Aromatic olefin resin composition as well as preparation method and application thereof

Abstract

The invention discloses an aromatic olefin resin composition which comprises the following components in parts by weight: 60-120 parts of a divinyl aromatic compound; 60-120 parts of a polyfunctional group vinyl aromatic copolymer; 5-15 parts of an aromatic olefin cross-linking agent; 80 to 150 parts of a filling material; 5-12 parts of a toughening agent; and 0.2-3 parts of an initiator. The invention also discloses a preparation method and application of the compound. The aromatic olefin resin composition is adopted, and the aromatic olefin crosslinking agent is introduced to modify the organic resin, so that the strength of the material can be effectively enhanced through modification, and the material is not easy to deform or degrade in a high-temperature environment; meanwhile, the dielectric constant and the loss factor of the material are reduced, so that the material shows more excellent electrical performance in circuit application.

Description

Technical Field

[0001] The invention belongs to the technical field of resins, and in particular relates to an aromatic olefin resin composition, a preparation method and application thereof. Background Art

[0002] Currently, the dielectric properties and heat resistance of printed circuit boards (PCBs) face many challenges. Since traditional substrates such as epoxy resins contain a large number of polar groups, their dielectric constants and dielectric losses are high, making it difficult to meet the needs of high-frequency communications for low-loss, high-speed transmission. In addition, the glass transition temperatures of these materials are low, which makes them prone to deformation or degradation in high-temperature environments, affecting the reliability and life of electronic products.

[0003] In this context, a preparation method of an aromatic olefin resin composition and its application have emerged. The invention aims to achieve regulation of the properties of aromatic olefin resins by optimizing the synthesis path and improving the process conditions to meet the specific needs of different fields.

[0004] Aromatic olefin resin is a material with excellent dielectric properties and high heat resistance. Its molecular structure contains a large number of aromatic rings, which makes the material have high thermal and chemical stability and can maintain its performance under high temperature conditions. At the same time, aromatic olefin resin also has a low dielectric constant and dielectric loss, which can significantly reduce the energy loss in the signal transmission process and improve the working efficiency and performance of electronic equipment.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] One of the objects of the present invention is to provide an aromatic olefin resin composition.

[0007] The second object of the present invention is to provide a metal-clad laminate material for a circuit board made using the above-mentioned aromatic olefin resin composition, wherein the metal-clad laminate material has excellent low dielectric properties, high heat resistance and mechanical properties, and is suitable for the production of high-frequency and high-speed printed circuit boards (PCBs).

[0008] The third object of the present invention is to use the aromatic olefin resin composition.

[0009] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0010] The present invention provides an aromatic olefin resin composition, which comprises the following components in parts by weight:

[0011] 60-120 parts of divinyl aromatic compound;

[0012] 60-120 parts of multifunctional vinyl aromatic copolymer;

[0013] 5-15 parts of aromatic olefin crosslinking agent;

[0014] 80-150 parts of filling material;

[0015] 5-12 parts of toughening agent;

[0016] Initiator 0.2-3 parts;

[0017] The structural formula of the divinyl aromatic compound is as shown in formula (I),

[0018]

[0019] Where R 1 C 1 ~C 6 Straight-chain or branched alkanes, ~O~ or ~S~.

[0020] In a preferred embodiment of the present invention, the divinyl aromatic compound has a structural formula as shown in formula (II),

[0021]

[0022] In a preferred embodiment of the present invention, the multifunctional vinyl aromatic copolymer comprises the following components calculated by molar percentage:

[0023] Monovinyl aromatic compounds are 40-57%;

[0024] Toluene: 20-40%;

[0025] Vinylphenyl is 1 to 8%;

[0026] Styrene is 2-5%.

[0027] In a preferred embodiment of the present invention, the structure of the aromatic olefin cross-linking agent is shown in formula (III):

[0028]

[0029] Wherein R1 and R2 are independently selected from H, a C1-C10 alkyl chain or a saturated alkyl chain.

