Resin composition, insulating film, printed circuit board and semiconductor device

Abstract

The invention provides a resin composition. The resin composition comprises resin and a triazine compound. The triazine compound has a structure as shown in formula (I), and each symbol in the formula (I) is as defined in the specification. Therefore, the metal adhesive force of the resin composition can be improved, and the dielectric loss coefficient of the resin composition can be reduced.

Description

Technical Field

[0001] This invention relates to a resin composition, an insulating film, a printed circuit board, and a semiconductor device, and particularly to a resin composition having high metal adhesion and a low dielectric loss coefficient, and an insulating film prepared therefrom. Background Technology

[0002] With the development of high-speed and high-frequency transmission technologies, the circuit design of electronic devices is becoming increasingly complex, and integrated circuit substrates have also evolved into multi-layer structures, enabling them to support higher-density circuit architectures. Multi-layer integrated circuit substrates can have a core layer, and add-in materials are used on both sides of the core layer to increase the number of layers. The add-in materials can be drilled or wired to form precise vias and lines, ultimately achieving a high-density, multi-layered packaging structure.

[0003] Multilayer integrated circuit substrates are often fabricated using copper foil and epoxy resin to form an alternating layered structure. However, due to differences in material properties, poor adhesion between the copper foil and resin can easily occur, causing the layered structure to separate. Furthermore, changing the resin properties to improve the adhesion between the copper foil and resin may increase the dielectric loss of the resin, which in turn affects the heat dissipation capacity and signal transmission performance of the substrate.

[0004] In view of this, the development of an insulating material that can be used in multilayer substrates and has both high metal adhesion and low dielectric loss coefficient has become the goal of relevant companies. Summary of the Invention

[0005] The purpose of this invention is to provide a resin composition that, by adjusting the composition of the resin composition, can improve the metal adhesion of the resin composition and reduce its dielectric loss coefficient.

[0006] One embodiment of the present invention provides a resin composition comprising a resin and a triazine compound. The triazine compound has a structure as shown in formula (I):

[0007]

[0008] Wherein, R is an alkyl group, or a structure as shown in formula (1), (2), (3), (4), (5), (6), (7), (8), (9), or (10):

[0009]

[0010] Based on the aforementioned resin composition, the resin may be selected from a group consisting of polybutadiene, polyether, divinylbenzene polymer, styrene-butadiene copolymer and styrene-isoprene copolymer.

[0011] According to the aforementioned resin composition, in the styrene-butadiene copolymer, the weight percentage of styrene can be 10% to 60%, and the weight percentage of butadiene can be 40% to 90%.

[0012] According to the aforementioned resin composition, in the styrene-isoprene copolymer, the weight percentage of styrene can be 10% to 60%, and the weight percentage of isoprene can be 40% to 90%.

[0013] Based on the aforementioned resin composition, the resin accounts for 20% to 70% of the weight of the resin composition.

[0014] According to the aforementioned resin composition, the triazine compound may account for 0.1% to 5.0% of the weight of the resin composition.

[0015] The aforementioned resin composition may further include an initiator, and the initiator may include at least one of dicumyl peroxide and 2,5-dimethyl-2,5-bis(tert-butoxy)hexane.

[0016] Based on the aforementioned resin composition, the initiator may account for 2% to 8% of the weight of the resin composition.

[0017] The aforementioned resin composition may further include multiple inorganic filler particles, and the inorganic filler particles may account for 30% to 80% of the weight of the resin composition.

[0018] Based on the aforementioned resin composition, each inorganic filler particle may be spherical, and the average particle size of the inorganic filler particles may be from 0.1 μm to 2.5 μm.

[0019] Based on the aforementioned resin composition, each inorganic filler particle may be a silica particle.

[0020] The aforementioned resin composition may further include 4,4'-diamine diphenyl sulfone, and the weight percentage of 4,4'-diamine diphenyl sulfone in the resin composition may be from 0.5% to 3.0%.

[0021] Another embodiment of the present invention provides an insulating film made of the aforementioned resin composition.

[0022] Another embodiment of the present invention provides a printed circuit board comprising the aforementioned insulating film.

[0023] Another embodiment of the present invention provides a semiconductor device comprising the aforementioned insulating film.

