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 a polyfunctional group vinyl compound; 60 to 120 parts of 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, and the polyfunctional group vinyl compound and the isocyanurate resin are introduced, so that the overall performance of the composite material is remarkably improved.

Description

Technical Field

[0001] The invention belongs to the technical field of resins, and in particular relates to a low dielectric resin composition, a preparation method thereof and applications thereof. Background Art

[0002] Traditional substrates such as resins contain a large number of polar groups, and 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 temperature of these materials is low, which makes them prone to deformation or degradation in high-temperature environments, affecting the reliability and life of electronic products.

[0003] The invention adopts a low dielectric resin composition and introduces a multifunctional vinyl compound and an isocyanurate resin, thereby significantly improving the overall performance of the composite material.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] One of the objects of the present invention is to provide a low dielectric resin composition.

[0006] A second object of the present invention is to provide a method for preparing a metal-clad plate material using the low dielectric resin composition.

[0007] 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).

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

[0009] In order to achieve the above-mentioned purpose of the present invention, the technical scheme adopted is as follows:

[0010] A low dielectric resin composition, calculated by weight, comprises the following components:

[0011] 60-120 parts of a multifunctional vinyl compound;

[0012] 60-120 parts of isocyanurate resin;

[0013] Aromatic olefin cross-linking agent 5-15 parts;

[0014] Flame retardant 10-30 parts;

[0015] 80-150 parts of filling material;

[0016] 5-12 parts of toughening agent;

[0017] Initiator 0.2-3 parts;

[0018] The multifunctional vinyl compound has a structure shown in Formula 1:

[0019]

[0020] Where R 1 , is any one of Formula 2 to Formula 5;

[0021]

[0022]

[0023] wherein n, m is a positive integer ≥ 1, and R2-R9 are the same or independent methyl groups.

[0024] In a preferred embodiment of the present invention, the multifunctional vinyl compound is OPE-2ST having a structure shown in Formula 6 below:

[0025]

[0026] In a preferred embodiment of the present invention, the isocyanurate resin has a structure as shown in Formula 7 below:

[0027]

[0028] Wherein R10 is a C1-C15 straight chain alkane.

[0029] In a preferred embodiment of the present invention, the isocyanurate resin has a structure as shown in Formula 8 below:

[0030]

[0031] In a preferred embodiment of the present invention, the structure of the aromatic olefin cross-linking agent is shown in Formula 9:

[0032]

[0033] Wherein R1 and R2 are independently selected from any one of H, C1-C10 alkyl, or C1-C10 haloalkyl.

[0034] In a preferred embodiment of the present invention, the aromatic olefin cross-linking agent is obtained by the following reaction formula:

[0035]

[0036] The reaction conditions are: reacting in the environment of a reaction stock solution of pyridinium p-toluenesulfonate to obtain an aromatic olefin crosslinking agent.

[0037] In a preferred embodiment of the present invention, the structural formula of the aromatic olefin cross-linking agent is shown in Formula 10 below:

[0038]

[0039] In a preferred embodiment of the present invention, the structure of the phosphorus-containing flame retardant is as shown in Formula 11:

[0040]

[0041] 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 0.01-24 μm and a purity of more than 99.0%. Spherical silica is preferred, and its main function is to increase the binding force and reduce the cost of raw materials.

[0042] 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.

[0043] 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.

[0044] A method for preparing a metal-clad plate material using a low dielectric resin composition comprises the following steps:

[0045] The first step is to fully mix the solid components and the solvent in the low dielectric resin composition until the resin is completely dissolved to obtain a modified low dielectric resin composition;

[0046] The solvent is benzene, butanone, acetone, dimethylformamide, methyl ethyl ketone or propylene glycol methyl ether;

[0047] 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;

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] In a preferred embodiment of the present invention, the metal foil is 1 / 3oz, Hoz, 1oz, 2oz, 3oz, 4oz or RTF metal foil.

[0053] A use of a low dielectric resin composition, the use being for preparing a high-frequency and high-speed printed circuit board.

[0054] The beneficial effects of the present invention are:

[0055] The present invention adopts a low dielectric resin composition, introduces a multifunctional vinyl compound and an isocyanurate resin, thereby significantly improving the overall performance of the composite material, especially the mechanical properties and the dielectric properties. At the same time, the introduction of long-chain alkanes into the isocyanurate resin can effectively reduce the dielectric loss of the material, and can effectively enhance the strength, hardness and temperature resistance of the material, so that the material exhibits more excellent electrical properties in circuit applications. DETAILED DESCRIPTION

[0056] 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.

[0057] The aromatic olefin cross-linking agent in this embodiment is a C1 compound.

