JP2014028929A - Method of producing electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing an electronic component which makes it possible to obtain a cured product having high heat resistance of 200°C or more and also superior in mechanical strength.SOLUTION: A method of producing an electronic component using a curable resin composition, comprises a step of molding the curable resin composition, and a step of post-curing the obtained molded body, in which the post-curing temperature is a temperature higher than the molding temperature by 30°C or more.

Description

The present invention relates to a method for manufacturing an electronic component. More specifically, the present invention relates to a method for manufacturing an electronic component using a curable resin composition.

Curable resin compositions are used in various industrial fields including the electric field. One of the uses is a sealing material used for a substrate on which an electronic component or a semiconductor chip is mounted. Mounting methods for mounting electronic components, semiconductor chips, etc. on a substrate are often surface mounting methods because high-density mounting is possible, and in this case, sealing is performed with an electrically insulating sealing material. As such a sealing material, a resin composition containing an epoxy resin and its curing agent as an organic main component is widely used.

With respect to conventional curable resin compositions, for example, an epoxy resin, an epoxy resin composition composed of a reaction product of an organosiloxane and a predetermined epoxy resin, silica, and a curing agent is disclosed (for example, Patent Document 1).
Moreover, regarding the manufacturing method of the hardened | cured material using the conventional curable resin composition, after carrying out the transfer molding in the metal mold | die heated at 180 degreeC, for example, the resin composition for semiconductor sealing, it is postcure at 150 degreeC or 180 degreeC A technique for making them is disclosed (for example, Patent Document 2).

Japanese Patent Laid-Open No. 2-102217 Japanese Patent Laid-Open No. 10-30050

Some electronic components and semiconductor chips that use sealing materials are used in high-temperature environments, and the sealing materials used to protect chips that operate at high temperatures affect the performance of the semiconductor. Heat resistance is required. Particularly in recent years, SiC devices, which are attracting attention because of their low power consumption and their ability to control high currents and voltages, operate most efficiently in a high temperature region of 200 ° C. or higher. The cured product is also required to have high heat resistance of 200 ° C. or higher.
However, since a cured product of a resin composition containing a conventional epoxy resin has a heat resistance of about 175 ° C. at the highest, a method for producing a cured product with further increased heat resistance is required.
Moreover, since the sealing material is also required to have excellent mechanical strength so that the coating film of the sealing material is not peeled off or chipped, there is a demand for a method for producing a cured product that can meet these requirements.

The present invention has been made in view of the above-described situation, and provides a method for manufacturing an electronic component that can obtain a cured product (electronic component) having high heat resistance of 200 ° C. or higher and excellent mechanical strength. The purpose is to provide.

The inventors of the present invention have studied various manufacturing methods that can be preferably applied to electronic parts, particularly sealing materials, and include a step of molding a curable resin composition and a step of post-curing the obtained molded body. The present inventors have found that a cured product having high heat resistance of 200 ° C. or higher and excellent mechanical strength can be obtained by a production method in which the post-curing temperature is set to 30 ° C. or higher than the molding temperature. As a result, the inventors have conceived that the above problems can be solved brilliantly and have reached the present invention.

That is, the present invention is a method for producing an electronic component using a curable resin composition, which comprises a step of molding the curable resin composition and post-curing the obtained molded body. The method for manufacturing an electronic component includes a step, wherein the post-curing temperature is 30 ° C. or more higher than the molding temperature.

The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

〔Production method〕
The method for producing an electronic component of the present invention includes a step of molding a curable resin composition and a step of post-curing the obtained molded body, and the post-curing temperature is higher by 30 ° C. than the molding temperature. It is characterized by temperature.
By using the production method of the present invention, a cured product having high heat resistance of 200 ° C. or higher and excellent mechanical strength can be obtained.

