TWI776065B - Resin compositions, prepregs, laminates, and foil-clad laminates - Google Patents

Abstract

The invention relates to an epoxy resin composition and a prepreg, a laminate and a metal foil-clad laminate made by using the same. The epoxy resin composition of the present invention comprises epoxy resin (A), phenolic curing agent (B), high molecular weight resin (C) and optional inorganic filler (D), wherein the high molecular weight resin (C) has a The structure and weight average molecular weight represented by formula (1), formula (2), formula (3) and formula (4) are between 100,000 and 200,000, and the epoxy resin (A) containing a naphthalene ring skeleton and the epoxy resin (A) containing a naphthalene ring skeleton The content of phenolic curing agent (B) is 0%. The epoxy resin composition of the present invention and the prepreg, laminate and metal foil-clad laminate prepared by using the same have the characteristics of good heat resistance, low modulus and low thermal expansion coefficient.

Description

Resin compositions, prepregs, laminates, and foil-clad laminates

The present invention relates to the technical field of packaging for electronic products, in particular to a resin composition and a prepreg, a laminate and a metal foil-clad laminate prepared by using the same.

With the development of packaging forms, the packaging density is getting higher and higher, such as POP packaging (package stacking technology), MCP packaging (multi-chip packaging), etc., the requirements for the coefficient of thermal expansion (CTE) and rigidity of the packaging substrate are becoming more and more high. For packages with a single package form, such as BGA packages (ball grid array packages), low XY CTE and high rigidity package substrates can show the effect of reducing warpage. However, for the package form with complex package shape, due to its fixedness, the warpage requirements of different parts are different, which is obviously not applicable. At the same time, the thermal stress generated by components such as wafers during the installation process cannot be relieved, and cracking of the pads is very easy to cause the circuit to fail. Moreover, the continuous improvement of the use environment temperature also puts forward higher requirements on the heat resistance of the package substrate.

The object of the present invention is to provide a resin composition, the prepreg, laminate and metal foil-clad laminate prepared by using the resin composition have the characteristics of good heat resistance, low modulus and low thermal expansion coefficient.

In order to achieve the above objects, the present invention adopts the following technical means.

式（1）

式（2）

式（3）

式（4） k、l、m和n為莫耳分率，其中，k+l+m+n≤1，0＜k≤0.10，0.01≤l≤0.30，0.20≤m≤0.80，0.05≤n≤0.20；式（2）中，R₁ 為氫原子或1~8個碳原子的烷基；式（3）中，R₂ 、R₃ 各自獨立的為氫原子或1~8個碳原子的烷基；式（4）中，R₄ 為氫原子或18個碳原子的烷基，R₅ 為1~8個碳原子的烷基、苯基（Ph）、-COO(CH₂ )₂ Ph或-COOCH₂ Ph。One aspect of the present invention provides an epoxy resin composition, comprising: an epoxy resin (A); a phenolic curing agent (B); ) and a high molecular weight resin (C) with a weight average molecular weight of 100,000 to 200,000; and optional inorganic fillers (D), including epoxy resin (A) containing naphthalene ring skeleton and epoxy resin containing naphthalene ring skeleton The content of phenolic curing agent (B) is 0%,

Formula 1)

Formula (2)

Formula (3)

Formula (4) k, l, m and n are molar fractions, where k+l+m+n≤1, 0<k≤0.10, 0.01≤l≤0.30, 0.20≤m≤0.80, 0.05≤n ≤0.20; in formula (2), R ₁ is a hydrogen atom or an alkyl group of 1 to 8 carbon atoms; in formula (3), R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group of 1 to 8 carbon atoms Alkyl; in formula (4), R ₄ is a hydrogen atom or an alkyl group of 18 carbon atoms, and R ₅ is an alkyl group of 1 to 8 carbon atoms, phenyl (Ph), -COO(CH ₂ ) ₂ Ph or -COOCH ₂ Ph.

Optionally, R ₁ is a hydrogen atom or a methyl group; R ₂ is a hydrogen atom or a methyl group; R ₃ is an alkyl group of 1 to 8 carbon atoms; and R ₄ is a hydrogen atom or a methyl group.

Optionally, the epoxy resin (A) and/or the phenolic curing agent (B) contain an aralkyl or dicyclopentadienyl structure.

