Benzoxazine compositions and uses thereof

Abstract

To provide a benzoxazine composition having self-recovery when formed into a cured material.SOLUTION: A benzoxazine compound according to one embodiment of the present invention includes a specific compound, a cross-linking agent and a metal complex.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to benzoxazine compositions and their uses. [Background technology]

[0002] Phenol resins, epoxy resins, etc. are used as raw materials for electronic components, semiconductor encapsulation materials, etc. In recent years, benzoxazine resins have been used because of their excellent heat resistance.

[0003] For example, Patent Document 1 describes a resin composition containing a thermosetting resin having a dihydrobenzoxazine ring, an epoxy resin, a phenolic resin, an ion scavenger, and an inorganic filler, in which the resin components have a specific melt viscosity and the content of the ion scavenger is within a specific range. Patent Document 1 also describes that the resin composition has moisture resistance, moldability, etc. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-47391 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the above-mentioned Patent Document 1 does not disclose or suggest anything about the self-repairing properties of the cured product of the resin composition. An object of the present invention is to provide a benzoxazine composition that has self-repairing properties when made into a cured product. [Means for solving the problem]

[0006] As a result of intensive research to solve the above problems, the present inventors have found that a cured product of a benzoxazine composition containing a specific compound, a crosslinker, and a metal complex has self-repairing properties, and have completed the present invention. That is, one aspect of the present invention includes the following features.

[0007] <1> The composition includes a compound represented by the following formula (1) as a component (A), a crosslinking agent represented by the following formula (2) as a component (B), and a metal complex as a component (C), A benzoxazine composition, wherein the component (C) is a salt of one or more metals selected from aluminum, zinc, iron, magnesium, cobalt, copper, nickel, and calcium.

[0008] [ka]

[0009] In formula (1), n is an integer, R1 is an aromatic group and / or an aliphatic group, R2 to R5 each independently represent one selected from the group consisting of a halogen atom, an alkyl group, a halogenated alkyl group, a hydroxy group, a carboxyl group, an amino group, and an alkoxy group, and R6 and R7 each independently represent one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, a hydroxy group, a carboxyl group, an amino group, and an alkoxy group.

[0010] [ka]

[0011] In formula (2), R8 is an aromatic group and / or an aliphatic group, and X and Y are functional groups that react with a hydroxyl group. <2> The composition contains 15 parts by weight or more of the component (C) relative to 100 parts by weight of the component (A), <1> The benzoxazine composition according to claim 1. <3> Furthermore, the component (D) contains a compound having an imidazole group. <1> or <2> The benzoxazine composition according to claim 1. <4> <1> ~ <3> A cured product obtained by curing the benzoxazine composition according to any one of the preceding items. <5> <4> A method for repairing a cured product, comprising the step of heating the cured product described in 1. [Effects of the Invention]

[0012] According to one aspect of the present invention, a benzoxazine composition can be provided that has self-repairing properties when cured. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 2 is a diagram showing an example of a mechanism by which damage is repaired on the surface of a cured product of a benzoxazine composition according to one embodiment of the present invention. [Figure 2] FIG. 2 is a diagram showing an observed image of scratches made on a cured product according to an example of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0014] One embodiment of the present invention will be described below, but the present invention is not limited thereto. Unless otherwise specified in this specification, the expression "A to B" representing a range of numerical values means "A or more and B or less."

[0015] 1. Benzoxazine Compositions A benzoxazine composition according to one embodiment of the present invention (hereinafter also referred to as the present benzoxazine composition) comprises a compound represented by the following formula (1) as a component (A), a crosslinking agent represented by the following formula (2) as a component (B), and a metal complex as a component (C), The component (C) is one or more selected from the group consisting of salts of aluminum, zinc, iron, magnesium, cobalt, copper, nickel, and calcium.

[0016] [ka]

[0017] (In formula (1), n is an integer; R1 is an aromatic group and / or an aliphatic group; R2 to R5 each independently represent one selected from the group consisting of a halogen atom, an alkyl group, a halogenated alkyl group, a hydroxy group, a carboxyl group, an amino group, and an alkoxy group; and R6 and R7 each independently represent one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, a hydroxy group, a carboxyl group, an amino group, and an alkoxy group.)

