Unsaturated carbon-containing thermosetting resin, and method for preparing the same

Abstract

To provide an unsaturated carbon-containing thermosetting resin, and a method for preparing the same.SOLUTION: An unsaturated carbon-containing thermosetting resin has a structure represented by formula (1), in which each symbol in formula (1) is defined in the specification. The unsaturated carbon-containing thermosetting resin is prepared from a polyphenylene ether compound and a maleimide compound having high rigidity and high thermal stability, and is reactive with a crosslinking agent. Thereby, the unsaturated carbon-containing thermosetting resin is applied to a packaging process of a printed circuit board, and a printed circuit board material excellent in heat resistance can be obtained.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a resin and a method for preparing the same, and more particularly to an unsaturated carbon-containing thermosetting resin that can improve the physical properties of the resin and a method for preparing the same. [Background technology]

[0002] In recent years, electronic products have developed toward thinner, lighter, more integrated, and faster speeds. The current trend in printed circuit board (PCB) industry technology, both for rigid and flexible substrates, is toward higher frequencies, higher speeds, and higher density. This demand for materials is becoming increasingly stringent. Furthermore, mobile communication demands greater data transmission, leading to increasingly high-frequency (1 GHz and above) related processes and materials. Key material properties include low dielectric constant (κ dielectric; Dk), low dielectric loss (Dissipation factor; Df), high heat resistance, and good mechanical strength. Thermosetting resins, with their chemical resistance, rigidity, thermal stability, insulating properties, and low dielectric loss, meet the application requirements of printed circuit boards, making them widely used materials.

[0003] However, conventional thermosetting resins have poor adhesion to substrates and require improvements in thermal stability and mechanical strength. Furthermore, conventional thermosetting resins have inconsistent molecular weights between production lots during actual production, which affects the stability of the packaging process used for subsequent printed circuit boards.

[0004] In view of this, it is necessary to develop a thermosetting resin with a good rigid structure, high thermal stability, and stable weight-molecular-weight distribution, which can be used in printed circuit board substrates, contributing to obtaining printed circuit board substrates with good mechanical strength and advantageously improving the stability of the packaging process of printed circuit boards. Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides an unsaturated carbon-containing thermosetting resin with excellent mechanical properties and thermal stability, and a method for preparing the same. The polymer chain segments of the unsaturated carbon-containing thermosetting resin have a rigid structure, which can improve the mechanical strength and thermal stability of the material, and the resin has a high glass transition temperature (Tg). When the unsaturated carbon-containing thermosetting resin is used in printed circuit boards, the thermal stability of the unsaturated carbon-containing thermosetting resin contributes to the production stability of the printed circuit board process under the high-temperature environment of the printed circuit board lamination and soldering processes. Furthermore, because the molecular structure of the unsaturated carbon-containing thermosetting resin is symmetrical, the material has a low dielectric loss factor (Df), which meets the material requirements for high-frequency printed circuit boards and reduces signal loss during high-frequency transmission through the printed circuit board. [Means for solving the problem]

[0006] According to one aspect of the present invention, there is provided a compound having a structure represented by the following formula (1): [ka] X is -CH2-, -CH(CH3)-, or -C(CH3)2-; R1, R2, R3, R4, R5, R6, R7, and R8 are each independently a hydrogen atom or a C1-C3 hydrocarbon; a and b are each independently a number from 2 to 500; Y is a structure represented by formula (2); c and d are each independently a number from 1 to 300; [ka] R9 is C4-C 20 E is a structure represented by formula (3), F is a structure represented by formula (4), and e and f are each independently a number from 1 to 200; [ka] R 10 is a C2-C6 straight or branched chain hydrocarbon, [ka] Z provides an unsaturated carbon-containing thermosetting resin having the structure shown in formula (5). [ka]

[0007] According to the unsaturated carbon-containing thermosetting resin described in the previous paragraph, Y may be a structure shown in formula (6): [ka] R 15 is a C1-C3 hydrocarbon, and R 11 , R 12 , R 18 and R 19 are each independently a C1-C5 hydrocarbon; R 13 , R 14 , R 16 and R 17 are each independently a hydrogen atom or a C1-C3 hydrocarbon.

