Maleimide resin mixture, method for producing the same, and composition containing maleimide resin mixture

Abstract

To provide a maleimide resin mixture having high photocurability, high heat resistance, and superior compatibility with resins, and to provide a cured resin composition having sufficient photocurability without impairing heat resistance and insulation properties.SOLUTION: The above problem can be solved by a maleimide resin mixture represented by the following formula (I) and a resin composition containing the same. (Each R1 is independently the same or different, and at least one of the R1 is a linear or branched hydrocarbon group, and n is a repetition number representing a real number of 0≤n<10).SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a maleimide resin mixture, a method for producing a maleimide resin, and a composition containing the maleimide resin mixture.

Background Art

[0002] Maleimide resins are compounds that have heat resistance superior to epoxy resins, have moldability equivalent to that of epoxy resins, and further have properties such as a low coefficient of linear expansion and a high Tg. Maleimide compounds can be crosslinked alone or reacted with various maleimide compounds or crosslinking agents to provide materials with excellent heat resistance and flame retardancy, and have been used in various applications such as sealing materials, substrate materials, and insulating materials. In particular, they are used in applications such as high heat-resistant substrate materials, flexible substrate materials, high heat-resistant low dielectric materials, high heat-resistant materials for CFRP (carbon fiber composite materials), and high heat-resistant sealing materials for in-vehicle SiC power devices, which require both extremely high heat resistance and moldability.

[0003] In recent years, a CFRP material obtained by curing a prepreg using a bismaleimide resin and a bisphenol resin has been developed. Because it has high heat resistance, is lightweight and has high strength, it is applied to the aviation industry and the space industry.

[0004] However, although bismaleimide resins are excellent in heat resistance due to their rigid structure, they have problems in that they have high crystallinity, are solid at room temperature, have a considerably high melting point and softening point, and are difficult to melt and mix. Also, due to their high crystallinity, they have problems in compatibility with other resins. On the other hand, in recent years, liquid bismaleimide resins have also been developed, but although they have good solubility, they have problems in that their Tg is low and their heat resistance is inferior.

[0005] Therefore, there is a demand for a new maleimide resin that is liquid at room temperature, has good compatibility and handleability, and exhibits high heat resistance after curing.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0007] Accordingly, an object of the present invention is to provide a maleimide resin mixture that is liquid at room temperature and has high curability, heat resistance, and excellent solubility, and to provide a cured resin composition that has sufficient curability without impairing heat resistance.

Means for Solving the Problems

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that a maleimide compound mixture having a specific structure and a resin composition containing the same can solve the above problems, and have completed the present invention.

[0009] That is, the present invention relates to the following [1] to [5].

[0010] [1] A maleimide resin mixture represented by the following formula (1).

[0011]

Chemical formula

[0012] (R1 are each independently the same or different, and at least one of R1 is a linear or branched hydrocarbon group, n is the number of repetitions, and represents a real number of 0 ≦ n < 10.)

[0013] [2] The maleimide resin according to [1], wherein in the formula (I), R1 is any one or more of the following general formulas (V), and at least one is a linear or branched alkyl group represented by (A-1) to (A-5).

[0014]

Chem.

[0015] (In formulas (A-1) to (A-5), the wavy line represents the bonding site with the nitrogen atom.)

[0016] [3] The maleimide resin mixture according to [1], wherein the weight average molecular weight of the maleimide resin of the formula (I) is 2000 or less and it is liquid at room temperature.

[0017] [4] A maleimide resin composition comprising the maleimide resin mixture represented by the formula (I) according to any one of [1] to [3], a curable resin, and / or a curing accelerator.

[0018] [5] A method for producing a maleimide resin, which is an isocyanate compound mixture represented by the following formula (II).

[0019]

Chem.

[0020] (R1 are independent of each other and may be the same or different, at least one of R1 is a linear or branched hydrocarbon group, n is the number of repetitions, and represents a real number of 0 ≦ n < 10), and a tertiary alcohol represented by the following formula (III) or a substituted benzyl alcohol represented by the following formula (IV) are reacted, and

[0021]

Chem.

