Composition containing waterborne epoxy emulsion and waterborne phenolic resin emulsion as well as preparation method and application of composition

Abstract

The invention discloses a composition containing water-based epoxy emulsion and water-based phenolic resin emulsion as well as a preparation method and application of the composition. The composition comprises the following raw materials in parts by weight: 50-80 parts of water-based epoxy emulsion; 20-60 parts of a water-based phenolic resin emulsion; 0.1-1 part of a catalyst; 10 to 30 parts of filler; 10 to 30 parts of a flame retardant; and 0.5-1 part of a silane coupling agent. Compared with the prior art, the water-based epoxy emulsion and the water-based phenolic resin emulsion are combined, and other appropriate components are added, so that when the composition is used for manufacturing copper-clad plates and prepregs, the defects of a traditional solvent type system are overcome, and a series of excellent properties are shown.

Description

Technical Field

[0001] The invention relates to a composition containing an aqueous epoxy emulsion and an aqueous phenolic resin emulsion, a preparation method and application thereof, and belongs to the technical field of aqueous epoxy materials. Background Art

[0002] In the electronics industry, copper-clad laminates (CCLs) and prepregs are key building blocks for printed circuit boards (PCBs), and their performance requirements are constantly increasing. While traditional solvent-based epoxy and curing agent systems can meet these requirements to a certain extent, they pose a risk of volatile organic compound (VOC) emissions, which not only pollute the environment but also potentially impact the health of operators. Furthermore, overall performance in terms of heat resistance, mechanical properties, PCB processability, and electrical performance still needs to be improved, making it difficult to meet the stringent requirements of modern high-performance electronic devices for PCB materials. Therefore, the development of a novel, environmentally friendly, and high-performance composition for the manufacture of CCLs and prepregs is urgent. Summary of the Invention

[0003] Purpose of the invention: In order to solve the above technical problems, the present invention provides a composition containing an aqueous epoxy emulsion and an aqueous phenolic resin emulsion, as well as a preparation method and application thereof. The composition does not contain VOCs and has excellent heat resistance, mechanical properties, PCB processability and electrical properties, and is suitable for the manufacture of copper clad laminates and prepregs.

[0004] Technical solution: In order to achieve the above purpose, the present invention adopts the following technical solution:

[0005] A composition containing an aqueous epoxy emulsion and an aqueous phenolic resin emulsion, the composition comprising the following raw materials in parts by weight:

[0006] 50-80 parts of water-based epoxy emulsion;

[0007] 20-60 parts of water-based phenolic resin emulsion;

[0008] 0.1-1 part of catalyst;

[0009] 10-30 parts of filler;

[0010] 10-30 parts of flame retardant;

[0011] Silane coupling agent 0.5-1 part.

[0012] As a specific embodiment, the aqueous epoxy emulsion is selected from liquid bisphenol A / F epoxy emulsion, or solid bisphenol A / F epoxy emulsion.

[0013] As a specific implementation scheme, the water-based phenolic resin is bisphenol A type / bisphenol F type, and has a softening point of 80-120 degrees Celsius.

[0014] As a specific embodiment, the catalyst is selected from imidazole or triphenylphosphine.

[0015] As a specific embodiment, the filler is selected from one or a combination of silicon micropowder, talc powder, and mica powder; the flame retardant is selected from one or a combination of diethyl aluminum phosphinate, aluminum hydroxide, and magnesium hydroxide.

[0016] As a specific embodiment, the silane coupling agent is selected from one or a combination of epoxy silane coupling agents, amino silane coupling agents, phenylamino silane coupling agents, vinyl silane coupling agents, isocyanate silane coupling agents, acrylic silane coupling agents, isobutylene silane coupling agents, styrene silane coupling agents, urea silane coupling agents, chloropropyl silane coupling agents, sulfide silane coupling agents.

[0017] The present invention also provides a method for preparing the composition containing the aqueous epoxy emulsion and the aqueous phenolic resin emulsion, comprising the following steps:

[0018] The aqueous epoxy emulsion and the aqueous phenolic resin emulsion are mixed, and then a catalyst, a filler, a flame retardant and a silane coupling agent are added, and the mixture is fully mixed under stirring to obtain the composition.

[0019] As a specific implementation scheme, the stirring speed is 200-1000 rpm and the temperature is 30-60 degrees Celsius.

