Double-peak nano-system anti-bonding master batch for MLCC (multilayer ceramic capacitor) base film and preparation method

Abstract

The invention relates to the technical field of release film materials, in particular to a bimodal nano-system anti-bonding master batch for an MLCC (multilayer ceramic capacitor) base film and a preparation method of the bimodal nano-system anti-bonding master batch. The anti-bonding master batch comprises the following components in parts by weight: 85-98 parts of thermoplastic resin; 1 to 15 parts of a modified inorganic nanoparticle complex; 0.1 to 1 part of an auxiliary agent; the modified inorganic nanoparticle complex is prepared from the following raw materials: a silane coupling agent and an inorganic nanoparticle complex; the inorganic nano particle complex comprises SiO2 and Al2O3, and the inorganic nano particle complex comprises SiO2 and Al2O3; the particle size of the inorganic nano particle complex is 50 to 500 nm. The technical problems that inorganic nanoparticles are poor in dispersity and easy to agglomerate in PET resin are solved through a bimodal nanoparticle compounding and surface modification technology, the surface of the MLCC release film is endowed with ultralow roughness, and the comprehensive performance of an MLCC product is remarkably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of release film materials, and in particular to a bimodal nanosystem anti-bonding masterbatch for MLCC base films and a preparation method thereof. Background Art

[0002] Multilayer ceramic capacitors (MLCCs), key components in electronic circuits, have found widespread application in a wide range of fields, including consumer electronics, automotive electronics, and communications equipment, thanks to their numerous advantages, including compact size, high capacitance, low loss at high frequencies, ease of mass production, cost-effectiveness, and stable performance. In recent years, with the continued surge in market usage and sales of products like smartphones and electric vehicles, market demand for MLCCs has shown strong growth.

[0003] In the MLCC production process, release film is an indispensable carrier material, and biaxially oriented polyester film (BOPET) is usually used as the base film material. The surface properties of the release film play a decisive role in the final quality and production efficiency of the MLCC. Specifically, the MLCC release film must have excellent anti-sticking properties, outstanding heat resistance, and extremely low surface roughness. These properties ensure that the ceramic sheet can be evenly coated during the MLCC manufacturing process, and the surface roughness is controlled to an extremely low level, thus meeting the stringent technical requirements of MLCC for high capacitance, miniaturized design, and high reliability.

[0004] Currently, existing anti-sticking masterbatches for MLCC release films on the market still present several challenges. For one thing, these anti-sticking masterbatches exhibit poor dispersion in the resin matrix, leading to the agglomeration of inorganic nanoparticles. This results in a noticeably uneven surface and high roughness, adversely impacting the performance and reliability of the MLCC. Furthermore, precisely controlling the surface roughness of the base film while ensuring compliance with anti-sticking performance remains a major technical challenge. Existing anti-sticking masterbatches struggle to meet the demanding surface quality requirements of high-end MLCC products.

[0005] Chinese invention patent application CN104177685A discloses an infrared reflecting / emitting thermal insulation plastic functional masterbatch and a preparation method thereof. By using nano-antimony doped tin dioxide or nano-cerium and other materials in the infrared reflecting / emitting thermal insulation plastic, combined with hollow microbeads and synthetic resin, a high-efficiency infrared reflecting / emitting thermal insulation plastic is prepared. This solves the time-consuming and labor-intensive spraying and environmental pollution problems of existing infrared reflecting thermal insulation coatings, and achieves efficient infrared light reflection and energy emission. Chinese invention patent CN101142277B discloses a resin composition comprising 50 to 100 weight percent of a resin component and 0 to 50 weight percent of an inorganic filler (component D), wherein the resin component comprises: (i) an aromatic polycarbonate (component A) having a specific viscosity-average molecular weight; and (ii) a polyethylene glycol ester (component B) having a specific intrinsic viscosity (IV), a terminal carboxyl group content, and a ratio (Mw / Mn) of weight-average molecular weight (Mw) to number-average molecular weight (Mn). By using low-viscosity PET and SVG molding in the resin composition, combined with an inorganic filler and a rubbery polymer, the problems of insufficient fluidity and chemical resistance of the resin composition are solved, thereby achieving an automotive exterior material with high fluidity and good appearance.