Optionally, based on the total weight of the epoxy resin (A) and the phenolic curing agent (B) as 100 parts by weight, the amount of the high molecular weight resin (C) is 10-90 parts by weight, preferably 20-85 parts by weight The weight part is more preferably 30 to 70 parts by weight.

Optionally, based on the total weight of the epoxy resin (A) and the phenolic curing agent (B) as 100 parts by weight, the amount of the inorganic filler (D) is 0-100 parts by weight, preferably 10-70 parts by weight share.

Another aspect of the present invention provides a prepreg comprising a base material and the above-mentioned resin composition attached to the base material by impregnation or coating.

Another aspect of the present invention provides a laminate comprising at least one sheet of the above-mentioned prepreg.

Another aspect of the present invention provides a metal foil-clad laminate, wherein the metal foil-clad laminate includes at least one of the above-mentioned prepregs and metal foils coated on one or both sides of the prepreg.

The resin composition provided by the present invention has the advantages of good heat resistance, low thermal expansion coefficient and low modulus, and the prepregs, laminates and metal foil-clad laminates prepared by using the resin composition have good heat resistance and low The thermal expansion coefficient and modulus help to reduce the warpage of the package carrier, which is suitable for packages with various package shapes.

In order to better illustrate the present invention, some specific embodiments of the present invention are described in detail, but the embodiments of the present invention are not limited to these, and various changes can be made within the scope of the patent application.

The epoxy resin composition of the present invention contains: epoxy resin (A), phenolic curing agent (B), high molecular weight resin (C) and optional inorganic filler (D), and may also contain optional curing accelerator (E) and other additives. Among them, the epoxy resin (A) and the phenolic curing agent (B) are used as matrix resins, and each component will be described in detail below.

<Matrix resin (epoxy resin (A) + phenolic curing agent (B))>

Except that the epoxy resin containing a naphthalene ring skeleton and the phenolic curing agent containing a naphthalene ring skeleton are not used, the epoxy resin (A) and the phenolic curing agent (B) constituting the matrix resin are not particularly limited in the present invention. Both epoxy resins and phenolic curing agents can be selected.

The epoxy resin and phenolic curing agent of the present invention do not contain a naphthalene ring skeleton in the structure, thereby reducing the rigidity of the matrix resin, so that the prepreg, laminate and metal foil-clad laminate prepared from the resin composition have low modulus properties.

The epoxy resin (A) that can be used in the present invention is selected from organic compounds containing at least two epoxy groups in the molecular structure, examples of which may include: bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol S type epoxy resin, novolac type epoxy resin, cresol Novolac epoxy resin, bisphenol A novolac epoxy resin, brominated bisphenol A epoxy resin, brominated novolac epoxy resin, trifunctional phenolic epoxy resin, tetrafunctional phenolic epoxy resin, benzene Oxygen type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, dicyclopentadiene novolac type epoxy resin, aralkyl type epoxy resin, aralkyl novolac type epoxy resin, Isocyanate-modified epoxy resin, cycloaliphatic epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, silicon-containing epoxy resin, nitrogen-containing epoxy resin, bromine-containing epoxy resin, glycidyl amine, glycidol esters, or compounds obtained by epoxidizing double bonds such as butadiene, and the like. These epoxy resins mentioned above may be used alone or in combination as required.

The phenolic curing agent (B) that can be used in the present invention is selected from organic compounds containing at least two phenolic groups in the molecular structure, such as phenolic resins, including phenolic novolac resins, cresol novolac resins and the like. In addition to the phenolic curing agent containing a naphthalene skeleton in its structure, all known phenolic curing agents for epoxy resin compositions can be selected, and can be one kind or a mixture of at least two kinds.

The inventors found that: when the epoxy resin (A) and/or the phenolic curing agent (B) (that is, at least one of the epoxy resin and the phenolic curing agent) contains an aralkyl or dicyclopentadienyl structure, the The resin composition of the present invention has a low modulus while having higher heat resistance and lower thermal expansion coefficient. The epoxy resin containing an aralkyl group may be selected from aralkyl type epoxy resins, aralkyl novolac type epoxy resins, and the like. The epoxy resin containing a dicyclopentadienyl group may be selected from a dicyclopentadiene type epoxy resin, a dicyclopentadiene novolac type epoxy resin, and the like. The aralkyl-containing phenolic curing agent can be selected from aralkyl-type phenolic resins and the like. The dicyclopentadienyl group-containing phenolic curing agent can be selected from dicyclopentadiene-type phenolic resins and the like.

