Resin composition and warpage suppressing film

Abstract

A resin composition includes a resin component, a cross-linking agent, an inorganic filler, a dispersant and a warpage inhibitor. The resin component comprises liquid thermosetting resin, solid thermosetting resin and thermoplastic resin. The warpage inhibitor comprises at least one of a polysiloxane compound and a phosphazene compound, and the content of the warpage inhibitor ranges from 1 wt% to 6.5 wt% on the basis that the total amount of the resin composition is 100 wt%. The invention also provides a warping inhibition film formed by drying a resin solution, and the resin solution comprises a solvent and the resin composition. According to the present invention, through the specific component type and the specific content range of the warpage inhibitor, the warpage inhibition film thermally bonded with the substrate or the wafer forms the warpage inhibition layer after curing, the warpage inhibition layer inhibits the warpage degree of the substrate or the wafer after processing, and the warpage inhibition layer further passes the ethyl acetate wiping resistance test.

Description

Technical Field

[0001] The present invention relates to a composition of a polymer compound and applications thereof, in particular to a resin composition and a warping suppression film formed by the resin composition. Background Art

[0002] Substrates can be fabricated into integrated circuit substrates or printed circuit boards (PCBs). However, during the processing of these substrates, they may warp due to uneven thermal or mechanical stress. Excessive substrate warping can negatively impact subsequent manufacturing processes, such as resulting in a poor yield of the resulting IC substrate or PCB.

[0003] Furthermore, wafers can be processed into integrated circuit products. During this process, the wafers are thermally bonded to films made of different materials. Because these films have different coefficients of thermal expansion, the wafers may warp after thermal bonding. Excessive wafer warpage can negatively impact subsequent manufacturing processes, such as reducing the yield of the resulting integrated circuit products.

[0004] Therefore, in order to avoid excessive warping of the substrate or the wafer after the processing, it is necessary to perform warping suppression treatment on the substrate or the wafer before processing, such as setting a warping suppression layer on the surface of the substrate or the wafer, so that the warping suppression layer can suppress the degree of warping of the substrate or the wafer after processing.

[0005] Furthermore, the warpage suppression layer typically needs to undergo a chemical resistance test, typically by subjecting it to an ethyl acetate wipe test. Failure of this test can negatively impact subsequent manufacturing processes, such as causing the redistribution layer (RDL) process to fail. Summary of the Invention

[0006] An object of the present invention is to provide a resin composition for forming a warpage suppression layer to suppress the degree of warpage of a substrate or wafer after processing.

[0007] The resin composition of the present invention comprises a resin component, a crosslinking agent, an inorganic filler, a dispersant, and a warpage inhibitor. The resin component comprises a liquid thermosetting resin, a solid thermosetting resin, and a thermoplastic resin. The warpage inhibitor comprises at least one of a polysiloxane compound and a phosphazene compound, and the content of the warpage inhibitor ranges from 1 wt% to 6.5 wt% based on 100 wt% of the total resin composition.

[0008] In the resin composition of the present invention, the warpage inhibitor is composed of the polysiloxane compound. Based on 100 wt % of the total amount of the resin composition, the content of the polysiloxane compound is in a range of 1 wt % to 4 wt %.

[0009] In the resin composition of the present invention, the warpage inhibitor is composed of the phosphazene compound. Based on 100 wt % of the total amount of the resin composition, the content of the phosphazene compound is in a range of 3 wt % to 4 wt %.

[0010] In the resin composition of the present invention, the warpage inhibitor is composed of the polysiloxane compound and the phosphazene compound. Based on the total amount of the resin composition as 100wt%, the content of the polysiloxane compound ranges from 1wt% to 2.5wt%, and the content of the phosphazene compound ranges from 3wt% to 4wt%.

[0011] In the resin composition of the present invention, the polysiloxane compound is epoxy silicone resin.

[0012] The resin composition of the present invention, the phosphazene compound has a cyclic structure repeatedly formed by formula (I),

[0013] Formula (I)

[0014] n is a positive integer greater than or equal to 3, and X may be the same or different and each independently selected from phenoxy, methylphenoxy, propenylphenoxy, or hydroxyphenoxy.

[0015] In the resin composition of the present invention, the liquid thermosetting resin is selected from at least one of liquid bisphenol F epoxy resin, liquid bisphenol A epoxy resin, liquid novolac epoxy resin, 4,4'-diaminodiphenylmethane epoxy resin, hydrogenated bisphenol A epoxy resin, and alicyclic epoxy resin, and the content of the liquid thermosetting resin is in a range of 0.5 wt % to 6 wt % based on 100 wt % of the total weight of the resin composition.

