WO2016047565A1 - 樹脂層付きワーク固定シート - Google Patents
樹脂層付きワーク固定シート Download PDFInfo
- Publication number
- WO2016047565A1 WO2016047565A1 PCT/JP2015/076548 JP2015076548W WO2016047565A1 WO 2016047565 A1 WO2016047565 A1 WO 2016047565A1 JP 2015076548 W JP2015076548 W JP 2015076548W WO 2016047565 A1 WO2016047565 A1 WO 2016047565A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin layer
- meth
- curable resin
- mass
- sensitive adhesive
- Prior art date
Links
Images
Classifications
-
- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- 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
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
-
- 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
Definitions
- the present invention relates to a work fixing sheet with a resin layer comprising a pressure-sensitive adhesive layer on a base film and a curable resin layer on the pressure-sensitive adhesive layer.
- the workpiece fixing sheet with a resin layer comprising an adhesive layer on a base film and a curable resin layer on the adhesive layer includes, for example, a step of picking up a semiconductor chip after dicing a semiconductor wafer.
- the picked-up semiconductor chip is suitable for use in processes up to die bonding for bonding to a substrate, a lead frame, or another semiconductor chip.
- the curable resin layer of the workpiece fixing sheet with the resin layer functions as an adhesive film for die bonding, and the workpiece fixing sheet with the resin layer is attached to the semiconductor wafer with the curable resin.
- the work fixing sheet with a resin layer is used as a dicing die bonding sheet.
- the workpiece fixing sheet with a resin layer is used, for example, as a semiconductor wafer or semiconductor chip (flip chip) protective film and a dicing sheet, or when a flip chip is bonded to a chip mounting portion. It can also be used as an adhesive film and a back grind sheet.
- the work fixing sheet with a resin layer is stuck to the semiconductor chip by the curable resin layer, and the pressure-sensitive adhesive layer is peeled from the curable resin layer together with the base film. At this time, if necessary, the adhesiveness of the pressure-sensitive adhesive layer may be lowered by performing a polymerization reaction in the pressure-sensitive adhesive layer.
- the strength of the curable resin layer of the work fixing sheet with a resin layer is improved by containing a filler.
- the filler may fall off from the cured film after the curable resin layer containing the filler is cured. Therefore, a work fixing sheet with a resin layer provided with a curable resin layer substantially containing no filler is desired.
- an adhesive sheet in which an adhesive layer is directly attached to a semiconductor wafer without using a curable resin layer.
- an adhesive sheet for example, an adhesive layer using a base polymer having a structural unit derived from a methacrylate monomer having an alkyl group having 10 to 17 carbon atoms and two other specific monomers.
- a base polymer having a structural unit derived from a methacrylate monomer having an alkyl group having 10 to 17 carbon atoms and two other specific monomers. The thing provided with (refer patent document 1) is disclosed.
- Patent Document 1 does not describe or suggest the provision of a curable resin layer on the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet and the constituent components of the curable resin layer. And, when using a work fixing sheet with a resin layer provided with a curable resin layer that does not substantially contain a filler, normally a semiconductor chip can be easily picked up without applying a large external force, so-called easy pickup There was a problem that would decrease.
- the present invention has been made in view of the above circumstances, and is provided with a pressure-sensitive adhesive layer on a base film and a curable resin layer substantially free of a filler on the pressure-sensitive adhesive layer. It is an object of the present invention to provide a work fixing sheet with a resin layer, which has an easy pick-up property for a chip.
- the present invention is a work fixing sheet with a resin layer comprising a pressure-sensitive adhesive layer on a base film and a curable resin layer on the pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer Contains a (meth) acrylic acid alkyl ester polymer obtained by polymerizing a monomer containing a (meth) acrylic acid alkyl ester having 10 to 18 carbon atoms in the alkyl group, and the curable resin layer comprises a polymer component (A) and a curable component (b) are contained, and the total content of the polymer component (a) and the curable component (b) of the curable resin layer is based on the total amount of the curable resin layer.
- the pressure-sensitive adhesive layer Contains a (meth) acrylic acid alkyl ester polymer obtained by polymerizing a monomer containing a (meth) acrylic acid alkyl ester having 10 to 18 carbon atoms in the alkyl group
- the curable resin layer comprises a polymer component (A) and
- the curable resin layer contains an acrylic resin as the polymer component (a), and the acrylic resin is contained with respect to the total solid content of the curable resin layer.
- the amount is preferably 50% by mass or more.
- the content of the curable component (b) in the curable resin layer is 1 to 100 masses with respect to 100 mass parts of the polymer component (a). What is a part is preferable.
- an adhesive layer on a base film and a curable resin layer that does not substantially contain a filler, that is, has no effect at all or contains a filler.
- a work fixing sheet with a resin layer which is provided with a curable resin layer containing a filler to a negligible level on the pressure-sensitive adhesive layer and has an easy pick-up property for a semiconductor chip.
- the work fixing sheet with a resin layer according to the present invention is a work fixing sheet with a resin layer comprising a pressure-sensitive adhesive layer on a base film and a curable resin layer on the pressure-sensitive adhesive layer, the pressure-sensitive adhesive
- the layer contains a (meth) acrylic acid alkyl ester polymer obtained by polymerizing a monomer containing a (meth) acrylic acid alkyl ester having 10 to 18 carbon atoms in the alkyl group
- the curable resin layer comprises a polymer A component (a) and a curable component (b) are contained, and the total content of the polymer component (a) and the curable component (b) in the curable resin layer is based on the total amount of the curable resin layer.
- the laminated structure of the base film and the pressure-sensitive adhesive layer is referred to as a workpiece fixing sheet.
- polymerization includes both homopolymerization of a single type of monomer (also referred to as a monomer) and copolymerization of a plurality of types of monomers. Therefore, in this specification, the “polymer” includes both a homopolymer obtained by homopolymerizing a single type of monomer and a copolymer obtained by copolymerizing a plurality of types of monomers.
- the workpiece fixing sheet with a resin layer is, for example, a die that bonds a picked-up semiconductor chip to a substrate, a lead frame, or another semiconductor chip through a process of picking up a semiconductor chip after dicing a semiconductor wafer. It is suitable for use in processes up to bonding.
- the curable resin layer functions as an adhesive film for die bonding
- the work fixing sheet with the resin layer is diced with the curable resin layer attached to a semiconductor wafer.
- the workpiece fixing sheet with the resin layer is used as a dicing die bonding sheet.
- the work fixing sheet with a resin layer has a sufficiently easy pick-up property that allows a work (semiconductor chip) to be picked up easily even with a small external force. Therefore, breakage such as cracks when picking up a thin semiconductor chip is suppressed.
- the pressure-sensitive adhesive layer contains a compound capable of undergoing a polymerization reaction, such easy pick-up property is further improved by a decrease in the pressure-sensitive adhesive property of the pressure-sensitive adhesive layer after the polymerization reaction.
- the curable resin layer does not substantially contain a filler, the above-described easy pick-up property is deteriorated.
- the pressure-sensitive adhesive layer is polymerized with a monomer containing a (meth) acrylic acid alkyl ester having an alkyl group having 10 to 18 carbon atoms (meth).
- a monomer containing a (meth) acrylic acid alkyl ester having an alkyl group having 10 to 18 carbon atoms (meth) By containing an acrylic acid alkyl ester polymer, even if the curable resin layer does not substantially contain a filler, it has good easy pick-up properties.
- the carbon number of the alkyl group of the (meth) acrylic acid alkyl ester used for the pressure-sensitive adhesive layer is 9 or less
- the curable resin layer does not substantially contain a filler
- the work fixing sheet with a resin layer is The semiconductor chip does not have an easy pick-up property.
- the alkyl group of the (meth) acrylic acid alkyl ester used in the pressure-sensitive adhesive layer has 19 or more carbon atoms, it is difficult to handle because of its low solubility.
- the semiconductor chip is peeled off from the pressure-sensitive adhesive layer after dicing (pickup) To do).
- the pressure-sensitive adhesive layer contains a component that is polymerized by irradiation with energy rays
- the pressure-sensitive adhesive layer can be picked up after irradiating the pressure-sensitive adhesive layer with the energy rays to reduce the adhesiveness of the pressure-sensitive adhesive layer.
- the semiconductor chip is fixed to the curable resin layer using a workpiece fixing sheet with a resin layer, after dicing, the semiconductor chip is peeled off from the adhesive layer while being integrated with the curable resin layer.
- the adhesive layer is peeled off (pick up).
- the work fixing sheet with a resin layer is not easy to peel as described above, and the peelability (easy pick-up property) tends to be inferior to that of the work fixing sheet without the curable resin layer.
- the work fixing sheet with a resin layer according to the present invention is excellent in peelability (easy pick-up property) by adopting the above configuration.
- the work fixing sheet with a resin layer according to the present invention is also suitable for use as a protective film forming sheet for protecting the back surface of the flip chip.
- the curable resin layer functions as a film for forming a flip-chip protective film, and when dicing is performed with a work fixing sheet with a resin layer attached to a semiconductor wafer with a curable resin layer. Further, it is used as a semiconductor wafer or a semiconductor chip (flip chip) protective sheet and a dicing sheet.
- the work fixing sheet with a resin layer is a method in which a curable resin layer is attached to an electrode forming surface of a semiconductor wafer for flip chip, and a surface opposite to the electrode forming surface of the semiconductor wafer is ground, It can also be used when the work fixing sheet is peeled off leaving the curable resin layer on the forming surface.
- the curable resin layer (resin layer) functions as an adhesive film when the flip chip is subsequently bonded to the chip mounting portion, and the work fixing sheet with the resin layer serves as both the adhesive film and the back grind sheet.
- FIG. 1 is a cross-sectional view schematically showing a workpiece fixing sheet with a resin layer according to the present invention.
- a workpiece fixing sheet 10 with a resin layer shown in FIG. 1 includes an adhesive layer 12 on a base film 11 and a curable resin layer 13 on the adhesive layer 12. In this configuration, a curable resin layer 13 is provided on the pressure-sensitive adhesive layer 12.
- the work fixing sheet 10 with a resin layer further includes a release film 14 on the curable resin layer 13.
- the pressure-sensitive adhesive layer 12 is laminated on the surface 11 a of the base film 11, and the curable resin layer 13 is laminated on a part of the surface 12 a of the pressure-sensitive adhesive layer 12.
- the peeling film 14 is laminated
- the work fixing sheet with a resin layer according to the present invention is not limited to that shown in FIG.
- the material of the base film is preferably various resins, specifically, polyethylene (low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE, etc.)), polypropylene, polybutene. , Polybutadiene, polymethylpentene, polyvinyl chloride fill, vinyl chloride polymer, polyethylene terephthalate, polybutylene terephthalate, polyurethane, polyurethane acrylate, polyimide, ethylene vinyl acetate polymer, ionomer resin, ethylene / (meth) acrylic acid polymer, Examples thereof include ethylene / (meth) acrylic acid ester polymers, polystyrene, polycarbonate, fluororesin, water additives, modified products, cross-linked products or polymers of any of these resins.
- LDPE low density polyethylene
- LLDPE linear low density polyethylene
- HDPE high density polyethylene
- Polypropylene polybutene.
- Polybutadiene polymethylpenten
- the base film may be composed of one layer (single layer), may be composed of two or more layers, and when it is composed of a plurality of layers, the material of each layer may be the same or all may be different. Well, only a part may be the same.
- the thickness of the base film can be appropriately selected depending on the purpose, but is preferably 50 to 300 ⁇ m, and more preferably 60 to 100 ⁇ m.
- Said "thickness of a base film” is a value represented by the average which measured thickness with the contact-type thickness meter in arbitrary five places.
- the surface may be subjected to oxidation treatment such as irradiation treatment, flame treatment, chromic acid treatment, and hot air treatment.
- the base film may have a surface subjected to primer treatment.
- the base film is preferably one whose surface has been subjected to electron beam irradiation treatment from the viewpoint that generation of fragments of the base film due to blade friction during dicing is suppressed.
- the pressure-sensitive adhesive layer contains the (meth) acrylic acid alkyl ester polymer.
- the pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing a target component such as the (meth) acrylic acid alkyl ester polymer. And the ratio of content of the non-volatile components in an adhesive composition becomes the same ratio also in an adhesive layer.
- the thickness of the pressure-sensitive adhesive layer can be appropriately selected depending on the purpose, but is preferably 1 to 100 ⁇ m, more preferably 1 to 60 ⁇ m, and particularly preferably 1 to 30 ⁇ m.
- Said "thickness of an adhesive layer” is the value represented by the average which measured thickness with the contact-type thickness meter in arbitrary five places.
