator added is preferably 5% by weight of the mixed monomers.

Further, the adding amount of the coupling agent is 4-10% of the weight of the mixed monomer. The amount of the coupling agent added is preferably 10%.

Further, the addition amount of the surfactant is 1.5-10% of the weight of the mixed monomer. Further, the addition amount of the surfactant is 4% by weight of the mixed monomer.

Furthermore, the addition amount of the deionized water is 2.5-5 times of the weight of the mixed solvent.

The present invention also provides a method for preparing the diffusing fine particles, which are prepared by an aqueous emulsion polymerization method, comprising the steps of:

(1) adding a surfactant into deionized water, and mechanically stirring to obtain a uniformly dispersed emulsification system;

(2) adding a mixed monomer and a coupling agent into the uniformly dispersed emulsification system obtained in the step (1), and continuously stirring to obtain an oil-in-water emulsion;

(3) adding a free radical initiator into the oil-in-water emulsion obtained in the step (2), heating to a reaction temperature while stirring, initiating a polymerization reaction, stopping the reaction after the reaction is fully performed, and cooling to room temperature;

(4) and (4) filtering the reaction product obtained in the step (3), washing with pure water, drying, and obtaining the diffusion particles after drying.

Further, in the step (4), after the reaction product is filtered by filter paper, the reaction product is washed three times by pure water, and then the reaction product is vacuumized and dried in a vacuum drying oven, so that the diffusion particles are prepared after the drying is finished.

Further, in the preparation method of the diffusion particles, the polymerization reaction temperature in the step (3) is 40-90 ℃, and the polymerization reaction time is 4-8 h.

Further, the polymerization reaction temperature in the step (3) is 40-80 ℃, and the polymerization reaction time is 4-8 h. Further, the polymerization reaction temperature in the step (3) is 75-80 ℃, and the polymerization reaction time is 6-8 h.

Further, in the step (1), the mechanical stirring is carried out at the speed of 800-. Further, the mechanical stirring is carried out at the speed of 800-. Further, the mixture was stirred for 5 min.

Further, in the step (2), the mechanical stirring is carried out at the speed of 800-1500r/min for 5-10 min. Further, the mechanical stirring is carried out at the speed of 800-. Further, the mixture was stirred for 10 min.

In the invention, whether the reaction is complete or not is judged by monitoring the content of carbon-carbon double bonds through an infrared spectrometer. The disappearance of the 1636cm peak indicating the absorption of the carbon-carbon double bond was judged as completion of the reaction.

Further, in the preparation method of the diffusion microparticle, the filter paper in the step (4) is water-based filter paper with the pore size of 0.5-10 μm; the drying conditions are that the vacuum pressure is 0.1MPa, the temperature is 80 ℃, and the drying is carried out for 24 hours.

The particle size of the prepared diffusion particles is 1-35 μm.

The diffusion particles prepared by the method have better water-oil balance and better dispersion performance in a water-based adhesive system, and are particularly suitable for preparing optical films produced by the water-based adhesive system.

The micro-morphology of the prepared diffusion particles is spherical, the particle size of the prepared diffusion particles can be effectively controlled by controlling the addition amount of an emulsifier (namely a surfactant) in emulsion polymerization, and the particle size distribution of the prepared diffusion particles is 1-35 mu m.

The prepared diffusion particles have both hydrophilic groups and lipophilic groups, and can realize better water-oil balance. The diffusing particles are prepared from N-vinyl pyrrolidone (NVP) and methyl methacrylate or butyl methacrylate or styrene by an aqueous emulsion polymerization method. Amide bonds on the structure of the prepared diffusion particles (polymerization products) are hydrophilic groups, and provide hydrophilicity for the diffusion particles; the ester bond or benzene ring structure is a lipophilic group, and provides lipophilicity for the diffusion particles.

Furthermore, the stirring mode in the preparation method of the diffusion particles is mechanical stirring, and the stirring speed is 200-.

The micro-morphology of the prepared diffusion particles is spherical or elliptical, and the particle size is 1-35 mu m; the larger the average particle diameter of the diffusing fine particles, the higher the luminance can be provided.

The prepared diffusion particles have a refractive index of 1.40-1.60.

The water-based adhesive system is a water-based adhesive system.

The diffusion particles provided by the invention are not suitable for the current solvent glue system.

In the invention, hydrophilicity means that the water-based adhesive can be well dispersed in a water-based adhesive system and water, and the more hydrophilic groups, the easier the water-based adhesive is dispersed in water; however, the more hydrophilic groups, the greater the swelling degree in aqueous glue system and water, the less stable and better the physical properties of the particles are, which is not favorable for the stability of practical production.

The diffusion particles provided by the present invention achieve such a balance: the dispersion in water or aqueous glue system is better, and the swelling degree in water or aqueous glue system is smaller.

