Low-dielectric resin composition as well as preparation method and application thereof

Abstract

The invention discloses a low-dielectric resin composition which is characterized by comprising the following components in parts by weight: 60-120 parts of polyphenyl ether resin; 60 to 120 parts of triallyl isocyanurate resin; 5-15 parts of an aromatic olefin cross-linking agent; 10 to 30 parts of a flame retardant; 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 low-dielectric resin composition is adopted, the polyphenyl ether and the triallyl isocyanurate resin are used as the resin composition, the aromatic olefin cross-linking agent is used for modifying the organic resin, and the dielectric constant and the dielectric loss of the low-dielectric resin composition are remarkably reduced under the condition that the tensile strength, the impact strength, the thermal stress, the T288 and the thermal expansion coefficient are not sacrificed. Therefore, 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 a low dielectric resin composition and 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] Polyphenylene ether (PPE) resin is known for its excellent heat resistance, chemical resistance and low dielectric constant. These properties make PPE resin widely used in high-performance PCBs, especially in situations where extreme temperatures and harsh environments are required. In addition, PPE resin also has good flame retardant properties and can meet strict safety standards.

[0004] As a high-performance cross-linking agent, TAIC can significantly improve the heat resistance and mechanical strength of the resin while maintaining good electrical properties. The combination of TAIC and PPE resin can give full play to the advantages of both and prepare a PCB resin composition with excellent comprehensive performance. This combination can not only provide higher thermal stability and mechanical strength, but also maintain a low dielectric constant and loss, thereby improving the efficiency and reliability of signal transmission.

[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 a low dielectric resin composition.

[0007] A second object of the present invention is to provide a method for preparing a metal-clad plate material for a circuit board made using the low dielectric resin composition.

[0008] The metal-clad plate material has excellent low dielectric and high heat resistance properties, heat resistance and mechanical properties, and is suitable for the production of high-frequency and high-speed printed circuit boards (PCBs).

[0009] A third object of the present invention is to provide an application of a low dielectric resin composition.

[0010] In order to achieve the above-mentioned purpose of the present invention, the technical solution adopted is:

[0011] A low dielectric resin composition, calculated by weight, comprises the following components:

[0012] 60-120 parts of polyphenylene ether resin;

[0013] 60-120 parts of triallyl isocyanurate resin;

[0014] Aromatic olefin cross-linking agent 5-15 parts;

[0015] Flame retardant 10-30 parts;

[0016] 80-150 parts of filling material;

[0017] 5-12 parts of toughening agent;

[0018] Initiator 0.2-3 parts;

[0019] The end-capping group of the polyphenylene ether resin is at least one or both of a methacrylate end-capping group and a styrene end-capping group;

[0020] The triallyl isocyanurate resin is shown in the following formula (I):

[0021]

[0022] The structure of the aromatic olefin cross-linking agent is shown in formula (II):

[0023]

[0024] Wherein R1 and R2 are independently selected from any one or more of H, C1-C10 alkyl chain or unsaturated alkyl chain.

[0025] In a preferred embodiment of the present invention, the synthesis process of the aromatic olefin cross-linking agent is shown in the following reaction formula 1:

[0026]

[0027] The reaction conditions of the reaction formula 1 are: the reaction is obtained in the environment of the reaction stock solution of pyridinium p-toluenesulfonate.

[0028] In a preferred embodiment of the present invention, the aromatic olefin cross-linking agent is represented by the following structural formula (III):

[0029]

[0030] In a preferred embodiment of the present invention, the phosphorus flame retardant has a structure as shown in formula (IV):

[0031]

[0032] In a preferred embodiment of the present invention, the filler material is any one of crystalline silica, synthetic silica, spherical silica, fused silica, or a combination of two or more thereof. The filler material has a particle size of 0.01-24 μm and a purity of more than 99.0%.

[0033] The preferred filler material is spherical silica with a particle size of 0.01-24 μm and a purity of more than 99.0%. Its main function is to increase the binding force and reduce the cost of raw materials.

