Resin composition

Abstract

To provide materials for high-frequency printed circuit boards that have both high glass transition temperature and low dielectric loss tangent, as well as excellent electrical properties.SOLUTION: The disclosure provides a resin composition which includes: 30 wt.% to 60 wt.% of a bismaleimide resin; 1 wt.% to 10 wt.% of a liquid rubber resin; and 20 wt.% to 50 wt.% of a filler, based on the total weight of the resin composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition, and in particular to a resin composition. [Background technology]

[0002] With the recent development of 5G and millimeter-wave communications, higher frequencies (6-77 GHz) have been applied to mobile phones, base stations, servers, and other devices. This necessitates the use of higher-frequency circuit board materials suitable for 5G high frequencies. In addition, copper-clad circuit boards must also be developed to lower their dielectric properties. While current low-dielectric formulations can incorporate a specific proportion of liquid rubber to reduce the dielectric loss tangent to less than 0.0020, they have low glass transition temperatures. Therefore, one of the most pressing issues in the field of printed circuit boards is how to develop materials that possess both high glass transition temperatures and low dielectric loss tangents, which are essential for high-frequency printed circuit boards, as well as excellent electrical properties. Summary of the Invention [Problem to be solved by the invention]

[0003] The present invention provides a resin composition, comprising 30% by weight to 60% by weight of a compound selected from the group consisting of hydroxybenzoates, ... Maleimide It contains a resin, 1% by weight to 10% by weight of a liquid rubber resin, and 20% by weight to 50% by weight of a filler. [Means for solving the problem]

[0004] In one embodiment of the present invention, Maleimide The resin includes DCPD-BMI, KI-50P, KI-70, or a combination thereof.

[0005] In one embodiment of the invention, the liquid rubber resin comprises LDM-03-07, LDM-02, 1,2-SBS, or a combination thereof.

[0006] In one embodiment of the present invention, the resin composition further comprises 0.1% by weight to 3% by weight of a coupling agent and 0.1% by weight to 2% by weight of a catalyst.

[0007] In one embodiment of the present invention, the resin composition further contains 10% by weight to 20% by weight of a flame retardant.

[0008] The present invention provides an electronic component including a substrate formed from the resin composition.

[0009] In one embodiment of the present invention, the glass transition temperature of the substrate is 250° C. or higher.

[0010] In one embodiment of the invention, the substrate has a dissipation factor of less than or equal to 0.002 at a frequency of about 10 GHz.

[0011] In one embodiment of the invention, the substrate has a dielectric constant of less than or equal to 3.2 at a frequency of about 10 GHz.

[0012] In one embodiment of the present invention, the substrate is a copper foil substrate. [Effects of the Invention]

[0013] Based on the above, when the resin composition of the present invention is applied to a copper foil substrate, it can achieve a high glass transition temperature (250°C or higher) and a low dielectric loss tangent (0.002 or lower). In addition, since the resin composition of the present invention has a non-polar skeleton structure, it is difficult to polarize in an electric field, thereby significantly reducing the dielectric constant (3.2 or lower). DETAILED DESCRIPTION OF THE INVENTION

[0014] The following describes in detail the embodiments of the present invention. The implementation details provided in the embodiments are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. Those skilled in the art can modify or change these implementation details according to the requirements of actual implementation.

[0015] Ranges may be expressed herein as from "about" one particular value to "about" another particular value, which may be expressed directly as the one particular value and / or the other particular value. When a range is expressed, in another embodiment, it includes the one particular value and / or to the other particular value. Similarly, when values ​​are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each range may or may not be expressly related to the other endpoint.

[0016] In this embodiment, non-limiting terms (eg, may, can, or similar terms) refer to non-essential or optional implementations, inclusions, additions, or presences.

[0017] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by a person skilled in the art to which this invention belongs. Furthermore, it should be understood that terms (e.g., terms defined in commonly used dictionaries) should be interpreted to have a meaning consistent with the meaning in the relevant technical context, and should not be interpreted in an idealized or overly formal sense unless explicitly defined.

[0018] As used herein, a so-called "divalent organic group" is an organic group that has two bonding positions, and the "divalent organic group" can form two chemical bonds via these two bonding positions.