The diffusion particles provided by the invention achieve better water-oil balance, have better dispersion performance in an aqueous adhesive system, are particularly suitable for the field of manufacturing optical films produced by the aqueous adhesive system, and are suitable for diffusion films, brightness enhancement films, light homogenizing films, protective films, quantum dot films and the like in the optical films, but are not limited to the products listed above.

Drawings

FIG. 1 is an SEM micrograph of diffusion particles prepared according to example 1 of the present invention;

FIG. 2 is an infrared spectrum of a polymerization process of diffusion particles prepared in example 1 of the present invention;

fig. 3 is a schematic structural diagram of an optical film prepared by preparing a diffusion coating solution from the diffusion particles provided by the present invention and then coating the diffusion coating solution on a PET substrate.

Detailed Description

The present invention will be further described with reference to the following examples and the accompanying drawings, wherein the following examples are only illustrative of the present invention and are not intended to limit the scope of the present invention. The method is a conventional method unless otherwise specified. The starting materials are, unless otherwise specified, commercially available products.

Fig. 1 is a microscopic morphology image of the diffusion particles prepared in example 1 photographed by SEM, and it can be seen that the microscopic morphology of the prepared diffusion particles is spherical.

As shown in FIG. 2, the polymerization process of example 1 was monitored by monitoring the double bond content by means of an infrared spectrometer with transmittance on the ordinate and wave number/cm on the abscissa^-1。

In FIG. 2, the a-curve is a sample before the reaction, the b-curve is a sample after the reaction for 4h, and the c-curve is a sample after the reaction. 1636cm in the figure^-1The absorption peak is the characteristic absorption peak of the carbon-carbon double bond,with the progress of the reaction, carbon-carbon double bonds continuously participate in the polymerization reaction, the absorption intensity of the characteristic peak gradually weakens, and 1636cm is obtained when the reaction is finished^-1The absorption peak at (b) substantially disappeared, indicating that the reaction was complete.

The invention relates to the evaluation of basic physical properties and optical properties of water-oil equilibrium diffusion particles. The required materials and equipment are all the existing materials and equipment.

Wherein, the diffusing particles EXM-8 (manufactured by Sekisui company, Japan) of the solvent type glue system which is suitable for producing the optical film in the market is selected as a comparison sample.

Wherein the evaluation of the physical properties of the diffusing particles comprises:

1. and (3) testing the refractive index: the optical refractive index was measured by the Becker method. Specifically, it was measured using Cargille's standard refractant. That is, the diffusing fine particles are placed on the sliding glass, and the refractive liquid is dropped. The diffusing particles and the refracting liquid were mixed well and the sodium lamp was irradiated from below. The particle profile was observed from above, and when the profile was not observed, it was judged that the refractive indexes of the refractive liquid and the fine particles were equal.

2. Average particle size test: the average particle size of the dispersed particles was measured by a calibration method according to Multisizer3 user manual issued by Beckman Coulter corporation using appropriate pores corresponding to the average particle size. A precision particle size distribution measuring apparatus (Multisizer 3/Coulter Counter, Beckman Coulter) was used for the measurement. Specifically, 0.1g of diffusing fine particles was pre-dispersed in 10ml of a nonionic surfactant solution having a mass concentration of 0.1% by using ultrasonic waves, slowly stirred, and then dropped by a pipette into a beaker filled with an electrolyte for test so that the mass concentration of the diffusing particles in the diffusing particle dispersion was maintained at about 10%, and then the test was started. In the measurement, the inside of the beaker was stirred slowly to such an extent that no air bubbles entered, and the measurement was terminated when 10 ten thousand of the diffused fine particles were measured.

3. Testing the dispersibility in water: and (3) taking 40g of diffusion particles, adding 50g of deionized water, mechanically stirring at normal temperature for 2h, coating the mixed solution on a PET (polyethylene terephthalate) substrate by using a wire rod, drying in an oven at 100 ℃, and observing whether the film surface has a white point agglomeration phenomenon, wherein if the dispersion is poor NG, the dispersion is OK.

4. Testing swelling performance in water: taking 20g of the diffusion particles, adding 50g of deionized water, standing for 4h at normal temperature, and testing the viscosity of the mixed component, wherein the more viscous the mixed component is, the more severe the swelling of the diffusion particles in water is. The smaller the swelling degree, the better the dispersion particles applied to optical film production, and the smaller the swelling degree, the production stability is facilitated. In Table 1, "+" indicates a small degree of swelling and a good resistance to swelling, "+ +" indicates a small degree of swelling and a good resistance to swelling, and "+ + +" indicates a small degree of swelling and a good resistance to swelling. The swelling degree is whether the diffusion fine particles are easily swollen, and a larger swelling degree indicates that the diffusion fine particles are more easily swollen, and a smaller swelling degree indicates that the diffusion fine particles are less easily swollen. The more readily swellable the diffusing particles indicates the lower the anti-swelling properties of the diffusing particles. The less swelling of the diffusing particles indicates better swelling resistance of the diffusing particles.

