A bismaleimide resin composition, a prepreg and a laminate prepared therefrom

Abstract

The present application relates to a kind of bismaleimide resin compositions and the semi-cured sheet and laminated plate prepared therefrom, comprising components: bismaleimide compound, allyl phenol compound and oxetane compound, the equivalent ratio range of double bond in the bismaleimide compound and double bond in the allyl phenol compound is 3~0.3, the oxetane compound accounts for 0.5~5% of the overall resin, the preparation process of semi-cured sheet and laminated plate includes the following preparation steps: step S1, the glue liquid prepared by bismaleimide resin composition is infiltrated into glass fiber cloth, and then baked and dried to obtain semi-cured sheet;Step S2, the surface of semi-cured sheet is covered with metal foil, and high-temperature pressing is formed, the advantage of the present application is that the glue liquid of resin composition, semi-cured sheet has good storage property, and the laminated plate prepared therefrom has excellent heat resistance, copper foil bonding force and moisture resistance.

Description

TECHNICAL FIELD

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

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

[0003] Bismaleimide resin is one of high-performance resin matrices, which has excellent heat resistance, moisture resistance, high rigidity, low thermal expansion coefficient and other advantages, but its cured product has high crosslinking density and high brittleness, and it is difficult to be used alone, and generally needs to be modified for use. The current mainstream modification method is to modify bismaleimide resin with allyl phenol compound, but there are still problems such as short storage period of prepolymer and poor moisture resistance of cured product.

[0004] It should be noted that the information disclosed in the above background section is only used to strengthen the understanding of the background of the present disclosure, and therefore can include information that does not constitute prior art known to those of ordinary skill in the art. SUMMARY

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

[0006] The technical solutions adopted by the present application are as follows:

[0007] A bismaleimide resin composition, comprising components: a bismaleimide compound, an allyl phenol compound and an oxetane compound, the equivalent ratio of double bonds in the bismaleimide compound to double bonds in the allyl phenol compound ranges from 3 to 0.3, and the oxetane compound accounts for 0.5-5% of the overall resin.

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

[0009] Further, the bismaleimide compound includes bis(4-maleimide phenyl) methane and 2,2-bis{4-(4-maleimide phenoxy)-phenyl} propane.

[0010] Further, the allyl phenol compound is one of diallyl bisphenol A and allyl phenolic aldehyde or a mixture of both.

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

[0012] Further, the bismaleimide compound and allyl phenol compound are mixed and reacted in advance to obtain a modified bismaleimide prepolymer, and then the oxetane compound is added to finally obtain the bismaleimide resin composition.

[0013] Further, the reaction temperature of the bismaleimide compound and the allyl phenol compound is 100-170°C, and the reaction time is 30-240 min.

[0014] A laminated board prepared using the bismaleimide resin composition, the preparation process of which comprises the following preparation steps:

[0015] Step S1, preparing a glue solution of the bismaleimide resin composition, the glue solution infiltrates the glass fiber cloth, and then baking and drying to obtain a prepreg;

[0016] Step S2, covering the surface of the prepreg with a metal foil, and high-temperature pressing to form.

[0017] Further, in step S1, the process window of baking and drying is a baking temperature of 100-200°C and a baking time of 1-10 min.

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

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

[0020] 1. The allyl part in the allyl phenol compound undergoes a diene addition reaction with the carbon-carbon double bond (C=C) in the imide group in the BMI to form an intermediate, which reacts with the bismaleimide at a higher temperature to realize chain growth and crosslinking, and the oxetane compound is introduced into the prepolymer system of the bismaleimide and the allyl phenol compound, which on one hand optimizes the bonding interface of the glue solution and the glass fiber cloth by using its lower viscosity to improve the wet heat resistance, and on the other hand, the nucleophilicity of the oxygen atom in the oxetane has a certain stability to the poor electron double bond of the bismaleimide to improve the storage property; at the same time, the cation ring-opening of the oxetane does not adversely affect the reaction of the bismaleimide and the allyl phenol.