[0020] Finally, the present invention provides the use of the composition containing the aqueous epoxy emulsion and the aqueous phenolic resin emulsion in the preparation of copper clad laminates or prepregs.

[0021] As an embodiment, the application includes coating the composition on a copper foil, drying, and hot pressing to prepare a copper clad laminate.

[0022] Technical Effect: Compared with the existing technology, the present invention overcomes many disadvantages of traditional solvent-based systems when manufacturing copper clad laminates and prepregs by rationally combining water-based epoxy emulsion and water-based phenolic resin emulsion and adding appropriate other components. The main advantages are as follows:

[0023] 1. It does not contain VOC, is green and environmentally friendly, effectively reduces pollution to the environment and potential harm to the health of operators, and meets the environmental protection requirements of the modern electronics manufacturing industry.

[0024] 2. It has excellent heat resistance and can work stably for a long time in high temperature environment, meeting the high requirements of electronic equipment for material heat resistance during operation, and improving the reliability and service life of copper clad laminates and prepregs.

[0025] 3. Excellent mechanical properties, able to withstand various mechanical processing stresses in the PCB manufacturing process, such as drilling, cutting, etc., ensuring the integrity and stability of the circuit board and reducing the scrap rate in the production process.

[0026] 4. PCB has good processability and is easy to carry out various PCB manufacturing processes, such as lamination and etching, which improves production efficiency and product quality.

[0027] 5. Excellent electrical performance, able to meet the strict requirements of electronic equipment for signal transmission, insulation and other electrical properties, ensuring the normal operation and high performance of electronic equipment. DETAILED DESCRIPTION

[0028] The present invention will be further illustrated below with reference to specific examples.

[0029] Unless otherwise defined herein, scientific and technical terms used in this application shall have the meanings commonly understood by one of ordinary skill in the art.

[0030] 1) The raw materials of the following examples and comparative examples are as follows:

[0031] Water-based bisphenol A liquid epoxy emulsion (HDL-1200, 60% solid content, purchased from Handai Chemical);

[0032] Water-based phenolic resin emulsion (phenolic resin purchased from Shandong Dongrun New Materials, emulsified with conventional emulsifier, 60% solid content);

[0033] The catalyst was 2-methylimidazole, purchased from Aladdin.

[0034] The filler was spherical silica (5 μm, purchased from Jiangsu Lianrui);

[0035] The flame retardant was aluminum diethylphosphinate (purchased from Qingdao Oupure);

[0036] The silane coupling agent was KH-560 (purchased from Nanjing Shuguang).

[0037] 2) The product performance testing methods of the following examples and comparative examples are as follows:

[0038] The peel strength is tested according to the [IPC-TM650 2.4.8] standard.

[0039] Dk and Df: Tested using the SPDR (split post dielectric resonator) method, according to [IPC-TM6502.5.5.13] standard, test conditions are state A, and the frequency is 10 GHz;

[0040] Solder immersion test: Immerse a 100mm x 100mm copper clad laminate in molten tin at 288°C for 5 minutes and visually inspect the laminate for delamination or bubbling. If no delamination or bubbling occurs, mark it as "passed."

[0041] Coefficient of Thermal Expansion (Z-axis): Test the coefficient of thermal expansion in the z-axis using IPC-TM-650 2.4.24, over a temperature range of -55°C to 288°C.

[0042] Example 1

[0043] Aqueous epoxy emulsion (50 parts) and aqueous phenolic resin emulsion (50 parts) were mixed in a certain proportion, and then a catalyst (2-methylimidazole, 0.2 parts), a flame retardant (aluminum diethylphosphinate, 30 parts), a filler (spherical silica, 5 μm, 10 parts) and a silane coupling agent (KH-560, 0.5 parts) were added. The mixture was stirred at 45 degrees Celsius and 800 rpm for 30 minutes to obtain a composition A.

[0044] Composition A was coated on a copper foil, and after drying (170 degrees Celsius for 4 minutes) and hot pressing (200 degrees Celsius for 2 hours, 150 psi) steps, a copper clad laminate sample was prepared.

[0045] Example 2

[0046] Similar to Example 1, except that the ratio of the aqueous epoxy emulsion to the aqueous phenolic resin emulsion was adjusted (60 parts / 40 parts, respectively), and the amounts of the catalyst, flame retardant, filler and silane coupling agent were kept unchanged, a composition B was obtained, and then a copper clad laminate sample was prepared.