The dosage of epoxy resin and phenolic curing agent is not particularly limited, as long as the laminate and metal foil-clad laminate can be fully cured under certain curing conditions.

<High molecular weight resin (C)>

式（1）

式（2）

式（3）

式（4） k、l、m和n為莫耳分率，其中，k+l+m+n≤1，0＜k≤0.10，0.01≤l≤0.30，0.20≤m≤0.80，0.05≤n≤0.20；式（2）中，R₁ 為氫原子或1~8個碳原子的烷基；式（3）中，R₂ 、R₃ 各自獨立的為氫原子或1~8個碳原子的烷基；式（4）中，R₄ 為氫原子或1~8個碳原子的烷基，R₅ 為1~8個碳原子的烷基、苯基（Ph）、-COO(CH₂ )₂ Ph或-COOCH₂ Ph。The high molecular weight resin (C) of the present invention has a structure represented by formula (1), formula (2), formula (3) and formula (4), and has a weight average molecular weight of 100,000 to 200,000.

Formula 1)

Formula (2)

Formula (3)

Formula (4) k, l, m and n are molar fractions, where k+l+m+n≤1, 0<k≤0.10, 0.01≤l≤0.30, 0.20≤m≤0.80, 0.05≤n ≤0.20; in formula (2), R ₁ is a hydrogen atom or an alkyl group of 1 to 8 carbon atoms; in formula (3), R ₂ and R ₃ are each independently a hydrogen atom or an alkyl group of 1 to 8 carbon atoms Alkyl; in formula (4), R ₄ is a hydrogen atom or an alkyl group of 1 to 8 carbon atoms, and R ₅ is an alkyl group of 1 to 8 carbon atoms, phenyl (Ph), -COO (CH ₂ ) ₂ Ph or -COOCH ₂ Ph.

Optionally, R ₁ is a hydrogen atom or a methyl group; R ₂ is a hydrogen atom or a methyl group; R ₃ is an alkyl group with 1 to 8 carbon atoms; R ₄ is a hydrogen atom or a methyl group.

In the high molecular weight resin (C) having a structure represented by at least the formula (2), the formula (3) and the formula (4) among the formula (1), the formula (2), the formula (3) and the formula (4), the formula The order of the structures (1), (2), (3) and (4) is not limited, and the structures of formula (1), (2), (3) or (4) may be continuous or continuous. Discontinuous.

The structure of formula (2) in the high molecular weight resin (C) contains epoxy groups, which can improve the curing strength of the high molecular weight resin (C) and the matrix resin, thereby improving the heat resistance and damp heat resistance of the resin composition. For the content of epoxy group, the content of the structure of formula (2) in the high molecular weight resin (C) can be 0.01~0.30 (in molar fraction), and the epoxy value of the high molecular weight resin (C) can be 0.10 eq/kg In the range of ~0.80 eq/kg, the epoxy value is the equivalent number of epoxy groups in 1 kg of high molecular weight resin (C). If the epoxy value of the high molecular weight resin (C) is less than 0.10 eq/kg, the number of epoxy groups that the high molecular weight resin (C) can react with the phenolic curing agent is insufficient, and the high molecular weight resin (C) is contained in the resin composition. It exhibits a rubbery state, has poor compatibility with other components of the resin composition, and reduces the heat resistance of prepregs, laminates and metal foil-clad laminates. If the epoxy value of the high molecular weight resin (C) is higher than 0.80 eq/kg, the crosslinking density between the high molecular weight resin (C) and the resin composition increases, and the elasticity and modulus of the laminate and the metal-clad laminate decrease. improve.

The high molecular weight resin (C) has a weight average molecular weight of 100,000 to 200,000. When the weight average molecular weight of the high molecular weight resin (C) is 100,000 or less, the heat resistance of the high molecular weight resin (C) will deteriorate. When the weight-average molecular weight of the high molecular weight resin (C) is 200,000 or more, the compatibility of the high molecular weight resin (C) with other components of the resin composition will deteriorate, and the viscosity of the varnish liquid (stage A state) of the resin composition will be too large. , affecting the dispersion uniformity of the inorganic filler (D) in the resin composition and the wettability of the varnish liquid of the resin composition to the substrate.

