CN101542721A - Film for sealing and semiconductor device using the same - Google Patents

Abstract

Disclosed is a sealing film having a resin layer which contains the component (A), (B) and (C) described below and has a flow amount at 80 DEG C of 150-1800 [mu]m. The sealing film is excellent in fillability and adhesion. Also disclosed are a method for producing such a sealing film, and a semiconductor device using such a sealing film. (A) a resin component containing a polymer component (a1) containing a crosslinkable functional group and having a weight average molecular weight of not less than 100,000 and a Tg within the range from -50 DEG C to 50 DEG C, and a thermosetting component (a2) mainly composed of an epoxy resin (B) a filler having an average particle diameter of 1-30 [mu]m (C) a coloring agent Also disclosed is a sealing film having a resin layer which contains the above-described component (A), (B) and (C) and has a viscosity at 50-100 DEG C as determined by thermosetting viscoelasticity measurement of the film in the stage B of 10,000-100,000 Pa s. This sealing film is excellent in adhesion and shape retention characteristics. A semiconductor device using such a sealing film is further disclosed.

Description

Film for sealing and use its semiconductor device

Technical field

The present invention relates to the diaphragm seal of fillibility and sealing excellence and use its semiconductor device.In more detail, the present invention relates to have defencive function and fillibility, be used for the protection of semiconductor chip and filling, the flowability when filling and make more excellent film for sealing of fillibility, adaptation, shape maintains and the semiconductor device that uses it by control.

Background technology

All the time, the miniaturization lightweight of electronic equipment is all in continuous development, and what accompany therewith is, requires the high-density installation to substrate, carries miniaturization in the semiconductor packages of electronic equipment, slimming, lightweight also in continuous development.In the past, have be known as LOC (Lead On Chip: Lead-on-Chip encapsulation) and QFP (Quad Flat Package: four limit flat packaging) etc. encapsulation, ball grid array) and CSP (Chip Size Package: encapsulation such as chip size packages) developing than LOC and QFP etc. and encapsulating the light-weighted μ BGA of miniaturization more (Ball Grid Array:.Also the circuit face at the exploitation semiconductor element is Flip-Chip Using, WL-CSP (WaferLevel Chip Size Package: the crystal wafer chip dimension encapsulation) etc. towards flip chip type encapsulation semiconductor wiring substrate side, so-called.

Above-mentioned encapsulation by utilizing the transfer molding method with solid-state epoxy sealing forming materials, obtains sealed package, but it is just difficult to be encapsulated as when slim or large-scale moulding.In addition, when the content of inorganic filler increased, the melt viscosity during transfer molding increased usually, and this can produce following problem, that is, residual clearance, die cavity are filled the increase etc. of bad, linear flow output and level displacement (stage shift) and the problems such as quality reduction of article shaped during moulding.

In addition, in recent years, among flip-chip, the WL-CSP etc. the goods with overshooting shape electrode are arranged, in order to protect its jut and to fill between the projection and often use encapsulant, be difficult to but fill with solid-state epoxy sealing material.Therefore, someone has proposed based on the diaphragm seal of epoxy resin, inorganic filler (for example, with reference to Japanese kokai publication hei 5-283456 communique, Japanese kokai publication hei 5-190697 communique, Japanese kokai publication hei 8-73621 communique, TOHKEMY 2005-60584 communique).

Summary of the invention

But, when the diaphragm seal that uses in the past, seal the encapsulation that for example has the overshooting shape electrode or during to the conditional encapsulation of shape after the sealing, be difficult to the control flowability sometimes, can not satisfy fillibility and sealing.

The object of the present invention is to provide and have defencive function and fillibility, be used for the protection of semiconductor chip and filling, the flowability when filling and make more excellent film for sealing of fillibility, adaptation, shape maintains and the semiconductor device that uses it by control.

The present invention is a feature with the item that following (1)～(9) are put down in writing.

(1) a kind of diaphragm seal with resin bed, described resin bed contain following (A), (B) and (C), and are 150～1800 μ m 80 ℃ discharge.

(A) resinous principle wherein, comprises: to contain bridging property functional group, weight average molecular weight be more than 100,000 and Tg is-50～50 ℃ high molecular weight components (a1); With epoxy resin is the thermosetting composition (a2) of principal component,

(B) average grain diameter is the filler of 1～30 μ m,

(C) colouring agent.

(2) a kind of film for sealing with resin bed, described resin bed contain following (A), (B) and (C), and 50～100 ℃ viscosity in the hot curing determination of viscoelasticity of the film of B scalariform attitude is 10000～100000Pas.

(A) resinous principle, it comprises: to contain bridging property functional group, weight average molecular weight be more than 100,000 and Tg is-50～50 ℃ high molecular weight components (a1); With epoxy resin is the thermosetting composition (a2) of principal component,

(B) average grain diameter is the filler of 1～30 μ m,

(C) colouring agent.

(3) according to above-mentioned (1) described film for sealing, wherein, contain resin 10 mass parts of the described thermosetting composition (a2) of the described high molecular weight components (a1) of 5～85 quality % and 15～95 quality % with respect to described (A) resinous principle, contain described (B) filler of 1～300 mass parts, described (C) colouring agent of 0.01～10 mass parts.

(4) according to above-mentioned (1) or (2) described diaphragm seal, wherein, described (A) resinous principle contains the described high molecular weight components (a1) of 5～80 quality %, the described thermosetting composition (a2) of 15～85 quality %.

(5), wherein,, contain described (B) filler of 1～300 mass parts, described (C) colouring agent of 0.01～10 mass parts with respect to described (A) resinous principle 10 mass parts according to above-mentioned (4) described film for sealing.

(6), wherein, on the single face of described resin bed, further have the substrate layer of thickness 5～300 μ m, and the thickness of described resin bed is 5～800 μ m according to each described diaphragm seal in above-mentioned (1)～(5).

(7) according to each described diaphragm seal in above-mentioned (1)～(5); wherein, on a face of described resin bed, have the substrate layer of thickness 5～300 μ m, on another face of described resin bed, have the protective layer of thickness 5～300 μ m; and the thickness of described resin bed is 5～800 μ m.

(8) according to each described diaphragm seal in above-mentioned (1)～(7), wherein, described (B) filler is inorganic filler.

(9) according to each described diaphragm seal in above-mentioned (1)～(8), wherein, described (C) colouring agent is the color beyond the white.

(10) according to each described diaphragm seal in above-mentioned (1)～(9), wherein, 35 ℃ storage modulus described resin bed, that solidify after 1 hour for 170 ℃ times are 100～20000MPa.

(11) a kind of semiconductor device that uses each described diaphragm seal in above-mentioned (1)～(10).

(12) a kind of to have 80 ℃ discharge be the manufacture method of diaphragm seal of the resin bed of 150～1800 μ m, it is characterized in that, comprises: add solvent in the resin bed composition of following to containing (A), (B), (C), make the operation of varnish; Described varnish is coated on the operation of substrate layer or base material; Varnish to described coating carries out 3～30 minutes operation of at least one time heat drying under 60～200 ℃ temperature,

Wherein, (A) resinous principle, it comprises: to contain bridging property functional group, weight average molecular weight be more than 100,000 and Tg is-50～50 ℃ high molecular weight components (a1); With epoxy resin is the thermosetting composition (a2) of principal component,

(B) average grain diameter is the filler of 1～30 μ m,

(C) colouring agent.

(13) 50～100 ℃ the viscosity of a kind of film of the B of having scalariform attitude in the hot curing determination of viscoelasticity is the manufacture method of diaphragm seal of the resin bed of 10000～100000Pas, it is characterized in that, comprise: add solvent in the resin bed composition of following to containing (A), (B), (C), make the operation of varnish; Described varnish is coated on the operation of substrate layer or base material; Varnish to described coating carries out 3～30 minutes operation of at least one time heat drying under 60～200 ℃ temperature,

Wherein, (A) resinous principle, it comprises: to contain bridging property functional group, weight average molecular weight be more than 100,000 and Tg is-50～50 ℃ high molecular weight components (a1); With epoxy resin is the thermosetting composition (a2) of principal component,

(B) average grain diameter is the filler of 1～30 μ m,

(C) colouring agent.

Description of drawings

Fig. 1 is the schematic diagram of the diaphragm seal that formed by substrate layer 1 and resin bed 2.

Fig. 2 is the schematic diagram of the diaphragm seal that formed by substrate layer 1, resin bed 2 and protective layer 3.

Fig. 3 is the ideograph that diaphragm seal is laminated to the operation on the semiconductor substrate.

