JP2017039799A - Material for protecting semiconductor element and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material for protecting a semiconductor capable of obtaining a cured article excellent in coating property and heat releasing property and capable of protecting the semiconductor satisfactorily.SOLUTION: The material for protecting a semiconductor element contains a thermosetting compound, a curing agent and a curing catalyst and an inorganic filler with thermal conductivity of 10 W/m K or more and has viscosity at 25°C and 10 rpm is 40 Pa s to 140 Pa s and viscosity at 25°C and 1 rpm is 50 Pa s to 300 Pa s.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a semiconductor element protecting material that is used by coating on the surface of the semiconductor element in order to protect the semiconductor element. The present invention also relates to a semiconductor device using the semiconductor element protecting material.

  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 1-5, 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.

  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.

  The present invention provides a semiconductor element protecting material used for forming a cured product on the surface of a semiconductor element by applying the semiconductor element on the surface of the semiconductor element to protect the semiconductor element in a semiconductor device. The purpose is to do.

  Furthermore, an object of the present invention is to provide a semiconductor element protecting material capable of obtaining a cured product having excellent coating properties and excellent heat dissipation in the above applications, and capable of protecting the semiconductor elements satisfactorily. It is. Another object of the present invention is to provide a semiconductor device using the semiconductor element protecting material.

  In a broad aspect of the present invention, in order to protect a semiconductor element, a material for protecting a semiconductor element, which is applied on the surface of the semiconductor element and used to form a cured product on the surface of the semiconductor element, Thermosetting compound, unlike the one that forms a cured product that is disposed between a semiconductor element and another connection target member and adheres and fixes the semiconductor element and the other connection target member so as not to peel off. And a curing agent or a curing catalyst and an inorganic filler having a thermal conductivity of 10 W / m · K or more, a viscosity at 25 ° C. and 10 rpm is 40 Pa · s or more and 140 Pa · s or less, There is provided a semiconductor element protecting material having a viscosity at 1 rpm of 50 Pa · s or more and 300 Pa · s or less.

  In a specific aspect of the semiconductor element protecting material according to the present invention, the ratio of the viscosity at 25 ° C. and 1 rpm to the viscosity at 25 ° C. and 10 rpm is 1.2 or more and 3.0 or less.

  In a specific aspect of the semiconductor element protecting material according to the present invention, the viscosity at 25 ° C. and 10 rpm after storage at 40 ° C. for 6 hours is from 50 Pa · s to 150 Pa · s, and at 40 ° C. for 6 hours. The viscosity at 25 ° C. and 1 rpm after storage is 60 Pa · s or more and 300 Pa · s or less.

  On the specific situation with the semiconductor element protection material which concerns on this invention, the said thermosetting compound contains an epoxy compound or a silicone compound.

  On the specific situation with the semiconductor element protection material which concerns on this invention, the said hardening | curing agent is an allyl phenol novolak compound.

  On the specific situation with the semiconductor element protection material which concerns on this invention, the said thermosetting compound contains a flexible epoxy compound.

  On the specific situation with the semiconductor element protection material which concerns on this invention, the said thermosetting compound contains the epoxy compound different from the said flexible epoxy compound and a flexible epoxy compound.

  In a specific aspect of the semiconductor element protecting material according to the present invention, the flexible epoxy compound contained in the semiconductor element protecting material has a polyalkylene glycol di having a structural unit in which nine or more alkylene glycol groups are repeated. Glycidyl ether.

  The material for protecting a semiconductor element according to the present invention forms a cured product on the surface of the semiconductor element to protect the semiconductor element, and a protective film on the surface opposite to the semiconductor element side of the cured product In order to protect the semiconductor element, a cured product is formed on the surface of the semiconductor element and opposite to the semiconductor element side of the cured product. Is used to obtain a semiconductor device having a surface exposed.

  According to a wide aspect of the present invention, the semiconductor device includes a semiconductor element and a cured product disposed on the first surface of the semiconductor element, and the cured product is a cured product of the semiconductor element protecting material described above. A semiconductor device 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.

  On the specific situation with the semiconductor device which concerns on this invention, the protective film is arrange | positioned on the surface on the opposite side to the said semiconductor element side of the said hardened | cured material, or it is opposite to the said semiconductor element side of the said hardened | cured material The surface of is exposed.

  The material for protecting a semiconductor element according to the present invention includes a thermosetting compound, a curing agent or a curing catalyst, and an inorganic filler having a thermal conductivity of 10 W / m · K or more, and has a viscosity at 25 ° C. and 10 rpm. Since it is 40 Pa · s or more and 140 Pa · s or less and the viscosity at 25 ° C. and 1 rpm is 50 Pa · s or more and 300 Pa · s or less, it is excellent in coating property. Furthermore, it is excellent in the heat dissipation of the hardened | cured material of the semiconductor element protection material which concerns on this invention. Therefore, the semiconductor element protecting material according to the present invention can be satisfactorily protected by applying and curing the surface of the semiconductor element in order to protect the semiconductor element.

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

  Hereinafter, the present invention will be described in detail.