[0008] According to the unsaturated carbon-containing thermosetting resin described in the previous paragraph, Y may have a structure shown in formula (7). [ka]

[0009] According to another aspect of the present invention, there is provided a method for preparing an unsaturated carbon-containing thermosetting resin, the method including the steps of: providing a polymer solution containing a polyphenylene ether compound, a phenol compound, a maleimide compound, and a first solvent; prepolymerizing the polymer solution and an alkaline solution at a prepolymerization reaction temperature for a prepolymerization reaction time to form a prepolymer solution; and polymerizing the prepolymer solution, a benzene compound solution, and a styrene compound solution at a polymerization reaction temperature for a polymerization reaction time to form a polymer solution containing the unsaturated carbon-containing thermosetting resin described in the previous paragraph.

[0010] According to the method for preparing an unsaturated carbon-containing thermosetting resin described in the previous paragraph, the phenolic compound may be a bisphenol A derivative.

[0011] According to the method for preparing the unsaturated carbon-containing thermosetting resin described in the previous paragraph, the prepolymerization reaction temperature may be 35°C to 65°C, and the prepolymerization reaction time may be 3 hours to 7 hours.

[0012] According to the method for preparing the unsaturated carbon-containing thermosetting resin described in the previous paragraph, the prepolymerization reaction may be carried out in an environment with a pH value of 7.5 to 10.5.

[0013] According to the method for preparing an unsaturated carbon-containing thermosetting resin described in the previous paragraph, the benzene compound solution contains a benzene compound that may be selected from the group consisting of 1,3-bis(trichloromethyl)benzene, 1,4-bis(trichloromethyl)benzene, 1,4-bis(chloromethyl)benzene, 2,4-bis(chloromethyl)trimethylbenzene, and 4,4'-bis(chloromethyl)biphenyl.

[0014] According to the method for preparing an unsaturated carbon-containing thermosetting resin described in the previous paragraph, the styrene compound solution includes a styrene compound which may be 2-chloromethylstyrene, 3-chloromethylstyrene, or 4-chloromethylstyrene.

[0015] According to the method for preparing the unsaturated carbon-containing thermosetting resin described in the previous paragraph, the polymerization reaction temperature may be 35°C to 65°C, and the polymerization reaction time may be 12 hours to 18 hours. [Brief explanation of the drawings]

[0016] The following description of the accompanying drawings will make the above and other objects, features, advantages and embodiments of the present invention clearer and easier to understand. [Figure 1] 2 shows a process flow chart of a method for preparing an unsaturated carbon-containing thermoset resin according to another embodiment of the present invention. [Figure 2]1 shows the infrared spectra of Example 4, Comparative Example 1, BMI-H, and SA90. DETAILED DESCRIPTION OF THE INVENTION

[0017] Hereinafter, several embodiments of the present invention will be described with reference to the drawings. For clarity, many practical details will be set forth in the following description. However, the reader should understand that these practical details are not intended to limit the present invention. That is, in some embodiments of the present invention, these practical details are not required. Also, to simplify the drawings, some conventional structures and elements are shown simply and diagrammatically in the drawings. Duplicate elements may be designated by the same numerals.

[0018] <Unsaturated carbon-containing thermosetting resin>

[0019] The unsaturated carbon-containing thermosetting resin of the present invention has a structure represented by the following formula (1): [ka] X is -CH2-, -CH(CH3)-, or -C(CH3)2-; R1, R2, R3, R4, R5, R6, R7, and R8 are each independently a hydrogen atom or a C1-C3 hydrocarbon; a and b are each independently a number from 2 to 500; Y is a structure represented by formula (2); c and d are each independently a number from 1 to 300; [ka] R9 is C4-C 20 E is a structure represented by formula (3), F is a structure represented by formula (4), and e and f are each independently a number from 1 to 200; [ka] R 10 is a C2-C6 straight or branched chain hydrocarbon, [ka] Z is a structure shown in formula (5). [ka]

[0020] Preferably, Y may be a structure of formula (6): [ka] R 15 is a C1-C3 hydrocarbon, and R 11 , R 12 , R 18 , R 19 are each independently a C1-C5 hydrocarbon; R 13 , R 14 , R 16 , R 17 are each independently a hydrogen atom or a C1-C3 hydrocarbon, which allows the molecular chain segments of the unsaturated carbon-containing thermosetting resin of the present invention to have a rigid structure, thereby providing good mechanical strength.

