JP6093880B2 - Curable composition, method for producing curable composition, and semiconductor device - Google Patents

Description

  The present invention relates to a curable composition suitably used for forming a cured product on the surface of the semiconductor element in order to protect the semiconductor element and a method for producing the curable composition. The present invention also relates to a semiconductor device using the curable composition.

  The performance of semiconductor devices is increasing. Along with this, there is an increasing need to dissipate heat generated from the semiconductor device. In the semiconductor device, the electrode of the semiconductor element is electrically connected to, for example, an electrode in another connection target member having the electrode on the surface.

  In a semiconductor device, for example, after an epoxy resin composition is disposed between a semiconductor element and another connection target member, the semiconductor element and the other connection target member are bonded and bonded by curing the epoxy resin composition. It is fixed. In addition, the hardened | cured material of the said epoxy resin composition arrange | positioned between a semiconductor element and another connection object member differs from the material for protecting the surface of a semiconductor element.

  In a semiconductor device, an epoxy resin composition may be used to seal a semiconductor element.

  The above epoxy resin composition is disclosed by the following patent documents 1-4, for example.

  Patent Document 1 below discloses an epoxy resin, a phenolic curing agent, a curing accelerator that is tris (2,6-dimethoxyphenyl) phosphine or tris (2,4,6-trimethoxyphenyl) phosphine, and alumina. An epoxy resin composition is disclosed. In the Example of patent document 1, the epoxy resin composition which is powder is described. Regarding the use of the epoxy resin composition, Patent Document 1 describes that it is suitably used for sealing semiconductor devices such as ICs, LSIs, transistors, thyristors, and diodes, and for manufacturing printed circuit boards. .

  Patent Document 2 listed below discloses an epoxy resin composition for sealing containing an epoxy resin, a phenol resin curing agent, a curing accelerator, and an inorganic filler. In the Example of patent document 2, the epoxy resin composition for sealing which is a powder is described. Regarding the use of the epoxy resin composition, in Patent Document 2, it can be used as a general molding material, but it is used as a sealing material for a semiconductor device, and is particularly thin, multi-pin, long wire, narrow pad pitch, or In addition, it is described that it is suitably used as a sealing material for a semiconductor device in which a semiconductor chip is disposed on a mounting substrate such as an organic substrate or an organic film.

  Patent Document 3 below discloses an epoxy resin composition containing a bisphenol F-type liquid epoxy resin, a curing agent, and an inorganic filler. In the Example of patent document 3, the epoxy resin composition (melt viscosity is 75 degreeC or more) which is solid is described. Regarding the use of the epoxy resin composition, in Patent Document 3, although it can be used as a general molding material, a semiconductor device, for example, a multi-pin thin package such as TQFP, TSOP, and QFP, particularly a semiconductor device using a matrix frame It is described that it is suitably used as a sealing material.

  Patent Document 4 below discloses an epoxy resin composition for semiconductor encapsulation containing an epoxy resin, a phenol resin curing agent, a high thermal conductive filler, and an inorganic filler. In the Example of patent document 4, the epoxy resin composition for semiconductor sealing which is powder is described. Regarding the use of the epoxy resin composition for semiconductor encapsulation, Patent Document 4 describes that it is used as a sealing material for electronic components such as semiconductor elements.

  Patent Document 5 listed below includes a first agent containing a bisphenol A type epoxy resin, a flexible epoxy resin in the skeleton, a second agent containing an acid anhydride compound and a curing accelerator, A two-component type epoxy resin composition having the following is disclosed. Patent Document 5 describes that the two-pack type epoxy resin composition is useful as an in-case filler.

JP-A-5-86169 JP 2007-217469 A JP-A-10-176100 Japanese Patent Laying-Open No. 2005-200533 JP 2014-40538 A

  Patent Documents 1 to 4 specifically disclose an epoxy resin composition that is a powder or a solid. Such a powder or solid epoxy resin composition has low applicability and is difficult to place accurately in a predetermined region.

  Moreover, in the hardened | cured material of the conventional epoxy resin composition, heat dissipation may be low. Furthermore, the cured product of the conventional epoxy resin composition may have low flexibility. If the flexibility of the cured product is low, the cured product may be peeled off due to, for example, deformation stress of the semiconductor element.

  Moreover, in patent documents 1-4, the sealing use is mainly described as a specific use of an epoxy resin composition. In patent document 5, as a specific application of the epoxy resin composition, a case-filler application is mainly described. On the other hand, in a semiconductor device, it is desirable to sufficiently protect a semiconductor element without sealing the semiconductor element. Moreover, generally the epoxy resin composition of patent documents 1-5 is not apply | coated and used on the surface of this semiconductor element, in order to protect a semiconductor element.

  In recent years, there has been a demand for reducing the number of IC drivers from the viewpoint of device thinness and design. If the number of IC drivers is reduced, the burden on the semiconductor element increases, and it becomes easier to get a considerable amount of heat. Conventional cured products have low heat dissipation properties, and therefore, cured products with high heat dissipation properties are required. Furthermore, in a conventional cured product, peeling is likely to occur due to deformation stress. Moreover, in order to obtain a highly reliable semiconductor element, it is desirable that the cured product has high moisture resistance.

  The present invention provides a curable composition suitably used for forming a cured product on the surface of a semiconductor element in order to protect the semiconductor element in a semiconductor device, and a method for producing the curable composition. With the goal.

  Furthermore, the objective of this invention is providing the manufacturing method of the curable composition which can obtain the hardened | cured material excellent in applicability | paintability and excellent in heat dissipation, a softness | flexibility, and moisture resistance, and a curable composition. Another object of the present invention is to provide a semiconductor device using the curable composition.

  In a wide aspect of the present invention, a flexible epoxy compound, an epoxy compound different from the flexible epoxy compound, a curing agent, spherical alumina, and a dispersant are included, and the amine value of the dispersant is 5 KOH mg / g. Thus, a curable composition is provided in which the acid value of the dispersant is 5 KOHmg / g or more.

  In a specific aspect of the curable composition according to the present invention, the amine value of the dispersant is 40 KOHmg / g or more and 95 KOHmg / g or less, and the acid value of the dispersant is 45 KOHmg / g or more and 95 KOHmg / g. It is as follows.

  On the specific situation with the curable composition concerning this invention, the absolute value of the difference of the amine value of the said dispersing agent and the acid value of the said dispersing agent is 10 or less.

  On the specific situation with the curable composition which concerns on this invention, the said curable composition does not contain a solvent or contains a solvent in less than 0.5 weight%.

  On the specific situation with the curable composition which concerns on this invention, content of the said spherical alumina becomes like this. Preferably it is 60 volume% or more, More preferably, it is 70 volume% or more.

  In a specific aspect of the curable composition according to the present invention, the spherical alumina includes a spherical alumina having an average particle diameter of 0.1 μm or more and less than 10 μm, and a spherical alumina having an average particle diameter of 10 μm or more and 80 μm or less. Including.

