WO2017098736A1 - ダイシングシートおよびダイシングシートの製造方法 - Google Patents

ダイシングシートおよびダイシングシートの製造方法 Download PDF

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Publication number
WO2017098736A1
WO2017098736A1 PCT/JP2016/053016 JP2016053016W WO2017098736A1 WO 2017098736 A1 WO2017098736 A1 WO 2017098736A1 JP 2016053016 W JP2016053016 W JP 2016053016W WO 2017098736 A1 WO2017098736 A1 WO 2017098736A1
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Prior art keywords
resin
dicing sheet
base film
temperature
resin layer
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PCT/JP2016/053016
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English (en)
French (fr)
Japanese (ja)
Inventor
有紀 仁藤
田矢　直紀
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リンテック株式会社
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Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to JP2017552524A priority Critical patent/JP6246989B2/ja
Priority to CN201680056932.5A priority patent/CN108140566B/zh
Priority to KR1020187012348A priority patent/KR102476430B1/ko
Publication of WO2017098736A1 publication Critical patent/WO2017098736A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors

Definitions

  • the present invention relates to a dicing sheet to which the object to be cut is attached when the object to be cut such as a semiconductor wafer is cut and separated into element pieces, and a method for manufacturing the dicing sheet.
  • semiconductor wafers such as silicon and gallium arsenide, substrates such as glass substrates and alumina substrates, and various packages (in this specification, these are collectively referred to as “objects to be cut”) are manufactured in a large diameter state, These are cut and separated (diced) into element pieces (herein referred to as “chips”) and individually separated (picked up), and then transferred to the next process, the mounting process.
  • an object to be cut such as a semiconductor wafer is attached to a pressure-sensitive adhesive sheet in advance and subjected to dicing, cleaning, drying, expanding, pick-up, and mounting processes.
  • the object to be cut attached to the dicing process is opposite to the side where the cutting tool for cutting is close to the dicing sheet for the purpose of ensuring the handleability of the object and chips in the dicing process and the subsequent processes.
  • a polyolefin film or a polyvinyl chloride film is usually used as a base film, and an adhesive layer is provided on the base film.
  • an object to be cut is cut by a rotating round blade.
  • the pressure-sensitive adhesive layer may be cut, and a part of the base film may be cut to ensure that the article to be cut to which the dicing sheet is stuck is cut.
  • a cut piece made of the material constituting the pressure-sensitive adhesive layer and the base film is generated from the dicing sheet, and the obtained chip may be contaminated by the cut piece.
  • One form of such a cutting piece is a thread-like cutting piece that adheres on the dicing line or near the cross section of the chip separated by dicing.
  • a dicing blade with a thicker blade width is used than when dicing a semiconductor wafer, and dicing cuts are made.
  • the depth also becomes deeper. For this reason, since the amount of the base film that is cut and removed during dicing increases as compared with the case of the semiconductor wafer, the generation amount of the thread-like cutting pieces also tends to increase.
  • Patent Document 1 discloses an invention in which a polyolefin film irradiated with an electron beam or ⁇ (gamma) ray of 1 to 80 Mrad is used as a base film of a dicing sheet. Is disclosed. In the said invention, it is thought that the bridge
  • Patent Document 1 irradiation of radiation such as electron beam or ⁇ -ray is performed after the above resin is once formed into a film, so that the manufacturing process is increased by one, and the manufacturing cost is generally increased. It tends to be higher than the base film. Moreover, since the crystallinity of resin in a base film is lost when irradiated with an electron beam, the solvent resistance of the obtained base film is relatively low.
  • the dicing sheet is required to have good expandability.
  • the base film in which cross-linking by covalent bond is formed by irradiation of radiation as disclosed in Patent Document 1 shows a relatively high elastic modulus
  • the dicing sheet disclosed in Patent Document 1 is sufficient. Cannot expand.
  • the present invention has been made in view of such a situation, and can be manufactured without the need for radiation irradiation, can suppress the generation of thread-like cutting pieces, and has good expandability. It aims at providing the dicing sheet shown.
  • the present invention is a dicing sheet comprising a base film and an adhesive layer laminated on one side of the base film, wherein the base film is
  • the pressure-sensitive adhesive layer has at least a resin layer positioned at the nearest position, and the melting point of the resin constituting the resin layer is 60 ° C. or more and 170 ° C. or less, and the difference between the melting point of the resin and the fluidization temperature is Provided is a dicing sheet that is 40 ° C. or higher and 190 ° C. or lower (Invention 1).
  • the dicing sheet according to the invention (Invention 1) has a melting point of the resin constituting the base film and a temperature difference between the melting point and the fluidization temperature within the above range, so that frictional heat is generated by dicing. Resin fluidization hardly occurs.
  • the thread-shaped cutting piece is generated by softening the cutting piece by frictional heat generated during dicing and further extending into a thread shape. Therefore, in the dicing sheet, the fluidization of the resin is less likely to occur, and as a result, the generation of thread-like cutting pieces is suppressed.
