JP2014028923A - Curable resin composition and sealing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition having high thermal resistance and excellent in flexibility and mechanical strength, capable of be used for a sealing material of a semiconductor having high thermostability.SOLUTION: A curable resin composition contains an epoxy resin, a silane compound and a curing agent, and the silane compound has a siloxane bond and is a compound represented by the average composition formula: XYZSiO(1), where X is same or different and represents an organic skeleton containing an imide bond, Y is same or different and represents at least one kind selected from a group consisting of a hydrogen atom, a hydroxyl group, a halogen atom and an OR group, R is same or different and represents at least one group selected from a group consisting of an alkyl group, an acyl group, an aryl group and an unsaturated aliphatic residue, Z is same or different and represents an organic skeleton not containing the imide bond, a is a value of 0 or less than 3, b is a value of 0 or less than 3, c is a value of 0 or less than 3, d is a value of less than 2 not 0 and a+b+c+2d=4, and the curing agent contains a phenol resin and an aromatic amine compound.

Description

The present invention relates to a curable resin composition and a sealing material. More specifically, the present invention relates to a curable resin composition and a sealing material that can be suitably used as a material for a sealing material for a mounting substrate of an electronic component or a semiconductor chip.

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. One application of such a curable resin is a sealing material used for a substrate on which an electronic component or the like is mounted. When mounting electronic components, semiconductor chips, etc. on a substrate, high-density mounting is possible, so there are many surface mounting methods, and at that time, sealing is performed with an electrically insulating sealing material. As such a sealing material, a resin composition containing an epoxy resin or the like is widely used.

Regarding curable resin compositions used for conventional sealing material applications, for example, Patent Document 1 discloses an epoxy resin composition comprising an epoxy resin, a reaction product of an organosiloxane and a predetermined epoxy resin, silica, and a curing agent. It is disclosed that a novolac type phenol resin is preferable as a curing agent. Patent Document 2 discloses an epoxy resin composition for semiconductor encapsulation comprising an epoxy resin, a phenol resin curing agent, an inorganic filler, and a curing accelerator. Further, Patent Document 3 discloses a resin composition for a semiconductor sealing material containing an epoxy resin, a phenol resin that acts as a curing agent for the epoxy resin, a metal hydroxide, and an organic phosphorus compound.

Japanese Patent Laid-Open No. 2-102217 JP-A-9-316176 JP 2001-234037 A

Some electronic components and semiconductor chips that use sealing materials are used in high-temperature environments, and the sealing materials used to protect chips that operate at high temperatures affect the performance of the semiconductor. Heat resistance is required. In recent years, SiC devices, which are attracting attention because of their low power consumption and their ability to control high current and high voltage, operate most efficiently in a high temperature region of 200 ° C. or higher. In addition, high heat resistance of 200 ° C. or higher is required. However, since the resin composition containing the conventional epoxy resin has a high heat resistance of about 175 ° C., further increase in the heat resistance of the resin composition is required. Moreover, since the sealing material is also required to have excellent flexibility and mechanical strength so that the coating film of the sealing material is not peeled off or chipped, development of a resin composition that meets these requirements is required. Yes.

The present invention has been made in view of the above situation, and has high heat resistance, is excellent in flexibility and mechanical strength, and can be suitably used for a semiconductor sealing material having high heat resistance. It aims at providing a conductive resin composition.

The present inventor has studied various curable resin compositions having high heat resistance and excellent flexibility and mechanical strength. In a resin composition containing an epoxy resin, in addition to a phenol resin curing agent, aromatic If an amine compound is used as a curing agent and further contains a silane compound having a specific structure, the resulting resin composition has a high glass transition temperature and excellent heat resistance, as well as excellent flexibility and mechanical strength. It has been found that the resin composition can be suitably used for sealing material applications that require the above high heat resistance, and has reached the present invention.

That is, the present invention is a curable resin composition containing an epoxy resin, a silane compound, and a curing agent, wherein the silane compound has a siloxane bond and has the following average composition formula (1):
_{X a Y b Z c SiO d} (1)
(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 is the same or different and 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. Are the same or different and represent an organic skeleton that does not contain an imide bond, a is a number of 0 or less than 3, b is a number of 0 or less than 3, c is a number of 0 or less than 3, and d is not 0 and less than 2. Wherein a + b + c + 2d = 4), and the curing agent is a curable resin composition containing a phenol resin and an aromatic amine compound.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

Although the curable resin composition of this invention contains an epoxy resin, a silane compound, a phenol resin, and an aromatic amine compound, these may be included 1 type each, or 2 or more types may be included. Good. Moreover, as long as the epoxy resin, the silane compound, the phenol resin, and the aromatic amine compound are included, other components may be included.
In the following description, an aromatic amine compound, a silane compound, a phenol resin, and an epoxy resin, which are essential components of the curable resin composition of the present invention, are described in order, and then the curable resin composition of the present invention can be included. Other ingredients are described.

