Nanometer anti-bonding master batch for MLCC base film, preparation method and application thereof

Abstract

The application discloses a kind of nanometer anti-adhesion masterbatch for MLCC base film, and preparation raw materials include unmodified PET resin 80-95 parts, carboxyl modified PET resin 2-10 parts, anti-adhesion composition 1-10 parts, dispersing agent 0.1-2 parts, antioxidant 0.1-3 parts by weight.The nanometer silicon dioxide grafted with epoxy group is used in the application, and the carboxyl modified PET resin is combined to prepare the anti-adhesion masterbatch.The surface flatness of the MLCC base film produced by the anti-adhesion masterbatch is high, and the anti-adhesion performance is good.The carboxyl modified PET resin with molecular weight of 9800 g / mol and carboxyl number of 40-50 per mol is used in the application, and the viscosity of the obtained anti-adhesion masterbatch is suitable, and there is no adverse effect on subsequent processing and production.The roughness of the prepared MLCC base film can be less than 15 nm, and the anti-adhesion performance is excellent, which can meet the technical requirements of high capacitance and miniaturization of MLCC.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of polyester composite materials, in particular to a nano anti-bonding masterbatch for MLCC base film and its preparation method and application. BACKGROUND

[0002] MLCC (multilayer ceramic capacitor) is a kind of capacitor with large capacitance, which is widely used in the fields of smart phones, automotive electronics, wearable devices, 5G communication base stations, etc. The MLCC release film is an important material for generating MLCC. The MLCC release film usually uses polyester film as the base film, and the MLCC release base film is obtained by adding micron-sized anti-adhesion particles to the polyester material. However, the base film prepared in this way has problems such as high surface roughness, poor anti-adhesion performance, poor heat resistance, etc., which further affects the thickness and surface roughness of the ceramic sheet, making it difficult to meet the technical requirements of high capacitance and miniaturization of MLCC. Therefore, it is crucial to develop an anti-adhesion masterbatch for film that has low surface roughness and also guarantees excellent flatness and anti-adhesion performance.

[0003] Chinese invention patent CN118684916B discloses a high-temperature-resistant MLCC release film base film and its preparation method. The esterification-polycondensation reaction is carried out using terephthalic acid, 2-(pyridine-3-yl) terephthalic acid, and ethylene glycol as raw materials. The product is reacted with 1,3-propane sulfonate lactone to obtain zwitterionic resin particle powder. Sodium-based montmorillonite suspension is added, and the base film is obtained by melt extrusion. The base film has a smooth surface, small roughness, and high-temperature resistance. However, the preparation process is complicated. Chinese invention patent CN118906611A discloses a base film applied to MLCC release film and its preparation method. The special masterbatch is prepared from KH550 modified inorganic filler and semi-aromatic polyamide. The special masterbatch enables the film material to have excellent mechanical properties and heat resistance, and also has low roughness, avoiding the risk of inorganic particle precipitation. However, the multi-layer composite film has a high thickness, which cannot meet the miniaturization requirement. SUMMARY

[0004] In order to develop an anti-adhesion masterbatch for film with low surface roughness and excellent flatness and anti-adhesion performance, the first aspect of the present application provides a nano anti-adhesion masterbatch for MLCC base film. The preparation raw materials include, by weight, 80-95 parts of unmodified PET resin, 2-10 parts of carboxyl modified PET resin, 1-10 parts of anti-adhesion composition, 0.1-2 parts of dispersant, and 0.1-3 parts of antioxidant.

[0005] As a preferred embodiment, the preparation raw materials include, by weight, 89-92 parts of unmodified PET resin, 5-6 parts of carboxyl modified PET resin, 2-5 parts of anti-adhesion composition, 0.1-0.2 parts of dispersant, and 0.1-0.2 parts of antioxidant.

[0006] As a preferred embodiment, the average molecular weight of the carboxyl-modified PET resin is 5000-10000 g / mol, and the carboxyl number is 40-50 per mol.

[0007] As a preferred embodiment, the average molecular weight of the carboxyl-modified PET resin is 9800 g / mol, and the carboxyl number is 48 per mol.

