JP2008258429A - Insulating film, method of manufacturing electronic component apparatus, and electronic component apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an insulating film which improves a handleable property at ordinary temperature and is capable of uniformly coating the surface of a mount in use for surface mounting or semiconductor sealing, an electronic component apparatus employing the insulating film, and a method of manufacturing the electronic component apparatus. <P>SOLUTION: The present invention relates to an insulating film which contains a curing component (a), a hardener (b), a high-molecular weight polymer (c) and an inorganic filler (e) and in which a storage elastic modulus (E1) at 30°C of the insulating film before curing is settled within the range of 1×10<SP>4</SP>to 1×10<SP>6</SP>Pa, a minimum storage elastic modulus (E2) at 30°C or higher is settled within the range of 1×10<SP>2</SP>to 3×10<SP>4</SP>Pa, and a ratio (E1)/(E2) of the storage elastic modulus (E1) and the minimum storage elastic modulus (E2) is settled within the range of 2 to 500. The invention also relates to an electronic component apparatus 1 including an insulating layer 4 constituted of a cured object of the insulating film, and a method of manufacturing the electronic component apparatus 1. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an insulating film suitable for forming an insulating part of an electronic component device in which an electronic component element such as a semiconductor element is mounted on a substrate. More specifically, the present invention has excellent handleability at room temperature, for example, The present invention relates to an insulating film capable of uniformly covering the surface of an adherend when used for surface mounting or semiconductor sealing, a method for manufacturing an electronic component device using the insulating film, and an electronic component device .

  In order to achieve high performance and miniaturization of a semiconductor device configured by mounting a semiconductor element on a substrate, a surface mounting technique that does not use a bonding wire has been used. An example of this type of mounting technique is disclosed in, for example, Patent Document 1 below. In the case of using surface mounting technology, various insulating materials are used in order to bond a semiconductor element on a substrate or to insulate between electrodes.

  An insulating material used for a semiconductor device is required to withstand a large electric capacity depending on the application. It is also required to be suitable for a mounting process such as the above surface mounting technology.

  Further, for high-current applications, there is a strong demand for excellent heat resistance, specifically, that it is difficult to cause deterioration when left at high temperatures or subjected to a cold cycle. In particular, there is a strong demand for the occurrence of cracks that cause power loss in such an environment.

Conventionally, an insulating material made of polyimide resin, epoxy resin, or the like has been developed. This type of insulating material is disclosed in Patent Documents 2 and 3 below. However, the insulating materials described in Patent Documents 2 and 3 tend to be inferior in handleability at room temperature. In addition, when these insulating materials are formed into a film and used for, for example, surface mounting or semiconductor sealing, the surface of the adherend may not be uniformly coated.
Japanese Unexamined Patent Publication No. 8-1155953 JP 2001-323224 A JP 2002-129125 A

  The object of the present invention is excellent in handleability at room temperature in view of the current state of the prior art described above, and uniformly coats the surface of an adherend when used, for example, for surface mounting or semiconductor sealing. An insulating film that can be used, an electronic component device using the insulating film, and a method of manufacturing the electronic component device.

The insulating film according to the present invention contains a curable compound (a), a curing agent (b), a high molecular weight polymer (c), and an inorganic filler (e), and the insulating film before curing at 30 ° C. The storage elastic modulus (E1) is in the range of 1 × 10 ⁴ to 1 × 10 ⁶ Pa, the minimum storage elastic modulus (E2) at 30 ° C. or higher is in the range of 1 × 10 ^{2 to} 3 × 10 ⁴ Pa, and The ratio (E1) / (E2) between the storage elastic modulus (E1) and the minimum storage elastic modulus (E2) is in the range of 2 to 500.

  In a specific aspect of the insulating film according to the present invention, the curable compound (a) has two or more epoxy groups in one molecule, and at least a part of the main chain is a polycyclic hydrocarbon skeleton. Have

  In another specific aspect of the present invention, the insulating film further includes a rubber component (f). The rubber component (f) is preferably rubber fine particles.

  In another specific aspect of the insulating film according to the present invention, the high molecular weight polymer (c) is contained in a proportion of 5 to 60% by weight in 100% by weight of the total resin content in the insulating film.

  In still another specific aspect of the insulating film according to the present invention, the inorganic filler (e) is spherical silica, and the amount of spherical silica is 100 to 600 parts by weight with respect to 100 parts by weight of the total resin in the insulating film. Included as a percentage.

  In another specific aspect of the insulating film according to the present invention, the electronic component device is a semiconductor device using a semiconductor element as an electronic component element, and the insulating film is an insulating film for a semiconductor device.

  In still another specific aspect of the insulating film according to the present invention, the semiconductor element is a power device element.

  A method of manufacturing an electronic component device according to the present invention is a method of manufacturing an electronic component device using an insulating film configured according to the present invention, and includes at least a periphery of the electronic component device on a substrate on which the electronic component device is mounted. A step of covering a part with an insulating film to form an insulating layer, a step of irradiating the insulating layer with high-density energy rays, forming a hole for wiring in the insulating layer, and a step of filling the hole with a wiring material; And forming a wiring pattern electrically connected to the wiring material filled in the hole on the surface of the insulating layer.

  In a specific aspect of the method for manufacturing an electronic component device according to the present invention, a semiconductor element is used as the electronic component element, and a semiconductor device is manufactured as the electronic component device.

  An electronic component device according to the present invention is an electronic component device having an insulating layer made of a cured product of an insulating film configured according to the present invention, and includes a substrate, an electronic component element mounted on the substrate, and the present invention. An insulating layer formed of a cured product of the configured insulating film, provided so as to cover at least a part of the periphery of the electronic component element, and having a hole continuous with the surface, and an insulating layer It is characterized by comprising a wiring material filled in the holes and a wiring pattern formed on the surface of the insulating layer so as to be electrically connected to the wiring material.

