TW201246280A - Semiconductor wafer with adhesive layer, fabricating method of semiconductor device and semiconductor device - Google Patents

Abstract

This invention relates to a semiconductor wafer with an adhesive layer which includes: a semiconductor wafer and an adhesive layer formed on a surface of the semiconductor wafer, and the adhesive layer is formed inside the circumferential portion. This invention also relates to a fabricating method of a semiconductor device which includes: a step of forming an adhesive containing adhesive layer on a surface of a semiconductor wafer at a position inside the circumferential portion and a step of converting the adhesive layer to B-stage.

Description

201246280 4U873pif VI. [Technical Field] The present invention relates to a semiconductor wafer with an adhesive layer, a method of manufacturing a semiconductor device, and a semiconductor device. More specifically, the present invention relates to a wafer bonding used as a bonding material (wafer bonding material) when a semiconductor element such as a 1C or an LSI is laminated with a lead member such as a lead frame or an insulating supporting substrate or a semiconductor wafer. A semiconductor wafer with an adhesive layer, a method of manufacturing a semiconductor device using the semiconductor wafer with the adhesive layer, and a semiconductor device. [Prior Art] It is known that the bonding material of the body element and the supporting member or the bonding material when the semiconductor wafer is laminated with each other is known as a film of the stiletto imine resin. Or an adhesive film for bonding an inorganic filler. The semiconductor device is mounted on the semiconductor wafer, and the assembly step of the 1 bobble conductor device as described above is performed to make it more efficient: as the semiconductor wafer is borrowed, and the following application is used, the application is followed. ^Chemical bonding is followed by a step. The W is coated by spin coating. The ink is applied to the entire surface of the semiconductor wafer. The film is coated on the substrate or the semiconductor wafer by the dicing step. Bull-conductor cymbals attached to semiconductors The entire surface of semiconductor wafers is widely known. 4 201246280 Spin coating method, that is, coating a liquid adhesive by rotating at high speed on a semiconductor wafer. [PRIOR ART DOCUMENT] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2_-98213, Gong Hao [Patent Document 2] Japanese Patent Special Fair 5-54, No. In the lamination, it is easy to waste the adhesive film of the portion other than the wafer. And H is sprayed onto the semiconductor wafer by spin coating; in the case where the liquid adhesive extends to the end of the semiconductor wafer, the adhesive layer is easily applied to the end layer. The uniformity is easy to roll the air bubbles when laminating the dicing film. In the cutting step, the wafer flute problem is caused. Further, 匕 = thickness unevenness of the undercoat layer - in the difficult lamination step: the load applied to the bulk wafer becomes uneven, and thus the damage of the special-shaped conductor wafer may occur. SUMMARY OF THE INVENTION The present invention has been made in view of the above-described facts, and an object thereof is to provide a semiconductor film having a film thickness formed on a semiconductor wafer, and a semiconductor wafer using the same (four) The manufacturing method of the two sets and the semiconductor device. 4 The present invention provides a semiconductor wafer with an adhesive layer, a package of human conductor wafers; and a layer of I formed on the semiconductor wafer, the adhesive layer being formed on the periphery of the semiconductor wafer The inside of the department. 201246280 40873pif Ding - "The adhesive for the adhesive." The main semiconductor device also provides a semiconductor device in which a surface of the +conductor wafer is formed by a method of forming an adhesive layer; and the bonding is given a prescribed shape. The layer of the adhesive. The thickness of the film is uniform. The inkjet printing method, the spin coating method or the gap coating brush method is preferably the above-mentioned adhesive agent in the hunger layer. The effect of the invention is to provide a semiconductor wafer having a uniform film thickness on the semiconductor wafer +f # a subsequent layer, and a semiconductor wafer using the same A method of manufacturing a semiconductor device and a semiconductor device. [Embodiment] Hereinafter, a preferred embodiment of a semiconductor wafer, a method of manufacturing a semiconductor device, and a semiconductor device according to the present invention will be described in detail with reference to the drawings. The present invention is not limited to the following embodiments. <Semiconductor wafer with adhesive layer> The semiconductor wafer with the adhesive layer of the present embodiment includes a semiconductor wafer and one of the semiconductor wafers. The adhesive layer on the surface, 6 201246280 The adhesive layer is formed on the inner side of the peripheral portion of the semiconductor wafer. Fig. 1 is a view showing an embodiment of a semiconductor wafer with an adhesive layer. A cross-sectional view is shown in Fig. 1. An adhesive layer 7 is formed on the semiconductor wafer 6. The semiconductor wafer 6 is used to form a semiconductor wafer 6 in a semiconductor package (refer to Figure 6). The semiconductor wafer 13a and the semiconductor wafer (10) (refer to Fig. 6). The semiconductor wafer 6 is typically a stone wafer. On the semiconductor wafer 6, a circuit may also be formed as a step. It is preferable to use it as a liquid-like adhesive agent, and it can be formed using a thermosetting or photosensitive adhesive. It is preferable that the thermosetting adhesive of this embodiment contains (a) rail hardening. Resin (hereinafter referred to as "(4) component"), (b) solvent (hereinafter referred to as "(8) component"), (c) thermoplastic resin (hereinafter referred to as "(C) component"). (A) The thermosetting resin is not particularly limited as long as it is a component containing a reactive compound which can cause a crosslinking reaction by heating. Examples of the component (A) include an epoxy resin, a cyanate resin, a maleimide resin, an allyl quinone imine resin, a phenol resin, a urea resin, a melamine resin, an alkyd resin, and an acrylic resin. Unsaturated polyester resin, diallyl phthalate resin, fluorenone resin, resorcinol formaldehyde resin, diterpene benzene resin, husband, sapphire, polyamine phthalate resin, g resin , a cyanuric acid cyanurate resin, a polyisocyanate resin, a resin containing tris(2-hydroxyethyl) vinegar, a triacetate containing trimellitic acid, and a ring A thermosetting resin synthesized by a woman, and a thermosetting resin formed by the trimerization of aromatic dicyandiamide. Among them, in the combination with the polyimide resin, 7 201246280 4U873pif can have excellent adhesion at high temperatures, and the component (A) is preferably an epoxy resin, a maleimide resin, and an alkene. Propyl quinone imine resin. Further, these thermosetting resins may be used singly or in combination of two or more. The epoxy resin is preferably an epoxy resin containing at least two epoxy groups in the molecule, and more preferably a glycidyl ether type of phenol from the viewpoints of thermocompression bonding property, hardenability, and cured property. Epoxy resin. Examples of such a resin include bisphenol A type (or AD type, S type, and F type) glycidyl ether, vaporized biguanide type A glycidol test, and epoxy ethylene burn adduct double a-type glycidyl ether. Propylene oxide adduct bisphenol A type glycidyl ether, glycidyl ether of phenolic novolac resin, glycidyl ether of cresol acetal resin, glycidyl ether of bisphenol A novolac resin, shrinkage of naphthalene resin Glycerol ether, trifunctional (or tetrafunctional) glycidyl ether, dicyclopentadiene benzene resin glycidol, glycidyl dimer acid, trifunctional (or 4 g type) glycidylamine And glycidylamine of naphthalene resin. These epoxy resins may be used singly or in combination of two or more. Further, as the % oxygen secreting grease, from the viewpoint of preventing electromigration (eiectr〇 migrati〇n) or preventing corrosion of the metal conductor circuit, it is preferred to use an alkali metal ion as an impurity ion, an alkaline earth metal ion, and a functional ion. In particular, a high-purity product having a gas ion or a hydrolyzable gas reduced to 3 〇〇 ppm or less. The amount of the epoxy resin is preferably from 1% to 80% by mass based on the total amount of the adhesive, and more preferably from 20% by mass to 60% by mass from the viewpoint of reliability of the adhesive. If the amount exceeds 8% by mass, there is a tendency that the viscosity of the adhesive of 8 201246280 40873pif is high and the printability is lowered. On the other hand, when the amount of the epoxy resin is less than 1% by mass, it tends to be difficult to obtain sufficient thermal pressure bondability and high temperature adhesion. (A) 5% mass reduction temperature of thermosetting resin is preferably 1 or more. More preferably, it is 18 (rc or more, and more preferably 2 〇 (rc or more. Here, 'so-called 5% The mass reduction temperature is 5% mass reduction temperature when the thermosetting resin is measured at a heating rate of thief/min and nitrogen gas using a thermogravimetric/thermal differential synchronization analyzer (Seiko Electronics Nano Co., Ltd. TW). 5% by mass of thermosetting tree with high temperature reduction 9 volatilization during crimping or thermosetting. This type of resistance: hard epoxy resin, from the viewpoint of adhesion = A, can be used particularly well 3 Functional type (or "glycidamine, bisphenol A type (&lt; AD this 1) shrink, ~Ί« 'in the case of epoxy resin, it is better to follow the mouth Amine, alicyclic amine J歹J amine, aliphatic acid liver, month of the ring family 2 = eve ♦, poly-branched amine, organic acid two ugly brand, three gasification of the amine error: gas based two brewed two Indoleamine derivatives, dicarboxylic acid di 4: /carbazoles, dicyanophenyl scales, 2-ethyl-4-4-fusin 7*^ phosphine, tetrasuccinic boric acid, tetras, 3,5-diindole Base_ki) County Amine ' == acid Τ丞 acrylic acid _. ^ (4AD type, S type, F type) shrinkage agent 9 201246280 40873pif _2_(0-[l_methylpropyleneamino]carboxyamino)ethyl ester , hydrazine, 8-diazabicyclo[5.4.0]undecene-7-tetraphenylborate and tertiary amine'. Among these, from the viewpoint of solubility and dispersibility, it is preferred. It is preferable to contain an imidazole as a hardening accelerator from the viewpoint of the bonding, the heterogeneity, and the storage stability. The amount of the hardening accelerator is preferably 相对 with respect to 100 parts by mass of the oxy-lipid. 