Thermosetting resin composition as well as prepreg and laminated board prepared from thermosetting resin composition

Abstract

The invention provides a thermosetting resin composition which comprises a modified bismaleimide prepolymer and a fluorescent whitening agent, and the weight ratio of the modified bismaleimide prepolymer to the fluorescent whitening agent is 100: (0.01-5). The modified bismaleimide prepolymer is prepared by reacting bismaleimide and an allyl phenol compound at the temperature of 100 to 170 DEG C in advance for 30 to 240 minutes. According to the invention, a certain proportion of the fluorescent whitening agent is added into the allyl phenol compound modified bismaleimide prepolymer, so that the obtained composition glue solution and prepreg have better storage property; the laminated board prepared from the prepreg obtained from the resin composition consisting of the bismaleimide prepolymer modified by the allyl phenol compound and the fluorescent whitening agent has excellent heat resistance, heat and humidity resistance and cohesiveness.

Description

Technical Field

[0001] The present invention relates to the technical field of electronic materials, and in particular to a thermosetting resin composition and a prepreg and a laminate made using the same. Background Art

[0002] 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. Allylphenol compound-modified bismaleimide resin is currently the more mainstream modification method. The modified resin not only retains the traditional advantages of bismaleimide resin to a large extent, but also has excellent solubility, excellent toughness and adhesion. However, bismaleimide resin modified with allylphenol compounds still has problems such as short prepolymer storage period and poor moisture and heat resistance of cured product.

[0003] In order to solve the above problems, some companies have tried to add solvent dioxolane to the resin component, but this method only improves the storage performance of the glue solution, and the storage effect of the semi-cured sheet is not significantly improved. In addition, there is also a method of adding glycidyl ether type epoxy resin to the resin component, but the proportion of epoxy resin required to achieve the effect is relatively high, resulting in a decrease in the glass transition temperature. Summary of the invention

[0004] The technical problem to be solved by the present invention is to overcome the defects of the prior art. The present invention proposes a thermosetting resin composition and a semi-cured sheet and a laminate made using the same, which improves the storage life of the semi-cured sheet prepared by the thermosetting resin composition, and improves the heat resistance, moisture and heat resistance and copper foil adhesion of the prepared laminate.

[0005] In order to solve the above technical problems, the technical solution adopted by the present invention is: a thermosetting resin composition, comprising a modified bismaleimide prepolymer and a fluorescent whitening agent, wherein the weight ratio of the bismaleimide prepolymer to the fluorescent whitening agent is 100:0.01-5;

[0006] The modified bismaleimide prepolymer is prepared by pre-reacting bismaleimide and allylphenol compound at 100-170° C. for 30-240 minutes;

[0007] The bismaleimide compound is a compound containing two or more imide ring groups as shown in Formula 1 below in one molecular structure;

[0008]

[0009] In formula 1, R1 is H or an alkyl compound having 1 to 3 carbon atoms.

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

[0011] Furthermore, the double bond in the bismaleimide compound and the double bond in the allylphenol compound have an equivalent of 3-0.3.

[0012] Furthermore, the fluorescent whitening agent is selected from any one of the following two structures:

[0013]

[0014] Furthermore, a semi-cured sheet made of a thermosetting resin composition is prepared by dissolving the thermosetting resin composition and a catalyst in a solvent to prepare a glue solution, soaking a glass fiber cloth in the glue solution and baking it at 100-200° C. for 1-10 minutes to prepare the semi-cured sheet.

[0015] Furthermore, a laminate made of a thermosetting resin composition is obtained by coating metal foil on one or both sides of several prepregs and pressing at a pressure of 0.2-5 MPa and a temperature of 180-250° C. for 2-4 hours.

[0016] Compared with the prior art, the beneficial effects of the present invention include:

[0017] 1) Since the fluorescent whitening agent compound contains a large number of "oxygen" atoms, "nitrogen" atoms, and "sulfur" atoms, the nucleophilicity of these atoms themselves has a strong inhibitory effect on the bismaleimide resin containing electron-poor double bonds. Therefore, by adding a certain proportion of fluorescent whitening agent to the allylphenol compound-modified bismaleimide prepolymer, the obtained composite glue and prepreg have better storage properties;

[0018] 2) Since the fluorescent brightener compound has a strong inhibitory effect on the bismaleimide resin prepolymer, the reaction speed is slow in the later stage, the molecular weight gradually increases, and the interface bonding between the resin composition and the glass cloth is good, so that the obtained plate has excellent moisture and heat resistance;

