Resin composition and cured product thereof

Abstract

The glass transition temperature of the cured product of a resin composition containing a benzoxazine having a terminal unsaturated hydrocarbon group is improved. A resin composition according to an embodiment contains compounds of formula (1) and formula (2). JPEG0007659692000032.jpg74167

Description

[Technical field]

[0001] An embodiment of the present invention relates to a resin composition containing benzoxazine and biscitraconimide, and a cured product thereof. [Background technology]

[0002] Benzoxazine is a compound having a benzoxazine ring formed by a condensation reaction of a phenol, an amine, and formaldehyde. Benzoxazine is a thermosetting monomer that is cured by heating through ring-opening polymerization of the benzoxazine ring.

[0003] For example, Patent Document 1 discloses a benzoxazine having two benzoxazine rings in one molecule, which is obtained by a condensation reaction between phenol, 4,4'-diaminodiphenylmethane, and paraformaldehyde. Patent Document 2 discloses a benzoxazine having benzoxazine rings at the 3- and 4-positions of a diphenyl ether group, which is obtained by a condensation reaction between phenol, 3,4'-diaminodiphenyl ether, and formaldehyde.

[0004] On the other hand, it is known that biscitraconimide is used as a material for printed circuit boards, for example. Biscitraconimide does not cure by itself, but it is known that it can be cured by adding a crosslinking agent (curing agent).

[0005] For example, Patent Document 3 describes that benzoxazine may be added as a curing agent to a resin material containing a maleimide compound having a skeleton derived from dimer diamine, and that the maleimide compound may be a citraconic imide compound. Patent Document 4 describes that benzoxazine may be added as a crosslinking agent to a film-forming material for lithography containing a polycitraconimide compound. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 4647398 [Patent Document 2] JP 2018-184533 A [Patent Document 3] International Publication No. 2020 / 045408 [Patent Document 4] International Publication No. 2020 / 004316 Summary of the Invention [Problem to be solved by the invention]

[0007] Some benzoxazines have an allyl group at the molecular end. Such terminal unsaturated hydrocarbon groups do not react with the thermal ring-opening polymerization of benzoxazine, but can react with other polymerizable monomers. When such benzoxazines having terminal unsaturated hydrocarbon groups are used as, for example, printed circuit board materials, it is required to increase the glass transition temperature of the cured product.

[0008] An object of an embodiment of the present invention is to improve the glass transition temperature of a cured product of a resin composition containing a benzoxazine having a terminal unsaturated hydrocarbon group. [Means for solving the problem]

[0009] The present invention includes the embodiments set forth below. [1] A compound represented by the following general formula (1) and a compound represented by the following general formula (2), [ka] In formula (1), R 1 represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may contain a heteroatom; R 2 and R 3 each independently represents an alkanediyl group having 1 to 10 carbon atoms; R 4 and R 5 each independently represents a hydrogen atom or a methyl group; R 6 and R7 each independently represents a methyl group or an ethyl group, p and q each independently represent an integer of 0 to 2, [ka] In formula (2), R 8 represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may contain a heteroatom.

[0010] [2] R in the above formula (1) 1 is a divalent aromatic ring-containing hydrocarbon group having 6 to 50 carbon atoms which may contain a heteroatom. [3] The compound represented by the formula (1) is represented by the following general formula (1A): [ka] In formula (1A), R 11 represents a single bond, -CH2-, -CH(CH3)-, -C(CH3)2-, or -O-; R 12 and R 13 each independently represents a methyl group or an ethyl group, s and t each independently represent an integer of 0 to 4, R 2 and R 3 each independently represents an alkanediyl group having 1 to 10 carbon atoms; R 4 and R 5 each independently represents a hydrogen atom or a methyl group; R 6 and R 7 each independently represents a methyl group or an ethyl group, and p and q each independently represent an integer of 0 to 2. The resin composition according to [1].

[0011] [4] R in the above formula (2) 8 The resin composition according to any one of [1] to [3], wherein is a divalent aromatic ring-containing hydrocarbon group having 6 to 50 carbon atoms which may contain a heteroatom. [5] The compound represented by formula (2) is represented by the following general formula (2A): [ka] In formula (2A), R21 represents a single bond, -CH2-, -CH(CH3)-, -C(CH3)2-, -O-, or a group represented by the following formula (21A), R 22 and R 23 each independently represents a methyl group or an ethyl group, u and v each independently represent an integer of 0 to 4, [ka] In formula (21A), R 24 and R 25 each independently represents -CH2-, -CH(CH3)-, -C(CH3)2-, or -O-.