[0022] (R2 are independent of each other and may be the same or different organic groups)

[0023] [Chemical formula]

[0024] (wherein R3 is an organic group) The following formula (I) obtained by reacting maleic anhydride under acidic conditions

[0025] [Chemical formula]

[0026] (wherein R1 may be the same or different independently of each other, at least one of R1 is a linear or branched hydrocarbon group, n is the number of repetitions, and represents a real number of 0 ≦ n < 10) A method for producing a maleimide resin mixture represented by [Advantages of the Invention]

[0027] According to the present invention, it is possible to provide a maleimide resin, a production method thereof, and a maleimide resin composition that are excellent in compatibility and handleability, do not require high temperature during melt mixing, have good curability, and can obtain a cured product excellent in heat resistance after curing. [Brief Description of the Drawings]

[0028]

Figure 1

Figure 2

[0029] Hereinafter, modes for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following present embodiment is an exemplification for explaining the present invention, and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of its gist.

[0030] The maleimide resin mixture of the present invention is represented by the following formula (I).

[0031] [Chemical formula]

[0032] In the formula (I), each R1 is independently of the others, may be the same or different, and at least one of R1 is a linear or branched hydrocarbon group. It is preferable that at least one of R1 is a linear or branched hydrocarbon group having 3 to 10 carbon atoms, and more preferably a linear or branched hydrocarbon group having 4 to 9 carbon atoms.

[0033] It is preferable that at least one of R1 of the maleimide resin (I) is a linear or branched alkyl group represented by the following formulas (A-1) to (A-5).

[0034] [Chemical formula]

[0035] In the formulas (A-1) to (A-5), the wavy line indicates the bonding site with the nitrogen atom.

[0036] It is preferable that the R1 are the same, and it is preferable that all of R1 are any of the linear or branched alkyl groups represented by the above formulas (A-1) to (A-5). More preferably, all of R1 are any of the linear or branched alkyl groups represented by the above formulas (A-1) to (A-3), and still more preferably, all of R1 are the linear or branched alkyl group represented by the above formula (A-2).

[0037] n is the number of repetitions and represents a real number of 0 ≦ n < 10. It is preferable that 0 ≦ n < 8, and more preferably 0 ≦ n < 5.

[0038] <Method for Producing Maleimide Resin Mixture> The specific synthesis method of the maleimide resin mixture will be described. For example, a polyisocyanate having an isocyanurate ring represented by the following formula (II) is carbamate-formed to obtain a carbamate compound represented by the following formula (VI), then an amine or an amine salt is obtained under acidic conditions, and then maleic anhydride is used for maleimidation to obtain a maleimide resin (I).

[0039]

Chemical formula

[0040] In the above formulas (II) and (V), R1 and n have the same meanings as R1 and n in the above formula (I).

[0041] In the above formula (V), X represents a residue obtained by removing a hydrogen atom from the hydroxy group of a tertiary alcohol represented by the following formula (III) or a residue obtained by removing a hydrogen atom from the hydroxy group of a substituted benzyl alcohol represented by the following formula (IV).

[0042]

Chemical formula

[0043] R2 are each independently an organic group which may be the same or different. The organic group of R2 may contain an ester bond, an ether bond, an amide bond, a urethane bond, and is one kind of organic group selected from the group consisting of a halogen group, a cyano group, a nitro group, a sulfonyl group, a chain aliphatic group, an aliphatic group containing a cyclic structure, and an aromatic group.

[0044]

Chemical formula

[0045] R3 is an organic group. The organic group of R3 is one kind of organic group selected from the group consisting of an alkoxy group, a halogen group, a cyano group, a nitro group, and a sulfonyl group.

[0046] The reaction can be carried out either without a solvent or with a solvent. The solvents that can be used are not particularly limited. For example, aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone, etc. These are non-aqueous solvents, but not limited thereto, and two or more of them can be used in combination. In addition to the non-aqueous solvent, an aprotic polar solvent can also be used in combination. For example, dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, etc. can be mentioned, and two or more of them can be used in combination.