[0021] 2、Strictly control the equivalent ratio of double bond in maleimide compound and double bond in allyl phenol compound, when the equivalent ratio is lower than 0.3, the crosslinking density is low, the heat resistance is reduced, when the equivalent ratio is higher than 3, the prepolymer is easy to precipitate.

[0022] 3、Strictly control the content ratio of oxetane is 0.5-5%, when the equivalent ratio is lower than 0.5, there is not enough oxetane to play the role of interface optimization and reaction control, so the storage period, adhesion and moisture resistance are reduced, when the equivalent ratio is higher than 5, the crosslinking density of the composition is reduced, so the heat resistance is reduced. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 It is a schematic diagram of the steps of the preparation method of the bismaleimide resin composition. DETAILED DESCRIPTION

[0024] The specific embodiment of the present application will be described below in combination with the drawings.

[0025] Example 1:

[0026] A bismaleimide resin composition and its preparation process, first, add 140 parts of allyl bisphenol A and 200 parts of bis(4-maleimide phenyl) methane in a beaker, react at 130℃ for 60min, and obtain a prepolymer P1 after cooling, then use 97 parts of prepolymer P1, add 3 parts of 3-ethyl-3-hydroxymethyl oxetane (East Asia synthesis OXT-101) and 0.1 parts of triphenyl sulfonium salt after dissolving in acetone solvent, and prepare a glue solution with a solid content of 65%.

[0027] A laminated board prepared using the bismaleimide resin composition, as shown in Figure 1 , comprising the following steps:

[0028] Step S1, immerse the 7628 glass fiber cloth in the prepared glue solution, and bake in an oven at 170℃ for 5min to obtain a prepreg.

[0029] Step S2, stack 8 prepregs in order, put one 35um electrolytic copper foil on the top and the bottom, and press in a vacuum hot press to obtain a copper-clad plate with a core plate thickness of 1.57mm. The specific pressing process is to press for 4 hours at a pressure of 2.0-3.0Mpa and a temperature of 220℃ to obtain the laminated board.

[0030] Example 2:

[0031] A bismaleimide resin composition and a preparation process thereof, in a beaker, allyl phenolic 100 parts, 2,2-bis{4-(4-maleimide phenoxy)-phenyl} propane 200 parts, react at 130°C for 40 min, and after cooling, a prepolymer P2 is obtained. Take the prepolymer P2-95 parts, dissolve in acetone solvent, add 3-ethyl-3-{[[(3-ethyloxetane-3-yl)methoxy]methyl} oxetane (East Asia synthesis OXT-221) 5 parts, triphenyl sulfonium salt 0.15 parts, and prepare a glue solution with a solid content of 65%.

[0032] A laminated board prepared using a bismaleimide resin composition, as shown, comprising the following steps: Figure 1

[0033] Step S1, dip 7628 glass fiber cloth in the prepared glue solution, and bake in a 170°C oven for 5 min to obtain a prepreg.

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

[0035] Comparative Example 1:

[0036] Use the prepolymer P1-100 parts in Example 1, dissolve in acetone solvent, and prepare a glue solution with a solid content of 65%, then dip 7628 glass fiber cloth in the above glue solution, and bake in a 170°C oven for 3 min to obtain a prepreg.

[0037] Prepare a laminated board by the same process.

[0038] Comparative Example 2:

[0039] Use the prepolymer P1-100 parts in Example 1, dissolve in acetone / dioxolane mixed solvent (acetone / dioxolane=1 / 1), and prepare a glue solution with a solid content of 65%, then dip 7628 glass fiber cloth in the above glue solution, and bake in a 170°C oven for 3 min to obtain a prepreg.

[0040] Prepare a laminated board by the same process.