[0034] In a preferred embodiment of the present invention, the toughening agent is 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.

[0035] 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.

[0036] A method for preparing a metal-clad plate using the low dielectric resin composition comprises the following steps:

[0037] The first step is to fully mix the solid components in the low dielectric resin composition and the organic solvent until the resin is completely dissolved to obtain a modified low dielectric resin composition;

[0038] The second step is to coat the low dielectric resin composition as an adhesive on the glass fiber cloth, and dry and cure it to volatilize the solvent to obtain a prepreg;

[0039] The third step is to laminate and press the prepreg obtained in step 2 with the metal foil to obtain the metal-clad plate, and prepare the circuit board by the metal-clad plate;

[0040] The organic solvent is any one or more of toluene, butanone, acetone, dimethylformamide, methyl ethyl ketone or propylene glycol methyl ether.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] In a preferred embodiment of the present invention, the metal foil is 1 / 3oz, Hoz, 1oz, 2oz, 3oz, 4oz or RTF metal foil.

[0045] A use of the low dielectric resin composition is to prepare a high-frequency and high-speed printed circuit board.

[0046] The beneficial effects of the present invention are:

[0047] The present invention adopts a low dielectric resin composition, using polyphenylene ether and triallyl isocyanurate resin as the resin composition, and an aromatic olefin crosslinking agent to modify the organic resin, thereby significantly reducing the dielectric constant and dielectric loss without sacrificing tensile strength, impact strength, thermal stress, T288 and thermal expansion coefficient, so that the material exhibits more excellent electrical properties in circuit applications. DETAILED DESCRIPTION

[0048] 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.

[0049] The aromatic olefin cross-linking agent in the embodiment is prepared by the following method:

[0050]

[0051] Under nitrogen protection, 900g of the reactant was dissolved in 4.5kg of xylene, heated to 140°C, 9g of p-tert-butylcatechol was added, then cooled to 110°C, 90g of pyridine p-toluenesulfonate was added, and then heated to 140°C, and the reaction was kept warm for 3h, and the reaction was completed. The reaction system was cooled to 80°C, 2700g of water was added, and stirred for 1h. After standing and stratification, the organic phase was taken, concentrated under reduced pressure, 1000g of petroleum ether was added for pulping, filtered, and solids were taken. 2700g of toluene was added, stirred at 30°C, washed twice with 500g of deionized water, concentrated under pressure, and dried to obtain 630g of product compound (C1), with a yield of 96.1% and a purity of 99.8%.

[0052] In this embodiment, the polyphenylene ether resin is Tongyu TPO9500.

[0053] In this embodiment, the triallyl isocyanurate resin is Nippon Chemical Industry WH60.

[0054] The flame retardant in the present invention is Shanghai Jianchao DPPB, 1,4-bis(diphenylphosphine)butane.

[0055] The initiator in the present invention is Luoyang Saitu STR9100 and benzoyl peroxide.

[0056] The toughening agent in the present invention is Japanese Asahi Chemical H1041, styrene-ethylene butylene-styrene copolymer.

[0057] The inorganic filler in the present invention 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 ).

[0058] The present invention will be further explained and illustrated by specific embodiments below:

[0059] The preparation method of the resin glue of the present invention is as follows:

[0060] 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 ratio in Table 1) and dissolve them in the solvent;

[0061] 2. Gluing to obtain a prepreg;

[0062] a. Circulate the adhesive to the gluing machine, and after pre-impregnation and main impregnation, evenly coat the adhesive on the glass fiber cloth; the line speed of the gluing machine is controlled at 15m / min;

[0063] 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;

[0064] 3. Typesetting and pressing;

[0065] The prepreg is cut into the same size, 6 sheets in a group, overlapped with metal foil, and then pressed.

[0066] 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):

[0067] a. Pressure: 70-600psi;

[0068] b. Temperature: 70-240℃;

[0069] c. Vacuum degree: 0.02-0.1MPa;

[0070] d. Curing time: 80min;

[0071] e. Pressing time: 150min.