[0006] However, none of these existing technologies solves the ultra-low roughness requirements of high-end MLCC products for the base film surface, and the anti-sticking properties are limited. There is an urgent need to provide a low-roughness, anti-sticking material that can meet the requirements of MLCC products. Summary of the Invention

[0007] Existing BOPET products still have the following technical problems: 1) poor dispersion of nanoparticles and easy agglomeration; 2) high surface roughness of MLCC release films, which is difficult to reach a level below 30nm; and 3) difficulty in balancing anti-adhesion performance and surface roughness. In order to solve the above technical problems, the present invention provides a bimodal nanosystem anti-adhesion masterbatch for MLCC base film and a preparation method thereof. By combining bimodal nanoparticle composite with surface modification technology, the technical problems of poor dispersion and easy agglomeration of inorganic nanoparticles in PET resin are solved, and the surface of MLCC release film is given ultra-low roughness, which significantly improves the overall performance of MLCC and fully meets the strict standards and quality requirements for base film materials put forward by high-end MLCC production.

[0008] The first aspect of the present invention provides a bimodal nano-system anti-sticking masterbatch for MLCC base film, wherein the anti-sticking masterbatch comprises the following components in parts by weight:

[0009] 85-98 parts of thermoplastic resin;

[0010] 1-15 parts of modified inorganic nanoparticle complex;

[0011] 0.1-1 part of additive;

[0012] The raw materials for preparing the modified inorganic nanoparticle composite include a silane coupling agent and an inorganic nanoparticle composite.

[0013] Thermoplastic resin:

[0014] Examples of the thermoplastic resin include PET (polyethylene terephthalate), PETG (polyethylene terephthalate-1,4-cyclohexanedimethanol ester), PBT (polybutylene terephthalate), PE (polyethylene), PP (polypropylene), PI (polyimide), PC (polycarbonate), etc.; further, at least one of PET, PETG, and PBT can be selected; more preferably, PET can be selected.

[0015] Modified inorganic nanoparticle composite:

[0016] Examples of the inorganic nanoparticles include SiO2, Al2O3, TiO2, CNT (carbon nanotube), CaCO3, CaSiO3, CaAl2Si2O8, montmorillonite, feldspar powder, talc powder, mica powder, etc. In the present invention, a bimodal nano-composite system is preferably used as the modified inorganic nanoparticle composite. The bimodal nano-composite system refers to a system composed of two different-sized nanoparticles compounded together, named after its particle size distribution showing two peaks. This composite system can integrate and fully utilize the advantages of different-sized nanoparticles to achieve synergistic improvement and optimization of performance.

[0017] Optionally, the inorganic nanoparticle composite includes SiO2 and Al2O3.

[0018] Optionally, the particle size of the inorganic nanoparticle composite is 50-500 nm; further, it can be 80-400 nm.

[0019] Optionally, the particle size of SiO2 is larger than that of Al2O3.

[0020] Optionally, the particle size of SiO2 is 250-500 nm, and examples include 250 nm, 260 nm, 270 nm, 280 nm, 290 nm, 300 nm, 310 nm, 320 nm, 330 nm, 340 nm, 350 nm, 360 nm, 370 nm, 380 nm, 390 nm, 400 nm, 420 nm, 440 nm, 460 nm, 480 nm, 500 nm; further, it can be 280-350 nm; most preferably, it is 300 nm.

[0021] Optionally, the particle size of the Al2O3 is 50-150 nm, which can be exemplified as 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm; more preferably 100 nm.

[0022] Optionally, the weight ratio of the SiO2 and Al2O3 is (1-5):(1-5); more preferably (1-3):1, which can be exemplified as 1:1, 2:1, 3:1.