[0021] Preferably, Y may be a structure of formula (7): [ka] This allows the molecular chain segments of the unsaturated carbon-containing thermosetting resin of the present invention to have a rigid and planar structure, providing good mechanical strength. Furthermore, the good molecular symmetry and low polarity of the material are advantageous for subsequent application to high-frequency printed circuit boards with low dielectric loss (Df).

[0022] Please refer to FIG. 1, which shows a process flow chart of a method 100 for preparing an unsaturated carbon-containing thermosetting resin according to another embodiment of the present invention, which includes steps 110, 120, and 130.

[0023] Step 110 provides a polymer solution including a polyphenylene ether compound, a phenol compound, a maleimide compound, and a first solvent, where the first solvent may be dimethylacetamide (DMAc). The phenol compound may be a bisphenol A derivative. A bisphenol A derivative is a compound obtained using bisphenol A as a source. For example, the bisphenol A derivative may be 2,2'-diallylbisphenol A.

[0024] Step 120 is a prepolymerization step in which the polymer solution and the alkaline solution are prepolymerized at a prepolymerization temperature for a prepolymerization time to form a prepolymer solution. The prepolymerization temperature may be 35°C to 65°C, the pH may be 7.5 to 10.5, and the prepolymerization time may be 3 to 7 hours, to obtain a prepolymer solution. The alkaline solution may be a potassium hydroxide (KOH) solution.

[0025] Step 130 is a polymerization step in which the preliminary polymer solution, the benzene compound solution, and the styrene compound solution are polymerized at a polymerization temperature for a polymerization time to form a polymer solution containing an unsaturated carbon-containing thermosetting resin. The polymerization temperature may be 35°C to 65°C, and the polymerization time may be 12 to 18 hours. The benzene compound solution contains a benzene compound that may be selected from the group consisting of 1,3-bis(trichloromethyl)benzene, 1,4-bis(trichloromethyl)benzene, 1,4-bis(chloromethyl)benzene, 2,4-bis(chloromethyl)trimethylbenzene, and 4,4'-bis(chloromethyl)biphenyl. The styrenic compound solution includes a styrenic compound which may be 2-(Chloromethyl)styrene, 3-(Chloromethyl)styrene, or 4-(Chloromethyl)styrene.

[0026] The following specific examples are intended to further illustrate and explain the present invention and enable those skilled in the art to fully utilize and practice the present invention without the need for undue interpretation; these examples should not be construed as limiting the scope of the present invention, but are used to explain how to carry out the materials and methods of the present invention.

[0027] Example 1

[0028] 90±5Kg of NORYL TMA polyphenylene ether compound, SA90 (a Sabic patented structure, hereinafter referred to as SA90), and 3.2±0.3 kg of a bisphenol A derivative were dissolved in 280±20 kg of dimethylacetamide and charged into a reactor. The reactor was equipped with a feed tube, a stirring blade, a thermometer, and a pH meter, and a heating pack was installed outside the reactor to adjust the temperature inside. The stirring blade was operated to homogenize the solution in the reactor, and the solution in the reactor was stirred for 0.5 to 1.5 hours. Then, 5±1.5 kg of a maleimide compound, Bismaleimide-H (hereinafter referred to as BMI-H), was added through the feed tube to form a polymer solution, and the liquid in the reactor was stirred for 1 to 2.5 hours.

[0029] 7.4±1.5 kg of potassium hydroxide solution was added to the reactor through the supply pipe, the temperature in the reactor was adjusted to 35°C to 65°C, and the pH value was in the range of 7.5 to 10.5. At the same time, the solution in the reactor was stirred, and after pre-polymerization reaction for 3 to 7 hours, a pre-polymer solution was formed.