  The material for protecting a semiconductor element according to the present invention is applied to form a cured product on the surface of the semiconductor element by coating the surface of the semiconductor element in order to protect the semiconductor element. The material for protecting a semiconductor element according to the present invention is a cured product that is disposed between a semiconductor element and another connection target member and adheres and fixes the semiconductor element and the other connection target member so as not to peel off. It is different from what is formed (material).

  The material for protecting a semiconductor element according to the present invention comprises (A) a thermosetting compound, (B) a curing agent or a curing catalyst ((B1) curing agent or (B2) curing catalyst), and (C) a thermal conductivity. And an inorganic filler that is 10 W / m · K or more. The material for protecting a semiconductor element according to the present invention is preferably liquid at 23 ° C. and not solid at 23 ° C. in order to be applied on the surface of the semiconductor element. In addition, viscous paste is also contained in liquid form.

  The viscosity of the semiconductor element protecting material according to the present invention at 25 ° C. and 10 rpm is 40 Pa · s or more and 140 Pa · s or less. The viscosity of the semiconductor element protecting material according to the present invention at 25 ° C. and 1 rpm is 50 Pa · s or more and 300 Pa · s or less.

  Since the semiconductor element protecting material according to the present invention has the above-described configuration, it has excellent coating properties and can suppress unintended flow during coating. The semiconductor element protecting material can be satisfactorily applied on the surface of the semiconductor element. For example, the semiconductor element protecting material can be selectively and accurately applied onto the surface of a portion where it is desired to improve the heat dissipation of the semiconductor element.

  Furthermore, since the semiconductor element protecting material according to the present invention has the above-described configuration, the shape retention after application is high and the heat dissipation of the cured product is excellent. 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.

  Therefore, the semiconductor element protecting material according to the present invention can be satisfactorily protected by applying and curing the surface of the semiconductor element in order to protect the semiconductor element.

  From the viewpoint of improving applicability, the viscosity of the semiconductor element protecting material at 25 ° C. and 10 rpm is 40 Pa · s or more and 140 Pa · s or less. From the viewpoint of further improving applicability, the viscosity of the semiconductor element protecting material at 25 ° C. and 10 rpm is preferably 50 Pa · s or more, and preferably 130 Pa · s or less.

  From the viewpoint of improving shape retention after coating, the viscosity of the semiconductor element protecting material at 25 ° C. and 1 rpm is 50 Pa · s or more and 300 Pa · s or less. From the viewpoint of further improving the shape retention after application, the viscosity of the semiconductor element protecting material at 25 ° C. and 1 rpm is preferably 60 Pa · s or more, and preferably 280 Pa · s or less.

  Regarding the semiconductor element protecting material before storage, the ratio of the viscosity at 25 ° C. and 1 rpm to the viscosity at 25 ° C. and 10 rpm is preferably 1.2 or more, more preferably 1.3 or more, and preferably 3. It is 0 or less, more preferably 2.8 or less.

  From the viewpoint of enhancing the storage stability and further improving the coating property after storage, the viscosity at 25 ° C. and 10 rpm after storing the semiconductor element protecting material at 40 ° C. for 6 hours is preferably 50 Pa · s or more. , Preferably 150 Pa · s or less. After storage, the temperature of the semiconductor element protecting material is lowered to 25 ° C. over 60 minutes.

  From the viewpoint of enhancing the storage stability and further enhancing the shape retention after coating after storage, the viscosity at 25 ° C. and 1 rpm after storing the semiconductor element protecting material at 40 ° C. for 6 hours is preferably 60 Pa · s or more, preferably 300 Pa · s or less. After storage, the temperature of the semiconductor element protecting material is lowered to 25 ° C. over 60 minutes.

  The viscosity is measured using a B-type viscometer (“TVB-10 type” manufactured by Toki Sangyo Co., Ltd.).

  From the viewpoint of further improving the curability, the semiconductor element protecting material preferably includes (B1) a curing agent and (D) a curing accelerator.

  In addition, from the viewpoint of increasing the wettability of the semiconductor element protecting material to the surface of the semiconductor element, further enhancing the flexibility of the cured product, and further enhancing the moisture resistance of the cured product, the semiconductor element protecting material is: (E) It is preferable that a coupling agent is included.

  Hereinafter, details of each component that can be used for the semiconductor element protecting material will be described.

((A) thermosetting compound)
(A) Examples of the thermosetting compound include oxetane compounds, epoxy compounds, episulfide compounds, (meth) acrylic compounds, phenolic compounds, amino compounds, unsaturated polyester compounds, polyurethane compounds, silicone compounds, and polyimide compounds. (A) As for a thermosetting compound, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of effectively exerting the effects of the present invention, further increasing the heat resistance, and further reducing the occurrence of cracks, (A) the thermosetting compound is (A1) an epoxy compound or (A2) silicone. It is preferable to include a compound. (A) The thermosetting compound may contain (A1) an epoxy compound, and (A2) may contain a silicone compound.

  In 100% by weight of the semiconductor element protecting material, the content of the (A) thermosetting compound is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 20% by weight or less, more preferably 15% by weight. Hereinafter, it is further preferably 10% by weight or less, particularly preferably 8% by weight or less. (A) When content of a thermosetting compound is more than the said minimum and below the said upper limit, the applicability | paintability of a semiconductor element protection material, the softness | flexibility of cured | curing material, moisture resistance, and the adhesiveness with respect to the semiconductor element of cured | curing material are more. It becomes much better and sticking to the protective film can be further suppressed.