[0024] Accordingly, the resin composition of the present invention, by adding triazine compounds, which have specific chemical structures, can improve the metal adhesion of the insulating film made of the resin composition and maintain the low dielectric loss properties of the insulating film, which is beneficial for use in printed circuit boards and semiconductor devices, thereby improving the signal transmission stability and structural strength of printed circuit boards and semiconductor devices. Detailed Implementation

[0025] The various embodiments of the present invention will be discussed in more detail below. However, these embodiments can be applied to various disclosed concepts and can be implemented in various different specific scopes. The specific embodiments are for illustrative purposes only and are not limited to the scope of disclosure.

[0026] In this invention, compound structures are sometimes represented using a skeleton formula, which can omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. If a functional group is explicitly drawn in the structural formula, the drawing shall prevail.

[0027] One embodiment of the present invention provides a resin composition comprising a resin and a triazine compound. The resin may be selected from the group consisting of polybutadiene, polyether, divinylbenzene polymers, styrene-butadiene copolymers, and styrene-isoprene copolymers, and the resin may constitute 20% to 70% of the resin composition by weight. Thus, different application requirements can be met by adjusting the type or proportion of the resin.

[0028] In detail, the polybutadiene can be maleic anhydride-adducted polybutadiene, which can have a structure as shown in formula (A):

[0029]

[0030] Where x, y, z, and MA can be positive numbers. This allows for the simultaneous provision of the material properties of both polybutadiene and maleic anhydride, and increases the peel strength and compatibility of the resin with polar or inorganic materials.

[0031] Divinylbenzene polymers can have a structure as shown in formula (B):

[0032]

[0033] Among them, n1, n2 and n3 can be positive numbers.

[0034] The polyether can be a self-crosslinking thermosetting polyether, which can improve the adhesion and glass transition temperature of the resin, while reducing the dielectric loss of the resin.

[0035] The styrene-butadiene copolymer can be a hydrogenated styrene-butadiene copolymer or a non-hydrogenated styrene-butadiene copolymer. In the styrene-butadiene copolymer, the weight percentage of styrene can be 10% to 60%, and the weight percentage of butadiene can be 40% to 90%. This allows the styrene-butadiene copolymer to provide better thermal stability and flow processability, and increases the compatibility of the resin with non-polar materials. Furthermore, the weight percentage of styrene can be 40% to 60%, and the weight percentage of butadiene can be 40% to 60%.

[0036] In styrene-isoprene copolymers, the weight percentage of styrene can be 10% to 60%, and the weight percentage of isoprene can be 40% to 90%. This allows the ratio of styrene to isoprene to be adjusted according to application requirements, thereby altering the material properties of the resin. Alternatively, the weight percentage of styrene can be 20% to 30%, and the weight percentage of isoprene can be 70% to 80%.

[0037] In addition, the resin may contain hydrocarbon-based low-dielectric resin, which can increase the compatibility of the resin with rigid materials, reduce the dielectric loss of the resin, and improve the peel strength between the resin and the metal material.

[0038] Triazine compounds have a structure as shown in formula (I):

[0039]

[0040] Wherein, R is an alkyl group, or a structure as shown in formula (1), (2), (3), (4), (5), (6), (7), (8), (9), or (10):

[0041]

[0042]

[0043] In detail, triazine compounds can be synthesized by the reaction of the following formula (C):

[0044]

[0045] In this structure, X and its associated undefined structures (i.e., the portion shown by the wavy line) may contain epoxy, amino, alkenyl, acryloxy, isocyanate, or merbato groups, and Y may contain amino, hydroxyl, carboxyl, halogen, acyl halide, epoxy, isocyanate, sulfonic acid, acrylate, alkyl, or alkenyl groups. Therefore, the corresponding X and Y structures can be selected for synthesis according to the desired R structure.

[0046] Furthermore, the triazine compound can account for 0.1% to 5.0% of the resin composition by weight, the melting point of the triazine compound can be 80°C to 90°C, and the thermal decomposition temperature (T) of the triazine compound is... d5 The temperature can be from 200°C to 250°C to provide the resin composition with appropriate material properties.

