Bismaleimide resin composition and prepreg and laminated board prepared from bismaleimide resin composition

Abstract

The invention relates to a bismaleimide resin composition and a prepreg and a laminated board prepared from the bismaleimide resin composition, the bismaleimide resin composition comprises the following components: a bismaleimide compound, an allyl phenol compound and an oxetane compound, the equivalence ratio range of double bonds in the bismaleimide compound to double bonds in the allyl phenol compound is 3-0.3, and the equivalence ratio range of the double bonds in the bismaleimide compound to the double bonds in the oxetane compound is 1-3. The oxetane compound accounts for 0.5-5% of the whole resin, and the preparation process of the prepreg and the laminated board comprises the following preparation steps: step S1, preparing a glue solution from the bismaleimide resin composition, infiltrating glass fiber cloth with the glue solution, and then baking and drying to obtain the prepreg; s2, the surface of the prepreg is covered with metal foil, and high-temperature compression molding is carried out. The resin composition glue solution and the prepreg have good storage performance, and a laminated board prepared from the resin composition glue solution has excellent heat resistance, copper foil binding power and heat and humidity resistance.

Description

Technical Field

[0001] The invention relates to the field of electronic materials, and in particular to a bismaleimide resin composition and a prepreg and a laminate prepared therefrom. Background Art

[0002] The resin composition can be applied to high heat resistance, high density interconnect (HDI), and integrated circuit (IC) packaging, and the performance of the resin composition is related to the quality of circuit packaging.

[0003] As a high-performance resin matrix, bismaleimide resin has the advantages of excellent heat resistance, moisture and heat resistance, high rigidity, low thermal expansion coefficient, etc. However, its cured product has high cross-linking density and great brittleness, making it difficult to use alone and generally needs to be modified before use. The current mainstream modification method is to modify bismaleimide resin with allylphenol compounds, but there are still problems such as short prepolymer storage period and poor moisture and heat resistance of cured product.

[0004] It should be noted that the information disclosed in the above background technology section is only used to enhance the understanding of the background of the present disclosure, and therefore may include information that does not constitute the prior art known to ordinary technicians in the field. Summary of the invention

[0005] In view of the deficiencies in the prior art, the present invention discloses a bismaleimide resin composition and a prepreg and a laminate prepared therefrom.

[0006] The technical solution adopted by the present invention is as follows:

[0007] A bismaleimide resin composition comprises components: a bismaleimide compound, an allylphenol compound and an oxetane compound, wherein the equivalent ratio of double bonds in the bismaleimide compound to double bonds in the allylphenol compound is in the range of 3 to 0.3, and the oxetane compound accounts for 0.5 to 5% of the overall resin.

[0008] Furthermore, the bismaleimide compound substructure contains two imide ring groups, and the structure is Wherein R is H or an alkyl compound of 1 to 3 carbon atoms.

[0009] Furthermore, the bismaleimide compound includes bis(4-maleimidophenyl)methane and 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane.

[0010] Furthermore, the allylphenol compound is one of diallyl bisphenol A and allyl phenol formaldehyde or a mixture of the two.

[0011] Furthermore, the oxetane compound is one or a mixture of oxetane, 3-ethyl-3-hydroxymethyloxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane and other alkyloxetanes, 3-methyl-3-methoxymethyloxetane, 3-ethyl-3-{[[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane and the like.

[0012] Furthermore, the bismaleimide compound and the allylphenol compound are pre-mixed and reacted to obtain a modified bismaleimide prepolymer, and then an oxetane compound is added to finally react to obtain a bismaleimide resin composition.

[0013] Furthermore, the reaction temperature of the bismaleimide compound and the allylphenol compound is 100 to 170° C., and the reaction time is 30 to 240 min.

[0014] A laminate prepared using a bismaleimide resin composition, wherein the preparation process comprises the following preparation steps:

[0015] Step S1, using a glue prepared from a bismaleimide resin composition to soak a glass fiber cloth, and then baking and drying to obtain a prepreg;

[0016] Step S2: Cover the surface of the prepreg with metal foil and press it at high temperature.

[0017] Furthermore, in step S1, the process window for baking and drying is a baking temperature of 100 to 200°C and a baking time of 1 to 10 minutes.

[0018] Further, in step S2, the process window of high temperature pressing is a pressure range of 0.2 to 5 MPa, a temperature range of 180 to 250°C and a pressing time range of 2 to 4 hours.