  The total content of (A1) epoxy compound and (A2) silicone compound in 100% by weight of the semiconductor element protecting material is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 20% by weight. Hereinafter, it is more preferably 15% by weight or less. When the total content of (A1) epoxy compound and (A2) silicone compound is not less than the above lower limit and not more than the above upper limit, the coatability of the semiconductor element protecting material, the flexibility of the cured product, the moisture resistance, Adhesiveness to the semiconductor element is further improved, and sticking to the protective film can be further suppressed.

(A1) Epoxy compound:
In 100% by weight of the semiconductor element protecting material, the content of the (A1) epoxy compound is preferably 1% by weight or more, more preferably 2% by weight or more, preferably 10% by weight or less, more preferably 8% by weight or less. It is. (A1) When the content of the epoxy compound is not less than the above lower limit and not more than the above upper limit, the coatability of the semiconductor element protecting material, the flexibility of the cured product, the moisture resistance, and the adhesion of the cured product to the semiconductor element are even better. Thus, sticking to the protective film can be further suppressed.

  (A1) As an epoxy compound, the epoxy compound different from (A11) flexible epoxy compound and (A12) flexible epoxy compound is mentioned. From the viewpoint of effectively demonstrating the effects of the present invention, (A) the thermosetting compound contains (A11) a flexible epoxy compound and (A12) an epoxy compound different from the flexible epoxy compound. Is preferred.

  (A12) An epoxy compound different from a flexible epoxy compound does not have flexibility. By using the (A12) epoxy compound together with the (A11) flexible epoxy compound, the moisture resistance of the cured product of the semiconductor element protecting material can be increased, and the adhesion to the protective film can be reduced. (A12) As for an epoxy compound, only 1 type may be used and 2 or more types may be used together.

  The (A) thermosetting compound preferably contains (A11) a flexible epoxy compound. (A11) The flexibility of the cured product can be increased by using a flexible epoxy compound. (A11) By using a flexible epoxy compound, it becomes difficult to cause damage to the semiconductor element due to deformation stress of the semiconductor element, and it is also possible to make it difficult to peel the cured product from the surface of the semiconductor element. (A11) As for a flexible epoxy compound, only 1 type may be used and 2 or more types may be used together.

  (A11) Examples of the flexible epoxy compound include polyalkylene glycol diglycidyl ether, polybutadiene diglycidyl ether, sulfide-modified epoxy resin, and polyalkylene oxide-modified bisphenol A type epoxy resin. From the viewpoint of further enhancing the flexibility of the cured product, polyalkylene glycol diglycidyl ether is preferred.

  From the viewpoint of further increasing the flexibility of the cured product and improving the adhesive strength, 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 semiconductor element protecting material, the content of the (A11) 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. % Or less. (A11) When the content of the flexible epoxy compound is not less than the above lower limit, the flexibility of the cured product is further increased. (A11) When the content of the flexible epoxy compound is not more than the above upper limit, the applicability of the semiconductor element protecting material is further enhanced.

  The total content of (A11) flexible epoxy compound and (A12) epoxy compound in 100% by weight of the semiconductor element protecting material 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. (A11) When the total content of the flexible epoxy compound and (A12) epoxy compound is not less than the above lower limit and not more than the above upper limit, the coatability of the semiconductor element protecting material, the flexibility of the cured product, the moisture resistance, The adhesiveness of the cured product to the semiconductor element is further improved, and sticking to the protective film can be further suppressed.

  (A12) 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. (A12) The epoxy compound is preferably not a polyalkylene glycol diglycidyl ether.

  Since the effect of the present invention is further improved, the (A12) 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.

  (A11) The content of the (A12) epoxy compound 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. (A12) When the content of the epoxy compound is not less than the above lower limit, the applicability of the semiconductor element protecting material is further enhanced, and the adhesiveness of the cured product to the semiconductor element is further enhanced. (A12) When the content of the epoxy compound is not more than the above upper limit, the flexibility of the cured product is further increased.

  (A2) The silicone compound includes, for example, a silicone compound having an alkenyl group bonded to a silicon atom and a silicone compound having a hydrogen atom bonded to a silicon atom. A silicone compound having an alkenyl group bonded to a silicon atom may not have a hydrogen atom bonded to a silicon atom.

  The silicone compound having an alkenyl group bonded to a silicon atom is a silicone compound represented by the following formula (1A), a silicone compound represented by the following formula (2A), or a silicone compound represented by the following formula (3A). It is preferable that

(R1R2R3SiO _1/2 ) _a (R4R5SiO _2/2 ) _b (1A)

  In the above formula (1A), a and b satisfy 0.01 ≦ a ≦ 0.2 and 0.8 ≦ b ≦ 0.99, and 1 mol% or more and 20 mol% or less of R1 to R5 represent an alkenyl group. 80 to 99 mol% of R1 to R5 represent a methyl group and a phenyl group, and R1 to R5 other than the alkenyl group, the methyl group and the phenyl group represent an alkyl group having 2 to 6 carbon atoms.

