JP5848638B2 - Curable resin composition, method for producing the same, and electronic packaging material - Google Patents

Description

The present invention relates to a curable resin composition, a method for producing the same, and an electronic packaging material.

The curable resin is a resin having a property of being cured by light or heat, and a curable resin having physical properties required for each application is used in various industrial fields including the electrical and mechanical fields. Applications of such curable resins include, for example, copper-clad laminates for printed wiring boards, multilayer wiring board adhesives, semiconductor sealing materials, semiconductor mounting adhesives, semiconductor mounting modules, etc., automobiles Parts for automobiles, aircraft, building materials, fuel cells, various secondary batteries, etc., and curable resins require heat resistance with excellent stability and reliability at high temperatures and high humidity Is done. In particular, in recent years, power devices such as inverters are frequently used in hybrids, electric vehicles, and distributed power supplies, and the power density has increased dramatically, and silicon carbide (SiC) that operates at a high temperature of 200 ° C. or higher. The appearance of devices is also expected. In addition, since an electronic control unit (ECU) using a normal semiconductor chip is mounted from the vehicle compartment to the engine room where the environment is severe, heat resistance that can withstand severe conditions is also required.

Recently, a resin composition containing a benzoxazine compound is attracting attention as a new curable resin. A benzoxazine compound is a compound having a benzoxazine ring formed by the condensation of an oxazine and a benzene ring, and is cured by a ring-opening polymerization reaction of the benzoxazine ring. The cured product has characteristics such as excellent dimensional stability, flame retardancy, and heat resistance.

Examples of the resin composition containing the benzoxazine compound include a thermosetting benzoxazine resin composition (see Patent Document 1) containing two kinds of compounds having a specific structure having a benzoxazine ring, and a benzoxazine resin. An adhesive composition containing a thermosetting compound, a polymer, and a thermosetting agent and having a melt viscosity and gel time at a bonding temperature within a specific range (see Patent Document 2) and the like is disclosed.

JP 2008-195907 A JP 2011-157529 A

As described above, in recent years, research on benzoxazine compounds is being made. However, since the glass transition temperature (Tg) of a cured product obtained by curing a benzoxazine compound alone is about 200 ° C. even at a high level, it cannot exhibit the high level of heat resistance required in recent years. There was room for ingenuity. Further, the resin compositions of Patent Documents 1 and 2 have room for improvement in order to further improve heat resistance.

The present invention has been made in view of the above-mentioned present situation, can provide a cured product having excellent heat resistance, is useful for various uses, a method for producing the same, and the curable resin composition. An object of the present invention is to provide an electronic packaging material using a product.

The present inventors have studied variously about the curable resin composition, and found that the benzoxazine compound alone is not yet sufficient in heat resistance of the cured product, and in addition to the benzoxazine compound, a siloxane skeleton and an imide bond It has been found that the glass transition temperature (Tg) of the cured product is improved, and at the same time, the thermal decomposition resistance is enhanced, and a high level of heat resistance is imparted to the cured product. This is considered to contribute not only to the heat blocking effect due to the incorporation of an inorganic silane compound but also to the silane compound being incorporated into the polymer skeleton (resin skeleton) of the benzoxazine compound and uniformly dispersed. It is done. Moreover, when the polyfunctional maleimide compound and the imidazole compound were further included in addition to these two components, it was found that the heat resistance of the cured product was further improved by the interaction between the components. Furthermore, the curable resin composition containing a benzoxazine compound, a polyfunctional maleimide compound, and an imidazole compound can also be found to improve the Tg and heat decomposability of the cured product, and can solve the above-mentioned problems in an excellent manner. I came up with it. Moreover, when manufacturing these curable resin compositions, it has been found that the handling property in the manufacturing process is improved by specifying the order in which the raw material components are charged, and the present invention has been achieved.

That is, the present invention is a curable resin composition containing a benzoxazine compound and a silane compound having a siloxane skeleton and an imide bond.
The present invention is also a curable resin composition containing a benzoxazine compound, a polyfunctional maleimide compound, and an imidazole compound.
The present invention is also a method for producing the curable resin composition, wherein the production method comprises introducing a part or all of raw material components other than the benzoxazine compound into a reaction vessel, and then adding the benzoxazine to the reaction vessel. It is also a method for producing a curable resin composition into which a compound is added.
The present invention further relates to a method for producing the curable resin composition, wherein the production method comprises introducing a part or all of raw material components other than the benzoxazodine compound and the imidazole compound into a reaction vessel, It is also a method for producing a curable resin composition in which a benzoxazine compound is charged into a reaction vessel and then an imidazole compound is charged.
The present invention is also an electronic packaging material using the curable resin composition. The present invention is described in detail below.

The curable resin composition of the present invention includes a benzoxazine compound and a silane compound having a siloxane skeleton and an imide bond (hereinafter also simply referred to as “silane compound”). Or 2 or more types can be used and the addition amount is not specifically limited. Moreover, as long as these are essential, other components can be included as appropriate, but the total mass of the benzoxazine compound and the silane compound is 20% by mass or more with respect to 100% by mass of the total amount of the curable resin composition. Is preferred. More preferably, it is 30 mass% or more.

In the curable resin composition, the mass ratio of the benzoxazine compound and the silane compound (benzoxazine compound / silane compound) is preferably 1 to 99 / 99-1. More preferably, it is 1-80 / 99-20, and by being in this range, the silane compound is more sufficiently dispersed, the crosslink density of the cured product is made more uniform, and the heat resistance is further improved. become. More preferably, it is 1-65 / 99-35, Most preferably, it is 1-50 / 99-50.

In the curable resin composition, the benzoxazine compound may be a compound having at least one benzoxazine ring (also referred to as a benzoxazine group) in the molecule. For example, the following general formula (1) or (2) ;

(In the formula, n represents an integer of 1 to 4. R ^a is the same or different and represents ^a lower alkyl group, a cycloalkyl group, an aryl group, an allyl group, or an aralkyl group. R ^b is the same or different. Te, a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group, an allyl group, an aralkyl group, or, .R ^c representing a 1-4-valent organic group represented by the following general formula (a) ~ (t) The same or different and each represents a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group, an allyl group or an aralkyl group, and R ^d is the same or different and represents a lower alkyl group, a cycloalkyl group, an aryl group or an allyl group. , An aralkyl group, or a mono- to tetravalent organic group represented by the following general formulas (a) to (o)) is preferable.

Among the benzoxazine compounds, it is preferable to have two or more benzoxazine rings in one molecule. More preferred are compounds having a benzoxazine ring at both ends.