Although it does not specifically limit as a process (henceforth a molding process) which shape | molds the said curable resin composition, For example, shape | molding using a molding machine etc. is mentioned.
The molding machine is not particularly limited as long as it is normally used, and examples thereof include a transfer mold molding machine, a heating compression molding machine, and an injection molding machine.
The molding temperature is preferably 150 to 190 ° C., more preferably 160 to 180 ° C., still more preferably 170 to 180 ° C., particularly from the viewpoint of the gelation time of the curable resin composition to be used. Preferably it is 175 degreeC.
The molding time is preferably 1 to 10 minutes, more preferably 2 to 6 minutes, and further preferably 3 to 6 minutes, from the viewpoint of the mechanical strength of the obtained molded body.
Moreover, it does not specifically limit as a shape of the molded object obtained by the said formation process, For example, molded objects, such as a deformed product, a film, a sheet | seat, a pellet, etc. are mentioned.

As a step of post-curing the obtained molded body (hereinafter also referred to as a post-curing step), the molded body is further heated to further cure.
The post-curing step can be performed, for example, by using an oven, a heated press plate, or the like and placing the molded body therein.
In the present invention, the post-curing temperature is 30 ° C. higher than the molding temperature. Thereby, a cured product having a high Tg is obtained, and a cured product having a high heat resistance of 200 ° C. or higher and excellent mechanical strength is obtained. The post-curing temperature is preferably 40 ° C. or more higher than the molding temperature. Further, from the viewpoint of preventing cracks in the cured product, the post-curing temperature is preferably a temperature that is 90 ° C. or higher than the molding temperature.
The post-curing temperature is preferably 200 to 250 ° C., more preferably 220 to 250 ° C., and still more preferably 230 to 250 ° C., from the viewpoint of obtaining a cured product having high heat resistance and excellent mechanical strength. is there.
The post-curing time is preferably 1 to 10 hours, more preferably 2 to 10 hours, and further preferably 3 to 10 hours from the viewpoint of obtaining a cured product having high heat resistance and excellent mechanical strength. is there.

[Cured product]
A cured product (electronic component) obtained by the production method of the present invention is also one of the preferred embodiments of the present invention.
The glass transition temperature (Tg) of the cured product obtained by the production method of the present invention is preferably 200 ° C. or higher. Thereby, the said hardened | cured material becomes what has high heat resistance of 200 degreeC or more, For example, it can utilize more suitably for electronic mounting materials, such as a sealing material of a mounting board | substrate. More preferably, it is 210 degreeC or more, More preferably, it is 230 degreeC or more, Most preferably, it is 250 degreeC or more. The upper limit of Tg is not particularly limited, and the cured product is preferably stable (glass state) in any thermal environment.
The glass transition temperature can be measured by a thermomechanical analyzer (TMA).

Since the cured product is obtained from the production method of the present invention, it has a high glass transition temperature and is excellent in heat resistance and mechanical strength.For example, mounting use, optical use, opto device use, It is useful for electronic component applications such as display device applications. Specifically, it is preferably used for electronic packaging materials such as sealing materials, potting materials, underfill materials, conductive pastes, insulating pastes, die pond materials, and the like. Especially, it is more preferable to use for an electronic packaging material, and it is very useful especially for the sealing material of a mounting board | substrate. A semiconductor sealing material is particularly preferable as the sealing material. Moreover, the semiconductor device etc. comprised using the said hardened | cured material are also contained in the preferable form of this invention.

The sealing material is, for example, a member used when sealing a semiconductor component. For example, a curing accelerator, a stabilizer, a release agent, a coupling agent, a colorant, a plastic is used as necessary. Agents, flexibilizers, various rubber-like materials, photosensitizers, fillers, flame retardants, pigments and the like. Moreover, since the sealing material may cause problems when it contains a large amount of volatile components, it is desired that the sealing material does not contain volatile components. For example, the content of volatile components in 100% by mass of the sealing material is desired. The amount is preferably 10% by mass or less. More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less, Most preferably, it does not contain a volatile component substantially.

[Curable resin composition]
The method for producing an electronic component of the present invention uses a curable resin composition, and the curable resin composition will be described below.
The curable resin composition in the present invention has, for example, an epoxy resin, a curing agent, a silane compound, and silica from the viewpoint that a cured product having high heat resistance of 200 ° C. or higher and excellent mechanical strength can be obtained. It is preferable to contain. Moreover, the manufacturing method of an electronic component using such a curable resin composition is also one of the preferable forms of this invention.
Each component contained in the curable resin composition (hereinafter also referred to as a resin composition) may be used alone or in combination of two or more. Moreover, other components can also be included as appropriate. Other components (additives) are as described later.