- the whole film is similar to the above in a state where other films such as a base film and a release material to be described later are overlapped. You may calculate by measuring thickness and taking the difference with the thickness (what was measured by the method similar to the above) of the other film overlaid.
- the (meth) acrylic acid alkyl ester polymer is obtained by polymerizing a monomer containing a (meth) acrylic acid alkyl ester having 10 to 18 carbon atoms in the alkyl group constituting the alkyl ester.
- the simple description of “(meth) acrylic acid alkyl ester” refers to the above “(meth) acrylic acid alkyl ester having 10 to 18 carbon atoms in the alkyl group” unless otherwise specified. Shall mean.
- the alkyl group having 10 to 18 carbon atoms of the (meth) acrylic acid alkyl ester may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic.
- the linear or branched chain is preferred.
- Preferred alkyl (meth) acrylates having 10 to 18 carbon atoms in the alkyl group are decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate).
- esters isobornyl (meth) acrylate, and (meth Such as acrylic acid dicyclopentanyl (meth) acrylic acid cycloalkyl esters can be exemplified.
- examples of the (meth) acrylic acid alkyl ester having an alkyl group having 10 to 18 carbon atoms include dodecyl (meth) acrylate (lauryl (meth) acrylate) or isooctadecyl (meth) acrylate.
- (Isostearyl (meth) acrylate) is particularly preferable from the viewpoint of obtaining an effect of improving the easy pick-up property for a workpiece.
- an energy ray-polymerizable polymer that is polymerized by irradiation with energy rays can also be used.
- Preferred examples of such polymers include a hydroxyl group and a urethane.
- bonding can be illustrated.
- Such a (meth) acrylic acid alkyl ester polymer is crosslinked, for example, by the reaction of the hydroxyl group of the polymer with an isocyanate group in an isocyanate-based crosslinking agent described later.
- such an acrylate polymer has a polymerizable group in the side chain, for example, by using a low molecular weight energy beam polymerizable compound separately and causing a polymerization reaction by irradiation with energy rays.
- a low molecular weight energy beam polymerizable compound separately and causing a polymerization reaction by irradiation with energy rays.
- the effect of improving the peelability from the adherend and the ease of picking up the workpiece can be obtained.
- a low molecular weight energy ray polymerizable compound since it is not necessary to use a low molecular weight energy ray polymerizable compound separately, as described later, when a curable resin layer is formed on the pressure-sensitive adhesive layer, such a low molecular weight energy ray polymerizable compound is used. The transition from the pressure-sensitive adhesive layer to the curable resin layer is suppressed, and the change in the characteristics of the curable resin layer is suppressed.
- the above-mentioned preferable (meth) acrylic acid alkyl ester polymer is usually obtained by polymerizing the above (meth) acrylic acid alkyl ester and a hydroxyl group-containing monomer to obtain a polymer, It can be obtained by reacting an isocyanate group of a compound having an isocyanate group and a polymerizable group with the hydroxyl group of the polymer.
- a catalyst such as an organic tin compound.
- This catalyst remains in the reaction system after completion of the reaction, but it is difficult to completely remove from the obtained (meth) acrylic acid alkyl ester polymer, or even if it can be removed, there is a step for that purpose. By adding, the operation becomes complicated and the productivity also decreases. Therefore, since a method in which the catalyst is not removed from the reaction system after completion of the reaction is usually employed, the catalyst remains in the obtained (meth) acrylic acid alkyl ester polymer.
- the catalyst remaining in the (meth) acrylic acid alkyl ester polymer is capable of causing an undesired crosslinking reaction when the pressure-sensitive adhesive composition using such a polymer is stored.
- This tendency is particularly strong when the number of moles of isocyanate groups in the isocyanate-based crosslinking agent is large relative to 1 mole of hydroxyl groups in the (meth) acrylic acid alkyl ester polymer.
- the use of a reaction retarder described later suppresses the progress of the crosslinking reaction which is not intended as described above. Is done.
- the residual amount (content) of the said catalyst is 2 mass% or less, and the said (meth) acrylic-acid alkylester polymer is 1 mass% or less. Is more preferable, and it is further more preferable that it is 0.5 mass% or less.
- more preferable polymers include those monomers having the (meth) acrylic acid alkyl ester and a hydroxyl group-containing (meth) acrylic acid ester as essential monomers.
- a reaction product of a copolymer of the above and a compound having an isocyanate group and a polymerizable group, wherein the hydroxyl group of the copolymer is combined with the isocyanate group of the compound having the isocyanate group and the polymerizable group The said reaction material can be illustrated.
- hydroxyl group-containing (meth) acrylic acid ester examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.
- Examples of the compound having an isocyanate group and a polymerizable group include isocyanate group-containing (meth) acrylic acid alkyl esters such as 2-methacryloyloxyethyl isocyanate.
- the preferred (meth) acrylic acid alkyl ester polymer may be obtained by further reacting an arbitrary compound, and the monomer is polymerized as the optional compound. May be good.
- the optional monomer include a hydroxyl group-free (meth) acrylic ester, (meth) acrylic acid, itaconic acid, and a non (meth) acrylic monomer that do not correspond to the (meth) acrylic acid alkyl ester. Can be illustrated.
- Examples of the hydroxyl group-free (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth ) Hexyl acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid alkyl esters in which the alkyl group constituting the alkyl ester is linear or branched and having 1 to 9 carbon atoms, such as isononyl acid; aralkyl (meth) acrylates such as benzyl (meth) acrylate; Cycloalkenyl (me
- non- (meth) acrylic monomer examples include vinyl acetate, acrylonitrile, styrene, and N-methylolacrylamide.
- the (meth) acrylic acid alkyl ester polymer such as the (meth) acrylic acid alkyl ester, the hydroxyl group-containing (meth) acrylic acid ester, the compound having an isocyanate group and a polymerizable group, and the above-mentioned arbitrary compound.
- a component constitutituent component of the said polymer
- all may be only 1 type and 2 or more types may be sufficient as it.
- the (meth) acrylic acid alkyl ester polymer (as described above, the preferred (meth) acrylic acid alkyl ester polymer has a hydroxyl group and further has a polymerizable group in the side chain via a urethane bond.
- the ratio of the alkyl group (meth) acrylic acid alkyl ester having 10 to 18 carbon atoms in the alkyl group is 60% by mass or more with respect to the total mass of all monomers used in the polymerization. A thing of 70 mass% or more is more preferable, and a thing of 75 mass% or more is especially preferable.
- the proportion of the alkyl group (meth) acrylic acid alkyl ester having 10 to 18 carbon atoms in the alkyl group is the sum of the masses of all monomers used in the polymerization. On the other hand, it is 100 mass% or less.
- the said (meth) acrylic-acid alkylester polymer which an adhesive layer contains may be only 1 type, and 2 or more types may be sufficient as it.
- the other contained monomer is not particularly limited, but for example, the alkyl (meth) acrylate Examples include hydroxyl group-containing (meth) acrylic acid esters that do not correspond to esters, hydroxyl group-free (meth) acrylic acid esters, (meth) acrylic acid, itaconic acid, and non- (meth) acrylic monomers.
- Specific examples of the (meth) acrylic acid ester, the hydroxyl group-free (meth) acrylic acid ester, and the non- (meth) acrylic monomer are the same as those described above.
- the content of the (meth) acrylic acid alkyl ester polymer is preferably 75% by mass or more, and more preferably 80% by mass or more.
- content of the said (meth) acrylic-acid alkylester polymer of the said adhesive composition is with respect to the total amount of all components other than the solvent in an adhesive composition. It is preferable that it is 75 mass% or more, and it is more preferable that it is 80 mass% or more. Moreover, 100 mass% may be sufficient as content of the (meth) acrylic-acid alkylester polymer of said adhesive composition.
- Preferred examples of the pressure-sensitive adhesive composition include those containing an isocyanate-based crosslinking agent and a reaction retarder in addition to the (meth) acrylic acid alkyl ester polymer. Since such an adhesive composition suppresses the progress of an unintended cross-linking reaction during storage, changes in properties such as viscosity during storage are suppressed, and the storage stability is high.
- the isocyanate-based crosslinking agent is not particularly limited as long as it is a crosslinking agent having an isocyanate group (—N ⁇ C ⁇ O), and preferred examples include 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4,4′-diisocyanate; diphenylmethane-2,4′-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4 , 4′-diisocyanate; dicyclohexylmethane-2,4′-diisocyanate; all or part of hydroxyl groups of polyols such as trimethylolpropane, tolylene diiso
- the isocyanate-based crosslinking agent contained in the pressure-sensitive adhesive composition may be only one type or two or more types.
- the number of moles of isocyanate groups contained in the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition is 0.2 times the number of moles of hydroxyl groups contained in the alkyl (meth) acrylate polymer in the pressure-sensitive adhesive composition.
- the above is preferable. By comprising in this way, an adhesive layer becomes less adhesive to a workpiece
- the number of moles of isocyanate groups possessed by the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition is the number of moles of hydroxyl groups possessed by the (meth) acrylic acid alkyl ester polymer in the pressure-sensitive adhesive composition. Is preferably 3 times or less.
- production of the by-product of isocyanate type crosslinking agents becomes higher. That is, the number of moles of the isocyanate group possessed by the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition is 0. 0 relative to the number of moles of the hydroxyl group possessed by the (meth) acrylic acid alkyl ester polymer in the pressure-sensitive adhesive composition. A range of 2 to 3 times is preferable.
- the content of the isocyanate-based crosslinking agent in the pressure-sensitive adhesive composition may be appropriately adjusted so that the number of moles of isocyanate groups falls within the above-mentioned range. ) It is preferably 3 to 20 parts by mass, more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the alkyl acrylate polymer.
- reaction retarder suppresses the progress of an unintended cross-linking reaction in the pressure-sensitive adhesive composition during storage.
- the (meth) acrylic acid alkyl ester polymer usually contains the catalyst used for its preparation as described above.
- the reaction retarding agent include those that inhibit the action of this catalyst in the pressure-sensitive adhesive composition, and preferable examples thereof include those that form a chelate complex by chelation with respect to the catalyst.
- the said catalyst is an organotin compound, what forms a chelate complex with tin as a reaction retarder can be illustrated.
- reaction retardant examples include those having two or more carbonyl groups (—C ( ⁇ O) —) in the molecule, and those having two carbonyl groups in the molecule.
- examples include dicarboxylic acid, keto acid, and diketone.
- reaction retardant examples include those having a carbonylmethylcarbonyl group (—C ( ⁇ O) —CH 2 —C ( ⁇ O) —), and more specifically, malonic acid, ⁇ -keto acids such as acetoacetic acid; Methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, isobutyl acetoacetate, tert-butyl acetoacetate, methyl propionyl acetate, ethyl propionyl acetate, n-propyl propionyl acetate, propionyl acetic acid Isopropyl, n-butyl propionyl acetate, tert-butyl propionyl acetate, methyl butyryl acetate, ethyl butyryl acetate, n-
- the reaction retarder contained in the pressure-sensitive adhesive composition may be only one kind or two or more kinds.
- the pressure-sensitive adhesive composition preferably contains 0.01 to 2% by mass of a reaction retardant with respect to the total amount of all components.
- the content of the reaction retardant is equal to or higher than the lower limit, the pressure-sensitive adhesive composition has a higher effect of suppressing the progress of an undesired crosslinking reaction during storage.
- the pressure-sensitive adhesive layer is provided by applying and drying the pressure-sensitive adhesive composition because the content of the reaction-retarding agent is not more than the upper limit, the reaction time-retarding agent is volatilized by drying, and the pressure-sensitive adhesive layer It is possible to prevent the reaction retarder from remaining excessively therein.
- the content of the reaction retarding agent in the pressure-sensitive adhesive composition may be appropriately adjusted so that the mass ratio in the total amount of all the components of the pressure-sensitive adhesive composition falls within the above range.
- the content of the (meth) acrylic acid alkyl ester polymer is preferably 0.01 to 10 parts by mass, and 0.05 to 5 parts by mass with respect to 100 parts by mass. Is more preferable.
- the pressure-sensitive adhesive composition further contains a photopolymerization initiator in addition to the (meth) acrylic acid alkyl ester polymer, the isocyanate-based crosslinking agent, and the reaction retarder.
- the photopolymerization initiator may be a known one, specifically, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, ⁇ -hydroxy- ⁇ , ⁇ ′-dimethylacetophenone, ⁇ -ketol compounds such as 2-methyl-2-hydroxypropiophenone and 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl Acetophenone compounds such as -1- [4- (methylthio) -phenyl] -2-morpholinopropane-1; benzoin ether compounds such as benzoin ethyl ether, benzoin isopropyl ether and anisoin methyl ether; ketals such as benzyldimethyl ketal Compounds; 2-naphtha Aromatic sulfonyl chloride compounds such as sulfonyl chlor
- the content of the photopolymerization initiator in the pressure-sensitive adhesive composition is preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid alkyl ester polymer.