Although the said benzoxazine compound can be obtained by reaction of primary amines, aldehydes, and phenols, for example, you may use a commercial item. Commercially available products include, for example, benzoxazine manufactured by Shikoku Kasei Kogyo Co., Ltd. (Pd type which is a both-end benzoxazine, Fa type which is a non-terminal benzoxazine, etc.); BXZ-1 manufactured by Konishi Chemical Co., Ltd. (BS-BXZ9), BXZ-2 (BF-BXZ), BXZ-3 (BA-BXZ) and the like are available.

In the above curable resin composition, the silane compound is a compound having a siloxane skeleton (main chain skeleton in which a siloxane bond is essential) and an imide bond, and preferably an organic residue having an imide bond in a silicon atom. In this form, a group and an oxygen atom are bonded and a siloxane skeleton is formed through the oxygen atom. That is, an organic skeleton having one or more imide bonds, one or more oxygen atoms, and optionally other skeletons are bonded to silicon atoms, and an organic skeleton having an imide bond, oxygen atoms, and other skeletons. A mode in which the total number of bonds is 4 is preferable. In such a form, the number of bonds of the organic skeleton having an imide bond bonded to a silicon atom is suitably 1 to 3, preferably 1 to 2, more preferably 1. The number of bonds of oxygen atoms (oxygen atoms bonded to silicon atoms bonded to an organic skeleton having an imide bond) is suitably 1 to 3, preferably 2 to 3, more preferably 3. . The number of bonds of other organic skeletons is suitably 0 to 2, preferably 0 to 1, and more preferably 0. As a suitable combination (number of bonds) of the skeleton (group) bonded to the silicon atom, (organic skeleton having an imide bond, oxygen atom, other skeleton) is (1, 3, 0), (2, 2, 0 ), (1, 2, 1), (3, 1, 0), (2, 1, 1), (1, 1, 2).

The other skeleton is preferably at least one selected from the group consisting of an organic group having no imide bond, a hydrogen atom, a hydroxyl group, a halogen atom, and an OR group (R is the same or different, an alkyl group, It represents at least one group selected from the group consisting of an acyl group, an aryl group, and an unsaturated aliphatic residue, and may have a substituent.
The organic group having no imide bond is preferably at least one selected from the group consisting of an aromatic residue such as an alkyl group, an aryl group, and an aralkyl group, and an unsaturated aliphatic residue. It may have a substituent. More preferably, it is a C1-C8 alkyl group which may have a substituent, or aromatic residues, such as an aryl group and an aralkyl group. Specifically, for example, methyl group, ethyl group, phenyl group, vinyl group, chloropropyl group, mercaptopropyl group, (epoxycyclohexyl) ethyl group, glycidoxypropyl group, N-phenyl-3-aminopropyl group, (Meth) acryloxypropyl group, hexyl group, decyl group, octadecyl group, trifluoropropyl group and the like are preferable.

As the siloxane skeleton (main chain skeleton requiring a siloxane bond) of the silane compound, any siloxane bond (Si—O—Si bond) may be used. Either a chain shape or a branched shape may be used, and a polysilsesquioxane having a ladder shape, a cage shape, a cubic shape, or the like is preferable.

In the silane compound, the proportion of the siloxane skeleton is preferably 80 to 10% by mass in 100% by mass of the silane compound. More preferably, it is 70-15 mass%, More preferably, it is 50-20 mass%.
In the silane compound, the proportion of the organic skeleton having an imide bond is preferably 100 to 20 mol with respect to 100 mol of silicon atoms contained in the silane compound. More preferably, it is 100-50 mol, More preferably, it is 100-70 mol.

When a suitable form of the silane compound is represented by an average composition formula, the following average composition formula:
XaYbZcSiOd
(In the formula, X is the same or different and represents an organic skeleton containing an imide bond. Y is the same or different and represents at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom and an OR group. R may be the same or different and each represents at least one group selected from the group consisting of an alkyl group, an acyl group, an aryl group, and an unsaturated aliphatic residue, and may have a substituent. The same or different, and represents an organic group containing no imide bond, a is a number of 3 or less that is not 0, b and c are the same or different and are 0 or a number of less than 3, and d is 0 Is a number less than 2 and a + b + c + 2d = 4), and the form in which the silane compound is represented by the average composition formula is one of the preferred forms of the present invention.
In the above average composition formula, the coefficient a of X is a number 0 <a ≦ 3, the coefficient b of Y is a number 0 ≦ b <3, and the coefficient c of Z is 0 ≦ c <3. The number is 3. The coefficient d of O is 0 <d <2.

In the above average composition formula, Y is preferably a hydroxyl group or an OR group. An OR group is more preferable, and an OR group in which R is an alkyl group having 1 to 8 carbon atoms is more preferable. Z is preferably at least one selected from the group consisting of aromatic residues such as alkyl groups, aryl groups and aralkyl groups, and unsaturated aliphatic residues (these have a substituent). May be.) More preferably, it is a C1-C8 alkyl group which may have a substituent, or aromatic residues, such as an aryl group and an aralkyl group.

The silane compound also includes, for example, the following formula:

(In the formula, X, Y and Z are the same as described above. N ₁ and n ₂ represent the degree of polymerization. N ₁ is a non-zero positive integer, and n ₂ is 0 or positive. It is an integer.) "Y / Z-" represents that Y or Z is bonded, " _X1-2- " represents that 1 or 2 X are bonded, and "(Z / Y) ₁ “ _˜2- ” represents that one Z or Y is bonded, two Z or Y are bonded, or two Z and Y are bonded in total, one in total. “Si— (X / Y / Z) ₃ ” indicates that any three selected from X, Y, and Z are bonded to a silicon atom.
In the above formula, Si-Om ₁ and Si-Om ₂ is not intended to define the binding order of Si-Om ₁ and Si-Om _2, for example, Si-Om ₁ and Si-Om ₂ is alternately or randomly A co-condensed form, a form in which a polysiloxane composed of Si—Om ₁ and a polysiloxane of Si—Om ₂ are bonded are suitable, and the condensed structure is arbitrary.

The silane compound can be represented by the above-described average composition formula: XaYbZcSiOd, but the siloxane skeleton of the silane compound (the main chain skeleton that requires a siloxane bond) can also be represented as (SiO _m ) _n . The structure other than (SiO _m ) _n is an organic skeleton having an imide bond (a structure in which an imide bond is essential) X, Y such as a hydrogen atom or a hydroxyl group, and an organic group Z not including an imide bond. Bonded to the silicon atom of the main chain skeleton.
X, Y and Z may or may not be included in the repeating unit in the form of a “chain”. For example, one or more Xs may be contained in one molecule as a side chain. In the above (SiO _m ) _n , n represents the degree of polymerization, and the degree of polymerization represents the degree of polymerization of the main chain skeleton, and n organic skeletons having an imide bond may not necessarily exist. In other words, an organic skeleton having one imide bond in one unit of (SiO _m ) _n is not necessarily present. In addition, one or more organic skeletons having an imide bond may be included in one molecule, but when a plurality of organic skeletons are included, as described above, an organic skeleton having two or more imide bonds in one silicon atom. It may be bonded. The same applies to the following.