[0030] 2.4±0.15 kg of benzene compound solution and 16.5±1.5 kg of styrene compound solution were added to the reactor through the supply pipe, the temperature in the reactor was adjusted to 35°C to 65°C, and the solution in the reactor was stirred at the same time. After a polymerization reaction for 12 to 18 hours, a polymer solution containing an unsaturated carbon-containing thermosetting resin was formed, and the unsaturated carbon-containing thermosetting resin of Example 1 (hereinafter abbreviated as Example 1) having the structure shown in Formula (1) was obtained. [ka] X is -C(CH3)2-, R1, R2, R7, and R8 are each independently -CH3, R3, R4, R5, and R6 are each independently a hydrogen atom, a and b are each independently a number from 2 to 35, Y is a structure represented by formula (7), and c and d are each independently a number from 1 to 4, [ka] E is a structure represented by formula (3), F is a structure represented by formula (4), and e and f are each independently a number from 1 to 6. [ka] R 10 is -C(CH3)2-, [ka] Z is a structure shown in formula (5). [ka]

[0031] <Example 2>

[0032] The unsaturated carbon-containing thermosetting resin of Example 2 (hereinafter referred to as Example 2) was produced by a preparation method similar to that of Example 1 and had a structure similar to that of Example 1, except that the amount of BMI-H added when preparing Example 2 was 11±1.5 kg, and other preparation conditions were the same as those of Example 1.

[0033] Example 3

[0034] The unsaturated carbon-containing thermosetting resin of Example 3 (hereinafter referred to as Example 3) was prepared by a similar preparation method to Example 1 and had a similar structure to Example 1, except that the amount of BMI-H added when preparing Example 3 was 17±1.5 kg, and other preparation conditions were the same as Example 1.

[0035] Example 4

[0036] The unsaturated carbon-containing thermosetting resin of Example 4 (hereinafter referred to as Example 4) was prepared by a similar preparation method to Example 1 and had a similar structure to Example 1, except that the amount of BMI-H added when preparing Example 4 was 23±1.5 kg, and other preparation conditions were the same as those of Example 1.

[0037] <Example 5>

[0038] The unsaturated carbon-containing thermosetting resin of Example 5 (hereinafter referred to as Example 5) was prepared by a similar preparation method to Example 1 and had a similar structure to Example 1, except that the amount of BMI-H added when preparing Example 5 was 29±1.5 kg, and other preparation conditions were the same as those of Example 1.

[0039] <Comparative Example 1>

[0040] The unsaturated carbon-containing thermosetting resin of Comparative Example 1 (hereinafter referred to as Comparative Example 1) was prepared by a similar preparation method to Example 1, except that BMI-H was not added when preparing Comparative Example 1, and Comparative Example 1 had a structure shown in formula (8): [ka] X is —C(CH3)2—, R1, R2, R7, and R8 are each independently —CH3, R3, R4, R5, and R6 are each independently a hydrogen atom, a and b are each independently a number from 2 to 35, E is a structure represented by formula (3), F is a structure represented by formula (4), and e and f are each independently a number from 1 to 6, [ka] R 10 is -C(CH3)2-, [ka] Z is a structure shown in formula (5). [ka]

[0041] <Infrared spectroscopy (IR)>

[0042] See Figure 2, which shows the infrared spectra of Example 4, Comparative Example 1, BMI-H, and SA90. Example 4 is an unsaturated carbon-containing thermosetting resin containing a maleimide structure, while Comparative Example 1 is an unsaturated carbon-containing thermosetting resin without a maleimide structure. Compared to Comparative Example 1, the infrared spectrum of Example 4 shows a higher peak at 1710 cm ‐1 The characteristic peak of the C=O double bond of the amide group observed in Fig. 1 was the same as the characteristic peak of BMI-H, which indicated that the unsaturated carbon-containing thermosetting resin of the present invention has a maleimide graft structure on the polymer chain of SA90.

