Resin composition

Abstract

To provide a resin composition that meets all requirements such as short-circuit testing, low water absorption, and low dielectric properties.SOLUTION: A resin composition according to the present invention includes a resin. The resin includes a benzoxazine resin, an epoxy resin, and a modified maleimide resin. The modified maleimide resin is formed from a dicyclopentadiene (DCPD)-based resin having an amino group and a maleic anhydride through condensation polymerization. The dicyclopentadiene-based resin having an amino group is formed through the nitration and hydrogenation of a dicyclopentadiene phenolic resin.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin composition. [Background technology]

[0002] In recent years, with the development of 5G communication technology, there is an increasing demand for reliability and electrical performance of electronic substrates such as printed circuit boards. Therefore, one of the goals to be achieved by those skilled in the art is to develop a resin composition that can satisfy short circuit tests (such as CAF (Conductive Anodic Filament) tests), low water absorption, and low dielectric properties, and to make electronic substrates manufactured using the resin composition competitive. Summary of the Invention [Problem to be solved by the invention]

[0003] The present invention provides a resin composition that can satisfy all the requirements such as short circuit test, low water absorption, low dielectric property, etc. Therefore, such a resin composition has a competitive edge. [Means for solving the problem]

[0004] The resin composition includes a resin. The resin includes a benzoxazine resin, an epoxy resin, and a modified maleimide resin. The modified maleimide resin is formed by condensing a dicyclopentadiene (DCPD) resin having an amino group with maleic anhydride. The dicyclopentadiene resin having an amino group is formed by nitrating and hydrogenating a dicyclopentadiene phenol resin.

[0005] In one embodiment of the present invention, the modified maleimide resin has the following structural formula: [ka] In the formula, L represents a dicyclopentadienyl group, a divalent organic group derived from a phenol compound, or a combination thereof. 1 and L2 each represents a divalent organic group derived from a phenol compound. m represents an integer of 0 to 18.

[0006] In one embodiment of the present invention, the weight ratio of the modified maleimide resin to the total weight of the resin in the resin composition is in the range of 40% by weight to 80% by weight.

[0007] In one embodiment of the present invention, the weight ratio of the benzoxazine resin to the total weight of the resins in the resin composition is in the range of 10% by weight to 30% by weight.

[0008] In one embodiment of the present invention, the weight ratio of the epoxy resin to the total weight of the resin in the resin composition is in the range of 5% by weight to 20% by weight.

[0009] In one embodiment of the present invention, the resin composition further comprises a catalyst, a flame retardant, silicon dioxide, a siloxane coupling agent, or a combination thereof.

[0010] In one embodiment of the present invention, the amount of catalyst used is 0.05 phr to 2 phr.

[0011] In one embodiment of the present invention, the amount of flame retardant used is 10 phr to 30 phr.

[0012] In one embodiment of the present invention, the weight ratio of silicon dioxide used is 30% to 50% by weight.

[0013] In one embodiment of the present invention, the amount of siloxane coupling agent used is 0.1 phr to 5 phr. Effect of the Invention

[0014] Based on the above, the resin composition of the present invention is formed by selecting a bismaleimide (BMI) resin, which has excellent performance in short circuit tests, as the main structure system. Furthermore, in order to achieve good dielectric properties and water absorption, the resin composition of the present invention further modifies the molecular structure of the maleimide resin to obtain a modified maleimide resin containing a dicyclopentadiene structure in the main chain, and combines this modified maleimide resin with other resins (such as benzoxazine resins and epoxy resins). In this way, the requirements for short circuit tests, low water absorption, low dielectric properties, etc. can all be met, and the resin composition can be competitive.

[0015] In order to make the above mentioned features and advantages of the present invention more clear and understandable, the following embodiments are described in specific details. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Hereinafter, embodiments of the present invention will be described in detail, however, these embodiments are merely examples and the present invention is not limited to these embodiments.

[0017] In this specification, the ranges indicated as "a certain value to another value" are general expressions to avoid listing all the values ​​within the range, and therefore, the description of a specific numerical range includes any value within that numerical range and any smaller numerical range enclosed by any value within that numerical range, just as if the specification contained any numerical value and any smaller numerical range.