<Aromatic amine compound>
The aromatic amine compound contained in the curable resin composition of the present invention is preferably a compound having a melting point at 100 ° C. or higher. When the melting point is 100 ° C. or higher, the strength and Tg of the cured product obtained from the curable resin composition can be more sufficiently improved, and a cured product having more excellent heat resistance can be obtained. The melting point of the aromatic amine compound is preferably 102 ° C or higher, more preferably 105 ° C or higher, still more preferably 110 ° C or higher. The upper limit of the melting point of the aromatic amine compound is preferably 200 ° C. or less. As will be described later, in the curable resin composition of the present invention, a form in which the silane compound is uniformly dispersed in the aromatic amine compound is preferable, but when the melting point of the aromatic amine compound is within such a range, Since the compound can be sufficiently mixed with the compound at the molecular level, the effect of using the aromatic amine compound and the silane compound can be more fully exhibited. More preferably, it is 190 degrees C or less.
In the present specification, the melting point means a temperature (° C.) at which a crystal melts and becomes liquid under an inert atmosphere. Therefore, amorphous compounds and those already in liquid form at room temperature do not have a melting point.
The melting point of the aromatic amine compound and the silane-containing composition described later can be measured, for example, by differential scanning calorimetry (DSC).

The aromatic amine compound is an amine compound having an aromatic ring skeleton in its structure, and examples thereof include primary amine compounds, secondary amine compounds, and tertiary amine compounds. It is preferable to use a secondary amine compound. The number of amino groups in one molecule is not particularly limited, but is preferably 1 to 10, for example. More preferably, it is 2-4.

The molecular weight of the aromatic amine compound is preferably 100 to 1000, for example. If the polymer compound exceeds 1000, there is a possibility that it cannot be sufficiently mixed with the silane compound. Moreover, when it is less than 100, it becomes a compound which does not contain an aromatic ring skeleton substantially, and there exists a possibility that heat-resistant decomposition property etc. may not become enough. More preferably, it is 100-800, More preferably, it is 100-600.

Examples of the aromatic amine compound include the following compounds.

In the formula, A ¹ represents a direct bond (—), —C (CF ₃ ) ₂ —, —C (CH ₃ ) ₂ —, or —SO ₂ —. A ² represents a direct bond (−), —C (CF ₃ ) ₂ —, —C (CH ₃ ) ₂ —, —S—, —SO ₂ —, —O—, or — (CH ₂ ) _p —. Represents. p is a number of 1 or more, for example, a number of 1 to 5 is preferable. A ³ is the same or different and represents an amino group (—NH ₂ ) or a methylamino group (—CH ₂ NH ₂ ). R ^a and R ^b are the same or different and each represents a hydrogen atom (—H), a methyl group (—CH ₃ ), an amino group (—NH ₂ ), or a fluorine atom (—F). R ^c is the same or different and represents a hydrogen atom (—H) or a methyl group (—CH ₃ ).

It is preferable that content of the said aromatic amine compound in the curable resin composition of this invention is 5-100 mass% with respect to 100 mass% of epoxy resins which a curable resin composition contains. By including the aromatic amine compound in such a ratio, the cured product obtained from the curable resin composition has sufficient heat resistance. More preferably, it is 10-80 mass% with respect to 100 mass% of epoxy resins, More preferably, it is 15-60 mass%.

<Silane compound>
In the curable resin composition of the present invention, the silane compound is a compound having a siloxane bond (Si—O—Si bond) and represented by the average composition formula (1). By including such a silane compound, it becomes possible to give a cured product having excellent heat resistance, pressure resistance, mechanical / chemical stability, and thermal conductivity. Moreover, the hardened | cured material by which various physical-property fall was suppressed also in severe environments, such as high temperature high pressure, can be formed, and can be used suitably for mounting uses, such as a semiconductor sealing material.

In the silane compound, the structure of the siloxane skeleton (main chain skeleton requiring a siloxane bond) is preferably, for example, a chain (straight or branched), ladder, network, ring, cage, cubic, etc. Illustrated. Especially, since the effect is easily exhibited even if the addition amount of the silane compound is small, a ladder shape, a net shape, or a cage shape is preferable. More preferably, it is a basket shape. That is, the silane compound preferably includes polysilsesoxane.
In addition, as a ratio for which the siloxane skeleton accounts in the said silane compound, it is preferable that it is 10-80 mass% in 100 mass% of silane compounds. More preferably, it is 15-70 mass%, More preferably, it is 20-50 mass%.

In the above average composition formula (1): X _a Y _b Z _c SiO _d , the preferred form of X is as described later, and as Y, a hydroxyl group or an OR group is preferred. Among them, 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 an aromatic residue such as an alkyl group, an aryl group, and an aralkyl group, and an unsaturated aliphatic residue (these have a substituent). You may). 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 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 a number less than 0 ≦ c <3. , O is a number d such that 0 <d <2.

It is preferable that at least one of X, Y and Z in the average composition formula: X _a Y _b Z _c SiO _d has a polymerizable functional group. When the silane compound in the present invention has at least one polymerizable functional group, a crosslinked structure can be formed in the silane compound by adding an imide component described later, and the curable resin composition of the present invention is obtained. It can be made more heat resistant.
Examples of the polymerizable functional group include unsaturated hydrocarbon groups such as alkenyl groups and alkynyl groups, hydroxyl groups, halogen atoms, amino groups, carboxyl groups, epoxy groups, isocyanate groups, and the like. Absent.
In the case where X is represented by formula (3) described below, at least when X has a polymerizable functional group, the aromatic ring represented by R ^1, is selected from the group consisting of heterocyclic and alicyclic 1 In addition to the case where the ring structure of the species has a polymerizable functional group as a substituent, a part of at least one ring structure selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring represented by R ¹ is polymerizable. The case of the unsaturated hydrocarbon structure is also included.
Similarly, when X is represented by formulas (3-1) to (3-6) described later, when X has a polymerizable functional group, the ring structure has the polymerizable functional group as a substituent. In some cases, a part of the ring structure is a polymerizable unsaturated hydrocarbon structure.