  In a specific aspect of the electronic component device according to the present invention, the electronic component element is a semiconductor element, and the semiconductor device is formed as the electronic component device.

In the insulating film according to the present invention, the storage elastic modulus (E1) at 30 ° C. of the insulating film before curing is in the range of 1 × 10 ⁴ to 1 × 10 ⁶ Pa, and the minimum storage elastic modulus (E2) at 30 ° C. or higher. Is in the range of 1 × 10 ^{2 to} 3 × 10 ⁴ Pa and (E1) / (E2) is in the range of 2 to 500, the handleability at room temperature is excellent. In addition, for example, when used for surface mounting or semiconductor sealing, the surface of the adherend can be uniformly coated.

  In the method for manufacturing an electronic component device according to the present invention, at least a part of the periphery of an electronic component element mounted on a substrate is covered with the insulating film of the present invention and cured to form an insulating layer, and the insulating layer In accordance with the present invention, the surface is formed by irradiating the substrate with high-density energy rays, forming wiring holes in the insulating layer, filling the holes with a wiring material, and forming a wiring pattern on the insulating layer surface. An electronic component device provided with a uniformly coated insulating layer can be provided.

  Details of the present invention will be described below.

  The insulating film according to the present invention contains a curable compound (a), a curing agent (b), a high molecular weight polymer (c), and an inorganic filler (e).

  In the present invention, for example, by appropriately adjusting the types and blending amounts of the curable compound (a), the high molecular weight polymer (c) and the inorganic filler (e), the behavior of the storage elastic modulus before and after the softening start point, that is, storage The elastic modulus (E1) and the minimum storage elastic modulus (E2) can be easily controlled within the above ranges. Moreover, storage elastic modulus (E1) / minimum storage elastic modulus (E2) can be easily controlled to the said range by adjusting suitably the kind and compounding quantity of resin components other than an inorganic filler (e).

The storage elastic modulus (E1) at 30 ° C. of the insulating film before curing is in the range of 1 × 10 ⁴ to 1 × 10 ⁶ Pa. When the storage elastic modulus (E1) is less than 1 × 10 ⁴ Pa, the insulating film is too soft and inferior in handleability. When it exceeds 1 × 10 ⁶ Pa, the insulating film is too hard and the insulating film is easily damaged. Become. The storage elastic modulus (E1) is more preferably in the range of 1 × 10 ⁴ to 1 × 10 ⁵ Pa.

The minimum storage elastic modulus (E2) at 30 ° C. or higher of the insulating film before curing is in the range of 1 × 10 ^{2 to} 3 × 10 ⁴ Pa. When the minimum storage elastic modulus (E2) is less than 1 × 10 ² Pa, the insulating film is too soft and the insulating film flows during lamination. Therefore, for example, when used for coating a semiconductor element or the like, the film thickness of the insulating film tends to become extremely thin at the edge portion of the semiconductor element. If the minimum storage elastic modulus (E2) exceeds 3 × 10 ⁴ Pa, the insulating film is too hard to follow the unevenness of the adherend surface during lamination, and tearing or the like tends to occur. The minimum storage elastic modulus (E2) is more preferably in the range of 1 × 10 ³ to 2 × 10 ⁴ Pa.

  Moreover, ratio (E1) / (E2) of the said storage elastic modulus (E1) and the said minimum storage elastic modulus (E2) of an insulating film exists in the range of 2-500. When (E1) / (E2) is less than 2, the insulating film does not stretch sufficiently at the time of lamination, and it is difficult to follow the irregularities on the surface of the adherend, or tearing easily occurs. When (E1) / (E2) exceeds 500, the insulating film becomes soft at the time of laminating, so that the film thickness of the insulating film tends to be reduced entirely or partially. (E1) / (E2) is more preferably in the range of 3 to 100, still more preferably 5 to 50.

  The storage elastic modulus (E1) and the minimum storage elastic modulus (E2) are, for example, a rheometer / VAR-100 (manufactured by Rheologica Instruments) for a disc-shaped insulating film having a thickness of 200 μm and a diameter of 20 mm. It is measured under the conditions of 1 Hz, strain: 1%, and heating rate of 30 ° C./min.

  The insulating film contains a curable compound (a). By including the curable compound (a), the heat resistance is enhanced.

  The curable compound (a) is not particularly limited. For example, amino resins such as urea resins and melamine resins, phenolic resins, unsaturated polyester resins, thermosetting urethane resins, pentadiene type epoxy resins, and the like. Examples thereof include epoxy resins other than naphthalene type epoxy resins, thermosetting polyimide resins, aminoalkyd resins, and the like. These thermosetting resins may be used alone or in combination of two or more.

  As the curable compound (a), since the heat resistance is improved, an epoxy resin having two or more epoxy groups in one molecule and having a polycyclic hydrocarbon skeleton in at least a part of the main chain is used. preferable. The polycyclic hydrocarbon skeleton means a hydrocarbon skeleton formed by combining two or more cyclic skeletons.