[0019] The present invention provides a resin composition, comprising 30% by weight to 60% by weight of a compound selected from the group consisting of hydroxybenzoates, ... Maleimide The present invention comprises a (BMI) resin, 1% by weight to 10% by weight of a liquid rubber resin, and 20% by weight to 50% by weight of a filler. Maleimide The resin is combined with a liquid rubber resin and a filler, which can improve the heat resistance of the high frequency substrate material and reduce the dielectric loss tangent of the high frequency substrate material.

[0020] In some embodiments, based on the total weight of the resin composition: Maleimide The weight percentage of the resin is between 30% and 60% by weight, such as 35%, 45%, or 55% by weight.

[0021] In some embodiments, Maleimide The resin has a structure represented by the following formula (1): [ka] Here, L represents a dicyclopentadienyl group, a divalent organic group derived from a phenolic compound, or a combination thereof; 1 and L 2 represents a divalent organic group derived from a phenol compound, and m represents an integer of 0 to 18.

[0022] In some embodiments, the phenolic compound includes phenol. In some embodiments, the divalent organic group is preferably a divalent organic group including a maleimide group. In some embodiments, L is preferably a combination of dicyclopentadienyl and a divalent organic group derived from a phenolic compound. In some embodiments, L represents the following formula (1-1), the following formula (1-2), the following formula (1-3), or a combination thereof: * represents the attachment point. In some embodiments, L 1 and L 2 respectively represent the following formula (1-4): * represents the bond position. [ka]

[0023] In some embodiments, Maleimide The resin has a structure represented by the following formula (2): [ka] Here, m represents an integer of 0 to 18, and is preferably 2 to 10.

[0024] for example, Maleimide The resin synthesis method includes the following: First, 1 mole of dicyclopentadiene phenol resin (manufactured by Songyuan Co., Ltd., trade name ERM6140, weight average molecular weight 1,300) and 1.25 moles of 4-halonitrobenzene (wherein the halogen can be fluorine, chlorine, bromine, or iodine) are added to 6 moles of dimethylacetamide (DMAC) used as a reaction solution, and the mixture is reacted at a temperature of 120°C for 300 minutes to carry out a nitration reaction. Next, hydrogen gas is introduced to form a modified dicyclopentadiene-type diamine, and the mixture is reacted at a temperature of 90°C for 480 minutes to carry out a hydrogenation reaction. Next, a dicyclopentadiene-type diamine whose main chain contains a dicyclopentadiene structure (abbreviated as DCPD-BMI) has a structure represented by formula (2), and the average molecular weight may be 800 to 10,000, preferably 1,000 to 4,000. Maleimide To produce the second resin, 3 moles of maleic anhydride and 9.7% by weight of toluenesulfonic acid are added and reacted at a temperature of 120° C. for 420 minutes.

[0025] In some embodiments, the weight percentage of the liquid rubber resin is 1 wt % to 10 wt %, such as 2 wt %, 5 wt %, or 8 wt %, based on the total weight of the resin composition. In some embodiments, the liquid rubber resin comprises LDM-03-07, LDM-02, 1,2-SBS, or a combination thereof.

[0026] In some embodiments, the weight percentage of the filler is 20 wt% to 50 wt%, such as 30 wt%, 35 wt%, or 40 wt%, based on the total weight of the resin composition. In some embodiments, the filler is spherical, and the particle size (D50) of the filler is 0.3 μm to 3 μm. In some embodiments, the filler has a maximum particle size (D99) of 10 μm or less. In some embodiments, the filler includes a surface modification such as acrylic or vinyl. In some embodiments, the filler is SiO2, a filler provided by Third Age Technology.

[0027] In some embodiments, the resin composition further comprises a coupling agent. In some embodiments, the weight percentage of the coupling agent is 0.1 wt % to 3 wt %, such as 0.5 wt %, 1 wt %, or 1.5 wt %, based on the total weight of the resin composition. The addition of a coupling agent can improve the compatibility and degree of crosslinking of the resin composition with the glass fiber cloth or powder. In some embodiments, the content of the coupling agent in the resin composition is 0.1 parts per hundred parts by weight (phr) to 3 phr. In some embodiments, the content of the coupling agent in the resin composition is about 1 phr. In some embodiments, the coupling agent is a siloxane coupling agent. In some embodiments, the coupling agent is a vinyl silane or an acrylic silane. In some embodiments, the coupling agent is a coupling agent available from DOW under the trade name Z-6030.

