JP5585985B2 - A polybenzoxazine-modified bismaleimide resin and a polybenzoxazine-modified bismaleimide resin composition. - Google Patents

Description

  The present invention relates to a polybenzoxazine-modified bismaleimide resin excellent in heat resistance and a polybenzoxazine-modified bismaleimide resin composition that can be used for the resin.

In power devices used for electric vehicles and hybrid vehicles, high-efficiency operation at high temperatures is essential.
The conventional insulation and sealing technology for such power devices is difficult to cope with both mechanical load and heat resistance to the connection part, and a new high heat resistant sealing material that reaches 300 ° C is required. It is said.

Polybenzoxazine is a thermosetting resin obtained by ring-opening polymerization of benzoxazine, which is a monomer having a cyclic moiety, and is expected as a novel phenol resin that can overcome the disadvantages of conventional phenol resins.
Polymerization of benzoxazine is ring-opening polymerization, and the resulting resin not only has the same heat resistance, flame retardancy, and electrical properties as conventional phenolic resins, but also requires no polymerization catalyst, and the degree of freedom in molecular design The advantages such as being high, few by-products and good dimensional stability are attracting attention.
Furthermore, polybenzoxazine is advantageous in improving toughness because phenol is connected by a Mannich base and the distance between cross-linking points is long. From these characteristics, utilization of polybenzoxazine as the sealing material is expected.

  Furthermore, in addition to such polybenzoxazine, a resin whose heat resistance is further improved by polymerizing a mixture containing benzoxazine and bismaleimide is disclosed (for example, see Non-Patent Document 1).

Takeichi et al., Polymer. 49, 1173-1179, 2008

  However, the resin described in Non-Patent Document 1 has a glass transition point (Tg) of at most 275 ° C., and there is still room for improvement from the viewpoint of high heat resistance reaching 300 ° C.

  The present invention has been made in view of the above circumstances, and provides a polybenzoxazine-modified bismaleimide resin excellent in heat resistance and a polybenzoxazine-modified bismaleimide resin composition that can be used for the resin. With the goal.

［式中、Ｘ^１及びＸ^２は、それぞれ独立に、炭素数１〜１０のアルキレン基、下記一般式（３）で表される基、式「−ＳＯ_２−」若しくは「−ＣＯ−」で表される基、酸素原子、又は単結合である。］

［式中、Ｙは、芳香族環を有する炭素数６〜３０の炭化水素基であり、ｎは１〜３の整数である。］
（２）本発明のポリベンゾオキサジン変性ビスマレイミド樹脂は、前記Ｘ^１及びＸ^２が、それぞれ独立に炭素数１〜３の直鎖状若しくは分岐鎖状のアルキレン基、又は下記式（ｉ）〜（ｉｉｉ）のいずれかで表される基であることが好ましい。

（３）本発明のポリベンゾオキサジン変性ビスマレイミド樹脂組成物は、下記一般式（１）で表される化合物と、該化合物に対して０．２〜０．５倍モル量の下記一般式（２）で表される化合物と、を含むことを特徴とする。

［式中、Ｘ^１及びＸ^２は、それぞれ独立に、炭素数１〜１０のアルキレン基、下記一般式（３）で表される基、式「−ＳＯ_２−」若しくは「−ＣＯ−」で表される基、酸素原子、又は単結合である。］

［式中、Ｙは、芳香族環を有する炭素数６〜３０の炭化水素基であり、ｎは１〜３の整数である。］
（４）本発明のポリベンゾオキサジン変性ビスマレイミド樹脂組成物は、前記Ｘ^１及びＸ^２が、それぞれ独立に炭素数１〜３の直鎖状若しくは分岐鎖状のアルキレン基、又は下記式（ｉ）〜（ｉｉｉ）のいずれかで表される基であることが好ましい。

(1) The polybenzoxazine-modified bismaleimide resin of the present invention includes a compound represented by the following general formula (1) and a 0.2 to 0.5-fold molar amount of the following general formula (2) relative to the compound. And a compound containing the compound represented by the formula:

[Wherein, X ¹ and X ² are each independently an alkylene group having 1 to 10 carbon atoms, a group represented by the following general formula (3), a formula “—SO ₂ —” or “—CO—”. Or a single bond. ]

[In formula, Y is a C6-C30 hydrocarbon group which has an aromatic ring, and n is an integer of 1-3 . ]
(2) In the polybenzoxazine-modified bismaleimide resin of the present invention, the X ¹ and X ² are each independently a linear or branched alkylene group having 1 to 3 carbon atoms, or the following formulas (i) to A group represented by any one of (iii) is preferable.