[0018] [ka]

[0019] (In formula (2), R8 is an aromatic group and / or an aliphatic group, and X and Y are functional groups that react with a hydroxyl group.) As described above, the present inventors have succeeded in producing a cured product of a benzoxazine composition containing a specific compound, a crosslinker, and a metal complex, which has self-repairing properties. Surprisingly, no benzoxazine composition has ever existed before, and this cured product has such self-repairing properties.

[0020] In this specification, the term "having self-repairing properties" means that when a cured product having scratches is heated, the width and / or length of the scratches become smaller than before heating.

[0021] The mechanism of self-repairing properties in a cured product of the present benzoxazine composition may be, for example, as shown in Figure 1. Note that the reaction scheme shown in Figure 1 is an example of a reaction when the present benzoxazine composition contains the compounds shown in the Examples as components (A) to (C), and does not limit the reaction mechanism of the present invention.

[0022] The repair mechanism of the cured product will be explained below using FIG. 1. First, when the present benzoxazine composition does not contain component (C), the phenolic hydroxyl groups of component (A) and the epoxy groups of component (B) are crosslinked in the cured product of the present benzoxazine composition, as shown in state 10 in FIG. 1. In this case, even if the damaged cured product is heated, the crosslinked state continues, and the cured product does not have self-repair properties. On the other hand, when the present benzoxazine composition contains component (C) in addition to components (A) and (B), an aluminum atom contained in component (C) coordinates to the oxygen of the phenolic hydroxyl group of component (A), as shown in state 20 in FIG. 1. This alleviates the above-mentioned crosslinked state, and coordinate bonds are formed between the phenolic hydroxyl groups of component (A) via the aluminum atom. Furthermore, when component (A) contains a polyether chain, hydrogen bonds are formed between the polyether chain and the phenolic hydroxyl groups of component (A). When a cured product containing these coordinate bonds and hydrogen bonds is damaged and heated, the molecular motion of component (A) is promoted, and new hydrogen bonds and / or coordinate bonds are formed through supramolecular interactions. Therefore, by combining components (A) to (C), self-repairing properties can be achieved.

[0023] Thus, the present benzoxazine composition can provide a self-repairable cured product by the simple operation of heating, and therefore the cured product of the present benzoxazine composition can be used for a long period of time.

[0024] Furthermore, with the above-described configuration, even if the hardened material is damaged, it can be repaired by heating and reused, which can contribute to achieving and realizing Goal 12 of the Sustainable Development Goals (SDGs), "Ensure sustainable consumption and production patterns."

[0025] <1-1. (A) Component> The component (A) is a compound represented by the following formula (1).

[0026] [ka]

[0027] In the formula (1), n is an integer. From the viewpoint of self-repairing properties, the weight-average molecular weight of component (A) is preferably 3,000 to 20,000, more preferably 4,000 to 20,000, and even more preferably 5,000 to 20,000. Note that, since n in the formula (1) obtained by GPC measurement is calculated as an average value, it is difficult to accurately specify the range of n.

[0028] In the formula (1), R1 is an aromatic group and / or an aliphatic group. R1 may be an aliphatic group, preferably an aliphatic group containing an ether bond. When R1 is an aliphatic group containing an ether bond, the self-repairing property of the cured product of the benzoxazine composition is improved.

[0029] Examples of the aromatic group include a phenylene group, a biphenylene group, a naphthylene group, an anthranylene group, a phenanthrylene group, a pyrenylene group, a coronylene group, a terphenylene group, a furanylene group, a thienylene group, and a fluorenylene group.

[0030] In this specification, the aromatic group also includes a structure in which two or more of the same or different phenylene, biphenylene, naphthylene, anthranylene, phenanthrylene, pyrenylene, coronylene, terphenylene, furanylene, thienylene, or fluorenylene groups are linked together by one or more divalent linking groups. The aromatic group also includes a non-benzene-based aromatic group and a heteroaromatic group.

[0031] Examples of the divalent linking group include an alkylene group, an ether group, a carbonyl group, an amide group, an imino group, an azo group, a sulfide group, a sulfonyl group, a sulfide group, an isopropylidene group, and a hexafluorinated isopropylidene group.

[0032] When the aromatic group has a substituent, examples of the substituent include a halogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, a hydroxyl group, a carboxyl group, an amino group, an alkoxy group, a cyano group, an aryloxy group, and an aralkyloxy group.

[0033] The aromatic group preferably has 6 to 50 carbon atoms, more preferably 6 to 40 carbon atoms, and even more preferably 6 to 30 carbon atoms.

