JP6227954B2 - Curable resin composition and use thereof - Google Patents

Description

The present invention relates to a curable resin composition and its use. More specifically, the present invention relates to a curable resin composition, a sealing material, and a semiconductor device that are useful in various industrial fields including electric, mechanical, and automobile fields.

The curable resin composition is a composition containing a resin having a property of being cured by light or heat, and development of a curable resin composition having physical properties required for each application is progressing in various industrial fields. One application of such a curable resin composition is a sealing material used for a substrate on which an electronic component, a semiconductor chip, or the like is mounted. Mounting methods for mounting electronic components, semiconductor chips, etc. on a substrate are often surface mounting methods because high-density mounting is possible, and in this case, sealing is performed with an electrically insulating sealing material. As such a sealing material, conventionally, a curable resin composition containing an epoxy resin as an organic main component has been widely used. However, when the cured product obtained from such a resin composition is left at a high temperature of, for example, 200 ° C. or more for a long time, the weight is remarkably reduced and the mechanical strength is also reduced. Improvement is demanded.

Furthermore, in sealing material applications, not only heat resistance but also adhesion (adhesion) with a base material such as a lead frame or a component such as wiring existing inside the semiconductor device is very important. If the adhesiveness is not sufficient, the sealing material peels off from the constituent members, and cracks may occur in the semiconductor device due to the peeling. Therefore, from the viewpoint of improving the reliability of the semiconductor device, the sealing material includes a sealing material from the constituent member even when the semiconductor device is used for a long period of time or repeatedly exposed to a high temperature environment in addition to heat resistance. It is required to have sufficient adhesiveness so as not to peel off.

Examples of the composition used for the sealing material include a resin paste composition containing an epoxy resin, a curing agent, a filler, and a benzotriazole compound (see Patent Document 1); an epoxy resin, a phenol resin, a curing accelerator, An epoxy resin composition for semiconductor encapsulation containing an inorganic filler and 2-amino-4,6-dimercapto-s-triazine (see Patent Document 2); an epoxy resin, a phenol resin, a curing accelerator, an inorganic filler, and 2- Epoxy resin composition for semiconductor encapsulation containing mercaptopyrimidine as an essential component (see Patent Document 3); semiconductor lead frame surface-treated with a surface treatment agent containing a triazole compound and a solvent (see Patent Document 4); epoxy resin Semiconductor encapsulant containing mixture, phenolic resin mixture, inorganic filler and benzotriazole derivative Use resin composition (Patent Document 5 references) it has been disclosed.

On the other hand, as a curable resin composition capable of giving a cured product having excellent heat resistance, a silane compound having a structural unit in which at least one organic skeleton having an imide bond is bonded to a silicon atom forming a siloxane bond, and an organic resin Has been developed (see Patent Document 6). This curable resin composition is excellent in various physical properties such as heat resistance, and can provide a cured product having a low decrease in various physical properties even under harsh environments such as high temperature and high pressure and high humidity. It is a curable resin composition.

JP-A-11-92740 JP 2005-132888 A JP 2005-154485 A JP 2006-80324 A JP 2010-65160 A Special table 2010-518182

As described above, a curable resin composition containing an epoxy resin as an organic main component has been widely used as a sealing material. However, since the heat resistance is not sufficient, it is represented by Patent Document 6. Various techniques for imparting or improving heat resistance are being studied. However, in order to make it more suitable for the sealing material application, not only heat resistance but also components constituting the base material and wiring inside the semiconductor device, especially metals constituting the lead frame and wiring (especially copper and nickel) In addition, there was room for improvement to obtain a cured product having excellent adhesion with the alloy. Moreover, the hardened | cured material which was further excellent by heat resistance and adhesiveness with a metal was not able to be obtained also by the technique of patent documents 1-5.

The present inventors have developed a plurality of reactive functionalities such as 3,5-diamino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, and benzotriazole-4-carboxylic acid. As a result of intensive studies focusing on nitrogen-containing cyclic compounds having a group and a ring nitrogen atom, it has been found that this problem can be solved. However, when these nitrogen-containing cyclic compounds are used as a sealing material, the viscosity of the curable resin composition rises rapidly at the molding temperature, which shortens the pot life and poses a serious practical problem. there were.

The present invention has been made in view of the above situation, and can provide a cured product having sufficient heat resistance and excellent adhesion to metals (especially copper, nickel and alloys thereof), It aims at providing the curable resin composition which can show sufficient pot life. Another object of the present invention is to provide a sealing material and a semiconductor device using such a curable resin composition.

As a result of various studies on materials that can be preferably applied to sealing material applications and the like, the present inventors have found that a curable resin composition to which a nitrogen-containing cyclic compound having a plurality of reactive functional groups and a ring nitrogen atom is added as described above. Focused on the fact that it can give a cured product with excellent heat resistance and adhesion to metals (especially copper, nickel and its alloys), while reducing the pot life during molding. . Therefore, when an aromatic amide compound having an amide bond and an aromatic ring containing a hydroxyl group is used in place of the nitrogen-containing cyclic compound, the adhesiveness to a plurality of metals and the pot life in molding can be improved in the cured product. I found out that I can do it, and I found it useful as a material for sealing materials. And if it was set as the curable resin composition containing an epoxy resin, a hardening | curing agent, and the aromatic amide compound of this invention, it discovered that it could give the hardened | cured material which is very high intensity | strength and excellent in the adhesiveness and heat resistance with respect to copper. It was. Further, the curable resin composition was found to give a cured product having excellent adhesion to nickel, and the curable resin composition was found to be particularly suitable for sealing material applications. Furthermore, a semiconductor device using the same is extremely useful for applications such as electric / electronic parts, automobile parts, mechanical parts, etc., which are strongly required to have no deterioration in physical properties even under harsh environments such as high temperature and pressure and high humidity. As a result, the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly.