[0047] Examples of the polyisocyanate having an isocyanurate ring include, but are not particularly limited to, tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate (TMDI), lysine diisocyanate (LDI), 1,4-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate (H12MDI), norbornene diisocyanate (NBDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 1,4-diphenyl diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), 2,4-diphenylmethane diisocyanate (MDI), 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, o-tolidine diisocyanate, polyphenylmethane polyisocyanate (crude MDI), triphenylmethane triisocyanate, and tris(isocyanatophenyl) thiophosphate. One or more oligomer polyisocyanates such as these can be trimerized by a known method to obtain a polyisocyanate. Among these, polyisocyanates obtained by trimerizing tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, or 2,2,4-trimethylhexamethylene diisocyanate (TMDI) are particularly preferred because the maleimide resin becomes liquid at room temperature when these polyisocyanates are used.

[0048] The carbamate reaction product can be synthesized by reacting the polyisocyanate with a tertiary alcohol compound and / or a substituted benzyl alcohol.

[0049] Examples of the tertiary alcohol compounds include tert-butanol, 1-methylcyclohexanol, 2-methyl-2-butanol, 2-methyl-2-pentanol, 3-quinuclidinyl benzoate, 3-methylpentanol, 2-methylisoborneol, 1-adamantanol, acetocyanohydrin, 1,3-adamantanediol, diacetone alcohol, triacetone alcohol, triphenylmethanol, and the like.

[0050] Examples of the substituted benzyl alcohol include p-methoxybenzyl alcohol, p-ethoxybenzyl alcohol, p-acetoxybenzyl alcohol, p-chlorobenzyl alcohol, p-cyanobenzyl alcohol, p-nitrobenzyl alcohol, p-sulfonylbenzyl alcohol, and the like.

[0051] In the carbamation reaction, it can be carried out without a catalyst or a known catalyst can be used. Examples of the catalyst include metal catalysts such as butyltin dilaurate (DBTL), bismuth neodecanoate, and zinc octanoate, and basic catalysts such as triethylamine (TEA), imidazole, diazabicyclooctane (DABCO), and tertiary amines.

[0052] In the above carbamation reaction, the reaction temperature can be 40°C to 150°C. A range of 60°C to 120°C is more preferable. By carrying out the reaction at the above reaction temperature, the target compound can be efficiently obtained. If the reaction temperature is too low, the reaction time may be long, and if the reaction temperature is too high, decomposition of the reacted carbamate site may occur.

[0053] A method for obtaining the maleimide compound from the carbamate reaction product will be described. By using an acid catalyst for the carbamate reaction product, an amine or an amine salt can be generated in the reaction system.

[0054] The acid catalyst is not particularly limited, and examples include hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, Lewis acids such as aluminum chloride and zinc chloride, solid acids such as activated clay, acid clay, white carbon, zeolite, and silica alumina, and acidic ion exchange resins. These can be used alone or in combination of two or more. From the viewpoint of being able to be used as the same acid catalyst in the subsequent maleimidation step, methanesulfonic acid and p-toluenesulfonic acid are preferred. The amount of the acid catalyst used is 0.01 to 10.0 moles, preferably 0.05 to 5.0 moles, per 1.0 mole of the amine group generated. If the amount of the catalyst is too small, there is a risk that the carbamate reaction product will remain, and if the amount of the catalyst is too large, purification after the reaction may become difficult.

[0055] Next, a maleimide resin is obtained by a maleimidation reaction using maleic anhydride with respect to an amine or an amine salt. In the maleimidation reaction, the reaction temperature can be 80°C to 150°C. From the viewpoint of discharging the water generated during the reaction out of the system, a range of 100°C to 130°C is more preferred. Also, by reacting at the above reaction temperature, the target maleimide resin can be obtained. If the reaction temperature is too low, the reaction may not proceed, and if the reaction temperature is too high, there is a risk of polymerization due to the polymerization of unsaturated groups.

[0056] The weight average molecular weight Mw of the maleimide resin of the present invention is preferably 400 or more and 4000 or less, and more preferably 500 or more and 2000 or less. By setting the value of the weight average molecular weight Mw within the above upper limit, the handleability and solubility can be further improved. The weight average molecular weight Mw of the maleimide resin of the present invention can be determined as a polystyrene equivalent value by gel permeation chromatography analysis, and can be determined by the method described in the following examples.