  On the specific situation with the curable composition which concerns on this invention, the said hardening | curing agent is an allylphenol novolak compound.

  On the specific situation with the curable composition which concerns on this invention, content of the epoxy compound different from the said flexible epoxy compound is 10 weight part or more and 100 weight with respect to 100 weight part of said flexible epoxy compounds. Or less.

  In a specific aspect of the curable composition according to the present invention, the curable composition comprises a silane coupling agent having a weight loss at 100 ° C. of 10% by weight or less, and a weight loss at 100 ° C. of 10% by weight. A titanate coupling agent which is the following, or an aluminate coupling agent whose weight loss at 100 ° C. is 10% by weight or less.

  On the specific situation with the curable composition which concerns on this invention, the said hardening | curing agent is a hardening | curing agent which is a liquid at 23 degreeC.

  On the specific situation with the curable composition which concerns on this invention, the said curable composition contains a hardening accelerator.

  On the specific situation with the curable composition which concerns on this invention, the said curable composition is arrange | positioned between a semiconductor element and another connection object member, The said semiconductor element and the said other connection object member are used. It differs from what forms the hardened | cured material which adheres and fixes so that it may not peel.

  In a specific aspect of the curable composition according to the present invention, the curable composition is for protecting a semiconductor element used to form a cured product on the surface of the semiconductor element in order to protect the semiconductor element. Material.

  On the specific situation with the curable composition which concerns on this invention, in order to protect a semiconductor element, the said curable composition is a semiconductor element protection material used by apply | coating on the surface of the said semiconductor element.

  According to a wide aspect of the present invention, there is provided a method for producing the curable composition described above, the flexible epoxy compound, an epoxy compound different from the flexible epoxy compound, the curing agent, and the spherical shape. There is provided a method for producing a curable composition comprising a mixing step of mixing alumina and the dispersant to obtain a curable composition.

  According to a broad aspect of the present invention, a semiconductor comprising a semiconductor element and a cured product disposed on the first surface of the semiconductor element, wherein the cured product is a cured product of the curable composition described above. An apparatus is provided.

  In a specific aspect of the semiconductor device according to the present invention, the semiconductor element has a first electrode on a second surface side opposite to the first surface side, and the first electrode of the semiconductor element Are electrically connected to the second electrode in the connection target member having the second electrode on the surface.

  The curable composition according to the present invention includes a flexible epoxy compound, an epoxy compound different from the flexible epoxy compound, a curing agent, spherical alumina, and a dispersant, and the amine value of the dispersant is Since it is 5 KOHmg / g or more and the acid value of the dispersant is 5 KOHmg / g or more, the coating property is excellent. Furthermore, it is excellent in the heat dissipation of the hardened | cured material of the curable composition concerning this invention, a softness | flexibility, and moisture resistance. Therefore, when the curable composition according to the present invention is cured on the surface of the semiconductor element in order to protect the semiconductor element, the semiconductor element can be well protected.

FIG. 1 is a partially cutaway front sectional view showing a semiconductor device using a curable composition according to a first embodiment of the present invention. FIG. 2 is a partially cutaway front sectional view showing a semiconductor device using a curable composition according to a second embodiment of the present invention.

  Hereinafter, the present invention will be described in detail.

  The curable composition concerning this invention is used suitably in order to form hardened | cured material on the surface of the said semiconductor element, in order to protect a semiconductor element. The curable composition according to the present invention is preferably applied on the surface of the semiconductor element in order to protect the semiconductor element. The curable composition according to the present invention comprises (A) a flexible epoxy compound, (B) an epoxy compound different from the flexible epoxy compound, (C) a curing agent, (E) spherical alumina, F) a dispersant.

  The manufacturing method of the curable composition which concerns on this invention is a manufacturing method of the curable composition used suitably in order to form hardened | cured material on the surface of the said semiconductor element, in order to protect a semiconductor element. The manufacturing method of the curable composition which concerns on this invention is a manufacturing method of the curable composition apply | coated on the surface of the said semiconductor element, and being used suitably, in order to protect a semiconductor element. The method for producing a curable composition according to the present invention comprises (A) a flexible epoxy compound, (B) an epoxy compound different from the flexible epoxy compound, (C) a curing agent, and (E) a spherical alumina. And (F) a dispersing step is mixed to obtain a curable composition. During mixing, the components (A), (B), (C), (E), and (F) (if necessary (D) a curing accelerator) may be mixed at one time, and some All of the components may be mixed and then mixed. Moreover, at the time of this mixing, without mixing the one part component of (A) (B), (C), (E), (F) component ((D) hardening accelerator as needed), A mixture in which some of the components are mixed may be obtained and used. The said mixing process is a process of obtaining the curable composition by which all (A) (B), (C), (E), (F) component ((D) hardening accelerator is mixed as needed) was mixed. .

  In the curable composition according to the present invention and the method for producing the curable composition according to the present invention, the amine value of the (F) dispersant is 5 KOHmg / g or more, and the acid value of the (F) dispersant is 5 KOHmg / g. g or more.

  The curable composition is preferably liquid at 23 ° C. and preferably not solid at 23 ° C. so that it can be coated on the surface of the semiconductor element. In addition, viscous paste is also contained in liquid form.

  Since the curable composition according to the present invention and the curable composition obtained by the method for producing the curable composition according to the present invention have the above-described configuration, they have excellent applicability and are not intended at the time of application. Flow can be suppressed. The said curable composition can be favorably apply | coated on the surface of a semiconductor element. For example, the curable composition can be selectively and accurately applied onto the surface of a portion where the heat dissipation of the semiconductor element is desired to be increased, and a cured product of the curable composition can be formed.

  Furthermore, since the curable composition which concerns on this invention is equipped with the structure mentioned above, it is excellent in the heat dissipation of hardened | cured material. For this reason, by arrange | positioning hardened | cured material on the surface of a semiconductor element, heat can fully be dissipated from the surface of a semiconductor element via hardened | cured material. For this reason, the thermal degradation of the semiconductor device can be effectively suppressed.

  Furthermore, the cured product of the curable composition according to the present invention is excellent in flexibility. For this reason, it becomes difficult to cause damage to the semiconductor element due to deformation stress of the semiconductor element, and further, it is difficult to peel the cured product from the surface of the semiconductor element.

  Moreover, in order to obtain a highly reliable semiconductor element, it is desirable that the cured product has high moisture resistance. In the curable composition concerning this invention, since the structure mentioned above is provided, the moisture resistance of hardened | cured material can also be improved.

  Therefore, in order to protect the semiconductor element, the semiconductor element can be well protected by curing the curable composition according to the present invention on the surface of the semiconductor element. Moreover, in order to protect a semiconductor element, in order to protect a semiconductor element, the said semiconductor element can be favorably protected by apply | coating on the surface of the said semiconductor element, and making it harden | cure.

