JP5301597B2 - Curable resin composition and semiconductor device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a means that can, while securing enough heat resistance, even after curing, control at minimum the decrease of the adhesive strength with a noble metal (especially copper or the alloy) or the like composing a lead frame, a wiring or the like in a curable resin composition that can be used for a semiconductor seal material or the like. <P>SOLUTION: The curable resin composition including a curable resin, further includes: (A) a nitrogen-containing cyclic compound that has two or more reactive functional groups, and has two or more ring nitrogen atoms; and (B) a silane compound which is shown by the average composition formula: X<SB POS="POST">a</SB>Y<SB POS="POST">b</SB>Z<SB POS="POST">c</SB>SiO<SB POS="POST">d</SB>and has a structure unit in which at least one of organic groups X bonds with a silicon atom forming a siloxane bond, in the formula, X each independently denotes a group having an organic skeleton including an imide bond; Y is each independently chosen from the group consisting of a hydrogen atom, a hydroxy group, a halogen atom, and OR group, wherein R is each independently chosen from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkenyl group; Z each independently denotes an organic group not including an imide bond; and a, b, c and d each satisfy 0&lt;a&le;3, 0&le;b&lt;3, 0&le;c&lt;3, 0&lt;d&lt;2, and a+b+c+2d=4. <P>COPYRIGHT: (C)2013,JPO&amp;INPIT

Description

  The present invention relates to a curable resin composition and a semiconductor device using the same. The curable resin composition provided by the present invention can be suitably used for applications such as a semiconductor encapsulant for encapsulating a semiconductor element in a semiconductor device, for example.

  In recent years, electronic components and semiconductor devices such as integrated circuits (ICs), large-scale integrated circuits (LSIs), and very large-scale integrated circuits (VLSIs) have a tendency toward higher density and higher integration. In response to such a flow, these mounting methods are shifting from insertion mounting to surface mounting. In addition, semiconductor devices represented by surface mount type QFP (Quad Flat Package) and the like have been put into practical use because of demands for miniaturization, weight reduction, and lead pin multi-pinning of semiconductor devices. These semiconductor devices are mainly sealed with a semiconductor sealing material made of an epoxy resin composition, which is a kind of curable resin composition, from the viewpoint of excellent balance of productivity, cost, reliability and the like. It has become. The performance required for such semiconductor encapsulants is very diverse. For this reason, research on a semiconductor sealing material using a curable resin composition is still active, and many techniques have been proposed.

  In particular, in various materials such as mechanical component materials, electrical / electronic component materials, and automotive component materials, materials that can withstand use under severe conditions are demanded in addition to high performance products. For example, as a new semiconductor material, a wide gap semiconductor such as silicon carbide (SiC) or gallium nitride (GaN) can be given. These semiconductor materials have high operating upper limit temperature, high pressure resistance, mechanical / chemical stability, high thermal conductivity, etc., compared with conventional silicon (Si) semiconductor devices, Since the addition (doping) is easy and there are many similarities to the manufacturing process of Si semiconductor devices, it is said that the manufacturing technical hurdles for device commercialization are low. Therefore, by using these materials as the substrate of the power semiconductor device, high breakdown voltage, low power loss and high temperature operation are realized, and the power loss due to the semiconductor device can be halved. For this reason, application as a rectifier, a switching power supply IC for home appliances and PCs, a motor drive IC for an electric vehicle, and an inverter IC is progressing.

  Especially in recent years, with the rise of electric cars and hybrid cars, the trend of car electronics has been intense, but various electronic control units, actuators, sensors, and communication ICs have been integrated in order to provide a wide indoor space and freedom in the interior layout. It is required to be close to high temperature environments such as engines and transmissions. Furthermore, in automobile applications, the suppression of malfunctions is more severe than conventional consumer electronics applications from the viewpoint of passenger safety. For this reason, a plastic material having a small decrease in various physical properties in a higher temperature range than before is eagerly desired as a plastic material for mechanical parts, electrical / electronic parts, and automobile parts.

  Even in such fields, an epoxy resin composition has been generally used as a sealing material. However, when left for a long time at a high temperature of, for example, 200 ° C. or more, the weight is significantly reduced and the mechanical strength is reduced. The improvement in heat resistance has been demanded.

  In view of such a conventional state of the art, Patent Document 1 proposes a silane compound including a structural unit in which a group having an organic skeleton including an imide bond is bonded to a silicon atom forming a siloxane bond. Specifically, heat resistance, pressure resistance, water resistance, low moisture absorption, which can be suitably used for mounting applications, etc. by blending a predetermined silane compound with a curable resin such as an epoxy resin to form a resin composition Resin composition capable of forming cured products with excellent properties, low dielectric properties, mechanical / chemical stability, thermal conductivity, and low degradation of various physical properties even under harsh environments such as high temperature, high pressure, and high humidity I'm going to get it.

  By the way, the technique regarding utilization of a nitrogen-containing cyclic compound is conventionally proposed in the technical field of the resin composition for semiconductor sealing used for sealing a semiconductor device (for example, refer patent documents 2-6).

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

  Here, according to description of the Example of patent document 1 mentioned above, the weight decreasing rate under the high temperature conditions (220 degreeC) of the film which consists of an epoxy resin composition is significantly reduced by the mixing | blending of the said predetermined | prescribed silane compound. It has been demonstrated that the heat resistance can be improved compared to the case where the silane compound is not blended.

  However, according to the study by the present inventors, it has been found that even in the case where the technique described in Patent Document 1 described above is used, a problem in another sense regarding heat resistance can occur. That is, when a semiconductor device is sealed using a curable resin composition containing a predetermined silane compound described in Patent Document 1, a noble metal (especially copper) that constitutes a lead frame, wiring, etc. It has been found that the adhesive strength between the sealing material and the like is not sufficiently ensured. This problem becomes apparent as a phenomenon in which the sealing material is peeled off from the constituent members of the semiconductor device described above when the semiconductor device is exposed to a high temperature condition for a long period of time or repeatedly.

  In addition, none of the techniques described in Patent Documents 2 to 6 described above are directly directed to solving the above-described problems found by the present inventors.

  Therefore, the present invention provides a curable resin composition that can be used for a semiconductor encapsulant or the like, while ensuring sufficient heat resistance, and a noble metal (in particular, copper or an alloy thereof) that constitutes a lead frame, wiring, etc. even after curing. It is an object of the present invention to provide a means capable of minimizing a decrease in adhesive strength with the above.

  The present inventors have conducted intensive studies in view of the above problems. In the process, in addition to the silane compound including a structural unit formed by bonding a group having an organic skeleton including an imide bond to a silicon atom forming a siloxane bond proposed in Patent Document 1, a plurality of reactive functional groups An attempt was made to blend a nitrogen-containing cyclic compound having three or more ring nitrogen atoms into the curable resin composition. Unexpectedly, it is insufficient to solve the above-mentioned problems only by blending only one of these two kinds of additives alone, and these two kinds of additives It has been found that the above-mentioned problems can be solved by the combined use, and the present invention has been completed.

That is, according to one aspect of the present invention,
(A) a nitrogen-containing cyclic compound having a plurality of reactive functional groups and having three or more ring nitrogen atoms,
(B) The following average composition formula (B):

Where
Each X independently represents a group having an organic skeleton containing an imide bond;
Y is independently a hydrogen atom, a hydroxy group, a halogen atom and an OR group (wherein R is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or non-substituted group). Selected from the group consisting of substituted aryl groups and substituted or unsubstituted unsaturated aliphatic residues),
Each Z independently represents an organic group containing no imide bond;
a, b, c, and d satisfy 0 <a ≦ 3, 0 ≦ b <3, 0 ≦ c <3, 0 <d <2, and a + b + c + 2d = 4, respectively.
A silane compound including a structural unit in which at least one of the organic groups X is bonded to a silicon atom forming a siloxane bond, and
(C) A curable resin composition containing a curable resin is provided.

  The curable resin composition provided by the present invention has sufficient heat resistance. In addition, the curable resin composition is suppressed to a minimum in the decrease in adhesive strength with a noble metal (particularly copper or an alloy thereof) constituting a lead frame, wiring or the like even after curing. Thus, according to the present invention, it is possible to provide a curable resin composition that can exhibit excellent heat resistance in a true sense when used in a semiconductor encapsulant or the like.

  Hereinafter, embodiments of the present invention will be described, but the technical scope of the present invention should be determined based on the description of the scope of claims, and is not limited by the following specific embodiments.

[Curable resin composition]
The curable resin composition according to one embodiment of the present invention includes (A) a predetermined nitrogen-containing cyclic compound, (B) a predetermined silane compound, and (C) a curable resin. Hereinafter, each component contained in the composition of the present embodiment will be described in detail.

<< Component (A): Nitrogen-containing cyclic compound >>
Component (A) is a nitrogen-containing cyclic compound having a plurality of reactive functional groups and a plurality of ring nitrogen atoms.

  The nitrogen-containing cyclic compound has a plurality of reactive functional groups. Here, the “reactive functional group” means a functional group that can form a complex by reacting with a noble metal or its ions constituting a lead frame, wiring, or the like, or can form an ionic bond, and other specific examples. There is no particular limitation on the form. Moreover, the several reactive functional group which a nitrogen-containing cyclic compound has may be mutually the same, and may differ.