That is, the present invention is a curable resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an aromatic amide compound, wherein the aromatic amide compound includes an aromatic ring containing a hydroxyl group, It is a curable resin composition which is a compound having an amide bond.
The present invention is also a sealing material using the curable resin composition.
The present invention is also a semiconductor device using the sealing material.
The present invention is described in detail below. In addition, what combined 2 or 3 or more of the preferable form of this invention described in a paragraph in the following is also a preferable form of this invention.

[Curable resin composition]
The curable resin composition of the present invention includes (A) an epoxy resin, (B) a curing agent, and (C) an aromatic amide compound, and each of these components may be used alone or in combination of two or more. it can. Moreover, as long as these are essential, (D) silane compound, (E) maleimide compound, and (F) other components can also be included suitably.
In the present specification, (A) epoxy resin, (B) curing agent, (D) silane compound and (E) maleimide compound are also referred to as “curable resin component”.

(A) Epoxy resin As the epoxy resin, one or two or more of those that are compatible with a curing agent and an aromatic amide compound described later can be used as appropriate. In the present specification, the glycidyl group is also included in the epoxy group.

The epoxy resin is not particularly limited as long as it is a compound containing one or more epoxy groups in the molecule, and can be obtained, for example, by a condensation reaction of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) and epihalohydrin. Epibis type glycidyl ether type epoxy resin; high molecular weight epibis type glycidyl ether type epoxy resin obtained by further reacting the epoxy resin with bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); phenols ( Phenol, cresol, xylenol, naphthol, resorcin, catechol, bisphenol A, bisphenol F, sphenol S, etc.), formaldehyde, acetoaldehyde, propionaldehyde, benzalde Polyhydric phenols obtained by condensation reaction of benzene, hydroxybenzaldehyde, salicylaldehyde, dicyclopentadiene, terpene, coumarin, paraxylylene glycol dimethyl ether, dichloroparaxylylene, bishydroxymethylbiphenyl, etc., and further condensed with epihalohydrin Novolac aralkyl type glycidyl ether type epoxy resin obtained by reaction; aromatic crystalline epoxy resin obtained by condensation reaction of tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol and the like with epihalohydrin; the aromatic crystal In addition to the above-mentioned bisphenols, tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalenediol High molecular weight aromatic crystalline epoxy resin obtained by addition reaction of bisphenols; Trisphenol type epoxy resins; Aliphatic glycols obtained by hydrogenating the above bisphenols and aromatic skeletons (tetramethylbiphenol, tetramethylbisphenol F) , Hydroquinone, naphthalene diol, etc.) or mono / polysaccharide (ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, PEG600, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, PPG, Glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and its multimer, pentaerythritol and its multimer, (Lucose, fructose, lactose, maltose, etc.) and an epihalohydrin condensation reaction with an aliphatic glycidyl ether type epoxy resin; an aliphatic glycidyl ether type epoxy resin further obtained by addition reaction with the above bisphenols Molecular weight aliphatic glycidyl ether type epoxy resin; (3,4-epoxycyclohexane) epoxy resin having an epoxycyclohexane skeleton such as methyl 3 ′, 4′-epoxycyclohexyl carboxylate; tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid Glycidyl ester type epoxy resin obtained by condensation reaction of acid etc. with epihalohydrin; obtained by condensation reaction of epidanhydrin with hydantoin, cyanuric acid, melamine, benzoguanamine etc. Tertiary amine-containing glycidyl ether type epoxy resin of a solid can be mentioned temperature.

Among these epoxy resins, it is preferable to use at least an epoxy resin having an aromatic moiety. 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.

The epoxy resin preferably has an epoxy equivalent of 70 to 500 g / mol. More preferably, it is 80-450 g / mol, More preferably, it is 90-400 g / mol.

The epoxy resin preferably has a weight average molecular weight of 150 to 20000. When an epoxy resin having such a molecular weight is used, a cured product having a good viscosity at the time of molding of the curable resin composition and not filled at the time of molding can be obtained. More preferably, it is 180-15000, More preferably, it is 200-10000.
The weight average molecular weight of an epoxy resin can be calculated | required by GPC measurement under the GPC measurement conditions mentioned later, for example.

The content of the epoxy resin is preferably 1 to 99 parts by weight with respect to 100 parts by weight of the total curable resin component contained in the curable resin composition. More preferably, it is 10-80 weight part, More preferably, it is 30-70 weight part.

(B) Curing agent The curing agent is not particularly limited, and one or more commonly used ones may be used. For example, acid anhydrides, polyhydric phenols, amines, BF ₃ complexes, sulfonium salts, imidazoles and the like can be mentioned. Among them, it is preferable to use acid anhydrides, polyhydric phenols and / or amines. Thereby, the curable resin composition is more fully cured, and it becomes possible to give a cured product that is more excellent in various physical properties such as heat resistance.

Examples of the acid anhydrides include succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, dodecyl succinic anhydride, dodecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. , Methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrabromophthalic anhydride, trialkyltetrahydrophthalic anhydride, 2,4-diethyl glutaric anhydride, hymic anhydride (5-norbornene-2,3-dicarboxylic anhydride Product), methyl hymic acid anhydride, methyl nadic acid anhydride (methyl-5-norbornene-2,3-dicarboxylic acid anhydride), chlorendic acid anhydride, diphenic acid anhydride, 3,4-dimethyl-6- (2-Methyl-1-propenyl) -1,2,3,6-tetrahydride Monofunctional acid anhydrides such as phthalic anhydride, 1-isopropyl-4-methyl-bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride; pyromellitic dianhydride, Maleated alloocimene, benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetrabisbenzophenone tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimate), methylcyclohexene tetracarboxylic dianhydride , Biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-Dicarboxyphenyl) methane dianhydride, 2,2-bis (3 Bifunctional acid anhydrides such as 4-dicarboxyphenyl) propane dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride; and acid anhydrides having a free acid such as γ-aconitic anhydride, glycolic anhydride, trimellitic anhydride, polyazeline acid anhydride, and the like.

