Release agent, release film for MLCC, and method for manufacturing the same

Abstract

The application discloses a release agent for MLCC, a release film and a preparation method thereof. The release agent comprises the following raw material components in parts by weight: 5-20 parts of non-silicon release agent, 5-20 parts of vinyl silicone oil, 0.55-2.2 parts of peeling force additive, 0.85-0.38 parts of hydrogen-containing silicone oil, 0.04-0.16 parts of adhesive, 0.1-0.3 parts of platinum gold catalyst and 50-200 parts of solvent. The long-chain alkane release agent in the release agent formula of the application enhances the anchoring to the base material through the polar group amino in the structure, and the long-chain methyl improves the compatibility of the long-chain alkane release agent and the silicone release agent, so that the release film of the application has both low peeling force to the ceramic green sheet and excellent wettability of the ceramic green sheet to the surface of the release film, and the problem of roughness of the release film surface caused by the aggregation of various resins during drying is avoided.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of release materials, in particular to a release agent for MLCC, a release film and a preparation method thereof. BACKGROUND

[0002] Multi-layer ceramic capacitors (MLCC) have the advantages of small size, large capacitance, low loss rate at high frequency, low price, etc., and are widely used in computer, communication and consumer electronics fields, especially in communication circuits, having functions of filtering, coupling, energy storage, bypass, etc. This not only brings considerable development prospects for MLCC localization, but also brings severe technical challenges. The clay layer required by MLCC is obtained by uniformly casting and coating ceramic slurry on the surface of a release film, and then drying, shaping and peeling. Since the release film plays a role in bearing the clay during casting and coating, the release surface of the release film must be "infiltrable", and at the same time, the release force must be stable and moderate, and the release film can be easily peeled off after drying. Therefore, the adaptability, roughness and cleanliness of the MLCC release film can directly affect the quality of the finished MLCC product. When a non-silicon release agent is used to peel off the ceramic green sheet, the release force is relatively large, and thin ceramic green sheets are damaged. The release force of the organic silicon release agent is light, but the residual is relatively low, and the wettability of the substrate is poor, resulting in an increase in the roughness of the MLCC release film. The solubility of the adhesive resin and silicone resin components of the release layer in organic solvents and the surface tension of their respective solubility solutions are quite different, so the solubility becomes poor after passing through the oven, and each resin coagulates into a protrusion, which causes the roughness of the surface of the release layer to increase. When the thickness of the ceramic green sheet is less than 1.0 μm, or even less than 0.6 μm, even a slight increase in the surface roughness can cause the defect rate of the laminated ceramic capacitor to deteriorate, so it is required to further improve the smoothness and release property of the release film.

[0003] A kind of release material for MLCC and its preparation method (CN 115010977A Jiangsu Hua Guan New Material Technology Co., Ltd.) adds nano microspheres to organic silicon oil, which prevents adhesion and adsorption after multi-layer stacking and is not easy to peel off, and also has a certain anti-scratch effect to avoid local release defects. However, this method adds particles to the release coating, increasing the surface roughness.

[0004] A kind of solvent type high temperature resistant non-silicon release agent and its preparation method (CN 111471366B Guangzhou Meigu Chemical Co., Ltd.), by adding active amine, alkali catalyst, rigid cyclopropene acid monomer, long chain acrylic acid monomer, through multiple reaction stages, adding isocyanate to obtain the final product, which has good high temperature resistance. However, the preparation process of this release agent is complex, the reaction process is difficult to control, and the release force is large, which is difficult to peel off.

[0005] Therefore, there is a need for improvement in the prior art to provide a more reliable solution. SUMMARY

[0006] The technical problem solved by the present application is to provide a release agent for MLCC, a release film and a preparation method thereof to solve the problems in the prior art.

[0007] To solve the above technical problems, the technical scheme adopted by the present application is as follows: In a first aspect, the present application provides a release agent for MLCC, comprising the following raw material components by weight: non-silicon release agent 5-20 parts, vinyl silicone oil 5-20 parts, release force additive 0.55-2.2 parts, hydrogen-containing silicone oil 0.85-0.38 parts, adhesion agent 0.04-0.16 parts, platinum catalyst 0.1-0.3 parts, and solvent 50-200 parts.

[0008] Preferably, the solvent is one or more of butanone, isopropyl alcohol, toluene, and 120# solvent oil.

[0009] Preferably, the solvent includes a first portion of solvent and a second portion of solvent, the first portion of solvent being toluene, and the second portion of solvent being a mixture of 120# solvent oil, butanone, and isopropyl alcohol.