  • the base film in which the melting point of the resin and the temperature difference are in the above-mentioned range has a relatively low elastic modulus, it exhibits good expandability.
  • the base film in which the melting point of the resin and the temperature difference are within the above ranges can be produced without being irradiated with radiation such as electron beams or ⁇ rays. Therefore, in the said dicing sheet, compared with the dicing sheet manufactured by the method including the process of radiation irradiation, manufacturing cost can be held down.
  • the resin preferably has a plurality of molecular chains containing an olefin as a constituent component, and the molecular chains are preferably bonded by a temperature-dependent dynamic covalent bond (Invention 2). ).
  • the molecular chain is an ethylene copolymer containing ethylene and a radically polymerizable acid anhydride as structural units, and the resin is a polyhydric alcohol compound having two or more hydroxy groups.
  • the temperature-dependent dynamic covalent bond is preferably an ester bond formed between a carboxy group derived from the radical polymerizable acid anhydride and a hydroxy group of the polyhydric alcohol compound ( Invention 3).
  • the resin further includes a reaction accelerator that promotes the binding reaction and dissociation reaction of the temperature-dependent dynamic covalent bond (Invention 4).
  • the resin layer preferably has a tensile elastic modulus at 23 ° C. of 30 MPa or more and 500 MPa or less (Invention 5).
  • the melt flow rate of the resin at a temperature of 190 ° C. and a load of 2.16 kg is 0.5 g / 10 min or more and 10 g / 10 min or less (Invention 6).
  • the base film further includes a second resin layer on the opposite side of the resin layer from the pressure-sensitive adhesive layer (Invention 7).
  • the present invention is a method for producing the dicing sheet (Invention 1 to 7), the step of copolymerizing structural units containing at least ethylene and a radical polymerizable acid anhydride to obtain an ethylene copolymer, And a carboxyl group derived from the radically polymerizable acid anhydride in the ethylene copolymer in the presence of a reaction accelerator that promotes a bonding reaction and a dissociation reaction of a temperature-dependent dynamic covalent bond,
  • a method for producing a dicing sheet comprising the step of ester-bonding with a hydroxy group in a polyhydric alcohol compound having two or more hydroxy groups to obtain the resin (Invention 8).
  • the dicing sheet according to the present invention can be manufactured without requiring irradiation of radiation, can suppress the generation of thread-like cutting pieces, and exhibits good expandability.
  • FIG. 1 is a cross-sectional view of a dicing sheet according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of a dicing sheet according to the second embodiment of the present invention.
  • These dicing sheets 1 include a base film 2 and a pressure-sensitive adhesive layer 3 laminated on one side of the base film 2.
  • the dicing sheet according to the present embodiment may be used only for dicing, or may be a dicing / die bonding sheet used also for die bonding.
  • the base film 2 includes at least the resin layer 21 positioned in the closest position to the pressure-sensitive adhesive layer 3.
  • the base film 2 is composed only of the resin layer 21.
  • the base film 2 is present at the position closest to the pressure-sensitive adhesive layer 3 and the resin layer 21 on the opposite side of the pressure-sensitive adhesive layer 3.
  • a second resin layer 22 is present at the position closest to the pressure-sensitive adhesive layer 3 and the resin layer 21 on the opposite side of the pressure-sensitive adhesive layer 3.
  • the melting point of the resin constituting the resin layer 21 is 60 ° C. or higher and 170 ° C. or lower, and the melting point and fluidization temperature of the resin. The difference is 40 ° C. or higher and 190 ° C. or lower.
  • the resin constituting the resin layer 21 has a sufficiently high fluidization temperature. Therefore, even if frictional heat is generated during dicing, the fluid constituting the resin layer 21 is suppressed from fluidizing due to the frictional heat. As a result, in the dicing sheet 1 according to the present embodiment, generation of thread-like cutting pieces is suppressed. In addition, since the difference between the melting point of the resin layer 21 and the temperature is within the above-described range, the elastic modulus of the resin constituting the resin layer 21 is relatively low. Thereby, the dicing sheet 1 which concerns on this embodiment shows favorable expandability.
  • the base film 2 in which the difference between the melting point of the resin layer 21 and the temperature is in the above-described range can be produced without being irradiated with radiation such as electron beams or ⁇ rays.
  • the dicing sheet 1 which concerns on this embodiment can be manufactured at low cost compared with the dicing sheet manufactured by the method including the process of radiation irradiation.
  • the melting point of the resin constituting the resin layer 21 is 60 ° C. or higher as described above, preferably 70 ° C. or higher, and particularly preferably 80 ° C. or higher.
  • the melting point of the resin is 170 ° C. or lower as described above, preferably 140 ° C. or lower, particularly preferably 120 ° C. or lower.
  • the melting point is 60 ° C. or higher
  • the base film 1 is not tacky and does not stick to the roll, so that the base film 1 can be efficiently obtained by extrusion molding.