[0018] In the present invention, a "divalent organic group" is an organic group having two bonding positions, and the "divalent organic group" may form two chemical bonds via these two bonding positions.

[0019] In this embodiment, the resin composition includes a benzoxazine resin, an epoxy resin, and a modified maleimide resin. The modified maleimide resin is formed by condensing a dicyclopentadiene resin having an amino group with maleic anhydride, and the dicyclopentadiene resin having an amino group is formed by nitrating and hydrogenating a dicyclopentadiene phenol resin. As described above, the resin composition of the present invention is formed by selecting a bismaleimide (BMI) resin having excellent performance in a short circuit test as a main structure system. Furthermore, in order to achieve good dielectric properties and water absorption, the molecular structure of the maleimide resin is further modified to obtain a modified dicyclopentadiene bismaleimide (dicyclopentadiene maleimide, DCPD-BMI) containing a dicyclopentadiene structure in the main chain, and this modified maleimide resin is combined with other resins (benzoxazine resin, epoxy resin, etc.). In this way, all requirements such as short circuit test, low water absorption, and low dielectric properties can be met, and the resin composition can be competitive.

[0020] Furthermore, the selection and modification of the resins of the present invention creates a synergistic effect in the molecular structures of these resins. In this way, the situation of poor performance in short circuit tests when polyphenylene ether (PPE) is used as the main structural system in current applications (such as low dielectric constant copper clad laminates) can be avoided. At the same time, the reliability performance of unmodified maleimide resin can be effectively improved. For example, the glass transition temperature of the substrate made of the resin composition of the present invention is higher than 220°C, the dielectric constant (Dk) is 3.3 to 3.7, and the dielectric loss (Df) is less than 0.004, but the present invention is not limited thereto.

[0021] In some embodiments, the resin composition may be, but is not limited to, free of polyphenylene ether resin to further reduce the adverse effect of polyphenylene ether resin in short circuit testing.

[0022] The specific contents of the modified maleimide resin, benzoxazine resin, and epoxy resin will be described in detail below.

[0023] Modified Maleimide Resin

[0024] In some embodiments, examples of commercially available dicyclopentadiene resins having phenolic groups include ERM6140 (trade name, manufactured by SONGWON, weight average molecular weight 1300), ERM6105 (trade name, manufactured by SONGWON, weight average molecular weight 800), ERM6115 (trade name, manufactured by SONGWON, weight average molecular weight 1100), or other suitable dicyclopentadiene phenolic resins.

[0025] In some embodiments, the weight ratio of the modified maleimide resin to the resin ranges from 40% by weight to 80% by weight, although the invention is not limited thereto.

[0026] Method for preparing modified maleimide resin

[0027] First, the dicyclopentadiene phenol resin was subjected to a nitration reaction and a hydrogenation reaction to form a dicyclopentadiene resin having an amino group. The method of performing the nitration and hydrogenation reaction of the dicyclopentadiene phenol resin is not particularly limited in the present invention. For example, a known nitration and hydrogenation method can be adopted, but detailed description is omitted here. Next, the dicyclopentadiene resin having an amino group was subjected to a condensation polymerization reaction with maleic anhydride to form a modified maleimide resin. In this embodiment, the equivalent ratio of the number of moles of the amino group of the dicyclopentadiene resin having an amino group to the number of moles of the maleic anhydride group of the maleic anhydride is 1:1 to 1:10, preferably 1:1 to 1:3.

[0028] The modified maleimide resin has a structure represented by the following formula (1): In this embodiment, the weight average molecular weight of the modified maleimide resin is 800-10,000, and preferably 1,000-4,000.

[0029] [ka]

[0030] In formula (1), L represents a dicyclopentadienyl group, a divalent organic group derived from a phenol compound, or a combination thereof, and is preferably a combination of a dicyclopentadienyl group and a divalent organic group derived from a phenol compound, and the divalent organic group is preferably a divalent organic group containing a maleimide group. L 1 and L 2 each represents a divalent organic group derived from a phenol compound. m represents an integer of 0 to 18, and preferably 2 to 10.