  Examples of reactive functional groups include amino groups (primary amino groups, secondary amino groups, tertiary amino groups), mercapto groups (—SH), carboxy groups (—COOH), hydroxy groups ( -OH), isocyanate group (-NCO), silanol group (-SiOH), cyanate ester group (-OCN) and the like. In other words, in one embodiment, at least two of the plurality of reactive functional groups of the nitrogen-containing cyclic compound are an amino group, a mercapto group, a carboxy group, a hydroxy group, an isocyanate group, a silanol group, and a cyanate ester group. Each group can be independently selected. Of these, amino groups (particularly primary amino groups), mercapto groups, and carboxy groups are preferably employed as reactive functional groups. The nitrogen-containing cyclic compound may have one or two or more functional groups other than the reactive functional group as long as it has a plurality of reactive functional groups.

  On the other hand, the basic skeleton of the nitrogen-containing cyclic compound may be any cyclic compound having a plurality of ring nitrogen atoms. Examples of the basic skeleton that satisfies such conditions include a triazole skeleton, a triazine skeleton, a benzotriazole skeleton, a thiazole skeleton, and an imidazole skeleton. Among them, the nitrogen-containing cyclic compound is any one of a triazole skeleton, a triazine skeleton, and a benzotriazole skeleton from the viewpoint that the adhesive strength when the cured product derived from the curable resin composition is exposed to a high temperature can be further increased. It is preferable to have a triazole skeleton or a benzotriazole skeleton.

  The nitrogen-containing cyclic compound can be used without particular limitation as long as it satisfies the above-described conditions. As an example of the nitrogen-containing cyclic compound, for example, as a compound having a triazole skeleton, 3,5-diamino-1,2,4-triazole (having two primary amino groups), 3-amino-5- Mercapto-1,2,4-triazole (having one primary amino group and one mercapto group), 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole (primary amino group) 2 and one mercapto group), 3-amino-5-methylthio-1H-1,2,4-triazole (having one primary amino group and one secondary amino group), 3- Amino-1,2,4-triazole (having one primary amino group and one secondary amino group), 3-amino-1,2,4-triazole-5-carboxylic acid (primary amino group) 1 base and cap 1), 4,4′-di (1,2,3-triazolyl) disulfide (having 2 secondary amino groups), 3-mercapto-1,2,4-triazole (mercapto group) Having 1, and 1 secondary amino group), 1,2,4-triazole-3-carboxamide (having 1 primary amino group and 1 secondary amino group); having a triazine skeleton 2,4-diamino-s-triazine (having two primary amino groups), 2,4,6-triamino-s-triazine (having three primary amino groups), 2,4- Dimercapto-s-triazine (having two mercapto groups), 2,4,6-trimercapto-s-triazine (having three mercapto groups), 2-amino-4,6-dimercapto-s-triazine (no. First grade 1 mino group and 1 mercapto group), 2,4,6-trimethylhexahydro-1,3,5-triazine (having 3 secondary amino groups), 6-amino-1,3 , 5-triazine-2,4-diol (having two hydroxy groups and one primary amino group), 2,4-diamino-6-hydroxy-1,3,5-triazine (primary amino group) 2 and 1 hydroxy group), 6-anilino-1,3,5-triazine-2,4-dithiol (having 2 mercapto groups and 1 secondary amino group), 4-amino-1 , 3,5-triazin-2 (1H) -one (having one primary amino group and one secondary amino group), 2,4-diamino-6-phenyl-1,3,5-triazine (Having two primary amino groups), 2-chloro-4 , 6-Diamino-1,3,5-triazine (having two primary amino groups), 2,4-diamino-6-butylamino-1,3,5-triazine (two primary amino groups) And a secondary amino group), 2,4-diamino-6-diallylamino-1,3,5-triazine (having two primary amino groups), 2,4-diamino-6- Diethylamino-1,3,5-triazine (having two primary amino groups), 2,4-diamino-6-dimethylamino-1,3,5-triazine (having two primary amino groups) 2,4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl] -1,3,5-triazine (having two primary amino groups), 2,4-diamino-6 -Methyl-1,3,5-triazine (having two primary amino groups) 2,4-diamino-6- [2- (2-undecyl-1-imidazolyl) ethyl] -1,3,5-triazine (having two primary amino groups), 6- (dibutylamino) -1 , 3,5-triazine-2,4-dithiol (having two mercapto groups) and the like; as having a benzotriazole skeleton, benzotriazole-4-carboxylic acid (secondary amino group and carboxy group one by one) 2-amino-2H-benzotriazole (having one primary amino group and one secondary amino group), 2-mercapto-2H-benzotriazole (one secondary amino group and one mercapto group) 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4-t-octylphenol] (has two hydroxy groups) ) 2,2 '-[[(Methyl-1H-benzotriazol-1-yl) methyl] imino] bisethanol (having two hydroxy groups), 1- (1', 2'-dicarboxyethyl) benzotriazole (Having two carboxy groups), 1- (2,3-dicarboxypropyl) benzotriazole, etc .; as having a thiazole skeleton, 6-amino-2-mercaptobenzothiazole (one primary amino group and Having 1 mercapto group), thiazolidine-2,4-dicarboxylic acid (having 2 carboxy groups), etc .; 5 (4) -amino-4 (5)-(aminocarbonyl) imidazole having an imidazole skeleton (Having two primary amino groups), 2-aminobenzimidazole (one primary amino group and secondary amino group 1) 2-amino-4,5-dicyano-1H-imidazole (having one primary amino group and one secondary amino group), 4-amino-1H-imidazole-5-carbonitrile (Having one primary amino group and one secondary amino group), 5-amino-2-mercaptobenzimidazole (one primary amino group, one secondary amino group and one mercapto group) 5-benzimidazolecarboxylic acid (having one secondary amino group and one carboxy group) 4,5-bis (hydroxymethyl) imidazole (having one secondary amino group and two hydroxy groups) 5-chloro-2-mercaptobenzimidazole (having one secondary amino group and one mercapto group), 5-cyano-1H-imidazole-4-carboxyl Amide (having one primary amino group and one secondary amino group), 5-ethoxy-2-benzimidazolethiol (having one secondary amino group and one mercapto group), 2-hydroxy Benzimidazole (having one secondary amino group and one hydroxy group), 2- (1-hydroxyethyl) benzimidazole (having one secondary amino group and one hydroxy group), 2- (hydroxy Methyl) benzimidazole (having one secondary amino group and one hydroxy group), 4-hydroxymethyl-5-methylimidazole (having one secondary amino group and one hydroxy group), 2- ( 3-hydroxypropyl) benzimidazole (having one secondary amino group and one hydroxy group), 4-imidazolecarbo Acid (having one secondary amino group and one carboxy group), imidazole-4,5-dicarboxamide (having two primary amino groups and one secondary amino group), 1H-imidazole- 4,5-dicarboxylic acid (having one secondary amino group and two carboxy groups), 2-mercaptobenzimidazole (having one secondary amino group and one mercapto group), 2-mercapto-5 -Benzimidazole carboxylic acids (having one secondary amino group, one mercapto group and one carboxy group).

  As a nitrogen-containing cyclic compound, when a commercial item exists, what purchased the commercial item may be used, and this may be obtained by synthesizing by itself. A method for synthesizing a nitrogen-containing cyclic compound by itself is obvious to those skilled in the art by taking into account the common general knowledge at the time of filing this application.

  There is no particular limitation on the content of the nitrogen-containing cyclic compound as the component (A) in the curable resin composition according to the present invention (the total amount when two or more nitrogen-containing cyclic compounds are used), which will be described later. Preferably it is 0.05-5 mass parts with respect to 100 mass parts of component (C) (curable resin) to do, More preferably, it is 0.1-4 mass parts, More preferably, it is 0.3-3. Part by mass. By setting the blending amount of component (A) to a value within such a range, a noble metal constituting a lead frame, wiring, etc. while maintaining the curing speed and mechanical strength within the usable range of the curable resin composition The advantage that it becomes possible to improve the adhesive strength to is obtained.

  The nitrogen-containing cyclic compounds described above are usually present in a solid state at room temperature. Conventionally, these industrial treatments are carried out as a solution in which the compound is dissolved in an appropriate (usually volatile) solvent. Generally done. In contrast, in the present invention, since the curable resin is usually present in a liquid state at room temperature, the nitrogen-containing cyclic compound in the composition of the present invention is handled as a solution dissolved in a liquid component such as a curable resin. It can be broken. Therefore, the present invention also has an advantageous effect in that it is not necessary to separately use a solvent for handling the nitrogen-containing cyclic compound.

<< Component (B): Silane Compound >>
Component (B) is a silane compound. The silane compound (hereinafter also referred to as “silane compound (B)”) has the following average composition formula (B):

It is represented by

  In the average composition formula (B), each X independently represents a group having an organic skeleton containing an imide bond. Y is independently selected from the group consisting of a hydrogen atom, a hydroxy group, a halogen atom and an OR group. Here, each R independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkynyl. Selected from the group consisting of groups. Z each independently represents an organic group containing no imide bond. A, b, c, and d satisfy 0 <a ≦ 3, 0 ≦ b <3, 0 ≦ c <3, 0 <d <2, and a + b + c + 2d = 4, respectively.

