Polymer compounds and resin compositions

Abstract

To provide polymer compounds and resin compositions with low dielectric loss tangent. [Solution] A polymer compound comprising a first repeating unit represented by the following general formula (1) and a second repeating unit represented by the following general formula (2a) or (2b), wherein the total mol% ratio of the first repeating unit and the second repeating unit is 90 mol% or more. JPEG0007864417000018.jpg107168

Description

Technical Field

[0001] The present disclosure relates to a polymer compound and a resin composition.

Background Art

[0002] Patent Documents 1 and 2 disclose polymer compounds. The polymer compound can be used, for example, in resin compositions, resin films, prepregs, laminates, printed wiring boards, semiconductor packages, high heat-resistant substrate materials, flexible substrate materials, high heat-resistant low dielectric materials, high heat-resistant CFPR materials, high heat-resistant encapsulation materials for in-vehicle SiC power devices, and the like.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] A polymer compound may be used in a place where a high-frequency alternating electric field occurs. In this case, the polymer compound is required to have a small dielectric loss tangent in order to suppress energy loss. In one aspect of the present disclosure, it is preferable to provide a polymer compound and a resin composition having a small dielectric loss tangent.

Means for Solving the Problems

[0005] One aspect of the present disclosure is a polymer compound including a first repeating unit represented by the following general formula (1) and a second repeating unit represented by the following general formula (2a) or (2b), wherein the total of the mol% ratio of the first repeating unit and the mol% ratio of the second repeating unit is 90 mol% or more. The polymer compound of one aspect of the present disclosure has a small dielectric loss tangent.

[0006] [ka]

[0007] Another aspect of this disclosure is a polymer compound comprising a first repeating unit represented by the following general formula (1), a second repeating unit represented by the following general formula (2a) or (2b), and a third repeating unit represented by the following general formula (3a) or (3b), wherein the sum of the mol% ratio of the first repeating unit, the mol% ratio of the second repeating unit, and the mol% ratio of the third repeating unit is 90 mol% or more. In formula (3b), R is an alkyl chain having 4 to 24 carbon atoms. The polymer compound of this other aspect of this disclosure has a small dielectric loss tangent.

[0008] [ka]

[0009] [ka] [Brief explanation of the drawing]

[0010] [Figure 1] This is an explanatory diagram illustrating the reaction involved in the synthesis of polymer compounds. [Modes for carrying out the invention]

[0011] Exemplary embodiments of this disclosure will be described with reference to the drawings. 1. Composition of polymer compound A Polymer compound A comprises a first repeating unit ru1 represented by the following general formula (1) and a second repeating unit ru2 represented by the following general formula (2a) or (2b).

[0012] [ka]

[0013] The second repeating unit ru2 may consist only of the repeating unit ru2a represented by the general formula (2a), may consist only of the repeating unit ru2b represented by the general formula (2b), or may contain both the repeating unit ru2a and the repeating unit ru2b. The repeating unit ru2a is indene. The repeating unit ru2b is styrene.

[0014] In the polymer compound A, the total m of the mol% ratio of the first repeating unit ru1 and the mol% ratio of the second repeating unit ru2 tA is 90 mol% or more. m tA is preferably 95 mol% or more, more preferably 98 mol% or more, still more preferably 99 mol% or more, and particularly preferably 100 mol%. m tA When m is 100 mol%, in the polymer compound A, all repeating units other than the first repeating unit ru1 consist of the second repeating unit ru2.

[0015] The mol% ratio of the second repeating unit ru2 is the sum of the mol% ratio of the repeating unit ru2a and the mol% ratio of the repeating unit ru2b. When the second repeating unit ru2 does not contain the repeating unit ru2b, the mol% ratio of the second repeating unit ru2 is equal to the mol% ratio of the repeating unit ru2a. When the second repeating unit ru2 does not contain the repeating unit ru2a, the mol% ratio of the second repeating unit ru2 is equal to the mol% ratio of the repeating unit ru2b.

[0016] In the polymer compound A, the mol% ratio of the first repeating unit ru1 is preferably 1 mol% or more and 50 mol% or less, more preferably 3 mol% or more and 40 mol% or less, still more preferably 4 mol% or more and 35 mol% or less, and particularly preferably 5 mol% or more and 30 mol% or less.

[0017] In any of the cases where the second repeating unit ru2 consists only of repeating unit ru2a, where the second repeating unit ru2 consists only of repeating unit ru2b, or where the second repeating unit ru2 contains both repeating unit ru2a and repeating unit ru2b, the mol% ratio of the second repeating unit ru2 in polymer compound A is preferably 50 mol% or more and 99 mol% or less, more preferably 60 mol% or more and 97 mol% or less, even more preferably 65 mol% or more and 96 mol% or less, and particularly preferably 70 mol% or more and 95 mol% or less.