[0034] The aliphatic group may be either linear or cyclic, and may be either saturated or unsaturated. Furthermore, when the aliphatic group is linear, it may be either linear or branched. Examples of linear aliphatic groups include alkylene groups, alkenylene groups, and alkynylene groups. Furthermore, examples of cyclic aliphatic groups include cycloalkylene groups.

[0035] Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. Examples of the alkenylene group include a vinylene group, a 1-methylvinylene group, a propenylene group, a butenylene group, and a pentenylene group. Examples of the alkynylene group include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, and a hexynylene group. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

[0036] Furthermore, one or more hydrogen atoms contained in the aliphatic group may be substituted with a halogen atom, a hydroxy group, or an alkoxy group.

[0037] The number of carbon atoms in the aliphatic group is preferably 3 to 100, more preferably 10 to 60, and even more preferably 20 to 50. When the number of carbon atoms is within the above range, the self-repairing property is excellent.

[0038] In the formula (1), R2 to R5 each independently represent one selected from the group consisting of a halogen atom, an alkyl group, a halogenated alkyl group, a hydroxy group, a carboxyl group, an amino group, and an alkoxy group. In the formula (1), R6 and R7 each independently represent one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, a hydroxy group, a carboxyl group, an amino group, and an alkoxy group. R6 and R7 may both be hydrogen atoms.

[0039] For example, the compound represented by the following formula (3) can be used as the component (A).

[0040] [ka]

[0041] Component (A) may be, for example, a reaction product of a benzoxazine compound and a compound containing two or more phenolic hydroxyl groups. The benzoxazine compound and the compound containing two or more phenolic hydroxyl groups are not particularly limited as long as they can produce the reaction product represented by formula (1).

[0042] The benzoxazine compound may, for example, be a compound represented by the following formula (4).

[0043] [ka]

[0044] In the formula (4), R1 to R5 are as described above.

[0045] Specifically, the benzoxazine compound may be a compound represented by the following formula (5).

[0046] [ka]

[0047] The compound containing two or more phenolic hydroxyl groups includes a compound represented by the following formula (6).

[0048] [ka]

[0049] In formula (6), R6 and R7 are as defined above.

[0050] Examples of the compound represented by formula (6) that can be used include resorcinol, alkylresorcinols (2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-ethylresorcinol, 2-propylresorcinol, 2-n-butylresorcinol, 2-tert-butylresorcinol, 5-n-pentylresorcinol, and 5-n-heptylresorcinol), alkoxyresorcinols (2-methoxyresorcinol and 5-methoxyresorcinol), 2-aminoresorcinol, pyrogallol, and 5-methylpyrogallol.

[0051] The content of component (A) in the present benzoxazine composition is preferably 30 to 99 wt %, more preferably 35 to 90 wt %, and even more preferably 40 to 80 wt %. When the content of component (A) is within the above range, the composition has excellent self-repairing properties.

[0052] Component (A) may be chemically synthesized or a commercially available product may be used. When component (A) is chemically synthesized, it can be synthesized, for example, by the methods described in Production Examples 1 and 2 below.

[0053] Specifically, for example, the benzoxazine compound and the compound containing two or more phenolic hydroxyl groups are mixed in equimolar amounts and reacted at a temperature of 150°C or less, particularly 100°C or less, to obtain component (A).

[0054] <1-2.(B) Component> The component (B) is a crosslinking agent represented by the following formula (2).

[0055] [ka]

[0056] In formula (2), R8 is an aromatic group and / or an aliphatic group, and X and Y are functional groups that react with a hydroxyl group.

[0057] In the formula (2), X and Y each independently represent a functional group reactive with a hydroxyl group. X and Y may be the same functional group or different functional groups. Examples of the functional group reactive with a hydroxyl group include an epoxy group, a carboxyl group, an acid anhydride group, an isocyanate group, and an oxazoline group. From the viewpoint of high reactivity with the phenolic hydroxyl group of component (A) and low generation of by-products, the functional group reactive with a hydroxyl group may be an epoxy group.

[0058] The content of component (B) in the present benzoxazine composition is preferably 1 to 50 wt%, more preferably 5 to 45 wt%, and even more preferably 10 to 40 wt%. When the content of component (B) is within the above range, the self-repairing property is improved and the present benzoxazine composition can be more easily mixed uniformly.