  The silane compound (B) includes a structural unit in which at least one group having an organic skeleton including an imide bond is bonded to a silicon atom (hereinafter also referred to as “structural unit (1)”), a siloxane bond (siloxane skeleton), It is what has. Since the silane compound (B) has such a structure, it has excellent heat resistance, pressure resistance, mechanical / chemical stability, thermal conductivity, and imparts various properties such as excellent heat resistance to various materials. be able to.

  In the silane compound (B), the “group having an organic skeleton including an imide bond” is not particularly limited as long as it requires an imide bond, but (1) an imide structure and an alkylene group having 1 to 6 carbon atoms. (2) a structure containing an imide structure and a secondary amino group, (3) a structure containing an imide structure and a tertiary amino group, and the like. Among these, (1) a structure containing an imide structure and an alkylene group having 1 to 6 carbon atoms is preferable from the viewpoint that the thermal stability of the silane compound can be improved.

  In the silane compound (B), the content of the “group having an organic skeleton including an imide bond” is preferably 100 to 20 moles with respect to 100 moles of silicon atoms contained in the silane compound (B). Preferably it is 100-50 mol, More preferably, it is 100-70 mol, Most preferably, it is 100-80 mol, Most preferably, it is 100 mol. According to such a form, it can be set as the silane compound which can improve the heat resistance of a silane compound, hydrolysis resistance, etc., and has improved the solubility to curable resin.

  At least one “group having an organic skeleton including an imide bond” and at least one oxygen atom are bonded to a silicon atom to which a group having an organic skeleton including an imide bond is bonded. A siloxane skeleton is formed. That is, in addition to the “group having an organic skeleton containing an imide bond”, an oxygen atom and optionally “other group” are bonded to the silicon atom to which the “group having an organic skeleton containing an imide bond” is bonded. The total number of these bonds is 4, and one or more “groups having an organic skeleton including an imide bond” and oxygen atoms are bonded together.

  The above-mentioned “other skeleton” is an organic group having no imide bond derived from the above “Z”, or consists of a hydrogen atom, a hydroxy group, a halogen atom, and an OR group derived from the “Y”. It is selected from the group. The “organic group having no imide bond” derived from “Z” is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted group. An alkenyl group or a substituted or unsubstituted alkynyl group. In this specification, when a certain group is “substituted or unsubstituted”, examples of the substituent when the group is substituted include, for example, 1 to 20 carbon atoms (preferably 1 to 1 carbon atoms). Twelve, more preferably 1-8, more preferably 1-4, alkyl groups, 1-20 carbon atoms (preferably 1-12, more preferably 1-8, even more preferably 1 4) alkoxy group, halogen atom (preferably fluorine atom or chlorine atom), carboxy group, 2 to 20 carbon atoms (preferably 2 to 12, more preferably 2 to 8, more preferably 2 to 4) ) Acyl group, amino group, 1 to 20 carbon atoms (preferably 1 to 12, more preferably 1 to 8, more preferably 1 to 4) alkylamino group, nitro group, and mercapto group. Cited . However, “alkyl group having 1 to 20 carbon atoms” is excluded from the range of substituents in “substituted (substituted) alkyl group”.

  Here, “Y” is preferably a hydroxy group or an OR group, more preferably an OR group, and still more preferably R is an alkyl group having 1 to 20 carbon atoms (more preferably 1 to 8 carbon atoms). OR group (that is, an alkoxy group having 1 to 8 carbon atoms). The “organic group having no imide bond (Z)” is particularly preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (more preferably 1 to 8 carbon atoms), substituted or unsubstituted carbon. It is an aryl group having 6 to 20 carbon atoms (more preferably 6 to 12 carbon atoms), or a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms (more preferably 7 to 12 carbon atoms). Specific examples of the “organic group having no imide bond” include, for example, methyl, ethyl, phenyl, vinyl, chloropropyl, mercaptopropyl, (epoxycyclohexyl) ethyl, glycidoxypropyl, N-phenyl-3-amino Propyl, (meth) acryloxypropyl, hexyl, decyl, octadecyl, trifluoropropyl and the like are preferred.

  The number of bonds of the “group having an organic skeleton including an imide bond” to the silicon atom is 1 to 3, preferably 1 to 2, and more preferably 1. The number of oxygen atoms bonded to the silicon atom bonded to the “group having an organic skeleton including an imide bond” is 1 to 3, preferably 2 to 3, and more preferably 3 is there.

  The number of bonds of the “other group” bonded to the silicon atom bonded to the “group having an organic skeleton including an imide bond” is 0 to 2, preferably 0 to 1, more preferably 0. It is. When these are put together, a suitable combination of the number of bonds of the group bonded to the silicon atom is (1, 3, 0), (2) as (group having an organic skeleton including an imide bond, oxygen atom, other group). 2, 0), (1, 2, 1), (3, 1, 0), (2, 1, 1), (1, 1, 2).

  The silane compound (B) has a siloxane skeleton (main chain skeleton). As such a siloxane skeleton, any structure may be used as long as a siloxane bond is essential, and the structure of the siloxane skeleton may be either linear or branched, ladder shape, cage shape, cubic shape. A polysilsesquioxane having a structure such as the above is preferable. In the silane compound (B), the proportion of the siloxane skeleton is preferably 80 to 10% by mass, more preferably 70 to 15% by mass with respect to 100% by mass of the silane compound (B). Preferably it is 50-20 mass%.

  The silane compound (B) is not particularly limited as long as it has the above-described configuration, but as a preferred embodiment, (i) a main component having a siloxane bond and an imide bond, and a siloxane bond (polysiloxane bond) being essential. A form having a structure in which a structure having a chain skeleton and an imide bond essential is bonded to the main chain skeleton, (ii) an organic skeleton including an imide bond is bonded to a silicon atom, and A structure in which a structural unit in which at least one oxygen atom is bonded to a silicon atom is essential, and the silicon atom in the structural unit forms a siloxane skeleton through the oxygen atom, (iii) a main clavicle composed of a siloxane bond And an organic skeleton containing an imide bond, and a constitutional unit containing, as an essential unit, a structural unit in which at least a part of silicon atoms of the main chain skeleton is bonded to the organic skeleton (Iv) It has a main chain skeleton including a siloxane bond and an organic skeleton including an imide bond, and the polyskeleton bond is essential, and the organic skeleton including the imide bond is at least one silicon atom in the main chain skeleton. The form etc. which couple | bond together are mentioned.

  In the preferred embodiment (i), “a structure in which an imide bond is essential is bonded to a main chain skeleton” means that at least one of the structures in which the imide bond is essential (an organic skeleton including an imide bond) is used. Any structure bonded to the main chain skeleton (siloxane skeleton) of the silane compound (B) may be used. That is, the structure in which the imide bond is essential may be any structure other than the main chain skeleton. Specifically, the silane compound (B) preferably has a structure having a structure in which an imide bond is essential in the side chain. In this case, the structure in which an imide bond is essential is not limited to a structure having a repeating unit in the form of a “chain”, and one or more side chains may be included.

  In the preferred embodiment (ii), “a structural unit in which at least one organic skeleton including an imide bond is bonded to a silicon atom, and at least one oxygen atom is bonded to the silicon atom”. Is the following general formula:

It is preferable to be represented by In this general formula, X has the same definition as described above, and is a group having an organic skeleton containing an imide bond. Moreover, s is an integer of 1 to 3, 2t is an integer of 1 to 3, and s + 2t = 4.

  In the average composition formula (B) representing the silane compound (B), the coefficient a of X is a number satisfying 0 <a ≦ 3, the coefficient b of Y is a number satisfying 0 ≦ b <3, and Z Is a number satisfying 0 ≦ c <3. The coefficient d of O is a number that satisfies 0 <d <2.

  In the silane compound (B), the solubility of the silane compound in the curable resin can be improved by increasing the bonding ratio of the “group having an organic skeleton including an imide bond” to the silicon atom. From the viewpoint of solubility in the curable resin, the coefficient a of X in the average composition formula (B) preferably satisfies 0.2 ≦ a. If the coefficient a of X, which is a group having an organic skeleton containing an imide bond, is 0.2 or more, sufficient solubility in the curable resin is ensured, and the resin composition is obtained by dissolving the silane compound in the curable resin. When the product is formed, the characteristics of the silane compound can be sufficiently exhibited. The coefficient a of X is more preferably 0.5 ≦ a, further preferably 0.7 ≦ a, particularly preferably 0.8 ≦ a, and most preferably 1.0 ≦ a. is there.

  On the other hand, from the viewpoint of heat resistance of the silane compound (B), it is preferable that a ≦ 1.0. In summary, the coefficient a of X is 0.2 ≦ a ≦ from the viewpoint of obtaining superior heat resistance, improving solubility in curable resins, and improving hydrolysis resistance. 1.0, preferably 0.5 ≦ a ≦ 1.0, more preferably 0.7 ≦ a ≦ 1.0, and particularly preferably 0.8 ≦ a ≦ 1. 0, most preferably a = 1.0. In the average composition formula (B), a + b + c is preferably 0.5 or more, more preferably 0.7 or more, still more preferably 0.7 or more and 1.0 or less, and particularly preferably 1 It is. Further, d which is a coefficient of oxygen is preferably 1.50.