Fig. 4 is the schematic diagram with semiconductor element of the overshooting shape electrode that seals with diaphragm seal.

Embodiment

Constituting the resin bed of diaphragm seal of the present invention, contain following (A), (B) and (C), is 150～1800 μ m 80 ℃ discharges.

(A) resinous principle, it comprises: to contain bridging property functional group, weight average molecular weight be more than 100,000 and Tg is-50～50 ℃ high molecular weight components (a1); With epoxy resin is the thermosetting composition (a2) of principal component,

(B) average grain diameter is the filler of 1～30 μ m,

(C) colouring agent.

In addition, constitute the resin bed of diaphragm seal of the present invention, contain above-mentioned (A) resinous principle, above-mentioned (B) filler and (C) colouring agent, and 50～100 ℃ the viscosity of the film of B scalariform attitude in the hot curing determination of viscoelasticity is 10000～100000Pas.

Below, describe being used for material of the present invention.

＜macromolecule component (a1) 〉

(A) of the present invention as being configured for weight average molecular weight resinous principle, that contain bridging property functional group is more than 100,000 and Tg is-50～50 ℃ high molecular weight components (a1), there is no particular restriction, is preferably the monomer that will have a bridging property functional group and contains epoxy radicals (methyl) acrylic copolymer as what constitute that the unit contains.In the present invention, said " (methyl) acrylic acid " be the expression " acrylic acid " and " methacrylic acid " the two.In addition, as bridging property functional group, also can enumerate acrylic, methacrylic acid group, NCO, carboxyl etc.

For example contain epoxy radicals (methyl) acrylate copolymer as containing epoxy radicals (methyl) acrylic copolymer, can using, contain epoxy radicals acrylic rubber etc., more preferably contain the epoxy radicals acrylic rubber.Acrylic rubber is to be principal component with the acrylate, mainly by butyl acrylate and acrylonitrile etc. the rubber that constitutes of the copolymer etc. of copolymer, ethyl acrylate and acrylonitrile etc.As weight average molecular weight be more than 100,000 and Tg for-50～50 ℃ contain the epoxy radicals acrylic rubber, HHTR-860P-3DR that commercially available Nagase chemical Co., Ltd makes etc. is for example arranged.

In addition, as above-mentioned epoxy radicals (methyl) acrylic copolymer that contains, also can use (methyl) glycidyl acrylate etc. to have the copolymer that the epoxy radicals monomer carries out polymerization that contains of bridging property functional group, also can use this to contain the copolymer that the epoxy radicals monomer further carries out copolymerization with monomers such as (methyl) ethyl acrylate and (methyl) butyl acrylates.

Contain the amount that contains the epoxy radicals monomer in epoxy radicals (methyl) acrylic copolymer, be preferably 0.5～6.0 quality %, more preferably 0.5～5.0 quality % is preferably 0.8～5.0 quality % especially.When the amount that contains the epoxy radicals monomer is in this scope, not only can guarantee bonding force, also can prevent gelation.When the amount that contains the epoxy radicals monomer during less than 0.5 quality %, have the tendency that the bonding force of the resin bed that obtains reduces, when surpassing 6.0 quality %, have the tendency that the storage stability of the resin bed that obtains reduces.

When the above-mentioned monomer of polymerization, make weight average molecular weight more than 100,000 and Tg during for-50～50 ℃ high molecular weight components (a1), as its polymerization, there is no particular restriction, can use for example known method such as pearl polymerisation, polymerisation in solution, in addition, for polymerizing condition, as long as consider weight average molecular weight, the glass transition temperature of the monomer that uses and concentration thereof, high molecular weight components (a1) wait and carry out suitable decision, there is no particular restriction.

In the present invention, above-mentioned high molecular weight components (a1) is more than 100,000, is preferably 300,000～3,000,000, more preferably 500,000～2,000,000.When weight average molecular weight during in this scope, intensity, pliability and the being clamminess property made when membranaceous are suitable, in addition, can guarantee the adaptation between resin bed and the adherend.In the present invention, said weight average molecular weight is expression value gel permeation chromatography, that use the polystyrene standard calibration curve to convert.

The glass transition temperature of above-mentioned high molecular weight components (a1) (hereinafter referred to as " Tg ") is preferably more than-50 ℃, below 50 ℃, more preferably-40 ℃ more than, below 50 ℃, be preferably especially more than-40 ℃, below 40 ℃.When Tg is more than-50 ℃, below 50 ℃ the time, the being clamminess property of the B scalariform attitude of resin bed is fit to, and is no problem on operability.

In the total amount of (A) resinous principle, the use level of above-mentioned high molecular weight components (a1) is preferably 5～85 quality %, and more preferably 5～80 quality % are preferably 10～80 quality % especially, most preferably are 10～75 quality %.When the use level of (A1) high molecular weight components during less than 5 quality %, the pliability deficiency of the resin bed that obtains may become fragile, and when surpassing 85 quality %, the flowability of the resin bed that obtains may reduce.

＜thermosetting composition (a2) 〉

The thermosetting composition (a2) of the formation of using among the present invention (A) resinous principle, thereby so long as by heat solidify the performance bonding effect material get final product, there is no particular restriction, preferably is the material of principal component with epoxy resin.As such epoxy resin, can use for example phenolic resin varnish type epoxy resins such as bifunctional epoxy resin, phenol novolak type epoxy resin and cresols phenolic resin varnish type epoxy resin such as bisphenol A type epoxy resin etc.In addition, can use polyfunctional epoxy resin, glycidyl amine type epoxy resin, contain usually known substances such as heterocyclic ring epoxy resins or alicyclic epoxy resin.

As above-mentioned bisphenol A type epoxy resin, can enumerate the Epikote 807,815,825,827,828,834,1001,1004,1007,1009 that oiling shell epoxy Co., Ltd. makes; The DER-330,301,361 that Dow Chemical makes; YD8125, YDF8170 etc. that Toto Kasei KK makes.As above-mentioned phenol novolak type epoxy resin, can enumerate the Epikote 152,154 that oiling shell epoxy Co., Ltd. makes; The EPPN-201 that Nippon Kayaku K. K makes; The DEN-438 that Dow Chemical makes etc., in addition, as above-mentioned cresols phenolic resin varnish type epoxy resin, can enumerate EOCN-102S, 103S, 104S, 1012,1025,1027 as Nippon Kayaku K. K's manufacturing of o-cresol phenolic epoxy varnish; The YDCN701,702,703 that Toto Kasei KK makes, 704 etc.As above-mentioned polyfunctional epoxy resin, can enumerate the Epon 1031S that oiling shell epoxy Co., Ltd. makes; The love jail that Ciba Co., Ltd makes reaches 0163; Denacoal EX-611,614, the 614B, 622,512,521,421,411 that Nagase chemical Co., Ltd makes, 321 etc.As above-mentioned glycidyl amine type epoxy resin, can enumerate the Epikote 604 that oiling shell epoxy Co., Ltd. makes; The YH-434 that Toto Kasei KK makes; TETRAD-X, TETRAD-C that Mitsubishi Gas Chemical Co., Ltd makes; The ELM-120 that Sumitomo Chemical Co makes etc.As the above-mentioned heterocyclic ring epoxy resins that contains, the love jail that can enumerate the manufacturing of Ciba Co., Ltd reaches PT810 etc.; The ERL4234,4299,4221 that UCC company makes, 4206 etc.As above-mentioned alicyclic epoxy resin, can enumerate Epolead series that Daisel chemical industry Co., Ltd makes, Ceroxide series etc.These epoxy resin can use separately, perhaps make up 2 kinds with on use.

In the total amount of (A) resinous principle, the use level of above-mentioned thermosetting composition (a2) is preferably 15～95 quality %, and more preferably 15～85 quality % are preferably 20～80 quality % especially, most preferably are 20～75 quality %.When the use level of (a2) thermosetting composition during less than 15 quality %, the thermal endurance of the resin bed that obtains and flowability may reduce, and when surpassing 95 quality %, the pliability of the resin bed that obtains may reduce.

＜(A) resinous principle 〉

(A) resinous principle among the present invention except above-mentioned high molecular weight components (a1) and above-mentioned thermosetting composition (a2), also can use above-mentioned following resinous principle in addition as required.For example, can use phenoxy resin, polyamide, polyamide-imide resin/or its precursor, polyimide resin/or resinous principle such as its precursor.