  • the melting point of the resin constituting the resin layer 21 is 60 ° C. or higher, the resin has appropriate crystallinity, thereby making the resin layer 21 excellent in solvent resistance.
  • the melting point of the resin constituting the resin layer 21 is 170 ° C. or less, the crystallinity of the resin is not excessively high, and the base film 1 can effectively exhibit excellent expandability.
  • the difference between the melting point of the resin constituting the resin layer 21 and the fluidization temperature is 40 ° C. or higher as described above, preferably 50 ° C. or higher, particularly 60. It is preferable that the temperature is not lower than ° C. Further, the difference between the melting point and the fluidization temperature of the resin is 190 ° C. or lower, preferably 135 ° C. or lower, as described above, and particularly preferably 80 ° C. or lower. The effect which suppresses a thread-shaped cutting piece can be favorably acquired because the said difference is 40 degreeC or more. Further, when the difference is 190 ° C. or less, the resin exhibits an appropriate fluidization temperature, and the processability is excellent.
  • the fluidization temperature of the resin constituting the resin layer 21 is preferably 100 ° C. or higher, particularly preferably 120 ° C. or higher, and more preferably 140 ° C. or higher. Is preferred.
  • the fluidization temperature of the resin is preferably 360 ° C. or less, particularly preferably 275 ° C. or less, and more preferably 200 ° C. or less.
  • the fluidization temperature of the resin is 100 ° C. or higher, the above-described effect of suppressing the occurrence of the thread-like cutting pieces can be obtained favorably. Further, when the fluidization temperature is 360 ° C. or lower, the processability is excellent.
  • the tensile elastic modulus at 23 ° C. of the resin layer 21 is preferably 30 MPa or more, particularly preferably 40 MPa or more, and further preferably 50 MPa or more. Further, the tensile elastic modulus is preferably 500 MPa or less, particularly preferably 300 MPa or less, and further preferably 200 MPa or less.
  • the dicing sheet 1 has an appropriate strength and is excellent in mountability. Specifically, the occurrence of slack in the dicing sheet 1 when the dicing sheet 1 is attached to a wafer and a ring frame is suppressed, and the occurrence of errors during conveyance is effectively suppressed.
  • the tensile elastic modulus is 500 MPa or less, it is avoided that excessive stress is applied to the dicing sheet 1 during the expanding process, and the dicing sheet 1 is not peeled off from the ring frame even during the expanding process. Retained.
  • the said tensile elasticity modulus is measured based on JISK7127: 1999, The specific measuring method is as showing to the below-mentioned test method.
  • the resin constituting the resin layer 21 preferably has a melt flow rate at a temperature of 190 ° C. and a load of 2.16 kg of 0.5 g / 10 min or more, particularly 0.7 g / It is preferably 10 min or more, and more preferably 1 g / 10 min or more. Further, the melt flow rate is preferably 10 g / 10 min or less, particularly preferably 8 g / 10 min or less, and more preferably 7 g / 10 min or less. When the melt flow rate is within the above range, uniform film thickness accuracy can be effectively achieved when the base film 2 including the resin layer 21 is formed by extrusion molding. The melt flow rate is measured at a temperature of 190 ° C. and a load of 2.16 kg in accordance with JIS K7210: 2014.
  • the thickness of the resin layer 21 is preferably 20 ⁇ m or more, preferably 40 ⁇ m or more, and more preferably 60 ⁇ m or more. Preferably there is. Furthermore, the thickness is preferably 600 ⁇ m or less, preferably 300 ⁇ m or less, and more preferably 200 ⁇ m or less. Moreover, when the base film 2 is composed of the resin layer 21 and the second resin layer 22 as shown in FIG. 2, the thickness of only the resin layer 21 is preferably 10 ⁇ m or more, and 20 ⁇ m or more. It is preferable that the thickness is 30 ⁇ m or more.
  • the thickness is preferably 300 ⁇ m or less, preferably 120 ⁇ m or less, and more preferably 100 ⁇ m or less.
  • the thickness of the resin layer 21 is 20 ⁇ m or more when the base film 2 is made of only the resin layer 21, and is 10 ⁇ m or more when the base film 2 is made of the resin layer 21 and the second resin layer 22.
  • the thickness of the resin layer 21 is 600 ⁇ m or less when the base film 2 is composed of only the resin layer 21, and is 300 ⁇ m or less when the base film 2 is composed of the resin layer 21 and the second resin layer 22.
  • the dicing sheet 1 can effectively exhibit excellent expandability.
  • the resin constituting the resin layer 21 is not particularly limited as long as the above physical properties can be achieved.
  • the resin constituting the resin layer 21 is a resin having a plurality of molecular chains containing an olefin as a constituent component, and the molecular chains are temperature-dependent dynamic.
  • a resin bonded by a covalent bond is preferred.