[0018] The mass-average molecular weight of polymer compound A is preferably 500 to 100,000, more preferably 500 to 50,000, and particularly preferably 500 to 10,000. For example, the mass-average molecular weight of polymer compound A is 3,000 to 10,000, or 3,500 to 10,000.

[0019] 2. Composition of polymer compound B Polymer compound B contains a first repeating unit ru1 represented by the following general formula (1), a second repeating unit ru2 represented by the following general formula (2a) or (2b), and a third repeating unit ru3 represented by the following general formula (3a) or (3b). In formula (3b), R is an alkyl chain having 4 to 24 carbon atoms.

[0020] [ka]

[0021] [ka]

[0022] The second repeating unit ru2 may consist only of repeating units ru2a represented by general formula (2a), or only of repeating units ru2b represented by general formula (2b), or it may include both repeating units ru2a and ru2b.

[0023] The third repeating unit ru3 may consist only of repeating units ru3a represented by general formula (3a), or only of repeating units ru3b represented by general formula (3b), or may contain both repeating units ru3a and ru3b. Repeating unit ru3a is acenaphthylene.

[0024] In polymer compound B, the sum of the mol% ratios of the first repeating unit ru1, the second repeating unit ru2, and the third repeating unit ru3 is m tB It is 90 mol% or more. tB The concentration is preferably 95 mol% or more, more preferably 98 mol% or more, even more preferably 99 mol% or more, and particularly preferably 100 mol%. tB When the concentration is 100 mol%, in polymer compound B, all repeating units other than the first repeating unit ru1 consist of either the second repeating unit ru2 or the third repeating unit ru3.

[0025] The mol% ratio of the second repeating unit ru2 is the sum of the mol% ratio of repeating unit ru2a and the mol% ratio of repeating unit ru2b. If the second repeating unit ru2 does not contain repeating unit ru2b, the mol% ratio of the second repeating unit ru2 is equal to the mol% ratio of repeating unit ru2a. If the second repeating unit ru2 does not contain repeating unit ru2a, the mol% ratio of the second repeating unit ru2 is equal to the mol% ratio of repeating unit ru2b.

[0026] Furthermore, the mol% ratio of the third repeating unit ru3 is the sum of the mol% ratio of repeating unit ru3a and the mol% ratio of repeating unit ru3b. If the third repeating unit ru3 does not contain repeating unit ru3b, the mol% ratio of the third repeating unit ru3 is equal to the mol% ratio of repeating unit ru3a. If the third repeating unit ru3 does not contain repeating unit ru3a, the mol% ratio of the third repeating unit ru3 is equal to the mol% ratio of repeating unit ru3b.

[0027] In polymer compound B, the mol% ratio of the first repeating unit ru1 is preferably 1 mol% or more and 50 mol% or less, more preferably 3 mol% or more and 40 mol% or less, even more preferably 4 mol% or more and 35 mol% or less, and particularly preferably 5 mol% or more and 30 mol% or less.

[0028] In any of the cases where the second repeating unit ru2 consists only of repeating unit ru2a, where the second repeating unit ru2 consists only of repeating unit ru2b, or where the second repeating unit ru2 contains both repeating unit ru2a and repeating unit ru2b, the mol% ratio of the second repeating unit ru2 in polymer compound B is preferably 1 mol% or more and 98 mol% or less, more preferably 1 mol% or more and 96 mol% or less, even more preferably 1 mol% or more and 95 mol% or less, and particularly preferably 1 mol% or more and 94 mol% or less. The mol% ratio of the second repeating unit ru2 is, for example, 70 mol% or more and 85 mol% or less, or 75 mol% or more and 80 mol% or less.

[0029] In any of the cases where the third repeating unit ru3 consists only of repeating unit ru3a, where the third repeating unit ru3 consists only of repeating unit ru3b, or where the third repeating unit ru3 contains both repeating unit ru3a and repeating unit ru3b, the mol% ratio of the third repeating unit ru3 in polymer compound B is preferably 1 mol% or more and 98 mol% or less, more preferably 1 mol% or more and 96 mol% or less, even more preferably 1 mol% or more and 95 mol% or less, and particularly preferably 1 mol% or more and 94 mol% or less. The mol% ratio of the third repeating unit ru3 is, for example, 5 mol% or more and 15 mol% or less, or 7 mol% or more and 13 mol% or less.

[0030] The mass-average molecular weight of polymer compound B is preferably 500 to 100,000, more preferably 500 to 50,000, and particularly preferably 500 to 10,000. For example, the mass-average molecular weight of polymer compound B is 4,500 to 6,500, or 5,000 to 6,000.

[0031] 3. Method for producing polymer compound A (1) Synthesis of precursor resins A precursor resin is prepared as a raw material for polymer compound A. The precursor resin contains a maleic anhydride unit ru0 represented by general formula (4) and a second repeating unit ru2.