(R1R2R3SiO _1/2 ) _a (SiO _4/2 ) _b (2A)

  In the above formula (2A), a and b satisfy 0.7 ≦ a ≦ 0.9 and 0.1 ≦ b ≦ 0.3, and 1 mol% or more and 33 mol% or less of R1 to R3 represent an alkenyl group. 80 to 99 mol% of R1 to R3 represent a methyl group and a phenyl group, and R1 to R3 other than the alkenyl group, the methyl group and the phenyl group represent an alkyl group having 2 to 6 carbon atoms.

(R1R2R3SiO _1/2 ) _a (R4R5SiO _2/2 ) _b (R6SiO _3/2 ) _c (3A)

  In the above formula (3A), a, b and c satisfy 0.05 ≦ a ≦ 0.3, 0 ≦ b ≦ 0.8, 0.15 ≦ c ≦ 0.85, and 2 mol% of R1 to R6 As mentioned above, 20 mol% or less represents an alkenyl group, 80 mol% or more of R1 to R6, 95 mol% or less represents a methyl group and a phenyl group, and R1 to R6 other than the alkenyl group, the methyl group and the phenyl group have 2 to 2 carbon atoms. Represents an alkyl group of 6;

  The silicone compound having a hydrogen atom bonded to the silicon atom is preferably a silicone compound represented by the following formula (1B).

(R1R2R3SiO _1/2 ) _a (R4R5SiO _2/2 ) _b (1B)

  In the above formula (1B), a and b satisfy 0.1 ≦ a ≦ 0.67 and 0.33 ≦ b ≦ 0.9, and 1 mol% or more and 25 mol or less% of R1 to R5 represent hydrogen atoms. , R1 to R5 of 75 mol% or more and 99 mol% or less represent a methyl group and a phenyl group, and R1 to R5 other than a hydrogen atom, a methyl group and a phenyl group represent an alkyl group having 2 to 6 carbon atoms.

  (A2) The silicone compound preferably contains a silicone compound represented by the above formula (1A). (A2) The silicone compound includes a silicone compound represented by the above formula (1A) and a silicone compound represented by the above formula (2A), or a silicone compound represented by the above formula (1A) and And a silicone compound represented by the above formula (3A).

  In 100% by weight of the semiconductor element protecting material, the content of the (A2) silicone compound is preferably 5% by weight or more, more preferably 8% by weight or more, preferably 20% by weight or less, more preferably 15% by weight or less. It is. (A2) When the content of the silicone compound is not less than the above lower limit and not more than the above upper limit, the coatability of the semiconductor element protecting material, the flexibility of the cured product, the moisture resistance, and the adhesion of the cured product to the semiconductor element are even better. Thus, sticking to the protective film can be further suppressed.

  The content of the silicone compound having an alkenyl group bonded to the silicon atom is preferably 10 parts by weight or more, preferably 400 parts by weight or less with respect to 100 parts by weight of the silicone compound having a hydrogen atom bonded to the silicon atom. . If this content relationship is satisfied, the coating property of the semiconductor element protecting material, the flexibility of the cured product, the moisture resistance, the adhesion of the cured product to the semiconductor device will be further improved, and the sticking to the protective film will be further enhanced. Can be suppressed.

((B) curing agent or curing catalyst)
(B) As a curing agent or a curing catalyst, (B1) a curing agent may be used, or (B2) a curing catalyst may be used. When (A1) an epoxy compound is used, (B1) a curing agent is preferred. When (A2) a silicone compound is used, (B2) a curing catalyst is preferred.

  (B1) The curing agent may be liquid at 23 ° C. or solid. From the viewpoint of further improving the applicability of the semiconductor element protecting material, the (B1) curing agent is preferably a curing agent that is liquid at 23 ° C. Moreover, the wettability with respect to the surface of the semiconductor element of the semiconductor element protection material becomes high by using a curing agent that is liquid at 23 ° C. (B1) Only 1 type may be used for a hardening | curing agent and 2 or more types may be used together. (B2) Only one type of curing catalyst may be used, or two or more types may be used in combination.

  Examples of (B1) curing agents include amine compounds (amine curing agents), imidazole compounds (imidazole curing agents), phenolic compounds (phenol curing agents), and acid anhydrides (acid anhydride curing agents). (B1) The curing agent may not be an imidazole compound.

  From the viewpoint of further suppressing the generation of voids in the cured product and further increasing the heat resistance of the cured product, the (B1) curing agent is preferably a phenol compound.

  From the viewpoint of further improving the coating property of the semiconductor element protecting material, further suppressing the generation of voids in the cured product, and further enhancing the heat resistance of the cured product, the (B1) curing agent has an allyl group. It is preferable that the phenol compound has an allyl group.

  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.

  When (B1) curing agent is used, the content of (B1) curing agent is preferably 50 parts by weight or more, more preferably 75 parts by weight or more, with respect to 100 parts by weight of (A) thermosetting compound. The amount is preferably 100 parts by weight or more, preferably 250 parts by weight or less, more preferably 225 parts by weight or less, and still more preferably 200 parts by weight or less. (B1) When content of a hardening | curing agent is more than the said minimum, the semiconductor element protection material can be hardened favorably. When the content of the (B1) curing agent is not more than the above upper limit, the residual amount of the (B1) curing agent that did not contribute to curing in the cured product is reduced.

  (B2) Examples of the curing catalyst include metal catalysts such as hydrosilylation reaction catalysts and condensation catalysts.

