Thermosetting resin composition and substrate

Abstract

The application discloses a thermosetting resin composition, characterized by comprising the following components: 5-40 parts of polybutadiene modified resin; 3-30 parts of DOPO derivative flame retardant; 20-70 parts of modified polyphenyl ether resin; 15-20 parts of crosslinking agent; 1-2 parts of initiator; and 60-70 parts of silicon powder; the polybutadiene modified resin is specifically a mixture of polybutadiene modified silicon resin, bis(3-ethyl-5-methyl-4-maleimide phenyl) methane and polybutadiene; or a mixture of polybutadiene modified silicon resin, bis(3-ethyl-5-methyl-4-maleimide phenyl) methane, polybutadiene and styrene-butadiene copolymer; and the application further provides a substrate. The application utilizes the special chain structure of the polybutadiene modified silicon resin, so that the polybutadiene modified silicon resin has good toughness, compatibility and chemical resistance; the silicon-oxygen bond can be well bonded with a copper foil, so that the peeling strength and other performances between the resin and the copper foil are improved; and the flame retardant can realize excellent flame retardant performance by utilizing the phosphorus-silicon synergistic effect.

Description

Technical Field

[0001] This invention relates to the field of resin composition manufacturing, and more specifically to a thermosetting resin composition and substrate. Background Technology

[0002] In recent years, with the development of high-performance, high-functionality, and networked computer and information communication equipment, operating signals have tended to be higher frequency in order to transmit and process large amounts of information at high speeds, thus placing demands on the materials of circuit boards. For a long time, polybutadiene or copolymers of polybutadiene and styrene have received widespread attention due to their good dielectric properties, making them suitable for use in high-frequency, high-speed circuit boards. However, circuit boards prepared from these resins currently exhibit poor interlayer adhesion and copper foil peel strength, requiring the addition of halogen- or phosphorus-containing flame retardants to achieve the required flame retardant rating.

[0003] U.S. Patent No. 5,223,568 discloses a moldable thermoplastic composition for circuit boards, comprising a mixture of one of a polybutadiene resin or a polyisoprene resin that is liquid at room temperature and has a molecular weight of less than 5,000, and a solid butadiene or isoprene containing a thermoplastic elastomer. This U.S. patent, besides requiring high-temperature curing (i.e., hot-pressing temperature > 250°C), still does not solve the problem of polybutadiene's high viscosity, which makes continuous automated production of copper foil substrates difficult. Furthermore, polybutadiene is flammable, requiring the addition of more flame retardants to achieve the UL-94V0 standard.

[0004] US5571609 discloses the preparation of glass fiber reinforced circuit boards by using polybutene / polybutene-styrene copolymers of different molecular weights and adding a large amount of silicon micropowder as filler. Although the dielectric properties are excellent, the prepreg prepared has poor processability and low rigidity.

[0005] During combustion degradation, silicon can migrate to the polymer surface, forming a protective layer rich in silicon-oxygen and carbon-silicon bonds, effectively isolating oxygen and heat and thus inhibiting combustion. Phosphorus, on the other hand, promotes char formation during combustion degradation and achieves flame retardancy by quenching the active groups of oxygen free radicals. By chemically bonding phosphorus-containing groups and siloxane molecules, flame retardants can achieve excellent flame-retardant properties through the phosphorus-silicon synergistic effect, making it one of the current research hotspots in flame-retardant polymer materials.

[0006] However, traditional polybutadiene resin structures have poor flame retardancy, and more flame retardants must be added to compensate for the flame retardancy properties. However, the addition of flame retardants will affect other important physical properties, such as insufficient heat resistance, reduced glass transition temperature (Tg), and high electrical properties. Summary of the Invention

[0007] In order to overcome the above-mentioned defects of the prior art, the present invention aims to provide a thermosetting resin composition that effectively improves the defects of traditional polybutadiene resin structure, such as poor flame retardancy, and the fact that the addition of flame retardants can affect other important physical properties, such as insufficient heat resistance, reduced glass transition temperature (Tg), and high electrical properties.

[0008] To achieve the objectives of this invention, the technical solution adopted is as follows:

[0009] A thermosetting resin composition comprising:

[0010] 5-40 parts of polybutadiene-modified resin;

[0011] 3-30 parts of DOPO derivative flame retardant;

[0012] 20-70 parts of modified polyphenylene ether resin;

[0013] 15-20 parts crosslinking agent;

[0014] 1-2 parts initiator;

[0015] 60-70 parts silica powder;

[0016] The polybutadiene-modified resin is specifically a mixture of polybutadiene-modified silicone resin, bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane, and polybutadiene;

[0017] Or a mixture of polybutadiene-modified silicone resin, bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane, polybutadiene, and styrene-butadiene copolymer.