Examples of the polyhydric phenols include phenol novolac resin, cresol novolac resin, triphenolmethane type phenol resin, terpene modified phenol resin, bisphenol A novolac resin, dicyclopentadiene phenol resin, phenylene skeleton, biphenylene skeleton or naphthylene skeleton. And phenol aralkyl resins having a phenylene skeleton or a biphenylene skeleton, bisphenol compounds, and the like. In addition, from the viewpoint of curability, the hydroxyl equivalent of the polyhydric phenols is preferably 90 to 500 g / eq, for example.

The polyhydric phenols are preferably compounds having an aralkyl group containing a phenylene skeleton, biphenylene skeleton or naphthylene skeleton in the structure. A cured product obtained by using such a compound has a low phenolic hydroxyl group, and therefore can achieve low water absorption, and therefore can further improve solder reflow resistance. In addition, since a compound containing a naphthylene skeleton has a high glass transition temperature and a low coefficient of linear expansion, for example, when the cured product is applied to a semiconductor device, it exhibits a sufficiently low warpage. It becomes possible.

The polyhydric phenols are more preferably the following general formula (1):

(In the formula, R ¹ represents a phenylene group, a biphenylene group, or a naphthylene group. —R ² (OH) — represents a hydroxyphenylene group, a 1-hydroxynaphthylene group, or a 2-hydroxynaphthylene group. R ³ And R ⁴ are groups introduced into R ¹ and R ² , respectively, and are the same or different and each represent a hydrocarbon group having 1 to 10 carbon atoms, and the average value of p is a number of 1 to 10 , Q is an integer of 0 to 5, and r is an integer of 0 to 5). Such a compound is preferably 10% by mass or more with respect to 100% by mass of the total amount of the polyhydric phenols, and thereby can further exhibit solder reflow resistance and low warpage. More preferably, it is 30 mass% or more, More preferably, it is 50 mass% or more. Incidentally, -R 2 ^(OH) - in the case of hydroxy naphthylene group, as described above, by reduction of the increase and the linear expansion coefficient of the glass transition temperature, the effect of improving the low warping property is obtained, further Since it has a large amount of aromatic carbon, it is possible to improve the flame resistance.

As said amine, what has 1 or 2 or more of primary amines or secondary amines in a molecule | numerator is preferable, for example, diethylenetriamine, trielalentetraamine, tetraethylenepentamine, trimethylhexamethylenediamine, 2- Aliphatic amines such as methylpentamethylenediamine; cycloaliphatic amines such as isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane; N-amino Piperazine-type amines such as ethylpiperazine and 1,4-bis (2-amino-2-methylpropyl) piperazine; m-xylenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, 4,4′-diaminodiphenyl Sulfone, diethyltoluenediamine, trimethylenebis (4-aminobenzoate), polytetramethylene oxide-di-p-aminobenzoate, 3,3′-diethyl-4,4′-diaminophenylmethane, 3,3 ′, 5 , 5'-tetramethyl-4,4'-diaminophenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminophenylmethane, 2,4-diaminotoluene, diaminobenzene, methylenedianiline , Aromatics such as bis (chloroanilino) methane, oxydianiline, bis (hydroxyanilino) methane, bis [(aminophenoxy) phenyl] sulfone, bis (aminophenoxy) benzene, bis (aminophenoxy) biphenyl, dimethyldiaminobiphenyl Amine; and the like. Among these amines, aromatic amines are preferable from the viewpoint of increasing the strength of the cured product and the glass transition temperature.

As a content rate of the said hardening | curing agent, it is suitable to set it as 1-99 weight part with respect to 100 weight part of all the curable resin components contained in curable resin composition. More preferably, it is 10-80 weight part, More preferably, it is 20-70 weight part.

(C) Aromatic amide compound The aromatic amide compound is a compound having an aromatic ring containing a hydroxyl group and an amide bond. The aromatic ring containing a hydroxyl group is preferably a structure in which a hydroxyl group is bonded to an aromatic ring, that is, a phenol skeleton. That is, the aromatic amide compound is preferably a compound having at least one phenol skeleton and one amide bond in one molecule. By including an aromatic amide compound having such a structure, the curable resin composition of the present invention exhibits a sufficient pot life, and the cured product is against metal (especially copper, nickel or an alloy thereof), etc. It is possible to exhibit excellent adhesion.

The aromatic amide compound is preferably the following general formula (2):

(Wherein R ⁵ represents at least one structure selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom, a nitrogen atom, a heterocyclic ring and an aromatic ring), and a compound having a salicylamide structure represented by It is. It is preferable to have one or more such salicylamide structures in the molecule. Thus, a form in which the aromatic amide compound is a compound having a salicylamide structure represented by the general formula (2) is also a preferred form of the present invention.

In the general formula (2), R ⁵ represents at least one structure selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom, a nitrogen atom, a heterocyclic ring and an aromatic ring.
As said alkyl group, a C1-C30 alkyl group is preferable and may have a substituent.
The heterocycle preferably has a structure having a nitrogen atom, a sulfur atom, or an oxygen atom as a hetero atom. More preferred is a structure having a nitrogen atom as a hetero atom. Moreover, although it is preferable that it is a 3-10 membered ring, a 4-6 membered ring structure is more preferable.
Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring.
Note that R ⁵ is also preferably a structure containing a heterocyclic ring and an aromatic ring.

R ⁵ in the general formula (2) also preferably contains a plurality of ring nitrogen atoms. That is, the aromatic amide compound is preferably a compound having two or more ring nitrogen atoms in one molecule. As a result, the adhesion of a cured product formed using the curable resin composition to a metal (particularly copper, nickel, or an alloy thereof) or the like becomes stronger and the heat resistance is also improved. Thus, the form in which R ⁵ in the above general formula (2) contains a plurality of ring nitrogen atoms is also a preferred form of the present invention.