[0057] The above maleimide resin mixture is preferably liquid at room temperature of 15 to 25°C, and preferably liquid at 25°C.

[0058] The composition containing the maleimide resin mixture of the present invention is characterized by containing a maleimide resin mixture represented by the formula (I). The composition can be cured by applying light or heat. The composition is preferably a thermosetting composition. The composition can contain, as a curable resin, an epoxy resin, a phenol resin, a benzoxazine resin, a polyimide resin, a polyamideimide resin, a cyanate resin, an active ester resin, a radically polymerizable resin, an acid anhydride resin, a carbodiimide resin, and an amine resin, if necessary.

[0059] When blending a curable resin, the content thereof is 0.1 to 2000 parts by weight, preferably 0.1 to 1500 parts by weight, and more preferably 0.1 to 1000 parts by weight with respect to 100 parts by weight of the maleimide resin.

[0060] The composition containing the maleimide resin mixture of the present invention can use a curing accelerator as needed. As the curing accelerator, there is no particular limitation as long as it is a compound that promotes the reaction of the maleimide resin and the curable resin. For example, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, amines such as triethylamine, tributylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 4-dimethylaminopyridine, 1,8-diazabicyclo-undecene, benzyldimethylamine, phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, hexadecyltrimethylammonium hydroxide, quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, tetrabutylphosphonium salt, transition metal compounds (transition metal salts) such as tin octylate, zinc carboxylates (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate), etc. can be mentioned, but it is not limited to these. Also, these can be used alone or in combination of multiple kinds.

[0061] When blending a curing accelerator, its content is 0.1 to 20 parts by weight, preferably 0.1 to 15 parts by weight, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight in total of the maleimide resin and the curable resin. Zinc compounds (zinc salts) such as zinc stearyl phosphate can be mentioned above.

[0062] Furthermore, the maleimide resin composition of the present invention can also improve its curability by adding a polymerization initiator. A polymerization initiator is a compound capable of polymerizing olefin functional groups such as ethylenically unsaturated bonds, and examples thereof include olefin metathesis polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, radical polymerization initiators, and the like. Among these, it is preferable to use a radical polymerization initiator having curability and appropriate stability. A radical polymerization initiator refers to a compound that generates radicals upon irradiation with ultraviolet light or visible light or heating, and initiates a chain polymerization reaction. Examples of radical polymerization initiators that can be used include organic peroxides, azo compounds, benzopinacols, etc., but are not limited thereto. These may be used alone or in combination of two or more.

Examples

[0063] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

[0064] <Gel Permeation Chromatography (GPC)> Using a polystyrene standard solution, the weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated in terms of polystyrene. GPC: HLC-8320GPC (manufactured by Tosoh Corporation) Column: TSKgel SuperMultipre HZ-M Linked eluent: Tetrahydrofuran Column temperature: 40 °C Detection: RI (Differential Refractometer)

[0065] Example 1 Into a four-necked flask equipped with a stirring device, a thermometer, a condenser, and a nitrogen line, 179.5 g of an isocyanurate-modified product of hexamethylene diisocyanate (Coronate HXLV manufactured by Tosoh Corporation, isocyanate group content 23.4% by mass), 81.4 g (1.1 mol) of 2-methyl-2-propanol, and 11.2 g (0.1 mol) of 1,4-diazabicyclo[2,2,2]octane were added. While blowing nitrogen into the system, the temperature was raised to 90 °C and the reaction was carried out at the same temperature for 16 hours. It was confirmed by infrared spectrum that the absorption at 2250 cm -1 which is the characteristic absorption of the isocyanate group completely disappeared. Subsequently, 128 g of toluene and 156 g of N-methylpyrrolidone were added, and 96.1 g of methanesulfonic acid was added dropwise at 40 °C for 2 hours, and then the temperature was raised to 60 °C. 0.4 g of dibutylhydroxytoluene and 117.6 g of maleic anhydride were added and stirred at 80 °C for 1 hour. Then the temperature was further raised, and a reflux dehydration reaction was carried out for 14 hours and then cooled. Toluene was added to the obtained solution, and it was washed with ion-exchanged water and an aqueous sodium hydroxide solution until the pH of the aqueous layer became neutral. The organic layer was dried under reduced pressure to obtain 190 g of maleimide A, which is a pale yellow viscous liquid. The viscosity at room temperature (25 °C) was 1280 Pa·s, the number average molecular weight Mn by GPC analysis was 840, and the weight average molecular weight Mw was 990. 1H-NMR is shown in Figure 1.