[0047] The resin composition may further include an initiator, which may include at least one of dicumyl peroxide (DCP) and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and the initiator may account for 2% to 8% of the weight of the resin composition. Thus, by adding an initiator, the curing condition and material properties of the resin composition can be further adjusted to meet application requirements.

[0048] The resin composition may further include multiple inorganic filler particles, each of which may be spherical and may be silica particles, to improve the strength of the resin composition and reduce its dielectric loss. The inorganic filler particles may constitute 30% to 80% of the weight of the resin composition, and their average particle size may be 0.1 μm to 2.5 μm, thereby further adjusting the peel strength between the resin composition and the metal material. Furthermore, the inorganic filler particles may be surface-treated to improve their dispersibility in the resin composition or increase their compatibility with other materials.

[0049] The resin composition may further contain 4,4'-diaminodiphenylsulfone, and the weight percentage of 4,4'-diaminodiphenylsulfone in the resin composition may be 0.5% to 3.0%, thereby allowing adjustment of the curing state and material properties of the resin composition to meet application requirements.

[0050] Furthermore, the resin composition may also contain a phosphazene flame retardant, which may have a structure as shown in formula (D):

[0051]

[0052] The phosphazene flame retardant can account for 0.5% to 3.0% of the weight of the resin composition. Therefore, by adding the phosphazene flame retardant, good flame-retardant properties can be provided without affecting the material properties of the resin composition.

[0053] Furthermore, the resin composition may also contain triallyl isocyanate (TAIC) or an aromatic compound, wherein the triallyl isocyanate accounts for 4% to 8% of the weight of the resin composition, and the aromatic compound accounts for 1% to 5% of the weight of the resin composition. Thus, by adding triallyl isocyanate or aromatic compound, the curing state and material properties of the resin composition can be further adjusted to meet application requirements.

[0054] Furthermore, the resin composition may contain a dispersant, and the dispersant may account for 1% to 5% of the weight of the resin composition. This can improve the uniformity of the mixture of various materials in the resin composition, thereby enhancing the material properties of the resin composition.

[0055] Another embodiment of the present invention provides an insulating film made of the aforementioned resin composition, wherein the insulating film has high metal adhesion and low dielectric loss coefficient, and can be used as a build-up material for electronic device substrates or as an encapsulation material for electronic components.

[0056] Another embodiment of the present invention provides a printed circuit board comprising the aforementioned insulating film.

[0057] Another embodiment of the present invention provides a semiconductor device comprising the aforementioned insulating film.

[0058] The present invention will be further illustrated by the following specific embodiments, which are intended to enable those skilled in the art to fully utilize and practice the invention without excessive interpretation. These embodiments should not be regarded as limiting the scope of the invention, but are used to illustrate how to implement the materials and methods of the invention.

[0059] <Comparative Examples and Examples>

[0060] The material formulations of the comparative and example samples tested in subsequent experiments are listed in Table 1 below:

[0061]

[0062]

[0063]

[0064] In Table 1, "-" indicates materials not used in the corresponding embodiments or comparative examples, and the materials used in Table 1 are described in detail below:

[0065] (1) Phosphazene flame retardant was purchased from Otsuka Chemical Co., Ltd., product code SPV-100.

[0066] (2) The polybutadiene is maleic anhydride-based polybutadiene, purchased from Cray Valley, product code Ricon142MA3.

[0067] (3) The low dielectric resin is a hydrocarbon-based low dielectric resin purchased from Denka Co., Ltd., with product code LDM-03-07.

[0068] (4) Triallyl isocyanate was purchased from Evonik, product code:

[0069] (5) Both polyether (I) and polyether (II) are self-crosslinking thermosetting polyethers, purchased from JSR Corporation, with product codes HC-G0024 and HC-G0037 respectively.

[0070] (6) Divinylbenzene polymer was purchased from Shiming New Materials Research Institute Co., Ltd., with the product code SDO electronic resin.

[0071] (7) The aromatic compounds were purchased from JSR Corporation, product code PJ0004.

[0072] (8) The styrene-isoprene copolymer was purchased from KRATON, product code D-1119PT, in which the weight percentage of styrene was 22% and the weight percentage of isoprene was 78%.

