Aminolytically decomposable benzoxazine resin cured product, method for producing the same, and aminolytic decomposition method

Abstract

Provided are a cured product of an aminodecomposable benzoxazine resin, a method for producing the same, and an aminodecomposition method. 【Solution means】A method for producing a cured product of an aminodecomposable benzoxazine resin, including a mixing step of melting and uniformly mixing a benzoxazine resin and a phenolic compound to obtain a resin composition, and a curing step of heating the resin composition to a curing temperature of 160°C to 230°C to form a cured product of an aminodecomposable benzoxazine resin. By selecting a low curing temperature for curing and adding a phenolic compound, the curing reaction is promoted, the produced cured product of benzoxazine resin has good material properties and chemical decomposability, and further solves the problem that the recovery of the cured product of benzoxazine resin is not easy, achieving the goal of sustainable use.

Description

Technical Field

[0001] The present disclosure relates to a cured benzoxazine resin, a method for producing the same, and an aminolysis method, and particularly relates to a cured aminolyzable benzoxazine resin, a method for producing the same, and an aminolysis method.

Background Art

[0002] The amount of carbon dioxide emitted during the production of printed circuit boards (PCBs) and the treatment of their waste is larger than that of PCBs and ranks first among current electronic product components. Therefore, how to effectively recover discarded PCBs to reduce carbon emissions has become an issue faced by related industries. Currently, as a method for recovering discarded PCBs, after pulverizing the PCBs, the metal materials therein are often taken out and recycled. However, the plastic materials (including insulating resins and glass fiber cloths) in PCBs account for about 54.5%. Most of the resins in the plastic materials are thermosetting polymers with stable properties. Since the recovery rate of plastic materials is lower than 3% and it is difficult to recover and the recovery cost is too high, currently, discarded PCBs are mainly treated by methods such as combustion and landfill. 2 Among many resin materials, benzoxazine (BZ) resin can be selected as one of the manufacturing materials for PCBs. Benzoxazine resin is obtained by reacting phenols, formaldehyde, and primary amine compounds. It has a special six-membered heterocyclic structure. By changing the types of phenols and amines, the chemical structure of benzoxazine resin can be adjusted, giving benzoxazine resin a very large molecular design space. In addition, since the cured product of benzoxazine resin has good mechanical properties, thermal properties, electrical properties, and low surface energy, it is also widely applied in fields such as PCBs and electronic packaging materials.

[0003] Among many resin materials, benzoxazine (BZ) resin can be selected as one of the manufacturing materials for PCBs. Benzoxazine resin is obtained by reacting phenols, formaldehyde, and primary amine compounds. It has a special six-membered heterocyclic structure. By changing the types of phenols and amines, the chemical structure of benzoxazine resin can be adjusted, giving benzoxazine resin a very large molecular design space. In addition, since the cured product of benzoxazine resin has good mechanical properties, thermal properties, electrical properties, and low surface energy, it is also widely applied in fields such as PCBs and electronic packaging materials.

[0004] In view of this, how to improve the decomposition ability and recovery rate of the cured benzoxazine resin remains a problem to be solved.

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present disclosure is to provide a cured benzoxazine resin in which the cured product is easily decomposed and recovered by adjusting the chemical structure of the benzoxazine resin.

Means for Solving the Problems

[0006] One embodiment of the present disclosure is Diamino derivative a benzoxazine resin and , an epoxy resin, and having an amount used of 20 phr to 25 phr (the number of added parts per 100 parts (by mass) of resin, parts per hundred parts of resin), which is bisphenol A or a phenolic resin, and the diamino derivative a mixing step of melting and uniformly mixing a phenolic compound for accelerating the curing of the benzoxazine resin to obtain a resin composition, and a curing step of heating the resin composition to a curing temperature of 160°C to 230°C to form an aminodecomposable cured benzoxazine resin. shows that the equivalent ratio of the epoxy resin and the diamino derivative benzoxazine resin is 1 or less A method for producing an aminodecomposable cured benzoxazine resin is provided.

[0007] Thereby, the method for producing an aminodecomposable cured benzoxazine resin of the present disclosure cures by selecting a low curing temperature, promotes the curing reaction by adding a phenolic compound, and the produced cured benzoxazine resin has good material properties and chemical decomposability. Furthermore, the problem that the recovery of the cured benzoxazine resin is not easy is solved, and the goal of sustainable use is achieved.