〇 1 part by mass to 刈 mass is used as the imidazole, and the reaction initiation temperature is preferably 50. (: Above, more preferably more than saki, and most preferably · c or more. If the reaction starting temperature is less than fC, the storage stability is lowered. Therefore, there is a tendency that the viscosity of the adhesive increases and the control of the thickness becomes difficult. Further, the imidazoles preferably use an average particle diameter of preferably 1 〇 μηη = more preferably 疋 8 μπι or less, and most preferably The compound is below 5 μπι. Hunting uses this particle size (four) de' to inhibit the viscosity change of the adhesive, The precipitation of the azoles, and the formation of the film can be achieved by reducing the unevenness of the surface to obtain a uniform film. In the curing, the hardening of the adhesive can be carried out uniformly, and therefore it is considered that the outgassing can be reduced. Good storage stability can be obtained by using a material having poor solubility in an epoxy resin towel. - As an imidazole, an imidazole dissolved in an epoxy resin can also be used. Further, the unevenness of the surface at the time of film formation is further reduced. The imidazoles are not particularly limited, and examples thereof include 2_ethyl_4_methyl hydrazine, cyanoethyl 2-methylpyranium, and 1- Cyanoethyl-2-ethyl halocidyl carbazole, 1-cyanoethyl-2-phenylimidazole, 1-benzyl-2-methylimidazole and 201246280 4U8/Jpit 1-benzyl-2- Phenyl imidazole. Further, the above-mentioned adhesive may also contain a phenolic compound as a curing agent. More preferably, the compound is a phenolic compound having at least two or more phenolic groups in the molecule. Examples of such a compound include a phenolic age ether varnish, a cresol novolac, a third butyl phenol novolak, a dicyclopentadiene cresol novolac, a dicyclopentadiene phenol novolac, and a benzene dimethyl modification. Phenolic novolak, naphthol compound, trisphenol compound, tetraphenyl aging varnish, bisphenol A novolac, poly(p-vinylphenol) and phenol aralkyl resin 1 are preferred among the phenolic compounds. The number average molecular weight is a variegated compound in the range of 4 〇〇 to 4 〇〇〇. Thereby, it is possible to suppress outgassing during heating which is caused by contamination of a semiconductor element or a device during heating during assembly of the semiconductor device. The amount of the phenolic compound is preferably 10 parts by mass to just parts by mass, more preferably 1 part by mass to 70 parts by mass, per part by mass of the thermosetting resin bismuth (8). As the solvent of the component (B), it is preferred to prevent the solvent in the step, the layer and the solvent in the step of volatilization, and to select a agent having a point of 100 ° C or higher. The viscosity of the adhesive can be adjusted by (8) solvent'. In addition, the upper limit of the boiling point of /the agent is about 300. A can be converted to methyl 2·trans, diethylene glycol diglyme, _glyme, and triethylene glycol dioxime (also known as tri-gamma-butyl) Lactone 'iso-isoethyl alcohol diethyl ether, 2-(2-decyloxyethoxy)ethanol, 2-imidazolium pyridinium, Ehr/iso, carbitol, carbitol acetate, 1, 3-dimercaptoethyl cymbal shovel 7 △ acid_2_(2_butoxyethoxy)ethyl ester, ethyl sialophane, vinegar, butyl cyanidin, dioxane, cyclohexanone , benzoquinone 11 201246280 40873pif ^, and used as a solvent for the ink used for brushing, the solvent used for petroleum steaming cranes. These solvents can be used to paste or lightly use two kinds of (B) solvent. It is formulated such that the solid content of the adhesive is from 2% by mass to 90% by mass, more preferably 25 mass%/% by mass%, and still more preferably 30% by mass to 60% by mass. When the solid content is 30% by mass or more, it is preferable from the viewpoint of suppressing the shape change of the volume reduction after the adhesive drying, and if it is 9% by mass or less, the fluidity and workability of the adhesive are improved. View of sex The thermoplastic resin as the component (C) is preferably 15 (rCw, more preferably 12 (TC or less, still more preferably 10 (TC or less, particularly preferably 疋80C or less). When the Tg exceeds 15 〇, in the case of 〇, there is a tendency for the viscosity of the adhesive to rise. Moreover, when the thermocompression is bonded to the adherend, the product has a high temperature of 150 C or more, so that it becomes easy to be crystallized. The lower limit of the Tg of the thermoplastic resin is about -100 ° C. Further, from the viewpoint of the viscosity after the B-stage, it is preferred that the component (C) is in the room. The temperature is 15°C to 35°C. The term “Tg” is the main dispersion peak temperature when the component (C) is formed into a film. The viscoelastic analyzer “RSA- manufactured by Rheometrics” is used. 2" (trade name), measured at a film thickness of 1 〇〇μηι, a heating rate of 5 ° C / min, a frequency of 1 Hz, and a measurement temperature of -150 ° C to 300 ° C, and the Tg is close The peak temperature of tan5 is taken as the main dispersion peak temperature. (C) The weight average molecular weight of the component is preferably controlled at 5000 to 1 2 201246280 4U« /^pir 500000, in terms of the high degree of thermocompression bonding and high-temperature adhesion, it is more preferably 1〇000~3〇〇〇〇0. Here, the so-called " The weight average molecular weight is a weight average molecular weight measured by a high performance liquid chromatography "C-R4A" (trade name) manufactured by Shimadzu Corporation, and measured in terms of polystyrene. Ester resin, polyether resin, polyamide resin, polyamidamine resin, polyimine resin, polyether phthalimide resin, oxymethylene phthalimide resin, polyester phthalimide resin, poly Amino phthalate resin, polyurethane quinone imide resin, polyamino phthalate amide quinone imine resin, copolymer of these resins, precursors of these resins (polyproline) Etc.), polybenzoxazole resin, phenoxy resin, polyfluorene resin, polyether stone resin, polyphenylene sulfide resin, polycarbonate resin, polyether ketone resin, weight average molecular weight of 10,000~1〇〇 Wanzhi (acrylic) acrylic copolymer, phenolic varnish resin and phenolic resin. These resins may be used alone or in combination of two or more. Further, the component (c) may be a resin obtained by imparting a diol group such as ethylene glycol or propylene glycol, a carboxyl group and/or a hydroxyl group to the main chain and/or the side chain of the resins. Among these resins, the component (C) is preferably a resin having a quinone imine group from the viewpoint of high-temperature adhesion and heat resistance. Examples of the resin having a quinone imine group include a polyimide resin, a polyamide amide resin, a polyether quinone resin, a polyamino phthalate quinone imide resin, and a polyamino phthalate. Amidoxime resin, a decylene polyimine resin, a polyester phthalimide resin, and a copolymer of these resins. The polyamidene resin can be obtained by a condensation reaction of tetrahydro acid dianhydride with diamine 13 201246280 40873pif by a known method. That is, in the organic solvent, it is preferred that the total amount of the diamine is 〇.5, and the total amount of the diamine is preferably 1 〇mo, or the total amount of the diamines. m 〇 1 〜 2 0 , more preferably in the range of 0·8 mol to 1.0 mol, and the composition ratio is adjusted (the order of addition of the components is arbitrary) 'the reaction temperature is 80 ° C or less, preferably 〇 ° c 〜 6〇. Addition reaction is carried out under 〇. As the reaction proceeds, the viscosity of the reaction solution gradually rises to form a precursor of the polyimine resin, i.e., polylysine. Further, in order to suppress the deterioration of the properties of the adhesive, the above-mentioned tetracarboxylic acid dianhydride is preferably subjected to recrystallization purification treatment in an acetic acid needle. Regarding the composition ratio of the tetracarboxylic dianhydride to the diamine in the above condensation reaction, the total amount of the diamine is more than 2.0 mol, and the total amount of the diamine is more than 2.0 mol, which is present in the obtained polyimine. In the resin, the amount of the polyamidimide oligomer at the amine end tends to increase, and the weight average molecular weight of the polyimide resin tends to be low, and various properties including heat resistance of the adhesive tend to be insufficient. On the other hand, when the total amount of the diamine is less than mol5 mol based on the total of the tetracarboxylic dianhydride and the total amount of the dicarboxylic acid dianhydride is less than 5 mol, the amount of the polyimine resin oligomer having an acid end tends to increase, and The weight average molecular weight of the polyimide resin is low, and various properties including heat resistance of the adhesive tend to be insufficient. The polyimine resin can be obtained by subjecting the above reactant (polyglycolic acid) to dehydration ring closure. The dehydration ring closure can be carried out by a thermal ring closure method which performs heat treatment, a chemical ring closure method using a dehydrating agent, or the like. The tetracarboxylic dianhydride used as a raw material of the polyamidene resin is not particularly limited, and examples thereof include pyromellitic dianhydride, 3,3,4,4,_biphenyltetradecene 201246280 4U8/ipit 'acid dianhydride, 2,2,,3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis (2, 3-Dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride , bis(2,3-dicarboxyphenyl)decane dianhydride, bis(3,4-dicarboxyphenyl)decane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 3, 4,9,10-perylene tetraphthalic acid dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, benzene-1,2,3,4-tetradecanoic acid dianhydride, 3,4 , 3',4'-dibenzophenone tetradecanoic acid dianhydride, 2,3,2',3,-dibenzophenone tetradecanoic acid dianhydride, 3,3,3',4'-diphenylhydrazine Ketotetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetraphthalic acid dianhydride, 1,4,5,8-naphthalene tetraphthalic acid dianhydride, 2,3,6,7-naphthalene tetradecanoic acid Anhydride, 1,2,4,5-naphthalene tetraphthalic acid dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetradecanoic acid dianhydride, 2,7-dichloronaphthalene-1,4 ,5,8-tetradecanoic dianhydride, 2,3,6,7-tetra-naphthalene-1,4,5,8-tetradecanoic acid Anhydride, phenanthrene-1,2,7,8-tetradecanoic acid dianhydride, phenanthrene-1,2,6,7-tetradecanoic acid dianhydride, phenanthrene-1,2,9,10-tetradecanoic acid dianhydride, . ratio. Qin-2,3,5,6-tetradecanoic dianhydride, porphin-2,3,4,5-tetradecanoic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride , 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3:,3'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) Mercapto phthalic anhydride, bis(3,4-dicarboxyphenyl)nonylphenyl phthalane dianhydride, bis(3,4-dicarboxyphenyl)diphenyl phthalane dianhydride, 1,4-double (3 , 4-dicarboxyphenyl decyl decyl benzene phthalic anhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetradecyldicyclohexane dianhydride , p-phenylene bis (powdered triacetic acid anhydride), ethane tetraphthalic acid dianhydride, 1,2,3,4-butane tetraphthalic acid dianhydride, decalin-1,4,5,8 - tetradecanoic acid dianhydride, 4,8-dimercapto-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetradecanoic acid dianhydride, cyclopentane-1 , 2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetradecanoic acid dianhydride, 1,2,3,4-cyclobutane tetradecanoic acid dianhydride, double Bicyclo[2.2.1]heptane-2,3-diphthalic acid dianhydride, bicyclo-[2.2.2]-oct-7-ene-2,3,5,6-tetradecanoic acid dianhydride, 2,2 - 15 201246280 40873pif bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane II 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide Dihydride, 1,4-bis(2-hydroxyhexafluoroisopropyl)benzenebis(trimellitic acid) anhydride, 1,3-bis(2-hydroxyhexafluoroisopropyl)benzenedi(trimellitic acid) Anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-indolyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, tetrahydrofuran-2,3,4,5-tetradecanoic acid The dianhydride and the tetracarboxylic dianhydride represented by the following formula (7): In the following formula (7), a represents an integer of 2 to 20.