[0023] The present invention preferably uses large-particle-size SiO2 and small-particle-size Al2O3 to form an inorganic nano-composite system. Applying it to the PET resin system can endow the masterbatch with good chemical tolerance and electrical properties, and further enhance the wear resistance and heat resistance of the material. Further preferably, 300 nm SiO2 and 100 nm Al2O3 are compounded at a specific weight ratio. On the one hand, the particle sizes of 300 nm SiO2 and 100 nm Al2O3 are complementary, forming a gradient distribution of concave and convex structures on the film surface, avoiding the risk of local adhesion caused by a single particle size; the small-particle-size Al2O3 can fill the vacancies on the film surface that are not distributed by the large-particle-size SiO2, improving the uniformity of the surface roughness, reducing the contact area, thereby effectively suppressing the interlayer adhesion of the film and enhancing the anti-bonding performance of the release film. Compared with inorganic nano-particles of a single particle size and type, the bimodal nano-composite system of the present invention can more fully occupy the film surface, reduce the surface site vacancies, and thus effectively reduce the surface roughness of the film; on the other hand, the large-particle-size particles dominate the macroscopic anti-bonding effect, and the small-particle-size particles optimize the microscopic surface smoothness. The two complement each other in performance, and after compounding, they give full play to the synergistic effect, making the material have a variety of excellent properties such as light transmittance (low haze), chemical stability, insulation, high hardness and thermal stability, meeting the use requirements of the anti-bonding masterbatch for MLCC release film under complex working conditions, and having high practical value.

[0024] Silane coupling agent:

[0025] Examples of the silane coupling agent include vinyltriethoxysilane (commonly known as A-151), γ-methacryloxypropyltrimethoxysilane (commonly known as A174 or KH570), vinyltrimethoxysilane (commonly known as A-171), vinyltris(β-methoxyethoxy)silane (commonly known as A-172), γ-aminopropyltriethoxysilane (commonly known as A-1100 or KH-550), γ-aminopropyltrimethoxysilane (commonly known as KH-551), γ-(2,3-epoxypropoxy)propyltrimethoxysilane (commonly known as KH-560), etc.; further preferably, it can be vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane; more preferably, it can be KH570.

[0026] The weight ratio of the silane coupling agent to the inorganic nanoparticle complex is (0.1 - 5):(1 - 10), and further preferably 0.5:(2 - 4).

[0027] The present invention preferably uses a silane coupling agent (especially KH570) to modify the surface of the bimodal nanocomposite system, endowing the inorganic nanoparticles with better interfacial compatibility. After surface modification, an "organic-inorganic" biphasic anchoring structure is formed, which can form a good interfacial bond with the PET resin, promoting the uniform dispersion of the inorganic nanoparticle complex in the PET resin, avoiding the agglomeration effect of the nanoparticles, and thus better exerting the improvement effect of the nanoparticles on the material properties, enhancing the anti-sticking performance of the film material and reducing the surface roughness.

[0028] Auxiliaries:

[0029] Examples of the auxiliaries include antioxidants, lubricants, antistatic agents, bacteriostatic agents, etc., which can be flexibly selected according to the usage requirements of the MLCC.

[0030] Optionally, the auxiliaries include 0.1 - 0.5 parts of antioxidant and 0.1 - 0.3 parts of lubricant.

[0031] Examples of the antioxidant include pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (commonly known as antioxidant 1010), octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (commonly known as antioxidant 1076), butylated hydroxyanisole (commonly known as antioxidant BHT), tris(2,4-di-tert-butylphenyl) phosphite (commonly known as antioxidant 168), bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite (commonly known as antioxidant 626), 2,6-di-tert-butyl-p-cresol (commonly known as antioxidant 264 or BHA), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (commonly known as antioxidant 2246 or MMB), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (commonly known as antioxidant 330), 4,4'-thiobis(6-tert-butyl-3-methylphenol) (commonly known as antioxidant 300), condensate of diphenylamine and p-phenylenediamine (commonly known as antioxidant DNP), N,N'-di(β-naphthyl)-p-phenylenediamine (commonly known as antioxidant H), dilauryl thiodipropionate (commonly known as antioxidant DLTP or DLTDP), distearyl thiodipropionate (commonly known as antioxidant DSTP), N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine (commonly known as antioxidant 1098), etc.; antioxidant 1010 can be selected.

[0032] Examples of the lubricant include calcium stearate, zinc stearate, oleic acid amide, erucic acid amide, ethylene bisstearamide (EBS), polyethylene wax (PE wax), oxidized polyethylene wax (OPE wax), silicone oil, etc.; calcium stearate can be selected.

