TW201104738A - Semiconductor chip manufacturing method - Google Patents

Abstract

The present invention provides a semiconductor chip manufacturing method which increases the yield by preventing the protection film for chips from damage during processing wafers, simultaneously provides excellent cutting properties during the cutting step, and reduces the wrap of the wafers. The present invention provides a semiconductor chip manufacturing method comprising the steps of adhering a substrate film and a flake for forming a semiconductor chip protection film to the back of a semiconductor wafer through the contact way, in which the substrate is one-sided detachable and the flake is set on the one-sided detachable face and composed of thermal curing resin compositions; then hardening the protection film; and peeling off the substrate film from the hardened protection film thereafter.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a semiconductor wafer having a protective film for wafer for preventing backside defects on a wafer when a semiconductor wafer is cut. [Prior Art] In order to reduce the mounting area of a semiconductor wafer, a flip chip connection method is used. The connection method generally includes the following steps: (1) forming a circuit and connecting bumps on the front side of the semiconductor wafer, (2) honing the back surface of the semiconductor wafer to a specific thickness, and (3) cutting the semiconductor The wafer is obtained as a semiconductor wafer, (4) the circuit forming surface of the wafer is connected to the substrate side, and then (5) a resin package or the like for protecting the semiconductor wafer is performed. However, in the honing step of (2), minute strip-like flaws are formed on the back surface of the wafer, which are the cause of cracking after the cutting step or packaging. Therefore, there has been proposed a method of forming a protective film (protective film for wafer) on the back surface after the honing step (2), even if such strip scratches occur in the honing step, and there is no adverse effect on the subsequent steps. Further, as a sheet for forming the protective film, a protective film forming layer formed of a release sheet and a release surface thereof is proposed (Patent Document 1 and Patent Document 2). [Prior Art Document] [ [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A-2002-260190 (Patent Document 2) JP-A-2004-260190 (Summary of the Invention) [Problems to be Solved by the Invention] On the other hand, in the above cutting step, It is known that the wafer is damaged by the vibration of the rotary blade (hereinafter referred to as "chipping"). The protective film for the wafer is also expected to prevent the state of debris during the cutting step, but for self-hardening. In the process of removing the base film by the protective film of the wafer, when the surface of the protective film for the wafer is slightly attached with a contact flaw, the yield is lowered. Further, since the portion having the flaw becomes uneven, a gap is formed between the dicing film and the protective film for the wafer, and a portion where the dicing film and the protective film are not in contact with each other occurs. As a result of the unevenness of the protective film, a non-uniform air layer is generated between the protective film for the wafer and the dicing film, and there is a problem that the rotating blade vibrates during the cutting of the wafer to further damage the wafer. A wafer for a protective film for a wafer has a semiconductor circuit on the opposite side surface from the back surface on which the protective film is used. The surface further has a soldering hole and a circuit protective layer for protecting the surface circuit of the wafer and electrically connecting the circuit to the mounting substrate. Usually, the protective film or the circuit protective layer is composed of an organic material, and the coefficient of linear expansion is larger than that of the single crystal germanium constituting the wafer. Therefore, when the circuit surface of the semiconductor wafer is used as the upper surface, warpage which becomes convex downward is caused. This warpage causes stress on the wafer, and when the stress is too large, it becomes a cause of debris. Therefore, the problem of the present invention is to solve the problem by providing a wafer with a protective film damage during the wafer processing of the anti--6-201104738, and improving the yield, and the cutting property is excellent in the cutting step, and the wafer is Warpage also results in a reduced manufacturing method for semiconductor wafers. [Means for Solving the Problems] As a result of the above-described problems, the present invention provides a method for producing a semiconductor wafer, comprising: providing a substrate film having releasability on one side and a sheet for forming a protective film of a protective film for a semiconductor wafer formed of a thermosetting resin on the one surface of the base film, such that the protective film is bonded to the back surface of the semiconductor wafer, and then The protective film is cured, and then the substrate film is peeled off from the cured protective film. [Effect of the Invention] In the method for producing a semiconductor wafer of the present invention, the protective film for a semiconductor wafer is cured in a state in which the base film is bonded to the base film, so that it is less likely to be damaged during the pre-hardening treatment, and the yield is improved. Further, since the flatness of the protective film is improved and the warpage of the semiconductor wafer is suppressed, the state of debris can be prevented. The cutting property at the time of cutting is also excellent. [Embodiment] Hereinafter, the present invention will be described in more detail. The "weight average molecular weight" (also referred to simply as Mw) referred to in the present specification means a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography of 201104738. (Constituent for forming a protective film) The composition for forming a protective film for a semiconductor wafer is not particularly limited as long as it is a thermosetting resin composition, and examples thereof include a phenoxy resin composition and a polyimide resin composition. (Meth)acrylic resin composition, epoxy resin composition, maleic imine resin composition, and the like. These are generally contained in an amount of from about 5 to about 1,500 parts by mass of the inorganic cerium or aluminum oxide, such as cerium oxide or aluminum oxide, in an amount of from 5 to 1,500 parts by mass, and further contain an effective amount of a curing catalyst and / or hardener. The resin, the chelating agent, the hardening catalyst, and the like may be used alone or in combination of two or more. The optimum thermosetting resin composition used in the present invention is a composition comprising the following components: (A) 1 part by mass selected from the group consisting of a phenoxy resin, a polyimide resin, and a (meth)acrylic resin. At least one resin of the group, (B) 5 to 200 parts by mass of the epoxy resin, (C) 10 to 900 parts by mass of the chelating agent, and (D) an effective epoxy curing agent. - selected from (A) phenoxy resin, polyimine resin and (meth)acrylic resin - phenoxy resin: phenoxy resin is derived from epichlorohydrin and bisphenol A or bisphenol resin ρ Resin. The weight average molecular weight in terms of polystyrene is preferably -8-201104738 1 0,000 to 200,000, more preferably 20, 〜 1 to 00,000, and most preferably 3 0,000 to 8 0,000. When the weight average molecular weight is less than the above lower limit, it is difficult to form a film. On the other hand, when the weight average molecular weight is larger than the above upper limit, it is difficult to obtain sufficient flexibility to follow the unevenness of the surface of the substrate having the fine circuit pattern and to embed the gap. Examples of the phenoxy resin are listed under the trade names PKHC, PKHH, PKHJ (both manufactured by Ba Chemical Co., Ltd.), bisphenol A and bisphenol F, and sold under the trade names Epikote 4250, Epikote 4275, Epikote 1 25 5 HX3. 0 sellers (all manufactured by Nippon Kayaku Co., Ltd.), Epikote 5 580BPX40 (both manufactured by Sakamoto Chemical Co., Ltd.) using brominated epoxy groups, and YP-50 and YP-50S under bisphenol A type. YP-55, YP-70 sellers (all manufactured by Dongdu Chemical Co., Ltd.) are sold under the trade names JER E 1 256, E4250, E4275, YX6954BH30, YL 7 2 9 0 B Η 3 0 Made by Resin Company). In view of the above preferred weight average molecular weight, JER Ε 1256 is preferably used. The phenoxy polymer has an epoxy group at its terminal end and reacts with a component (s) described later. The phenoxy resin may be used singly or in combination of two or more. 醯 Polyimide resin: The polyimine resin may be a compound having a repeating unit represented by the following formula (1). 201104738 【化1】