[0043] <Gel permeation chromatography (GPC)>

[0044] The weight-average molecular weights (Mw) of Examples 1 to 5 and Comparative Example 1 were analyzed by gel permeation chromatography, and the measurement results are listed in Table 1 below. Examples 1 to 5 are unsaturated carbon-containing thermosetting resins containing a maleimide structure, while Comparative Example 1 is an unsaturated carbon-containing thermosetting resin without a maleimide structure. As can be seen from Table 1, compared to Comparative Example 1, the unsaturated carbon-containing thermosetting resins of Examples 1 to 5 of the present invention had higher weight-average molecular weights due to the maleimide structure grafted onto the SA90 polymer chain. Furthermore, the maleimide structure on the polymer chain provided a rigid molecular structure, further improving the mechanical properties of the material. [Table 1]

[0045] <Thermal characteristic evaluation>

[0046] The glass transition temperatures (Tg) of Examples 1 to 5 and Comparative Example 1 were measured using a differential scanning calorimeter (DSC) to evaluate the thermal properties, and the measurement results are shown in Table 2 below. The DSC heating conditions were as follows: a first temperature increase at a rate of 20°C / min, from 50°C to 350°C, followed by a temperature decrease from 350°C to 50°C at a rate of 80°C / min, and the temperature was maintained at 50°C for 2 minutes, followed by a second temperature increase at a rate of 20°C / min, from 50°C to 350°C.

[0047] See Table 2, which shows the glass transition temperature data for Examples 1 to 5 and Comparative Example 1. As can be seen from Table 2, Examples 1 to 5 of the present invention have higher glass transition temperatures than Comparative Example 1. The planar structure of the maleimide structure on the polymer chain facilitates alignment between the polymer chains, further increasing the glass transition temperature of the unsaturated carbon-containing thermosetting resin. This indicates that the unsaturated carbon-containing thermosetting resin of the present invention has good thermal stability. [Table 2]

[0048] <Preparation of gel recipe>

[0049] To evaluate the thermal stability of unsaturated carbon-containing thermosetting resin products used in gel processing of printed circuit boards, gel recipes were prepared for Examples 1 to 5 and Comparative Example 1. The gel recipe preparation process included the following: 100±2 g of each of Examples 1 to 5 and Comparative Example 1 was added to 110±5 g of methyl ethyl ketone (MEK), and 67±1 g of triallyl isocyanurate (TAIC) as a crosslinker was added. The mixture was stirred at room temperature until the solids were completely dissolved. 10±0.5 g of an initiator containing 10 wt% dicumyl peroxide (DCP) and methyl ethyl ketone was added to obtain the respective gel recipes. A gel process was performed at 170±1.5°C using the gel recipe prepared in Example 1, and the resulting cured product was Example 6 (hereinafter abbreviated as Example 6). A cured product prepared by using Example 2 instead of Example 1 and following a preparation method similar to that of Example 6 was obtained as Example 7 (hereinafter abbreviated as Example 7). A cured product prepared by using Example 3 instead of Example 1 and following a preparation method similar to that of Example 6 was obtained as Example 8 (hereinafter abbreviated as Example 8). A cured product prepared by using Example 4 instead of Example 1 and following a preparation method similar to that of Example 6 was obtained as Example 9 (hereinafter abbreviated as Example 9). A cured product prepared by using Example 5 instead of Example 1 and following a preparation method similar to that of Example 6 was obtained as Example 10 (hereinafter abbreviated as Example 10). A cured product prepared by using Comparative Example 1 instead of Example 1 and following a preparation method similar to that of Example 6 was obtained as Comparative Example 2 (hereinafter abbreviated as Comparative Example 2).

[0050] <Evaluation of thermal properties of cured products>

[0051] For Examples 6 to 10 and Comparative Example 2, the glass transition temperature (Tg) was measured using a differential scanning calorimeter (DSC), and the thermal properties were evaluated using the measurement results shown in Table 3 below. The DSC heating conditions were as follows: a first temperature increase at a heating rate of 20°C / min, from 50°C to 350°C, followed by a temperature decrease from 350°C to 50°C at a heating rate of 80°C / min, and the temperature was maintained at 50°C for 2 minutes, followed by a second temperature increase at a heating rate of 20°C / min, from 50°C to 350°C.