[0073] (9) Hydrogenated styrene-butadiene copolymer was purchased from KRATON, product code MD1623, in which styrene accounted for 43% by weight and butadiene accounted for 57% by weight.

[0074] (10) The styrene-butadiene copolymer was purchased from Globalprene Co., Ltd., with the product code Globalprene DP3790, wherein the weight percentage of styrene was 50% and the weight percentage of butadiene was 50%.

[0075] (11) Silica particles (I) were purchased from Zhejiang Sanshiji Technology Co., Ltd., product code EQ0610-SSM. Silica particles (I) are spherical with an average particle size of 0.6 μm and have been surface treated with acrylic silane.

[0076] (12) Silica particles (II), (III), (IV), and (V) were all purchased from Jiangsu Huimai Powder Technology Co., Ltd., with product codes HM052BNJQ, HM052YJQ, HM052BYJQ, and HM052, respectively. Silica particles (II) are spherical with an average particle size of 0.5 μm and have undergone aniline silane surface treatment. Silica particles (III) are spherical with an average particle size of 0.5 μm and have undergone vinyl silane surface treatment. Silica particles (IV) are spherical with an average particle size of 0.5 μm and have undergone methacrylyl silane surface treatment. Silica particles (V) are spherical with an average particle size of 0.5 μm and have not undergone surface treatment.

[0077] (13) The dispersant was purchased from Evonik, product code: Dispers 1010.

[0078] <Materials Testing of Resin Composition and Insulating Film>

[0079] In this experiment, insulating films were prepared from the resin compositions of the comparative example and Examples 1 to 11, and subjected to rheometer analysis, peel strength testing, thermomechanical analysis, and EAC resistance testing. The rheometer analysis was performed using a multi-functional rheometer (TA Instruments; model HR-20) at a temperature range of 25°C to 180°C and a heating rate of 10°C / min. A complex viscosity curve was obtained, and the lowest value of the complex viscosity curve was recorded as the minimum melt viscosity of the insulating film. The viscosity at 100°C was also recorded.

[0080] The peel strength test involves bonding an insulating film between a copper plate and a 1cm strip of copper foil and then curing it (curing conditions: 190℃ × 2 hours). The copper plate in the test sample is then fixed in a fixture of a universal testing machine (manufacturer: Guanglai Instrument Co., Ltd.; model: QC-548). The non-overlapping 1cm strip of copper foil in the test sample is then folded back 180 degrees and a tensile force is applied (peel angle: 180 degrees and tensile speed: 100mm / min). The tensile force at which the strip of copper foil is pulled apart from the copper plate is the peel strength of the test sample.

[0081] Thermomechanical analysis is performed using a thermomechanical analyzer (TA Instruments; model DiscoveryTMA 450) to test the cured insulating film (curing conditions: 190℃ × 2 hours) under operating conditions of 25℃ to 260℃ and a heating rate of 10℃ / min. The results are obtained as follows: the first coefficient of thermal expansion of the cured insulating film from 30℃ to 150℃, and the second coefficient of thermal expansion from 150℃ to 240℃. The glass transition temperature is the temperature at which the curve inflection point is measured.

[0082] The EAC resistance test involves wetting a cleanroom cloth with ethyl acetate (EAC) and then wiping one surface of the cured insulating film (curing conditions: 190℃ × 2 hours) with the wet cloth. The surface is then visually inspected for any wiping marks. If wiping marks are present, meaning the surface is uneven after being wiped with the wet cloth, the cured insulating film is deemed to have failed the EAC resistance test; if no wiping marks are present, the cured insulating film is deemed to have passed the EAC resistance test. The test results are shown in Table 2 below:

[0083]

[0084]

[0085] As can be seen from the comparative examples, the first embodiment, and the second embodiment, by adding a triazine compound, the triazine compound can form a coordination covalent bond with the metal surface, which can increase the peel strength between the insulating film and the copper metal. Furthermore, as the proportion of the triazine compound increases, the peel strength can be further improved. In addition, by adding a triazine compound, the coefficient of thermal expansion of the insulating film can also be reduced.

[0086] As can be seen from the third and fourth embodiments, when the proportion of silica particles treated with aniline silane increases, the peel strength between the insulating film and the copper metal can be improved.