[0016] In the resin composition of the present invention, the solid thermosetting resin is selected from at least one of a solid bisphenol A epoxy resin, a solid bisphenol F epoxy resin, a benzoxazine resin, a dicyclopentadiene novolac epoxy resin, a bisphenol A novolac epoxy resin, a phenol novolac epoxy resin, and a cresol novolac epoxy resin, and the content of the solid thermosetting resin is in a range of 5 wt % to 15 wt % based on 100 wt % of the total weight of the resin composition.

[0017] In the resin composition of the present invention, the thermoplastic resin is selected from at least one of a phenoxy resin, a thermoplastic saturated copolyester resin, an acrylic resin, and a polyvinyl butyral resin, and the content of the thermoplastic resin is greater than 0.5 wt % and less than 8 wt % based on 100 wt % of the total weight of the resin composition.

[0018] In the resin composition of the present invention, the crosslinking agent is selected from at least one of dicyandiamide, adipic acid dihydrazide and phenolic resin, and the content of the crosslinking agent ranges from 0.1 wt % to 2.5 wt % based on 100 wt % of the total amount of the resin composition.

[0019] In the resin composition of the present invention, the inorganic filler is selected from at least one of silicon dioxide, aluminum oxide, aluminum nitride, boron nitride, titanium oxide, zinc oxide, magnesium oxide, aluminum hydroxide, and magnesium hydroxide, and the content of the inorganic filler is in a range of 50 wt % to 90 wt % based on the total weight of the resin composition as 100 wt %.

[0020] In the resin composition of the present invention, the dispersant is an acrylic block copolymer, and based on 100 wt % of the total amount of the resin composition, the content of the dispersant ranges from 0.5 wt % to 2.5 wt %.

[0021] The resin composition of the present invention further comprises a dye, which includes a dye and a liquid dispersion medium. Based on the total weight of the resin composition being 100 wt %, the content of the dye is greater than 0 wt % and less than 2 wt %.

[0022] The resin composition of the present invention further comprises a leveling agent, which is epoxy polyether modified silicone oil. Based on the total amount of the resin composition being 100 wt %, the content of the leveling agent is greater than 0 wt % and less than 1 wt %.

[0023] The resin composition of the present invention further includes a weathering agent, wherein the weathering agent is selected from at least one of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, dihydro-3-[3-(triethoxysilyl)propyl]furan-2,5-dione and epoxysilane oligomer, and the content of the weathering agent is greater than 0 wt% and less than 2 wt% based on the total amount of the resin composition as 100 wt%.

[0024] Another object of the present invention is to provide a warpage suppression film for forming a warpage suppression layer to suppress the degree of warpage of a substrate or wafer after processing, wherein the warpage suppression layer passes an ethyl acetate wiping resistance test.

[0025] The warpage suppression film of the present invention is formed by drying a resin solution, wherein the resin solution includes a solvent and the resin composition described above.

[0026] The present invention has the beneficial effect of including the warp inhibitor in a specific component type and content range in the resin composition of the present invention. The warp-suppression film formed from the resin composition can be thermally bonded to a substrate or wafer and cured to form a warp-suppression layer. This warp-suppression layer not only suppresses post-processing warping of the substrate or wafer but also passes an ethyl acetate wipe resistance test. Furthermore, when the warp inhibitor includes the phosphazene compound, the warp-suppression layer further meets the UL-94 (V-0 rating) flame retardancy test. DETAILED DESCRIPTION

[0027] <Resin composition>

[0028] The resin composition of the present invention comprises a resin component, a cross-linking agent, an inorganic filler, a dispersant and a warpage inhibitor.

[0029] The resin components include a liquid thermosetting resin, a solid thermosetting resin, and a thermoplastic resin. The liquid thermosetting resin and the solid thermosetting resin react with the crosslinking agent to solidify the warp-suppressing film formed by the resin composition, thereby forming a warp-suppressing layer. The thermoplastic resin imparts ductility to the warp-suppressing layer.

[0030] The type of the liquid thermosetting resin is not limited. In certain embodiments, for example, but not limited to, the liquid thermosetting resin is selected from at least one of liquid bisphenol F epoxy resin, liquid bisphenol A epoxy resin, liquid novolac epoxy resin, 4,4'-diaminodiphenylmethane epoxy resin, hydrogenated bisphenol A epoxy resin, and alicyclic epoxy resin. The content of the liquid thermosetting resin is not limited. In certain embodiments, for example, but not limited to, the content of the liquid thermosetting resin ranges from 0.5 wt% to 6 wt% based on 100 wt% of the total weight of the resin composition.

[0031] The type of the solid thermosetting resin is not limited. In certain embodiments, for example, but not limited to, the solid thermosetting resin is selected from at least one of a solid bisphenol A epoxy resin, a solid bisphenol F epoxy resin, a benzoxazine resin, a dicyclopentadiene novolac epoxy resin, a bisphenol A novolac epoxy resin, a phenol novolac epoxy resin, and a cresol novolac epoxy resin. The content of the solid thermosetting resin is not limited. In certain embodiments, for example, but not limited to, based on 100 wt% of the total weight of the resin composition, the content of the solid thermosetting resin ranges from 5 wt% to 15 wt%.