[0012] [6] The resin composition according to any one of [1] to [5], which is used as a printed circuit board material. [7] A cured product obtained by curing the resin composition according to any one of [1] to [6]. Effect of the Invention

[0013] According to an embodiment of the present invention, the glass transition temperature of a cured product of a resin composition containing a benzoxazine having a terminal unsaturated hydrocarbon group can be improved. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The resin composition according to the present embodiment contains a compound represented by the following general formula (1) (hereinafter referred to as compound (1)). Compound (1) is a compound composed of one molecule of diamine, two molecules of phenols, and four molecules of formaldehyde, and has two benzoxazine rings in the molecule. [ka]

[0015] In formula (1), R 1 R represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may contain a heteroatom. 1The number of carbon atoms in the hydrocarbon group is preferably 2 to 70, more preferably 3 to 50, more preferably 5 to 30, and further preferably 6 to 20. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, a fluorine atom, and a silicon atom. An oxygen atom is preferable. 1 It is preferred that does not contain any heteroatoms.

[0016] R 1 The hydrocarbon group of R preferably contains an aromatic ring (i.e., is an aromatic ring-containing hydrocarbon group), more preferably contains a benzene ring, and further preferably contains two or three benzene rings. 1 The hydrocarbon group has more preferably 6 to 50 carbon atoms, more preferably 12 to 30 carbon atoms, and further preferably 12 to 20 carbon atoms.

[0017] In formula (1), R 2 and R 3 each independently represents an alkanediyl group (also called an alkylene group) having 1 to 10 carbon atoms. The alkanediyl group may be a straight chain or a branched chain. 2 and R 3 are each independently an alkanediyl group having 1 to 5 carbon atoms, more preferably an alkanediyl group having 1 to 3 carbon atoms, more preferably an ethylene group (-CHCH-) or a methylene group (-CH-), and even more preferably a methylene group. 4 and R 5 Each independently represents a hydrogen atom or a methyl group, and more preferably a hydrogen atom. 4 R 2 - and H2C=CR 5 R 3 The unsaturated hydrocarbon group represented by - is represented by CR so that it has an allyl group (H2C=CH-CH2-) or a methallyl group (H2C=C(CH3)-CH2-) at its terminal. 4 or CR 5 It is preferred that the carbon adjacent to is a methylene group.

[0018] In formula (1), R 6 and R 7 each independently represents a methyl group or an ethyl group, more preferably a methyl group. In formula (1), p and q each independently represent an integer of 0 to 2, more preferably each independently represents 0 or 1, and further preferably 0.

[0019] In formula (1), H2C=CR 4 R 2 - and H2C=CR 5 R 3 - and an unsaturated hydrocarbon group represented by R 6 and R 7 For the substituents represented by the formula (I), their bonding positions on the benzene ring are preferably set as follows: One unsaturated hydrocarbon group and 0 to 2 substituents are bonded to the benzene ring, provided that at least one of the ortho and para positions with respect to the oxygen atom bonded to the benzene ring is unsubstituted (i.e., a hydrogen atom). Preferably, the unsaturated hydrocarbon group is bonded to the ortho position with respect to the oxygen atom.

[0020] Compound (1) is more preferably represented by the following general formula (1A). [ka]

[0021] In formula (1A), R 11 represents a single bond, -CH2-, -CH(CH3)-, -C(CH3)2-, or -O-. 11 is preferably a single bond, -CH2-, or -O-, more preferably a single bond or -CH2-. 11 The bond position of Ph-R 11 A group represented by -Ph (wherein Ph is a substituent R 12 or R 13 The bonding positions of the benzoxazine ring to the benzene ring which may have the formula:

[0022] In formula (1A), R 12 and R 13 R each independently represents a methyl group or an ethyl group, and is more preferably a methyl group. 12 and R 13 When a plurality of are present in one molecule, they may be the same or different. s and t each independently represent an integer of 0 to 4, more preferably an integer of 0 to 2, and further preferably 0 or 1.

[0023] In formula (1A), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , p and q are R in formula (1), 2 , R 3 , R 4 , R 5 , R 6 , R 7 , p and q.

[0024] In one embodiment, compound (1) is preferably represented by the following general formula (1B). [ka] In formula (1B), R 11 , R 12 , R 13 , R 2 , R 3 , R 4 , R 5 , s and t are R in formula (1A), 11 , R 12 , R 13 , R 2 , R 3 , R 4 , R 5 , s and t.