The optical properties of the diffused fine particles were evaluated by preparing the diffused fine particles as a diffusion coating solution and coating the solution on a PET substrate to form an optical film, wherein 101 is a protective layer, 102 is a PET substrate layer, 103 is a functional layer, and 104 is the diffused fine particles, as shown in fig. 3. And testing the optical performance of the prepared optical film.

The formula of the diffusion coating liquid (diffusion particles + aqueous gel system) is as follows:

component A of the aqueous adhesive system: 50 parts (product model: manufactured by BURNOCK WKC-593 Nippon DIC company, hydroxyl value is 35mg KOH/g, solid content is 46%),

b component of the water-based adhesive system: 6.25 parts (product type: BURNOCK DNW-5500, manufactured by NIPPON DIC corporation, NCO value 13% -14%, solid content 80%),

diffusing the particles: 45 parts (inventive example, comparative example, or EXM-8 comparative sample),

deionized water: 40-60 parts of (by weight),

the parts are parts by mass.

The main optical properties of an optical film (diffusion film) prepared using the diffusion fine particles provided by the present invention were tested in the following manner.

1. Light transmittance or haze test: a sheet of the prepared diffusion film with the size of A4 is taken and put into a haze tester to measure the light transmittance or haze value. The higher the light transmittance, the better, and the higher the haze, the better.

2. And (3) testing the brightness: a prepared diffusion film with the size of A4 was placed in a 20-inch backlight module according to the test configuration, lit at a voltage of 24V, and the brightness was measured with a luminance meter (BH-7). The higher the brightness, the better.

For the diffusion particles of the following examples, the reaction process was monitored by infrared spectroscopy to determine the completion of the reaction. And (4) drying the prepared diffusion particles, and observing the micro-morphology of the diffusion particles by using an SEM.

Example 1

The invention provides a diffusion particle, wherein the raw material of the diffusion particle comprises a mixed monomer; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is methyl methacrylate; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 50:50, and the total mass portion of the mixed monomers is 100.

The raw material of the diffusion particles also comprises a coupling agent, and the addition amount of the coupling agent is 5% of the weight of the mixed monomer.

The raw material of the diffusion particles also comprises an initiator, and the addition amount of the initiator is 10% of the weight of the mixed monomer.

The raw materials of the diffusion particles also comprise a surfactant and deionized water, and the addition amount of the deionized water is 3 times of the weight of the mixed monomers; the addition amount of the surfactant is 5% of the weight of the mixed monomer.

Specifically, the diffusion fine particles are prepared by the following method:

at room temperature, 10g of ammonium lauryl sulfate surfactant and 600g of deionized water are added into a 2L three-neck flask, mechanical stirring is carried out for 5min at the speed of 800r/min, then a mixed monomer of 100g N-vinyl pyrrolidone and 100g of methyl methacrylate and 10g of coupling agent ethylene glycol dimethacrylate are added, 20g of initiator potassium persulfate is added, stirring is carried out for 10min, uniform mixing is carried out to obtain stable emulsion, the temperature is raised to 80 ℃, polymerization reaction is started, after reaction for 6h, heating is stopped, and cooling is carried out to the room temperature. Filtration through a 2 μm pore size aqueous filter paper and 3 washes with deionized water yielded white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. To obtain diffusion particles No. 1.

Example 3

The invention provides a diffusion particle, wherein the raw material of the diffusion particle comprises a mixed monomer; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is methyl methacrylate; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 15:85, and the total mass portion of the mixed monomers is 100.

The raw material of the diffusion particles also comprises an initiator, and the addition amount of the initiator is 5% of the weight of the mixed monomer.

The raw materials of the diffusion particles also comprise a surfactant and deionized water, and the addition amount of the deionized water is 2.5 times of the weight of the mixed monomers; the addition amount of the surfactant is 5% of the weight of the mixed monomer.

at room temperature, 10g of ammonium lauryl sulfate surfactant and 500g of deionized water are added into a 1L three-neck flask, mechanical stirring is carried out for 5min at the speed of 800r/min, then a mixed monomer of 30g N-vinyl pyrrolidone and 170g of methyl methacrylate and 10g of coupling agent ethylene glycol dimethacrylate are added, 10g of initiator ammonium persulfate is added, stirring is carried out for 10min, uniform mixing is carried out to obtain stable emulsion, the temperature is increased to 80 ℃, polymerization reaction is started, after reaction is carried out for 6h, heating is stopped, and cooling is carried out to the room temperature. Filtration through a 5 μm pore size aqueous filter paper and 3 washes with deionized water yielded white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. To obtain diffusion particles No. 3.