The silane compound is, for example, the following formula (2):

(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 one or two 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. “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 (2), 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 alternating Or the form which co-condenses at random, the form which the polysiloxane which consists of Si-Om _1, and the polysiloxane of Si-Om ₂ couple | bond are suitable, and a condensation structure is arbitrary.

The silane compound can be represented by the above average composition formula (1), but the siloxane skeleton (main chain skeleton in which a siloxane bond is essential) of the silane compound can also be represented as (SiO _m ) _n . The structure other than (SiO _m ) _n in such a silane compound 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 not containing an imide bond. Z, which are 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.
As the silane compound when n is 2, the structural unit (hereinafter also referred to as “structural unit (I)”) in which at least one organic skeleton (X) having an imide bond is bonded to a silicon atom is 2 And a form in which only one structural unit (I) is contained. Specifically, the following formula:

(Wherein A is Y or Z, and X, Y and Z are each the same as above) and the like, and a homopolymer form 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 of the structural units (I).

In the above average composition formula (1), X represents an organic skeleton containing an imide bond, and the compatibility with the aromatic amine compound is improved by having the imide bond. The proportion of the organic skeleton having such an imide bond is preferably 20 to 100 mol with respect to 100 mol of silicon atoms contained in the silane compound. More preferably, it is 50-100 mol, More preferably, it is 70-100 mol.

X in the average composition formula (1) is preferably a structural unit represented by the following formula (3). That is, in the silane compound of the present invention, X in the average composition formula (1) is 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 a structural unit represented by 0 or 1). By including such a silane compound, the heat resistance of the cured product is further improved.

In the structural unit represented by 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, but is 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 composed of 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.
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 (3-1) 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 (3-2). When R ¹ is a naphthylidene group, the structural unit is represented by the following formula (3-3), and R ¹ is 2 of norbornene. When it is a valent group, it is a structural unit represented by the following formula (3-4), and when R ¹ is a cyclohexenyl group, it is a structural unit represented by the following formula (3-5).
In addition, when the aromatic, heterocyclic ring and alicyclic ring have a substituent, the substituent includes a halogen atom, hydroxyl group, methyl group, ethyl 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.

In the above formulas (3-1) to (3-5), x, y and z are the same as in the above formula (3).
In formula (3-1), R ^{2 to} R ⁵ are the same or different and are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, and an aromatic group having 6 to 14 carbon atoms. It represents at least one structure. As the ^R 2 to R ^5, all are hydrogen atom forms are preferred.
In the above formula (3-2), R ^{6 to} R ⁹ and R ^{6 ′ to} R ^{9 ′} are the same or different and are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom, and 6 to 14 carbon atoms. It represents at least one structure selected from the group consisting of aromatics. 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 (3-3), R < ¹⁰ > -R < ¹⁵ > is the same or different, and is chosen from the group which consists of a hydrogen atom, a C1-C12 alkyl group, a halogen atom, and a C6-C14 aromatic. It represents at least one structure. As said R < ¹⁰ > -R < ¹⁵ >, the form whose all are hydrogen atoms or the form whose all are fluorine atoms is preferable. More preferred is a form in which all are hydrogen atoms.
In said formula (3-4), R < ¹⁶ > -R < ²¹ > is the same or different, and is chosen from the group which consists of a hydrogen atom, a C1-C12 alkyl group, a halogen atom, and a C6-C14 aromatic. It represents at least one structure. 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 ^{(3-5), R 22 ~R 25} , R 22' and ^{R 25 'are} the same or different, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom and having 6 to 14 carbon atoms It represents at least one structure selected from the group consisting of aromatics. 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 structural units represented by the above formula (3), the following formula (3-6):

(Wherein R ²⁶ represents a structural unit represented by at least one structure selected from the group consisting of aromatics having 6 to 14 carbon atoms, heterocyclic rings and alicyclic rings). . That is, the silane compound of the present invention preferably includes a silane compound in which X in the average composition formula (1) is a structural unit represented by the formula (3-6). Incidentally, ^{R 26} in the formula (3-6) in is preferably the same as ^{R 1} described in the above formula (3).