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

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

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

The epoxy resin preferably has a weight average molecular weight of 200 to 20000. When such an epoxy resin having a molecular weight is used, a cured product that is sufficiently cured can be obtained. More preferably, it is 220-18000, More preferably, it is 250-15000.
The said weight average molecular weight can be calculated | required as a molecular weight of polystyrene conversion of a gel permeation chromatography (GPC), for example. In the present invention, the weight average molecular weight is measured by the method described in Examples below.

The epoxy equivalent in the curable resin composition is preferably 100 to 450 g / mol from the relationship between the crosslinking density of the epoxy resin and the flexibility of the cured product obtained. More preferably, it is 120-420 g / mol, More preferably, it is 150-400 g / mol.

As content of an epoxy resin, it is preferable to set it as 1-20 mass% with respect to 100 mass% of curable resin compositions from the point of the mechanical strength of the hardened | cured material obtained. More preferably, it is 3-15 mass%, More preferably, it is 5-10 mass%.

<Curing agent>
As a hardening | curing agent, an acid anhydride, an amine compound, a phenol compound etc. are mentioned, for example. These can be used alone or in combination of two or more.

In the curable resin composition, the curing agent preferably has a melting point of 100 ° C. or higher. Thereby, since Tg of the hardened | cured material obtained using the said curable resin composition can fully be improved, the hardened | cured material excellent in heat resistance and mechanical strength can be obtained, Furthermore, at high temperature There is also an effect that cracks do not occur in the cured product even after post-curing.
The melting point of the curing agent is preferably 102 ° C. or higher, more preferably 105 ° C. or higher, and still more preferably 110 ° C. or higher.
The upper limit of the melting point of the curing agent is preferably 200 ° C. or less. Thereby, since it can mix with a silane compound more fully at a molecular level, fluidity | liquidity can also be provided to a resin composition. More preferably, it is 190 degrees C or less.
In the present specification, the melting point means a temperature (° C.) at which a crystal melts and becomes liquid under an inert atmosphere. Therefore, amorphous compounds and those already in liquid form at room temperature do not have a melting point.
The melting point can be measured, for example, by differential scanning calorimetry (DSC).

The acid anhydride is not particularly limited as long as it can cure the epoxy resin, and examples thereof include aliphatic acid anhydrides, alicyclic acid anhydrides, and aromatic acid anhydrides. From the viewpoint of obtaining a cured product having high heat resistance, an aromatic acid anhydride is preferred.
Examples of the aliphatic acid anhydride include tetrapropenyl succinic anhydride, octenyl succinic anhydride, and the like.
Examples of the alicyclic acid anhydride include 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and the like.
Examples of the aromatic acid anhydride include ethylene glycol bisanhydro trimellitate, glycerin bisanhydro trimellitate monoacetate, and the like.

Although it will not specifically limit as said amine compound if an epoxy resin can be hardened, For example, an aromatic amine compound, an aliphatic amine compound, etc. are mentioned.

The aromatic amine compound is an amine compound having an aromatic ring skeleton in its structure, and examples thereof include a primary amine compound, a secondary amine compound, and a tertiary amine compound. Further, it is preferable to use a primary amine compound and / or a secondary amine compound. Further, the number of amino groups in one molecule is not particularly limited, but is preferably 1 to 10, more preferably 2 to 4.
Examples of the aromatic amine compound include the following compounds.

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

Examples of the aliphatic amine compound include a chain aliphatic polyamine and a cyclic aliphatic polyamine.
Examples of the chain aliphatic polyamine include diethyltriamine and triethylenetetramine.
Examples of the cycloaliphatic polyamine include N-aminoethylpiperazine and mensendiamine.
The amine compound is preferably an aromatic amine compound from the viewpoint of obtaining a cured product having high heat resistance.