(wherein X is a tetravalent organic group containing an aromatic ring or an aliphatic ring, γ is a divalent organic group, and 9 is an integer of 1 to 300). The polyamidene resin preferably has a weight average molecular weight of from 10,000 to 200,000, more preferably from 20,000 to 100,000, most preferably from 30,000 to 80,000. When the weight average molecular weight is less than the above lower limit, it is difficult to form a film. On the other hand, when the weight average molecular weight is larger than the above upper limit, it is difficult to obtain sufficient flexibility between the unevenness of the surface of the substrate having the fine circuit pattern and the buried void. The above polyiminoimine polyanione resin can be obtained by dehydrating and ring-closing a polyamido resin having a repeating unit represented by the following formula (2) by a usual method. [Chemical 2]

(wherein X, Y, and q are as defined above). The polyamic acid resin represented by the above formula can be subjected to a usual method to give a tetracarboxylic dianhydride represented by the following formula (3): -10- 201104738 [Chemical 3]

Ο Ο (wherein χ represents the same meaning as described above), and a diamine represented by the following formula (4) is obtained by reacting in an organic solvent in almost the same molar amount: Η2Ν-Υ-ΝΗ2 (4) (where γ Indicates the same meaning as above). In the above, the tetracarboxylic dianhydride represented by the above formula (3) is exemplified as the following ones, and these may be used alone or in combination of two or more. -11 - 201104738

[Chemical 4] 0 〇bO Λ θ. °^ο 〇d〇 0 0 ο ch3 ch3

In terms of solubility in an organic solvent, adhesion to a substrate, low elasticity, and flexibility, Si-O-Si ch3 ch3 is preferably a diamine represented by the above formula (4), -12-201104738 Preferably, it is 80% by mole, more preferably, it is a diamine-based oxoxane compound represented by the following formula (5). 【化5】

(wherein R1 is independently a divalent organic group having 3 to 9 carbon atoms, and R2 and R3 are each independently unsubstituted or substituted ones having 1 to 8 carbon atoms, and 111 is 1 to 200; Integer). The above divalent organic group having 3 to 9 carbon atoms is exemplified by, for example, -(CH2)3-> -(CH2)4-'-CH2CH(CH3)-, -(CH2)6-, -(ch2)8- The extension of the base is represented by any of the following formulas: [Chem. 6]

An alkyl group having an alkyl group, an alkyl group, a - (ch2) 3-0 ·, - (CH2) 4-0- or the like, an alkyl group represented by any one of the following formulas:

Ch3 is a divalent hydrocarbon group which may have an ether bond, such as an alkyl group represented by the following formula: an unsubstituted or substituted carbon atom represented by R2 and R3. 13-201104738 Hydrocarbyl groups are exemplified by, for example, methyl, ethyl, propyl, isopropyl, tert-butyl, hexyl, cyclohexyl, 2-ethylhexyl, allyl, propenyl, isopropenyl, butenyl An alkenyl group such as an alkenyl group such as an aryl group, an aryl group such as a phenyl group, a tolyl group or a xylyl group, or a bromoethyl group bonded to a carbon atom of the hydrocarbon group or a halogen atom such as fluorine, bromine or chlorine. A halogen-substituted alkyl group such as 3,3,3-trifluoropropyl or the like is preferred. The diaminocarboxane compound of the formula (5) may be used in combination of two or more. The diamine oxime represented by the above formula (5) is a diamine represented by the above formula (4), for example, p-benzodiazepine 4,4'-diaminodiphenylmethane, 4,4'-diamine. Bis(4-aminophenyl)propane, 4,4'-diaminodiphenyldiphenyl sulfide, 1,4-bis(3-aminophenoxy)phenylphenoxy)benzene , 1,4-bis(p-aminophenylsulfonate (m-aminophenylsulfonyl)benzene, 1,4-bis(p-benzene, I,4-bis(m-aminophenyl) Thioether) benzene, 2,2-oxy)phenyl]propane, 2,2-bis[3-methyl-4-(4-yl)propane, 2,2-bis[3-chloro-4-( 4-aminophenoxy 3 1,1-bis[4·(4-aminophenoxy)phenyl]ethane, (4-aminophenoxy)phenyl]ethane, 1,1-double [3-: oxy)phenyl]ethane ' 1,1 bis[3,5-dimethyl-4-)phenyl]ethane, bis[4-(4-aminophenoxy)benzene An alkylisobutenyl group, a hexenyl group, a benzyl group, a benzylidene group, or the like, such as a chloromethyl group, a phenyl group, or the like, wherein a group is used alone or in addition to a compound.癸, m-phenylenediamine, phenyl ether, 2,2'-biguanide, 4,4 '-diamino group: 1,4_ (4-Amine [yl)benzene, 1,4-diaminophenyl sulfide) bis[4-(4-aminoanilinophenoxy)benzene^)phenyl]propane, 1,1-double [ 3-methyl-4- gas-4-(4-aminophenyl(4-aminophenoxy)methane, bis[3- -14- 201104738 methyl-4-(4-aminophenoxy) Phenyl]methane, bis[3_chloro_4_(4-aminophenoxy)phenyl]methane 'bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl) Methane, bis[4-(4-aminophenoxy)phenyl] maple, 2,2-bis[4-(4-aminophenoxy)phenyl]perfluoropropane, etc. Amine, etc., preferably p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether 'i,4-double ( 3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2 - bis[3-methyl-4-(4-aminophenoxy)phenyl]propane, etc. Preferably, the polyimine resin has a phenolic hydroxyl group in terms of adhesion of the protective film. The hydroxyl group can be provided by using a phenolic hydroxyl group as a diamine compound, and the diamines are listed, for example, as follows. Constructors (6) of. [Chemical Formula 9]