[0008] According to the method for producing an aminodecomposable cured benzoxazine resin, the curing temperature may be 180°C to 200°C.

[0009] According to the method for producing an aminodecomposable cured benzoxazine resin , e the equivalent ratio of the epoxy resin and Diamino derivative the benzoxazine resin may be 0.7 or less.

[0010] Another embodiment of the present disclosure provides a cured aminodecomposable benzoxazine resin containing a phenoxy structure, which is produced by the method for producing a cured aminodecomposable benzoxazine resin.

[0011] Another embodiment of the present disclosure provides a method for aminodecomposing a cured aminodecomposable benzoxazine resin, which includes a pre-decomposition mixing step of mixing a cured aminodecomposable benzoxazine resin and an aliphatic amine compound to obtain a mixture to be aminodecomposed, and a heating step of heating the mixture to be aminodecomposed so as to decompose the cured aminodecomposable benzoxazine resin in the mixture.

[0012] According to the method, in the heating step, the mixture to be aminodecomposed is heated at an aminodecomposition temperature, and the aminodecomposition temperature may be 100°C to 200°C. Further, the aminodecomposition temperature may be 130°C to 150°C.

[0013] According to the method, the aliphatic amine compound may be triethylenetetramine.

[0014] According to the method, the weight of the aliphatic amine compound may be 2 times or more the weight of the cured aminodecomposable benzoxazine resin. Further, the weight of the aliphatic amine compound may be 2 to 10 times the weight of the cured aminodecomposable benzoxazine resin.

Brief Description of the Drawings

[0015] The following description of the accompanying drawings is for making the above and other objects, features, merits and examples of the present disclosure clearer and easier to understand.

Figure 1

Figure 2

Best Mode for Carrying Out the Invention

[0016] Each embodiment of the present disclosure will be described in more detail below. However, this embodiment may be an application of various inventive concepts and may be specifically implemented in various specific ranges. The specific embodiments are for illustrative purposes only and are not limited by the scope of the disclosure.

[0017] In the present disclosure, the structure of a compound may be shown by a skeleton formula, but this representation method may omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. In the structural formula, when a functional group is clearly shown, the shown one shall be the reference.

[0018] Please refer to FIG. 1, which is a flowchart of the steps of the method 100 for producing a cured aminodecomposable benzoxazine resin according to the present disclosure. One embodiment of the present disclosure provides a method 100 for producing a cured aminodecomposable benzoxazine resin, including step 110 and step 120.

[0019] Step 110 is a mixing step of melting and uniformly mixing a benzoxazine resin and a phenolic compound for accelerating the curing of the benzoxazine resin to obtain a resin composition.

[0020] Step 120 is a curing step of heating the resin composition to a curing temperature of 160°C to 230°C to form a cured aminodecomposable benzoxazine resin.

[0021] Specifically, compared with conventional phenolic resins, the crosslinking behavior during the curing of benzoxazine resins is affected by the curing temperature. When the curing temperature is low, after the ring-opening crosslinking of the six-membered heterocycle in the benzoxazine resin, a phenoxy structure is formed. The Mannich crosslinking structure in this phenoxy structure is similar to the Mannich crosslinking structure on the six-membered heterocycle in the benzoxazine resin before curing. However, the carbon-oxygen bond of the Mannich crosslinking structure in the phenoxy structure is unstable, and structural rearrangement is likely to occur at high temperatures. Therefore, the lone pair of electrons on the oxygen atom resonates and crosslinks at the ortho position, finally forming a stable phenolic structure.

[0022] In addition, the carbon atoms in the Mannich crosslinking structure of the benzoxazine resin can undergo a nucleophilic addition reaction with primary amine compounds. Therefore, in the present disclosure, by utilizing the above characteristics, the benzoxazine resin and phenolic compounds are mixed, and ring-opening polymerization is carried out at a low curing temperature. Finally, the obtained cured product of the aminodecomposable benzoxazine resin has many phenoxy structures. This phenoxy structure is similar to the properties of the six-membered heterocycle of the benzoxazine resin, and the cured product of the aminodecomposable benzoxazine resin of the present disclosure can be decomposed by amine compounds. Therefore, compared with the well-known cured product of benzoxazine resin, the decomposition ability of the cured product of the aminodecomposable benzoxazine resin of the present disclosure is greatly enhanced.