[0032] [ka]

[0033] When polymer compound A is produced from a precursor resin, the maleic anhydride units ru0 contained in the precursor resin become the first repeating units ru1. The second repeating units ru2 contained in the precursor resin remain as they are and become part of polymer compound A. Depending on the composition of polymer compound A to be produced, the mol% ratio of maleic anhydride units ru0 and the second repeating units ru2 in the precursor resin can be set.

[0034] One method for synthesizing precursor resins involves dissolving a repeating unit containing maleic anhydride unit ru0 and a second repeating unit ru2 in an organic solvent, adding a radical polymerization initiator, and carrying out thermal polymerization.

[0035] Examples of organic solvents used in the synthesis of precursor resins include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, methyl ethyl ketone, methyl isobutyl ketone, and Ipsol 100 (trade name, manufactured by Idemitsu Kosan Co., Ltd.).

[0036] Examples of radical polymerization initiators used in the synthesis of precursor resins include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), benzoyl peroxide, lauroyl peroxide, and dicumyl peroxide.

[0037] The polymerization temperature in the synthesis of the precursor resin is preferably 50 to 250°C. The reaction time in the synthesis of the precursor resin is preferably 2 to 100 hours, and more preferably 3 to 20 hours.

[0038] After the polymerization reaction is complete, the precursor resin can be extracted by solidifying the molten precursor resin while distilling off the organic solvent. Alternatively, the precursor resin may be extracted by adding the polymerization solution to a poor solvent such as hexane and filtering and drying the precipitated precursor resin.

[0039] (2) Synthesis of polymer compound A The obtained precursor resin can be reacted with 4,4'-diamino-2,2'-dimethylbiphenyl and maleic anhydride, and dehydrated to synthesize polymer compound A. This reaction can be carried out in a solvent.

[0040] This reaction is shown in Figure 1. In this reaction, the maleic anhydride unit ru0 in the precursor resin reacts with 4,4'-diamino-2,2'-dimethylbiphenyl and maleic anhydride, undergoing dehydration and cyclization to transform into the first repeating unit ru1. The second repeating unit ru2 contained in the precursor resin remains and becomes part of polymer compound A. Heating and cooling can be performed as needed during the reaction. The water produced as a by-product during the reaction can be removed from the system by azeotrope with the solvent.

[0041] Examples of solvents that can be used in the synthesis of polymer compound A include ethers such as tetrahydrofuran (THF), diethyl ether, diisopropyl ether, di-n-butyl ether, and 1,4-dioxane; hydrocarbons such as n-hexane, n-heptane, benzene, toluene, and xylene; aprotic polar solvents such as acetonitrile, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), and N-methylpyrrolidone; and chlorinated organic solvents such as methylene chloride, chloroform, and carbon tetrachloride.

[0042] The reaction temperature for the synthesis of polymer compound A is preferably -20 to 150°C, and more preferably 0 to 120°C. The reaction time for the synthesis of polymer compound A is preferably 5 minutes to 24 hours, and more preferably 1 to 20 hours.

[0043] In the synthesis of polymer compound A, the dehydration reaction can be accelerated by using an acid catalyst or a base catalyst. The acid catalyst used is not particularly limited. Examples of acid catalysts that can be used include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, and phosphoric acid. The amount of acid catalyst used is usually 0.1 to 50% by mass, preferably 1 to 25% by mass, relative to the mass of the precursor resin.

[0044] The resulting reaction solution can be purified using known purification methods used for the purification of organic compounds. Purification can increase the purity of polymer compound A.

[0045] 4. Method for producing polymer compound B Basically, polymer compound B can be manufactured in the same manner as polymer compound A. However, the precursor resin used in the manufacturing process includes maleic anhydride unit ru0, a second repeating unit ru2, and a third repeating unit ru3.

[0046] When polymer compound B is produced from a precursor resin, the maleic anhydride unit ru0 contained in the precursor resin becomes the first repeating unit ru1. The second repeating unit ru2 and the third repeating unit ru3 contained in the precursor resin remain as they are and become part of polymer compound B. Depending on the composition of polymer compound B to be produced, the mol% ratio of maleic anhydride unit ru0, the second repeating unit ru2, and the third repeating unit ru3 in the precursor resin can be set.

[0047] 5. Effects of polymer compounds A and B Polymer compounds A and B have low dielectric loss tangents. Polymer compounds A and B have high heat resistance and high elastic modulus.

[0048] 6.Resin composition The resin composition of this disclosure comprises polymer compound A or polymer compound B. The resin composition of this disclosure has a low dielectric loss tangent. The resin composition of this disclosure has high heat resistance and high elastic modulus. From the viewpoint of heat resistance and flame retardancy, the resin composition of this disclosure preferably further contains a curing accelerator. The curing accelerator is not particularly limited.

[0049] Examples of curing accelerators include acid catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine, and tributylamine; imidazole compounds such as methylimidazole, phenylimidazole, and isocyanate-masquimidazole (e.g., the addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole); tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; organic peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexine-3, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, and α,α'-bis(t-butylperoxy)diisopropylbenzene; and carboxylates of metals such as manganese, cobalt, and zinc.