[0033] The second aspect of the present invention provides a method for preparing an anti-blocking masterbatch for a bimodal nanocomposite system for MLCC base film. The preparation steps of the anti-blocking masterbatch include:

[0034] S1. Prepare a modified inorganic nanoparticle complex;

[0035] S2. Add the thermoplastic resin, the modified inorganic nanoparticle complex, and the additives into an extruder, melt and blend them, and then extrude and pelletize to obtain the finished anti-blocking masterbatch.

[0036] Optionally, the step S1 includes:

[0037] S1.1 Mix SiO2 and Al2O3, add a dispersion medium, and perform ultrasonic dispersion;

[0038] S1.2 Add a silane coupling agent after ultrasonic dispersion for surface treatment;

[0039] S1.3 Centrifuge, wash, and dry after surface treatment to obtain the modified inorganic nanoparticle complex.

[0040] To ensure that the inorganic nanoparticles can be fully and uniformly dispersed in the system and effectively avoid the occurrence of their agglomeration phenomenon, in some embodiments, the power of the ultrasonic dispersion is 200 - 400 W, and the time of the ultrasonic dispersion is 30 - 60 min; optionally, the power of the ultrasonic dispersion is 200 W, and the time of the ultrasonic dispersion is 45 min.

[0041] The dispersion medium is not particularly limited as long as it can achieve the purpose of ultrasonic dispersion; for example, ethanol.

[0042] To promote the full surface modification of the inorganic nanoparticles by the silane coupling agent, in some embodiments, the temperature of the surface treatment is 50 - 80 °C, and the time of the surface treatment is 2 - 4 h; optionally, the temperature of the surface treatment is 60 - 70 °C.

[0043] In some embodiments, the rotational speed of the centrifugation is 5000 - 8000 r / min, and the time of the centrifugation is 5 - 10 min.

[0044] In some embodiments, the temperature of the drying is 60 - 80 °C, and the time of the drying is 6 - 12 h; optionally, the temperature of the drying is 70 °C, and the time of the drying is 8 h.

[0045] The reagent used for washing is not limited as long as it can remove impurities and unreacted silane coupling agent, etc.; for example, ethanol.

[0046] Moreover, their preparation technologies are mature and the supply is stable, which is beneficial to reducing costs and realizing industrial production. In some embodiments, the temperature of the melt blending is 200 - 290 °C, and the output is 300 - 600 kg / h; optionally, the temperature of the melt blending is 270 °C, and the output is 350 kg / h.

[0047] In some embodiments, the S2 step realizes the mixing and extrusion of materials through a twin-screw extruder; optionally, the thermoplastic resin is added to the twin-screw extruder in the main feeding mode, and the materials other than the thermoplastic resin are added to the twin-screw extruder in the side feeding mode.

[0048] In some embodiments, the rotational speed of the twin-screw extruder is 300 - 600 r / min, and optionally, the rotational speed is 400 r / min.

[0049] The process for preparing the modified inorganic nanoparticle composite and the anti-blocking masterbatch of the present invention is simple, safe and environmentally friendly. The overall preparation technology is mature, which can ensure the stable supply of the masterbatch, is beneficial to reducing costs from the source end, and realizes industrial mass production.

[0050] Beneficial effects:

[0051] The present invention provides a bimodal nano-system anti-adhesion masterbatch for MLCC base film and a preparation method, which has the following advantages:

[0052] (1) By combining bimodal nanoparticle compounding and surface modification technologies, the present invention solves the technical problems of poor dispersibility and easy agglomeration of inorganic nanoparticles in PET resin, endows the surface of the MLCC release film with ultra-low roughness, significantly improves the comprehensive performance of MLCC, and fully meets the strict standards and quality requirements for base film materials in high-end MLCC production.

[0053] (2) The present invention preferably uses large-particle-size SiO2 and small-particle-size Al2O3 to form an inorganic nano-composite system, which can more fully occupy the film surface and effectively reduce the film surface roughness; at the same time, the large-particle-size particles dominate the macroscopic anti-adhesion effect, and the small-particle-size particles optimize the microscopic surface smoothness. After the two are compounded, they give full play to the synergistic effect, making the material have both light transmittance.