- the pressure-sensitive adhesive composition more preferably contains a solvent in addition to the (meth) acrylic acid alkyl ester polymer.
- the solvent is not particularly limited, and preferred examples include hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropan-1-ol), and 1-butanol; Examples include esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides (compounds having an amide bond) such as dimethylformamide and N-methylpyrrolidone.
- the solvent which the said adhesive composition contains only 1 type may be sufficient and 2 or more types may be sufficient.
- the content of the solvent is preferably 40 to 90% by mass, more preferably 50 to 80% by mass with respect to the total mass of the pressure-sensitive adhesive composition. .
- the pressure-sensitive adhesive composition does not fall under the isocyanate-based crosslinking agent, reaction retarder, photopolymerization initiator, and solvent within a range not impairing the effects of the present invention.
- Other components may be contained.
- the other components may be known ones and can be arbitrarily selected according to the purpose, and are not particularly limited. Preferred examples include dyes, pigments, deterioration inhibitors, antistatic agents, flame retardants, silicone compounds, and Various additives such as a chain transfer agent can be exemplified.
- the said adhesive composition is obtained by mix
- the order of addition at the time of blending the above components is not particularly limited, and two or more components may be added simultaneously.
- the method of mixing each component at the time of compounding is not particularly limited, for example, a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, a method of mixing by adding ultrasonic waves, etc. What is necessary is just to select suitably from these methods.
- the temperature and time at the time of addition and mixing of each component are not particularly limited as long as each compounding component is not deteriorated, and may be appropriately adjusted. However, the temperature is preferably 15 to 30 ° C.
- the curable resin layer contains a polymer component (a) and a curable component (b), and the total content of the polymer component (a) and the curable component (b) in the curable resin layer is: It is 95 mass% or more with respect to the whole quantity of the said curable resin layer, 97 mass% or more is preferable, 98 mass% or more is more preferable, and 100 mass% may be sufficient.
- a curable resin layer does not substantially contain a filler (a filler (c) described later). And in this invention, even if it has such a curable resin layer, the said workpiece
- the work fixing sheet with a resin layer according to the present invention has a characteristic that the filler is a curable resin.
- the filler is a curable resin.
- the curable resin layer does not substantially contain a filler means that the curable resin layer does not contain a filler at all or the effect of using a filler is ignored. It means that the curable resin layer contains only a small amount of filler to the extent obtained.
- the filler contained in the curable resin layer is less than 5% by mass, preferably less than 3% by mass relative to the total solid content of the curable resin composition forming the curable resin layer. Preferably, it means a case of less than 1% by mass.
- the curable resin layer can be formed using a curable resin composition containing desired components such as the polymer component (a) and the curable component (b). And the ratio of content of the non-volatile components in curable resin composition becomes the same also in a curable resin layer.
- the polymer component (a) is a component that can be regarded as formed by polymerization reaction of a polymerizable compound.
- the curable component (b) is a component that can undergo a curing (polymerization) reaction.
- the polymerization reaction includes a polycondensation reaction.
- the polymer component (a) and the curable component (b) are main components of the curable resin layer that are necessary for the curable resin layer to exhibit its effects.
- hardenable component (b) such a component is not a sclerosing
- the thickness of the curable resin layer can be appropriately selected depending on the purpose, but is preferably 1 to 100 ⁇ m, more preferably 5 to 75 ⁇ m, and particularly preferably 5 to 50 ⁇ m.
- the average thickness of the curable resin layer can be obtained by the same measurement method as the average thickness of the pressure-sensitive adhesive layer described above.
- the above-mentioned “thickness of the curable resin layer” is a value represented by an average obtained by measuring the thickness with a contact-type thickness meter at any five locations.
- a contact thickness meter directly to the pressure-sensitive adhesive layer the same as the above in a state where other layers such as a base film, a pressure-sensitive adhesive layer, and a release material to be described later are overlapped. By measuring the overall thickness, and taking the difference from the thickness of the other layers superimposed (measured by the same method as described above or measured by the adhesive layer measurement method described above) It may be calculated.
- the curable resin layer preferably has pressure-sensitive adhesive properties, preferably has heat-curable properties, and more preferably has both pressure-sensitive adhesive properties and heat-curable properties.
- the curable resin layer having both pressure-sensitive adhesiveness and heat curable property can be attached by lightly pressing on various adherends in an uncured state.
- the curable resin layer may be one that can be applied to various adherends by heating and softening.
- the curable resin layer undergoes thermosetting and eventually becomes a cured product with high impact resistance. Such cured product has excellent shear strength and maintains sufficient adhesive properties even under severe high temperature and high humidity conditions. obtain.
- the polymer component (a) is a polymer compound for imparting film-forming properties, flexibility and the like to the curable resin layer.
- the polymer component (a) may also correspond to the curable component (b).
- a phenoxy resin, an acrylic resin having an epoxy group in a side chain, and the like correspond to the polymer component (a) and may correspond to the curable component (b).
- Such a component is handled as the polymer component (a).
- a polymer component (a) may be used individually by 1 type, and may use 2 or more types together.
- an acrylic resin a polyester resin, a urethane resin, an acrylic urethane resin, a silicone resin, a rubber polymer, or a phenoxy resin can be used, and an acrylic resin is preferable.
- the weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,500,000. If the weight average molecular weight of the acrylic resin is too small, the adhesive force between the curable resin layer and the pressure-sensitive adhesive layer is increased, which may cause a pickup failure of the semiconductor chip. If the weight average molecular weight of the acrylic resin is too large, the curable resin layer may not follow the uneven surface of the adherend, which may cause voids and the like.
- the weight average molecular weight is a polystyrene conversion value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
- the glass transition temperature (Tg) of the acrylic resin is preferably ⁇ 60 to 70 ° C., and more preferably ⁇ 30 to 50 ° C. If the Tg of the acrylic resin is too low, the peeling force between the curable resin layer and the pressure-sensitive adhesive layer becomes large, which may cause a pickup failure of the semiconductor chip. Further, if the Tg of the acrylic resin is too high, the adhesive force for fixing the semiconductor wafer may be insufficient.
- Monomers constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n- Octyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate , Tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, hexadecyl (meth) acrylate (palmityl (meth)
- the acrylic resin may be one obtained by polymerizing monomers such as acrylic acid, methacrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, or N-methylolacrylamide.
- the monomer constituting the acrylic resin may be only one type or two or more types.
- the term “polymer” or “resin” or the like used for a substance in which a monomer is polymerized is a “polymer” composed of structural units derived from the monomer (also referred to as repeating units) or It means “resin” or the like.
- the “polymer” or “resin” and the like when the amount of the monomer used for the production thereof is described with a ratio such as mass or number of moles, such ratio is Can be read as the ratio of the structural unit derived from the monomer to the total amount of polymerized “polymer” or “resin”. That is, for example, when it is explained that the monomers X and Y are used to polymerize the polymer Z by using 20% by mass and 80% by mass, respectively, in the polymer Z, the polymer Z It can be read that the ratio of the structural unit derived from the monomer X and the structural unit derived from the monomer Y to the total mass is 20% by mass and 80% by mass, respectively.
- the acrylic resin may have a functional group capable of binding to other compounds such as a vinyl group, a (meth) acryloyl group, an amino group, a hydroxyl group, a carboxyl group, and an isocyanate group. Bonding with another compound may be performed via a crosslinking agent (f) described later, or the functional group may be directly bonded to another compound without passing through the crosslinking agent (f). .
- the acrylic resin is bonded by these functional groups, the package reliability of the semiconductor device using the work fixing sheet with the resin layer tends to be improved.
- the content of the acrylic resin in the curable resin composition is 50 with respect to the total solid content of the curable resin composition. It is preferable that it is mass% or more. With such a range, when the curable resin layer is used for a process of collectively curing the semiconductor chip during resin sealing, the curable resin layer has a preferable property. This is because, in such a process, wire bonding to the chip is performed before the resin sealing of the semiconductor chip, but even when the curable resin layer before curing is exposed to a high temperature, it has a certain degree of hardness. This is because wire bonding can be performed in a state where the above is maintained.
- the content of the acrylic resin in the curable resin composition is relatively large, the storage elastic modulus of the curable resin layer can be increased even before thermosetting. For this reason, even when the curable resin layer is uncured or semi-cured, the vibration and displacement of the chip during wire bonding are suppressed, and wire bonding can be performed stably.
- the curable resin composition contains an acrylic resin as the polymer component (a)
- the content of the acrylic resin in the curable resin composition is the total solid content of the curable resin composition. More preferably, it is 50 to 90% by mass.
- the content of the acrylic resin is relatively large as described above, the adhesiveness between the pressure-sensitive adhesive layer and the curable resin layer tends to be high and the adhesive force tends to be high.
- the adhesive force between the pressure-sensitive adhesive layer and the curable resin layer is reduced, and the easy pick-up property of the semiconductor chip is improved.
- the content of the acrylic resin in the curable resin layer is preferably 50% by mass or more, and 50 More preferably, it is -90 mass%.
- thermoplastic resin other than an acrylic resin
- the thermoplastic resin preferably has a weight average molecular weight of 1,000 to 100,000, more preferably 3,000 to 80,000.
- the glass transition temperature (Tg) of the thermoplastic resin is preferably ⁇ 30 to 150 ° C., and more preferably ⁇ 20 to 120 ° C.
- the thermoplastic resin include polyester resin, urethane resin, phenoxy resin, polybutene, polybutadiene, and polystyrene.
- One of the above thermoplastic resins may be used alone, or two or more may be used in combination.
- thermoplastic resin By using the thermoplastic resin, the above-described effects can be obtained.
- the curable resin layer before curing is reduced in hardness when exposed to high temperature, and is curable resin in an uncured or semi-cured state. There is a concern that the wire bonding suitability of the layer may be reduced. Therefore, it is preferable to set the content of the acrylic resin in the curable resin composition in consideration of such influence.
- the thermoplastic resin is preferably used in combination with an acrylic resin.
- curable component (b) examples include an epoxy thermosetting resin, a thermosetting polyimide resin, a urethane resin, an unsaturated polyester resin, and a silicone resin. Among these, an epoxy thermosetting resin is preferable.
- the curable component (b) may correspond to the polymer component (a), but such a component is handled as the polymer component (a).
- Epoxy-type thermosetting resin consists of an epoxy resin and a thermosetting agent. Epoxy thermosetting resin may be used individually by 1 type, and may use 2 or more types together.
- epoxy resin examples include known ones, specifically, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, orthocresol novolac epoxy resins, dicyclopentadiene type epoxy resins.
- Biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenylene skeleton type epoxy resin can be exemplified as bifunctional or higher functional epoxy compounds.
- an epoxy resin having an unsaturated hydrocarbon group may be used as the epoxy resin.
- the epoxy resin having an unsaturated hydrocarbon group include a compound obtained by converting a part of an epoxy resin of a polyfunctional epoxy resin into a group containing an unsaturated hydrocarbon group. Such a compound can be produced, for example, by addition reaction of acrylic acid to an epoxy group.
- the compound etc. which the group containing an unsaturated hydrocarbon group directly couple
- the unsaturated hydrocarbon group is a polymerizable unsaturated group, and specifically includes an ethenyl group (vinyl group), 2-propenyl group (allyl group), acryloyl group, methacryloyl group, acrylamide group, and methacrylamide. Examples thereof include an acryloyl group.
- An epoxy resin having an unsaturated hydrocarbon group is more compatible with an acrylic resin than an epoxy resin having no unsaturated hydrocarbon group. For this reason, the package reliability of a semiconductor device improves by using the curable resin composition containing the epoxy resin which has an unsaturated hydrocarbon group.
- the epoxy resin preferably has a softening point or a high glass transition temperature from the viewpoint of improving easy pick-up property.
- the number average molecular weight of the epoxy resin is not particularly limited, but is preferably 300 to 30,000, more preferably 400 to 10,000 from the viewpoints of curability of the curable resin layer, strength after curing, and heat resistance. A range of 500 to 3000 is particularly preferable.
- the epoxy equivalent of the epoxy resin is preferably 100 to 1000 g / eq, and more preferably 300 to 800 g / eq.
- the epoxy resin may be used alone or in combination of two or more.
- thermosetting agent functions as a curing agent for the epoxy resin.
- a thermosetting agent the compound which has 2 or more of functional groups which can react with an epoxy group in 1 molecule can be illustrated.