[0050] Among these curing accelerators, imidazole compounds, organic peroxides, and carboxylates are preferred from the viewpoint of heat resistance, glass transition temperature, and storage stability, with organic peroxides being more preferred. Examples of organic peroxides include t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine, dicumyl peroxide, di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di-t-hexyl peroxide, and t-butylcumyl peroxide.

[0051] The content of the curing accelerator in the resin composition of this disclosure is not particularly limited. The mass of the curing accelerator contained in the resin composition is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 3% by mass, based on the mass of the total resin components contained in the resin composition. The total resin components contained in the resin composition refer to the components of the resin composition excluding inorganic fillers and organic solvents. By setting the content of the curing accelerator within this range, the curability and storage stability of the resin composition are further improved.

[0052] Furthermore, the resin composition of this disclosure further includes, for example, components for printed circuit boards. Components for printed circuit boards are components included in insulating resin compositions for printed circuit boards of ordinary electronic devices. Examples of components for printed circuit boards include thermosetting resins, elastomers, inorganic fillers, organic fillers, flame retardants, functional resins, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, adhesion improvers, organic solvents, and the like. The resin composition of this disclosure may contain one or more of these components for printed circuit boards.

[0053] Examples of organic fillers include organic powders. Examples of organic powders include silicone powder, tetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.

[0054] Examples of flame retardants include phosphorus-based flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphate ester compounds, phosphazene, and red phosphorus; and inorganic flame retardant additives such as antimony trioxide and zinc molybdate.

[0055] Functional resins, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, adhesion enhancers, and organic solvents that can be incorporated into insulating resin compositions for printed circuit boards of ordinary electronic devices can be used.

[0056] 7. Application Products The resin compositions of this disclosure can be used, for example, in the following application products. These application products have a low dielectric loss tangent, high heat resistance, and high elastic modulus. (1) Resin films and prepregs The resin film of this disclosure is formed using the resin composition of this disclosure. As a method for manufacturing the resin film, for example, one method is to apply the resin composition to a release film, and then partially cure it by heating or the like to form a film. Partial curing is, for example, B-stage curing.

[0057] The prepreg of this disclosure comprises the resin composition of this disclosure. The method for manufacturing the prepreg is not particularly limited. The prepreg can be manufactured using known prepreg manufacturing methods. For example, the prepreg can be manufactured by impregnating or coating a fibrous substrate with the resin composition of this disclosure and then semi-curing it by heating or the like. Semi-curing is, for example, B-stage formation. Alternatively, the prepreg can be manufactured by laminating the resin film of this disclosure onto a fibrous substrate.

[0058] The heating temperature for semi-curing the resin composition is preferably above the boiling point of the organic solvent. When the heating temperature is above the boiling point of the organic solvent, the organic solvent can be efficiently removed along with the semi-curing of the resin composition. The heating temperature for semi-curing is preferably 80 to 200°C, and more preferably 140 to 180°C.

[0059] The overall thickness of the prepreg can be adjusted as appropriate depending on the thickness of the inner layer circuitry, etc. From the viewpoint of moldability and workability, the overall thickness of the prepreg is preferably 10 to 700 μm, more preferably 10 to 500 μm, even more preferably 10 to 250 μm, and particularly preferably 10 to 150 μm.

[0060] (2) Laminate The laminate of this disclosure comprises a prepreg and a metal foil. The laminate comprises, for example, a prepreg and a metal foil for circuit formation placed on both sides thereof. The laminate of this disclosure is a metal-clad laminate.

[0061] Preferably, the metal contained in the metal foil is copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metallic elements.

[0062] Preferred alloys include copper-based alloys, aluminum-based alloys, and iron-based alloys. Examples of copper-based alloys include copper-nickel alloys. Examples of iron-based alloys include iron-nickel alloys. An example of an iron-nickel alloy is 42 alloy. Among these, copper, nickel, and 42 alloy are more preferred as the metal, and copper is even more preferred from the viewpoint of availability and cost. The thickness of the metal foil is not particularly limited. The thickness of the metal foil is, for example, 3 to 210 μm, and preferably 5 to 140 μm.

[0063] (3) Printed circuit board The printed circuit boards of this disclosure include the prepregs or laminates of this disclosure. The printed circuit boards of this disclosure can be manufactured, for example, by forming a wiring pattern on a metal-clad laminate of this disclosure. The method for forming the wiring pattern is not particularly limited. Examples of known methods for forming the wiring pattern include the subtractive process, the fully additive process, the semi-additive process (SAP), and the modified semi-additive process (m-SAP).

[0064] (4) Semiconductor packages The semiconductor package of this disclosure comprises a printed circuit board of this disclosure and semiconductor elements mounted on the printed circuit board. The semiconductor package of this disclosure can be manufactured by mounting semiconductor elements such as semiconductor chips and memory at predetermined positions on the printed circuit board.