  In the silane compound (B), the following calculation formula (α):

It is preferable that the ratio of the amount of silanol groups calculated | required by is 0.1 or less. According to such a form, the composition containing the silane compound (B) can be remarkably reduced in viscosity, and the composition and its cured product can be extremely excellent in moisture absorption resistance. The amount of silanol groups determined by the above formula (α) is more preferably 0.05 or less, still more preferably 0.01 or less, and particularly preferably the silane compound (B) has residual silanol groups. What is not (that is, α = 0). Here, [Si—OH bond mole number] represents the bond number between Si and OH in moles. For example, when two OH groups are bonded to each 1 mol of Si atoms, the [number of moles of Si—OH bond] is 2 mol. The number of moles of Si—O bonds is counted similarly.

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

It is represented by In the above general formula, X, Y and Z have the same definitions as above. N ₁ and n ₂ each represent a degree of polymerization, n ₁ is a non-zero positive integer (that is, a natural number), and n ₂ is 0 or a positive integer. In the above general formula, Y / Z- represents that Y or Z is bonded, X _1-2- represents that one or two X are bonded, and (Z / Y) _1-2 − means that only one of Z and Y is bonded, only two of Z and Y are bonded, or two of Z and Y are bonded in total. Represents. Si- (X / Y / Z) ₃ represents that any three selected from X, Y and Z are bonded to a silicon atom. Further, _{Si-O m1} and _{Si-O m @ 2} is not intended to define the binding order of the _{Si-O m1} and _{Si-O m @ 2,} for example, a _{Si-O m1} and _{Si-O m @ 2} is alternately or randomly The description includes a co-condensed form, a form in which a polysiloxane composed of Si—O _m1 and a polysiloxane composed of Si—O _m2 are bonded, and the like, and the condensed structure is arbitrary.

The siloxane skeleton of the silane compound (B) (main chain skeleton that requires a siloxane bond) can also be expressed as (SiO _m ) _n . (SiO _m ) Structures other than _n include “X” derived “group having an organic skeleton including an imide bond”, “Y” derived “hydrogen atom, hydroxy group, etc.”, “Z” derived “imide bond” These are any of the “organic groups not contained”, and these will be 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 groups having an organic skeleton including an imide bond are not necessarily present. Also good. In other words, a group having an organic skeleton containing one imide bond does not necessarily exist in one unit of (SiO _m ) _n . In addition, one or more groups having an organic skeleton including an imide bond may be included in one molecule, but when a plurality of groups are included, as described above, one silicon atom includes two or more imide bonds. A group having an organic skeleton may be bonded.

In the main chain skeleton (SiO _m ) _n , m is preferably a number of 1.0 or more and less than 2.0. More preferably, m = 1.5 to 1.8. Particularly preferably, m = 1.5. In the main chain skeleton (SiO _m1 ) n1 and (SiO _m2 ) _n2 , the range of (n1 + 1) / (n1 + n2 + 1) is preferably the same as the preferable range of a in the average composition formula (B). Further, in the above general formula, the number of X bonded to the silicon atom bonded to (X / Y / Z) ₃ and the number of X bonded to the silicon atom in (SiO _m1 ) are each one. It is preferable.

  n represents a degree of polymerization, and is preferably 1 to 5000, more preferably 1 to 2000, still more preferably 1 to 1000, and particularly preferably 1 to 200.

  In the case where n is 2, the silane compound (B) includes two structural units (structural units (1)) in which at least one group having an organic skeleton including an imide bond is bonded to a silicon atom. And a form in which only one of the structural unit (1) is included. Specifically, the following general formula:

A structure represented by In the above general formula, A has the same definition as Y or Z, and X, Y, and Z have the same definition as above. As is clear from the above general formula, the silane compound (B) in the case where n is 2 includes a homopolymer form including two identical structural units (1) and two different structural units (1). There may be a homopolymer form containing and a copolymer form (form of co-condensation structure) containing only one constitutional unit (1).

  The silane compound (B) has the above structure, and X in the average composition formula (B) of the silane compound (B) is the following chemical formula (1):

(The silane compound (B) according to this embodiment is also referred to as “silane compound (1)”), and more preferably includes the group represented by formula (1). In the chemical formula (1), R ¹ represents a structure selected from the group consisting of a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring, and a substituted or unsubstituted alicyclic ring. Here, the structure selected from the group consisting of a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring and a substituted or unsubstituted alicyclic ring is a ring structure (aromatic ring) in which R ¹ is an aromatic compound. Means a group selected from the group consisting of a group having a ring structure (heterocycle) of a heterocyclic compound and a group having a ring structure (alicyclic ring) of an alicyclic compound. Here, examples of the aromatic ring include benzene, biphenylene, terphenylene, naphthalene, anthracene, and penylene. Examples of the saturated aliphatic cyclic hydrocarbon in the alicyclic ring include cyclobutane, cyclopentane, cyclohexane, cyclooctane, norbornane, decahydronaphthalene and the like, and as the unsaturated aliphatic cyclic hydrocarbon in the alicyclic ring, Examples thereof include cyclobutene, cyclopentene, cyclohexene, cyclooctene, norbornene and the like. Furthermore, examples of the heterocyclic ring include pyrrole, furan, thiophene, pyridine, pyrazole, and imidazole. Among these, as R ¹ , for example, a phenylene group, a naphthylidene group, a norbornene divalent group, an (alkyl) cyclohexylene group, a cyclohexenyl group and the like are preferable.

  In the chemical formula (1), x and z are each independently an integer of 0 to 5. X + y may be an integer of 0 to 10, preferably 3 to 7, more preferably 3 to 5, and particularly preferably 3. In the above chemical formula (1), y is 0 or 1, preferably 0.

In the above chemical formula (1), when R ¹ is a phenylene group, “X” in the average composition formula (B) is the following chemical formula (2):

(The silane compound (B) according to this embodiment is also referred to as “silane compound (2)”). In the chemical formula (2), R ^{2 to} R ⁵ are each independently a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom and a substituted or unsubstituted aryl group, All are preferably hydrogen atoms. X and z are each independently an integer of 0 to 5, y is 0 or 1, and preferred forms thereof are the same as described above.

In the above chemical formula (1), when R ¹ is an (alkyl) cyclohexylene group, “X” in the average composition formula (B) is the following chemical formula (3):

(The silane compound (B) according to this embodiment is also referred to as “silane compound (3)”). In the chemical formula (3), R ^{6 to} R ⁹ and R ^{6 ′ to} R ^{9 ′} are each independently a group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom, and a substituted or unsubstituted aryl group. Or a form in which R ⁷ or R ⁸ is a methyl group and the rest are all hydrogen atoms, or a form in which all of R ^{6 to} R ⁹ and R ^{6 ′ to} R ^{9 ′} are hydrogen atoms. Or a form in which all of R ^{6 to} R ⁹ and R ^{6 ′ to} R ^{9 ′} are fluorine atoms. More preferably, R ⁷ or R ⁸ is a methyl group and the rest are all hydrogen atoms. X and z are each independently an integer of 0 to 5, y is 0 or 1, and preferred forms thereof are the same as described above.

In the chemical formula (1), when R ¹ is a naphthylidene group, “X” in the average composition formula (B) is the following chemical formula (4):

(The silane compound (B) according to this embodiment is also referred to as “silane compound (4)”). In the chemical formula (4), R ^{10 to} R ¹⁵ are each independently a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom and a substituted or unsubstituted aryl group, A form in which all are hydrogen atoms or a form in which all are fluorine atoms is preferred. More preferred is a form in which all are hydrogen atoms. X and z are each independently an integer of 0 to 5, y is 0 or 1, and preferred forms thereof are the same as described above.

In the chemical formula (1), when R ¹ is a divalent group of norbornene, “X” in the average composition formula (B) is the following chemical formula (5):

(The silane compound (B) according to this embodiment is also referred to as “silane compound (5)”). In the chemical formula (5), R ^{16 to} R ²¹ are each independently a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom and a substituted or unsubstituted aryl group, A form in which all are hydrogen atoms, a form in which all are fluorine atoms, or a form in which all are chlorine atoms is preferred. More preferred is a form in which all are hydrogen atoms. X and z are each independently an integer of 0 to 5, y is 0 or 1, and preferred forms thereof are the same as described above.

In the above chemical formula (1), when R ¹ is a cyclohexenyl group, “X” in the average composition formula (B) represents the following chemical formula (6):

(The silane compound (B) according to this embodiment is also referred to as “silane compound (6)”). In the chemical formula (6), R ^{22 to} R ²⁵ , R ^{22 ′} and R ^{25 ′} are each independently a group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom and a substituted or unsubstituted aryl group. A form in which all are hydrogen atoms, a form in which all are fluorine atoms, or a form in which all are chlorine atoms is preferable. More preferred is a form in which all are hydrogen atoms. X and z are each independently an integer of 0 to 5, y is 0 or 1, and preferred forms thereof are the same as described above.

  Since the silane compound (5) and the silane compound (6) have an unsaturated bond inside the molecule and build a crosslinked structure by the same mechanism as the maleimide compound described later, the silane compound (5) and the silane compound It is also a preferable form to mix any of (6) and a maleimide compound together. However, as the silane compound (B), the silane compound (5) is more preferable than the silane compound (6). In addition, it is preferable that the compounding ratio of a silane compound (B) and the maleimide compound mentioned later is 10 / 90-90 / 10 by the equivalent ratio of both unsaturated bonds, More preferably, it is 15 / 85-85 / 15. Yes, more preferably 20/80 to 80/20.