[0019] 3) Since the fluorescent whitening agent compound contains a large number of "oxygen" atoms, "nitrogen" atoms, and "sulfur" atoms, and these atoms themselves have a strong ability to bind with metal foil, the adhesion between the obtained sheet and the metal foil is improved to a certain extent;

[0020] 4) The laminated board made of the semi-cured sheet obtained by the resin composition composed of the allylphenol compound modified bismaleimide prepolymer and the fluorescent whitening agent has excellent heat resistance, moisture resistance and adhesion. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The disclosure of the present invention is described with reference to the accompanying drawings. It should be understood that the drawings are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. In the accompanying drawings, the same reference numerals are used to refer to the same components. Among them:

[0022] Figure 1 Schematically showing the effect diagram of the pressing plate in Example 1, Example 2, Comparative Example 3 and Comparative Example 4;

[0023] Figure 2 The effect diagram of the pressing plate in Comparative Example 1 and Comparative Example 2 is schematically shown. DETAILED DESCRIPTION

[0024] It is easy to understand that according to the technical solution of the present invention, without changing the essential spirit of the present invention, a person skilled in the art can propose a variety of interchangeable structural modes and implementation modes. Therefore, the following specific implementation modes and drawings are only exemplary descriptions of the technical solution of the present invention, and should not be regarded as the whole of the present invention or as a limitation or restriction to the technical solution of the present invention.

[0025] A thermosetting resin composition comprising:

[0026] Bismaleimide compounds;

[0027] Allylphenol compounds;

[0028] Fluorescent brightener;

[0029] Wherein, bismaleimide and allylphenol compound are pre-reacted at 100-170°C for 30-240min, and a modified bismaleimide prepolymer is obtained after cooling, wherein the double bond equivalent ratio of the maleimide compound to the double bond in the allylphenol compound is 3-0.3. If the equivalent ratio is lower than 0.3, the heat resistance decreases; if the equivalent ratio is higher than 3, the prepolymer is easily precipitated after being dissolved in the solvent. The weight ratio of the fluorescent whitening agent added to the above-mentioned prepolymer resin is 0.01-5 based on 100 parts of the total amount. If the weight ratio is lower than 0.01, the storage period and adhesion of the semi-cured sheet decrease; if the weight ratio is higher than 5, the heat resistance decreases.

[0030] A semi-cured sheet made of a thermosetting resin composition is prepared by dissolving the thermosetting resin composition and a catalyst in a solvent to prepare a glue solution, soaking a glass fiber cloth in the glue solution and baking it at 100-200°C for 1-10 minutes to prepare the semi-cured sheet.

[0031] A laminated board made of the prepreg is obtained by coating metal foil on one or both sides of several prepregs and pressing them at a pressure of 0.2-5MPa and a temperature of 180-250°C for 2-4h to obtain the laminated board.

[0032] The technical effects of the present application are described in detail below with reference to the embodiments.

[0033] Synthesis Example 1: 150 parts of allyl bisphenol A and 200 parts of bis(4-maleimidophenyl)methane were added into a beaker, reacted at 135° C. for 60 minutes, and cooled to obtain prepolymer P1.

[0034] Synthesis Example 2: 100 parts of allylphenol formaldehyde and 200 parts of 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane were added into a beaker, reacted at 170° C. for 40 minutes, and cooled to obtain prepolymer P2.

[0035] Embodiment 1:

[0036] 199 parts of the prepolymer P of Synthesis Example 1 were dissolved in acetone solvent and 1 part of a fluorescent brightener (structural formula 3, commercially available) was added to prepare a 65% solid content adhesive solution. 7628 glass fiber cloth was then impregnated with the above adhesive solution and baked in an oven at 170°C for 5 minutes to obtain a semi-cured sheet.

[0037] The 8 prepregs are neatly stacked, and a 35um electrolytic copper foil is placed on each side, and then pressed 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℃ for 4 hours.

[0038] The properties of the obtained copper clad laminate are shown in Table 1.

[0039] Embodiment 2:

[0040] 97 parts of prepolymer P2 of Synthesis Example 2 were dissolved in acetone solvent and 3 parts of fluorescent brightener (structural formula 2, commercially available) were added to prepare a 65% solid content glue solution, and then 7628 glass fiber cloth was impregnated with the above glue solution and baked in an oven at 170°C for 5 minutes to obtain a semi-cured sheet.

[0041] The hot pressing process is the same as in Example 1, and the properties of the obtained copper clad laminate are shown in Table 1.

[0042] Comparative Example 1: 100 parts of the prepolymer P1 of Synthesis 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.