  Moreover, the hardened | cured material of the said curable composition is excellent also in heat resistance, and it is hard to produce a crack. Furthermore, the cured product of the curable composition is also excellent in dimensional stability.

  Moreover, in this invention, since the specific (F) dispersing agent is used, a dispersion state becomes favorable and the applicability | paintability of a curable composition becomes favorable. In the present invention, since a specific (F) dispersant is used, it is not necessary to use a solvent (content of the solvent is 0% by weight (not contained)), and even when a solvent is used, good dispersion is achieved. In order to obtain the state, the content of the solvent can be reduced. For example, even if the solvent content is less than 0.5% by weight, a good dispersion state can be obtained. Moreover, if there is little content of a solvent, generation | occurrence | production of the void at the time of discharge of a curable composition and hardened | cured material will be suppressed.

  In addition, from the viewpoint of enhancing the wettability of the curable composition to the surface of the semiconductor element, further enhancing the flexibility and adhesive strength of the cured product, and further enhancing the moisture resistance of the cured product, the curable composition is (G) It is preferable that a coupling agent is included.

  It is preferable that the curable composition according to the present invention includes (D) a curing accelerator from the viewpoint of proceeding curing well and obtaining a cured product that is more excellent in heat dissipation, flexibility, and moisture resistance.

  Hereinafter, the detail of each component which can be used for the said curable composition is demonstrated.

((A) Flexible epoxy compound)
(A) By using a flexible epoxy compound, the softness | flexibility and adhesive force of hardened | cured material can be improved. (A) As for a flexible epoxy compound, only 1 type may be used and 2 or more types may be used together.

  (A) As an index of flexibility in a flexible epoxy compound, it is defined as an epoxy resin having a durometer ShoreD measurement of 30 or less when cured with a stoichiometric amount of diethylenetriamine (“DETA”). The

  (A) A flexible epoxy compound is an epoxy compound which has a flexible part in a molecule | numerator, for example. (A) The flexible epoxy compound is not particularly limited. For example, polyalkylene glycol diglycidyl ether, polybutadiene diglycidyl ether, sulfide modified epoxy resin, polyalkylene oxide modified bisphenol A type epoxy resin, aliphatic modified epoxy resin. , Ε-caprolactone-modified epoxy resin, rubber-modified epoxy resin, urethane-modified epoxy resin, amine-modified epoxy resin, dimer acid-modified epoxy resin, and the like. From the viewpoint of effectively increasing the flexibility and adhesive strength of the cured product, the (A) flexible epoxy compound preferably has two or more epoxy groups. From the viewpoint of further enhancing the flexibility and adhesive strength of the cured product, polyalkylene glycol diglycidyl ether is preferable.

  From the viewpoint of further enhancing the flexibility and adhesive strength of the cured product, the polyalkylene glycol diglycidyl ether preferably has a structural unit in which 9 or more alkylene glycol groups are repeated. The upper limit of the number of repeating alkylene groups is not particularly limited. The number of repeating alkylene groups may be 30 or less. The alkylene group preferably has 2 or more carbon atoms, preferably 5 or less carbon atoms.

  Examples of the polyalkylene glycol diglycidyl ether include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polytetramethylene glycol diglycidyl ether.

  In 100% by weight of the curable composition, the content of the (A) flexible epoxy compound is preferably 3% by weight or more, more preferably 5% by weight or more, preferably 10% by weight or less, more preferably 8% by weight. It is as follows. (A) The softness | flexibility and adhesive force of hardened | cured material become it higher that content of a flexible epoxy compound is more than the said minimum. (A) The applicability | paintability of a curable composition becomes it still higher that content of a flexible epoxy compound is below the said upper limit.

((B) Epoxy compound different from flexible epoxy compound)
(B) An epoxy compound different from the flexible epoxy compound does not have flexibility. By using the (B) epoxy compound together with the (A) flexible epoxy compound, the moisture resistance of the cured product of the curable composition is increased, and the sticking property to the protective film can be reduced. (B) As for an epoxy compound, only 1 type may be used and 2 or more types may be used together.

  (B) As an epoxy compound, an epoxy compound having a bisphenol skeleton, an epoxy compound having a dicyclopentadiene skeleton, an epoxy compound having a naphthalene skeleton, an epoxy compound having an adamantane skeleton, an epoxy compound having a fluorene skeleton, an epoxy having a biphenyl skeleton Examples thereof include an epoxy compound having a bi (glycidyloxyphenyl) methane skeleton, an epoxy compound having a xanthene skeleton, an epoxy compound having an anthracene skeleton, and an epoxy compound having a pyrene skeleton. These hydrogenated products or modified products may be used. (B) It is preferable that an epoxy compound is not polyalkylene glycol diglycidyl ether.

  Since the effect of the present invention is further improved, the (B) epoxy compound is preferably an epoxy compound having a bisphenol skeleton (bisphenol type epoxy compound).

  Examples of the epoxy compound having a bisphenol skeleton include an epoxy monomer having a bisphenol A type, bisphenol F type, or bisphenol S type bisphenol skeleton.

  Examples of the epoxy compound having a dicyclopentadiene skeleton include dicyclopentadiene dioxide and a phenol novolac epoxy monomer having a dicyclopentadiene skeleton.

  Examples of the epoxy compound having a naphthalene skeleton include 1-glycidylnaphthalene, 2-glycidylnaphthalene, 1,2-diglycidylnaphthalene, 1,5-diglycidylnaphthalene, 1,6-diglycidylnaphthalene, 1,7-diglycidyl. Naphthalene, 2,7-diglycidylnaphthalene, triglycidylnaphthalene, 1,2,5,6-tetraglycidylnaphthalene and the like can be mentioned.

  Examples of the epoxy compound having an adamantane skeleton include 1,3-bis (4-glycidyloxyphenyl) adamantane and 2,2-bis (4-glycidyloxyphenyl) adamantane.

  Examples of the epoxy compound having a fluorene skeleton include 9,9-bis (4-glycidyloxyphenyl) fluorene, 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene, and 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 and 9,9-bis (4-glycidyloxy-3,5-dibromophenyl) Orange, and the like.

  Examples of the epoxy compound having a biphenyl skeleton include 4,4'-diglycidylbiphenyl and 4,4'-diglycidyl-3,3 ', 5,5'-tetramethylbiphenyl.

  Examples of the epoxy compound having a bi (glycidyloxyphenyl) methane skeleton include 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'-bi (2,7-glycidyloxynaphthyl) methane, 1,2'-bi (3,7-glycidyloxynaphthyl) Examples include methane and 1,2′-bi (3,5-glycidyloxynaphthyl) methane.

  Examples of the epoxy compound having a xanthene skeleton include 1,3,4,5,6,8-hexamethyl-2,7-bis-oxiranylmethoxy-9-phenyl-9H-xanthene.