In addition, as (A) resinous principle, preferably contain known epoxy curing agent or curing accelerator catalyst as above-mentioned thermosetting composition (a2).As epoxy curing agent, can enumerate the bisphenols that has 2 above phenol hydroxyls in the 1 such molecule of for example amine, polyamide, acid anhydrides, polysulfide, boron trifluoride and bisphenol-A, Bisphenol F, bisphenol S and phenolic resins such as phenol novolac resin, bisphenol-A phenolic varnish gum or cresols novolac resin etc.The angle of the electrocorrosion-resisting excellence during especially from moisture absorption is considered, is preferably phenolic resins such as phenol novolac resin, bisphenol-A phenolic varnish gum or cresols novolac resin.As preferred phenolic resins, can enumerate Dainippon Ink. ﹠ Chemicals Inc for example makes, trade name: Pliophen LF2882, Pliophen LF2822, PliophenLF4871, Pliophen TD-2090, Pliophen TD-2149, Pliophen VH-4150, PliophenVH4170 etc.

In addition, as above-mentioned curing accelerator, can use for example quaternary alkylphosphonium salt system, quaternary ammonium salt system, imidazoles system, DBU soap system, metal-chelating system, slaine system, triphenylphosphine system etc.

＜(B) filler 〉

As (B) filler among the present invention, as long as average grain diameter is 1～30 μ m, there is no particular restriction, is preferably inorganic filler, can use for example crystalline silica, amorphous silica, aluminium oxide, titanium oxide, calcium carbonate, magnesium carbonate, aluminium nitride, boron nitride etc.

(B) average grain diameter of filler is preferably 1～25 μ m, and more preferably 2～25 μ m are preferably 2～20 μ m especially.When the average grain diameter of (B) filler during less than 1 μ m, the tendency that flowability with the resin bed that obtains reduces, the reliability of semiconductor device reduces, on the other hand, when surpassing 30 μ m, the concave-convex surface with the resin bed that obtains increases, the tendency of embedding reduction.

The use level of above-mentioned (B) filler with respect to above-mentioned (A) resinous principle 10 mass parts, is preferably 1～300 mass parts, and more preferably 5～300 mass parts are preferably 5～250 mass parts especially, most preferably are 5～200 mass parts.When the use level of (B) filler during less than 1 mass parts, the diaphragm seal that obtains may deliquescing, causes the reliability of the semiconductor device that obtains to reduce, and when surpassing 300 mass parts, the diaphragm seal that obtains and the adaptation of semiconductor substrate may reduce.

＜(C) colouring agent 〉

As above-mentioned (C) colouring agent among the present invention, there is no particular restriction, can use for example pigment or dyestuffs such as carbon black, graphite, titanium carbide, manganese dioxide, phthalocyanine.Consider dispersiveness, laser marking, the colouring agent beyond the whites such as preferred carbon black.

The use level of above-mentioned (C) colouring agent with respect to above-mentioned (A) resinous principle 10 mass parts, is preferably 0.01～10 mass parts, and more preferably 0.2～8 mass parts is preferably 0.3～6 mass parts especially, most preferably is 0.5～5 mass parts.When the use amount of (C) colouring agent during less than 0.01 mass parts, have the tendency of the visibility variation behind painted insufficient, the laser marking of the diaphragm seal that obtains, when surpassing 10 mass parts, the diaphragm seal that obtains and the adaptation of semiconductor substrate may reduce.

＜resin bed 〉

Resin bed among the present invention except above-mentioned (A) resinous principle, (B) filler with (C) the colouring agent, can contain additives such as coupling agent as required.As coupling agent, can enumerate silane system, titanium system, aluminium system etc., but most preferably silane is coupling agent.

As above-mentioned silane is coupling agent, there is no particular restriction, can use vinyl trichlorosilane, vinyl three ('beta '-methoxy ethyoxyl) silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl methyl dimethoxysilane, β-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyl dimethoxysilane, γ-glycidoxy propyl group methyldiethoxysilane, N-β (aminoethyl) gamma-amino propyl trimethoxy silicane, N-β (aminoethyl) gamma-amino propyl group methyl dimethoxysilane, γ-An Jibingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl trimethoxy silicane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, 3-aminopropyl methyldiethoxysilane, 3-urea groups propyl-triethoxysilicane, 3-urea groups propyl trimethoxy silicane, the 3-TSL 8330,3-aminopropyl-three (2-methoxyl group-ethyoxyl-ethyoxyl) silane, N-methyl-3-TSL 8330, triamido propyl group-trimethoxy silane, 3-4,5-glyoxalidine-1-base-propyl trimethoxy silicane, 3-methacryloxy-trimethoxy silane, 3-sulfydryl propyl group-methyl dimethoxysilane, 3-chloropropyl-methyl dimethoxysilane, 3-chloropropyl-dimethoxy silane, 3-cyanogen propyl group-triethoxysilane, hexamethyldisiloxane, N, two (trimethyl silicon based) acetamides of O-, methyltrimethoxy silane, methyl triethoxysilane, ethyl trichlorosilane, the n-pro-pyl trimethoxy silane, the isobutyl group trimethoxy silane, the amyl group trichlorosilane, octyltri-ethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, methyl three (methacryloxy ethyoxyl) silane, methyl three (glycidoxypropyl) silane, N-β (N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane, octadecyl dimethyl [3-(trimethoxysilyl) propyl group] ammonium chloride, γ-chloropropyl dimethyl dichlorosilane (DMCS), gamma-chloropropylmethyldimethoxysilane, γ-chloropropyl methyldiethoxysilane, trimethylsilyl isocyanate, the dimetylsilyl isocyanates, methyl silicane base triisocyanate, vinyl silicyl triisocyanate, phenyl silicyl triisocyanate, tetraisocyanate silane, Ethoxysilane isocyanates etc., these can be used alone or in combination with two or more kinds and use.

As above-mentioned titanium is coupling agent; there is no particular restriction; can use for example isopropyl three caprylyl titanate esters; isopropyl dimethyl propylene enoyl-isostearoyl base titanate esters; isopropyl (three-tridecyl) benzenesulfonyl titanate esters; isopropyl stearyl two acryloyl group titanate esters; isopropyl three (dioctylphosphate) titanate esters; isopropyl three cumenyl phenyl titanium acid esters; isopropyl three (dioctylphyrophosphoric acid salt) titanate esters; isopropyl three (positive aminoethyl) titanate esters; two (dioctylphosphate) titanate esters of tetra isopropyl; two (two-tridecyl phosphite) titanate esters of four octyl groups; four (2; 2-two allyloxy methyl isophthalic acid-butyl) two (two-tridecyl) phosphite ester titanate esters; two cumenyl phenoxyethanoic acid ester titanate esters; two (dioctylphyrophosphoric acid salt) fluoroacetic acid ester titanate esters; tetra isopropyl titanate; the tetra-n-butyl titanate esters; the butyltitanate dimer; four (2-ethylhexyl) titanate esters; titanium acetylacetone; poly; ethohexadiol acid titanium; the titanium lactate ammonium salt; the lactic acid titanium; the titanium lactate ethyl ester; titanium triethanolamine thing; poly-hydroxy stearic acid titanium; positive metatitanic acid tetramethyl ester; positive tetraethyl titanate; positive metatitanic acid orthocarbonate; positive metatitanic acid four isobutyl esters; the metatitanic acid stearyl ester; metatitanic acid toluene ester monomer; metatitanic acid toluene ester polymer; diisopropoxy-two (2; 4-pentanedione acid esters) titanium (IV); diisopropyl-two-triethanolamine base titanate esters; the ethohexadiol titanate esters; four n-butoxy titanium polymers; the tri-n-butoxytitanium monostearate polymer; tri-n-butoxytitanium monostearate etc.; these can use a kind, and also two or more kinds may be used.

As above-mentioned aluminium is coupling agent, there is no particular restriction, can use for example ethyl acetoacetate aluminium diisopropyl alcohol ester, aluminium three (ethyl acetoacetate), alkyl acetoacetic ester aluminium diisopropyl alcohol ester, aluminium single acetyl acetic acid esters two (ethyl acetoacetate), aluminium three (acetoacetic ester), aluminium-single isopropoxy list oil oxygen base ethyl acetoacetate, aluminium-two n-butoxy-list-ethyl acetoacetate, aluminium-two-isopropoxy-aluminium chelate compounds such as list-ethyl acetoacetate; Aluminium alcoholates such as aluminium isopropoxide, Mono-sec-butoxyaluminium diisopropylate, aluminium secondary butylate, aluminium ethylate etc., these can use separately, also can make up 2 kinds with on use.

In addition, additives such as above-mentioned coupling agent with respect to (A) resinous principle 100 mass parts, are preferably the following use level of 50 mass parts.When the use level of above-mentioned additive than 50 mass parts for a long time, the thermal endurance of the diaphragm seal that obtains may reduce.