The amount of the high molecular weight resin (C) is 10 to 90 parts by weight based on the total weight of the epoxy resin (A) not containing a naphthalene ring skeleton and the phenolic curing agent (B) not containing a naphthalene ring skeleton as 100 parts by weight , preferably 20 to 85 parts by weight, more preferably 30 to 70 parts by weight. If the content of the high molecular weight resin (C) is too low, the resin composition, prepreg, laminate and metal foil-clad laminate do not have low modulus properties. If the content of the high molecular weight resin (C) is too high, the viscosity of the resin composition in the varnish state is too high, making it difficult to effectively wet the substrate, and the crosslinking density between the high molecular weight resin (C) and the matrix resin is low, and the resin composition, The heat resistance of prepregs, laminates, and metal-clad laminates decreased.

<Inorganic filler (D)>

The inorganic filler (D) of the present invention can improve the heat resistance of the resin composition and the laminate, and can also improve the dimensional stability of the laminate and the metal foil-clad laminate, reduce the thermal expansion coefficient, and reduce the cost.

The type of inorganic filler (D) is not limited, and can be selected from crystalline silica, fused silica, amorphous silica, spherical silica, hollow silica, aluminum hydroxide, magnesium hydroxide, One or more of mulusite, molybdenum oxide, zinc molybdate, titanium dioxide, zinc oxide, boron nitride, aluminum nitride, silicon carbide, aluminum oxide, composite silicon powder, glass powder, short glass fiber or hollow glass. In order to make the resin composition have higher heat resistance, moist heat resistance and dimensional stability, crystalline silica, fused silica, amorphous silica, spherical silica, hollow silica, hydroxide One or more of aluminum, magnesium hydroxide, boehmite, boron nitride, aluminum nitride, silicon carbide, alumina, composite silicon micropowder, glass powder, short glass fiber or hollow glass, more preferably spherical silica.

The amount of the inorganic filler (D) may be 0 to 100 parts by weight based on the total weight of the epoxy resin (A) without a naphthalene ring skeleton and the phenolic curing agent (B) without a naphthalene ring skeleton as 100 parts by weight , from the viewpoint of improving the heat resistance and moist heat resistance of the resin composition without increasing the modulus of the resin composition, it is preferably 10 to 70 parts by weight.

In order to improve the compatibility of the inorganic filler (D) with the resin composition, a coupling agent can be added for surface treatment. The coupling agent is not limited, and is generally selected from silane coupling agents. The type of silane coupling agent is not limited, but epoxy silane coupling agent, amino silane coupling agent, vinyl silane coupling agent, styryl silane coupling agent, isobutenyl silane coupling agent, acryl Silane coupling agent, ureidosilane coupling agent, mercaptosilane coupling agent, chloropropylsilane coupling agent, sulfide-based silane coupling agent, isocyanate-based silane coupling agent, etc.

<Curing accelerator (E) and other additives>

In order to completely cure the resin composition, the resin composition of the present invention can also add an accelerator (E) as required, the accelerator (E) is selected from the curing accelerator that can accelerate the epoxy resin and the phenolic curing agent, which Specifically, organic salts of metals such as copper, zinc, cobalt, nickel, and manganese, imidazole and its derivatives, tertiary amines, etc. can be used, and one or more of them can be used in combination.

In addition, in order to make the resin composition have better processability and performance, various additives can be added to the resin composition as required, such as flame retardants, heat stabilizers, light stabilizers, antioxidants, lubricants, etc. .

The resin composition of the present invention can be prepared by dissolving, mixing, prepolymerizing, prereacting, and stirring the epoxy resin (A) not containing a naphthalene ring skeleton, the phenolic curing agent (B) not containing a naphthalene ring skeleton, having the following In formula (1), formula (2), formula (3) and formula (4), at least the structure represented by formula (2), formula (3) and formula (4) and the weight average molecular weight is as high as 100,000 to 200,000 Molecular weight resin (C), inorganic filler (D), etc.

It is necessary to use an organic solvent to dissolve the resin, as long as the various resins can be completely dissolved without separation during mixing. Examples include alcohols such as methanol, ethanol, butanol, ethyl cellosolve, butyl cellosolve, and ethylene glycol. - Methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether and other ethers, acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones, toluene, xylene, Aromatic hydrocarbons such as mesitylene, esters such as ethoxyethyl acetate and ethyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylacetamide Nitrogen-containing solvents such as yl-2-pyrrolidone. The above-mentioned solvents may be used alone, or two or more of them may be used in combination as necessary.