[0052] See Table 3 for the glass transition temperature data of Examples 6 to 10 and Comparative Example 2. As can be seen from Table 3, Examples 6 to 10 had higher glass transition temperatures and better thermal stability than Comparative Example 2. Therefore, using the unsaturated carbon-containing thermosetting resin of the present invention in a printed circuit board process contributes to the production stability of the printed circuit board process. [Table 3]

[0053] In summary, the unsaturated carbon-containing thermosetting resin of the present invention is easy to synthesize and convenient for mass production, has a good rigid structure, and a high glass transition temperature, and when used in a printed circuit board substrate, can contribute to obtaining a printed circuit board substrate with excellent mechanical strength and excellent thermal stability.

[0054] The present invention has been disclosed in the above embodiments, but these are not intended to limit the present invention, and any person skilled in the art can make various modifications and improvements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention is subject to those defined in the scope of the patent application attached later. [Explanation of symbols]

[0055] 100: Method for preparing unsaturated carbon-containing thermosetting resin 110, 120, 130: Process

Claims

1. It has the structure shown in formula (1) below: 【Chemical 1】 X is -CH ２ -, -CH(CH ３ ) - or - C(CH ３ ) ２ - and R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ and R ８ are each independently a hydrogen atom or C １ -C ３ a and b are each independently a number from 2 to 500; Y is a structure represented by formula (2), c and d are each independently a number from 1 to 300, 【Chemistry 2】 R ９ is C ４ -C ２０ is a hydrocarbon of E is a structure represented by formula (3), F is a structure represented by formula (4), and e and f are each independently a number from 1 to 200. 【Chemistry 3】 R １０ is C ２ -C ６ is a straight or branched chain hydrocarbon of 【Chemistry 4】 Z is an unsaturated carbon-containing thermosetting resin having a structure represented by formula (5). 【Chemistry 5】

2. Y is a structure shown in formula (6), 【Chemistry 6】 R １５ is C １ -C ３ and R １１ , R １２ , R １８ and R １９ are each independently C １ -C ５ and R １３ , R １４ , R １６ and R １７ are each independently a hydrogen atom or C １ -C ３ 2. The thermosetting resin according to claim 1, wherein the unsaturated carbon-containing hydrocarbon is:

3. 2. The unsaturated carbon-containing thermosetting resin according to claim 1, wherein Y has a structure represented by formula (7). 【Chemistry 7】

4. providing a polymer solution comprising a polyphenylene ether compound, a phenol compound, a maleimide compound, and a first solvent; a step of pre-polymerizing the polymer solution and the alkaline solution at a pre-polymerization reaction temperature for a pre-polymerization reaction time to form a pre-polymer solution; a step of polymerizing the preliminary polymer solution, the benzene compound solution, and the styrene compound solution at a polymerization reaction temperature for a polymerization reaction time to form a polymer solution containing the unsaturated carbon-containing thermosetting resin; 2. A method for preparing the unsaturated carbon-containing thermoset resin of claim 1, comprising:

5. 5. The method for preparing an unsaturated carbon-containing thermosetting resin according to claim 4, wherein the phenol compound is a bisphenol A derivative.

6. 5. The method for preparing an unsaturated carbon-containing thermosetting resin according to claim 4, wherein the prepolymerization reaction temperature is 35° C. to 65° C., and the prepolymerization reaction time is 3 hours to 7 hours.

7. 5. The method for preparing an unsaturated carbon-containing thermosetting resin according to claim 4, wherein the prepolymerization reaction is carried out in an environment having a pH value of 7.5 to 10.

5.

8. 5. The method for preparing an unsaturated carbon-containing thermosetting resin according to claim 4, wherein the benzene compound solution contains a benzene compound selected from the group consisting of 1,3-bis(trichloromethyl)benzene, 1,4-bis(trichloromethyl)benzene, 1,4-bis(chloromethyl)benzene, 2,4-bis(chloromethyl)trimethylbenzene, and 4,4′-bis(chloromethyl)biphenyl.

9. 5. The method for preparing an unsaturated carbon-containing thermosetting resin according to claim 4, wherein the styrene compound solution contains a styrene compound selected from the group consisting of 2-chloromethylstyrene, 3-chloromethylstyrene, and 4-chloromethylstyrene.

10. 5. The method for preparing an unsaturated carbon-containing thermosetting resin according to claim 4, wherein the polymerization reaction temperature is 35° C. to 65° C., and the polymerization reaction time is 12 hours to 18 hours.

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