[0031] L,L 1 and L 2 represents a divalent organic group derived from phenol. In this embodiment, L represents the compounds shown below or a combination thereof. * represents a bonding position. [ka] L preferably represents a combination of the following compounds: * represents a bonding position. [ka] L 1 and L 2 may represent the compounds shown below, respectively. * represents a bond position. [ka]

[0032] In this embodiment, the modified maleimide resin has a structure represented by the following formula (2): In this embodiment, the modified maleimide resin is a modified multi-maleimide resin.

[0033] [ka]

[0034] In the formula (2), m represents an integer of 0 to 18, and preferably 2 to 10.

[0035] Benzoxazine resin and epoxy resin

[0036] In some embodiments, the benzoxazine resin may be a commercially available BZ resin, but the present invention is not limited thereto. Epoxy resins can be classified into various types of epoxy resins according to the difference in the main skeleton. For example, various epoxy resins can be further classified into bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins; novolac type epoxy resins such as biphenyl aralkyl novolac type epoxy resins, phenol novolac type epoxy resins, alkylphenol novolac type epoxy resins, cresol novolac type epoxy resins, naphthol alkylphenol copolymer novolac type epoxy resins, naphthol aralkyl cresol copolymer novolac type epoxy resins, bisphenol A novolac type epoxy resins, and bisphenol F novolac epoxy resins; stilbene type epoxy resins; epoxy resins having a triazine skeleton; epoxy resins having a fennel skeleton; naphthalene type epoxy resins; anthracene type epoxy resins; triphenylmethane type epoxy resins; biphenyl type epoxy resins; xylene type epoxy resins; and alicyclic epoxy resins such as dicyclopentadiene type epoxy resins.

[0037] In some embodiments, the weight ratio of the benzoxazine resin to the total weight of the resin in the resin composition is in the range of 10% by weight to 30% by weight, although the invention is not limited thereto.

[0038] In some embodiments, the weight ratio of the epoxy resin to the total weight of the resin in the resin composition is in the range of 5% by weight to 20% by weight, although the present invention is not limited thereto.

[0039] In some embodiments, the resin composition only adopts modified maleimide resin. That is, in order to achieve better water absorption and dielectric properties, the resin composition may not contain unmodified maleimide resin, but the present invention is not limited thereto. In other embodiments, according to the actual application and product requirements, the resin composition may further include unmodified maleimide resin, that is, the resin composition may include unmodified maleimide resin and modified maleimide resin at the same time, where the unmodified maleimide resin may be commercially available products such as BMI-50P, KI-70, etc., but the present invention is not limited thereto.

[0040] In some embodiments, when the resin composition contains an unmodified maleimine resin, the combined weight ratio of the unmodified maleimine resin and the modified maleimine resin to the total weight of the resin in the resin composition is in the range of 40% by weight to 80% by weight, although the present invention is not limited thereto.

[0041] In some embodiments, the resin composition further comprises a catalyst, a flame retardant, silica, a siloxane coupling agent, or a combination thereof, where the amount of catalyst used is 0.05 phr to 2 phr, and the amount of flame retardant used is 10 phr to 30 phr. The weight ratio of silica to the weight of resin, flame retardant, and silica in the resin composition is in the range of 30 wt% to 50 wt%. The amount of siloxane coupling agent used is in the range of 0.1 phr to 5 phr, but the present invention is not limited thereto. Here, the unit of "phr" can be defined as parts by weight of other materials added per 100 parts by weight of resin in the resin composition. The weight ratio of silicon dioxide is based on the weight of the resin in the resin composition plus the weight of the flame retardant.

[0042] In some embodiments, the catalyst may be 2-ethyl 4-methylimidazole (2E4MZ; CAS: 931-36-2) to catalyze better reaction of the resin during thermal curing, but the present invention is not limited thereto. [ka]

[0043] In some embodiments, the flame retardant is a halogen-free flame retardant, and a specific example may be a phosphorus-based flame retardant. The phosphorus-based flame retardant may be selected from phosphoric acid esters such as triphenyl phosphate (TPP), resorcinol diphosphate (RDP), bisphenol A bis(diphenyl)phosphate (BPAPP), bisphenol A bis(dimethyl)phosphate (BBC), resorcinol diphosphate (CR-733S), resorcinol-bis(di-2,6-dimethylphenylphosphate) (PX-200), and phosphazenes such as polybis(phenoxy)phosphazene (SPB-100), and may be selected from ammonium polyphosphate, melamine polyphosphate (Melamine Polyphosphate, MPP), melamine cyanurate (Melamine Polyphosphate, MPP), and melamine cyanurate (Melamine Polyphosphate, MPP). cyanurate; a combination of two or more of DOPO flame retardants such as DOPO (e.g., having structural formula (C)), DOPO-HQ (e.g., having structural formula (D)), and bisDOPO derivative structures (e.g., having structural formula (E)); or an aluminum-containing hypophosphite (e.g., having structural formula (F)). [ka]