The present invention also provides a prepreg, a laminate and a metal foil-clad laminate made by using the above epoxy resin composition.

The prepreg of the present invention is formed from the resin composition of the present invention and a base material in a semi-cured state. Specifically, the prepreg is formed by a process in which a resin composition in a varnish state impregnates a base material, and is heated to volatilize a solvent and convert it to a semi-cured state.

The substrate described in the present invention is not particularly limited, and can be selected from known substrates for making various printed circuit board materials. Specifically, inorganic fibers (such as E glass, D glass, L glass, M glass, S glass, T glass, NE glass, Q glass, quartz and other glass fibers), organic fibers (such as polyimide, polyamide, polyamide, etc.) esters, polyphenylene ethers, liquid crystal polymers, etc.). The form of the substrate is usually textile, non-woven, roving, staple fiber, fiber paper and the like. Among the above-mentioned substrates, the substrate according to the present invention is preferably glass fiber cloth.

The laminate of the present invention includes at least one of the above-mentioned prepregs.

The metal foil-clad laminate of the present invention includes at least one of the above-mentioned prepregs and metal foils coated on one or both sides of the prepreg. For example, a metal foil-clad laminate can be produced by stacking 1 to 20 prepregs, and laminating and molding with a structure in which metal foils such as copper and aluminum are arranged on one or both sides of the prepreg.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

<Resin composition raw material>

Epoxy resin (A1): Biphenyl aralkyl type novolac epoxy resin (NC-3000H, provided by Nippon Kayaku Co., Ltd.)

Epoxy resin (A2): Phenyl aralkyl type novolac epoxy resin (NC-2000, provided by Nippon Kayaku Co., Ltd.)

Epoxy resin (A3): Dicyclopentadiene novolac epoxy resin (HP-7200H, provided by DIC Corporation)

Epoxy resin (A4): Bisphenol A type epoxy resin (EPICLON® 1055, supplied by DIC Corporation)

Epoxy resin (A5): Naphthol novolac epoxy resin (NC-7300L, provided by Nippon Kayaku Co., Ltd.)

Phenolic curing agent (B1): Biphenyl aralkyl type phenolic resin (MEHC-7851H, provided by Meiwa Chemical Co., Ltd.)

Phenolic curing agent (B2): dicyclopentadiene phenolic resin (DPNE9501, provided by Jiashengde)

Phenolic curing agent (B3): Novolak resin (HF-4M, provided by Meiwa Chemical Co., Ltd.)

Phenolic curing agent (B4): Naphthol phenolic resin (MEH-7000, provided by Meiwa Chemical Co., Ltd.)

High molecular weight resin (C1): "PMS-22-1" manufactured by Nagase ChemteX, weight average molecular weight 100,000, epoxy value 0.63 eq/kg

High molecular weight resin (C2): "PMS-22-1 changed to MW1" manufactured by Nagase ChemteX, weight average molecular weight 200,000, epoxy value 0.63 eq/kg

High molecular weight resin (C3): "PMS-22-1 changed to MW1" manufactured by Nagase ChemteX, weight average molecular weight 150,000, epoxy value 0.63 eq/kg

High molecular weight resin (C4): "PMS-22-1 changed to EP1" manufactured by Nagase ChemteX, weight average molecular weight 100,000, epoxy value 0.40 eq/kg

High molecular weight resin (C5): "PMS-22-2" manufactured by Nagase ChemteX, weight average molecular weight 100,000, epoxy value 0.13 eq/kg

High molecular weight resin (C6): "PMS-22-2 changed to EP1" manufactured by Nagase ChemteX, weight average molecular weight 100,000, epoxy value 0.08 eq/kg

High molecular weight resin (C7): "PMS-22-1 to MW2" manufactured by Nagase ChemteX, with a weight average molecular weight of 80,000 and an epoxy value of 0.63 eq/kg

High molecular weight resin (C8): "PMS-22-1 modified to MW3" manufactured by Nagase ChemteX, with a weight average molecular weight of 400,000 and an epoxy value of 0.63 eq/kg

Wherein (C1)~(C8) have structures represented by formula (1), formula (2), formula (3) and formula (4), k+l+m+n≤1, 0<k≤0.10, 0.01 ≤l≤0.30, 0.20≤m≤0.80, 0.05≤n≤0.20.

