Modified maleimide resin and method for producing same

Abstract

To provide a modified maleimide resin that delivers superior dielectric properties and heat resistance.SOLUTION: This invention provides a modified maleimide resin. The modified maleimide resin is formed by condensation polymerization between an amino group-containing dicyclopentadiene (DCPD) resin and maleic anhydride. The amino group-containing dicyclopentadiene resin is formed by a nitration reaction and a hydrogenation reaction of dicyclopentadiene phenolic resin.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to maleimide resins, and more particularly to modified maleimide resins. [Background technology]

[0002] 2. Description of Related Art Bismaleimide resins have good heat resistance, moisture resistance, dielectric constant (Dk) and dissipation factor (Df) and other properties, and are therefore usually applied in insulating materials for high frequency printed circuit boards and other electronic substrates. However, the dielectric properties of currently used bismaleimide resins limit their application to electronic products based on the 5th generation mobile network. Summary of the Invention [Problem to be solved by the invention]

[0003] Technical issues The present invention provides modified maleimide resins that provide good dielectric properties and heat resistance. [Means for solving the problem]

[0004] Solutions to the challenges The modified maleimide resin of the present invention is formed by condensation polymerization of dicyclopentadiene (DCPD) resin with amino groups and maleic anhydride. The dicyclopentadiene resin with amino groups is formed by nitration and hydrogenation of dicyclopentadiene-phenol resin.

[0005] In one preferred embodiment of the present invention, the equivalent ratio of the number of moles of amino groups in the dicyclopentadiene resin having amino groups to the number of moles of maleic anhydride groups in the maleic anhydride is 1:1 to 1:10.

[0006] In one preferred embodiment of the present invention, the modified maleimide resin has a weight average molecular weight of 800 to 10,000.

[0007] The modified maleimide resin of the present invention has a structure represented by the following formula (1): [ka] In formula (1), L represents a dicyclopentadienylene group, a divalent organic group derived from a phenolic compound, or a combination thereof; L 1 and L 2 each represents a divalent organic group derived from a phenolic compound; m represents an integer from 0 to 18.

[0008] In one preferred embodiment of the present invention, the phenolic compound comprises phenol.

[0009] In one embodiment of the present invention, L is [ka] [ka] or a combination thereof, where * represents the bond position.

[0010] In one preferred embodiment of the present invention, L 1 and L 2 Each of [ka] and * represents the bond position. Effect of the Invention

[0011] Based on the above, the present invention provides a maleimide resin whose main chain contains a dicyclopentadiene structure (dicyclopentadiene maleimide (DCPD-MI)), which has good dielectric properties and heat resistance.

[0012] In order to make the features and advantages of the present invention more easily understandable, the following embodiments are described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Description of the embodiments The following are embodiments to describe the contents of the present invention in detail. The implementation details provided in this embodiment are for illustrative purposes and are not intended to limit the protection scope of the contents of the present invention. Those with ordinary technical knowledge can modify or change these implementation details according to the needs of actual implementation.

[0014] As used herein, a "divalent organic group" is an organic group that has two bonding sites and is capable of forming two chemical bonds through these two bonding sites.

[0015] The present invention provides a dicyclopentadiene resin having an amino group which is formed by condensation polymerization with maleic anhydride, and the dicyclopentadiene resin having an amino group is formed by nitration and hydrogenation of dicyclopentadiene-phenol resin.

[0016] Therefore, the modified maleimide resin of the present invention has a structure in which the main chain contains dicyclopentadiene, which gives the modified maleimide resin good dielectric properties and heat resistance.

[0017] Specific examples of commercially available dicyclopentadiene resins having phenol groups can include ERM6140 (trade name; manufactured by Songwon Industrial Co., Ltd.; weight average molecular weight 1300), ERM6105 (trade name; manufactured by Songwon Industrial Co., Ltd.; weight average molecular weight 800), ERM6115 (trade name; manufactured by Songwon Industrial Co., Ltd.; weight average molecular weight 1100), or other suitable dicyclopentadiene-phenol resins.