When R ⁵ in the general formula (2) includes a plurality of ring nitrogen atoms, examples of the aromatic amide compound include ring nitrogen such as a triazole skeleton, a triazine skeleton, a benzotriazole skeleton, a thiazole skeleton, and an imidazole skeleton. A compound having one or more skeletons is preferable. Among these ring nitrogen-containing skeletons, from the viewpoint that the change over time of various physical properties is sufficiently small even after the cured product is exposed to a high temperature environment, and excellent physical properties such as adhesion can be stably expressed. A skeleton, a triazine skeleton, and / or a benzotriazole skeleton are preferable. As a result, it has excellent adhesion to metals and heat resistance, and gives a cured product that stably exhibits excellent physical properties such as adhesiveness with sufficiently small changes in various physical properties even after being exposed to a high temperature environment. This makes it possible to further exhibit the effect of the present invention. More preferably, it is a triazole skeleton. As the aromatic amide compound having a triazole skeleton, N- (2H-1,2,4-triazol-5-yl) salicylamide is particularly suitable.

The molecular weight of the aromatic amide compound is preferably 100 to 1000, for example. If the polymer compound exceeds 1000, the viscosity of the curable resin composition may be very high. 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.

For example, the aromatic amide compound is preferably 0.001 to 30 parts by weight with respect to 100 parts by weight of the total curable resin component contained in the curable resin composition. More preferably, it is 0.01-20 weight part, More preferably, it is 0.1-10 weight part.

(D) Silane Compound The curable resin composition of the present invention preferably further comprises (D) a silane compound. Thereby, it becomes possible to give the hardened | cured material excellent in mechanical strength, heat resistance, and an insulation characteristic. Thus, the form in which the curable resin composition further contains (D) a silane compound is also a preferred form of the present invention.

The silane compound has a siloxane bond (Si—O—Si bond) and has the following average composition formula (I):
_{X a Y b Z c SiO d} (I)
(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. And a number represented by a + b + c + 2d = 4) is preferable. By including such a silane compound, it becomes possible to give a cured product that is superior in heat resistance, pressure resistance, mechanical and chemical stability. Moreover, the hardened | cured material by which various physical-property fall was suppressed more can be formed also in severe environments, such as high temperature high pressure, and it can use it 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. That is, the silane compound preferably contains silsesquioxane.
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 (I): X _a Y _b Z _c SiO _d , preferred forms of X are as described later, and as Y, a hydroxyl group or an OR group is preferred. R is an alkyl group, and an alkyl group having 1 to 8 carbon atoms is particularly 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. Further, a is a number 0 ≦ a <3, b is a number 0 ≦ b <3, c is a number less than 0 ≦ c <3, and d is 0 <d <2. Is the number of

The silane compound is, for example, the following formula (3):

(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 (3), 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 (I), 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 in the case where n is 2, the structural unit (hereinafter also referred to as “structural unit (1)”) 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 of the structural unit (1) is included. 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 (1), There are a homopolymer form containing two different structural units (1) and a copolymer form (cocondensed structure form) containing only one of the structural units (1).

X in the average composition formula (I) is preferably a structural unit represented by the following formula (4). That is, in the silane compound of the present invention, X in the average composition formula (I) is represented by the following formula (4):

(Wherein R ⁶ 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 (4), 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.

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

In the above formulas (4-1) to (4-5), x, y and z are the same as in the above formula (4).
In said formula (4-1), R < ⁷ > -R < ¹⁰ > 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 < ⁷ > -R < ¹⁰ >, the form whose all are hydrogen atoms is preferable.

In the formula (4-2), R ^{11 to} R ¹⁴ and R ^{11 ′} to R ^{14 ′} 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 11 ^{to R 14} and ^R 11' ^{to R 14',} forms all ^{R 12} or ^{R 13} are the remaining methyl group is a hydrogen atom, ^or, R 11 ^{to R 14} and ^R 11' ^{to R 14 'all} are hydrogen atom form ^or embodiment R 11 ^{to R 14} and ^R 11' ^{to R 14'} all are a fluorine atom is preferable. More preferably, R ¹² or R ¹³ is a methyl group and the rest are all hydrogen atoms.

In the above formula (4-3), R ^{15 to} R ²⁰ 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. As said R < ¹⁵ > -R < ²⁰ >, 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 the above formula (4-4), R ^{21 to} R ²⁶ 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. As said R < ²¹ > -R < ²⁶ >, the form in which all are a hydrogen atom, the form that 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 ^{(4-5), R 27 ~R 30} , R 27' and ^{R 30'} are the same or different, a hydrogen atom, an alkyl group, at least one selected from the group consisting of halogen atoms and the aromatic Represents the structure. As the ^R 27 ^{to R 30, R 27 'and R 30',} it 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 (4), the following formula (4-6):

(Wherein R ³¹ represents a structural unit represented by at least one structure selected from the group consisting of aromatic, heterocyclic 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 (I) is a structural unit represented by the formula (4-6). R ³¹ in the above formula (4-6) is preferably the same as R ⁶ described in the above formula (4).

Particularly preferable forms of the silane compound include poly (γ-phthalimidopropylsilsesquioxane) in which R ³¹ is a phenylene group; poly {γ- (hexahydro-4-methyl) in which R ³¹ is a methylcyclohexylene group. Phthalimido) propylsilsesquioxane}; poly {γ- (1,8-naphthalimido) propylsilsesquioxane} in which R ³¹ is a naphthylidene group; poly {γ- (R ³¹ is a norbornene divalent group) 5-norbornene-2,3-imido) propylsilsesquioxane}; poly [(cis-4-cyclohexene-1,2-imido) propylsilsesquioxane] in which R ³¹ 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 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) 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 epoxy resin or the curing agent. On the other hand, if it is less than 100, there is a risk that the thermal decomposition resistance and the like may not be sufficient. More preferably, it is 500-5000, More preferably, it is 1000-5000. The weight average molecular weight is preferably 100 to 10,000. More preferably, it is 500-5000, More preferably, it is 1000-5000. 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 following measurement conditions.

<GPC measurement conditions for molecular weight>
Measuring instrument: “HLC-8220GPC” manufactured by Tosoh Corporation
Column: “Asahipak GF-7M HQ” x 2 manufactured by Showa Denko KK Eluent: N, N-dimethylformamide
Flow rate: 0.6 mL / min Temperature: 40 ° C
Calibration curve: Prepared using polystyrene standard sample (manufactured by Tosoh Corporation).