The molecular weight of the amine compound is preferably 100 to 1000, for example. If the polymer compound exceeds 1000, there is a possibility that it cannot be sufficiently mixed with the silane compound. On the other hand, if it is less than 100, there is a risk that the thermal decomposition resistance or the like may not be sufficient. More preferably, it is 100-800, More preferably, it is 100-600.

The phenol compound is not particularly limited as long as it can cure the epoxy resin, and examples thereof include polyhydric phenol compounds and phenol novolac compounds. From the viewpoint of reducing the viscosity of the curable resin composition, a phenol novolac compound is preferable.
Examples of the phenol novolak compound include bisphenol A novolak and bisphenol B novolak.

As the polyhydric phenol compound, those having a structure in which aromatic skeletons having at least one phenolic hydroxyl group are bonded via an organic skeleton having 2 or more carbon atoms can be suitably used. In the polyhydric phenol compound, the aromatic skeleton is an aromatic ring having at least one phenolic hydroxyl group. This aromatic skeleton is a part having a structure such as a phenol type, and a phenol type, a hydroquinone type, a naphthol type, an anthracenol type, a bisphenol type, a biphenol type and the like are preferable. Of these, the phenol type is preferred. Further, these sites having a phenol type structure or the like may be appropriately substituted with an alkyl group, an alkylene group, an aralkyl group, a phenyl group, a phenylene group, or the like.

In the above polyhydric phenol compound, the organic skeleton means a part that binds the aromatic ring skeletons constituting the polyhydric phenol compound and requires carbon atoms. The organic skeleton having 2 or more carbon atoms preferably has a ring structure. The ring structure is a structure having a ring such as an aliphatic ring or an aromatic ring, and the ring is preferably a cyclopentane ring, a cyclohexane ring, a benzene ring, a naphthalene ring, an anthracene ring or the like. Furthermore, the organic skeleton preferably has a ring structure containing a nitrogen atom such as a triazine ring or a phosphazene ring and / or an aromatic ring, and particularly preferably has a triazine ring and / or an aromatic ring. The polyhydric phenol compound may have an aromatic skeleton or an organic skeleton other than those described above, and the aromatic skeleton having at least one phenolic hydroxyl group is an organic skeleton having 1 carbon atom (methylene ) May be simultaneously bonded.

As content of a hardening | curing agent, it is preferable to set it as 20-200 mass% with respect to 100 mass% of epoxy resins which a curable resin composition contains from the point which obtains the hardened | cured material excellent in mechanical strength. More preferably, it is 25-100 mass%, More preferably, it is 30-70 mass%.

<Silane compound>
In the said curable resin composition, fluidity | liquidity can further be provided to the resin composition with a high glass transition temperature by containing a silane compound.
In the curable resin composition, the silane compound is a compound having a siloxane bond (Si—O—Si bond) and represented by an average composition formula (1): X _a Y _b Z _c SiO _d . By including such a silane compound, it becomes possible to give a cured product having excellent heat resistance, pressure resistance, mechanical / chemical stability, and thermal conductivity. Moreover, the hardened | cured material by which various physical-property fall was suppressed also in severe environments, such as high temperature high pressure, can be formed, and can be used suitably for mounting uses, such as a semiconductor sealing material.

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

In the above average composition formula (1): X _a Y _b Z _c SiO _d , the preferred form of X is as described later, and as Y, a hydroxyl group or an OR group is preferred. Among them, an OR group is more preferable, and an OR group in which R is an alkyl group having 1 to 8 carbon atoms is more preferable. Z is preferably at least one selected from the group consisting of an aromatic residue such as an alkyl group, an aryl group, and an aralkyl group, and an unsaturated aliphatic residue (these have a substituent). You may). More preferably, it is a C1-C8 alkyl group which may have a substituent, or aromatic residues, such as an aryl group and an aralkyl group. The coefficient a of X is a number 0 ≦ a <3, the coefficient b of Y is a number 0 ≦ b <3, and the coefficient c of Z is a number less than 0 ≦ c <3. , O is a number d such that 0 <d <2.