[0010] Preferably, in the second portion of solvent, the mass ratio of 120# solvent oil: butanone: isopropyl alcohol is 5:4:1.

[0011] Preferably, the non-silicon release agent is RP-20 from Japan Catalyst, the release force additive is CRA17 from Wacker, and the adhesion agent is HF86 from Wacker.

[0012] Preferably, the vinyl silicone oil is D955 from Wacker, and the hydrogen-containing silicone oil is V60 from Wacker.

[0013] In a second aspect, the present application provides a preparation method of the release agent for MLCC as described above, comprising the following steps:

[0014] S1, adding non-silicon release agent to a first portion of solvent and heating to dissolve;

[0015] S2, adding vinyl silicone oil and release force additive to the solution obtained in step S1 and stirring for 15-60 min;

[0016] S2, adding a second portion of solvent, hydrogen-containing silicone oil, adhesion agent, and platinum catalyst to the product obtained in step S2 and stirring for 15-60 min to obtain the release agent for MLCC.

[0017] In a third aspect of the present application, a release film for MLCC is provided, which is obtained by coating the release agent for MLCC as described above on a substrate and then drying.

[0018] Preferably, the release film for MLCC is prepared by the following method:

[0019] The release agent for MLCC is uniformly coated on the PET film with a coating thickness of 400-600 nm, and then baked at 110-130°C for 30-120 s to obtain the release film for MLCC.

[0020] Preferably, the release film for MLCC is prepared by the following method:

[0021] The release agent for MLCC is uniformly coated on the PET film with a coating thickness of 500 nm, and then baked at 120°C for 60 s to obtain the release film for MLCC.

[0022] The present application has the following advantages:

[0023] The present application provides a release agent for MLCC and a release film for MLCC based on the release agent. In the formula of the release agent of the present application, the vinyl silicone oil and the hydrogen-containing silicone oil undergo a silicon-hydrogen addition reaction under the action of a platinum gold catalyst in a high temperature environment. The long-chain alkane release agent in the present application enhances the anchoring to the substrate through the polar group amino in its structure, and the long-chain methyl improves the compatibility of the long-chain alkane release agent with the silicone release agent, so that the release film of the present application has both low peeling force for ceramic green sheets and excellent wettability of the ceramic green sheets to the surface of the release film, avoiding the problem of roughness of the release film surface caused by the aggregation of various resins during drying. DETAILED DESCRIPTION

[0024] The present application will be further described in detail below with reference to the examples, so that those skilled in the art can implement the present application according to the description.

[0025] It should be understood that the terms such as "have", "contain" and "include" used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0026] The test methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, etc. used in the following examples can be obtained commercially unless otherwise specified. The specific conditions not specified in the following examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not specified by the manufacturer, but are conventional products that can be obtained commercially.

[0027] The application provides a release agent for MLCC, which comprises the following raw material components in parts by weight: non-silicon release agent 5-20 parts, vinyl silicone oil 5-20 parts, release force additive 0.55-2.2 parts, hydrogen-containing silicone oil 0.85-0.38 parts, adhesion agent 0.04-0.16 parts, platinum gold catalyst 0.1-0.3 parts, and solvent 50-200 parts.

[0028] In a preferred embodiment, the solvent is one or more of butanone, isopropyl alcohol, toluene, and 120# solvent oil. In a further preferred embodiment, the solvent comprises a first portion of solvent and a second portion of solvent, the first portion of solvent being toluene and the second portion of solvent being a mixture of 120# solvent oil, butanone, and isopropyl alcohol. In a still further preferred embodiment, the mass ratio of 120# solvent oil:butanone:isopropyl alcohol in the second portion of solvent is 5:4:1.

[0029] In a preferred embodiment, the non-silicon release agent is RP-20 from Japan Catalyst, the release force additive is CRA17 from Wacker, and the adhesion agent is HF86 from Wacker.

[0030] In a preferred embodiment, the vinyl silicone oil is D955 from Wacker, and the hydrogen-containing silicone oil is V60 from Wacker.

[0031] The application also provides a preparation method of the release agent for MLCC as above, comprising the following steps:

[0032] S1, adding the non-silicon release agent into the first portion of solvent and heating to dissolve;

[0033] S2, adding the vinyl silicone oil and the release force additive into the solution obtained in step S1 and stirring for 15-60 min;

[0034] S2, adding the second portion of solvent, the hydrogen-containing silicone oil, the adhesion agent, and the platinum gold catalyst into the product obtained in step S2 and stirring for 15-60 min to obtain the release agent for MLCC.