(3) The polybenzoxazine-modified bismaleimide resin composition of the present invention comprises a compound represented by the following general formula (1) and the following general formula (0.2 to 0.5-fold molar amount relative to the compound: And a compound represented by 2).

[Wherein, X ¹ and X ² are each independently an alkylene group having 1 to 10 carbon atoms, a group represented by the following general formula (3), a formula “—SO ₂ —” or “—CO—”. Or a single bond. ]

[In formula, Y is a C6-C30 hydrocarbon group which has an aromatic ring, and n is an integer of 1-3 . ]
(4) Polybenzoxazine modified bismaleimide resin composition of the present invention, the is X ¹ and X ^2, each independently represent a linear or branched alkylene group having 1 to 3 carbon atoms, or the following formula (i ) To (iii) are preferred.

Since the polybenzoxazine-modified bismaleimide resin of the present invention is excellent in heat resistance, it is preferably used as a power device for electric vehicles and hybrid vehicles.
According to the polybenzoxazine-modified bismaleimide resin composition of the present invention, a polybenzoxazine-modified bismaleimide resin excellent in heat resistance can be provided.

It is a figure which shows the result of the differential scanning calorimetry in Example 2 and Comparative Examples 1-3, 5, and 7. It is a figure which shows the result of the FT-IR measurement in Experimental example 1. It is the figure which plotted the BMI (bismaleimide) content (mass%) in resin on the horizontal axis, and Tg (degreeC) on the vertical axis | shaft using the data of Examples 3-7 and Comparative Examples 8-15.

Hereinafter, the present invention will be described in detail.
[Polybenzoxazine-modified bismaleimide resin composition]
The polybenzoxazine-modified bismaleimide resin composition of the present invention comprises a compound represented by the following general formula (1), and the following general formula (2) in an amount of 0.2 to 0.5 times the molar amount of the compound. And a compound represented by

［式中、Ｘ^１及びＸ^２は、それぞれ独立に、炭素数１〜１０のアルキレン基、下記一般式（３）で表される基、式「−ＳＯ_２−」若しくは「−ＣＯ−」で表される基、酸素原子、又は単結合である。］

[Wherein, X ¹ and X ² are each independently an alkylene group having 1 to 10 carbon atoms, a group represented by the following general formula (3), a formula “—SO ₂ —” or “—CO—”. Or a single bond. ]

［式中、Ｙは、芳香族環を有する炭素数６〜３０の炭化水素基であり、ｎは０以上の整数である。］

[Wherein Y is a hydrocarbon group having 6 to 30 carbon atoms having an aromatic ring, and n is an integer of 0 or more. ]

[Compound represented by the general formula (1)]
In the general formula (1), X ¹ is an alkylene group having 1 to 10 carbon atoms, a group represented by the general formula (3), a group represented by the formula “—SO ₂ —” or “—CO—”. , An oxygen atom, or a single bond.

The alkylene group for X ¹ is preferably a linear or branched alkylene group.
Specific examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decanylene group, a trimethylene group, and a tetramethylene group. , Pentamethylene group, hexamethylene group and the like.
As the branched alkylene group, _{specifically, -C (CH 3) 2 -} ( isopropylene _{group), - CH (CH 3)} -, - CH (CH 2 CH 3) -, - C (CH _{3) (CH 2 CH 3)} -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - alkyl groups such as; -CH _(CH 3) CH _{2 -, - CH (CH 3)} CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH 3) 2 -CH 2 And an alkylethylene group such as-.
The number of carbon atoms of the alkylene group in X ¹ is preferably 1 to 10, more preferably 1 to 7, and particularly preferably 1 to 3.
Specific examples include a methylene group, an ethylene group, a propylene group, and an isopropylene group.