[0008] The molecular weight of the carboxyl-modified PET resin used is 9800 g / mol, and the weight ratio of the carboxyl-modified PET resin to the anti-adhesion composition is (2-10):(1-10), and the viscosity of the anti-adhesion masterbatch obtained is suitable and has no adverse effect on subsequent processing production, because the carboxyl-modified PET resin with a molecular weight of 9800 g / mol and the anti-adhesion composition in the preferred weight ratio, the film-forming property and film flatness of the anti-adhesion masterbatch obtained during processing are good, beyond the preferred weight ratio, the roughness of the MLCC base film produced by the anti-adhesion masterbatch is large, and the anti-adhesion property is reduced, which affects the actual application of the MLCC release base film.

[0009] As a preferred embodiment, the melting point of the carboxyl-modified PET resin is 180-220℃, and the acid value is 200-250 mgKOH / g.

[0010] As a preferred embodiment, the melting point of the carboxyl-modified PET resin is 200℃, and the acid value is 230 mgKOH / g.

[0011] As a preferred embodiment, the intrinsic viscosity of the unmodified PET resin is 0.6-0.9 dL / g.

[0012] As a preferred embodiment, the intrinsic viscosity of the unmodified PET resin is 0.675 dL / g.

[0013] As a preferred embodiment, the anti-adhesion composition is modified nano-silica, and the modified nano-silica is epoxy group grafted nano-silica.

[0014] As a preferred embodiment, the particle size of the modified nano-silica is 100-500 nm, and the morphology of the modified nano-silica is spherical.

[0015] As a preferred embodiment, the modified nano-silica is obtained by reacting silane with nano-silica, and the weight ratio of the silane to the nano-silica is (0.2-0.4):1. Preferably, the weight ratio of the silane to the nano-silica is 0.2:1.

[0016] As a preferred embodiment, the silane is an epoxy silane selected from at least one of gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, and gamma-glycidoxypropyltrimethoxysilane.

[0017] As a preferred embodiment, the method for preparing the modified nano-silica comprises the following steps: melting the epoxy silane in an aqueous ethanol solution, the mass fraction of the epoxy silane in the aqueous ethanol solution being 4%, then adding nano-silica, uniformly mixing, stirring at 50 DEG C for 2h, then suction filtering, drying at 200 DEG C in a drying tank for 1h, and obtaining the modified nano-silica.

[0018] As a preferred embodiment, the volume ratio of ethanol to water in the aqueous ethanol solution is 8:2.

[0019] The nano-silica modified by the epoxy group grafting and the carboxyl-modified PET resin are combined to prepare the anti-adhesion master batch, and the MLCC base film produced by the anti-adhesion master batch has high flatness and good anti-adhesion performance. Because spherical silica is used as the main anti-adhesion additive, the nano-silica has high surface energy and a hydrophilic group of hydroxyl, and has poor dispersibility in the polymer. The surface of the nano-silica is modified by grafting propyl trimethoxysilane, the propyl trimethoxysilane reacts with the hydroxyl of the nano-silica, and the epoxy group is grafted to the surface of the nano-silica, thereby improving the poor dispersibility of the hydrophilic group of the nano-silica. The epoxy group grafted nano-silica and the terminal carboxyl group of the carboxyl-modified PET resin are subjected to ester exchange reaction. Because the number of the carboxyl groups of the carboxyl-modified PET resin reaches 48 / mol, the epoxy group grafted nano-silica can react with the terminal carboxyl group of the PET as much as possible, the compatibility of the nano-silica and the PET is increased, the nano-silica has high dispersibility in the PET system, and the effects of low roughness and high flatness of the MLCC base film are achieved.

[0020] As a preferred embodiment, the antioxidant includes but is not limited to phenolic antioxidants, alcohol ester antioxidants, and phosphate antioxidants. Preferably, the antioxidant is beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecyl ester.

[0021] As a preferred embodiment, the dispersant includes but is not limited to wax dispersants, ethylene bis-stearamide, and pentaerythritol stearate.