[0059] Component (B) may be an epoxy resin. The epoxy resin may be one or more selected from the group consisting of bisphenol A epoxy resins, bisphenol F epoxy resins, novolac epoxy resins, brominated epoxy resins, hydrogenated epoxy resins, bisphenol S epoxy resins, naphthalene epoxy resins, phosphorus-containing epoxy resins, biphenyl epoxy resins, trishydroxyphenylmethane epoxy resins, tetraphenylethane epoxy resins, and dicyclopentadiene epoxy resins. Component (B) may be, for example, a bisphenol A epoxy resin.

[0060] Examples of bisphenol A type epoxy resins include those manufactured by Mitsubishi Chemical Corporation under the trade name JER828EL, those manufactured by Japan Epoxy Resins Co., Ltd. under the trade names jER828, jER1001, and jER1002, those manufactured by ADEKA Corporation under the trade names ADEKA RESIN EP-4100E and ADEKA RESIN EP-4300E, those manufactured by Nippon Kayaku Co., Ltd. under the trade names RE-310S and RE-410S, those manufactured by DIC Corporation under the trade names Epiclon 840S, Epiclon 850S, Epiclon 1050, and Epiclon 7050, and those manufactured by Tohto Kasei Co., Ltd. under the trade names Epotohto YD-115, Epotohto YD-127, and Epotohto YD-128.

[0061] Examples of the bisphenol F type epoxy resin include jER806 and jER807 manufactured by Japan Epoxy Resins Co., Ltd.; ADEKA Resin EP-4901E, ADEKA Resin EP-4930, and ADEKA Resin EP-4950 manufactured by ADEKA Corporation; RE-303S, RE-304S, RE-403S, and RE-404S manufactured by Nippon Kayaku Co., Ltd.; Epiclon 830 and Epiclon 835 manufactured by DIC Corporation; and Epotohto YDF-170, Epotohto YDF-175S, and Epotohto YDF-2001 manufactured by Tohto Kasei Co., Ltd.

[0062] Examples of the novolac epoxy resin include phenol novolac epoxy resin and cresol novolac epoxy resin. Examples of the phenol novolac epoxy resin include jER152 and jER154 (trade names) manufactured by Japan Epoxy Resins Co., Ltd., EPPN-201-L (trade name) manufactured by Nippon Kayaku Co., Ltd., Epiclon N-740 and Epiclon N-770 (trade names) manufactured by DIC Corporation, and Epotohto YDPN-638 (trade name) manufactured by Tohto Kasei Co., Ltd. Examples of the cresol novolac epoxy resin include EOCN-1020, EOCN-102S, EOCN-103S, and EOCN-104S (trade names) manufactured by Nippon Kayaku Co., Ltd., and Epiclon N-660, Epiclon N-670, Epiclon N-680, and Epiclon N-695 (trade names) manufactured by DIC Corporation.

[0063] Examples of the brominated epoxy resin include Epiclon 152 and Epiclon 153, both of which are trade names manufactured by DIC Corporation.

[0064] Examples of the hydrogenated epoxy resin include hydrogenated bisphenol A epoxy resins, such as those available under the trade names jERYX8000, jERYX8034, and jERYL7170 manufactured by Japan Epoxy Resins Co., Ltd., ADEKA Resin EP-4080E manufactured by ADEKA Corporation, Epiclon EXA-7015 manufactured by DIC Corporation, and Epotohto YD-3000 and Epotohto YD-4000D manufactured by Tohto Kasei Co., Ltd.

[0065] An example of the bisphenol S type epoxy resin is Epiclon EXA-1514, a product name of DIC Corporation.

[0066] Examples of the naphthalene type epoxy resin include Epiclon HP-4032, Epiclon HP-4700, and Epiclon HP-4200, both of which are trade names manufactured by DIC Corporation, and NC-7000L, which is a trade name manufactured by Nippon Kayaku Co., Ltd.

[0067] Examples of the biphenyl type epoxy resin include those manufactured by Japan Epoxy Resins Co., Ltd. under the trade names jERYX4000, jERYL6121H, jERYL6640, and jERYL6677, and those manufactured by Nippon Kayaku Co., Ltd. under the trade names NC-3000 and NC-3000H.

[0068] Examples of the dicyclopentadiene type epoxy resin include XD-1000 (trade name) manufactured by Nippon Kayaku Co., Ltd. and Epiclon HP-7200 (trade name) manufactured by DIC Corporation.