In the group represented by the general formula (3), Y is a hydrocarbon group having 6 to 30 carbon atoms having an aromatic ring, and n is an integer of 0 or more.
The C6-C30 hydrocarbon group having an aromatic ring may be composed only of an aromatic ring or may have a hydrocarbon group other than the aromatic ring. Y may have one aromatic ring or two or more aromatic rings, and in the case of two or more, these aromatic rings may be the same or different. The aromatic ring may be either a monocyclic structure or a polycyclic structure.
Preferred examples of the hydrocarbon group having 6 to 30 carbon atoms having an aromatic ring include nuclei of aromatic compounds such as benzene, biphenyl, naphthalene, anthracene, fluorene, phenanthrene, indacene, terphenyl, acenaphthylene, and phenalene. And a divalent group in which two hydrogen atoms are removed.
Moreover, these aromatic hydrocarbon groups may have a substituent. Here, that the aromatic hydrocarbon group has a substituent means that part or all of the hydrogen atoms constituting the aromatic hydrocarbon group are substituted by the substituent. Examples of the substituent include an alkyl group.
The alkyl group as a substituent is preferably a chain alkyl group. The number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, and a sec-butyl group.

  Y preferably has a group obtained by removing two hydrogen atoms from benzene or naphthalene. The group represented by the general formula (3) is more preferably a group represented by any of the following formulas (i) to (iii).

  In the group represented by the general formula (3), n is preferably an integer of 0 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In the present invention, in the compound represented by the general formula (1), the X ¹ is a linear or branched alkylene group having 1 to 3 carbon atoms, or the formulas (i) to (iii). A group represented by any one is preferable.

  Specific examples of the compound represented by the general formula (1) are shown below, but the compound of the present invention is not limited to the following examples.

[Compound represented by formula (2)]
In the general formula (2), X ² is an alkylene group having 1 to 10 carbon atoms, a group represented by the general formula (3), a group represented by the formula “—SO ₂ —” or “—CO—”. , An oxygen atom, or a single bond.

X ² in the general formula (2) is the same as X ¹ in the general formula (1).
X ¹ and X ² may be the same as or different from each other.

In the present invention, in the compound represented by the general formula (2), the X ² is a linear or branched alkylene group having 1 to 3 carbon atoms, or the formulas (i) to (iii). A group represented by any one is preferable.

  Specific examples of the compound represented by the general formula (2) are shown below, but the compound of the present invention is not limited to the following examples.

  In the present invention, a compound represented by the following general formula (4) is not used. Compared with the compound represented by the general formula (4), a resin having a higher heat resistance can be obtained by using the compound represented by the general formula (2).

［式中、Ｘ^２は、前記一般式（２）におけるものと同じである。］

[Wherein, X ² is the same as that in the general formula (2). ]

[Other ingredients]
In addition to the compound represented by the general formula (1) and the compound represented by the general formula (2), the polybenzoxazine-modified bismaleimide resin composition of the present invention can contain other components. Examples of other components include a curing accelerator.
As a hardening accelerator, it does not specifically limit and a well-known thing can be used. Specifically, a phosphine compound, a compound having a phosphonium salt, an aromatic amine compound, and the like can be given.
Examples of the phosphine compound include alkyl phosphines such as ethylphosphine and propylphosphine, primary phosphines such as phenylphosphine, dialkylphosphines such as dimethylphosphine and diethylphosphine, secondary phosphines such as diphenylphosphine, methylphenylphosphine, and ethylphenylphosphine; Trialkylphosphine such as phosphine, triethylphosphine, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, alkyldiphenylphosphine, dialkylphenylphosphine, tribenzylphosphine, tritolylphosphine, tri-p-styrylphosphine, tris ( 2,6-dimethoxyphenyl) phosphine, tri-4-methylphenylphosphi , Tri-4-methoxyphenyl phosphine, tertiary phosphines such as tri-2-cyanoethyl phosphine, and the like.
Examples of the compound having a phosphonium salt include a compound having a tetraphenylphosphonium salt, an alkyltriphenylphosphonium salt, and the like. Specifically, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium tetra-p-methylphenylborate, butyltriphenyl. Examples thereof include phosphonium thiocyanate.
Examples of the aromatic amine compound include imidazoles, specifically, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 -Hydroxymethylimidazole, 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole 1-cyano Chill-2-undecyl imidazole, 1-cyanoethyl-2-phenylimidazole, and the like.
These curing accelerators may be produced by a conventional method, or commercially available products may be used.
Moreover, a hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.
When a curing accelerator is blended in the polybenzoxazine-modified bismaleimide resin composition of the present invention, the blending amount of the curing accelerator is represented by the compound represented by the above general formula (1) and the above general formula (2). 0.1 to 5.0 parts by mass, more preferably 0.1 to 3.0 parts by mass, and 0.3 to 1.5 parts by mass with respect to 100 parts by mass in total with the compound. Part is particularly preferred.
However, the polybenzoxazine-modified bismaleimide resin composition of the present invention can be sufficiently polymerized without using a curing accelerator.