[0035] The application also provides a release film for MLCC, which is prepared by the following method:

[0036] The release agent for MLCC as above is uniformly coated on a PET film with a coating thickness of 400-600 nm, and then baked at 110-130℃ for 30-120 s to obtain the release film for MLCC.

[0037] In the present application, the vinyl silicone oil and the hydrogen-containing silicone oil undergo a silicon-hydrogen addition reaction under the action of a platinum gold catalyst in a high-temperature environment; the long-chain alkane releasing agent enhances the anchoring to the substrate through the polar group amino in its structure, and the long-chain methyl improves the compatibility of the long-chain alkane releasing agent and the silicone releasing agent. The releasing film of the present application has both low release force for the ceramic green sheet and the wettability of the ceramic green sheet to the surface of the releasing film, avoiding the problem of roughness of the releasing film surface caused by the aggregation of each resin during drying.

[0038] The above is the general idea of the present application, and the following provides detailed examples and comparative examples based thereon to further illustrate the present application.

[0039] Example 1

[0040] A releasing film for MLCC is prepared by the following method:

[0041] 1) Preparation of a releasing agent for MLCC:

[0042] S1, 10g of non-silicone releasing agent (RP-20 catalyst) was added to 50g of toluene and heated to dissolve;

[0043] S2, 10g of vinyl silicone oil (D955 Wacker), 1.1g of release force additive (CRA17 Wacker) was added to the solution obtained in step S1, the amount ratio of non-silicone releasing agent (RP-20 catalyst) to vinyl silicone oil (D955 Wacker) was 1:1, and stirring for 30min;

[0044] S2, 50g of the second part of the solvent (120# solvent oil: butanone: isopropyl alcohol in a mass ratio of 5:4:1), 0.19g of hydrogen-containing silicone oil (V60 Wacker), 0.08g of adhesion agent (HF86 Wacker) and 0.2g of platinum gold catalyst (C05 Wacker) were added to the product obtained in step S2, and stirring for 30min to obtain a releasing agent for MLCC.

[0045] 2) The releasing agent for MLCC was uniformly coated on a PET film with a coating thickness of 500nm, and then baked at 120℃ for 60s to obtain a releasing film for MLCC. (Note: trace ingredients can be added by dilution method)

[0046] Example 2

[0047] A releasing film for MLCC is prepared by the following method:

[0048] 1) Preparation of a releasing agent for MLCC:

[0049] S1, 12g of non-silicone releasing agent (RP-20 catalyst) was added to 50g of toluene and heated to dissolve;

[0050] S2, 8 g of vinyl silicone oil (D955 Wacker) and 1.1 g of release force additive (CRA17 Wacker) were added to the solution obtained in step S1, the ratio of non-silicon release agent (RP-20 Catalyst) to vinyl silicone oil (D955 Wacker) was 1.5:1, and stirring was performed for 30 min;

[0051] S2, 50 g of a second solvent (120# solvent oil: butanone: isopropyl alcohol in a mass ratio of 5:4:1), 0.19 g of hydrogen-containing silicone oil (V60 Wacker), 0.08 g of an adhesion agent (HF86 Wacker), and 0.2 g of a platinum gold catalyst (C05 Wacker) were added to the product obtained in step S2, stirring was performed for 30 min, and a release agent for MLCC was obtained.

[0052] 2) The release agent for MLCC was uniformly coated on a PET film to a thickness of 500 nm, and then baked at 120°C for 60 s to obtain a release film for MLCC. (Note: trace components can be added by a dilution method)

[0053] Example 3

[0054] A release film for MLCC was prepared by the following method:

[0055] 1) Preparation of a release agent for MLCC:

[0056] S1, 8 g of non-silicon release agent (RP-20 Catalyst) was added to 50 g of toluene and heated to dissolve;

[0057] S2, 12 g of vinyl silicone oil (D955 Wacker) and 1.1 g of release force additive (CRA17 Wacker) were added to the solution obtained in step S1, the ratio of non-silicon release agent (RP-20 Catalyst) to vinyl silicone oil (D955 Wacker) was 1:1.5, and stirring was performed for 30 min;

[0058] S2, 50 g of a second solvent (120# solvent oil: butanone: isopropyl alcohol in a mass ratio of 5:4:1), 0.19 g of hydrogen-containing silicone oil (V60 Wacker), 0.08 g of an adhesion agent (HF86 Wacker), and 0.2 g of a platinum gold catalyst (C05 Wacker) were added to the product obtained in step S2, stirring was performed for 30 min, and a release agent for MLCC was obtained.