[0043] The hot pressing process is the same as in Example 1, and the properties of the obtained copper clad laminate are shown in Table 1.

[0044] Comparative Example 2: 1100 parts of the prepolymer P1 of Synthesis 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.

[0045] The hot pressing process is the same as in Example 1, and the properties of the obtained copper clad laminate are shown in Table 1.

[0046] Comparative Example 3 uses 197 parts of the prepolymer P of Synthesis Example 1, and after dissolving with solvent, adds 3 parts of diphenylphenol epoxy (Nippon Kayaku NC3000H) and 0.01 parts of 2-phenylimidazole, then impregnates the above-mentioned glue with 7628 glass fiber cloth and bakes in an oven at 170°C for 3 minutes to obtain a semi-cured sheet.

[0047] The hot pressing process is the same as in Example 1, and the properties of the obtained copper clad laminate are shown in Table 1.

[0048] Comparative Example 4 uses 85 parts of the prepolymer of Synthesis Example 1, and after dissolving with a solvent, adds 15 parts of bisphenol A novolac epoxy and 0.03 parts of 2-phenylimidazole to prepare a glue solution with a solid content of 65%. Then, 7628 glass fiber cloth is impregnated with the above glue solution and baked in an oven at 170°C for 3 minutes to obtain a semi-cured sheet.

[0049] The hot pressing process is the same as in Example 1, and the properties of the obtained copper clad laminate are shown in Table 1.

[0050] Table 1 Comprehensive performance obtained using different embodiments and comparative examples

[0051]

[0052]

[0053] As can be seen from Table 1, in Comparative Example 1, no fluorescent whitening agent component was added, the copper foil adhesion was low, the moisture and heat resistance was poor, and the storage period of the glue and prepreg was poor; in Comparative Example 2, dioxolane solvent was used, although the storage period of the glue was improved, but the copper foil adhesion, moisture and heat resistance, and storage period of the prepreg were insufficient; in Comparative Example 3, some epoxy resin was tried to improve the storage performance, and the copper foil adhesion and moisture and heat resistance were improved to a certain extent, but the storage period of the glue and prepreg was still insufficient; in Comparative Example 4, a larger proportion of epoxy resin was used to improve the storage performance, and Tg decreased significantly. Figure 1-2 As shown, the copper-clad laminates obtained by using PP pressed boards stored at 45°C for 7 days in Comparative Examples 1 and 2 have dried flowers on their surfaces. It should be noted that the number and position of dried flowers on the surfaces of the different copper-clad laminates obtained are slightly different, while the surfaces of the copper-clad laminates obtained by using PP pressed boards stored at 45°C for 7 days in Example 1, Example 2, Comparative Examples 3 and Comparative Examples 4 are smooth and have no abnormalities.

[0054] The technical scope of the present invention is not limited to the contents in the above description. Those skilled in the art can make various deformations and modifications to the above embodiments without departing from the technical idea of ​​the present invention, and these deformations and modifications should all fall within the protection scope of the present invention.

Claims

1. A thermosetting resin composition, characterized in that It comprises a modified bismaleimide prepolymer and a fluorescent whitening agent, wherein the weight ratio of the bismaleimide prepolymer to the fluorescent whitening agent is 100:0.01-5; The modified bismaleimide prepolymer is prepared by pre-reacting bismaleimide and allylphenol compound at 100-170° C. for 30-240 minutes; The bismaleimide compound is a compound containing two or more imide ring groups as shown in Formula 1 below in one molecular structure; In formula 1, R1 is H or an alkyl compound having 1 to 3 carbon atoms.

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

3. The thermosetting resin composition according to claim 1, characterized in that The double bond in the bismaleimide compound is equivalent to the double bond in the allylphenol compound in an amount of 3-0.

3.

4. The thermosetting resin composition according to claim 1, characterized in that The fluorescent whitening agent is selected from any one of the following two structures:

5. A prepreg made from the thermosetting resin composition according to claim 1, characterized in that: The thermosetting resin composition and the catalyst described in claim 1 are dissolved in a solvent to prepare a glue solution, and the glass fiber cloth is soaked in the glue solution and then baked at 100-200° C. for 1-10 minutes to prepare a semi-cured sheet.

6. A laminate made of the prepreg according to claim 5, characterized in that: The laminated board can be obtained by coating metal foil on one or both sides of several prepregs as claimed in claim 5 and pressing them at a pressure of 0.2-5 MPa and a temperature of 180-250° C. for 2-4 hours.

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