(7) The tetracarboxylic dianhydride represented by the above formula (7) can be synthesized, for example, from trimellitic anhydride monoterpene gas and the corresponding diol, and specifically, 1,2-(extended ethyl) bis ( Trimellitic anhydride ester), 1,3-(triphenylene)bis(trimellitic anhydride), 1,4-(tetramethylene)bis(trimellitic anhydride), 1,5-( Wu's fluorenyl) bis(trimellitic anhydride), 1,6-(hexamethylene) bis(trimellitic anhydride), 1,7-(sevenindolyl) bis(p-benzotrifluoride) Anhydride ester), 1,8-(octadecyl)bis(trimellitic anhydride), 1,9-(nonamidino)bis(trimellitic anhydride), 1,10-(ten Yttrium) bis(trimellitic anhydride), 1,12-(tw-indenyl)bis(trimellitic anhydride), 1,16-(hexamethylene)bis (p-benzoic acid) A phthalic anhydride ester) and 1,18-(octadecyl) bis(trimellitic anhydride ester). 201246280 ^tLfO / ^pil and "for the four slow two needles, from the viewpoint of giving good solubility in the solvent and =^ relative to the transparency of 365 nm light, 'better of the private (8) or The four ships and two needles of the formula (9). [Chemical 2]

The tetracarboxylic dianhydride as described above may be used alone or in combination of two or more. In order to further increase the strength of the bonding, the component (C) may be a polyazide having a carboxyl group and/or a phenolic hydroxyl group. Amine resin. Preferably, the diamine used as a raw material of the above-mentioned polyimine resin containing a carboxyl group and/or a phenolic hydroxyl group includes the following formula (10), formula (U), formula (12) or formula (13) An aromatic diamine represented by jin. [4匕 3] 17 201246280 40873pif

The other diamine used as a raw material of the above polyimine resin is not particularly limited, and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3'3-fee-based diphenyl bond, and 3 , 4'-diaminodiphenyl light, 4,4'-diaminodiphenyl ether, 3,3,-diaminodiphenyl decane, 3,4,-diaminodiphenylmethane, 4, 4,-Diaminodiphenylnonane, bis(4-amino-3,5-diamidinophenyl)decane, bis(4-amino-3,5-diisopropylphenyl) Decane, 3,3'-diaminodiphenyldifluorodecane, 3,4'-diaminodiphenyldifluorodecane, 4,4'-diaminodiphenyldifluoromethane , 3,3'-diaminodiphenyl sulfone, 3,4,-diaminodiphenyl sulfone, 4,4,-diaminomonophenyl base, 3,3'-diaminodiphenyl Sulfur mystery, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diamine Diphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis(3-aminophenyl)propane, 2,2'-(3,4'-diaminodiphenyl ) propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-(3,diaminediphenyl) Hexafluoro 201246280 ^υδ /όριί Propylene, 2,2-bis(4-aminophenyl)hexafluoropropene, bis-aminophenoxybenzene, 1,4-bis(3-aminophenoxyl) Base) stupid, double (amino) phenoxy) benzene, 3,3'-(1,4-phenylene bis(1-fluorenylethylene)) bisaniline, 3 4, _ (14 benzene) Bis(1-mercaptoethylidene))diphenylamine, 4,4,-(ι,4-phenylphenylbis(ι-decylethylene)diphenylamine, 2,2-bis(4- (3-aminophenyloxy)phenyl)propane, 2,2-bis(4-(3-amine basic oxy)phenyl)hexafluoropropane, 2,2-bis (4-(4-amino) Phenoxy)phenyl)hexafluoropropane, bis(4-(3-aminophenyloxy)phenyl) sulfide, bis(4-(4-aminophenoxy)phenyl) sulfide, double (4) -(3_Aminophenoxy)phenyl)sulfone, bis(4-(4-aminophenoxy)phenyl)sulfone, 3,3,-dihydroxy-4,4,-diaminobiphenyl And an aromatic diamine such as 3,5-diaminobenzoic acid, 13-bis(aminomethyl)cyclohexane, 2,2-bis(4-aminophenoxy)propane, and the following The aliphatic ether diamine represented by the formula (14) and the alkoxyalkyl diamine represented by the following formula (15). In the above diamine, from the viewpoint of imparting compatibility with other components, an aliphatic ether diamine represented by the following formula (14), more preferably ethylene glycol and/or propylene glycol, is preferred. Is a diamine. In the following formula (14), R1, R2 and R3 each independently represent an alkylene group having a carbon number of 1 to 10, and b represents an integer of 2 to 80. H2N Rl—^*0—〇—妒—NH 2 C 1 4) Specific examples of such an aliphatic ether diamine include JEFFAMINE D-230, D- manufactured by Sun Techno Chemical Co., Ltd. 400, D-2000, D-4000, ED-600, ED-900, ED-2000, EDR-148, 19 201246280 40873pif Polyurethane D-230, D-400, D-2000, etc. manufactured by BASF An aliphatic diamine such as an alkyl diamine. These diamines are preferably compatible with other compounding components such as (A) a thermosetting resin, and a high degree of compatibility between thermocompression bonding and high temperature bonding. More preferably, it is more than 50% by mole. Further, the diamine is preferably an anthraquinone diamine represented by the following formula (15) in terms of adhesion to the room temperature and adhesion. In the following formula (15), R4 and R9 each independently represent an alkylene group having a number of 1 to 5 or a phenyl group which may have a substituent, and r5, r6^R7 and R8 are in a tactile manner to represent carbon. The number is 丨~5 filament, phenyl or base 'd' represents an integer from 1 to 5. [Chemical 5]

Some of the amines are preferably all of the diamines q ^ can be highly compatible with the thermocompression bonding m8 〇 Mo - better! Moer % ~ 5G =, 冋 / 接 性 性 石 石 皿 皿 皿 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 石 石 石Pure to μ mol%, then) the compatibility of the components, the ancient "right (10) mole %' exists in the same direction as 4: the tendency of the temperature to decrease the adhesion. The formula (ΐ5) ί g is expressed Shixi oxygen-burning diamine, specifically 1 money-burning diamine can be listed as 20 201246280 *+υο /^pn bis(4-aminophenyl) bismuth oxide, 1,1,3,3- Tetraphenoxy-1,3-bis(4-aminoethyl)dioxane, 1,1,3,3-tetraphenyl·1,3-bis(2-aminoethyl)difluorene Oxyalkane, 1,1,3,3.·tetraphenyl-1,3-bis(3-aminopropyl)dioxane; ι,ι,3,3-tetradecyl-1,3 - bis(2-aminoethyl)dioxane, m3·tetradecyl_ι,3_bis(3-radylpropyl)doxazepine, ι,ι,3,3-tetramethyl _ι,3_bis(3-aminobutyl)dioxane and 1,3-dimercapto-1,3-dimethoxyl_1,3-bis(4-aminobutyl)di Examples of the oxirane diamine wherein d is 2, hydrazine, 3,3,5,5-hexamethylene-1,5-bis(4-aminophenyl)trioxane, Tetraphenyl_3,3-dimercapto-1,5-bis(3-aminopropyl)trioxane, 1155_tetraphenyl_3,3-dimethoxy-1,5-double (4-aminobutyl)trioxane, four Base_3,3_dimethoxy-1,5-bis(5-aminopentyl)trioxane, tetradecyl_3,3-dimethoxy-1,5-bis(2-amine Base ethyl)trioxane, 1,1,5,5-tetradecyl_3,3-dimethoxy-1,5.bis(4-aminobutyl)trioxane, 1, 1,5,5-tetramethyl-3,3-dimethoxyoxy_ι,5-bis(5-aminopentyl) trioxane, 1,1,3,3,5,5-six曱,_ι,5_bis(3-aminopropyl)trioxane, U,3,3,5,5··hexaethyl],5-bis(3-aminopropyl)tri矽 烷 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Further, the above-mentioned polyimine resin may be used singly or in combination of two or more kinds as needed, and as described above, when determining the composition of the polyimide resin, it is preferred to 15 (designed as rc or less, as a polyamine, a diamine of a raw material of an amine tree n) is particularly preferably an aliphatic ether diamine represented by the above formula ((4). 21 201246280 40873pif in the above-mentioned polyanilin resin In the synthesis, by the following formula (16) A compound such as a compound represented by the formula (Π) or the formula (18), such as a mono-supplement, and/or an early introduction of the amine into the condensation reaction liquid, may introduce an acid anhydride or a function other than the diamine at the terminal of the polymer. Further, by this, the molecular weight of the polymer can be lowered, the viscosity of the adhesive resin can be lowered, and the thermocompression bonding property can be improved. [Chemical 6]

Qx^°(i8) 0 is a functional group having a function of promoting the hardening of the epoxy resin in the main chain and/or the side chain of the component (c). The imidazole may be obtained, for example, by using a diamine having a monoterpene skeleton as the following formula (19) and formula (20) f]. [化7] 22 201246280 4U8/Jpit

As the polyamino phthalate oxime imide resin, a resin represented by the following formula (I) can be used. In the formula (I), R1 represents a divalent organic group containing an aromatic ring or an aliphatic ring, R2 represents a divalent organic group having a molecular weight of 100 to 10,000, and R3 represents a tetravalent organic group containing 4 or more carbons, and η And m are each independently an integer from 1 to 100. [化8]

The divalent organic group containing an aromatic ring or an aliphatic ring represented by R1 in the formula (I) is a diisocyanate residue, preferably 10 mol% to 100 mol% of the following formula (II) The structure represented. [Chem. 9] 23 (II) 201246280 40873pif

Further, the remaining diisocyanate residues may be exemplified by the following formula: [Chemical 10] CH2tX'-ch2