[0065] 8. Examples (8-1) Synthesis of precursor resins (i) Synthesis of precursor resin pre1 A flask equipped with a temperature sensor, condenser, and stirrer was placed in a container containing 128 g of Ipsol 100 and heated to 160°C under a nitrogen atmosphere. Separately, a solution was prepared by mixing 128 g of Ipsol 100, 9 g of maleic anhydride, 166 g of indene, and 15.8 g of dicumyl peroxide (DCPO). This solution was added dropwise to the flask described above over 4 hours. The reaction was continued for another hour after the addition was complete. After the reaction was complete, the solvent was removed by distillation under reduced pressure and heating to obtain 164 g of precursor resin pre1. The acid value of precursor resin pre1 was 61, and the yield was 86%. The acid value was measured according to the method compliant with JIS K-0070:1992.

[0066] Table 1 shows the design compositions and acid values ​​of precursor resin pre1 and precursor resins pre2 to pre9, which will be described later. Precursor resin pre1 consists of maleic anhydride unit ru0 and repeating unit ru2a. Precursor resins pre2 to pre9 are each composed of the repeating units shown in Table 1. The mol% ratio of each repeating unit is as shown in Table 1.

[0067] [Table 1]

[0068] (ii) Synthesis of precursor resin pre2 A flask equipped with a temperature sensor, condenser, and stirrer was placed in a container containing 128 g of Ipsol 100 and heated to 160°C under a nitrogen atmosphere. Separately, a solution was prepared by mixing 128 g of Ipsol 100, 18 g of maleic anhydride, 157 g of indene, and 15.8 g of dicumyl peroxide (DCPO). This solution was added dropwise to the flask described above over 4 hours. The reaction was continued for another hour after the addition was complete. After the reaction was complete, the solvent was removed by distillation under reduced pressure and heating to obtain 169 g of the precursor resin pre2. The acid value of the precursor resin pre2 was 119, and the yield was 89%.

[0069] (iii) Synthesis of precursor resin pre3 A flask equipped with a temperature sensor, condenser, and stirrer was placed in a container containing 128 g of Ipsol 100 and heated to 160°C under a nitrogen atmosphere. Separately, a solution was prepared by mixing 128 g of Ipsol 100, 31 g of maleic anhydride, 145 g of indene, and 15.8 g of dicumyl peroxide (DCPO). This solution was added dropwise to the flask described above over 4 hours. The reaction was continued for another hour after the addition was complete. After the reaction was complete, the solvent was removed by distillation under reduced pressure and heating to obtain 175 g of the precursor resin pre3. The acid value of the precursor resin pre3 was 202, and the yield was 92%.

[0070] (iv) Synthesis of precursor resin pre4 A flask equipped with a temperature sensor, condenser, and stirrer was placed in a container containing 128 g of Ipsol 100 and heated to 160°C under a nitrogen atmosphere. Separately, a solution was prepared by mixing 128 g of Ipsol 100, 42 g of maleic anhydride, 133 g of indene, and 15.8 g of dicumyl peroxide (DCPO). This solution was added dropwise to the flask described above over 4 hours. The reaction was continued for another hour after the addition was complete. After the reaction was complete, the solvent was removed by distillation under reduced pressure and heating to obtain 181 g of the precursor resin pre4. The acid value of the precursor resin pre4 was 273, and the yield was 95%.

[0071] (v) Synthesis of precursor resin pre5 A flask equipped with a temperature sensor, condenser, and stirrer was placed in a container containing 128 g of Ipsol 100 and heated to 160°C under a nitrogen atmosphere. Separately, a solution was prepared by mixing 128 g of Ipsol 100, 19 g of maleic anhydride, 156 g of styrene, and 15.8 g of dicumyl peroxide (DCPO). This solution was added dropwise to the flask described above over 4 hours. The reaction was continued for another hour after the addition was complete. After the reaction was complete, the solvent was removed by distillation under reduced pressure and heating to obtain 189 g of the precursor resin pre5. The acid value of the precursor resin pre5 was 120, and the yield was 99%.

[0072] (vi) Synthesis of precursor resin pre6 A flask equipped with a temperature sensor, condenser, and stirrer was placed in a container containing 128 g of Ipsol 100 and heated to 160°C under a nitrogen atmosphere. Separately, a solution was prepared by mixing 128 g of Ipsol 100, 19 g of maleic anhydride, 82 g of indene, 74 g of styrene, and 15.8 g of dicumyl peroxide (DCPO). This solution was added dropwise to the flask described above over 4 hours. The reaction was continued for another hour after the addition was complete. After the reaction was complete, the solvent was removed by distillation under reduced pressure and heating to obtain 189 g of the precursor resin pre6. The acid value of the precursor resin pre6 was 118, and the yield was 95%.