[0032] The type of thermoplastic resin is not limited. In certain embodiments, for example, but not limited to, the thermoplastic resin is selected from at least one of a phenoxy resin, a thermoplastic saturated copolyester resin, an acrylic resin, and a polyvinyl butyral resin. The content of the thermoplastic resin is not limited. In certain embodiments, for example, but not limited to, the content of the thermoplastic resin is greater than 0.5 wt% and less than 8 wt% based on 100 wt% of the total weight of the resin composition.

[0033] The crosslinking agent is used to crosslink with the liquid thermosetting resin and the solid thermosetting resin, allowing the warp-suppressing film formed by the resin composition to solidify and form the warp-suppressing layer. The type of crosslinking agent is not limited. In certain embodiments, for example, but not limited to, the crosslinking agent is selected from at least one of dicyandiamide, adipic acid dihydrazide, and phenolic resin. The content of the crosslinking agent is not limited. In certain embodiments, for example, but not limited to, the content of the crosslinking agent ranges from 0.1 wt% to 2.5 wt% based on 100 wt% of the total weight of the resin composition.

[0034] The function of the inorganic filler is to allow the warping suppression layer to have a low coefficient of thermal expansion and a high Young's modulus. The type of the inorganic filler is not limited. In certain embodiments, for example but not limited to, the inorganic filler is selected from at least one of silicon dioxide, aluminum oxide, aluminum nitride, boron nitride, titanium oxide, zinc oxide, magnesium oxide, aluminum hydroxide, and magnesium hydroxide. The content of the inorganic filler is flexibly adjusted according to the size of the inorganic filler. In certain embodiments, for example but not limited to, when the average particle size of the inorganic filler is in the range of 0.4 μm to 3.0 μm, based on the total amount of the resin composition being 100 wt%, the content of the inorganic filler is in the range of 50 wt% to 90 wt%. In an exemplary embodiment, when the inorganic filler is composed of a mixture of silica with an average particle size of 0.4 μm and silica with an average particle size of 3.0 μm to achieve a densest packing effect, the content of the inorganic filler is 72 wt % based on 100 wt % of the total amount of the resin composition.

[0035] The function of the dispersant is to uniformly disperse the inorganic filler in the resin composition. The type of the dispersant is not limited. In certain embodiments, for example, but not limited to, the dispersant is an acrylic block copolymer. The content of the dispersant is not limited. In certain embodiments, for example, but not limited to, the content of the dispersant ranges from 0.5 wt % to 2.5 wt % based on 100 wt % of the total weight of the resin composition.

[0036] The warp inhibitor comprises at least one of a polysiloxane compound and a phosphazene compound, and the content of the warp inhibitor ranges from 1 wt% to 6.5 wt% based on 100 wt% of the total weight of the resin composition. This allows the warp inhibitor film formed from the resin composition to be thermally bonded to a substrate or wafer and cured to form a warp inhibitor layer capable of suppressing post-processing warpage of the substrate or wafer, and the warp inhibitor layer also passes an ethyl acetate wipe test, used to assess chemical resistance. If the warp inhibitor content is less than 1 wt%, the resulting warp inhibitor layer may not effectively suppress post-processing warpage of the substrate or wafer, resulting in excessive warpage of the substrate or wafer, adversely affecting subsequent processes. If the warp inhibitor content is greater than 6.5 wt%, the resulting warp inhibitor layer may fail the ethyl acetate wipe test, adversely affecting subsequent processes.

[0037] The mechanism by which both the polysiloxane compound and the phosphazene compound impart a warp-suppressing effect to the warp-suppressing layer is as follows: Due to the polysiloxane structure of the polysiloxane compound, the warp-suppressing layer can relieve stress generated during processing of the substrate or wafer, thereby suppressing post-processing warping. The phosphazene compound does not participate in the crosslinking reaction between the liquid thermosetting resin and the solid thermosetting resin and the crosslinking agent, but does hinder the crosslinking reaction. This allows the warp-suppressing layer formed by the crosslinking reaction to suppress post-processing warping of the substrate or wafer.

[0038] In certain embodiments, for example but not limited to, the polysiloxane compound is an epoxy silicone resin. In an exemplary embodiment, the polysiloxane compound is a polymer of methyl (3- (oxiranyl methoxy) propyl) siloxane and phenyl silsesquioxane, and the chemical structure is p and q are positive numbers. In some embodiments, the sources of the polysiloxane compound are listed as follows: DOWSIL TM AY 42-119.