  • the temperature-dependent dynamic covalent bond refers to a covalent bond in which a binding reaction and a dissociation reaction occur reversibly depending on temperature (by heating and cooling).
  • molecular chains are constrained by covalent bonds in a temperature-dependent manner, so that the fluidization temperature is increased compared to a resin in which molecular chains are not always bonded to each other.
  • the effect of suppressing the occurrence of the thread-like cutting pieces as described above can be favorably obtained.
  • the molecular chains are covalently bonded to each other in a temperature-dependent manner, it is not necessary to perform a process such as electron beam irradiation for producing the covalent bond when the base film 2 is manufactured, and as a result, the manufacturing cost is increased. Can be suppressed.
  • Examples of the plurality of molecular chains containing the above-described olefin as a constituent component include an ethylene-based copolymer containing ethylene and a radical polymerizable acid anhydride as a constituent unit. Since the ethylene copolymer is not relatively high in polarity, the resin obtained from the ethylene copolymer is excellent in solvent resistance.
  • radically polymerizable acid anhydrides contained as constituent units in ethylene-based copolymers include maleic anhydride, itaconic anhydride, citraconic anhydride, endic anhydride, 1-butene-3,4-dicarboxylic anhydride Thing etc. are mentioned. These may be used alone or in combination of two or more. Of these, maleic anhydride is preferably used from the viewpoints of reactivity and economy.
  • the content of the radical polymerizable acid anhydride in the ethylene copolymer is preferably 0.1% by mass or more, particularly 0.3% by mass or more, among the constituent units constituting the ethylene copolymer. It is preferable that Further, the content is preferably 20% by mass or less, and particularly preferably 5.0% by mass or less, among the constituent units constituting the ethylene copolymer.
  • the resin constituting the resin layer 21 can sufficiently perform the temperature-dependent dynamic covalent bonding described above, and the generation of the above-described thread-like cutting pieces is generated. The effect which suppresses can be acquired favorably.
  • the above-described temperature-dependent dynamic covalent bond is generated at an appropriate density, whereby the elastic modulus of the resin layer 21 becomes appropriate, and the dicing sheet 1 is Exhibits superior expandability.
  • the ethylene-based copolymer may contain a structural unit other than ethylene and a radical polymerizable acid anhydride (hereinafter sometimes referred to as “third monomer”).
  • third monomer a radical polymerizable acid anhydride
  • structural units other than ethylene and radical polymerizable acid anhydrides include: ethylenically unsaturated ester compounds, ethylene unsaturated amide compounds, ethylene unsaturated carboxylic acid compounds, ethylene unsaturated ether compounds, ethylene unsaturated A hydrocarbon compound etc. are mentioned.
  • the third monomer examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, (meth ) Benzyl acrylate, methyl fumarate, ethyl fumarate, dimethyl maleate, diethyl maleate, vinyl acetate, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethylacrylamide, (meth) acrylic acid, Examples include fumaric acid, methyl vinyl ether, methyl allyl ether, styrene, butadiene, and acrylonitrile. These may be used alone or in combination of two or more.
  • “(meth) acrylic acid” in the present specification means both acrylic acid and methacrylic acid. The same applies to other similar terms.
  • the content thereof is preferably 30% by mass or less, and particularly preferably 25% by mass or less, among the structural units constituting the ethylene copolymer. By being 30 mass% or less, it is suppressed that melting
  • the above-described temperature-dependent dynamic covalent bond is an ester bond.
  • the resin constituting the resin layer 21 further includes a polyhydric alcohol compound having two or more hydroxy groups, and the temperature-dependent dynamic As a covalent bond, an ester bond is preferably generated between the hydroxy group of the polyhydric alcohol compound and the carboxy group derived from the radical polymerizable acid anhydride.
  • the ethylene copolymers are cross-linked by the polyhydric alcohol compound.
  • fluidization temperature becomes high compared with resin which does not always contain a crosslinked structure, and generation
  • polyhydric alcohol compound examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, trimethylolethane, trimethylolpropane, and pentaerythritol.
  • Intramolecular such as arbitol, sorbitol, xylose, glucose, saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyolefin oligomer having two or more hydroxyl groups in one molecule, ethylene-hydroxyethyl (meth) acrylate copolymer
  • the melting point of these polyhydric alcohol compounds is desirably 300 ° C. or less from the viewpoint of easy mixing with other compounds when producing an ethylene-based copolymer.
  • the amount of the polyhydric alcohol compound used is preferably such that the molar ratio of the hydroxy group derived from the polyhydric alcohol to the carboxy group derived from the radical polymerizable acid anhydride is 0.01 or more. It is preferable that it is 05 or more.
  • the molar ratio is preferably 10 or less, and particularly preferably 5 or less.
  • temperature-dependent dynamic covalent bond examples include a covalent bond generated by a Diels-Alder reaction.