Inorganic filler (D1): Spherical silica ("SC2050-MB" manufactured by Admatechs, D50: 0.5 µm)

Inorganic filler (D2): Spherical alumina ("AO-502" manufactured by Admatechs, D50: 0.7 µm)

Inorganic filler (D3): Boehmite ("BG-601" manufactured by Onestone, D50: 0.5 µm)

Accelerator (E): 2-ethyl-4-methylimidazole ("2E4MI" manufactured by Shikoku Chemical Co., Ltd.)

Weaving base material: glass fiber cloth (1078 glass fiber cloth manufactured by Nittobo Co., Ltd., unit weight 47g/m ² )

All components in the examples and comparative examples of the present invention are calculated as solids.

(Prepreg)

The epoxy resin, phenolic curing agent, high molecular weight resin, inorganic filler and accelerator are blended according to the mass parts shown in Table 1 (Example) or Table 2 (Comparative Example), dissolved and diluted with propylene glycol methyl ether and methyl ethyl ketone , to prepare a resin composition in a varnish state.

Then the resin composition in the varnish state is soaked in the 1078 glass fiber cloth made by Nittobo, and it is heated and dried in a blast oven at 150~170ºC for 5~7 minutes, so that the resin composition in the varnish state is converted into the resin composition in the semi-cured state. material, the thickness is controlled at 90 µm, and the prepreg is produced from this.

(metal-clad laminate)

2 sheets and 9 sheets of the above-mentioned prepregs were respectively stacked, and 18 μm thick electrolytic copper foils were pressed on both sides of them, and were cured in a press for 2 hours, and the curing pressure was 45 kg/cm ² . The temperature was 190°C.

(laminate)

Metal foil-clad laminate After etching the metal foil, a laminate with a thickness of about 0.18 mm and 0.81 mm was obtained.

For the laminates and metal foil-clad laminates prepared by using the resin composition of the present invention, the heat resistance (Tg, T300), modulus and in-plane thermal expansion coefficient (CTE) were tested, and the test results were further given as the following examples Detailed description and description.

The test methods for the physical properties in the table are as follows:

Glass transition temperature (Tg): The copper-clad laminate samples prepared in the examples and comparative examples were etched away from the copper foil, and the laminates with a length of 60 mm, a width of 8-12 mm, and a thickness of 0.81 mm were taken. As a sample, the dynamic mechanical thermal analyzer (DMA) was used for measurement, and the heating rate was 10°C/min, and the result was the transition peak temperature of tanδ, in ºC.

T300 with copper: A metal-clad laminate with a length of 6.5 mm, a width of 6.5 mm, and a thickness of 0.81 mm was taken as a sample. The sample was dried in a 105ºC oven for 2 hours and then cooled to room temperature in a desiccator. The thermal analysis mechanical method (TMA) is used for measurement, the heating rate is 10ºC/min, the temperature is raised from room temperature to 300ºC, and the constant temperature is maintained at 300ºC. The stratification time is the time from the constant temperature inflection point to the stratification, and the unit is min. For samples that start to delaminate below 300ºC, record the temperature at which delamination begins, in ºC.

XY thermal expansion coefficient: The copper clad laminate samples prepared in the examples and comparative examples were etched away from the copper foil, and the laminates with a length of 60 mm, a width of 4 mm, and a thickness of 0.18 mm were taken as samples, glass fiber The warp direction is X direction, and the glass fiber weft direction is Y direction. The samples are dried in a 105ºC oven for 1 hour and then cooled to room temperature in a desiccator. The thermal analysis mechanical method (TMA) was used for the measurement, the heating rate was 10ºC/min, and the temperature was raised from room temperature to 300ºC.

Peel strength: Take a metal foil-clad laminate with a length of 50 mm and a width of 50 mm as a sample, and use tape or other methods to prepare a sample strip with a metal foil width of 3.0 mm on the sample. Use an anti-peel tester or other equivalent instrument to apply pressure in the vertical direction at a speed of 50mm/min to make the metal foil peel off the laminate, and the peel strength of the metal foil-clad laminate can be obtained, in N/mm.

Flexural modulus: The copper clad laminate samples prepared in the examples and comparative examples were etched away from the copper foil, and the laminates with a length of 76.2 mm, a width of 25.4 mm, and a thickness of 0.81 mm were taken as samples, and the material test was used. The measurement is carried out with the machine, the span is 25.4 mm, and the unit is GPa.