[0054] (3) The present invention preferably uses a silane coupling agent (especially KH570) to modify the surface of the bimodal nano-composite system, endows the inorganic nanoparticles with good interfacial compatibility, and forms an "organic-inorganic" biphasic anchoring structure after surface modification, which can form a good interfacial bond with PET resin, improve the anti-adhesion performance of the film material and reduce the surface roughness.

[0055] (4) The present invention preferably uses specific antioxidants and wetting agents as additives, further improving the anti-adhesion performance and low roughness of the material, and can precisely control the surface roughness of the MLCC release film to reach a level below 40 nm, which can meet the use requirements of the MLCC release film.

[0056] (5) The anti-adhesion performance of the release film often needs to rely on a rough concave-convex surface to achieve, making it difficult to balance the anti-adhesion and low roughness of existing anti-adhesion masterbatches; the present invention effectively solves the above problems through reasonable formulation design and preparation process, can achieve ultra-low surface roughness while ensuring excellent anti-adhesion performance, and the performance of the final product is significantly better than that of market products.

[0057] (6) The anti-adhesion masterbatch provided by the present invention can also endow the resin with various excellent properties, including chemical stability, insulation, high hardness and thermal stability, etc., greatly broadening the application window of PET resin, and the masterbatch has broad application prospects.

[0058] (7) The process for preparing the modified inorganic nanoparticle composite and the anti-adhesion masterbatch of the present invention is simple, safe and environmentally friendly, and the overall preparation technology is mature, which can ensure the stable supply of the masterbatch, is conducive to reducing costs from the source, and realizing industrial mass production. Detailed implementation mode

[0059] Note: Unless otherwise specified, the raw materials and equipment involved in the present invention are commercially available; the sources of some raw materials are as follows:

[0060] Thermoplastic resin: PET, sourced from Sinopec Yizheng Chemical Fiber Co., Ltd., with the grade FG600.

[0061] SiO2: with a particle size of 300 nm, sourced from Tianjin Zhongke New Materials Co., Ltd.

[0062] Al2O3: with a particle size of 100 nm, sourced from Hubei Huifu Nanomaterials Co., Ltd., model ALuna-100.

[0063] Silane coupling agent KH-570: CAS No. 2530-85-0; Antioxidant 1010: CAS No. 6683-19-8; Lubricant calcium stearate: CAS No. 1592-23-0; The supplier is not particularly limited.

[0064] Examples

[0065] Example 1

[0066] In the first aspect of this example, a bimodal nano-system anti-adhesion masterbatch for MLCC base film is provided. By weight, the anti-adhesion masterbatch includes the following components:

[0067] Thermoplastic resin (PET) 96 parts;

[0068] Modified inorganic nanoparticle complex 3.5 parts, and the preparation raw materials include silane coupling agent (KH570) 0.5 part and inorganic nanoparticle complex 3 parts;

[0069] Auxiliary agent 0.5 part, including antioxidant (Antioxidant 1010) 0.3 part and lubricant (calcium stearate) 0.2 part.

[0070] The inorganic nanoparticle complex includes SiO2 (2 parts) and Al2O3 (1 part), the particle size of SiO2 is 300 nm, and the particle size of Al2O3 is 100 nm.

[0071] In the second aspect of this example, a preparation method of a bimodal nano-composite system anti-adhesion masterbatch for MLCC base film is provided. The preparation steps of the anti-adhesion masterbatch include:

[0072] S1. Prepare the modified inorganic nanoparticle complex, including:

[0073] S1.1 Mix SiO2 and Al2O3, completely immerse them in the dispersion medium (anhydrous ethanol), and then perform ultrasonic dispersion at 200 W for 45 min;

[0074] S1.2 Slowly add the silane coupling agent after ultrasonic dispersion, stir and react at 65 °C for 3 h for surface treatment;

[0075] After surface treatment, centrifuge at 6000 r / min for 8 min, wash 3 times with absolute ethanol, and vacuum dry at 70 °C for 8 h to obtain the modified inorganic nanoparticle complex.