[0039] In certain embodiments, for example but not limited to, the phosphazene compound has a cyclic structure repeatedly formed by formula (I),

[0040] Formula (I)

[0041] Wherein, n is a positive integer greater than 3, X can be the same or different and each independently selected from phenoxy, methylphenoxy, propenylphenoxy or hydroxyphenoxy. In an exemplary embodiment, n is 3, X is the same and is phenoxy, and the specific chemical structure is That is, the phosphazene compound is hexaphenoxycyclotriphosphazene. In an exemplary embodiment, n is 3, X is different and is phenoxy and methylphenoxy, respectively. The specific chemical structure is In an exemplary embodiment, n is 3, X is different and is phenoxy and propenylphenoxy, respectively, and the specific chemical structure is In an exemplary embodiment, n is 3, X is different and is phenoxy and hydroxyphenoxy, respectively, and the specific chemical structure is In certain embodiments, the phosphazene compound is derived from the following: SPB-100, SPB-100L, SPV-100, and SPH-100 from Otsuka Chemical. Furthermore, the phosphazene compound imparts flame retardancy to the warp-suppressing film formed from the resin composition.

[0042] In certain embodiments, the warpage inhibitor comprises the polysiloxane compound, and the content of the polysiloxane compound ranges from 1 wt% to 4 wt% based on 100 wt% of the total weight of the resin composition. In an exemplary embodiment, the warpage inhibitor comprises the polysiloxane compound, and the content of the polysiloxane compound is 4.0 wt% based on 100 wt% of the total weight of the resin composition.

[0043] In certain embodiments, the warpage inhibitor comprises the phosphazene compound, and the content of the phosphazene compound ranges from 3 wt % to 4 wt % based on 100 wt % of the total weight of the resin composition. In an exemplary embodiment, the warpage inhibitor comprises the phosphazene compound, and the content of the phosphazene compound is 4.0 wt % based on 100 wt % of the total weight of the resin composition.

[0044] In certain embodiments, the warpage inhibitor comprises the polysiloxane compound and the phosphazene compound. Based on 100 wt% of the total weight of the resin composition, the polysiloxane compound comprises 1 wt% to 2.5 wt%, and the phosphazene compound comprises 3 wt% to 4 wt%. In an exemplary embodiment, the warpage inhibitor comprises the polysiloxane compound and the phosphazene compound. Based on 100 wt% of the total weight of the resin composition, the polysiloxane compound comprises 1.6 wt%, the phosphazene compound comprises 4.0 wt%, and the total weight of the warpage inhibitor is 5.6 wt%.

[0045] In some embodiments, the resin composition of the present invention further comprises a dye. The function of the dye is to give color to the warpage suppression film formed by the resin composition. The type of the dye is not limited. In some embodiments, for example but not limited to, the dye includes a dye and a liquid dispersion medium. For example but not limited to, the dye is carbon black. For example but not limited to, the liquid dispersion medium is liquid bisphenol F epoxy resin. The content of the dye and the liquid dispersion medium in the dye is not limited. In some embodiments, for example but not limited to, based on the total amount of the resin composition as 100wt%, the content of the dye is in the range of greater than 0wt% and less than 2wt%, the content of the liquid dispersion medium is in the range of greater than 0wt% and less than 6wt%, and the content of the dye is in the range of greater than 0wt% and less than 8wt%.

[0046] In certain embodiments, the resin composition of the present invention further comprises a leveling agent. The function of the leveling agent is to impart good leveling properties to the resin composition, thereby facilitating coating. The type of the leveling agent is not limited. In certain embodiments, for example, but not limited to, the leveling agent is an epoxy polyether modified silicone oil. The content of the leveling agent is not limited. In certain embodiments, for example, but not limited to, the content of the leveling agent is greater than 0 wt% and less than 1 wt% based on 100 wt% of the total weight of the resin composition.

[0047] In some embodiments, the resin composition of the present invention further comprises a weathering agent. The function of the weathering agent is to make the warping suppression film formed by the resin composition weather-resistant. The type of the weathering agent is not limited. In some embodiments, for example but not limited to, the weathering agent is selected from at least one of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, dihydro-3-[3-(triethoxysilyl)propyl]furan-2,5-dione and epoxysilane oligomers. The content of the weathering agent is not limited. In some embodiments, for example but not limited to, the content of the weathering agent is greater than 0wt% and less than 2wt% based on the total amount of the resin composition as 100wt%. In some embodiments, the sources of the weathering agent are listed as follows: CB-660E of Hengqiao Industrial Co., Ltd., CB-660M of Hengqiao Industrial Co., Ltd., Wacker Corporation (Wacker) GF-20, Momentive Performance Materials Inc.'s CoatOSil TM MP 200.

[0048] Warping Suppression Film

[0049] The warpage suppression film of the present invention is formed by drying a resin solution, wherein the resin solution includes a solvent and the resin composition described above.