[0059] 2) The release agent for MLCC was uniformly coated on a PET film to a thickness of 500 nm, and then baked at 120°C for 60 s to obtain a release film for MLCC. (Note: trace components can be added by a dilution method)

[0060] Example 4

[0061] A release film for MLCC was prepared by the following method:

[0062] 1) Preparation of a release agent for MLCC:

[0063] S1, 5 g of a non-silicon release agent (RP-20 Catalyst) was added to 50 g of toluene and dissolved by heating;

[0064] S2, 15 g of a vinyl silicone oil (D955 Wacker) and 1.1 g of a release force additive (CRA17 Wacker) were added to the solution obtained in step S1, the amount ratio of the non-silicon release agent (RP-20 Catalyst) to the vinyl silicone oil (D955 Wacker) was 1:3, and stirring was performed for 30 min;

[0065] S2, 50 g of a second solvent (120# solvent oil: butanone: isopropyl alcohol in a mass ratio of 5:4:1), 0.19 g of a hydrogen-containing silicone oil (V60 Wacker), 0.08 g of an adhesion agent (HF86 Wacker), and 0.2 g of a platinum gold catalyst (C05 Wacker) were added to the product obtained in step S2, and stirring was performed for 30 min, thereby obtaining a release agent for MLCC.

[0066] 2) The release agent for MLCC was uniformly coated on a PET film to a thickness of 500 nm, and then baked at 120°C for 60 s, thereby obtaining a release film for MLCC. (Note: trace components can be added by a dilution method)

[0067] Example 5

[0068] A release film for MLCC was prepared by the following method:

[0069] 1) Preparation of a release agent for MLCC:

[0070] S1, 15 g of a non-silicon release agent (RP-20 Catalyst) was added to 50 g of toluene and dissolved by heating;

[0071] S2, 5 g of a vinyl silicone oil (D955 Wacker) and 1.1 g of a release force additive (CRA17 Wacker) were added to the solution obtained in step S1, the amount ratio of the non-silicon release agent (RP-20 Catalyst) to the vinyl silicone oil (D955 Wacker) was 3:1, and stirring was performed for 30 min;

[0072] S2, 50 g of a second solvent (120# solvent oil: butanone: isopropyl alcohol in a mass ratio of 5:4:1), 0.19 g of a hydrogen-containing silicone oil (V60 Wacker), 0.08 g of an adhesion agent (HF86 Wacker), and 0.2 g of a platinum gold catalyst (C05 Wacker) were added to the product obtained in step S2, and stirring was performed for 30 min, thereby obtaining a release agent for MLCC.

[0073] 2) The MLCC release agent was uniformly coated on a PET film to a thickness of 500 nm, and then baked at 120°C for 60 seconds to obtain a MLCC release film. (Note: trace ingredients can be added by dilution method)

[0074] Comparative Example 1

[0075] A MLCC release film was prepared by the following method:

[0076] 1) Preparation of a MLCC release agent:

[0077] 20 g of vinyl silicone oil (D955 Wacker) and 1.1 g of release force additive (CRA17 Wacker) were mixed, and after stirring for 30 min, 100 g of solvent (toluene: 120# solvent oil: butanone: isopropyl alcohol at a mass ratio of 10:5:4:1), 0.19 g of hydrogen-containing silicone oil (V60 Wacker), 0.08 g of adhesion agent (HF86 Wacker), and 0.2 g of platinum gold catalyst (C05 Wacker) were added, and stirred for 30 min to obtain a MLCC release agent.

[0078] 2) The MLCC release agent was uniformly coated on a PET film to a thickness of 500 nm, and then baked at 120°C for 60 seconds to obtain a MLCC release film. (Note: trace ingredients can be added by dilution method)

[0079] Comparative Example 2

[0080] A MLCC release film was prepared by the following method:

[0081] 1) Preparation of a MLCC release agent:

[0082] 20 g of non-silicone release agent (RP-20 Catalyst) was added to 50 g of toluene and heated to dissolve, and after stirring for 30 min, 50 g of solvent (120# solvent oil: butanone: isopropyl alcohol at a mass ratio of 5:4:1) was added, and stirred for 30 min to obtain a MLCC release agent.

[0083] 2) The MLCC release agent was uniformly coated on a PET film to a thickness of 500 nm, and then baked at 120°C for 60 seconds to obtain a MLCC release film. (Note: trace ingredients can be added by dilution method)

[0084] The release force and roughness of the release films prepared in Examples 1-5 and Comparative Examples 1-2 were tested, and the specific test method is as follows.