[0018] In a preferred embodiment of the present invention, the polybutadiene-modified silicone resin is prepared from polybutadiene resin and trimethoxysilane, and the specific preparation method is as follows:

[0019] The trimethoxysilane was added dropwise to polybutadiene resin and catalyzed using a tetramethyldivinyldisiloxane platinum complex catalyst.

[0020] The double bond content in the polybutadiene resin and the molar ratio of silane groups in trimethoxysilane are 1:0.80-1:1.20, and the dropping time is 25-70 min.

[0021] The polybutadiene resin has the structure shown in Formula 1:

[0022]

[0023] Where X is an integer from 1 to 50, and Y is an integer from 1 to 50;

[0024] The number-average molecular weight of the polybutadiene resin is 800-20000 g / mol;

[0025] A further preferred value is 1200-8000 g / mol;

[0026] The polybutadiene resin has a Brookfield viscosity of 2300-15000 cps.

[0027] Preferred polybutadiene resins include "B-1000" (liquid polybutadiene) manufactured by Nippon Soda Corporation, "B-3000" (liquid polybutadiene) manufactured by Nippon Soda Corporation, "G-3000" (liquid polybutadiene) manufactured by Nippon Soda Corporation, "LBR-302" (liquid polybutadiene) manufactured by Kuraray Corporation, and "LBR-305" (liquid polybutadiene) manufactured by Kuraray Corporation.

[0028] In a preferred embodiment of the present invention, the structure of the DOPO derivative flame retardant is shown in Formula 2 below:

[0029]

[0030] Z is any one of the following equations 3, 4, 5, and 6:

[0031]

[0032] In Equation 6, m is an integer from 1 to 50.

[0033] In a preferred embodiment of the present invention, the DOPO derivative flame retardant is specifically the flame retardant PQ60 from Chin I Chemical Co., Ltd. in Taiwan, China.

[0034] In a preferred embodiment of the present invention, the modified polyphenylene ether resin is a modified thermosetting polyphenylene ether resin, specifically an olefin-modified thermosetting polyphenylene ether resin.

[0035] Further preferred are methacrylate-modified thermosetting polyphenylene ether resins; the number average molecular weight of the methacrylate-modified thermosetting polyphenylene ether resin is 500-13000 g / mol, preferably 700-5000 g / mol. Specifically, it is methyl methacrylate-terminated polyphenylene ether resin; or a mixture of styrene-terminated polyphenylene ether resin and methyl methacrylate-terminated polyphenylene ether resin.

[0036] In a preferred embodiment of the present invention, the initiator is azobisisobutyronitrile.

[0037] A substrate, the substrate comprising:

[0038] The thermosetting resin composition is dissolved in an organic solvent, coated onto glass fiber cloth, and baked to obtain a semi-cured sheet; the organic solvent is specifically methyl ethyl ketone or toluene.

[0039] The prepreg is cut and then stacked with copper foil, and then pressed to obtain a substrate.

[0040] In a preferred embodiment of the present invention, the linear speed of the gluing machine during the gluing process is controlled to be 8-25 m / min.

[0041] In a preferred embodiment of the present invention, the baking temperature range is 110°C to 230°C.

[0042] In a preferred embodiment of the present invention, the cutting specifically involves cutting the prepreg into sheets of the same size, in groups of 1 to 20 sheets.

[0043] In a preferred embodiment of the present invention, the suppression parameters are as follows:

[0044] a. Pressure: 70–600 psi;

[0045] b. Temperature: 70~240℃;

[0046] c. Vacuum degree: 0.02~0.1Mpa;

[0047] d. Curing time: 50–130 min;

[0048] e. Compression time: 70-200 min.

[0049] In a preferred embodiment of the present invention, the substrate has the following dimensions: 36×48, 37×49, 40×48, 40.5×48.5, 41×49, 42.5×48.5, 43×49 (unit: inches).

[0050] In a preferred embodiment of the present invention, the glass fiber cloth is NE grade, with specifications of 1035, 1078, 1080, 2113, 2116, and 3313.

[0051] In a preferred embodiment of the invention, the copper foil is 1 / 3 oz, Hoz, 1 oz, 2 oz, 3 oz, 4 oz or RTF copper foil.