[0041] Comparative Example 3:

[0042] Use the prepolymer P1-97 parts in Example 1, add biphenyl phenolic epoxy resin (Japan Chemical NC3000H) 3 parts, 2-phenylimidazole 0.01 parts after dissolving in solvent, then dip 7628 glass fiber cloth in the above glue solution, and bake in a 170°C oven for 3 min to obtain a prepreg. ​

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

[0044] Comparative Example 4:

[0045] The prepolymer P1 in Example 1 was used 85 parts, after solvent dissolution, bisphenol A phenolic epoxy 15 g, 2-phenylimidazole 0.03 parts were added, and a glue solution with a solid content of 65% was prepared. Then, the above glue solution was impregnated on 7628 glass cloth, and a prepreg was prepared by baking in an oven at 170℃ for 3 min.

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

[0047] Comprehensive performance test:

[0048] Random samples were taken from the laminated boards prepared in Examples 1-2 and Comparative Examples 1-4 for performance testing, and the specific test results are shown in Table 1.

[0049] Table 1, comprehensive performance test table of laminated board

[0050]

[0051] Analysis of test results:

[0052] Comparative Example 1: Compared with Example 1, Comparative Example 1 did not add an oxetane compound, the copper foil adhesion was lower, the moisture resistance was poor, and the storage period of the glue solution and the prepreg was poor.

[0053] Comparative Example 2: Compared with Example 1, Comparative Example 2 used dioxolane solvent, although the storage period of the glue solution was improved, but the copper foil adhesion, moisture resistance, and prepreg storage were insufficient.

[0054] Comparative Example 3: Compared with Example 1, Comparative Example 2 used a combination of 2-phenylimidazole and bisphenol aldehyde epoxy resin, the copper foil adhesion and moisture resistance were improved to some extent, but the storage period of the glue solution and the prepreg was still insufficient.

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

[0056] The technical features of the above-described examples can be combined arbitrarily. In order to make the description simple, all possible combinations of the technical features in the above-described examples are not described, however, as long as the combination of the technical features does not exist contradictory, it should be considered as the scope of the present description.

[0057] The above embodiments only express several implementation manners of the present application, and the description is relatively specific and detailed, but should not be understood as a limitation on the patent scope of the present application. It should be noted that, for ordinary skilled persons in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. A bismaleimide resin composition, characterized by comprising: The composition comprises components: a bismaleimide compound, an allyl phenol compound and an oxetane compound, the equivalent ratio of double bonds in the bismaleimide compound to double bonds in the allyl phenol compound ranges from 3 to 0.3, and the oxetane compound accounts for 0.5-5% of the overall resin; The bismaleimide compound contains two imide ring groups in its substructure, and has a structure of (Formula 1), wherein R is H or an alkyl compound of 1 to 3 carbon atoms, and the bismaleimide compound includes bis(4-maleimidephenyl)methane and 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane; The allyl phenol compound is one or a mixture of the other two of diallyl bisphenol A and allyl phenol formaldehyde; The oxetane compound is one or a mixture of oxetane, 3-ethyl-3-hydroxymethyl oxetane, 2-methyl oxetane, 2,2-dimethyl oxetane, 3-methyl oxetane, 3,3-dimethyl oxetane, 3-methyl-3-methoxymethyl oxetane and 3-ethyl-3-{[(3-ethyloxetane-3-yl)methoxy]methyl} oxetane; The bismaleimide compound and the allyl phenol compound are pre-mixed and reacted to obtain a modified bismaleimide prepolymer, and then the oxetane compound is added to obtain a bismaleimide resin composition, wherein the reaction temperature of the bismaleimide compound and the allyl phenol compound is 100-170°C, and the reaction time is 30-240 min.

2. A laminate prepared using the bismaleimide resin composition according to any one of claims 1, characterized by The preparation process comprises the following preparation steps: Step S1, the glue solution prepared from the bismaleimide resin composition is used to soak the glass fiber cloth, and then baking and drying are performed to obtain a prepreg; Step S2, the surface of the prepreg is covered with a metal foil, and high-temperature pressing is performed to form a product.

3. The laminate of claim 2, wherein: In step S1, the process window for baking and drying is a baking temperature of 100-200°C and a baking time of 1-10 min.

4. The laminate of claim 2, wherein: In step S2, the process window for high-temperature pressing is a pressure range of 0.2-5 MPa, a temperature range of 180-250°C and a pressing time range of 2-4 h.

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