[0073] (vii) Synthesis of precursor resin pre7 A flask equipped with a temperature sensor, condenser, and stirrer was placed in a container containing 128 g of Ipsol 100 and heated to 160°C under a nitrogen atmosphere. Separately, a solution was prepared by mixing 128 g of Ipsol 100, 42 g of maleic anhydride, 70 g of indene, 63 g of styrene, and 15.8 g of dicumyl peroxide (DCPO). This solution was added dropwise to the flask described above over 4 hours. The reaction was continued for another hour after the addition was complete. After the reaction was complete, the solvent was removed by distillation under reduced pressure and heating to obtain 184 g of the precursor resin pre7. The acid value of the precursor resin pre7 was 269, and the yield was 96%.

[0074] (viii) Synthesis of precursor resin pre8 A flask equipped with a temperature sensor, condenser, and stirrer was placed in a container containing 128 g of Ipsol 100 and heated to 160°C under a nitrogen atmosphere. Separately, a solution was prepared by mixing 128 g of Ipsol 100, 20 g of maleic anhydride, 133 g of indene, 23 g of acenaphthylene, 63 g of styrene, and 15.8 g of dicumyl peroxide (DCPO). This solution was added dropwise to the flask described above over 4 hours. The reaction was continued for another hour after the addition was complete. After the reaction was complete, the solvent was removed by distillation under reduced pressure and heating to obtain 187 g of the precursor resin pre8. The acid value of the precursor resin pre8 was 122, and the yield was 98%.

[0075] (ix) Synthesis of precursor resin pre9 A flask equipped with a temperature sensor, condenser, and stirrer was placed in a container containing 128 g of Ipsol 100 and heated to 160°C under a nitrogen atmosphere. Separately, a solution was prepared by mixing 128 g of Ipsol 100, 19 g of maleic anhydride, 70 g of indene, 63 g of styrene, and 15.8 g of dicumyl peroxide (DCPO). This solution was added dropwise to the flask described above over 4 hours. The reaction was continued for another hour after the addition was complete. After the reaction was complete, the solvent was removed by distillation under reduced pressure and heating to obtain 183 g of the precursor resin pre9. The acid value of the precursor resin pre9 was 118, and the yield was 96%.

[0076] (8-2) Synthesis of polymer compounds A, B, and R (i) Synthesis of polymer compound A-1 A flask equipped with a temperature sensor, condenser, and stirrer contained 125g of toluene, 54g of N,N-dimethylacetamide (DMAC), 125g of precursor resin pre1, and 21g of 4,4'-diamino-2,2'-dimethylbiphenyl, and the mixture was reacted under reflux conditions in a nitrogen atmosphere for 9 hours.

[0077] Subsequently, 20 g of maleic anhydride, 20 g of toluene, and 2.5 g of p-toluenesulfonic acid were added, and the mixture was reacted under reflux conditions for 6 hours. After the reaction was complete, the reaction solution was added to 1000 g of methanol, and the product was precipitated. The precipitated solid was filtered off and vacuum-dried at 70°C to obtain 110 g of polymer compound A-1. The yield of polymer compound A-1 was 66%.

[0078] Table 2 shows the composition ratio of repeating units, the mass-average molecular weight, and the structural formula of X in polymer compound A-1, and polymer compounds A-2 to A-7, B-1 to B-2, and R-1 to R-3, which will be described later. Polymer compounds A-1 to A-7 correspond to polymer compound A. Polymer compounds B-1 to B-2 correspond to polymer compound B.

[0079] [Table 2]

[0080] (ii) Synthesis of polymer compound A-2 A flask equipped with a temperature sensor, condenser, and stirrer contained 141 g of toluene, 60 g of N,N-dimethylacetamide (DMAC), 100 g of precursor resin pre2, and 34 g of 4,4'-diamino-2,2'-dimethylbiphenyl, and the mixture was reacted under reflux conditions in a nitrogen atmosphere for 9 hours.

[0081] Subsequently, 32 g of maleic anhydride, 32 g of toluene, and 4.1 g of p-toluenesulfonic acid were added, and the mixture was reacted under reflux conditions for 6 hours. After the reaction was complete, the reaction solution was added to 1000 g of methanol, and the product was precipitated. The precipitated solid was filtered off and vacuum-dried at 70°C to obtain 98 g of polymer compound A-2. The yield of polymer compound A-2 was 59%.

[0082] (iii) Synthesis of polymer compound A-3 A flask equipped with a temperature sensor, condenser, and stirrer contained 162g of toluene, 69g of N,N-dimethylacetamide (DMAC), 79g of precursor resin pre3, and 45g of 4,4'-diamino-2,2'-dimethylbiphenyl, and the mixture was reacted under reflux conditions in a nitrogen atmosphere for 9 hours.