[0022] As a preferred embodiment, the dispersant is polyethylene wax.

[0023] The first aspect of the present application provides a method for preparing a nano-scale anti-adhesion master batch for an MLCC base film, comprising the following steps:

[0024] S1 carboxyl modified PET resin is added into the extruder, and the temperature is raised to 200-250 DEG C, and the carboxyl modified PET resin is melted and sheared;

[0025] S2 the anti-adhesion composition, antioxidant, dispersing agent are added into the extruder through the front end feeding port of the extruder, and are pre-mixed with the carboxyl modified PET resin at 200-250 DEG C;

[0026] S3 unmodified PET resin is added into the extruder through the front end feeding port of the extruder, and the temperature is raised to 270-280 DEG C, and the mixture of step S2 is mixed, and then is extruded and granulated through a double screw extruder to obtain the nanoscale anti-adhesion masterbatch for MLCC base film.

[0027] The third aspect of the present application provides a use of the nanoscale anti-adhesion masterbatch for MLCC base film in the preparation of the MLCC base film.

[0028] As a preferred embodiment, the preparation method of the MLCC base film comprises the following steps: the PET resin and the prepared anti-adhesion masterbatch are weighed by the loss weight balance and fed into the extruder, and after being filtered and melted at 250-300 DEG C, the PET resin and the prepared anti-adhesion masterbatch are extruded from the die, cast on the cooling roller with a temperature of 30-35 DEG C, stretched 3-4 times through the longitudinal preheating and stretching section with a preheating temperature of 70-75 DEG C, cooled to 40-50 DEG C through the cooling section, then enter the transverse stretching preheating and stretching box, stretched 3-4 times through the transverse stretching section with a preheating temperature of 90-95 DEG C and a stretching temperature of 95-100 DEG C, and then shaped through the heat setting section with a temperature of 210-220 DEG C, cooled and wound up to obtain the MLCC base film.

[0029] As a preferred embodiment, the preparation method of the MLCC base film comprises the following steps: the PET resin and the prepared anti-adhesion masterbatch are weighed by the loss weight balance and fed into the extruder, and after being filtered and melted at 250-300 DEG C, the PET resin and the prepared anti-adhesion masterbatch are extruded from the die, cast on the cooling roller with a temperature of 30-35 DEG C, stretched 3-4 times through the longitudinal preheating and stretching section with a preheating temperature of 70-75 DEG C, cooled to 40-50 DEG C through the cooling section, then enter the transverse stretching preheating and stretching box, stretched 3-4 times through the transverse stretching section with a preheating temperature of 90-95 DEG C and a stretching temperature of 95-100 DEG C, and then shaped through the heat setting section with a temperature of 210-220 DEG C, cooled and wound up to obtain the MLCC base film.

[0030] As a preferred embodiment, the weight ratio of the PET resin and the prepared anti-adhesion masterbatch is 7:(1-5).

[0031] As a preferred embodiment, the weight ratio of the PET resin and the prepared anti-adhesion masterbatch is 7:3.

[0032] Compared with the prior art, the present application has the following beneficial effects:

[0033] (1) The MLCC base film nanoscale anti-bonding masterbatch of the present application uses the nanosilica grafted with epoxy groups and the carboxyl modified PET resin to prepare the anti-bonding masterbatch, and the MLCC base film produced by the anti-bonding masterbatch has high surface flatness and good anti-bonding performance.

[0034] (2) The MLCC base film nanoscale anti-bonding masterbatch of the present application uses the carboxyl modified PET resin with a molecular weight of 9800 g / mol and a carboxyl number of 40-50 / mol, and the viscosity of the obtained anti-bonding masterbatch is suitable and has no adverse effect on subsequent processing and production.

[0035] (3) The MLCC base film nanoscale anti-bonding masterbatch of the present application has a characteristic viscosity of 0.639 dL / g, which has no obvious difference compared with the traditional processing technology, does not need to introduce new equipment for processing and production, and has low production cost.

[0036] (4) The MLCC base film nanoscale anti-bonding masterbatch of the present application can prepare the MLCC base film with a roughness of less than 15 nm, and has excellent anti-bonding performance, which can meet the technical requirements of high capacitance and miniaturization of MLCC.