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

(In the formula, X, Y and Z are the same as described above. N ₁ and n ₂ represent the degree of polymerization. N ₁ is a non-zero positive integer, and n ₂ is 0 or positive. It is an integer.)
"Y / Z-" represents that Y or Z is bonded, " _X1-2- " represents that one or two X are bonded, and "(Z / Y _1-2 ) "represents that one Z or Y is bonded, two Z or Y are bonded, or two Z and Y are bonded in total. “Si— (X / Y / Z) ₃ ” indicates that any three selected from X, Y, and Z are bonded to a silicon atom.
In the above formula (2), Si-Om ₁ and Si-Om ₂ is not intended to define the binding order of Si-Om ₁ and Si-Om _2, for example, Si-Om ₁ and Si-Om ₂ alternating Or the form which co-condenses at random, the form which the polysiloxane which consists of Si-Om _1, and the polysiloxane of Si-Om ₂ couple | bond are suitable, and a condensation structure is arbitrary.

The silane compound can be represented by the above average composition formula (1), but the siloxane skeleton (main chain skeleton in which a siloxane bond is essential) of the silane compound can also be represented as (SiO _m ) _n . The structure other than (SiO _m ) _n in such a silane compound is an organic skeleton having an imide bond (a structure in which an imide bond is essential) X, Y such as a hydrogen atom or a hydroxyl group, and an organic group not containing an imide bond. Z, which are bonded to the silicon atom of the main chain skeleton.
X, Y and Z may or may not be included in the repeating unit in the form of a “chain”. For example, one or more Xs may be contained in one molecule as a side chain. In the above (SiO _m ) _n , n represents the degree of polymerization, and the degree of polymerization represents the degree of polymerization of the main chain skeleton, and n organic skeletons having an imide bond may not necessarily exist. In other words, an organic skeleton having one imide bond in one unit of (SiO _m ) _n is not necessarily present. In addition, one or more organic skeletons having an imide bond may be included in one molecule, but when a plurality of organic skeletons are included, as described above, an organic skeleton having two or more imide bonds in one silicon atom. It may be bonded. The same applies to the following.

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

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

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

X in the average composition formula (1) is preferably a structural unit represented by the following formula (3). That is, in the silane compound of the present invention, X in the average composition formula (1) is the following formula (3):

(In the formula, R ¹ represents at least one structure selected from the group consisting of aromatic, heterocyclic and alicyclic rings. X and z are the same or different and are integers of 0 or more and 5 or less, y Is preferably a structural unit represented by 0 or 1). By including such a silane compound, the heat resistance of the cured product is further improved.

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

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

In the above formulas (3-1) to (3-5), x, y and z are the same as in the above formula (3).
In the above formula (3-1), R ^{2 to} R ⁵ are the same or different and represent at least one structure selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic. As the ^R 2 to R ^5, all are hydrogen atom forms are preferred.
In the formula ^(3-2), R 6 ~R ⁹ and ^{R 6'to R 9'are} the same or different, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, halogen atoms and 6 to 16 carbon atoms It represents at least one structure selected from the group consisting of aromatics. As the ^R 6 to R ⁹ and ^{R 6'to R 9',} form all ^{R 7} or ^{R 8} are the remaining methyl group is a hydrogen atom, ^or, R 6 to R ⁹ and ^R 6'to R ^{9 'all} are hydrogen atom form ^or embodiment R 6 to R ⁹ and ^{R 6'to R 9'all} are a fluorine atom is preferable. More preferably, R ⁷ or R ⁸ is a methyl group and the rest are all hydrogen atoms.