[0023] The phenolic compound may be, for example, bisphenol A or a phenolic resin, but is not limited thereto. In order to promote the ring-opening reaction of the benzoxazine resin, contribute to the improvement of the crosslinking degree of the benzoxazine resin, and generate many phenoxy structures, the amount of the phenolic compound used may be 20 phr or more. Further, in order to appropriately control the crosslinking degree of the benzoxazine resin, the amount of the phenolic compound used may be 20 phr to 25 phr. However, in order to ensure that the produced aminodecomposable benzoxazine resin cured product has a specific chemical structure and excellent physical and chemical properties and decomposition ability, the present disclosure may use only the phenolic compound to promote the crosslinking reaction of the benzoxazine resin, that is, other accelerators (for example, aldehydes, amines, etc.) may not be added.

[0024] The curing temperature may be 180°C to 200°C. At this curing temperature, the curing reaction of the benzoxazine resin is more complete, which contributes to the improvement of the material properties of the benzoxazine resin cured product. The relationship between the curing temperature and the curing degree of the benzoxazine resin will be explained in detail in later experiments, so it will not be explained in detail here.

[0025] Further, the resin composition may further contain an epoxy resin, and the addition amount of the epoxy resin can be controlled by adjusting the equivalent ratio of the epoxy resin and the benzoxazine resin. The calculation form of the equivalent ratio is the equivalent value of the epoxy resin / the equivalent value of the benzoxazine resin. Specifically, in the method for producing the aminodecomposable benzoxazine resin cured product of the present disclosure, the epoxy resin may or may not be added when the benzoxazine resin and the phenolic compound are mixed. When the equivalent ratio is 0, it means that no epoxy resin is added to the aminodecomposable benzoxazine resin cured product. When the equivalent ratio is in the range of 0 to 1, it means that the epoxy resin is added to the aminodecomposable benzoxazine resin cured product. When the equivalent ratio is 1, it means that the equivalent ratio of the epoxy resin and the benzoxazine resin in the aminodecomposable benzoxazine resin cured product is 1:1.

[0026] The equivalent ratio of the epoxy resin to the benzoxazine resin may be 1 or less. By adding the epoxy resin, the material properties of the cured benzoxazine resin can be adjusted and the manufacturing cost can be reduced. Further, the equivalent ratio of the epoxy resin to the benzoxazine resin may be 0.7 or less. Thereby, by controlling the ratio of the epoxy resin, the excellent decomposability of the cured benzoxazine resin is maintained.

[0027] Please refer to FIG. 2, which is a flowchart of the steps of the aminolytic decomposition method 200 of the aminolytic benzoxazine resin cured product of the present disclosure. Another embodiment of the present disclosure provides an aminolytic decomposition method 200 of the aminolytic benzoxazine resin cured product including steps 210 and 220.

[0028] Step 210 is a pre-decomposition mixing step of mixing the aminolytic benzoxazine resin cured product and an aliphatic amines compound to obtain a mixture to be aminolytically decomposed. The aliphatic amines compound may be triethylenetetramine (TETA). To ensure a good decomposition effect of the cured benzoxazine resin, the weight of the aliphatic amines compound may be 2 times or more the weight of the aminolytic benzoxazine resin cured product. Also, to avoid excessive residue of the aliphatic amines compound and affecting subsequent processing, the weight of the aliphatic amines compound may be 2 to 10 times the weight of the aminolytic benzoxazine resin cured product.

[0029] Step 220 is a heating step of heating the mixture to be aminolytically decomposed so as to decompose the aminolytic benzoxazine resin cured product in the mixture to be aminolytically decomposed. However, the aminolytic benzoxazine resin cured product of the present disclosure has many phenoxy structures as the break point of amine decomposition and undergoes an amine decomposition reaction as shown in the chemical reaction formula of the following figure.

Chemical formula

[0030] Specifically, in the heating step, the mixture to be aminolyzed is heated at the aminolysis temperature, and the aminolysis temperature may be 100°C to 200°C in order to provide sufficient reaction energy. Further, the aminolysis temperature may be 130°C to 150°C in order to further promote the aminolysis reaction.

[0031] For the advantage of those skilled in the art of the present disclosure, the present disclosure is further illustrated using the following specific examples, and the present disclosure can be fully utilized and implemented without excessive interpretation, and these examples should not be regarded as limiting the scope of the present disclosure, but are used to illustrate how to implement the materials and methods of the present disclosure.