Example 4

The invention provides a diffusion particle, wherein the raw material of the diffusion particle comprises a mixed monomer; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is methyl methacrylate; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 10:90, and the total mass portion of the mixed monomer is 100.

The raw material of the diffusion particles also comprises a coupling agent, and the addition amount of the coupling agent is 10% of the weight of the mixed monomer.

The raw materials of the diffusion particles also comprise a surfactant and deionized water, and the addition amount of the deionized water is 2.5 times of the weight of the mixed monomers; the addition amount of the surfactant is 4% of the weight of the mixed monomer.

at room temperature, 8g of ammonium lauryl sulfate surfactant and 500g of deionized water are added into a 1L three-neck flask, mechanical stirring is carried out for 5min at the speed of 800r/min, then a mixed monomer of 20g N-vinyl pyrrolidone and 180g of methyl methacrylate and 20g of tripropylene glycol diacrylate as a coupling agent are added, 10g of potassium persulfate as an initiator is added, stirring is carried out for 10min, uniform mixing is carried out to obtain stable emulsion, the temperature is raised to 80 ℃, polymerization reaction is started, after reaction is carried out for 6h, heating is stopped, and cooling is carried out to the room temperature. Filtration through a 5 μm pore size aqueous filter paper and 3 washes with deionized water yielded white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. To obtain diffusion particles No. 4.

Example 5

The invention provides a diffusion particle, wherein the raw material of the diffusion particle comprises a mixed monomer; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is methyl methacrylate; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 5:95, and the total mass portion of the mixed monomer is 100 parts.

The raw material of the diffusion particles also comprises a coupling agent, and the addition amount of the coupling agent is 4% of the weight of the mixed monomer.

The raw materials of the diffusion particles also comprise a surfactant and deionized water, and the addition amount of the deionized water is 2.5 times of the weight of the mixed monomers; the addition amount of the surfactant was 2.5% by weight of the mixed monomer.

at room temperature, 5g of ammonium lauryl sulfate as a surfactant and 500g of deionized water are added into a 1L three-neck flask, mechanical stirring is carried out for 5min at the speed of 800r/min, then a mixed monomer of 10g N-vinyl pyrrolidone and 190g of methyl methacrylate and 8g of tripropylene glycol diacrylate as a coupling agent are added, 10g of sodium persulfate as an initiator is added, stirring is carried out for 10min, then uniform mixing is carried out to obtain stable emulsion, the temperature is raised to 80 ℃, polymerization reaction is started, after reaction is carried out for 6h, heating is stopped, and cooling is carried out to the room temperature. Filtration through a 5 μm pore size aqueous filter paper and 3 washes with deionized water yielded white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. To obtain 5# diffusion particles.

Example 6

The invention provides a diffusion particle, wherein the raw material of the diffusion particle comprises a mixed monomer; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is methyl methacrylate; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 4:96, and the total mass portion of the mixed monomers is 100.

The raw material of the diffusion particles also comprises an initiator, and the addition amount of the initiator is 2% of the weight of the mixed monomer.

The raw materials of the diffusion particles also comprise a surfactant and deionized water, and the addition amount of the deionized water is 1 time of the weight of the mixed monomers; the addition amount of the surfactant was 2.5% by weight of the mixed monomer.

at room temperature, 5g of ammonium lauryl sulfate as a surfactant and 200g of deionized water are added into a 1L three-neck flask, mechanical stirring is carried out for 5min at the speed of 1000r/min, then a mixed monomer of 8g N-vinyl pyrrolidone and 192g of methyl methacrylate and 20g of tripropylene glycol diacrylate as a coupling agent are added, 4g of sodium persulfate as an initiator are added, stirring is carried out for 10min, then uniform mixing is carried out to obtain stable emulsion, the temperature is raised to 80 ℃, polymerization reaction is started, after reaction for 6h, heating is stopped, and cooling is carried out to the room temperature. Filtration through a 5 μm pore size aqueous filter paper and 3 washes with deionized water yielded white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. To obtain diffusion particles No. 6.

Example 7

The diffusing particles as provided in embodiment 5 wherein the initiator is added in an amount of 4% by weight of the mixed monomers.

at room temperature, 5g of ammonium lauryl sulfate as a surfactant and 500g of deionized water are added into a 1L three-neck flask, mechanical stirring is carried out for 5min at the speed of 800r/min, then a mixed monomer of 10g N-vinyl pyrrolidone and 190g of methyl methacrylate and 8g of tripropylene glycol diacrylate as a coupling agent are added, 8g of sodium persulfate as an initiator is added, stirring is carried out for 10min, then uniform mixing is carried out to obtain stable emulsion, the temperature is raised to 80 ℃, polymerization reaction is started, after reaction is carried out for 6h, heating is stopped, and cooling is carried out to the room temperature. Filtration through a 5 μm pore size aqueous filter paper and 3 washes with deionized water yielded white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. To obtain 7# diffusion particles.