[0076] S2. Add the thermoplastic resin to the twin-screw extruder in the main feeding mode, and add the modified inorganic nanoparticle complex and additives to the twin-screw extruder in the side feeding mode, melt and blend at 270 °C, with a production rate of 350 kg / h and the rotational speed of the twin-screw extruder being 400 r / min; then melt, plasticize and extrude into pellets to obtain the finished anti-blocking masterbatch.

[0077] Example 2

[0078] This example provides a bimodal nano-system anti-blocking masterbatch for MLCC base film and its preparation method. The specific implementation method is the same as that of Example 1; the difference is that the addition amount of the thermoplastic resin is 95 parts, and the addition amount of the modified inorganic nanoparticle complex is 4.5 parts (0.5 part of KH570 and 3 parts of inorganic nanoparticle complex).

[0079] Example 3

[0080] This example provides a bimodal nano-system anti-blocking masterbatch for MLCC base film and its preparation method. The specific implementation method is the same as that of Example 1; the difference is that the addition amount of the thermoplastic resin is 97 parts, and the addition amount of the modified inorganic nanoparticle complex is 2.5 parts (0.5 part of KH570 and 2 parts of inorganic nanoparticle complex).

[0081] Comparative Example 1

[0082] This comparative example provides a bimodal nano-system anti-blocking masterbatch for MLCC base film and its preparation method. The specific implementation method is the same as that of Example 1; the difference is that the addition amount of the silane coupling agent is 0 (i.e., the inorganic nanoparticle complex is not modified), and the addition amount of the thermoplastic resin is 96.5 parts.

[0083] Comparative Example 2

[0084] This comparative example provides a bimodal nano-system anti-blocking masterbatch for MLCC base film and its preparation method. The specific implementation method is the same as that of Example 1; the difference is that the addition amount of Al2O3 is 0 (i.e., there is no Al2O3 in the inorganic nanoparticle complex), and the addition amount of the thermoplastic resin is 97 parts.

[0085] Comparative Example 3

[0086] This comparative example provides a bimodal nano-system anti-adhesion masterbatch for MLCC base film and its preparation method. The specific implementation is the same as that of Example 1; the difference is that the addition amount of SiO2 is 0 (that is, there is no SiO2 in the inorganic nano-particle complex), and the addition amount of the thermoplastic resin is 98 parts.

[0087] Performance Test

[0088] Prepare test film samples: 80 parts by mass of PET resin and 20 parts by mass of anti-adhesion masterbatch (i.e., the finished products prepared in the examples and comparative examples) are fed into the core layer feeding section of a twin-screw extruder through a loss-in-weight feeder, melted and filtered at 270 °C, and then extruded from the die head, cast on a cooling roll at a temperature of 25 °C, preheated at 100 °C, stretched in the stretching section, and then cooled to room temperature (25 °C) in the cooling section to obtain PET film samples (i.e., MLCC release films), and the samples are tested as follows.

[0089] 1. Haze

[0090] Refer to the national standard GB / T 2410-2008 to measure the haze of the samples, and the test results are recorded in Table 1.

[0091] 2. Adhesion

[0092] Use the Danisco adhesion tester MODEL D9047 to measure the adhesion of the samples according to the ATSM D 3354-2015 standard. Measure the adhesion A1 between the corona-treated MLCC release films and the adhesion A2 between the corona-treated MLCC release film and the non-corona-treated MLCC release film respectively. The test results are recorded in Table 1; the lower the adhesion, the better the anti-adhesion property.

[0093] 3. Surface Roughness (Ra)

[0094] Use a surface roughness measuring machine (produced by Kosaka Laboratory Ltd., model SE3500) to measure the surface roughness of the samples with reference to JISB0601-1994, and the test results are recorded in Table 1.

[0095] Table 1 Performance test results of samples prepared with the anti-adhesion masterbatches of Examples 1-3 and Comparative Examples 1-3

[0096]

[0097] As can be seen from the test results of the examples and comparative examples shown in Table 1, when the anti-adhesion masterbatch prepared by the simultaneous presence of the specific modified inorganic nano-complex, antioxidant, and lubricant of the present invention is used for PET films, the obtained films have low haze, excellent anti-adhesion performance, and ultra-low surface roughness.