[0028] In some embodiments, the resin composition further comprises a flame retardant. In some embodiments, the weight percentage of the flame retardant is 10% to 20% by weight, such as 12%, 15%, or 18% by weight, based on the total weight of the resin composition. In some embodiments, the flame retardant is a phosphorus-based flame retardant. In some embodiments, the flame retardant is a flame retardant available from Daihachi Chemical Industry Co., Ltd. under the trade name PX200.

[0029] In some embodiments, the resin composition further comprises a catalyst. In some embodiments, the weight percentage of the catalyst is 0.1 wt % to 2 wt %, such as 0.5 wt %, 1 wt %, or 1.5 wt %, based on the total weight of the resin composition. In some embodiments, the content of the catalyst in the resin composition is preferably 0.5 phr to 1.2 phr. In some embodiments, the catalyst is a catalyst available from ARKEMA under the trade name DCP.

[0030] The resin composition of the present invention is suitable for forming a substrate for an electronic component. In some embodiments, the substrate is a copper foil substrate. In some embodiments, the substrate has the following specifications: a glass transition temperature (Tg) greater than 250°C (e.g., about 250°C to 260°C) and a dielectric loss tangent (Df) of about 0.02 or less. In some embodiments, the dielectric constant (Dk) of the substrate is about 3.2 or less (e.g., about 3.0 to 3.15). In some embodiments, the peel strength of the substrate is about 4.5 lb / in (e.g., about 4.5 lb / in to 5.2 lb / in). In some embodiments, the heat resistance of the substrate passes a test.

[0031] The implementation and effects of the present invention will be described in detail below using copper foil substrates made of resin compositions of the present embodiment and comparative examples, although the present invention is not limited to the following embodiments and comparative examples.

[0032] Based on the composition ratios in Table 1 below, the resin composition is mixed with MEK to form a varnish of the thermosetting resin composition. The resulting varnish is applied to Nanya glass fiber cloth (NANYA The prepreg was impregnated into a cloth (Plastics Industry Co., Ltd., cloth model 1078LD) and then dried at about 130 °C (the temperature of the impregnation machine) for several minutes to obtain a prepreg with a resin content of 60 wt%. After that, four pieces of prepreg were laminated between two pieces of copper foil with a thickness of about 35 μm and a pressure of 25 kg / cm. 2 The temperature is maintained at 85°C under pressure for 20 minutes, heated to 210°C at a heating rate of 3°C per minute, maintained at a constant temperature for 120 minutes, and then slowly cooled to 130°C to produce a 0.5 mm thick copper foil substrate.

[0033] In Examples 1 to 6, the "DCPD-BMI" used has a structure represented by formula (2): Maleimide It is a resin (DCPD-MI).

[0034] In Examples 2 to 4, "KI-50P" and "KI-70" are the trade names of the KI-50P and KI-70 series sold by KI Kasei Co., Ltd., respectively. Maleimide It is a resin.

[0035] In Examples 1, 2, 4, 5, and Comparative Example 5, "LDM-03-07" and "LDM-02" used are liquid rubber resins of the LDM-03-07 and LDM-02 series, respectively, sold by Dainippon Ink and Chemicals, Inc.

[0036] In Examples 3 and 6, Comparative Examples 1, 3, and 5, the "1,2-SBS" used is a liquid rubber resin sold by Nippon Soda under the trade name 1,2-SBS series.

[0037] In Comparative Examples 1 to 6, "RI 257" and "RI 184" used are liquid rubber resins of the RI 257 and RI 184 series, respectively, sold by CRAY VALLEY.

[0038] In Examples 1 to 6 and Comparative Examples 1 to 6, the "PX200" used is a flame retardant in the PX200 series, a trade name sold by Daihachi Chemical Industry Co., Ltd.

[0039] In Examples 1 to 6 and Comparative Examples 1 to 6, the "DCP" used is a catalyst sold by ARKEMA under the trade name DCP series.

[0040] In Examples 1 to 6 and Comparative Examples 1 to 6, the "Z-6030" used is a siloxane coupling agent of the Z-6030 series, a trade name sold by DOW.

[0041] In Examples 1 to 6 and Comparative Examples 1 to 6, the SiO2 used is an SiO2 filler sold by Third Age Technology.

[0042] The copper foil substrates were evaluated for properties such as glass transition temperature, dielectric constant, dielectric loss tangent, peel strength, and heat resistance by the methods described below. The evaluation results are shown in Table 1.