  In 100% by weight of the curable composition, the total content of (A) the flexible epoxy compound and (B) the epoxy compound is preferably 5% by weight or more, more preferably 8% by weight or more, preferably 15% by weight. % Or less, more preferably 12% by weight or less. When the total content of (A) flexible epoxy compound and (B) epoxy compound is not less than the above lower limit and not more than the above upper limit, applicability of the curable composition, flexibility of the cured product, moisture resistance, and curing. The adhesion of the object to the semiconductor element is further improved, and sticking to the protective film can be further suppressed.

  (A) The content of the epoxy compound (B) is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, preferably 100 parts by weight or less, more preferably 90 parts by weight with respect to 100 parts by weight of the flexible epoxy compound. Less than parts by weight. (B) When content of an epoxy compound is more than the said minimum, the applicability | paintability of a curable composition becomes still higher, and the adhesiveness with respect to the semiconductor element of hardened | cured material becomes still higher. (B) The softness | flexibility of hardened | cured material becomes it still higher that content of an epoxy compound is below the said upper limit.

(Curing agent)
From the viewpoint of further improving the applicability of the curable composition, the (C) curing agent is preferably liquid at 23 ° C. Moreover, the wettability with respect to the surface of the semiconductor element of a curable composition becomes high by use of the hardening | curing agent which is liquid at 23 degreeC. However, in the present invention, the (C) curing agent may not be liquid at 23 ° C. (C) Only 1 type may be used for a hardening | curing agent and 2 or more types may be used together.

  (C) As a hardening | curing agent, an amine compound (amine hardening | curing agent), an imidazole compound (imidazole hardening | curing agent), a phenol compound (phenol hardening | curing agent), an acid anhydride (acid anhydride hardening | curing agent), etc. are mentioned. However, when these curing agents are used, a curing agent that is liquid at 23 ° C. is selected. (C) The curing agent may not be an imidazole compound.

  From the viewpoint of further increasing the heat resistance of the cured product, the (C) curing agent is preferably a phenol compound.

  From the viewpoint of further improving the applicability of the curable composition and further improving the heat resistance of the cured product, the (C) curing agent preferably has an allyl group, and the phenol compound has an allyl group. preferable.

  Examples of the phenol compound include phenol novolak, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiene cresol, polyparavinylphenol, bisphenol A type novolak, xylylene modified novolak, decalin modified novolak, poly (di -O-hydroxyphenyl) methane, poly (di-m-hydroxyphenyl) methane, poly (di-p-hydroxyphenyl) methane, and the like.

  The total content of (A) flexible epoxy compound and (B) epoxy compound is 100 parts by weight, and the content of (C) the curing agent is preferably 10 parts by weight or more, more preferably 20 parts by weight or more. The amount is preferably 30 parts by weight or more, preferably 100 parts by weight or less, more preferably 90 parts by weight or less, and still more preferably 80 parts by weight or less. (C) A curable composition can be hardened favorably as content of a hardening | curing agent is more than the said minimum. When the content of (C) the curing agent is not more than the above upper limit, the residual amount of (C) curing agent that has not contributed to curing in the cured product is reduced.

((D) curing accelerator)
(D) By using a curing accelerator, the curing rate can be increased and the curable composition can be efficiently cured. (D) Only 1 type may be used for a hardening accelerator and 2 or more types may be used together.

  (D) As a hardening accelerator, an imidazole compound, a phosphorus compound, an amine compound, an organometallic compound, etc. are mentioned. Especially, since the effect of this invention is further excellent, an amine compound is preferable.

  Examples of the imidazole compound include 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2 ′ -Methyl Midazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6 [2′-Ethyl-4′-methylimidazolyl- (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 and 2-phenyl-4-methyl-5-dihydroxymethylimidazole Can be mentioned. Moreover, a well-known imidazole-type latent hardening | curing agent can be used. Specific examples include PN23, PN40, and PN-H (trade names, all manufactured by Ajinomoto Fine Techno Co., Ltd.). In addition, a curing accelerator, which is also called microencapsulated imidazole, added to a hydroxyl group of an epoxy adduct of an amine compound, for example, Novacure HX-3088, Novacure HX-3941, HX-3742, HX-3722 (trade name, Asahi Kasei E-Materials Co., Ltd.). Furthermore, inclusion imidazole can also be used. Specific examples include TIC-188 (trade name, manufactured by Nippon Soda Co., Ltd.).

  Examples of the phosphorus compound include triphenylphosphine.

  Examples of the amine compound include 2,4,6-tris (dimethylaminomethyl) phenol, diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, 4,4-dimethylaminopyridine, dioctabicycloundecene octylate, and the like. Is mentioned.

  Examples of the organometallic compound include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and trisacetylacetonate cobalt (III).

  The content of (D) the curing accelerator is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight, based on 100 parts by weight of the total of (A) the flexible epoxy compound and (B) the epoxy compound. It is at least 10 parts by weight, more preferably at most 8 parts by weight. (D) When content of a hardening accelerator is more than the said minimum, a curable composition can be hardened favorably. When the content of (D) the curing accelerator is not more than the above upper limit, the residual amount of (D) the curing accelerator that has not contributed to curing in the cured product is reduced.

((E) spherical alumina)
(E) By using spherical alumina, it is possible to improve the heat dissipation of the cured product while maintaining high applicability of the curable composition and maintaining high flexibility of the cured product. (E) The spherical alumina is not particularly limited. (E) As a spherical alumina, only 1 type may be used, for example, 2 or more types from which an average particle diameter differs may be used together.

  (E) Spherical alumina is spherical. The spherical shape means that the aspect ratio (major axis / minor axis) is 1 or more and 1.3 or less.

  (E) The average particle diameter of the spherical alumina is preferably 0.1 μm or more, and preferably 150 μm or less. (E) When the average particle diameter of the spherical alumina is not less than the above lower limit, (E) the spherical alumina can be easily filled at a high density. (E) The applicability | paintability of a curable composition becomes it still higher that the average particle diameter of spherical alumina is below the said upper limit.

  In the mixing step, from the viewpoint of effectively enhancing the applicability of the curable composition and the heat dissipation of the cured product, (E) as spherical alumina, (E1) has an average particle size of 0.1 μm or more and less than 10 μm. It is preferable to use spherical alumina and (E2) spherical alumina having an average particle diameter of 10 μm or more and 80 μm or less. The curable composition preferably contains (E1) a spherical alumina having an average particle diameter of 0.1 μm or more and less than 10 μm, and (E2) a spherical alumina having an average particle diameter of 10 μm or more and 80 μm or less.

  The “average particle diameter” is an average particle diameter obtained from a volume average particle size distribution measurement result measured by a laser diffraction particle size distribution measuring apparatus.

  In 100% by volume of the curable composition, the content of (E) spherical alumina is preferably 55% by volume or more, more preferably 60% by volume or more, still more preferably 70% by volume or more, and preferably 80% by volume or less. . (E) The heat dissipation of hardened | cured material becomes it higher that content of spherical alumina is more than the said minimum. (E) The coating property of a curable composition becomes it still higher that content of spherical alumina is below the said upper limit.