  • a bonding reaction in which a 6-membered ring structure is generated from a conjugated diene structure and a dienophile structure
  • a dissociation reaction in which a conjugated diene structure and a dienophile structure are generated from the 6-membered ring structure occur in a temperature-dependent manner.
  • a temperature-dependent dynamic covalent bond for example, a combination of a molecular chain having a conjugated diene structure in the side chain and a compound having a plurality of dienophile structures is used. In this case, the molecular chain is crosslinked by a compound having a plurality of dienophile structures.
  • Examples of molecular chains having a conjugated diene structure in the side chain include molecular chains having a furan ring in the side chain. Such a molecular chain can be obtained by grafting a conjugated diene compound to a molecular chain having an amine group via the amine group.
  • conjugated diene compounds include furfurylamine, 5-methylfurfurylamine, N-methyl-furfurylamine, pyrrole, 1-aminopyrrole, imidazole, 1- (3-aminopropyl) imidazole, 2- (2- Aminoethyl) thiophene, pyrazole, 3-aminopyrazole, 3-amino-5-methylisoxazole, triazole, 3-amino-1,2,4 triazole, 4-amino-1,2,4 triazole and the like.
  • Examples of compounds having a plurality of dienophile structures include bis (3-ethyl-5-methyl-4maleimidophenyl) methane, 4,4′-bismaleimidediphenylmethane, 1,2-bis (maleimido) ethane, 1,6 -Bis (maleimido) hexane, N, N'-1,3-phenylenebismaleimide, N, N'-1,4-phenylenebismaleimide and the like.
  • the resin when the molecular chains are bonded to each other by a temperature-dependent dynamic covalent bond, the resin promotes a reaction that promotes the bonding reaction and dissociation reaction of the temperature-dependent dynamic covalent bond It is preferable to further contain an agent.
  • the reaction accelerator increases the bonding rate and dissociation rate of the temperature-dependent dynamic covalent bond, so that a reversible phase transition is rapidly performed. Thereby, it becomes easy to heat and melt the resin to form a film. As a result, it is possible to achieve both suppression of the thread-like cutting piece as described above and excellent film forming properties.
  • reaction accelerator examples include a metal salt of a carboxylic acid or a metal salt of a polymer containing a carboxy group.
  • metal salts of carboxylic acids include acetic acid, butyric acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, succinic acid, benzoic acid, terephthalic acid, pyromellitic acid
  • a metal salt of a group IA, IIA, IIB, or IIIB element eg, Li, Na, K, Mg, Ca, Zn, Al, etc.
  • metal salts of polymers containing carboxyl groups include some or all of the carboxyl groups of ethylene- (meth) acrylic acid copolymers and elements of groups IA, IIA, IIB, IIIB of the periodic table Examples thereof include metal salts with (for example, Li, Na, K, Mg, Ca, Zn, Al, etc.) or copolymers of ethylene and ethylene- (meth) acrylic acid metal salts. Moreover, you may use the 3rd monomer mentioned above as a monomer of the polymer containing a carboxyl group.
  • reaction accelerator may be obtained by graft polymerization of an unsaturated carboxylic acid metal salt to a polyolefin resin such as polyethylene or polypropylene.
  • reaction accelerator include triethylamine, trimethylamine, tetramethylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetramethylammonium bromide, tetraethylammonium bromide and the like.
  • reaction accelerators may be used alone or in combination of two or more. Of these reaction accelerators, it is preferable to use a carboxylic acid metal salt from the viewpoint of ease of handling and economy.
  • the usage-amount of a reaction accelerator can be suitably adjusted according to the kind, generally it is 0.001 mass part or more with respect to 100 mass parts of ethylene-type copolymers before side chain introduction
  • a commercially available product may be used as the resin constituting the resin layer 21.
  • Lexpearl series which is a thermoplastic resin manufactured by Nippon Polyethylene
  • Lexpearl ES323Y or Lexpearl ES333Y is preferably used.
  • These commercially available products are resins containing the above-mentioned ethylene copolymer, the above-mentioned polyhydric alcohol compound and a reaction accelerator, and can take a state in which the ethylene-based copolymers are crosslinked via the polyhydric alcohol compound.
  • the physical properties relating to the melting point and fluidization temperature described above can be achieved.
  • the resin layer 21 includes various additives such as pigments, dyes, flame retardants, plasticizers, antistatic agents, lubricants, fillers, and the like as long as the above-described physical properties relating to the melting point and fluidization temperature are achieved. It may be.
  • the pigment include titanium dioxide and carbon black.
  • the filler include organic materials such as melamine resin, inorganic materials such as fumed silica, and metal materials such as nickel particles.
  • the surface of the resin layer 21 on the pressure-sensitive adhesive layer 3 side may be subjected to surface treatment such as primer treatment, corona treatment, plasma treatment or the like in order to improve the adhesion with the pressure-sensitive adhesive layer 3.
  • surface treatment such as primer treatment, corona treatment, plasma treatment or the like in order to improve the adhesion with the pressure-sensitive adhesive layer 3.