[0050] The type of solvent is not limited. In certain embodiments, for example, but not limited to, the solvent is selected from at least one of ethyl acetate, butyl acetate, and butanone. The amount (by weight) of the solvent is not limited. In certain embodiments, for example, but not limited to, the ratio of the solvent to the resin composition is in the range of 0.25 to 1.5, which facilitates coating of the resin solution and ensures good thickness uniformity of the resulting warp-suppressing film.

[0051] After the resin solution is applied to the surface of a release film, the solvent is evaporated by drying the resin solution applied on the release film, thereby forming the warp suppression film on the release film. The warp suppression film can be used to thermally bond with a substrate or a wafer and then solidify to form a warp suppression layer, and the warping degree of the substrate or the wafer after processing can be suppressed by the warp suppression layer. In addition, the warp suppression layer can also pass the ethyl acetate wipe resistance test, so it will not have an adverse effect on subsequent processes. In an exemplary embodiment, the drying temperature range is 80°C to 120°C, and the drying time range is 5 minutes to 20 minutes. In an exemplary embodiment, a hot roller machine is used to thermally bond the warp suppression film to the substrate, the thermal bonding temperature range is 80°C to 100°C, and the thermal bonding speed range is 0.5 m / min to 2 m / min. In an exemplary embodiment, the curing temperature is 175°C and the curing time is 1 hour.

[0052] The present invention will be further described with reference to the following examples. However, it should be understood that the examples are for illustration only and should not be construed as limiting the present invention.

[0053] <Example 1>

[0054] A resin composition was prepared by mixing a resin component, a crosslinking agent, an inorganic filler, a dispersant, a dye, a leveling agent, a weathering agent, and a warp inhibitor. The resin component included a liquid thermosetting resin, a solid thermosetting resin, and a thermoplastic resin. The warp inhibitor was composed of a polysiloxane compound and contained 4.0 wt% of the total resin composition (100 wt%). The contents of the remaining components are shown in Table 1.

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

[0056] Examples 2 to 3 and Comparative Examples 1 to 2 were carried out in the same manner as Example 1, except that the type and content of the warpage inhibitor were changed, and the amounts of the liquid thermosetting resin and the solid thermosetting resin were adjusted accordingly, as shown in Table 1.

[0057] The sources of the components used in the manufacture of the resin compositions in Examples 1 to 3 and Comparative Examples 1 and 2 are summarized as follows:

[0058]

[0059] Evaluation Items

[0060] The resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated as follows. The following evaluation procedures are described using the resin composition of Example 1 as a representative. The remaining Examples and Comparative Examples were analyzed using the same procedures. The evaluation results are shown in Table 1.

[0061] Detection of FR-5 substrate warpage

[0062] 75 parts by weight of the resin composition of Example 1 was added to 25 parts by weight of a solvent to obtain a resin solution having a solid content of 75 wt%. The solvent was ethyl acetate / butanone = 4 / 1 (wt. / wt.), and the ratio of the solvent to the resin composition was 0.33. The resin solution was applied to the surface of a release film. The resin solution applied to the release film was then dried at 80°C to 120°C for 5 to 20 minutes to remove the solvent. A warp-suppressing film having a thickness of 150 μm was formed on the surface of the release film to produce a bonding sheet.

[0063] The warp suppression film in the bonding sheet was thermally bonded to the surface of an FR-5 substrate (circular in shape, 12 cm in diameter, and 250 μm thick) at 80°C to 100°C. The excess bonding sheet was then cut off according to the size of the FR-5 substrate, and the release film in the bonding sheet was removed. The warp suppression film was then cured by heating at 175°C for 1 hour, thereby forming a warp suppression layer on the surface of the FR-5 substrate. The sample was then allowed to stand at room temperature (25°C) for 1 hour to obtain a test sample.

[0064] The test sample is placed flat, and the maximum vertical height of the test sample is measured to obtain the warpage amount of the FR-5 substrate of the test sample.

[0065] Copper foil peel strength test

[0066] 75 parts by weight of the resin composition of Example 1 was added to 25 parts by weight of a solvent to obtain a resin solution having a solid content of 75 wt%. The solvent was ethyl acetate / butanone = 4 / 1 (wt. / wt.), and the ratio of the solvent to the resin composition was 0.33. The resin solution was applied to the surface of a release film. The resin solution applied to the release film was then dried at 80°C to 120°C for 5 to 20 minutes to remove the solvent. A warp-suppressing film having a thickness of 150 μm was formed on the surface of the release film to produce a bonding sheet.