[0072] The samples in Examples 1-5 and Comparative Examples 1-4 were tested for various properties according to the following methods:

[0073] 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. The specific test standards are as follows:

[0074] 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;

[0075] 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;

[0076] 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℃.

[0077] 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;

[0078] Dielectric constant (Dk) and dielectric loss factor (Df): The dielectric constant and dielectric loss factor test methods are in accordance with the test specified in IPC-TM-650 2.5.5.9.

[0079] Table 1

[0080]

[0081]

[0082] The above table is a continuation of Table 1.

[0083] From Table 1, it can be seen that the present invention adopts a low dielectric resin composition, with polyphenylene ether and triallyl isocyanurate resin as the resin composition, and an aromatic olefin cross-linking agent is used to modify the organic resin. Compared with the comparative example, the dielectric constant and dielectric loss are significantly reduced without sacrificing tensile strength, impact strength, thermal stress, T288 and thermal expansion coefficient.

Claims

1. A low dielectric resin composition, characterized in that: Calculated by weight, it contains the following components: 60-120 parts of polyphenylene ether resin; 60-120 parts of triallyl isocyanurate resin; Aromatic olefin cross-linking agent 5-15 parts; Flame retardant 10-30 parts; 80-150 parts of filling material; 5-12 parts of toughening agent; Initiator 0.2-3 parts; The end-capping group of the polyphenylene ether resin is at least one or both of a methacrylate end-capping group and a styrene end-capping group; The triallyl isocyanurate resin is shown in the following formula (I): The structure of the aromatic olefin cross-linking agent is shown in formula (II): Wherein R1 and R2 are independently selected from any one or more of H, C1-C10 alkyl chain or unsaturated alkyl chain.

2. A low dielectric resin composition as claimed in claim 1, characterized in that: The synthesis process of the aromatic olefin cross-linking agent is shown in the following reaction formula 1: The reaction conditions of the reaction formula 1 are: the reaction is obtained in the environment of a reaction stock solution of pyridinium p-toluenesulfonate.

3. A low dielectric resin composition as claimed in claim 1, characterized in that: The aromatic olefin cross-linking agent is shown in the following structural formula (III): In a preferred embodiment of the present invention, the phosphorus flame retardant has a structure as shown in formula (IV):

4. A low dielectric resin composition as claimed in claim 1, characterized in that: The filler material is any one of crystalline silica, synthetic silica, spherical silica, and fused silica, or a combination of two or more thereof. The filler material has a particle size of 0.01-24 μm and a purity of more than 99.0%.

5. A low dielectric resin composition as claimed in claim 1, characterized in that: The toughening agent is 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.

6. A method for preparing a metal-clad plate using the low dielectric resin composition, characterized in that: The steps include: The first step is to fully mix the solid components in the low dielectric resin composition and the organic solvent until the resin is completely dissolved to obtain a modified low dielectric resin composition; The second step is to coat the low dielectric 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 laminate and press the prepreg obtained in step 2 with the metal foil to obtain the metal-clad plate, and prepare the circuit board by the metal-clad plate; The organic solvent is any one or more of toluene, butanone, acetone, dimethylformamide, methyl ethyl ketone or propylene glycol methyl ether.

7. The method for preparing a metal-clad plate using the low dielectric resin composition according to claim 6, characterized in that: 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; The glass cloth-based metal foil-clad plate can have various specifications and sizes, such as 36×48, 37×49, 40×48, 40.5×48.5, 41×49, 42.5×48.5, and 43×49; The glass fiber cloth is of grade E, with specifications of 1035, 1078, 1080, 2113, 2116 or 3313; The metal foil is 1 / 3oz, Hoz, 1oz, 2oz, 3oz, 4oz or RTF metal foil.

8. A use of a low dielectric resin composition as described in any one of claims 1 to 5, characterized in that: The application is to prepare high-frequency and high-speed printed circuit boards.

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