  • the various coating films may be provided in the surface on the opposite side to the adhesive layer 3 in the resin layer 21.
  • the material constituting the second resin layer 22 is not particularly limited,
  • the resin film used for the base material of a typical dicing sheet can be used.
  • Specific examples of such resin films include ethylene-based copolymer such as ethylene-vinyl acetate copolymer film, ethylene- (meth) acrylic acid copolymer film, and ethylene- (meth) acrylic acid ester copolymer film.
  • Polyethylene films such as polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, ethylene-norbornene copolymer film, norbornene resin film; Polyethylene film such as polyvinyl chloride film and vinyl chloride copolymer film Polyvinyl chloride film; Polyester film such as polyethylene terephthalate film and polybutylene terephthalate film; Polyurethane film; Polyimide film; Polystyrene film; Polycarbonate Bo sulfonate film; and a fluorine resin film.
  • polyethylene film examples include a low density polyethylene (LDPE) film, a linear low density polyethylene (LLDPE) film, and a high density polyethylene (HDPE) film.
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • HDPE high density polyethylene
  • modified films such as these crosslinked films and ionomer films are also used.
  • the base material may be a film made of one of these, or a laminated film in which two or more of these are combined.
  • ethylene copolymer films particularly ethylene-vinyl acetate copolymer films, ethylene- (meth) acrylic. Acid copolymer film and ethylene- (meth) acrylic acid ester copolymer film; polyolefin film, in particular, polyethylene film, polypropylene film, polybutene film, ethylene-norbornene copolymer film and norbornene resin film; polyurethane film; polystyrene It is preferable to use a film or a fluororesin film.
  • the second resin layer 22 may contain various additives such as pigments, dyes, flame retardants, plasticizers, antistatic agents, lubricants, fillers, and the like in addition to the resin. .
  • Various coating films may be provided on the surface of the second resin layer 22 opposite to the pressure-sensitive adhesive layer.
  • the thickness of the second resin layer 22 is not particularly limited, but is preferably 10 ⁇ m or more, preferably 40 ⁇ m or more, and more preferably 50 ⁇ m or more. Furthermore, the thickness is preferably 300 ⁇ m or less, preferably 120 ⁇ m or less, and more preferably 100 ⁇ m or less. When the thickness of the second resin layer 22 is 10 ⁇ m or more, the dicing sheet 1 has an appropriate strength, and mountability is improved. When the thickness of the second resin layer 22 is 300 ⁇ m or less, the dicing sheet 1 can effectively exhibit excellent expandability.
  • the thickness of the base film 2 is not particularly limited, and the same thickness as the base film of a general dicing sheet is used. Can do.
  • the thickness is preferably 20 ⁇ m or more, preferably 40 ⁇ m or more, and more preferably 60 ⁇ m or more. It is preferable that Furthermore, the thickness is preferably 600 ⁇ m or less, preferably 300 ⁇ m or less, and more preferably 200 ⁇ m or less.
  • the base film when the base film 2 is composed of the resin layer 21 and the second resin layer 22, the base film includes both the resin layer 21 and the second resin layer 22.
  • the thickness of 2 is preferably 20 ⁇ m or more, preferably 60 ⁇ m or more, and more preferably 80 ⁇ m or more. Further, the thickness is preferably 600 ⁇ m or less, preferably 240 ⁇ m or less, and more preferably 200 ⁇ m or less.
  • the base film 2 is preferably permeable to ultraviolet rays. .
  • the base film 2 has the transparency with respect to an electron beam.
  • the base film 2 can be manufactured by a general method.
  • the resin layer 21 can be formed by molding the resin into a film by a melt extrusion molding method, a calendar method, or the like. Thereby, the base film 2 which consists only of the resin layer 21 can be obtained.
  • an ethylene copolymer is obtained by copolymerizing at least a structural unit containing ethylene and a radical polymerizable acid anhydride, and then in the presence of the reaction accelerator described above. And a method in which an ester bond is formed between the carboxy group derived from the radically polymerizable acid anhydride in the ethylene-based copolymer and the hydroxy group in the polyhydric alcohol compound described above. As a result, a resin having a structure in which ethylene copolymers are cross-linked from the polyhydric alcohol compound is obtained.
  • the resin layer 21 can be formed by forming the commercially available product into a film by a melt extrusion molding method, a calendering method, or the like.
  • the base film 2 in which the resin layer 21 and the second resin layer 22 are laminated is obtained by a general coextrusion method or a lamination method. Can do.
  • the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 3 is not particularly limited, and those usually used as the dicing sheet 1 can be used.
  • An ether-based pressure-sensitive adhesive is used, and may be an energy ray-curable pressure-sensitive adhesive (including an ultraviolet-curing type) or a heat-curable pressure-sensitive adhesive.
  • an adhesive, a thermoplastic adhesive, a B stage adhesive, etc. that simultaneously have a wafer fixing function and a die bonding function. Is used.