Example 8

The invention provides a diffusion particle, wherein the raw material of the diffusion particle comprises a mixed monomer; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is butyl methacrylate; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 50:50, and the total mass portion of the mixed monomers is 100.

The raw material of the diffusion particles also comprises a coupling agent, and the addition amount of the coupling agent is 1% of the weight of the mixed monomer.

The raw material of the diffusion particles also comprises an initiator, and the addition amount of the initiator is 3% of the weight of the mixed monomer.

at room temperature, 10g of ammonium lauryl sulfate surfactant and 500g of deionized water are added into a 1L three-neck flask, mechanical stirring is carried out for 5min at the speed of 1000r/min, then a mixed monomer of 100g N-vinyl pyrrolidone and 100g of butyl methacrylate and 2g of tripropylene glycol diacrylate as a coupling agent are added, 6g of ammonium persulfate as an initiator are added, stirring is carried out for 10min, uniform mixing is carried out to obtain stable emulsion, the temperature is raised to 40 ℃, polymerization reaction is started, after 8h of reaction, heating is stopped, and the temperature is cooled to the room temperature. Filtration through an aqueous filter paper with a pore size of 1 μm and washing 3 times with deionized water gave white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. To obtain 8# diffusion particles.

Example 9

The invention provides a diffusion particle, wherein the raw material of the diffusion particle comprises a mixed monomer; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is butyl methacrylate; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 10:90, and the total mass portion of the mixed monomer is 100.

The raw material of the diffusion particles also comprises an initiator, and the addition amount of the initiator is 5% of the weight of the mixed monomer. The raw materials of the diffusion particles also comprise a surfactant and deionized water, and the addition amount of the deionized water is 5 times of the weight of the mixed monomers; the addition amount of the surfactant was 1.5% by weight of the mixed monomers.

at room temperature, 3g of ammonium lauryl sulfate as a surfactant and 1000g of deionized water are added into a 2L three-neck flask, mechanical stirring is carried out for 5min at the speed of 1000r/min, then a mixed monomer of 20g N-vinyl pyrrolidone and 180g of butyl methacrylate and 8g of tripropylene glycol diacrylate as a coupling agent are added, 10g of sodium persulfate as an initiator is added, stirring is carried out for 10min, then uniform mixing is carried out to obtain stable emulsion, the temperature is raised to 80 ℃, polymerization reaction is started, after reaction is carried out for 6h, heating is stopped, and cooling is carried out to the room temperature. Filtration through a 5 μm pore size aqueous filter paper and 3 washes with deionized water yielded white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. To obtain the diffusion particles 9 #.

Example 10

The invention provides a diffusion particle, wherein the raw material of the diffusion particle comprises a mixed monomer; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is butyl methacrylate; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 15:85, and the total mass portion of the mixed monomers is 100.

The raw material of the diffusion particles also comprises a coupling agent, and the addition amount of the coupling agent is 8% of the weight of the mixed monomer.

The raw materials of the diffusion particles also comprise a surfactant and deionized water, and the addition amount of the deionized water is 5 times of the weight of the mixed monomers; the addition amount of the surfactant is 10% of the weight of the mixed monomer.

at room temperature, 20g of ammonium lauryl sulfate as a surfactant and 1000g of deionized water are added into a 2L three-neck flask, mechanical stirring is carried out for 5min at the speed of 1000r/min, then a mixed monomer of 30g N-vinyl pyrrolidone and 170g of butyl methacrylate and 16g of tripropylene glycol diacrylate as a coupling agent are added, 10g of sodium persulfate as an initiator is added, stirring is carried out for 10min, then uniform mixing is carried out to obtain stable emulsion, the temperature is raised to 80 ℃, polymerization reaction is started, after reaction is carried out for 6h, heating is stopped, and cooling is carried out to the room temperature. Filtration through an aqueous filter paper with a pore size of 0.5 μm and washing 3 times with deionized water gave white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. To obtain the diffusion particles No. 10.

Example 11

The process of example 10 wherein the initiator is added in an amount of 6% by weight of the mixed monomers. Diffusion particles 11# were prepared.

Example 12

In example 10, the temperature was raised to 75 ℃ to start the polymerization reaction, and after 6 hours of the reaction, the heating was stopped and the reaction mixture was cooled to room temperature. To obtain diffusion particles No. 12.