B is any of the following: -15- 201104738

The representative group of the above B is a group represented by the following formula. [化1 0]

(wherein R4 is independently a hydrogen atom; a halogen atom such as fluorine, bromine or iodine; or an unsubstituted or substituted one or more carbon atom having 1 to 8 carbon atoms; the substituent attached to each aromatic ring may also be η is an integer of 0 to 5; each of A and B may be a single one or a combination of two or more; each R is independently a hydrogen atom, a halogen atom or an unsubstituted or substituted one-valent hydrocarbon group). The unsubstituted or substituted one-valent hydrocarbon group having 1 to 8 carbon atoms may, for example, be exemplified in the above R2 and R3, and an alkenyl group such as a vinyl group, a propenyl group, a butenyl group or a hexenyl group. Further, other diamines having a phenolic hydroxyl group are exemplified by the formula (7): -16- 201104738

(In the above formula, R is a halogen atom such as a hydrogen atom, fluorine, bromine or iodine; or an unsubstituted or substituted alkyl group, alkenyl group, alkynyl group, trifluoromethyl group or phenyl group having 1 to 8 carbon atoms; The halogen may be substituted with a monovalent hydrocarbon group, and the substituent attached to each aromatic ring may be different, and X is a single bond, a methyl group or a propyl group. Among the diamine compounds having the above phenolic hydroxyl group, in particular, those represented by the formula (6) are preferably a diamine compound represented by the following formula (8). [1 2]

(wherein R4 is as defined above). The compounding amount of the diamine compound having the above phenolic hydroxyl group is 5 to 60% by mass, preferably 1 to 4% by mass based on the whole of the diamine compound. When the amount of the polyamidene polyoxyalkylene resin in this range is used, the adhesion can be increased and a soft adhesive layer can be formed. Further, in order to introduce a phenolic hydroxyl group, a monoamine having a phenolic hydroxyl group may be used, and examples thereof include a monoamine having the following structure. -17- 201104738 【化1 3】

(where D is: [Chem. 1 4]