Resin bed among the present invention is 150～1800 μ m 80 ℃ discharges, is preferably 200～1600 μ m, more preferably 400～1400 μ m.When this discharge is less than 150 μ m, the reliability of adaptation between gained diaphragm seal and the semiconductor substrate or semiconductor device is reduced, if surpass 1800 μ m, during then with the diaphragm seal sealing semiconductor element that obtains, it is mobile to be difficult to control, the operation reduction.

Above-mentioned discharge is the value of following mensuration: the above-mentioned resin bed of the B scalariform attitude of thickness 150 μ m is layered on the substrate layer, punching becomes 10 * 20mm to make long narrow square sample, adopt thermo-compressed experimental rig (manufacturings of Tester Industry Co., Ltd) at hot plate temperature: under 80 ℃, the condition of pressure: 0.2MPa it to be pressurizeed for 18 seconds, then the value of the length of the resin that mensuration flows out from the end of sample under light microscope.

This discharge, can reduce by the following method: the loading that for example increases (B) filler in the resin bed, or use polyfunctional epoxy resin to improve the crosslink density of resin bed as above-mentioned thermosetting composition (a2), or the thermal history when increasing filming (particularly, be to remove the heat drying condition of resin bed with the solvent that contains in the varnish), improve the curing degree of B scalariform attitude.

The resin bed of film for sealing of the present invention, 50～100 ℃ the viscosity of the film of its B scalariform attitude in the hot curing determination of viscoelasticity (below, be also referred to as " film viscosity ") be 10000～100000Pas, be preferably 10000～95000, more preferably 10000～90000, be preferably 15000～90000 especially.When 50～100 ℃ viscosity during less than 10000Pas, has the film for sealing deliquescing, the tendency that causes the reliability of the semiconductor device that obtains to reduce when surpassing 100000Pas, has the tendency that the film for sealing that obtains and the adaptation between the semiconductor substrate reduce.

Above-mentioned film viscosity, be only resin bed (thickness the is 150 μ m) punching of film for sealing to be become that diameter 8mm's is discoid, adopt viscosity determination of viscoelasticity device (RheostressRS 600 types that Thermo Haake company makes), at constant deformation pattern, frequency: 1Hz, add deformation: programming rate 1%: measure under the condition of 5 ℃/min.

This film viscosity, be can be by for example increasing the loading of (B) filler in the resin bed, or use mobile excellent filler as (B) filler, or use polyfunctional epoxy resin as the crosslink density of above-mentioned thermosetting composition (a2) with the raising resin bed, or the thermal history when increasing membranization (particularly, be to remove the heat drying condition of resin bed with the solvent that contains in the varnish), the curing degree of raising B scalariform attitude reduces.

As mobile excellent filler, can use spherical filler.

Resin bed among the present invention, storage modulus in the dynamic viscous-elastic behaviour determinator 35 ℃ under of 170 ℃ of curing after 1 hour is preferably 100～20000MPa, 100～19000MPa more preferably, more preferably 200～18000MPa is preferably 500～16000MPa especially.When storage modulus during less than 500MPa, the film for sealing and the adaptation between the semiconductor element that obtain may reduce, and when surpassing 20000MPa, the reliability of semiconductor device may reduce.

Above-mentioned storage modulus is the above-mentioned resin bed to the B scalariform attitude of thickness 150 μ m, the dynamic viscoelastic spectrometer (DVE-4 type) that adopts Rheology company to make, the value of measuring under 35 ℃, the condition of 10Hz.

This storage modulus, can increase by the following method: the loading that for example increases (B) filler, or the mobile excellent filler of use, or use polyfunctional epoxy resin as the crosslink density of above-mentioned thermosetting composition (a2) with the raising resin bed, or the thermal history when increasing membranization, improve the curing degree of B scalariform attitude.

＜diaphragm seal of the present invention 〉

Diaphragm seal of the present invention as shown in Figure 1, can have substrate layer 1 on the single face of above-mentioned resin bed 2.The thickness of the resin bed when having substrate layer is preferably more than the 5 μ m, more preferably more than the 10 μ m, is preferably especially more than the 20 μ m, most preferably is more than the 30 μ m.In addition, the thickness of this resin bed is preferably below the 800 μ m, more preferably below the 600 μ m, is preferably especially below the 500 μ m, most preferably is below the 400 μ m.When the thickness of resin bed during less than 5 μ m, may reduce with the adaptation of semiconductor element, when surpassing 800 μ m, the thickness of semiconductor element increases, and may hinder package design.

The thickness of substrate layer is preferably 5～300 μ m, and more preferably 5～200 μ m are preferably 5～100 μ m especially, most preferably are 10～100 μ m.If the thickness of substrate layer is less than 5 μ m, then because the undercapacity during film production and might make not membrane self even the thickness of film surpasses the also special advantage of nothing of 300 μ m, also may make film self become expensive.

As the material that can be used as above-mentioned substrate layer, there is no particular restriction, can use plastic films such as poly tetrafluoroethylene, PETG film, polyethylene film, polypropylene screen, polymethylpentene film, poly (ethylene naphthalate) film, poly (ether sulfone) film, polyetheramides film, polyetheramides acid imide film, polyamide membrane, polyamidoimide film, polyimide film.In addition, as required, also can carry out surface treatments such as priming paint coating, UV processing, Corona discharge Treatment, milled processed, etch processes, demoulding processing.

In addition, diaphragm seal of the present invention as shown in Figure 2, can have above-mentioned substrate layer 1 on a face of above-mentioned resin bed 2, have above-mentioned protective layer 3 on another side.

Diaphragm seal of the present invention can have protective layer on the single face of above-mentioned resin bed, its thickness is preferably 5～300 μ m, and more preferably 5～200 μ m are preferably 5～100 μ m especially, most preferably are 10～100 μ m.The thickness of protective layer is less than 5 μ m, and diaphragm even the thickness of film surpasses 300 μ m, also there is no special advantage fully, also may make film self become expensive.

As the material that can be used as above-mentioned protective layer; there is no particular restriction, can use plastic films such as poly tetrafluoroethylene, PETG film, polyethylene film, polypropylene screen, polymethylpentene film, poly (ethylene naphthalate) film, poly (ether sulfone) film, polyetheramides film, polyetheramides acid imide film, polyamide membrane, polyamidoimide film, polyimide film.In addition, as required, also can carry out surface treatments such as priming paint coating, UV processing, Corona discharge Treatment, milled processed, etch processes, demoulding processing.

The manufacturing of＜diaphragm seal 〉

Below, diaphragm seal of the present invention is described.

Diaphragm seal of the present invention can be made as follows.For example, containing above-mentioned (A) resinous principle, (B) filler at least and (C) adding solvent in the resin bed composition of colouring agent, make varnish.When diaphragm seal has substrate layer, this varnish of coating on substrate layer, when perhaps only being made of resin bed, this varnish of coating on model etc. then, removes by heat drying and to desolvate, and the resin bed that forms B scalariform attitude is made.

In the present invention, be used for the solvent of resin bed with varnish, there is no particular restriction, can enumerate for example ether series solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether; Sulfur-bearing series solvents such as dimethyl sulfoxide (DMSO), diethyl sulfoxide, dimethyl sulfone, sulfolane; Ester such as gamma-butyrolacton, cellosolve acetate series solvent; Ketone such as cyclohexanone, methyl ethyl ketone series solvent; N-methyl pyrrolidone, dimethylacetylamide, 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2 (1H)-nitrogenous series solvents such as pyrimidone; Aromatic hydrocarbon such as toluene, dimethylbenzene series solvent etc., these can use separately, perhaps make up 2 kinds with on use.

Above-mentioned heat drying condition is different because of the composition and the solvent types of resin bed, usually, is to heat under 60～200 ℃ temperature 3～30 minutes.Because above-mentioned heat drying condition is influential to the value of " discharge " of diaphragm seal of the present invention, " film viscosity ", therefore, in discharge, when film viscosity is too small, can suitably regulate by improving increase thermal histories such as heat drying temperature, lengthening heat drying time or increase heat drying number of times.

In addition, there is no particular restriction for the coating process of varnish, but consider operation etc., preferably uses multi-function coating machine (multicoater) to be coated with.

The semiconductor device of＜use diaphragm seal of the present invention 〉

Being characterized as of semiconductor device of the present invention used diaphragm seal of the present invention.Below, about its Production Example and mode, use accompanying drawing to illustrate, but the present invention is not limited to following record.