[0019] The beneficial effects of the present invention are as follows:

[0020] 1. The allyl part in the allylphenol compound reacts with the carbon-carbon double bond (C=C) in the imide group in BMI to form an intermediate. At a relatively high temperature, the intermediate reacts with bismaleimide to achieve chain growth and crosslinking. The oxetane compound is introduced into the prepolymerization system of bismaleimide and the allylphenol compound. On the one hand, its lower viscosity is utilized to optimize the bonding interface between the adhesive and the glass fiber cloth and improve the moisture and heat resistance; on the other hand, the nucleophilicity of the oxygen atom in the oxygen heterocycle has a certain stability on the poor double bond of the bismaleimide, thereby improving the storage property; at the same time, the cationic ring opening of the oxetane will not have an adverse effect on the reaction between bismaleimide and allylphenol.

[0021] 2. Strictly control the equivalent ratio of double bonds in maleimide compounds to double bonds in allylphenol compounds. If the equivalent ratio is lower than 0.3, the crosslinking density will be low and the heat resistance will be reduced. If the equivalent ratio is higher than 3, the prepolymer will easily precipitate.

[0022] 3. Strictly control the content ratio of oxetane to 0.5-5%. If the equivalent ratio is lower than 0.5, there will not be enough oxygen heterocycles to optimize the interface and control the reaction, and the storage period, adhesion and moisture and heat resistance will be reduced. If the equivalent ratio is higher than 5, the crosslinking density of the composition will decrease, and the heat resistance will decrease. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 The present invention is a schematic diagram of the steps of a method for preparing a bismaleimide resin composition. DETAILED DESCRIPTION

[0024] The specific implementation of the present invention is described below in conjunction with the accompanying drawings.

[0025] Embodiment 1:

[0026] A bismaleimide resin composition and a preparation process thereof. First, 140 parts of allyl bisphenol A and 200 parts of bis(4-maleimide phenyl)methane are added into a beaker, reacted at 130°C for 60 minutes, and a prepolymer P1 is obtained after cooling. Then, 97 parts of the prepolymer P1 are dissolved in acetone solvent, and 3 parts of 3-ethyl-3-hydroxymethyloxetane (Toa Synthetic OXT-101) and 0.1 parts of triphenylsulfonium salt are added to prepare a glue solution with a solid content of 65%.

[0027] A laminate prepared using a bismaleimide resin composition, such as Figure 1 As shown, the following steps are included:

[0028] Step S1, immersing 7628 glass fiber cloth in the prepared glue solution, and baking in an oven at 170° C. for 5 minutes to obtain a prepreg.

[0029] Step S2: neatly stack 8 prepregs, place a 35um electrolytic copper foil on each top and bottom, and press them in a vacuum hot press to obtain a copper-clad laminate with a core thickness of 1.57mm. The specific pressing process is to press at a pressure of 2.0-3.0Mpa and a temperature of 220°C for 4 hours to obtain a laminate.

[0030] Embodiment 2:

[0031] A bismaleimide resin composition and a preparation process thereof, wherein 100 parts of allylphenol aldehyde and 200 parts of 2,2-bis{4-(4-maleimide phenoxy)-phenyl}propane are added into a beaker, reacted at 130°C for 40 minutes, and cooled to obtain a prepolymer P2. 95 parts of the prepolymer P2 are taken, dissolved in acetone solvent, and then 5 parts of 3-ethyl-3-{[[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane (Toa Synthetic OXT-221) and 0.15 parts of triphenylsulfonium salt are added to prepare a glue solution with a solid content of 65%.

[0032] A laminate prepared using a bismaleimide resin composition, such as Figure 1 As shown, the following steps are included:

[0033] Step S1, immersing 7628 glass fiber cloth in the prepared glue solution, and baking in an oven at 170° C. for 5 minutes to obtain a prepreg.

[0034] Step S2: neatly stack 8 prepregs, place a 35um electrolytic copper foil on each top and bottom, and press them in a vacuum hot press to obtain a copper-clad laminate with a core thickness of 1.57mm. The specific pressing process is to press at a pressure of 2.0-3.0Mpa and a temperature of 220°C for 4 hours to obtain a laminate.

[0035] Comparative Example 1:

[0036] 100 parts of the prepolymer P1 in Example 1 were dissolved in acetone solvent to prepare a glue solution with a solid content of 65%. 7628 glass fiber cloth was then impregnated with the glue solution and baked in an oven at 170° C. for 3 minutes to obtain a prepreg.

[0037] The laminated board was prepared by the same process.

[0038] Comparative Example 2:

[0039] 100 parts of the prepolymer P1 in Example 1 were dissolved in an acetone / dioxolane mixed solvent (acetone / dioxolane = 1 / 1) to prepare a glue solution with a solid content of 65%. 7628 glass fiber cloth was then impregnated with the glue solution and baked in an oven at 170°C for 3 minutes to obtain a semi-cured sheet.