R4 is the same as the above. Each of R4 attached to each aromatic ring may be the same or different, D may be used alone or in combination of two or more, and 卩 is an integer of 丨~3. Using a monoamine having a phenolic hydroxyl group The amount of the compound is 1 to 10 mol% based on the total amount of the diamine compound. The polyamic acid resin can be synthesized by dissolving the above respective starting materials in a solvent under an inert atmosphere, usually at 80 ° C or lower, preferably at 0 to 40 t. The polypyrimidine can be synthesized by heating the obtained polyglycolic acid resin to a temperature of usually 100 to 20 (TC, preferably 150 to 200 ° C ' to partially dehydrate the acid amide of the polyaminic acid resin. The solvent may be any one which is inert to the obtained polyaminic acid, and may not be completely soluble in the starting material. For example, tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, Butyrolactone, N-methylpyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide and dimethylhydrazine, preferably aprotic polar solvents, most It is preferably N-methylpyrrolidone, cyclohexanone or butyrolactone. These solvents may be used singly or in combination of two types of -18-201104738. In order to make the above-mentioned dehydration ring closure easier, toluene is preferably used. An azeotropic dehydrating agent such as xylene, or an acetic anhydride/pyridine mixed solvent, which can be dehydrated and closed at a low temperature. Further, in order to adjust the molecular weight of the polyaminic acid and the polyimine resin, it is also possible to use polyglycine. To the synthesis, a dicarboxylic anhydride such as maleic anhydride or phthalic anhydride, and/or aniline or n-butylamine is added. The monoamine of the above-mentioned phenolic hydroxyl group. However, the amount of the dicarboxylic anhydride added is usually 〇 2 parts by mass per 100 parts by mass of the tetracarboxylic dianhydride, and the amount of the monoamine added is 100 parts by mass of the diamine. It is usually 0 to 2 parts by mass. The (meth)acrylic resin is exemplified by, for example, two or more selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid ester monomer, and other derivatives of (meth)acrylic acid. A monomer-derived (meth) acrylate copolymer, wherein the (meth) acrylate monomer is preferably an alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms, such as (meth)acrylic acid. Methyl ester, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, etc. Further, other derivatives of (meth)acrylic acid may, for example, be glycidol (meth)acrylate Ethyl ester, hydroxyethyl (meth) acrylate, etc.. Copolymerization by using glycidyl methacrylate or the like as a comonomer. When a glycidyl group is introduced into a (meth)acrylic resin, it can be improved as described later. Thermosetting type The compatibility of the epoxy resin of the component and the improvement of the Tg of the protective film after hardening also improve the heat resistance. Further, by introducing a hydroxyl group into the acrylic polymer with hydroxyethyl acrylate, the protective film can be made to the -19-201104738 pair. It is easy to control the adhesion or adhesiveness of the semiconductor wafer. The weight average molecular weight of the (meth)acrylic resin is preferably 100,000 or more, more preferably 150,000 to 1,000,000. Further, glass transfer of (meth)acrylic resin The temperature is preferably 20 ° C or less, more preferably about -70 to 0 ° C, and has adhesiveness at normal temperature (23 ° C). - (B) Epoxy resin - a ring used as the component (B) in the present invention The oxygen resin is a compound having at least two epoxy groups in the molecule. Particularly, the epoxy equivalent is preferably from 50 to 5,000 g/eq, more preferably from 1 to 500 g/eq. The epoxy resin has a weight average molecular weight of usually less than 1,000,000, preferably from 400 to 9000, more preferably from 50,000 to 8,000. Such epoxy resins are exemplified by, for example, bis(4-hydroxyphenyl)methane, 2,2'-bis(4-hydroxyphenyl)propane, or a diglycidyl ether of such halides; and the compounds a condensed polymer (so-called bisphenol F type epoxy resin, bisphenol A type epoxy resin, etc.); butadiene diepoxide; vinyl cyclohexene dioxide; diglycidyl ether of resorcinol; 1,4 -bis( 2,3-epoxypropoxy)benzene; 4,4'-bis(2,3-epoxypropoxy)diphenyl ether, 1,4-bis(2,3 -epoxypropoxy)cyclohexene; bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; 1,2-dihydroxybenzene, resorcinol, etc. a phenol or an epoxy glycidyl ether obtained by condensing a polyvalent alcohol with epichlorohydrin, or a polyglycidyl ester; a phenol novolac resin, a cresol novolac type lacquer, ie, a phenolic resin varnish Or clear aldehyde phenol phenol phenolic ring-shaped fat obtained tree lacquer clear acetal oxime chlorine table and the like} resin lacquer phenol phenol-20- 201104738 novolac type epoxy resin; by peroxidation Epoxidized polyepoxidation Olefin, epoxidized polybutadiene; epoxy resin containing naphthalene ring; bisphenol epoxy resin; phenol aralkyl epoxy resin; biphenyl aralkyl epoxy resin; cyclopentadiene epoxy Resin, etc. Among these, as the component (B), a bisphenol F-type epoxy resin or a bisphenol A-type epoxy resin which is liquid at room temperature is preferred. These epoxy resins may be used singly or in combination of two or more. The blending amount of the epoxy resin of the component (B) is 5 to 200 parts by mass, preferably 10 to 1 part by mass, per part by mass of the resin of the component (A). When the amount of the epoxy resin is too small, the adhesion of the adhesive composition may be deteriorated, and if it is too large, the flexibility of the adhesive layer may be insufficient. - (C) 塡-filling agent - As the chelating agent, an inorganic chelating agent such as conductive particles such as cerium oxide, aluminum oxide, titanium oxide, carbon black or silver particles or a polyoxymethylene resin powder can be used. For the polysiloxane resin-based powder, for example, a crosslinked spheroidal dimethyl polyoxy siloxane fine powder having a structure in which dimethylpolysiloxane is crosslinked can be used (JP-A-3-93 8 34) A spheroidal polymethylsilsesquioxane fine powder (Japanese Unexamined Patent Publication No. Hei No. 347 848), which is coated with polymethylsilsesquioxane particles and coated with a fine powder of a crosslinked spherical polyoxyalkylene rubber surface. Kaiping 7-1 968 1 5, JP-A-9-2063 No. 1 (hereinafter referred to as "polyoxyethylene rubber fine particles coated with polymethylsesquioxane particles"). The blending amount of the sputum is '100 parts by mass relative to (A) component, and -21 to 201104738 is preferably 10 to 900 parts by mass, preferably 100 to 400 parts by mass, more preferably 150 to 350 parts by mass, most preferably It is 150 to 300 parts by mass. When the amount of the compounding is too small, it is difficult to achieve the low water absorbability, low linear expansion property, and the like for the purpose of the blending agent. On the other hand, when there is too much, the viscosity of the composition for forming a protective film is increased, and the fluidity at the time of application to the film substrate is deteriorated. (C) the chelating agent, preferably 1 〇 to 1 〇〇 part by mass, more preferably 20 to 70 parts by mass of the polyoxyxacarbane resin coated with the polyorganosilsesquioxane resin, by inclusion of the poly The polysulfonated rubber microparticles coated with the organic sesquioxane resin can significantly improve the cuttability of the protective film. When the compounding amount is less than the above lower limit 値, it is difficult to improve the cutting property of the protective film in the state of chipping at the time of cutting. On the other hand, when the upper limit is exceeded, the viscosity of the composition for forming a protective film is too high, and the fluidity of the composition applied to the film substrate is deteriorated. Further, the protective film lacks an adhesive force on the wafer, and when it is attached to the wafer, it needs to have a higher temperature. It is likely to be peeled off from the wafer, and the reliability of the protective film is lowered. The polysiloxane rubber fine particles coated with the polyorganosilsesquioxane resin can be produced by the method described in the above-mentioned publication (Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei. Further, a polyfluorene composite powder can be used, for example, a commercial product of the trade name KMP 60 0 series (manufactured by Shin-Etsu Chemical Co., Ltd.). As the chelating agent of the component (C), the hydrazine other than the rubber granules coated with the polyorganosilsesquioxane resin is preferably an inorganic ruthenium, more preferably ruthenium oxide. As the cerium oxide, for example, cerium oxide produced by a deflagration method, fused cerium oxide, and crystalline cerium oxide are preferably used. The average particle diameter of yttrium oxide -22-201104738 is preferably from 0.1 to 10 μm, more preferably from 0.5 to 7 μm. When the average particle diameter is within this range, the smoothness of the coating layer can be obtained. Further, in recent years, the thickness of the adhesive layer is large; 15~5 Ομιη, but if the average particle diameter of cerium oxide is within the above range, it is easy to satisfy the requirement in the secondary agglomerated particles. Preferably, the cerium oxide to be produced, particularly the spherical cerium oxide cerium oxide produced by the deflagration method, may be subjected to a surface treatment which is easily wetted by the resin component. The surface treatment agent is preferably a decane-based (decane coupling agent) such as its versatility and cost advantage. As the decane coupling agent, decyloxymethyltrimethoxydecane, oxymethyltriethoxydecane, α-glycidoxyethyl decane, α-glycidoxyethyltriethyl, and α-glycidoxyethyltriethyl are preferably used. Oxydecane, S-oxyethyltrimethoxydecane, /3-glycidoxyethyldecane, α-glycidoxypropyltrimethoxydecane, α-oxypropyltriethoxy Decane, glycidoxypropyl decane, A-glycidoxypropyl-glycidoxypropyl decane, r-glycidoxypropyltrimethoxydecane, r-oxypropylmethyldiethyl Oxydecane, α-glycidoxyoxydecane, α-glycidoxybutyltriethoxydecane glyceryloxybutyltrimethoxydecane, glycidoxyoxydecane, r-glycidyloxy Butyl butyl trimethoxy decane glyceryl oxy butyl triethoxy decane, (5-glycidoxy oxy decane ' 5- glycidoxy butyl triethoxy decane, oxycyclohexyl) methyl The good requirements of trimethoxy decane and (3,4-epoxy ruthenium oxide) are even if there is a deflagration method. In terms of the method, the alkoxy glycidyl trimethoxy glycidol triethoxy glycidyl trimethoxy triethoxy glycidyl butyl trimethyl, cold-condensed butyl triethyl, r - shrinkable butyl Trimethyl (3,4-cyclohexyl) -23- 201104738 methyl triethoxy decane, /9-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, /3-(3,4 -Epoxycyclohexyl)ethyltriethoxydecane, s-(3,4-epoxycyclohexyl)ethyltripropoxydecane,/5-(3,4-epoxycyclohexyl) Ethyl tributoxy decane, /9-(3,4-epoxycyclohexyl)ethyltriphenoxydecane, r-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 7-(3,4-Epoxycyclohexyl)propyltriethoxydecane' <5-(3,4-epoxycyclohexyl)butyltrimethoxydecane, δ-( 3,4- a trialkoxy decane such as epoxycyclohexyl)butyltriethoxydecane; Ν-callo(aminoethyl)r-aminopropyltrimethoxydecane, Ν-/3-(amino group) Ethyl)aminopropylmethyldiethoxydecane, r-aminopropyltrimethoxydecane, N-phenyl-7-aminopropyl Methoxydecane, trimethoxydecyl propyl naphthol diamine anhydride, etc., 7-3⁄4⁄4 propyl propyl trimethoxy decane, 7*-mercaptopropyl triethoxy decane - (D) epoxy resin The epoxy resin hardening catalyst of the curing catalyst-(D) component is exemplified by a phosphorus-based catalyst, an amine-based catalyst, etc. The phosphorus-based catalyst is exemplified by triphenylphosphine Η phenyl phenyl triphenyl borate. Tetraphenyl quaternary tetraphenyl borate ' and compound represented by the following formula-24- 201104738 【化1 5】 R8 R12