[0066] [Chemical formula]

[0067] (In the above formula, n is an integer of 0 or more and less than 10)

[0068] Example 2 Into a four-necked flask equipped with a stirring device, thermometer, condenser, and nitrogen line, 178.7 g of an isocyanurate-modified pentadiisocyanate ("Stabio D-376N" manufactured by Mitsui Chemicals, isocyanate group content 23.5% by mass), 88.8 g (1.2 mol) of 2-methyl-2-propanol, and 11.2 g (0.1 mol) of 1,4-diazabicyclo[2,2,2]octane were added. While blowing nitrogen into the system, the temperature was raised to 90 °C and reacted at the same temperature for 16 hours. It was confirmed by infrared spectrum that the absorption at 2250 cm -1 corresponding to the characteristic absorption of isocyanate groups completely disappeared. Subsequently, 128 g of toluene and 156 g of N-methylpyrrolidone were added, and 96.1 g of methanesulfonic acid was added dropwise at 40 °C over 2 hours, and then the temperature was raised to 60 °C. 0.4 g of dibutylhydroxytoluene and 117.6 g of maleic anhydride were added and stirred at 80 °C for 1 hour. Then the temperature was further raised, and a reflux dehydration reaction was carried out for 14 hours and then cooled. Toluene was added to the obtained solution, and it was washed with ion-exchanged water and an aqueous sodium hydroxide solution until the pH of the aqueous layer became neutral. The organic layer was dried under reduced pressure to obtain 195 g of maleimide A2 as a pale yellow viscous liquid. The viscosity at room temperature (25 °C) was 47 Pa·s, the number average molecular weight Mn by GPC analysis was 712, and the weight average molecular weight Mw was 831. 1H-NMR is shown in Figure 2.

[0069] [Chemical formula]

[0070] (In the above formula, n is an integer from 0 or more to less than 10)

[0071] Comparative Example 1 Into a four-necked flask equipped with a stirring device, thermometer, condenser, and nitrogen line, 179.5 g of an isocyanurate-modified hexamethylene diisocyanate ("Coronate HXLV" manufactured by Tosoh Corporation, isocyanate group content 23.4% by mass), 108.0 g of maleic anhydride, 5.06 g of triethylamine, and 0.3 g of dibutylhydroxytoluene were added and stirred at 80 °C for 1 hour. Then the temperature was further raised, and during the process of carrying out a reflux dehydration reaction for 2 hours, gelation occurred and no resin was obtained.

[0072] Example 3 20 parts by weight of maleimide resin A1 obtained in Example 1, 60 parts by weight of dicyclopentadiene type epoxy resin XD-1000 (manufactured by Nippon Kayaku Co., Ltd., softening point 73 °C, epoxy equivalent 253 g / eq), and 39 parts by weight of phenol novolac resin (softening point 83 °C, hydroxyl equivalent 106 g / eq) were mixed and kneaded to obtain a mixture B1.

[0073] Example 4 Example 3 was repeated except that maleimide resin A1 of Example 3 was changed to maleimide resin A2 obtained in Example 2, and the epoxy resin was changed to orthocresol novolac type epoxy resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., softening point 92 °C, epoxy equivalent 217 g / eq) to obtain a mixture B2.

[0074] Comparative Example 2 80 parts by weight of dicyclopentadiene type epoxy resin XD-1000 (manufactured by Nippon Kayaku Co., Ltd., softening point 73 °C, epoxy equivalent 253 g / eq) and 35 parts by weight of phenol novolac resin (softening point 83 °C, hydroxyl equivalent 106 g / eq) were mixed and kneaded to obtain a mixture B3.