[0025] In one embodiment, compound (1) may be a compound represented by the following general formula (1C). [ka] In formula (1C), R 2 , R 3 , R 4 and R 5 are R in formula (1A), 2 , R 3 , R 4 and R 5 is the same as:

[0026] In one embodiment, compound (1) may be a compound represented by the following general formula (1D). [ka] In formula (1D), R 12 , R 13 , R 2 , R 3 , R 4 and R 5 are R in formula (1A), 12 , R 13 , R 2 , R 3 , R 4 and R 5 is the same as:

[0027] The method for producing the compound (1) is not particularly limited, and for example, the compound (1) can be obtained by a condensation reaction of a phenol, a diamine, and formaldehyde. In detail, in the presence of a solvent, a phenol represented by the following formula (3), a diamine represented by the following formula (4), and formaldehyde (e.g., paraformaldehyde, i.e., (HCHO) n ) and agitating and mixing the mixture and subjecting it to a dehydration condensation reaction under heating. After the condensation reaction, the mixture may be purified by separation washing, recrystallization, column purification, or the like. [ka]

[0028] In formula (3), R 14 is H2C=CR in the above formula (1). 4 R 2 - or H2C=CR 5 R 3 - is the same as R15 is R in the above formula (1). 6 or R 7 and r is the same as p or q in formula (1). In formula (4), R 1 is R in the above formula (1). 1 is the same as:

[0029] Examples of the solvent include organic solvents capable of dissolving benzoxazine, such as toluene, xylene, cumene, monochlorobenzene, methyl ethyl ketone, ethyl acetate, butyl acetate, chloroform, dichloromethane, THF, dioxane, dimethylformamide, etc. These may be used alone or in combination of two or more.

[0030] Regarding the ratio of phenols, diamines, and formaldehyde, the target compound represented by formula (1) is obtained by reacting 2 moles of phenols and 4 moles of formaldehyde with 1 mole of diamine, so the amount of charge can be set based on this. For example, the amount of phenols charged is preferably 2.0 to 2.5 moles, more preferably 2.0 to 2.2 moles, and even more preferably 2.0 to 2.1 moles, per mole of diamine. The amount of formaldehyde charged is preferably 3.9 to 5.0 moles, more preferably 4.0 to 4.5 moles, and even more preferably 4.0 to 4.3 moles, per mole of diamine.

[0031] The reaction product obtained by the above-mentioned condensation reaction usually contains, together with the compound (1) as the main product, by-products such as a one-ring-opening product in which one of the two benzoxazine rings of the compound (1) is not closed but is opened, and a polymer (including an oligomer) of the compound (1). The resin composition according to the embodiment may contain, as the benzoxazine, a by-product corresponding to the compound (1) together with the compound (1). That is, the compound (1) and the by-product (as an optional component) corresponding to the compound (1) are collectively referred to as benzoxazine, and the resin composition according to the embodiment contains the benzoxazine. In the benzoxazine, the proportion of the compound (1) is not particularly limited, but is preferably 40% or more, more preferably 45% or more, and even more preferably 50% or more. The upper limit is not particularly limited, but the proportion of the compound (1) is usually 80% or less, and may be 70% or less. Here, the proportion of the compound (1) is the ratio of the peak area by GPC analysis.

[0032] The resin composition according to the present embodiment contains a compound represented by the following general formula (2) (hereinafter referred to as compound (2)). Compound (2) is a biscitraconimide having two citraconimide groups. [ka]

[0033] In formula (2), R 8 R represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may contain a heteroatom. 8 The number of carbon atoms in the hydrocarbon group is preferably 2 to 70, more preferably 3 to 50, more preferably 5 to 30, and further preferably 6 to 20. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, a fluorine atom, and a silicon atom. An oxygen atom is preferable. 8 It is preferred that does not contain any heteroatoms.

[0034] R 8The hydrocarbon group of R preferably contains an aromatic ring (i.e., is an aromatic ring-containing hydrocarbon group), more preferably contains a benzene ring, and further preferably contains two or three benzene rings. 8 The hydrocarbon group has more preferably 6 to 50 carbon atoms, more preferably 12 to 30 carbon atoms, and further preferably 12 to 20 carbon atoms.

[0035] The compound (2) is more preferably represented by the following general formula (2A). [ka]

[0036] In formula (2A), R 21 represents a single bond, -CH2-, -CH(CH3)-, -C(CH3)2-, -O-, or a group represented by the following formula (21A). [ka] In formula (21A), R 24 and R 25 each independently represents -CH2-, -CH(CH3)-, -C(CH3)2-, or -O-.

[0037] In formula (2A), R 21 is preferably a single bond, -CH2-, -O-, or a group represented by formula (21A), and more preferably a single bond or -CH2-. 21 The bond position of Ph-R 21 A group represented by -Ph (wherein Ph is a substituent R 22 or R 23 The bonding positions of the citraconimide groups to the benzene ring (which may have the formula:

[0038] In formula (21A), R 24 and R 25are preferably each independently -CH2-, -CH(CH3)-, or -C(CH3)2-, and more preferably -C(CH3)2-. 24 and R 25 The bonding position of is preferably the meta or para position, more preferably the meta position.

[0039] In formula (2A), R 22 and R 23 R each independently represents a methyl group or an ethyl group, and is more preferably a methyl group. 22 and R 23 When a plurality of are present in one molecule, they may be the same or different. u and v each independently represent an integer of 0 to 4, more preferably an integer of 0 to 2, and further preferably 0 or 1.