In said formula (3-3), R < ¹⁰ > -R < ¹⁵ > is the same or different and represents at least 1 type of structure chosen from the group which consists of a hydrogen atom, an alkyl group, a halogen atom, and aromatic. As said R < ¹⁰ > -R < ¹⁵ >, the form whose all are hydrogen atoms or the form whose all are fluorine atoms is preferable. More preferred is a form in which all are hydrogen atoms.
In the above formula (3-4), R ^{16 to} R ²¹ are the same or different and represent at least one structure selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic. As said R < ¹⁶ > -R < ²¹ >, the form in which all are hydrogen atoms, the form in which all are fluorine atoms, or the form in which all are chlorine atoms is preferable. More preferred is a form in which all are hydrogen atoms.
In the formula (3-5), R ^{22 to} R ²⁵ , R ^{22 ′} and R ^{25 ′} are the same or different and are at least one selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic. Represents the structure. As the ^R 22 ^{~R 25, R 22'} and ^{R 25 ',} forms all are hydrogen atom, and all are a fluorine atom form or any form of embodiment all is a chlorine atom is preferable. More preferred is a form in which all are hydrogen atoms.

Among the structural units represented by the above formula (3), the following formula (3-6):

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

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

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

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

As content of a silane compound, it is preferable that it is 10-200 mass% with respect to 100 mass% of aromatic amine compounds which curable resin composition contains. More preferably, it is 100-180 mass%, More preferably, it is 130-170 mass%.
There exists a possibility that sufficient fluidity | liquidity cannot be provided to curable resin composition as a silane compound is less than 10 mass%.

<Silica>
The silica is not particularly limited as long as it is used as an inorganic filler, and examples thereof include fused silica and crystalline silica. From the viewpoint of imparting high fillability to the curable resin composition, fused silica is preferable.

The average particle diameter of the silica is preferably 10 to 50 μm. More preferably, it is 15-40 micrometers, More preferably, it is 20-30 micrometers.
The average particle diameter can be measured by using a laser diffraction particle size distribution measuring apparatus.

As content of the said silica, it is preferable that it is 50-95 mass% from the point which obtains hardened | cured material with a smaller linear expansion coefficient with respect to 100 mass% of curable resin compositions. More preferably, it is 60-93 mass%, More preferably, it is 70-90 mass%.
By using a large amount of silica in this way, when the curable resin composition of the present invention is used, for example, to obtain a sealing material for a mounting substrate, the occurrence of warping of the substrate after curing can be sufficiently prevented. It becomes possible. In addition, even if the curable resin composition of this invention contains a large amount of silica, since it has a silane compound, fluidity | liquidity improves and it can prepare easily.

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

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

(Wherein R ²⁷ is

Or

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

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

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

<Other ingredients>
The curable resin composition may contain additives other than the above-described components (hereinafter also referred to as other components).
Examples of the other components include volatile components such as organic solvents and diluents, curing accelerators, stabilizers, mold release agents, coupling agents, coloring agents, plasticizers, flexible agents, various rubber-like materials, A photosensitizer, a flame retardant, a pigment, etc. are mentioned. These can be used alone or in combination of two or more.

It does not specifically limit as said volatile component, What is necessary is just to use what is normally used.
Here, the curable resin composition of the present invention can be used for applications in which it is desired to contain as little volatile components as possible, for example, electronic parts applications such as mounting applications, optical applications, and opto device applications. In this case, the content of the volatile component in 100% by mass of the curable resin composition is preferably 10% by mass or less. More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less, Most preferably, it does not contain a volatile component substantially. “Substantially free of volatile components” means that the content of volatile components is less than the amount capable of dissolving the composition, for example, 1 mass in 100 mass% of the curable resin composition. % Or less is preferable.

Examples of the curing accelerator include organic phosphorus compounds such as triphenylphosphine, tributylhexadecylphosphonium bromide, tributylphosphine, and tris (dimethoxyphenyl) phosphine. These can be used alone or in combination of two or more.

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

The method for producing the curable resin composition is not particularly limited. For example, after mixing the said hardening | curing agent and a silane compound, it can manufacture by adding and mixing an epoxy resin, a silica, and another component as needed.
Since the curable resin composition of the present invention can improve fluidity and workability by using a silane compound, the mixing step with the above components can be easily performed without requiring a special machine. . For example, the mixing step can be suitably carried out using any mixer that is usually used in heating and mixing, such as a kneader, a roll, a single screw extruder kneader, or a twin screw extruder kneader.