  (E1) With respect to 100 parts by volume of spherical alumina having an average particle diameter of 0.1 μm or more and less than 10 μm, the content of (E2) spherical alumina having an average particle diameter of 10 μm or more and 80 μm or less is preferably 40 Volume parts or more, more preferably 50 parts by volume or more, preferably 70 parts by volume or less, more preferably 60 parts by volume or less.

((F) Dispersant)
The amine value of (F) dispersant is 5 KOHmg / g or more, and the acid value of (F) dispersant is 5 KOHmg / g or more. By using such a specific dispersant, the effect of the present invention is exhibited. (F) Only 1 type may be used for a dispersing agent and 2 or more types may be used together. The amine value of the dispersant can be measured according to JIS K7237, and the acid value of the dispersant can be measured according to JIS K0070.

  From the viewpoint of further improving the applicability of the curable composition, the amine value of the (F) dispersant is preferably 20 KOHmg / g or more, more preferably 40 KOHmg / g or more, preferably 110 KOHmg / g or less, more preferably 95 KOH mg / g or less.

  From the viewpoint of further improving the applicability of the curable composition, the acid value of the (F) dispersant is preferably 20 KOH mg / g or more, more preferably 45 KOH mg / g or more, preferably 110 KOH mg / g or less, more preferably. Is 95 KOHmg / g or less.

  From the viewpoint of further improving the applicability of the curable composition, the absolute value of the difference between the amine value of (F) the dispersant and the acid value of (F) the dispersant is preferably 10 KOHmg / g or less, more Preferably it is 7 KOHmg / g or less. The absolute value of the difference between the amine value of the (F) dispersant and the acid value of the (F) dispersant may be 0 KOH mg / g (the amine value and the acid value are the same).

  Specific examples of the (F) dispersant include polycarboxylates, alkyl ammonium salts, alkylol ammonium salts, phosphate ester salts, acrylic block copolymers, and polymer salts. Since the effect of the present invention is further improved, the dispersant (F) is preferably a polycarboxylic acid salt, an alkylol ammonium salt, or a phosphate ester salt.

  In 100% by weight of the curable composition, the content of the (F) dispersant is preferably 0.05% by weight or more, more preferably 0.1% by weight or more, preferably 2% by weight or less, more preferably 1% by weight. % Or less. (F) When the content of the dispersant is not less than the above lower limit, (E) the dispersibility of the spherical alumina is further enhanced. (F) The coating property of a curable composition becomes it still higher that content of a dispersing agent is below the said upper limit.

((G) coupling agent)
The curable composition preferably contains (G) a coupling agent. (G) By using a coupling agent, the moisture resistance and adhesive force of the hardened | cured material of a curable composition become still higher. (G) As for a coupling agent, only 1 type may be used and 2 or more types may be used together.

  In 100% by weight of the curable composition, the content of the (G) coupling agent is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, preferably 2% by weight or less, more preferably 1%. % By weight or less. (G) When content of a coupling agent is more than the said minimum, the moisture resistance of the hardened | cured material of a curable composition will become still higher.

  The (G) coupling agent is a silane coupling agent whose weight loss at 100 ° C. is 10% by weight or less, a titanate coupling agent whose weight loss at 100 ° C. is 10% by weight or less, or at 100 ° C. It is preferable to include an aluminate coupling agent having a weight loss of 10% by weight or less. When using these preferable silane coupling agents, only 1 type may be used for these silane coupling agents, and 2 or more types may be used together.

  When the weight loss at 100 ° C. is 10% by weight or less, the volatilization of the (G) coupling agent is suppressed during curing, and the amount of voids generated can be suppressed. Thus, the heat dissipation of the cured product is further enhanced. Moreover, tackiness can be improved.

  The weight decrease at 100 ° C. was measured by using an infrared moisture meter (“FD-720” manufactured by Kett Scientific Laboratory) at a temperature increase rate of 50 ° C./min. It can be determined by measuring the decrease.

(Other ingredients)
The said curable composition does not contain a solvent or when the solvent is contained, it is preferable that the content of the solvent is small.

  Examples of the solvent include water and organic solvents. Among these, an organic solvent is preferable from the viewpoint of further improving the removability of the residue. Examples of the organic solvent include alcohols such as ethanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, and methylcarbitol. , Glycol ethers such as butyl carbitol, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether, ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve Acetate, carbitol acetate, butyl carbitol acetate, propylene glycol mono Chill ether acetate, dipropylene glycol monomethyl ether acetate, esters such as propylene carbonate, octane, aliphatic hydrocarbons decane, and petroleum ether, petroleum solvents such as naphtha.

  When the curable composition contains the solvent, the content of the solvent is preferably less than 0.5% by weight and more preferably less than 0.3% by weight in 100% by weight of the curable composition. .

  If necessary, the curable composition may be a natural wax such as carnauba wax, a synthetic wax such as polyethylene wax, a higher fatty acid such as stearic acid or zinc stearate and a metal salt thereof, or a mold release agent such as paraffin; carbon black Colorants such as Bengala; flame retardants such as brominated epoxy resins, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, phosphazene; inorganic ion exchangers such as bismuth oxide hydrate; silicone Various additives such as an oil trapping agent such as an oil or silicone rubber; an antioxidant; an ion exchanger such as an anion exchanger, a cation exchanger or an amphoteric ion exchanger may be included.

  The curable composition may contain a spherical filler having a thermal conductivity of 10 W / m · K or more as necessary, for example, spherical synthetic magnesite, spherical crystalline silica, spherical Boron nitride, spherical aluminum nitride, spherical silicon nitride, spherical silicon carbide, spherical zinc oxide, spherical magnesium oxide, or the like may be included.

(Other details of curable composition and semiconductor device)
The curable composition is preferably used by coating on the surface of the semiconductor element in order to protect the semiconductor element. The curable composition is preferably a material for protecting a semiconductor element that is used by coating on the surface of the semiconductor element in order to protect the semiconductor element. The curable composition is preferably a coating material that covers the surface of the semiconductor element. It is preferable that the said curable composition is not apply | coated on the side surface of a semiconductor element. The curable composition is preferably different from a material for sealing the semiconductor element, and is preferably not a sealing agent for sealing the semiconductor element. The curable composition is preferably not an underfill material. The semiconductor element has a first electrode on a second surface side, and the curable composition is used by being applied on a first surface opposite to the second surface side of the semiconductor element. It is preferred that The curable composition is preferably used for forming a cured product on the surface of the semiconductor element in order to protect the semiconductor element in the semiconductor device. The curable composition is preferably a semiconductor element protecting material used to form a cured product on the surface of the semiconductor element in order to protect the semiconductor element in the semiconductor device. The curable composition is preferably used for forming a cured product on the surface of the semiconductor element to protect the semiconductor element, and on the surface of the cured product opposite to the semiconductor element side. It is suitably used for arranging a protective film to obtain a semiconductor device. The curable composition is disposed between a semiconductor element and another connection target member, and forms a cured product that adheres and fixes the semiconductor element and the other connection target member so as not to peel off. Are preferably different.