[0069] As the epoxy resin, for example, a bisphenol A type epoxy resin, which is represented by the following formula (7) and is available under the trade name JER828EL manufactured by Mitsubishi Chemical Corporation, can be used.

[0070] [ka]

[0071] <1-3.(C) component> Component (C) is a metal complex, which is a salt of one or more metals selected from aluminum, zinc, iron, magnesium, cobalt, copper, nickel, and calcium. Component (C) may be a single metal complex, or a mixture of two or more metal complexes. Examples of such salts include acetates, nitrates, hydrochlorides, sulfates, and phosphates. Component (C) may also be a hydrate of the salts.

[0072] From the standpoint of the HSAB rule, the component (C) is preferably aluminum chloride, iron chloride, zinc chloride, or a hydrate thereof.

[0073] Component (C) may be, for example, aluminum chloride hexahydrate represented by the following formula (8):

[0074] [ka]

[0075] The content of component (C) in the present benzoxazine composition is preferably 15 parts by weight or more, more preferably 17 parts by weight or more, and even more preferably 20 parts by weight or more, per 100 parts by weight of component (A). The upper limit of component (C) is not particularly limited, but may be, for example, 40 parts by weight or less. If the content of component (C) is within the above range, the present benzoxazine composition can be easily mixed uniformly.

[0076] <1-4.(D) component> The present benzoxazine composition preferably further contains a compound having an imidazole group as component (D). Component (D) acts as an epoxy curing agent in the present benzoxazine composition. That is, component (D) acts as a curing agent for component (B), and thus, similar to component (C) described above, it moderates the crosslinking state between components (A) and (B). Normally, increasing the amount of component (B), which has heat resistance, in the present benzoxazine composition reduces self-repairing properties. However, by including component (D) in the present benzoxazine composition, it is possible to increase the content of component (B) while maintaining self-repairing properties, resulting in improved heat resistance of the cured product of the present benzoxazine composition.

[0077] The component (D) is not particularly limited, but examples thereof include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, etc. The component (D) may be a single compound, or a mixture of two or more compounds. The content of component (D) in the present benzoxazine composition is preferably 0 to 3% by weight, more preferably 0.1 to 3% by weight, and even more preferably 0.2 to 3% by weight.

[0078] (others) The present benzoxazine composition may contain, as needed, a filler, a mold release agent, a flame retardant, a colorant, a coupling agent, etc. These may be mixed when the present benzoxazine composition is produced, or may be mixed when the present benzoxazine composition is cured.

[0079] [2. Cured product] A cured product can be obtained by curing the present benzoxazine composition. The method for curing the cured product is not particularly limited, but since the present benzoxazine composition is thermosetting, the present benzoxazine composition may be cured by heating.

[0080] The heating temperature when curing the present benzoxazine composition by heating is not particularly limited as long as it can sufficiently cure the present benzoxazine composition, and may be, for example, 120 to 240°C. Similarly, the heating time is also not particularly limited, and may be, for example, 5 minutes to 24 hours. The heating temperature may be constant during heating, or may be changed appropriately as needed. Furthermore, heating may be carried out all at once or in multiple steps. Even when heating is carried out multiple times, the heating temperature and time do not need to be constant.

[0081] The cured product preferably contains reinforcing fibers from the viewpoint of improving the mechanical strength of the cured product. Examples of reinforcing fibers include inorganic fibers, organic fibers, metal fibers, and hybrid reinforcing fibers that combine these. The reinforcing fibers may be one type or two or more types.

[0082] Examples of inorganic fibers include carbon fibers, graphite fibers, silicon carbide fibers, alumina fibers, tungsten carbide fibers, boron fibers, and glass fibers. Examples of organic fibers include aramid fibers, high-density polyethylene fibers, and other common nylon fibers and polyester fibers. Examples of metal fibers include stainless steel and iron fibers. Examples of metal fibers include carbon-coated metal fibers, which are metal fibers coated with carbon. Among these, carbon fibers are preferred as the reinforcing fibers from the viewpoint of increasing the strength of the cured product.

[0083] Generally, the carbon fibers are subjected to a sizing treatment, but they may be used as they are, or, if necessary, fibers containing a small amount of sizing agent may be used, or the sizing agent may be removed by an existing method such as organic solvent treatment, heat treatment, etc. Alternatively, the carbon fiber bundles may be opened in advance using air or a roller, and a treatment may be performed to facilitate impregnation of the resin between the carbon fiber single yarns.