Example 13

As in example 10, wherein, at room temperature, 20g of ammonium lauryl sulfate as a surfactant and 1000g of deionized water were placed in a 2L three-necked flask, mechanically stirred at a rate of 1200r/min for 10min, then a mixed monomer of 30g N-vinylpyrrolidone and 170g of butyl methacrylate and 16g of tripropylene glycol diacrylate as a coupling agent were added, 10g of sodium persulfate as an initiator was further added, and after stirring for 5min, the mixture was uniformly mixed to obtain a stable emulsion, the temperature was raised to 80 ℃ to start a polymerization reaction, and after 6 hours of the reaction, the heating was stopped and the mixture was cooled to room temperature. Filtration through an aqueous filter paper with a pore size of 0.5 μm and washing 3 times with deionized water gave white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. To obtain 13# diffusion particles.

Example 14

The invention provides a diffusion particle, wherein the raw material of the diffusion particle comprises a mixed monomer; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is styrene; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 50:50, and the total mass portion of the mixed monomers is 100.

The raw material of the diffusion particles also comprises a coupling agent, and the addition amount of the coupling agent is 15% of the weight of the mixed monomer.

The raw material of the diffusion particles also comprises an initiator, and the addition amount of the initiator is 7.5% of the weight of the mixed monomer.

The raw materials of the diffusion particles also comprise a surfactant and deionized water, and the addition amount of the deionized water is 2.5 times of the weight of the mixed monomers; the addition amount of the surfactant is 1% of the weight of the mixed monomer.

at room temperature, 2g of ammonium lauryl sulfate surfactant and 500g of deionized water are added into a 1L three-neck flask, mechanical stirring is carried out for 5min at the speed of 1500r/min, then mixed monomer of 100g N-vinyl pyrrolidone and 100g of styrene and 30g of coupling agent ethylene glycol dimethacrylate are added, 15g of initiator ammonium persulfate is added, stirring is carried out for 10min, uniform mixing is carried out, stable emulsion is obtained, the temperature is increased to 80 ℃, polymerization reaction is started, after reaction is carried out for 7h, heating is stopped, and cooling is carried out to the room temperature. Filtration through a 5 μm pore size aqueous filter paper and 3 washes with deionized water yielded white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. To obtain diffusion particles No. 14.

Example 15

The invention provides a diffusion particle, wherein the raw material of the diffusion particle comprises a mixed monomer; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is butyl methacrylate; the mass part ratio of the N-vinyl pyrrolidone to the butyl methacrylate is 30:70, and the total mass part of the mixed monomer is 100 parts.

The raw material of the diffusion particles also comprises a coupling agent, and the addition amount of the coupling agent is 20% of the weight of the mixed monomer.

The raw material of the diffusion particles also comprises an initiator, and the addition amount of the initiator is 2.5% of the weight of the mixed monomer.

at room temperature, 2g of ammonium lauryl sulfate surfactant and 500g of deionized water are added into a 1L three-neck flask, mechanical stirring is carried out for 5min at the speed of 1000r/min, then a mixed monomer of 60g N-vinyl pyrrolidone and 140g of butyl methacrylate and 40g of coupling agent ethylene glycol dimethacrylate are added, 5g of initiator ammonium persulfate is added, stirring is carried out for 10min, uniform mixing is carried out to obtain stable emulsion, the temperature is raised to 60 ℃, polymerization reaction is started, after reaction is carried out for 8h, heating is stopped, and cooling is carried out to the room temperature. Filtration through a 10 μm pore size aqueous filter paper and 3 washes with deionized water yielded white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. To obtain the diffusion particles No. 15.

Example 16

The invention provides a diffusion particle, wherein the raw material of the diffusion particle comprises a mixed monomer; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is styrene; the mass portion ratio of the N-vinyl pyrrolidone to the styrene is 10:90, and the total mass portion of the mixed monomer is 100.

at room temperature, 8g of ammonium lauryl sulfate surfactant and 500g of deionized water are added into a 1L three-neck flask, mechanical stirring is carried out for 5min at the speed of 1500r/min, then a mixed monomer of 20g N-vinyl pyrrolidone and 180g of styrene and 40g of dipropylene glycol diacrylate as a coupling agent are added, 15g of ammonium persulfate as an initiator are added, stirring is carried out for 10min, uniform mixing is carried out to obtain stable emulsion, the temperature is increased to 80 ℃, polymerization reaction is started, after reaction is carried out for 7h, heating is stopped, and cooling is carried out to the room temperature. Filtration through a 2 μm pore size aqueous filter paper and 3 washes with deionized water yielded white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. And (4) preparing the required water-oil balanced diffusion particles 16 #.