  Examples of the curing catalyst include a tin-based catalyst, a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst. Since the transparency can be increased, a platinum-based catalyst is preferable.

  The hydrosilylation catalyst is a catalyst that causes a hydrosilylation reaction between a hydrogen atom bonded to a silicon atom in a silicone compound and an alkenyl group in the silicone compound. As for the said catalyst for hydrosilylation reaction, only 1 type may be used and 2 or more types may be used together.

  Examples of the platinum-based catalyst include platinum powder, chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, and a platinum-carbonyl complex. In particular, a platinum-alkenylsiloxane complex or a platinum-olefin complex is preferable.

  Examples of the alkenylsiloxane in the platinum-alkenylsiloxane complex include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3,5,7-tetramethyl-1,3,5. , 7-tetravinylcyclotetrasiloxane and the like. Examples of the olefin in the platinum-olefin complex include allyl ether and 1,6-heptadiene.

  Since stability of the platinum-alkenylsiloxane complex and platinum-olefin complex can be improved, alkenylsiloxane, organosiloxane oligomer, allyl ether or olefin is added to the platinum-alkenylsiloxane complex or platinum-olefin complex. Is preferred. The alkenylsiloxane is preferably 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. The organosiloxane oligomer is preferably a dimethylsiloxane oligomer. The olefin is preferably 1,6-heptadiene.

  When using the (B2) curing catalyst, the content of the (B2) curing catalyst is preferably 0.001 part by weight or more, more preferably 0.01% by weight with respect to 100 parts by weight of the (A) thermosetting compound. Part or more, more preferably 0.05 part by weight or more, preferably 2 parts by weight or less, more preferably 1 part by weight or less, still more preferably 0.5 parts by weight or less. (B2) When the content of the curing catalyst is not less than the above lower limit, the semiconductor element protecting material can be cured well. When the content of the (B2) curing catalyst is not more than the above upper limit, the residual amount of the (B2) curing catalyst that has not contributed to the curing in the cured product is reduced.

((C) Inorganic filler having a thermal conductivity of 10 W / m · K or more)
(C) By using an inorganic filler having a thermal conductivity of 10 W / m · K or more, a cured product while maintaining high applicability of the semiconductor element protecting material and maintaining high flexibility of the cured product. The heat dissipation can be improved. (C) As for an inorganic filler, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of further improving the heat dissipation of the cured product, the thermal conductivity of the (C) inorganic filler is preferably 10 W / m · K or more, more preferably 15 W / m · K or more, and even more preferably 20 W / m ·. K or more. (C) The upper limit of the thermal conductivity of the inorganic filler is not particularly limited. Inorganic fillers having a thermal conductivity of about 300 W / m · K are widely known, and inorganic fillers having a thermal conductivity of about 200 W / m · K are easily available.

  From the viewpoint of effectively improving the heat dissipation of the cured product, the (C) inorganic filler is preferably alumina, aluminum nitride, or silicon carbide. When using these preferable inorganic fillers, only 1 type may be used for these inorganic fillers, and 2 or more types may be used together. (C) As an inorganic filler, you may use suitably inorganic fillers other than the above.

  From the viewpoint of effectively increasing the heat dissipation of the cured product while effectively maintaining the applicability of the semiconductor element protecting material and effectively maintaining the flexibility of the cured product, (C) inorganic The filler is preferably an inorganic filler having a thermal conductivity of 10 W / m · K or more and a spherical shape. The spherical shape means that the aspect ratio (major axis / minor axis) is 1 or more and 2 or less.

  (C) The average particle diameter of the inorganic filler is preferably 0.1 μm or more, and preferably 150 μm or less. (C) When the average particle diameter of an inorganic filler is more than the said minimum, (C) an inorganic filler can be filled with high density easily. (C) When the average particle diameter of the inorganic filler is not more than the above upper limit, the coating property of the semiconductor element protecting material is further enhanced.

  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 weight of the semiconductor element protecting material, the content of (C) inorganic filler is preferably 60% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and particularly preferably 82% by weight or more. , Preferably 92% by weight or less, more preferably 90% by weight or less. (C) The heat dissipation of hardened | cured material becomes it higher that content of an inorganic filler is more than the said minimum. (C) When content of an inorganic filler is below the said upper limit, the applicability | paintability of a semiconductor element protection material becomes still higher.

((D) curing accelerator)
(D) By using a curing accelerator, the curing rate can be increased, and the semiconductor element protecting material 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 imidazole 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, etc. Is 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, and 4,4-dimethylaminopyridine.

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

  (A) The content of the (D) curing accelerator is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, preferably 10 parts by weight with respect to 100 parts by weight in total with the thermosetting compound. It is 8 parts by weight or less, more preferably 8 parts by weight or less. (D) When content of a hardening accelerator is more than the said minimum, a semiconductor element protection material 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) coupling agent)
The semiconductor element protecting material preferably includes (E) a coupling agent. (E) By using a coupling agent, the moisture resistance of the hardened | cured material of a semiconductor element protection material becomes still higher. (E) 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 semiconductor element protecting material, the content of the (E) coupling agent is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, preferably 2% by weight or less, more preferably 1% by weight or less. (E) The moisture resistance of the hardened | cured material of a semiconductor element protection material becomes it still higher that content of a coupling agent is more than the said minimum. (E) When content of a coupling agent is below the said upper limit, the applicability | paintability of the semiconductor element protection material becomes still higher.