Fig. 3 is that expression adopts diaphragm seal of the present invention (resin bed) as rolled seal film 8, comes the schematic diagram of the operation of the electrode on the sealing semiconductor substrate.Here; when use has the diaphragm seal of the present invention of formation shown in Figure 1; it is the mode that contacts with the electrode surface of semiconductor substrate 4 with resin bed 2; when use has the diaphragm seal of the present invention of formation shown in Figure 2; be after peeling off protective layer 3, make the even tension of film on the roller 9, the mode that contacts with the electrode surface of semiconductor substrate 4 with resin bed 2; with laminating roll 10 laminating seal films, come the electrode on the sealing semiconductor substrate.Laminating temperature in the lamination operation, the angle consideration that never semiconductor substrate is produced load and operation excellence is preferably below 180 ℃, more preferably below 140 ℃, more preferably below 120 ℃.In addition, diaphragm seal of the present invention is particularly suitable for the situation that above-mentioned electrode is the overshooting shape electrode.

In addition, sealing by diaphragm seal realization of the present invention, be not limited to the method for above-mentioned employing film lamination, also can use method, diaphragm seal directly is adhered to method of semiconductor element etc. by hot pressing semiconductor substrate thermo-compressed or vacuum compressing diaphragm seal.The shape of the kind of the diaphragm seal that bases such as crimping condition are used to seal, semiconductor substrate or element and different.

Fig. 4 is the schematic diagram with semiconductor element 7 of the overshooting shape electrode that seals with diaphragm seal of the present invention (resin bed).Such semiconductor element after operation comes the overshooting shape electrode 5 of sealing semiconductor substrate as shown in Figure 3, for example obtains through following operation: the operation of the substrate layer of peel seal film; Come the operation of curing resin layer 2 by heating; On overshooting shape electrode 5, carry the operation of solder ball 6; In semiconductor substrate and operation resin bed sealed sides opposition side upper strata crush-cutting rubber tapping band; Semiconductor substrate is cut into the operation of the size of regulation; To have the semiconductor substrate of overshooting shape electrode 5 and the operation that dicing tape is peeled off.Further, the assigned position of mounting semiconductor element on circuit substrate by obtaining can obtain semiconductor device.

As above-mentioned semiconductor substrate 4 with overshooting shape electrode, there is no particular restriction, can enumerate for example silicon wafer etc.In addition, make semiconductor element with such method after, also can be from diaphragm seal side irradiation YAG laser etc., demonstrate the identifying information that is used to discern goods.

By sealing the semiconductor element that obtains,, in addition, also can be used for the sealing of various devices, various transducers etc. such as SAW device because therefore excellences such as reliability can be used for various semiconductor devices with film for sealing of the present invention.

Embodiment

Below, describe the present invention in detail by embodiment, but the present invention is not limited to this.

(embodiment 1)

The making of＜diaphragm seal 〉

To (Nagase chemical Co., Ltd makes by the epoxy radicals acrylic rubber that contains as high molecular weight components (a1), trade name HHTR-860P-3DR, weight average molecular weight: 800,000, Tg:-7 ℃) 12.4 mass parts, bisphenol f type epoxy resin (Toto Kasei KK's manufacturing as thermosetting composition (a2), trade name YD-8170C, epoxide equivalent 160) (Mitsui Chemicals, Inc makes for 33.6 mass parts and phenol terephthaldehyde diethylene glycol dimethyl ether copolymer resins, trade name Mirex XLC-LL, hydroxyl equivalent 174) (Shikoku Chem makes 33.8 mass parts and 1-cyano group-1-phenylimidazole, trade name Curezole 2PZ-CN) 0.1 mass parts, silica filler (the gloomy manufacturing of Co., Ltd. dragon as (B) filler, trade name TFC-24, the about 8 μ m of average grain diameter) 356.24 mass parts, resin system processed pigment (adret pigment Co., Ltd. manufacturing as (C) colouring agent, trade name FP BLACK 308, carbon black containing ratio 29.0 quality %) 8.3 mass parts, and as the γ-glycidoxypropyltrime,hoxysilane of coupling agent (eastern beautiful DOW CORNING Co., Ltd. makes, trade name SH6040) in the composition that 1.0 mass parts constitute, adding cyclohexanone mixes, vacuum degassing obtains the varnish of the about 60 quality % of nonvolatile component (after, note into NV by abridging).Mensuration, the computational methods of NV are as follows.

NV (quality %)=(the varnish amount (g) before varnish amount (the g)/heat drying behind the heat drying) * 100

The ※ drying condition: 170 ℃ 1 hour

The above-mentioned varnish that obtains is coated on substrate layer, and (film Co., Ltd. of Supreme Being people Du Pont makes, trade name PurexA31B, the PETG film is handled in the surface demoulding, thickness 38 μ m) on, 90 ℃ of heat dryings 5 minutes, 140 ℃ of heat dryings 5 minutes, the resin bed thickness of making behind the heat drying was filming of 150 μ m, obtains the diaphragm seal A of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

To the above-mentioned diaphragm seal A (resin bed) that obtains, estimate discharge, film viscosity, tensile modulus of elasticity, Tg, thermal decomposition initial temperature, embedding and laser marking visibility as described below.Conclusion the results are shown in the table 1.

Discharge

The above-mentioned diaphragm seal A punching that obtains is become the long narrow square sample of 10 * 20mm, under the stacked state of diaphragm seal and substrate layer, adopt thermo-compressed experimental rig (manufacturing of Tester Industry Co., Ltd), at hot plate temperature: under 80 ℃, pressure: 0.2MPa after 18 seconds of pressurization, under light microscope, measure the length of the resin that flows out from the end of sample, with it as discharge.

Film viscosity

The above-mentioned varnish that obtains is coated on substrate layer, and (film Co., Ltd. of Supreme Being people Du Pont makes, trade name PurexA31B, the PETG film is handled in the surface demoulding, thickness 38 μ m) on, 90 ℃ of heat dryings 5 minutes, 140 ℃ of heat dryings 5 minutes, the resin bed thickness of making behind the heat drying was filming of 150 μ m, obtains the film A of B scalariform attitude.Only resin bed (the thickness 150 μ m) punching of the film A that obtains is become that diameter 8mm's is discoid, adopt viscosity determination of viscoelasticity device (Rheostress RS 600 types that Thermo Haake company makes), at constant deformation pattern, frequency: 1Hz, add deformation: programming rate 1%: measure 50 ℃ to 100 ℃ film viscosity under the condition of 5 ℃/min.In table 1, express 50 ℃ film viscosity, 100 ℃ film viscosity.

Storage modulus and Tg

Descend curing after 1 hour at 170 ℃ the above-mentioned diaphragm seal A that obtains, by dynamic viscoelastic spectrometer (the DVE-4 type that Rheology company makes), resin bed is partly measured storage modulus (35 ℃, 10Hz) and glass transition temperature (frequency 10Hz, 2 ℃ of programming rates/min).

The thermal decomposition initial temperature

By differential thermobalance (Seiko instrument Co., Ltd. make, SSC5200 type), at programming rate: 10 ℃/min, atmosphere: under the conditions of air, measure the thermal decomposition initial temperature of the resin bed of diaphragm seal A.

Embedding

(great achievement laminating machine Co., Ltd. makes to use the hot-roll lamination machine, trade name VA-400III type), the above-mentioned diaphragm seal A that obtains is attached (lamination: 80 ℃, 0.2MPa, 0.5m/min) be formed with the semiconductor substrate (spacing dimension: 5.3 * 6.3mm of distribution and copper post, score line: 100 μ m, copper column diameter: 300 μ m, copper post height: 100 μ m).Behind the lamination, partly cut off the semiconductor substrate that is pasted with diaphragm seal A, with its cross section of observation by light microscope, with following benchmark evaluation embedding (evaluation zero and △ are qualified) at the copper post.

Zero: do not produce the cavity that is caused because of the embedding deficiency

△: only produce a little cavity that is caused because of the embedding deficiency (cavity generation rate: less than copper post sum 10%)

*: produce some cavities that caused because of the embedding deficiency (cavity generation rate: copper post sum 10～50%)

* *: almost all produces on whole because of the cavity that the embedding deficiency is caused (generation rate in cavity: more than 50% of copper post sum)

The visibility of laser marking

(great achievement laminating machine Co., Ltd. makes to use the hot-roll lamination machine, trade name VA-400III type), the above-mentioned diaphragm seal A that obtains is attached to (lamination: 80 ℃ on the thick silicon wafer minute surface of 300 μ m, 0.2MPa, 0.5m/min), after obtaining having the silicon wafer of diaphragm seal, peel off substrate layer, and 170 ℃ of curing 1 hour, resin bed side at such silicon wafer that has resin bed, utilize the YAG laser of power output 5.0J/ pulse to carry out laser marking, confirm its visibility (sample number: each 100).