(In the formula, R8 to R15 are each independently a hydrogen atom, a halogen atom such as fluorine 'bromine or iodine, 'alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, and an alkyl group having 1 to 8 carbon atoms, a vinyl group, an allylic group. a acetylene group having 2 to 8 carbon atoms such as an alkenyl group having 2 to 8 carbon atoms, a propynyl group and a butynyl group, and an aryl group having 6 to 8 carbon atoms such as a phenyl group or a tolyl group. a substituted hydrocarbon group, at least a part of which is substituted with a halogen atom such as fluorine, bromine or iodine, and a substituted hydrocarbon group such as a trifluoromethyl group, and is also exemplified by a methoxy group, an ethoxy group or a propyl group. a hydrocarbyl group substituted with an alkoxy group having 1 to 8 carbon atoms such as an oxy group or a butoxy group. All of the substituents in the substituted one-valent hydrocarbon group may be the same or different. The most preferable example of the phosphorus-based catalyst is Triphenylphosphine, triphenyltristriphenyl borate, tetraphenyltriphenyltetraborate, etc. The amine catalyst is exemplified by, for example, dicyanodiamine, 2-methylimidazole, 2-ethyl Imidazole derivatives such as 4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, etc. Preferred among these are dicyano Diamine, 2 -Phenyl-4,5-dihydroxymethylimidazole. The catalyst of the component (D) may be used alone or in combination of two or more kinds. It is preferred to use dicyanoguanamine. The amount of the epoxy resin hardening catalyst is an effective amount, specifically, 5 to 50 parts by mass per 100 parts by mass of the (A) component resin. -25- 201104738 - Other optional components - · Protective film formation used in the present invention In addition to the above components, the composition may contain other components and various additives as needed. • The monoepoxy compound may be used in addition to the epoxy resin (having two or more epoxy groups) of the component (B), without impairing the object of the present invention. It is also possible to formulate a single epoxy compound. For example, the monoepoxy compound is exemplified by styrene oxide, cyclohexene oxide, propylene oxide, methyl glycidyl ether, ethyl glycidyl ether, phenyl glycidol. Ether, allyl glycidyl ether, octylene oxide, epoxy decane, etc. • Hardener for epoxy resin: Hardener is not necessary, but control of the resin matrix is possible by adding a hardener, and can be expected Low linear expansion rate, For the curing agent, various hardeners for conventionally known epoxy resins can be used, and examples thereof include diethylenetriamine, triethylenetetramine, and diethylaminopropylamine. N-Aminoethylpiperidine, bis(4-amino-3-methylcyclohexyl)methane, m-xylenediamine, methanediamine, 3,9-bis(3-aminopropyl)-2 , an amine compound such as 4,8,10-tetraoxaspiro[5.5]undecane; an epoxy resin-diethylenetriamine adduct, an amine-ethylene oxide adduct, an arylethylation Modified aliphatic polyamines such as polyamines: bisphenol A, trimethylol allyloxyphenol, low polymerization degree phenol novolac resin, epoxidized or butylated phenol resin, &quot;Super Beckcite&quot;1001[Japan Reichhold Chemical Industry Co., Ltd.] -26- 201104738 , &quot;Hitanol&quot; 4010 [made by Nippon Seisakusho Co., Ltd.], Scado form L.9 (made by Scado Zwoll, Netherlands), Methylon 75108 (made by General Electric Company of USA), etc. a phenolic resin containing at least two phenolic hydroxyl groups in the molecule known by the trade name; "Beckamine" P.138 [Japan Reichhold Chemical Industry Co., Ltd. ], &quot;MERAN&quot; [Hitachi Manufacturing Co., Ltd.], &quot;U-Van&quot; 10R [Toyo High Pressure Industrial Co., Ltd.] and other known carbon resins; amine resins such as melamine resin and aniline resin; HS ( C2H4OCH2OC2H4SS ) nC2H4OCH2OC2H4SH (an integer of n=l ～1 0) represents a polythioether resin having at least two fluorenyl groups in one molecule; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, An organic acid such as pyromellitic anhydride, methylnaphthalenediamine, dodecane succinic anhydride or chlorendic anhydride or an anhydride thereof (anhydride). The phenol-based resin (especially the phenol novolak resin) in the above-mentioned curing agent can impart good moldability to the protective film-forming composition used in the present invention, and at the same time impart excellent moisture resistance, no toxicity, and is relatively inexpensive. Preferably. The above-mentioned hardeners may be used singly or in combination of two or more kinds depending on the hardening properties of the respective hardeners. The amount of the curing agent is appropriately adjusted depending on the type thereof insofar as it does not interfere with the reaction of the phenoxy resin of the component (A) with the epoxy resin of the component (B). In general, it is used in an amount of from 1 to 1 part by mass, preferably from 5 to 50 parts by mass, per part by mass of the epoxy resin. When it exceeds 100 parts by mass, in addition to being economically disadvantageous, there is a case where the epoxy resin is diluted and it takes a long time to harden, and the physical properties of the cured product are lowered to cause disadvantage. -27- 201104738 • Solvent: Solvents such as cyclohexanone, MIBK, MEK, etc. may be used as needed in the composition, and other components may be dissolved or dispersed to improve coatability. • Other additives: In the composition for forming a protective film to be used in the present invention, an inorganic or organic pigment, a coloring agent such as a dye, a decane coupling agent, an antioxidant, and a flame retardant can be added to the extent that the effects of the present invention are not impaired. Agent, antistatic agent, heat stabilizer, etc. For example, when formulating pigments, dyes, etc., to color the protective film, and laser marking, etc., the identification or the identification performance of the optical device is improved. The protective film may have a thickness of 5 to ΙΟΟμπι after drying, preferably 10 to 6 μm, and a composition for forming a protective film obtained by mixing the above components on a substrate film by a conventional method such as a gravure coater. [Substrate film] The base film is preferably a heat-resistant film, and examples of the heat resistance are, for example, a polyethylene terephthalate film, a polyimide film, or a fluororesin film. It is necessary for the base film to have releasability on one side. Although the peeling property does not necessarily need to be subjected to mold release treatment such as a fluororesin film, the surface of the base film is preferably subjected to release treatment. Specifically, it can be provided by providing a release agent layer by applying a release agent. The release agent is preferably a polyoxymethylene resin release agent or an alkyd resin release agent. Preferably, the release agent layer is provided with a release agent layer of polyethylene terephthalate -28-201104738 ethylene glycol film. The substrate film thickness is 5 to 200 μm, preferably 10 to 150 μm, preferably 20 to 1 μm. The average thickness of the release agent layer in the dry state is not particularly limited, but is preferably 0.01 to ΙΟμηι, more preferably 0.03 to 0·3 μπι. When the average thickness of the release agent layer exceeds the above upper limit ,, when the release sheet is wound into a roll shape, the surface of the release agent layer comes into contact with the back surface of the release sheet, and both of them are easily blocked, so that the release property of the release agent layer is caused by The situation of lowering the bite. Both the polyoxyxylene resin release agent and the alkyd resin release agent can be used conventionally. The polyoxymethylene resin-based release agent is preferably an addition reaction-curing type having dimethylpolysiloxane as a basic skeleton. Further, it is more preferable to contain a non-functional long-chain polyoxynium ion or a polyoxynized rubber. The alkyd resin release agent contains a polycondensate (alkyd resin) of a polybasic acid and a polyvalent alcohol as a main component, and also includes a thermosetting alkyd resin modified with a modifier. The polybasic acid is exemplified by an aromatic polybasic acid such as phthalic anhydride or terephthalic acid, an aliphatic polybasic acid such as succinic acid, adipic acid, maleic acid, maleic anhydride or fumaric acid. The polyvalent alcohol is exemplified by a divalent alcohol such as ethylene glycol, diethylene glycol or propylene glycol, a trivalent alcohol such as glycerin or trimethylolpropane, a polyvalent alcohol such as pentaerythritol, dipentaerythritol or sorbitol. The modifiers are exemplified by stearic acid, ricinoleic acid, oleic acid, linoleic acid and the like. The weight average molecular weight of the alkyd resin is preferably from 1,000 to 80,000, more preferably from 3,000 to 20,000. More specifically, the method of the present invention is to fabricate a semi--29-201104738 conductor wafer, for example, as described below. (1) The protective film side of the protective film forming sheet composed of the base film and the protective film is attached to the back surface of the semiconductor wafer on which the circuit (positive) surface is formed, and (2) the base film is attached. The step of attaching to the protective film, directly heating to cure the protective film, (3) the step of peeling off the substrate film from the protective film, and (4) the step of cutting the semiconductor wafer and the protective film. The cutting of the step (4) can be carried out by using a cutting sheet in accordance with a conventional method. A semiconductor wafer having a protective film on the back surface is obtained by cutting. The wafer is picked up by a conventional method such as Colette and placed on a substrate. By using the protective film of the present invention, it is difficult to cause minute damage on the wafer cut surface, and the semiconductor device can be manufactured at a high yield. [Examples] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the examples described below. <Preparation of Composition for Forming Protective Film> In each of the examples and comparative examples, the component (A) shown in Table 1 was dissolved in about 50% of cyclohexanone. The resulting solution was mixed with the other components in the amounts shown in Table 1 to obtain a composition having a solid content of about 70% by mass. The components shown in Table 1 are as follows. • (A) Ingredients -30- 201104738 (Al) phenoxy resin: ^^ about 60,000,] £11 1256 (manufactured by Nippon Epoxy Co., Ltd.) (A-2) Polyimine resin: winner of the synthesis method described later 〇(A-3 ) Acrylic resin: 55 parts by mass of butyl acrylate, 15 parts by mass of methyl methacrylate, 20 parts by mass of glycidyl methacrylate, and copolymer of 15 parts by mass of 2-hydroxyethyl acrylate (weight Average molecular weight of 900,000, glass transition temperature of -28 ° C) • (B) component epoxy resin: RE310S (manufactured by Nippon Kayaku Co., Ltd.), viscosity at 25 ° C is 15 Pa·s (bisphenol A epoxy resin) • (C) component cerium oxide: SE2050, average particle size 0.5μιη, maximum particle size 5μιη, ΚΒΜ-403 treated product, manufactured by Admatechs Co., Ltd. (spherical cerium oxide produced by deflagration method) Alkyl resin-coated polyfluorene microparticles (trade name: KMP 6 00), manufactured by Shin-Etsu Chemical Co., Ltd.) • (D) Dicyanodicimide (DICY-7): Made by Japan Epoxy Resin Co., Ltd. Synthesis of polyimine resin (A-2): equipped with attached reflow A 1 liter separable flask of a 25 ml moisture metering receiver, a thermometer, and a stirrer of a condenser plug was fed with 49.01 parts by mass of a diamine oxirane represented by the following formula (KF-8010, Shin-Etsu Chemical Co., Ltd. Manufactured, 100 parts by mass of 2-methyl-31 - 201104738 pyridone as a reaction solvent, and stirred at 80 ° C to disperse the diamine. A solution of 42.68 parts by mass of 6FDA (2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane) as an acid anhydride and 1 part by mass of 2-methylpyrrolidone was added dropwise thereto. The reaction was carried out by warm stirring for 2 hours, whereby an acid anhydride-rich proline oligomer was synthesized. [Chemical 1 6] ch3 —(—Si 〇-^- ch3 h2n (ch2) 3 —(CH〇)3-NH; CH 3 ch 3 Next, 8.31 parts by mass of a diamine having a phenolic hydroxyl group represented by the following formula ( HAB, Wakayama Refinery): [Chem. 1 7]