  X in the average composition formula (B) of the silane compound (B) is represented by the following chemical formula (7):

It is preferable that it contains the group represented by this, and it is more preferable that it consists of the said group. In the chemical formula (7), R ²⁶ has the same definition as R ¹ described above, and is a group consisting of a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring and a substituted or unsubstituted alicyclic ring. The preferable form is also the same as that of R ¹ described above.

As a particularly preferable form of the silane compound (B) when X includes a group represented by the chemical formula (7), poly (γ-phthalimidopropylsilsesquioxane) in which R ²⁶ is a phenylene group, R ²⁶ Is a methylcyclohexylene group, poly {γ- (hexahydro-4-methylphthalimide) propylsilsesquioxane}, and R ²⁶ is a naphthylidene group, poly {γ- (1,8-naphthalimide) propylsilsesquioxane. Sun}, poly {γ- (5-norbornene-2,3-imido) propylsilsesquioxane} in which R ²⁶ is a norbornene divalent group, and poly [(cis-4-) in which R ²⁶ is a cyclohexenyl group. Cyclohexene-1,2-imido) propylsilsesquioxane]. The structures of these compounds can be identified by measuring ¹ H-NMR, ¹³ C-NMR, and MALDI-TOF-MS.

  In the average composition formula (B), the number of bonds of silicon atoms to which X is bonded to oxygen atoms is preferably 3. According to such a form, since the silicon atom to which X is bonded is not bonded to another functional group, a silane compound having excellent heat resistance, moisture resistance, and hydrolysis resistance can be obtained. For example, when a silicon atom to which X is bonded is bonded to one oxygen atom and has another functional group, heat resistance, moisture resistance, and hydrolysis resistance are not sufficiently ensured depending on the type of the functional group. There is a fear. The number of bonds between silicon atoms and oxygen atoms constituting the siloxane bond is preferably 3. According to such a form, since the silicon atom constituting the siloxane bond is not bonded to a functional group other than the organic group represented by X, the silane compound is more excellent in heat resistance and hydrolyzability. Can do.

  Examples of the molecular structure of the silane compound (B) include a chain structure (straight and branched), a ladder structure, a network, a ring, a ring structure composed of a ladder, and a cage. However, from the viewpoint that the effect is easily exhibited even if the addition amount of the silane compound (B) is small, it is preferably a ladder shape, a net shape, or a cage shape. More preferable molecular structure depends on the desired effect.For example, by using a cage-like molecular structure, the viscosity of the silane compound-containing composition is further reduced, and the moisture absorption of the cured product can be significantly reduced. Become. That is, a cage-like molecular structure is suitable for realizing a decrease in viscosity and a remarkable reduction in moisture absorption. Thus, a form in which the silane compound (B) has a cage-like molecular structure is also included in the present invention. This is one of the preferred forms. By having a cage-like molecular structure, the composition containing the silane compound (B) is remarkably reduced in viscosity, and the composition and its cured product are extremely excellent in low hygroscopicity. Mechanical strength and heat resistance can be further improved. For this reason, it becomes possible to make it especially useful for various uses (especially use for electronic component devices, such as a sealing material for semiconductors). On the other hand, when a ladder-like structure is adopted, the viscosity of the silane compound-containing composition is further reduced, and the heat absorption can be remarkably improved although the moisture absorption of the cured product is not so remarkable. That is, a form in which the silane compound (B) has a ladder-like molecular structure is also a preferred form of the present invention. Here, ladder-like, network-like, and cage-like molecular structures are, for example, the following structural formulas:

Can be expressed as

In the above structural formula, R represents an organic skeleton represented by “X _a Y _b Z _c ” in the average composition formula. The structural formula (a) is a random (network structure), the structural formula (b) is a ladder structure, and the structural formula (c) is an incomplete cage structure (Incomplete). (condensed cage) and structural formulas (d) to (f) represent a caged structure (Complementary condensed structures). As exemplified by the structural formulas (c) to (f), the silane compound (B) having a cage-like molecular structure preferably has a form in which the inorganic skeleton is a core portion and the organic skeleton layer is a shell portion. It is.

  As the silane compound (B) having the cage-like molecular structure described above, X in the average composition formula (B) is preferably in a form having a ring structure, and in particular, X is represented by the general formula (1). It is preferred that it is represented. According to such a form, the composition and the silane compound (B) -containing composition is remarkably reduced in viscosity, and the above-described effect of the composition and its cured product being extremely excellent in low moisture absorption is further sufficiently obtained. Can be demonstrated.

More preferably, as the silane compound (B) having the cage-like molecular structure described above, X represented by the general formula (1) is a structure represented by the general formulas (2) to (7). That is, it is any one of the silane compounds (2) to (7), and particularly preferably, R ¹ in the general formula (1) is either a benzene ring or a norbornene structure.

Here, an example of the compound contained in the form in which R ¹ in the general formula (1) has a norbornene structure is shown below.

  When the silane compound (B) is a silane compound having the above-described cage-like molecular structure, the ratio of the amount of silanol groups determined by the above-described formula (α) is more preferably 0.1 or less. According to such a form, the above-mentioned effect that the composition containing the silane compound (B) is remarkably reduced in viscosity and the composition and its cured product are extremely excellent in moisture absorption resistance is further sufficiently obtained. Can be demonstrated. In this embodiment, α is more preferably 0.05 or less, and particularly preferably 0.01 or less. Most preferably, the silane compound (B) has no residual silanol group (that is, α = 0).

  When the silane compound (B) is a silane compound having the above-described cage-like molecular structure, in the average composition formula (B), a + b + c is preferably 0.5 or more, more preferably It is 0.7 or more, more preferably 0.7 or more and 1.0 or less, and particularly preferably 1. Further, d which is a coefficient of oxygen is preferably 1.50.

There is no restriction | limiting in particular about the method of preparing the silane compound (B) represented by an average composition formula (B), It can prepare by referring suitably the description of the Example mentioned later and a conventionally well-known knowledge. The silane compound (B) is preferably obtained, for example, by the following methods (a) and (b). For details of these manufacturing methods, Patent Document 1 (Special Table 2010-518182) can be referred to.
(A) Average composition formula having a group (X ′) having an organic skeleton containing an amide bond and a siloxane bond corresponding to the “group (X) having an organic skeleton containing an imide bond” in the silane compound (B): X _'a Y _b Z _c (consisting silane compound) represented by a SiO _d manufacturing method intermediates comprising the step of imidization.
(I) Silane in which a group having an organic skeleton containing an imide bond corresponding to “group (X) having an organic skeleton containing an imide bond” in the silane compound (B) is bonded to a silicon atom and has a hydrolyzable group The manufacturing method including the process of hydrolyzing and condensing the intermediate body which consists of a compound.

  There is no particular limitation on the content of the silane compound as the component (B) in the curable resin composition according to the present invention (the total amount when two or more silane compounds are used), and the components (C ) (Curable resin) The amount is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and still more preferably 3 to 35 parts by mass with respect to 100 parts by mass. By setting the blending amount of component (B) within such a range, oxygen deterioration does not occur even when left in air at a high temperature exceeding 200 ° C., and excellent insulation characteristics and mechanical strength over a long period of time. The advantage that can be expressed is obtained.

<< Component (C): Curable resin >>
Component (C) is a curable resin. There is no restriction | limiting in particular about curable resin, The curable resin which is compatible with the nitrogen-containing cyclic compound of the component (A) mentioned above and the silane compound of component (B) may be used suitably. Specific examples of the curable resin include, for example, an epoxy resin, a phenol resin, and a urethane resin, and among them, an epoxy resin can be preferably used from the viewpoint of a high use record in a semiconductor mounting application. Examples of the epoxy resin include bisphenols such as bisphenol A, bisphenol F, bisphenol S, and the like, which are obtained by condensation reaction of bisphenols such as bisphenol A, bisphenol F, and bisphenol S with epihalohydrin. High molecular weight epibis type glycidyl ether type epoxy resin obtained by further addition reaction with phenol; phenols such as phenol, cresol, xylenol, naphthol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, and formaldehyde, acetoaldehyde・ Propionaldehyde ・ Benzaldehyde ・ Hydroxybenzaldehyde ・ Salicylaldehyde ・ Dicyclopentadiene ・ Terpene ・A novolak aralkyl type glycidyl ether type epoxy resin obtained by further condensing polyhydric phenols obtained by condensation reaction of marine, paraxylylene glycol dimethyl ether, dichloroparaxylylene, bishydroxymethylbiphenyl, etc. with epihalohydrin; Aromatic crystalline epoxy resins obtained by condensation reaction of tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, etc. and epihalohydrin, and the above bisphenols, tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, etc. A high molecular weight product of an aromatic crystalline epoxy resin obtained by addition reaction of bisphenols and tetramethylbiphenyl Alicyclic glycols with hydrogenated aromatic skeletons such as ethylene, tetramethylbisphenol F, hydroquinone, naphthalene diol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, PEG600, propylene glycol, dipropylene glycol, tri Propylene glycol / tetrapropylene glycol / polypropylene glycol / PPG / glycerol / diglycerol / tetraglycerol / polyglycerol / trimethylolpropane and its multimer / pentaerythritol and its multimer / glucose, fructose, lactose, maltose, etc. Aliphatic glycidyl ether type epoxy resin obtained by condensation reaction of saccharide and epihalohydrin; (3,4-epoxy Cyclohexane) epoxy resin having an epoxycyclohexane skeleton such as methyl 3 ′, 4′-epoxycyclohexyl carboxylate; glycidyl ester type epoxy resin obtained by condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and epihalohydrin And a tertiary amine-containing glycidyl ether type epoxy resin solid at room temperature obtained by condensation reaction of hydantoin, cyanuric acid, melamine, benzoguanamine and epihalohydrin. As other curable resins, for example, high heat-resistant curable resins such as bismaleimide resin, cyanate ester resin, and benzoxazine resin may be used. When these high heat-resistant curable resins are used, the curability particularly suitable for sealing a semiconductor device made of a wide gap semiconductor material such as silicon carbide (SiC) or gallium nitride (GaN) and having a high maximum operating temperature. A resin composition may be provided.