[0052] The beneficial effects of this invention are as follows:

[0053] This invention utilizes the special chain structure of polybutadiene-modified silicone resin, which gives it good toughness, compatibility, and chemical resistance; the silicon-oxygen bonds can also bond well with copper foil, improving the peel strength and other properties between the resin and the copper foil; the flame retardant can achieve excellent flame retardant performance by utilizing the phosphorus-silicon synergistic effect. Detailed Implementation

[0054] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below through embodiments. However, it should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of the invention. Furthermore, in the following descriptions, well-known structures and technologies are omitted to avoid unnecessarily obscuring the concept of the invention.

[0055] The design concept of this invention is as follows:

[0056] This invention utilizes the special chain structure of polybutadiene-modified silicone resin, which gives it good toughness, low permeability to air and moisture, better compatibility between resins, good strength and toughness, and excellent chemical resistance.

[0057] Silicon-oxygen bonds can also bond well with copper foil, improving the peel strength between the resin and the copper foil. They have a high affinity for olefin resins and, due to their high curing activity, also exhibit good chemical resistance, light resistance, and electrical properties. During combustion degradation, silicon can migrate to the polymer surface to form a protective layer rich in silicon-oxygen bonds and carbon-silicon bonds, effectively isolating oxygen and heat and thus inhibiting combustion.

[0058] During combustion and degradation, phosphorus promotes the formation of char layer and quenches the active groups of oxygen free radicals to achieve flame retardancy. Flame retardants can achieve excellent flame retardant performance by utilizing the phosphorus-silicon synergistic effect.

[0059] The specific structure and effects of the present invention will be described below with reference to Examples 1-6:

[0060] Table 1

[0061]

[0062]

[0063] The components involved in Table 1 are as follows:

[0064] Resin 1 is a modified polyphenylene ether resin:

[0065] SA9000: Sabik methyl methacrylate-terminated polyphenylene ether resin;

[0066] OPE-2ST2200: Mitsubishi Gas styrene-terminated polyphenylene ether resin;

[0067] Initiator: Azobisisobutyronitrile;

[0068] Crosslinking agent:

[0069] Ricon 181: Cray Valley Corporation butadiene-styrene copolymer;

[0070] Resin 2 is a polybutadiene-modified resin:

[0071] H1043: Asahi Kasei styrene-butadiene copolymer;

[0072] B2000: Polybutadiene from Nippon Soda;

[0073] B3000: Polybutadiene from Nippon Soda;

[0074] Polybutadiene-modified silicone resin: self-made;

[0075] The polybutadiene-modified silicone resins in Examples 1-6 were specifically prepared in the following manner:

[0076] 120 parts by weight of polybutadiene and 0.15 parts by weight of tetramethyldivinyldisiloxane platinum complex catalyst were stirred and mixed. The mixture was heated to 70°C and 15 parts by weight of trimethoxysilane were added dropwise. After the addition was completed, the temperature was raised to 80°C and maintained for 5 hours until the reaction was complete. Then the temperature was raised to 90°C, the solvent was removed under vacuum, and the mixture was cooled to 50°C to discharge the product, which yielded polybutadiene-modified silicone resin.

[0077] The specific tetramethyldivinyldisiloxane platinum complex catalyst used in this invention is IOTA-8100: tetramethyldivinyldisiloxane platinum complex from Anhui Aiyota Company;

[0078] BMI-70: KI bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane (Japan);

[0079] Flame retardant: PQ60, Chin I Chemical Co., Ltd., Taiwan, China;

[0080] Packing material: Inorganic packing material, silica fume, Zhejiang Sanshiji;

[0081] Glass cloth: L-Glass AST's 2116L;

[0082] Copper foil: Mitsui HS2 1oz.

[0083] Table 2

[0084]

[0085] The data in Tables 1 and 2 were measured using the following methods or standards:

[0086] Thermal stratification time: determined using a TMA instrument according to the T288 test method specified in IPC-TM-650 2.4.24.1;

[0087] Peel strength: Tested according to IPC-TM-6502.4.8 method;

[0088] Flame retardancy: Tested according to UL94 method.

[0089] Dielectric constant (Dk) and dielectric loss factor (Df): determined according to the SPDR method;

[0090] From Tables 1 and 2, in Examples 1-6, polybutadiene-modified silicone resin and phosphorus-containing flame retardant were used. This not only improved the dielectric properties and increased the adhesion between the copper foil and the resin, but also improved the peel strength of the substrate. The phosphorus-silicon combination also played a synergistic role, enabling the substrate to achieve a V-0 flame retardant rating.