The evaluation method of visibility is to carry out IMAQ by the surface of scanner after to laser marking, carries out two contrastizations of mark part and the non-mark part around it with image processing software (the trade name PHOTSHOP that Adobe company makes).Operate in 256 grades that are divided into black and white on the lightness by this.Then, obtain mark and partly be expressed as " threshold value on the border of two contrastizations " that white, non-mark partly are expressed as black, and mark part also is expressed as black and mark/non-mark does not partly have the value of border " threshold value on the border of two contrastizations ", its value is evaluated as visibility good (estimating zero) when above 40, its difference be more than 30 less than being evaluated as visibility good substantially (estimating △) at 40 o'clock, its difference is less than being evaluated as visibility bad (evaluation *) at 30 o'clock.In the table 1, expression is equivalent to estimate zero, △, * sample number.

The making of＜semiconductor device and evaluation 〉

(great achievement laminating machine Co., Ltd. makes to use the hot-roll lamination machine, trade name VA-400III type), the above-mentioned diaphragm seal A that obtains is attached (lamination: 80 ℃, 0.2MPa, 0.5m/min) be formed with the semiconductor substrate (spacing dimension: 5.3 * 6.3mm of distribution and copper post, score line: 100 μ m, copper column diameter: 300 μ m, copper post height: 100 μ m), peel off substrate layer after, through 170 ℃ the heating came curing resin layer in 1 hour operation; The grinding resin bed makes the copper post be exposed to the operation on surface; On the copper post, form the operation of outside terminal; Cutting action; Pick up the semiconductor element that obtains and be installed on the operation of organic substrate, thereby produce semiconductor device.

Then, to this semiconductor device, carry out 1000 circulations so that-55 ℃/30min ← → 125 ℃/30min is the thermal cycling test (sample number 10) of 1 circulation, whether the investigation resin bed produces the crack.The results are shown in the table 1.Table 1 expression (resin bed produces the number of the semiconductor device in crack)/(gross sample number).

(embodiment 2)

The making of＜diaphragm seal 〉

Except the drying condition that will be coated on the varnish on the substrate layer made into 90 ℃, 10 minutes and 140 ℃, 10 minutes from 90 ℃, 5 minutes and 140 ℃, 5 minutes, carry out 1 identical operation with embodiment, obtain the diaphragm seal B of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

The above-mentioned diaphragm seal B that obtains is carried out the 1 identical evaluation with embodiment.Conclusion the results are shown in the table 1.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal B that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 1.

(embodiment 3)

The making of＜diaphragm seal 〉

Except the drying condition that will be coated on the varnish on the substrate layer made into 90 ℃, 7 minutes and 140 ℃, 7 minutes from 90 ℃, 5 minutes and 140 ℃, 5 minutes, carry out 1 identical operation with embodiment, obtain the diaphragm seal C of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

The above-mentioned diaphragm seal C that obtains is carried out the 1 identical evaluation with embodiment.Conclusion the results are shown in the table 1.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal C that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 1.

(embodiment 4)

The making of＜diaphragm seal 〉

Except the drying condition that will be coated on the varnish on the substrate layer made into 90 ℃, 3 minutes and 140 ℃, 3 minutes from 90 ℃, 5 minutes and 140 ℃, 5 minutes, carry out 1 identical operation with embodiment, obtain the diaphragm seal D of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

The above-mentioned diaphragm seal D that obtains is carried out the 1 identical evaluation with embodiment.Conclusion the results are shown in the table 1.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal D that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 1.

(embodiment 5)

The making of＜diaphragm seal 〉

To (Nagase chemical Co., Ltd makes by the epoxy radicals acrylic rubber that contains as high molecular weight components (a1), trade name HHTR-860P-3DR, weight average molecular weight: 800,000, Tg:-7 ℃) 12.4 mass parts, bisphenol f type epoxy resin (Toto Kasei KK's manufacturing as thermosetting composition (a2), trade name YD-8170C, epoxide equivalent 160) (Mitsui Chemicals, Inc makes for 33.6 mass parts and phenol terephthaldehyde diethylene glycol dimethyl ether copolymer resins, trade name Mirex XLC-LL, hydroxyl equivalent 174) (Shikoku Chem makes 33.8 mass parts and 1-cyano group-1-phenylimidazole, trade name Curezole 2PZ-CN) 0.1 mass parts, silica filler (Long Sen manufacturer of Co., Ltd. name of an article: TFC-24 as (B) filler, average grain diameter: 152.6 mass parts about 8 μ m), resin system processed pigment (adret pigment Co., Ltd. manufacturing as (C) colouring agent, trade name FP BLACK 308, carbon black containing ratio 29.0 quality %) 8.55 mass parts, and as the γ-glycidoxypropyltrime,hoxysilane of coupling agent (eastern beautiful DOW CORNING Co., Ltd. makes, trade name: SH6040) in the composition that 1.0 mass parts constitute, add cyclohexanone and mix, vacuum degassing obtains the varnish of the about 60 quality % of NV.

The above-mentioned varnish that obtains is coated on substrate layer, and (film Co., Ltd. of Supreme Being people Du Pont makes, trade name PurexA31B, the PETG film is handled in the surface demoulding, thickness 38 μ m) on, 90 ℃ of heat dryings 10 minutes, 140 ℃ of heat dryings 10 minutes, the resin bed thickness of making behind the heat drying was filming of 150 μ m, obtains the diaphragm seal E of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

To the above-mentioned diaphragm seal E that obtains, carry out 1 identical evaluation with embodiment.Conclusion the results are shown in the table 1.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal E that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 1.

Table 1

^*1: the acrylic rubber (weight average molecular weight: 800,000, Tg:-7 ℃) that contains epoxy radicals

^*2: bisphenol f type epoxy resin (epoxide equivalent 160)

^*3: phenol terephthaldehyde diethylene glycol dimethyl ether copolymer resins (hydroxyl equivalent 174)

^*4: cresols phenolic resin varnish type epoxy resin (epoxide equivalent 210)

^*5: the phenol novolac resin

^*6: silica filler (the about 8 μ m of average grain diameter)

^*7: silica filler (average grain diameter: about 4 μ m)

^*8: silica filler (average grain diameter: about 10 μ m)

^*9: silica filler (the about 0.5 μ m of average grain diameter)

^*10: resin system processed pigment (carbon black containing ratio 29.0 quality %)

^*11:1-cyano group-1-phenylimidazole

^*12: γ-glycidoxypropyltrime,hoxysilane

^*13: γ-Qiu Jibingjisanjiayangjiguiwan

^*14: γ-urea groups propyl trimethoxy silicane

(comparative example 1)

The making of＜diaphragm seal 〉

To (Nagase chemical Co., Ltd makes by the epoxy radicals acrylic rubber that contains as high molecular weight components (a1), trade name HHTR-860P-3DR, weight average molecular weight: 800,000, Tg:-7 ℃) 12.4 mass parts, bisphenol f type epoxy resin (Toto Kasei KK's manufacturing as thermosetting composition (a2), trade name YD-8170C, epoxide equivalent 160) (Mitsui Chemicals, Inc makes for 33.6 mass parts and phenol terephthaldehyde diethylene glycol dimethyl ether copolymer resins, trade name Mirex XLC-LL, hydroxyl equivalent 174) (Shikoku Chem makes 33.8 mass parts and 1-cyano group-1-phenylimidazole, trade name Curezole 2PZ-CN) 0.1 mass parts, resin system processed pigment (adret pigment Co., Ltd. manufacturing as (C) colouring agent, trade name FP BLACK 308, carbon black containing ratio 29.0 quality %) 8.3 mass parts, and as the γ-glycidoxypropyltrime,hoxysilane of coupling agent (eastern beautiful DOW CORNING Co., Ltd. makes, trade name: SH6040) in the composition that 1.0 mass parts constitute, add cyclohexanone and mix, vacuum degassing obtains the varnish of the about 60 quality % of NV.

The above-mentioned varnish that obtains is coated on substrate layer, and (film Co., Ltd. of Supreme Being people Du Pont makes, trade name PurexA31B, the PETG film is handled in the surface demoulding, thickness 38 μ m) on, 90 ℃ of heat dryings 20 minutes, 140 ℃ of heat dryings 20 minutes, make that the resin bed thickness is filming of 150 μ m behind the heat drying, obtain the diaphragm seal F of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

To the above-mentioned diaphragm seal F that obtains, carry out 1 identical evaluation with embodiment.Conclusion the results are shown in the table 2.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal F that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 2.