[0032] <Example 1> 2 grams (0.0092 eq) of a diamino diphenyl ether-based benzoxazine resin (product code PF3500 manufactured by Changchun Artificial Resin Co., Ltd.), 0.86 grams (0.0018 eq) of a bisphenol A chain extension epoxy resin (epoxy KP-158 manufactured by Shanghai Weidong New Materials Co., Ltd. with an epoxy equivalent of 470 g / eq) and 20 phr of bisphenol A were melted and uniformly mixed to obtain a resin composition. Next, the resin composition was applied in a metal aluminum dish, placed in an oven, heated to 150°C and held for a certain time, then gradually heated to 180°C to complete the cross-linking reaction, and finally a film of the aminolyzable benzoxazine resin cured product was obtained.

[0033] However, the cross-linking reaction of the benzoxazine resin and the phenolic compound started at 150°C. Any person skilled in the art can freely select an appropriate reaction time according to the content of the benzoxazine resin, the content of the phenolic compound and the selected equipment at the temperature disclosed in the present disclosure, so as to completely react the benzoxazine resin and the phenolic compound to obtain the aminolyzable benzoxazine resin cured product of the present disclosure.

[0034] <Example 2> 2 grams (0.0092 eq) of a diaminodiphenyl ether-based benzoxazine resin (product code PF3500 manufactured by Changchun Synthetic Resin Co., Ltd.), 0.86 grams (0.0018 eq) of a bisphenol A type chain extender epoxy resin (epoxy KP-158 manufactured by Swancor Industrial Co., Ltd.), and 20 phr of a phenolic resin (PN) were melted and uniformly mixed to obtain a resin composition. Next, the resin composition was applied in a metal aluminum dish, placed in an oven, heated to 150 °C and held for a certain period of time, then gradually heated to 180 °C to complete the crosslinking reaction, and finally a film of the aminodecomposable benzoxazine resin cured product was obtained.

[0035] <Example 3> The amount of the bisphenol A type chain extender epoxy resin used in the resin composition of Example 2 was adjusted to 1.07 grams (0.0023 eq), and the other components and processes were the same as those in Example 2.

[0036] <Example 4> The amount of the bisphenol A type chain extender epoxy resin used in the resin composition of Example 2 was adjusted to 1.23 grams (0.0026 eq), and the other components and processes were the same as those in Example 2.

[0037] <Example 5> The final temperature for the gradual temperature increase in Example 2 was adjusted to 200 °C, and the other components and processes were the same as those in Example 2.

[0038] <Example 6> 1.5 grams (0.0069 eq) of a diaminodiphenyl ether-based benzoxazine resin (product code PF3500 manufactured by Changchun Synthetic Resin Co., Ltd.), 0.42 grams (0.0023 eq) of a bisphenol A type epoxy resin (product code BE188 manufactured by Changchun Synthetic Resin Co., Ltd.), and 20 phr of bisphenol A were melted and uniformly mixed to obtain a resin composition. Next, the resin composition was applied in a metal aluminum dish, placed in an oven, heated to 150 °C and held for a certain period of time, then gradually heated to 180 °C to complete the crosslinking reaction, and finally a film of the aminodecomposable benzoxazine resin cured product was obtained.

[0039] <Example 7> The amount of the diaminodiphenyl ether-based benzoxazine resin in the resin composition of Example 6 was adjusted to 2 grams (0.0092 eq), and the amount of the bisphenol A type epoxy resin was adjusted to 0.84 grams (0.0046 eq). Other components and procedures were the same as those in Example 6.

[0040] <Example 8> The amount of the diaminodiphenyl ether-based benzoxazine resin in the resin composition of Example 6 was adjusted to 2 grams (0.0092 eq), and the amount of the bisphenol A type epoxy resin was adjusted to 1.13 grams (0.0061 eq). Other components and procedures were the same as those in Example 6.

[0041] <Example 9> The final temperature of the gradually increasing temperature in Example 6 was adjusted to 200 °C. Other components and procedures were the same as those in Example 6.