As content of the said silane compound (solid content), it is suitable that it is 1-50 weight part with respect to 100 weight part of all the curable resin components contained in curable resin composition. If the silane compound is less than 1 part by weight, the mechanical strength, heat resistance, and insulation properties may not be sufficient, and if it exceeds 50 parts by weight, the viscosity of the resin composition is extremely high. May be high. More preferably, it is 2-30 weight part, More preferably, it is 3-20 weight part.

(E) Maleimide compound The curable resin composition of the present invention preferably further comprises (E) a maleimide compound. Thereby, it becomes possible to give the hardened | cured material excellent in heat resistance. Thus, the form in which the curable resin composition further contains (E) a maleimide compound is also a preferred form of the present invention.

As said maleimide compound, the compound which has a some maleimide group in a molecule | numerator from a viewpoint of raising reactivity more is preferable. Specifically, bismaleimide compounds (also referred to as bismaleimide resins) are exemplified. The bismaleimide compound (bismaleimide resin) is not particularly limited as long as it is a compound having two or more maleimide groups in the molecule, and one kind or two or more kinds can be used.

Examples of the bismaleimide compound include 4,4′-diphenylmethane bismaleimide, N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N′-m-phenylene bismaleimide, N, N′-p-phenylenebismaleimide, 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′-diphenyldimethylsilylbismaleimide, N, N′-4,4′- Diphenyl ether bismaleimide, N, N′-methylenebis (3-chloro-p-phenylene) bismaleimide, N, N′-4,4 ′ Diphenylsulfone bismaleimide, N, N′-4,4′-dicyclohexylmethane bismaleimide, N, N′-dimethylenecyclohexane bismaleimide, N, N′-m-xylene bismaleimide, N, N′-4,4 Examples include '-diphenylcyclohexane bismaleimide and N-phenylmaleimide.

The bismaleimide compound also has the following general formula (5):

(Wherein R ³² represents the following formula:

The bivalent group represented by these is represented. 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 this may be sufficient.

Specific examples of the bismaleimide compound represented by the general formula (5) include 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-hexafluoro Propane, 4,4-bis (3-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (3-male Imidophenoxy) phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, General formula (6):

(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, 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).

As a content rate of the said maleimide compound, it is suitable to set it as 1-25 weight part with respect to 100 weight part of all the curable resin components contained in curable resin composition. More preferably, it is 2-15 weight part, More preferably, it is 3-10 weight part.

(F) Other components The curable resin composition is also added as necessary (D) as described above (A) epoxy resin, (B) curing agent, (C) aromatic amide compound (D ) Other components other than the silane compound and (E) maleimide compound may be contained. Examples include curing accelerators; inorganic fillers; volatile components such as organic solvents and diluents; flame retardants; coupling agents; mold release agents; colorants and the like, and one or more of these may be used. it can.

Examples of the curing accelerator include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-phenylimidazole, and 1-benzyl-2-methylimidazole; Tertiary amine compounds such as triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, 1,8-diazabicyclo [5.4.0] undecene-7; triphenylphosphine, tributylphosphine, tri (p-methylphenyl) Phosphine, tri (nonylphenyl) phosphine, triphenylphosphine / triphenylborate, tetraphenylphosphine / tetraphenylborate, tributylhexadecylphosphonium bromide, tris (dimethoxyphenyl) phosphine In addition to organometallic compounds such as aluminum and zirconium; heterocycle-type amine compounds, boron complex compounds, organic ammonium salts, organic sulfonium salts, organic peroxides, and reactants thereof. These 1 type (s) or 2 or more types can be used.
The content of the curing accelerator is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total curable resin component contained in the curable resin composition, for example. More preferably, it is 0.05-5 weight part, More preferably, it is 0.1-3 weight part.

It does not specifically limit as said inorganic filler, What is necessary is just to use what is used by the sealing material etc. of a normal mounting substrate etc. 1 type, or 2 or more types. For example, fused silica, crystalline silica, fine silica, alumina, silicon nitride, magnesia and the like can be mentioned.
It is suitable for the content rate of the said inorganic filler to be 200-550 weight part with respect to 100 weight part of all the curable resin components contained in curable resin composition, for example. More preferably, it is 250-520 weight part, More preferably, it is 300-500 weight part. 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.

It does not specifically limit as said volatile component, What is necessary is just to use what is used normally 1 type, or 2 or more types. For example, the solvent etc. which contain the compound which has at least 1 or more structure chosen from the group which consists of an ether bond, an ester bond, and a nitrogen atom mentioned above are mentioned.
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.

Although it does not specifically limit as said flame retardant, What is necessary is just to use what is used normally by 1 type, or 2 or more types, A non-halogen compound and a non-antimony compound are suitable. For example, phosphorus-containing compounds such as phosphate ester, triphenylphosphine oxide, red phosphorus; nitrogen-containing compounds such as melamine, melamine derivatives, melamine-modified phenol resins, cyanuric acid derivatives, isocyanuric acid derivatives, triazine ring-containing compounds; cyclophosphazenes, etc. Phosphorus compounds and nitrogen-containing compounds; zinc compounds such as zinc oxide, zinc borate, molybdenum zinc and zinc stannate; metal oxides such as iron oxide and molybdenum oxide; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; And metal complex compounds such as dicyclopentadienyl iron.
The content ratio of the flame retardant is preferably 1 to 80 parts by weight with respect to 100 parts by weight of the total curable resin component contained in the curable resin composition, for example. More preferably, it is 2 to 40 parts by weight.

The coupling agent is not particularly limited, and one or more commonly used ones may be used. For example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ- (methacryloxypropyl) trimethoxysilane, etc. A silane coupling agent etc. are mentioned.
It is suitable for the content rate of the said coupling agent to be 0.1-10 weight part with respect to 100 weight part of all the curable resin components contained in curable resin composition, for example. More preferably, it is 1 to 5 parts by weight.