Wait. These diisocyanate residues may be used alone or in combination of two or more. The divalent organic group having a molecular weight of 100 to 10,000 represented by R2 in the formula (I) is a diol residue. The diol residue is, for example, polybutadiene diol, polyisoprene diol, polycarbonate diol, polybutadiene diol, polyether diol, polyester diol, polycaprolactone II A group derived from a diol such as an alcohol or an anthrone diol. R2 preferably contains 10 mol% to 100 mol% of a structure comprising a repeating unit represented by the following formula (III) as a diol residue. Further, (gh2-ch2-ch2-oh2 - (ΠΙ) Further, the remaining diol residue may have the following formula: 24 201246280 ^two / jpil [Chemical 12] - (gh2-ch(ch3) -o)·, -(C H2~CH2~〇)~ x -&lt;ch2-ch2-c^-ch2-o)-, -{d-^-CH(CH3)-0)a-&lt;CH2 -CH2O)b- (copolymer of a/b=9 to 1/1 to 9 mol%), -[co-(ch2)4-co-o-(ch2)2-〇]-v-[CO- (C; H2) 4-GO-〇-(CH2)2-CHCH2VO]' -[CCHOH^-CO-O-CHa-ChKCHshO]-' -[CO-(CH2)4-C0-〇-(CF^ ) 4-0]-, -[CCHCHzVCO-O - (ch2)6-0]' -[C0-(GH2VC0-0-CH2-C(CH3)2-CH2-0]-v -[CO - (gh2v ~co-o-(ch2>6-〇k -[G0-(CH2)g-0]-, -[C0-O-(CH2)5-0]w' -R4-(Si(GH3)2- 〇)-R4-(R« is a diol residue having a repeating unit such as an organic group having a carbon number of 丨~丨〇. These diol residues may be used in combination or in combination of two or more. The average molecular weight of the alcohol residue is preferably from 100 to 10,000, more preferably from 500 to 5,000. The tetravalent organic group containing four or more carbons represented by R3 in the formula (I) is a tetrahydroester residue. List the following formula: [Chem. 13] 25 201246280 40873pif

磐四验_基 will enable those who are willing to use the button. The n&amp;m of the formula (1) is independently an integer of the order, and more preferably an integer of 1 to 50. The polyamino phthalate oxime imide resin can be synthesized by a usual method such as solution polymerization. In the case of the solution polymerization method, the diisocyanate component and the diol are dissolved in a solvent for dissolving the produced polyaminophthalate quinone imide resin, for example, N-mercapto-2-indolyl 11 ketone (NMP). After the ingredients, at 70. . The reaction is carried out at 180 ° C for 1 hour to 5 hours to synthesize an amino phthalate oligomer, further adding tetracarboxylic dianhydride and reacting at 70 ° C to 180 ° C for 1 hour to 10 hours, thereby obtaining A NMP solution of a polyamine phthalate imine resin. Further, a monovalent alcohol, an anthracene, an amine, an isocyanate, an acid anhydride or the like may be further added as the case may be, and the reaction may be continued to modify the terminal end of the polyaminophthalate oxime imide resin. Further, in the synthesis of a polyamino phthalate ruthenium imide resin, 26 201246280 40873pif may also use water, an alcohol, a tertiary amine or the like as a catalyst. The obtained polyamino phthalic acid acetate/imine resin solution may also be subjected to separation of a polyamino phthalate imide resin by a water reprecipitation method or the like as needed. The composition of the diisocyanate component and the diol component which constitute the amino phthalate oligomer is preferably 0.1 mol to 1.0 mol based on 1.0 mol of the diisocyanate component. The composition of the polyaminocarbamate methacrylate and the tetracarboxylic dianhydride constituting the polyamino phthalate ylide resin is preferably 1.0 mol relative to the polyamino phthalate oligomer. The acid-reducing liver is 〇^1~2.0 mol. The polystyrene-equivalent average molecular weight of the polyamino phthalate yttrium imide resin measured by gel permeation chromatography using tetrahydrofuran as a developing solvent = preferably from 5,000 to 500,000, more preferably 1,000 Å. 〜2〇〇〇〇〇: If the average molecular weight is less than 5,000, the strength of the resin is low, and if it exceeds 5 Å, the solubility of the resin tends to be poor. (C) The amount of the thermoplastic resin is preferably -95% by mass relative to the total amount of the components other than (b) in the adhesive agent, that is, the nonvolatile matter. From the viewpoint of sex, = is H) mass% ~ 7 〇 mass%. If the component (c) is insufficient (7), the toughness of the cured product after the thermal curing of the adhesive exceeds ≤ mass%, and the adhesive strength after the Β·stage is increased. Photosensitive adhesive t, _s ((A) component), (9) Radiation polymerizable compound mouth, Buji 2" "(9) component), (8) Photopolymerization initiator (hereinafter referred to as "(E) ingredient"). 27 201246280 40873pif (D) The radiation-polymerizable compound may, for example, be a compound having an ethylenically unsaturated group, and the ethylenically unsaturated group may specifically be a vinyl group, an allyl group, a propynyl group, a T-alkenyl group, an ethyl group or a phenyl group. Silk, maleic imine, dyslipidimide and (meth)propenyl. From the viewpoint of reactivity, the ethylenically unsaturated group is preferably a (meth)acryl group, and preferably contains ?D1) monos-sb (indenyl) acrylate as the component (d). By adding a monofunctional (meth) acrylate, especially when the B_staged exposure is used, the crosslinking density of the adhesive can be reduced, so that the thermal crimping property after exposure, low stress, and adhesion can be made. Good state. . The monofunctional (fluorenyl) acrylate is preferably a 5% mass reduction temperature of 100 C or more, more preferably 120 ° C or more, still more preferably 15 〇〇 c = upper, and most preferably 18 Å. (: Above. Here, the so-called 5% mass reduction temperature 疋 uses a thermogravimetric/thermal differential synchronization analyzer (TG/DTA6300 manufactured by Seiko Instruments Inc.) at a heating rate of 1 〇t:/min, nitrogen. The 5% mass reduction temperature at the time of measuring the radiation polymerizable compound at a flow rate (400 mL/min). By using a monofunctional (fluorenyl) enoate having a high 5% mass reduction temperature, B- can be suppressed by exposure. The unreacted monofunctional (fluorenyl) acrylate remaining after the stepping is volatilized at the time of thermocompression bonding or thermosetting. The monofunctional (fluorenyl) acrylate is not particularly limited, and examples thereof include glycidol. (meth) acrylate, phenol E 〇 modified (meth) propane acrylate, phenol p 〇 modified (fluorenyl) acrylate, phenol phenol E 〇 modified (fluorenyl) acrylate, phenol P〇 modified (fluorenyl) acrylate, (meth) acrylate containing hydroxyl group, hydroxy group-containing (mercapto) acrylate, phenyl benzene hexyl acrylate (mercapto) acrylate and (fluorenyl) Benzene acrylate 28 201246280 4U«/3pit base ethyl 曰 4 aromatic system Acrylic acid, a (fluorenyl) acrylate containing a quinone imine group, a (fluorenyl) acrylate containing a carboxyl group, a (fluorenyl) acrylate containing an isobornyl group, and a dicyclopentadienyl group (Mercapto) acrylate and isobornyl (meth)acrylate. ^As a soap-functional (fluorenyl) acrylate, the adhesion to the adherend after B-staged, and the adhesion after hardening From the viewpoint of heat resistance, it is preferred to have an amino phthalate group, an iso-trisocyanate group, a quinone imine group, a hydroxyl group, and particularly preferably a monofunctional group having a quinone imine group in the molecule (A) Further, it is preferred to use a monofunctional (meth) acrylonitrile having an epoxy group as a monofunctional (meth)acrylic acid vinegar having an epoxy group, self-preserving, low in oxime m For the viewpoint of outgassing, heat resistance and moisture resistance reliability, it is preferable that the 5% mass reduction temperature is 1503⁄4 or more, more preferably, the uppermost surface is fine. M methyl) propyl vinegar is not particularly limited and can be made by massing 5%. 15()(: The above polyfunctional epoxy resin is used as a raw material to satisfy the limitation::: (meth)acrylic acid vinegar, there is no special "methyl propyl glycidyl (tetra), glycerol glycerol =, propylene is intended to shrink water (4), vinegar and glutinous rice _, in addition to the compound with epoxy group =; = and ethylenically unsaturated group 盥 multi-soil compound. As the ship pr Gan, 夕吕 this clothing The oxidative resin is obtained by a reaction, and examples thereof include, for example, a cyano cyanide group, and no particular hydrazine... a mouse I valent group, a carboxyl group, a phenolic hydroxyl group, a hydroxyl group, 29 201246280 40873 pif anhydride, an amine group, a decyl group, and a decylamine. These compounds may be used alone or in combination of two or more. The monofunctional (fluorenyl) acrylate having an epoxy group can be obtained, for example, by triphenylphosphine or tetrabutyl bromide. In the presence of ammonium, a polyfunctional epoxy resin having at least two or more epoxy groups in the i molecule is reacted with 0.1 equivalent to 0.9 equivalent of (meth)acrylic acid per equivalent of the epoxy group. Moreover, the &amp; polyfunctional isocyanate is combined in the presence of dibutyltin dilaurate Reacting with a hydroxyl group-containing (meth) acrylate and a hydroxy==epoxy compound, or reacting a polyfunctional epoxy resin with an isocyanate group-containing (mercapto) acrylate, thereby obtaining shrinkage Glyceryl (mercapto) acrylamide phthalate. Soil a octa-epoxy monofunctional (fluorenyl) acrylate, self-storing, connecting, shouting heating and low-lying county From the viewpoint of gas permeability, hydrazine and moisture resistance, the 5% mass reduction temperature is in the aspect of suppressing volatilization or segregation on the surface caused by heat drying of the film shape, preferably 15 (rc) In the above, it is possible to suppress the Ι Λ Λ Λ 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 及 热 热 Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι In terms of pores and peeling caused by volatilization, it is preferably C or more. Such a monofunctional (fluorenyl) acrylic acid having an epoxy group is a compound having an aromatic ring in the molecule. Oxyl monofunctional (meth) acrylate, self, migration or From the viewpoint of preventing corrosion of the metal conductor circuit, it is used to make the alkali metal ion or alkaline earth metal as the impurity ion from the 201246280 4U «73pit, the _ element ion, the shaft material or the product. For example, by using the test :foot=^;:==Oxygen resin for “When measuring W. The content of all gas can be based on melon.