[0042] <Example 10> 1.5 grams (0.0069 eq) of a diaminodiphenyl ether-based benzoxazine resin (product code PF3500 manufactured by Changchun Artificial Resin Co., Ltd.), 0.42 grams (0.0023 eq) of a bisphenol A type epoxy resin (product code BE188 manufactured by Changchun Artificial Resin Co., Ltd.) and 20 phr of a phenol resin (PN) were melted and uniformly mixed to obtain a resin composition. Next, the resin composition was applied in a metal aluminum dish, placed in an oven, heated to 150 °C and held for a certain time, then gradually heated to 180 °C to complete the cross-linking reaction, and finally a film of the aminodecomposable benzoxazine resin cured product was obtained.

[0043] <Example 11> The amount of the diaminodiphenyl ether-based benzoxazine resin in the resin composition of Example 10 was adjusted to 2 grams (0.0092 eq), and the amount of the bisphenol A type epoxy resin was adjusted to 0.84 grams (0.0046 eq). Other components and procedures were the same as those in Example 10.

[0044] <Example 12> The amount of the diaminodiphenyl ether-based benzoxazine resin in the resin composition of Example 10 was adjusted to 2 grams (0.0092 eq), and the amount of the bisphenol A type epoxy resin was adjusted to 1.13 grams (0.0061 eq). Other components and procedures were the same as those in Example 10.

[0045] <Example 13> The final temperature of gradually increasing the temperature in Example 10 was adjusted to 200 °C. Other components and procedures were the same as those in Example 10.

[0046] <Example 14> 3 grams (0.0137 eq) of a diaminodiphenyl ether-based benzoxazine resin (product code PF3500 manufactured by Changchun Artificial Resin Co., Ltd.) and 20 phr of bisphenol A were melted and uniformly mixed to obtain a resin composition. Next, the resin composition was applied in a metal aluminum dish, placed in an oven, heated to 150 °C and held for a certain period of time, then gradually heated to 180 °C to complete the cross-linking reaction, and finally a film of the aminodecomposable benzoxazine resin cured product was obtained.

[0047] <Example 15> 3 grams (0.0137 eq) of a diaminodiphenyl ether-based benzoxazine resin (product code PF3500 manufactured by Changchun Artificial Resin Co., Ltd.) and 20 phr of a phenol resin (PN) were melted and uniformly mixed to obtain a resin composition. Next, the resin composition was applied in a metal aluminum dish, placed in an oven, heated to 150 °C and held for a certain period of time, then gradually heated to 200 °C to complete the cross-linking reaction, and finally a film of the aminodecomposable benzoxazine resin cured product was obtained.

[0048] <Comparative Example 1> 2 grams (0.0092 eq) of a diaminodiphenyl ether-based benzoxazine resin (product code PF3500 manufactured by Changchun Artificial Resin Co., Ltd.), 0.86 grams (0.0018 eq) of a bisphenol A type chain extender epoxy resin (epoxy KP-158 manufactured by Showa Highpolymer Co., Ltd.) and 2 phr of bisphenol A were melted and uniformly mixed to obtain a resin composition. Next, the resin composition was applied in a metal aluminum dish, placed in an oven, heated to 120 °C and held for a certain period of time, and then gradually heated to 150 °C to complete the crosslinking reaction and form a film.

[0049] <Comparative Example 2> The amount of bisphenol A used in the resin composition of Comparative Example 1 was adjusted to 5 phr, and all other components and processes were the same as in Comparative Example 1.

[0050] <Comparative Example 3> The amount of bisphenol A used in the resin composition of Comparative Example 1 was adjusted to 10 phr, and all other components and processes were the same as in Comparative Example 1.

[0051] <Comparative Example 4> The amount of bisphenol A used in the resin composition of Comparative Example 1 was adjusted to 15 phr, and all other components and processes were the same as in Comparative Example 1.

[0052] <Comparative Example 5> The amount of bisphenol A used in the resin composition of Comparative Example 1 was adjusted to 20 phr, and all other components and processes were the same as in Comparative Example 1.

[0053] <Comparative Example 6> 2 grams (0.0092 eq) of a diaminodiphenyl ether-based benzoxazine resin (product code PF3500 manufactured by Changchun Synthetic Resin Co., Ltd.), 0.86 grams (0.0018 eq) of a bisphenol A-type chain extender epoxy resin (epoxy KP-158 manufactured by Swancor Industrial Co., Ltd.) and 20 phr of a phenolic resin (PN) were melted and uniformly mixed to obtain a resin composition. Next, the resin composition was applied in a metal aluminum dish, placed in an oven, heated to 120 °C and held for a certain period of time, and then gradually heated to 150 °C to complete the crosslinking reaction and form a film.