  • the thickness of the pressure-sensitive adhesive layer 3 is not particularly limited, and is preferably 3 ⁇ m or more, for example, and more preferably 5 ⁇ m or more. Further, the thickness is preferably 100 ⁇ m or less, and particularly preferably 80 ⁇ m or less.
  • the dicing sheet 1 may include a release sheet on the surface of the pressure-sensitive adhesive layer 3 opposite to the base film 2.
  • the release sheet is used to protect the adhesive surface of the adhesive layer 3.
  • release sheets include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane Film, ethylene vinyl acetate film, ionomer resin film, ethylene- (meth) acrylic acid copolymer film, ethylene- (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, fluororesin film, etc. Can be used. Moreover, you may use these bridge
  • the release surface of the release sheet (the surface in contact with the pressure-sensitive adhesive layer 3) is preferably subjected to a release treatment.
  • the release agent used for the release treatment include alkyd, silicone, fluorine, unsaturated polyester, polyolefin, and wax release agents.
  • the thickness of the release sheet is not particularly limited, and is preferably 20 ⁇ m or more and 150 ⁇ m or less, for example.
  • the manufacturing method of the dicing sheet 1 can be manufactured by a general method except that the base film 2 is manufactured by the method described above.
  • a coating composition containing a pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 3 and, if desired, a solvent is prepared.
  • this coating agent is applied on the release surface of the release sheet produced as described above by a die coater, curtain coater, spray coater, slit coater, knife coater, and the like, and dried to produce an adhesive layer 3.
  • the dicing sheet 1 is obtained by bonding the surface opposite to the release sheet of the pressure-sensitive adhesive layer 3 and one surface of the base film 2.
  • the base film 2 contains the 2nd resin layer 22, the surface at the side of the resin layer 21 of the base film 2 and the adhesive layer 3 are bonded.
  • the properties of the coating agent are not particularly limited as long as it can be applied.
  • the coating agent may contain a component for forming the pressure-sensitive adhesive layer 3 as a solute or a dispersoid.
  • the dicing sheet 1 in which the adhesive layer 3 is formed on the base film 2 can be obtained by applying and drying the coating agent.
  • the resins constituting the resin layer 21 are composed of molecular chains that are bonded to each other by temperature-dependent dynamic covalent bonding. Therefore, the molecular chain is appropriately restrained, and the fluidization temperature is increased as compared with a resin not subject to such restraint. As a result, it is possible to satisfactorily achieve both the effect of suppressing the generation of the thread-like cutting pieces as described above and the expandability. Further, since the molecular chains are covalently bonded to each other in a temperature-dependent manner, it is not necessary to perform a process such as electron beam irradiation for generating a covalent bond, and as a result, an increase in manufacturing cost can be suppressed.
  • another layer may be interposed between the base film 2 and the pressure-sensitive adhesive layer 3 in the dicing sheet 1.
  • Example 1 Preparation of base film Ethylene-based copolymer containing ethylene and radical polymerizable acid anhydride as structural unit, polyhydric alcohol compound having two or more hydroxy groups, and temperature-dependent dynamic covalent bonding and dissociation reactions
  • a thermoplastic resin containing a reaction accelerator for promoting the reaction wherein the carboxyl group derived from the radical polymerizable acid anhydride in the ethylene copolymer and the hydroxy group in the polyhydric alcohol compound promote the reaction.
  • a thermoplastic resin ester-bonded in the presence of an agent manufactured by Nippon Polyethylene Co., Ltd., product name “Lexpearl ES323Y”, melt flow rate at a temperature of 190 ° C.
  • Example 2 Ethylene-based copolymer containing ethylene and radically polymerizable acid anhydride as a structural unit, polyhydric alcohol compound having two or more hydroxy groups, and temperature-dependent dynamic covalent bond binding and dissociation reactions A carboxy group derived from the radical polymerizable acid anhydride in the ethylene copolymer and a hydroxy group in the polyhydric alcohol compound in the presence of the reaction accelerator.
  • an ester-bonded thermoplastic resin manufactured by Nippon Polyethylene Co., Ltd., product name “Lexpearl ES333Y”, temperature 190 ° C. and melt flow rate at a load of 2.16 kg: 6 g / 10 min
  • a dicing sheet was obtained.
  • thermoplastic resin a polyethylene resin having a density of 924 kg / m 3 (manufactured by Sumitomo Chemical Co., Ltd., product name “Sumikasen L405”, melt flow rate at a temperature of 190 ° C. and a load of 2.16 kg: 3.7 g / 10 min) is used. In the same manner as in Example 1, a dicing sheet was obtained.
  • thermoplastic resin As a thermoplastic resin, except that a random copolymer of propylene (manufactured by Prime Polymer Co., Ltd., product name “Prime Polypro F-744NP”, temperature 190 ° C. and melt flow rate at load 2.16 kg: 7 g / 10 min) is used. A dicing sheet was obtained in the same manner as in Example 1.