[0040] The laminated board was prepared by the same process.

[0041] Comparative Example 3:

[0042] 7 parts of the prepolymer P1-9 in Example 1 were used, and after being dissolved in a solvent, 3 parts of biphenyl phenolic epoxy resin (Nippon Kayaku NC3000H) and 0.01 parts of 2-phenylimidazole were added, and then 7628 glass fiber cloth was impregnated with the above-mentioned glue solution and baked in an oven at 170°C for 3 minutes to obtain a semi-cured sheet.

[0043] The laminated board was prepared by the same process.

[0044] Comparative Example 4:

[0045] 5 parts of the prepolymer P1-8 in Example 1 were used, and after being dissolved in a solvent, 15 g of bisphenol A novolac epoxy and 0.03 parts of 2-phenylimidazole were added to prepare a glue solution with a solid content of 65%. Then 7628 glass fiber cloth was impregnated with the above glue solution and baked in an oven at 170°C for 3 minutes to obtain a semi-cured sheet.

[0046] The laminated board was prepared by the same process.

[0047] Comprehensive performance testing:

[0048] Samples were randomly selected from the laminates prepared in Examples 1 to 2 and Comparative Examples 1 to 4 for performance testing. The specific test results are shown in Table 1.

[0049] Table 1, comprehensive performance test table of laminate

[0050]

[0051] Test result analysis:

[0052] Comparative Example 1: Compared with Example 1, no oxetane compound was added to Comparative Example 1, the copper foil adhesion was low, the moisture and heat resistance was poor, and the storage period of the glue and the prepreg was poor.

[0053] Comparative Example 2: Compared with Example 1, Comparative Example 2 uses a dioxolane solvent. Although the storage period of the adhesive solution is improved, the copper foil adhesion, moisture and heat resistance, and prepreg storage performance are insufficient.

[0054] Comparative Example 3: Compared with Example 1, Comparative Example 2 uses a combination of 2-phenylimidazole and biphenyl phenolic epoxy resin, and the adhesion and moisture and heat resistance of the copper foil are improved to a certain extent, but the storage period of the glue and the semi-cured sheet is still insufficient.

[0055] Comparative Example 4: Compared with Example 1, a larger proportion of epoxy resin was used, and Tg decreased significantly.

[0056] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0057] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A bismaleimide resin composition, characterized in that The invention comprises components: a bismaleimide compound, an allylphenol compound and an oxetane compound, wherein the equivalent ratio of double bonds in the bismaleimide compound to double bonds in the allylphenol compound is in the range of 3 to 0.3, and the oxetane compound accounts for 0.5 to 5% of the total resin.

2. The bismaleimide resin composition according to claim 1, characterized in that: The bismaleimide compound substructure contains two imide ring groups, and the structure is Wherein R is H or an alkyl compound of 1 to 3 carbon atoms.

3. The bismaleimide resin composition according to claim 2, characterized in that: The bismaleimide compounds include bis(4-maleimidophenyl)methane and 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane.

4. The bismaleimide resin composition according to claim 1, characterized in that: The allylphenol compound is one of diallyl bisphenol A and allyl phenol formaldehyde or a mixture of the two.

5. The bismaleimide resin composition according to claim 1, characterized in that: The oxetane compound is one or a mixture of oxetane, 3-ethyl-3-hydroxymethyloxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane and other alkyloxetanes, 3-methyl-3-methoxymethyloxetane, 3-ethyl-3-{[[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane and the like.

6. The bismaleimide resin composition according to claim 1, characterized in that: The bismaleimide compound and the allylphenol compound are pre-mixed and reacted to obtain a modified bismaleimide prepolymer, and then an oxetane compound is added to finally react to obtain a bismaleimide resin composition.

7. The bismaleimide resin composition according to claim 6, characterized in that: The reaction temperature of the bismaleimide compound and the allylphenol compound is 100-170° C., and the reaction time is 30-240 minutes.

8. A prepreg and laminate prepared using the bismaleimide resin composition according to any one of claims 1 to 7, characterized in that: The preparation process includes the following steps: Step S1, using a glue prepared from a bismaleimide resin composition to soak a glass fiber cloth, and then baking and drying to obtain a prepreg; Step S2: Cover the surface of the prepreg with metal foil and press it at high temperature.

9. The laminate according to claim 8, characterized in that: In step S1, the process window for baking and drying is a baking temperature of 100 to 200°C and a baking time of 1 to 10 minutes.

10. The laminate according to claim 8, characterized in that: In step S2, the process window of high temperature pressing is a pressure range of 0.2 to 5 MPa, a temperature range of 180 to 250°C and a pressing time range of 2 to 4 hours.

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