As a particularly preferred form of the silane compound, poly (γ-phthalimidopropylsilsesquioxane) in which R ²⁶ is a phenylene group; poly {γ- (hexahydro-4-methyl) in which R ²⁶ is a methylcyclohexylene group Phthalimido) propylsilsesquioxane}; poly {γ- (1,8-naphthalimido) propylsilsesquioxane} in which R ²⁶ is a naphthylidene group; poly {γ- (R ²⁶ is a norbornene divalent group) 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 (a) and (b) etc. are mentioned.
(A) An average composition formula X ′ _a Y _b Z _c SiO _d having an organic skeleton X ′ having an amide bond corresponding to the organic skeleton X including an imide bond in the silane compound and a siloxane bond (silane The manufacturing method including the process of imidating the intermediate body which consists of a compound.
(B) Hydrolysis / condensation of an intermediate composed of a silane compound in which an organic skeleton having an imide bond corresponding to the organic skeleton X including an imide bond in the silane compound is bonded to a silicon atom and has a hydrolyzable group The manufacturing method including the process to make.

The molecular weight of the silane compound is preferably, for example, a number average molecular weight of 100 to 10,000. If the polymer compound exceeds 10,000, there is a possibility that it cannot be sufficiently mixed with the aromatic amine compound. On the other hand, if it is less than 100, there is a risk that the thermal decomposition resistance or the like may not be sufficient. More preferably, it is 100-800, More preferably, it is 100-600. The weight average molecular weight is preferably 100 to 10,000. More preferably, it is 100-800, More preferably, it is 100-600.
The molecular weight (number average molecular weight and weight average molecular weight) of the silane compound can be determined, for example, by GPC (gel permeation chromatography) measurement under the measurement conditions described later.

As content of the said silane compound, it is suitable that it is 10-90 weight part with respect to 100 weight part of total amounts of an aromatic amine compound and a silane compound. If the silane compound is less than 10 parts by weight, there is a possibility that the effect of eliminating the melting point of the aromatic amine compound described later may not be sufficiently exhibited, and the softening point of the silane-containing composition is sufficiently reduced. You may not be able to. On the other hand, if it exceeds 90 parts by weight, the silane compound cannot be sufficiently dispersed in the aromatic amine compound, and the crosslinked structure of the cured product may not be sufficiently uniform, and the heat resistance may not be improved. There is. More preferably, it is 20-80 weight part, More preferably, it is 25-75 weight part.

The curable resin composition of the present invention may contain an epoxy resin, a silane compound represented by the average composition formula (1), a phenol resin, and an aromatic amine compound. It is preferable to add to the resin composition a form that is uniformly dispersed in the compound, and it is preferable that the form is not a simple mixture of a silane compound and an aromatic amine compound, but an integrated form. When a silane compound in a form uniformly dispersed in an aromatic amine compound is added to a composition containing an epoxy resin and a phenol resin, the cured product obtained from the resin composition has a higher glass transition temperature, and more It has excellent heat resistance.
It is preferable that the silane compound in a form uniformly dispersed in the aromatic amine compound is solid at room temperature (20 ° C.). When it is solid at room temperature, it is easy to handle and work, and is also advantageous for storage and transport.
In the present invention, a form in which a silane compound is uniformly dispersed in an aromatic amine compound is also referred to as a silane-containing composition.

In the case where the silane compound is uniformly dispersed in the aromatic amine compound, the heat softening temperature (also referred to as softening point) is preferably 100 ° C. or lower. When the softening point is 100 ° C. or lower, for example, even when the silane-containing composition is used as a curing agent for the epoxy resin, the crosslinking reaction of the epoxy resin proceeds at the melting temperature of the silane-containing composition and the epoxy resin. This is preferable because it is suppressed. The softening point is more preferably 98 ° C. or lower, and still more preferably 95 ° C. or lower.
The softening point (° C.) is a value measured according to JIS K7234 (1986), and can be measured using, for example, a thermal softening temperature measuring device (product name “ASP-MG4”, manufactured by Meitec).

In order to obtain the silane-containing composition, for example, it is preferable to perform a step of devolatilizing the solvent after dissolving the aromatic amine compound in a silane compound solution containing the silane compound and the solvent. Thereby, the silane compound is uniformly dispersed in the aromatic amine compound, and it becomes possible to suitably obtain a silane-containing composition in a form in which these are integrated, so that the effect derived from the silane-containing composition is sufficiently obtained. It can be demonstrated. Thus, the manufacturing method of the silane containing composition including the process of volatilizing a solvent after dissolving an aromatic amine compound in the silane compound solution containing a silane compound and a solvent is also one of this invention. In addition, when using for the use which may contain a volatile component, it does not need to pass through a desolvent process.

In the above production method, the solvent (organic solvent) constituting the silane compound solution is not particularly limited as long as it can dissolve or disperse the silane compound. For example, the solvent includes an ether bond, an ester bond, and a nitrogen atom. A solvent containing a compound having at least one structure selected from the group is preferred.

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. Among these compounds, one or more kinds can be used.

As the usage-amount of the said solvent, it is suitable that it is 5-70 mass% with respect to 100 mass% of total amounts of a silane compound and a solvent. More preferably, it is 10-60 mass%, More preferably, it is 10-50 mass%.

In the method for producing the silane-containing composition, the method for dissolving the aromatic amine compound in the silane compound solution and the method for devolatilizing the solvent are not particularly limited, and may be performed by a normal method. Moreover, you may have another process as needed.