[0018] <Preparation of modified maleimide resin> First, a dicyclopentadiene-phenol resin is nitrated and hydrogenated to form a dicyclopentadiene-based resin having an amino group. The method of nitration and hydrogenation of the dicyclopentadiene-phenol resin is not particularly limited, and for example, well-known nitration and hydrogenation can be carried out, and will not be described in detail here. Next, a dicyclopentadiene-based resin having an amino group and maleic anhydride are condensation-polymerized to form a modified maleimide resin. In this embodiment, the equivalent ratio of the number of moles of amino groups in the dicyclopentadiene-based resin having an amino group to the number of moles of maleic anhydride groups in the maleic anhydride is 1:1 to 1:10, and preferably 1:1 to 1:3.

[0019] The modified maleimide resin has a structure represented by the following chemical formula (1): In this embodiment, the weight average molecular weight of the modified maleimide resin is 800 to 10,000, and preferably 1,000 to 4,000.

[0020] [ka]

[0021] In chemical formula (1), L represents a dicyclopentadienylene group, a divalent organic group derived from a phenolic compound, or a combination thereof, and is preferably a combination of a dicyclopentadienylene group and a divalent organic group derived from a phenolic compound, and this divalent group is preferably a divalent group containing a maleimide group; L 1 and L 2 each represents a divalent organic group derived from a phenolic compound; m represents an integer of from 0 to 18, preferably from 2 to 10;

[0022] L, L 1 and L 2 may represent a divalent group derived from a phenol. In this embodiment, L may [ka] or a combination thereof, [ka] and [ka] The combination of is preferably L. 1 and L 2 Each of [ka] where * represents the bond position.

[0023] In this embodiment, the modified maleimide resin has a structure represented by the following chemical formula (2): In this embodiment, the modified maleimide resin is a modified multimaleimide resin.

[0024] [ka]

[0025] In the chemical formula (2), m represents an integer of from 0 to 18, and preferably an integer of from 2 to 10.

[0026] Modified Maleimide Resin Examples Modified maleimide resin example 1 and comparative example 1 are described below:

[0027] Example 1 1 mole of hydroxyl group (trade name: ERM6140, manufactured by Songwon Industrial Co., Ltd.; weight average molecular weight: 1300) and 1.25 moles of 4-halonitrobenzene (halogen can be fluorine, chlorine, bromine, or iodine) were added into 6 moles of dimethylacetamide (DMAC) as a reaction solvent, and reacted at a temperature of 120°C for 300 minutes to carry out a nitration reaction. Then, hydrogen gas was inserted therein, and reacted at a temperature of 90°C for 480 minutes to carry out a hydrogenation reaction to form a dicyclopentadiene-based resin having an amino group. Then, 3 moles of maleic anhydride and 9.7 wt% of methylbenzenesulfonic acid were added therein, and reacted at a temperature of 120°C for 420 minutes. The modified maleimide resin of Example 1 was obtained, which has a main chain containing a dicyclopentadiene structure (DCPD-MI) and has a structure represented by chemical formula (2) (m represents an integer from 0 to 18). The resulting modified maleimide resin was evaluated by each of the following evaluation methods, and the results are shown in Table 1.

[0028] Comparative Example 1 The maleimide resin of Comparative Example 1 was a commercially available bismaleimide resin BMI-KI-70 (trade name; manufactured by KI CHEMICAL INDUSTRY Co., Ltd.; weight average molecular weight: 443). This maleimide resin was evaluated by each of the following evaluation methods, and the results are shown in Table 1.

[0029] [Table 1]

[0030] <Evaluation method> a. Glass transition temperature The prepared modified maleimide resin was measured for glass transition temperature (Tg) by dynamic mechanical analyzer (DMA). The higher the Tg, the better the modified maleimide resin's resistance to phase change, i.e., better heat resistance. Heating rate: 10℃ / min Temperature range: 30℃~300℃ (heating, cooling, heating)

[0031] b. Peel strength The prepared modified maleimide resin was coated on a substrate and baked at a temperature of 120°C for 2 minutes to form a resin film. Then, copper foil was laminated on the upper and lower surfaces of the resin film and hot pressed at 210°C for 3 hours to form a film having a thickness of 200 μm. The film was then measured for peel strength by a universal tensile machine. A higher peel strength indicates that the modified maleimide resin has good resistance to peeling from the substrate, i.e., good peel resistance.