(comparative example 2)

The making of＜diaphragm seal 〉

Except the drying condition that will be coated on the varnish on the substrate layer made into 90 ℃, 15 minutes and 140 ℃, 15 minutes from 90 ℃, 5 minutes and 140 ℃, 5 minutes, carry out and comparative example 1 identical operation, obtain the diaphragm seal G of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

The above-mentioned diaphragm seal G that obtains is carried out the 1 identical evaluation with embodiment.Conclusion the results are shown in the table 2.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal G that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 2.

(comparative example 3)

Except the drying condition that will be coated on the varnish on the substrate layer made into 90 ℃, 3 minutes and 115 ℃, 3 minutes from 90 ℃, 5 minutes and 140 ℃, 5 minutes, carry out and comparative example 1 identical operation, obtain the diaphragm seal H of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

The above-mentioned diaphragm seal H that obtains is carried out the 1 identical evaluation with embodiment.Conclusion the results are shown in the table 2.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal H that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 2.

Table 2

^*1～14: identical with table 1

As can be seen from Table 1, the embedding of the diaphragm seal of embodiment 1～5, all excellent with the adaptation and the laser marking visibility of semiconductor substrate.

(embodiment 6)

The making of＜diaphragm seal 〉

To (Nagase chemical Co., Ltd makes by the epoxy radicals acrylic rubber that contains as high molecular weight components (a1), trade name HTR-860P-3DR, weight average molecular weight: 800,000, Tg:-7 ℃) 33.4 mass parts, bisphenol f type epoxy resin (Toto Kasei KK's manufacturing as thermosetting composition (a2), trade name YD-8170C, epoxide equivalent 160) (Mitsui Chemicals, Inc makes for 33.6 mass parts and the phenol dimethyl ether of anti-benzene dimethanol copolymer resins, trade name Mirex XLC-LL, hydroxyl equivalent 174) (Shikoku Chem makes 33.8 mass parts and 1-cyano group-1-phenylimidazole, trade name Curezole 2PZ-CN) 0.5 mass parts, silica filler (Long Sen manufacturer of Co., Ltd. name of an article: TFC-12 as (B) filler, average grain diameter: 152.6 mass parts about 4 μ m), resin system processed pigment (adret pigment Co., Ltd. manufacturing as (C) colouring agent, trade name FP BLACK J308, carbon black containing ratio 29.0 quality %) in the composition that 2.5 mass parts constitute, add cyclohexanone and mix, vacuum degassing obtains the varnish of the about 60 quality % of nonvolatile component (brief note is NV later on).

The above-mentioned varnish that obtains is coated on substrate layer, and (film Co., Ltd. of Supreme Being people Du Pont makes, trade name PurexA31B, the PETG film is handled in the surface demoulding, thickness: 38 μ m), 90 ℃ of heat dryings 5 minutes, 140 ℃ of heat dryings 5 minutes, making thickness was filming of 188 μ m, obtains the film I (thickness of resin bed: 150 μ m) of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

To the above-mentioned diaphragm seal I that obtains, carry out 1 identical evaluation with embodiment.Conclusion the results are shown in the table 3.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal I that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 3.

(embodiment 7)

As (B) filler, use silica filler (Long Sen manufacturer of Co., Ltd. name of an article: TFC-24, average grain diameter: 152.6 mass parts about 8 μ m), replace silica filler (Long Sen manufacturer of Co., Ltd. name of an article: TFC-12, average grain diameter: 152.6 mass parts about 4 μ m), in addition, operate similarly to Example 6, obtain the film J (thickness of resin bed: 150 μ m) of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

To the above-mentioned diaphragm seal J that obtains, carry out 1 identical evaluation with embodiment.Conclusion the results are shown in the table 3.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal J that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 3.

(embodiment 8)

The making of＜diaphragm seal 〉

Use 1-cyano group-1-phenylimidazole (Shikoku Chem's manufacturing of 0.3 mass parts rather than 0.5 mass parts, trade name Curezole 2PZ-CN), as (B) filler, use silica filler (Long Sen manufacturer of Co., Ltd. name of an article: TFC-24, average grain diameter: 152.6 mass parts about 8 μ m), replace silica filler (Long Sen manufacturer of Co., Ltd. name of an article: TFC-12, average grain diameter: 152.6 mass parts about 4 μ m), in addition, operate similarly to Example 6, obtain the film K (thickness of resin bed: 150 μ m) of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

To the above-mentioned diaphragm seal K that obtains, carry out 1 identical evaluation with embodiment.Conclusion the results are shown in the table 3.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal K that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 3.

(embodiment 9)

The making of＜diaphragm seal 〉

As (B) filler, use silica filler (Long Sen manufacturer of Co., Ltd. name of an article: TFC-24, average grain diameter: 105.2 mass parts about 8 μ m), replace silica filler (Long Sen manufacturer of Co., Ltd. name of an article: TFC-12, average grain diameter: 152.6 mass parts about 4 μ m), in addition, operate similarly to Example 7, obtain the film L (thickness of resin bed: 150 μ m) of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

To the above-mentioned diaphragm seal L that obtains, carry out 1 identical evaluation with embodiment.Conclusion the results are shown in the table 4.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal L that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 4.

(embodiment 10)

The making of＜diaphragm seal 〉

As (B) filler, use silica filler (Long Sen manufacturer of Co., Ltd. name of an article: TFC-24, average grain diameter: 209.8 mass parts about 8 μ m), replace silica filler (Long Sen manufacturer of Co., Ltd. name of an article: TFC-12, average grain diameter: 152.6 mass parts about 4 μ m), in addition, operate similarly to Example 6, obtain the film M (thickness of resin bed: 150 μ m) of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

To the above-mentioned diaphragm seal M that obtains, carry out 1 identical evaluation with embodiment.Conclusion the results are shown in the table 4.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal M that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 4.

(embodiment 11)

The making of＜diaphragm seal 〉

As (B) filler, use silica filler (manufacturer of Deuki Kagaku Kogyo Co., Ltd name of an article: FB-35, average grain diameter: 152.6 mass parts about 10 μ m), replace silica filler (Long Sen manufacturer of Co., Ltd. name of an article: TFC-12, average grain diameter: 152.6 mass parts about 4 μ m), in addition, operate similarly to Example 7, obtain the film N (thickness of resin bed: 150 μ m) of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

To the above-mentioned diaphragm seal N that obtains, carry out 1 identical evaluation with embodiment.Conclusion the results are shown in the table 4.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal N that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 4.

Table 3

^*1～14: identical with table 1

Table 4

^*1～14: identical with table 1

(comparative example 4)

The making of＜diaphragm seal 〉

To (Nagase chemical Co., Ltd makes by the epoxy radicals acrylic rubber that contains as high molecular weight components (a1), trade name: HTR-860P-3DR, weight average molecular weight: 800,000, Tg:-7 ℃) 33.4 mass parts, bisphenol f type epoxy resin (Toto Kasei KK's manufacturing as thermosetting composition (a2), trade name YD-8170C, epoxide equivalent: 160) (Mitsui Chemicals, Inc makes for 33.6 mass parts and phenol terephthaldehyde diethylene glycol dimethyl ether copolymer resins, trade name Mirex XLC-LL, hydroxyl equivalent 174) (Shikoku Chem makes 33.8 mass parts and 1-cyano group-1-phenylimidazole, trade name Curezole2PZ-CN) 0.5 mass parts, silica filler (Admafine Co., Ltd. trade name: SO-C5 as (B) filler, average grain diameter: 152.6 mass parts about 0.4～0.6 μ m), resin system processed pigment (adret pigment Co., Ltd. manufacturing as (C) colouring agent, trade name: FP BLACK J308, carbon black containing ratio 29.0 quality %) in the composition that 2.5 mass parts constitute, add cyclohexanone and mix, vacuum degassing obtains the varnish of the about 60 quality % of nonvolatile component (brief note is NV later on).

The above-mentioned varnish that obtains is coated on substrate layer, and (film Co., Ltd. of Supreme Being people Du Pont makes, trade name PurexA31, the PETG film is handled in the surface demoulding, thickness 38 μ m) on, 90 ℃ of heat dryings 5 minutes, 140 ℃ of heat dryings 5 minutes, making thickness was filming of 188 μ m, obtains the film O (thickness of resin bed: 150 μ m) of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

To the above-mentioned diaphragm seal O that obtains, carry out 1 identical evaluation with embodiment.Conclusion the results are shown in the table 5.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal O that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 5.