NH2 and 100 parts by mass of 2-methylpyrrolidone were fed into a 1 liter separable flask equipped with a 25 ml moisture quantitative receiver, a thermometer, and a stirrer attached to a rotary plug connected to a reflux condenser, dispersed, and previously added After the anhydride-rich phthalic acid oligomer was stirred at room temperature for 16 hours, a polyaminic acid solution was synthesized. Subsequently, the temperature was raised after the injection of 25 ml of xylene, and refluxed at about 18 ° C for 2 hours. When the water quantitative receiver received a certain amount of water, it was confirmed that no water was discharged, and the effluent of the moisture quantitative receiver was removed, and xylene was removed at 180 °C. After the completion of the reaction, the obtained reaction liquid droplets were added to a large amount of methanol to precipitate a polymer, which was dried under reduced pressure to obtain a polyimine resin having a phenolic hydroxyl group in the skeleton. -32- 201104738 After measuring the infrared absorption spectrum of the obtained polyimine resin, no polyamine-based absorption showing unreacted functional groups was observed, and it was confirmed that the ruthenium-based group based on 1 780 CHT1 and 1 720 CIXT1 Absorption, and confirmation of absorption based on phenolic hydroxyl groups at 3 5 OOcnT1. The polystyrene of the obtained resin had a weight average molecular weight of 55,000 and a functional group equivalent of 760 g/eq. <Preparation of peelable base film> A base film having an alkyd resin release agent layer provided on one side was prepared as follows. Meyer Bar #4, a mixture of 100 parts by mass of stearyl modified alkyd resin and methylated melamine (manufactured by Hitachi Chemicals Co., Ltd., trade name "Tes fine 303", 20% by mass of the solid component, a thermosetting alkyd resin liquid obtained by mixing 3 parts by mass of an acid catalyst p-toluenesulfonic acid, and applied to an untreated polyethylene terephthalate resin film ( Made of Mitsubishi polyester film (stock), trade name "T-100", thickness 50μιη, center line average roughness (Ra) 0.0833μπι, maximum protrusion height (Rp) 〇·683 3 μηι) on one side, at 140 After drying at ° C for 1 minute, the release agent layer (thickness 0·1 μηι) was formed by heat hardening. • A base film provided with a polyoxyxylene resin release agent layer on one side was prepared as follows. In a wire rod #4, 2 parts by mass of a stripping polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "Silcon KS-847H", solid content 1 · 4 mass%) of 100 parts by mass is added. The release agent of the platinum catalyst (Shin-Etsu Chemical Co., Ltd.'s trade name "PL-50T") is applied to an untreated polyethylene terephthalate resin film (Mitsubishi polyester film (share)). Product name "T -1 0 0", thickness 5 0 μιη, center line average roughness (ra)