- the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and a group in which an acid group has been anhydrideized, and a group in which a phenolic hydroxyl group, an amino group, and an acid group have been anhydrideized. It is preferably a phenolic hydroxyl group or an amino group, more preferably a phenolic hydroxyl group.
- thermosetting agents examples include polyfunctional phenol resins, biphenols, novolac-type phenol resins, dicyclopentadiene-based phenol resins, and aralkyl phenol resins.
- examples of the amine-based curing agent examples include DICY (dicyandiamide).
- the thermosetting agent may have an unsaturated hydrocarbon group.
- the thermosetting agent having an unsaturated hydrocarbon group a compound obtained by substituting a part of the hydroxyl group of the phenol resin with a group containing an unsaturated hydrocarbon group, an unsaturated hydrocarbon group on the aromatic ring of the phenol resin. Examples thereof include a compound in which the containing group is directly bonded.
- the unsaturated hydrocarbon group in the thermosetting agent is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group described above.
- thermosetting agent is preferably one having a high softening point or glass transition temperature from the viewpoint of improving easy pick-up property.
- the number average molecular weight of the thermosetting agent is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000.
- thermosetting agent may be used alone or in combination of two or more.
- the content of the thermosetting agent in the curable resin composition is preferably 0.1 to 500 parts by mass and more preferably 1 to 200 parts by mass with respect to 100 parts by mass of the epoxy resin. preferable. If the content of the thermosetting agent is too small, the adhesiveness may not be obtained due to insufficient curing. If the content of the thermosetting agent is excessive, the moisture absorption rate of the curable resin layer increases and the package reliability is increased. May be reduced.
- the content of the curable component (b) in the curable resin composition (curable resin layer) is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the polymer component (a).
- the amount is more preferably 1.5 to 75 parts by mass, and particularly preferably 2 to 60 parts by mass.
- the adhesive force between the pressure-sensitive adhesive layer and the curable resin layer is reduced, and the easy pick-up property of the semiconductor chip is improved.
- the curable resin layer is a curable resin containing, in addition to the polymer component (a) and the curable component (b), if necessary, other components not corresponding to these in order to improve various physical properties. It may be formed using a composition. Examples of other components contained in the curable resin composition include a filler (c), a curing accelerator (d), a coupling agent (e), a crosslinking agent (f), and a general-purpose additive (g). .
- the curable resin composition usually contains the filler (c), so that the adjustment of the thermal expansion coefficient is facilitated. Therefore, using such a curable resin composition, the reliability of the package is improved by optimizing the thermal expansion coefficient of the curable resin layer after curing for a semiconductor chip, metal or organic substrate. Can do. Moreover, normally the moisture absorption rate of the curable resin layer after hardening can also be reduced by using the curable resin composition containing a filler (c).
- the filler (c) is a component that does not correspond to either the polymer component (a) or the curable component (b).
- the curable resin layer does not contain the filler (c), or the content of the filler (c) is more than 0% by mass and 5% by mass. Therefore, the content of the filler (c) of the curable resin composition is less than 5% by mass, preferably less than 3% by mass, based on the total amount of the solid content of the curable resin composition. Preferably it is less than 1 mass%.
- the filler (c) is preferably an inorganic filler (c), and preferred inorganic fillers include silica, alumina, talc, calcium carbonate, titanium white, bengara, silicon carbide, boron nitride and the like; these Examples thereof include beads obtained by spheroidizing silica or the like; single crystal fibers such as silica; glass fibers or the like.
- the inorganic filler is preferably a silica filler or an alumina filler.
- An inorganic filler (c) may be used individually by 1 type, and may use 2 or more types together.
- a hardening accelerator (d) is used in order to adjust the hardening rate of curable resin composition, and is a component which does not correspond to any of a polymer component (a) and a curable component (b).
- Preferred curing accelerators (d) include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-phenylimidazole, 2 -Imidazoles such as phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (groups in which one or more hydrogen atoms are other than hydrogen atoms) Substituted imidazole); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphin
- the content of the curing accelerator (d) in the curable resin composition is 0.01 to 10 parts by mass with respect to 100 parts by mass of the curable component (b).
- the amount is preferably 0.1 to 1 part by mass.
- the content of the curing accelerator (d) is within such a range, the curable resin layer has excellent adhesive properties even under high temperature / high humidity conditions, and is exposed to severe reflow conditions. However, high package reliability can be achieved.
- the effect by using a hardening accelerator (d) will not fully be acquired, but when the content of a hardening accelerator (d) is excessive, it will be highly polar.
- the curing accelerator (d) moves to the adhesion interface side with the adherend in the curable resin layer under high temperature and high humidity conditions, and segregates, thereby reducing the reliability of the package.
- the coupling agent (e) is a component that does not correspond to either the polymer component (a) or the curable component (b).
- the coupling agent (e) is preferably a compound having a functional group that reacts with the functional group of the polymer component (a), the curable component (b), etc., and is preferably a silane coupling agent.
- Preferred examples of the silane coupling agent include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ - (methacryloxy).
- the coupling agent (e) one of the above may be used alone
- the content of the coupling agent (e) in the curable resin composition is 100 parts by mass with respect to the total content of the polymer component (a) and the curable component (b).
- the amount is preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass.
- Crosslinking agent (f) When the above-mentioned acrylic resin having a functional group that can be bonded to a functional group of another compound such as an isocyanate group is used as the polymer component (a), the functional group is bonded to the other compound to be crosslinked. Therefore, a crosslinking agent (f) can be used. By the crosslinking using the crosslinking agent (f) as described above, the initial adhesive force and cohesive force of the curable resin layer can be adjusted.
- the crosslinking agent (f) include organic polyvalent isocyanate compounds and organic polyvalent imine compounds.
- a crosslinking agent (f) is a component which does not correspond to any of a polymer component (a) and a sclerosing
- organic polyvalent isocyanate compounds examples include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimers of these compounds, isocyanurates, and adducts (ethylene glycol, propylene glycol).
- a reaction product with a low molecular active hydrogen-containing compound such as neopentyl glycol, trimethylolpropane or castor oil, such as trimethylolpropane adduct xylylene diisocyanate), or an organic polyvalent isocyanate compound and a polyol compound.
- the terminal isocyanate urethane prepolymer obtained can be exemplified.
- organic polyvalent isocyanate compound 2,4-tolylene diisocyanate; 2,6-tolylene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; diphenylmethane-4,4 Diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; trimethylolpropane, etc.
- organic polyvalent imine compound examples include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxamide), trimethylolpropane-tri- ⁇ -aziridinylpropionate, tetramethylolmethane-tri Examples include - ⁇ -aziridinyl propionate, N, N′-toluene-2,4-bis (1-aziridinecarboxamide) triethylenemelamine, and the like.
- crosslinking agent (f) When using an isocyanate type crosslinking agent as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the acrylic resin that is the polymer component (a).
- a crosslinked structure can be easily introduced into the curable resin layer by a reaction between the crosslinking agent (f) and the acrylic resin.
- the content of the crosslinking agent (f) in the curable resin composition is 0.01 to 20 parts by mass with respect to 100 parts by mass of the polymer component (a). It is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass.
- General-purpose additive (g) examples include known plasticizers, antistatic agents, antioxidants, pigments, dyes, gettering agents and the like.
- the general-purpose additive (g) is a component that does not correspond to either the polymer component (a) or the curable component (b).
- the curable resin composition preferably further contains a solvent in order to improve the handleability by dilution.
- the solvent contained in the curable resin composition may be the same as the solvent in the above-mentioned pressure-sensitive adhesive composition.
- the solvent which a curable resin composition contains may be only 1 type, and 2 or more types may be sufficient as it.
- the solvent contained in the curable resin composition is preferably methyl ethyl ketone or the like from the viewpoint that the components used in the curable resin composition are uniformly mixed.
- a solvent is a component which does not correspond to any of a polymer component (a) and a sclerosing
- the total content of the polymer component (a) and the curable component (b) in the curable resin layer is 95% by mass or more and 97% by mass or more based on the total amount of the curable resin layer. Is more preferable, and 98% by mass or more is more preferable.
- the total content of the polymer component (a) and the curable component (b) of the curable resin composition is other than the solvent in the curable resin composition. It is 95 mass% or more with respect to the total amount of all the components of this, It is more preferable that it is 97 mass% or more, It is further more preferable that it is 98 mass% or more.
- the total content of the polymer component (a) and the curable component (b) in the curable resin layer may be 100% by mass with respect to the total amount of the curable resin layer.
- the curable resin composition is obtained by blending the above-described components for constituting the curable resin composition.
- the curable resin composition is obtained by the same method as the above-described pressure-sensitive adhesive composition except that the blending components are different.
- a solvent it may be used by mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance, or by diluting any compounding component other than the solvent in advance. You may use it by mixing a solvent with these compounding ingredients, without leaving.
- the easy pick-up property of the semiconductor chip described in the work fixing sheet with a resin layer according to the present invention is, for example, a semiconductor chip on the surface of the work fixing sheet with a resin layer, using a commercially available die bonder,
- the push-up height is set to a predetermined condition, and it can be evaluated whether or not the semiconductor chip can be picked up under this condition. At this time, for example, when a total of 100 chips are continuously picked up and all chips have been successfully picked up, or after one or more chips have been picked up successfully, the second and subsequent chips are used. If any one of the pickups fails, it can be determined that the ease of pickup is relatively good.
- the work fixing sheet with a resin layer according to the present invention includes, for example, forming a pressure-sensitive adhesive layer on the base film using the pressure-sensitive adhesive composition, and curing using the curable resin composition on the pressure-sensitive adhesive layer. Can be produced by forming a conductive resin layer.
- the pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive composition to the surface of the base film (the surface 11a of the base film 11 in FIG. 1) and drying it. At this time, you may bridge
- the heating conditions can be, for example, 100 to 130 ° C. for 1 to 5 minutes, but are not limited thereto.
- the pressure-sensitive adhesive layer can be formed by applying a pressure-sensitive adhesive composition to the surface of the release layer of the release material and drying it to attach the pressure-sensitive adhesive layer to the surface of the substrate film and removing the release material. .
- Application to the surface of the base film of the pressure-sensitive adhesive composition or the release layer surface of the release material may be performed by a known method, such as an air knife coater, blade coater, bar coater, gravure coater, roll coater, roll knife coater, Examples include a method using various coaters such as a curtain coater, a die coater, a knife coater, a screen coater, a Meyer bar coater, and a kiss coater.
- the curable resin layer can be formed using the curable resin composition in the same manner as in the case of forming the pressure-sensitive adhesive layer on the base film as described above, but is usually curable on the pressure-sensitive adhesive layer. It is difficult to apply the resin composition directly. Therefore, for example, the curable resin composition formed by applying the curable resin composition to the surface of the release layer of the release material and drying it is bonded to the surface of the pressure-sensitive adhesive layer, and the release material is removed. A method in which a resin layer is separately formed and bonded to the surface of the pressure-sensitive adhesive layer is preferable.
- the work fixing sheet with a resin layer according to the present invention includes, for example, a pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition, and a curable resin formed using the curable resin composition.
- the pressure-sensitive adhesive layer and the curable resin layer are laminated to form a laminate, and the substrate film can be bonded to the surface of the pressure-sensitive adhesive layer of the laminate.
- the conditions for forming the pressure-sensitive adhesive layer and the curable resin layer are the same as those described above.
- Example 1 A work fixing sheet with a resin layer having the configuration shown in FIG. 1 was produced. More specifically, it is as follows.
- LA lauryl acrylate
- HOA 2-hydroxyethyl acrylate
- benzoyl peroxide 0.2 parts by mass
- ethyl acetate 70 parts by mass
- toluene 30 parts by mass
- the compounding ratio of each component is shown in Table 1 below.
- MOI 2-methacryloyloxyethyl isocyanate
- DBTL dibutyltin laurate
- Isocyanate trimer adduct (“Coronate L” manufactured by Nippon Polyurethane Co., Ltd.) (7.5 parts by mass, with respect to 1 mol of residual hydroxyl group in acrylic ester polymer (A-1), 1 mol) was added and stirred at 23 ° C. to obtain a pressure-sensitive adhesive composition having a solid content concentration of 25% by mass.
- all the compounding parts in this "manufacture of an adhesive composition" are solid content conversion values.
- the compounding ratio of each component is shown in Table 1 below.