  The (E) 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 coupling agents, only 1 type may be used for these coupling agents, and 2 or more types may be used together.

  When the weight loss at 100 ° C. is 10% by weight or less, volatilization of the (E) coupling agent is suppressed during curing, the wettability to the semiconductor element is further increased, and the heat dissipation of the cured product is further increased. .

  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)
If necessary, the above-mentioned material for protecting a semiconductor element may include 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 Colorants such as black and bengara; flame retardants such as brominated epoxy resins, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, and phosphazene; inorganic ion exchangers such as bismuth oxide hydrate; Low stress components such as silicone oil and silicone rubber; various additives such as antioxidants may be included.

  The semiconductor element protecting material preferably contains a dispersant. Specific examples of the dispersant include polycarboxylic acid salts, alkyl ammonium salts, alkylol ammonium salts, phosphate ester salts, acrylic block copolymers, and polymer salts.

  In 100% by weight of the semiconductor element protecting material, the content of the dispersant is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, preferably 2% by weight or less, more preferably 1% by weight. It is as follows.

(Other details of semiconductor element protecting materials and semiconductor devices)
The said semiconductor element protection material is apply | coated and used on the surface of the said semiconductor element, in order to protect a semiconductor element. The semiconductor element protecting material is disposed between the semiconductor element and another connection target member to form a cured product that adheres and fixes the semiconductor element and the other connection target member so as not to peel off. Is different. The semiconductor element protecting material is preferably a coating material that covers the surface of the semiconductor element. The semiconductor element protecting material is preferably not applied on the side surface of the semiconductor element. The material for protecting a semiconductor element is preferably different from a material for sealing the semiconductor element, and is preferably not a sealant for sealing the semiconductor element. The semiconductor element protecting material is preferably not an underfill material. The semiconductor element has a first electrode on a second surface side, and the semiconductor element protecting material is applied on a first surface opposite to the second surface side of the semiconductor element. It is preferable to be used. The semiconductor element protecting material is suitably 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 semiconductor element protecting material 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. The protective film is preferably used for obtaining a semiconductor device.

  Examples of the method for applying the semiconductor element protecting material include a coating method using a dispenser, a coating method using screen printing, and a coating method using an inkjet device. The semiconductor element protecting material 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 semiconductor element protecting material 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 formed by curing the semiconductor element protecting material.

  In order to protect the semiconductor element, the semiconductor element protecting material 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 the surface of the cured product opposite to the semiconductor element side is used. It is preferably used to obtain an exposed semiconductor device.

  FIG. 1 is a partially cutaway front sectional view showing a semiconductor device using a semiconductor element protecting material 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 above-described semiconductor element protecting material. The cured product 3 is disposed in a partial region on the first surface 2 a of the semiconductor element 2.

  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 material of the semiconductor element protecting material 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 semiconductor element protecting material may be smaller than the thickness of the semiconductor element.

  FIG. 2 is a partially cutaway front sectional view showing a semiconductor device using a semiconductor element protecting material 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 semiconductor element protecting material described above. 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 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 a semiconductor device, and can be appropriately modified to an arrangement structure of a cured product of a semiconductor element protecting material.

  Although the heat conductivity of the hardened | cured material of a semiconductor element protection material is not specifically limited, It is preferable that it is 1.8 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.

(A1) Epoxy compound EX-821 (n = 4) ((A11) Flexible epoxy compound, manufactured by Nagase ChemteX Corporation, polyethylene glycol diglycidyl ether, epoxy equivalent: 185)
EX-830 (n = 9) ((A11) flexible epoxy compound, manufactured by Nagase ChemteX Corporation, polyethylene glycol diglycidyl ether, epoxy equivalent: 268)
EX-931 (n = 11) ((A11) flexible epoxy compound, manufactured by Nagase ChemteX Corporation, polypropylene glycol diglycidyl ether, epoxy equivalent: 471)
EX-861 (n = 22) ((A11) flexible epoxy compound, manufactured by Nagase ChemteX Corporation, polyethylene glycol diglycidyl ether, epoxy equivalent: 551)
PB3600 (manufactured by Daicel, polypudadiene-modified epoxy resin, epoxy equivalent: 200)
jER828 ((A12) epoxy compound, manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent: 188)
jER834 ((A12) epoxy compound, manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, softening point: 30 ° C., epoxy equivalent: 255)

(A2) Silicone Compound [Synthesis of Polymer A as Silicone Compound]
In a 1000 mL separable flask equipped with a thermometer, a dropping device and a stirrer, 164.1 g of dimethyldimethoxysilane, 20.1 g of methylphenyldimethoxysilane and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane 4.7 g was added and stirred at 50 ° C. A solution obtained by dissolving 2.2 g of potassium hydroxide in 35.1 g of water was slowly dropped therein, and after the dropwise addition, the mixture was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, volatile components were removed under reduced pressure, 2.4 g of acetic acid was added to the reaction solution, and the mixture was heated under reduced pressure. Thereafter, potassium acetate was removed by filtration to obtain polymer A.