a sriri ingredients, and are classified as qualified. It can be listed as double-type kl i, S-type, F-type) glycidinium, hydrogenation double A = water Gan_, epoxy Ethylene adduct double test A and / Or F-type shrinkage ^ Ί Ί 秘 秘 秘 伽 及 及 and / or F-type glycidol bond, 糸 糸 酸 清 清 ( ( ( ( ( ( ( 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 ( ( 四 ( ( ( ( ( ( ( ( ( ( a glycidyl ether, a glycidyl ether of a naphthalene resin, a trifunctional (or tetrafunctional) glycidyl ether, a glycidyl ether of a dicyclopentanyl resin, a glycidyl dimer acid, a trifunctional type ( Or a monofunctional (fluorenyl) acrylate component having a glycidylamine of a tetrafunctional type or a glycidylamine of a naphthalene resin as a raw material. In particular, in order to improve the thermocompression bonding property, the low stress property and the adhesion property, the number of the epoxy group and the ethylenically unsaturated group is preferably 3 or less, and particularly preferably the number of the ethylenically unsaturated groups is 2. Below. The compound is not particularly limited, and a compound represented by the following formula (丨), formula (2), formula (3), formula (4) or formula (5) can be preferably used. In the following general formulae (1) to (5), R12 and R16 represent a hydrogen atom or a fluorenyl group, R10, RU, Rl3 and R14 represent a divalent organic group, and R15 to R18 represent an epoxy group or an ethylene group. An organic group of a non-saturated group. 31 201246280 40873pif [化14] _R10—〇—^ ~IR”_〒H1. One tooth-C—0H2 ( 1 ) CH3 OH 0 _ _ R12 Δ_R^——CH?&quot;^&quot;-R1*- fCH2-〇-j{-C_CH2 ( 2 )

A -CH2 - 〇 -

&quot;&quot;Sr ’ / -OH2—|T H~7—ch3 OR13 R'7

RiJ

(4) R12 *—c58*. ch3 (3) ρ1β _ _ V. JteSSSSSi (5) /N_/ \—ch2—(i \—O—R10

Rte The amount of the above (Dl) monofunctional (fluorenyl) acrylate is preferably 20% by mass to 100% by mass, more preferably 4% by mass to 100% by mass, based on the (D) radiation polymerizable compound. The best is 50 mass 〇 ~ 100% by mass. By making the monofunctional (mercapto) acrylic acid vinegar the upper secret ship and the New Zealand. () Radiation 1-complex compound) Acrylic acid. The phthalic acid s has a sulphuric acid s or more, and is particularly limited, and examples thereof include a dibasic acid ester and a diethylene glycol dimethyl phthalate. Monool diacrylate, tetraethylene glycol dipropionic acid vinegar, tetraethylene glycol diacid acid 0, triethylene glycol dimethyl propylene soil acid brewing, tri-methyl propylene burning diacrylic acid 32 201246280 HUO / ^pil ester, trihydroxyf-propyl propylene diacrylate, trimethylol propyl dimethacrylate, trimethylolpropane tridecyl acrylate, 丨'4-butanediol diacrylate, 1, 6-. hexanediol diacrylate, 1,4-butanediol dimethyl propyl acrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol III Methacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, styrene, divinyl stupid, 4-vinyl benzene, 4-vinyl pyridine, N-ethylene Pyrrolidone, propanol-2-hydroxyethyl ester, 2-hydroxyethyl methacrylate, 1,3-propenyloxy-2 Hydroxypropane, hydrazine, 2_mercaptopropenyloxy-2-hydroxypropane, hydrazine bis acrylamide, N,N-dimethyl decylamine, N-hydroxydecyl acrylamide, tris(β - a hydroxyethyl) isocyanurate triacrylate, a compound represented by the following formula (6), an acrylamide amide, a decyl methacrylate, and a urethane acrylate. 1习-0-^CH2CH2〇

(6) R1) H2C=C- In the formula (6), R19 and R20 each independently represent a hydrogen atom or a fluorenyl group, and g and h each independently represent an integer of 1 to 20. These radiation-polymerizable compounds may be used singly or in combination of two or more kinds thereof. Among them, in order to sufficiently impart solvent resistance after curing, and having a low viscosity and a high 5% mass reduction temperature, it is preferred. The radiation polymerizable compound having a diol skeleton represented by the above formula (6). 33 201246280 40873pif Furthermore, by using a radiation polymerizable compound having a high functional group equivalent, it is possible to achieve low stress and low warpage. The radiation-polymerizable compound having a high functional group equivalent weight preferably has a polymerization functional group equivalent of 2 Å/g or more, more preferably 300 eq/g or more, and most preferably 4 〇〇eq/g or more. By using a radiation polymerizable compound having an anthracene skeleton having a polymerization functional group equivalent of 2 〇〇eq/g or more, an amine sulfonate group, and/or an iso-trisocyanate group, the adhesion of the adhesive can be improved. Further, it is possible to achieve low stress and low warpage, and a radiation polymerizable compound having a polymerization functional group equivalent of 2 〇〇eq/g or more and a radiation polymerizable compound having a polymerization functional group equivalent of less than eq/g. And use it. The amount of the second (D) radiation polymerizable compound is relative to the total amount of the binder. Fortunately, the 疋 10% by mass to 95% by mass is more preferably 20 mass 〇 / 〇 ~ 9 〇 mass % from the viewpoint of wettability of the wafer during crimping, since Β _ I5 white From the viewpoint of shape retention, the best is the mass % ~ such as quality / 〇. When the right (D) component is less than 1% by mass, the adhesive strength after the B_stage is increased. When the content exceeds 95% by mass, the subsequent strength after thermal curing tends to decrease. (D), the radiation t-complex compound is preferably liquid at room temperature (〖ye~ 35 ° C), and considering the detachment from the grid, it is preferable that the nucleus is mPa · The s-cho L step takes into account the flatness of the self-flow after printing, and the face is Li Xin·s below. If the viscosity exceeds 5000 mPa · s, there is a tendency to connect. Further, (D) Radiation polymerization: The lower limit of the viscosity of the brewed material is about 0.1 mPa·s. 34 201246280 HUO/jpil (D) The radiation polymerizable compound preferably has a 5% mass reduction temperature of 120 C or more, more preferably 150 ° C or more, and still more preferably i8 〇 ° C or more. Here, the so-called 5% mass reduction temperature is a thermogravimetric/thermal differential synchronization analyzer (TG/DTA6300 manufactured by Seiko Instruments Inc.). The heating rate is 1 (rc/min, nitrogen flow (4〇〇). 5%/min) The 5% mass reduction temperature at the time of measuring the radiation polymerizable compound. By using a radiation polymerizable compound having a high 5% mass reduction temperature, it is possible to suppress the unreacted radiation polymerizable compound from being subjected to thermocompression bonding or thermosetting. Volatilization. As a (, E) silk starter (starter), it is preferred that the molecular absorption coefficient of light with a wavelength of 365 nm is 100 mL/g · cm from the viewpoint of improving sensitivity. Above, more preferably 2 〇〇 mL / g · (10) or more, the molecular absorption coefficient can be obtained by: preparing a sample of G. OGl f % acetonitrile solution, using a spectrophotometer (Hitachi High-Tech Co., Ltd. , f] manufacture, "U-331G" (trade name)) and measure the absorbance of the solution. Such (E) component is, for example, 2 - benzyl 2 - didecylamine group (4 · Team County) Phenyl)-butanone + 2,2-dimethoxy has diphenylethyl ketone, 1-yl- Hexyl-phenyl, 2-methyl-low &amp; (methylthio)benzolinylacetone], 2,4_diethyl _, 2 _ ethyl onion and phenanthrene aromatic ketone Benzene oxime derivatives such as benzophenone ketal, 2-(o-chlorophenyl)·4,5-diphenyl(tetra)dimer, 2—(o-(m-methoxyphenyl)tetramer, weissene Κ5·Phenyl hydrazide Polymer, o-methoxyphenyl hydrazone 5•diphenyl mercapto dimer, 2_(p.35 201246280 40873pif oxy-based)-4,5-diphenyl σ m Dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer and 2-(2,4-dimethoxyoxyphenyl)-4,5-diphenylimidazole Dimers such as 2,4,5-triarylimidazole dimer, 9-phenyl acridine and anthracene, 7-bis(9,9'-acridinyl) heptane and other acridine derivatives, double (2, 6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide and bis(2,4,6-trimethylphenyl)-phenylphosphine oxide a bis-indenylphosphine oxide and a compound having a maleimide. These compounds may be used alone or in combination of two or more. Among the above photopolymerization initiators, solubility in a solvent-free adhesive In terms of Preferably, 2,2-dimethoxy-oxime, 2-diphenylethene-1-one 2-pyryl-2-didecylamino-_ι_(4_Ν-morphinylphenyl)-butanone 1 is used. 2'2-methoxy-1,2-phenylethene-1-yl, 2-mercaptomethylthio)phenyl)-2-N-morpholinylpropane_ι-ketone. In the air environment, also in the aspect of B_staged by exposure, 2-benzyldimethylamino-1-(4-indole-morpholinylphenyl) can be preferably used. _butanone heart, 2,2-dimethoxy-1,2-diphenylethidin-1·one, 2-mercapto-1-(4-(indolylthio)phenyl)-2- N-Merlinky is a small one. The (E) component may also contain a photoinitiator which exhibits a function of promoting the polymerization and/or reaction of the orbital by irradiation with radiation. Such a light starter may, for example, be a photobase generator which is produced by radiation emission, a photoacid generator which generates an acid by radiation irradiation, and the like, and is particularly preferably a photodetection generator. The bulk generating agent can further improve the adhesion and moisture resistance of the adhesive to the adhesive. It is considered that the reason is that the line formed by the photobase generator acts as a hardening of the ring (tetra) grease (IV) and efficiently functions as 36 201246280 HVJO / jpiv function to further increase the crosslinking density; moreover, the resulting hardened catalyst is corroded There are fewer phenomena such as substrates. Further, by allowing the binder to contain a photobase generator, the crosslinking density can be increased, and the outgas at the time of high temperature placement can be further reduced. In addition, the curing process temperature can be lowered and shortened. The photobase generator is not particularly limited as long as it is a compound which generates a base upon irradiation with radiation. As a result of the test, a strongly basic compound is preferred in terms of reactivity and curing speed. Examples of such tests for radiation irradiation include, for example, taste sputum, 2,4-mercapto-based miso, and 1-mercapto-flavored sputum derivatives, such as sputum and 2,5-dimercaptopurine. Piperazine derivatives such as azine and other derivatives of pyridine and i, 2_dimercaptopiperidine, proline derivatives, tridecylamine, triethylamine and triethanolamine oxime diamine derivatives , 4-mercaptoamine group. ratio. And 4_diamine-based bite is equal to 4-position pyridine derivative substituted with amine or alkylamine group, pyrrolidine derivative such as pyrrolidine and N-mercaptopyrrolidine, dihydropyridine derivative, three Alicyclic amine derivatives such as ethylamine and .1,8-diazabicyclo (5.4.0) eleven carbon diene (DBU), and mercaptobenzylamine, dimethylbenzylamine and diethylbenzyl A benzylamine derivative such as an amine. As a photodetector which produces the above-described test by radiation irradiation, for example, J.urnal 〇f can be used.