It does not specifically limit as said mold release agent, What is necessary is just to use what is used normally 1 type, or 2 or more types. Examples thereof include lauric acid, lauric acid Na, carnauba wax, and oxidized polyethylene.
The content of the release agent is preferably 5 to 20 parts by weight with respect to 100 parts by weight of the total curable resin component contained in the curable resin composition, for example. More preferably, it is 2 to 10 parts by weight.

It does not specifically limit as said coloring agent, What is necessary is just to use what is used normally 1 type, or 2 or more types. Examples thereof include carbon black, pigments, dyes, and compounds obtained by dispersing them in a resin.
The content ratio of the colorant is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total curable resin component contained in the curable resin composition, for example. More preferably, it is 0.5 to 3 parts by weight.

[Method for producing curable resin composition]
The preparation method of the curable resin composition of the present invention is not particularly limited as long as it contains (A) an epoxy resin, (B) a curing agent, and (C) an aromatic amide compound. It can be obtained by mixing. For example, after adding a curing agent and an aromatic amide compound to an epoxy resin to obtain a curable resin composition, other components blended as necessary are added simultaneously or sequentially, and each component is added using a mixer or the like. After mixing so as to be uniformly dispersed, it can be obtained by kneading using a kneader, a roll, a single screw extruder kneader, a twin screw extruder kneader, a planetary mixer or the like. In the mixing and kneading step, heating or cooling may be performed as necessary.

When the curable resin composition is cast at a low temperature, the state before curing is preferably in a liquid state at a low temperature (60 ° C.). Specifically, it is preferable that the crystal is not precipitated and is not a highly viscous fluid. Thereby, processing and shaping become easier, and the liquid sealing material is more suitable for use. Moreover, such a state may be confirmed visually, but it can also be determined by viscosity. Specifically, the viscosity at 60 ° C. is preferably 100 Pa · s or less, more preferably 80 Pa · s or less, and still more preferably 60 Pa · s or less. Moreover, it is suitable that it is 0.01 Pa.s or more.
The viscosity of the curable resin composition is, for example, using a dynamic viscoelasticity measuring apparatus (AERS-3, manufactured by TA Instruments), and measuring conditions [plate-plate measurement, sample thickness: 1 mm, frequency: 1 Hz, strain: 0.5%].

When the curable resin composition is cast at a high temperature, the viscosity at 175 ° C. is preferably 5 to 100 Pa · s. If the curable resin composition has such an appropriate viscosity, for example, it becomes excellent in handling properties when applied. More preferably, it is 10-90 Pa.s.
The 175 ° C. viscosity of the curable resin composition is measured using, for example, a flow tester (CFT-500D, manufactured by Shimadzu Corporation), and the measurement conditions are [die hole diameter 0.5 mm, die length 1 mm, cylinder pressure 0.98 MPa]. Can be obtained as

[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 hardening temperature, More preferably, it is 80-230 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.

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 the preferable forms of this invention.

The cured product preferably has a glass transition temperature of 180 ° 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 220 degreeC or more, More preferably, it is 230 degreeC or more.

The cured product is obtained from the curable resin composition of the present invention, and thus has a high glass transition temperature, excellent mechanical strength and adhesion to metal, and is used under severe environments such as high temperature and pressure and high humidity. Even after being exposed to the surface, the change over time of various physical properties is sufficiently small, and excellent physical properties such as adhesiveness can be expressed stably. For example, mounting applications, optical applications, optical device applications, display device applications, machine parts It is useful for various applications such as applications, electrical / electronic component applications, automotive component applications, and printing ink applications. 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 using the said curable resin composition is also one of this invention, and it is suitable that the said curable resin composition is a composition for sealing materials. 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. A semiconductor device using the sealing material is also one aspect of the present invention.

The sealing material is a member used when, for example, semiconductor components (elements) are sealed, but, for example, a curing accelerator and a stabilizer as needed within a range not impairing the effects of the present invention. , Release agents, coupling agents, colorants, plasticizers, plasticizers, various rubbery materials, photosensitizers, fillers, flame retardants, pigments, and the like. 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.

Specifically, as a semiconductor device using the sealing material, for example, a lead frame, a wired tape carrier, a wiring board, glass, a support member such as a silicon wafer, a semiconductor chip, a transistor, a diode, a thyristor, etc. Examples include an active element; a passive element such as a capacitor, a resistor, and a coil; and a necessary part is sealed with the curable resin composition of the present invention. As a method for sealing the element with the curable resin composition, a normal method such as a low-pressure transfer molding method, an injection molding method, or a compression molding method may be used.

In addition, examples of printed wiring boards configured using the above cured products include composite type laminated boards (single-sided, double-sided, multilayer, etc.), glass epoxy type laminated boards, aramid epoxy type laminated boards, metal-based wiring boards, build-ups, and the like. A type wiring board etc. are mentioned. These can be obtained, for example, by impregnating the curable resin composition of the present invention into a reinforcing material or applying the curable resin composition to a base material, drying it appropriately, and then curing it. The curable resin composition in this case preferably contains a solvent, and preferably further contains a curing accelerator, a flame retardant, a filler and the like.

The curable resin composition of the present invention has the above-described configuration, has sufficient heat resistance, and is excellent in adhesion to metals (particularly copper, nickel, and alloys thereof) and is exposed to harsh environments. Even after this, a change in various physical properties with time is sufficiently small, and a cured product that stably exhibits excellent physical properties such as adhesiveness can be obtained, and in addition, it has excellent molding viscosity and pot life. Therefore, it is useful as a material such as a sealing material for a mounting substrate. By using such a curable resin composition of the present invention, it becomes possible to suitably obtain a high-performance sealing material and the like that are extremely useful in applications such as electric / electronic parts, automobile parts, machine parts, etc. A semiconductor device using such a sealing material is extremely useful in the electric / electronic, automobile, and mechanical fields.

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 “% by mass”.