[0047] Example 3

[0048] Similar to Example 1, except that the ratio of the aqueous epoxy emulsion to the aqueous phenolic resin emulsion (70 parts / 30 parts, respectively) and the amounts of the catalyst, flame retardant, filler and silane coupling agent were adjusted, composition C was obtained, and then a copper clad laminate sample was prepared.

[0049] Comparative Example 1

[0050] Similar to Example 1, except that dicyandiamide was used instead of the aqueous phenolic resin emulsion, and the amounts of the catalyst, flame retardant, filler and silane coupling agent were maintained, a composition was obtained, and then a copper clad laminate sample was prepared.

[0051] Comparative Example 2

[0052] Similar to Example 1, except that a solution-type phenolic resin was used instead of the aqueous phenolic emulsion, and the amounts of the catalyst, flame retardant, filler and silane coupling agent were maintained, a composition was obtained, and then a copper clad laminate sample was prepared.

[0053] The test results of each sample are shown in the following table:

[0054]

[0055] The test results show that Examples 1-3 further optimize various performance indicators while maintaining the absence of VOCs. Compared with the system without the water-based phenolic curing agent, they perform better in heat resistance (such as solder resistance) and thermal expansion (Z-axis CTE), fully verifying the adjustability and excellent performance of the composition of the present invention.

[0056] Finally, it should be noted that the above specific implementation methods are only used to illustrate the technical solutions of the present invention and are not limiting. Although the present invention has been described in detail with reference to examples, those skilled in the art should understand that the technical solutions of the present invention can be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. A composition comprising an aqueous epoxy emulsion and an aqueous phenolic resin emulsion, characterized in that: The composition comprises the following raw materials in parts by weight: 50-80 parts of water-based epoxy emulsion; 20-60 parts of water-based phenolic resin emulsion; 0.1-1 part of catalyst; 10-30 parts of filler; 10-30 parts of flame retardant; Silane coupling agent 0.5-1 part.

2. The composition of claim 1, wherein the aqueous epoxy emulsion and the aqueous phenolic resin emulsion are The water-based epoxy emulsion is selected from liquid bisphenol A / F epoxy emulsion or solid bisphenol A / F epoxy emulsion.

3. The composition of aqueous epoxy emulsion and aqueous phenolic resin emulsion according to claim 1, wherein The water-based phenolic resin is bisphenol A type / bisphenol F type, and has a softening point of 80-120 degrees Celsius.

4. The composition of aqueous epoxy emulsion and aqueous phenolic resin emulsion according to claim 1, wherein The catalyst is selected from imidazole or triphenylphosphine.

5. The composition of aqueous epoxy emulsion and aqueous phenolic resin emulsion according to claim 1, wherein The filler is selected from one or a combination of silicon micropowder, talc powder, and mica powder; and the flame retardant is selected from one or a combination of diethyl aluminum phosphinate, aluminum hydroxide, and magnesium hydroxide.

6. The composition of aqueous epoxy emulsion and aqueous phenolic resin emulsion according to claim 1, characterized in that The silane coupling agent is selected from one or a combination of epoxy silane coupling agents, amino silane coupling agents, phenylamino silane coupling agents, vinyl silane coupling agents, isocyanate silane coupling agents, acrylic silane coupling agents, isobutylene silane coupling agents, styrene silane coupling agents, urea silane coupling agents, chloropropyl silane coupling agents, sulfide silane coupling agents.

7. The method for preparing a composition comprising an aqueous epoxy emulsion and an aqueous phenolic resin emulsion according to any one of claims 1 to 6, wherein: The following steps are involved: The aqueous epoxy emulsion and the aqueous phenolic resin emulsion are mixed, and then a catalyst, a filler, a flame retardant and a silane coupling agent are added, and the mixture is fully mixed under stirring to obtain the composition.

8. The method for preparing the composition of aqueous epoxy emulsion and aqueous phenolic resin emulsion according to claim 7, wherein The stirring speed is 200-1000 rpm and the temperature is 30-60 degrees Celsius.

9. Use of the composition of any one of claims 1 to 6 containing an aqueous epoxy emulsion and an aqueous phenolic resin emulsion in the preparation of copper-clad laminates or prepregs.

10. The use according to claim 9, characterized in that The application comprises coating the composition on a copper foil, drying, hot pressing, and preparing a copper clad laminate.

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