[0091] Compared to Examples 1 / 2 / 3, Example 5 shows that using small amounts of polybutadiene-modified silicone resin and phosphorus-containing flame retardants only improves one property and cannot achieve optimal peel strength and flame retardant performance. However, the simultaneous use of silicon allows it to migrate to the polymer surface during combustion degradation, generating a protective layer rich in silicon-oxygen and carbon-silicon bonds, effectively isolating oxygen and heat and thus inhibiting combustion. Phosphorus, during combustion degradation, promotes char formation and quenches the active groups of oxygen free radicals, thereby improving the material's flame resistance, compatibility, peel strength, and heat resistance.

[0092] As described above, compared with ordinary laminates, the present invention uses polybutadiene-modified silicone resin and phosphorus-containing flame retardant, and the substrate has superior flame retardant properties, high peel strength, and excellent dielectric properties, which can be better applied in high-speed circuit boards.

[0093] The foregoing has shown and described the basic principles and main features of the invention and the advantages of the invention.

[0094] Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the present invention. Various changes and modifications can be made to the present invention without departing from its spirit and scope. All such changes and modifications fall within the scope of the present invention as claimed, which is defined by the appended claims and their equivalents.

Claims

1. A thermosetting resin composition, characterized in that, include: 5-40 parts of polybutadiene-modified resin; 3-30 parts of DOPO derivative flame retardant; 20-70 parts of modified polyphenylene ether resin; 15-20 parts crosslinking agent; 1-2 parts initiator; 60-70 parts silica powder; The polybutadiene-modified resin is specifically a mixture of polybutadiene-modified silicone resin, bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane, and polybutadiene; Alternatively, a mixture of polybutadiene-modified silicone resin, bis(3-ethyl-5-methyl-4-maleimide-phenyl)methane, polybutadiene, and styrene-butadiene copolymer; wherein the polybutadiene-modified silicone resin is prepared from polybutadiene resin and trimethoxysilane, and the specific preparation method is as follows: The trimethoxysilane was added dropwise to the polybutadiene resin; The double bond content in the polybutadiene resin and the molar ratio of silane groups in trimethoxysilane are 1:0.80-1:1.20, and the dropping time is 25-70 min. The polybutadiene resin has the structure shown in Formula 1: Formula 1; Where X is an integer from 1 to 50, and Y is an integer from 1 to 50; The number-average molecular weight of the polybutadiene resin is 800-20000 g / mol; The polybutadiene resin has a Brookfield viscosity of 2300-15000 cps.

2. The thermosetting resin composition according to claim 1, characterized in that, The structure of the DOPO derivative flame retardant is shown in Formula 2 below: Formula 2; Z is any one of the following equations 3, 4, 5, and 6: Formula 3; Equation 4; Formula 5; Formula 6; In Equation 6, m is an integer from 1 to 50.

3. The thermosetting resin composition according to claim 1, characterized in that, The modified polyphenylene ether resin is a modified thermosetting polyphenylene ether resin, specifically an olefin-modified thermosetting polyphenylene ether resin.

4. The thermosetting resin composition according to claim 1, characterized in that, The initiator is azobisisobutyronitrile.

5. A substrate, characterized in that, The substrate includes: The thermosetting resin composition as described in any one of claims 1-4 is dissolved in an organic solvent, coated onto a glass fiber cloth, and baked to obtain a semi-cured sheet. The prepreg is cut and then stacked with copper foil, and then pressed to obtain a substrate.

6. A substrate as described in claim 5, characterized in that, The linear speed of the gluing machine during the gluing process is controlled at 8-25 m / min; The baking temperature range is 110℃~230℃; The cutting process specifically involves cutting the prepreg into pieces of the same size, in groups of 1 to 20 pieces.

7. A substrate as described in claim 5, characterized in that, The suppression parameters are as follows: a. Pressure: 70–600 psi; b. Temperature: 70~240℃; c. Vacuum degree: 0.02~0.1 MPa; d. Curing time: 50–130 min; e. Compression time: 70-200 min.

8. A substrate as described in claim 5, characterized in that, The substrate has the following dimensions: 36×48, 37×49, 40×48, 40.5×48.5, 41×49, 42.5×48.5, and 43×49, in inches.

9. A substrate as described in claim 5, characterized in that, The fiberglass cloth is NE grade, with specifications of 1035, 1078, 1080, 2113, 2116, and 3313. The copper foil is 1 / 3 oz, Hoz, 1 oz, 2 oz, 3 oz, 4 oz or RTF copper foil.

Images