In the main chain skeleton (SiO _m ) _n , m is preferably a number of 1 or more and less than 2. More preferably, m = 1.5 to 1.8.
The above n represents the degree of polymerization and is preferably 1 to 5000. More preferably, it is 1-2000, More preferably, it is 1-1000, Most preferably, it is 1-200.
The silane compound in the case where n is 2 is a structural unit in which at least one organic skeleton (X) having an imide bond is bonded to a silicon atom (a structure in which at least one X is bonded to this diatom atom). The unit is also referred to as “structural unit (I)”. Two forms are included, and the other is a form in which only one structural unit (I) is included. Specifically, the following formula:

(Wherein A is Y or Z, and X, Y, and Z are each the same as those described above) and the like, and the form of a homopolymer containing two identical structural units (I) There are a homopolymer form containing two different structural units (I) and a copolymer form (cocondensed structure form) containing only one structural unit (I).

In the above average composition formula: XaYbZcSiOd, X represents the following formula (3):

(In the formula, R ¹ represents at least one structure selected from the group consisting of aromatic, heterocyclic and alicyclic rings. X and z are the same or different and are integers of 0 or more and 5 or less, y Is preferably 0 or 1.). That is, the form in which the silane compound in the present invention is represented by the above-described average composition formula: XaYbZcSiOd and X is represented by the above formula (3) is preferable.

In the above formula (3), x and z are the same or different and are integers of 0 or more and 5 or less. Moreover, y is 0 or 1, and is preferably 0. x + z may be an integer of 0 or more and 10 or less, preferably 3 to 7, more preferably 3 to 5, and particularly preferably 3.

Also in the above formula (3), R ¹ represents at least one structure selected from the group consisting of aromatic, heterocyclic, and alicyclic. That is, R ¹ is a group having a ring structure (aromatic ring) of an aromatic compound, a group having a ring structure (heterocycle) of a heterocyclic compound, and a group having a ring structure (alicyclic ring) of an alicyclic compound It represents at least one group selected from the group consisting of
Specifically, R ¹ is preferably a phenylene group, a naphthylidene group, a divalent group of norbornene, an (alkyl) cyclohexylene group, a cyclohexenyl group, or the like.
The structural unit represented by the above formula (3) is a structural unit represented by the following formula (3-2) when R ¹ is a phenylene group, and R ¹ is an (alkyl) cyclohexylene group. In some cases, the structural unit is represented by the following formula (3-3). When R ¹ is a naphthylidene group, the structural unit is represented by the following formula (3-4), and R ¹ is 2 of norbornene. When it is a valent group, it becomes a structural unit represented by the following formula (3-5), and when R ¹ is a cyclohexenyl group, it becomes a structural unit represented by the following formula (3-6).

In the above formulas (3-2) to (3-6), x, y and z are the same as in the above formula (3).
In the above formula (3-2), R ^{2 to} R ⁵ are the same or different and represent at least one structure selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic.
In the above formula (3-3), R ^{6 to} R ⁹ and R ^{6 ′ to} R ^{9 ′} are the same or different and are at least one selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic. Represents the structure. As the ^R 6 to R ⁹ and ^{R 6'to R 9',} form all ^{R 7} or ^{R 8} are the remaining methyl group is a hydrogen atom, ^or, R 6 to R ⁹ and ^R 6'to R ^{9 'all} are hydrogen atom form ^or embodiment R 6 to R ⁹ and ^{R 6'to R 9'all} are a fluorine atom is preferable. More preferably, R ⁷ or R ⁸ is a methyl group and the rest are all hydrogen atoms.

In said formula (3-4), R < ¹⁰ > -R < ¹⁵ > is the same or different and represents at least 1 type of structure chosen from the group which consists of a hydrogen atom, an alkyl group, a halogen atom, and aromatic. As said R < ¹⁰ > -R < ¹⁵ >, the form in which all are hydrogen atoms, or the form in which all are fluorine atoms is preferable. More preferred is a form in which all are hydrogen atoms.
In said formula (3-5), R < ¹⁶ > -R < ²¹ > is the same or different and represents at least 1 type of structure chosen from the group which consists of a hydrogen atom, an alkyl group, a halogen atom, and aromatic. As said R < ¹⁶ > -R < ²¹ >, the form in which all are hydrogen atoms, the form in which all are fluorine atoms, or the form in which all are chlorine atoms is preferable. More preferred is a form in which all are hydrogen atoms.

In the above formula (3-6), R ^{22 to} R ²⁵ , R ^{22 ′} and R ^{25 ′} are the same or different and are at least one selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic. Represents the structure. As the ^R 22 ^{~R 25, R 22'} and ^{R 25 ',} forms all are hydrogen atom, and all are a fluorine atom form or any form of embodiment all is a chlorine atom is preferable. More preferred is a form in which all are hydrogen atoms.

Among the above formulas (3), the following formula (3-7):

(Wherein R ²⁶ represents a structural unit represented by at least one structure selected from the group consisting of aromatic, heterocyclic and alicyclic rings). That is, the embodiment in which the silane compound is a compound having a structural unit represented by the above formula (3-7) and a siloxane skeleton is preferable. Incidentally, ^{R 26} in the formula (3-7) is preferably the same as ^{R 1} described in the above formula (3).

As a particularly preferable form of the silane compound, poly (γ-phthalopropylpropylsilsesquioxane) in which R ²⁶ is a phenylene group, poly {γ- (hexahydro-4-methyl) in which R ²⁶ is a methylcyclohexylene group. phthalimido) propyl ^{silsesquioxane},} poly {.gamma. poly ^{R 26} is naphthylidene group {.gamma. (1,8-naphthalimide) propyl ^{silsesquioxane}, R 26} is divalent norbornene ( 5-norbornene-2,3-imido) propylsilsesquioxane}, poly [(cis-4-cyclohexene-1,2-imido) propylsilsesquioxane] in which R ²⁶ is a cyclohexenyl group.
The structures of these compounds can be identified by measuring ¹ H-NMR, ¹³ C-NMR, and MALDI-TOF-MS.