Scanning Electron Microscope (SEM): To observe whether the laminate filler is evenly dispersed, use a scanning electron microscope to observe. Sample pretreatment: The laminate is cut into a sample that is slightly smaller than the sample stage, and the sheared surface is smoothed by ion milling and other methods. A metal layer of about 10 nm is sprayed, usually gold. The morphology of the laminate section was observed with a scanning electron microscope under high vacuum conditions, and the dispersion and distribution of the inorganic fillers could be observed by zooming in. If agglomeration or local uneven distribution of the filler is observed, it is judged that the filler is not uniformly dispersed.

[Table 1 (Examples)] serial number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Epoxy A1 25 50 25 25 25 25 25 25 25 25 25 25 25 25 Epoxy A2 25 50 Epoxy A3 25 50 Epoxy A4 25 25 25 50 25 25 25 25 50 25 25 25 25 25 25 25 25 Phenolic curing agent B1 25 25 25 25 25 25 25 50 25 25 25 25 25 25 25 25 Phenolic curing agent B2 25 50 Phenolic curing agent B3 25 25 25 25 25 25 25 25 50 50 25 25 25 25 25 25 25 25 High molecular weight resin C1 50 50 50 50 50 50 50 50 50 50 50 50 8 95 50 50 High molecular weight resin C2 50 High molecular weight resin C3 50 High molecular weight resin C4 50 High molecular weight resin C5 50 Inorganic filler D1 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 5 100 Inorganic filler D2 30 Inorganic filler D3 30 Accelerator E 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Tg (ºC) 175 175 175 180 180 180 170 175 180 185 185 155 175 175 175 175 175 175 175 175 T300 with copper (min) >60 >60 >60 >60 >60 >60 >60 >60 >60 >60 >60 30 >60 >60 >60 >60 >60 40 >60 >60 X-direction thermal expansion coefficient (ppm/ºC) 9 9 9 9 9 9 9 9 9 9 9 12 9 9 9 9 11 6 9 7 Y-direction thermal expansion coefficient (ppm/ºC) 9 9 9 9 9 9 9 9 9 9 9 12 9 9 9 9 11 6 9 7 Peel Strength (N/mm) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.9 Flexural Modulus (GPa) 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 12 8 9 14 Whether the filler is evenly dispersed Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes Yes no Yes Yes

[Table 2 (Comparative Example)] serial number 1 2 3 4 5 6 7 Epoxy A1 25 25 25 25 25 Epoxy A4 50 25 25 25 25 25 Epoxy A5 50 Phenolic curing agent B1 25 25 25 25 25 Phenolic curing agent B3 50 25 25 25 25 25 Phenolic curing agent B4 50 High molecular weight resin C1 50 50 140 High molecular weight resin C6 50 High molecular weight resin C7 50 High molecular weight resin C8 50 Inorganic filler D1 30 30 30 30 30 30 30 Accelerator E 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Tg (ºC) 175 175 175 175 175 175 Can't measure T300 with copper (min) >60 >60 50 40 >60 >60 5 X-direction thermal expansion coefficient (ppm/ºC) 9 9 9 9 9 16 6 Y-direction thermal expansion coefficient (ppm/ºC) 9 9 9 9 9 16 6 Peel Strength (N/mm) 1.0 1.0 1.0 1.0 1.0 1.0 0.5 Flexural Modulus (GPa) 14 14 10 10 10 15 6 Whether the filler is evenly dispersed Yes Yes Yes Yes no Yes no

As can be seen from Tables 1 and 2, when the epoxy resin (A) or phenolic curing agent (B) used contains a naphthalene ring skeleton (Comparative Examples 1 and 2), the modulus increases; the high molecular weight resin used If the epoxy value of (C) is lower than 0.10 ep/kg (Comparative Example 3), the heat resistance may be affected due to insufficient crosslinking density; the weight-average molecular weight of the high molecular weight resin (C) used is lower than 100,000 (Comparative Example 4), the heat resistance will decrease; the weight average molecular weight of the high molecular weight resin (C) used is higher than 200,000 (Comparative Example 5), the filler will be unevenly dispersed; Molecular weight resin (C) (Comparative Example 6), the resin composition does not have the characteristics of low modulus and low thermal expansion coefficient; if the amount of high molecular weight resin (C) is too high (Comparative Example 7), the resin composition has heat resistance and peel strength. In the case of severe decline and uneven dispersion of inorganic fillers, Tg cannot be tested because low-elasticity resins dominate.