[0075] Comparative Example 3 20 parts by weight of 4,4'-diphenylmethane bismaleimide (manufactured by Tokyo Chemical Industry Co., Ltd.), 60 parts by weight of dicyclopentadiene type epoxy resin XD-1000 (manufactured by Nippon Kayaku Co., Ltd., softening point 73 °C, epoxy equivalent 253 g / eq), and 40 parts by weight of phenol novolac resin (softening point 83 °C, hydroxyl equivalent 106 g / eq) were mixed and kneaded to obtain a mixture B4.

[0076] Comparative Example 4 20 parts by weight of hexamethylene bismaleimide (manufactured by Tokyo Chemical Industry Co., Ltd.), 60 parts by weight of orthocresol novolac type epoxy resin EOCN-104S (manufactured by Nippon Kayaku Co., Ltd., softening point 92 °C, epoxy equivalent 217 g / eq), and 39 parts by weight of phenol novolac resin (softening point 83 °C, hydroxyl equivalent 106 g / eq) were mixed and kneaded to obtain a mixture B5.

[0077] <State of the mixture during heating and mixing> Each mixture was heated to 100 °C and 150 °C to check the solution state. A transparent solution state was marked as ○, and a cloudy, precipitated, or solid-dispersed state was marked as ×.

[0078]

Table 1

[0079] <Preparation of Compositions and Cured Products> To each of the mixtures B1 - 4 obtained in Examples 3 and 4 and Comparative Examples 2 and 3, 1 part by weight of triphenylphosphine was added as a curing accelerator, and they were mixed and kneaded, and cured under the curing conditions of 160 °C for 4 hours and 180 °C for 2 hours to obtain each cured product C1 - 4. Since the mixture of Comparative Example 4 did not become a uniform solution even at 150 °C, no cured product was prepared.

[0080] The physical property values of the cured products were measured under the following conditions. <Measurement Conditions for Heat Resistance (Tg)> Dynamic viscoelasticity measurement: Rheosol - G5000 Measurement temperature range: -30 to 300 °C Heating rate: 2 °C / min Tg: The peak point of tanδ was defined as Tg. <Measurement Conditions for Flexural Modulus> Measured in accordance with JIS K - 7074.

[0081]

Table 2

[0082] The composition containing the maleimide resin mixture of the present invention becomes a uniform solution state even at a low temperature of about 100 °C, and has excellent handleability compared to the comparative examples with bis - maleimide added. Also, the obtained cured product has improved heat resistance and elastic modulus compared to the comparative examples.

Claims

1. A maleimide resin mixture represented by the following general formula (I). 【Chemical 1】 (R １ may be the same or different and independent of each other, and at least one of R １ is a linear or branched hydrocarbon group, n is the number of repetitions, and represents a real number of 0 ≦ n < 10.)

2. In the above formula (I), R １ The maleimide resin mixture according to claim 1, wherein at least one of them is a linear or branched alkyl group represented by (A-1) to (A-5). 【Chemical 2】 (In formulas (A-1) to (A-5), the wavy line represents the bonding site with the nitrogen atom.)

3. The maleimide resin mixture according to Claim 1, wherein the weight average molecular weight of the maleimide resin of the formula (I) is 2000 or less and is liquid at room temperature.

4. A maleimide resin composition mixture containing the maleimide resin according to any one of Claims 1 to 3, a curable resin, and / or a curing accelerator.

5. A method for producing a maleimide resin, which is a mixture of isocyanate compounds represented by the following formula (II). 【Chemical 3】 (R １ may be the same or different and independent of each other, and at least one of R １ is a linear or branched hydrocarbon group, n is the number of repetitions, and represents a real number of 0 ≦ n < 10), and a tertiary alcohol represented by the following formula (III) or a substituted benzyl alcohol represented by the following formula (IV) are reacted reactant 【Chemical 4】 (R ２ are organic groups which may be the same or different and independent of each other) [Chemical Formula 5] (R ３ is an organic group), and maleic anhydride is reacted under acidic conditions to obtain the following formula (I) 【Chemical Formula 6】 (R １ may be the same or different and independent of each other, and at least one of R １ is a linear or branched hydrocarbon group, n is the number of repetitions, and represents a real number of 0 ≦ n < 10). A method for producing a maleimide resin mixture represented by

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