- the curable resin composition obtained above was applied onto a release liner (“SP-PET 381031” manufactured by Lintec Corporation) and dried at 100 ° C. for 1 minute to form a curable resin layer having a thickness of 20 ⁇ m. Furthermore, the same kind of release liner as above was bonded to the curable resin layer. Then, the cut release liner and the curable resin layer were further cut into a circle having a diameter of 150 mm, and unnecessary portions outside the circle were removed. Next, the release liner was removed from the work fixing sheet obtained above. Further, the release liner that had been half-cut from the curable resin layer was removed, and the pressure-sensitive adhesive layer of the workpiece fixing sheet was bonded to the surface of the curable resin layer to obtain a workpiece fixing sheet with a resin layer.
- SP-PET 381031 manufactured by Lintec Corporation
- the work fixing sheet with a resin layer was irradiated with UV light from the base film side under the conditions of 220 mW / cm 2 and 190 mJ / cm 2 .
- a die bonder (“BESTEM-D02” manufactured by Canon Machinery Co., Ltd.), it was evaluated whether the tip could be picked up when the needle push-up speed was 1 mm / s and the push-up height was 0.2 mm.
- the needle had an 8 mm square, 4 pin arrangement.
- the evaluation is performed by continuously performing pickup for 100 chips, and “A” indicates that all chips have been successfully picked up, and then the second and subsequent chips after one or more chips have been successfully picked up. Evaluation was made with “A1” as the failure of any of the pickups and “B” as the failure of the first chip. The results are shown in Table 1 below.
- Example 2 Comparative Examples 1 and 2, Reference Example 1
- a work fixing sheet with a resin layer is produced in the same manner as in Example 1 except that the blending components during the production of the alkyl acrylate polymer and the blending components during the production of the curable resin composition are as shown in Table 1 below. And evaluated. The results are shown in Table 1 below.
- the acrylic acid alkyl ester polymer obtained here was used as the acrylic acid alkyl ester polymer (A-2) (Example 2) and acrylic acid alkyl ester polymer (R-1) (Comparative Example 1), respectively.
- Acrylic acid alkyl ester polymer (R-2) (Comparative Example 2, Reference Example 1).
- the pressure-sensitive adhesive composition is adjusted to a solid content concentration of 25% by mass by adjusting the amount of methyl ethyl ketone.
- the work fixing sheets with resin layers of Examples 1 and 2 were used for the production of alkyl acrylate ester polymers (the polymers (A-1) and (A-2)).
- ester As the ester, LA (alkyl group having 12 carbon atoms) or ISTA (alkyl group having 18 carbon atoms) is used, and the total content of the polymer component (a) and the curable component (b) of the curable resin layer is determined. It was 98.9% by mass and had easy pick-up properties.
- the work fixing sheets with resin layers of Comparative Examples 1 and 2 were used as alkyl acrylates for the production of acrylic acid alkyl ester polymers (the polymers (R-1) and (R-2)).
- the work fixing sheet with a resin layer of Reference Example 1 uses MA as an alkyl acrylate ester in the production of an alkyl acrylate polymer, but includes a curable resin layer containing a filler, and is easily picked up. Had sex. As shown in Table 1, in each of the above examples, the case where one or more chips have been successfully picked up and the pick-up of any one of the second and subsequent chips has failed, that is, the ease of picking up is shown. An example for evaluation of “A1” was not found.
- the present invention can be used for manufacturing semiconductor chips and the like.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本出願は、2014年9月22日に日本に出願された特願2014-192505号に基づき、優先権を主張し、その内容をここに援用する。
いずれの用途でも、樹脂層付きワーク固定シートは、硬化性樹脂層により半導体チップに貼付された状態とされ、さらに粘着剤層が基材フィルムごと硬化性樹脂層から剥離される。このとき、必要に応じて、粘着剤層で重合反応を行うことで、粘着剤層の粘着性を低下させておくことがある。
本発明の樹脂層付きワーク固定シートは、前記硬化性樹脂層が、前記重合体成分(a)としてアクリル系樹脂を含有し、前記硬化性樹脂層の固形分の全量に対する前記アクリル系樹脂の含有量が、50質量%以上であるものが好ましい。
本発明の樹脂層付きワーク固定シートは、前記硬化性樹脂層の前記硬化性成分(b)の含有量が、前記重合体成分(a)の含有量100質量部に対して、1~100質量部であるものが好ましい。
本発明に係る樹脂層付きワーク固定シートは、基材フィルム上に粘着剤層を備え、前記粘着剤層上に硬化性樹脂層を備えてなる樹脂層付きワーク固定シートであって、前記粘着剤層は、アルキル基の炭素数が10~18の(メタ)アクリル酸アルキルエステルを含む単量体が重合した(メタ)アクリル酸アルキルエステル重合体を含有し、前記硬化性樹脂層は、重合体成分(a)及び硬化性成分(b)を含有し、前記硬化性樹脂層の前記重合体成分(a)及び硬化性成分(b)の総含有量が、前記硬化性樹脂層の全量に対して95質量%以上であることを特徴とする。
本明細書では、基材フィルム及び粘着剤層の積層構造を、ワーク固定シートと称する。
本明細書において、「重合」とは、単一種のモノマー(単量体ともいう)の単独重合、及び複数種のモノマーの共重合の両者を含む。したがって、本明細書において、「重合体」とは、単一種のモノマーが単独重合した単独重合体、及び複数種のモノマーが共重合した共重合体の両者を含む。
樹脂層付きワーク固定シートは、通常、硬化性樹脂層が充填材を実質的に含有しない場合には、上記の易ピックアップ性が低下してしまう。これに対して、本発明に係る樹脂層付きワーク固定シートは、粘着剤層が、アルキル基の炭素数が10~18の(メタ)アクリル酸アルキルエステルを含む単量体が重合した(メタ)アクリル酸アルキルエステル重合体を含有することにより、硬化性樹脂層が充填材を実質的に含有していなくても、良好な易ピックアップ性を有する。粘着剤層に用いる(メタ)アクリル酸アルキルエステルのアルキル基の炭素数が9以下であると、硬化性樹脂層が充填材を実質的に含有していない場合に、樹脂層付きワーク固定シートは、半導体チップの易ピックアップ性を有しない。一方、粘着剤層に用いる(メタ)アクリル酸アルキルエステルのアルキル基の炭素数が19以上のものは、溶解性が低いなど、取り扱いにくい。
一方、樹脂層付きワーク固定シートを用いて、その硬化性樹脂層に半導体チップを固定した場合には、ダイシング後に、半導体チップを、硬化性樹脂層と一体化した状態のまま粘着剤層から剥離させるか、場合によってはエネルギー線を照射した後に、粘着剤層から剥離させる(ピックアップする)。
そして、通常は、樹脂層付きワーク固定シートの方が、硬化性樹脂層を備えていないワーク固定シートよりも、上述の剥離が容易ではなく、剥離性(易ピックアップ性)が劣る傾向にある。
これに対して、本発明に係る樹脂層付きワーク固定シートは、上記の構成を採用することで、剥離性(易ピックアップ性)に優れる。
図1に示す樹脂層付きワーク固定シート10は、基材フィルム11上に粘着剤層12を備え、粘着剤層12上に硬化性樹脂層13を備えてなるものであり、ワーク固定シート1の粘着剤層12上に、硬化性樹脂層13を備えた構成のものである。また、樹脂層付きワーク固定シート10は、さらに、硬化性樹脂層13上に剥離フィルム14を備えている。
ワーク固定シート10において、粘着剤層12は、基材フィルム11の表面11a上に積層され、硬化性樹脂層13は、粘着剤層12の表面12aの一部に積層されている。そして、粘着剤層12の表面12aのうち、硬化性樹脂層13が積層されていない露出面と、硬化性樹脂層13の表面13a(上面及び側面)の上に、剥離フィルム14が積層されている。
ただし、本発明に係る樹脂層付きワーク固定シートは、図1に示すものに限定されない。
基材フィルムの材質は、各種樹脂であることが好ましく、具体的には、ポリエチレン(低密度ポリエチレン(LDPE)、直鎖低密度ポリエチレン(LLDPE)、高密度ポリエチレン(HDPE等))、ポリプロピレン、ポリブテン、ポリブタジエン、ポリメチルペンテン、ポリ塩化ビニルフィル、塩化ビニル重合体、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリウレタン、ポリウレタンアクリレート、ポリイミド、エチレン酢酸ビニル重合体、アイオノマー樹脂、エチレン・(メタ)アクリル酸重合体、エチレン・(メタ)アクリル酸エステル重合体、ポリスチレン、ポリカーボネート、フッ素樹脂、これらのいずれかの樹脂の水添加物、変性物、架橋物又は重合物等が例示できる。
なお、本明細書において、「(メタ)アクリル」とは、「アクリル」及び「メタクリル」の両方を包含する概念とする。
上記の「基材フィルムの厚さ」とは、任意の5箇所で、接触式厚み計で厚さを測定した平均で表される値である。
これらの中でも基材フィルムは、ダイシング時のブレードの摩擦による基材フィルムの断片の発生が抑制される点から、特に表面が電子線照射処理を施されたものが好ましい。
前記粘着剤層は、前記(メタ)アクリル酸アルキルエステル重合体を含有する。
粘着剤層は、前記(メタ)アクリル酸アルキルエステル重合体等の、目的とする成分を含有する粘着剤組成物を用いて形成できる。そして、粘着剤組成物中の非揮発性成分同士の含有量の比率は、粘着剤層においても同じ比率となる。
上記の「粘着剤層の厚さ」とは、任意の5箇所で、接触式厚み計で厚さを測定した平均で表される値である。なお、粘着剤層に直接に接触式厚み計を適用することが困難であるときは、基材フィルムや、後述する剥離材など、他のフィルムが重ねあわされた状態で上記と同様に全体の厚さを測定し、重ね合わせれていた他のフィルムの厚さ(上記と同様の方法で測定したもの)との差分を取ることで算出してもよい。