  Examples of such epoxy resins include epoxy resins having a dicyclopentadiene skeleton such as dicyclopentadiene dioxide and phenol novolac epoxy resins having a dicyclopentadiene skeleton, 1-glycidylnaphthalene, 2-glycidylnaphthalene, 1,2 -Diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-diglycidylnaphthalene, 1,7-diglycidylnaphthalene, 2,7-diglycidylnaphthalene, triglycidylnaphthalene, 1,2,5,6-tetra Epoxy resins having a naphthalene skeleton such as glycidylnaphthalene, epoxy resins having an adamantene skeleton such as 1,3-bis (4-glycidyloxyphenyl) adamantene, 2,2-bis (4-glycidyloxyphenyl) adamantene, 9 9-bis (4-glycidyloxyphenyl) fluorene, 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene, 9,9-bis (4-glycidyloxy-3-chlorophenyl) fluorene, 9,9 -Bis (4-glycidyloxy-3-bromophenyl) fluorene, 9,9-bis (4-glycidyloxy-3-fluorophenyl) fluorene, 9,9-bis (4-glycidyloxy-3-methoxyphenyl) fluorene 9,9-bis (4-glycidyloxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-glycidyloxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-glycidyloxy) Epoxy resin having a fluorene skeleton such as -3,5-dibromophenyl) fluorene, 1,1 ' Bi (2,7-glycidyloxynaphthyl) methane, 1,8'-bi (2,7-glycidyloxynaphthyl) methane, 1,1'-bi (3,7-glycidyloxynaphthyl) methane, 1,8 ' -Bi (3,7-glycidyloxynaphthyl) methane, 1,1'-bi (3,5-glycidyloxynaphthyl) methane, 1,8'-bi (3,5-glycidyloxynaphthyl) methane, 1,2 Bis such as' -bi (2,7-glycidyloxynaphthyl) methane, 1,2'-bi (3,7-glycidyloxynaphthyl) methane, 1,2'-bi (3,5-glycidyloxynaphthyl) methane (Glycidyloxyphenyl) epoxy resin having methane skeleton, 1,3,4,5,6,8-hexamethyl-2,7-bis-oxiranylmethoxy-9-phenyl- Examples thereof include an epoxy resin having a xanthene skeleton such as 9H-xanthene, and an epoxy resin having an anthracene skeleton or a pyrene skeleton. As for these epoxy resins, only 1 type may be used and 2 or more types may be used together.

  As the curable compound (a), an epoxy resin having a fluorene skeleton and / or an epoxy resin having a naphthalene skeleton is preferably used.

  As a compounding quantity of the said sclerosing | hardenable compound (a), 40 to 95 weight% is preferable in 100 weight% of all the resin parts in an insulating film. More preferably, it is 50 to 90% by weight. If the amount of the curable compound (a) is too small, the heat resistance may be insufficient, such as a low Tg of the insulating film after curing or a high coefficient of thermal expansion, and if too large, the relatively high molecular weight polymer (c) ), The strength of the insulating film before curing is insufficient and the handling property may be inferior.

  The insulating film contains a high molecular weight polymer (c) as a film forming component.

  Although it does not specifically limit as said high molecular weight polymer (c), The polymer which has an epoxy group in the terminal and / or side chain (pendant position) is used suitably. For example, epoxy group-containing acrylic rubber, epoxy group-containing butadiene rubber, bisphenol type high molecular weight epoxy resin, epoxy group-containing phenoxy resin, epoxy group-containing (meth) acrylic resin, epoxy group-containing urethane resin, epoxy group-containing polyester resin, etc. It is done. Especially, since the mechanical strength and heat resistance after hardening are improved further, the epoxy group containing (meth) acrylic resin which has an epoxy group is preferable. Although the epoxy group content is not so high, a phenoxy resin is also preferable because the resin itself is excellent in mechanical strength and heat resistance. As for high molecular weight polymer (c), only 1 type may be used and 2 or more types may be used.

  The epoxy group-containing (meth) acrylic resin is obtained by radical polymerization of a monomer using a trigger such as heat or light, and after the monomer is mixed with a resin having a polycyclic hydrocarbon skeleton in the main chain. It can also be obtained by radical polymerization using a trigger such as heat or light.

  The weight average molecular weight of the high molecular weight polymer (c) is preferably 10,000 or more. More preferably, it is 50,000 or more, More preferably, it is 100,000 or more. If the weight average molecular weight is too small, the handling property when the insulating film is coated on the mounting device may be inferior.

  As a compounding quantity of the said high molecular weight polymer (c), 5 to 60 weight% is preferable in 100 weight% of all the resin parts in an insulating film. More preferably, it is 10 to 50% by weight. If the amount of the high molecular weight polymer (c) is too small, the strength of the insulating film may be insufficient and handleability may be poor, and if it is too large, the tackiness of the insulating film may be low and adhesiveness may be poor.

  The insulating film contains a curing agent (b). Examples of the curing agent (b) include, but are not limited to, heat curing acid anhydride curing agents, phenol curing agents, amine curing agents, latent curing agents such as dicyandiamide, and cationic catalyst curing agents. . These curing agents may be used alone or in combination of two or more.

  Typical examples of the heat-curing acid anhydride curing agent include acid anhydrides such as methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, and trialkyltetrahydrophthalic anhydride. System curing agent. Especially, since water resistance is improved, methyl nadic acid anhydride and trialkyl tetrahydro phthalic anhydride are used suitably. These acid anhydride curing agents may be used alone or in combination of two or more.

  Typical examples of the phenolic curing agent include, for example, phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, polyparavinylphenol, bisphenol A type novolak, and xylylene-modified. Examples include novolak, decalin-modified novolak, poly (di-o-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, and poly (di-p-hydroxyphenyl) methane. These phenolic curing agents may be used alone or in combination of two or more.

  In order to adjust the curing speed and the physical properties of the cured product, a curing accelerator may be used in combination with the curing agent.