[0083] Subsequently, 42 g of maleic anhydride, 42 g of toluene, and 5.4 g of p-toluenesulfonic acid were added, and the mixture was reacted under reflux conditions for 6 hours. After the reaction was complete, the reaction solution was added to 1000 g of methanol, and the product was precipitated. The precipitated solid was filtered off and vacuum-dried at 70°C to obtain 91 g of polymer compound A-3. The yield of polymer compound A-3 was 55%.

[0084] (iv) Synthesis of polymer compound A-4 A flask equipped with a temperature sensor, condenser, and stirrer contained 154 g of toluene, 66 g of N,N-dimethylacetamide (DMAC), 67 g of precursor resin pre4, and 51 g of 4,4'-diamino-2,2'-dimethylbiphenyl, and the mixture was reacted under reflux conditions in a nitrogen atmosphere for 9 hours.

[0085] Subsequently, 48 g of maleic anhydride, 48 g of toluene, and 6.2 g of p-toluenesulfonic acid were added, and the mixture was reacted under reflux conditions for 6 hours. After the reaction was complete, the reaction solution was added to 1000 g of methanol, and the product was precipitated. The precipitated solid was filtered off and vacuum-dried at 70°C to obtain 83 g of polymer compound A-4. The yield of polymer compound A-4 was 50%.

[0086] (v) Synthesis of polymer compounds A-5, A-6, B-1, and B-2 Polymer compounds A-5, A-6, B-1, and B-2 were synthesized using essentially the same method as the synthesis method for polymer compound A-2.

[0087] However, in the synthesis of polymer compound A-5, the same amount of precursor resin pre5 was used instead of precursor resin pre2. Similarly, in the synthesis of polymer compound A-6, the same amount of precursor resin pre6 was used instead of precursor resin pre2.

[0088] Furthermore, in the synthesis of polymer compound B-1, the same amount of precursor resin pre8 was used instead of precursor resin pre2. Similarly, in the synthesis of polymer compound B-2, the same amount of precursor resin pre9 was used instead of precursor resin pre2.

[0089] (vi) Synthesis of polymer compound A-7 Polymer compound A-7 was synthesized using essentially the same method as that used for polymer compound A-4. However, in the synthesis of polymer compound A-7, the same amount of precursor resin pre7 was used instead of precursor resin pre4.

[0090] (vii) Synthesis of polymer compound R-1 A flask equipped with a temperature sensor, condenser, and stirrer contained 141 g of toluene, 60 g of N,N-dimethylacetamide (DMAC), 101 g of precursor resin pre2, and 33 g of 4,4'-diaminodiphenyl ether, and the mixture was reacted under reflux conditions in a nitrogen atmosphere for 9 hours.

[0091] Subsequently, 32 g of maleic anhydride, 32 g of toluene, and 4.2 g of p-toluenesulfonic acid were added, and the mixture was reacted under reflux conditions for 6 hours. After the reaction was complete, the reaction solution was added to 1000 g of methanol, and the product was precipitated. The precipitated solid was filtered off and vacuum-dried at 70°C to obtain 96 g of polymer compound R-1. The yield of polymer compound R-1 was 58%.

[0092] (viii) Synthesis of polymer compound R-2 A flask equipped with a temperature sensor, condenser, and stirrer contained 149g of toluene, 64g of N,N-dimethylacetamide (DMAC), 76g of precursor resin pre2, and 66g of priamine 1075 (Cargill), and the mixture was reacted under reflux conditions in a nitrogen atmosphere for 9 hours.

[0093] Subsequently, 24 g of maleic anhydride, 24 g of toluene, and 3.1 g of p-toluenesulfonic acid were added, and the mixture was reacted under reflux conditions for 6 hours. After the reaction was complete, the reaction solution was added to 1000 g of methanol, and the product was precipitated. The precipitated solid was filtered off and vacuum-dried at 70°C to obtain 85 g of polymer compound R-2. The yield of polymer compound R-2 was 51%.

[0094] (ix) Synthesis of polymer compound R-3 A flask equipped with a temperature sensor, condenser, and stirrer contained 146g of toluene, 63g of N,N-dimethylacetamide (DMAC), 84g of precursor resin pre2, and 55g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and the mixture was reacted under reflux conditions in a nitrogen atmosphere for 9 hours.

[0095] Subsequently, 26 g of maleic anhydride, 26 g of toluene, and 3.4 g of p-toluenesulfonic acid were added, and the mixture was reacted under reflux conditions for 6 hours. After the reaction was complete, the reaction solution was added to 1000 g of methanol, and the product was precipitated. The precipitated solid was filtered off and vacuum-dried at 70°C to obtain 88 g of polymer compound R-3. The yield of polymer compound R-3 was 53%.

[0096] In polymer compounds R-1 to R-3, the maleic anhydride unit ru0 contained in the precursor resin becomes the repeating unit ruR represented by general formula (5). In general formula (5), X is X-1 as shown in general formula (6) for polymer compound R-1, X-2 as shown in general formula (7) for polymer compound R-2, and X-3 as shown in general formula (8) for polymer compound R-3. The "*" in general formulas (6) to (8) represents a bonding site.