前記(メタ)アクリル酸アルキルエステル重合体は、アルキルエステルを構成するアルキル基の炭素数が10~18の(メタ)アクリル酸アルキルエステルを含む単量体が重合したものである。なお、本明細書において、単なる「(メタ)アクリル酸アルキルエステル」との記載は、特に断りのない限り、上記の「アルキル基の炭素数が10~18の(メタ)アクリル酸アルキルエステル」を意味するものとする。
前記(メタ)アクリル酸アルキルエステルの、炭素数が10~18のアルキル基は、直鎖状、分岐鎖状及び環状のいずれでもよく、環状である場合、単環状及び多環状のいずれでもよいが、直鎖状又は分岐鎖状であることが好ましい。
これに対して、本発明においては、たとえ、上述のイソシアネート基のモル数が大きい場合であっても、後述する反応遅延剤を用いることで、上述のような目的としない架橋反応の進行が抑制される。そして、この抑制効果がより向上する点から、前記(メタ)アクリル酸アルキルエステル重合体は、前記触媒の残存量(含有量)が2質量%以下であることが好ましく、1質量%以下であることがより好ましく、0.5質量%以下であることがさらに好ましい。
前記任意の単量体としては、前記(メタ)アクリル酸アルキルエステルに該当しない水酸基非含有(メタ)アクリル酸エステル、(メタ)アクリル酸、イタコン酸、及び非(メタ)アクリル系単量体等が例示できる。
また、アルキル基の炭素数が10~18の(メタ)アクリル酸アルキルエステルを含む単量体において、他に含まれる単量体としては、特に限定されないが、例えば、前記(メタ)アクリル酸アルキルエステルに該当しない水酸基含有(メタ)アクリル酸エステル、水酸基非含有(メタ)アクリル酸エステル、(メタ)アクリル酸、イタコン酸、及び非(メタ)アクリル系単量体等が例示でき、水酸基含有(メタ)アクリル酸エステル、水酸基非含有(メタ)アクリル酸エステル、及び非(メタ)アクリル系単量体の具体例としては前述したものと同じである。
前記イソシアネート系架橋剤は、イソシアネート基(-N=C=O)を有する架橋剤であれば特に限定されず、好ましいものとしては、2,4-トリレンジイソシアネート;2,6-トリレンジイソシアネート;1,3-キシリレンジイソシアネート;1,4-キシレンジイソシアネート;ジフェニルメタン-4,4’-ジイソシアネート;ジフェニルメタン-2,4’-ジイソシアネート;3-メチルジフェニルメタンジイソシアネート;ヘキサメチレンジイソシアネート;イソホロンジイソシアネート;ジシクロヘキシルメタン-4,4’-ジイソシアネート;ジシクロヘキシルメタン-2,4’-ジイソシアネート;トリメチロールプロパン等のポリオールのすべて若しくは一部の水酸基に、トリレンジイソシアネート及びヘキサメチレンジイソシアネートのいずれか一方又は両方を付加した化合物;リジンジイソシアネート等が例示できる。
一方、本発明においては、前記粘着剤組成物中のイソシアネート系架橋剤が有するイソシアネート基のモル数は、前記粘着剤組成物中の前記(メタ)アクリル酸アルキルエステル重合体が有する水酸基のモル数に対して3倍以下であることが好ましい。このように構成することで、イソシアネート系架橋剤同士の副生成物の発生を抑制する効果がより高くなる。
即ち、上記の粘着剤組成物中のイソシアネート系架橋剤が有するイソシアネート基のモル数は、粘着剤組成物中の(メタ)アクリル酸アルキルエステル重合体が有する水酸基のモル数に対して、0.2~3倍の範囲であることが好ましい。
前記反応遅延剤は、保存中の前記粘着剤組成物において、目的としない架橋反応の進行を抑制するものである。
前記(メタ)アクリル酸アルキルエステル重合体は、通常、上述のように、その調製に用いた触媒を含有する。反応遅延剤としては、この触媒の粘着剤組成物中における作用を阻害するものが例示でき、好ましいものとしては、前記触媒に対するキレートによって、キレート錯体を形成するものが例示できる。例えば、前記触媒が有機スズ化合物である場合には、反応遅延剤としてスズとキレート錯体を形成するものが例示できる。
好ましい反応遅延剤として、より具体的には、分子中にカルボニル基(-C(=O)-)を2個以上有するものが例示でき、分子中にカルボニル基を2個有するものであれば、ジカルボン酸、ケト酸、及びジケトン等が例示できる。
アセト酢酸メチル、アセト酢酸エチル、アセト酢酸n-プロピル、アセト酢酸イソプロピル、アセト酢酸n-ブチル、アセト酢酸イソブチル、アセト酢酸tert-ブチル、プロピオニル酢酸メチル、プロピオニル酢酸エチル、プロピオニル酢酸n-プロピル、プロピオニル酢酸イソプロピル、プロピオニル酢酸n-ブチル、プロピオニル酢酸tert-ブチル、ブチリル酢酸メチル、ブチリル酢酸エチル、ブチリル酢酸n-プロピル、ブチリル酢酸イソプロピル、ブチリル酢酸n-ブチル、ブチリル酢酸tert-ブチル、イソブチリル酢酸メチル、イソブチリル酢酸エチル、イソブチリル酢酸n-プロピル、イソブチリル酢酸イソプロピル、イソブチリル酢酸n-ブチル、イソブチリル酢酸tert-ブチル、3-オキソヘプタン酸メチル、3-オキソヘプタン酸エチル、3-オキソヘプタン酸n-プロピル、3-オキソヘプタン酸イソプロピル、3-オキソヘプタン酸n-ブチル、3-オキソヘプタン酸tert-ブチル、5-メチル-3-オキソヘキサン酸メチル、5-メチル-3-オキソヘキサン酸エチル、5-メチル-3-オキソヘキサン酸n-プロピル、5-メチル-3-オキソヘキサン酸イソプロピル、5-メチル-3-オキソヘキサン酸n-ブチル、5-メチル-3-オキソヘキサン酸tert-ブチル、4,4-ジメチル-3-オキソペンタン酸メチル、4,4-ジメチル-3-オキソペンタン酸エチル、4,4-ジメチル-3-オキソペンタン酸n-プロピル、4,4-ジメチル-3-オキソペンタン酸イソプロピル、4,4-ジメチル-3-オキソペンタン酸n-ブチル、4,4-ジメチル-3-オキソペンタン酸tert-ブチル、ベンゾイル酢酸メチル、マロン酸ジメチル、マロン酸ジエチル、マロン酸メチルエチル、マロン酸ジn-プロピル、マロン酸ジイソプロピル、マロン酸ジn-ブチル、マロン酸ジtert-ブチル、マロン酸メチルtert-ブチル等のβ-ケト酸エステル;
アセチルアセトン、ジベンゾイルメタン等のβ-ジケトン(1,3-ジケトン)等が例示できる。
前記粘着剤組成物は、前記(メタ)アクリル酸アルキルエステル重合体、イソシアネート系架橋剤及び反応遅延剤以外に、さらに光重合開始剤を含有するものがより好ましい。
前記光重合開始剤は、公知のものでよく、具体的には、4-(2-ヒドロキシエトキシ)フェニル(2-ヒドロキシ-2-プロピル)ケトン、α-ヒドロキシ-α,α’-ジメチルアセトフェノン、2-メチル-2-ヒドロキシプロピオフェノン、1-ヒドロキシシクロヘキシルフェニルケトン等のα-ケトール系化合物;メトキシアセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン、2,2-ジエトキシアセトフェノン、2-メチル-1-[4-(メチルチオ)-フェニル]-2-モルホリノプロパン-1等のアセトフェノン系化合物;ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、アニソインメチルエーテル等のベンゾインエーテル系化合物;ベンジルジメチルケタール等のケタール系化合物;2-ナフタレンスルホニルクロリド等の芳香族スルホニルクロリド系化合物;1-フェノン-1,1-プロパンジオン-2-(o-エトキシカルボニル)オキシム等の光活性オキシム系化合物;ベンゾフェノン、ベンゾイル安息香酸、3,3’-ジメチル-4-メトキシベンゾフェノン等のベンゾフェノン系化合物;チオキサンソン、2-クロロチオキサンソン、2-メチルチオキサンソン、2,4-ジメチルチオキサンソン、イソプロピルチオキサンソン、2,4-ジクロロチオキサンソン、2,4-ジエチルチオキサンソン、2,4-ジイソプロピルチオキサンソン等のチオキサンソン系化合物;カンファーキノン;ハロゲン化ケトン;アシルホスフィノキシド;アシルホスフォナート等が例示できる。
前記粘着剤組成物は、前記(メタ)アクリル酸アルキルエステル重合体以外に、さらに溶媒を含有するものがより好ましい。
前記溶媒は、特に限定されないが、好ましいものとしては、トルエン、キシレン等の炭化水素;メタノール、エタノール、2-プロパノール、イソブチルアルコール(2-メチルプロパン-1-オール)、1-ブタノール等のアルコール;酢酸エチル等のエステル;アセトン、メチルエチルケトン等のケトン;テトラヒドロフラン等のエーテル;ジメチルホルムアミド、及びN-メチルピロリドン等のアミド(アミド結合を有する化合物)等が例示できる。
前記粘着剤組成物が含有する溶媒は、1種のみでもよいし、2種以上でもよい。
前記粘着剤組成物は、前記(メタ)アクリル酸アルキルエステル重合体以外に、本発明の効果を損なわない範囲内において、前記イソシアネート系架橋剤、反応遅延剤、光重合開始剤及び溶媒に該当しないその他の成分を含有していてもよい。
前記その他の成分は、公知のものでよく、目的に応じて任意に選択でき、特に限定されないが、好ましいものとしては、染料、顔料、劣化防止剤、帯電防止剤、難燃剤、シリコーン化合物、及び連鎖移動剤等の各種添加剤が例示できる。
上記の各成分の配合時における添加順序は特に限定されず、2種以上の成分を同時に添加してもよい。
配合時に各成分を混合する方法は、特に限定されず、例えば、撹拌子又は撹拌翼等を回転させて混合する方法;ミキサーを用いて混合する方法;超音波を加えて混合する方法等、公知の方法から適宜選択すればよい。
各成分の添加及び混合時の温度並びに時間は、各配合成分が劣化しない限り、特に限定されず、適宜調節すればよいが、温度は15~30℃であることが好ましい。
前記硬化性樹脂層は、重合体成分(a)及び硬化性成分(b)を含有し、前記硬化性樹脂層の前記重合体成分(a)及び硬化性成分(b)の総含有量が、前記硬化性樹脂層の全量に対して95質量%以上のものであり、97質量%以上のものが好ましく、98質量%以上のものがより好ましく、100質量%のものであってもよい。このような硬化性樹脂層は、充填材(後述する充填材(c))を実質的に含有しないものとなる。そして、本発明においては、このような硬化性樹脂層を備えていても、前記樹脂層付きワーク固定シートが、上述のように易ピックアップ性を有する。また、硬化性樹脂層が充填材を実質的に含有していないことで、本発明に係る樹脂層付きワーク固定シートは、充填材を含有している場合に特有の、充填材が硬化性樹脂層で不均一に分散した状態となり、硬化性樹脂層を硬化させた後の硬化膜から充填材が脱落する、等の問題点を有しない。
なお、本明細書において、「硬化性樹脂層が充填材を実質的に含有しない」とは、硬化性樹脂層が充填材を全く含有しないか、又は充填剤を用いたことによる効果が無視し得る程度に、硬化性樹脂層が充填材を少量含有しているに過ぎないことを意味する。具体的には、硬化性樹脂層に含まれる充填材が、硬化性樹脂層をなす硬化性樹脂組成物の固形分の全量に対して5質量%未満であり、好ましくは3質量%未満、より好ましくは1質量%未満である場合を意味する。
重合体成分(a)及び硬化性成分(b)は、硬化性樹脂層がその効果を奏するために必要な、硬化性樹脂層の主たる構成成分である。なお、重合体成分(a)及び硬化性成分(b)の両方に該当する成分もあるが、このような成分は本発明においては、硬化性成分(b)ではなく重合体成分(a)として取り扱う。
上記の「硬化性樹脂層の厚さ」とは、任意の5箇所で、接触式厚み計で厚さを測定した平均で表される値である。なお、粘着剤層に直接に接触式厚み計を適用することが困難であるときは、基材フィルムや粘着剤層、後述する剥離材など、他の層が重ねあわされた状態で上記と同様に全体の厚さを測定し、重ね合わせられた他の層の厚さ(上記と同様の方法で測定したもの又は上述した粘着剤層の測定方法により測定したもの)との差分を取ることで算出してもよい。
重合体成分(a)は、硬化性樹脂層に、造膜性や可撓性等を付与するための重合体化合物である。重合体成分(a)は、硬化性成分(b)にも該当する場合がある。例えば、フェノキシ樹脂や、側鎖にエポキシ基を有するアクリル系樹脂等は、重合体成分(a)に該当し、かつ硬化性成分(b)にも該当することがある。このような成分は、重合体成分(a)として取り扱う。
重合体成分(a)は、1種を単独で用いてもよいし、2種以上を併用してもよい。
アクリル系樹脂の重量平均分子量(Mw)は、1万~200万であることが好ましく、10万~150万であることがより好ましい。アクリル系樹脂の重量平均分子量が小さ過ぎると、硬化性樹脂層と前記粘着剤層との接着力が高くなって、半導体チップのピックアップ不良が生じることがある。また、アクリル系樹脂の重量平均分子量が大き過ぎると、被着体の凹凸面へ硬化性樹脂層が追従できないことがあり、ボイド等の発生要因になることがある。
なお、本明細書において、重量平均分子量とは、特に断りのない限り、ゲル・パーミエーション・クロマトグラフィー(GPC)法により測定されるポリスチレン換算値である。
シクロアルキル(メタ)アクリレート、ベンジル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、イミド(メタ)アクリレート等の環状骨格を有する(メタ)アクリレート;
ヒドロキシメチル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート等の水酸基含有(メタ)アクリレート;
グリシジル(メタ)アクリレート等のグリシジル基含有(メタ)アクリレート等の(メタ)アクリル酸エステルが例示できる。
また、アクリル系樹脂は、アクリル酸、メタクリル酸、イタコン酸、酢酸ビニル、アクリロニトリル、スチレン、又はN-メチロールアクリルアミド等のモノマーが重合されたものでもよい。
アクリル系樹脂を構成するモノマーは、1種のみでもよいし、2種以上でもよい。
本明細書において、モノマーが重合された物質に対して使用される、用語「重合体」又は「樹脂」等は、前記モノマーから導かれる構成単位(繰り返し単位ともいう)からなる「重合体」又は「樹脂」等を意味する。また、本明細書において、前記「重合体」又は「樹脂」等に関し、それらの製造に使用されるモノマーの使用量が質量又はモル数等の比をもって説明される場合、かかる比は、前記モノマーが重合された「重合体」又は「樹脂」等の全体量に対する前記モノマーから導かれる構成単位の比として読むことができる。即ち、例えば、モノマーX及びYを、それぞれ20質量%及び80質量%使用して、これらを重合させて重合体Zが得られると説明されている場合、かかる重合体Zにおいて、重合体Zの総質量に対する、モノマーXから導かれる構成単位と、モノマーYから導かれる構成単位の割合は、それぞれ、20質量%及び80質量%であると読むことができる。