The number average molecular weight of the obtained polymer A was 15000. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer A had the following average composition formula.

(Me ₂ SiO _2/2 ) _0.85 (PhMeSiO _2/2 ) _0.10 (ViMe ₂ SiO _1/2 ) _0.05

  In the above formula, Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group. In the obtained polymer A, the content ratio of phenyl groups and methyl groups was 97.6 mol%, and the content ratio of vinyl groups was 2.4 mol%.

  The molecular weight of each polymer was measured by GPC measurement by adding 1 mL of tetrahydrofuran to 10 mg, stirring until dissolved. In GPC measurement, a measuring device manufactured by Waters (column: Shodex GPC LF-804 (length: 300 mm) x 2 manufactured by Showa Denko KK), measuring temperature: 40 ° C., flow rate: 1 mL / min, solvent: tetrahydrofuran, standard substance: Polystyrene) was used.

[Synthesis of Polymers B to D which are Silicone Compounds]
Polymers B to D were obtained in the same manner as the synthesis of polymer A except that the type and blending amount of the organosilicon compound used for the synthesis were changed.

Polymer B:
(SiO _4/2 ) _0.20 (ViMe ₂ SiO _1/2 ) _0.40 (Me ₃ SiO _1/2 ) _0.40
Number average molecular weight 2000
The content ratio of phenyl group and methyl group is 83.3 mol%, and the content ratio of vinyl group is 16.7 mol%.

Polymer C:
(MeSiO _3/2 ) _0.20 (PhMeSiO _2/2 ) _0.70 (ViMe ₂ SiO _1/2 ) _0.10
Number average molecular weight 4000
The content ratio of phenyl group and methyl group is 94.7 mol%, and the content ratio of vinyl group is 5.3 mol%.

Polymer D:
(PhSiO _3/2 ) _0.80 (ViMe ₂ SiO _1/2 ) _0.20
Number average molecular weight 1700
The content ratio of phenyl group and methyl group is 85.7 mol%, and the content ratio of vinyl group is 14.3 mol%.

[Synthesis of Polymer E as Silicone Compound]
In a 1000 mL separable flask equipped with a thermometer, a dropping device, and a stirrer, 80.6 g of diphenyldimethoxysilane and 45 g of 1,1,3,3-tetramethyldisiloxane were added and stirred at 50 ° C. Into this, a solution of 100 g of acetic acid and 27 g of water was slowly added dropwise. After the addition, the solution was stirred at 50 ° C. for 6 hours and reacted to obtain a reaction solution. Next, the polymer was obtained by removing the volatile component under reduced pressure. To the obtained polymer, 150 g of hexane and 150 g of ethyl acetate were added, washed 10 times with 300 g of ion-exchanged water, reduced in pressure to remove volatile components, and polymer E was obtained.

The number average molecular weight of the obtained polymer E was 850. As a result of identifying the chemical structure from ²⁹ Si-NMR, the polymer E had the following average composition formula.

(Ph ₂ SiO _2/2 ) _0.67 (HMe ₂ SiO _1/2 ) _0.33

  In the above formula, Me represents a methyl group, and Ph represents a phenyl group. In the obtained polymer E, the content ratio of phenyl groups and methyl groups was 74.9 mol%, and the content ratio of hydrogen atoms bonded to silicon atoms was 25.1%.

(B) Curing agent or curing catalyst Fuji Cure 7000 (Fuji Kasei Co., Ltd., liquid at 23 ° C., amine compound)
MEH-8005 (Maywa Kasei Co., Ltd., liquid at 23 ° C., allylphenol novolak compound)
TD-2131 (manufactured by DIC, solid at 23 ° C., phenol novolac compound)
1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum

(D) Curing accelerator SA-102 (manufactured by San Apro, DBU octylate)

(C) Inorganic filler FAN-f05 having a thermal conductivity of 10 W / m · K or more (Furukawa Electronics, aluminum nitride, thermal conductivity: 100 W / m · K, spherical, average particle size: 6 μm)
FAN-f50 (Furukawa Electronics, aluminum nitride, thermal conductivity: 100 W / m · K, spherical, average particle size: 30 μm)
CB-P05 (made by Showa Denko KK, aluminum oxide, thermal conductivity: 20 W / m · K, spherical, average particle size: 4 μm)
CB-P40 (made by Showa Denko KK, aluminum oxide, thermal conductivity: 20 W / m · K, spherical, average particle size: 44 μm)
SSC-A15 (manufactured by Shinano Denki Co., Ltd., silicon carbide, thermal conductivity: 100 W / m · K, spherical, average particle size: 19 μm)
SSC-A30 (manufactured by Shinano Denki Co., Ltd., silicon carbide, thermal conductivity: 100 W / m · K, spherical, average particle size: 34 μm)

(C ′) Other inorganic filler HS-306 (manufactured by Micron, silicon oxide, thermal conductivity: 2 W / m · K, spherical, average particle diameter: 2.5 μm)
HS-304 (Micron, silicon oxide, thermal conductivity: 2 W / m · K, spherical, average particle size: 25 μm)

(E) 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)
BYK-9076 (manufactured by BYK, dispersant)

Example 1
6.5 parts by weight of EX-821 (n = 4), 2.5 parts by weight of jER828, 5 parts by weight of Fujicure 7000, 0.5 parts by weight of SA-102, 42.5 parts by weight of CB-P05, 42.5 parts by weight of CB-P40 and 0.5 parts by weight of BYK-9076 were mixed and defoamed to obtain a semiconductor element protecting material.