  Examples of the method for applying the curable composition include a coating method using a dispenser, a coating method using screen printing, and a coating method using an inkjet apparatus. The curable composition is preferably used by being applied by a dispenser, screen printing, vacuum screen printing, or an application method using an inkjet apparatus. From the viewpoint of facilitating application and making it more difficult to generate voids in the cured product, the curable composition is preferably applied by a dispenser.

  A semiconductor device according to the present invention includes a semiconductor element and a cured product disposed on the first surface of the semiconductor element. In the semiconductor device according to the present invention, the cured product is a cured product of the curable composition described above, and is formed by curing the curable composition.

  In order to protect the semiconductor element, the curable composition forms a cured product on the surface of the semiconductor element, and a protective film is disposed on the surface of the cured product opposite to the semiconductor element side. In order to protect the semiconductor element, a cured product is formed on the surface of the semiconductor element, and a surface opposite to the semiconductor element side of the cured product is exposed. It is preferably used for obtaining a semiconductor device.

  FIG. 1 is a partially cutaway front sectional view showing a semiconductor device using a curable composition according to a first embodiment of the present invention.

  A semiconductor device 1 shown in FIG. 1 includes a semiconductor element 2 and a cured product 3 disposed on the first surface 2 a of the semiconductor element 2. The cured product 3 is formed by curing the curable composition described above. The cured product 3 is disposed in a partial region on the first surface 2 a of the semiconductor element 2. In this embodiment, the curable composition mentioned above is used as a semiconductor element protection material.

  The semiconductor element 2 has a first electrode 2A on the second surface 2b side opposite to the first surface 2a side. The semiconductor device 1 further includes a connection target member 4. The connection target member 4 has a second electrode 4A on the surface 4a. The semiconductor element 2 and the connection target member 4 are bonded and fixed via another cured product 5 (connection portion). The first electrode 2 </ b> A of the semiconductor element 2 and the second electrode 4 </ b> A of the connection target member 4 face each other and are electrically connected by the conductive particles 6. The first electrode 2 </ b> A and the second electrode 4 </ b> A may be electrically connected by being in contact with each other. Hardened | cured material 3 is arrange | positioned on the 1st surface 2a on the opposite side to the side by which the 1st electrode 2A of the semiconductor element 2 is arrange | positioned.

  A protective film 7 is disposed on the surface of the cured product 3 opposite to the semiconductor element 2 side. Thereby, not only the heat dissipation and the protection of the semiconductor element are enhanced by the cured product 3, but also the protection of the semiconductor element can be further enhanced by the protective film 7. Since the hardened | cured material 3 has the composition mentioned above, it can suppress sticking with respect to the protective film 7 of the hardened | cured material 3.

  Examples of the connection target member include a glass substrate, a glass epoxy substrate, a flexible printed substrate, and a polyimide substrate.

  On the surface of the semiconductor element, the thickness of the cured product of the curable composition is preferably 400 μm or more, more preferably 500 μm or more, preferably 2000 μm or less, more preferably 1900 μm or less. The thickness of the cured product of the curable composition may be thinner than the thickness of the semiconductor element.

  FIG. 2 is a partially cutaway front sectional view showing a semiconductor device using a curable composition according to a second embodiment of the present invention.

  A semiconductor device 1X illustrated in FIG. 2 includes a semiconductor element 2 and a cured product 3X disposed on the first surface 2a of the semiconductor element 2. The cured product 3X is formed by curing the above-described curable composition. The cured product 3 </ b> X is disposed in the entire region on the first surface 2 a of the semiconductor element 2. The protective film is not arranged on the surface opposite to the semiconductor element 2 side of the cured product 3X. The surface opposite to the semiconductor element 2 side of the cured product 3X is exposed. In this embodiment, the curable composition mentioned above is used as a semiconductor element protection material.

  In the semiconductor device, a protective film is disposed on the surface of the cured product opposite to the semiconductor element side, or the surface of the cured product opposite to the semiconductor element side is exposed. Is preferred.

  The structures shown in FIGS. 1 and 2 are merely examples of the semiconductor device, and can be appropriately modified to an arrangement structure of a cured product of the curable composition.

  Although the heat conductivity of the hardened | cured material of a semiconductor protective material is not specifically limited, It is preferable that it is 2.3 W / m * K or more.

  Hereinafter, the present invention will be clarified by giving specific examples and comparative examples of the present invention. The present invention is not limited to the following examples.

  The following materials were used.

(A) Flexible epoxy compound EX-821 (n (number of alkylene glycol groups) = 4) (manufactured by Nagase ChemteX Corporation, polyethylene glycol diglycidyl ether, epoxy equivalent: 185)
EX-830 (n = 9) (manufactured by Nagase ChemteX Corporation, polyethylene glycol diglycidyl ether, epoxy equivalent: 268)
EX-931 (n = 11) (manufactured by Nagase ChemteX Corporation, polypropylene glycol diglycidyl ether, epoxy equivalent: 471)
EX-861 (n = 22) (manufactured by Nagase ChemteX Corporation, polyethylene glycol diglycidyl ether, epoxy equivalent: 551)

(B) Epoxy compound different from flexible epoxy compound jER828 (Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent: 188)
jER834 (Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, softening point: 30 ° C., epoxy equivalent: 255)

(C) Curing agent Fuji Cure 7000 (Fuji Kasei Co., Ltd., liquid at 23 ° C., amine compound)
Rikacid MH-700 (manufactured by Shin Nippon Chemical Co., Ltd., liquid at 23 ° C, acid anhydride)
MEH-8005 (Maywa Kasei Co., Ltd., liquid at 23 ° C., allylphenol novolak compound)

(D) Curing accelerator SA-102 (manufactured by San Apro, DBU octylate)
HX-3742 (Asahi Kasei E-Materials, Microcapsule Imidazole)

(E) Spherical alumina AO-802 (manufactured by Admatechs, average particle size 0.7 μm)
CB-P05 (manufactured by Showa Denko KK, average particle size 5 μm)
CB-P15 (manufactured by Showa Denko KK, average particle size 15 μm)
CB-P40 (Showa Denko KK, average particle size 40 μm)
CB-A70 (manufactured by Showa Denko KK, average particle size 70 μm)

(E ') Crushed alumina AL-13-H (Showa Denko KK, average particle size 60 μm)
AL-42KT (manufactured by Showa Denko KK, average particle size 4.6 μm)