[0030] In a preferred embodiment of the present invention, the aromatic olefin cross-linking agent is synthesized by the following reaction formula:

[0031]

[0032] The reaction is obtained by reacting in the environment of the reaction stock solution of pyridinium p-toluenesulfonate.

[0033] In a preferred embodiment of the present invention, the structural formula of the aromatic olefin cross-linking agent is as shown in formula (IV):

[0034]

[0035] In a preferred embodiment of the present invention, the filler material is one or a combination of two or more of crystalline silica, synthetic silica, spherical silica, and fused silica, with a particle size of 0.01 to 24 μm and a purity of more than 99.0%. Spherical silica is preferred, and the filler material is mainly used to increase the bonding force and reduce the cost of raw materials.

[0036] In a preferred embodiment of the present invention, the toughening agent comprises one or more of polybutadiene, styrene-butadiene block copolymer, styrene-butadiene-styrene triblock copolymer, hydrogenated styrene / butadiene / styrene block copolymer, and maleic anhydride grafted styrene butadiene-styrene block copolymer elastomer.

[0037] In a preferred embodiment of the present invention, the initiator is any one or more of azobisisobutyronitrile, azobis(2-isopropyl)butyronitrile, azobishexamethylenedicarbonitrile, dibenzoyl peroxide, dimethylbenzoyl peroxide, diisopropyl peroxide, diisopropylbenzene peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicyclohexyl peroxide, benzoic acid peroxide, tert-butyl peroxide, butylbenzoic acid peroxide or tert-butylbenzoic acid peroxide.

[0038] A method for preparing a metal-clad laminate having the aromatic olefin resin composition comprises the following steps:

[0039] The first step is to fully mix the solid components in the aromatic olefin resin composition and the organic solvent until the resin is completely dissolved to obtain a modified aromatic olefin resin composition;

[0040] The second step is to coat the aromatic olefin resin composition as an adhesive on the glass fiber cloth, and dry and cure it to volatilize the solvent to obtain a prepreg;

[0041] The third step is to overlap and press the prepreg obtained in step 2 with the metal foil to obtain the metal-clad laminate, and to prepare the circuit board through the metal-clad laminate.

[0042] The solvent is any one or more of toluene, butanone, acetone, dimethylformamide, methyl ethyl ketone or propylene glycol methyl ether.

[0043] In a preferred embodiment of the present invention, the line speed of the glue coating is 8-25m / min; the temperature of the drying and curing is 110-230°C; the pressing pressure is 70-600psi, the temperature is 70-240°C, the vacuum degree is 0.02-0.1MPa, the curing time is 50-130min, and the pressing time is 70-200min.

[0044] In a preferred embodiment of the present invention, the glass cloth-based metal foil-clad plate can have various types of specifications and sizes, such as 36×48, 37×49, 40×48, 40.5×48.5, 41×49, 42.5×48.5, and 43×49.

[0045] In a preferred embodiment of the present invention, the glass fiber cloth is of grade E, with specifications of 1035, 1078, 1080, 2113, 2116 or 3313.

[0046] In a preferred embodiment of the present invention, the metal foil is 1 / 3oz, Hoz, 1oz, 2oz, 3oz, 4oz or RTF metal foil.

[0047] The invention discloses an application of an aromatic olefin resin composition, wherein the application is to prepare a PCB circuit board.

[0048] The beneficial effects of the present invention are:

[0049] The present invention adopts an aromatic olefin resin composition and modifies the organic resin by introducing an aromatic olefin cross-linking agent. The modification of the present invention can effectively enhance the strength of the material so that it is not easy to deform or degrade in a high temperature environment, and at the same time reduce its dielectric constant and loss factor so that the material exhibits better electrical properties in circuit applications.

[0050] In addition, the invention has the advantages of simple process and low cost, and is easy for large-scale production and application, which is of great significance for improving the technical level in related fields. DETAILED DESCRIPTION

[0051] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0052] Example

[0053] The aromatic olefin cross-linking agent in the embodiment is obtained by the following route:

[0054]

[0055] Specifically, under nitrogen protection, 900 g of reactant was dissolved in 4.5 kg of xylene, the temperature was raised to 140° C., 9 g of p-tert-butylcatechol was added, the temperature was lowered to 110° C., 90 g of pyridine p-toluenesulfonate was added, the temperature was raised to 140° C., the reaction was kept warm for 3 hours, and the reaction was completed.