The resin composition of the present invention adopts an epoxy resin and a phenolic curing agent that do not contain a naphthalene ring skeleton, and one of the two contains an aralkyl or dicyclopentadienyl structure, and has formulas (1) and (2) ), formula (3) and formula (4) and the high molecular weight resin with the weight average molecular weight of 100,000 to 200,000, improves the curing degree of the resin composition, and the prepreg prepared from the resin composition has high Heat resistance and properties of low modulus and coefficient of thermal expansion. The epoxy resin (A) and the phenolic curing agent (B) used in Example 12 do not contain aralkyl or dicyclopentadienyl structures, and the effects of improving heat resistance and reducing the thermal expansion coefficient are not as good as those of Examples 1 to 11. Therefore, it is preferable that the epoxy resin and/or phenolic curing agent contain an aralkyl or dicyclopentadienyl structure; the amount of the high molecular weight resin (C) used in Example 17 is slightly less than 10 parts by weight, and the modulus of the resin composition Compared with Examples 1 to 11, the coefficient of thermal expansion is slightly higher; the amount of the high molecular weight resin (C) used in Example 18 is slightly higher than 90 parts by weight, which will cause uneven dispersion of the filler and lower heat resistance.

The above examples are not intended to limit the content of the composition of the present invention. Any minor modifications, equivalent changes and modifications made to the above examples according to the technical essence of the present invention or the weight parts or content of the composition still belong to the present invention. within the scope of the technical solution of the invention.

The applicant declares that the present invention illustrates the detailed composition of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed composition, that is, it does not mean that the present invention must rely on the above-mentioned detailed composition to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims (6)

An epoxy resin composition, characterized in that the epoxy resin composition comprises: epoxy resin (A); phenolic curing agent (B); ) and the structure represented by formula (4), the weight average molecular weight is greater than or equal to 100,000 and less than 200,000, and the epoxy value is in the range of 0.10eq/kg~0.80eq/kg High molecular weight resin (C); and inorganic filler ( D); Wherein, the content of epoxy resin (A) containing naphthalene ring skeleton and phenolic curing agent (B) containing naphthalene ring skeleton is 0%;

k, l, m and n are mole fractions, where k+l+m+n

1, 0<k

0.10, 0.01

l

0.30, 0.20

m

0.80, 0.05

n

0.20; in formula (2), R ₁ is a hydrogen atom or an alkyl group of 1 to 8 carbon atoms; in formula (3), R ₂ and R ₃ are each independently a hydrogen atom or an alkane of 1 to 8 carbon atoms base; in formula (4), R ₄ is a hydrogen atom or an alkyl group of 1 to 8 carbon atoms, and R ₅ is an alkyl group of 1 to 8 carbon atoms, phenyl (Ph), -COO(CH ₂ ) ₂ Ph or -COOCH ₂ Ph, wherein the phenolic curing agent (B) contains a dicyclopentadienyl structure, and the total weight of the epoxy resin (A) and the phenolic curing agent (B) is 100 In parts by weight, the amount of the high molecular weight resin (C) is 10 to 90 parts by weight; based on the total weight of the epoxy resin (A) and the phenolic curing agent (B) being 100 parts by weight, the The amount of the inorganic filler (D) is 10 to 70 parts by weight. The epoxy resin composition according to claim 1, wherein R ₁ is a hydrogen atom or a methyl group; R ₂ is a hydrogen atom or a methyl group; R ₃ is an alkyl group of 1 to 8 carbon atoms; and R ₄ is hydrogen atom or methyl group. The epoxy resin composition according to claim 1, wherein the high molecular weight resin (C) is based on 100 parts by weight of the total weight of the epoxy resin (A) and the phenolic curing agent (B) The amount is 20 to 85 parts by weight. A prepreg, characterized in that the prepreg comprises a base material and the epoxy resin composition according to any one of claims 1 to 3 attached to the base material by impregnation or coating. A laminate, characterized in that the laminate comprises at least one prepreg according to claim 4. A metal foil clad laminate, characterized in that the metal foil clad laminate comprises at least one prepreg according to claim 4 and metal foils covered on one side or both sides of the prepreg.