  The polybenzoxazine-modified bismaleimide resin composition of the present invention may further contain a solvent. Preferable examples of the solvent include organic acids, inorganic acids, and organic solvents other than these. Organic solvents are more preferable, and solvents that become a uniform reaction system during the reaction are particularly preferable. Examples include dipolar solvents, ketone organic solvents such as acetone and methyl ethyl ketone, amide organic solvents such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide, sulfoxide organic solvents such as dimethyl sulfoxide, and ethers such as dioxane. A solvent is preferred.

[Polybenzoxazine-modified bismaleimide resin]
The polybenzoxazine-modified bismaleimide resin of the present invention is represented by the compound represented by the general formula (1) and the general formula (2) in an amount of 0.2 to 0.5 times the molar amount of the compound. And a mixture containing the other components as necessary.
By setting the molar amount in such a range, the Tg (glass transition point) of the resin is specifically increased, and the heat resistance is remarkably improved.
In particular, the molar amount of the compound represented by the general formula (2) is the molar amount of the compound represented by the general formula (1) because it is suitable for setting the Tg of the resin to 300 ° C. or higher. On the other hand, it is preferably 0.2 to 0.4 times.

The method for polymerizing the polybenzoxazine-modified bismaleimide resin composition is not particularly limited, and the polybenzoxazine-modified bismaleimide resin composition is heated, the polybenzoxazine-modified bismaleimide resin composition is irradiated with ultraviolet rays, etc. The method can be used.
The heating temperature and heating time for heating the polybenzoxazine-modified bismaleimide resin composition are not particularly limited, and it is preferable to appropriately determine the heating temperature and heating time according to the blending of the polybenzoxazine-modified bismaleimide resin composition.
For example, the heating temperature is preferably 100 to 240 ° C, and more preferably 180 to 220 ° C. The heating time is preferably 0.5 to 12 hours, preferably 1 to 10 hours, and particularly preferably 1 to 8 hours.
Moreover, when heating the polybenzoxazine-modified bismaleimide resin composition, it is also preferable to heat it while raising the temperature stepwise. Specifically, a method of heating at 180 to 220 ° C. for 3 to 6 hours, a method of heating at 140 to 180 ° C. for 0.5 to 2 hours, and a method of heating at 180 to 220 ° C. for 0.5 to 2 hours, etc. Can be mentioned.

  Here, a process of polymerizing a mixture containing the compound represented by the general formula (1) and the compound represented by the general formula (2) will be described.

The polymerization reaction is assumed to proceed as follows, for example.
The Pd-type benzoxazine represented by the general formula (2) is opened by heat, and the resulting polymer has an N, O-acetal structure in the main chain. The N, O-acetal structure is rearranged into a Mannich-type main chain by further heating, and is converted into a polymer composed of a Mannich-type main chain by heating above 200 ° C. (general formula (5)). Furthermore, a Pd-type benzoxazine and a bismaleimide represented by the general formula (1) are partially reacted to form a high heat resistant network polymer (general formula (6)).