[0040] In one embodiment, compound (2) is preferably represented by the following general formula (2B). [ka] In formula (2B), R 21 , R 22 , R 23 , u and v are R in formula (2A), 21 , R 22 , R 23 , u and v.

[0041] The method for producing compound (2) is not particularly limited, and it can be obtained, for example, by subjecting citraconic anhydride and diamine to a dehydration condensation reaction.

[0042] The resin composition according to the embodiment is a thermosetting resin composition containing compound (1) and compound (2). In detail, compound (1) has a benzoxazine ring, and therefore cures (thermosets) by thermal ring-opening polymerization as a monomer. In addition, H2C=CR 4 R 2 - and H2C=CR 5 R 3The unsaturated hydrocarbon group represented by - reacts with the citraconimide of compound (2), whereby compound (2) is thermally cured together with compound (1). Therefore, it is considered that the cured product of the resin composition according to the embodiment has a higher glass transition temperature than the case where compound (1) is cured alone. Furthermore, in the resin composition according to the embodiment, compound (2), which is a biscitraconimide, has higher solvent solubility than bismaleimide, which is a similar substance. Furthermore, the resin composition according to the embodiment has high reactivity in the curing reaction and excellent moldability of the cured product. Furthermore, the resin composition according to the embodiment has a low water absorption rate and excellent low water absorption.

[0043] In the resin composition according to the embodiment, the compounding ratio of the compound (1) and the compound (2) is not particularly limited, but may be set as follows in one embodiment. As described above, the compound (1) is usually produced together with by-products such as ring-opening products and polymerized products, so that it is preferable to set the compounding ratio with the compound (2) as benzoxazine containing these by-products. That is, the mass ratio of benzoxazine (BZO) consisting of the compound (1) and its by-products to biscitraconimide (CI) of the compound (2), that is, the mass ratio BZO / CI of BZO to CI, is preferably 0.35 to 4.0, more preferably 0.4 to 3.0, and more preferably 0.8 to 2.0. By setting the BZO / CI to 4.0 or less, the effect of improving the glass transition temperature of the cured product can be enhanced. By setting the BZO / CI to 0.35 or more, the moldability of the cured product can be improved.

[0044] The resin composition according to the embodiment may be composed of only the benzoxazine (BZO) containing the compound (1) and the biscitraconimide (CI) of the compound (2), or may contain, for example, other thermosetting resins and / or thermoplastic resins together with BZO and CI. The resin composition may also contain various known additives such as a solvent, a catalyst, a crosslinking agent, a curing accelerator, a colorant, a radical polymerization initiator, a leveling agent, a flame retardant, an antioxidant, and an inorganic filler.

[0045] In the resin composition, the total amount of benzoxazine (BZO) and biscitraconimide (CI) is preferably 50 mass% or more, more preferably 70 mass% or more, and further preferably 80 mass% or more, as a mass ratio excluding the solvent. In one embodiment, the resin composition is a resin solution containing a solvent. In this case, the content of the solvent in the resin composition is not particularly limited, and may be, for example, 30 to 70 mass% or 40 to 60 mass%.

[0046] Examples of the solvent contained in the resin composition include organic solvents capable of dissolving benzoxazine and biscitraconimide, such as toluene, xylene, cumene, monochlorobenzene, methyl ethyl ketone, ethyl acetate, butyl acetate, chloroform, dichloromethane, THF, dioxane, and dimethylformamide. These may be used alone or in combination of two or more. As the solvent, aromatic hydrocarbon solvents and ketone solvents are preferred. In addition, from the viewpoint of removability when removing the solvent by evaporation or the like during curing, non-halogen solvents having a boiling point of 150° C. or less are preferred.

[0047] Examples of the catalyst contained in the resin composition include imidazole catalysts such as 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, and 1,2-dimethylimidazole, and organophosphorus catalysts such as triphenylphosphine and tributylphosphine.

[0048] The cured product according to the present embodiment is obtained by curing the resin composition, and is usually cured by heating. The curing conditions are not particularly limited, and may be, for example, heated at 150°C to 250°C for 30 to 180 minutes. When the resin composition contains a solvent, the solvent may be evaporated by heating, and then the temperature may be further increased to perform thermal curing.

[0049] The resin composition according to this embodiment can be used for various purposes, such as an electrical insulating material or a matrix resin for composite materials.

[0050] In one embodiment, the resin composition is preferably used as a printed circuit board material. That is, the printed circuit board material according to one embodiment includes a resin composition containing compound (1) and compound (2). The printed circuit board material can be used to produce a printed circuit board such as a printed wiring board or a printed circuit board according to one embodiment.