  The curing accelerator is not particularly limited, and examples thereof include 3 such as benzyldimethylamine, picoline, DBU, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, and dimethylcyclohexylamine. Secondary amine, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl -S-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, isocyanuric acid adduct, 2-phenylimidazole isocyanuric Acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-me Imidazoles such as ru-5-hydroxymethylimidazole; imidazolines such as 2-methylimidazoline and 2-phenylimidazoline, 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6-vinyl- triazines such as s-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxy-s-triazine, 2,4-diamino-6-methacryloyloxy-s-triazine isocyanuric acid adduct, triphenylphosphine, Triparatolylphosphine, Trimetatolylphosphine, Triorthotolylphosphine, Tris (3,5-dimethylphenyl) phosphine, Tris (2,4,6-trimethylphenyl) phosphine, Tris (4-methoxyphenyl) phosphine, Tricyclohexylphosphine , Tetraethylphosphonium bromide, tetra-n-butylphosphonium bromide, tetra-n-butylphosphonium-o, o-diethylphosphorodithioate, tetra-n-butylphosphonium benzotriazole, tetra-n-butylphosphonium tetrafluoroborate, tetra- Organophosphorus compounds selected from n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate and the like; quaternary phosphonium salts such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide; 1,8-diazabicyclo [5, 4,0] Undecene-7 etc. and diazabicycloalkenes such as organic acid salts thereof; organometallic compounds such as zinc octylate, tin octylate and aluminum acetylacetone complex S; tetraethylammonium bromide, quaternary ammonium salts such as tetrabutylammonium bromide; boron trifluoride, boron compounds such as triphenyl borate, zinc chloride, metal halides such as stannic chloride.

  The curing accelerator further includes a high melting point imidazole compound, a dicyandiamide or a high melting point dispersion type latent accelerator such as an amine addition accelerator obtained by adding an amine to an epoxy resin, an imidazole-based, phosphorus-based or phosphine-based accelerator. Microcapsule-type latent accelerators coated with polymer, amine salt-type latent curing accelerators, high-temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts Representative latent curing accelerators can also be used. Especially, since it is easy to control the reaction system for adjusting a cure rate, the physical property of hardened | cured material, etc., a high melting point imidazole type hardening accelerator is used suitably. These curing accelerators may be used alone or in combination of two or more. Since the handleability is excellent, the curing accelerator preferably has a melting point of 100 ° C. or higher.

  When using a hardening accelerator, it is preferable to make the addition amount of a hardening | curing agent below the equivalent theoretically required with respect to an epoxy group. If the addition amount of the curing agent is excessive, chlorine ions may be easily eluted from the cured product by moisture.

  The insulating film contains an inorganic filler (e). The inorganic filler (e) is not particularly limited, and examples thereof include silica, alumina, silicon nitride, hydrotalcite, and kaolin. These may be used alone or in combination of two or more. Of these, spherical silica is preferable. When the insulating film contains spherical silica, for example, even when spherical silica is highly filled, a decrease in fluidity of the insulating film can be suppressed to a low level.

  As the inorganic filler (e), spherical silica, spherical alumina, spherical silicon nitride, and spherical aluminum silicate having an average particle size of 0.1 to 15 μm are preferably used. When the average particle size is less than 0.1 μm, high filling may be difficult, and when it exceeds 15 μm, it may not pass through the filtration mesh.

  As a compounding quantity of the said inorganic filler (e), 100-600 weight part is preferable with respect to 100 weight part of all the resin parts in an insulating film. More preferably, it is 200-500 weight part. If the amount of the inorganic filler (e) is too small, the CTE of the cured insulating film will be high and the heat resistance may be inferior. If it is too large, the amount of the resin component as the binder is small, so the adhesive strength and film strength are low. May be inferior.

  Moreover, when using an insulating film for the manufacturing process which has the process of forming a hole in the layer which consists of insulating films, the average particle diameter of an inorganic filler (e) becomes like this. More preferably, it is 0.1-6 micrometers. When the average particle diameter of the inorganic filler exceeds 6 μm, it may be difficult to form holes having a desired shape.

  Moreover, when the average particle diameter of the said inorganic filler (e) is 0.1-6 micrometers, the maximum particle diameter has preferable 10 micrometers or less. When the maximum particle diameter exceeds 10 μm, it may be difficult to form holes having a desired shape.

  The insulating film preferably contains a rubber component (f). The rubber component (f) is not particularly limited, but for example, acrylic rubber, butadiene rubber, isoprene rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, styrene isoprene rubber, urethane rubber, silicone rubber, fluorine rubber, natural rubber, etc. It can be used regardless. Since the glass transition temperature of the cured product can be maintained high as the rubber component (f), rubber fine particles are preferably used.

  By using the rubber component (f) and the inorganic filler (e) in combination, the insulating film has a low coefficient of linear thermal expansion and stress relaxation capability, and peeling, cracking, etc. occur under high temperature and cooling cycle conditions. Can be suppressed.

  The blending ratio of the rubber component (f) is preferably 0.1 to 40% by weight, more preferably 0.3 to 20% by weight in 100% by weight of the insulating film. When there are too few rubber components (f), the stress relaxation property of hardened | cured material may not fully be expressed, and when too large, it may be inferior to adhesiveness.

  As the rubber component (f), particles having a core-shell structure having a multilayer structure of two or more layers using the rubber fine particles as a core (core material) are more preferably used. In the case of particles having a core-shell structure composed of three or more layers, the shell means the outermost shell.

  The shell of the core-shell structure rubber fine particles may have a functional group that reacts with an epoxy group in the epoxy resin. The functional group that reacts with the epoxy group is not particularly limited, and examples thereof include an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, and an epoxy group. Therefore, a hydroxyl group or an epoxy group is preferable because the wettability and storage stability of the insulating film are not lowered. The shell may have a functional group that reacts with these epoxy groups alone, or may have two or more types.

  The average particle size of the rubber component (f) is preferably 30 μm or less. If the average particle diameter of the rubber fine particles exceeds 30 μm, the stress relaxation property of the cured product may not be sufficiently exhibited. A more preferable average particle size of the rubber component (f) is 0.1 to 5 μm.

  As the rubber fine particles (f), a compound (f1) having a siloxane skeleton as a main skeleton and having an organic substituent in a silyl group, or a fluorine compound (f2) is preferably used.