As the aromatic amine compound in the silane-containing composition, when the above-described one having a melting point of 100 ° C. or higher is used, the aromatic amine compound has excellent characteristics derived from the aromatic amine compound and the silane compound. As the melting point disappears, the composition has a unique property that it can be softened at a temperature of 100 ° C. or lower. Therefore, for example, when a silane-containing composition is used as a curing agent for an epoxy resin, an inorganic filler is further blended, and a composition containing at least these three components is to be melt-mixed, the silane-containing composition and the epoxy resin The epoxy resin does not proceed with crosslinking (curing) reaction at the melting temperature, can be easily melt-mixed with good handling properties, and has extremely high mechanical strength and glass transition temperature due to the aromatic amine compound. A high cured product can be provided. Therefore, when such a silane-containing composition is used for a curable resin composition containing an epoxy resin, it is possible to suitably obtain a high-performance sealing material and the like that are extremely useful for electrical and electronic component applications.

The silane compound represented by the above average composition formula X _a Y _b Z _c SiO _d can be obtained by any method, but is preferably obtained by the following production methods (a) and (b). (A) An average composition formula X ′ _a Y _b Z _c SiO _d having an organic skeleton X ′ having an amide bond corresponding to the organic skeleton X including an imide bond in the silane compound and a siloxane bond (silane A production method comprising a step of imidizing an intermediate (comprising a compound). (B) Hydrolysis / condensation of an intermediate composed of a silane compound in which the organic skeleton having an imide bond corresponding to the organic skeleton X containing an imide bond in the silane compound is bonded to a silicon atom and has a hydrolyzable group The manufacturing method including the process to make.

<Phenolic resin>
The curable resin composition of the present invention uses a phenol resin and an aromatic amine compound as a curing agent. By using a phenol resin, the curing rate can be increased as compared with the case where only an aromatic amine compound is used as a curing agent, and the resulting cured product can be excellent in flexibility and mechanical strength.
The phenolic resin contained in the curable resin composition of the present invention is not particularly limited as long as it acts as a curing agent for epoxy resin, but phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, dicyclopentadiene phenol resin Various phenol resins such as phenol aralkyl resin and terpene phenol resin; various phenols such as polyhydric phenol resin obtained by condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, and glyoxal Resins and the like can be used.

It is preferable that content of the phenol resin in the curable resin composition of this invention is 10-100 mass% with respect to 100 mass% of epoxy resins in a curable resin composition. More preferably, it is 15-80 mass%, More preferably, it is 20-60 mass%.

The blending ratio of the aromatic amine compound and the phenol resin in the curable resin composition of the present invention is preferably 80/20 to 20/80 in terms of the functional group equivalent (molar equivalent) ratio of both. When the aromatic amine compound acting as a curing agent and the phenol resin are in such a ratio, the cured product obtained from the curable resin composition of the present invention has all of high heat resistance, flexibility, and mechanical strength. The characteristics will be more balanced. The mass ratio of the aromatic amine compound and the phenol resin is more preferably 70/30 to 30/70, and still more preferably 60/40 to 40/60.

<Epoxy resin>
In the curable resin composition of the present invention, the epoxy resin is not particularly limited as long as it is a resin containing one or more epoxy groups in the molecule, and examples thereof include the following compounds.
Epibis type glycidyl ether type epoxy resin obtained by condensation reaction of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) and epihalohydrin; and the epoxy resin with bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) Further, high molecular weight epibis type glycidyl ether type epoxy resin obtained by addition reaction; phenols (phenol, cresol, xylenol, naphthol, resorcin, catechol, bisphenol A, bisphenol F, suphenol S, etc.), formaldehyde, aceto Artehydride, propionaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, dicyclopentadiene, terpene, coumarin, par A novolak-aralkyl-type glycidyl ether-type epoxy resin obtained by condensation reaction of polyphenols obtained by condensation reaction with xylylene glycol dimethyl ether, dichloroparaxylylene, bishydroxymethylbiphenyl, etc., and epihalohydrin; tetra Aromatic crystalline epoxy resin obtained by condensation reaction of methylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, etc. with epihalohydrin; in addition to the aromatic crystalline epoxy resin, the above bisphenols, tetramethylbiphenol, tetra High molecular weight polymer of aromatic crystalline epoxy resin obtained by addition reaction of methyl bisphenol F, hydroquinone, naphthalene diol, etc .; Trisphenol type epoxy Resin;

The above bisphenols, alicyclic glycols with hydrogenated aromatic skeletons (tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalenediol, etc.) or mono / polysaccharides (ethylene glycol, diethylene glycol, triethylene glycol, tetra Ethylene glycol, PEG600, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, PPG, glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and multimers thereof, pentaerythritol and multimers thereof , Glucose, fructose, lactose, maltose, etc.) and an epihalohydrin A high molecular weight aliphatic glycidyl ether type epoxy resin obtained by further subjecting the aliphatic glycidyl ether type epoxy resin to an addition reaction with the above bisphenols; (3,4-epoxycyclohexane) methyl 3 ′, An epoxy resin having an epoxycyclohexane skeleton such as 4′-epoxycyclohexylcarboxylate; a glycidyl ester type epoxy resin obtained by a condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and the like with an epihalohydrin; hydantoin, A tertiary amine-containing glycidyl ether type epoxy resin solid at room temperature obtained by a condensation reaction of cyanuric acid, melamine, benzoguanamine and the like with epihalohydrin;

Among these epoxy resins, aliphatic glycidyl ether type epoxy resins are preferable. In order to further improve the curability, it is preferable to use a compound (polyfunctional epoxy compound) containing two or more epoxy groups in the molecule.
In the present specification, the glycidyl group is also included in the epoxy group.