[0044] In some embodiments, the silicon dioxide (or "silica" in some examples) is preferably spherical silica, prepared using a synthesis method to reduce electrical properties and maintain flowability and gel-filling properties, where the spherical silica is surface-modified with acrylic or vinyl, has a purity of about 99.0% or more, and has an average particle size (D50) of about 2.0 μm to 3.0 μm, but the invention is not limited thereto. Other suitable methods can also be used to produce the silica.

[0045] In some embodiments, the siloxane coupling agent may include, for example, a siloxane compound. According to the type of functional group, the siloxane coupling agent may be divided into an aminosilane compound, an epoxysilane compound, a vinylsilane compound, an estersilane compound, a hydroxylsilane compound, an isocyanatesilane compound, a methacryloxysilane compound, and an acryloxysilane compound, and improves the compatibility and crosslinking degree between the glass fiber cloth and the powder in the circuit board, but the present invention is not limited thereto.

[0046] It should be noted that the resin composition of the present invention can be processed into prepreg and copper foil substrate (or in some instances, called "copper clad laminate (CCL)") according to actual design requirements, and the specific embodiments listed above are not intended to limit the present invention, as long as the resin composition system includes a benzoxazine resin, an epoxy resin, and a modified maleimide resin that fall within the protection scope of the present invention.

[0047] The effects of the present invention will be described below with reference to examples and comparative examples, but the scope of the present invention is not limited to these examples.

[0048] The copper foil substrates of the examples and comparative examples were evaluated according to the following methods.

[0049] "Glass transition temperature (°C)": Measured using a dynamic mechanical analyzer (DMA).

[0050] "Water absorption rate (%)": Calculated from the change in weight of the sample before and after heating the sample in a pressure cooker at 120°C and 2 atmospheres for 120 minutes.

[0051] "288°C solder heat resistance (seconds)": The sample was heated at 120°C in a pressure cooker at 2 atmospheres for 120 minutes, then immersed in a soldering furnace at 288°C, and the time until the sample exploded / peeled off was recorded.

[0052] "Dielectric constant Dk": Measured by testing the dielectric constant at a frequency of 10 GHz using a dielectric constant analyzer (model HP Agilent E4991A).

[0053] "Dielectric loss Df": Measured by testing the dielectric loss at a frequency of 10 GHz using a dielectric analyzer (model HP Agilent E4991A).

[0054] CAF test: The test conditions for the copper foil substrate were temperature and humidity 85°C / 85% RH, voltage 50V, time >1000 hours, opening: 0.35 mm, and opening interval: 0.3 mm.

[0055] <Examples 1 to 3, Comparative Examples 1 to 2>

[0056] Each resin composition shown in Table 1 was mixed with toluene to prepare a thermosetting resin composition varnish. This varnish was impregnated into Nanya glass fiber cloth (Cloth Type 1078LD, Nanya Plastics Co., Ltd.) at room temperature. It was then dried at 130°C (in an impregnation device) for several minutes to obtain a prepreg with a resin content of 70% by weight. Finally, four sheets of this prepreg were laminated between two layers of copper foil with a thickness of 35 μm, and the laminate was heated at a pressure of 25 kg / cm. 2The temperature was then raised to 210°C at a rate of 3°C / min, and the temperature was then held at a constant temperature for 120 minutes. The temperature was then gradually lowered to 130°C to obtain a copper foil substrate with a thickness of 0.59 mm. The modified maleimide resin in Table 1 was obtained by the following steps. Approximately 1 mole of dicyclopentadiene phenol resin containing hydroxyl groups (product name ERM6140, manufactured by SONGWON, weight average molecular weight 1,300) and approximately 1.25 moles of 4-halogen nitrobenzene (halogen may be fluorine, chlorine, bromine or iodine) were added to approximately 6 moles of dimethylacetamide (DMAC) as a reaction solvent, and the mixture was reacted at approximately 120°C for approximately 300 minutes to perform a nitration reaction. Next, hydrogen gas was introduced, and the mixture was reacted at a temperature of approximately 90°C for approximately 480 minutes to perform a hydrogenation reaction, forming a dicyclopentadiene resin having amino groups. Then, about 3 moles of maleic anhydride and about 9.7 weight % (wt%) of toluenesulfonic acid were added and reacted at a temperature of about 120°C for about 420 minutes to obtain the modified maleimide resin shown in Table 1. The modified maleimide resin is a maleimide resin (DCPD-MI, manufactured by our company) containing a dicyclopentadiene structure in the main chain and has the following structure (m represents an integer of 0 to 18). [ka]