(comparative example 5)

The making of＜diaphragm seal 〉

Except the drying condition that will be coated on the varnish on the substrate layer made into 90 ℃, 15 minutes and 140 ℃, 15 minutes from 90 ℃, 5 minutes and 140 ℃, 5 minutes, carry out 6 identical operations with embodiment, obtain the diaphragm seal P of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

The above-mentioned diaphragm seal P that obtains is carried out the 1 identical evaluation with embodiment.Conclusion the results are shown in the table 5.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal P that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 5.

(comparative example 6)

The making of＜diaphragm seal 〉

To (Nagase chemical Co., Ltd makes by the epoxy radicals acrylic rubber that contains as high molecular weight components (a1), trade name: HTR-860P-3DR, weight average molecular weight: 800,000, Tg:-7 ℃) 4.72 mass parts, bisphenol f type epoxy resin (Toto Kasei KK's manufacturing as thermosetting composition (a2), trade name YD-8170C, epoxide equivalent: 160) (Mitsui Chemicals, Inc makes for 47.04 mass parts and phenol terephthaldehyde diethylene glycol dimethyl ether copolymer resins, trade name Mirex XLC-LL, hydroxyl equivalent 174) (Shikoku Chem makes 47.32 mass parts and 1-cyano group-1-phenylimidazole, trade name Curezole2PZ-CN) 0.5 mass parts, resin system processed pigment (adret pigment Co., Ltd. manufacturing as (C) colouring agent, trade name: FP BLACK J308, carbon black containing ratio 29.0 quality %) in the composition that 2.5 mass parts constitute, add cyclohexanone and mix, vacuum degassing obtains the varnish of the about 60 quality % of nonvolatile component (brief note is NV later on).

The above-mentioned varnish that obtains is coated on substrate layer, and (film Co., Ltd. of Supreme Being people Du Pont makes, trade name PurexA31B, the PETG film is handled in the surface demoulding, thickness 38 μ m) on, 90 ℃ of heat dryings 5 minutes, 140 ℃ of heat dryings 5 minutes, making thickness was filming of 188 μ m, obtains the film Q (thickness of resin bed: 150 μ m) of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

To the above-mentioned diaphragm seal Q that obtains, carry out 1 identical evaluation with embodiment.Conclusion the results are shown in the table 5.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal Q that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 5.

(comparative example 7)

The making of＜diaphragm seal 〉

To (Nagase chemical Co., Ltd makes by the epoxy radicals acrylic rubber that contains as high molecular weight components (a1), trade name: HTR-860P-3DR, weight average molecular weight: 800,000, Tg:-7 ℃) 4.72 mass parts, bisphenol f type epoxy resin (Toto Kasei KK's manufacturing as thermosetting composition (a2), trade name YD-8170C, epoxide equivalent: 160) (Mitsui Chemicals, Inc makes for 47.04 mass parts and phenol terephthaldehyde diethylene glycol dimethyl ether copolymer resins, trade name Mirex XLC-LL, hydroxyl equivalent 174) (Shikoku Chem makes 47.32 mass parts and 1-cyano group-1-phenylimidazole, trade name: Curezole2PZ-CN) in the composition that 0.5 mass parts constitutes, add cyclohexanone and mix, vacuum degassing obtains the varnish of the about 60 quality % of nonvolatile component (brief note is NV later on).

The above-mentioned varnish that obtains is coated on substrate layer, and (film Co., Ltd. of Supreme Being people Du Pont makes, trade name PurexA31B, the PETG film is handled in the surface demoulding, thickness 38 μ m) on, 90 ℃ of heat dryings 5 minutes, 140 ℃ of heat dryings 5 minutes, making thickness was filming of 188 μ m, obtains the film R (thickness of resin bed: 150 μ m) of B scalariform attitude.

The evaluation of＜diaphragm seal (resin bed) 〉

To the above-mentioned diaphragm seal R that obtains, carry out 1 identical evaluation with embodiment.Conclusion the results are shown in the table 5.

The making of＜semiconductor device and evaluation 〉

Except using the above-mentioned diaphragm seal R that obtains to replace the diaphragm seal A, semiconductor device is made in operation similarly to Example 1, and it is estimated.The results are shown in the table 5.

Table 5

^*1～14: identical with table 1

Applicability on the industry

Film for sealing of the present invention has defencive function and fillibility, can be used for semiconductor chip protection and Fill, the flowability when filling by control makes fillibility, adaptation, shape maintains more excellent, therefore, Can be applied to various semiconductor devices, electronic unit etc.

Claims (13)

1. diaphragm seal with resin bed, described resin bed contain following (A), (B) and (C), and described resin bed is 150～1800 μ m 80 ℃ discharge,

(A) resinous principle, it comprises: to contain bridging property functional group, weight average molecular weight be more than 100,000 and Tg is-50～50 ℃ high molecular weight components (a1); And be the thermosetting composition (a2) of principal component with epoxy resin,

(B) average grain diameter is the filler of 1～30 μ m,

(C) colouring agent.

2. film for sealing with resin bed, described resin bed contain following (A), (B) and (C), and 50～100 ℃ the viscosity of described resin bed in the hot curing determination of viscoelasticity of the film of B scalariform attitude is 10000～100000Pas,

(A) resinous principle, it comprises: to contain bridging property functional group, weight average molecular weight be more than 100,000 and Tg is-50～50 ℃ high molecular weight components (a1); And be the thermosetting composition (a2) of principal component with epoxy resin,

(B) average grain diameter is the filler of 1～30 μ m,

(C) colouring agent.

3. film for sealing according to claim 1 wherein, with respect to described (A) resinous principle 10 mass parts, contains described (B) filler of 1～300 mass parts, described (C) colouring agent of 0.01～10 mass parts; Described (A) resinous principle contains the described high molecular weight components (a1) of 5～85 quality % and the described thermosetting composition (a2) of 15～95 quality %.

4. diaphragm seal according to claim 1 and 2, wherein, described (A) resinous principle contains the described high molecular weight components (a1) of 5～80 quality %, the described thermosetting composition (a2) of 15～85 quality %.

5. diaphragm seal according to claim 4 wherein, with respect to described (A) resinous principle 10 mass parts, contains described (B) filler of 1～300 mass parts, described (C) colouring agent of 0.01～10 mass parts.

6. according to each described diaphragm seal in the claim 1～5, wherein, on the single face of described resin bed, further have the substrate layer of thickness 5～300 μ m, and the thickness of described resin bed is 5～800 μ m.

7. according to each described diaphragm seal in the claim 1～6; wherein; the substrate layer that on a face of described resin bed, has thickness 5～300 μ m; the protective layer that on another face of described resin bed, further has thickness 5～300 μ m; and the thickness of described resin bed is 5～800 μ m.

8. according to each described diaphragm seal in the claim 1～7, wherein, described (B) filler is inorganic filler.

9. according to each described diaphragm seal in the claim 1～8, wherein, described (C) colouring agent is the colouring agent beyond the white.

10. according to each described diaphragm seal in the claim 1～9, wherein, 35 ℃ storage modulus described resin bed, that solidify after 1 hour for 170 ℃ times are 100～20000MPa.

11. semiconductor device that uses each described diaphragm seal in the claim 1～10.

12. one kind has 80 ℃ discharge is the manufacture method of diaphragm seal of the resin bed of 150～1800 μ m, it is characterized in that, comprises: add solvent in following to containing (A), (B) and the resin bed composition (C), make the operation of varnish; Described varnish is coated on the operation of substrate layer or base material; Varnish to described coating carries out 3～30 minutes operation of at least one time heat drying under 60～200 ℃ temperature,

(A) resinous principle, it comprises: to contain bridging property functional group, weight average molecular weight be more than 100,000 and Tg is-50～50 ℃ high molecular weight components (a1); And be the thermosetting composition (a2) of principal component with epoxy resin,

(B) average grain diameter is the filler of 1～30 μ m,

(C) colouring agent.

13. manufacture method with diaphragm seal of resin bed, 50～100 ℃ the viscosity of described resin bed in the hot curing determination of viscoelasticity of the film of B scalariform attitude is 10000～100000Pas, this manufacture method comprises: add solvent in following to containing (A), (B) and the resin bed composition (C), make the operation of varnish; Described varnish is coated on the operation of substrate layer or base material; Varnish to described coating carries out 3～30 minutes operation of at least one time heat drying under 60～200 ℃ temperature,

(A) resinous principle, it comprises: to contain bridging property functional group, weight average molecular weight be more than 100,000 and Tg is-50～50 ℃ high molecular weight components (a1); And be the thermosetting composition (a2) of principal component with epoxy resin,

(B) average grain diameter is the filler of 1～30 μ m,

(C) colouring agent.

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