[0084] The glass transition temperature (Tg) of the cured product is preferably −30° C. or higher, more preferably −20° C. or higher. There is no particular upper limit to Tg, but in practice it may be 150° C. or lower.

[0085] The 5% weight loss temperature (Td5) of the cured product is preferably 210°C or higher, more preferably 220°C or higher, and even more preferably 230°C or higher. When the Td5 of the cured product is 210°C or higher, the cured product has excellent heat resistance and is less likely to deteriorate when repaired by the method described below. In this specification, the "5% weight loss temperature (Td5)" refers to the temperature at which the uncured benzoxazine compound undergoes thermal decomposition and loses 5% weight, measured in an environment where the uncured benzoxazine compound is cured.

[0086] The cured product can be suitably used for electronic parts, laminates for printed wiring boards and printed wiring boards, semiconductor encapsulation materials, electronic materials such as semiconductor-mounted modules, automobiles or vehicles, aircraft parts, building materials, machine tools, etc. Among these, it can be used particularly for parts that require heat resistance.

[0087] [3. Repair method for hardened products] A method for repairing a cured product according to one embodiment of the present invention includes a step of heating a cured product of the present benzoxazine composition, and therefore, the present benzoxazine composition allows the cured product to be repaired simply by heating.

[0088] The heating temperature and heating time when repairing the cured product can be appropriately set depending on the composition, etc. The heating temperature may be, for example, 50 to 300° C., 100 to 250° C., or 200 to 250° C. The heating time may be, for example, 5 minutes to 5 hours, or 30 minutes to 2 hours.

[0089] [4. Prepreg or semipreg] A prepreg or semipreg according to one embodiment of the present invention is obtained by impregnating reinforcing fibers with the present benzoxazine composition. In this specification, semipreg refers to a composite in which reinforcing fibers are partially impregnated with the present benzoxazine composition (semi-impregnated state) and integrated.

[0090] Furthermore, a prepreg can be obtained from the semipreg. For example, the semipreg can be further heated and melted to impregnate the reinforcing fibers with a resin, thereby obtaining a prepreg.

[0091] As the reinforcing fibers used in the prepreg or semipreg, those described above in [2. Cured product] can be used as appropriate.

[0092] The content of the resin impregnated into the reinforcing fibers is preferably 10 to 60% by weight, more preferably 20 to 50% by weight. The resin content refers to the weight ratio of the resin to the combined weight of the resin and the reinforcing fibers.

[0093] The prepreg or semipreg can be heated and pressed together with a metal foil to produce a laminate for a printed wiring board, and a circuit can be formed on the laminate to produce a printed wiring board. The printed wiring board thus produced has excellent heat resistance and mechanical properties, and is therefore suitable for use as a semiconductor mounting substrate, etc.

[0094] The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention. [Example]

[0095] Hereinafter, one embodiment of the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0096] [Test method] (Structural analysis of benzoxazine compounds) The molecular structure of benzoxazine compounds was analyzed using a nuclear magnetic resonance spectrometer (NMR, Bruker, AVANCEIII 400MHz) at room temperature with 16 accumulations. 1 This was done by measuring H-NMR.

[0097] (Molecular weight measurements of benzoxazine compounds and reaction products of benzoxazine compounds and 2-methylresorcinol) The molecular weights of benzoxazine compounds and reaction products of benzoxazine compounds and 2-methylresorcinol were evaluated using a gel permeation chromatograph (GPC) (Shimadzu Corporation, Prominence UFLC) under the following conditions: eluent: DMF containing 0.01 mol / L lithium chloride; three TSKgel GMHHR-M columns connected in series; flow rate: 1 mL / min; injection volume: 20 μL; column temperature: 40°C; UV detector; and polystyrene as the calibration curve sample.

[0098] (glass transition temperature (Tg) of cured product) The DSC curve of the cured product was measured using a differential scanning calorimeter (DSC, Hitachi High-Tech Science Corporation, DSC7000X) under conditions of a nitrogen flow rate of 40 mL / min and 10°C / min. The extrapolated glass transition onset temperature obtained from the obtained DSC curve (the intersection of the straight line extrapolated from the baseline before the inflection point to the higher temperature side and the tangent to the inflection point) was taken as the glass transition temperature in this example.