[0032] c.Water absorption rate The prepared modified maleimide resin was placed in a thermo-hygroscopic box, and the water absorption rate was measured when the temperature reached 85°C and the humidity reached 85%. The smaller the water absorption rate, the better the moisture resistance of the modified maleimide resin.

[0033] d. Dielectric constant (Dk) The prepared modified maleimide resin was coated on a substrate, baked at a temperature of 120°C for 2 minutes, and hot pressed at a temperature of 210°C for 3 hours to form a film with a thickness of 100 μm. The film was then measured for dielectric constant (Dk) at a frequency of 10 GHz by a dielectric analyzer (model: E4991A; Agilent Technologies). The smaller the dielectric constant, the better the modified maleimide resin has dielectric properties.

[0034] e. Dissipation factor (Df) The prepared modified maleimide resin was coated on a substrate, baked at a temperature of 120°C for 2 minutes, and hot pressed at a temperature of 210°C for 3 hours to form a film with a thickness of 100 μm. The film was then measured for dissipation factor (Df) at a frequency of 10 GHz by a dielectric analyzer (model: E4991A; Agilent Technologies). The smaller the dissipation factor, the better the dielectric properties of the modified maleimide resin.

[0035] <Evaluation Results> From Table 1, it can be seen that when the modified maleimide resin has a structure in which the main chain contains dicyclopentadiene (Example 1), the modified maleimide resin simultaneously has good heat resistance, peel resistance, moisture resistance, and dielectric properties.

[0036] In addition, compared with the maleimide resin whose main chain does not have a dicyclopentadiene structure (Comparative Example 1), the modified maleimide resin whose main chain has a dicyclopentadiene structure (Example 1) has a higher glass transition temperature, a higher peel strength, a lower moisture absorption, a lower dielectric constant, and a lower dissipation factor, i.e., better heat resistance, moisture resistance, and dielectric properties.

[0037] Based on the above, the modified polyimide resin of the present invention has a structure in which the main chain contains dicyclopentadiene, and therefore has good heat resistance, peel strength, moisture resistance and dielectric properties. Therefore, the modified polyimide resin has good applicability.

[0038] Although the present invention has been disclosed in the embodiments, these embodiments are not intended to limit the present invention. Anyone with ordinary knowledge in the relevant technical field can make changes and modifications without departing from the spirit and scope of the present invention. The scope of protection of the present invention is governed by what is defined by the appended claims. [Industrial Applicability]

[0039] The modified maleimide resins of the present invention can be applied to insulating materials in high frequency printed circuit boards and other electronic substrates.

Claims

1. A first step of forming a dicyclopentadiene-based resin having amino groups by nitration and hydrogenation of a dicyclopentadiene-phenolic resin; a second step of condensing and polymerizing the dicyclopentadiene resin having an amino group with maleic anhydride to form a modified maleimide resin; The modified maleimide resin has a structure represented by the following chemical formula (1): 【Chemistry 1】 In the chemical formula (1), L is 【Chemistry 2】 or a combination thereof, * represents a bond position, L 1 and L 2 Each of 【Chemistry 3】 represents a bond position, m represents an integer from 0 to 18; The modified maleimide resin has a weight average molecular weight of 800 to 10,000.

2. 2. The method for producing a modified maleimide resin according to claim 1, wherein in the second step, the equivalent ratio of the number of moles of amino groups of the dicyclopentadiene resin having amino groups to the number of moles of maleic anhydride groups of the maleic anhydride is 1:1 to 1:

10.

3. A modified maleimide resin having a structure represented by the following chemical formula (1): 【Chemistry 4】 In the chemical formula (1), L is 【Chemistry 5】 or a combination thereof, * represents a bond position, L 1 and L 2 Each of 【Chemistry 6】 represents a bond position, m represents an integer from 0 to 18; The weight average molecular weight is 800 to 10,000. Modified maleimide resin.

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