Photopolymer Science and Technology, Vol. 12, pp. 313-314 (1999) or Chemistry Chemistry (Chemistry〇fMaterials), Vol. 11, pp. 170-176 (1999), etc. . These compounds are most suitable for the hardening of epoxy resins by irradiating active light to form a highly basic trialkylamine. 37 201246280 40873pif Photobase generators can also be used in the Jcmmal Μ American Chemical Society, Volume 127, Page 12925 (1996) or Polymer Journal, Vol. 28, 795 (1996) Amino phthalic acid derivatives described in the years). By irradiating the active light to produce a photobase generator, it is possible to use 2 4 dimethoxy-1,2-diphenylethen-1-one, ι,2-octanedione, ι_[4_(笨武Fragmented base-2((o-benzonitrile)] or ethyl ketone and ι_[9_ethyl_6_(2曱基笨$^)-9H-carbazol-3-yl] small (o-ethylidene) An anthracene derivative, or a 2-benzyl-2-didecylamine group (4) π% phenylphenyl)-butanone-1, 2, 2·2, commercially available as a photoradical generator.曱oxy-i,2-diphenylethane, fluorenylmethyl 1 (4-(fluorenylthio)-yl)-2_N-morphinyl-propyl _i_g, 2_节美2-methyl Amino-1-(4-anthracene-phenylenephenyl)-butanthene-I, hexa-aryl double-calling. Sit, organism (substituting a substituent such as a _, an alkoxy group, a nitro group, or a phenyl group on a phenyl group), and a benzoxazolinone derivative. The alkali-based base generator can also be used for introducing a compound having a test group into the main chain and/or the side chain of the polymer. The molecular weight in this case is preferably from 1000 to 1 Å, more preferably from 5 〇〇, from the viewpoints of adhesion, fluidity, and heat resistance of the agent. 〇~3〇〇〇(). ± t The above photobase generator does not exhibit reactivity with the epoxy resin in the unexposed state, and therefore has excellent storage stability at room temperature. In the case of the step of B-staged by exposure, the sensitizer may be used in combination as needed. Examples of the sensitizer include camphorquinone, benzoin, hydrazine, benzoin dimethyl hydrazine, benzoin ethyl ketal, and benzoin bis(2-methoxyethyl) condensate. Ketone, 4,4, dimethylbenzene 38 201246280. HUO/jpu • 乳思03⁄4, z-虱恩醌-sweet-dimercapto-fermentation], 蒽g Kun, 醌, 1-hydroxy 蒽醌, Dimethyl hydrazine, 2_ethyl hydrazine, bromine oxime, thioxanthone, 2-. isopropyl thioxanthone, 2-nitrothioxanthone, 2-methylthioxanthone, 2,4- Dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-trifluorotrifluoromethylthioxanthone, thioxanthone-1〇, 1〇 - dioxide, thioxanthene 1-10-oxide, benzoin ether, benzoin ethyl ether, diisopropyl ether, benzoin isobutyl ether, dinonanone, bis(4-didecylamino) ketone, 4,4·_ bis-ethylaminobenzophenone and a compound containing an azide group. These compounds may be used singly or in combination of two or more.

At the time of the step of B-staged by exposure, the adhesive t of the present embodiment is inferior to the force-reducing property, the adhesion to the body to be bonded, and the heat C to the heat. The above (c) thermoplastic resin may also be contained. The binder of the present embodiment in the case of the step of B-staged by exposure may optionally use a thermal radical generating agent. The best heat is organic peroxides. The organic peroxide is preferably an organic peroxide having a Ϊ minute bundle = a temperature of 8 Gt or more, more preferably an organic peroxide having a temperature of HKTC or more at a temperature of 2 minutes, and the best is a sour acid. Divanic peroxybenzene, tert-butylperoxy 1 ethylhexyloxylocene tert-oxy-2-ethylhexanoic acid vinegar, m (t-butylperoxy)_3,3,5. The methyl ring has been calcined, bismuth (Third hexylperoxy) &gt; 3,3,5- 39 201246280 40873pif trimethylcyclohexane and bis(4-t-butylcyclohexyl)peroxydicarbonate. These compounds may be used singly or in combination of two or more kinds. The organic peroxide is used to react the unreacted radiopolymerizable compound remaining in the exposure, thereby achieving low gas escaping and high adhesion. The amount of the radical generating agent is preferably 0.01% by mass to 2% by mass based on the total amount of the radiation polymerizable compound, more preferably α1% by mass to 10% by mass, still more preferably 〇5 by mass. When the amount of the thermal radical generator is less than 0.01% by mass, the hardenability is lowered, and the effect of addition is small; if it is more than 5% by mass, In the case of the thermal radical generating agent, the half-life temperature is 8 〇β (the above compound is not particularly limited, and examples thereof include perhexa 25B (manufactured by NOF Corporation), 2'5-dimercapto-2,5-di (t-butylperoxyhexanone) (] minute half-life temperature of 180 〇C), Pemmiyl D (manufactured by Oyster Oil Co., Ltd.), and bismuth peroxide (The one-minute half-life temperature is 175. 而且. Moreover, the occurrence of bubbles and pores in the formation of the adhesive layer is remarkable, and it is effective to add an antifoaming agent, a nucleating agent, a bubble to the above (8) solvent or (D) radiation polymerizable compound. Additives such as the side, etc. The amount of the additives added is based on the total amount of the (8) solvent or (5) (4) and the combination of the (10) compound, and the read quality is fine. From the viewpoint of the stability of the next or side viscosity, it is preferably 1% by mass or less. In the present specification, the "lowest viscosity" is a heating step which is expressed in a tank at 4 C for 8 hours. Or use the amount of light for the side ^ 24462 In the exposure step of light of 80 μυδ/^pu, the adhesive layer of the B-staged adhesive layer was measured using a viscoelasticity measuring apparatus ares (manufactured by Rheometric Scientific FE Ltd). (: Melting of 300 ° C The minimum value of the viscosity. In addition, the measuring plate is a parallel plate having a diameter of 8 mm, and the measurement condition is a temperature rise of 5 ° C / min, and the measurement temperature is 20. (: ~ 30 (TC, frequency is 1 Hz. The above B-stage The lowest melt viscosity after that is preferably 2 〇〇〇〇 or less, more preferably 18,000 Pa·s or less, and even more preferably 15,000 Pa·s or less. By having the lowest melt viscosity within the above range, sufficient low-temperature thermocompression bonding property can be ensured, and good adhesion can be imparted even to a substrate having irregularities. The lower limit of the minimum melt viscosity is not particularly limited, and is preferably 1 〇 Pa·s or more in terms of workability. In the adhesive of the present embodiment, in order to impart storage stability, process suitability, or oxidation resistance, bismuth, polyphenols, phenols, and phosphites may be further added in a range that does not impair the curability. And polymerization inhibitors or antioxidants such as sulfur. Further, a suitable filler may be contained in the adhesive of the present embodiment. Examples of the filler include metal filler alumina such as silver powder, gold powder, copper powder, and nickel powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium citrate, magnesium ruthenate, calcium oxide, magnesium oxide, and aluminum oxide. Inorganic fillers such as aluminum nitride, crystalline-oxidized oxide, amorphous dioxane, nitrogen (tetra), titanium dioxide, glass, iron, and ceramics, and organic fillers such as carbon and tree fillers. The above filler can be used without particular limitation, regardless of the type and shape. The above fillers can be used separately depending on the desired function. For example, a metal filler 41 201246280 40873pif is added for the purpose of imparting electrical, thermal conductivity and thixotropy to the fourth layer, and a non-metallic inorganic filler is added for the purpose of imparting thermal conductivity, low thermal expansion, and low thirst resistance to the adhesive layer. The organic filler is added to the adhesive layer. These metal fillers, inorganic fillers or organic fillers may be used alone or in combination of two or more. Among them, the conductivity, thermal conductivity, low moisture absorption characteristics, = = and 5 'preferable base metal filler, inorganic filler secret filler, # filler or insulating filler towel, relative to resin varnish Dispersion 2: In terms of the high adhesion force when preheating, it is better that two

