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

Abstract

The invention discloses a composition containing water-based epoxy emulsion and water-based benzoxazine 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 to 60 parts of a water-based benzoxazine 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 benzoxazine 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 present invention relates to a composition containing a waterborne epoxy emulsion and a waterborne benzoxazine emulsion, its preparation method and application, and belongs to the technical field of waterborne epoxy materials. Background Art

[0002] In the electronics industry, copper clad laminates and prepregs, as key basic materials for printed circuit boards, have continuously increasing requirements for their performance. Although traditional solvent-based epoxy and curing agent systems can meet application requirements to a certain extent, they have the problem of volatile organic compound (VOC) emissions, which not only pollute the environment but may also affect the health of operators. At the same time, the comprehensive performance in terms of heat resistance, mechanical properties, processability, and electrical properties still needs to be further improved to better adapt to the trend of modern electronic devices developing towards high performance and high reliability. Therefore, it is of great practical significance to develop a new type of environmentally friendly and excellent-performance composition for the manufacture of copper clad laminates and prepregs. Summary of the Invention

[0003] Object of the Invention: To solve the above technical problems, the present invention provides a composition containing a waterborne epoxy emulsion and a waterborne benzoxazine emulsion, its preparation method and application. This composition does not contain VOCs and has good heat resistance, mechanical properties, processability, and electrical properties, and is suitable for the manufacture of copper clad laminates and prepregs.

[0004] Technical Solution: To achieve the above object, the present invention adopts the following technical solutions:

[0005] A composition containing a waterborne epoxy emulsion and a waterborne benzoxazine emulsion, the composition comprising the following raw materials in parts by weight:

[0006] 50 - 80 parts of waterborne epoxy emulsion;

[0007] 20 - 60 parts of waterborne benzoxazine emulsion;

[0008] 0.1 - 1 part of catalyst;

[0009] 10 - 30 parts of filler;

[0010] 10 - 30 parts of flame retardant;

[0011] 0.5 - 1 part of silane coupling agent.

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

[0013] As a specific implementation, the benzoxazine in the waterborne benzoxazine emulsion is bisphenol A / bisphenol F type, diamine type or heterocyclic type.

[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 several of silica powder, talc powder, and mica powder; the flame retardant is selected from one or a combination of several of aluminum diethylphosphinate, aluminum hydroxide, and magnesium hydroxide.

[0016] As a specific embodiment, the silane coupling agent is selected from one or a combination of several of epoxy group silane coupling agent, amino group silane coupling agent, phenylamino group silane coupling agent, vinyl group silane coupling agent, isocyanate group silane coupling agent, propenyl group silane coupling agent, isobutenyl group silane coupling agent, styryl group silane coupling agent, ureido group silane coupling agent, chloropropyl group silane coupling agent, sulfhydryl group silane coupling agent, and sulfide group silane coupling agent.

[0017] The present invention also provides a preparation method of the composition of the aqueous epoxy emulsion and the aqueous benzoxazine emulsion, comprising the following steps:

[0018] Mix the aqueous epoxy emulsion and the aqueous benzoxazine emulsion, then add the catalyst, filler, flame retardant, and silane coupling agent, and mix well under stirring conditions to obtain the composition.

[0019] As a specific embodiment, the stirring speed is 200 - 1000 rpm, and the temperature is 30 - 60 °C.

[0020] Finally, the present invention provides an application of the composition of the aqueous epoxy emulsion and the aqueous benzoxazine emulsion in the preparation of a copper clad laminate or a prepreg.

[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 effects: Compared with the prior art, by combining the aqueous epoxy emulsion and the aqueous benzoxazine emulsion and adding appropriate other components, the present invention overcomes the drawbacks of the traditional solvent-based system when manufacturing copper clad laminates and prepregs, and exhibits a series of excellent properties. The main advantages are as follows:

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

[0024] 2. It has good heat resistance, can maintain stable performance in a high-temperature environment, meets the high requirements for the heat resistance of materials during the operation of electronic devices, and effectively improves the reliability and service life of copper clad laminates and prepregs.

[0025] 3. Excellent mechanical properties, able to withstand various mechanical stresses of electronic equipment during production, use and transportation, ensuring the integrity and stability of the circuit board.

[0026] 4. Good processability, easy to process in the manufacturing process of copper clad laminates and prepregs, such as coating, pressing and other operations, improving 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 is further illustrated below in conjunction with 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 type liquid epoxy emulsion (HDL-1200, 60% solid content, purchased from Han Dai Chemical);

[0032] Benzoxazine emulsion (CB4200, bisphenol F type benzoxazine, purchased from Keyi Polymer, 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 embodiments and comparative examples are as follows:

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

[0039] Dk and Df: The test is carried out using the SPDR (split post dielectric resonator) method, referring to the [IPC-TM6502.5.5.13] standard, the test condition is state A, and the frequency is 10GHz;

[0040] Immersion soldering test: Immerse a copper clad laminate of 100mm×100mm in molten tin at 288°C for 5 minutes, and visually observe whether there is delamination or bubbling on the copper clad laminate; if there is no delamination or bubbling, it is marked as "passed".