The epoxy resin preferably has a weight average molecular weight of 200 to 20,000. When such an epoxy resin having a molecular weight is used, a cured product that is sufficiently cured can be obtained. More preferably, it is 220-18000, More preferably, it is 250-15000.
The weight average molecular weight of an epoxy resin can be calculated | required by GPC (gel permeation chromatography) measurement under the measurement conditions mentioned later, for example.

Moreover, it is suitable that the epoxy equivalent in the said curable resin composition is 100-450 g / mol. More preferably, it is 120-420 g / mol, More preferably, it is 150-400 g / mol.

It is preferable that content of the epoxy resin in the curable resin composition of this invention is 1-20 mass% with respect to 100 mass% of the whole curable resin composition. More preferably, it is 2-15 mass%, More preferably, it is 3-10 mass%.

<Compound having imide group>
The curable resin composition of the present invention preferably further contains a compound having an imide group. When the silane compound contained in the curable resin composition of the present invention has a polymerizable unsaturated carbon bond inside the molecule, the silane compound can form a crosslinked structure if it contains a compound having an imide group. Thereby, the hardened | cured material obtained from the resin composition of this invention can be made into a thing with higher heat resistance.

As the compound having an imide group, a maleimide compound is preferable.
Examples of the maleimide compound include bismaleimides such as N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N′-m-phenylene bismaleimide, and N, N′-p-phenylenebis. Maleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1,1,3,3,3-hexafluoro-2 , 2-bis [4- (4-maleimidophenoxy) phenyl] propane, N, N′-p, p′-diphenyldimethylsilyl bismaleimide, N, N′-4,4′-diphenyl ether bismaleimide, N, N '-Methylenebis (3-chloro-p-phenylene) bismaleimide, N, N'-4,4'-diphenylsulfone bismaleimide, N, N'- , 4′-dicyclohexylmethane bismaleimide, N, N′-dimethylenecyclohexane bismaleimide, N, N′-m-xylene bismaleimide, N, N′-4,4′-diphenylcyclohexane bismaleimide, N-phenylmaleimide A co-condensate of aldehyde compounds such as formaldehyde, acetaldehyde, benzaldehyde and hydroxyphenylaldehyde is preferred. In addition, the following general formula:

(Wherein R ²⁷ is

Or

Represents a divalent group. Q ¹ is a group directly connected to two aromatic rings, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, a sulfinyl group, a sulfonyl group, and an oxide. It represents at least one group selected from the group consisting of groups. The bismaleimide compound represented by) is preferred. Specifically, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,2- [4- (3-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl ] Butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (3-male Midofenokishi) phenyl] sulfoxide, bis [4- (3-maleimido phenoxy) phenyl] sulfone, bis [4- (3-maleimido phenoxy) phenyl] ether, the following general formula:

(Wherein Q ² represents a divalent group comprising an aromatic ring which may have a substituent. N represents the number of repetitions and is an average of 0 to 10). Etc. are suitable. Specifically, the Q ² is preferably a divalent group such as a phenyl group, a biphenyl group, or a naphthyl group (such as a phenylene group, a biphenylene group, or a naphthylidene group).

When the unsaturated imide compound of the present invention is a polymer compound, the weight average molecular weight of the unsaturated imide compound is preferably 200 to 5,000. When the molecular weight of the unsaturated imide compound is in such a range, a cured product having excellent heat resistance and the like can be obtained. More preferably, it is 220-4500, More preferably, it is 250-4000.
The weight average molecular weight of the unsaturated imide compound can be measured in the same manner as the weight average molecular weight of the epoxy resin.

When the curable resin composition of the present invention includes a compound having an imide group, the compounding ratio of the silane compound and the compound having an imide group is 10/90 to 90/10 in terms of the equivalent (molar equivalent) ratio of the unsaturated bonds of both. More preferably, it is 15 / 85-85 / 15, More preferably, it is 20 / 80-80 / 20.

<Inorganic filler>
The curable resin composition of the present invention preferably further contains an inorganic filler. It does not specifically limit as an inorganic filler, What is necessary is just to use what is used by the sealing material etc. of a normal mounting board | substrate. For example, a silica filler etc. are mentioned.

As a content rate of the inorganic filler in the said curable resin composition, it is suitable to set it as 50-95 mass% with respect to 100 mass% of total amounts of a curable resin composition. More preferably, it is 60-93 mass%, More preferably, it is 70-90 mass%. By using a large amount of the inorganic filler in this way, for example, when used for obtaining a sealing material for a mounting substrate, it is possible to sufficiently prevent the substrate from being warped after curing.
The curable resin composition of the present invention can be easily prepared with good handling properties even if it contains a large amount of an inorganic filler, and sufficiently exhibits the performance derived from an aromatic amine compound and an epoxy resin. It is something that can be done.