≪Other ingredients≫
The curable resin composition of the present invention may contain other components as necessary as long as the effects of the present invention are not adversely affected. Examples of other components that can be contained in the curable resin composition of the present invention include a curing agent, a curing accelerator, a filler, a diluent, a flame retardant, a coupling agent, and a colorant.

  The curing agent only needs to have a function of curing the curable resin in response to an external stimulus such as heating, and conventionally known knowledge can be referred to as appropriate.

As the curing agent, one or more of acid anhydrides, polyhydric phenols, amines, BF ₃ complexes, sulfonium salts, imidazoles and the like can be used as the curing agent.

  For example, specific examples of acid anhydrides include succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, dodecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl Tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrabromophthalic anhydride, 2,4-diethyl glutaric anhydride, hymic anhydride (also known as 5-norbornene-2,3-dicarboxylic anhydride), methyl nadic anhydride (Alternative name: methyl-5-norbornene-2,3-dicarboxylic anhydride), monofunctional acid anhydrides such as dodecyl succinic anhydride, chlorendic anhydride, trialkyltetrahydrophthalic anhydride, diphenic anhydride; Pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol Colebis (anhydrotrimate), methylcyclohexene tetracarboxylic anhydride (also known as: 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride ), Biphenyltetracarboxylic anhydride, diphenylethertetracarboxylic anhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic anhydride, benzophenonetetracarboxylic anhydride, bicyclo [2.2.2] oct-7 -Bifunctional acid anhydrides such as ene-2,3,5,6-tetracarboxylic acid anhydride; liberation of β, γ-aconitic acid anhydride, glycolic acid anhydride, trimellitic acid anhydride, polyazeline acid anhydride, etc. An acid anhydride having an acid is exemplified. In addition, these hardening | curing agents may be used individually by 1 type, and may use 2 or more types together.

For example, specific examples of polyhydric phenols include phenol novolac resins, cresol novolac resins, triphenolmethane type phenol resins, terpene modified phenol resins, dicyclopentadiene modified phenol resins, phenol aralkyl resins having a phenylene skeleton, and biphenylene skeletons. Phenol aralkyl resins having a phenylene skeleton, naphthol aralkyl resins having a phenylene skeleton, naphthol aralkyl resins having a biphenylene skeleton, bisphenol compounds, and the like. These may be used alone or in combination of two or more. From the viewpoint of curability, the hydroxyl equivalent of polyhydric phenols is preferably 90 g / eq or more and 250 g / eq or less. Moreover, it is preferable that polyhydric phenols contain the compound represented by following General formula (8). Since the compound represented by the following general formula (8) has an aralkyl group containing a phenylene, biphenylene, or naphthylene skeleton, the distance between the cross-linking points is longer than that of a novolac-type phenol resin. Since the cured product has a low elastic modulus at high temperatures and a small amount of phenolic hydroxyl groups, it is possible to achieve low water absorption. The development of these characteristics can contribute to improvement of solder reflow resistance. Furthermore, in compounds containing a naphthylene skeleton, low warpage in area surface-mount semiconductor packages due to an increase in Tg due to rigidity due to the naphthalene ring and a decrease in linear expansion coefficient due to intermolecular interaction due to its planar structure. Can be improved. In the compound represented by the following general formula (8), the aromatic group containing a phenolic hydroxyl group (—R ²⁸ (OH) —) is a hydroxyphenylene group, a 1-hydroxynaphthylene group, 2- Any hydroxy naphthylene group may be used, and particularly in the case of a hydroxy naphthylene group, as in the case of the compound containing the naphthylene skeleton described above, the effect of improving low warpage can be achieved by increasing Tg or decreasing linear expansion coefficient. Further, since it has a large amount of aromatic carbon, it is possible to improve the flame resistance.

  Examples of the compound represented by the following general formula (8) include a phenol aralkyl resin containing a phenylene skeleton, a phenol aralkyl resin containing a biphenylene skeleton, a phenol aralkyl resin containing a naphthylene skeleton, and a naphthol aralkyl containing a phenylene skeleton. Although resin is mentioned, if it is a structure of Formula (8), it will not specifically limit.

Where
—R ²⁷ — represents a phenylene group, a biphenylene group or a naphthylene group, —R ²⁸ (OH) — represents a hydroxyphenylene group, a 1-hydroxynaphthylene group or a 2-hydroxynaphthylene group, R ²⁹ and R ³⁰ Are groups introduced into R ²⁸ and R ²⁷ , each independently a hydrocarbon group having 1 to 10 carbon atoms, the average value of n6 is a positive number of 1 to 10, and k6 is 0 to 5 M6 is an integer of 0-8.

  The blending ratio of the compound represented by the general formula (8) in the polyhydric phenols is preferably 10% by weight or more, more preferably 30% by weight or more, and particularly preferably 50% by weight or more. When the compounding ratio of the compound represented by the general formula (8) is within the above range, an effect of improving solder reflow resistance and low warpage can be obtained.

  For example, specific examples of amines include those containing two or more primary amines or secondary amines capable of forming a covalent bond with an epoxy group in an epoxy resin. In particular, these molecular weights and structures are not limited. Examples of such amines include diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine aliphatic polyamine, isophoronediamine, 1,3-bis. Aminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine; alicyclic polyamines such as 1,2-diaminocyclohexane, N-aminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) Piperazine-type polyamines such as piperazine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis (4-aminobenzoate), polytetra Aromatic polyamines such as tylene oxide-di-p-aminobenzoate, 3,3′-diethyl-4,4′-diaminophenylmethane, 3,3 ′, 5,5′-tetramethyl-4,4′- Aromatic diamino such as diaminophenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminophenylmethane, 2,4-diaminotoluene, 1,4-diaminobenzene, 1,3-diaminobenzene A diphenylmethane compound etc. are mentioned. These curing agents may be used alone or in combination with two or more curing agents.

  There is no restriction | limiting in particular about content of the hardening | curing agent as another component, Preferably it is 2-65 mass parts with respect to 100 mass parts of component (C) (curable resin) mentioned above, More preferably, it is 5-60. It is a mass part, More preferably, it is 10-50 mass parts.

  Any curing accelerator may be used as long as the above-described curing agent has a function of accelerating the action of curing the curable resin, and conventionally known knowledge can be appropriately referred to.

  Curing accelerators include, for example, imidazole compounds; tertiary amine compounds, organometallic compounds such as aluminum and zirconium; organophosphorus compounds such as phosphine; other heterocyclic amine compounds, boron complex compounds, organic ammonium salts, organic Examples include sulfonium salts, organic peroxides, and reactants thereof. Specifically, imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole (2E4MZ), 2-phenyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole; Phosphorus compounds such as phenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, triphenylphosphine / triphenylborate, tetraphenylphosphine / tetraphenylborate; triethylamine, benzyldimethylamine, Tertiary amine compounds such as α-methylbenzyldimethylamine and 1,8-diazabicyclo [5.4.0] undecene-7 are exemplified. Besides these, a microcapsule type curing accelerator or the like may be used. Of these, imidazole compounds are preferred. In addition, these hardening accelerators may be used individually by 1 type, and may use 2 or more types together.

  There is no restriction | limiting in particular about content of the hardening accelerator as another component, Preferably it is 0.01-10 mass parts with respect to 100 mass parts of component (C) (curable resin) mentioned above, More preferably It is 0.05-5 mass parts, More preferably, it is 0.1-3 mass parts.

  The filler can give the curable resin composition of the present invention performances such as low thermal expansion and improved workability, and has the effect of reducing raw material costs. The filler is not particularly limited, and a conventionally known filler can be used. Examples thereof include fused silica, crystalline silica, differential silica, alumina, silicon nitride, and magnesia. These may be used alone or in combination of two or more. In addition, the addition amount in the case of adding a filler becomes like this. Preferably it is 50-1500 mass parts with respect to 100 mass parts of component (C) (curable resin) mentioned above, More preferably, it is 70-1000 mass parts. is there.