[0037] (5) The MLCC base film nanoscale anti-bonding masterbatch of the present application has good dispersion in the system without obvious agglomeration, and the obtained anti-bonding masterbatch system is stable, has low haze, good dispersibility and low adhesion, and can achieve the effect of anti-bonding. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 The MLCC base film nanoscale anti-bonding masterbatch prepared for Example 1 is observed by electron microscope to observe the dispersion of the section.

[0039] Figure 2 The MLCC base film nanoscale anti-bonding masterbatch prepared for Example 2 is observed by electron microscope to observe the dispersion of the section.

[0040] Figure 3 The MLCC base film nanoscale anti-bonding masterbatch prepared for Comparative Example 1 is observed by electron microscope to observe the dispersion of the section.

[0041] Figure 4 The MLCC base film nanoscale anti-bonding masterbatch prepared for Comparative Example 2 is observed by electron microscope to observe the dispersion of the section.

[0042] Figure 5 The MLCC base film nanoscale anti-bonding masterbatch prepared for Comparative Example 3 is observed by electron microscope to observe the dispersion of the section. DETAILED DESCRIPTION

[0043] Example 1

[0044] A nanoscale anti-blocking masterbatch for MLCC base film, the raw materials include, by weight, 91.7 parts of unmodified PET resin, 6 parts of carboxyl modified PET resin, 2 parts of anti-blocking composition, 0.1 part of dispersant, and 0.2 part of antioxidant.

[0045] The unmodified PET resin has an intrinsic viscosity of 0.675 dL / g. It is purchased from Yizheng Chemical Fiber, with a brand name of FG600.

[0046] The carboxyl modified PET resin has an average molecular weight of 9800 g / mol, a carboxyl number of 48 / mol, a melting point of 200 ℃, and an acid value of 230 mgKOH / g. It is purchased from Wuhan Hyperbranched Resin Technology Co., Ltd., with a brand name of C304.

[0047] The anti-blocking composition is modified nanosilica.

[0048] The preparation method of the modified nanosilica includes the following steps: melting epoxy silane in an ethanol aqueous solution, the mass fraction of the epoxy silane in the ethanol aqueous solution is 4%, then adding nanosilica, uniformly mixing, stirring at 50 ℃ for 2 h, then suction filtering, drying at 200 ℃ in a drying tank for 1 h, to obtain the modified nanosilica.

[0049] The epoxy silane is γ-glycidoxypropyl triethoxysilane, and the weight ratio of the silane to nanosilica is 0.5:1.

[0050] The nanosilica has a particle size of 500 nm and a spherical morphology, and is purchased from Dongguan Xiniujin Industrial Co., Ltd., with a brand name of XWJ-SQNM80500.

[0051] The volume ratio of ethanol to water in the ethanol aqueous solution is 8:2.

[0052] The antioxidant is β-(3,5-di-tert-butyl 4-hydroxyphenyl) octadecanol propionate.

[0053] The dispersant is polyethylene wax. It is purchased from Clariant, with a brand name of E.

[0054] A preparation method of a nanoscale anti-blocking masterbatch for MLCC base film, including the following steps:

[0055] S1 adding the carboxyl modified PET resin into an extruder, and heating to 240 ℃ for melting and shearing;

[0056] S2 adding the anti-blocking composition, antioxidant, and dispersant into the extruder through the front end side feeding port of the extruder, and pre-mixing with the carboxyl modified PET resin at 200-250 ℃;

[0057] S3 adds the unmodified PET resin into the extruder through the feeding port at the front end side of the extruder, and heats to 275℃, melts and mixes with the mixture of step S2, and then extrudes and granulates through the double screw extruder to obtain the nanoscale anti-blocking masterbatch for MLCC base film.

[0058] The slice dispersibility electron microscope graph of the prepared anti-blocking masterbatch is shown in Figure 1 .