<Other ingredients>
The curable resin composition of the present invention may also contain additives other than the above-described components (also referred to as other components). For example, volatile components such as organic solvents and diluents, curing accelerators, stabilizers, mold release agents, coupling agents, colorants, plasticizers, plasticizers, various rubbers, photosensitizers, flame retardants, A pigment etc. are mentioned, These 1 type (s) or 2 or more types can be used.

It does not specifically limit as said volatile component, What is necessary is just to use what is normally used.
Here, the curable resin composition of the present invention is used in applications where it is desired not to contain volatile components as much as possible, that is, for example, mounting applications, optical applications, optical device applications, machine component applications, electrical / electronic component applications, automobile parts. In this case, the volatile component content in 100% by mass of the curable resin composition is preferably 10% by mass or less. More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less, Most preferably, it does not contain a volatile component substantially. “Substantially free of volatile components” means that the content of volatile components is less than the amount capable of dissolving the composition, for example, 1 mass in 100 mass% of the curable resin composition. % Or less is preferable. In addition, when used for an application that may contain a volatile component such as a printing ink application, the curable resin composition may contain a volatile component, and such a form is also suitable for the present invention. It is one of the embodiments.

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.

As a content rate of the other component in the said curable resin composition, it is suitable that the total amount is 20 mass% or less with respect to 100 mass% of total amounts of a curable resin composition. More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.

The method for producing the curable resin composition of the present invention is not particularly limited. For example, after obtaining a silane-containing composition by the above-described method for producing a silane-containing composition, an epoxy resin, a phenol resin, and optionally a compound having an imide group, an inorganic filler, and other components are added thereto. It can manufacture by adding and mixing. By using the silane-containing composition, the curable resin composition of the present invention has a unique property of the silane-containing composition (that is, the melting point of the aromatic amine compound disappears and can be softened at a temperature of 100 ° C. or lower. Property), the silane-containing composition, the epoxy resin, the compound having an imide group that is added as necessary, an inorganic filler, and other components. The mixing step can be easily performed without requiring a special machine. For example, the mixing step can be suitably carried out using any mixer that is usually used in heating and mixing, such as a kneader, a roll, a single screw extruder kneader, or a twin screw extruder kneader.

The curable resin composition of the present invention preferably has a viscosity at 175 ° C. of 5 to 100 Pa · s. When the curable resin composition has such an appropriate viscosity, for example, it becomes excellent in handling properties when sealing an electronic component package. More preferably, it is 10-90 Pa.s.
The viscosity of the curable resin composition can be measured at 175 ± 1 ° C. using, for example, a flow tester (manufactured by Shimadzu Corporation).

[Cured product]
The curable resin composition of this invention can be made into hardened | cured material by thermosetting, for example. The curing method is not particularly limited, and a normal thermosetting method may be adopted. For example, 70-250 degreeC is suitable for thermosetting temperature, More preferably, it is 100-250 degreeC. Moreover, 1-15 hours are suitable for hardening time, More preferably, it is 2-10 hours.
As for the shape of the said hardened | cured material, molded objects, such as a deformed product, a film, a sheet | seat, a pellet, etc. are mentioned, for example. Thus, the hardened | cured material (hardened | cured material formed from the curable resin composition of this invention) using the curable resin composition of this invention is also one of this invention.

The cured product preferably has a glass transition temperature of 230 ° C. or higher by a thermomechanical analyzer (TMA). Thereby, for example, it can be suitably used for an electronic packaging material such as a sealing material for a mounting board. More preferably, it is 240 degreeC or more, More preferably, it is 245 degreeC or more, Most preferably, it is 250 degreeC or more.

Since the cured product is obtained from the curable resin composition of the present invention, it has a remarkably high glass transition temperature and extremely excellent mechanical strength. It is useful for various applications such as an optical device application, a display device application, a machine component application, an electrical / electronic component application, an automobile component application, and a printing ink application. Specifically, it is preferably used for electronics mounting materials such as sealing materials, potting materials, underfill materials, conductive pastes, insulating pastes, die pond materials, printing inks and the like. Especially, it is more preferable to use for an electronic packaging material, and it is very useful especially for the sealing material of a mounting board | substrate. Thus, the sealing material characterized by using the said curable resin composition is also one of this invention. A semiconductor sealing material is particularly preferable as the sealing material. Moreover, the semiconductor device or printed wiring board comprised using the said hardened | cured material is also contained in the preferable form of this invention.

The sealing material is, for example, a member used when sealing a semiconductor component. For example, a curing accelerator, a stabilizer, and a mold release may be used as necessary within the range that does not impair the effects of the present invention. An agent, a coupling agent, a colorant, a plasticizer, a plasticizer, various rubbery materials, a photosensitizer, a filler, a flame retardant, a pigment, and the like can be included. Moreover, since the sealing material may cause problems when it contains a large amount of volatile components, it is desired that the sealing material does not contain volatile components. For example, the content of volatile components in 100% by mass of the sealing material is desired. The amount is preferably 10% by mass or less. More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less, Most preferably, it does not contain a volatile component substantially.

The curable resin composition of the present invention has the above-described configuration, and has high heat resistance that can be suitably used as a sealing material for semiconductor chips having high heat resistance such as SiC devices, and is also flexible and mechanical. That provides a cured product that is excellent in mechanical strength and sufficiently suppressed from occurrence of defects such as peeling and cracking of the sealing material, and can be suitably used as a sealing material for electronic components, semiconductor chips, etc. It is.