  As the compound (f1) having the siloxane bond as a main skeleton and an organic substituent in the silyl group, polymethylsilsesquioxane and methylsilicone are preferably used. In addition, core-shell structured particles having a multilayer structure of two or more layers using these rubber fine particles as a core (core material) are more preferably used.

  The fluorine compound (f2) is not particularly limited. For example, polytetrafluoroethylene, ethyltetrafluoroethylene, polychlorotetrafluoroethylene, polyvinylfluorene, polyfluoroacrylate, polyfluoroacetate polyvinyl difluorene, etc. Is mentioned. Moreover, the core-shell structure particle | grains which consist of two or more layers multilayer structure which used these rubber fine particles as a core (core material) are used suitably.

  The insulating film may contain a thermoplastic resin as necessary.

  The thermoplastic resin is not particularly limited, but examples thereof include vinyl acetate resins, ethylene-vinyl acetate copolymers, acrylic resins, polyvinyl acetal resins such as polyvinyl butyral resins, styrene resins, Examples thereof include saturated polyester resins, thermoplastic urethane resins, polyamide resins, thermoplastic polyimide resins, ketone resins, norbornene resins, and styrene-butadiene block copolymers. These thermoplastic resins may be used alone or in combination of two or more.

  The insulating film may contain a thixotropic agent, a dispersant, a flame retardant, and a colorant as necessary.

  The thixotropic agent is not particularly limited, and examples thereof include a polyamide resin, a fatty acid amide resin, a polyamide resin, and a dioctyl phthalate resin.

  Examples of the dispersant include anionic dispersants such as fatty acid soap, alkyl sulfate, sodium dialkylsulfosuccinate and sodium alkylbenzenesulfonate, cation dispersants such as decylamine acetate, trimethylammonium chloride and dimethyl (benzyl) ammonium chloride, Nonionic dispersants such as polyethylene glycol ether, polyethylene glycol ester, sorbitan ester, sorbitan ester ether, monoglyceride, polyglycerin alkyl ester, fatty acid diethanolamide, alkyl polyetheramine, amine oxide, ethylene glycol distearate and the like.

  The flame retardant is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, dawsonite, calcium aluminate, dihydrate gypsum, calcium hydroxide and other metal hydroxides, red phosphorus, ammonium polyphosphate, Phosphoric esters such as phenyl phosphate, tricyclohexyl phosphate, phosphorus, phosphorus-containing epoxy resins, phosphorus-containing phenoxy resins, phosphorus-containing resins such as phosphorus-containing vinyl compounds, phosphorus compounds, melamine, melamine cyanurate, melamine isocyanurate, phosphorus Nitrogen compounds such as melamine acid and melamine derivatives surface-treated with these, layered double hydrates such as hydrotalcite, antimony compounds such as antimony trioxide and antimony pentoxide, decabromodiphenyl ether, trialis Brominated compounds such as isocyanurates 6 bromides, such as bromine-containing epoxy resins such as tetrabromobisphenol A and the like. Of these, metal hydroxides and melamine derivatives are preferably used.

  Examples of the colorant include pigments and dyes such as carbon black, graphite, fullerene, titanium carbon, manganese dioxide, and phthalocyanine.

  The insulating film has a film shape. A method for processing the above-described material into a film is not particularly limited, but for example, a solvent casting method, an extrusion film forming method, or the like is preferable. Defoaming is preferred when processing into a film.

  Although it does not specifically limit as a film thickness of the said film, 50-300 micrometers is preferable. More preferably, it is 100-200 micrometers. If the film thickness is too thin, the insulating property may be inferior. If it is too thick, the conduction process between the electrodes may be complicated.

The initial adhesive strength of the insulating film is preferably 400 N / 25 mm ² or more. The initial adhesive strength refers to a 1 mm x 30 mm x 100 mm square copper plate with an insulating film cut into a 30 mm x 50 mm square attached to the edge of the insulating film, after peeling off the release PET film. Stack copper sheets of the same size while sandwiching the sheets, heat and cure in a 200 ° C oven for 1 hour, attach a jig to the opposite end of the two copper sheets, and move up and down at a pulling speed of 5 mm / min. It means the value obtained when tensile and the maximum breaking strength (N / 25 mm ² ) are obtained.

The adhesive strength after the high temperature standing test of the insulating film is preferably 350 N / 25 mm ² or more, and the amount of change in the adhesive strength after the high temperature standing test from the initial adhesive strength is preferably less than 100 N / 25 mm ² , more preferably 50 N / It is less than 25 mm ² . The adhesive strength after the high-temperature standing test is that a silicon chip is soldered on a copper substrate, and then the entire substrate is laminated with a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho) at 40 ° C. It means a value obtained when a test sample prepared by heating and curing in a 200 ° C. oven for 1 hour is left in the 200 ° C. oven for 500 hours and then the adhesive strength is measured by the same method as the initial adhesive strength.

  The insulating film of the present invention has extremely excellent coating followability because the elastic modulus behavior in a specific temperature region is controlled in a state before curing, and for example, an electronic component is mounted on a substrate, and the substrate surface is uneven. Even if it has, it is extremely excellent in laminating properties. Therefore, it can be suitably used particularly for surface mounting applications and semiconductor sealing applications. For example, in a substrate on which a semiconductor element is mounted, it can be particularly suitably used as an insulating film that covers the substrate and the semiconductor element at once or as a covering insulating film for a mounting type semiconductor.

  The insulating film of the present invention is an insulating film for electronic component devices, and examples of such electronic component devices include semiconductor devices. That is, it can be suitably used for a semiconductor device in which a semiconductor element is mounted on a substrate. In this case, the semiconductor element is preferably surface-mounted on the substrate for curing, but the insulating film of the present invention is also applied to a semiconductor device in which the semiconductor element is mounted on the substrate by a bonding wire. Can be used. Furthermore, the insulating film can also be used for an electronic component device in which electronic component elements other than semiconductor elements are mounted on a substrate.