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[Examples 1-8, Comparative Examples 1-3]
(Differential scanning calorimetry)
Differential scanning calorimetry (DSC) shows the curing reaction behavior of the compound represented by formula (1-1) (hereinafter referred to as BMI) and the compound represented by formula (2-1) (hereinafter referred to as Pd-type benzoxazine). ).
BMI and Pd-type benzoxazine mixed in the molar ratio shown in Table 1, methylene chloride Was added and dissolved to obtain a uniform solution. Then, deaeration treatment was performed in a 45 ° C. vacuum oven, and a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation) was used in a nitrogen atmosphere (20 mL / min) at a rate of temperature increase (10 ° C./min). An exothermic peak was observed to confirm the curing reaction characteristics. Table 1 shows Tonset as the curing start temperature and Tpeak as the exothermic peak temperature. The results of differential scanning calorimetry are shown in FIG.

  The position of the exothermic peak and the shape of the exothermic peak in Example 1 and Example 2 are changed as compared with Comparative Example 1 and Comparative Example 7 which are single systems. In Example 1 and Example 2 having a large BMI equivalence ratio, the peak is shifted to a low temperature side and the peak intensity on the low temperature side is increased as compared with Comparative Examples 2 to 6 having a small BMI equivalence ratio. From the above, it was confirmed that the Pd-type benzoxazine interacts with BMI in the examples. Further, it was confirmed that the reaction temperature in the examples was around 180 ° C.

(Experimental example 1)
(Fourier transform infrared spectroscopy (FT-IR) measurement)
A reaction investigation by FT-IR under a curing condition of 200 ° C. for 4 hours was performed on a single system of only Pd-type benzoxazine and BMI, or a mixed system of Pd-type benzoxazine + BMI (1: 1). The results are shown in FIG.

Alone system, for both mixed system, by heating of 200 ° C. 4 hours, disappearance of the peak of the Pd-type benzoxazine oxazine peak and BMI from the 945 cm ^-1 double bonds derived from 3100 cm ^-1 was confirmed.
Further, it was confirmed that a peak of 1181 cm ⁻¹ that was not found in the single cured product was generated in the mixed cured product. This is derived from an ether group generated by the reaction between Pd-type benzoxazine and BMI.
Further, in the cured product of the mixed system and the cured product of the Pd-type benzoxazine alone system, a peak of 1382 cm ^{−1 and} a peak derived from the phenolic hydroxyl group of 813 cm ⁻¹ were confirmed, and the Pd-type benzoxazine was a Mannich type structure. It was confirmed that the reaction was in progress until.

[Examples 3-7, Comparative Examples 8-15]
BMI and Pd-type benzoxazine were mixed at a molar ratio shown in Table 2 to prepare a polybenzoxazine-modified bismaleide resin. The molding in Comparative Examples 8 to 13 and Example 3 was performed under the conditions of melting-mixing 120 ° C. for 30 minutes, casting-degassing 120 ° C. for 30 minutes, and curing at 200 ° C. for 4 hours. Molding in Examples 4 to 7 and Comparative Example 14 was performed under the conditions of melting-mixing 160 ° C. for 10 minutes, casting-degassing 160 ° C. for 10 minutes, and curing at 200 ° C. for 4 hours. The molding in Comparative Example 15 was performed under the conditions of melting-mixing 160 ° C. for 60 minutes, casting-degassing 160 ° C. for 10 minutes, and curing at 200 ° C. for 4 hours.

(Glass transition point / thermal expansion coefficient)
Using the polybenzoxazine-modified bismaleide resin obtained as described above, thermomechanical analysis (TMA) was performed to examine the glass transition point (Tg) and the coefficient of thermal expansion (CTE).
Specifically, measurement was performed using a TMA-60 (trade name) manufactured by Shimadzu Corporation at a heating rate of 5 ° C./min, a compression method, a load of 5 g, and air of 100 ml / min. A sample of a polybenzoxazine-modified bismaleide resin sample was polished to 5 (length) × 5 (width) × 10 (height) mm, heated for 10 minutes at the final curing temperature, and then measured for strain. From the slope of the TMA curve, Tg (° C.) and CTE (ppm) at 50 to 100 ° C. were calculated. The results are shown in Table 2.