[0054] <Comparative Example 7> 1.5 grams (0.0069 eq) of a diaminodiphenyl ether-based benzoxazine resin (product code PF3500 manufactured by Changchun Synthetic Resin Co., Ltd.), 0.42 grams (0.0023 eq) of a bisphenol A-type epoxy resin (product code BE188 manufactured by Changchun Synthetic Resin Co., Ltd.) and 20 phr of bisphenol A were melted and uniformly mixed to obtain a resin composition. Next, the resin composition was applied in a metal aluminum dish, placed in an oven, heated to 120 °C and held for a certain period of time, and then gradually heated to 150 °C to complete the crosslinking reaction and form a film.

[0055] <Comparative Example 8> 1.5 grams (0.0069 eq) of a diaminodiphenyl ether-based benzoxazine resin (product code PF3500 manufactured by Changchun Synthetic Resin Co., Ltd.), 0.42 grams (0.0023 eq) of a bisphenol A-type epoxy resin (product code BE188 manufactured by Changchun Synthetic Resin Co., Ltd.) and 20 phr of a phenolic resin (PN) were melted and uniformly mixed to obtain a resin composition. Next, the resin composition was applied in a metal aluminum dish, placed in an oven, heated to 120 °C and held for a certain period of time, and then gradually heated to 150 °C to complete the crosslinking reaction and form a film.

[0056] <Comparative Example 9> 3 grams (0.0137 eq) of a diaminodiphenyl ether-based benzoxazine resin (product code PF3500 manufactured by Changchun Artificial Resin Co., Ltd.) was melted and applied in a metal aluminum dish, placed in an oven, heated to 150 °C and held for a certain period of time, and then gradually heated to 180 °C to complete the cross-linking reaction and form a film.

[0057] <Comparative Example 10> 2 grams (0.0092 eq) of a diaminodiphenyl ether-based benzoxazine resin (product code PF3500 manufactured by Changchun Artificial Resin Co., Ltd.) and 0.86 grams (0.0018 eq) of a bisphenol A type chain extender epoxy resin (epoxy KP-158 manufactured by Showa Highpolymer Co., Ltd.) were melted and uniformly mixed to obtain a resin composition. Next, the resin composition was applied in a metal aluminum dish, placed in an oven, heated to 150 °C and held for a certain period of time, and then gradually heated to 180 °C to complete the cross-linking reaction and form a film.

[0058] <Comparative Example 11> 1.5 grams (0.0069 eq) of a diaminodiphenyl ether-based benzoxazine resin (product code PF3500 manufactured by Changchun Artificial Resin Co., Ltd.) and 0.42 grams (0.0023 eq) of a bisphenol A type epoxy resin (product code BE188 manufactured by Changchun Artificial Resin Co., Ltd.) were melted and uniformly mixed to obtain a resin composition. Next, the resin composition was applied in a metal aluminum dish, placed in an oven, heated to 150 °C and held for a certain period of time, and then gradually heated to 180 °C to complete the cross-linking reaction and form a film.

[0059] <Comparative Example 12> 2 grams (0.0092 eq) of a diaminodiphenyl ether-based benzoxazine resin (product code PF3500 manufactured by Changchun Synthetic Resin Co., Ltd.), 1.13 grams (0.0061 eq) of a bisphenol A-type epoxy resin (product code BE188 manufactured by Changchun Synthetic Resin Co., Ltd.) and 20 phr of bisphenol A were melted and uniformly mixed to obtain a resin composition. Next, the resin composition was applied in a metal aluminum dish, placed in an oven, heated to 150 °C and held for a certain period of time, and then gradually heated to 240 °C to complete the crosslinking reaction and form a film.

[0060] <Comparative Example 13> 2 grams (0.0092 eq) of a diaminodiphenyl ether-based benzoxazine resin (product code PF3500 manufactured by Changchun Synthetic Resin Co., Ltd.), 1.13 grams (0.0061 eq) of a bisphenol A-type epoxy resin (product code BE188 manufactured by Changchun Synthetic Resin Co., Ltd.) and 20 phr of a phenolic resin (PN) were melted and uniformly mixed to obtain a resin composition. Next, the resin composition was applied in a metal aluminum dish, placed in an oven, heated to 150 °C and held for a certain period of time, and then gradually heated to 240 °C to complete the crosslinking reaction and form a film.