[0041] Coefficient of thermal expansion (Z-axis): Using IPC-TM-650 2.4.24, test the coefficient of thermal expansion of the material in the z-direction in the temperature range of -55 to 288°C.

[0042] Example 1

[0043] Mix the waterborne epoxy emulsion (50 parts) and the waterborne benzoxazine emulsion (50 parts) in a certain proportion, then add an appropriate amount of catalyst (2-methylimidazole, 0.2 parts), flame retardant (aluminum diethylphosphinate, 30 parts), filler (spherical silica, 5um, 10 parts) and silane coupling agent (KH-560, 0.5 parts), and mix well under stirring conditions. The stirring speed is 600 rpm and the temperature is 45°C to obtain Composition A.

[0044] Coat Composition A on the copper foil, and obtain a copper clad laminate sample through the process steps of drying (170°C for 4 minutes) and hot pressing (200°C for 2 hours, 150 psi).

[0045] Example 2

[0046] Similar to Example 1, only the proportions of the waterborne epoxy emulsion and the waterborne benzoxazine emulsion (60 parts / 40 parts respectively) are adjusted, as well as the dosages of the catalyst, flame retardant, filler and silane coupling agent, to obtain Composition B, and then a copper clad laminate sample is prepared.

[0047] Example 3

[0048] Similar to Example 1, only the proportions of the waterborne epoxy emulsion and the waterborne benzoxazine emulsion (70 parts / 30 parts respectively) are adjusted, as well as the dosages of the catalyst, flame retardant, filler and silane coupling agent, to obtain Composition C, and then a copper clad laminate sample is prepared.

[0049] Comparative Example 1

[0050] Similar to Example 1, only the phenolic resin emulsion (the phenolic resin is purchased from Shandong Shengquan and emulsified with a conventional emulsifier, 60% solid content) is used instead of the waterborne benzoxazine emulsion, and the dosages of the catalyst, flame retardant, filler and silane coupling agent are adjusted to obtain a composition, and then a copper clad laminate sample is prepared.

[0051] Comparative Example 2

[0052] Similar to Example 1, except that an aqueous amine curing agent (tetraethylenepentamine, purchased from Nanjing Beihua Chemical Industry) was used instead of the aqueous benzoxazine emulsion, and the amounts of the catalyst, flame retardant, filler, and silane coupling agent were adjusted to obtain a composition, and then a copper clad laminate sample was prepared.

[0053]

[0054]

[0055] The test results show that based on maintaining no VOCs, the performance indicators of Examples 1-3 are further optimized. Compared with the system without benzoxazine curing agent, it shows more excellent performance in heat resistance (such as dip soldering 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 embodiments 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 the examples, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered within the scope of the claims of the present invention.

Claims

1. A composition comprising an aqueous epoxy emulsion and an aqueous benzoxazine 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 aqueous benzoxazine emulsion; Catalyst 0.1-1 part; 10-30 parts of filler; Flame retardant 10-30 parts; Silane coupling agent 0.5-1 part 2. The composition of aqueous epoxy emulsion and aqueous benzoxazine emulsion according to claim 1, characterized in that: The aqueous epoxy emulsion is selected from liquid bisphenol A type / F type epoxy emulsion or solid bisphenol A type / F type epoxy emulsion.

3. The composition of aqueous epoxy emulsion and aqueous benzoxazine emulsion according to claim 1, characterized in that: The benzoxazine in the aqueous benzoxazine emulsion is of bisphenol A type / bisphenol F type, diamine type or heterocyclic type.

4. The composition of aqueous epoxy emulsion and aqueous benzoxazine emulsion according to claim 1, characterized in that: The catalyst is selected from imidazole or triphenylphosphine.

5. The composition of aqueous epoxy emulsion and aqueous benzoxazine emulsion according to claim 1, characterized in that: The filler is selected from one or a combination of silicon micropowder, talcum powder, and mica powder; 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 benzoxazine emulsion according to claim 1, characterized in that: The silane coupling agent is selected from one or a combination of epoxy silane coupling agent, amino silane coupling agent, phenylamino silane coupling agent, vinyl silane coupling agent, isocyanate silane coupling agent, acryl silane coupling agent, isobutylene silane coupling agent, styrene silane coupling agent, urea silane coupling agent, chloropropyl silane coupling agent, sulfur silane coupling agent and sulfurized silane coupling agent.

7. A method for preparing a composition comprising an aqueous epoxy emulsion and an aqueous benzoxazine emulsion according to any one of claims 1 to 6, characterized in that: The following steps are involved: The aqueous epoxy emulsion and the aqueous benzoxazine 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 benzoxazine emulsion according to claim 7, characterized in that: The stirring speed is 200-1000 rpm and the temperature is 30-60 degrees Celsius.

9. Use of the composition of the aqueous epoxy emulsion and the aqueous benzoxazine emulsion according to any one of claims 1 to 6 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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