[0099] (Thermal stability of the cured product) The 5% weight loss temperature (Td5) of the cured product was evaluated using a thermogravimetric analyzer (STA7200, manufactured by Hitachi High-Tech Science Corporation) at a temperature increase rate of 5°C / min under a nitrogen gas flow of 200 mL / min.

[0100] (Evaluation of the repairability of the cured product) The cured product was cut into the surface with a cutter, and then heated in air at 100°C or 150°C for 1 hour. The cut before and after heating was observed with a digital microscope (Keyence VHX-200) to evaluate repairability.

[0101] [Production Example 1] Jeffamine ED-900 (Huntsman) (10.0357 g, 0.0112 mol) and paraformaldehyde (Wako) (1.5644 g, 0.0489 mol) were added to a reaction vessel equipped with a stirrer and stirred at 100 °C for 30 minutes. Subsequently, 2,4-dimethylphenol (Tokyo Chemical Industry Co., Ltd. (TCI)) (2.7191 g, 0.0225 mol) was added to the reaction solution and stirred at 100 °C for 14 hours. After the reaction solution was cooled to room temperature, 60 mL of chloroform was added to the reaction solution, and the mixture was separated three times with 100 mL of 0.1 mol / L sodium hydroxide solution and three times with 100 mL of pure water. The organic layer was mixed with 100 mL of hexane, and the supernatant was collected. The solvent was then removed using an evaporator at 30 °C under reduced pressure to obtain the target benzoxazine compound. The molecular weight of the target product was measured by GPC and found to be 4,600. 1 By measuring with H-NMR (heavy solvent: DMSO-d6), the disappearance of the peak of 2,4-dimethylphenol (raw material) at 6.8 ppm and the appearance of peaks of benzoxazine compounds (products) at 3.9 ppm and 4.9 ppm were observed, confirming that the target product had been synthesized.

[0102] [Production Example 2] The benzoxazine compound (5.0027 g, 0.0042 mol) obtained in Production Example 1 and 2-methylresorcinol (0.5207 g, 0.0042 mol) were added to a reaction vessel and stirred at 100°C for 3 hours to obtain a reaction product of the benzoxazine compound and 2-methylresorcinol. The molecular weight of the obtained target product was measured by GPC, and the weight average molecular weight (Mw) was found to be 6900, confirming that the compound of formula (3) was obtained.

[0103] [Raw material compound] The raw materials used in the following examples and comparative examples are as follows.

[0104] <Component (A): Compound represented by formula (1)> The compound of formula (3) synthesized in Production Example 2 <Component (B): Crosslinking agent represented by formula (2)> Bisphenol A epoxy resin represented by the above formula (4) (Mitsubishi Chemical, JER828EL) <Component (C): Metal Complex> Aluminum chloride hexahydrate (Wako) <Component (D): Compound having an imidazole group> 2-Ethyl 4-methylimidazole Example 1 100 parts by weight (0.0803 g) of component (A) and 24 parts by weight (0.0196 g) of component (C) were dissolved in methanol. To this methanol solution, a tetrahydrofuran (THF) solution containing 14 parts by weight (0.0115 g) of component (B) was added and stirred at room temperature for 1 hour. The solution was then poured into a perfluoroalkoxy (PFA) resin container, and the solvent was removed in a vacuum oven at 30°C. The benzoxazine composition was then cured by heating at 60°C for 30 minutes, 120°C for 30 minutes, 180°C for 1 hour, and 200°C for 30 minutes to obtain a cured product.

[0105] Example 2 100 parts by weight (0.0806 g) of component (A) and 24 parts by weight (0.0194 g) of component (C) were dissolved in methanol. To this methanol solution, a THF solution containing 41 parts by weight (0.0353 g) of component (B) and 1.2 parts by weight (0.0015 g) of component (D) was added and stirred at room temperature for 1 hour. The solution was then poured into a perfluoroalkoxy (PFA) resin container. The solvent was removed in a vacuum oven at 30°C, and the benzoxazine composition was cured by heating at 60°C for 30 minutes, 120°C for 30 minutes, 180°C for 1 hour, and 200°C for 30 minutes to obtain a cured product.

[0106] Example 3 100 parts by weight (0.0799 g) of component (A) and 24 parts by weight (0.0194 g) of component (C) were dissolved in methanol. To this methanol solution, a THF solution containing 67 parts by weight (0.0541 g) of component (B) and 2.0 parts by weight (0.0016 g) of component (D) was added and stirred at room temperature for 1 hour. The solution was then poured into a perfluoroalkoxy (PFA) resin container. The solvent was removed in a vacuum oven at 30°C, and the benzoxazine composition was cured by heating at 60°C for 30 minutes, 120°C for 30 minutes, 180°C for 1 hour, and 200°C for 30 minutes to obtain a cured product.