[0061] <Physical properties of aminodecomposable benzoxazine resin cured product> The following experimental results were obtained by measuring the glass transition temperature (T g , °C) and the remaining heat release amount (J / g) after curing of the above examples and comparative examples using a differential scanning calorimeter (DSC). The heating rate during the measurement was 10 °C / min, and the measurement results are shown in Table 1 below.

[0062]

Table 1

[0063] As can be seen from the results in Table 1, the glass transition temperatures of the cured products of the aminodecomposable benzoxazine resins produced in Examples 1 to 13 containing epoxy resins can all reach 115°C or higher. Moreover, in Examples 1 to 13 where phenolic compounds were added, compared with Comparative Examples 10 and 11 without the addition of phenolic compounds, the remaining heat release amount after curing decreased significantly (both were less than 35 J / g). In addition, in Examples 14 and 15 and Comparative Example 9 without epoxy resins, it was found that the remaining heat release amount after curing of Examples 14 and 15 with the addition of phenolic compounds decreased significantly compared with Comparative Example 9 without the addition of phenolic compounds. It was proved that by adding phenolic compounds, the ring-opening of epoxy resins and benzoxazine resins at 180°C and 200°C can be promoted, and furthermore, the degree of crosslinking increases.

[0064] Also, in Comparative Examples 5 to 8, the amount of phenolic compounds added was constant, and the curing temperature decreased to 150°C. From the results in Table 1, it was found that the remaining heat release amount after curing in Comparative Examples 5 to 8 was higher than that in Examples 1, 2, 6, and 10 with curing temperatures of 180°C and 200°C. It was proved that the curing reaction can be made more complete at curing temperatures of 180°C and 200°C.

[0065] Also, as can be seen from the measurement results in Comparative Examples 1 to 5, after the amount of phenolic compounds used increased up to 20 phr, the remaining heat release amount after curing decreased significantly, the reactivity of the curing reaction was improved with the increase in phenolic compounds, and it was shown that no significant improvement effect can be obtained unless the amount of phenolic compounds used reaches a certain level.

[0066] When the usage amount of the phenolic compound is lower than 20 phr, the ability to catalyze the ring-opening of the benzoxazine resin and the epoxy resin is inferior, the degree of crosslinking of the entire resin composition decreases, the remaining heat dissipation amount becomes excessive, and when applied to a PCB, it affects subsequent processing. When the usage amount of the phenolic compound is higher than 25 phr, since the molecules of the phenolic compound are small, it affects the polymer sequence after introduction, the heat resistance of the entire cured product deteriorates, and the glass transition temperature and decomposition effect of the cured product decrease.

[0067] <Amino-decomposable ability of benzoxazine resin cured product> The following experimental results are obtained by immersing the films produced in the above examples and comparative examples in triethylenetetramine, putting them into an oven at 135 °C and heating for 1.5 hours, observing the changes in the films and evaluating the decomposable ability, and listing the observation results in Table 2 below.

[0068]

Table 2

[0069] Note that in Comparative Examples 1 to 8, since the remaining heat dissipation amount after curing obtained in the previous experiment is excessive, indicating that the curing reaction is incomplete, the decomposable ability of Comparative Examples 1 to 8 is not examined here.

[0070] As can be seen from the results in Table 2, Examples 1 to 15 with curing temperatures of 180 °C and 200 °C can all be decomposed by the method of the present disclosure, and Examples 1, 10, and 14 are all completely dissolved. In other examples, small pieces or colloidal lumps without strength are formed after decomposition. By comparison, Comparative Examples 9 to 11 have decomposable ability, but since no phenolic compound is added, the remaining heat dissipation amount after curing measured in the previous experiment is large (all larger than 35 J / g), indicating that the degree of curing of Comparative Examples 9 to 11 is inferior, and there are certain limitations in application. Also, Comparative Examples 12 and 13 with a curing temperature of 240 °C cannot be decomposed into fragments without strength, indicating that the decomposition effect is not good.

[0071] As can be seen from the above experimental results, the decomposing ability of the cured product was related to the crosslinking mechanism of the benzoxazine resin at different temperatures. The Mannich-type phenoxy structure formed by crosslinking at low temperatures (curing temperatures of 180°C and 200°C) was more susceptible to the attack of the lone pair of electrons of the primary amine compound than the Mannich-type phenol group structure formed by crosslinking at high temperatures (curing temperature of 240°C), and further decomposition effects were obtained.