Although it does not specifically limit as a method to obtain the said silane compound, For example, the following manufacturing method etc. are mentioned as a method in the case of obtaining the silane compound represented by the said average compositional formula.
(A) An intermediate (consisting of a silane compound) represented by an average composition formula X′aYbZcSiOd having an organic skeleton X ′ having an amide bond corresponding to the organic skeleton X containing an imide bond in the silane compound and a siloxane bond The manufacturing method including the process of imidating.
(B) The organic skeleton having an imide bond corresponding to the organic skeleton X containing an imide bond in the silane compound is hydrolyzed / condensed by an intermediate composed of a silane compound bonded to a silicon atom and having a hydrolyzable group. A manufacturing method including a process.

It is preferable that the curable resin composition further contains a polyfunctional maleimide compound. That is, a curable resin composition containing a benzoxazine compound, a silane compound, and a polyfunctional maleimide compound is one of the preferred embodiments of the present invention. In this case, Tg of hardened | cured material can further be improved and the hardened | cured material which shows higher heat resistance can be obtained. The cured product of such a curable resin composition is considered to have a structure in which a silane compound is incorporated in the resin skeleton generated by the reaction between the polyfunctional maleimide compound and the benzoxazine compound. Compared to a maleimide compound alone, it is easy to cure and has good moldability at the time of curing.

The blending amount of the polyfunctional maleimide compound is, for example, such that the ratio of the functional groups of the polyfunctional maleimide compound and the benzoxazine compound (maleimide group / benzoxazine group; molar ratio) is 1 / 0.01 to 1. It is preferable to set. Thereby, the crosslinking density of the cured product is further improved, the Tg of the cured product is further improved, and the thermal decomposition resistance is further increased. More preferably, it is 1 / 0.05-0.8, More preferably, it is 1 / 0.1-0.5.

The said polyfunctional maleimide compound should just be a compound which has two or more maleimide groups in a molecule | numerator, and can use 1 type (s) or 2 or more types. For example, the following compounds are preferably used.
N, N′-m-phenylene bismaleimide, N, N′-p-phenylene bismaleimide, N, N′-m-toluylene bismaleimide, N, N′-4,4′-biphenylene bismaleimide, N, N′-4,4 ′-[3,3′-dimethyl-biphenylene] bismaleimide, N, N′-4,4 ′-[3,3′-dimethyldiphenylmethane] bismaleimide, N, N′-4, 4 ′-[3,3′-diethyldiphenylmethane] bismaleimide, N, N′-4,4′-diphenylmethane bismaleimide, N, N′-4,4′-diphenylpropane bismaleimide, N, N′-4 , 4′-diphenyl terbismaleimide, N, N′-3,3′-diphenylsulfone bismaleimide, N, N′-4,4′-diphenylsulfone bismaleimide, 2,2-bis [4- ( 4-maleimidophenoxy ) Phenyl] nonane, 2,2-bis [3-tert-butyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-secondary-butyl-4- (4-maleimidophenoxy) ) Phenyl] propane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] decane, 1,1-bis [2-methyl-4- (4-maleimidophenoxy) -5-tert-butylphenyl ] -2-methylpropane, 4,4′-cyclohexylidene-bis [1- (4-maleimidophenoxy) -2- (1,1-dimethylethyl) benzene], 4,4′-methylene-bis [1 -(4-maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4,4'-methylene-bis [1- (4-maleimidophenoxy) -2,6- Secondary-butylbenzene], 4,4′-cyclohexylidene-bis [1- (4-maleimidophenoxy) -2-cyclohexylbenzene], 4,4′-methylene-bis [1- (maleimidophenoxy) -2 -Nonylbenzene], 4,4 '-(1-methylethylidene) -bis [1- (maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene, 4,4'-(2-ethyl) Hexylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4 ′-(1-methylheptylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4′-cyclohexylene Den-bis [1- (maleimidophenoxy) -3-methylbenzene] and the like.

The polyfunctional maleimide compound can be obtained, for example, by further subjecting polyfunctional maleamic acid obtained by reacting maleic anhydride and polyfunctional diamine to dehydration ring-closing imidization. Moreover, it is possible to obtain a prepolymer by reacting the polyfunctional maleimide compound thus obtained with a polyfunctional amine or polyfunctional allylphenol compound at a temperature of 200 ° C. or lower.

It is preferable that the curable resin composition further contains an imidazole compound. That is, a curable resin composition containing a benzoxazine compound, a silane compound, and an imidazole compound is also one preferred embodiment of the present invention, whereby the crosslink density of the cured product is further improved, and the cured product is obtained. Tg of this will be further improved. More preferred is a form containing a benzoxazine compound, a silane compound, a polyfunctional maleimide compound, and an imidazole compound.

The compounding amount of the imidazole compound may be set so that, for example, the functional group ratio (imidazole group / benzoxazine group; molar ratio) between the imidazole compound and the benzoxazine compound is 1/5 to 50. Is preferred. Thereby, the crosslinking density of the cured product is further improved, the Tg of the cured product is further improved, and the thermal decomposition resistance is further increased. More preferably, it is 1/10 to 40, and still more preferably 1/15 to 30.

The said imidazole compound should just be a compound which has at least 1 imidazole group in a molecule | numerator, and can use 1 type (s) or 2 or more types. For example, the following compounds are preferably used.
Imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 -Benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -Cyanoethyl-2-phenylimidazole, 1-aminomethyl-2-methylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole and the like.

The curable resin composition may also contain components other than the raw material components described above (also referred to as “other components”) as long as the original properties are not impaired. For example, volatile components such as organic solvents and diluents, curing accelerators, stabilizers, mold release agents, coupling agents, colorants, plasticizers, flexible agents, various rubber-like materials, photosensitizers, fillers, A flame retardant, a pigment, etc. are mentioned, These 1 type (s) or 2 or more types can be used.
The volatile component is not particularly limited, and a commonly used one may be used, but the organic solvent described below is suitable.
As said hardening accelerator, 1 type (s) or 2 or more types, such as organic phosphorus compounds, such as a triphenyl phosphine, a tributyl hexadecyl phosphonium bromide, a tributyl phosphine, a tris (dimethoxyphenyl) phosphine, are suitable, for example.

The present invention is also a curable resin composition containing a benzoxazine compound, a polyfunctional maleimide compound, and an imidazole compound. Such a curable resin composition is also industrially useful because it can impart a cured product having a high glass transition temperature (Tg) and at the same time having a high thermal decomposition resistance. About each component, it is as above-mentioned, and can use 1 type (s) or 2 or more types, respectively. Furthermore, the above-mentioned other components may be contained.
In such a curable resin composition, the composition of benzoxazine compound, polyfunctional maleimide compound and imidazole compound is such that the ratio of these functional groups (benzoxazine group / maleimide group / imidazole group; molar ratio) is 5 It is preferable to set so that it will be -60 / 30-90 / 0.1-10. More preferably, it is 20-45 / 55-80 / 0.3-3.