[0085] Release film roughness measurement: The roughness of the release film was measured using a white light interferometer, the average roughness of the area surface (Sa) was measured 5 times, and the maximum protrusion height (Rp) was measured 7 times, and the maximum value of 5 times excluding the maximum and minimum values was used.

[0086] Ceramic green sheet preparation method: 38.3 g of toluene, 38.3 g of ethanol, 64.8 g of barium titanate, 6.5 g of polyvinyl butyral, and 3.3 g of dioctyl phthalate were weighed and mixed by stirring, and a ball mill using glass beads of 0.5 mm in diameter as a dispersion medium was used for dispersion for 60 min to obtain a ceramic slurry. The ceramic slurry was coated on the release surface of the obtained release film sample using an applicator so that the thickness of the slurry was 10 micrometers, and was dried at 90°C for 1 min to form a ceramic green sheet. After the obtained release film with a ceramic green sheet was charged, it was cut into a sample of 30 mm in width, and was peeled at a peeling angle of 90 degrees and a peeling speed of 10 m / min to measure the peeling force.

[0087] The measurement results are shown in Table 1 below:

[0088] Table 1

[0089] Peeling force (mN / mm 2 ) Sa (nm) Rp (nm) Example 1 2.2 0.9 35 Example 2 2.3 0.8 34 Example 3 2.1 0.9 35 Example 4 2.1 0.9 37 Example 5 2.4 0.8 33 Comparative Example 1 1.2 1.8 72 Comparative Example 2 3.2 1.4 58

[0090] As can be seen from the comparison of the test data in the table, in the embodiments of the present application, by using the means of combining vinyl silicone oil with non-silicon release agents, the roughness can be greatly reduced while maintaining a relatively low peeling force of the ceramic film, mainly due to the long-chain alkane improving the wettability of the release agent to the substrate.

[0091] Although the embodiments of the present application have been disclosed as above, they are not limited only to the applications listed in the specification and embodiments, and can be fully applied to various fields suitable for the present application, and additional modifications can be easily made by those skilled in the art, and therefore the present application is not limited to specific details, without departing from the general concept defined by the claims and equivalent scope.

Claims

1. A release agent for MLCCs, characterized in that, It includes the following raw material components by weight: 5-20 parts non-silicone release agent, 5-20 parts vinyl silicone oil, 0.55-2.2 parts peel strength additive, 0.85-0.38 parts hydrogen-containing silicone oil, 0.04-0.16 parts adhesive, 0.1-0.3 parts platinum catalyst, and 50-200 parts solvent; The non-silicone release agent is RP-20 from Nippon Shokubai, the peel strength additive is CRA17 from Wacker, and the adhesion agent is HF86 from Wacker. The vinyl silicone oil is Wacker's D955, and the hydrogen-containing silicone oil is Wacker's V60.

2. The release agent for MLCCs according to claim 1, characterized in that, The solvent is one or more of butanone, isopropanol, toluene, and 120# solvent oil.

3. The release agent for MLCCs according to claim 2, characterized in that, The solvent includes a first part solvent and a second part solvent. The first part solvent is toluene, and the second part solvent is a mixture of 120# solvent oil, butanone, and isopropanol.

4. The release agent for MLCCs according to claim 3, characterized in that, In the second part of the solvent, the mass ratio of 120# solvent oil: butanone: isopropanol is 5:4:

1.

5. A method for preparing a release agent for MLCCs as described in any one of claims 3-4, characterized in that, Includes the following steps: S1. Add the non-silicone release agent to the solvent in the first part and heat to dissolve; S2. Add vinyl silicone oil and peeling force additive to the solution obtained in step S1, and stir for 15-60 min. S2. Add the second part of solvent, hydrogen-containing silicone oil, adhesive and platinum catalyst to the product obtained in step S2, stir for 15-60 min to obtain the release agent for MLCC.

6. A release film for MLCCs, characterized in that, The MLCC described in any one of claims 1-4 is obtained by coating a substrate with a release agent and then drying it.

7. The release film for MLCCs according to claim 6, characterized in that, It is prepared by the following method: The MLCC release agent is uniformly coated onto a PET film with a coating thickness of 400-600 nm, and then baked at 110-130℃ for 30-120 s to obtain the MLCC release film.

8. The release film for MLCCs according to claim 7, characterized in that, It is prepared by the following method: MLCC release agent is uniformly coated on PET film with a coating thickness of 500nm, and then baked at 120℃ for 60s to obtain the MLCC release film.