[0067] After cutting the laminating sheet into a size of 4 cm x 1 cm, the warp suppression film on the laminating sheet was heat-bonded to an aluminum sheet (5 cm x 1 cm) at 80°C to 100°C. The release film was then removed from the laminating sheet. The other side of the warp suppression film was then heat-bonded to a long strip of copper foil (13 cm x 1 cm) in the same manner. Finally, the warp suppression film was cured by heating at 175°C for 1 hour, thereby forming a warp suppression layer between the long strip of copper foil and the aluminum sheet. A test sample was obtained. The term "flush-bonded" refers to the alignment of the warp suppression film, the aluminum sheet, and the long strip of copper foil with a length of 1 cm as the reference. The warp suppression film, the aluminum sheet, and the long strip of copper foil overlapped by 4 cm, leaving 1 cm of overlap on the aluminum sheet and 9 cm of overlap on the long strip of copper foil.

[0068] The aluminum sheet in the test sample was fixed with a fixture in a universal tensile testing machine (source: Guanglei Instrument Co., Ltd.; model: QC-548). The non-overlapping long strips of copper foil in the test sample were then folded 180 degrees and a tensile force was applied (peeling angle of 180 degrees and tensile speed of 100 mm / min). The tensile force when the long strips of copper foil and the aluminum sheet were pulled apart was the copper foil peel strength of the test sample.

[0069] Detection of room temperature storage modulus

[0070] 75 parts by weight of the resin composition of Example 1 was added to 25 parts by weight of a solvent to obtain a resin solution having a solid content of 75 wt%. The solvent was ethyl acetate / butanone = 4 / 1 (wt. / wt.), and the ratio of the solvent to the resin composition was 0.33. The resin solution was applied to the surface of a release film. The resin solution applied to the release film was then dried at 80°C to 120°C for 5 to 20 minutes to remove the solvent. A warp-suppressing film having a thickness of 150 μm was formed on the surface of the release film to produce a bonding sheet.

[0071] The laminating sheet was cut into a size of 4 cm×0.6 cm, and then heated at 175° C. for 1 hour to cure the warpage suppression film to form a warpage suppression layer. The release film in the laminating sheet was then removed to obtain a test sample.

[0072] The test samples were tested using a dynamic mechanical analyzer (TA Instruments, model: Discovery DMA850) at a temperature range of 25°C to 260°C, a heating rate of 5°C / min, and a frequency of 1 Hz. The room-temperature storage modulus at 30°C was obtained. The industry generally requires a room-temperature storage modulus between 3,000 and 12,000 at 30°C.

[0073] Thermal expansion coefficient detection

[0074] 75 parts by weight of the resin composition of Example 1 was added to 25 parts by weight of a solvent to obtain a resin solution having a solid content of 75 wt%. The solvent was ethyl acetate / butanone = 4 / 1 (wt. / wt.), and the ratio of the solvent to the resin composition was 0.33. The resin solution was applied to the surface of a release film. The resin solution applied to the release film was then dried at 80°C to 120°C for 5 to 20 minutes to remove the solvent. A warp-suppressing film having a thickness of 150 μm was formed on the surface of the release film to produce a bonding sheet.

[0075] The laminating sheet was cut into a size of 3.5 cm×0.4 cm, and then heated at 175° C. for 1 hour to cure the warpage suppression film to form a warpage suppression layer. The release film in the laminating sheet was then removed to obtain a test sample.

[0076] The test sample was tested using a thermomechanical analyzer (source: TA Instruments; model: Discovery TMA 450) under operating conditions of a temperature range of 25°C to 260°C and a heating rate of 10°C / min to obtain a first thermal expansion coefficient of the test sample in a range of 30°C to 150°C and a second thermal expansion coefficient in a range of 160°C to 240°C.

[0077] Minimum melt viscosity test

[0078] 75 parts by weight of the resin composition of Example 1 was added to 25 parts by weight of a solvent to obtain a resin solution having a solid content of 75 wt%. The solvent was ethyl acetate / butanone = 4 / 1 (wt. / wt.), and the ratio of the solvent to the resin composition was 0.33. The resin solution was applied to the surfaces of multiple release films of the same size. The resin solution applied to each release film was then dried at 80°C to 120°C for 5 to 20 minutes to remove the solvent. A warp-suppressing film having a thickness of 150 μm was formed on the surface of each release film, thereby producing multiple lamination sheets.

[0079] The release films in the laminating sheets were removed respectively, and the warpage suppression films in the laminating sheets were thermally laminated to each other at 80° C. to 100° C. to obtain a test sample composed of the warpage suppression films and having a thickness ranging from 950 μm to 1050 μm.

[0080] The test sample was tested using a multifunctional rheometer (TA Instruments, model: Discovery HR 20) at a temperature range of 25°C to 180°C and a heating rate of 10°C / min to obtain a complex viscosity curve. The minimum value of the complex viscosity curve was recorded as the minimum melt viscosity of the test sample.