さらに、硬化性樹脂組成物が、重合体成分(a)としてアクリル系樹脂を含有する場合、硬化性樹脂組成物のアクリル系樹脂の含有量は、前記硬化性樹脂組成物の固形分の全量に対して50~90質量%であることがより好ましい。アクリル系樹脂の含有量が、上記のように比較的多い場合、粘着剤層と硬化性樹脂層との密着性が高くなり、接着力が高くなる傾向にあるが、本発明における粘着剤層を用いることにより、粘着剤層と硬化性樹脂層との間の接着力が低減され、半導体チップの易ピックアップ性が向上する。
このように、硬化性樹脂層が、重合体成分(a)としてアクリル系樹脂を含有する場合、硬化性樹脂層中のアクリル系樹脂の含有量は、50質量%以上であることが好ましく、50~90質量%であることがより好ましい。
前記熱可塑性樹脂は、重量平均分子量が1000~10万のものが好ましく、3000~8万のものがより好ましい。
前記熱可塑性樹脂のガラス転移温度(Tg)は、-30~150℃であることが好ましく、-20~120℃であることがより好ましい。
前記熱可塑性樹脂としては、ポリエステル樹脂、ウレタン樹脂、フェノキシ樹脂、ポリブテン、ポリブタジエン、又はポリスチレン等が例示できる。
前記熱可塑性樹脂は、上記の内の1種を単独で用いてもよいし、2種以上を併用してもよい。
本発明においては、前記熱可塑性樹脂をアクリル系樹脂と併用することが好ましい。
硬化性成分(b)としては、エポキシ系熱硬化性樹脂、熱硬化性ポリイミド樹脂、ウレタン樹脂、不飽和ポリエステル樹脂、シリコーン樹脂等が例示でき、これらの中でも、エポキシ系熱硬化性樹脂が好ましい。硬化性成分(b)は、重合体成分(a)にも該当する場合があるが、このような成分は重合体成分(a)として取り扱う。
エポキシ系熱硬化性樹脂は、エポキシ樹脂及び熱硬化剤からなる。
エポキシ系熱硬化性樹脂は、1種を単独で用いてもよいし、2種以上を併用してもよい。
不飽和炭化水素基を有するエポキシ樹脂は、不飽和炭化水素基を有しないエポキシ樹脂よりもアクリル系樹脂との相溶性が高い。このため、不飽和炭化水素基を有するエポキシ樹脂を含む硬化性樹脂組成物を用いることで、半導体装置のパッケージ信頼性が向上する。
前記エポキシ樹脂のエポキシ当量は、100~1000g/eqであることが好ましく、300~800g/eqであることがより好ましい。
熱硬化剤としては、1分子中にエポキシ基と反応し得る官能基を2個以上有する化合物が例示できる。前記官能基としては、フェノール性水酸基、アルコール性水酸基、アミノ基、カルボキシル基、及び酸基が無水物化された基等が例示でき、フェノール性水酸基、アミノ基、酸基が無水物化された基であることが好ましく、フェノール性水酸基、アミノ基であることがより好ましく、フェノール性水酸基であることが特に好ましい。
前記熱硬化剤のうち、アミン系硬化剤(アミノ基を有する硬化剤)としては、DICY(ジシアンジアミド)等が例示できる。
不飽和炭化水素基を有する熱硬化剤としては、フェノール樹脂の水酸基の一部を、不飽和炭化水素基を含む基で置換してなる化合物、フェノール樹脂の芳香環に、不飽和炭化水素基を含む基が直接結合した化合物等が例示できる。熱硬化剤における不飽和炭化水素基は、上述の不飽和炭化水素基を有するエポキシ樹脂における不飽和炭化水素基と同様のものである。
硬化性樹脂組成物が含有する他の成分としては、充填材(c)、硬化促進剤(d)、カップリング剤(e)、架橋剤(f)、汎用添加剤(g)等が例示できる。
硬化性樹脂組成物は、通常、充填材(c)を含有することにより、その熱膨張係数の調整が容易となる。したがって、このような硬化性樹脂組成物を用いて、半導体チップや金属又は有機基板に対して、硬化後の硬化性樹脂層の熱膨張係数を最適化することで、パッケージ信頼性を向上させることができる。
また、通常、充填材(c)を含有する硬化性樹脂組成物を用いることにより、硬化後の硬化性樹脂層の吸湿率を低減することもできる。
充填材(c)は、重合体成分(a)及び硬化性成分(b)のいずれにも該当しない成分である。
これらの中でも、無機充填材は、シリカフィラー又はアルミナフィラーであることが好ましい。
無機充填材(c)は、1種を単独で用いてもよいし、2種以上を併用してもよい。
硬化促進剤(d)は、硬化性樹脂組成物の硬化速度を調整するために用いられ、重合体成分(a)及び硬化性成分(b)のいずれにも該当しない成分である。
好ましい硬化促進剤(d)としては、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス(ジメチルアミノメチル)フェノール等の第3級アミン;2-メチルイミダゾール、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール、2-フェニル-4,5-ジヒドロキシメチルイミダゾール、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール等のイミダゾール類(1個以上の水素原子が水素原子以外の基で置換されたイミダゾール);トリブチルホスフィン、ジフェニルホスフィン、トリフェニルホスフィン等の有機ホスフィン類(1個以上の水素原子が有機基で置換されたホスフィン);テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレート等のテトラフェニルボロン塩等が例示できる。
硬化促進剤(d)は、1種を単独で用いてもよいし、2種以上を併用してもよい。
カップリング剤(e)として、無機化合物と反応する官能基及び有機官能基と反応する官能基を有するものを用いることにより、硬化性樹脂層の被着体に対する接着性及び密着性を向上させることができる。また、カップリング剤(e)を用いることで、硬化性樹脂層を硬化して得られる硬化物について、その耐熱性を損なうことなく、耐水性を向上させることができる。
カップリング剤(e)は、重合体成分(a)及び硬化性成分(b)のいずれにも該当しない成分である。
好ましい前記シランカップリング剤としては、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルメチルジエトキシシラン、β-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、γ-(メタクリロキシプロピル)トリメトキシシラン、γ-アミノプロピルトリメトキシシラン、N-6-(アミノエチル)-γ-アミノプロピルトリメトキシシラン、N-6-(アミノエチル)-γ-アミノプロピルメチルジエトキシシラン、N-フェニル-γ-アミノプロピルトリメトキシシラン、γ-ウレイドプロピルトリエトキシシラン、γ-メルカプトプロピルトリメトキシシラン、γ-メルカプトプロピルメチルジメトキシシラン、ビス(3-トリエトキシシリルプロピル)テトラスルファン、メチルトリメトキシシラン、メチルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリアセトキシシラン、及びイミダゾールシラン等が例示できる。
カップリング剤(e)は、上記の内の1種を単独で用いてもよいし、2種以上を併用してもよい。
重合体成分(a)として、イソシアネート基等の他の化合物が有する官能基と結合可能な官能基を有する、上述のアクリル系樹脂を用いる場合、この官能基を他の化合物と結合させて架橋するために架橋剤(f)を用いることができる。上記のような、架橋剤(f)を用いた架橋により、硬化性樹脂層の初期接着力及び凝集力を調節できる。
架橋剤(f)としては、有機多価イソシアネート化合物、有機多価イミン化合物等が例示できる。
架橋剤(f)は、重合体成分(a)及び硬化性成分(b)のいずれにも該当しない成分である。
汎用添加剤(g)としては、公知の可塑剤、帯電防止剤、酸化防止剤、顔料、染料、ゲッタリング剤等が例示できる。
汎用添加剤(g)は、重合体成分(a)及び硬化性成分(b)のいずれにも該当しない成分である。
硬化性樹脂組成物は、希釈によってその取り扱い性を良好とするために、さらに溶媒を含有するものが好ましい。
硬化性樹脂組成物が含有する溶媒は、上述の粘着剤組成物における溶媒と同様のものでよい。
硬化性樹脂組成物が含有する溶媒は、1種のみでもよいし、2種以上でもよい。
硬化性樹脂組成物が含有する溶媒は、硬化性樹脂組成物で用いる各成分を均一に混合する点から、メチルエチルケトン等であることが好ましい。
溶媒は、重合体成分(a)及び硬化性成分(b)のいずれにも該当しない成分である。
また、上記の硬化性樹脂層における重合体成分(a)及び硬化性成分(b)の総含有量は、硬化性樹脂層の全量に対して100質量%であってもよい。
溶媒を用いる場合には、溶媒を溶媒以外のいずれかの配合成分と混合してこの配合成分を予め希釈しておくことで用いてもよいし、溶媒以外のいずれかの配合成分を予め希釈しておくことなく、溶媒をこれら配合成分と混合することで用いてもよい。
本発明に係る樹脂層付きワーク固定シートは、例えば、基材フィルム上に前記粘着剤組成物を用いて粘着剤層を形成し、前記粘着剤層上に前記硬化性樹脂組成物を用いて硬化性樹脂層を形成することで製造できる。
この場合の粘着剤層及び硬化性樹脂層の形成条件は、上述の方法と同じである。
[実施例1]
図1に示す構成の樹脂層付きワーク固定シートを製造した。より具体的には、以下のとおりである。
冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、アクリル酸ラウリル(以下、「LA」と略記する)80質量部、アクリル酸-2-ヒドロキシエチル(以下、「HEA」と略記する)(20質量部)、過酸化ベンゾイル(0.2質量部)、酢酸エチル(70質量部)、トルエン(30質量部)を入れ、窒素気流中において60℃で8時間重合反応を行うことで、アクリル系ポリマー(A)を得た。各成分の配合比を下記表1に示す。
このアクリル系ポリマー(A)に、2-メタクリロイルオキシエチルイソシアネート(以下、「MOI」と略記する)(22質量部、HEAに対して約80モル%)、ジブチルスズラウリレート(以下、「DBTL」と略記する)(0.13質量部)を加え、空気気流中において23℃で12時間付加反応を行うことで、目的とするアクリル酸アルキルエステル重合体(A-1)を47質量%溶液の状態で得た。各成分の配合比を下記表1に示す。
上記で得られたアクリル酸アルキルエステル重合体(A-1)(100質量部)に対し、光重合開始剤(Z-1)(チバ・スペシャルティー・ケミカルズ社製「イルガキュア651」、ベンジルジメチルケタール)(3質量部)、反応遅延剤としてアセチルアセトン(1質量部)を加えて、メチルエチルケトンで希釈した後、よく撹拌し、さらにここへイソシアネート系架橋剤(B-1)としてトリメチロールプロパンのトリレンジイソシアネート三量体付加物(日本ポリウレタン社製「コロネートL」)(7.5質量部、アクリル酸エステル重合体(A-1)中の残存水酸基1モルに対して、有しているイソシアネート基が1モルとなる量)を加えて23℃で撹拌することで、固形分濃度が25質量%の粘着剤組成物を得た。なお、この「粘着剤組成物の製造」における配合部数は、すべて固形分換算値である。各成分の配合比を下記表1に示す。
ポリエチレンテレフタレート(PET)剥離ライナーのシリコーン処理を施した剥離面上に、上記で得られた粘着剤組成物を塗布し、120℃で2分間加熱乾燥させ、厚さ10μmの粘着剤層を形成した。次いで、この粘着剤層の表面に、基材フィルムとしての厚さ100μmのエチレン-メタクリル酸重合体フィルムを貼り合せ、23℃で168時間保存することにより、ワーク固定シートを得た。
アクリル系樹脂(ナガセケムテックス社製「SG-P3」)(87.8質量部)、エポキシ樹脂(日本化薬社製「NC-3000」)(12質量部)、フェノール樹脂(明和化成社製「MEH-7851-H」)(10質量部)、硬化促進剤としてのトリフェニルホスフィン(0.2質量部)、及びシランカップリング剤(信越シリコーン社製「KBM403」、3-グリシドキシプロピルトリメトキシシラン)(1質量部)をメチルエチルケトンに溶解させて、硬化性樹脂組成物として固形分濃度が20質量%であるメチルエチルケトン溶液を得た。
剥離ライナー(リンテック社製「SP-PET381031」)上に、上記で得られた硬化性樹脂組成物を塗布し、100℃で1分間乾燥させて、厚さ20μmの硬化性樹脂層を形成した。さらに、硬化性樹脂層に上記と同種の剥離ライナーを貼り合わせた。そして、さらに貼り合わせた剥離ライナーと硬化性樹脂層を切断するように、直径150mmの円形にハーフカットを施した上で、円形の外側の不要部分を除去した。次いで、上記で得られたワーク固定シートから剥離ライナーを除去した。また、この硬化性樹脂層から共にハーフカットした剥離ライナーを除去して、硬化性樹脂層の表面に、ワーク固定シートの粘着剤層を貼り合せることにより、樹脂層付きワーク固定シートを得た。
上記で得られた樹脂層付きワーク固定シートについて、下記方法により、易ピックアップ性を評価した。
テープマウンター(リンテック社製「Adwill RAD2500」)を用いて、シリコンウエハ(150mm径、厚さ100μm)の2000番研磨面に、上記で得られた樹脂層付きワーク固定シートを60℃で貼付した。次いで、これをウエハダイシング用リングフレームに固定した後、ダイシング装置(ディスコ社製「DFD651」)を用いて、10mm×10mmのサイズにシリコンウエハをダイシングして、チップを得た。このダイシングのとき、基材フィルムを表面から20μmだけ切り込むようにした。次いで、紫外線照射装置(リンテック社製「Adwill RAD2000」)を用いて、220mW/cm2、190mJ/cm2の条件で、基材フィルム側から樹脂層付きワーク固定シートに紫外線を照射した。次いで、ダイボンダー(キャノンマシナリー社製「BESTEM-D02」)を用いて、ニードルの突上げスピードを1mm/sとし、突き上げ高さが0.2mmの際にチップがピックアップできるかどうかを評価した。ニードルは8mm四方4ピン配置とした。評価は100個のチップについて連続してピックアップを実行することにより行い、すべてのチップのピックアップが成功した場合を「A」、1個以上のチップのピックアップが成功した後、2個目以降のチップのいずれかのピックアップに失敗した場合を「A1」、初めのチップで失敗した場合を「B」として、それぞれ評価した。結果を下記表1に示す。
[実施例2、比較例1~2、参考例1]
アクリル酸アルキルエステル重合体製造時の配合成分、硬化性樹脂組成物製造時の配合成分を、下記表1に示すとおりとした点以外は、実施例1と同様に樹脂層付きワーク固定シートを製造し、評価した。結果を下記表1に示す。