[0043] Glass transition temperature (Tg)

[0044] The glass transition temperature (Tg) of the resin composition in the copper foil substrate was measured using a dynamic mechanical analyzer (DMA). A high Tg indicates that the resin composition has a good ability to resist phase change, i.e., good heat resistance.

[0045] Dielectric constant (Dk)

[0046] The dielectric constant at a frequency of about 10 GHz was measured using a dielectric analyzer (Model E4991A, manufactured by Agilent Technologies, Inc.) A small dielectric constant indicates that the resin composition in the copper foil substrate has good dielectric properties.

[0047] Dissipation factor (Df)

[0048] The dielectric loss tangent at a frequency of about 10 GHz was measured using a dielectric analyzer (Model E4991A, manufactured by Agilent Technologies, Inc.) A small dielectric loss tangent indicates that the resin composition in the copper foil substrate has good dielectric properties.

[0049] Peel strength

[0050] The peel strength between the prepreg and the copper foil was tested according to the IPC-TM-650-2.4.8 test method.

[0051] heat resistance

[0052] The copper foil substrate samples were heated in a pressure cooker at 120°C and 2 atm pressure for 120 minutes, then immersed in a soldering oven at 288°C, and the time required for the board to burst was recorded. Boards that took longer than 10 minutes to burst were marked as OK, and boards that took less than 10 minutes were marked as NG.

[0053] [Table 1] JPEG0007731408000004.jpg225150JPEG0007731408000005.jpg30150

[0054] <Evaluation results>

[0055] From Examples 1 to 6 in Table 1, it can be seen that the copper foil substrates made from the resin compositions having the component ratios of the present invention have Tg values ​​higher than 250°C, dielectric loss tangents Df less than 0.002, and dielectric constants Dk less than 3.2. Furthermore, the copper foil substrates of Examples 1 to 6 also exhibit good peel strength (≧4.5 lb / in) and good heat resistance.

[0056] From Comparative Examples 1 to 6 in Table 1, Maleimide It can be seen that when the weight percentage of the resin is less than 30% by weight or more than 60% by weight, the measured Tg values ​​are all lower than 250° C. In addition, it can be seen from Comparative Examples 1, 3, and 5 that when the weight percentage of the liquid rubber resin is higher than 10% by weight, the measured Tg is lower than 165° C., and the peel strength and heat resistance performance are poor. [Industrial Applicability]

[0057] In summary, the resin composition of the present invention is Maleimide The resin composition of the present invention, which is used together with a liquid rubber resin as the main structure, not only provides a high glass transition temperature and a low dielectric loss tangent, but also a non-polar skeletal structure. This makes it less likely to polarize in an electric field, thereby significantly reducing the dielectric constant. Additionally, the resin composition of the present invention can be applied directly or indirectly to copper foil substrates and further processed into other consumer, industrial, or suitable electronic components or products (e.g., circuit boards or copper foil substrates). Furthermore, when applied to copper foil substrates, the resin composition of the present invention contributes to a lower dielectric loss tangent, improved peel strength, and / or improved heat resistance.

Claims

1. Based on the total weight of the resin composition, 30% to 60% by weight of a maleimide resin; 1% by weight to 10% by weight of a liquid rubber resin; 20% to 50% by weight of a filler; Including, The maleimide resin has a structure represented by the following formula: 【Chemical 1】 In the formula, m represents an integer of 0 to 18. Resin composition.

2. The liquid rubber resin contains a compound represented by the following formula: 【Chemistry 2】 In the formula, the ratio of o to p to q is 1:8:1, the sum of a and b is 100%, and a / (a +b) is 80% or more, the number average molecular weight is 4500, and the viscosity measured at 45°C is is 1200 poise, The resin composition according to claim 1.

3. further comprising 0.1 wt% to 3 wt% of a coupling agent and 0.1 wt% to 2 wt% of a catalyst; The resin composition according to claim 1.

4. further comprising 10% to 20% by weight of a flame retardant; The resin composition according to claim 3.

5. A prepreg formed from the resin composition according to claim 1 and glass fiber cloth; and two pieces of copper foil, the prepreg being positioned between the two pieces of copper foil. Electronic components.

6. The glass transition temperature of the substrate is 250°C or higher. The electronic component according to claim 5 .

7. the substrate has a dielectric loss tangent of 0.002 or less at a frequency of 10 GHz; The electronic component according to claim 5 .

8. The substrate has a dielectric constant of 3.2 or less at a frequency of 10 GHz. The electronic component according to claim 5 .

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