Mto said that the best is the average practice of 1 () division, and the largest grain one:. If the average particle size exceeds one and the most: : In the case where it is difficult to obtain the effect of improving the planting, the lower limit of the maximum grain size of the average grain is not particularly limited to 0.001 or more. The amount of the above filler may be preferably from the total of ==11% by mass to 40% by mass based on the total of the imparted == points and the filler, and more preferably 3 times lower by ▲ liters/°. By increasing the amount of filler, it is possible to achieve low alpha, wet, and south elastic modulus, which can improve the cutting property and wire bonding (the super sound mu i 1 is improved by the cutting knife.曰 放 放 ) 、 、 、 、 、 、 、 、 、 、 、 、 若 若 若 若 若 若 若 若 若 若 若 若 若 若 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 The balance of the amount, the amount of mixing in the case of the use of the filler, the combination of better, can also add a variety of coupling agents. Coupled agents such as two: alkane, titanium and aluminum bismuth coupling agents. In other words, it is preferred to use a Wei system coupling agent, and it is better to have a radiation such as = (4) coffee or the decomposition temperature is difficult (9). The point of the eH secret agent and / / step is better. · c to = Guangzhou The decomposition temperature of the coffee is 20叱 or more, and it is preferable to use the Buddha's point and/or the == agent. The amount of the above coupling agent is from the effect of V: the base thorn (10) parts by mass is relative to the used one.苟ϋ.01 parts by mass to 2 parts by mass. Moisture absorbing such ions _ enchantment (four) 纟, can be 4-4 feeding agent. Compounds, as disclosed in the following: triazine thiolation inhibitors are known to be known as = oxidized by copper ionization, m, m ^ material: powdery material, lanthanide, magnesium Department, compound. _无_: 定43 201246280 4〇873pif Division of inorganic ion trapping agent, trade name, IXE_3〇〇 (锑), IXE-500 (“:), IXE_6〇〇 (锑,铋 mixed system), IXE 7〇〇 (magnesium, Ming mixed system), ΙΧΕ-800 (zirconium), ΙΧΕ-1100 (calcium), etc. These compounds may be used singly or in combination of two or more. The amount of the ion trapping agent is preferably 1 part by mass to 1 part by mass based on 100 parts by mass of the adhesive agent, in terms of effect, heat resistance and cost. When the layer is next, it is considered that the paste of the adhesive can be stably supplied from the opening of the screen printing plate before printing, and the thixotropic index of the adhesive is preferably i0 to 80. From the viewpoint of the peeling off of the paste from the opening of the mesh, it is more preferable that 10~^ = after the printing, the above-mentioned butterfly is spontaneous From the viewpoint of flattening the gas of the adhesive layer or the trace of the mesh, it is particularly preferable that the above-mentioned thixotropic index is 〇.〇 or more, ^ the above-mentioned supply and coating by the printing method ==Production: Yes, keep it good. In addition, it can produce the "gap" or whiteness in the paste that can be suppressed and coated by the self-printing ship. The cloth's viscosity (25ΐ &gt; (4) The right to operate on the right side of the brush _, the difficulty is G lp to | l〇〇〇Pa.s, from the printing paste from ^ a * better Gi Pa · s ~ 3 (8) p miscellaneous ^ The point of view of the mouth refers to the 'sexual flow and the adhesive agent Lu Zhiji: S' is self-deprecating after printing by the paste, the viewpoint of the flattening of the trace of the excellent === 44 201246280 HUO / Jpii It is a value measured by an E-type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.) under the conditions of a 3° cone, 25° C., and a rotation speed of 0.5 rpm. The thixotropic index is the ratio of the value measured by the E-type rotational viscometer at 25 rpm and the rpm, and the value measured at 25 〇c and the rotation speed is 1 〇卬. And define it. The thixotropy index = viscosity at 1 rpm / viscosity at 1 rpm <Semiconductor device> - Figs. 2 to 5 are schematic views showing an embodiment of a method of manufacturing a semiconductor device of the present invention. The method of manufacturing a semiconductor device according to the present embodiment includes a step of forming an adhesive layer 7 containing the above-described adhesive on one surface of the semiconductor wafer 6 (adhesive layer forming step); and heating or exposure is followed by Step 7B_staged step (B•staged step of cutting the semiconductor wafer 6 with the Β·staged adhesive layer 8_ (cutting step). (Binder layer forming step) as an adhesive layer The method is not particularly limited. For example, as shown in FIG. 2, 'the surface (back surface) on the opposite side of the surface on which the circuit of the semiconductor wafer 6 is formed' is printed by the screen printing method.彡H can be attached to (4) the above-mentioned adhesive 5 in the above-mentioned casting method. Further, 'in the adhesive coating step of the screen printing method, the printing portion of the printing plate 3 is provided with a printing plate of a pure semiconductor wafer. As a result, as shown in FIG. 1, a uniform thickness of the adhesive layer 7 is formed on the semiconductor screed surface 4' inwardly with respect to the peripheral portion of the semiconductor wafer 6 inwardly = 45 201246280 40873pif. The periphery of the semiconductor wafer 6 In the case of the inner side dot, the adhesive layer 7 does not cover the semiconductor wafer 6 = layer = the end of the low adhesive layer 7 is mixed, and the adhesive / dimorphism can be improved. By the peripheral portion of the semiconductor wafer 6 The thickness of the inner layer of the adhesive layer 7 becomes uniform, and in the later == layer 7', the pressure applied on the wafer can be more uniform, and the second step can be easily formed. The thickness of the agent layer 7 becomes a problem in which the 'single-chip half-piece is low-=== on the self-cut film is called "wafer flying out". ^艮羊降::::Printing: Usually, it is roughly divided into two types. One is used in the opening process of the _ gastric printing plate, and the metal printing plate is placed on the object to be printed, which is called the squeegee 4. The black cloth ink carried on the gold ship is swept by the money board. By this step, the ink is applied according to the shape of the opening pattern on the metal printing plate. As another screen printing method, there is a use only The residue is prepared by weaving the yarn without the town, nylon, and the material of the material. The part to be coated is the one to be coated, and the rest is filled with resin or the like. The so-called grid printing version of Wei Yi. In this process, 1 is called the resin of the scraper or the ink of the metal plaque printing press. By this step, the ink is saturated into the stone of the grid printing plate. The opening part of the landfill such as fat. Secondly, it is swept on the screen printing plate using the position 4 made of polyamine bismuth citrate or yum gum. By this step 46 201246280 W5/Jpll ' In the printing step, the ink that has penetrated into the opening is transferred to the printing target. The printing process can be performed only with the adhesive, so that it can be reduced to less than the desired position and region. Selectively apply the waste of the adhesive, and the material yield is excellent. In the process of printing the craft towel, if it is printed in the range of (4), there is no part in the opening part, so in the opening part The stress from the printing plate with respect to the pressure of the squeegee is not generated, the pressure is concentrated on the center of the squeegee, and the center portion of the squeegee is strongly attracted to the opening, so that the film thickness tends to decrease in the center of the opening. That is, in general, the wider the opening portion is, the more the center portion of the squeegee is pressed in, and the film thickness at the center tends to decrease. On the other hand, in the process of using the grid printing plate, there is also a mesh wire in the opening portion, thus generating stress from the grid printing plate with respect to the pressure of the blade. That is, in the center portion of the squeegee, since the mesh member of the opening portion functions as a supporting member, the squeegee is not strongly pressed into the opening portion. Therefore, a uniform adhesive layer can be obtained at the center of the squeegee without lowering the film thickness. In the screen printing method of the present embodiment, it is preferable to use a process of using a grid printing plate from the viewpoint of providing a film thickness uniform adhesive layer over a relatively wide range of the entire surface of the semiconductor wafer. In the adhesive layer forming step, in addition to the above-described screen printing method, the adhesive layer 7 may be formed in a predetermined region of the semiconductor wafer 6 by an inkjet printing method, a spin coating method, a gap coating method or the like. 201246280 40873pif ^〇t ' ^ ^ , by attaching the microdroplet adhesive to the semiconductor wafer 6 as the printing target from the r:* of 4 = + this forms an adhesive in the target area Layer 7. Further, at = H can be subsequently applied to the semiconductor wafer 6 having the masking tape on the peripheral portion, and then the masking tape is peeled off, and the region is formed into the adhesive layer 7. In addition, in the gap coating, the 屯T is attached to the peripheral portion by the flat substrate, and the mask is placed on the peripheral portion, and the second portion of the semiconductor wafer 6 is placed next to the second wafer to make the desired gap. The height applicator moves in parallel, and after the adhesive is applied to the sunday, the masking tape is peeled off, thereby forming the adhesive layer 7 in the target area. (Β-staged step) The above-mentioned adhesive 7 is an adhesive having adhesion to the adhesive after being subjected to heating or exposure. The adhesive layer applied to the rider is subjected to the step of forming the adhesive layer 7 by a heating means or an exposure means such as (4). In the case of a thermosetting adhesive, the solvent of the household 23 in the adhesive is volatilized by heating, or the thermosetting resin is reversed while volatilizing the solvent, and the thermal hardening property of the step is followed by The agent layer has suitable adhesion and adhesion. Specifically, the adhesive layer is fixed on a semiconductor wafer. On the other hand, in the case of a photosensitive adhesive, the photopolymerization initiator contained in the photosensitive adhesive is combined with radiation polymerization by exposure, and the polymerization reaction is carried out. The layer of the agent then has suitable adhesion and adhesion. Specifically, the sensitivity is determined by the semi-conducting 48 201246280 4U8/ipif body wafer. From the viewpoint of avoiding the inhibition of the photopolymerization reaction by oxygen, it is preferred to carry out the exposure in a state of a nitrogen atmosphere, a vacuum condition τ, or a state in which the photosensitive substrate and the transparent cover are embossed. More specifically, the adhesive layer 8 which is formed by heating or exposure has a suitable adhesion which can be detached from the support when dicing by dicing and cutting, and for semiconductor wafers and glass The adhesion of the substrate or the like to the adherend. The adhesive layer is staged according to the surface adhesive force at 3 Å &lt; t after the heating or exposure is 200 gf/cm 2 or less. If the surface adhesion at 30 ° C exceeds 2 〇〇 gf / cm 2 , the adhesion of the surface having the adhesive layer to room temperature becomes high, and the workability is lowered: The peeling property of the latter dicing film is lowered, and the pick-up property tends to fall. Moreover, if the surface adhesion under the thief is 1 gf/cm2, there is the following: the adhesiveness of the adhesive becomes low, and the water is immersed at the interface between the adhesive and the film during cutting, from « . The surface adhesion of the adhesive layer after heating or exposure at 12 〇〇c is preferably 200 gf/cm2 or more. If at 12 〇. The surface adhesion of the underarm is less than 200 gf/cm ′, which has the following tendency: loss of thermal crimping property, generation of voids during thermocompression bonding, and high temperature of thermocompression bonding. Further, when the surface adhesive force is 500 gf/cm2 or more, there is a tendency that excessive diffusion and diffusion occur during thermocompression bonding, and an adhesive is oozing out on the wafer side. The above surface adhesion is measured in the following manner. When the adhesive is applied to the broken wafer by screen printing or the like, in the case of the step of heating by B-stage 49 201246280 40873, the heating step of 80 ° C and 4 hours is carried out in the oven. In the case of the step of B-staged by exposure, the obtained coating film was separately B-staged by an exposure step using light having a light amount of 1000 mJ/cm 2 . Thereafter, a probe overlap tester manufactured by RHESCA CQ_ati〇n Umit^ was used with a probe diameter of 51 mm, a peeling speed of 10 mm/s, a contact load of 1 〇〇gf/cm2, and a contact time of 1 second. The adhesion of the surface of the adhesive layer 8 at 30 ° C and 120 ° C is measured. (Cutting step) Next, the semiconductor wafer 6 coated with the adhesive is cut from the semiconductor wafer side to make a single sheet. Sliced semiconductor wafers. That is, the semiconductor wafer 6 is cut by the cutter to divide the semiconductor wafer 6 into a plurality of semiconductor wafers 13a and 13b. Preferably, before the cutting step, the back surface of the semiconductor wafer 6 coated with the above-mentioned adhesive is attached. If necessary, the surface is heated - the surface is attached. For example, it is preferable to use a dicing blade in a state in which the entire film is fixed to the frame (ring ring) 9 by cutting the film 1 (see Fig. 4). The semiconductor wafer of the singulated adhesive layer can be picked up using a wafer bonding apparatus or the like (see Fig. 5). As shown in Fig. 6, the semiconductor wafer 13a obtained by the dicing step is disposed on a further support member 14 and the semiconductor wafer is pre-bonded to the semiconductor wafer 13a on the support member. In this case, the semiconductor wafer 2 and the support member 14' and the semiconductor wafer 13b are bonded to the semiconductor wafer 12a followed by the 'semiconductor crystal' or the semiconductor (9) by thermal bonding followed by the contact 16 and the adhesive layer 1γ. fixed. 50 201246280 4 ϋ ρ ρ 其 其 其 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = U minus 4 as shown in FIG. 6 is a manufacturing method of the semiconductor package described above, and it is conceivable that the semiconductor wafer and the supporting member are subsequently bonded by the printing worksheet. Whatever the composition, it can be changed by printing: the desired film thickness. Therefore, the waste of the adhesive for the semiconductor package can be reduced, and the coating can be applied as a plurality of [examples] by a single adhesive. However, the present invention is more specifically described below by the following examples, and is not limited by the following examples. (Synthesis of Thermoplastic Resin) — Winter' BenQ-Hybrid*-4,4-Iso-II Acid (IQ m〇i), Diphenylmethyl--2,4'-Diisocyanate g ( 1〇m〇1) and poly-anol (0.8m〇1) with an average molecular weight of 诵 and 丨_曱基·2_pyrrolidine_ were mixed, and reacted under nitrogen for 1 hour under i〇oc, added 4,4'-oxybisphthalic acid (1.0 mol) and ι_mercapto-2_〇 ratio σ were determined to be further stirred at i4 ° °c for 3 hours. Secondly, add m^(Q2m〇i) in step by step,