[0059] Example 2

[0060] A nanoscale anti-blocking masterbatch for MLCC base film, the raw materials for preparation include, by weight, 89.7 parts of unmodified PET resin, 5 parts of carboxyl modified PET resin, 5 parts of anti-blocking composition, 0.1 part of dispersant, and 0.2 part of antioxidant.

[0061] The remaining embodiments are the same as example 1.

[0062] The slice dispersibility electron microscope graph of the prepared anti-blocking masterbatch is shown in Figure 2 .

[0063] Comparative Example 1

[0064] A nanoscale anti-blocking masterbatch for MLCC base film, the raw materials for preparation include, by weight, 97.6 parts of unmodified PET resin, 0 part of carboxyl modified PET resin, 2 parts of anti-blocking composition, 0.2 part of dispersant, and 0.2 part of antioxidant.

[0065] The remaining embodiments are the same as example 1.

[0066] The slice dispersibility electron microscope graph of the prepared anti-blocking masterbatch is shown in Figure 3 .

[0067] Comparative Example 2

[0068] A nanoscale anti-blocking masterbatch for MLCC base film, the raw materials for preparation include, by weight, 94.7 parts of unmodified PET resin, 0 part of carboxyl modified PET resin, 5 parts of anti-blocking composition, 0.1 part of dispersant, and 0.2 part of antioxidant.

[0069] The anti-blocking composition is modified silicon dioxide.

[0070] The particle size of the silicon dioxide is 3 μm, and the morphology is irregular, and it is purchased from Guangzhou Shenna Trading Co., Ltd., and the brand is K720.

[0071] The remaining embodiments are the same as example 1.

[0072] The slice dispersibility electron microscope graph of the prepared anti-blocking masterbatch is shown in Figure 4 .

[0073] Comparative Example 3

[0074] A nanoscale anti-blocking masterbatch for MLCC base film is prepared from the following raw materials in parts by weight: unmodified PET resin 89.7 parts, carboxyl-modified PET resin 5 parts, inorganic composition 5 parts, dispersant 0.1 part, and antioxidant 0.2 part.

[0075] The inorganic composition is nanosilica.

[0076] The nanosilica has a particle size of 500 nm and a spherical morphology, and is commercially available from Foshan Oulite New Material Technology Co., Ltd. under the trade designation L500.

[0077] A slice dispersion electron microscope image of the prepared anti-blocking masterbatch is shown in Figure 5 .

[0078] Performance test

[0079] 1. Viscosity: The viscosity was determined using an IVS300 automatic Ubbelohde viscosity measurement system according to the GB / T 14190-2017 standard, and the test results are shown in Table 1.

[0080] Table 1

[0081] Viscosity (dL / g) Example 1 0.639 Example 2 0.600 Comparative Example 1 0.626 Comparative Example 2 0.608 Comparative Example 3 0.612

[0082] Application Example 1

[0083] The nanoscale anti-blocking masterbatch for MLCC base film prepared in Example 1 was used to prepare a MLCC base film. The preparation method of the MLCC base film included the following steps: the PET resin and the prepared anti-blocking masterbatch were weighed into an extruder at a temperature of 280°C, melted and filtered, and then extruded from a die. The extruded material was cast onto a cooling roll at a temperature of 30°C, stretched 3.5 times in a longitudinal preheating and stretching section at a preheating temperature of 70°C, cooled to 50°C in a cooling section, and then entered a transverse stretching preheating and transverse stretching box. The preheating temperature was 90°C, the transverse stretching temperature was 100°C, and the stretching section was stretched 3.5 times. After that, the material was shaped in a heat setting section at a temperature of 220°C, cooled and wound up to obtain the MLCC base film.

[0084] The weight ratio of the PET resin to the prepared anti-blocking masterbatch was 7:3. The PET resin was commercially available from Yizheng Chemical Fibre Co., Ltd. under the trade designation FG600.

[0085] Application Example 2

[0086] The nanoscale anti-blocking masterbatch for MLCC base film prepared in Example 2 was used to prepare a MLCC base film. The remaining implementation manners were the same as in Application Example 1.