[0097] [ka]

[0098] [ka]

[0099] (8-3) Production of resin composition The resin compositions of Examples 1-9 and Comparative Examples 1-5 were obtained by kneading each component in the amounts shown in Tables 3 and 4. The unit of the amount is parts by mass.

[0100] [Table 3]

[0101] [Table 4]

[0102] The abbreviations for the polymer compounds in Tables 3 and 4 used in the production of the resin composition mean the following, respectively: BMI-2300: Phenylmethane maleimide manufactured by Yamato Chemical Industries, Ltd. BMI-70: Bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, manufactured by Kei-I Kasei Co., Ltd. Perhexine 25B: A thermal radical polymerization initiator manufactured by NOF Corporation. (8-4) Measurement of dielectric loss tangent, glass transition temperature Tg, and elastic modulus For each example and comparative example, the resin composition was cured at 230°C for 1 hour, after which the dielectric loss tangent, glass transition temperature (Tg), and elastic modulus were measured. The measurement method was as follows.

[0103] (i) Method for measuring dielectric loss tangent Measurements were performed using the cavity resonator perturbation method with a 10GHz cavity resonator manufactured by AET Co., Ltd. The sample was a rectangular plate. The sample dimensions were 15 mm in width, 30 mm in length, and 1 mm in thickness.

[0104] (ii) Method for measuring the glass transition temperature Tg The glass transition temperature (Tg) was measured using a dynamic viscoelasticity tester. The temperature at which tanδ reached its maximum value was defined as the glass transition temperature (Tg). The unit of the glass transition temperature (Tg) is °C.

[0105] (iii) Method for measuring the modulus of elasticity The elastic modulus was measured using a dynamic viscoelasticity analyzer (DMA-850, manufactured by TA-instruments). The value at which the storage modulus of elasticity is measured at 40°C was used as the elastic modulus. The unit of elastic modulus is GPa. The measurement temperature range was 40°C to 350°C. The heating rate was 4°C / min. The sample shape was a rectangular plate. The sample dimensions were 3 mm in width, 50 mm in length, and 1 mm in thickness.

[0106] (iv) Measurement results The measurement results are shown in Tables 3 and 4. In each example, the glass transition temperature Tg was 200°C or higher, the elastic modulus was 4.0 GPa or higher, and the dielectric loss tangent was 0.0022 or less. Note that a higher glass transition temperature Tg indicates higher heat resistance.

[0107] Comparative Examples 2 and 5 had low glass transition temperatures (Tg). Comparative Examples 1-3 and 5 had low elastic modulus. Comparative Examples 1-5 had high dielectric loss tangent.

[0108] <Other Embodiments> Although embodiments of the present disclosure have been described above, the present disclosure is not limited to the embodiments described above and can be implemented in various modified forms.

[0109] (1) The function of one component in each of the above embodiments may be divided among multiple components, or the function of multiple components may be performed by one component. Also, some of the configurations of each of the above embodiments may be omitted. Also, at least some of the configurations of each of the above embodiments may be added to, replaced with, etc., the configurations of other embodiments.

[0110] (2) In addition to the polymer compounds described above, this disclosure can also be realized in various forms, such as products that use the polymer compounds as components, and methods for producing the polymer compounds.

Claims

1. The first repeating unit is represented by the following general formula (1), A second repeating unit represented by the following general formula (2a) or (2b), Includes, The sum of the mol% ratio of the first repeating unit and the mol% ratio of the second repeating unit is 90 mol% or more. High molecular compound. 【Chemistry 1】

2. A polymer compound according to claim 1, The mol% ratio of the first repeating unit is 1 mol% or more and 50 mol% or less. The mol% ratio of the second repeating unit is 50 mol% or more and 99 mol% or less. High molecular compound.

3. A polymer compound according to claim 1 or 2, The mass-average molecular weight is between 500 and 100,000. High molecular compound.

4. The first repeating unit is represented by the following general formula (1), A second repeating unit represented by the following general formula (2a) or (2b), A third repeating unit represented by the following general formula (3a) or (3b), Includes, The sum of the mol% ratio of the first repeating unit, the mol% ratio of the second repeating unit, and the mol% ratio of the third repeating unit is 90 mol% or more. High molecular compound. (In formula (3b), R is an alkyl chain having 4 to 24 carbon atoms.) 【Chemistry 1】 【Chemistry 2】

5. A polymer compound according to claim 4, The mol% ratio of the first repeating unit is 1 mol% or more and 50 mol% or less. The mol% ratio of the second repeating unit is 1 mol% or more and 98 mol% or less. The mol% ratio of the third repeating unit is 1 mol% or more and 98 mol% or less. High molecular compound.

6. A polymer compound according to claim 4 or 5, The mass-average molecular weight is between 500 and 100,000. High molecular compound.

7. A resin composition comprising the polymer compound described in claim 1 or 4.

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