[0081] Ethyl acetate wipe resistance test

[0082] 75 parts by weight of the resin composition of Example 1 was added to 25 parts by weight of a solvent to obtain a resin solution having a solid content of 75 wt%. The solvent was ethyl acetate / butanone = 4 / 1 (wt. / wt.), and the ratio of the solvent to the resin composition was 0.33. The resin solution was applied to the surface of a release film. The resin solution applied to the release film was then dried at 80°C to 120°C for 5 to 20 minutes to remove the solvent. A warp-suppressing film having a thickness of 150 μm was formed on the surface of the release film to produce a bonding sheet.

[0083] The warp suppression film in the bonding sheet was thermally bonded to the surface of an FR-5 substrate (circular in shape, 12 cm in diameter, and 250 μm thick) at 80°C to 100°C. The excess bonding sheet was then cut off according to the size of the FR-5 substrate, and the release film in the bonding sheet was removed. The bonding sheet was then heated at 175°C for 1 hour to cure the warp suppression film to form a warp suppression layer. The bond was then allowed to stand at room temperature (25°C) for 1 hour to obtain a test sample.

[0084] Wet a clean cloth with ethyl acetate (EAC) and wipe one surface of the test sample with the wetted cloth. Visually inspect the surface for any wiping marks. If the surface shows any wiping marks, meaning it is uneven after being wiped with the wetted cloth, the test sample is considered to have failed the ethyl acetate wipe resistance test. If the surface shows no wiping marks, the test sample is considered to have passed the ethyl acetate wipe resistance test.

[0085] UL-94 (V-0 grade) flame retardant test

[0086] 75 parts by weight of the resin composition of Example 1 was added to 25 parts by weight of a solvent to produce a resin solution having a solid content of 75 wt%. The solvent was ethyl acetate / butanone = 4 / 1 (wt. / wt.), with a solvent to resin composition ratio of 0.33. The resin solution was then applied to the surfaces of five release films of equal size. The resin solution applied to each release film was then dried at 80°C to 120°C for 5 to 20 minutes to remove the solvent. A 150 μm thick warp-suppressing film was formed on the surface of each release film, resulting in five laminated sheets.

[0087] Each laminating sheet was cut into a size of 122 mm x 13 mm and heated at 175°C for 1 hour to cure each warp suppression film to form a warp suppression layer. The release film was then removed from each laminating sheet to obtain five test samples.

[0088] According to the UL-94 test standard, a vertical combustion test is performed on each test sample using a fixture and a single flame source. The test determines whether the first combustion time (t1) or the second combustion time (t2) of each test sample is greater than 10 seconds, whether the total combustion time (t1 + t2) of the five test samples is greater than 50 seconds, whether the sum of the second combustion time and the spark combustion time (t3) of each test sample is greater than 30 seconds, whether the embers or afterflame of each test sample burns into the fixture, and whether the dripping particles generated by each burning test sample ignite the cotton. If any of the above judgment conditions is "yes" for any test sample, the test sample is judged to have "failed" the UL-94 (V-0 rating) flame retardancy test. If all of the above judgment conditions are "no" for each test sample, the test sample is judged to have "passed" the UL-94 (V-0 rating) flame retardancy test.

[0089] Table 1

[0090]

[0091]

[0092] As shown in Table 1, the FR-5 substrate warpage and ethyl acetate rub resistance test results demonstrate that, compared to Comparative Example 1, which contains no warpage inhibitor in the resin composition, and Comparative Example 2, which contains a 7.3 wt% warpage inhibitor, Examples 1 to 3, due to the warpage inhibitor content ranging from 1 wt% to 6.5 wt%, not only exhibit lower FR-5 substrate warpage after curing, but also pass the ethyl acetate rub resistance test. Furthermore, due to the inclusion of a phosphazene compound in the resin composition, the warpage inhibitor films formed from the resin compositions of Examples 2 and 3 also pass the UL-94 (V-0 rating) flame retardancy test after curing.

[0093] In summary, by including the specific components and content ranges of the warp inhibitor in the resin composition of the present invention, the warp-suppression film of the present invention formed from the resin composition can be thermally bonded to a substrate or wafer and cured to form a warp-suppression layer. This warp-suppression layer not only suppresses post-processing warping of the substrate or wafer but also passes the ethyl acetate wipe resistance test, thus effectively achieving the objectives of the present invention. Furthermore, when the warp inhibitor includes a phosphazene compound, the warp-suppression film and layer further meet the UL-94 (V-0 rating) flame retardancy test.

[0094] However, the above is only an embodiment of the present invention and should not be used to limit the scope of the present invention. Any simple equivalent changes and modifications made according to the claims and description of the present invention are still within the scope of the present invention.