なお、ここで得られたアクリル酸アルキルエステル重合体を、それぞれ、アクリル酸アルキルエステル重合体(A-2)(実施例2)、アクリル酸アルキルエステル重合体(R-1)(比較例1)、アクリル酸アルキルエステル重合体(R-2)(比較例2、参考例1)とする。
また、すべての実施例、比較例及び参考例において、粘着剤組成物はメチルエチルケトンの量を調整して固形分濃度を25質量%に調整している。
また、「充填材」は、アドマテックス社製「SC2050MA」である。
また、配合成分の欄の「-」は、この成分が未配合であることを意味する。
これに対して、比較例1~2の樹脂層付きワーク固定シートは、アクリル酸アルキルエステル重合体(前記重合体(R-1)、(R-2))の製造に、アクリル酸アルキルエステルとして、MA(アルキル基の炭素数が1)又は2EHA(アルキル基の炭素数が8)を用いたものであり、易ピックアップ性を有していなかった。
参考例1の樹脂層付きワーク固定シートは、アクリル酸アルキルエステル重合体の製造に、アクリル酸アルキルエステルとしてMAを用いたが、硬化性樹脂層に充填剤を含有させたものであり、易ピックアップ性を有していた。
なお、表1に示すように、上記の各例においては、1個以上のチップのピックアップが成功した後、2個目以降のチップのいずれかのピックアップに失敗したケース、即ち、易ピックアップ性が「A1」の評価となる例は見られなかった。
Claims (3)
- 基材フィルム上に粘着剤層を備え、前記粘着剤層上に硬化性樹脂層を備えてなる樹脂層付きワーク固定シートであって、
前記粘着剤層は、アルキル基の炭素数が10~18の(メタ)アクリル酸アルキルエステルを含む単量体が重合した(メタ)アクリル酸アルキルエステル重合体を含有し、
前記硬化性樹脂層は、重合体成分(a)及び硬化性成分(b)を含有し、
前記硬化性樹脂層の前記重合体成分(a)及び硬化性成分(b)の総含有量が、前記硬化性樹脂層の全量に対して95質量%以上であることを特徴とする樹脂層付きワーク固定シート。 - 前記硬化性樹脂層が、前記重合体成分(a)としてアクリル系樹脂を含有し、
前記硬化性樹脂層の固形分の全量に対する前記アクリル系樹脂の含有量が50質量%以上であることを特徴とする請求項1に記載の樹脂層付きワーク固定シート。 - 前記硬化性樹脂層の前記硬化性成分(b)の含有量が、前記重合体成分(a)の含有量100質量部に対して、1~100質量部であることを特徴とする請求項1又は2に記載の樹脂層付きワーク固定シート。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020177000230A KR102421250B1 (ko) | 2014-09-22 | 2015-09-17 | 수지층이 형성된 워크 고정 시트 |
SG11201610483UA SG11201610483UA (en) | 2014-09-22 | 2015-09-17 | Workpiece securing sheet with attached resin layer |
JP2016550156A JP6817813B2 (ja) | 2014-09-22 | 2015-09-17 | 樹脂層付きワーク固定シート |
CN201580037767.4A CN106661395B (zh) | 2014-09-22 | 2015-09-17 | 带有树脂层的工件固定片 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014192505 | 2014-09-22 | ||
JP2014-192505 | 2014-09-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016047565A1 true WO2016047565A1 (ja) | 2016-03-31 |
Family
ID=55581092
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/076548 WO2016047565A1 (ja) | 2014-09-22 | 2015-09-17 | 樹脂層付きワーク固定シート |
Country Status (6)
Country | Link |
---|---|
JP (1) | JP6817813B2 (ja) |
KR (1) | KR102421250B1 (ja) |
CN (1) | CN106661395B (ja) |
SG (1) | SG11201610483UA (ja) |
TW (1) | TWI688633B (ja) |
WO (1) | WO2016047565A1 (ja) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111886309B (zh) * | 2018-03-30 | 2022-06-10 | 琳得科株式会社 | 固化密封体的防翘曲用层叠体、以及固化密封体的制造方法 |
CN109456708B (zh) * | 2018-11-06 | 2021-03-02 | 合肥鑫晟光电科技有限公司 | 胶膜、显示面板的封装方法及显示装置 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004083602A (ja) * | 2002-07-04 | 2004-03-18 | Hitachi Chem Co Ltd | 接着シート並びに半導体装置及びその製造方法 |
JP2006299226A (ja) * | 2005-03-23 | 2006-11-02 | Furukawa Electric Co Ltd:The | ダイシングダイボンドシート |
JP2007245389A (ja) * | 2006-03-14 | 2007-09-27 | Nitto Denko Corp | 半導体用粘着シート |
JP2011174042A (ja) * | 2010-02-01 | 2011-09-08 | Nitto Denko Corp | 半導体装置製造用フィルム及び半導体装置の製造方法 |
JP2015183172A (ja) * | 2014-03-26 | 2015-10-22 | リンテック株式会社 | ワーク固定シート及び樹脂層付きワーク固定シート |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4275522B2 (ja) * | 2003-12-26 | 2009-06-10 | 日東電工株式会社 | ダイシング・ダイボンドフィルム |
JP2006245352A (ja) * | 2005-03-04 | 2006-09-14 | Nitta Ind Corp | ウエハのダイシング用テープ、半導体チップのピックアップ方法 |
JP2007258437A (ja) * | 2006-03-23 | 2007-10-04 | Nippon Steel Chem Co Ltd | ダイボンドダイシング積層フィルム |
JP2007254590A (ja) * | 2006-03-23 | 2007-10-04 | Nippon Steel Chem Co Ltd | ダイボンドダイシングフィルム |
JP4717051B2 (ja) * | 2007-11-08 | 2011-07-06 | 日東電工株式会社 | ダイシング・ダイボンドフィルム |
EP2151858A2 (en) * | 2008-08-04 | 2010-02-10 | Nitto Denko Corporation | Dicing die-bonding film |
JP4628479B2 (ja) * | 2008-08-04 | 2011-02-09 | 日東電工株式会社 | ダイシング・ダイボンドフィルム |
JP4845065B2 (ja) * | 2009-08-05 | 2011-12-28 | 古河電気工業株式会社 | 粘着フィルム及び半導体ウエハ加工用テープ |
JP5143196B2 (ja) * | 2009-09-28 | 2013-02-13 | 日東電工株式会社 | 半導体装置用フィルム |
KR101083959B1 (ko) * | 2010-02-01 | 2011-11-16 | 닛토덴코 가부시키가이샤 | 반도체 장치 제조용 필름 및 반도체 장치의 제조 방법 |
WO2012017568A1 (ja) * | 2010-08-05 | 2012-02-09 | 古河電気工業株式会社 | 粘着フィルム及び半導体ウエハ加工用テープ |
JP5781302B2 (ja) | 2010-12-28 | 2015-09-16 | 日東電工株式会社 | 放射線硬化型粘着剤組成物及び粘着シート |
JP5184685B1 (ja) * | 2011-09-26 | 2013-04-17 | 古河電気工業株式会社 | 半導体ウエハ加工用テープ |
JP5294358B2 (ja) * | 2012-01-06 | 2013-09-18 | 古河電気工業株式会社 | ウエハ加工用テープ及びこれを使用した半導体装置の製造方法 |
-
2015
- 2015-09-17 SG SG11201610483UA patent/SG11201610483UA/en unknown
- 2015-09-17 CN CN201580037767.4A patent/CN106661395B/zh active Active
- 2015-09-17 KR KR1020177000230A patent/KR102421250B1/ko active IP Right Grant
- 2015-09-17 TW TW104130756A patent/TWI688633B/zh active
- 2015-09-17 WO PCT/JP2015/076548 patent/WO2016047565A1/ja active Application Filing
- 2015-09-17 JP JP2016550156A patent/JP6817813B2/ja active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004083602A (ja) * | 2002-07-04 | 2004-03-18 | Hitachi Chem Co Ltd | 接着シート並びに半導体装置及びその製造方法 |
JP2006299226A (ja) * | 2005-03-23 | 2006-11-02 | Furukawa Electric Co Ltd:The | ダイシングダイボンドシート |
JP2007245389A (ja) * | 2006-03-14 | 2007-09-27 | Nitto Denko Corp | 半導体用粘着シート |
JP2011174042A (ja) * | 2010-02-01 | 2011-09-08 | Nitto Denko Corp | 半導体装置製造用フィルム及び半導体装置の製造方法 |
JP2015183172A (ja) * | 2014-03-26 | 2015-10-22 | リンテック株式会社 | ワーク固定シート及び樹脂層付きワーク固定シート |
Also Published As
Publication number | Publication date |
---|---|
KR102421250B1 (ko) | 2022-07-14 |
KR20170058910A (ko) | 2017-05-29 |
JP6817813B2 (ja) | 2021-01-20 |
TW201623505A (zh) | 2016-07-01 |
CN106661395A (zh) | 2017-05-10 |
CN106661395B (zh) | 2021-05-28 |
SG11201610483UA (en) | 2017-03-30 |
TWI688633B (zh) | 2020-03-21 |
JPWO2016047565A1 (ja) | 2017-06-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5917215B2 (ja) | 接着剤組成物、接着シートおよび半導体装置の製造方法 | |
JP6924243B2 (ja) | 保護膜形成用複合シート | |
JP6250265B2 (ja) | 接着剤組成物、接着シートおよび半導体装置の製造方法 | |
JP6379389B2 (ja) | ダイシングダイボンディングシート | |
JP6333596B2 (ja) | 樹脂層付きワーク固定シートの製造方法 | |
JP6678641B2 (ja) | フィルム状接着剤複合シート及び半導体装置の製造方法 | |
JP7233377B2 (ja) | 熱硬化性樹脂フィルム及び第1保護膜形成用シート | |
JP2012167174A (ja) | 接着剤組成物、接着シートおよび半導体装置の製造方法 | |
JP5951207B2 (ja) | ダイシング・ダイボンディングシート | |
JP6978890B2 (ja) | ダイシングダイボンディングシート及び半導体チップの製造方法 | |
WO2013157567A1 (ja) | 接着剤組成物、接着シートおよび半導体装置の製造方法 | |
JP6817813B2 (ja) | 樹脂層付きワーク固定シート | |
JP6205646B2 (ja) | ダイ接着用複合シート | |
JP5727811B2 (ja) | 半導体チップのピックアップ方法および半導体装置の製造方法 | |
JP6547220B2 (ja) | ダイ接着用接着剤 | |
JPWO2019189173A1 (ja) | 半導体チップの製造方法 | |
JP6547221B2 (ja) | ダイ接着用接着剤 | |
JP2016143676A (ja) | ダイボンディングシート | |
JP6029536B2 (ja) | 接着剤組成物、接着シートおよび半導体装置の製造方法 | |
JP5951206B2 (ja) | ダイシング・ダイボンディングシート |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15844286 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016550156 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20177000230 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15844286 Country of ref document: EP Kind code of ref document: A1 |