  The diluent is added for the purpose of reducing the viscosity of the curable resin composition. The diluent is not particularly limited, and a conventionally known diluent can be used. For example, n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, lauryl glycidyl ether, p-sec-butylphenyl glycidyl ether, nonylphenyl glycidyl ether, carbinol Glycidyl ether, glycidyl methacrylate, vinylcyclohexene monoepoxide, α-pinene oxide, glycidyl ether of tertiary carboxylic acid, diglycidyl ether, glycidyl ether of (poly) ethylene glycol, glycidyl ether of (poly) propylene glycol, bisphenol A Propylene oxide adduct, partial adduct of bisphenol A type epoxy resin and polymerized fatty acid Polymerized fatty acid polyglycidyl ether, butanediol diglycidyl ether, vinylcyclohexene dioxide, neopentyl glycol diglycidyl ether, diglycidyl aniline, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin diglycidyl ether, glycerin A triglycidyl ether etc. are mentioned. These may be used alone or in combination of two or more. In addition, the addition amount in the case of adding a diluent becomes like this. Preferably it is 0.5-20 mass parts with respect to 100 mass parts of component (C) (curable resin) mentioned above, More preferably, it is 1-10 masses. Part.

  The flame retardant is added for the purpose of improving the flame retardancy of the curable resin composition. The flame retardant is not particularly limited, and a conventionally known flame retardant can be used. For example, brominated epoxy resin or antimony trioxide may be used, but it is preferable to use a non-halogen or non-antimony flame retardant. For example, red phosphorus coated with a thermosetting resin such as red phosphorus, phenol resin, phosphorous ester, phosphorus compound such as triphenylphosphine oxide, melamine, melamine derivative, melamine modified phenolic resin, compound having triazine ring, Nitrogen-containing compounds such as cyanuric acid derivatives and isocyanuric acid derivatives, phosphorus and nitrogen-containing compounds such as cyclophosphazene, metal complex compounds such as dicyclopentadienyl iron, zinc oxide, zinc stannate, zinc borate, and zinc molybdate Examples include zinc compounds, metal oxides such as iron oxide and molybdenum oxide, and metal hydroxides such as aluminum hydroxide and magnesium hydroxide. These may be used alone or in combination of two or more. In addition, the addition amount in the case of adding a flame retardant is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass with respect to 100 parts by mass of the component (C) (curable resin) described above. is there.

  Specific examples of the coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane. A silane coupling agent is mentioned. Examples of the colorant include pigments and dyes such as carbon black.

  In addition to those described above, the curable resin composition of the present invention includes higher fatty acids, higher fatty acid metal salts, ester waxes, polyolefin waxes, polyethylene, polyethylene oxide and other mold release agents, silicone oils and silicone rubber powders. A stress relieving agent such as can be blended as necessary.

  Moreover, in this invention, when resin other than bismaleimide resin is used as component (C) (curable resin) mentioned above, it is preferable that curable resin composition contains a maleimide compound. According to such a form, when the silane compound has a terminal double bond, a cross-linked structure is formed between the maleimide compound and the silane compound, and the cross-linked structure obtained by curing a normal curable resin A mutual network structure may be formed. As a result, properties such as durability, heat resistance, and adhesive strength of the cured product are further improved.

  As the maleimide compound, any compound having two or more maleimide groups in one molecule can be used without particular limitation. As the maleimide compound, bismaleimide such as 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′-diphenylsulfone bismaleimide, N, N′-4,4′-dicyclohexylmethane bismaleimide, N, N′-dimethylenecyclohexane bismaleimide, N, N′-m-xylene bismaleimide, N, N ′ Examples thereof include cocondensates of -4,4'-diphenylcyclohexane bismaleimide and N-phenylmaleimide with aldehyde compounds such as formaldehyde, acetaldehyde, benzaldehyde and hydroxyphenylaldehyde. In addition to these, maleimide compounds exemplified in Patent Document 1 (Japanese Patent Publication No. 2010-518182) can be used in the same manner. In addition, the addition amount in the case of adding a maleimide compound is preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the component (C) (curable resin) described above. is there.

  The curable resin composition of the present invention comprises components (A) to (C) which are essential components, and various additives which are optional components as necessary, simultaneously or sequentially so as to have a predetermined content. And it can manufacture by mixing with a mixer etc. so that each component may disperse | distribute uniformly, and knead | mixing with a roll, a kneader, etc. after that. In addition, you may perform a heat processing and a cooling process as needed at the time of mixing and kneading | mixing. Moreover, there is no restriction | limiting in particular in the order which mix | blends each component.

[Usage]
The above-described curable resin composition (preferably, a curable resin composition containing an epoxy resin) can be used, for example, for uses such as manufacturing an electronic component device by sealing an element. That is, according to one form of this invention, the resin composition for semiconductor sealing which consists of a curable resin composition mentioned above is provided.

  As an electronic component device obtained by sealing an element with the curable resin composition of the present invention, a lead frame, a wired tape carrier, a wiring board, glass, a support member such as glass, a silicon wafer, a semiconductor chip, a transistor, Examples include an electronic component device in which active elements such as diodes and thyristors, passive elements such as capacitors, resistors, and coils are mounted, and necessary portions are sealed with the sealing epoxy resin composition of the present invention. As such an electronic component device, for example, a semiconductor element is fixed on a lead frame, a terminal portion of an element such as a bonding pad and a lead portion are connected by wire bonding or bump, and then the curable resin composition of the present invention is used. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outlet) General resin-encapsulated ICs such as package (TSP), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package) It is. Moreover, TCP (Tape Carrier Package) etc. which sealed the semiconductor chip connected with the tape carrier by the bump with the curable resin composition of this invention etc. are mentioned. Furthermore, active elements such as semiconductor chips, transistors, diodes, thyristors, etc. and / or passive elements such as capacitors, resistors, coils, etc. connected to the wiring formed on the wiring board or glass by wire bonding, flip chip bonding, solder, etc. On the surface of an organic substrate in which a terminal for connecting a wiring board is formed on the back surface, such as a COB (Chip On Board) module, a hybrid IC, a multi-chip module, etc. sealed with the curable resin composition of the present invention After mounting the element, connecting the element and the wiring formed on the organic substrate by bump or wire bonding, the element is sealed with the curable resin composition of the present invention, BGA (Ball Grid Array), CSP (Chip Size Package). ) And the like.

  As a method for sealing an element using the curable resin composition of the present invention, a low-pressure transfer molding method is most common, but an injection molding method, a compression molding method, or the like may be used. The curable resin composition of the present invention is diluted with a solvent as necessary, and further mixed with the above curing accelerator, filler, flame retardant, etc. to obtain an insulating material for wiring boards, and impregnated with various reinforcing materials. As an electrical wiring board obtained by applying to various base materials, drying and removing the solvent, and then curing, single-sided, double-sided, multilayer composite type laminates, glass epoxy type laminates, aramid epoxy type laminates A board, a metal base wiring board, a build-up type wiring board, etc. are mentioned. As the solvent, those having at least one structure consisting of an ether bond, an ester bond and a nitrogen atom are preferred, so that the optimum viscosity of the impregnation or coating process is achieved, or depending on the drying process conditions, or two or more kinds Can be used as a mixture. Moreover, as a filler and a flame retardant, the same thing as having mentioned above can be used. Furthermore, the reinforcing material is particularly preferably a woven or non-woven fabric of glass fiber or polyaramid fiber, and these can be used alone or in combination of two or more.

  Hereinafter, although embodiment of this invention is described in detail using an Example etc., the technical scope of this invention is not limited by the following Example etc.

[Measurement method of physical properties]
The methods for measuring the number average molecular weight and the weight average molecular weight of the compounds obtained in the following synthesis examples are as follows.

<Method for measuring number average molecular weight and weight average molecular weight>
Measurement was performed using GPC. The equipment used (product name “HLC-8120GPC” manufactured by Tosoh Corporation), the column used (product name “GF-7MHQ” manufactured by Showa Denko KK), tetrahydrofuran as a developing solvent, and polystyrene as a standard sample were used.

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

  Subsequently, 53.4 g of deionized water was added all at once, and the temperature was raised so that by-product methanol was refluxed in the cooling pipe. After holding for 6 hours, the cooling pipe was replaced with a partial condenser, and the temperature was raised again. The reaction liquid temperature was allowed to reach 120 ° C. over 3 hours while collecting by-product methanol and condensed water. When the temperature reached 120 ° C., 7.9 g of pyridine was added and the temperature was raised as it was. The temperature reached 160 ° C. over 3 hours while collecting condensed water, and the temperature was maintained at the same temperature for 2 hours and cooled to room temperature.

The reaction product was a dark brown high-viscosity liquid with a non-volatile content of 74.3%. The molecular weight measured by GPC was a number average molecular weight of 2041 and a weight average molecular weight of 2838. ¹ H-NMR and ¹³ C-NMR were measured and confirmed to contain a compound of the following chemical formula (I).

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

<Synthesis Example 2>
Synthesis of poly {γ- (5-norbornene-2,3-imido) propylsilsesquioxane} 35.1 g of diglyme previously dried with molecular sieves in a 300 mL four-necked flask equipped with a stirrer, temperature sensor, and condenser. Then, 30.8 g of 3-aminopropyltrimethoxysilane was added, and the temperature was raised to 100 ° C. under a flow of dry nitrogen while stirring to remove moisture in the system. Next, 28.2 g of 5-norbornene-2,3-dicarboxylic acid anhydride was added in 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 the 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 solution temperature was reached to 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 was a dark brown high-viscosity liquid with a non-volatile content of 58.2%. When the molecular weight was measured by GPC, the number-average molecular weight was 2340 and the weight-average molecular weight was 2570. ¹ H-NMR and ¹³ C-NMR were measured, and it was confirmed that the compound of formula (II) was contained.