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. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

The weight average molecular weights of the silane compound and the epoxy resin were determined by GPC (gel permeation chromatography) measurement under the following measurement conditions.
Measuring instrument: HLC-8120GPC (trade name, manufactured by Tosoh Corporation)
Molecular weight column: TSK-GEL GMHXL-L and TSK-GELG5000HXL (both manufactured by Tosoh Corporation) are connected in series. Eluent: Tetrahydrofuran (THF)
Standard material for calibration curve: Polystyrene (manufactured by Tosoh Corporation)
Measurement method: The molecular weight was measured using a measurement sample dissolved in THF so that the solid content was about 0.2% by mass and filtered through a filter.

Synthesis Example 1 (Synthesis of poly {γ- (5-norbornene-2,3-imido) aminopropylsilsesquioxane})
Into a 300 mL four-necked flask equipped with a stirrer, temperature sensor, and cooling tube, 35.1 g of diglyme previously dried with molecular sieves and 30.8 g of 3-aminopropyltrimethoxysilane were added, and while flowing dry nitrogen, The temperature was raised to 100 ° C. to remove water in the system. Next, 28.2 g of 5-norbornene-2,3-dicarboxylic acid anhydride was added in four portions over 30 minutes while maintaining the reaction solution temperature 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.
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. The temperature reached 160 ° C. over 3 hours while collecting condensed water, and the temperature was kept at the same temperature for 2 hours and cooled to room temperature.
The reaction product is a dark brown high-viscosity liquid with a non-volatile content of 58.2% (this reaction product liquid is referred to as “silane compound solution”). The molecular weight measured by GPC was a number average molecular weight of 2340 and a weight average molecular weight of 2570. It was. ¹ H-NMR and ¹³ C-NMR are measured, and the silane compound (poly {γ- (5-norbornene-2,3-imido) aminopropylsilsesquioxane}) represented by the following chemical formula is contained. confirmed.

Examples 1-3
First, a composition in which an aromatic amine and a silane compound are uniformly dispersed by adding an aromatic amine curing agent to the above silane compound solution and depressurizing the solvent component by heating and stirring at 150 ° C. for 2 hours to remove the solvent component. Got. This and other resin composition raw materials shown in Table 1 were kneaded at 80 ° C. and compression molded at 175 ° C. for 6 minutes using a heating press molding machine. The obtained molded product was cured at 250 ° C. for 3 hours to obtain a cured product. About the obtained hardened | cured material, the three-point bending test was done for the glass transition temperature (Tg) by the TMA measurement using the Instron universal testing machine, and the elasticity modulus and the bending strength were measured. The results are shown in Table 1.
The values of the resin compositions of Examples 1 to 3 and Comparative Example 1 shown in Table 1 are all parts by weight.

Comparative Example 1
The resin composition raw materials shown in Table 1 were kneaded at 80 ° C., and compression molded at 175 ° C. for 6 minutes using a heating press molding machine. The obtained molded product was cured at 250 ° C. for 3 hours to obtain a cured product. About the obtained hardened | cured material, the glass transition temperature (Tg), the elasticity modulus, and the bending strength were measured by the method similar to Examples 1-3. The results are shown in Table 1.

The silica component described in Table 1 is fused silica. Each other component is as follows. The silane compound synthesized in Synthesis Example 1 was used.
Epoxy resin: Tris (hydroxyphenyl) methane type epoxy resin (EPPN-501HY, manufactured by Nippon Kayaku Co., Ltd.)
Phenol curing agent A: Phenol novolac curing agent (TD-2131, manufactured by DIC)
Phenol curing agent B: polyfunctional phenol curing agent (MEH-7500, manufactured by Meiwa Kasei Co., Ltd.)
Amine curing agent: 4,4′-diaminodiphenyl sulfone (Seika Cure S, Wakayama Seika Kogyo Co., Ltd.)
Imide component: Polyphenylmethane maleimide (BMI2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.)

From the results of Table 1, the cured products obtained from the resin compositions of Examples 1 to 3 using a phenol curing agent and an amine curing agent in combination have a high Tg and are flexible and strong while maintaining high heat resistance. It was confirmed to be a cured product. On the other hand, in Comparative Example 1 using only a phenol curing agent, it was confirmed that Tg was lower than Examples 1 to 3 and inferior in heat resistance.

Claims (4)

A curable resin composition containing an epoxy resin, a silane compound, and a curing agent,
The silane compound has a siloxane bond and has the following average composition formula (1):
_{X a Y b Z c SiO d} (1)
(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 is the same or different and 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. Are the same or different and represent an organic skeleton that does not contain an imide bond, a is a number of 0 or less than 3, b is a number of 0 or less than 3, c is a number of 0 or less than 3, and d is not 0 and less than 2. A + b + c + 2d = 4)),
The curing agent contains a phenol resin and an aromatic amine compound. The curable resin composition according to claim 1, wherein the aromatic amine compound is a compound having a melting point of 100 ° C. or higher. The curable resin composition according to claim 1, wherein the curable resin composition further contains an inorganic filler. A sealing material comprising the curable resin composition according to claim 1.