(F) Dispersant ANTI-TERRA-U 100 (BYK, acid value 50 KOH mg / g, amine value 35 KOH mg / g)
BYK-9076 (manufactured by BYK, acid value 38 KOH mg / g, amine value 44 KOH mg / g)
DISPERBYK-180 (BYK, acid value 94 KOH mg / g, amine value 94 KOH mg / g)
DISPERBYK-142 (BYK, acid value 46 KOHmg / g, amine value 43 KOHmg / g)
ANTI-TERRA-204 (BYK, acid value 41 KOH mg / g, amine value 37 KOH mg / g)
DISPERBYK-145 (BYK, acid value 76 KOHmg / g, amine value 71 KOHmg / g)
(F ′) Other dispersant DISPERBYK-102 (BYK, acid value 101 KOHmg / g)
DISPERBYK-109 (manufactured by BYK, amine value 140 KOHmg / g)

(G) Coupling agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane, weight loss at 100 ° C .: more than 10% by weight)
A-LINK599 (product of Momentive, 3-octanoylthio-1-propyltriethoxysilane, weight loss at 100 ° C .: 10% by weight or less)
TOG (IPA cut) (Nihon Soda Co., Ltd., titanium-i-propoxyoctylene glycolate, weight loss at 100 ° C .: 10% by weight or less)
AL-M (Ajinomoto Fine Techno Co., Ltd., acetoalkoxyaluminum diisopropylate, weight loss at 100 ° C .: 10% by weight or less)

(Other ingredients)
KYOWARD 500PL (Kyowa Chemical Co., Ltd., ion trapping agent)

(solvent)
MFDG (manufactured by Nippon Emulsifier Co., Ltd., boiling point 187 ° C)
DBDG (manufactured by Nippon Emulsifier Co., Ltd., boiling point 254 ° C)

Example 1
EX-821 (n = 4) is 5.5 parts by weight, jER828 is 2.5 parts by weight, Fujicure 7000 is 2 parts by weight, SA-102 is 0.5 parts by weight, and ANTI-TERRA-U 100 is 0.5 parts by weight. Part by weight, 35 parts by weight of CB-P05, 35 parts by weight of CB-A70, and 0.1 parts by weight of KYOWARD 500PL were mixed and defoamed to obtain a semiconductor element protecting material (curable composition). .

(Examples 2-27 and Comparative Examples 1-7)
The semiconductor element protecting material (curable composition) was obtained in the same manner as in Example 1 except that the types and amounts of the components were changed (units are parts by weight) as shown in Tables 1 to 4 below. It was.

(Evaluation)
(1) Measurement of viscosity at 25 ° C. Using a B-type viscometer (“TVB-10 type” manufactured by Toki Sangyo Co., Ltd.), measure the viscosity (Pa · s) at 10 rpm at 25 ° C. of the semiconductor element protecting material. did. The viscosity was determined according to the following criteria.

[Criteria for viscosity]
○: 60 Pa · s or more, less than 125 Pa · s Δ: 125 Pa · s or more, less than 150 Pa · s ×: 150 Pa · s or more, or impossible to measure

(2) Thermal conductivity The obtained material for protecting a semiconductor element was heated at 150 ° C. for 2 hours and cured to obtain a cured product of 100 mm × 100 mm × thickness 50 μm. This cured product was used as an evaluation sample.

  The thermal conductivity of the obtained evaluation sample was measured using a thermal conductivity meter “rapid thermal conductivity meter QTM-500” manufactured by Kyoto Electronics Industry Co., Ltd. The thermal conductivity was determined according to the following criteria.

[Criteria for thermal conductivity]
○: Thermal conductivity of 3.0 W / m · K or more Δ: Thermal conductivity of 2.3 W / m · K or more, less than 3.0 W / m · K ×: Thermal conductivity of 2.3 W / m · K Less than

(3) Coating property After the obtained semiconductor element protecting material is directly discharged from a dispenser device ("SHOTMASTER-300" manufactured by Musashi Engineering Co., Ltd.) onto a polyimide film so as to have a diameter of 5 mm and a height of 2 mm, semiconductor element protection is performed. The material was cured by heating at 150 ° C. for 2 hours. The applicability was determined from the shape of the semiconductor element protecting material after curing according to the following criteria.

[Criteria for applicability]
◯: Diameter 5.45 mm or more and height less than 1.75 mm (with fluidity)
○: Diameter exceeding 5.3 mm, less than 5.45 mm, height exceeding 1.75 mm, less than 1.8 mm (with fluidity)
Δ: Over 5.15 mm in diameter, less than 5.3 mm, over 1.8 mm in height and less than 1.9 mm (with little fluidity)
△△: More than 5 mm in diameter, less than 5.15 mm, more than 1.9 mm in height and less than 2 mm (with little fluidity)
X: 5 mm in diameter and 2 mm in height (no fluidity) or impossible to apply

(4) Moisture resistance The obtained semiconductor element protecting material was heated at 150 ° C. for 2 hours and cured to obtain a cured product of 100 mm × 100 mm × thickness 50 μm. This cured product was used as an evaluation sample.

  Using the obtained evaluation sample, and using DSM-8104 (manufactured by Hioki Electric Co., Ltd., digital super insulation / microammeter), electrode for flat plate sample: SME-8310 (manufactured by Hioki Electric Co., Ltd.), the volume resistivity is determined. It was measured.

  Next, a pressure cooker test was conducted with an advanced accelerated life test apparatus EHS-211 (manufactured by Espec). After being left for 24 hours under the conditions of 121 ° C., humidity 100% RH and 2 atm, and then allowed to stand for 24 hours in an environment of 23 ° C. and humidity 50% RH, the volume resistivity was measured. The decrease rate of the volume resistivity before and after the pressure cooker test was calculated, and the moisture resistance was judged according to the following criteria.

[Criteria for moisture resistance]
○: Decrease rate of volume resistivity before and after the test is 10% or less Δ: Decrease rate of the volume resistivity before and after the test exceeds 10% and 20% or less ×: Decrease rate of the volume resistivity before and after the test is 20% Exceed

(5) Generated amount of voids 100 g of the obtained semiconductor element protecting material was discharged onto a polyimide film from a dispenser device (“SHOTMASTER-300” manufactured by Musashi Engineering Co., Ltd.). Whether or not voids were generated during the discharge of 100 g of the semiconductor element protecting material was confirmed. The amount of voids generated was determined according to the following criteria. When the semiconductor element protecting material was cured by heating at 150 ° C. for 2 hours, voids generated during discharge remained in the cured product. In addition, when the void has generate | occur | produced, it confirmed that the heat dissipation of hardened | cured material tends to become low in the part with a void. Further, the vicinity of the part where the void is present becomes a starting point of unintended peeling.

[Criteria for the amount of void generation]
○: No void is generated Δ: 1-2 voids are generated ×: 3 or more voids are generated

(6) Adhesive strength (die shear strength)
On the polyimide substrate, a semiconductor element protecting material was applied so that the adhesion area was 3 mm × 3 mm, and a 1.5 mm square Si chip was placed thereon to obtain a test sample.