[0087] Application Comparative Example 1

[0088] The nanoscale anti-blocking masterbatch for MLCC base film prepared in Comparative Example 1 was used to prepare a MLCC base film. The remaining implementation manners were the same as in Application Example 1.

[0089] Application Comparative Example 2

[0090] The MLCC base film prepared in Application Comparative Example 2 was prepared into a MLCC base film with a nanoscale antibonding masterbatch, and the rest of the implementation was the same as Application Example 1.

[0091] Application Comparative Example 3

[0092] The MLCC base film prepared in Application Comparative Example 3 was prepared into a MLCC base film with a nanoscale antibonding masterbatch, and the rest of the implementation was the same as Application Example 1.

[0093] Performance Test

[0094] 2. Haze: Haze was determined according to the standard GB / T 2410-2008.

[0095] 3. Adhesion: A Denison Adhesion Tester Model D9047 was used to determine the adhesion according to the ATSM D 3354-2015 standard. The adhesion between the MLCC base films treated by corona (corona vs. corona), and the adhesion between the MLCC base films treated by corona and the MLCC base films not treated by corona (corona vs. non-corona) were tested, respectively;

[0096] 4. Roughness (Ra determination): A surface roughness tester SE3500 produced by the Xikakenkyusho Co. was used to determine the roughness according to the JIS B0601-1994 standard.

[0097] The test results are shown in Table 2.

[0098] Table 2

[0099]

[0100]

Claims

1. A nano-scale anti-sticking masterbatch for MLCC base film, characterized in that: The raw materials for the preparation include, by weight, 80-95 parts of unmodified PET resin, 2-10 parts of carboxyl-modified PET resin, 1-10 parts of anti-sticking composition, 0.1-2 parts of dispersant, and 0.1-3 parts of antioxidant; The anti-sticking composition is epoxy group grafted modified nano-silica.

2. The nano-scale anti-sticking masterbatch for MLCC base film according to claim 1, characterized in that: The average molecular weight of the carboxyl-modified PET resin is 5000-10000 g / mol, and the number of carboxyl groups is 40-50 / mol.

3. The nano-scale anti-sticking masterbatch for MLCC base film according to claim 1, characterized in that: The carboxyl-modified PET resin has a melting point of 180-220° C. and an acid value of 200-250 mgKOH / g.

4. The nano-scale anti-sticking masterbatch for MLCC base film according to claim 1, characterized in that: The intrinsic viscosity of the unmodified PET resin is 0.6-0.9 dL / g.

5. The nano-scale anti-sticking masterbatch for MLCC base film according to claim 1, characterized in that: The epoxy group grafted modified nano-silica is obtained by reacting silane with nano-silica, and the weight ratio of the silane to the nano-silica is (0.2-0.4):

1.

6. The nano-scale anti-sticking masterbatch for MLCC base film according to claim 5, characterized in that: The particle size of the nano-silicon dioxide is 100-500nm; the morphology of the nano-silicon dioxide is spherical.

7. The nano-scale anti-sticking masterbatch for MLCC base film according to claim 5, characterized in that: The silane is an epoxy silane, and the epoxy silane is selected from at least one of γ-glycidyloxypropyltriethoxysilane, γ-glycidyloxypropylmethyldiethoxysilane, and γ-glycidyloxypropyltrimethoxysilane.

8. A method for preparing the nano-scale anti-sticking masterbatch for MLCC base film according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1 adds carboxyl modified PET resin into the extruder, heats it to 200-250℃, and melts and shears it; S2: adding the anti-sticking composition, antioxidant, and dispersant into the extruder at the front end side feed port of the extruder, and pre-mixing them with the carboxyl modified PET resin by melting at 200-250° C.; In step S3, unmodified PET resin is added into the extruder at the front end side feed port of the extruder, the temperature is raised to 270-280°C, melt-mixed with the mixture of step S2, and then extruded and granulated through a twin-screw extruder to obtain a nano-scale anti-adhesive masterbatch for MLCC base film.

9. An application of the nano-scale anti-sticking masterbatch for MLCC base film according to any one of claims 1 to 7, characterized in that: Used in the preparation of MLCC base film.

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