[0051] Examples of printed circuit board materials include rigid printed circuit board materials for producing single-sided boards, double-sided boards, multilayer boards, build-up boards, etc., and flexible printed circuit board materials for producing film- or sheet-shaped flexible printed circuit boards. EXAMPLES

[0052] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited thereto.

[0053] <Measurement and evaluation methods> [Purity of the main product in benzoxazine] BZO to 4 of Synthesis Examples 1 to 2 and Comparative Synthesis Examples 3 to 4 were dissolved in THF so that the concentration of the reaction product was about 0.2 mg / ml, and GPC measurement was performed using a gel permeation chromatography (GPC) (Prominence, Shimadzu Corporation) connected to four columns (Shodex GPC columns KF-601, KF-602, KF-603, KF-604, Resonac Corporation) filled with polystyrene gel. The measurement conditions were a column oven temperature of 40°C, a flow rate of 0.6 ml / min, and a differential refractive index detector (Shodex RI-504, Resonac Corporation). After removing the peak derived from the solvent (toluene) from the obtained chromatogram, the purity of the main product was calculated as the peak area ratio (%).

[0054] [Solubility] The components were mixed in the proportions (units are g) shown in Tables 1 and 2. Those that dissolved uniformly at room temperature were classified as "A." Those that dissolved uniformly when heated to 50°C were classified as "B." Those that still contained insoluble matter even when heated to 50°C were classified as "C."

[0055] [Moldability] For the Examples and Comparative Examples in which the solubility evaluation was A or B, the resin composition prepared according to the formulation (g) shown in Table 1 or Table 2 was placed in an aluminum cup with an upper diameter of 60 mm, a lower diameter of 54 mm, and a depth of 16 mm, and heated on a hot plate at 120°C for 1 hour to distill off the solvent. The hot plate was then heated to 250°C and heated for 1 hour to perform thermal curing, and the plate was allowed to cool to room temperature to produce a flat plate. Plates with noticeable appearance defects such as bubbles, cracks, and poor curing were given a "B" rating, and plates with minor or no appearance defects were given an "A" rating.

[0056] [Glass transition temperature (Tg)] For the examples and comparative examples in which the solubility evaluation was A or B, the resin composition prepared with the formulation (g) shown in Table 1 or Table 2 was placed in an aluminum cup with an upper diameter of 60 mm, a lower diameter of 54 mm, and a depth of 16 mm, and heated on a hot plate at 120 ° C. for 1 hour to distill off the solvent. The hot plate was then heated to 250 ° C. and heated for 1 hour to perform thermal curing, and cooled to room temperature to produce a flat plate. For those in which the moldability evaluation was A, a test piece with a width of 5 mm, a thickness of about 1 mm, and a length of 30 mm was prepared from the obtained flat plate. Next, the glass transition temperature was measured using a dynamic viscoelasticity measuring device: Rheogel-E4000 (manufactured by UBM Co., Ltd.). The temperature at which the loss tangent (tan δ) measured for the test piece under the conditions of a tensile sine wave, dynamic strain of 5 μm, frequency of 1 Hz, and temperature rise rate of 3 ° C. / min took a maximum value was determined as the glass transition temperature.

[0057] [Water absorption rate] Test pieces similar to those used in the glass transition temperature measurements of Examples 1 to 11 and Comparative Example 5 were prepared, and the mass increase rate (%) was measured before and after immersion in water at 25°C for 24 hours, and calculated as the water absorption rate at 25°C. Similarly, the mass increase rate (%) was measured before and after immersion in water at 40°C for 24 hours, and calculated as the water absorption rate at 40°C.

[0058] <Synthesis Example 1> In a 5L reactor equipped with a condenser, a Dean-Stark apparatus, and a stirrer, 521.0g of 4,4'-diaminodiphenylmethane, 705.2g of 2-allylphenol, and 1569.3g of toluene were added and dissolved at 75°C. Next, 343.1g of 92% by mass paraformaldehyde was added in 5 portions, and the reaction liquid was heated to distill off the water generated by the dehydration condensation reaction. The reaction liquid was further heated to 105-110°C and the reaction was continued for 6 hours, and the reaction liquid was cooled to room temperature, and then 301.7g of toluene was added to dilute it. 784.6g of 10% by mass sodium hydroxide aqueous solution was added thereto, stirred for 15 minutes, and allowed to stand to separate and remove the aqueous layer. This operation was repeated twice. 627.7g of water and 156.9g of isopropyl alcohol (IPA) were further added to the obtained organic layer, stirred for 15 minutes, and allowed to stand to separate and remove the aqueous layer. This operation was repeated five times. The water and IPA in the obtained organic layer were distilled off under reduced pressure using a rotary evaporator to obtain a toluene solution (BZO1) containing the reaction product at a concentration of 49.8% by mass. The obtained reaction product was benzoxazine containing the compound represented by the following formula as the main product, and the purity of the main product by GPC analysis was 56.2%. [ka]