[0057] The physical properties of the produced copper foil substrate were tested. The results are shown in Table 1. Comparing the results of Examples 1 to 3 and Comparative Examples 1 and 2 in Table 1, the following can be seen. Comparative Example 1 is a structure based on polyphenylene ether, and has poor performance in the short circuit (CAF) test, making it prone to short circuit conduction problems. Comparative Example 2 uses only unmodified maleimide resin, and is therefore inferior in water absorption and dielectric properties. All of Examples 1 to 3 passed the short circuit test, achieving both low water absorption and low dielectric properties.

[0058] [Table 1] JPEG2025035978000011.jpg38161

[0059] From the above, the resin composition of the present invention is formed by selecting a bismaleimide (BMI) resin, which has excellent performance in a short circuit test, as the main structure system. Furthermore, in order to achieve good dielectric properties and water absorption, the resin composition of the present invention further modifies the molecular structure of the maleimide resin to obtain a modified maleimide resin containing a dicyclopentadiene structure in the main chain, and combines this modified maleimide resin with other resins (benzoxazine resin, epoxy resin, etc.). In this way, the requirements such as short circuit test, low water absorption, and low dielectric properties can all be met, and the resin composition can be competitive.

[0060] Although the present invention has been disclosed as the above embodiments, these embodiments are not intended to limit the present invention. Those skilled in the art can make some changes and modifications without departing from the spirit and scope of the present invention, and the protection scope of the present invention is defined by the appended claims. [Industrial Applicability]

[0061] The resin composition of the present invention can be applied to electronic substrates.

Claims

1. The resin includes a benzoxazine resin, an epoxy resin, and a modified maleimide resin, The modified maleimide resin is formed by condensing a dicyclopentadiene resin having an amino group with maleic anhydride, and the dicyclopentadiene resin having an amino group is formed by nitrating and hydrogenating a dicyclopentadiene phenol resin.

2. 2. The resin composition according to claim 1, wherein the modified maleimide resin has the following structural formula: 【Chemistry 1】 In the formula, L represents a dicyclopentadienyl group, a divalent organic group derived from a phenol compound, or a combination thereof. １ and L ２ each represents a divalent organic group derived from the phenol compound, and m represents an integer of 0 to 18.

3. 2. The resin composition according to claim 1, wherein a weight ratio of the modified maleimide resin to a total weight of resin in the resin composition is in the range of 40% by weight to 80% by weight.

4. 2. The resin composition according to claim 1, wherein the weight ratio of the benzoxazine resin to the total weight of resins in the resin composition is in the range of 10% by weight to 30% by weight.

5. The resin composition according to claim 1, wherein a weight ratio of the epoxy resin to a total weight of resins in the resin composition is in the range of 5% by weight to 20% by weight.

6. 10. The resin composition of claim 1, further comprising a catalyst, a flame retardant, silicon dioxide, a siloxane coupling agent, or a combination thereof.

7. The resin composition according to claim 6, wherein the amount of the catalyst used is 0.05 phr to 2 phr.

8. The resin composition according to claim 6, wherein the amount of the flame retardant used is 10 phr to 30 phr.

9. The resin composition according to claim 6, wherein the weight ratio of the silicon dioxide is 30% by weight to 50% by weight.

10. The resin composition according to claim 6, wherein the amount of the siloxane coupling agent used is 0.1 phr to 5 phr.

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