(Examples 2 to 21 and Comparative Examples 1 to 3)
A semiconductor element protecting material was obtained in the same manner as in Example 1 except that the types and blending amounts of the blending components were changed as shown in Tables 1 and 2 below.

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

  Next, the semiconductor element protecting material was stored at 40 ° C. for 6 hours. After storage, using a B-type viscometer (“TVB-10 type” manufactured by Toki Sangyo Co., Ltd.), the viscosity of the semiconductor element protecting material at 10 rpm at 25 ° C. (Pa · s) and 1 rpm at 25 ° C. The viscosity (Pa · s) was measured.

(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.

(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, the semiconductor element is protected. 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 5.3 mm or more, height less than 1.8 mm (with fluidity)
Δ: Over 5 mm in diameter, less than 5.3 mm, over 1.8 mm in height and less than 2 mm (with little fluidity)
×: 5 mm in diameter and 2 mm in height (no fluidity)

(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.

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

  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) 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 3 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).

[Die shear strength criteria]
○: Die share strength is 10N or more △: Die share strength is 6N or more and less than 10N △△: Die share strength is 5N or more and less than 6N ×: Die share strength is less than 5N

(6) 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 left for 24 hours, the tackiness of the surface of the evaluation sample was measured using a tack tester TA-500 (manufactured by UBM).

[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

(7) Film warpage After directly discharging the obtained semiconductor element protecting material from a dispenser device ("SHOTMASTER-300" manufactured by Musashi Engineering Co., Ltd.) onto a polyimide film so as to be 20 mm long, 100 mm wide, and 10 mm high, The semiconductor element protecting 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 △: Slight warpage of polyimide film (no problem in use)
×: Warpage of polyimide film (problems in use)

(8) 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.

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

  Next, the sample was left 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 test is 5% or less ○: Decrease rate of volume resistivity before and after test exceeds 5% and 10% or less △: Decrease rate of volume resistivity before and after test is 10% Over 20% or less ×: Volume resistivity decrease rate before and after the test exceeds 20%

  The compositions and results are shown in Tables 1 and 2 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 (12)

A material for protecting a semiconductor element, which is applied to form a cured product on the surface of the semiconductor element by coating on the surface of the semiconductor element in order to protect the semiconductor element.
Unlike what forms the hardened | cured material which is arrange | positioned between a semiconductor element and another connection object member, and adhere | attaches and fixes so that the said semiconductor element and said other connection object member may not peel,
Including a thermosetting compound, a curing agent or a curing catalyst, and an inorganic filler having a thermal conductivity of 10 W / m · K or more,
The viscosity at 25 ° C. and 10 rpm is 40 Pa · s or more and 140 Pa · s or less,
A material for protecting a semiconductor element, having a viscosity at 25 ° C. and 1 rpm of 50 Pa · s to 300 Pa · s.   The material for protecting a semiconductor element according to claim 1, wherein the ratio of the viscosity at 25 ° C and 1 rpm to the viscosity at 25 ° C and 10 rpm is 1.2 or more and 3.0 or less. The viscosity at 25 ° C. and 10 rpm after storage at 40 ° C. for 6 hours is 50 Pa · s or more and 150 Pa · s or less,
The material for protecting a semiconductor element according to claim 1 or 2, wherein the viscosity at 25 ° C and 1 rpm after storage at 40 ° C for 6 hours is from 60 Pa · s to 300 Pa · s.   The semiconductor element protecting material according to claim 1, wherein the thermosetting compound contains an epoxy compound or a silicone compound.   The semiconductor element protecting material according to any one of claims 1 to 4, wherein the curing agent is an allylphenol novolac compound.   The semiconductor element protecting material according to claim 1, wherein the thermosetting compound includes a flexible epoxy compound.   The semiconductor element protecting material according to claim 6, wherein the thermosetting compound includes the flexible epoxy compound and an epoxy compound different from the flexible epoxy compound.   The semiconductor element protecting device according to claim 6 or 7, wherein the flexible epoxy compound contained in the semiconductor element protecting material is a polyalkylene glycol diglycidyl ether having a structural unit in which 9 or more alkylene glycol groups are repeated. material.   In order to protect a semiconductor element, a cured product is formed 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 to obtain a semiconductor device. In order to protect a semiconductor element, a cured product is formed on the surface of the semiconductor element, and a surface of the cured product opposite to the semiconductor element side is exposed. The semiconductor element protecting material according to claim 1, which is used for the purpose. A semiconductor element;
A cured product disposed on the first surface of the semiconductor element,
The semiconductor device whose said hardened | cured material is a hardened | cured material of the semiconductor element protection material of any one of Claims 1-9.   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 thereof The semiconductor device according to claim 10, wherein the semiconductor device is electrically connected to the second electrode.   The protective film is arrange | positioned on the surface opposite to the said semiconductor element side of the said hardened | cured material, or the surface opposite to the said semiconductor element side of the said hardened | cured material is exposed. A semiconductor device according to 1.

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