Preparation Example 1
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 and ¹ H-NMR, ¹³ C-NMR, and MALDI-TOF-MS were measured, and the following chemical formula (i):

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 was a dark brown high-viscosity liquid with a non-volatile content of 58.2%, and the number average molecular weight was 2340 and the weight average molecular weight was 2570 as measured by GPC. ¹ H-NMR and ¹³ C-NMR were measured, and the following chemical formula (ii):

It was confirmed that the compound represented by the formula (silane compound 1) 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

Example 1
In a four-necked flask equipped with a stirrer and a solvent distillation apparatus with a Liebig condenser tube connected to the connecting tube, the resin shown in Table 1 and the silane compound 1 obtained in Preparation Example 1 (poly {γ- (5 -Norbornene-2,3-imido) propylsilsesquioxane})-containing liquid was charged in the composition shown in Table 1, heated and stirred at 150 ° C. under inflow of dry nitrogen, and the pressure was reduced to 3 KPa over 3 hours. The solvent was distilled off to obtain a silane compound-containing epoxy resin composition.
In this silane compound-containing epoxy resin composition, the curing agent, bismaleimide, flame retardant, silica, carbon black and nitrogen-containing compound shown in Table 1 were blended in the composition shown in Table 1, and kneaded and dispersed with a three roll. Thereafter, vacuum degassing was performed to prepare a curable resin composition (sealing epoxy resin composition).
About this curable resin composition, the copper adhesive strength (MPa) and the pot life (60 degreeC / h) were measured with the following method. The results are shown in Table 1.

Examples 2-3 and Comparative Examples 1-4
Except having changed the raw material and the usage-amount as shown in Table 1, it carried out similarly to Example 1, and carried out the curable resin composition (Epoxy resin composition for sealing) of Examples 2-3 and Comparative Examples 1-4. ) Were prepared. About each obtained curable resin composition, it carried out similarly to Example 1, and measured copper adhesive strength (MPa) and pot life (60 degreeC / h). The results are shown in Table 1.

<Copper bond strength>
The curable resin composition 0.15 mg was pressure-bonded to a size of 12.5 mm × 15 mm (thickness 0.2 mm) with a copper plate, and 120 ° C./1.5 hours, 230 using an inert oven (manufactured by Yamato Scientific Co., Ltd.). ° C. / cured at 3 hours _(N under ₂ atmosphere), the tensile test using an Instron universal testing machine (model 55R1185), the adhesive strength was measured at room temperature (23 ° C.) (MPa).

<Pot life>
Using a dynamic viscoelasticity measuring device (AERS-3, manufactured by TA Instruments), the measurement conditions are [plate-plate measurement, sample thickness: 1 mm, frequency: 1 Hz, strain: 0.5%], 60 ° C. The viscosity at was measured. When the viscosity after 1 hour was 1.5 times or less, it was judged as “◎”, when it exceeded 1.5 times and 2 times or less, “◯”, and when it exceeded 2 times, it was judged as “x”.

Example 4
To a four-necked flask equipped with a stirrer and a solvent distillation device with a Liebig condenser tube attached to a toroidal tube connection tube, 4,4′-diaminodiphenylsulfone (product name “Seika Cure S”, Wakayama Seika Kogyo Co., Ltd.) Manufactured), and the poly {γ- (5-norbornene-2,3-imido) propylsilsesquioxane} -containing liquid prepared by the above preparation method is charged in the composition shown in Table 2 and heated to 160 ° C. under inflow of dry nitrogen. The mixture was heated and stirred, the pressure was reduced to 3 kPa, and the solvent was distilled off over 3 hours to obtain a silane compound-containing diamine curing agent. Various raw materials were blended in the composition shown in Table 2, kneaded at 80 ° C. for 3 minutes using a three-roll kneader, and then pulverized to produce a curable resin composition (an epoxy resin composition for sealing). .
About this curable resin composition, the copper adhesive strength (MPa), the nickel adhesive strength (MPa), the viscosity (175 degreeC), and the glass transition temperature were measured with the following method. The results are shown in Table 2.

Examples 5-6, Comparative Examples 5-6
Except having changed the raw material and the usage-amount as shown in Table 2, it carried out similarly to Example 4, and curable resin composition (epoxy resin composition for sealing) of Examples 5-6 and Comparative Examples 5-6 ) Was produced. About each obtained epoxy resin composition for sealing, it carried out similarly to Example 4, and measured copper adhesive strength (MPa), nickel adhesive strength (MPa), the viscosity (175 degreeC), and the glass transition temperature. The results are shown in Table 2.

<Copper and nickel bond strength>
The resin composition was bonded to each lead frame of copper and nickel in a size of φ2 mm × 2 mm at 175 ° C. for 3 minutes, and then cured at 250 ° C. for 3 hours in a nitrogen atmosphere, and a bond tester (“Dage series 4000 ”(manufactured by Dage) was used to measure the adhesive strength (MPa) at room temperature (23 ° C.).

<175 ° C viscosity>
Using a flow tester (CFT-500D, manufactured by Shimadzu Corporation), the viscosity at 175 ° C. was measured at a die hole diameter of 0.5 mm, a die length of 1 mm, and a cylinder pressure of 0.98 MPa.

<Glass transition temperature>
Using a hot press molding machine, pressure molding was carried out at 175 ° C. for 3 minutes to obtain a flat molded product of 90 mm × 60 mm × 4 mm. The obtained molded product was cured in a nitrogen atmosphere at 250 ° C. for 3 hours, then cut to 5 mm × 4 mm × 10 mm, subjected to thermomechanical measurement (TMA4000SA, manufactured by Bruker), and glass transition temperature was measured.