[0059] <Synthesis Example 2> In a 5L reactor equipped with a condenser, a Dean-Stark apparatus and a stirrer, 436.9g of 4,4'-diamino-2,2'-dimethylbiphenyl, 552.0g of 2-allylphenol and 1257.6g of toluene were added and dissolved at 75°C. Next, 268.7g of 92% by mass paraformaldehyde was added in 5 portions, and the reaction liquid was heated to distill off the water generated by the dehydration condensation reaction. The reaction liquid was further heated to 105-110°C and the reaction was continued for 6 hours, and the reaction liquid was cooled to room temperature, and then 168.4g of toluene was added to dilute. 503.0g of 10% by mass aqueous sodium hydroxide solution and 125.8g of IPA were added, stirred for 15 minutes, left to stand and the aqueous layer was separated and removed twice, and then 179.2g of toluene was added to the obtained organic layer to dilute it. 503.0g of water and 125.8g of IPA were added to the mixture, stirred for 15 minutes, allowed to stand, and the aqueous layer was separated and removed. This operation was repeated five times. The water and IPA in the resulting organic layer were distilled off under reduced pressure to obtain a toluene solution (BZO2) containing the reaction product at a concentration of 51.4% by mass. The resulting reaction product was benzoxazine containing the compound represented by the following formula as the main product, and the purity of the main product by GPC analysis was 61.7%. [ka]

[0060] <Synthesis Example 3> In a 500mL reactor equipped with a condenser, a Dean-Stark apparatus, and a stirrer, 149.2g of citraconic anhydride and 845.5g of toluene were added and mixed. A solution of 120.0g of 4,4'-diaminodiphenylmethane dissolved in 360.0g of N-methylpyrrolidone (NMP) was added dropwise to the reaction mixture and reacted for 30 minutes. After adding 11.5g of paratoluenesulfonic acid monohydrate to the reaction mixture, the reaction mixture was heated and the water generated by the dehydration condensation reaction was distilled out of the system while the reaction was continued at 105-110°C for 4 hours, and the reaction mixture was cooled to 85°C. 360.0g of water was added to the reaction mixture, and the mixture was stirred at 75-85°C, left to stand, and the aqueous layer was separated and removed. This operation was repeated three times, and the resulting organic layer was concentrated with a rotary evaporator to obtain a solution of about 50% by mass. This solution was poured into 4678 g of IPA, and the precipitated solid was collected and dried in vacuum at 60° C. to obtain citraconimide (CI1) represented by the following formula. [ka]

[0061] <Synthesis Example 4> In a 500mL reactor equipped with a condenser, a Dean-Stark apparatus and a stirrer, 17.9g of citraconic anhydride and 47.7g of toluene were added and mixed. A solution of 25.0g of 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene dissolved in 100.0g of toluene and 12.0g of NMP was added dropwise and reacted for 30 minutes. After adding 1.4g of paratoluenesulfonic acid monohydrate to this reaction solution, the reaction solution was heated and the reaction was continued at 105-110°C for 3 hours while distilling off the water generated by the dehydration condensation reaction, and the reaction solution was cooled to 100°C. 75.0g of water was added to this, and the mixture was stirred at 75-85°C, left to stand and the aqueous layer was separated and removed three times. The organic layer obtained was concentrated with a rotary evaporator to obtain a toluene solution (CI2) containing 35.5% by mass of biscitraconimide represented by the following formula. [ka]

[0062] <Synthesis Example 5> In a 500mL reactor equipped with a condenser, a Dean-Stark apparatus, and a stirrer, 20.0g of 4,4'-diamino-2,2'-dimethylbiphenyl, 142.1g of toluene, and 7.8g of NMP were added and mixed. 23.2g of citraconic anhydride was added dropwise to this and reacted for 30 minutes. After adding 1.8g of paratoluenesulfonic acid monohydrate to this reaction solution, the reaction solution was heated and the water generated by the dehydration condensation reaction was distilled out of the system while the reaction was continued for 4 hours at 105-110°C. 54.3g of NMP was added to the reaction solution and the reaction was continued for another hour, after which the reaction solution was cooled to 100°C. 60.0g of water was added here, stirred at 75-85°C, left to stand, and the aqueous layer was separated and removed. This operation was repeated three times, and the resulting organic layer was concentrated with a rotary evaporator to obtain a solution of about 40%. This solution was poured into 754 g of IPA, and the precipitated solid was collected and dried in vacuum at 60° C. to obtain biscitraconimide (CI3) represented by the following formula. [ka]