  Among electronic component apparatuses, when the semiconductor element is a power device element for a large current, the advantage can be exhibited particularly, which is preferable. Moreover, as a structure of an electronic component device, a surface mounting type can exhibit superiority and is preferable.

  The method for manufacturing an electronic component device of the present invention is characterized by using the insulating film of the present invention. In this case, at least a part of the periphery of the electronic component element on the substrate on which the electronic component element such as a semiconductor element is mounted is covered with the insulating film and then cured to form an insulating layer. The coating can be performed using, for example, a vacuum laminator or the like.

  Next, a hole for wiring is formed by irradiating the insulating layer with a high-density energy beam. The hole is filled with a metal material as a wiring material. Thereafter, a wiring pattern that is electrically connected to the wiring material is formed on the surface of the insulating layer. An appropriate metal material can be used for this wiring pattern as well as the wiring material.

  FIG. 1 is a schematic front sectional view showing a semiconductor device as an example of an electronic component device manufactured according to the present invention.

  A semiconductor device 1 shown in FIG. 1 has a substrate 2, and a semiconductor element 3 is mounted on the substrate 2. An insulating layer 4 made of the insulating film of the present invention is provided so as to cover at least a part of the semiconductor element 3. The holes 4a and 4b are formed in the insulating layer 4 according to the method described above. A wiring pattern 6 is formed on the surface of the insulating layer 4 so that the holes 4a and 4b are filled with the wiring materials 5a and 5b and are electrically connected to the wiring materials 5a and 5b.

  When other electronic component elements are used instead of the semiconductor element 3, an electronic component device other than the semiconductor device can be provided.

  In the semiconductor device 1, since the insulating layer 4 is formed of the cured product of the insulating film of the present invention, as described above, the semiconductor device 1 is excellent in resistance to high-temperature storage and thermal cycle resistance. Heat resistance can be improved.

  A semiconductor device 11 as a modification of the semiconductor device 1 is shown in FIG. The same components as those in the semiconductor device are denoted by the same reference numerals, and the description thereof is omitted.

  As shown in FIG. 2, the semiconductor chip 3 is mounted on the substrate 2, and the insulating layer 12 made of the insulating film of the present invention is formed on the uneven surface. In the semiconductor device 11, the thickness of the insulating layer 12 between the flat portion and the corner portion, that is, a, c, d, and b shown in FIG. Since the insulating layer 12 is formed using the insulating film having the storage elastic modulus in the specific range, the followability of the insulating layer 12 to the uneven surface is enhanced, and the insulating layer 12 is also near the corner of the unevenness. Is sufficiently thick. Since the insulating layer 12 has high followability to the uneven surface and the insulating layer 12 is sufficiently thick in the vicinity of the corners of the unevenness, the heat resistance of the semiconductor device 11 can be improved.

  Thus, the thickness of the insulating layer formed using the insulating film is almost equal in any part, and in particular, the ratio of the corner part thickness (b) to the flat part thickness (a, c, d) (corner part thickness / The flat portion thickness) is preferably in the range of 0.6 to 1.0, more preferably 0.8 to 1.0. By forming the insulating layer using an insulating film in which the storage elastic modulus in the temperature range from 20 ° C. to the softening point and the storage elastic modulus in the temperature at which the insulating layer is formed are in the specific range, The ratio of the partial thickness to the flat partial thickness can be easily within the above range.

  Hereinafter, the present invention will be clarified by giving specific examples and comparative examples of the present invention. In addition, this invention is not limited to a following example.

  In the examples and comparative examples, the following materials were used.

(Curable compound (a))
(1) Dicyclopentadiene type solid epoxy resin (manufactured by Dainippon Ink and Chemicals, trade name: EXA-7200HH)
(2) Xanthene type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name EXA-7336)
(3) Fluorene type epoxy resin (product name: EX-1010, manufactured by Onfine)
(4) Naphthalene type liquid epoxy resin (manufactured by Dainippon Ink and Chemicals, trade name: HP-4032D)
(5) Dinaphthalene skeleton epoxy resin (Dainippon Ink & Chemicals, trade name: HP-4700)
(6) Bisphenol A type epoxy resin (trade name: Epicoat 828, monocyclic structure, manufactured by Japan Epoxy Resin Co., Ltd.)
(7) Cresol novolac type epoxy resin (manufactured by DIC, trade name: N-665, monocyclic structure)
(8) Trifunctional glycidyldiamine type epoxy resin (trade name: Epicoat 630, glycidylamine skeleton, manufactured by Japan Epoxy Resin Co., Ltd.)
(9) Cyclohexanedimethanol liquid epoxy resin (manufactured by Nagase ChemteX Corporation, trade name: EX216-L)
(10) Hexahydrophthalic acid type liquid epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: AK-601)
(11) Dicyclopentadiene type liquid epoxy resin (manufactured by Adeka, EP4088)
(High molecular weight polymer (c))
(1) Fluorene type phenoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: FX293, weight average molecular weight 43,700)
(2) Biphenyl type phenoxy resin (manufactured by Japan Epoxy Resin, trade name: YX8100, weight average molecular weight 38,000)
(3) Epoxy group-containing acrylic resin (manufactured by NOF Corporation, trade name: Marproof G0250S, weight average molecular weight 200,000)
(Curing agent (b))
(1) Acid anhydride curing agent (trade name: MH-700, manufactured by Shin Nippon Rika Co., Ltd.)
(2) Phenol-based curing agent (manufactured by Sumitomo Chemical Co., Ltd., trade name: EP415)
(3) Isocyanur-modified solid dispersion type imidazole (imidazole curing accelerator, manufactured by Shikoku Kasei Co., Ltd., trade name: 2MZA-PW)
(Inorganic filler (e))
(1) Surface hydrophobized fumed silica (manufactured by Tokuyama Corporation, trade name: MT-10, average particle size 15 nm)
(2) Spherical silica (manufactured by Tokuyama Corporation, trade name: SE-5, average particle size 5 μm)
(3) Layered silicate (trade name: STN65meq-w1 manufactured by Co-op Chemical)
(4) Silicon nitride (Denka Co., Ltd., trade name: SN-7, average particle size 44 μm)
(5) Alumina (Denka Co., Ltd., trade name: DAM-10, average particle size 10 μm)
(Rubber component (f))
(1) Core-shell type rubber fine particles (f) (manufactured by Mitsubishi Rayon Co., Ltd., trade name: KW4426, rubber fine particles having a shell made of methyl methacrylate and a core made of butyl acrylate, an average particle size of 5 μm)
(2) Silicone rubber fine particles (f1) (manufactured by Dow Corning Toray, trade name: Trefil E601, average particle size 2 μm)
(3) Fluororubber fine particles (f2) (manufactured by Daikin Industries, Ltd., trade name: Lubron L20, average particle size 2 μm)
(Additive)
(1) Epoxysilane coupling agent (trade name: KBM303, manufactured by Shin-Etsu Chemical Co., Ltd.)
(solvent)
(1) Methyl ethyl ketone (2) Dimethylformamide (3) Methyl isobutyl ketone (Example 1)
Using a homodisper type stirrer, each material was blended at a ratio shown in Table 1 below, and kneaded uniformly with a solvent to prepare an insulating material.