Abbreviations in Tables 1 and 2 are as follows.
Epoxy resin 1: Naphthalene type epoxy resin (product name “HP-4032D”, manufactured by DIC Corporation)
Epoxy resin 2: bisphenol F type epoxy resin (product name “EXA-830-LVP”, manufactured by DIC Corporation)
Epoxy resin 3: triglycidyl isocyanurate (product name “TEPIC-S”, manufactured by Nissan Chemical Co., Ltd.)
Epoxy resin 4: Trisphenol methane type epoxy resin (product name “EPPN-501HY”, manufactured by Nippon Kayaku Co., Ltd.)
Hardener 1: Methyltetrahydrophthalic anhydride (product name “HN2000”, manufactured by Hitachi Chemical Co., Ltd.)
Hardener 2: Methyl-5-norbornene-2,3-dicarboxylic anhydride (product name “Kayahard MCD”, manufactured by Nippon Kayaku Co., Ltd.)
Curing agent 3: 4,4′-diaminodiphenyl sulfone (product name “Seika Cure S”, manufactured by Wakayama Seika Kogyo Co., Ltd.)
Curing agent 4: novolac type phenol (product name “TD-2131”, manufactured by DIC Corporation)
Silane compound (silane compound 1): poly {γ- (5-norbornene-2,3-imido) propylsilsesquioxane}
Bismaleimide 1: 4-methyl-1,3-phenylenebismaleimide (product name “BMI-7000”, manufactured by Daiwa Kasei Kogyo Co., Ltd.)
Bismaleimide 2: Phenylmethane maleimide oligomer (Product name “BMI-2300”, manufactured by Daiwa Kasei Kogyo Co., Ltd.)
Flame retardant 1: Magnesium hydroxide (Product name “Magseees S-6”, manufactured by Kamijima Chemical Co., Ltd.)
Flame retardant 2: Phosphazene compound (Product name “SPE-100”, manufactured by Otsuka Chemical Co., Ltd.)
Flame retardant 3: Aluminum hydroxide (Product name “Hijilite H-42M” manufactured by Showa Denko KK)
Silica 1: Silica (Product name “S3020”, manufactured by Micron)
Silica 2: Silica (product name “HS104”, manufactured by Micron)
Carbon black: Carbon black (product name “MA600”, manufactured by Mitsubishi Chemical Corporation)
Mold release agent: Carnauba wax (product name “TOWAX-132”, manufactured by Toa Kasei Co., Ltd.)
Curing accelerator: 2-phenyl-4-methyl-5-hydroxymethylimidazole (product name “2P4MHZ-PW”, manufactured by Shikoku Chemicals)
Coupling agent (Product name “KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.)
Nitrogen-containing compound 1: 3,5-diamino-1,2,4-triazole (reagent)
Nitrogen-containing compound 2: 3-amino-5-mercapto-1,2,4-triazole (reagent)
Nitrogen-containing compound 3: benzotriazole-4-carboxylic acid (manufactured by Nippon Carbide)
Nitrogen-containing compound 4: N- (2H-1,2,4-triazol-5-yl) salicylamide (product name “ADK STAB CDA-1M”, manufactured by Adeka)

From Table 1, the following was confirmed.
The nitrogen-containing compound 4 is a suitable example of the aromatic amide compound in the present invention, whereas the nitrogen-containing compounds 1 to 3 do not correspond to the aromatic amide compound in the present invention.
Under these differences, when Example 2 and Comparative Example 2 in which the curable resin composition was obtained under the same conditions except that the nitrogen-containing compound 4 or the nitrogen-containing compound 3 was used were compared, the nitrogen-containing compound 4 In Example 2 using NO, it can be seen that, compared with Comparative Example 2 using nitrogen-containing compound 3, the copper adhesive strength of the cured product is high, and the pot life of the resin composition is good without decreasing. Moreover, when Example 3 which obtained the epoxy resin composition for sealing on the same conditions except the point which used the nitrogen-containing compound 4 or the nitrogen-containing compound 2 is compared with the comparative example 1, in Example 3, it is a comparative example. It can be seen that 1 is remarkably superior in pot life.

From Table 2, the following was confirmed.
Comparing Example 5 and Comparative Example 6 in which the curable resin composition was obtained under the same conditions except that the nitrogen-containing compound 4 or the nitrogen-containing compound 2 was used, in Example 5 using the nitrogen-containing compound 4, Compared to Comparative Example 6 using the nitrogen-containing compound 2, the nickel adhesion strength of the cured product is remarkably high, the viscosity is low, and the viscosity is good. Moreover, when Example 4 and Example 6 which obtained the curable resin composition on the substantially same conditions except the point which used the silane compound and the bismaleimide compound are contrasted, a silane compound and a bismaleimide compound are copper and nickel. It can be seen that there is no effect on the adhesive strength.

In the above examples, only the nitrogen-containing compound 4 was used as the aromatic amide compound in the present invention, but a compound having an aromatic ring containing a hydroxyl group and an amide bond (preferably a salicylamide represented by the general formula (2) above) As long as it is a compound having a structure, more preferably a compound in which R ⁵ in the general formula (2) contains a plurality of ring nitrogen atoms, the mechanism of action that produces the effects of the present invention is the same. That is, in the present invention, there is an essential feature of the present invention in that the above-mentioned aromatic amide compound is used as an additive, and if it has the same structure as the aromatic amide compound, it has the same chemical characteristics. Therefore, the effects as shown in this embodiment can be obtained.

Claims (6)

A curable resin composition comprising (A) an epoxy resin, (B) a curing agent , ( C) an aromatic amide compound , and (D) a silane compound ,
The aromatic amide compound has the following general formula (2):

(Wherein, R ⁵ is. Of a heterocyclic structure having a triazole skeleton) Ri compound der having a salicylamide structure represented by,
The silane compound has a siloxane bond and has the following average composition formula (I):
_{X a Y b Z c SiO d} (I)
(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)). A curable resin composition characterized by being expressed by: The curable resin composition according to claim 1, further comprising (E) a maleimide compound. The curable resin composition according to claim 2 , wherein the maleimide compound is a compound having a plurality of maleimide groups in a molecule. The said curable resin composition is a composition for sealing materials, The curable resin composition in any one of Claims 1-3 characterized by the above-mentioned. An encapsulant comprising the curable resin composition according to claim 4 . A semiconductor device comprising the sealing material according to claim 5 .