(Raw material mass decrease temperature / residue amount)
Using the polybenzoxazine-modified bismaleide resin obtained as described above, thermogravimetry (TGA) was performed, and the temperature at which the raw material mass decreased and the amount of residue were examined.
Specifically, using a TGA-50 (trade name) manufactured by Shimadzu Corporation, measurement was performed at a temperature rising rate of 5 ° C./min and nitrogen of 20 ml / min, and the mass was 5% based on the mass at 40 ° C. The temperature when the amount was reduced was Td ₅ , and the temperature when the amount was reduced by 10% was Td ₁₀ . The results are shown in Table 2.
Moreover, the amount of residue (mass%) at the time of heating to 800 degreeC was calculated | required on the basis of the mass at the time of 40 degreeC, and chemical heat resistance was evaluated. The results are shown in Table 2. Further, using the data of Examples 3 to 7 and Comparative Examples 8 to 15, the BMI content (% by mass) in the resin was plotted on the horizontal axis and the Tg (° C.) was plotted on the vertical axis. The results are shown in FIG.

From the above results, it was confirmed that the polybenzoxazine-modified bismaleide resins of Examples 3 to 7 according to the present invention had significantly higher Tg and excellent heat resistance as compared with Comparative Examples 8 to 15.
As apparent from FIG. 3, the Tg curve does not rise gently in the region where the molar ratio of Pd-type benzoxazine is 0.2 to 0.5 (BMI content 62.2 to 80.5 mass%). However, the value of Tg at this time is as high as never before. FIG. 3 shows that Tg specifically increases in this region. In particular, the molar ratio of Pd-type benzoxazine is 0.2 to 0.4 (BMI content 67.2 to 80.5% by mass), and further 0.25 to 0.35 (BMI content 70.1.2). 76.7% by mass), the value of Tg is remarkably high, and a value of 300 ° C. or higher is realized.
Further, the polybenzoxazine-modified bismaleide resins of Examples 3 to 7 showed high values of T _d5 and T _d10 , and it was found that these resins were excellent in both physical and chemical heat resistance. Furthermore, in the coefficient of thermal expansion (CTE), a low value was obtained as compared with 70 ppm / ° C. of the general-purpose epoxy resin.
In this embodiment, the curing is performed under the condition of curing at 200 ° C. for 4 hours, but the same result can be obtained even when the curing temperature is 240 ° C.

Claims (4)

A mixture comprising a compound represented by the following general formula (1) and a compound represented by the following general formula (2) in an amount of 0.2 to 0.5 times the molar amount of the compound is polymerized. A polybenzoxazine-modified bismaleimide resin characterized by the above.

[Wherein, X ¹ and X ² are each independently an alkylene group having 1 to 10 carbon atoms, a group represented by the following general formula (3), a formula “—SO ₂ —” or “—CO—”. Or a single bond. ]

[In formula, Y is a C6-C30 hydrocarbon group which has an aromatic ring, and n is an integer of 1-3 . ] X ¹ and X ² are each independently a linear or branched alkylene group having 1 to 3 carbon atoms, or a group represented by any of the following formulas (i) to (iii): 2. The polybenzoxazine-modified bismaleimide resin according to 1.

A polycrystal comprising a compound represented by the following general formula (1) and a compound represented by the following general formula (2) in an amount of 0.2 to 0.5 times the molar amount of the compound: A benzoxazine-modified bismaleimide resin composition.

[Wherein, X ¹ and X ² are each independently an alkylene group having 1 to 10 carbon atoms, a group represented by the following general formula (3), a formula “—SO ₂ —” or “—CO—”. Or a single bond. ]

[In formula, Y is a C6-C30 hydrocarbon group which has an aromatic ring, and n is an integer of 1-3 . ] X ¹ and X ² are each independently a linear or branched alkylene group having 1 to 3 carbon atoms, or a group represented by any of the following formulas (i) to (iii): 4. The polybenzoxazine-modified bismaleimide resin composition according to 3.

Images