[0063] <Comparative Synthesis Example 1> In a 500mL reactor equipped with a condenser, a Dean-Stark apparatus, and a stirrer, 15.7g of maleic anhydride and 62.8g of toluene were added and mixed. A solution of 25.0g of 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene dissolved in 100.0g of toluene and 7.0g of NMP was added dropwise to the reaction mixture and reacted for 30 minutes. After adding 1.4g of paratoluenesulfonic acid monohydrate to the reaction mixture, the reaction mixture was heated and the water generated by the dehydration condensation reaction was distilled out of the system while the reaction was continued at 105-110°C for 4 hours, and the reaction mixture was cooled to 100°C. 75.0g of water was added to the reaction mixture, and the mixture was stirred at 75-85°C, left to stand, and the aqueous layer was separated and removed. This operation was repeated three times, and the resulting organic layer was concentrated with a rotary evaporator to obtain a solution of about 50%. This solution was poured into 366 g of IPA, and the precipitated solid was collected and dried in vacuum at 60° C. to obtain bismaleimide (MI2) represented by the following formula. [ka]

[0064] <Comparative Synthesis Example 2> In a 500mL reactor equipped with a condenser, a Dean-Stark apparatus, and a stirrer, 20.3g of maleic anhydride and 140.9g of toluene were added and mixed. A solution of 20.0g of 4,4'-diamino-2,2'-dimethylbiphenyl dissolved in 60.0g of NMP was added dropwise to the reaction mixture and reacted for 30 minutes. After adding 1.8g of paratoluenesulfonic acid monohydrate to the reaction mixture, the reaction mixture was heated and the water generated by the dehydration condensation reaction was distilled out of the system while the reaction was continued at 105-110°C for 4 hours, and the reaction mixture was cooled to 100°C. 60.0g of water was added to the reaction mixture, and the mixture was stirred at 75-85°C, left to stand, and the aqueous layer was separated and removed. This operation was repeated three times, and the resulting organic layer was concentrated with a rotary evaporator to obtain a solution of about 60%. This solution was poured into 702 g of IPA, and the precipitated solid was collected and dried in vacuum at 60° C. to obtain bismaleimide (MI3) represented by the following formula. [ka]

[0065] <Comparative Synthesis Example 3> In a 500 mL reactor equipped with a cooler, a Dean-Stark apparatus, and a stirrer, 79.3 g of 4,4'-diaminodiphenylmethane, 75.3 g of phenol, and 206.8 g of toluene were added and dissolved at 75 ° C. Next, 52.2 g of 92 mass% paraformaldehyde was added in 5 portions. The reaction liquid was heated to 105 ° C. over about 3 hours, and the water generated by the dehydration condensation reaction was distilled out of the system, and then the reaction liquid was cooled to room temperature. The reaction liquid was poured into 1034 g of IPA, and the precipitated solid was collected and vacuum dried at 50 ° C. to obtain a reaction product (BZO3). The obtained reaction product was benzoxazine containing the compound represented by the following formula as the main product, and the purity of the main product by GPC analysis was 44.1%. [ka]

[0066] <Comparative Synthesis Example 4> In a 300 mL reactor equipped with a cooler, a Dean-Stark apparatus and a stirrer, 21.2 g of 4,4'-diamino-2,2'-dimethylbiphenyl, 18.8 g of phenol and 53.0 g of toluene were added and dissolved at 75 ° C. Next, 13.0 g of 92 mass% paraformaldehyde was added in 5 portions, and the reaction liquid was heated to distill off the water generated by the dehydration condensation reaction. The reaction liquid was further heated to 105-110 ° C. and the reaction was continued for 4 hours, and the reaction liquid was cooled to room temperature. This reaction liquid was poured into 530 g of methanol, and the precipitated solid was collected and vacuum dried at 40 ° C. to obtain a reaction product (BZO4). The obtained reaction product was benzoxazine containing the compound represented by the following formula as the main product, and the purity of the main product by GPC analysis was 45.1%. [ka]

[0067] <Examples 1 to 6 and Comparative Examples 1 to 5> Resin compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were prepared according to the formulations (parts by mass) shown in Table 1 below, and the solubility, moldability, glass transition temperature (Tg), and water absorption were evaluated or measured. Note that "BZO / CI" in the table is the mass ratio of benzoxazine (BZO) to biscitraconimide (CI), but in Comparative Examples 2 to 4, it is the mass ratio of benzoxazine (BZO) to maleimide (MI).

[0068] [Table 1]

[0069] As shown in Table 1, the resin compositions of Examples 1 to 6 using the allyl group-containing benzoxazine BZO1 in combination with biscitraconimide showed a significantly improved glass transition temperature of the cured product compared to the resin composition of Comparative Example 1 using the allyl group-containing benzoxazine BZO1 alone. In addition, Comparative Examples 2 to 4 using a similar substance, bismaleimide, instead of biscitraconimide, showed poor solvent solubility, but Examples 1 to 6 using biscitraconimide in combination showed good solvent solubility and excellent moldability compared to Comparative Examples 2 to 4. In addition, Comparative Example 5 using benzoxazine BZO3 without an allyl group showed a high water absorption rate and poor water absorption of the cured product compared to Examples 1 to 6.