  • Example 3 As in Example 1, except that high-density polyethylene (manufactured by Nippon Polypro Co., Ltd., product name “NOVATEC HY540”, temperature 190 ° C. and melt flow rate at load 2.16 kg: 1 g / 10 min) is used as the thermoplastic resin. To obtain a dicing sheet.
  • high-density polyethylene manufactured by Nippon Polypro Co., Ltd., product name “NOVATEC HY540”
  • temperature 190 ° C. temperature 190 ° C.
  • melt flow rate at load 2.16 kg 1 g / 10 min
  • thermoplastic resin a high-pressure low-density polyethylene that is an ethylene homopolymer (manufactured by Sumitomo Chemical Co., Ltd., product name “Sumikasen F101-1”, melt flow rate at a temperature of 190 ° C. and a load of 2.16 kg: 0.3 g / 10 min)
  • a dicing sheet was obtained in the same manner as in Example 1 except that was used.
  • Example 5 As in Example 1, except that low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., product name “Sumikasen G801”, melt flow rate at a temperature of 190 ° C. and a load of 2.16 kg: 20 g / 10 min) is used as the thermoplastic resin. To obtain a dicing sheet.
  • low density polyethylene manufactured by Sumitomo Chemical Co., Ltd., product name “Sumikasen G801”
  • Example 1 with the exception of using a polypropylene-based elastomer (product name “Toughmer PN2070”, temperature 190 ° C. and melt flow rate: 3.2 g / 10 min at a load of 2.16 kg) as the thermoplastic resin.
  • a dicing sheet was obtained in the same manner.
  • Example 7 Example except that ethylene- ⁇ -olefin (manufactured by Mitsui Chemicals, product name “Toughmer 4070S”, temperature 190 ° C. and melt flow rate at a load 2.16 kg: 3.6 g / 10 min) is used as the thermoplastic resin.
  • a dicing sheet was obtained in the same manner as in 1.
  • Test Example 1 (Measurement of tensile modulus)
  • the base film obtained in Examples and Comparative Examples was cut into 15 mm ⁇ 140 mm test pieces, and the tensile elastic modulus was measured according to JIS K7127: 1999. Specifically, the test piece was set to a distance between chucks of 100 mm with a tensile tester (manufactured by Shimadzu Corporation, product name “Autograph AG-IS 500N”), and then subjected to a tensile test at a speed of 200 mm / min. The tensile modulus (MPa) was measured. The results are shown in Table 1. However, in the case where the base film could not be formed satisfactorily and the tensile modulus could not be measured, “-” was displayed in Table 1.
  • thermoplastic resins used in the examples and comparative examples were measured using a differential scanning calorimeter (DSC, manufactured by DS Instruments, product name “Q2000”) according to JIS K7121.
  • DSC differential scanning calorimeter
  • Test Example 6 Evaluation of mountability Regarding the dicing sheets of Examples and Comparative Examples in which the film forming property was evaluated as good in Test Example 4, a 6-inch wafer was attached to the adhesive layer, and then the dicing sheet was mounted on a flat frame. Thereafter, when the flat frame was lifted parallel to the ground, the dicing sheet did not sag, and the sagging occurred as x. The results are shown in Table 1.
  • Test Example 7 Evaluation of expandability With respect to the dicing sheets of Examples and Comparative Examples in which the mount suitability was evaluated as “good” in Test Example 6, dicing was performed using the same apparatus as in Test Example 4 under the same conditions.
  • the ultraviolet-ray was irradiated from the base film side (light quantity: 160mJ / cm ⁇ 2 >).
  • the dicing sheet was pulled down 20 mm at a speed of 2 mm / sec. At that time, the dicing sheet is not torn or the dicing sheet is not peeled off from the frame, and the one that can be expanded without any problems is marked as ⁇ , and the dicing sheet is torn or the dicing sheet is peeled off from the frame ⁇ It was evaluated. The results are shown in Table 1.
  • the dicing sheets produced in the examples hardly formed thread-like cut pieces and exhibited excellent expandability. Further, the dicing sheets produced in the examples were excellent in film forming properties, mountability and solvent resistance.
  • the dicing sheet according to the present invention is suitably used for dicing semiconductor wafers and various packages.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
PCT/JP2016/053016 2015-12-08 2016-02-02 ダイシングシートおよびダイシングシートの製造方法 WO2017098736A1 (ja)

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US7141300B2 (en) * 2001-06-27 2006-11-28 Nitto Denko Corporation Adhesive sheet for dicing
WO2004011521A1 (ja) * 2002-07-29 2004-02-05 Sumitomo Chemical Company, Limited 熱硬化性樹脂組成物及び接着性フィルム
JP4554908B2 (ja) * 2003-10-24 2010-09-29 日東電工株式会社 ダイシング用粘着シート、ダイシング方法および半導体素子の製造方法
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