As for the curable resin composition of this invention, it is preferable that the glass transition temperature (Tg) of the hardened | cured material is 250 degreeC or more. When Tg is high, it is more suitable when used as a member used at high temperatures. More preferably, it is 280 degreeC or more, More preferably, it is 310 degreeC or more, Most preferably, it is 330 degreeC or more.

The curable resin composition preferably has a 5% mass reduction temperature of 300 ° C. or higher. Since the 5% mass reduction temperature is high, that is, the heat decomposition resistance (heat resistance) is excellent, it is more suitable when used as a member used at a high temperature. The 5% mass reduction temperature is more preferably 320 ° C. or higher, further preferably 340 ° C. or higher, particularly preferably 360 ° C. or higher, and most preferably 400 ° C. or higher. The 10% mass reduction temperature is also preferably 300 ° C. or higher, more preferably 320 ° C. or higher, further preferably 340 ° C. or higher, particularly preferably 360 ° C. or higher, and most preferably 400 ° C. or higher.

The curable resin composition preferably further has, for example, a viscosity at 150 ° C. of 0.01 to 60 Pa · s. When it has such a suitable viscosity, it will be excellent in the handling property (handleability) at the time of obtaining hardened | cured material. More preferably, it is 0.02 to 40 Pa · s.
The viscosity can be measured at 150 ± 1 ° C. using, for example, a viscometer (“CAP2000” manufactured by BROOFIELD).

The curable resin composition of the present invention may be prepared so as to include the above-described raw material components, but from the viewpoint of handling, it is preferable to set the order in which the raw material components are charged into the reaction vessel. That is, first, it is preferable that a part or all of the raw material components other than the benzoxazine compound are charged into the reaction vessel, and then the benzoxazine compound is charged. When a benzoxazine compound and an imidazole compound are used in combination, first, a part or all of the raw material components other than the benzoxazine compound and the imidazole compound are charged into the reaction vessel, and then the benzoxazine compound is charged. Further, it is preferable to add an imidazole compound thereafter. By setting the charging order in this way, handling is improved, and the composition can be efficiently obtained without gelation when the composition is obtained.
As described above, a method for producing a curable resin composition in which a part or all of raw material components other than a benzoxazine compound are charged into a reaction vessel, and then the benzoxazine compound is charged into the reaction vessel; a benzoxazodine compound and an imidazo -A method for producing a curable resin composition in which a part or all of raw material components other than a ruthel compound are charged into a reaction vessel, a benzoxazine compound is charged into the reaction vessel, and then an imidazole compound is charged; Moreover, it is included in the present invention.

In the above production method, the method for adding the raw material components to the reaction vessel is not particularly limited, and for example, a normal method such as divided charging or batch charging is employed.
In addition, when a raw material component is solid, it is suitable to make the said raw material component into a pulverized state or a molten state beforehand, and handling becomes still better by this.

In the above production method, heating and mixing are performed after adding the raw material components described above, but an organic solvent may be present or in a molten state. The heating temperature is not particularly limited and is preferably 40 to 200 ° C, for example. More preferably, it is 60-180 degreeC, More preferably, it is 80-160 degreeC. In addition, a solvent removal step may be performed as necessary, and it is preferable to add a cross-linking agent and stir after heating and mixing (further after the solvent removal step if necessary).

As the organic solvent, for example, a compound having at least one structure selected from the group consisting of an ether bond, an ester bond and a nitrogen atom is suitably used.
Examples of the compound having an ether bond include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, butyl vinyl ether, anisole, phenetole, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, and benzyl ethyl. Ether, diphenyl ether, dibenzyl ether, peratrol, propylene oxide, 1,2-epoxybutane, dioxane, trioxane, furan, 2-methylfuran, tetrahydrofuran, tetrahydropyran, thionel, 1,2-dimethoxyethane, 1,2-di Ethoxyethane, 1,2-dibutoxyethane, glycerin ether, crown ether, methylal, acetal, methyl cellosol , Ethyl cellosolve, butyl cellosolve, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol, Triethylene glycol monomethyl ether, tetraethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol methyl ether, propylene glycol dimethyl ether, propylene glycol propyl ether Propylene glycol butyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, 2- Methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, 2-phenoxyethanol, 2- (Benzyloxy) ethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, etc. are preferred It is.

Examples of the compound having an ester bond include methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-acetate Butyl, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate , Ethylene glycol monoacetate, diethylene glycol monoacetate, monoacetin, diacetin, triacetin, monobutyrin, dimethyl carbonate, diethyl carbonate, dipropyl carbonate Dibutyl carbonate, butyric acid ester, isobutyric acid ester, isovaleric acid ester, stearic acid ester, benzoic acid ester, ethyl cinnamate, abietic acid ester, adipic acid ester, γ-butyrolactone, shu Acid esters, malonic acid esters, maleic acid esters, tartaric acid esters, citric acid esters, sebacic acid esters, phthalic acid esters, ethylene diacetate and the like are suitable.

Examples of the compound containing the nitrogen atom include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitrobenzene, acetonitrile, propionitrile, succinonitrile, butyronitrile, isobutyronitrile, valeronitrile, Benzonitrile, α-tolunitrile, formamide, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N, N-diethylacetamide, 2 -Pyrrolidone, N-methylpyrrolidone, ε-caprolactam and the like are preferred.

Examples of the compound having a plurality of structures selected from the group consisting of the ether bond, ester bond and nitrogen atom include N-ethylmorpholine, N-phenylmorpholine, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, and butyl cellosolve acetate. , Phenoxyethyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether Acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol propyl ether acetate, dipropylene glycol butyl ether acetate, tripropylene glycol methyl ether acetate are preferable.

As the usage-amount of the said organic solvent, it is preferable to set it as 5-1000 weight part with respect to 100 weight part of total amounts of all the raw material components (solid content). More preferably, it is 10 to 300 parts by weight.