[0107] Comparative Example 1 100 parts by weight (0.0302 g) of component (A) and 14 parts by weight (0.0174 g) of component (B) were mixed in a PFA container and heated at 60°C for 30 minutes, at 180°C for 1 hour, and at 200°C for 30 minutes to cure the benzoxazine composition and obtain a cured product.

[0108] Comparative Example 2 A THF solution containing 100 parts by weight (0.0804 g) of component (A), 33 parts by weight (0.0298 g) of component (B), and 1.0 part by weight (0.0008 g) of component (D) was stirred at room temperature for 1 hour. The solution was then poured into a PFA container, and the solvent was removed in a vacuum oven at 30°C. The benzoxazine composition was cured by heating at 60°C for 30 minutes, 90°C for 3 hours, 150°C for 3 hours, and 200°C for 30 minutes to obtain a cured product.

[0109] Comparative Example 3 A THF solution containing 100 parts by weight (0.0805 g) of component (A), 54 parts by weight (0.0446 g) of component (B), and 1.6 parts by weight (0.0013 g) of component (D) was stirred at room temperature for 1 hour. The solution was then poured into a PFA container, and the solvent was removed in a vacuum oven at 30°C. The benzoxazine composition was cured by heating at 60°C for 30 minutes, 90°C for 3 hours, 150°C for 3 hours, and 200°C for 30 minutes to obtain a cured product.

[0110] The composition structure and physical properties of the cured product for each example and comparative example are shown in Table 1. Figure 2 shows digital microscope images of the cuts in each example and comparative example before heating, after heating at 100°C for 1 hour, and after further heating at 150°C for 1 hour.

[0111] [Table 1]

[0112] (Conclusion) From Table 1 and Figure 2, it was found that Example 1 exhibited self-repairing properties that were not observed in Comparative Example 1 (which contained the same amount of component (B) as Example 1 but did not contain component (C)). Furthermore, Examples 2 and 3, which contained a greater amount of component (B) than Example 1, also exhibited self-repairing properties, similar to Example 1. On the other hand, Comparative Examples 2 and 3 (which contained more component (B) than Comparative Example 1), which did not contain component (C) like Comparative Example 1, did not exhibit self-repairing properties. Furthermore, it was found that Examples 2 and 3, which contained component (D), had higher Tg and Td5 than Example 1, and were superior in thermal stability.

[0113] From the above, the composition of the present invention that contains a combination of components (A), (B), and (C) can exhibit self-repairing properties. [Industrial Applicability]

[0114] The present invention can be suitably used in electronic components, laminates for printed wiring boards and printed wiring boards, semiconductor encapsulation materials, electronic materials such as semiconductor-mounted modules, automobiles or vehicles, aircraft parts, building materials, machine tools, etc.

Claims

1. The composition includes a compound represented by the following formula (1) as a component (A), a crosslinking agent represented by the following formula (2) as a component (B), and a metal complex as a component (C), The benzoxazine composition, wherein the component (C) is a salt of one or more metals selected from aluminum, zinc, iron, magnesium, cobalt, copper, nickel, and calcium. 【Chemistry 1】 (In formula (1), n ​​is an integer, R １ is an aromatic and / or aliphatic group, R ２ ~R ５ each independently represents one selected from the group consisting of a halogen atom, an alkyl group, a halogenated alkyl group, a hydroxyl group, a carboxyl group, an amino group, and an alkoxy group; R ６ and R ７ each independently represents one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, a hydroxyl group, a carboxyl group, an amino group, and an alkoxy group. 【Chemistry 2】 (In formula (2), R ８ is an aromatic group and / or an aliphatic group, and X and Y are functional groups that react with a hydroxyl group.

2. The benzoxazine composition according to claim 1, comprising 15 parts by weight or more of the component (C) relative to 100 parts by weight of the component (A).

3. The benzoxazine composition according to claim 1 or 2, further comprising a compound having an imidazole group as component (D).

4. A cured product obtained by curing the benzoxazine composition according to any one of claims 1 to 3.

5. A method for repairing a cured product, comprising the step of heating the cured product according to claim 4.

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