[0056] The reaction system was cooled to 80°C, 2700 g of water was added, and the mixture was stirred for 1 h. After standing for stratification, the organic phase was taken, concentrated under reduced pressure, 1000 g of petroleum ether was added for pulping, and the solid was filtered. 2700 g of toluene was added, and the mixture was stirred at 30°C. The mixture was washed twice with 500 g of deionized water, concentrated under pressure, and dried to obtain 630 g of an aromatic olefin crosslinker product with a yield of 96.1% and a purity of 99.8%.

[0057] The divinyl aromatic compound in the embodiment is selected from Shanghai Sheng-16BVXS;

[0058] The multifunctional vinyl aromatic copolymer in the embodiment is selected from Nippon Steel LF-310T50;

[0059] In the comparative example, the crosslinking agent is Luoyang Saitu STR6400, triallyl isocyanurate resin;

[0060] The initiator in the embodiment is selected from Luoyang Saitu STR9100, benzoyl peroxide;

[0061] The toughening agent in the embodiment is selected from Japan Asahi Chemical H1041;

[0062] The inorganic filler in the embodiment is SP0045 manufactured by Jiangsu Lianrui New Materials Technology Co., Ltd., spherical silica (D50 is 3 μm, density is 2.20×10 3 kg / m 3 ).

[0063] The preparation method of the resin glue is as follows:

[0064] 1. Weigh the modified divinyl aromatic compound, multifunctional vinyl aromatic copolymer, aromatic olefin crosslinking agent, filler, toughening agent and initiator according to the formula amount (based on the material selection and proportion in Table 1) and dissolve them in the solvent;

[0065] 2. Gluing to obtain a prepreg;

[0066] a. Circulate the adhesive to the gluing machine, and evenly coat the adhesive on the glass fiber cloth after pre-impregnation and main impregnation; the line speed of the gluing machine is controlled at 15m / min;

[0067] b. The glass fiber cloth coated with adhesive is baked in a drying oven at 140°C to evaporate the solvent and initially react and solidify the adhesive to obtain a prepreg;

[0068] 3. Typesetting and pressing;

[0069] The prepreg is cut into the same size, 6 sheets in a group, overlapped with metal foil, and then pressed.

[0070] The suppression parameters are as follows (the range of values ​​indicates that the suppression parameters can be achieved within this range and the effects are equivalent):

[0071] a. Pressure: 70-600psi;

[0072] b. Temperature: 70-240℃;

[0073] c. Vacuum degree: 0.02-0.1MPa;

[0074] d. Curing time: 80min;

[0075] e. Pressing time: 150min.

[0076] The samples in Examples 1 to 5 and Comparative Examples 1 to 4 were tested for various properties according to the following methods:

[0077] Tensile strength: According to the standard of IPC~TM~650 2.2.1, the tensile strength of the sample is tested using a universal mechanical testing machine;

[0078] Impact strength: According to the standard of IPC~TM~650 2.4.23, the tensile strength of the sample is tested using a tensile impact testing machine;

[0079] Thermal stress tinning time test: Use a 50×50mm double-sided metal sample, immerse it in a 288℃ tin furnace, and record the time for the sample surface to delaminate and bubble;

[0080] 288℃ heat resistance test (T288): Place a 8mm×8mm metal foil substrate on a thermomechanical analyzer (TMA). Raise the temperature from room temperature to 288℃ at a heating rate of 10℃ / min and maintain at 288℃. Observe the dimensional change of the sample and record the time when the plate burst occurs after 288℃.

[0081] Thermal expansion coefficient: According to the standard specified in IPC-TM-650 2.4.24, the thermal expansion coefficient of the sample is measured using a TMA instrument;

[0082] Dielectric constant (Dk) and dielectric loss factor (Df): The dielectric constant and dielectric loss factor test method is in accordance with the test specified in IPC~TM~650 2.5.5.9, and the results obtained are shown in Table 1.