  The obtained test sample was heated at 150 ° C. for 2 hours to cure the semiconductor element protecting material. Next, the die shear strength at 25 ° C. was evaluated at a speed of 300 μm / second using a die shear tester (“DAGE 4000” manufactured by Arctech).

[Adhesion criteria]
○: Die shear strength is 10N or more △: Die shear strength is 5N or more and less than 10N ×: Die shear strength is less than 5N

(7) Tack (protective film sticking property)
The obtained semiconductor element protecting material was heated at 150 ° C. for 2 hours and cured to obtain a cured product of 100 mm × 100 mm × thickness 50 μm. This cured product was used as an evaluation sample.

  The obtained evaluation sample was allowed to stand for 24 hours in an atmosphere of 23 ° C. and humidity 50% RH. Immediately after being allowed to stand for 24 hours, stress was measured using a tack tester TA-500 (manufactured by UBM) in order to evaluate the tackiness (tackiness) of the surface of the evaluation sample.

[Criteria for tackiness]
○: Stress is less than 50 gf / cm ² Δ: Stress is 50 gf / cm ² or more, less than 100 gf / cm ² ×: Stress is 100 gf / cm ² or more

(8) Film warp (flexibility)
After the obtained semiconductor element protecting material was directly discharged from a dispenser device (“SHOTMASTER-300” manufactured by Musashi Engineering Co., Ltd.) onto the polyimide film so as to have a length of 20 mm, a width of 100 mm, and a height of 10 mm, the semiconductor element protection material Was cured by heating at 150 ° C. for 2 hours. After curing, the warpage of the polyimide film was visually confirmed, and the film warpage was determined according to the following criteria.

[Criteria for film warpage]
○: No warpage of polyimide film ×: Warpage of polyimide film

(9) Heat resistance The obtained material for protecting a semiconductor element was heated at 150 ° C. for 2 hours and cured to obtain a cured product of 100 mm × 100 mm × thickness 50 μm. This cured product was used as an evaluation sample.

  Using the obtained evaluation sample, and using DSM-8104 (manufactured by Hioki Electric Co., Ltd., digital super insulation / microammeter), electrode for flat plate sample: SME-8310 (manufactured by Hioki Electric Co., Ltd.), the volume resistivity is determined. It was measured.

  Next, the evaluation sample was allowed to stand at 180 ° C. for 100 hours, and then left at 23 ° C. and a humidity of 50% RH for 24 hours, and then the volume resistivity was measured. The decrease rate of the volume resistivity before and after the heat test was calculated, and the heat resistance was judged according to the following criteria.

[Criteria for heat resistance]
○: Decrease rate of volume resistivity before and after the test is 10% or less Δ: Decrease rate of the volume resistivity before and after the test exceeds 10% and 20% or less ×: Decrease rate of the volume resistivity before and after the test is 20% Exceed

  The compositions and results are shown in Tables 1 to 4 below.

DESCRIPTION OF SYMBOLS 1,1X ... Semiconductor device 2 ... Semiconductor element 2a ... 1st surface 2b ... 2nd surface 2A ... 1st electrode 3, 3X ... Hardened | cured material 4 ... Connection object 4a ... Surface 4A ... 2nd electrode 5 ... Other cured products 6 ... conductive particles 7 ... protective film

Claims (20)

A flexible epoxy compound that is a polyalkylene glycol diglycidyl ether, an epoxy compound different from the flexible epoxy compound, a curing agent, spherical alumina, and a dispersing agent,
The curable composition whose amine value of the said dispersing agent is 5 KOHmg / g or more, and whose acid value of the said dispersing agent is 5 KOHmg / g or more.   The curable composition according to claim 1, wherein the dispersant has an amine value of 40 KOH mg / g or more and 95 KOH mg / g or less, and the dispersant has an acid value of 45 KOH mg / g or more and 95 KOH mg / g or less.   The curable composition of Claim 1 or 2 whose absolute value of the difference of the amine value of the said dispersing agent and the acid value of the said dispersing agent is 10 or less.   The curable composition of any one of Claims 1-3 which does not contain a solvent or contains a solvent in less than 0.5 weight%.   The curable composition according to any one of claims 1 to 4, wherein the content of the spherical alumina is 60% by volume or more.   The curable composition according to claim 5, wherein the content of the spherical alumina is 70% by volume or more.   The spherical alumina includes spherical alumina having an average particle diameter of 0.1 μm or more and less than 10 μm, and spherical alumina having an average particle diameter of 10 μm or more and 80 μm or less. The curable composition as described.   The curable composition according to any one of claims 1 to 7, wherein the curing agent is an allylphenol novolak compound. The content of the epoxy compound different from the flexible epoxy compound is 10 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the flexible epoxy compound that is the polyalkylene glycol diglycidyl ether. The curable composition of any one of 1-8.   Silane coupling agent whose weight loss at 100 ° C is 10% by weight or less, titanate coupling agent whose weight loss at 100 ° C is 10% by weight or less, or weight loss at 100 ° C is 10% by weight or less The curable composition of any one of Claims 1-9 containing an aluminate coupling agent.   The curable composition according to any one of claims 1 to 10, wherein the curing agent is a curing agent that is liquid at 23 ° C.   The curable composition of any one of Claims 1-11 containing a hardening accelerator.   It differs from what forms the hardened | cured material which is arrange | positioned between a semiconductor element and another connection object member, and adheres and fixes so that the said semiconductor element and said other connection object member may not be peeled. 13. The curable composition according to any one of 12 above.   The curable composition of any one of Claims 1-13 which is a semiconductor element protection material used in order to form a hardened | cured material on the surface of the said semiconductor element in order to protect a semiconductor element.   The curable composition of any one of Claims 1-14 which is a semiconductor element protection material used by apply | coating on the surface of the said semiconductor element in order to protect a semiconductor element. In order to protect the semiconductor element, it is a semiconductor element protecting material used by applying on the surface of the semiconductor element,
Contains a curing accelerator,
The curable composition according to any one of claims 1 to 14, wherein the curing agent is a curing agent that is liquid at 23 ° C.   It differs from what forms the hardened | cured material which is arrange | positioned between a semiconductor element and another connection object member, and adheres and fixes so that the said semiconductor element and said other connection object member may not be peeled. The curable composition according to any one of 16. A method of manufacturing a curable composition according to any one of claims 1 to 17
Mixing a flexible epoxy compound that is the polyalkylene glycol diglycidyl ether, an epoxy compound different from the flexible epoxy compound, the curing agent, the spherical alumina, and the dispersing agent, and curing The manufacturing method of a curable composition provided with the mixing process which obtains a composition. A semiconductor element, and a cured product disposed on the first surface of the semiconductor element,
The cured product is a cured product of a curable composition according to any one of claims 1 to 17 semiconductor devices. The semiconductor element has a first electrode on a second surface side opposite to the first surface side, and the first electrode of the semiconductor element has a second electrode on the surface. The semiconductor device according to claim 19 , wherein the semiconductor device is electrically connected to the second electrode in a member.

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