Comparative example 1

Preparing a diffusion particle, wherein the raw material of the diffusion particle comprises mixed monomers; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is methyl methacrylate; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 3:97, and the total mass portion of the mixed monomers is 100 parts.

at room temperature, 5g of ammonium lauryl sulfate as a surfactant and 200g of deionized water are added into a 1L three-neck flask, mechanical stirring is carried out for 5min at the speed of 1000r/min, then a mixed monomer of 6g N-vinyl pyrrolidone and 194g of methyl methacrylate and 20g of tripropylene glycol diacrylate as a coupling agent are added, 10g of sodium persulfate as an initiator is added, stirring is carried out for 10min, then uniform mixing is carried out to obtain stable emulsion, the temperature is raised to 80 ℃, polymerization reaction is started, after reaction is carried out for 6h, heating is stopped, and cooling is carried out to the room temperature. Filtration through a 5 μm pore size aqueous filter paper and 3 washes with deionized water yielded white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. Diffusion particles are produced.

Comparative example 2

Preparing a diffusion particle, wherein the raw material of the diffusion particle comprises mixed monomers; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is methyl methacrylate; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 1:99, and the total mass portion of the mixed monomers is 100.

at room temperature, 5g of ammonium lauryl sulfate as a surfactant and 200g of deionized water are added into a 1L three-neck flask, mechanical stirring is carried out for 5min at the speed of 800r/min, then a mixed monomer of 2g N-vinyl pyrrolidone and 198g of methyl methacrylate and 8g of tripropylene glycol diacrylate as a coupling agent are added, 10g of sodium persulfate as an initiator is added, stirring is carried out for 10min, then uniform mixing is carried out to obtain stable emulsion, the temperature is raised to 80 ℃, polymerization reaction is started, after reaction for 6h, heating is stopped, and the temperature is cooled to room temperature. Filtration through a 5 μm pore size aqueous filter paper and 3 washes with deionized water yielded white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. Producing diffusion particles

Comparative example 3

Preparing a diffusion particle, wherein the raw material of the diffusion particle comprises mixed monomers; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is butyl methacrylate; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 5:95, and the total mass portion of the mixed monomer is 100 parts.

The raw material of the diffusion particles also comprises an initiator, and the addition amount of the initiator is 1 percent of the weight of the mixed monomer

at room temperature, 10g of ammonium lauryl sulfate surfactant and 500g of deionized water are added into a 1L three-neck flask, mechanical stirring is carried out for 5min at the speed of 1000r/min, then a mixed monomer of 10g N-vinyl pyrrolidone and 190g of butyl methacrylate and 2g of tripropylene glycol diacrylate as a coupling agent are added, 2g of ammonium persulfate as an initiator are added, stirring is carried out for 10min, uniform mixing is carried out to obtain stable emulsion, the temperature is raised to 40 ℃, polymerization reaction is started, after 8h of reaction, heating is stopped, and the temperature is cooled to room temperature. Filtration through an aqueous filter paper with a pore size of 1 μm and washing 3 times with deionized water gave white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. Diffusion particles are produced.

Comparative example 4

Preparing a diffusion particle, wherein the raw material of the diffusion particle comprises mixed monomers; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is butyl methacrylate; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 2:98, and the total mass portion of the mixed monomers is 100.

at room temperature, 10g of ammonium lauryl sulfate surfactant and 500g of deionized water are added into a 1L three-neck flask, mechanical stirring is carried out for 5min at the speed of 1000r/min, then a mixed monomer of 4g N-vinyl pyrrolidone and 196g of butyl methacrylate and 10g of tripropylene glycol diacrylate as a coupling agent are added, 6g of ammonium persulfate as an initiator are added, stirring is carried out for 10min, uniform mixing is carried out to obtain stable emulsion, the temperature is raised to 40 ℃, polymerization reaction is started, after 8h of reaction, heating is stopped, and the temperature is cooled to the room temperature. Filtration through an aqueous filter paper with a pore size of 1 μm and washing 3 times with deionized water gave white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. Diffusion particles are produced.

Comparative example 5

Preparing a diffusion particle, wherein the raw material of the diffusion particle comprises mixed monomers; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is selected from one of methyl methacrylate, butyl methacrylate or styrene; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 1:99, and the total mass portion of the mixed monomers is 100.

The raw materials of the diffusion particles also comprise a surfactant and deionized water, and the addition amount of the deionized water is 2 times of the weight of the mixed monomers; the addition amount of the surfactant is 5% of the weight of the mixed monomer.

at room temperature, 10g of ammonium lauryl sulfate surfactant and 400g of deionized water are added into a 1L three-neck flask, mechanical stirring is carried out for 5min at the speed of 1000r/min, then a mixed monomer of 2g N-vinyl pyrrolidone and 198g of butyl methacrylate and 8g of coupling agent ethylene glycol dimethacrylate are added, 10g of initiator sodium persulfate is added, stirring is carried out for 10min, uniform mixing is carried out to obtain stable emulsion, the temperature is raised to 90 ℃, polymerization reaction is started, after 4h of reaction, heating is stopped, and cooling is carried out to the room temperature. Filtration through an aqueous filter paper with a pore size of 1 μm and washing 3 times with deionized water gave white powdery particles. And putting the white powdery particles into a vacuum drying oven for vacuum drying, and drying for 24 hours under the conditions of vacuum pressure of 0.1MPa and temperature of 80 ℃. Diffusion particles are produced.