[0098] The test results of Examples 1-3 show that when the inorganic nano-composite is surface-modified and the mass ratio of inorganic nano-particles SiO2 and Al2O3 is controlled within the preferred range, the anti-blocking masterbatch prepared is used for PET films, the haze of the obtained film is as low as below 6%, the adhesion is as low as 10 g / cm 2 Below, the surface roughness is as low as below 16 nm, and the product performance is significantly better than the market product level.

[0099] Comparing the test results of Comparative Example 1 and Comparative Examples 1-3, it can be seen that when the inorganic nano-composite is not modified or the modified inorganic nano-composite system is not used, the product performance deteriorates significantly when the anti-blocking masterbatch prepared is used to prepare PET films. The obtained film has poor anti-blocking performance, and the surface roughness cannot reach the ideal ultra-low level.

[0100] In summary, through reasonable formulation design and preparation process, the bimodal nano-composite anti-blocking masterbatch prepared with surface-modified inorganic nano-composite, antioxidant and lubricant can endow the MLCC release film with a lower haze when used to prepare PET films, and the anti-blocking performance of the film is significantly improved, and the surface roughness is reduced to the ideal level, which can meet the strict requirements of high-end MLCC for the surface performance of the base film and significantly improve the product quality.

Claims

1. A bimodal nano-system anti-adhesion masterbatch for MLCC base film, characterized in that By weight parts, the anti-blocking masterbatch comprises the following components: 85 - 98 parts of thermoplastic resin; 1 - 15 parts of modified inorganic nanoparticle complex; 0.1 - 1 part of additives; The preparation raw materials of the modified inorganic nanoparticle complex include silane coupling agent and inorganic nanoparticle complex; The inorganic nanoparticle complex includes SiO2 and Al2O3; the particle size of the inorganic nanoparticle complex is 50 - 500 nm.

2. The bimodal nano-system anti-sticking masterbatch for MLCC base film according to claim 1, characterized in that, The particle size of SiO2 is larger than that of Al2O3.

3. The bimodal nano-system anti-blocking masterbatch for MLCC base film according to claim 1 or 2, characterized in that, The particle size of SiO2 is 250 - 500 nm; the particle size of Al2O3 is 50 - 150 nm.

4. The bimodal nano-system anti-blocking masterbatch for MLCC base film according to claim 3, characterized in that, The weight ratio of SiO2 to Al2O3 is (1 - 5):(1 - 5); Preferably, the weight ratio of SiO2 to Al2O3 is (1 - 3):

1.

5. The bimodal nano-system anti-sticking masterbatch for MLCC base film according to claim 1, characterized in that, The thermoplastic resin includes at least one of PET, PETG, and PBT; Preferably, the thermoplastic resin is PET.

6. The bimodal nano-system anti-adhesion masterbatch for MLCC base film according to claim 1, wherein The additives at least include: 0.1 - 0.5 part of antioxidant; 0.1 - 0.3 part of lubricant.

7. A preparation method of the bimodal nano-system anti-blocking masterbatch for the MLCC base film according to any one of claims 1-6, characterized in that, The preparation steps of the anti-blocking masterbatch include: S1. Prepare the modified inorganic nanoparticle complex; S2. Add the thermoplastic resin, modified inorganic nanoparticle complex, and additives into an extruder, melt and blend them, then extrude and pelletize to obtain the finished anti-blocking masterbatch.

8. The preparation method of the bimodal nano-system anti-adhesion masterbatch for the MLCC base film according to claim 7, characterized in that, The step S1 includes: S1.1 Mix SiO2 and Al2O3, add a dispersion medium and then ultrasonically disperse; S1.2 After ultrasonic dispersion, add the silane coupling agent for surface treatment; S1.3 After surface treatment, centrifuge, wash, and dry to obtain the modified inorganic nanoparticle complex.

9. The preparation method of the bimodal nano-system anti-adhesion masterbatch for MLCC base film according to claim 8, characterized in that, The temperature of the surface treatment is 50 - 80 °C, and the time of the surface treatment is 2 - 4 h.

10. The preparation method of the bimodal nano-system anti-adhesion masterbatch for MLCC base film according to claim 7, characterized in that, The temperature of the melt blending is 200 - 240 °C.

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