[0058] The synthetic route of the specific embodiment of the present invention is:

[0059]

[0060] 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, stirred for 1h, and the organic phase was taken after standing and stratification, 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, with a yield of 96.1% and a purity of 99.8%.

[0061] In the embodiment of the present invention, the multifunctional vinyl compound is Mitsubishi Gas OPE-2St.

[0062] In the embodiment of the present invention, the isocyanurate resin is selected from L-DAIC produced by Shikoku Chemical.

[0063] In the embodiment of the present invention, the flame retardant is selected from Shanghai Jianchao DPPB, 1,4-bis(diphenylphosphine)butane.

[0064] In the embodiment of the present invention, the initiator is selected from Luoyang Saitu STR9100 and benzoyl peroxide.

[0065] In the embodiment of the present invention, the toughening agent is selected from Japan Asahi Chemical H1041, styrene-ethylene butylene-styrene copolymer.

[0066] In the embodiment of the present invention, the inorganic filler is SP0045 manufactured by Jiangsu Lianrui New Materials Technology Co., Ltd., spherical silica (D50 is 3 μm, density is 2.20×103kg / m 3 ).

[0067] The present invention will be further explained and illustrated by specific embodiments below:

[0068] The preparation method of the resin glue of the present invention is as follows:

[0069] 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;

[0070] 2. Gluing to obtain a prepreg;

[0071] 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;

[0072] 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;

[0073] 3. Typesetting and pressing;

[0074] The prepreg is cut into the same size, 6 sheets in a group, overlapped with metal foil, and then pressed.

[0075] 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):

[0076] a. Pressure: 70-600psi;

[0077] b. Temperature: 70-240℃;

[0078] c. Vacuum degree: 0.02-0.1MPa;

[0079] d. Curing time: 80min;

[0080] e. Pressing time: 150min.

[0081] The samples in Examples 1-5 and Comparative Examples 1-4 were tested for various properties according to the following methods:

[0082] 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;

[0083] 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;

[0084] 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;

[0085] 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℃.

[0086] 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;

[0087] 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.

[0088] Combining Tables 1 and 2, it can be seen that the present invention improves the tensile strength and impact strength simultaneously, while the thermal expansion coefficient reaches the V0 level, and the dielectric constant and dielectric loss are significantly reduced.

[0089] The data of each embodiment are shown in Table 1:

[0090]

[0091] The comparative data are shown in Table 2:

[0092]

[0093]

Claims

1. A low dielectric resin composition, characterized in that: Calculated by weight, it contains the following components: 60-120 parts of multifunctional vinyl compound; 60-120 parts of isocyanurate resin; 5-15 parts of aromatic olefin cross-linking agent; Flame retardant 10-30 parts; 80-150 parts of filling material; 5-12 parts of toughening agent; Initiator 0.2-3 parts; The multifunctional vinyl compound has a structure shown in Formula 1: Wherein R1 is any one of Formula 2 to Formula 5; wherein n, m is a positive integer ≥ 1, and R2-R9 are the same or independent methyl groups.

2. A low dielectric resin composition as claimed in claim 1, characterized in that: The multifunctional vinyl compound is OPE-2ST having a structure shown in Formula 6 below:

3. A low dielectric resin composition as claimed in claim 1, characterized in that: The isocyanurate resin has a structure as shown in Formula 7 below: Wherein R10 is a C1-C15 straight chain alkane.

4. A low dielectric resin composition as claimed in claim 1, characterized in that: The isocyanurate resin has a structure as shown in Formula 8 below:

5. A low dielectric resin composition as claimed in claim 1, characterized in that: The structure of the aromatic olefin cross-linking agent is shown in Formula 9: Wherein R1 and R2 are independently selected from any one of H, C1-C10 alkyl, or C1-C10 haloalkyl.

6. A low dielectric resin composition as claimed in claim 1, characterized in that: The aromatic olefin cross-linking agent is obtained by the following reaction formula: The reaction conditions are: reacting in the environment of a reaction stock solution of pyridinium p-toluenesulfonate to obtain an aromatic olefin crosslinking agent.

7. A low dielectric resin composition as claimed in claim 1, characterized in that: The structural formula of the aromatic olefin cross-linking agent is shown in Formula 10 below:

8. A low dielectric resin composition as claimed in claim 1, characterized in that: The structure of the phosphorus-containing flame retardant is shown in Formula 11: 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 0.01-24 μm and a purity of more than 99.0%; 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.

9. A method for preparing a metal-clad plate material using a low dielectric resin composition as described in any one of claims 1 to 8, characterized in that: The steps include: The first step is to fully mix the solid components and the solvent in the low dielectric resin composition until the resin is completely dissolved to obtain a modified low dielectric resin composition; The solvent is benzene, butanone, acetone, dimethylformamide, methyl ethyl ketone or propylene glycol methyl ether; 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.

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

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