The curable resin composition of this invention can be made into hardened | cured material by adding a hardening accelerator etc. as needed and thermosetting. 70-300 degreeC is suitable for hardening temperature, More preferably, it is 80-250 degreeC. Moreover, 0.1 to 15 hours are suitable for hardening time, More preferably, it is 0.5 to 10 hours. The thermosetting may be performed in two or more stages.
In addition, the manufacturing method of the curable resin composition mentioned above is applicable also to the manufacturing method of hardened | cured material. That is, a method for producing a cured product of the curable resin composition, wherein a part or all of raw material components other than a benzoxazine compound are charged into a reaction vessel, and then a benzoxazine compound is charged into the reaction vessel A cured product comprising a curing step; a method for producing a cured product of the curable resin composition, wherein a part or all of raw material components other than the benzoxazodine compound and the imidazole compound are reacted in a reaction vessel A method for producing a cured product comprising a step of introducing a benzoxazine compound into the reaction vessel and then introducing an imidazole compound, and a curing step is also a preferred embodiment of the present invention.

Examples of the shape of the cured product include a molded product (molded product) such as a deformed product, a film, a sheet, a pellet, and the like, and a cured product using the curable resin composition of the present invention (the present invention). A cured product obtained by curing the curable resin composition is also a preferred embodiment of the present invention.

The curable resin composition includes, for example, mounting applications, optical applications, optical device applications, display device applications, machine component applications, electrical / electronic component applications, automobile component applications, aircraft component applications, building member applications, fuel cell applications, It is suitably used for various applications such as various secondary battery applications and printing ink applications. Specifically, copper-clad laminates for printed wiring boards, adhesives for multilayer wiring boards, semiconductor sealing materials, semiconductor mounting adhesives, electronic mounting materials such as semiconductor mounting modules, potting materials, underfill It is preferably used for materials, conductive pastes, insulating pastes, die bond materials, printing inks and the like. Especially, the hardened | cured material of the curable resin composition of this invention will be used especially suitably for the electronics mounting material by which high heat resistance is requested | required from a viewpoint which is excellent in heat resistance. Thus, an electronic packaging material using the curable resin composition is also one aspect of the present invention. Moreover, the said curable resin composition can be suitably employ | adopted also in a hybrid vehicle, an electric vehicle, and a distributed power supply.

The electronic packaging material is not particularly limited as long as it is a material that can be used for electronic components and the like. For example, a semiconductor sealing material that is used when sealing semiconductor components is suitable. In such an electronic packaging material, for example, a curing accelerator, a stabilizer, a mold release agent, a coupling agent, a colorant, a plasticizer, and a flexible agent may be used as long as the effects of the present invention are not impaired. Agents, various rubbery materials, photosensitizers, fillers, flame retardants, pigments and the like.

Since the curable resin composition of this invention is the above structures, it can give the hardened | cured material excellent in heat resistance, and is useful for various uses. Further, when such a curable resin composition is produced, the use of the production method of the present invention is industrially useful because the handleability in the production process is good.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Note that “%” means “mass%” unless otherwise specified.
In the following examples, the Tg of the cured product of the curable resin composition is measured using a dynamic viscoelasticity measuring device (RSA-3 TA Instruments Co., Ltd.), the measurement conditions are three-point bending mode, amplitude 0.2%, Tg is the temperature at which the loss tangent (tan δ) value of the measurement result is the maximum as the frequency 6.28 Hz, the temperature range 100 ° C. to 350 ° C., the heating rate 5 ° C./min, and the test piece shape (5 × 50 × 2 mm). It was.
Moreover, the mass decreasing temperature at the time of a heating was measured using the differential thermal balance (the apparatus name "TG-DTA2000SA", the Bruker company make). The measurement conditions were a heating rate of 10 ° C./min and an air flow of 100 ml / min.

Synthesis Example 1 (Preparation of Silane Compound Solution 1)
Synthesis of poly (γ-phthaloimidopropylsilsesquioxane) Into a 500 mL four-necked flask equipped with a stirrer, a temperature sensor, and a condenser tube, 86.6 g of diglyme previously dried with molecular sieve and 3-aminopropyltrimethoxysilane 179.4 g was added, and the temperature was raised to 100 ° C. under a flow of dry nitrogen while stirring to remove moisture in the system. Next, 148.2 g of phthalic anhydride was added in four portions over 30 minutes while maintaining the reaction solution temperature at 80 ° C. It was confirmed by high performance liquid chromatography that phthalic anhydride was completely consumed in 3 hours after the completion of the addition.
The reaction product was sampled and ¹ H-NMR, ¹³ C-NMR, and MALDI-TOF-MS were measured, and the following chemical formula (i-1):

It confirmed that it contained the compound represented by these.
¹ H-NMR: 0.72 (t, 2H), 1.81 (m, 2H), 3.48 (dd, 2H), 3.72 (s, 9H), 4.71 (bs, 1H), 7.56-7.72 (m, 2H), 7.73-7.86 (m, 2H), 11.0 (bs, 1H)
¹³ C-NMR: 9.1, 22.2, 40.6, 50.5, 122.3, 122.4, 122.5, 132.4, 134.0, 134.2, 168.7, 172 .0
MALDI-TOF-MS: 334 (M + Li)

Subsequently, 54.2 g of deionized water was added all at once, and the temperature was raised so that by-product methanol was refluxed in the cooling pipe. After holding for 6 hours, the cooling pipe was replaced with a partial condenser, and the temperature was raised again. The reaction liquid temperature was allowed to reach 120 ° C. over 3 hours while collecting raw methanol and condensed water. When the temperature reached 120 ° C., 7.9 g of pyridine was added and the temperature was raised as it was. The temperature reached 160 ° C. over 3 hours while collecting condensed water, and the temperature was maintained at the same temperature for 2 hours and cooled to room temperature. The reaction product thus obtained is designated as “Silane Compound Solution 1” (solid content concentration 80.6%).
The reaction product was a dark brown high-viscosity liquid with a non-volatile content of 80.6%. The molecular weight measured by GPC was a number average molecular weight of 2310 and a weight average molecular weight of 2830. ¹ H-NMR and ¹³ C-NMR were measured, and the following chemical formula (i-2):

It was confirmed that the compound represented by the formula (poly (γ-phthalimidopropylsilsesquioxane)) was contained.
¹ H-NMR: 0.3-0.9 (bs, 2H), 1.5-1.8 (bs, 2H), 3.4-3.6 (bs, 2H), 7.1-7. 7 (bs, 4H)
¹³ C-NMR: 10.0, 22.1, 40.4, 123.1, 132.3, 133.7, 168.1