[0072] In summary, according to the cured product of the amino-decomposable benzoxazine resin of the present disclosure, by selecting a low curing temperature, it cures, and by adding phenolic compounds, the curing reaction is promoted. Therefore, the produced cured benzoxazine resin has good material properties and chemical decomposability, and further solves the problem that the recovery of the cured benzoxazine resin is not easy, achieving the goal of sustainable use.

[0073] The molding form of the cured product of the amino-decomposable benzoxazine resin of the present disclosure is not limited to the form disclosed in the examples of the present disclosure, and can be applied to drawing molding, thermoforming, injection molding or other molding forms, etc.

[0074] Although the present disclosure has been disclosed as described above by way of examples, it is not limited to the above-described embodiments, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure. Therefore, the protection scope of the present disclosure is based on the content specified in the following claims.

Explanation of Reference Signs

[0075] 100: Method for producing a cured product of an amino-decomposable benzoxazine resin 200: Amino-decomposition method for a cured product of an amino-decomposable benzoxazine resin 110, 120, 210, 220: Steps

Claims

1. A mixing step of melting and uniformly mixing a benzoxazine resin and a phenolic compound for promoting the curing of the benzoxazine resin to obtain a resin composition; A curing step of heating the resin composition to a curing temperature of 160°C to 230°C to form a cured product of an aminodecomposable benzoxazine resin; A method for producing a cured product of an aminodecomposable benzoxazine resin, characterized by comprising the above.

2. The method for producing a cured product of an aminodecomposable benzoxazine resin according to claim 1, wherein the amount of the phenolic compound used is 20 phr or more.

3. The method for producing a cured product of an aminodecomposable benzoxazine resin according to claim 2, wherein the amount of the phenolic compound used is 20 phr to 25 phr.

4. The method for producing a cured product of an aminodecomposable benzoxazine resin according to claim 1, wherein the phenolic compound is bisphenol A or a phenolic resin.

5. The method for producing a cured product of an aminodecomposable benzoxazine resin according to claim 1, wherein the curing temperature is 180°C to 200°C.

6. The method for producing a cured product of an aminodecomposable benzoxazine resin according to any one of claims 1 to 5, wherein the resin composition further contains an epoxy resin, and the equivalent ratio of the epoxy resin to the benzoxazine resin is 1 or less.

7. The method for producing a cured product of an aminodecomposable benzoxazine resin according to claim 6, wherein the equivalent ratio of the epoxy resin to the benzoxazine resin is 0.7 or less.

8. A cured aminodecomposable benzoxazine resin produced by the method for producing a cured aminodecomposable benzoxazine resin according to any one of claims 1 to 5, characterized by containing a phenoxy structure.

9. A cured aminodecomposable benzoxazine resin produced by the method for producing a cured aminodecomposable benzoxazine resin according to claim 6, characterized by containing a phenoxy structure.

10. A cured aminodecomposable benzoxazine resin produced by the method for producing a cured aminodecomposable benzoxazine resin according to claim 7, characterized by containing a phenoxy structure.

11. In the method for aminodecomposing a cured aminodecomposable benzoxazine resin according to claim 8, a pre-decomposition mixing step of mixing the cured aminodecomposable benzoxazine resin and an aliphatic amines compound to obtain a mixture to be aminodecomposed; a heating step of heating the mixture to be aminodecomposed so as to decompose the cured aminodecomposable benzoxazine resin in the mixture to be aminodecomposed; The method for aminodecomposing a cured aminodecomposable benzoxazine resin, characterized by comprising the above.

12. The method according to claim 11, characterized in that in the heating step, the mixture to be aminodecomposed is heated at an aminodecomposition temperature of 100°C to 200°C.

13. The method according to claim 12, characterized in that the aminodecomposition temperature is 130°C to 150°C.

14. The method according to claim 11, characterized in that the aliphatic amines compound is triethylenetetramine.

15. The method according to claim 11, characterized in that the weight of the aliphatic amines compound is 2 times or more the weight of the cured aminodecomposable benzoxazine resin.

16. The weight of the aliphatic amine compound is 2 to 10 times the weight of the cured product of the aminodecomposable benzoxazine resin, and the method according to claim 15 is characterized by this.

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