[0070] <Examples 7 to 11 and Comparative Examples 6 to 11> Resin compositions of Examples 7 to 11 and Comparative Examples 6 to 11 were prepared according to the formulations (parts by mass) shown in Table 2 below, and the solubility, moldability, glass transition temperature (Tg), and water absorption were evaluated or measured. Note that "BZO / CI" in the table is the mass ratio of benzoxazine (BZO) to biscitraconimide (CI), but in Comparative Examples 7 to 8, it is the mass ratio of benzoxazine (BZO) to maleimide (MI).

[0071] [Table 2]

[0072] As shown in Table 2, the resin compositions of Examples 7 to 11, in which allyl-group-containing benzoxazine BZO2 and biscitraconimide were used in combination, had a significantly improved glass transition temperature of the cured product compared to the resin composition of Comparative Example 6, in which allyl-group-containing benzoxazine BZO2 was used alone. In addition, Comparative Examples 7 and 8, in which a similar substance, bismaleimide, was used instead of biscitraconimide, had poor solvent solubility, but Examples 7 to 11, in which biscitraconimide was used in combination, had good solvent solubility and excellent moldability compared to Comparative Examples 7 and 8. In addition, in the resin compositions of Comparative Examples 9 to 11, in which other allyl-group-containing compounds (allyl 1, 2) or benzoxazine BZO4 without an allyl group was used instead of the allyl-group-containing benzoxazine, the moldability was deteriorated, and a satisfactory cured plate could not be obtained, and a test piece for measuring the glass transition temperature could not be obtained.

[0073] In addition, the various numerical ranges described in the specification can be arbitrarily combined with their upper and lower limits, and all such combinations are considered to be preferred numerical ranges described in the specification. In addition, a numerical range described as "X to Y" means from X to Y.

[0074] Although several embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, substitutions, and modifications can be made without departing from the gist of the invention. These embodiments and their omissions, substitutions, modifications, etc. are included in the scope and gist of the invention as well as the invention and its equivalents described in the claims. [Industrial Applicability]

[0075] The resin composition according to this embodiment can be used, for example, as a printed circuit board material, a semiconductor sealing resin, a matrix resin for composite materials, a paint, an adhesive, and the like.

Claims

1. The present invention includes a compound represented by the following general formula (1) and a compound represented by the following general formula (2), 【Chemistry 1】 In formula (1), R １ represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may contain a heteroatom; R ２ and R ３ each independently represents an alkanediyl group having 1 to 10 carbon atoms; R ４ and R ５ each independently represents a hydrogen atom or a methyl group; R ６ and R ７ each independently represents a methyl group or an ethyl group; p and q each independently represent an integer of 0 to 2; 【Chemistry 2】 In formula (2), R ８ represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may contain a heteroatom; Resin composition.

2. R in the formula (1) １ The resin composition according to claim 1, wherein is a divalent aromatic ring-containing hydrocarbon group having 6 to 50 carbon atoms which may contain a heteroatom.

3. The compound represented by formula (1) is represented by the following general formula (1A): 【Chemistry 3】 In formula (1A), R １１ is a single bond, -CH ２ -, -CH(CH ３ ) -, -C(CH ３ ) ２ represents - or -O-; R １２ and R １３ each independently represents a methyl group or an ethyl group, s and t each independently represent an integer of 0 to 4, R ２ and R ３ each independently represents an alkanediyl group having 1 to 10 carbon atoms; R ４ and R ５ each independently represents a hydrogen atom or a methyl group; R ６ and R ７ Each of independently represents a methyl group or an ethyl group, and each of p and q independently represents an integer of 0 to 2. The resin composition according to claim 1 .

4. R in the formula (2) ８ The resin composition according to claim 1, wherein is a divalent aromatic ring-containing hydrocarbon group having 6 to 50 carbon atoms which may contain a heteroatom.

5. The compound represented by formula (2) is represented by the following general formula (2A): 【Chemistry 4】 In formula (2A), R ２１ is a single bond, -CH ２ -, -CH(CH ３ ) -, -C(CH ３ ) ２ -, -O-, or a group represented by the following formula (21A), R ２２ and R ２３ each independently represents a methyl group or an ethyl group; u and v each independently represent an integer of 0 to 4; 【Chemistry 5】 In formula (21A), R ２４ and R ２５ Each independently represents -CH ２ -, -CH(CH ３ ) -, -C(CH ３ ) ２ The resin composition according to claim 1, wherein the aryl group represents - or -O-.

6. The resin composition according to any one of claims 1 to 5, which is used as a printed circuit board material.

7. A cured product obtained by curing the resin composition according to any one of claims 1 to 5.

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