The ratio of N-vinylpyrrolidone in comparative example 1, comparative example 2, comparative example 4, and comparative example 5 was too low, and the prepared diffusion fine particles were inferior in dispersibility in water. The amount of the initiator added in comparative example 3 was too low, and the dispersion of the resulting diffusion particles in water was poor.

The evaluation results of the physical properties and optical properties of the diffusion particles prepared in examples and comparative examples 1 to 5, and comparative example EXM-8 are shown in table 1 below.

TABLE 1 Performance test results of diffusion particles provided in inventive and comparative examples, comparative example EXM-8

As can be seen from the data shown in table 1, the diffusion particles provided by the present invention can effectively control the particle size of the prepared diffusion particles by controlling the addition amounts of the surfactant and the initiator, and the smaller the surfactant is added, the smaller the initiator amount is, the more favorable the preparation of the diffusion particles with larger average particle size is. The dispersion performance of the prepared diffusion particles in water can be effectively regulated and controlled by regulating the mass ratio of the N-vinyl pyrrolidone to the lipophilic monomer, when the mass ratio of the N-vinyl pyrrolidone in the mixed monomer is more than 10%, the prepared diffusion particles have better dispersion performance in water, and the larger the mass ratio of the N-vinyl pyrrolidone is, the better the hydrophilicity of the prepared diffusion particles is, and the better the dispersibility in water is. The swelling degree of the prepared diffusion fine particles in water becomes larger as the mass ratio of the amount of N-vinylpyrrolidone in the mixed monomer becomes larger, and it is required that the smaller the swelling degree of the diffusion fine particles in the production process of the optical film, the better. The light transmittance, haze and brightness of the optical properties of the diffusing particles are also related to the average particle size and material of the diffusing particles.

The comparative sample EXM-8 is synthesized by all oil-soluble monomers, has poor dispersion performance in water, and is not suitable for coating production of optical films of aqueous adhesive systems.

In summary, when the mass ratio of the N-vinyl pyrrolidone to the oily monomer is 15: 85-4: 96, the prepared diffusion particles have better dispersibility in water and smaller swelling degree in water, so that the water-oil balance can be better achieved. Examples 3, 4 and 5 according to the present invention,

The diffusion particles provided in examples 6, 7, 9, 10 and 16 have better overall performance, and the diffusion particle provided in example 4 has the best overall performance.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. All equivalent changes and modifications made according to the disclosure of the present invention are covered by the scope of the claims of the present invention.

Claims

1. A diffusing particulate characterized in that a raw material of the diffusing particulate comprises a mixed monomer; the mixed monomer comprises N-vinyl pyrrolidone (NVP) and another oily monomer; the other oily monomer is selected from one of methyl methacrylate, butyl methacrylate or styrene; the mass portion ratio of the N-vinyl pyrrolidone to the other oily monomer is 15: 85-4: 96, and the total mass portion of the mixed monomer is 100; the raw material of the diffusion particles also comprises a coupling agent, and the addition amount of the coupling agent is 4-20% of the weight of the mixed monomer; the raw material of the diffusion particles also comprises an initiator, and the addition amount of the initiator is 2-7.5% of the weight of the mixed monomer.

2. The diffusing particle of claim 1, wherein the raw material of the diffusing particle further comprises a surfactant and deionized water, and the amount of the deionized water added is 1 to 5 times the weight of the mixed solvent; the addition amount of the surfactant is 1-10% of the weight of the mixed monomer.

3. The diffusing particle of claim 2, wherein the surfactant is selected from the group consisting of a nonionic surfactant, and/or an anionic surfactant, or a combination of at least two thereof.

4. The diffusing particle of claim 1 wherein the coupling agent is selected from the group consisting of ethylene glycol dimethacrylate, tripropylene glycol diacrylate and dipropylene glycol diacrylate.

5. Diffusing particulate according to claim 1, wherein the initiator is selected from one or a combination of at least two of azo or peroxy initiators.

6. A method of making the diffusing particulate of claim 2 wherein the diffusing particulate is made by an aqueous emulsion polymerization process comprising the steps of:

7. The method of claim 6, wherein the polymerization temperature in the step (3) is 40 to 90 ℃ and the polymerization time is 4 to 8 hours.