C-33-201104738 0.08 33 μηι, maximal protrusion height (Rp) 0.6 8 3 3 μηι ) on one side, dried at 130 ° C for 1 minute to form a release agent layer (thickness 〇.ΐμπ〇. <Protective film formation [Production of Sheet] The above-prepared composition for forming a protective film was applied as a doctor blade at 0. lm/min to a PET film having an alkyd-based release agent layer prepared above and provided with polyoxyl After the peeling agent layer side of the PET film of the resin-based release agent layer was heated and dried at 1 1 ° C for 1 , to form a protective film having a thickness of 25 μm to prepare a sheet for forming a protective film. A protective film having a thickness of 25 μm was formed on the single side of the untreated PET film having a thickness of 50 μm to form a sheet for forming a protective film. <Evaluation Test> A sheet was formed using the above protective film, and the protective film obtained by the method of the present invention was evaluated as follows. The results are shown in Table 1. • Scratch test: The protective film side of the protective film forming sheet prepared above was bonded to one surface of a 220 pm x 45 mm x 45 mm sand wafer at 70 ° C (矽 wafer surface temperature). Next, the PET film was subjected to a scratch test before the PET film was cured and peeled off from the protective film. Further, the PET film was cured by peeling off the protective film exposed from the protective film to perform a scratch test. Next, the protective film was examined. Whether there is any scratch. The scratch test is performed by using a tensile test device (manufactured by KNT Co., Ltd.) on a protective film with a PET film or directly on the protective film at a speed of 2 mm/cm -34 to 201104738, 4 cm. 10 times back and forth. • Warpage measurement test: KJR-651 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), which is a protective layer of an organic resin circuit, is spin-coated at a particle size of 220 μm on a mirror surface of 8 μm wafer. A circuit protection layer having a thickness of 8 μm was obtained, and the warpage amount of the 8 Å wafer was 300 μm. Then, the protective film prepared above was bonded at 70 ° C on the back surface of the 8 吋矽 wafer having the circuit protection layer. After the protective film side of the sheet was formed, it was heat-hardened at 1 90 ° C for 1 hour. Then, a warpage measurement was performed at room temperature with a warpage measuring device (manufactured by AKROMETRIX Co., Ltd., trade name: PS400). Upward, the amount of warpage at the time of the display warpage of the bulge below is indicated by a positive 。. The height difference between the two points of the outermost portion of the warp and the central portion is used as the amount of warpage. • • Debris state test: Using the protective film forming sheet obtained above, a protective film bonding apparatus (FM-114 manufactured by TechnoVision Co., Ltd.) was used, and a wafer having a thickness of 725 μm was bonded at 70 ° C (using DAG-810 manufactured by DISCO) #2000 honed 8 inches of unhoned wafers and became wafers with a thickness of 22〇μηι). Subsequently, after peeling off the base sheet from the protective film, the wafer was cut into a wafer having a side length of 10 mm×10 mm under the following conditions, and a microscope section photograph of the obtained wafers was taken to examine whether or not the length of the cross section was 25 μηι or more. Debris state. Cutting conditions: Using device: DISCO cutting knife DAD-341 Cutting method: single -35- 201104738 Knife rotation speed: 30000rpm Knife speed: 50mm/sec Cutting film thickness 85μηι, cutting into the cutting film: 15μηι [Table 1] η Example Ratio i bite case 1 2 3 4 5 6 1 2 3 4 5 6 (Α) phenoxy resin JER1256 100 100 100 100 (Α) polyimine resin 100 100 100 100 (Α) acrylic resin 100 100 100 100 (Β Epoxy Resin RE310S 100 100 100 100 100 100 100 100 100 100 100 100 (C) Polyoxyethylene Rubber Microparticles 10600 10 10 10 10 10 10 10 10 10 10 10 10 10 (D) Hardening Catalyst DICY-7 5 5 5 5 5 5 5 5 5 5 5 5 (C) 塡 SE SE2050 250 250 250 250 250 250 250 250 250 250 250 250 矽 Wafer curing method with substrate film attached! Release agent! Thin coating film Hard &lt; peeling PET ✓ PET film with adhesive coating of alkyd peeling layer is cured with untreated film hard 1 IPET 匕 no PET film hardening protective film characteristics scratch test for flaws ΑτΓ- tearing no flaws no noIns, pick no Arvf arch has warpage test test warp a 80 50 100 80 50 100 PET is not peeled, can not be measured -170 -200 -150 Debris state performance 25μηι above the state of debris no Λ Γ Γ The protective film of Comparative Example 1 was found to contain a surface-lipophilic group having a higher surface area than that of the present invention, so that the protective film had poor cutting properties and caused a broken shoulder state. On the other hand, the protective film of the examples was excellent in adhesion, and the occurrence of scratches was small, the amount of warpage of the wafer was small, and the wafer crumb state was well prevented. [Possibility of industrial use] The protective film of the present invention can improve the yield of a wafer. It can be used for the manufacture of a semiconductor device. -37-