The reaction liquid was obtained by stirring at 1 °C for 1 hour. The obtained reaction liquid was placed in vigorously stirred water, and the precipitate was separated by filtration, and dried under vacuum at 6 CTC for 48 hours to obtain a polyamino phthalate.醯imine resin. The molecular weight of the obtained polyamino phthalate ruthenium imide resin was measured by GPC 51 201246280 40873pif, and the weight average molecular weight (Mw) was 937 Å in terms of polyphenylene oxide, and the number average knife was used.畺(Μη) is 38800. Moreover, the obtained polyurethane imidate resin has a semi-solid shape at room temperature, and the glass transition temperature (Tg) is _40 C 〇 (adjusted by an adhesive) (liquid form) Next, 1) parts by mass of the above-mentioned polyurethane phthalimide resin: 50 parts by mass of YDCN700-7" (anthraquinone novolac type epoxy resin, manufactured by Dongdu Chemical Co., Ltd., trade name), "TrisP-PA" (4,4'-[l-[4-[l-(4-hydroxyphenyl)-丨-mercaptoethyl]phenyl]B_1:1_diyl], phenol, Manufactured under the name of Honshu Chemical Industry Co., Ltd., 5 enamel partitions and carbitol acetate (made by Wako Pure Chemical Co., Ltd.) 16 parts by mass was placed in a flask placed in an oil bath, and heated and stirred under a nitrogen atmosphere at 8 Torr to prepare a solution. To the obtained solution, "SO-C2" (cerium oxide filler, Adrnatechs) was added. 10.0 parts by mass and rTPPK" (manufactured by Co., Ltd., trade name), 0.2 parts by mass of tetraphenylboronic acid tetraphenyl sulphate, manufactured by Tokyo Chemical Industry Co., Ltd., and placed in a kneading machine for kneading. Further, the antifoaming kneading was carried out for 1 hour at 5 Torr or less. Next, 5.0 parts by mass of carbitol acetate was added as a solvent for printing, and the viscosity was adjusted by defoaming and kneading to obtain a viscosity of 26 Pa at a rotational speed of 0.5 rPm. s, liquid liquid adhesive 1 with a thixotropic index of 1.1 (liquid adhesive 2) 52 201246280 -TW / -/ ΜΑλ "YDCN700-7" 30 parts by mass and "Aronix m] 4" 40 parts by mass of (N_acryloyloxyethylhexa-phenylene f light amine, manufactured by Toagosei Co., Ltd., trade name) was placed in a flask set in an oil bath under a nitrogen atmosphere at 60 ° C Heating and stirring to dissolve it. Then, add "I_379EG" (2_(didecylamino)_2(4_methylbenzyl)-1-(4··Ν-morpholinylphenyl)butane_anthone, ciba in the flask.叩(10) Manufactured, trade name) 0.4 parts by mass, r1B2pz" (1_benzyl-2-phenylimidazole, manufactured by Shikoku Chemicals Co., Ltd., trade name) 〇 2 parts by mass, stirred, obtained at the number of revolutions A liquid adhesive 2 having a viscosity of 13 Pa·s at a rpm of 5 rpm and a thixotropic index of 1.0. (Formation of the adhesive layer) Example 1 to Example 4 MK_838SV printing machine (manufactured by MINAMI Co., Ltd.) equipped with a V-screen V50 grid printing plate (manufactured by NBC MESHTEC Co., Ltd.) was used to crystallize at 5 吋 ^ The back of the circle is dead, and the liquid adhesive or the liquid adhesive 2 is printed and coated on the periphery of the wafer (hereinafter also referred to as "end portion") without forming an adhesive layer. Shapes, respectively, to make a wafer with an adhesive layer. By visually confirming the tweezers of the adhesive after printing, as a result, there is no flying white or the like, and a uniform adhesive layer can be provided. Comparative Example 1 In the same manner as the formation of the adhesive layer of the example, a Mk_838sv printer equipped with a v_screen V50 grid printing plate was used for printing and coating to produce a wafer to which the film was attached. However, the position of the 11 wafers of the five-leaf φ is changed. 53 201246280 W8 / jpif The printing is performed so that the printing plate covers the entire surface of the wafer, and the adhesive is applied to the end of the wafer. (Evaluation of Uniformity of Adhesive Layer) Wafers of Example ～~Example 3 and the adhesive layer of Comparative Example 1 prepared as described above were heated in an oven at 8 μl for 4 hours using an oven to form an adhesive layer B. - Staged. Further, using a parallel exposure machine (manufactured by Luminas Co., Ltd., trade name "ML-210FM mask alignment exposure machine"), the wafer of the adhesive layer of Example 4 was subjected to 1000 mj/cm 2 under a nitrogen atmosphere. Exposure, B-staged the adhesive layer. The distance between the end of the crucible wafer and the end of the adhesive layer was measured using a non-contact film thickness meter (manufactured by Keyence Co., Ltd., nickname "KS-1100") for each wafer having the adhesive layer. The thickness of the layer of the agent and the ridge of the end of the layer of the adhesive layer. The ridge of the end is the height difference between the flat portion of the adhesive layer and the highest point of the raised portion. The results obtained are shown in Table 1. [Table 1] Unit Example 1 Example 2 Example λ Example 4 Comparative Example 1 Liquid adhesive The distance between the i* portion and the end of the adhesive layer was followed by the thick layer of the enamel layer mm 1 1 1 2 1 5 2 2 1 0 The end of the layer of the adhesive layer is raised at the end of the adhesive layer. f 隆 相对 相对 相对 相对 相对 相对 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 28 In the agent layer, the ratio of the end ridges to the thickness of the adhesive layer was greatly reduced as compared with the comparative example. From this, it was confirmed that the uniformity of the adhesive layer was maintained even at the end of the adhesive layer by forming the adhesive layer on the inner side of the peripheral portion of the semiconductor wafer. 54 201246280 HUO/jpu Round-layer laminate cutting = t The adhesion agent (4) prepared in the comparative example has an effect on the flatness, and can be used without problems. 4=== Not in the case of Example 2~Example 4. I Private until the brakes are private. To the cutting step. Compared with: a曰: two problems without any problem, the process of direct film filming, in /, in the chopped wafer, in the cutting 'L' in the outer edge of the Shixi wafer, a small crack, causing twinning In addition, when the cut-out stone wafer is observed, the wafer is mainly ejected in the peripheral portion of the wafer. [Industrial Applicability] According to the present invention, a semiconductor wafer having an adhesive layer in which an adhesive layer is formed on a semiconductor wafer with a uniform film thickness, and a semiconductor wafer using the adhesive layer can be provided. A method of manufacturing a semiconductor device and a semiconductor device. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor wafer with an adhesive layer. s Fig. 2 is a schematic view showing an embodiment of a method of manufacturing a semiconductor device. Fig. 3 is a schematic view showing an embodiment of a method of manufacturing a semiconductor device. Fig. 4 is a schematic view showing a consistent embodiment of a method of manufacturing a semiconductor device. Figure 5 is a diagram showing the modulo 55 201246280 4〇 873pif of an embodiment of a method of manufacturing a semiconductor device. Fig. 6 is a schematic cross-sectional view showing an embodiment of a semiconductor device. [Description of main component symbols] 1 : Printed frame 2: Part of the grid printed with resin embedded in the screen 3: Opening in the screen printing plate 4: Scraper 6 7 9 Adhesive semiconductor wafer adhesive Layer/adhesive staged adhesive layer frame 1〇: dicing film 11: singulated adhesive layer of the adhesive semiconductor wafer 12: dicing blade 13a: semiconductor wafer 13b of the first stage: semiconductor of the second stage Wafer 14: support member 15: sealing material 16 - an adhesive 17 for bonding the semiconductor of the first stage to the support member: the semiconductor wafer of the second bonding layer layer is connected to the semiconductor wafer of the i-th segment 18: Bonding wire 56

Claims (1)

201246280. HUO / jpil VII. Patent application scope: A semiconductor wafer comprising: - an adhesive layer on one side, side. Day v; the inner periphery of the semiconductor wafer. 2. The wafer of claim i, wherein the adhesive layer is included in the semiconductor layer of the pounding layer. L 35c is a liquid connection 3. A method of manufacturing a semiconductor device, one of a semiconductor wafer and 3 a step of including an adhesive layer of an adhesive; further forming a layer of the adhesive layer B. Steps of phased. The method of manufacturing a semiconductor device according to the above-mentioned third aspect is formed by a screen printing method, a spray coating method or a gap coating method. The semiconductor device according to the third aspect or the fourth aspect of the invention is manufactured by the method of manufacturing a semiconductor device according to any one of claims 3 to 5. 57