[0087] As can be seen from Examples 4 to 6, using styrene-isoprene copolymer can achieve higher peel strength, but has a higher coefficient of thermal expansion.

[0088] As can be seen from the 6th and 7th embodiments, good peel strength can be obtained by using self-crosslinking thermosetting polyethers, and the peel strength can be adjusted by selecting different polyethers to meet different application requirements.

[0089] As can be seen from Examples 8 to 11, adding silica particles can achieve good peel strength. Moreover, under the same silica particle size, adding untreated silica particles can significantly improve peel strength because the surface of untreated silica particles has a large number of hydroxyl groups, which can react with the ethoxy group in the triazine compound at high temperature to form bonds, thereby increasing peel strength.

[0090] <Dielectric Property Testing of Resin Composition and Insulating Film>

[0091] In this experiment, the resin compositions of the comparative example and Examples 1 to 11 were respectively prepared into insulating films and cured (curing conditions: 190°C × 2 hours), and then tested using a split post dielectric resonator. The test results are shown in Table 3 below:

[0092]

[0093]

[0094] As can be seen from the test results in Table 3, the dielectric constant and loss factor of embodiments 1 to 11 can all be maintained at low values, which can provide lower dielectric loss properties, thereby reducing the capacitance effect during circuit signal transmission, reducing the heat generation of electronic devices, and improving the stability and lifespan of electronic devices.

[0095] In summary, the resin composition of the present invention, by adding triazine compounds with specific chemical structures, can improve the metal adhesion of the insulating film made of the resin composition and maintain the low dielectric loss properties of the insulating film, which is beneficial for its application in printed circuit boards and semiconductor devices, thereby improving the signal transmission stability and structural strength of printed circuit boards and semiconductor devices.

[0096] Although the present invention has been disclosed above by way of embodiments, it is not intended to limit the present invention. Any person skilled in the art can make various modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A resin composition, characterized in that, Include: A resin; and A triazine compound having a structure as shown in formula (I): Wherein, R is an alkyl group, or a structure as shown in formula (1), (2), (3), (4), (5), (6), (7), (8), (9), or (10):

2. The resin composition according to claim 1, characterized in that, The resin is selected from a group consisting of polybutadiene, polyether, divinylbenzene polymer, styrene-butadiene copolymer and styrene-isoprene copolymer.

3. The resin composition as described in claim 2, characterized in that, In this styrene-butadiene copolymer, the weight percentage of styrene is 10% to 60%, and the weight percentage of butadiene is 40% to 90%.

4. The resin composition as described in claim 2, characterized in that, In this styrene-isoprene copolymer, the weight percentage of styrene is 10% to 60%, and the weight percentage of isoprene is 40% to 90%.

5. The resin composition according to claim 1, characterized in that, The resin accounts for 20% to 70% of the weight of the resin composition.

6. The resin composition according to claim 1, characterized in that, The triazine compound accounts for 0.1% to 5.0% of the weight of the resin composition.

7. The resin composition according to claim 1, characterized in that, It further includes an initiator, wherein the initiator comprises at least one of dicumyl peroxide and 2,5-dimethyl-2,5-bis(tert-butoxy)hexane.

8. The resin composition according to claim 7, characterized in that, The initiator accounts for 2% to 8% of the weight of the resin composition.

9. The resin composition according to claim 1, characterized in that, It further contains multiple inorganic filler particles, and the multiple inorganic filler particles account for 30% to 80% of the weight of the resin composition.

10. The resin composition according to claim 9, characterized in that, Each of the inorganic filler particles is spherical, and the average particle size of the plurality of inorganic filler particles is 0.1 μm to 2.5 μm.

11. The resin composition as claimed in claim 9, characterized in that, Each of the inorganic filler particles is a silica particle.

12. The resin composition according to claim 1, characterized in that, It further contains 4,4'-diamine diphenyl sulfone, and the 4,4'-diamine diphenyl sulfone accounts for 0.5% to 3.0% of the weight of the resin composition.

13. An insulating film, characterized in that, It is made from a resin composition as described in any one of claims 1 to 12.

14. A printed circuit board, characterized in that, Include: The insulating film as described in claim 13.

15. A semiconductor device, characterized in that, Include: The insulating film as described in claim 13.

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