Claims (1)

201104738 VII. Patent Application Range: 1. A method for manufacturing a semiconductor wafer, comprising: a substrate film having releasability on one side and heat from a peeling single side of the substrate film; The protective film forming sheet for a protective film for a semiconductor wafer, which is composed of a curable resin composition, is bonded to the back surface of the semiconductor wafer, and then the protective film is cured, and then, the hardening is performed. The protective film peels off the substrate film. 2. The method of manufacturing a semiconductor wafer according to the first aspect of the invention, wherein the thermosetting resin composition is a composition comprising: (A) 1 part by mass selected from the group consisting of a phenoxy resin and a polyimide resin. And at least one resin of the group consisting of (meth)acrylic resin, (B) 5 to 200 parts by mass of the epoxy resin, (C) 10 to 900 parts by mass of the chelating agent, and (〇) the ring of the effective fi Oxygen resin hardening catalyst. 3. The method for producing a semiconductor wafer according to claim 1 or 2, wherein 10 to 100 parts by mass of the (C) chelating agent is a polyoxynoxy rubber fine particle coated with a polyorganosilsesquioxane resin. . 4. The method of producing a semiconductor wafer according to claim 1 or 2, wherein the base film is provided on one surface of the base film to form a film of a release agent. 5. The method of producing a semiconductor wafer according to claim 4, wherein the release agent is a polyoxynitride type release agent or an alkyd type release agent. -38- 201104738 Four designated representatives: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No 201104738 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention: no