Synthesis Example 2 (Preparation of Silane Compound Solution 2)
Synthesis of poly {γ- (5-norbornene-2,3-imido) propylsilsesquioxane} 35.1 g of diglyme previously dried with molecular sieves in a 300 mL four-necked flask equipped with a stirrer, temperature sensor, and condenser. Then, 30.8 g of 3-aminopropyltrimethoxysilane was added, and the temperature was raised to 100 ° C. under a flow of dry nitrogen while stirring to remove moisture in the system. Next, 28.2 g of 5-norbornene-2,3-dicarboxylic acid anhydride was added in 4 portions over 30 minutes while maintaining the temperature of the reaction solution at 100 ° C. It was confirmed by high performance liquid chromatography that 5-norbornene-2,3-dicarboxylic anhydride was completely consumed in 9 hours after the completion of the addition.
The reaction product was sampled to measure ¹ H-NMR, ¹³ C-NMR, and MALDI-TOF-MS, and the following chemical formula (ii-1):

It confirmed that it contained the compound represented by these.
¹ H-NMR: 0.40 (t, 2H), 1.35 (m, 2H), 1.46 (dd, 2H), 3.08-3.17 (m, 1H), 3.20 (dd 2H), 3.28-3.37 (m, 1H), 3.40 (s, 9H), 3.42 (m, 1H), 3.48 (m, 1H), 5.91 (s, 2H), 6.22 (bs, 1H), 11.0 (bs, 1H)
¹³ C-NMR: 8.1, 11.2, 40.6, 44.9, 45.8, 50.3, 50.6, 52.3, 134.5, 177.8, 178.1
MALDI-TOF-MS: 350 (M + Li)

Subsequently, 9.3 g of deionized water was added all at once, and the temperature was raised so that by-product methanol was refluxed in the cooling pipe. After holding at 95 ° C. for 10 hours, the cooling pipe was replaced with a partial condenser and the temperature was raised again. The reaction liquid temperature was allowed to reach 120 ° C. over 3 hours while collecting by-product methanol and condensed water. When the temperature reached 120 ° C., 1.4 g of pyridine was added and the temperature was raised as it was, and while recovering the condensed water, the temperature reached 160 ° C. over 3 o'clock, kept at the same temperature for 2 hours, and cooled to room temperature. The reaction product thus obtained is designated “Silane Compound Solution 2” (solid content concentration: 58.2%).
The reaction product was a dark brown high-viscosity liquid with a non-volatile content of 58.2%. When the molecular weight was measured by GPC, the number-average molecular weight was 2340 and the weight-average molecular weight was 2570. ¹ H-NMR and ¹³ C-NMR were measured, and the following chemical formula (ii-2):

It was confirmed that the compound represented by the formula (poly {γ- (5-norbornene-2,3-imido) propylsilsesquioxane}) was contained.
¹ H-NMR: 0.25-0.45 (bs, 2H), 1.2-1.45 (bs, 2H), 1.47 (dd, 2H), 3.0-3.2 (bs, 4H), 3.4-3.6 (bs, 2H), 5.8-6.0 (bs, 2H)
¹³ C-NMR: 9.7, 21.5, 40.4, 44.9, 45.7, 50.1, 134.2, 178.0

Synthesis Example 3 (Preparation of Silane Compound Solution 3)
Synthesis of poly [(cis-4-cyclohexene-1,2-imido) propylsilsesquioxane] In a 500 mL four-necked flask equipped with a stirrer, a temperature sensor and a condenser tube, 103.7 g of diglyme previously dried with molecular sieves. Then, 177.6 g of 3-aminopropyltrimethoxysilane was added, and the temperature was raised to 100 ° C. under a flow of dry nitrogen while stirring to remove moisture in the system. Next, 150.7 g of cis-4-cyclohexene-1,2-dicarboxylic acid anhydride was added in four portions over 30 minutes while maintaining the temperature of the reaction solution at 80 ° C. It was confirmed by high performance liquid chromatography that cis-4-cyclohexene-1,2-dicarboxylic anhydride was completely consumed within 3 hours after the completion of the addition.
The reaction product was sampled to measure ¹ H-NMR, ¹³ C-NMR, and MALDI-TOF-MS, and the following chemical formula (iii-1):

It confirmed that it contained the compound represented by these.
¹ H-NMR: 0.72 (t, 2H), 1.81 (m, 2H), 2.23 (dd, 4H), 2.74 (m, 1H), 2.91 (dd, 1H), 3.48 (dd, 2H), 3.72 (s, 9H), 5.74 (m, 2H), 11.0 (bs, 1H)
¹³ C-NMR: 9.1, 22.2, 25.5, 26.8, 40.6, 42.3, 43.1, 44.7, 131.7, 168.8, 172.7,
MALDI-TOF-MS: 338 (M + Li)

Subsequently, 53.4 g of deionized water was added all at once, and the temperature was raised so that by-product methanol was refluxed in the cooling pipe. After holding for 6 hours, the cooling pipe was replaced with a partial condenser, and the temperature was raised again. The reaction liquid temperature was allowed to reach 120 ° C. over 3 hours while collecting raw methanol and condensed water. When the temperature reached 120 ° C., 7.9 g of pyridine was added and the temperature was raised as it was. The temperature reached 160 ° C. over 3 hours while collecting condensed water, and the temperature was maintained at the same temperature for 2 hours and cooled to room temperature. The reaction product thus obtained is designated as “silane compound solution 3” (solid content concentration: 74.3%).
The reaction product was a dark brown high-viscosity liquid with a non-volatile content of 74.3%. The molecular weight measured by GPC was a number average molecular weight of 2041 and a weight average molecular weight of 2838. ¹ H-NMR and ¹³ C-NMR were measured, and the following chemical formula (iii-2):

(Poly [(cis-4-cyclohexene-1,2-imido) propylsilsesquioxane]).
¹ H-NMR: 0.25-0.55 (bs, 2H), 1.3-1.5 (bs, 2H), 2.0-2.5 (dd, 4H), 2.9-3. 1 (bs, 2H), 3.2-3.35 (bs, 2H), 5.65-5.8 (bs, 2H)
¹³ C-NMR: 10.0, 21.0, 23.8, 39.0, 41.1, 127.8, 180.5

Reference example 1
In a 200 mL flask equipped with a partial condenser, a collection tube, a vacuum pump, a temperature sensor, and a stirrer, 37.0 g of phenylethanemaleimide BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.) and Pd-type benzoxazine (Shikoku Kasei Kogyo) 13.0 g), heated to 150 ° C. in an oil bath, stirred for 1 hour and visually confirmed that a uniform solution was obtained, and then kept at 150 ° C. with a vacuum pump up to 5 kPa in the flask The volatile matter was removed under reduced pressure for 2 hours, and a composition 1 that was liquid at 150 ° C. and solid at room temperature was obtained. The composition 1 was poured into a PTFE mold and allowed to stand under a temperature condition of 200 ° C. × 3 hours + 250 ° C. × 1 hour to obtain a cured product.