The curable resin composition preferably has a viscosity at 175 ° C. of 5 to 100 Pa · s. When the curable resin composition has such an appropriate viscosity, the fluidity is excellent, and the handling property during application is excellent. More preferably, it is 10-90 Pa.s.
The viscosity of the curable resin composition can be measured at 175 ° C. using a flow tester.

By using the production method of the present invention, a cured product having high heat resistance of 200 ° C. or higher and excellent mechanical strength can be obtained. Therefore, if the manufacturing method of this invention is used, it will become possible to obtain the highly efficient sealing material etc. which are very useful for an electronic component use.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
The molecular weight (number average molecular weight and weight average molecular weight) of each component was determined by GPC (gel permeation chromatography) measurement under the following measurement conditions.
Measuring instrument: HLC-8120GPC (trade name, manufactured by Tosoh Corporation)
Molecular weight column: TSK-GEL GMHXL-L and TSK-GELG5000HXL (both manufactured by Tosoh Corporation) are used in series.
Eluent: Tetrahydrofuran (THF)
Standard material for calibration curve: Polystyrene (manufactured by Tosoh Corporation)
Measurement method: The measurement object is dissolved in THF so that the solid content is about 0.2% by mass, and the molecular weight is measured using an object obtained by filtration through a filter as a measurement sample.

Synthesis Example 1 (Synthesis of silane compound)
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 by-product methanol was refluxed in the cooling pipe. After holding at 95 ° C. for 10 hours, the cooling pipe was replaced with a partial condenser and the temperature was raised again. The reaction liquid temperature was allowed to reach 120 ° C. over 3 hours while collecting by-product methanol and condensed water. When the temperature reached 120 ° C., 1.4 g of pyridine was added, and the temperature was raised as it was. The temperature reached 160 ° C. over 3 hours while collecting condensed water, and the temperature was kept at the same temperature for 2 hours and cooled to room temperature.
The reaction product 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 confirmed to contain a compound represented by the following chemical formula (poly {γ- (5-norbornene-2,3-imido) propylsilsesquioxane}). .

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

Example 1 and Comparative Example 1
The compositions shown in Table 1 below were kneaded at 80 ° C. and compression molded at 175 ° C. for 6 minutes. Using the obtained molded product, a sample cured at 250 ° C. for 3 hours (Example 1) and a sample cured at 150 ° C. for 5 hours (Comparative Example 1) were obtained.
About these hardening samples, the glass transition temperature (Tg) was calculated | required using the thermomechanical analyzer (TMA4000SA, Bruker AXS company make). Moreover, the crack of the said hardening sample was observed visually using the loupe ((circle) has no crack and x has a crack). These results are shown in Table 2.

Each compound described in Table 1 is as follows.
Epoxy resin: Tris (hydroxyphenyl) methane type epoxy resin (EPPN-501HY, manufactured by Nippon Kayaku Co., Ltd.)
Curing agent: 4,4′-diaminodiphenyl sulfone, melting point 176-180 ° C. (Seika Cure, Wakayama Seika Kogyo Co., Ltd.)
Silane compound: Compound imide component prepared in Synthesis Example 1 above: Polyphenylmethane maleimide (BMI2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.)
Silica: fused silica (S270, manufactured by Nippon Steel Materials)

From the results of Table 2, Example 1 was able to obtain a cured product having a Tg of 40 ° C. or higher, extremely excellent heat resistance, and no cracks, as compared with Comparative Example 1.

As described above, the present invention includes a step of molding the curable resin composition and a step of post-curing the obtained molded body, and the post-curing temperature is 30 ° C. higher than the molding temperature. By using the method for manufacturing an electronic component according to the invention, it is considered that all the mechanisms of action are that the cured product having high heat resistance of 200 ° C. or more and excellent in mechanical strength can be obtained. .
Therefore, it can be said from the results of the above-described embodiments that the present invention can be applied in the entire technical scope of the present invention and in various forms disclosed in the present specification, and can exhibit advantageous effects.

Claims (1)

A method for producing an electronic component using a curable resin composition,
The production method includes a step of molding the curable resin composition, and a step of post-curing the obtained molded body.
The post-curing temperature is 30 ° C. or more higher than the molding temperature.