[0083] Table 1

[0084]

[0085]

[0086]

[0087] The above table is a continuation of Table 1.

[0088] As shown in Table 1, the present invention can meet the performance requirements of thermal stress and T288 while greatly improving the tensile strength, making it less likely to deform or degrade in a high temperature environment, and also significantly reduce the dielectric constant (Dk) and dielectric loss factor (Df). It can significantly reduce the energy loss in the signal transmission process and improve the working efficiency and performance of electronic equipment.

Claims

1. An aromatic olefin resin composition, calculated by weight, comprising the following components: 60-120 parts of divinyl aromatic compound; 60-120 parts of multifunctional vinyl aromatic copolymer; 5-15 parts of aromatic olefin crosslinking agent; 80-150 parts of filling material; 5-12 parts of toughening agent; Initiator 0.2-3 parts; The structural formula of the divinyl aromatic compound is as shown in formula (I), Wherein R1 is a C1~C6 straight chain or branched alkane, ~O~ or ~S~.

2. An aromatic olefin resin composition according to claim 1, characterized in that: The divinyl aromatic compound has a structural formula as shown in formula (II), 3. An aromatic olefin resin composition according to claim 1, characterized in that: The multifunctional vinyl aromatic copolymer comprises the following components calculated by mole percentage: Monovinyl aromatic compounds are 40-57%; Toluene: 20-40%; Vinylphenyl is 1 to 8%; Styrene is 2-5%.

4. An aromatic olefin resin composition according to claim 1, characterized in that: The structure of the aromatic olefin cross-linking agent is shown in formula (III): Wherein R1 and R2 are independently selected from H, a C1-C10 alkyl chain or a saturated alkyl chain.

5. An aromatic olefin resin composition as claimed in claim 4, characterized in that: The aromatic olefin cross-linking agent is synthesized by the following reaction formula: The reaction is obtained by reacting in the environment of the reaction stock solution of pyridinium p-toluenesulfonate.

6. The aromatic olefin resin composition according to claim 1, characterized in that: The structural formula of the aromatic olefin cross-linking agent is shown in formula (IV):

7. The aromatic olefin resin composition according to claim 1, characterized in that: The filling material is one or a combination of two or more of crystalline silica, synthetic silica, spherical silica and fused silica, with a particle size of 0.01 to 24 μm and a purity of more than 99.0%.

8. The aromatic olefin resin composition according to claim 1, characterized in that: The toughening agent comprises one or more of polybutadiene, styrene-butadiene block copolymer, styrene-butadiene-styrene triblock copolymer, hydrogenated styrene / butadiene / styrene block copolymer, maleic anhydride grafted styrene butadiene-styrene block copolymer elastomer; The initiator is any one or more of azobisisobutyronitrile, azobis(2-isopropyl)butyronitrile, azobishexamethylenedicarbonitrile, dibenzoyl peroxide, dimethylbenzoyl peroxide, diisopropyl peroxide, diisopropylbenzene peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicyclohexyl peroxide, benzoic acid peroxide, tert-butyl peroxide, butylbenzoic acid peroxide or tert-butylbenzoic acid peroxide.

9. A method for preparing a metal-clad laminate using the aromatic olefin resin composition as described in any one of claims 1 to 8, comprising the following steps: The first step is to fully mix the solid components in the aromatic olefin resin composition and the organic solvent until the resin is completely dissolved to obtain a modified aromatic olefin resin composition; The second step is to coat the aromatic olefin resin composition as an adhesive on the glass fiber cloth, and dry and cure it to volatilize the solvent to obtain a prepreg; The third step is to overlap and press the prepreg obtained in step 2 with the metal foil to obtain the metal-clad laminate, and to prepare the circuit board through the metal-clad laminate.

10. The use of the aromatic olefin resin composition according to any one of claims 1 to 8, characterized in that: The application is to prepare a PCB circuit board.

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