Reference example 2
In a 200 mL flask equipped with a partial condenser, a collection tube, a vacuum pump, a temperature sensor, and a stirrer, 37.0 g of phenylethanemaleimide BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.) and Pd-type benzoxazine (Shikoku Kasei Kogyo) 13.0 g), heated to 150 ° C. in an oil bath, stirred for 1 hour and visually confirmed that a uniform solution was obtained, and then kept at 150 ° C. with a vacuum pump up to 5 kPa in the flask Reduce pressure to remove volatiles for 2 hours, finally return to atmospheric pressure, add 0.5 g of 1-cyanoethyl-2-phenylimidazole, depressurize again to 5 kPa, degas for 3 minutes, liquid at 150 ° C. Thus, a room temperature solid composition 2 was obtained. The composition 2 was poured into a PTFE mold and allowed to stand under a temperature condition of 200 ° C. × 3 hours + 250 ° C. × 1 hour to obtain a cured product.

Example 3
In a 500 mL flask equipped with a partial condenser, a collecting tube, a vacuum pump, a temperature sensor, and a stirrer, 230 g of phenylethanemaleimide BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.) and the silane compound solution 1 (solid) obtained in Synthesis Example 1 (Partial concentration 80.6%) 197.2 g was charged, heated to 150 ° C., and stirred for 0.5 hour to obtain a uniform solution. Subsequently, the pressure in the flask was reduced to 5 kPa with a vacuum pump to remove volatile components over 3 hours. Thereafter, the temperature inside the flask was lowered to room temperature to obtain a mixture 1 of a room temperature solid.
In a 200 mL flask equipped with a partial condenser, a collecting tube, a vacuum pump, a temperature sensor, and a stirrer, premixed mixture 1 (15.8 g) and Pd type benzoxazine (manufactured by Shikoku Kasei Kogyo Co., Ltd.) 10.4 g And phenylethanemaleimide BMI-2300 (manufactured by Daiwa Kasei Kogyo Co., Ltd.) 23.8 g, heated to 150 ° C., stirred for 1 hour and visually confirmed that a uniform solution was obtained, then kept at 150 ° C. Reduce the pressure in the flask to 5 kPa with a vacuum pump, remove volatiles for 2 hours, finally return to normal pressure, add 0.5 g of 1-cyanoethyl-2-phenylimidazole, reduce the pressure to 5 kPa again, and remove for 3 minutes. The composition 3 was obtained as a liquid at room temperature and a solid at room temperature. The composition 3 was poured into a PTFE mold and allowed to stand under a temperature condition of 200 ° C. × 3 hours + 250 ° C. × 1 hour to obtain a cured product.

About each hardened | cured material obtained in Reference Examples 1-2 or Example 3 , the glass transition temperature (Tg) and mass reduction temperature (5 mass% reduction temperature and 10 mass% reduction temperature) were measured. The results are shown in Table 1.

From Table 1, the cured product obtained from the curable resin composition of the present invention has a glass transition temperature of 300 ° C. or higher, and 5% and 10% mass reduction temperatures are both 400 ° C. or higher. It was confirmed that it was excellent in property.

Claims (11)

Benzoxazine compounds, and, seen containing a silane compound having a siloxane skeleton and an imide bond,
The benzoxazine compound has the following general formula (1) or (2);

(In the formula, n represents an integer of 1 to 4. R ^a is the same or different and represents ^a lower alkyl group, a cycloalkyl group, an aryl group, an allyl group, or an aralkyl group. R ^b is the same or different. Te, a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group, an allyl group, an aralkyl group, or, .R ^c representing a 1-4-valent organic group represented by the following general formula (a) ~ (t) The same or different and each represents a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group, an allyl group or an aralkyl group, and R ^d is the same or different and represents a lower alkyl group, a cycloalkyl group, an aryl group or an allyl group. , An aralkyl group, or a monovalent to tetravalent organic group represented by the following general formulas (a) to (o).

)
The silane compound has the following average composition formula:
XaYbZcSiOd
(In the formula, X is the same or different and represents an organic skeleton containing an imide bond. Y is the same or different and represents at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, a halogen atom and an OR group. Z is the same or different and represents an organic group not containing an imide bond, and R is the same or different and is at least one selected from the group consisting of an alkyl group, an acyl group, an aryl group, and an unsaturated aliphatic residue. Represents one group and may have a substituent, a is a number of 3 or less that is not 0, b and c are the same or different, and are 0 or a number of less than 3, and d is 0 Is a number less than 2 and a + b + c + 2d = 4).
X in the formula is the following formula (3-7):

(Wherein R ²⁶ represents at least one structure selected from the group consisting of aromatic, heterocyclic and alicyclic rings) . 2. The curable resin composition according to claim 1, wherein the benzoxazine compound is a compound having two or more benzoxazine rings in one molecule. In the formula (3-7), R ²⁶ Represents a phenylene group, a naphthylidene group, a divalent group of norbornene, an (alkyl) cyclohexylene group or a cyclohexenyl group, The curable resin composition according to claim 1 or 2. The curable resin according to claim 1, wherein a mass ratio of the benzoxazine compound to the silane compound (benzoxazine compound / silane compound) is 1 to 80/99 to 20. Composition. Furthermore, a polyfunctional maleimide compound is contained, The curable resin composition in any one of Claims 1-4 characterized by the above-mentioned. The compounding amount of the polyfunctional maleimide compound is such that the ratio of the functional groups of the polyfunctional maleimide compound and the benzoxazine compound (maleimide group / benzoxazine group; molar ratio) is 1 / 0.01 to 1. The curable resin composition according to claim 5. Furthermore, an imidazole compound is included, The curable resin composition in any one of Claims 1-6 characterized by the above-mentioned. The amount of the imidazole compound is such that the ratio of the functional groups of the imidazole compound and the benzoxazine compound (imidazole group / benzoxazine group; molar ratio) is 1/5 to 50. The curable resin composition according to claim 7. A method for producing the curable resin composition according to any one of claims 1 to 6 ,
The method for producing a curable resin composition is characterized in that after a part or all of raw material components other than a benzoxazine compound are charged into a reaction vessel, the benzoxazine compound is charged into the reaction vessel. A method for producing the curable resin composition according to claim 7 or 8 ,
In the production method, after a part or all of raw material components other than the benzoxazodine compound and the imidazole compound are charged into a reaction vessel, the benzoxazine compound is charged into the reaction vessel, and then the imidazole compound is charged. A method for producing a curable resin composition. Electronics Packaging material characterized by using the curable resin composition according to any one of claims 1-8.