  The insulating material was applied to a 50 μm-thick release PET sheet to a thickness of 200 μm, and dried in a 70 ° C. oven for 1 hour to produce a 200 μm-thick insulating film.

(Examples 2 to 26 and Comparative Examples 1 to 5)
An insulating film was prepared in the same manner as in Example 1 except that the type and blending amount of the materials used were changed as shown in Tables 1 to 3 below.

(Evaluation of insulating films of Examples and Comparative Examples)
Each insulating film is as follows: (1) Storage elastic modulus (E1) of uncured insulating film at 30 ° C. and minimum storage elastic modulus (E2) at 30 ° C. or higher, (2) Insulating film after lamination Uniform coverage, (3) Handleability of uncured insulating film, (4) Glass transition temperature (Tg / ° C.) (5) Linear expansion coefficient (CTE / ppm), (6) Crack or peeling after cooling cycle test And (7) the occurrence of cracks or peeling after the high temperature storage test was evaluated.

(1) Storage elastic modulus (E1) at 30 ° C. of uncured insulating film and minimum storage elastic modulus (E2) at 30 ° C. or higher
A 200 μm-thick insulating film was cut into a disk shape having a diameter of 20 mm, and measured using a rheometer / VAR-100 (manufactured by Rheological Instruments) under the conditions of a frequency of 1 Hz, a strain of 1%, and a heating rate of 30 ° C./min. . The storage elastic modulus at 30 ° C. is determined as (E1), the minimum storage elastic modulus at 30 ° C. or higher is determined as (E2), and the storage elastic modulus is calculated as the ratio of (E1) to the minimum storage elastic modulus (E2) (E1) / (E2) was calculated.

(2) Uniform coverage of insulating film after lamination On a ceramic substrate on which a silicon chip having a thickness of 10 mm × 10 mm and a thickness of 300 μm is mounted, using a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho) at 40 ° C. And a test sample was prepared by heating and curing in an oven at 200 ° C. for 1 hour. The cross section of the produced test sample was observed with an optical microscope (TRANSFORMER-XN, manufactured by Nikon), and the uniform coverage was evaluated according to the following evaluation criteria.

Evaluation criteria for uniform coverage ○: The thickness of the thinnest portion of the silicon chip edge portion is 90% or more compared to the thickest portion of the insulating film after lamination on the silicon chip. Compared with the thickest part, the thickness of the thinnest part in the silicon chip edge part is 85% or more and less than 90%. ×: Compared with the thickest part of the insulating film after lamination, it is the thickest in the silicon chip edge part. The thickness of the thin part is less than 85%

(3) Handling property of uncured insulating film The insulating film was cut into A4 size, and the handling property when peeling from the release PET was evaluated according to the following evaluation criteria.
Evaluation criteria for handleability ◯: There is no deformation of the insulating film, and it can be easily peeled. △: The film can be peeled as an insulating film, but film elongation or breakage occurs.

(4) Glass transition temperature A 5 mm × 50 mm square cut out insulating film was cured in a 200 ° C. oven for 1 hour to prepare a test sample. The temperature is raised to -60 to 320 ° C. with a DMA mode (DVA-200, manufactured by IT Measurement & Control Co., Ltd.) in a pull mode, a distance between chucks of 24 mm, a heating rate of 5 ° C. per minute, a measurement frequency of 10 Hz, and 1% strain. Temperature-storage elastic modulus (E '), temperature-loss elastic modulus (E "), temperature-E" / E' (tan δ) slopes are measured, and the maximum peak temperature of tan δ is calculated as the glass transition temperature. did. As a glass transition temperature of an insulating film, 170 degreeC or more is preferable, More preferably, it is 180 degreeC or more, More preferably, it is 200 degreeC or more.

(5) Linear expansion coefficient What cut out the insulating film into the 3 mm x 25 mm square was hardened in 200 degreeC oven for 1 hour, and the test sample was produced. The temperature at which the temperature was raised once at 320 ° C. at 10 ° C. per minute with a TMA apparatus (TMA / SS6000, manufactured by Seiko Instruments Inc.) and then raised from 45 ° C. to 130 ° C. at 10 ° C. per minute— The slope of the TMA straight line was measured, and the reciprocal thereof was calculated as the linear expansion coefficient. The linear expansion coefficient of the insulating film is preferably 40 ppm or less, more preferably 30 ppm or less.