¹ H-NMR: 0.25-0.45 (bs, 2H), 1.2-1.45 (bs, 2H), 1.47 (dd, 2H), 3.0-3.2 (bs, 4H), 3.4-3.6 (bs, 2H), 5.8-6.0 (bs, 2H)
¹³ C-NMR: 9.7, 21.5, 40.4, 44.9, 45.7, 50.1, 134.2, 178.0

<Synthesis Example 3>
Synthesis of hydrolyzed cocondensate of γ- (5-norbornene-2,3-imido) propyltrimethoxysilane and tetramethoxysilane In a 300 mL four-necked flask equipped with a stirrer, temperature sensor, and condenser tube, a molecular sieve was previously prepared. N, N'-dimethylformamide (98 g), 3-aminopropyltrimethoxysilane (58.0 g) and tetramethoxysilane (49.2 g) were added and the temperature was raised to 100 ° C. under a flow of dry nitrogen while stirring. The water inside was removed. Next, 53.6 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, 40.8 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 solution temperature was reached to 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 was a dark brown high-viscosity liquid with a non-volatile content of 60.3%. When ¹ H-NMR and ¹³ C-NMR were measured, the following peaks were confirmed. -It was confirmed to contain a norbornene-2,3-imido) propyl group.

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
Furthermore, when the particle size distribution was measured using a particle size distribution measuring device (device name: LB-500, manufactured by Horiba Ltd.), the product was confirmed to be nanoparticles having an average particle size of 8 nm.

[Preparation Example of Resin Composition]
Diglime was devolatilized from the three silane compounds synthesized in Synthesis Examples 1 to 3 using a rotary evaporator to obtain a solid content. Then, it mixed using the kneader with the composition shown in the following Table 1, and obtained the uniform resin composition.

[Adhesive strength test and heat cycle test]
About the resin composition of the Example prepared above and a comparative example, the copper adhesive strength test was done according to JISK6850. In addition, the resin curing temperature at the time of preparation of the test piece was 120 ° C. × 1 hour + 200 ° C. × 3 hours. The obtained results are shown in Table 1 below as the values of the adhesive strength at 25 ° C. and 200 ° C., respectively.

  Moreover, the heat cycle test was done by exposing the test piece used for said copper bond strength test to the temperature change of "-40 degreeC x 30 minutes-> 200 degreeC x 30 minutes cycle 500 cycles." The obtained results are shown in Table 1 below. In the results shown in Table 1, when the test piece is not peeled at the resin cured product / copper interface, no change was observed before and after the test, and before the test, peeling at the interface or crack of the cured resin product was confirmed. Those in which changes were confirmed were marked with x.

As shown in Table 1 above, when no silane compound was blended (Comparative Example 1) or when a nitrogen-containing cyclic compound having no plurality of reactive functional groups was blended (Comparative Example 2), room temperature (25 As for the adhesive strength at (° C.), a certain high value was confirmed. However, the adhesive strength at high temperature (200 ° C.) exposure is significantly reduced. For this reason, when it used for the heat cycle test, peeling from copper and cracking of hardened | cured material were confirmed by the stress load accompanying expansion / contraction.

  Further, when the nitrogen-containing cyclic compound is not blended even if the silane compound proposed in Patent Document 1 is blended (Comparative Example 3 and Comparative Example 4), not only at the time of high temperature (200 ° C.) exposure but also at room temperature ( Even the adhesive strength at 25 ° C.) was not sufficient. Naturally, in the heat cycle test, peeling from copper was confirmed due to the stress load accompanying expansion and contraction. In Patent Document 1, it is said that heat resistance is improved by blending a predetermined silane compound. However, in another sense, which is a problem to be solved by the present invention (to ensure adhesive strength with noble metals such as copper). It was shown that is not able to demonstrate sufficient performance.

  In contrast to these comparative examples, in the examples, the adhesive strength of the cured product to copper was high for both room temperature (25 ° C.) and high temperature (200 ° C.) exposure. As described above, no change was observed before and after the test even when subjected to the heat cycle test because of the high adhesive strength under the high temperature condition.

  From the above, first, it can be seen that the curable resin composition provided by the present invention has sufficient heat resistance. In addition, the curable resin composition can suppress a decrease in adhesive strength with a noble metal (particularly copper or an alloy thereof) constituting a lead frame, a wiring or the like even after curing. Thus, according to the present invention, it is possible to provide a curable resin composition that can exhibit excellent heat resistance in a true sense when used in a semiconductor encapsulant or the like.

Claims (18)

(A) a nitrogen-containing cyclic structure having at least two reactive functional groups each independently selected from the group consisting of an amino group, a mercapto group, a carboxy group, and a hydroxy group, and having a plurality of ring nitrogen atoms compound, or
Baie benzotriazole-4-carboxylic acid,
(B) The following average composition formula (B):
Where
Each X independently represents a group having an organic skeleton containing an imide bond;
Y is independently a hydrogen atom, a hydroxy group, a halogen atom and an OR group (wherein R is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or non-substituted group). Selected from the group consisting of substituted aryl groups, substituted or unsubstituted alkenyl groups, and substituted or unsubstituted alkenyl groups),
Each Z independently represents an organic group containing no imide bond;
a, b, c, and d satisfy 0 <a ≦ 3, 0 ≦ b <3, 0 ≦ c <3, 0 <d <2, and a + b + c + 2d = 4, respectively.
A silane compound including a structural unit in which at least one of the organic groups X is bonded to a silicon atom forming a siloxane bond, and
(C) A curable resin composition containing a curable resin.   Component (A) is selected from the group consisting of 3,5-diamino-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, and benzotriazole-4-carboxylic acid The curable resin composition of Claim 1 containing 1 type, or 2 or more types.   The curable resin composition according to claim 1 or 2, wherein the curable resin is an epoxy resin.   The curable resin composition according to claim 1, wherein a coefficient a of X in the average composition formula (B) satisfies 0.5 ≦ a <3.   The curable resin composition of any one of Claims 1-4 whose number of bonds with the oxygen atom of the silicon atom to which X in the said average composition formula (B) couple | bonded is 3.   The curable resin composition of any one of Claims 1-5 whose number of bonds with the oxygen atom of the silicon atom which comprises the said siloxane bond is 3. In the silane compound, the following calculation formula (α):
The curable resin composition of any one of Claims 1-6 whose ratio of the amount of silanol groups calculated | required by is 0.1 or less.   The curable resin composition according to any one of claims 1 to 7, wherein the silane compound has a cage-like molecular structure. X in the average composition formula (B) is the following chemical formula (1):
Where
R ¹ represents a structure selected from the group consisting of a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring and a substituted or unsubstituted alicyclic ring;
x and z are each independently an integer of 0 to 5;
y is 0 or 1;
The curable resin composition of any one of Claims 1-8 containing group represented by these. X in the average composition formula (B) is the following chemical formula (2):
Where
R ^{2 to} R ⁵ are each independently a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom and a substituted or unsubstituted aryl group;
x and z are each independently an integer of 0 to 5;
y is 0 or 1;
The curable resin composition of Claim 9 containing group represented by these. X in the average composition formula (B) is the following chemical formula (3):
Where
R ^{6 to} R ⁹ and R ^{6 ′ to} R ^{9 ′} are each independently a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom, and a substituted or unsubstituted aryl group. Yes,
x and z are each independently an integer of 0 to 5;
y is 0 or 1;
The curable resin composition of Claim 9 containing group represented by these. X in the average composition formula (B) is the following chemical formula (4):
In the formula, R ^{10 to} R ¹⁵ are each independently a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom, and a substituted or unsubstituted aryl group;
x and z are each independently an integer of 0 to 5;
y is 0 or 1;
The curable resin composition of Claim 9 containing group represented by these. X in the average composition formula (B) is the following chemical formula (5):
Where
R ^{16 to} R ²¹ are each independently a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom and a substituted or unsubstituted aryl group;
x and z are each independently an integer of 0 to 5;
y is 0 or 1;
The curable resin composition of Claim 9 containing group represented by these. X in the average composition formula (B) is the following chemical formula (6):
Where
R ^{22 to} R ²⁵ , R ^{22 ′} and R ^{25 ′} are each independently a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom and a substituted or unsubstituted aryl group. Yes,
x and z are each independently an integer of 0 to 5;
y is 0 or 1;
The curable resin composition of Claim 9 containing group represented by these. X in the average composition formula (B) is the following chemical formula (7):
Where
R ²⁶ represents a structure selected from the group consisting of a substituted or unsubstituted aromatic ring, a substituted or unsubstituted heterocyclic ring and a substituted or unsubstituted alicyclic ring,
The curable resin composition of any one of Claims 1-14 containing group represented by these.   The curable resin composition according to claim 1, further comprising a filler.   The resin composition for semiconductor sealing which consists of a curable resin composition of any one of Claims 1-16. The semiconductor device formed by sealing a semiconductor element using the resin composition for semiconductor sealing of Claim 17.