Claims

1. A resin composition, characterized in that: The resin composition comprises Resin components, including liquid thermosetting resins, solid thermosetting resins and thermoplastic resins; cross-linking agent; Inorganic fillers; dispersants; and The warpage inhibitor includes at least one of a polysiloxane compound and a phosphazene compound, and based on 100 wt % of the total amount of the resin composition, the content of the warpage inhibitor ranges from 1 wt % to 6.5 wt %.

2. The resin composition according to claim 1, wherein: The warpage inhibitor is composed of the polysiloxane compound. Based on 100 wt % of the total amount of the resin composition, the content of the polysiloxane compound is in a range of 1 wt % to 4 wt %.

3. The resin composition according to claim 1, wherein: The warpage inhibitor is composed of the phosphazene compound. Based on 100 wt % of the total amount of the resin composition, the content of the phosphazene compound is in a range of 3 wt % to 4 wt %.

4. The resin composition according to claim 1, wherein: The warpage inhibitor is composed of the polysiloxane compound and the phosphazene compound. Based on 100 wt% of the total amount of the resin composition, the content of the polysiloxane compound is in a range of 1 wt% to 2.5 wt%, and the content of the phosphazene compound is in a range of 3 wt% to 4 wt%.

5. The resin composition according to claim 1, wherein: The polysiloxane compound is epoxy silicone resin.

6. The resin composition according to claim 1, wherein: The phosphazene compound has a cyclic structure repeatedly formed by formula (I), Formula (I) n is a positive integer greater than or equal to 3, and X may be the same or different and each independently selected from phenoxy, methylphenoxy, propenylphenoxy, or hydroxyphenoxy.

7. The resin composition according to claim 1, wherein: The liquid thermosetting resin is selected from at least one of liquid bisphenol F epoxy resin, liquid bisphenol A epoxy resin, liquid novolac epoxy resin, 4,4'-diaminodiphenylmethane epoxy resin, hydrogenated bisphenol A epoxy resin, and alicyclic epoxy resin. The content of the liquid thermosetting resin is in a range of 0.5 wt % to 6 wt % based on 100 wt % of the total weight of the resin composition.

8. The resin composition according to claim 1, wherein: The solid thermosetting resin is selected from at least one of a solid bisphenol A epoxy resin, a solid bisphenol F epoxy resin, a benzoxazine resin, a dicyclopentadiene novolac epoxy resin, a bisphenol A novolac epoxy resin, a phenol novolac epoxy resin, and a cresol novolac epoxy resin. The content of the solid thermosetting resin is in a range of 5 wt % to 15 wt % based on 100 wt % of the total amount of the resin composition.

9. The resin composition according to claim 1, wherein: The thermoplastic resin is selected from at least one of a phenoxy resin, a thermoplastic saturated copolyester resin, an acrylic resin, and a polyvinyl butyral resin, and the content of the thermoplastic resin is greater than 0.5 wt % and less than 8 wt % based on 100 wt % of the total amount of the resin composition.

10. The resin composition according to claim 1, wherein: The crosslinking agent is selected from at least one of dicyandiamide, adipic acid dihydrazide and phenolic resin, and the content of the crosslinking agent ranges from 0.1 wt % to 2.5 wt % based on 100 wt % of the total amount of the resin composition.

11. The resin composition according to claim 1, wherein: The inorganic filler is selected from at least one of silicon dioxide, aluminum oxide, aluminum nitride, boron nitride, titanium oxide, zinc oxide, magnesium oxide, aluminum hydroxide and magnesium hydroxide, and the content of the inorganic filler is in a range of 50 wt % to 90 wt % based on the total amount of the resin composition being 100 wt %.

12. The resin composition according to claim 1, wherein: The dispersant is an acrylic block copolymer, and based on 100 wt % of the total amount of the resin composition, the content of the dispersant ranges from 0.5 wt % to 2.5 wt %.

13. The resin composition according to claim 1, wherein: The resin composition further includes a dye, which includes a dye and a liquid dispersion medium. Based on 100 wt % of the total amount of the resin composition, the content of the dye is greater than 0 wt % and less than 2 wt %.

14. The resin composition according to claim 1, wherein: The resin composition further comprises a leveling agent, which is epoxy polyether modified silicone oil. Based on 100 wt % of the total amount of the resin composition, the content of the leveling agent is greater than 0 wt % and less than 1 wt %.

15. The resin composition according to claim 1, wherein: The resin composition further includes a weather resistance imparting agent, wherein the weather resistance imparting agent is selected from at least one of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, dihydro-3-[3-(triethoxysilyl)propyl]furan-2,5-dione and epoxysilane oligomer, and the content of the weather resistance imparting agent is greater than 0 wt% and less than 2 wt% based on the total amount of the resin composition as 100 wt%.

16. A warpage suppression film, characterized in that: The warpage suppression film is formed by drying a resin solution, wherein the resin solution includes a solvent and the resin composition according to any one of claims 1 to 15 .

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