(6) Presence or absence of cracks or peeling after the thermal cycle test After the silicon chip was soldered on the copper substrate, the whole substrate was insulated with a vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho) at 40 ° C. And then cured by heating in a 200 ° C. oven for 1 hour to prepare a test sample. This was carried out for 1000 cycles with a one-chamber cooling / heating cycle tester (WINTECH NT510, manufactured by ETACH) at −40 ° C., 20 minutes, and 125 ° C. for 20 minutes as one cycle. The presence or absence of cracks on the cured product surface after the test was observed with an optical microscope (TRANSFORMER-XN, manufactured by Nikon), and the presence or absence of peeling was observed with an ultrasonic flaw detector (mi-scope hyper, manufactured by Hitachi Construction Machinery Finetech). The number of test samples in which cracks or peeling occurred in 10 test samples was counted and evaluated according to the following criteria.
Criteria for the presence or absence of cracks or delamination after the thermal cycle test ○: Test samples with cracks or delamination out of 10 samples, 2 samples or less Δ: Test samples with cracks or delamination out of 10 samples, 3-4 samples ×: 5 or more of 10 test samples in which cracks or peeling occurred

(7) Presence or absence of crack or peeling after high temperature standing test After soldering a silicon chip on a copper substrate, an insulating film is applied to the entire substrate under a vacuum laminator (MVLP-500, made by Meiki Seisakusho) at 40 ° C. And then cured by heating in a 200 ° C. oven for 1 hour to prepare a test sample. This was left in a 200 ° C. oven for 1000 hours. The presence or absence of cracks on the cured product surface after the test was observed with an optical microscope (TRANSFORMER-XN, manufactured by Nikon), and the presence or absence of peeling was observed with an ultrasonic flaw detector (mi-scope hyper, manufactured by Hitachi Construction Machinery Finetech). The number of test samples in which cracks or peeling occurred in 10 test samples was counted and evaluated according to the following criteria.

Evaluation criteria for presence or absence of cracks or delamination after standing at high temperature ○: Test samples with cracks or delamination out of 10 samples, 2 samples or less Δ: Test samples with cracks or delamination out of 10 samples, 3-4 samples X: 5 or more test samples out of 10 test samples in which cracks or peeling occurred are shown in Tables 1 to 3 below.

BRIEF DESCRIPTION OF THE DRAWINGS The schematic front sectional drawing for demonstrating the semiconductor device as one Embodiment of the electronic component apparatus of this invention. The schematic front sectional drawing which shows the modification of the semiconductor device as one Embodiment of the electronic component apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Semiconductor device 2 ... Board | substrate 3 ... Semiconductor element 4 ... Insulating layer 4a, 4b ... Hole 5a, 5b ... Wiring material 6 ... Wiring pattern 11 ... Semiconductor device 12 ... Insulating layer

Claims (12)

Containing a curable compound (a), a curing agent (b), a high molecular weight polymer (c), and an inorganic filler (e);
The storage elastic modulus (E1) at 30 ° C. of the insulating film before curing is in the range of 1 × 10 ⁴ to 1 × 10 ⁶ Pa, and the minimum storage elastic modulus (E2) at 30 ° C. or higher is 1 × 10 ^{2 to} 3 ×. Insulation, characterized in that it is in the range of 10 ⁴ Pa and the ratio (E1) / (E2) of the storage elastic modulus (E1) and the minimum storage elastic modulus (E2) is in the range of 2 to 500 the film.   The insulating film according to claim 1, wherein the curable compound (a) has two or more epoxy groups in one molecule and has a polycyclic hydrocarbon skeleton at least in a part of the main chain.   The insulating film according to claim 1, further comprising a rubber component (f).   The insulating film according to claim 3, wherein the rubber component (f) is rubber fine particles.   The insulating film of any one of Claims 1-4 which contains the said high molecular weight polymer (c) in the ratio of 5 to 60 weight% in 100 weight% of all resin parts in an insulating film. The inorganic filler (e) is spherical silica;
The insulating film of any one of Claims 1-5 which contains the said spherical silica in the ratio of 100-600 weight part with respect to 100 weight part of all the resin parts in an insulating film.   The said electronic component apparatus is a semiconductor device which used the semiconductor element as an electronic component element, and is an insulating film for semiconductor devices, The insulating film of any one of Claims 1-6 characterized by the above-mentioned.   The insulating film according to claim 7, wherein the semiconductor element is a power device element. A method of manufacturing an electronic component device using the insulating film according to claim 1,
Covering at least a part of the periphery of the electronic component element of the substrate on which the electronic component element is mounted with the insulating film to form an insulating layer;
Irradiating the insulating layer with a high-density energy beam, and forming a wiring hole in the insulating layer;
Filling the hole with a wiring material;
Forming a wiring pattern electrically connected to the wiring material filled in the hole on the surface of the insulating layer.   The method of manufacturing an electronic component device according to claim 9, wherein a semiconductor device is manufactured as the electronic component device using a semiconductor element as the electronic component device. An electronic component device having an insulating layer made of a cured product of the insulating film according to any one of claims 1 to 8,
A substrate,
An electronic component element mounted on the substrate;
An insulating layer that is formed of a cured product of the insulating film, is provided so as to cover at least a part of the periphery of the electronic component element, and is formed with a hole continuous with the surface;
A wiring material filled in the holes of the insulating layer;
An electronic component device comprising: a wiring pattern formed on the surface of the insulating layer and provided so as to be electrically connected to the wiring material. The electronic component device according to claim 11, wherein the electronic component element is a semiconductor element, and a semiconductor device is formed as the electronic component device.

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